Rheologically modified polyethylene compositions having relatively high melt strength and methods of making pipes, films, sheets and articles made by blow moulding

FIELD: chemistry.

SUBSTANCE: composition contains a mixture of a low molecular weight polyethylene component and a high molecular weight polyethylene component and a binding agent containing at least 0.0025 wt % polysulphonyl azide. The mixture has sine peak on the lamella thickness distribution (LTD) curve.

EFFECT: prolonged wear resistance of pipes under gas or water pressure, resistance to cracking under stress associated with environmental factors, resistance to slow formation of cracks, to fast crack propagation and to creep under internal stress.

64 cl, 3 dwg, 24 tbl, 6 ex

 

This application claims the benefit of provisional patent application U.S. No. 60/637105, registered on December 17, 2004, which is included here by reference in its entirety.

The present invention relates to the linking of polyethylene with a relatively high melt strength, more specifically, to the linking of polyethylene with a relatively high melt strength for use in forming the tube obtained by extrusion blown films, sheets, films, fibers and molded articles, such as articles, molded, compression molded under pressure and molded by the blow.

Polyethylene pipes are light in weight, easy to handle and are dekorotivnymi. In addition, their rigidity is relatively high, so that they can be laid under the ground, in addition, their flexibility is such that they can follow the contours of the ground and to adapt to the movements of the earth. These preferred characteristics, the number of used polyethylene pipes is rapidly increasing in recent years.

In addition to the above desirable characteristics, polyethylene pipes must have (1) resistance, sufficient to for a long time to endure the blows received during that and the Les in as they are installed; and (2) excellent long-lasting durability under the pressure of a gas or water (in particular, resistance to cracking under the action of stresses associated with environmental factors, resistance to slow crack to rapid crack propagation and creep under the action of internal pressure). In addition, in the production of polymer pipes for pipes must demonstrate excellent stability against gravitational sagging in a fluid condition for successful extrusion of large diameter pipe with thick walls with a minimum eccentricity of the wall thickness. Similarly, polymers for films should exhibit an improved balance of extraterrest, stability sleeve film resistance at test impact strength falling sharpened cargo and FAR (evaluation of the appearance of the film), and at the same time, be able to successfully extruded with all commercially necessary linear speeds. The polymers obtained by blowing products, should provide resistance against sagging and a good balance of rigidity and ESCR (resistance to cracking under the action of environmental factors). Termoformowanie leaves also require polymers that provide good resistance against sagging and stretchability. Finally the properties of polymers are also desirable in other applications.

High molecular weight (HMW) homopolymers and copolymers of ethylene, generally show improved strength and mechanical properties, including high tensile strength, impact strength and puncture resistance. However, along with these improvements, there are problems with manufacturability and extraterrest these HMW polymers. One of their approaches to solving this problem is to increase the width of the distribution of molecular mass (MWD) HMW polyethylene. One way of achieving this lies in the choice of catalyst, for example, it is known that chromium catalysts are prone to getting product with a broader distribution of molecular weights, than either traditional catalysts of the Ziegler-Natta (Z-N)or newer catalysts based metallocenes.

Another method used to overcome difficulties in processing associated with HMW polyethylene, is to increase the MWD of the polymer by obtaining a mixture of HMW polymer with low molecular weight (LMW) polymer. The purpose of this production is the preservation of the excellent mechanical properties of high molecular weight polyethylene, at the same time, maintaining the improvements in technology, derived from the improvement of extraterrest more low molecular weight component. For example, U.S. patent No. 6458911 and 2002/0042472 Al describe the polymer DL the film from a bimodal polymer of ethylene, containing polymeric mixture of LMW component and the HMW component. Mixture, as described, is able to form thin films of high strength.

Developed polymer compositions with high strength melt containing a mixture of HMW and LMW polyethylene, are suitable for use in the manufacture of pipes and films, as described in U.S. patent No. 2003/0065097, which is included here as a reference. Although these compositions have high melt strength, a higher melt viscosity at very low shear rates are still desirable.

Higher melt viscosity can be achieved through technologies rheological modification. As used here, the term "rheological modification" means a change in melt viscosity of the polymer, as determined from measurements of creep and dynamic mechanical spectroscopy (DMS). Preferably, the strength or viscosity at low shear rate of the polymer melt increases, and at the same time, supported the viscosity of the polymer at high shear rates. Thus, reologicheskie modified polymer exhibits great resistance to gravitational flow, SAG or stretch during elongation of the molten polymer under conditions of low shear (i.e., the viscosity measured at shear, men who eat than 0.1 rad/sec, through measurements of DMS or creep), and does not detract from output under conditions of high shear (i.e., at approximately 10 rad/sec and more). Increasing the strength of the melt, typically observed when the polymer is introduced high-molecular particles, long-chain branching or similar structure.

Polyolefins are often reologicheskie modified using selective chemical mechanisms, including free radicals, generated, for example, using peroxides or high energy emission. However, the chemical mechanisms including the generation of free radicals at elevated temperatures, also reduces the molecular weight by breakage of the chains, especially in polymers containing tertiary hydrogen, such as copolymers of polystyrene, polypropylene, polyethylene, and the like. Another technology rheological modification is achieved through the linking of polymer chains together through reaction with polysulfonamide, as discussed, for example, in U.S. patent No. 6143829, 6160029, 6359073 and 6379623.

Polymer composition with a relatively high melt strength associated with polysulfonamide to obtain products with advanced superior durability melt. This new polymer composition with high strength is Yu melt contains a component LMW polyethylene component and HMW polyethylene, where the polymer composition is essentially a single peak in the distribution curve of the leafs thickness (LTD) and is PENT (Pennsylvania Notch Test), more roughly than 1000 hours, when characterized according to ASTM D-1473-97, at about 80°C and approximately 2.4 MPa. New polymer composition, when made in the shape of a tube meets and exceeds industry requirements PE 3408 and PE 100. New polymer composition can be used as a direct (replacement) replacement for polymers currently used in conventional methods of manufacture of pipes, and can be molded with all combinations of diameter and wall thickness of pipe, which are commonly found in industry. When the polymer is in the form of a film, the result is a film with high resistance when tested for impact strength falling sharpened load (ASTM D-1709-03 Method B) with good extraterrest and stability sleeve film, adaptability and high evaluation of the appearance of the film (FAR). Articles, blow molded, with improved properties can be made of a new polymer compositions due to its combination of high melt strength and resistance against sagging (characterized by the viscosity measured at a shear rate of less than 0.1 rad/sec by measuring the dynamic mechanical spectros is the opium (DMS) or creep) and excellent balance between rigidity (characterized by density, module bending and 2% secant modulus according to ASTM D-790-03 Method B), ESCR (characterized according to ASTM D-1693-01 Method B) and impact resistance (characterized according to ASTM D-256-03 Method A and ASTM D-1822-99).

In particular, the present invention provides a composition including the reaction product of:

(a) a first composition containing the component LMW polyethylene component and HMW polyethylene, and

(b) a second composition containing a binding amount of at least one polysulfonamide, and

where the first composition is essentially the only peak on the curve LTD, and

where the composition has a value of PENT greater than 1000 hours, at 80°C with an applied voltage of about 2.4 MPa.

In one of the embodiments, the composition has a value of PENT greater than 3000 hours, and preferably more than 6500 hours, at about 80°C and about 3 MPa.

In another embodiment, the composition has a density greater about than 0,940 g/cm3average molecular weight in the range from 200000 to 490,000 g/mol and the ratio of velocity of flow of the melt(I21/I5from 15 to 50.

In another embodiment, the HMW component polyethylene contains comonomer selected from the group consisting of C3-C10alpha-olefins, and in particular from C3-C10aliphatic alpha-olefins. In an additional embodiment, the wasp is estline, the content of the co monomer is in the range from greater than 0 to 6.0 wt.%, including all individual values and inner ranges from 0 to 6.0 wt.%.

In another embodiment, the component LMW polyethylene contains comonomer selected from the group consisting of C3-C10alpha-olefins, and in particular from C3-C10aliphatic alpha-olefins. In another embodiment, the content of the co monomer is in the range from greater than 0 to 3.0 wt.%, including all individual values and inner ranges from 0 to 3.0 wt.%.

In another embodiment, the first composition is bimodal or multimodal, as determined by GPC.

In another embodiment, the HMW component of the polyethylene ranges from 48 to 67 wt.%. the combined mass of the HMW component and the LMW component, in another embodiment, the component LMW polyethylene ranges from 33 to 52% wt. the combined mass of the HMW component and the LMW component.

In another embodiment, the composition has the following properties:

1) a density of at least 0,94 g/cm3as measured according to ASTM D-792-03 Method B;

2) the flow rate of melt (I5from 0.2 to 1.5 g/10 min;

3) the ratio of velocity of flow (I21/I5from 20 to 50; and

4) the distribution of molecular masses, Mw/mnfrom 15 to 40; and

where a component of the HMW polyethylene is and ranges from 30 to 70 wt.%. composition; has a density of at least 0,89 g/cm3as measured according to ASTM D-792-03 Method B; is the flow rate of melt (I2) from 0.01 to 0.2 g/10 min and the ratio of velocity of flow (I21/I2) from 20 to 65; and where the component LMW polyethylene is from 30 to 70 wt.%. composition; has a density of at least 0,940 g/cm3as measured according to ASTM D-792-03 Method B; is the flow rate of melt (I2from 40 to 2,000 g/10 min and has a ratio of flow rates (I21/I2) from 10 to 65.

In another embodiment, the concentration polysulfonamide up to 200 µg/g, and more preferably, less than 200 µg/g

The present invention also provides compositions containing combinations of two or more embodiments as described here.

The present invention also provides a product containing at least one component formed from the composition of the present invention. This product includes, but not limited to, articles, blow molded, pipes, films, sheets and other products.

In one of the embodiments, the present invention provides a pipe with wall thickness up to 4 inches (10.2 cm)or more. In another embodiment, the present invention provides a pipe with wall thickness less than 4 inches (0.2 cm).

In another embodiment, the present invention provides a film obtained from the composition, which is associated with less than 150 μg/g polysulfonamide. In another embodiment, the present invention provides a film which has a higher resistance when tested for impact strength falling sharpened cargo than film made from otherwise identical polymer composition in which no bonding agent. In an additional embodiment, the present invention provides a film which has a higher lateral stability sleeve film than film made from otherwise identical polymer composition in which no bonding agent. In another embodiment, the present invention provides a film which has a higher resistance when tested for impact strength falling sharpened cargo and more high transverse stability sleeve film than film made from otherwise identical polymer composition in which no bonding agent.

In another embodiment, the present invention provides a product molded by the blow, which has a higher strength under impact tensile and impact resistance according to Izod, and, IU the greater extent, the same values of ESCR, compared with the product, blow molded, made from otherwise identical polymer composition in which no bonding agent. In an additional embodiment, a product molded by the blow, is a bottle, a cylindrical barrel or part of the car.

The present invention also provides a method of manufacturing a pipe, including:

a) selecting a polymeric composition having essentially the only peak on the curve LTD;

b) linking the polymer composition polysulfonamide; and

c) extruding the polymer composition to form a pipe.

The present invention also provides a method of improving the behavior of the creep of the polymer that includes the interaction polysulfonamide with a composition that includes the LMW polyethylene component and HMW polyethylene, and where the composition has essentially the only peak on the curve LTD, and where the reacted composition has a value of PENT greater than 1000 hours, at 80°C and with an applied voltage of 2.4 MPa. In an additional embodiment of the present method, the composition after the binding reaction has a melt viscosity, at a shear rate of 1×10-5rad/sec, which is 2 times greater than the melt viscosity of the composition of the polymer at the same speed the engines. In another embodiment of the present method, the composition after the binding reaction has a melt viscosity, at a shear rate of 1×10-5rad/sec, which is 5 times greater than the melt viscosity of the composition of the polymer under the same shear rate. In another embodiment of the present method, the composition, after binding assays, has a melt viscosity, at a shear rate of 1×10-5rad/sec, which is 10 times or more greater than the melt viscosity of the composition of the polymer under the same shear rate.

The present invention also provides a composition including the reaction product of:

(a) a first composition containing the component of the polyethylene obtained in the presence of a system of catalysts based on chromium, and

(b) a second composition containing a binding amount of at least one polysulfonamide.

In one of the embodiments of this composition, the component polyethylene is odnodolnym, as determined by GPC. In another embodiment, the component polyethylene has a density of from 0,890 to 0,975 g/cm3and preferably, the density of 0,930 to 0,960 g/cm3. In another embodiment, the component polyethylene has a MI2 of from 0.01 to 20 g/10 min, and more preferably from 0.1 to 15 g/10 min In another embodiment, component a polyethylene which has on MI21 from 1 to 50 g/10 min, and MI21/MI2 from 4 to 200. In another embodiment, the component of the polyethylene polymerized, where comonomer, is selected from the group consisting of C3-C10alpha-olefins, and in particular, C3-C10aliphatic alpha-olefins. In another embodiment, comonomer is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-Heptene and 1-octene, and more preferably, comonomer is selected from the group consisting of 1-hexene and 1-octene. In another embodiment of this composition, the composition has a gel content that is less than 10 percent, preferably, less than 5 percent, more preferably less than 2% and even more preferably, less than 0.5 percent, as measured in accordance with ASTM D 2765-90. In another embodiment, the composition is associated with less than 200 µg/g polysulfonamide. The present invention also provides compositions containing combinations of two or more embodiments as described here. The present invention also provides for articles containing at least one component formed from such compositions, including, but not limited to, leaves, such as termoformowanie sheets, films, pipes, products, blow molded, and other products. This composition is particularly Ave is suitable for termoformovannyh sheets.

Figure 1 depicts the profiles nikodimou viscosity of the polymers of the present invention and comparative polymers.

Figure 2 depicts the profiles nikodimou viscosity of the polymers of the present invention and comparative polymers.

Figure 3 depicts the profiles of tan Delta polymers of the present invention and comparative polymers.

Embodiments of the present invention provide for a new polyethylene composition for the manufacture of pipes for water, oil or gas and other products such as sheet, film, tape, fiber, caps and lids, and a molded product by molding processes, including moulding, forming, pressing, and molding under pressure.

Embodiments of the present invention provide a method of manufacturing pipes for water, oil or gas. The method includes selecting a polymer composition having essentially the only peak on the curve LTD, and extruding the composition to form a pipe.

The new composition comprises a component LMW ethylene polymer component and HMW ethylene polymer. Preferably, the LMW component and the HMW component crystallize together in the composition, so that it shows only or essentially only the peak on the curve LTD. The ethylene polymer for LMW and HMW components can before the presentation itself or homopolymers, or interpolymer (or copolymer) of ethylene. Preferably, both components are interpolymer (or copolymer) of ethylene same or different composition (i.e., with the same or different comonomers). Bimodality MWD new songs connected with the difference in MW for the LMW component and the HMW component. The individual components preferably have odnomomentnoe MWD. Preferably, the molecular weight LMW and HMW components, individually, are distinct and differ from each other, so that when it is mixed, the resulting composition has an overall bimodal distribution of molecular masses. Polymers with multimodal MWD can also be used.

Preferred comonomers used in plastic components of the present invention include C3-C20aliphatic alpha-olefins, and more preferably, C3-C10aliphatic alpha-olefins. Preferred comonomer is selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-Heptene, 1-octene, 1-nonene, 1-mission 4-methyl-1-pentene. Particularly preferred comonomers are selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and more preferably, from 1-hexene and 1-octene. In another embodiment, the component polyethylene may also content is th at least one Polian, including, but not limited to, paired and unpaired diene.

In the following description, all numbers described here are approximate values, regardless of whether you use the word "about" or "approximate" in conjunction with them. They may differ by 1 percent, 2 percent, 5 percent, and sometimes 10 to 20 percent.

Once described a range of numbers with a lower limit of RLand the upper limit of RU, any number falling within the range, described specifically. In particular, describes the following numbers in the range R=RL+k·(RU-RL), where k represents a variable, in the range of 1 percent to 100 percent, in increments of 1 percent, that is, k is 1 percent, 2 percent, 3 percent, 4 percent, 5%,..., 50%, 51%, 52%,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100 percent. In addition, any numerical range defined by two numbers R, as defined above, is also described specifically. Here, we describe the numerical ranges for melt index, density, molecular weight, number of carbon atoms in the alpha-olefin and other properties.

The term "linking number", as used here, refers to the amount of a binding agent, which is effektivnym when linking polymer chains, but does not lead to significant cross-linking of the final polymer product, as demonstrated by the very low content of the gel or in his absence in the final polymer product.

The term "polymer" is used here to indicate homopolymer, interpolymer (or copolymer) or terpolymer. The term "polymer", as used here, includes interpolymer, such as those that get through copolymerization of ethylene with one or more C3-C10alpha-olefin or polypropylene with one or more C4-C10alpha-olefins.

The term "interpolymer", as used here, refers to polymers obtained by polymerization of at least two different types of monomers. The General term interpolymer, thus, includes copolymers commonly used to mention polymers derived from two different types of monomers, and polymers derived from more than two different types of monomers.

The term "ethylene/α-olefin", "ethylene interpolymer (or copolymer)" and similar terms, as used here, refer to interpolymer on the basis of ethylene, which contains at least 50 molar percent of ethylene and one or more additional comonomers.

The term "adenomegaly", as used here in connection with the General the m MWD comparable examples of or in connection with the MWD of the polymer component of the composition of the present invention, means that the MWD curve gel chromatography (GPC) essentially does not demonstrate a variety of polymeric components, that is, there is no humps, shoulders or tails of the curve GPC, or are they essentially can be neglected. In other words, DOS (degree of separation) is equal to zero or substantially close to zero.

The term "bimodal", as here used, means that the MWD on the GPC curve shows two polymer component, where one polymer component may even exist in the form of a hump, shoulder or tail in relation to the MWD of the other polymer component.

The term "multimodal"as here used, means that the MWD curve GPC shows more than two polymer components, where one polymer component may even exist in the form of a shoulder or tail, relative to the MWD of the other polymer component.

The term "different"as used in connection with MWD LMW component and the HMW component, means that there is no significant overlap of the two corresponding distributions of molecular mass on the obtained GPC curve. That is, each distribution of molecular masses is quite narrow, and their average molecular weight sufficiently different that the MWD of both components essentially shows the background level, as its HMW side, and on its LMW side, in other words, DOS is equal to at least 1, preferably, at least, 2, 4, 5, 7, 9 or 10.

The term LTD, used here, refers to the distribution of the thickness of the leafs, Lc polymer.

The term "essentially a single peak" or "single peak" is used here in connection with the curves LTD to indicate that the peak essentially does not show two or more peaks. But "essentially a single peak may not follow a Gaussian distribution may be wider than would show a Gaussian distribution, or to have a flatter peak than the Gaussian distribution. Some essentially singular peaks may have a tail on either side of the peak. In some embodiments, the implementation, it may be possible mathematical resolution "essentially the only peak on the curve LTD on two or more components by various methods. In some embodiments, the implementation of "essentially the only peak on the curve LTD follows the equation:

,

where Pirepresents a point on the curve LTD., having a value for the percentage mass fraction between the value of the highest mass fraction, Rnon the curve LTD and the lowest point, pLwith a value of Lc between the value of Lc for Piand the value of Lc for Pn. In some cases, this percentage difference is less about than 8 percent or less, about 7 percent of the century In some embodiments, the implementation is essentially a single peak has a difference of about 5 percent or less, or about 2.5 percent or less. Of course, in some embodiments, implementation, there is no point of PLbetween Piand Rnso the percentage difference is zero.

As used here, the term "rheological modification" means a change of melt viscosity of the polymer, as determined by measurements of creep and DMS.

The term "catalyst precursor", as used here, in particular connection with the catalysts of type a magnesium/titanium, refers to a mixture containing compounds of titanium and magnesium and electron donor base Lewis.

The term "inertly substituted" refers to substitution of atoms or groups who are not affected by unwanted manner on the desired reaction (reaction) or the desired properties of the obtained related polymers.

For the purposes of the present description, the reactor, in which conditions are conducive to the production of high molecular weight polymer, known as "high molecular weight reactor. Alternatively, the reactor in which conditions favor the production of low molecular weight polymer, known as the "low reactor".

The term "melt processing" is used to refer to any method in which the polymer softens or melts on the tea, but not limited to, extrusion, granulation, blowing and filling film, thermoforming, compounding in the form of a polymer melt.

The term "extruder" is used in its broadest meaning to include devices such as a device that extradiol granules or pellets.

The terms "blend" or "polymer blend", or similar terms, as used here, denotes a mixture of two or more polymers. This mixture may or may not be miscible. This mixture may or may not be divided into phases. This mixture may contain or may not contain one or more configurations of domains, as determined by electron microscopy of the passage.

The density of the polymer, measured by the Archimedes method displacement, ASTM D 792-03, Method B, in isopropanol. Samples measured within 1 hour from forming after conditioning on isopropanole bath at 23°C for 8 min to reach thermal equilibrium before measuring. Samples molded by extrusion in accordance with ASTM D-4703-00 Annex A, with 5 min initial heating period at about 190°C, and at a cooling rate of 15°C/min, according to Procedure C. the Sample is cooled to 45°C in the press with continued cooling until then, until it becomes cold to the touch".

Measuring the flow rate of the melt is carried out in accordance with ATM D-1238-03, Condition 190°C/2,16 kg and Condition 190°C/5.0 kg, which is known as the I2and I5, respectively. The flow rate of the melt is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the flow velocity of the melt, although the relationship is not linear. Determination of the flow velocity of the melt can also be carried out for higher masses, for example, in accordance with ASTM D-1238, Condition 190°C/10.0 kg and Condition 190°C/21,6 kg, and is known as the I10and I21, respectively. The ratio of flow rates (FRR) is the ratio of the flow velocity of the melt (I21) to the flow velocity of the melt (I2)if not stated otherwise. For example, in some cases, FRR can be expressed as I21/I5especially for polymers with higher molecular masses.

The number of fine particles of polymer in the sample is determined using the following method: 500 g of polymer added to a standard set of sieves consisting of the following cell size, USA: 10, 18, 35, 60, 120, 200 (2000 μm, 1000 μm, 500 μm, 250 μm, 125 μm, 75 μm), and pallet. Shaker Rotap or Gradex 2000 is used to separate particles. Materials that pass through a sieve of 120 mesh and remain on the pallet, are classified as fine particles. The geometric mean is used to calculate srednekamennogo R is smera particles (APS).

Bulk density of the polymer, determined using ASTM D1895-96 (re-approved 2003).

Is FAR get through a comparison of the extruded film with a set of comparative films, as for the pipe thickness of 1.5 mils (38 microns), and polymers for forming blown. The polymer film is produced with a thickness of 1 mil (25 μm) and compared with a standard film thickness of 1.5 mils (38 microns). Standards are available from The Dow Chemical Company (PEG Test Method #510 FAR). For all polymers, except for polymers for films, use the following method. The polymer is stabilized before extrusion through a thorough mixing with the polymer of 0.10, 0.05 and 0,08% wt., accordingly, the following additives: calcium stearate, zinc stearate and phenolic stabilizer, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, commercially available from Ciba Specialty Chemicals under the trade name Irganox 1076. Electrically heated extruder with air cooling Model CE-150-20, 38 mm (1.5 inches), L/D 20:1, MPM Custom Equipment, with 7 heating zones (3 cylinder, 1 sprue, 3 heads) are used to obtain samples of the film. A more specific description of the extruder is as follows:

Manufacturer of extruder: MPM Polymer Systems, Inc.

Type: Low Boy [610 mm (24 inches), Central line]

Heating: electric, 425°C, the controllers

Cooling: Only in the bunker (water)

Speed: Variable

Produced by the driver of the screw: MPM Polymer Systems, Inc.

Type: 20:1 standard auger low-density polyethylene, with a hole up the middle of the transition section.

Diameter: 38 mm (1.5 inches)

L to D: 20/1

Manufacturer of head: MPM Polymer Systems, Inc.

Diameter: 100 mm (4 inches)

Clearance: 30 mil (0,762 µm)

Type: deep side feeder

The blower manufacturer: Buffalo Forge

Damper control air flow to the pumping

The valves control the air flow on the issue

Motor: 1.5 HP (1120 W), 2 speed

Equalization chamber between the air blower and air environment

Manufacturer of air rings: MPM Polymer Systems, Inc.

Layout 708

Diameter: inner diameter 172 mm (6.75 inches)

Type: tunable cheek

Tower height: 914 mm (36 inches)

Length shapeways frame 343 mm (13.5 inches)

The conditions of extrusion to study FAR are as follows:

Auger Neutral

Fully running water for bunker

Temperature (°C)

Zone 1 210

Zone 2 210

Zone 3 210

The sprue 225

The adapter 225

Area head 1 225

Area head 2 225

Package sieves, stainless steel, cell 40/40

Output:

The speed of the auger 65 rpm

The ratio of the blown 2/1

The width of the flat paved portion 12 inches (304.8 mm)

The height of the line of solidification 103 inches (254 mm)

The height of the tower 36 " (914,4 mm)

Study to evaluate film:

The speed of pressure in the face of 254 ft/min (1,29 m/s)

The film thickness of 1.5 mils (0,038 µm)

The range of the film thickness of 1.3 to 1.7 mils (33-43,2 μm)

The speed of the auger can be adjusted to obtain the corresponding passage velocities. Line pour point is measured from the bottom of the air ring. The speed of the roller is changed, to obtain a film thickness of 1.5 mils (38 microns). The film thickness was measured using a Federal dial indicator gage in accordance with ASTM D 374.

After the extruder reaches thermal equilibrium and homogeneous film, a sample is taken film length 3 m Estimates are based on the worst section, seen in each sample. This assessment is based on the level of the gel particles observed in the film, the General term for discrete imperfections in the plastic film. The gel particles can be formed from a high molecular material, either transparent or colored, fibrous or other foreign contamination, or through cross-contamination of the polymer. Particles of the gel represent the most common defect found in the films, and accounted for a large part of the evaluation of the film. Other defects are noted, but not normally included in the value estimate for the appearance of the film. If necessary, during the evaluation is the comparison with a set of standards film of high density. Value Pref is incorporated in increments of 10 units, in the range from +50 (best) to -50 (worst).

All results are generated using a TA Instruments Model Q1000 DSC equipped with RCS (refrigerated cooling system), accessories for cooling and a device for automatic sampling. It uses a purge flow of gaseous nitrogen 50 ml/min Sample is pressed into a thin film using a press at 175°C and a maximum pressure of 1500 psi (10,3 MPa) for about 15 seconds, then cooled down to room temperature at atmospheric pressure. Then about 3-10 mg of material cut in the form of a disk with a diameter of 6 mm using a hole punch, weighed with an accuracy of 0.001 mg, placed in a light aluminum pan (about 50 mg), and then screwing the cap. thermal behavior of the sample tested at the following temperature profile: the Sample is rapidly heated to 180°C and maintained at constant temperature for 3 minutes to remove any previous thermal history. The sample was then cooled to -40°C, cooling rate 10°C/min, and maintained at -40°C for 3 minutes. The sample was then heated to 150°C at a heating rate of 10°C/min Register curves cooling and second heating.

Curve LTD refers to the schedule of percentage mass as a function of the thickness of the leafs, Lc. Additional information can be found in U.S. Pat is ntah U.S. No. 4981760 and 2004/0034169 Al, which are included here as a reference in their entirety.

Data LTD receive and analyze the following way. Samples cut out directly from the manufactured plastic products. Samples for DSC is withdrawn from the pipe wall, the film or of the dice used for measurements PENT. Samples can also be selected from granules to obtain information about the influence of pelleting on LTD. If the receipt does not provide uniform cooling/curing, the samples are selected from different parts of the product to reflect these differences. This may be important in the extruded pipe, if the pipe is cooled from outside to inside with cold water so that the cooling rate for this reason decreasing the outside of the pipe wall inside. To reflect these differences are selected, at least three samples of the outer, middle and inner layer of the pipe wall. Approximately 10 mg of sample analyzed by DSC using a heating rate of 10°C/min For better comparison of the differences caused by molecular variables, history of the cured sample is standardized as follows: Sample precrystallizer by melting a sample holder for sample DSC at 190°C, and then cooling it to 30°C, at a speed of 20°C/min, to eliminate artifacts on the DSC curve, which otherwise could nab adatsa due to previous manufacturing processes.

Use a three-stage procedure. Firstly, LTD products, such as pipes or film, are determined by scanning the sample from 30°C to 190°C at a heating rate of 10°C/min Characteristic obtained LTD is associated with variable material and machining conditions. The sample is maintained at 190°C for 1 minute for complete relaxation of the molecular chains. Secondly, the sample is cooled at a cooling rate of 20°C/min from 190°C to 30°C, to give the model the ability to recrystallization under controlled conditions. The temperature of the support at 30°C for 1 minute. Thirdly, the sample is heated at a rate of 10°C/min to determine LTD in the recrystallized sample. This LTD is used to study the influence of variable material through the elimination of factors of production. First, integrate DSC melting peak. Record the melting point and the corresponding integral partial area of the melting peak. Then the melting temperature is used to calculate the thickness of the leafs,crystal of polyethylene in accordance with the well-known equation Thomson-Gibbs from the melting temperature, Tm:

whererepresents the equilibrium melting point of the infinite crystal represents the surface free energy of the basal plane andrepresents the enthalpy of fusion per unit volume. InDieMakromolekulare Chemie, 1968, 113, 1-22, Illers and Hendus experimentally determined constant in equation (1). Then the thickness of the leafs, Lc(nm), can be calculated from the melting temperature, Tm(K), as follows:

For the melting point from DSC melting peak corresponding to the thickness of the leafs get from equation (2). Thickness distribution of the leafs are also discussed inPolymervol. 38, issue 23 (1997) by Zhou, Hongi, and Wilkes, the description of which is thus included as a reference. Integral partial area of the melting peak is used to calculate the differential percentage of the mass of the crystal for a given thickness of the leafs. Partial area, ΔHi, DSC melting peak, considered to be proportional to the percentage of the mass of the crystal leafs within this partial area. Differentiated percent mass percent mass. the leafs when the thickness of the Lc,i, therefore, determined using equation (3) as follows:

Graph of percentage mass of integral partial area as a function of the thickness of the leafs that gives the curve LTD. In addition, the total heat of fusion peak of the melt is to be placed can be used to determine crystallinity. The detailed method of data analysis is discussed next. Analysis curve LTD, obtained from the procedure described above can be made by analogy with the analysis (MWD) or index polydispersity (PDI) based on the weighted average (Mwand srednekamennogo (Mn) molecular weight, for this reason, average thickness, Ltand srednekislye, Lnthe thickness of the leafs is determined using equations (4) and (5) as follows:

Like index polydispersity (PDI = MWD = Mw/Mn), which provides information regarding the distribution of molecular weights, the index of dispersion of the leafs, LDI, therefore, is given by the equation:

Thus, LDI is a quantitative characteristic - width curve LTD.

The following procedure is used to determine the molecular structure of different polymer compositions. Chromatographic system consisting of a chromatograph for high-temperature gel chromatography Waters (Millford, MA) 150°C, equipped with a detector 2-angle laser light scattering Precision Detectors (Amherst, MA), Model 2040. The detector scattering angle of 15° is used for the purposes of calculation. Data collection is performed with the use of the software Viscotek TriSEC version 3 and 4 to the national Viscotek Data Manager DM400. The system is equipped with a device for on-line degassing of the solvent from Polymer Laboratories.

Carousel works Department at 140°C, and column compartment operates at 150°C. is Used columns represent the four columns Shodex HT-806M 300 mm, 13 μm and a column Shodex HT803M 150 mm, 12 μm. Used solvent is a 1,2,4-trichlorobenzene. Samples were obtained when the concentration of 0.1 gram of polymer in 50 milliliters of solvent. The chromatographic solvent and solvent to obtain a sample contains 200 µg/g of bottled hydroxytoluene (BHT). Both sources of solvent blown off with nitrogen. Samples of polyethylene gently stirred at 160°C for 4 hours. Used the amount of injection is equal to 200 microliters, and the flow velocity is equal to 0.67 ml/min

System calibration columns for GPC is carried out using 21 polystyrene standards with a narrow distribution of molecular weights, molecular weights ranging from 580 to 8400000 g/mol, which are distributed in 6 "cocktail" mixtures, at least within one order of magnitude between individual molecular weights. Standards of buy Polymer Laboratories (Shropshire, UK). Polystyrene standards prepared when 0,025 grams in 50 milliliters of solvent at a molecular mass equal to or greater than 1,000,000 g/mol, and 0.05 grams in 50 milliliters of RA is the solvent for molecular weights, less than 1,000,000 g/mol. Polystyrene standards dissolved at 80°C with gentle stirring for 30 minutes. A mixture of narrow standards run first, and in order of decreasing component with the highest molecular weight, in order to minimize degradation. Molecular weight peaks of polystyrene standards is converted into molecular weight polyethylene using equation 8 (as described in Williamsand Ward,J.Polym. Sci. Polym. Let.6, 621 (1968)):

M polyethylene = A × (M polystyrene)B(8),

where M represents the molecular weight, A has a value of 0.41 and B is 1.0.

A systematic approach to determine the multidetector amendments carried out in a manner consistent with that published Balke, Mourey, et al. (Mourey and Balke,Chromatography Polym.Chpt 12, (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey,Chromatography Polym.Chpt 13, (1992)), optimizing the double logarithmic results of the detectors from the broad Dow polystyrene 1683 results for calibration columns narrow standards of the calibration curve narrow standards using original software. Data on the molecular mass to determine the amendments are consistent with those published by Simon (Zimm,B.H.,J.Chem. Phys.,16, 1099 (1948)) and Kratochvila (Kratochvil, P.,Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injected concentration used is to determine the molecular weight, is obtained from the square of the refractive index of the sample and calibration of the detector refractive index from linear polyethylene homopolymer with a molecular weight of 115,000 g/mol, which is measured relative to polyethylene homopolymer, standard 1475 NIST. Chromatographic concentrations are low enough to make unnecessary adjustments for the effects of the 2nd virial coefficient (the effect of the concentration on the molecular weight).

Calculate the molecular weight exercise using the original software. Calculation srednekamennogo molecular weight, average molecular weight and z-average molecular weight is carried out in accordance with the following equations, assuming that the signal) is directly proportional to the mass fraction. The signal Refractometer with subtracted background can be directly substituted as the mass fraction in the equation below. Note that the molecular weight can be taken from a normal calibration curve or to be an absolute molecular weight of the signal of the light scattering signal of the Refractometer. Improved evaluation of z-average molecular weight, the signal light scattering with background subtracted, can be substituted as works average molecular Massie mass fraction in equation (9) below:

The term "bimodal", as here used, means that the MWD curve GPC shows two polymer component, where one polymer component may even exist in the form of a hump, shoulder or tail, relative to the MWD of the other polymer component. Bimodal MWD can be converted into two components: LMW component and the HMW component. After conversion can be obtained width of the peak at half maximum height (WAHM) and the average molecular mass (Mwfor each component. Then the degree of separation (DOS) between the two components can be calculated using equation 10, as follows:

where MHwand MLwrepresent the corresponding average molecular weight of the HMW component and the LMW component; andWAHMHandWAHMLrepresent the corresponding width of the peak at half maximum height of the transformed distribution curve of molecular masses for the HMW component and the LMW component. DOS for the new composition is about 0.01 or above. In some embodiments, implementation, DOS, above, about, than of 0.05, 0.1 and 0.5 or 0.8. Preferably, DOS for bimodal component at least equal to about 1 or higher. For example, DOS at least equal, 1,2, 1,5, 1,7, 2,0, 2,5, 3,0, 3,5, 4,0, 4,5 or 5.0. In kotoryj options implementation DOS is in the range between about 5.0 and about 100, between about 100 and 500, or between about 500 and 1000. It should be noted that DOS can represent any number in the above range. In other embodiments, implementation, DOS exceeds 1000.

In some embodiments, the implementation of bimodality distributions characterized by mass of the high-temperature peak in the data lucynova fractionation with increasing temperature (often simply referred to as "TREF") as described, for example, in Wild et al.,Journal of Polymer Science. Poly. Phvs. Ed.,Vol. 20, p. 441 (1982), in U.S. patent No. 4798081 (Hazlitt et al.) or in U.S. patent No. 5089321 (Chum et al.), descriptions of all of them are included here as reference. Mass fraction corresponding to the high-temperature peak, referred to as fraction of high density because it contains a small short-chained branching or does not contain it. The remaining fraction for this reason is referred to as fraction with short-chained branching (SCB), because it is a fraction, which contains almost all short-chained branching inherent in the polymer. This group also represents the fraction of low density.

In the analysis using analytical lucynova fractional fractionation with increasing temperature (as described in U.S. patent No. 4798081 and abbreviated KJV is inalsa here as "ATREF") composition, which is to be analyzed is dissolved in an appropriate hot solvent (for example, 1,2,4-trichlorobenzene) and has the ability to crystallize in a column containing an inert packing material (for example, the fraction of stainless steel), with slow temperature decrease. The column is supplied as an infrared detector, and the detector on the basis of differential viscometer (DV). Then the curve of the chromatogram ATREF-DV is generated by elution of the sample crystallized polymer from the column by slowly increasing the temperature of the eluting solvent (1,2,4-trichlorobenzene). The way ATREF-DV describes advanced in the application for international patent WO 99/14271, the description of which is included here as a reference. Application for international patent WO 99/14271 also describes the method of conversion for multi-component compositions of polymer blends. ATREF curve is often referred to as distribution of short-chained branch (SCBD), because it shows how evenly comonomer (e.g., hexene, is distributed across the sample, in this case, when the temperature of the elution decreases, the content of the co monomer is increased. The detector refractive index provides information on the distribution of short circuits and the detector on the basis of differential viscometer which provides an estimate of the average viscosity molecular weight. The discussion above can be found in L. G. Hazlitt,J. Appl. Polym. Sci.: Appl. Poly. Symp., 45, 25-37 (1990), which is included here as a reference.

The swelling of the polymer was measured by the method of the Dow Lab Swell, which consists in measuring the time required for extrudable strands of the polymer to undergo a specified distance 230 mm Gottfert Rheograph 2003, with 12 mm cylinder, equipped with a capillary cylinder, L/D 10, is used for measurement. The measurement is carried out at 190°C, at two fixed shear rate, 300 sec-1and 1000 sec-1, respectively. The more the polymer swells, the slower it moves the free end of the thread, and the more time he needs to go 230 mm Swelling is registered as the value of t300 and t1000 (s).

The sample is formed by extrusion in the form of a disk for rheological measurements. Discs get by pressing the samples in the form of die thickness 0,071 inch (1.8 mm), which are then cut in 1 inch (25.4 mm) drive. Procedure molding, compression is as follows: 365°F (185°C) for 5 minutes at 100 psi (689 kPa); 365°F (185°C) for 3 min at 1500 psi (10,3 MPa); cooling at 27°F (15°C/min to ambient temperature (approximately 23°C).

The rheology of the polymer is measured on ARES I (Advanced Rheometric Expansion System) Rheometer. ARES is a rheometer controlled deformation. atorny actuator (servomotor) applies shear deformation in the form of strain to the sample. In response, the sample generates a torque, which is measured by the transducer. Stretching and time are used to calculate the dynamic mechanical properties such as modulus of elasticity and viscosity. Viscoelastic properties of the sample measured in the melt using a system with parallel plates with constant tension (5%) and temperature (190°C), and a function of changing the frequency from 0.01 to 500 sec-1). The dynamic elastic modulus (G'), loss modulus (G"), tan Delta and complex viscosity (ETA*) of the polymer is determined with the use of the software Rheometrics Orchestrator (v. 6.5.8).

Rheological characteristics at low shear is carried out on a Rheometrics SR5000 mode control voltage, using a fixture for fixing 25 mm parallel plates. This type of geometry is preferred in comparison with the cone and plate, because it requires only minimal deformation when compressed during loading of the sample, thus reducing residual stresses.

Measurement of creep is carried out at 170°C and 190°C. After zeroing the gap between the parallel plates, the temperature is increased to 220°C for sample loading (about 5 minutes), to accelerate the relaxation of normal stresses, and then decreases to the temperature measurement. Research is zuchetti carried out at a voltage of 20 PA, which represents the best compromise to obtain a good relationship of signal to noise (S/N), at the same time, while remaining in the linear regime (small deformation). Deformation recorded in the times to 30000 seconds or as long as the viscosity does not vyrovnitsja, indicating that the stationary state is reached. Stationary viscosity is determined using automated software capabilities Rheometrics Orchestrator (v. 6.5.8). Several attempts to carry out until the standard error for stationary viscosity is below 4 percent.

Dynamic mechanical spectroscopy (DMS), also called frequency sweep, the study mode voltage control is carried out before and after the first experience with creep to check for degradation. Angular frequency varies from 0.1 to 100 rad/sec, when the amplitude of the stress of 1000 PA, which corresponds to the amplitudes of the deformations in the range between 0.1 percent (at 100 rad/sec) and 10% (at 0.1 rad/sec). Concludes that the stability is good. In subsequent experiments, the study of DMS carried out only after the study of creep, to prevent the introduction of perturbations due to the shear history.

The stationary point data on creep combined with the curve of viscosity on DMS, for the extension of the estimated range of speeds with the wig down to 10 -61/sec, and adjust using the 4-parameter model Caro-Asadi:

Antioxidants such as Irgafos 168 and Irganox 1010, typically used to protect the polymer against thermal and/or oxidative degradation. Irganox 1010 is a tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), available from Ciba Geigy Inc. Irgafos 168 is a Tris (2,4 di-tert-butylphenyl)FOSFA, available from Aldrich Chemical Company.

Sample preparation:pellets of the polyolefin is converted into a powder using a grinder Retsch Model ZM100 connected with a 1.0 mm sieve. 1.0 mm sieve gives particles with an average size of 0.5 mm Granules and crusher before chopping cooled using liquid nitrogen. Approximately 2 grams of the polymer is placed in a polystyrene Cup, and add about 50 ml of liquid nitrogen for cooling of the polymer. About 50 ml of liquid nitrogen was poured into the funnel crusher for cooling mechanical parts, followed by pouring the liquid and granules of polystyrene cups into the crusher.

Extraction:five grams of the powder is extracted with 40 ml of carbon disulfide (C2S) by shaking with an automatic shaker for 72 hours. Five ml of the extract is withdrawn from the clean, clear bottom layer of the extract CS2and dried under gently flowing stream of dry azo is and. The resulting residue is dissolved in 5 ml of isopropanol with gentle heating on a steam bath, cooled and filtered using a 0.2 μm syringe filter into a vial for sample HPLC, and analyzed by HPLC according to the following procedure.

Tool for HPLC is a HP 1090, available from Hewlett-Packard, Inc., with column Thermo Hypersil from Keystone Scientific. Packing for column represents a Waters Spherisorb ODS 2. The column size is 150×4.6 mm, pore size 80 angstroms and a particle size of 3 μm. The initial solvent is a mixture consisting of 30% water and 70% acetonitrile. 10 minute enter 100% acetonitrile, and then at 15 minutes introducing a mixture consisting of 80% acetonitrile and 20% isopropanol. Total experience time is 20 minutes at a flow rate of 1 ml per minute. Monitoring is carried out at a wavelength of 276 nm.

The calibration for each of the additive shall be implemented by the preparation of known concentration of the additive in isopropanol (about 0.03 g per 100 ml). For oxidized Irgafos 168 calibration is implemented by standard oxidation isopropanolic solution Irgafos 168 excess of hydrogen peroxide for 1 hour.

Specimen preparation:pellets of the polyolefin is converted into a powder using a grinder Retsch Model ZM100 connected with a 1.0 mm sieve. 1.0 m is a sieve gives particles with an average size of 0.5 mm Granules and crusher are cooled with liquid nitrogen before grinding. Approximately 2 grams of the polymer is placed in a polystyrene Cup, and add about 50 ml of liquid nitrogen for cooling of the polymer. About 50 ml of liquid nitrogen was poured into the funnel crusher for cooling mechanical parts, followed by pouring the liquid and granules of polystyrene cups into the crusher.

Extraction:Dionex Model 200 Accelerated Solvent Extractor (ASE) with the controller of the solvent used for the extraction bis-sulfonylated (BSA) and a by-product, 4,4'-dioxymethamphetamine (SA), powdery polymer. Approximately 0.5 g of the powdery polymer is placed in the extraction Cup (available from Dionex), and then a Cup fill about ¾ of the height of the small glass ball. The contents are mixed, and placed the Cup in 11 ml of the cell on the ASE. Conditions ASE are the following: pressure 1500 psig (10,3 MPa)120°C, preheating set for one minute, static time set for 5 minutes, the volume of flushing set at 150 percent, purge time set to 60 seconds, number of cycles = 3, cell volume = 11 ml, the volume of the collecting bottle 60 ml, the volume of extraction is equal to about 30 ml of the Solvent consists of a mixture of 95 wt.%. isopropanol and 5% wt. cyclohexane.

After extraction, ekstrak is directly filtered using a 0.45 µm syringe filter (25 mm, CR PTFE, available from Acrodisc), then evaporated to dryness under a gentle stream of dry nitrogen. The resulting residue is immediately dissolved in 0.5 ml of acetonitrile, and then, 0.5 ml nanocity water. This dissolution procedure is necessary in order to make possible good peak shape SA HPLC. The solution is filtered in a bottle device for automatic selection of samples for HPLC using a 0.2 μm syringe filter (13 MM, LC13 PVDV, available from Acrodisc). It is important to HPLC analysis followed directly after the extraction procedure in order to minimize the decomposition of the BSA.

Conditions for analysis of BSA and SA using HPLC are as follows:

Pump: Agilent 1100 Quaternary Pump

Mobile phase:A: Water
B: Methanol
C: no
D: Acetonitrile

Programming gradient

Time
(min)
%A%B%C%DFlow rate (ml/min)
0,05820400,75
1,05820400,75
2,040200400,75
9,040200400,75
9,1220960,75

Stop time: 15 min

Time after: 10 min

Column: Bond SB-Phenyl

Length: 15 cm

Diameter: 3.0 mm

Recommended diameter: 3.5 µm

Device for automatic collection of samples: Agilent 1100 Autosampler with injection volume = 10 μl

Detector: the Detector absorption Agilent 1100 DAD UV/Vis

Wavelength: 254 nm

Data collection: Agilent Chemstation

The initial peak width: 0,087 min

Check peak BSA is carried out by comparing retention time for the sample, the sample with the pulse BSA and known standard. Limit of detection equal to 50 billions of dollars of parts, mlgd, ng/g Levels of BSA measured between 2 and 20 mill the district shares, ppm, µg/g, with an accuracy of about 10 percent relative standard deviation (RSD).

The level of binding agent - sulfonylated - plastic polymer, determined indirectly by measuring the total sulfur content in the polymer using wavelength dispersive x-ray fluorescence analysis (XRF). Polymers with different levels of azide are characterized by the total sulfur content using analysis of fundamental parameters XRF. Software for fundamental parameters are calibrated using NIST standards for microscopic amounts of sulfur in the oil. Of these charakterisierung polyethylene polymers, generate a linear calibration curve in the x-ray spectrometer, covering the range from 10 to 42 ppm sulfur. Before characterization and analysis of an unknown sample, 10 g of the polymer formed in the form of 50 mm dice with the use of a press plate or its equivalent at a temperature sufficient to melt the polymer. The accuracy of the estimate on some days with% RSD 1,67 and estimated 95 per cent confidence interval 0,763 for one value.

The analysis of Al and Ti in polyethylene and polypropylene can be determined either by x-ray fluorescence (XRF)or atomic emission inductively coupled plasma (ICP). Any technique gives comparable the results at levels above 10 µg/g, for Al, and 1 µg/g for Ti, but at levels below these concentrations, the ICP analysis is preferred. For XRF analysis, 10 g of the polymer formed in the form of 50 mm dice, using a press plate or its equivalent at a temperature sufficient to melt the polymer. Polymer standards, which are characterized using ICP analysis, are used to calibrate the spectrometer wavelength dispersive XRF analysis. For ICP analysis, 4 g of the polymer turned into ashes in sulfuric acid at 500°C in a muffle furnace, and the remainder digeridoo in hot Aqua Regia. After dilution to 20 g, analyze ICP. ICP calibrated using aqueous solutions of microscopic quantities of NIST. The relative standard deviation or precision (% RSD) for Al and Ti with XRF and ICP analysis, usually less than 5 percent, depending on the concentration. The limit of quantification for Al and Ti by ICP analysis using the apparatus described above is 0.25 µg/g, but can be reduced by increasing the mass of the polymer used in the procedure.

Temperature krupenia, measured in accordance with ASTM D-746 Procedure A, using Tinius Olsen Brittle Point Tester with sample type 1 device for fastening type A, fixed point in accordance with Note 8. The heat transfer medium is a methanol or isopropanol.

Cat is Skye stability is measured in accordance with ASTM D-3350-02 by DSC techniques. Thermal stability is also referred to as the induction time of oxidation, the time to failure is measured at 210°C.

The minimum score required strength (MRS) is determined in accordance with ISO 9080, using 1-inch tubular sample with a standard size (SDR = diameter/minimum wall thickness) = 11. Tubular sample is pressurized at a known internal pressure and immersed in a water bath at the specified temperature.

The rigidity of the polymer is characterized by measuring the modulus of bending at the 5% strain and hewer module with 1% and 2% strain and at a test speed of 0.5 inch/min (13 mm/min) per ASTM D 790-99 Method B. Samples molded by extrusion in accordance with ASTM D-4703-00, Annex 1, with 5 min initial heating at about 190°C and a cooling rate of 15°C/min in accordance with Procedure C. the Sample is cooled to 45°C in the press with continued cooling until until he will not be cold to the touch".

The ultimate tensile strength and elongation at break measured in accordance with ASTM D-638-03. Both measurements carried out at 23°C on the hard samples of type IV, which is formed by extrusion in accordance with ASTM D 4703-00, Annex A-1, at 5-min initial heating period at about 190°C and a cooling rate of 15°C/min according to Procedure C. the Sample is cooled to 45°C at p is Jesse, with continued cooling until then, until it becomes cold to the touch".

The rapid spread of cracks is measured in accordance with ASTM F-2231-02a, using the obtained molding by pressing the sample according to ASTM F-1473-01, except that the thickness equal to 2 mm and a depth of cut equal to 1.5 mm, the Temperature in a car for testing equal to 23°C.

Pennsylvania Notch Test (PENT), the study of slow crack growth carried out by following the procedure described in ASTM F-1473-97 at 80°C and 2.4 MPa, unless otherwise stated. In the way that PENT, the test sample is notched on one edge exposed to a constant load in the furnace in a well-controlled temperature.

The time to failure can be measured with the timer, and the failure rate can be measured by using a microscope or a dial indicator. The depth of incision, usually equal to about 35 percent of the thickness of the sample. The width of the incision may vary from about 15 to about 25 mm, and the lateral grooves can vary from approximately 0.5 to approximately 1.0 mm, depending on the width of the sample.

The PENT test, make an incision in the sample by pushing the fresh razor blade into the sample at a speed of less than 0.25 mm/min Speed, smaller than 0.25 mm/min, to prevent damage to the tip of the cut and still provide a reasonably short time of incision. When the IC is rastah incision, large, approximately than 525 μm/min, the time to failure increases significantly. Speed incision for the lateral grooves are not particularly important. The device must ensure that the incision and lateral grooves were coplanar.

During the test, care must be taken to ensure that the grippers of the sample were located accordingly. To this end, the grips should be aligned and centered relative to the longitudinal axis of the sample. During capture, the incision should not be activated by bending or twisting of the sample. Combining holder can be used to assist in the appropriate capture sample in the alignment of the grippers and to prevent bending or twisting of the sample. In addition, the grips should have a serrated surface to prevent slippage, and the edges of the grips should be at least 10 mm from the cut.

The testing device may be a device with a direct load or device with lever load. The ratio arms of the lever 5:1, as found, is very convenient. Grips can be attached to the load machine by means of protrusions that have a universal effect, such that the applied load is a pure tension. The applied voltage refers to the area on Aracinovo section without an incision. The value of the applied voltage depends on the test temperature. The recommended value is such that gives a sharp break as quickly as possible. Higher voltages cause the plastic failure, and a lower voltage will extend the testing time. For samples of polyethylene, with a maximum voltage for brittle failure, the applied voltage must have a value of 5.6, 4,6, 4,2 and 2.4 MPa at temperatures of 23, 42, 50, 80°C, respectively. Typically, the voltage for brittle failure by slow crack growth should be less than half of the break point at a given temperature studies. The temperature should be controlled within ± 0.5°C. it is Not recommended that polyethylene was investigated above 80°C, because at the time of research can produce significant morphological changes. Typically, depending on the temperature studies, 1°C temperature change in the past will change the time to failure by 10-15 percent. The PENT test at 80°C modified to use the attached resume napriazheniia 3.0 MPa when tested pipe samples. It is a more severe test than universally adopted by the load voltage.

The resistance of the polymer to the formation of cracks under the action of environmental factors (ESCR) is measured according to the SNO ASTM-D 1693-01 Method B. Samples molded in accordance with ASTM D 4703-00 Annex A, with 5 min initial heating period at about 190°C and a cooling rate of 15°C/min under Procedura C. the Sample is cooled to 45°C in the press with continued cooling until then, until it becomes cold to the touch".

With this test the susceptibility of the polymer to mechanical failure by cracking is measured under conditions of constant strain and in the presence of the agent, accelerating the formation of cracks, such as Soaps, wetting agents, and the like. Measurements carried out on samples with a notch, a 10 percent, by volume, aqueous solution of Igepal CO-630 (get from Rhone-Poulec, NJ)maintained at 50°C. Estimated ten samples per dimension. The ESCR value for the polymer is given as F50calculated time for 50 percent of the failures from the graph of probability.

Impact strength according to Izod(futon/inch) determine molded by the pressing plates notched at 23°C and -40°C in accordance with ASTM D 256-03 A Method using the device Tinius Olsen Izod Manual Impact, pendulum, with nominal parameters 200 inch/lbs.

MeasurementStrength under impact tensile(ft·lb/in2) perform in accordance with ASTM D 1822-99, obtained by forming the pressing dies type SA, short, with holes and a width of 3/8 inch (9.5 mm),projections, Testing Machines Inc. Tensile Impact Model 43-02, with pendulum with nominal parameters 2 ft·lb (0,276 m·kg).

Molded molded die for Izod test and burst test receive in accordance with ASTM D 4703-00, Annex A, with 5 min initial heating period at about 190°C and a cooling rate of 15°C/min under Procedura C. the Sample is cooled to about 45°C in the press with continued cooling until then, until it becomes cold to the touch".

Research impact strength falling sharpened shippingcarried out in accordance with ASTM D 1709-04, Method A, by manual methods, with a pointed weight, falling on the circumference of the sample film using sample film thickness of 0.5 mil (13 μm) and 1.0 mil (25 microns). Samples taken from the line of blown film, after at least 3 min of blown film with a clean edge of the head to prevent scratching. To eliminate the effects of aging, resistance test impact strength falling sharpened load measured within 1 hour after sampling.

Pipe ekstragiruyut on extrusion lines Davis Standard 2.5 inch (63.5 mm), L/D of 24/1, provided with a tubular head for the production of nominally 1-inch (25.4 mm) IPS pipe (size iron pipes). The pre-polymer is mixed with carbon black loading in the system of the dispenser/blender McQuire, and transferred to the air in gravimetrically dispenser. The temperature profile and all conditions of the method are given in the example below. Method of vacuum calibration is used to calibrate the size of the pipe. Additional cooling water tank used for full curing of the pipe. Cooling water temperature of approximately 10°C. Use the device for removal with variable speed, which operates at a constant speed for the studied pipe sizes. Facing the pipe is cut into 18 inch (457,2 mm) segments for testing hydrostatic through the gap.

Features end-to-end gap for pipes shall be measured in accordance with ASTM D 1598-99, ASTM D 2837-02, ISO 1167 and ISO 9080, at temperatures and times indicated in Table 1.

The stability of the sleeves of the film is measured as the line speed of film directly before giving in ft/min (m/sec). Higher line speed film prior to failure, indicates higher stability of the film sleeve. Failure on the stability of the sleeves of the film is defined as the inability to control the sleeve films and formed film with excellent calibrated (thickness) homogeneity. The stability of the sleeves of the film is measured on the next line to get blown film, commercially available from Hosokawa Alpine Corporation, under the following conditions:

The profile of the extruder

Area of cylinder 1 390 °F (199 °C)

Area Qili the DRA 2 400 °F (204 °C)

The lower adapter 400 °F (204 °C)

Vertical adapter 410 °F (210 °C)

The lower head 410 °F (210 °C)

The average head 410 °F (210°C)

The upper cylinder 410 °F (210 °C)

The output rate of 100 lb/h (45,4 kg/hour)

The ratio of the bulge (BUR) of 4:1

Collar height 32 inches (0.81 m)

The height of the line of solidification 42 inches (1.07 m)

The melt temperature of 410 °F (210 °C)

Width laid flat film 25,25 inch (0,64 m)

The film thickness of 0.5 mil (13 μm)

Description of equipment for film blowing

System for stationary extrusion Alpine HS50S

- 50 mm input extruder with grooves, L/D 21:1

drive 60 HP (44742 W) DC

the extruder is a device for replacing a cylindrical sieve

- standard control panel with 9 RKC temperature controllers Alpine Die BF 10-25

- 12-spiral design

- padded insert for receiving the head diameter 100 mm Alpine Air Ring HK 300

- design with one input edge

air input flange for the head diameter 100 mm

- blower 7,5 HP (5593 W) with variable speed AC drive

Calibration sleeve film Iris Model KI 10-65

- band width laid flat (LFW) in the range from 7 to 39 inches (0,178-0,991 m)

Alpine Take-Off Model A8

- shapeways frame with side rails with slats of solid wood

- maximum LFW: 31 inches (0,787 m)

facial width Wali is a: 35 inches (0,889 m)

maximum sample rate: 500 ft/min (2.54 m/s)

- 4 needle roller

Winding unit Alpine model WS8

- maximum LFW: 31 inches (0,787 m)

the front roller width: 35 inches (0,889 m)

- maximum line speed: 500 FPM (2.54 m/s)

- automatic circumcision

Unless otherwise stated, is used introduction under the action of gravity. Blowing and the winding start and installed at output speeds of 100 lb/h (45,4 kg/hour), and the winding in of 82.5 ft/min (0,42 m/s), when the height of the cervical 32.0 inches (0.81 m), when the value of the width laid flat 24.5 " (0,622 m), with symmetrical sleeve, giving a film thickness of about 1.0 mil (25 microns). These conditions are maintained for at least for 20 minutes, then collect 10-foot (3.05 m) sample to estimate FAR, as described previously. Then the speed of withdrawal of the product from the extruder is increased to 165 ft/min (0.84 m/s), so that the film thickness is reduced to 0.5 mil (13 μm). The platen is withdrawn a sufficient amount of film to prevent wrinkles, to collect samples of at least 8 measurements of resistance when tested for impact strength falling sharpened cargo. Supported as the collar height and width laid flat. The sample is withdrawn, at least after 3 minutes of experience, with a net output of the head to prevent scratches. Support the conditions for output speed of 100 lb/h (45,4 kg/h), the speed of withdrawal of the product from the extruder 165 ft/min (0.84 m/s), cervical height of 32.0 inches (0.81 m) and width laid flat 24.5 inches (0,622 m), the film thickness of 0.5 mil (13 μm), sleeve film, blown in the way visually observed relative to the spiral instability or oscillations of the diameter of the sleeve film. The number of amps required for the extruder and the pressure of the extruder is logged, if this is desirable. Sleeve film is considered to be stable, as long as it is not observed any one of these conditions, even if there may be some jitter sleeve film.

Spiral instability involves reducing the diameter of the spiral patterns around the sleeves of the film. Oscillations diameter sleeve film includes alternating increase and decrease in diameter.

Also investigated the vertical stability of the film sleeve. In addition, the maximum stability of the sleeves of the film is measured by maintaining a constant output speed of the extruder 100 lb/HR (45,4 kg/h), while the rate of withdrawal of the product from the extruder is increased to reduce the thickness of the film, up until the sleeve film will not become unstable, or will not be observed're affected height of the cervix, or increase and decrease the height of the neck. The speed of removal of the product from the extruder is increased by steps of about 10 F. the t/min (0.05 m/sec), while the configuration of the blower with the air ring is regulated to maintain the height of the neck, as long as you will not be vertical're affected. The speed of withdrawal of the product from the extruder, when you register're affected with amplitude greater than 4 inches (100 mm), is registered as the value of the vertical stability of the film sleeve. It is registered in ft/min or m/sec.

In the embodiment, suitable for pipes, HMW component has a flow rate of melt, I2(190°C, the weight of 2.16 kg, ASTM 1238-03), in the range from 0.001 to 1.0 g/10 minutes, In some embodiments, the implementation of the flow rate of melt I2is in the range from 0.01 to 0.2 g/10 minutes, In some embodiments, the implementation of the flow velocity of the melt is equal to or less than 0.1 g/10 min, preferably, the component is characterized as having (I2from 0.001 to 0.1 g/10 min, more preferably 0.005 to 0.05 g/10 min, most preferably, from 0,0085 to 0,017 g/10 minutes All individual values and inner ranges from 0.001 to 1.0 g/10 min (I2) are included here and are described here. The flow rate of melt, I21, (190°C, the weight of 21.6 kg, ASTM 1238-03) may be in the range of from 0.20 to 5.0 grams per 10 minutes and is preferably in the range from 0.25 to 4 grams per 10 minutes. In some embodiments, the implementation, the flow velocity of the melt is within the Ah from 0.25 to 1.00 grams per 10 minutes. In one embodiment, the implementation of the flow velocity of the melt is in the range from 0.28 to 0.6, and in another embodiment, it ranges from 0.3 to 0.5 grams per 10 minutes. All individual values and inner ranges from 0.20 to 5.0 g/10 min (I21) are included here and are described here. The ratio of flow rates, I21/I2, the polymer may be in the range of from 20 to 65, and preferably from 22 to 50, and more preferably from 23 to 40, and most preferably from 23 to 35. All individual values and inner ranges from 20 to 65 (I21/I2) are included here and are described here.

Mwfor the HMW component is preferably in the range of 100000 to 600000 g/mol (as measured by gel permeation chromatography), more preferably in the range from 250,000 to 500,000 g/mol, and most preferably in the range from 260000 up to 450,000 g/mol. All individual values and inner ranges from 100,000 up to 600,000 g/mol (Mw) are included here and are described here. Mw/Mnfor the HMW component is preferably relatively narrow. That is, preferably, Mw/MnHMW

component is less than 8, more preferably equal to or less than the 7.5, most preferably, is in the range from 3 to 7, and in particular, within the t 3.5 to 6.5. All individual values and inner ranges from 3 to 8 (Mw/mn) are included here and are described here.

HMW component typically has a lower density than the LMW component, as described below. Density HMW component typically ranges from 0,890 to 0,945 g/cm3(ASTM 792-03), preferably in the range from 0.910 to 0,940 g/cm3. In some embodiments, the implementation of the density is in the range from 0,915 to 0.935 g/cm3and more preferably, from 0,920 to 0,932 g/cm3and most preferably, from 0,924 to 0,932 g/cm3. All individual values and inner ranges from 0,890 to 0,945 g/cm3are included here and are described here.

In the embodiment, suitable for films obtained by extrusion-blow process, the flow rate of melt, I21, high molecular weight polymer component is in the range from 0.01 to 50, preferably from 0.2 to 12, more preferably from 0.2 to 1, and most preferably, from 0.2 to 0.5 g/10 min. All individual values and inner ranges from 0.01 to 50 g/10 min (I21) are included here and are described here. The ratio of flow rates, I21/I5polymer mainly equal to at least 6, preferably at least 7, and preferably up to 15, more preferably up to 12. M is molecular weight, Mw(as measured by gel chromatography) of this polymer predominantly in the range of 135000 to 445000 g/mol, and more preferably from 200,000 to 440000, and most preferably from 250,000 to 435000. All individual values and inner ranges from 135000 to 445000 g/mol (Mw) are included here and are described here. The density of the polymer is predominantly equal to at least 0,860 g/cm3and preferably is in the range from 0,890 to 0,940 g/cm3more preferably, in the range from 0,920 to 0,932 g/cm3. All individual values and inner ranges from 0,860 to 0,940 g/cm3are included here and are described here.

In the embodiment, suitable for products, blow molded, the flow rate of melt, I21high-molecular polymer component mainly is in the range from 0.01 to 50, preferably in the range from 0.1 to 12, more preferably from 0.1 to 1.0 grams per 10 minutes, and most preferably from 0.15 to 0.8 g for 10 minutes. All individual values and inner ranges from 0.01 to 50 g/10 min (I21) are included here and are described here. The ratio of flow rates, I21/I2, the polymer may be in the range of from 20 to 65, and preferably in the range from 20 to 40. All individual who values and inner ranges from 20 to 65 (I 21/I2) are included here and are described here. The density of the polymer is predominantly equal to at least 0,860 g/cm3and preferably is in the range from 0,890 to 0,980 g/cm3more preferably, in the range from 0,920 to 0,980 g/cm3. All individual values and inner ranges from 0,860 to 0,980 g/cm3are included here and are described here.

In the embodiment, suitable for pipes, LMW component has, I2the velocity of the melt, which preferably is in the range from 40 to 2000 g/10 min, preferably, this component is characterized as having a flow rate of the melt I2from 80 to 1200 g/10 min, more preferably from 400 to 1100 g/10 min, and most preferably, from 600 to 1000 g/10 minutes, In some embodiments, the implementation, the flow velocity of the melt is in the range from 500 to 1000 g/10 minutes All individual values and inner ranges from 40 to 2000 g/10 (I2minutes are included here and are described here. The ratio of flow rates, I21/I2this polymer or copolymer may be in the range of from 10 to 65, and preferably is from 15 to 60, or 20 to 50. In some embodiments, the implementation, the ratio of velocity of flow of the melt ranges from 22 to 40. All individual values and inner ranges from 10 to 65 (I1 /I2) are included here and are described here.

Mwfor LMW component is preferably less than 100,000 g/mol. Preferably, Mwfor LMW component is in the range from 10,000 to 40,000, and more preferably in the range from 15,000 to 35,000 g/mol. In some embodiments, the implementation of Mwfor LMW component is in the range from 25,000 to over 31,000 g/mol. All individual values and inner ranges from 10000 to 40000 g/mol (Mw) are included here and are described here. Mw/Mnfor LMW component is preferably less than 5, more preferably is in the range from 1.5 to 4.8, or from 2 to 4.6, and most preferably in the range from 3.2 to 4.5. In some embodiments, the implementation of Mw/Mnis in the range from 2.5 to 3.5, or from 2.7 to 3.1. All individual values and inner ranges from 1.5 to 5 (Mw/Mn) are included here and are described here.

LMW component typically represents a component with a higher density. The density of the polymer or copolymer may be between 0,940 to 0,980 g/cm3and preferably is in the range from 0,945 to 0,975 g/cm3and more preferably, from 0,968 to 0,975 g/cm3. In some embodiments, implement, density of the LMW component is 0,955 to 0,965 g/cm3. All individual who values and inner ranges from 0,940 to 0,980 g/cm 3are included here and are described here. It is preferred to maintain the LMW component at the highest density, and thus to maximize the Delta difference of densities between this component and the HMW component.

In the embodiment, suitable for films obtained by extrusion-blow process, the flow rate of melt, I2, low-molecular weight polymer component is in the range from 0.5 to 3000 g/10 min, preferably from 1 to 1000 g/10 minutes All individual values and inner ranges from 0.5 to 3000 g/10 min (I2) are included here and are described here. The ratio of flow rates, I21/I5this polymer may be in the range of from 5 to 25, preferably from 6 to 12. All individual values and inner ranges from 5 to 25 (I21/I5) are included here and are described here. The molecular mass Mw(as measured by gel chromatography (GPC)), this polymer generally ranges from 15800 up to 55,000 g/mol. All individual values and inner ranges from 15800 up to 55,000 g/mol (Mw) are included here and are described here. The density of this polymer is at least to 0.900 g/cm3and preferably from 0,940 to 0,975 g/cm3and most preferably, from 0,960 to 0.97 g/cm 3. All individual values and inner ranges from to 0.900 to 0,975 g/cm3are included here and are described here. It is preferred to maintain the LMW component at the highest density and thus to maximize the Delta difference of densities between this component and the HMW component.

In the embodiment, suitable for products, blow molded, LMW component has I2the velocity of the melt, which preferably is in the range from 40 to 2000 g/10 min, preferably, this component is characterized as having (I2the flow rate of the melt from 100 to 1500 g/10 min, more preferably from 400 to 1200 g/10 minutes All individual values and inner ranges from 40 to 2000 g/10 min (I2) are included here and are described here. The ratio of flow rates, I21/I2this polymer or copolymer may be in the range of from 20 to 65, and preferably from 20 to 40. All individual values and inner ranges from 20 to 65 (I21/I2) are included here and are described here. The density of the LMW component may be in the range of from 0,940 to 0,980 g/cm3and preferably in the range from 0,960 to 0,975 g/cm3. All individual values and inner ranges from 0,940 to 0,980 g/cm3are included here and is described who are here. It is preferred to maintain the LMW component at the highest density, and thus to maximize the Delta, the difference of densities between this component and the HMW component.

In the embodiment, suitable for ligation, the mixture or the final product may have a flow rate of melt, I5, (190°C, 5,0 kg), ranging from 0.01 to 2.0 g/10 min, and preferably has a I5in the range from 0.05 to 1.0 g/10 minutes, In some embodiments, implement, I5the composition is from 0.1 to 0.9 g/10 min, and preferably is in the range from 0.01 to 0.5 g/10 min, more preferably from 0.05 to 0.45 g/10 min All individual values and inner ranges from 0.01 to 2.0 g/10 min (I5) are included here and are described here. The flow rate of melt I21is in the range from 2 to 50 g/10 minutes, In some embodiments, the implementation, the mixture has I21in the range of 3 to 20 g for 10 min, preferably from 4 to 10 grams per 10 minutes All individual values and inner ranges from 2 to 50 g/10 min (I21) are included here and are described here. The ratio of flow rates, I21/I5mixture may be in the range of from 10 to 50, and preferably is in the range from 15 to 45, or in the range from 20 to 42. All individual values and inner ranges from 10 to 50 (I21/I5are including the military here and are described here.

The molecular mass Mwmixture typically is in the range from 200000 to 490,000 g/mol. All individual values and inner ranges from 200000 to 490,000 g/mol (Mw) are included here and are described here. In some embodiments, the implementation, the mixture has a broad bimodal distribution of molecular masses. A wide distribution of molecular masses is reflected as the ratio of Mw/Mnfrom 15 to 48, preferably from 18 to 45, and most preferably, from 20 to 40. All individual values and inner ranges from 15 to 48 (Mw/Mn) are included here and are described here.

The polyethylene composition is further characterized as having a total density equal to or greater than 0,940 g/cm3preferably, in the range from 0,940 to 0,962 g/cm3more preferably, from 0,944 to 0,960 g/cm3and most preferably, from 0,945 to 0,955 g/cm3. All individual values and inner ranges from 0,940 to 0,962 g/cm3are included here and are described here.

The mass ratio of polymer or copolymer obtained in the high molecular weight reactor, the polymer or the copolymer obtained in the low molecular weight reactor, referred to as the partition coefficient of the polymeric composition. In some embodiments, the implementation, the partition coefficient of the polymer is s songs, described here, may be in the range of from 0.8:1 to 2.3:1, and preferably is in the range from 0.9:1 to 1.9:3. The optimum separation factor is from 1.2:1 to 1.6:1. In some embodiments, the implementation of the separation factor ranges from 1.0:1 to 2.0:1. All individual values and inner ranges from 0.8:1 to 2.3:1 are included here and are described here.

The separation factor can also essentially reflect the percent mass HMW component and the LMW component in the composition of the mixture. HMW polymer component may be present in the composition from 0.5 to 99.5 wt.%, with respect to the total weight of the HMW component and the LMW component. All individual values and inner ranges from 0.5 to 99.5 % wt. (HMW component) are included here and are described here. In some embodiments, the implementation, the composition comprises from 65 to 35 wt.%, more preferably, from 62 to 45 wt.%, HMW ethylene component. Similarly, the polymer composition may contain from 0.5 to 99.5% wt. LMW component, relative to the total weight of the HMW component and the LMW component. In some embodiments, the implementation of the new composition comprises from 35 to 65 wt.%, preferably from 38 to 55 wt.%, component LMW ethylene homopolymer high density. All individual values and inner ranges from 0.5 to 99.5% (LMW component) aplaydevices here and are described here.

Alternatively, a new composition can be characterized as having a ratio of MV1/MV2equal to or less than 0.8, preferably equal to or less than 0.6, more preferably equal to or less than 0.4, where Mv1represents the average viscosity molecular weight of the LMW component of high density, and MV2represents the average viscosity molecular weight of the HMW polymer (or interpolymer) of the component, as determined using an ATREF-DV analysis, as described in detail in the application for international patent WO 99/14271, the description of which is included here as a reference. Application for international patent WO 99/14271 also describes the method of conversion for multi-component compositions of polymer blends.

In a preferred embodiment, the compositions of the present invention do not contain propylene homopolymer or interpolymer based on propylene. As used here, the term "interpolymer based on propylene" refers to propylene to interpolymers containing at least 50 mole percent of propylene polymerized in them.

In the embodiment, suitable for films obtained by extrusion-blow process, the mass ratio of the polymer (or copolymer)obtained in the high molecular weight reactor the polymer (or copolymer), obtained in the low molecular weight reactor may be in the range of from 30:70 to 70:30, and preferably in the range from 40:60 to 60:40. All individual values and inner ranges from 30:70 to 70:30 are included here and are described here. The density of the mixture can comprise at least 0,940 g/cm3and preferably is in the range from 0,945 to 0,960 g/cm3. All individual values and inner ranges from 0,945 to 0,960 g/cm3are included here and are described here. Blend or final product when it is removed from the second reactor may have a flow rate of melt, I5in the range of 0.2 to 1.5 g/10 min, preferably from 0.25 to 1.0 g/10 min. All individual values and internal ranges (I5from 0.2 to 1.5 g/10 minutes are included here and are described here. The ratio of flow rates, I21/I5is in the range of from 20 to 50, preferably from 24 to 45. All individual values and internal ranges (I21/I5from 20 to 50 are included here and are described here. The molecular mass Mw, the final product usually ranges from 90000 to 420000 g/mol. All individual values and internal ranges (Mwfrom 90000 to 420000

g/mol are included here and are described here. Bulk density can be pre is Elah from 18 to 30 pounds per cubic foot, and preferably, more than 22 pounds per cubic foot (288, 481 and 352 kg/m3, respectively). All individual values and inner ranges from 18 to 30 pounds per cubic foot are included here and are described here. The mixture has a wide distribution of molecular masses, which, as noted, can be characterized as multi-modal. A wide distribution of molecular weights is recognised in respect of PDI (Mw/Mnfrom 15 to 48, preferably from 18 to 45. All individual values and inner ranges from 15 to 48 (Mw/Mn) are included here and are described here.

In the embodiment, suitable for products, blow molded, the mixture or the final product may have a flow rate of melt, I5, (190°C, 5,0 kg) in the range from 0.01 to 5.0 g/10 min, preferably in the range from 0.05 to 5.0 g/10 min, more preferably from 0.1 to 2.0 g/10 min All individual values and internal ranges (I5) from 0.01 to 5.0 g/10 minutes are included here and are described here. The flow rate of melt, I21is in the range from 2 to 60 g/10 min, preferably from 3 to 40 g/10 min, more preferably from 4 to 15 g/10 minutes All individual values and internal ranges (I21) from 2 to 60 g/10 minutes are included here and are described here. The ratio of flow rates, I 21/I5mixture may be in the range of from 10 to 50, preferably ranging from 15 to 48, or more preferably in the range from 15 to 42. All individual values and inner ranges from 10 to 50 (I21/I5) are included here and are described here. The composition of the polymer is further characterized as having a total density equal to or greater than 0,940 g/cm3preferably, in the range from 0,940 to 0,980 g/cm3more preferably, from 0,950 to 0,975 g/cm3. All individual values and inner ranges from 0,940 to 0,980 g/cm3are included here and are described here. The composition comprises from 75 to 35 wt.%, more preferably, from 70 to 40 wt.%, HMW component. All individual values and inner ranges from 75 to 35 are included here and are described here.

In one of the embodiments, the high molecular weight component and/or a low molecular weight component is a heterogeneously branched interpolymer (interpolymer), usually obtained with the aid of catalysts of the type Ziegler-Natta, and containing inhomogeneous distribution of co monomer among molecules interpolymer.

In another embodiment, the high molecular weight component and/or a low molecular weight component is a homogeneous linear or branched essentially inany interpolymer (interpolymer) or copolymer (copolymer) of ethylene.

The term "linear polymers of ethylene/α-olefin" is a polymer that does not have long chain branching, as for example, linear polyethylene polymers low density or linear polyethylene polymers of high density, obtained using the methods of polymerization with homogeneous branching distribution (i.e., homogeneous branched) (for example, U.S. patent No. 3645992 (Elston), the description of which is thus included here by reference in its entirety), and are of such polymers, in which comonomer randomly distributed within a given molecule interpolymer, and where essentially all the molecules of interpolymer have the same ratio of ethylene/comonomer inside this interpolymer. This is the opposite of heterogeneously branched interpolymers usually obtained with catalysts of the type Ziegler-Natta and containing inhomogeneous distribution of co monomer among molecules interpolymer. The term "linear polymers of ethylene/α-olefin" is not branched high-pressure polyethylene, which is known to specialists in this area has numerous long chain branches.

A substantially linear copolymers or interpolymer ethylene (also known as the "SLEP") are particularly preferred. "Essentially linear" means that h is of the polymer has a main chain, substituted from 0.01 to three long-chain branches per 1000 carbon atoms in the main chain, preferably, from 0.01 to one long-chain branches per 1000 carbon atoms, and more preferably, from 0.05 to one long-chain branches per 1000 carbon atoms.

Essentially linear interpolymer ethylene/α-olefin according to the present invention are described in U.S. patent No. 5272236 and in U.S. patent No. 5278272, each of which is included here in their entirety by reference. Suitable for use essentially linear interpolymer ethylene/α-olefin are those polymers in which comonomer randomly distributed within a given molecule interpolymer, and where essentially all the molecules of interpolymer have the same ratio of ethylene/comonomer inside this interpolymer. Essentially linear interpolymer ethylene/α-olefin also have a single melting peak, as opposed to heterogeneously branched linear polymers of ethylene, which have two or more melting peaks.

In one of the embodiments, interpolymer ethylene have a homogeneous distribution of co monomer, so that the content of co monomer fractions of the polymer, in the range of molecular masses interpolymer varies less than 10% wt., preferably, less than 8% wt., more preferably, less than 5% wt., and yet Bo is her preferred less than 2 % wt.

SLEP is characterized by a narrow distribution of molecular mass (MWD) and a narrow distribution of short-chained branch (SCBD), and can be obtained as described in United States patents No. 5272236 and 5278272 with the attitude of both patents are incorporated here as reference. SLEP demonstrates outstanding physical properties, due to their narrow MWD and narrow SCBD, in combination with long-chain branching (LCB). In one of the embodiments, the MWD is from 1 to 5, preferably from 1.5 to 4, and more preferably, from 2 to 3.

U.S. patent No. 5272236 (column 5, line 67 to column 6, line 28) describes obtaining SLEP through continuous controlled polymerization method, using at least one reactor, but allows for use of multiple reactors at a temperature and pressure of the polymerization, sufficient for SLEP with the desired properties. The polymerization preferably is carried out using the method of polymerization in solution at temperatures from 20°C to 250°C, using the technology of catalysts with limited geometry. Appropriate catalysts with limited geometry described in column 6, line 29 to column 13, line 50 U.S. patent No. 5272236.

Preferred SLEP has a number of different characteristics, one of which is pre which represents a content of ethylene, which is in the range between 20 and

90% wt., more preferably, between 30 and 89 wt.%, when this balance is one or more comonomers. The content of ethylene and co monomer refers to the mass of the SLEP and are selected to maintain the total content of the monomer is 100% by weight. For lengths of chains of up to six carbon atoms, the content of the SLEP of co monomer can be measured using C-13 NMR spectroscopy.

The polymer composition of the final product of polymerization is reologicheskie modified, also known as related by polyfunctional sulfonylation, as described in U.S. patent 6521306, which is included here as a reference.

To modify rheology, also referred to here as "linking"poly(sulfonylated) is used in reologicheskie modifying the number, that is, in a quantity effective to increase nikodimou viscosity (< 0,1 rad/sec) of the polymer, preferably at least about 5 percent, compared with the starting material polymer, but less than the transverse cross-linking number, i.e. the number, causing less than 1% wt. gel, as measured according to ASTM D 2765 - Procedure A. while the experts in this field will recognize that the amount of azide sufficient to increase nikodimou viscosity and cause me is it approximately than 1% wt. gel will depend on the molecular weight used azide and polymer, this amount is preferably less than about 5 wt.%, more preferably, less about than 2% wt., most preferably, less about than

1% wt. poly(sulfonylated), relative to the total weight of the polymer, when poly(sulfonylated) has a molecular mass of from 200 to 2000 g/mol. To achieve measurable rheological modification, the amount of poly(sulfonylated) is preferably at least 0,0025% wt., more preferably, at least, of 0.005 wt.%, most preferably, at least 0.01% wt., in relation to the total weight of the polymer.

The way rheological modification of polymers is described in more detail later in the text.

Compared to previous generations of industrial materials standard ASTM PE 3408, pipe, made from the polymers described herein have the meanings PENT of at least 1000 hours. Some pipes have values PENT greater than 5000 hours, and up to 25,000 hours or more at 2.4 MPa. Pipe with a value of PENT 25000 hours are 250 times more resistant to the slow crack growth (SCG), compared with more stringent requirements for gas pipes in ASTM D2513-99. Some pipes have values PENT greater than 1000 hours, and up to 11000 hours 15000 hours or more, at 3.0 MPa. Some of ruby, made from polyethylene, described here, are defined as polymers PE 100 with extrapolated lifetimes of 100 years, and ISO approved 9080-99 for life 250 years at 20°C. the Tubes also have excellent properties of rapid propagation of cracks when tested S-4 for the critical temperature Tc and critical pressure, Pc. Tc and Pc are determined in accordance with ISO 13477. Characteristics of properties under hydrostatic rupture (Categorized Required Stress)are aligned with the Plastics Pipe Institute (PPI) Technical Report TR-3, at 60 and 80°C, at least 6.3 and 4.0 MPa.

As shown in the Examples linked polymer composition has unexpectedly high viscosity at very low shear, that is, under conditions of creeping deformation. Approximately 10-fold increase in viscosity creeping deformation can be achieved essentially without the participation of other characteristics of a product or process.

A typical system of catalysts based on transition metals that can be used to obtain a mixture, are systems of catalysts based on magnesium/titanium, which may be illustrated by the system of the catalysts described in U.S. patent No. 4302565 systems; catalysts based on vanadium, such as those described in U.S. patent No. 4508842; 5332793; 5342907; and 5410003; and systems metallocene catalysts, such as those described in atento U.S. No. 4937299; 5317036; and 5527752. System catalysts, which use oxides of molybdenum on the native silicon dioxide - aluminum oxide, are also suitable for use. The preferred system catalysts for production of components for the mixtures of the present invention are systems of catalysts of the Ziegler-Natta and metallocene system catalysts.

In some embodiments, implementation of the preferred catalysts used in the method for obtaining the compositions according to the present invention are catalysts of the type of magnesium/titanium. In particular, for a given gas-phase polymerization, the catalyst made from a precursor containing the chlorides of magnesium and titanium in the solvent - electron donor. This solution is often precipitated by a porous carrier for a catalyst, or add a filler which, in the subsequent spray drying, provides additional mechanical strength of the particles. Solid particles of any ways for the media often suspendered in the diluent, giving a mixture of high viscosity, which is then used as the catalyst precursor. Exemplary types of catalysts are described in U.S. patent No. 6187866 and in U.S. patent No. 5290745, the complete contents of both of them is included here as a reference.

Can also be used in the system is s precipitiously/ crystallized catalysts, such as those described in U.S. patent No. 6511935 and U.S. patent No. 6248831, the complete contents of both of them is included here as a reference.

Preferably, the catalyst precursor has the formula MgdTi(OR)eXf(ED)gwhere R represents an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR'where R' is an aliphatic or aromatic hydrocarbon radical having 1-14 carbon atoms; each group OR may be the same as or different; X independently represents a chlorine, bromine or iodine; ED is an electron donor; d is 0.5 to 56; e is 0, 1, or 2; f is 2-116 and g is >2 and-1.5·d + 3. It is derived from compounds of titanium, magnesium compounds and electron donor.

The electron donor is an organic Lewis base, liquid at temperatures in the range from 0°C to 200°C, in which compounds of magnesium and titanium are soluble. Compounds of the electron donor is sometimes also referred to as base Lewis. The electron donor can be a difficult alkilany ether of aliphatic or aromatic carboxylic acids, aliphatic ketone, aliphatic amine, aliphatic alcohol, a simple alkilany or cycloalkenyl ether or mixtures thereof, each electron donor has 2-20 carbon atoms. Among e is their electron donor, preferred are simple alkalemia and cycloalkyl ethers having 2 to 20 carbon atoms; dialkyl-, diaryl - and alkylacrylate having 3-20 carbon atoms; and complex alkalemia, alkoxy, alkylalkoxy esters of alkyl - and arylcarboxylic acids having 2-20 carbon atoms. The most preferred electron donor represents tetrahydrofuran. Other relevant examples of electron donors are methylformate, ethyl acetate, butyl acetate, simple, ethyl ether, dioxane, simple di-n-propyl ether, simple disutility ether, ethanol, 1-butanol, ethyl formate, methyl acetate, ationist, ethylene carbonate resulting, tetrahydropyran and ethylpropane.

When a large excess of electron donors can be used initially to generate a reaction product compounds and titanium, an electron donor, the final catalyst precursor contains from about 1 to about 20 moles of electron donor per mole of titanium compounds, and preferably, from about 1 to about 10 moles of electron donor per mole of titanium compounds.

Because the catalyst will act as a template for the growth of polymer, the main thing is that the catalyst precursor was transformed into a solid product. Also important is that the resulting solid product was of appropriate size and shape of the particles for the doctrine of the polymer particles with a relatively narrow size distribution, small quantities of fine particles and good characteristics of fluidization. Although this solution Foundation Lewis, compounds of magnesium and titanium can impregnants in porous media and to be dried with the formation of the solid catalyst is preferred that the solution was converted to the solid catalyst by spray drying. Thus, each of these methods generates a "catalyst precursor on the media".

Obtained by spray drying the product catalyst is then preferably placed in suspension in mineral oil. The viscosity of the hydrocarbon diluent suspension is low enough so that the suspension can be conveniently pumped through the device prior to activation, and possibly in the polymerization reactor. The catalyst is entered using the input device for the suspension of the catalyst. Screw pump such as a Moyno pump, typically used in industrial reactive systems, while the plunger pump dual piston, generally used in the reaction systems of the pilot scale, where the threads of the catalyst is equal to or less than 10 cm3/h (2,78×10-9m3/s) of suspension.

Acetalization or activator is also introduced into the reactor to perform the polymerization. The full act is cultivation by means of additional socializaton required to achieve the activity in full. Full activation is usually carried out in the polymerization reactor, but can also be used technologies discussed in European patent EP 1200483.

Usually used socializaton, which are reducing agents, consist of aluminum compounds, but compounds of lithium, sodium and potassium, alkaline earth metals, and compounds of other rare-earth metals other than aluminum are possible. Connections are usually hydrides, ORGANOMETALLIC or halogen compounds. Utility and dibutylamine are examples of usable compounds other than aluminum.

An activator compound which is generally used in conjunction with any of the precursors of catalysts based on titanium, can have the formula AlRaXbHcwhere each X independently represents a chlorine, bromine, iodine, or or'; each R and R' independently represents a saturated aliphatic hydrocarbon radical having 1 to 14 carbon atoms; b is 0-1,5; c is 0 or 1; and a+b+c=3. Preferred activators include alkylamino mono - and dichloride, where each alkyl radical has 1 to 6 carbon atoms, and trialkylaluminium. Examples are diethylaluminum chloride and tri-n-hexylamine. From about 0.10 to 10 moles, and preferably is, from 0.15 to 2.5 moles of activator is used per mole of electron donor. The molar ratio of activator to titanium is in the range from 1:1 to 10:1, and preferably in the range from 2:1 to 5:1.

Socialization based hydrocellulose can be represented by the formula, R3Al or R2AlX, where each R independently represents alkyl, cycloalkyl aryl or hydrogen; at least one R is hydrocarbon; and two or three of the radicals R may be combined to form heterocyclic structures. Each of R, which represents hydrocarbonyl radical, can have 1-20 carbon atoms, and preferably has 1 to 10 carbon atoms. X represents halogen, preferably chlorine, bromine or iodine. Examples of compounds hydrocellulose represent the following: triisobutylaluminum, tri-n-hexylamine, di-isobutylamine hydride, dihexylfluorene hydride, di-isobutylamine, isobutyl dihexylfluorene, trimethylaluminum, triethylaluminum, Tripropylamine, triisopropanolamine, tri-n-butylamine, trioctylamine, tridecylamine, riddellii, tribenzylamine, triphenylamine, trinitroluene, tricholorethylene, dibutylamine chloride, diethylaluminium chloride, and ethylaluminum sesquichloride. Connection socialization can also serve quality is as activators and modifiers.

The activators may be added to the precursor either before and/or during the polymerization. In one procedure, the precursor is fully activated before polymerization. In another procedure, the predecessor of the partially activated before polymerization, and the activation is completed in the reactor. When instead of activator used the modifier, the modifier is usually dissolved in an organic solvent, such as isopentane, and when to use media, impregnants in the media after impregnating compound or complex of titanium, after which the catalyst precursor in the carrier is dried. In another case, the solution of the modifier add itself directly in the reactor. Modifiers are similar in chemical structure and function activators, since they represent socializaton. On options, see for example, U.S. patent No. 5106926 included here by reference in its entirety. Socialization preferably added separately, by itself, or in the form of a solution in an inert solvent, such as isopentane, to the polymerization reactor, at the same time, when it starts the flow of ethylene.

In those embodiments, implementation, using the media, the precursor is applied to the carrier of the inorganic oxide such as silicon oxide, aluminum phosphate is I, aluminum oxide, a mixture of silicon oxide/aluminum oxide, silicon oxide, which is modified alumoorganic connection, such as triethylaluminium, and silicon oxide, modified by diethylzinc. In some embodiments, the implementation of the oxide of silicon is a preferred carrier. A typical carrier is a solid, porous material in the form of particles, essentially inert with respect to polymerization. It is used in the form of a dry powder having an average particle size of from 10 to 250 μm, and preferably from 30 to 100 microns; a surface area of at least 200 m2/g, and preferably at least 250 m2/g; and a pore size of at least 100×10-10m, and preferably at least 200×10-10M. typically, the amount of the carrier is such that it provides from 0.1 to 1.0 millimole titanium per gram of the carrier, and preferably, from 0.4 to 0.9 millimole titanium per gram of the carrier. Impregnation of the above catalyst precursor in the carrier and silicon dioxide can be carried out by mixing the precursor and silica gel in solvent - electron donor or in another solvent, followed by removal of solvent under reduced pressure. When the media is not desired, the catalyst precursor can use isolates in liquid form.

In another embodiment, metallocene catalysts, one-catalysts and catalysts with limited geometry can be used when implementing the present invention. As a rule, the compounds of metallocene catalysts include half and full sandwich compounds having one or more π-bound ligands, including structure type cyclopentadienyl or other structures with similar function, such as pentadiene, cyclooctatetraene and imides. Typical compounds generally described as containing one or more ligands capable of π-bonding of the transition metal atom, usually, ligands or residues derived from cyclopentadienyl, in combination with transition metal selected from Groups 3 to 8, preferably 4, 5 or 6, or from a number of lanthanides and actinides of the Periodic table of elements.

Examples of compounds of catalysts of the type metallocenes described, for example, in U.S. patents№№: 4530914; 4871705; 4937299; 5017714; 5055438; 5096867; 5120867; 5124418; 5198401; 5210352; 5229478; 5264405; 5278264; 5278119; 5304614; 5324800; 5347025; 5350723; 5384299; 5391790; 5391789; 5399636; 5408017; 5491207; 5,455,366; 5534473; 5539124; 5554775; 5621126; 5684098; 5693730; 5698634; 5710297; 5712354; 5714427; 5714555; 5728641; 5728839; 5753577; 5767209; 5770753 and 5770664; publications of European patents: EP-A-0591756; EP-A-0520732; EP-A-0420436; EP-A-0485822; EP-A-0485823; EP-A-0743324; EP-A-0518092; and PCT publications requests for international patent: WO 9/04257; WO 92/00333; WO 93/08221; WO 93/08199; WO 94/01471; WO 96/20233; WO 97/15582; WO 97/19959; WO 97/46567; WO 98/01455; WO 98/06759 and WO 98/011144. All these sources are included here as reference in its entirety.

Catalysts suitable for use here, preferably include catalysts with limited geometry, as described in U.S. patent No. 5272236 and 5278272, they are included here as reference in its entirety.

Catalysts for polymerization of olefins based on mononitrobenzene transition metals discussed in U.S. patent No. 5026798, the concept of which is included here by reference, are also suitable as catalysts of the present invention.

The above catalysts may optionally be described as containing a coordination complex with a metal, comprising a metal of groups 3-10 or the number of lanthanides of the Periodic table of the elements and a delocalized π-bound residue, substituted residue, causing the limitation. This complex has limited the geometry around the metal atom. In addition, the catalyst contains activating socializaton.

Catalysts based on chromium and polymers

In a separate embodiment, another type of catalyst based on chromium is used in one reactor, although it is not limited to a single reactor and can use the be in two or more consecutive reactors.

Polyethylene polymers, polymerized with the use of these catalysts based on chromium, and methods for their preparation are well known in this field. They include methods of polymerization in the gas phase, solution phase and the phase of the suspension. Of particular interest for the present invention are polymers obtained in gas-phase method, the polymers that are obtained using chromium catalyst, and, in particular, the catalyst based on titaniumand chromium.

As a rule, suitable for use catalysts consist of compounds of chromium (VI) (usually in the form of oxide)supported on a carrier of heat-resistant oxide with high surface area. Typically, the carrier is an amorphous microspheroidal silicon oxide, silicon oxide - aluminum oxide, silicon oxide - titanium oxide or lumotast. The catalyst is prepared by activating the chromium-containing media at temperatures of 400-1000°C in dry oxygen-containing atmosphere. Modifying materials such as titanium and fluoride, as a rule, add before activating.

Typically, the catalysts are prepared by using commercially available silicon dioxide, which is added to the source of chromium. Media and silicon dioxide can be handled complex ether titanium (from used titanium, tetraisopropyl or titanium tetraethoxide), or after deposition of the compounds of Cr or before deposition. The media, as a rule, pre-dried at 150-200°C to remove physically adsorbed water. The titanate may be added in the form of a solution to a suspension of silicon dioxide in isopentanol solvent or directly onto a fluidized bed of media. If it is added in the form of a suspension, the suspension is dried. Typically, the connection of Cr, which can be transformed into Cr+6, are already added to the media. Then the carrier is converted into an active catalyst by calcination in air at temperatures up to 1000°C.

During activation, the titanium is converted to some type of surface oxide. The chromium compound (usually chromium (III) acetate) is converted into an oxide of Cr+5any type. Fluorinating agents can also be added during the method of activation for selective collapse some time in the media, modifying the sensitivity of the catalyst to the molecular mass. The activated catalyst before use can also be processed reducing agents such as carbon monoxide, in the fluidized bed, or other reducing agents, such as alkali aluminum, alkali boron, alkali lithium, and the fact of podobn the E.

Catalysts of this type are described in numerous patents, such as the application for international patent WO 2004094489, European patent EP 0640625, U.S. patent No. 4100105 and references cited therein. Each of these references is included by reference in its entirety. For example, suitable for use with the catalyst is a catalyst based on chromium-titanium on the carrier (or the catalyst oxide titaniumand chromium), which is essentially non-spherical or irregular in shape, and has a wide distribution of particle sizes, with at least 70 percent of its pore volume is in the range of pores with a diameter between 200 to 500 angstroms. Such media can be activated by heating in the presence of oxygen, at a temperature of from 850°C to the sintering temperature of the complex on the media. Catalysts such as those described in U.S. patent 6022933, also containing the component Cr+6are also suitable for use in the present invention. This link is also included here as a reference, in its entirety.

In a preferred embodiment, odnovalnye-based polymers, polyethylene polymers (based on Cr) and, in particular, on the basis of polymers, high density polyethylene, is linked by means of the azide method swazilan what I as described herein. In another embodiment, a mixture of two or more polymers containing at least one chromium catalyzed polyethylene polymer, bound by way of azide binding, as described here.

In one of the embodiments catalyzed Cr polymer has a flow rate of the melt I2(190°C, 2,16 kg mass, ASTM 1238-03) in the range of 0.01 to 20 g/10 minutes, In some embodiments, the implementation of I2is in the range from 0.1 to 15 g/10 minutes, In some embodiments, the implementation of I2equal to or less than 0.1 g/10 min, and preferably, the polymer is characterized as having (I2from 0.5 to 10 g/10 min, more preferably from 1 to 10 g/10 min In another embodiment, the I2is 0,0085 to 0,017 g/10 minutes All individual values and inner ranges of 0.001 to 20 g/10 min (I2) are included here and are described here.

The flow rate of melt, I21(190°C, the weight of 21.6 kg, ASTM 1238-03), for polymer-based chromium may be in the range from 1 to 50 grams per 10 minutes, and preferably is in the range from 2 to 30 grams per 10 minutes. In some embodiments, the implementation, the flow velocity of the melt is in the range from 5 to 20. All individual values and inner ranges from 1 to 50 g/10 (I21minutes are included here and are described here.

21/I2, the polymer may be in the range of from 40 to 200, and preferably from 50 to 150, and most preferably from 55 to 130. In another embodiment, the I21/I2for the polymer is in the range from 65 to 125, and preferably from 80 to 120. All individual values and inner ranges of 40 to 200 (I21/I2) are included here and are described here.

Mwthis polymer is preferably in the range of 100000 to 600000 g/mol (as measured by gel chromatography), more preferably in the range from 200000 to 500000 g/mol, and most preferably in the range from 210000 up to 450,000 g/mol. All individual values and inner ranges from 100,000 up to 600,000 g/mol (Mw) are included here and are described here.

This polymer has a density, which typically is in the range from 0,890 to 0,975 g/cm3(ASTM 792-03), preferably in the range from 0,920 to 0,970 g/cm3. In some embodiments, the implementation of the density is in the range from 0,930 to 0,960 g/cm3and more preferably in the range from 0,940 to 0,955 g/cm3. All individual values and inner ranges from 0,890 to 0,975 g/cm3are included here and are described here.

The polymer catalyzed chromium, can be obtained in a single reactor or can be obtained in the de mixture in two or more reactors, running in parallel, sequentially, or in some combination. In the preferred installation of the dual reactor, the catalyst precursor and socialization introduced into the first reactor and polymerized mixture is transferred to the second reactor for further polymerization. Additional methods of polymerization are described here.

A new composition containing the HMW component and the LMW component, as discussed in the previous sections, can be obtained by various methods. For example, it can be obtained by mixing or stirring the LMW polyethylene component and a HMW polymer component or by mixing of melts individually fused components. Alternatively, it can be obtained in situ in one or some of the polymerizers.

In the preferred installation of the dual reactor method according to the present invention, the catalyst precursor and socialization introduced into the first reactor and polymerized mixture is transferred to the second reactor for further polymerization. Insofar as the system is considered catalysts, only acetalization, if desired, is added to the second reactor from an external source. Optionally, the catalyst precursor can be partially activated before adding to p the actor, followed by an additional activation in the reactor using socializaton.

In the preferred installation of the dual reactor, relatively high molecular weight copolymer (low-index melt flow) are obtained in the first reactor. Alternatively, a low molecular weight copolymer can be obtained in the first reactor and the high molecular weight copolymer can be obtained in the second reactor. For the purposes of the present description, the reactor, in which conditions are conducive to a high molecular weight polymer, known as "high molecular weight reactor. Alternatively, the reactor, in which conditions are conducive to a low molecular weight polymer, known as the "low reactor". Regardless of which component a first mixture of a polymer and an active catalyst preferably is transferred from the first reactor to the second reactor by means of a connecting device, using nitrogen or recyclery gas from the second reactor as a migration environment.

Polymerization in each reactor is preferably carried out in the gas phase using a continuous method, fluidized bed. In a typical reactor with a fluidized bed, the layer is usually created from the same granular polymer, which must be created in the reactor. Thus, x is de polymerizatio, the layer has formed polymer particles, the growing polymer particles and catalyst particles, fluidized by means of the polymerized and modifying gaseous components introduced in the volumetric or linear flow rate sufficient to cause the particles to separate and act as a fluid medium. The fluidizing gas is obtained from the input initially starting materials, replenishable raw materials being recycled and gas, that is, of comonomers, and, if desired, modifiers and/or one or more inert carrier gases.

A typical system with fluidized bed contains a reaction chamber, the layer of the gas distribution plate, inlet and outlet pipes, compressor, refrigerant gas being recycled and release of the product. In the vessel, above the layer, there is a zone of lower velocity, and, in the layer of the reaction zone. Both of them are located above the gas distribution plate. A typical reactor with a fluidized bed is additionally described in U.S. patent No. 4482687, the full content of which is included here as a reference.

The streams of gaseous starting materials ethylene and other gaseous alpha-olefins and hydrogen, if used, is preferably introduced into the line for recycling the reactor as a liquid alpha-olefins and Rast the EOS socializaton. Optional liquid acetalization may be injected directly into the fluidized bed. Partially activated catalyst precursor is preferably injected into the fluidized bed as a slurry in mineral oil. Activating usually ends in reactors using socializaton. The composition of the product can be varied by changing the molar relationship of the monomers introduced into a fluidized bed. The product is continuously released in the form of granules or particles from the reactor, when the level of the layer increases during polymerization. The receive rate is controlled by adjusting the speed of introduction of the catalyst and/or the partial pressure of ethylene in both reactors.

The preferred mode is a boot selection quantities of product from the first reactor and transfer them to the second reactor using a pressure difference generated by the system compression gas being recycled. The system, similar to the one described in U.S. patent No. 4621952, the full content of which is included here by reference, is particularly useful.

The pressure is approximately the same as in the first and in the second reactor. Depending on the specific method used to transfer the mixture of polymer and catalyst contained from the first the first reactor to the second reactor, the pressure in the second reactor may be either higher or slightly lower than in the first. If the pressure in the second reactor is lower this pressure difference can be used to facilitate transfer of the mixture of polymer and catalyst from Reactor 1 to Reactor 2. If the pressure in the second reactor is higher, the pressure difference across the compressor being recycled gas can be used as a driving force to move the polymer. Pressure, that is, the total pressure in any reactor can be in the range of 200 to 500 psi (pounds per square inch, gauge) and preferably is in the range from 280 to 450 psi (1,38, 3,45, 1,93, and 3,10 MPa, respectively). The partial pressure of ethylene in the first reactor may be in the range of from 10 to 150 psi, and preferably is in the range from 20 to 80 psi, and more preferably in the range from 25 to 60 psi, (68,9, 103,4, 138, 552, 172 and 414 MPa, respectively). The partial pressure of ethylene in the second reactor is controlled in accordance with the amount of copolymer that wish to make in this reactor, to achieve the separation factor discussed above. It is noted that the increase in the partial pressure of ethylene in the first reactor leads to an increase in the partial pressure of ethylene in the second reactor. The balance of the total pressure to provide the indication of an alpha olefin, other than ethylene, and an inert gas such as nitrogen. Other inert hydrocarbons, such as induced condensing agent, for example, isopentane, hexane, also contribute to the total pressure in the reactor in accordance with the pressure of the vapour at the temperature and pressure experienced in the reactor.

The molar ratio of hydrogen:ethylene can be adjusted to control the average molecular masses. Alpha-olefins (other than ethylene) may be present in a total amount up to 15 wt.%. from the copolymer and, if used, is preferably included in the copolymer in a total amount from 0.5 to 10 wt.%, or more preferably, from 0.8 to 4 wt.%, in relation to the weight of the copolymer.

The residence time of the mixture of reagents, including gaseous and liquid reactants, catalyst and polymer in each of the fluidized bed can be in the range from 1 to 12 hours, and preferably in the range from 1.5 to 5 hours.

Reactors can operate in condensing mode, if this is desirable. Condensation mode is described in U.S. patent No. 4543399, 4588790 and 5352749, the full content of which is included here as a reference.

While the plastic mixture according to the present invention preferably get in the gas phase using different methods of low pressure, the mixture may also be obtained in the liquid phase, in solutions or susp is nsiah, or as a combination of slurry and gas phase or gas phase and solution, or suspension and solution, in any order, using conventional technology, again, at low pressures. How low pressure, generally carried out at pressures below 1000 psi, while the ways of high pressure, generally carried out at pressures above 15,000 psi (6,89 and 103 MPa, respectively).

Preferred operating temperatures vary depending on the desired density, i.e., a low temperature for lower densities and higher temperatures for higher densities. Operating temperature will vary from 70°C to 110°C. the Molar ratio of alpha-olefin to ethylene in this reactor can be in the range of from 0.01:1 to 0.8:1, and preferably is in the range of from 0.02:1 to 0.35:1. The molar ratio of hydrogen (if used) to ethylene in this reactor can be in the range of from 0.001:1 to 0.3:1, preferably from 0.01 to 0.2:1.

In the embodiment, suitable for pipes operating temperature generally is in the range from 70°C to 110°C. the operating temperature is preferably varies with the desired density, to prevent buildup in the reactor. The molar ratio of alpha-olefin to ethylene can be in the range of from 0:00001 to 0.6:1, predpochtitel is about, in the range from 0.0002:1 to 0,010:1. The molar ratio of hydrogen to ethylene can be in the range of from 0.01:1 to 3:1, and preferably in the range from 0.5:1 to 2.2:1.

In the embodiment, suitable for films obtained by extrusion-blow process, the operating temperature of high molecular weight reactor generally ranges from 70°C to 110°C. the Molar ratio of alpha-olefin to ethylene is less than is used in the high molecular weight reactor, and preferably equal to at least 0,0005:1, preferably at least 0,00001:1, and mainly, is equal to or less than 0.6:1, more predominantly, equal to or less than 0,42:1, preferably equal to or less than 0.01:1, more preferably equal to or less than 0,007:1, most preferably equal to or less than 0,0042:1. At least some amount of alpha-olefin accompanies the content of high molecular weight reactor. The molar ratio of hydrogen to ethylene can be in the range of from 0.01:1 to 3:1, and preferably in the range from 0.5:1 to 2.2:1.

In the embodiment, suitable for blow molding, the working temperature of high molecular weight reactor generally ranges from 70°C to 110°C. the Molar ratio of alpha-olefin to ethylene in this reactor can be in the range from 0.0:1 to 0.8:1 and preferably in the range from 0.0:1 to 0.1:1. Molar is the ratio of hydrogen (if used) to ethylene in this reactor can be in the range of from 0.001:1 to 0.3:1, preferably, 0.005 to 0.2:1. The working temperature of the low molecular weight reactor generally ranges from 70°C to 110°C. the Molar ratio of alpha-olefin to ethylene can be in the range from 0.0:1 to 0.6:1, preferably in the range from 0.0002:1 to 0.01:1. The molar ratio of hydrogen to ethylene can be in the range of from 0.01:1 to 3:1, and preferably in the range from 0.3:1 to 2:1.

Some mixtures will receive in a single reactor using a mixed catalyst. In these mixed systems of catalysts, the catalyst composition may contain a combination of two or more catalysts of the Ziegler-Natta, two or more catalysts based on metallocenes, such as those described in U.S. patent No. 4937299, 5317036 and 5527752, the full content of which is included here as reference in its entirety, or a combination of catalysts of the Ziegler-Natta and metallocene catalyst. In some embodiments, implementation, can be used dogancay metallocene catalyst.

Polymers based on ethylene of the present invention can be obtained in a single reactor or in multiple reactors. For example, ethylene can homopolymerization or copolymerizate at least one co monomer, in single or multi-stage method of polymerization in suspension (in the tank or loop), in single or multistage fashion polymerization in the gas phase, in single or multi-stage method of polymerization in solution, or combination of methods of polymerization, such as the method of polymerization in slurry and gas phase, or a method of polymerization in the gas phase is the solution. Multistage gas-phase methods described in U.S. patent No. 5047468 and 5149738, the full contents of both are included here as a reference. Two or more reactor can operate simultaneously or sequentially, or in combination.

The original materials of the catalysts can be selected from several configurations, including, but not limited to, a system of catalysts on a carrier, dried spray system catalysts or catalysts introduced into the solution or liquid. Polymerization catalysts usually contain a transition metal compound on the carrier, and an activator capable of converting the transition metal compound into a catalytically active complex of the transition metal.

The configuration of the catalyst on a carrier, typically contain at least one active in the polymerization of the compound of the metal with a porous carrier such as porous silicon oxide. Generally, the active compound of the metal integriruetsa in the porous metal oxide.

The morphology of the catalyst can be modified using the classification by size and/or group is a rotary modification of chemical properties.

Other forms of configuration catalysts include dried spray system solution or suspension, each of which contains an active metal. System catalyst may be dried by spraying directly into the reactor. These dried spray system may also contain fillers, binders, suspendresume agents and/or activators. Examples of spray dried systems catalysts are in U.S. patents№№ 5589539; 5317036; 5744556; 5693727, 5948871; 5962606, 6075101; 6391986; 6069213; 6150478; 6365659; 6365695; 6251817 and 6426394, which, each, are included here as a reference in their entirety. Additional examples of these systems catalysts are described in U.S. patent No. 6689847 and in the application for U.S. patent 2003/0036613, each of which is included here as a reference, in its entirety.

Additional configuration catalysts include active metal compounds deposited on precipitiously, having the form of microparticles, polymeric adducts of metals with the formation of round particles of micron size. Examples of appropriate carriers include microparticles of alkoxides of metals, magnesium alkoxides of metals of Group IVB or aryloxides residues. Such media can be grown in a round form, with particle sizes in the range between 5 and 50 microns. Examples of these systems catalysts are in the patent is SHA No. 6399532 and in the patent applications U.S. 2002/006195 and 2002/0037979, which, each, are included here as a reference in their entirety.

System of catalysts based on mixed metal containing two or more types of catalyst with different molecular structure, can also be used in a single reactor. For example, a mixed system containing a catalyst of the type Ziegler-Natta and catalyst type metallocene or catalyst type Ziegler-Natta and catalyst type chromium, can be used in a single reactor. In addition, the mixed system of catalysts containing two different catalyst of Ziegler-Natta, two different metallocene catalyst, or two different chromium catalyst can also be used in a single reactor.

In two or more reactors, a different type of catalyst can be used in each reactor. For example, the catalyst type Ziegler-Natta can be used in a single reactor, and catalyst type metallocene or catalyst type chromium can be used in another reactor. Two or more reactors may also contain, each, other appropriate catalyst of Ziegler-Natta, or is likely to contain other appropriate metallocene catalyst, or may each contain a different corresponding chromium catalyst.

The polymer composition is reologicheskie modified, also known is how connected, through functional sulfonylation, as described in U.S. patent No. 6521306, which is included here as a reference. Poly(sulfonylated) is any compound having at least two sulfasalazine group (-SO2N3)interacting with the polyolefin. Preferably poly(sulfonylated) have a structure X-R-X, where each X represents SO2N3and R represents an unsubstituted or inertly substituted hydrocarbonous group, a group of simple hidrocarburos ether or silicon-containing group, preferably containing a sufficient number of carbon atoms, oxygen or silicon, preferably carbon atoms, for separating essentially sulfonylating groups to allow easy interaction between the polyolefin and sulfonylation, more preferably at least 1, more preferably at least 2, most preferably at least 3 carbon atoms, oxygen or silicon, preferably carbon atoms between the functional groups. Although there is no critical limit of length R, each R is mainly at least one carbon atom or silicon between X and preferably is less than 50, more preferably less than 30, most preferably, less than 20 carbon atoms, oxygen ilikrineia. Within these limits, the more the better, for reasons including thermal and shock stability. When R represents an alkyl hydrocarbon straight chain, preferably has at least 4 carbon atoms between sulfanilamidnymi groups, to reduce the propensity nitrene to zamorachivatsja ago and interact with themselves. Silicon-containing groups include silanes and siloxanes, preferably siloxanes. The term inert substituted refers to the substitution of atoms or groups which do not interfere with unwanted manner in the desired reaction (reaction) or the desired properties of the obtained related polymers. Such groups include the group of fluorine, simple aliphatic or aromatic ether, siloxane, and sulfasalazine group when need to connect more than two polyolefin chains. Suitable for use structures include R as aryl, alkyl, arylacetylenes, arylalkylamine, siloxane or heterocyclic group and other groups which are inert and share sulfasalazine group as described. More preferably, R comprises at least one aryl group between sulfanilimide groups, most preferably, at least two aryl groups (for example, when R represents a 4,4'-di is Unilever or 4,4'-biphenyl). When R represents one of the aryl groups is preferable that the group had more than one ring, as in the case of naftilan bis(sulfonylated).

Poly(sulfonyl)azides include such compounds as 1,5-pentane bis(sulfonylated), 1,8-octanis(sulfonylated), 1,10-decanus(sulfonylated), 1,10-octadecane bis(sulfonylated), 1-octyl-2,4,6-benzene Tris(sulfonylated), 4,4'-diphenyl ether bis(sulfonylated), 1,6-bis(4'-sulfonatophenyl)hexane, 2,7-naphthalene bis(sulfonylated), and mixed sulfonylated chlorinated aliphatic hydrocarbons containing an average of from 1 to 8 chlorine atoms and from 2 up to 5 sulfonylating groups per molecule, and mixtures thereof. Preferred poly(sulfonylated) include hydroxy-bis(4-sulfonylamides), 2,7-naphthalene bis(sulfonylated), 4,4'-bis(sulfonylated)biphenyl, 4,4'-diphenyl ether bis(sulfonylated) (also known as 4,4'-diphenyl oxide bis(sulfonylated)) and bis(4-sulfonatophenyl)methane, and mixtures thereof. Most preferred is 4,4'-diphenil-oxide bis(sulfonylated) (also referred to here DPO-BSA).

Sulfonylated conveniently be obtained by reaction of sodium azide with the corresponding sulphonylchloride, although used, and the oxidation of sulfonylhydrazide different reagents (nitrous acid, diazol the tetroxide, nitrosodi tetrafluoroborate). On sulfonylated are also described in U.S. patent No. 6776924, which is included here by reference in its entirety.

To modify rheology, also referred to here as "linking"poly(sulfonylated) is used in reologicheskie modifying the number, that is, in a quantity effective to increase nikodimou viscosity (< 0,1 rad/sec) of the polymer, preferably at least about 5 percent, compared to the original polymer material, but less than an amount to provide cross-stitching, that is, in a quantity sufficient for the formation of less than 1% wt. gel, as measured according to ASTM D2765 - Procedure A. Although specialists in this field will recognize that the amount of azide sufficient to increase nikodimou viscosity and cause less about than 1% wt. gel will depend on the molecular weight used azide and polymer, this amount is preferably less than 5 percent, more preferably less than 2%, most preferably less than 1 wt.%. Oli(sulfonylated), relative to the total weight of the polymer, when poly(sulfonylated) has a molecular mass of from 200 to 2000 g/mol. To achieve measurable rheological modification, the amount of poly(sulfonylated) preferably is at least 0,0025% wt., more preferably, at least, of 0.005 wt.%, most predpochtite is) at least, 0,010% by weight. in relation to the total weight of the polymer.

For rheological modification sulfonylated mixed with the polymer and heated at least to the temperature of decomposition sulfonylated. Under the decomposition temperature azide refers to such a temperature at which the azide is converted to sulfonyl nitre, eliminating nitrogen and heat process, as determined by DSC. Poly(sulfonylated) begins to interact with kinetically significant speed (suitable for use in implementing the present invention at temperatures of about 130°C and almost completely communicates at about 160°C according to DSC (scanning at 10°C/min). The onset of decomposition, as found, occurs at about 100°C, according to the scanning Accelerated Rate Calorimetry (ARC)at 2°C/hour. The degree of reaction is a function of time and temperature. At low levels of azide used in the implementation of the present invention, the optimum properties is not achieved until azide does not react essentially completely. Temperature for use in implementing the present invention also determined using temperature softening or melting of the source of polymeric materials. For these reasons, the temperature is predominantly higher than 90°C, preferably greater than 120°C, more preferably is more than 150°C, most preferably, greater than 180°C.

Preferred times at the desired temperatures of decomposition are times that are sufficient for implementation of the response of a binding agent with the polymer (polymers), without undesirable thermal degradation of the polymer matrix. Preferred reaction times from the point of view of the half-life time of a binding agent, i.e. the time required to about half of the agent is reacted at a given temperature, approximately 5 half-lives of a binding agent. Half-life time is determined using DSC. In the case of bis(sulfonylated), for example, the reaction time is preferably at least about 4 minutes, at 200°C.

Mixing of the polymer and a coupling agent can conveniently be by any means known in this field. The desired distribution is different, in many cases, depending on what the rheological properties should be modified. In homopolymer or copolymer is desirable to have as homogeneous a distribution as possible, preferably reaching the solubility of the azide in the polymer melt.

Preferred methods include at least one method from the following: (a) dry mixing a binder is th agent with the polymer, preferably, the formation of essentially homogeneous mixture, and add this mixture in the equipment for melt processing, for example, in an extruder to melt, to achieve binding assays, at a temperature at least equal to the decomposition temperature of a binding agent; (b) the introduction of, for example, by injection, a bonding agent in liquid form, for example, dissolved this in the solvent or suspension of a binding agent in a liquid, the device containing the polymer, preferably softened, molten or liquid polymer, but the alternative in the form of particles, in solution or dispersion, more preferably, in the device for melt processing; (c) forming a first mixture of the first amount of the first polymer and a coupling agent, mainly, at a temperature less about than the decomposition temperature of the binding agent, preferably, by mixing of the melt, and then forming a second mixture from the first mixture with the second amount of the second polymer (e.g., concentrate linking agent, mixed with at least one polymer and optionally other additives, it is convenient to mix with the second polymer, or combination thereof, optionally with other additives, to modify the second polymer (polymers)); (d) introducing at least one with sousage agent, preferably, in solid form, more preferably crushed to fine condition, for example, to the powder directly into the softened or molten polymer, for example, in the equipment for melt processing, for example, in an extruder; or combinations thereof; (e) the selection of the lateral flow of the granular polymer particles, and a solution of a binding agent in methylenchloride solvent, combining them together, so that the solution of the solvent/binder agent covers all the particles of the granulated polymer from the side of the stream, and then drying the mixture methylenchloride solvent. The obtained dried polymer polymer has a binder, uniformly deposited on the polymer, which then may be injected similarly with additives in the procedure (c)above. Among the methods (a)to(e), the means (b), (c) and (e) are preferred, (c) and (e) are preferable. For example, the method (c) is useful to obtain a concentrate with a first polymer composition having a lower melting point, mainly, at a temperature below the temperature of decomposition of the binding agent, and the concentrate is mixed in the melt with the second polymer composition having a higher melting temperature. To complete the binding assays concentrates are especially predpochtitelnye, when temperatures are high enough to lead to the loss of a binding agent by evaporation or decomposition without causing reaction with the polymer, or other conditions that would lead to this effect. Alternatively, a binding is established during mixing the first polymer and a coupling agent, but a certain amount of a binding agent remains unreacted up until the concentrate is not added to the second polymer composition. Each polymer or polymer composition comprises at least one homopolymer, copolymer, terpolymer or interpolymer and optionally contains additives known in the field. When the binder is added in the dry form, is the preferred blending agent and a polymer in a softened or molten state below the temperature of decomposition of the binding agent, and then heating the resulting mixture to a temperature at least equal to the decomposition temperature of the binding agent. Another way of combining azide binding agent with the polymer described in U.S. patent No. 6776924, which is included here in its entirety.

The term "melt processing" is used to refer to any method in which the polymer softens or melts, such as extrusion, granulation, R is sduw and loading film, thermoforming, compounding in the form of a polymer melt, and other means associated with the melt.

The polyolefin (polyolefins) and a binder agent, it is convenient to combine in any way that leads to their desired interaction, preferably, by mixing a coupling agent with the polymer (polymers) under conditions which allow sufficient mixing before the reaction in order to eliminate the uneven size of the local interaction, and then acting on the mixture of heat, sufficient for the reaction. Preferably, essentially homogeneous mixture of a binding agent and a polymer is formed before exposure to conditions in which there is a linking of the chains. Essentially homogeneous mixture is a mixture in which the distribution of the binding agent in the polymer is sufficiently homogeneous that it was determined by the polymer having a melt viscosity after processing in accordance with the implementation of the present invention, or higher, at low angular frequency (for example, < 0,1 rad/sec), or approximately equal to or lower at a higher angular frequency (for example, 10 rad/sec)than the same polymer that is not treated with a binding agent, but which is exposed to the same shear and thermal history. Thisway, preferably, when carrying out the present invention, decomposition of the binding agent is carried out after mixing, sufficient to produce essentially homogeneous mixture of a binding agent and polymer. This mixing is preferably achieved for the polymer in the molten or liquid state, that is, above the melting temperature of the crystal, or in a dissolved or finely dispersed state, and not in the form of a solid mass or particles. The molten or liquid form is preferable to ensure homogeneity than the local concentration on the surface.

Any equipment is suitable for use; preferably, the equipment that provides sufficient mixing and temperature control in the same equipment, but mainly the implementation of the present invention takes place in devices such as an extruder or a static device for mixing polymers, such as a Brabender blender. The term extruder is used in its broadest meaning to include devices such as a device that extradiol granules or pellet mill. Useful when there is a stage melt extrusion between the receipt of the polymer and its use in at least one stage of the method according to the present invention has a place on studioextremes melt. Although it is within the present invention that the reaction takes place in a solvent or other medium, it is preferred that the reaction took place in the bulk phase, to eliminate subsequent stages of removal of the solvent or other environment. For this purpose, the polymer above the melting temperature of the crystal is advantageous for uniform mixing and to achieve the reaction temperature (temperature of decomposition sulfonylated).

In a preferred embodiment, the method according to the present invention takes place in a single device, i.e. the mixing of the binding agent and the polymer takes place in the same device, and heating the binding agent to the reaction temperature. Preferably, the device is a continuous mixer, but also mainly is a twin screw extruder or a bootable system mixer/extruder. More preferably, the device has at least two zones, which would take place the reaction mixture. The first zone is preferably at a temperature high enough to soften the polymer and provide opportunities for Association with a bonding agent through distributive mixing until essentially homogeneous mixture, and the second zone is at a temperature sufficient to whom eacli linking agent.

To eliminate additional stages and relevant costs for re-extrusion and to ensure that the binder is well mixed with the polymer, in alternative preferred embodiments, the implementation is preferred that the binding agent was added to the field after a reactor for processing of the polymer. For example, when the polymers get in the gas-phase method, the binding agent is preferably added in the form of either powder or liquid in the powdered polyethylene before sealing extrusion. In an alternative embodiment, in the method of producing polyethylene in suspension, the binding agent is added either in powder or liquid form to powdery polyethylene after the solvent is removed by desantirovaniya and before drying and a method of sealing extrusion. In an alternative embodiment, when the polymer is produced by a method in solution, the binding agent is preferably added to the polymer solution prior method of sealing extrusion process.

In the preferred embodiment, associated polymers essentially do not contain gel. To detect the presence, and when this is desirable, quantitative determination of insoluble particles of gel in the polymer composition, the composition is simply ropiteau in an appropriate solvent, such as xylene, is heated under reflux for 12 hours, as described in ASTM D 2765-90, Method B. Then any insoluble part of the song highlighted, dried and weighed, making appropriate adjustments based on the composition.

For example, the mass of polymer, soluble in the solvent component is subtracted from the initial mass and the mass of polymer insoluble in the solvent component is subtracted from both the initial and final mass. Retrieved insoluble polymer is reported as the percentage of gel (% gel). For the purposes of the present invention, "essentially not containing gel" means the percentage of the gel, which is preferably < 10%, more preferably < 8%, preferably < 5%, more preferably < 3%, even more preferably < 2%, even more preferably < 0.5 percent, and most preferably lower than the limits of detection, when the solvent used xylene. For certain end uses, where the particles of the gel are valid, the percentage of the gel may be higher.

Preferably, the compositions of the present invention do not contain peroxide and/or other type of agent for cross-linking. Examples of agents for cross-linkage described is carried out in the application for international patent WO/068530, included here as a reference, in its entirety. Examples of additional agents for cross-linking include phenols, azides, reaction products of aldehyde-amine, substituted urea, substituted guanidines; substituted xanthane; substituted dithiocarbamates; sulfur-containing compounds such as thiazole, imidazoles, sulfenamide, terminaology, elemental sulfur, parakinetic, dibenzobarrelenes or combinations thereof.

New reologicheskie modified composition is particularly suitable for use in the production of conductive or distribution pipes for water, gas, and other liquids or suspensions for performance pipe PE 3408, according to ASTM D-3350, and in particular, pipes that meet or exceed the performance evaluation PE 100. In other words, the new composition can be used to increase the service life of the pipe. Such tubes may be formed by extruding the compositions described herein, in any convenient way. U.S. patents№№ 6204349, 6191227, 5908679, 5683767, 5417561 and 5290498 describe the various pipes and methods of making pipes, which can be used in embodiments implementing the present invention. As such, the descriptions of all of the preceding patents are incorporated as references in their entirety.

In the production of pipes, especially pipes b is logo diameter and thick walls (> 2.0 inches (51 mm), high stability against gravitational sagging in fluid condition is a critical need. New compositions of polymers provide enhanced resistance against sagging up to, and including, a pipe with a wall thickness of 4 inch (101,6 mm), according to the sample data in Table 8. Under this demonstration experience, a new polymer composition shows a high melt strength, so that we can easily produce all sizes of pipe, commonly used in the industry worldwide.

Compared with other similar products of pipes, similar to the comparative sample (CS) F (DGDB-2480) or CS B (DGDP-2485), a new polymer of the present invention has a melt strength for the manufacture of pipes of all diameters and thicknesses of the walls, and excellent properties of characteristics in the solid state (PENT, RCP, and meet the testing requirements of pipe rupture PE-100). Comparative samples CS F & CS B have excellent melt strength, but the worst properties characteristics in the solid state (PENT, RCP, testing for tensile strength, especially at elevated temperatures), while CS has A superior properties characteristics in the solid state, but the worst strength of the melt. The polymer composition of the present invention has excellent durability races the lava, and excellent properties characteristics in the solid state, solving the problem of obtaining the best from both technologies in a single polymer.

Other useful fabricated articles can be manufactured from new reologicheskie modified compositions described herein. For example, the molding operation may be used to form useful fabricated articles or parts from the compositions described herein, including various ways of forming under pressure (for example, described in Modern Plastics Encyclopedia/89, Mid October 1988 Issue, Volume 65, Number 11, pp. 264-268, "Introduction to Injection Molding" by H. Randall Parker and on pp. 270-271, "Injection Molding Thermoplastics" by Michael W. Green, descriptions of which are included here as a reference) and blow molding (for example, described in Modern Plastics Encyclopedia/89, Mid October 1988 Issue, Volume 65, Number 11, pp. 217-218, "Extrusion-Blow Molding" by Christopher Irwin, the description of which is included here as a reference), extrusion profile (i.e., pipe), calendering, obtain a uniaxially oriented material, and the like. Fibers such as staple fibers, the fibers obtained by the melt blown, or fibers are extruded from the melt (using, for example, the system as described in U.S. patent No. 4340563, 4663220, 4668566, or 4322027, which all are included here as a reference), and the fibers extruded from the gel (for example, the system described in U.S. patent No. 4413110 including the IOM here as a reference), as woven and nonwoven materials (e.g., staple the fabric described in U.S. patent No. 3485706 included here as a reference) or structures made from such fibers (including, for example, blends of these fibers with other fibers, such as polyethylene terephthalate, PET or cotton), can also be made of the new compositions described here.

Received blown product of the present invention can be produced by blow molding the above linked polymeric composition through the use of conventional machines for blow molding, preferably, extrusion machines for blow molding, using conventional conditions. For example, in the case of extrusion blow molding, the temperature of the polymer is usually in the range between 180°C and 250°C. the above linked polymer composition having an appropriate temperature, extruded through a die in the form of a molten preform in the shape of a tube. Then the workpiece is maintained in a form for molding. Then gas, preferably air, nitrogen, or carbon dioxide, or fluorine, for improved barrier properties characteristics, blown into shape in order to form the workpiece in accordance with the profile form, obtain a hollow molded product. Examples obtained by the blown product is s include bottles, a cylindrical barrel and automotive products, such as fuel tank, seat, headrest, knee buffer, glovebox, instrument panel, facing the bumper beam bumper, center console, intake manifold, spoiler, side molding, front door jamb, cover for air bags, pass HVAC, cover for spare tires, a tank for liquid, a shelf in the rear window, the resonator, the Cup holder or armrest.

Adequate resistance against sagging of the workpiece and the melt strength of the polymer are required to obtain acceptable products, blow molded, particularly large products, blow molded, such as a cylindrical barrel and automotive products. If the melt strength of the polymer is too low, the weight of the workpiece may cause elongation of the workpiece, causing problems such as non-uniform wall thickness and mass for articles, blow molded, the gap parts under internal pressure, the formation of a neck, and the like. Too high melt strength can lead to rough blanks, inadequate blown, too large time cycles, and the like.

Alternatively, the binding can be carried out in the extruder, which also forms the pipe, film, sheet, product, molded blown, and t the th similar. In a machine for forming blown it preferably is an extrusion machine for forming blown. Polymer linking number sulfonylated and, optionally, additional components are introduced into the extruder for receiving the pipe, film, sheet or molding blown with the purpose of obtaining a polymer mixture. The mixture is exposed to temperature melt processing, sufficient for binding of the polymer with the formation of molten linked polymeric composition. Molten linked polymer composition is extruded in molten form of a cylinder, tube or film, or sheet, or in the form of a preform in the shape of a tube for forming articles, blow molded, such as described above.

Reologicheskie modified polymers are particularly useful as a film obtained by extrusion-blowing, for better stability sleeve film, as measured by nikodimou viscosity. Polymers, reologicheskie modified in accordance with the implementation of the present invention are excellent as compared with the corresponding non-modified polymer raw materials for these applications, due to increased viscosity, preferably at least 5 percent, at low shear rates (< 0,1 rad/sec) is sufficiently high strengths melt to eliminate deformation during heat treatment, to achieve the strength of the film sleeve during molding blown, and low viscosities (measured at a shear of 10 rad/sec using DMS) to facilitate molding and extrusion. The predominant strength and tensile strength of the original material is retained or improved.

Film and film structures especially benefit from the present invention and can be produced using conventional production technology film obtained by extrusion-blowing or other, preferably, biaxial, orientation methods, such as methods with frames for orientation and stretching of the film or with a double sleeve. Conventional methods for producing blown films are described, for example, in The Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, John Wiley & Sons, New York, 1981, Vol. 16, pp. 416-417 and Vol. 18, pp. 191-192. Method of manufacturing film biaxial orientation, such as is described as a "double sleeve", as in U.S. patent No. 3456044 (Pahlke), and the methods described in U.S. patent No. 4352849 (Mueller), U.S. patent No. 4597920 (Golike), U.S. patent No. 4820557 (Warren), U.S. patent No. 4837084 (Warren), U.S. patent No. 4865902 (Golike et al.), U.S. patent No. 4927708 (Herran et al.), U.S. patent No. 4952451 (Mueller), U.S. patent No. 4963419 (Lustig et al.) and in U.S. patent No. 5059481 (Lustig et al.), can also be used for the manufacture of thin film structures of the new compositions described herein. The film structure can also be manufactured as described for the technology with frames for ori is tiravanija and stretch film such as is used for oriented polypropylene.

Other technologies for the production of multilayer films for applications in food packaging is described in Packaging Foods With Plastics, by Wilmer A. Jenkins and James P. Harrington (1991), pp. 19-27, and in "Coextrusion Basics" by Thomas I. Butler, Film Extrusion Manual: Process, materials, Properties pp. 31-80 (published by TAPPI Press (1992)).

Film can be a single layer or multilayer films. The film fabricated using the present invention can also be ekstrudirovaniya with other layer (s), or the film may be laminated onto another layer (s) in a secondary operation, such as described in Packaging Foods With Plastics, by Wilmer A. Jenkins and James P. Harrington (1991) or that described in "Coextrusion for Barrier Packaging" by W.J. Schrenk and C.R. Finch, Society of Plastics Engineers RETEC Proceedings, June 15-17 (1981), pp. 211-229. If a single-layer film is produced via tubular film (i.e., technologies for films obtained by extrusion blown) or by means of flat head (i.e., liquid film), as described K.R. Osborn and W.A. Jenkins, "Plastic Films, Technology and Packaging Applications" (Technomic Publishing Co., Inc., 1992), the description of which is included here as a reference, then the film must go through an additional stage of postextrusion adhesive or extrusion lamination with other layers of the packaging material for the formation of the multilayer structure. If the film is the first result of the co-extrusion of two or more layers (also described by Osborn and Jenkins), the film can still be laminated with an additional layer of packaging material, depending on other physical requirements of the finished film. "Laminations vs. Coextrusion" by D. Dumbleton (Converting Magazine (September 1992), also describes the lamination in comparison with the joint extrusion. Single and jointly extrudable film may also pass through other technologies postextrusion, such as the method of radiation-induced cross-linking of the polymer and biaxial orientation.

Extrusion coating is another technology for producing multilayer film structures, using the new compositions described herein. New compositions contain at least one layer of the film structure. Like liquid film, extrusion coating is a technology using a flat head. The sealing agent may be applied by extrusion onto the substrate either in the form of a monolayer or jointly extruded extrudate.

Typically, the multilayer film structures, compositions described herein comprise at least one layer of the total multilayer film structure. Other layers of the multilayer structure include, but are not limited to, barrier layers and/or adhesive layers, and/or structural SL is I. For these layers can be used a variety of materials, some of them are used as more than one layer in the same film structure. Some of these materials include: foil, nylon, copolymers of ethylene/vinyl alcohol (EVOH), grades (PVDC), (PET), oriented polypropylene (OPP), copolymers of ethylene/vinyl acetate (EVA), copolymers of ethylene/acrylic acid (EAA)copolymers, ethylene/methacrylic acid (EMAA), LLDPE (linear low density polyethylene), HDPE, LDPE (low density polyethylene), nylon, graft adhesive polymers (e.g., polyethylene grafted maleic anhydride) and paper. Typically, the multilayer film structures contain from 2 to 7 layers.

Reologicheskie modified polymers and intermediate compounds used to obtain reologicheskie modified polymers can be used alone or in combination with one or more additional polymers in the polymer mixture. When there are additional polymers, they can get out of any modified or unmodified homogeneous polymers described above for the present invention, and/or any modified or unmodified heterogeneous polymers.

EXAMPLES of SREBRENICA

The following examples are intended is to illustrate the present invention, and not its limitations. Relations, parts and percentages are mass, unless approved otherwise. Examples (Cont'd.) the present invention are identified by numbers, while the comparative samples (CS) are indicated in alphabetical order and are not examples of the present invention.

Comparative sample A (CS A)

A polymer composition was prepared in two gas-phase reactors in series, with the catalyst Z-N (Ziegler-Natta), obtained in accordance with U.S. patent No. 6187866 and No. 5290745, enter only the first reactor. HMW polyethylene component a first. Socialization TEAL injected into both reactors. Reaction conditions in HMW or the first reactor are: H2/C2as a rule, in the range between 0.015 to 0.04:1, C6/C2as a rule, in the range from 0.025 to 0,065:1. The partial pressure of ethylene is controlled by 20-60 psi (138 to 414 kPa), the reaction temperature, 70-85°C. the Mode of condensation isopentane or hexane is used for static control. Reaction conditions in the second reactor are: H2/C2from 1.6 to 2.0:1. C6/C2from zero to 0.006:1, when the reactor temperature from 105°C to 115°C and a partial pressure of ethylene of from 70 to 110 psig (483 to 758 kPa).

HMW component has a I21from 0.20 to 0.5 g/10 min, hexenoic copolymer with a density of 0,925-0,932 g/cm3with Mw /Mnfrom 4 to 8. LMW component has a I2from 600 to 1000 g/10 min, hexenoic copolymer with a density of 0,965-0,980 g/cm3with Mw/Mnfrom 3.5 to 4.5. The concentration of HMW component is 55-65 percent of the polymeric composition. I2The final product is equal to 0.03-0.11 g/10 min; I21equal 5-11 g/10 min; density equals 0.946-0,951 g/cm3; Mw/Mnwell 22-35; MFR (I21/I2is 80-150 and MFR (I21/I5is 17-35. Evaluate own viscosity at 135°C (based on SEC Mw) for I21equal to 0.4 g/10 min, equal from 5.6 to 7.2 DG/l, and MI 500, it is equal to from 0.5 to 0.7 DG/l Mw for HMW equal to ~ at 225,000 g/mol. This product is a CS A.

Conditions in the reactor to obtain polymer A CS shown in Table 1, where the reduction of APS denotes the average particle size.

Table 1
Conditions of the method used to obtain CS A
Conditions in the reactorHMW ComponentLMW Component
Temperature, °C180110
Pressure, psi (kPa, gauge)282 (1944)421 (2903)
C PP, psi, absolute (kPa,abs.)40,3 (278)100,3 (692)
The relation of H2to C20,0281,79
The ratio of C6to C20,0580,003
N2, mol %75,929,4
H2, mol %0,37841,3
C2H4, mol %13,623
C2H6, mol %0,8873,99
C4H8, mol %0,0060,02
IC5, mol %8,562,31
C6H12, mol %0,790,058
Hexane, mol %00,069
Triethylaluminium (TEAL)
Flow, lb/h (kg/h)
9,9 (4,49)4,3(1,95)
Receive rate, cfont/hour (Mg/h)48,1 (21,8)35,2(16,0)
Source materials UCAT-J,
lb/h (kg/h)
18,0(8,16)0(0)
Raw materials C2cfont/hour (Mg/h)47,0(21,3)35,2(16,0)
Raw materials C6, lb/h (kg/h)1140(517)0,019(0,00862)
Source materials H2, lb/h (kg/h)0,66 (0,30)112,8(51,2)
Raw materials N2, lb/h (kg/h)1202(545)384(174)
The original materials of the IC5, lb/h (kg/h)880(399)2(0,91)
The flux ratio C6/C20,0240,001
Ventilation flow, lb/h (kg/h)5(2,27)40(18,1)
The mass layer, cfunc (Mg)94,8(43,0)193(87,5)
The top bulk density of the fluidized bed (FBD), lb/ft3(kg/m3)12,8(205)18,1(290)
Lower FBD, lb/ft3(kg/m3)13,9(223)20,6(330)
The layer level, ft (m)37,2(11,3)46,5(14,2)
The residence time, h22,3
The output of one pass per unit of time (STY), lb/(HR·ft3)[(kg/(h m3))]7,1[114]3,8[60,9]
Superficial gas velocity, viscosity (SGV), ft/sec (m/sec)1,78(0,543)1,87(0,570)
The percentage of condensation, % wt.6,330
The separation factor for the speed,
wt.%.
57,842,2
Ti, ug/g2,62 1,47
The ratio of Al to Ti81,8for 93.4
The flow rate of melt (I5), g/10 min-0,35
The flow rate of melt (I21), g/10 min0,39to 7.84
The ratio of flow rates, I21/I5-22,5
Density, kg/m3927,8948,9
Bulk density, lb/ft3(kg/m3)23,6(378)26,7(428)
The average particle size (APS),
in (mm)
0,028(0,711)0,030(0,762)
The percentage of fine particles,
wt.%.
2,43

Samples CS A contact DPO-BSA in the form for your preferred method (c) or (e), ranging from 75 to 200 mg/g, from 125 to 155 ág/g are the most preferred level. The gel particles are not formed, as shown by the high scores FAR, and phosphate additive about what a rule is not consumed. The product does not require special technology to improve FAR to acceptable levels +20 or better on the basis of reactor technology or technology azide chemical mechanism. This can be done, as discussed in U.S. patent 6485662, which is included here as a reference. The product provides the characteristics of the pipe type PE 3408, and pipe characteristics type MRS 10 in accordance with ISO 9080, which, with excellent values and PENT RCP poster setup differently defined as characteristics of PE 100, as shown in tables 2-4.

The new composition of the polymer embodies as excellent melt strength or resistance against sagging, making possible the formation of tubes of all diameters and thicknesses, as is generally found in industry standards around the world, and excellent properties of characteristics in the solid state. Demonstration experience illustrates the excellent nature of strength of the melt, because there may be a tube with walls up to 4 inches (100 mm), compared with the comparative samples CS B or F, which are known to experts in this field as having illustrated the strength of the melt. Another proof of the superiority in strength of the melt to a new composition represents approximately a 10-fold improvement in viscosity at the shear rate of 10-5sec (figure 1). Calculation of the viscosity profile for gravity flow, which are known to experts in this field, calculated that the viscosity of the polymer leads to a shear rate in the region of 10-5. Thus, the viscosity measurement shows that the new polymeric compositions have even a slightly higher viscosity than the comparative samples CS B or F, which are tested in these demonstration experiments.

The new composition of the polymer also contains excellent properties properties necessary for the performance PE 100. Values PENT greater than 10000, and even in excess of 15,000 hours, under conditions of accelerated tests PENT at 3.0 MPa demonstrate excellent resistance to slow growth of cracks and approximately 100-fold improvement compared with the strength of the melt leading industrial polymers for pipes. The resistance to F-2231 also showed significant four-fold improvement compared with the strength of the melt leading in the industry of polymers for pipes. Sample CS A, although it has excellent characteristics in the solid state has the worst durability of the melt and may not produce pipes with thick walls, as above.

Thus, pipe producers are continuously searching for the polymer which has both outstanding melt strength and excellent properties characteristics in the firmness of the home state. Now a new polymer composition solves this problem in a single polymer.

Table 2
Data about the fundamental properties of control samples and examples of polymers according to the present invention
CS AAve. 1CS AAve. 2Ave. 3CS or F (Industrial design)
Bonding conditions
Nominal level azide (ppm)01000100150not applicable
Azide, calculated by analysis of sulfur, mg/g01480107141-
The melt temperature, °C 225235258268270-
Receive rate, kg/h18618616,56016,56017,510-
The position of the sprue,% open2020414139-
The basic properties of polymer
The flow rate of melt, I2, g/10 min0,070,030,070,040,03-
The flow rate of melt, I5, g/10 min0,260,150,280,18 0,120,27
The flow rate of melt, I10, g/10 min1,060,741,100,860,62
The flow rate of melt, I21, g/10 min6,47the 4.76,45,3a 4.98,4
The ratio of the flow rate of the melt, I21/I524,931,323,329,440,831
The ratio of the flow rate of the melt, I21/I298,0146,991,4132,5163,3-
The ratio of the flow rate of the melt, I10/I216,123,215,7a 21.520,7 -
Density, g/cm30,94990,94940,94890,94830,94790,9454
The levels of antioxidant
Active Irganox - 1010, ug/g1,1371,0211,1191,4421,464
General hospit, ug/g1,2451,0231,2201,1781,065-
Active postit, ug/g1,1019361,1621,119with 1.009-
Inactive postit, ug/g1448759 5956-
The percentage of active phosphite8891959595-

114000
Table 3
Data on the structural properties of control samples and examples of polymers according to the present invention
CS AAve. 1CS AAve. 2Ave. 3
Data DSC
Melting point, °C130,5130,9130, 8mm131,0131,0
Heat of fusion, j/g209206197190190
Pace is the atur crystallization, °C117,1117,2117,0116,6116,8
The crystallization heat, j/g202207195190189
Thermal stability, °C250,1244,5248,3249,7243,5
Data ATREF
Share HD, %80,679,878,680,881,1
Share purge %9,510,310,9the 10.1the 9.7
Mvpurge7780084000109000102000
Mvaverage116000117000123000135000134000
Mvon SCB120000121000the 125,000139000to 136,000
Data civil
Conventional GPC
Mn, g/mol12250-621068705840
Mw, g/mol225600-200840214800259000
Mz, g/mol985000-983100 1030000of 1,320,000
Mw/Mn18,4-32,331,344,3
Absolute GPC
Mn, g/mol14500141008162110238868
Mw, g/mol256000258600202200208350240000
Mz(BB), g/mol104250011080008890009255001145000
Mz(abs), g/mol122400013100009270009296001053000
Mz+1, g/mol1900000 2004000162800017360002079000
MZ/MW4,785,074,594,464,39
Rheological data RMS
The viscosity at 10-2s-1, PA·s179000336000157000272000over 340,000
The viscosity at 10+2s-1, PA sec28212796275126462699
Ratio (viscosity at 10-2s-1) / (viscosity at 10+2·s-1)6312057103126
G'/G" at 10-2s-10,350,340,690,79
G'/G" at 10-1s-10,510,770,500,730,82

Table 4
Data on the physical properties of control samples and examples of polymers according to the present invention
PropertiesCS AAve. 1CS AAve. 2Ave. 3CS or F (Industrial design)
Tensile strength at break, psi (MPa)5700 (39,3)5660 (39,0)5820
(40,1)
5220
(36,0)
5260
(36,3)
-
% Elongation at break770700680660705850
3512
(24,2)
3620 (25,0)3150
(21,7)
3030
(20,9)
2910
(20,1)
3200
(22,1)
% Elongation at break--4,64,1a 3.9-
Bending modulus, cfont psi (GPA)173
(1,19)
171
(1,18)
179
(1,23)
171 (1,18)184
(1,27)
120
(0,827)
1% Secant modulus, cfont psi (GPA)149
(1,03)
122 (0,841)153
(1,05)
154
(1,06)
152
(1,05)
-
2% Secant modulus, cfont psi (GPA)125 (0,862)144 (0,993)127
(0,876)
128 (0,883)127 (0,876)-
PENT, h at 3.0 MPa6000 - 9990>15500-->6000<200
RCP poster installation, kJ/m2400453---108
Drums feature------
100000 hours, the intersection at 23°, psi (MPa)-1590
(11,0)
--1530
(10,5)
*
100000 hours, crossing at 60°, psi (MPa))-1067
(of 7.36)**
--1057
(7,29)**
***
100000 hours, crossing at 80°C, psi (MPa)- 706 (4,87)--778 (5,43)-
50 years, the intersection at 23°C, MPa-10,6--the 10.1-
50 years, crossing at 60°C, MPa-7,2--7,1-
50 years, crossing at 80°C, MPa-4,5--5,1-
Evaluation of the appearance of the film (FAR)4040405050-
* Meet Cell Class 345464C as per ASTM D-3350;
** Satisfies the foundations for hydrostatic design at 1000 psi (6,89 MPa) at 60°C;
*** Satisfies the foundations for hydrostatic design at 800 lb/quedui the (5,51 MPa) at 60°C

Data on the characteristics of the pipes at break, are shown in Table 4, are generated on the tube obtained by extrusion conditions shown in the following tables 5 and 6, and analyzed according to ASTM D 1598 and analyzed according to ASTM D 2837-99 and ISO 9080-99.

Table 5
The conditions of extrusion of pipes from polymer according to the present invention for testing at impact
PropertyExample 1Example 3
0092 CB MB, % wt.6,506,50
Temperatures. heating zones
Zone 1,°F(°C)350(177)380(193)
Zone 2, °F (°C)370(188)390(199)
Zone 3, °F (°C)380(193)400(204)
Zone 4, °F (°C)390(199)410(210)
Zone 5, °F (°C)400(204)438(226)
Head, °F (°C)409(209)-
The melt - sensor, °F (°C)425(218)-
The pressure cylinder
The head (the most high), the psi on the gauge (MPa sensor)2080 (14,3)2090(14,4)
The head (the bottom), the psi on the gauge (MPa sensor)2020(13,9)2030 (14,0)
The auger speed, R/min6270
The voltage at the motor, volts200230
The current through the motor, % of full load4740
The speed of the device for removal, ft/min (m/min)9,3 (2,8)9,5 THEN 9,7 (2,9 3,0 THAT)
Rate, lb/h (kg/h)119,2(54,1)121,2(55,0)
Pressure, mm Hg (kPa, in Dutch the ke) 10(33,9)9 (30,5)
OD glossOkGood
ID glossOkVery good
OD RoughnessOkGood
ID RoughnessOkGood
Particle gelNoNo
The output from the plate of the headOk
HazeNormalNormal
SmellNormalNormal
Pipe size
OD in (mm)1,325-1,328 (33,65-33,73)1,328-1,332 (33,73-33,83)
The wall (the highest), in (mm)0,130(3,30)0,129 (3,28)
Wall (lowest), in (mm)0,115(2,92)0,124(3,15)

Table 6
The conditions of extrusion of pipes from polymer according to the present invention and the control polymer for testing at impact
PropertyExample 1Control A
0092 CB MB, % wt.6,56,5
PA,% wt.2,12,1
Temperature. heating zonesRealReal
Zone 1,°F(°C)350(177)350(177)
Zone 2, °F (°C)370(188)370(188)
Zone 3, °F (°C)380(193)380(193)
Zone 4, °F (°C)390(199)390(199)
Zone 5, °F (°C)400 (204)404(207)
Head, °F (°C)409 (209)409 (209)
The melt - sensor, °F (°C)425(218)427(219)
The pressure cylinder
The head (the highest), the psi on the gauge (MPa sensor)2080 (14,3)2030 (14,0)
The head (the lowest), the psi on the gauge (MPa sensor)2020(13,9)1980(13,7)
The auger speed, R/min62,2562,28
The voltage at the motor, In200200
The current through the motor, % of full load4747
The speed of the device for removal, ft/min (m/min)9,3 (2,8)9,3 (2,8)
Rate, lb/h (kg/h)119,2(54,1)116,3(52,8)
Pressure, mm Hg (kPa sensor)/td> 10(33,9)5 (16,9)
OD glossOkDull
ID glossOkOk
OD RoughnessOkOk
ID RoughnessOkOk
Particle gelNoNo
The output from the plate of the headOkSome precipitation
HazeNormalNormal
SmellNormalNormal
Pipe size
OD in (mm)
The wall (the highest), in (mm)0,130(3,30)0,131 (3,33)
Article the NCA (the lowest), in (mm)0,120(3,05)0,122(3,10)

Examples 2 and 3;Comparative sample B: demonstration of the extrusion of large diameter pipe with thick walls

Pipes produced from CS B and Examples 2 and 3, as shown in Table 5. CS B is an industrial polymer pipe DGDP-2485. CS F or DGDB-2480 embodies the same technology for pipe, as and CS B. DGDP-2485 is a product for pipes, catalyzed chromium, and is manufactured in accordance with U.S. patent No. 6022933, which is included by reference in this patent in its entirety. Examples 2 and 3 represent the polymer A CS associated with the nominal levels azide 100 and 150 µg/g, respectively. The equipment used is a standard extruder with a smooth cylinder (L/D 30 : 1) with five heating zones in the zone of the cylinder. Used cylinder has an internal diameter 24,89 inch (0,6322 m) and the size of the mandrel 19,99 inch (0,5079 m). A method of calibrating the pressure used for forming the pipe. A method of calibrating the pressure for large diameter pipe is a one in which a series of pop-up stoppers used to seal and a gas pressure of about 12 psi (82,7 kPa) is used for the forced displacement of the polymer relative to the calibration sleeve. Pressure can support the change or be changed by adjusting the smaller orifice of the valve, attached to the end of the tube. This also makes it possible for influx and the release of gas from the interior of the pipe during cooling. Due to the relatively small internal volume of the pipe size 24 inch (061 m), dissipation of heat within the smaller tubes with thick walls even worse is controlled, compared with a pipe of large size with the same wall thickness, for example, 24 inches (0,61 m) SDR (standard size) of 7.3, compared with 36 inches (0,914 m), SDR 11, having the same wall thickness. SDR is equal to the outside diameter divided by the minimum wall thickness. For this reason, this test is for 24 inch (0,61 m) with thick walls is the final study for this polymer pipe. It is said that any polymer pipe, which can be successfully converted to 24 inch (0,61 m) pipe with thick walls, using the method of calibrating the pressure can probably be successfully converted into pipes of large dimensions at least equal or greater wall thickness.

Extrusion line for pipes used for this test has a calibration chamber with a length of 8 feet 2 inches (2,39 m), and the gap between the calibration box and Luggage for atomization of the water is 10 feet 3 inches (3.12 meters). Chamber for spraying water has a length of 57 feet (17.4 km). There is no extra intellego cooling after this camera, except for cooling in the environment. Cooling water is temperature 60°F (15.6°C (C), which is almost constant throughout the year. Vacuum calibration is not used in these larger sizes because of the cost and problems with buoyancy tubes.

Extrusion of Example 2 gives the pipe, which is within the tolerance of the wall thickness of 24 inches (0,61 m), the amount of SDR to 7.3 (3.3 inches) in wall (84 mm)). Turning to the example 3, for the same pipe size also produce pipe within specifications. The transition to SDR 6 (the wall of 4.0 inches (100 mm)) results in uniform wall thickness across the diameter of the pipe.

Observations in the manufacture of pipes from polymer according to the present invention are as follows. 1. The temperature profile for the polymers of the present invention, in comparison with the polymer industry standard DGDP-2485, should be lowered on the front edge to 350°F (177°C), and then on the last two sections to 325°F (163°C). 2. The speed of the extruder for polymer according to the present invention is adjustable from 35 rpm for DGDP-2485 approximately 47 rpm 3. Pressure heads remain the same, and an electric current of 20 amperes less, compared with 380 amperes for polymer DGDP-2485. 4. The temperature of the melt is increased from 388 to 403°F (198 to 227°C). 5. The outer surface of the pipe remains unchanged. 6. Wall thickness is within the specifications of the th, as for Example 2 and Example 3, and pounds per foot of pipe approximately 92 (302 kg/m).

The configuration of the head are presented in Table 7.

Table 7
Gap adjustment head
PositionThe head clearance
Top3.03 inches (0,0770 m)
3 hours2.53 in (0,0643 m)
Bottom1.92-inch (0,0488 m)
9 hours2.35 inches (0,0597 m)

The head has a floating outer ring so that the top, bottom and both sides can be adjusted. This experience made the adjustment needed to make the top and bottom of fairly homogeneous (for example, eccentricity, less than 12%), to estimate the strength of the melt. The variation of the wall thickness for the pipe is within the tolerance for the size of the pipe. Differences of head clearance between the top and bottom are defined as normal for this size. Hot outer diameter of the pipe and its end outer diameter are within the expected range.

The total output rate is equal to 780 lb/h (353 kg/h) for pipe with DR 7,3, and 650 lb/HR (295 kg/h) for pipe with SDR 6 and 5.

The conditions of extrusion of large diameter pipe with thick walls and pipe sizes are given in Table 8. The data in Table 8 are generated using the size of the head 23,892 inch (0,607 m), the size of the mandrel 19,998 inch (0,508 m) and the size of the previous" 24,678 " (0,601 m).

Table 8
Demonstration extrusion of large diameter pipe with thick walls and the eccentricity of the wall thickness
24 inches (0,610 m)
SDR 7,3
24 inches (0,610 m) SDR 7,324 inches (0,610 m) SDR 7,324 inches (0,610 m) SDR 6,024 inches (0,610 m) SDR 5,0
PolymerCS BExample 2Example 3Example 3Example 3
The speed of the extruder rpm35,146,746,746,746,7
Selection, inch/min (mm/min)of 1.74(44,2)of 1.74(44,2) of 1.74(44,2)a 1.08 (27,4)of 1.03(26,2)
Rate, lb/h (kg/h)772 (350)778 (353)780 (354)650 (295)650 (295)
The pace. extruder, °F (°C)380(193)360(182)360(182)360(182)360(182)
The pressure during heating, the psi on the gauge (MPa sensor)4453 (30,7)4464 (30,8)4464 (30,8)4226(29,1)4226(29,1)
The pace. cylinder, °F (°C)411, 392, 369, 350, 300, 300 (211, 200, 187, 177, 149, 149)350, 350, 350, 350, 325, 325 (177, 177, 177, 177, 163, 163)350, 350, 350, 350, 325, 325 (177, 177, 177, 177, 163, 163)350, 350, 350, 350, 325, 325 (177, 177, 177, 177, 163, 163)350, 350, 350, 350, 325, 325 (177, 177, 177, 177, 163, 163)
The pace. melt, °F (°C)388(198)420(216)403(206)403(206) 403(206)
The pace. oil heater, °F (°C)405(207)380(193)390(199)390(199)390(199)
The pace. dryer, °F (°C)125(51,7)100(37,8)125(51,7)125(51,7)125(5,1,7)
The speed of the dryer (drying), lb/h (kg/h)772(350)780(354)780(354)650(295)650(295)
Air (Control OD), the psi on the gauge (kPa sensor)12(82,7)12 (82,7)12 (82,7)11,6(80)11,6(80)
Specifies the sensor, the psi on the gauge (kPa sensor)3,0(20,7)3,0(20,7)5,0(34,5)7,0(48,3)7,0(48,3)
Hot OD, mm625,7626626 624,25624,25
Wall thickness, mm12 hours =84,8012 hours = 83,2812 hours = 82,6412 hours = 108,6812 hours = 121,40
Wall thickness, mm1 hour = of 86.001 hour = 85,121 hour = 86,651 hour = 111,501 hour = 119,07
Wall thickness, mm2 hours = 88,252 hours = 90,882 hours = 87,922 hours = of $ 111.302 hour = 127.31 sq.m
Wall thickness, mm3 hours = 87,903 hours = 91,223 hours = 87,373 hours = 106,923 hours = 144,30
Wall thickness, mm4 hours = 88,004 hours = 88, 174 hours = 85,404 hours = 101, 104 hours = 163,50
Wall thickness, mm5 hours = 87,885 hours = 86,635 hours =86,865 hours =102,525 hours = 180,10
Wall thickness, mm6 hours = 87,606 hours = 85,756 hours = 87,546 hours =102,086 hours 181,60
Wall thickness, mm7 hours = or roughly 85.607 hours = 90,447 hours = 90,357 hours =107, 107 hours = 169,50
Wall thickness, mm8 hours = 86,968 hours = 9 1,618 hours = 91,818 hours =108,328 hours = 158,90
Wall thickness, mm9 hours = 87,009 hours = 91, 789 hours = 89,309 hours =108,169 hours = 148,44
Wall thickness, mm 10 hours = 86,7010 hours=
87,33
10 hours = 84,8710 hours = 103,7010 hours = 143,55
Wall thickness, mm11 hours = 85,7011 hours = 85,2711 hours = 83,3011 hours = 102,4611 hours = 131,03
Eccentricity, %3,919,269,99was 9.3334,43

The improvement of the characteristics of the pipe, as expected, is called approximately 10-fold increase in melt viscosity related compositions, at very low shear rates from 10-5up to 10-6rad/sec, as shown in figure 1.

As described in the description of Methods of research, stationary measurement data on the creep combined with the curve of viscosity from DMS to expand the available range of shear rates up to 10-6s-1and adjusted using the 4-parameter model carro-Asady as defined previously in equation 11.

Parameter values carro-Asady are shown in Table 9.

Table 9
The calculated values of the parameters carro-Yasuda
CS BCS BCS ACS AExample 2Example 2Example 3Example 3
190°C170°C190°C170°C190°C170°C190°C170°C
C14,30E+073,01E+076,51E+056,97E+052,54E+071,92E+071,17E+086,12E+07
C24,60772,8825of 0.1330,067840,033290,2O69,76023,8445
C3 0,099710,10890,20080,21010,10360,11830,099390,1117
C40,044430,01273-0,1174-0,2569-0,2494-0,16850,03307-0,02598

Table 10
A comparison of the conditions of extrusion of the polymer of the present invention and the control polymer and film characteristics
The DATA FROM the LINE-EXTRUSION FILM ALPINE
ProductCS CCS AExample 2Example 3
Nominal level azide, ug/gNot applicable0100150
The melt temperature, °F (°C)409(209)410(210) 410(210)410(210)
Current auger, amps63767878
Pressure, psi on the gauge (MPa sensor)5590(38,5)5940(40,9)5760 (39,7)5570 (38,4)
Rate, lb/h (kg/h)99,9(45,3)100,1(45,4)100,8,(45,7)100,4(45,5)
The auger speed, R/min81,886,586,585,9
Drop weight 0.5 mil (13 μm), g333363471135
Drop weight of 1.0 mil (25 μm), g278390414216
Vertical stability sleeve film ft/min (m/sec)350(1,78)-350(1,78) 350(1,78)
Transverse stability of the film sleeve, the passage/
failure
PassingFailurePassingPassing
FAR40405050

Example film

Films produced from polymers CS C, CS A, and polymer from Examples 2 and 3, as shown in Table 10. The film is produced under the conditions shown in Table 10, with the equipment and conditions for the method of testing the stability of the sleeves of the film in the above sections.

Modification using azide improves the stability of the film sleeve to a commercially acceptable levels. What is unexpected is the fact that testing of polymer from Example 2 in impact strength falling sharpened cargo demonstrate excellent levels of resistance when tested for impact strength falling sharpened cargo, compared with the comparative polymer CS C, giving the perfect combination of stability sleeve film / resistance when tested for impact strength falling sharpened cargo. Example 2, when extruded in the form of a film, leads to the equivalent stability of a sleeve of film with you is okeh levels and improvements resistance test impact strength falling sharpened cargo compared to the industry standard 40 - about 50 percent, on the film of 0.5 and 1.0 mil (12.5 and 25 μm), respectively, and approximately 30 and 5 percent, compared with the control polymer CS A, film of 0.5 and 1.0 mil (12.5 and 25 μm), respectively. For this reason, the present invention improves the stability of the sleeves of the film by increasing levels of resistance when tested for impact strength falling sharpened cargo. The polymer of Example 3, as found, has the worst durability when tested for impact strength falling sharpened cargo. Thus, there is an optimum window of the binding, which achieves this improvement. From the point of view of use of the polymer at low shear rates the viscosity is improved by an order of magnitude without compromising extraterrest, and property characteristics in the solid state is retained or improved. Additional unexpected results is that the binding reaction does not impair the stability of the packaging, and method of granulating particles does not occur gel.

Manufacturers are always looking for improved properties characteristics in the solid state with equivalent or superior technology. Example 2 solves this problem through a combination of improved stability sleeve film/ resistance at test end-to-end gap. It can potentially accommodates the STI to appear more thin films.

Example products, molded blown

Postreactor modification of polymers via azide binding facilitates moulding, increasing the strength of the melt and reducing sagging of the workpiece. This makes possible the production of large parts with thinner walls. In addition, the improved rigidity of the polymer makes it possible vertical packaging 5 cylindrical barrels, compared with a limit of 3 cylindrical barrels available standard polymers for forming blown. Higher density improves rigidity without sacrificing performance ESCR, which is possible because the new design of the polymer is selectively increased the content of co monomer in the HMW component.

Improved combination of properties obtained by using the polymer of the present invention (Examples 2 and 3), shown in Table 11 and figures 2 and 3. Comparison of the viscosity at low shear (frequency of 0.02 rad/sec) figure 2 shows that the polymers of the present invention have improved or equivalent resistance against sagging compared with current obtained by moulding products large parts (LPBM). The decrease in the tan Delta of the polymer of the present invention (figure 3) is a result of an increase in the degree of cross-linkage, followed by policynapolitano and strength of the melt when linking. The polymers of the present invention have improved manufacturability (table 11), as demonstrated own low swelling (makes it possible to better control the programming of the workpiece, the higher the linear velocity of the polymer Ziegler-Natta, higher shear viscosity decreases (the ratio of the viscosity of 0.02 rad/s to the viscosity at 200 rad/sec) and higher ratio of flow rates of the melt, a broader distribution of molecular weights attached bimodal design, in combination with azide binding. The polymers of the present invention have better impact properties and excellent balance ESCR-rigidity, compared with the existing polymer products.

Table 11
Comparison of "excellent balance of handling/ESCR/ hardness of the examples of the present invention and control samples for use in the moulding
PropertiesExample 2Example 3CS ACS DCS E
Density, g/cm30,94830,94790,9489 0,95450,9524
The flow rate of melt, I21, g/10 min5,3a 4.96,45,615,1
The flow rate of melt, I5, g/10 min0,180,120,280,160,64
The ratio of flow rates, I21/I52941233624
Swelling and t1000, s4,85,04,58,5the 9.7
Swelling and t300, s14,6the 15.614,128,128,3
Viscosity at 0.02 seconds-1, PA·s202,719249,106147,464256,210 117,262
Ratio (viscosity at 0.02 seconds-1) /(viscosity at 200 sec-1)13316188185110
The Izod impact strength, ft·lb/in (N·m/mg) at 23°C14,9 (796)the 15.6
(833)
14,8 (790)-5,59 (299)
The Izod impact strength, ft·lb/in (N·m/mg) at -40°C8,50 (454)7,02 (375)6,24 (33,3)-2,00
(107)
The impact on the gap, ft·lb/dum2(kN·m/m2)324 (679)332 (696)279
(585)
277 (581)185
(388)
2% Secant modulus, cfont psi (GPA)128 (0,883)127
(0,876)
127 (0,876)153 (1,05)136 (0,938)
Bending modulus, cfont psi (GPA) 171 (1,18)184
(1,27)
179
(1,23)
223 (1,54)199
(1,37)
ESCR, F50, 10% Igepal, h>1000>1000>1000167110

Azide binding polymer catalyzed Cr

What follows is a description of a method of the reaction, together with granulation method and a description of the product, each of which embodies the technology of the present invention for extrusion and thermoforming thick leaves, and, in particular, thermoforming polymer HDPE sheet quality. Other applications may include the moulding of the polymer in the form of large size containers and fabrication of films and pipes. Every application will benefit from improved melt strength (as measured by ARES Rheotens) and improved viscosity at low shear rates, without compromising extraterrest, and retaining critical properties characteristics in the solid state.

Conditions for the synthesis of polymer:

The used catalyst is a UCAT™-B300, catalyst-based CrO, modified by connecting Ti(OR)4and, in particular, the compounds of the TiO-iPr) 4. UCAT™ is a trade name and is owned by Union Carbide Corporation and The Dow Chemical Company.

Polymerization takes place in one gas-phase reactor with a fluidized bed, the catalyst UCAT™-B 300, which is introduced in the form of a catalyst on the carrier or in the form of catalyst in suspension or in the form of a solution. The oxygen added to the reactor to adjust the flow properties of the melt and to increase the inclusion of co monomer. Relationship flows O2/C2are in the range of 0,005 0,050 ppm Upon receipt of the polymers, the temperature of reaction varies from 90 to 105°C. the Ratio of H2/C2is in the range from 0.02 to 0.10. The partial pressure of C2range from 75 to 275 psi. Relationship C6/C2are in the range between 0.001 and 0.004 for both reactors. The performance of the chromium is in the range from 1 to 5000000 pounds to pound. Typical particle sizes are as follows: the average particle size of between 0.020 and 0.045 inches (0.51 mm to 1.1 mm), with a bulk density in the range 20-35 pounds per cubic foot. Fine particles typically constitute less than 9 wt.%, from particles passing through a sieve of 120 mesh, preferably less than 1 wt.%, passed through a sieve of 120 mesh, and most preferably less than 0.5 wt.%, passed through a sieve of 120 mesh. The polymers can wt is to be with other additives, and usually compounders with one or more stabilizers such as Irganox-1010 and Iragos-168.

Product characteristics (main polymer):

The melt index of the product, as measured in accordance with MI21 is in the range of 5-20 g/10 min Density is within 0,940-0,955 g/cm3. The distribution of molecular weights, as measured by MI21/MI2, is in the range from 75 to 200, or within "Mw/mn" 7-25. As co monomer used hexene. The conditions of polymerization and the properties of the base polymer (unordered ethylene/1-hexene) is presented below.

The conditions of polymerization
Temperature °C99
Total pressure (psi sensor)348
The partial pressure of ethylene (psi)249
The molar ratio of H2/C20,05
The molar ratio of C6/C20,0019
The flow O2/C20,023
The speed of the introduction to the of telesfora (load/min) 1,0
Superficial gas velocity (ft/sec)1,69
The mass of the layer (lbs)80,7
Receive rate (lb/h)29,6
The time (hour)2,72
The bulk density of the fluidized bed (lb/ft3)19,1
STY (lb/h/ft3)7,0
Properties of the base polymer
MI(I2in the reactor0,14
MI(I5in the reactor0,66
FI(I21in the reactor12,6
MFR (I21/I2in the reactor92,6
MFR(I21/I5in the reactor19,1
Density (g/cm3)0,9486
Residual Cr0,28
Besieged volume is MNA density (lb/ft 3)30,2
APS (inches)0,037
Fine particles (through sieve #120 mesh)0,252

The polymer is subjected azide binding in terms of postreactor with DPO-BSA (4,4'-diphenil-oxide bis(sulfonylated)) in the form of molecular melt (MM), and in the presence of in the range from 50 to 200 ppm, or ranging from 25 to 200 ppm, DPO-BSA, with 75-125 ppm are optimal level of DPO-BSA, in the presence of stabilizing additives, such as Irganox-1010 and Irgafos-168.

Molecular melt (MM) is a trading name of eutectic mixtures/combinations, 3:1, Irganox 1010 and DPO-BSA. Carbowax 400 within 50-600 ppm added to preserve color during compounding of the polymer. MM add, as any other additive in the mixer. The gel is not formed, and, as a rule, is not consumed neither phenol nor Fofana additive. The final product has an improved melt strength, compared with the incoming raw materials or unmodified granular products. Improved melt strength is measured through research rheology at low shear rates, the strength of the Rheotens melt and viscosity tensile, at 1, 10, 20 inch/inch/sec.

"Molecular melt (MM)represents a specific Faure is the product azide binding receive from a manufacturer. He is essentially BSA with Irganox 1010 at a molar ratio of 1:3. It is not a physical mixture, but rather together precipitiously combination. This mixture is essentially eutectic, melting temperature may vary within certain limits through the preparation of a product with different levels of crystallinity. A more complete description of this mixture can be found in U.S. patent 6776924, which is included here as a reference, in its entirety. Molecular melt is treated like additive and added with other additives in packaging additives on the production installation.

Azide binding is carried out in an extruder ZSK-30. Then the samples are analyzed for data on the main characteristics of the polymer and rheological properties. Then make termoformowanie leaves. The compositions of the polymers are given in Table 12.

Industrial polymer S (Comm. S) is a polymer Solvay Fortiflex G50-100 (copolymer based on polyethylene with a density of 0,952 g/cm3and MI2 of 10.5 g/10 min).

Industrial polymer M (Comm. M) is a polymer of Chevron Phillips Marlex HXM 50-100 (copolymer based on polyethylene with a density of 0,948 g/cm3and MI2 10.0 g/10 min). The polymer D5110 is a obtained in the gas phase is a copolymer of ethylene/1-hexene with density 0,950 g/cm3and MI2 10 g/10 min and MI21/M 22,5.

The extrusion conditions shown in Table 13, and the properties of the polymer are presented in Table 14.

Table 12
Compositions of polymers
The base polymerComm. SComm. MD5110Pin-roleApp.1PRPRPRPRPR
Polymer (% wt.)10010010099,899,78999,77899,76799,75699,74699,735
I-1010
(% wt.)
0,10,10,10,10,10,10,1
1-168
(% wt.)
0,10,10,10,10,10,10,1
BSAMM
(% wt.)*
0,0110,0220,0330,0440,0540,065
Only100100100100100100100100100100
*BSA is present at about 23 wt.%. from molecular melt

Table 13
Conditions of the extruder for azide-linked sheet
ControlApp.1
25 ppm
PR
50 ppm
PR
75 ppm
PR
100 ppm
PR
125 ppm
PR
159 ppm
The pace. zone #1 (°C)145/150148147149149141148
The pace. zone #2 (°C)200/200200200200199199200
The pace. zone #3 (°C)200/200200200200200200199
The pace. zone #4 (°C)220/220220220220220220220
The pace. zone #5 (°C)223/22522422 225225223225
The pace. head (°C)230/230230230230230230230
The pace. RASPLAV (°C)227227226227227227227
The point of the extruder %31343630303332
rpm of the extruder151151151151152151151
Pressure head (psig sensor)710710712702 722714732
Feeder # (Arbo)30303030303030
Feeder # B2-------
The input device # 3 (liquid)-------
The speed of the chopper5555555
The pace. bath (°F)53[12]52[11]54[12]53[12]53[12] 52[11]56[13]
Potocnik open?NoNoNoNoNoNoNo
Output (lb/h) [kg/h]10[4,5]10[4,5]10[4,5]10[4,5]10[4,5]10[4,5]10[4,5]
Just collected, lb [kg]7[3,2]7[3,2]7 [3,2]7 [3,2]7[3,2]7[3,2]7[3,2]

of 7.75
Table 14
Properties of polymers
Comm. SComm. MD5110ControlApp.1PRPRPRPR PR
MI2
(g/10 min)
0,0630,06350,052being 0.0360,080,060,0510,0410,0370,038
MI5
(g/10 min)
0,380,360,320,260,370,370,2750,23of € 0.195has 0.168
MI10
(g/10 min)
1,521,58the 1.441,451,81,75the 1.441,171,090,946
MI21 (g/10 min)10,6910,7510,188,99at 10.6410,5108,17,47
MFR(MI21/MI2)169,7169,3195,8249,7133,0175,0196,1197,6of 209.5196,6
MFR (MI21/MI5)28,529,932,034,628,828,436,435,239,744,5
MFR(MI10/MI2)24,224,927,8of 40.322,529,228,228,529,524,9
Density (g/cm3), slow cooling according to ASTM)0,95000,94900,94960,95000,9507,9504 0,95040,95040,95050,9508
I-1010----797944955108011091690
I-168 Active----567523489466431678
I-168 Inactive----191185161162173215
I-168----758708 650628604893
% I-168 Active----74,873,9to 75.274,271,475,9
"S" ppm----7,81420273339
Designed azide---039,771,2101,7137,4167,9198,4
The strength of the Rheotens melt (SN) at 190°C20 181922263136
Speed Rheotens at failure (mm/sec)59847764524339
* Level azide calculated from the analysis of "S", and it represents the amount of BSA is included in the polymer.

Data on viscosity of the polymer are shown in Table 15. Data on viscosity, which is taken at the shear rate of 100 sec-1and simulate the viscosity of the polymer during extrusion. Data on viscosity, which is taken at the shear rate of 10-4s-1simulate the stability of the polymer against sagging, for example, resistance to sagging during thermoforming process.

On the basis of similar viscosities at the shear rate of 100 sec-1related polymers are expected to have similar extraterrest as unrelated control or industrial polymer (Comm. S). In addition, on the basis of similar viscosities at the speed of change is 10 -4s-1related polymers are expected to have similar or superior resistance to sagging, compared with unrelated control or industrial polymer (Comm. S).

Table 15
Data on viscosity for azide-linked polymers
Description polymerPolymerViscosity* at 10 sec-1, × 106Viscosity** 10 sec-1, × 103
ControlControl0,922,15
Example 1Linked 11,412,12
Example 2Linked 21,592,16
Example 3Related 31,712,12
Example 4Related 41,79to 2.06
Example 5 Related 52,052,11
Example 6Linked 61,961,99
Comm. SIndustrial polymer1,931,75
* Viscosity is determined from measurements of creep.
** Viscosity is determined from dynamic mechanical spectroscopy (DMS).

The polymers have a strain at break. Deformation at rupture is a measure of thermoformable polymer. The data are given in tables 16-23. The polymers of the present invention have comparable or superior results, compared with the control and industrial polymers.

Samples showing a large deformation at break (more tensile), can adapt to greater tension in the way with stretching. The polymers having a higher viscosity under tension, will have the ability to withstand the pulling behavior, and will have a reduced viscosity decreases for part of the way with strength. The polymers having a lower viscosity (or elasticity (G”/G')will be better to flow into the cavities forms and will be useful and to fill in the smaller details form. Linked polymers show relatively low hardening during deformation or nothing. Linked polymers have improved elongation and low viscosity, and thus, have improved properties thermoformable. These features, in addition to superior resistance to sagging, make the polymers of the present invention is particularly suitable for methods of thermoforming.

The hencky strain, sometimes referred to as the true deformation is a measure of deformation during elongation, which applies to both polymer melts and solid products. If you use a device such as an Instron tester, the hencky strain can be calculated as L(t)/L0-1, where L0represents the initial length and L(t) is the length at time t. Then the relative hencky strain is defined as 1/L(t)-dL(t)/dt is constant only if the sample length increases exponentially.

On the other hand, when using an extension device with a constant length of the sensor, such as a device with dual winding Sentmanat, (described in U.S. patent No. 6691569, the relevant parts are included here as a reference), constant relative hencky strain is obtained simply by setting a constant speed winding.

SER (Sentmanat Extensional Rheometer) is a PR is the industrial version of the device, described in U.S. patent No. 6691569. SER consists of additions to the rheometer to control deformation of ARES (TA Instruments, New Castle, Delaware (USA)). The addition is attached inside the chamber ARES with environmental conditions, where the temperature is controlled by a stream of hot nitrogen. The test carried out on strips cut from extruded under pressure of a sheet thickness of 0.5 mm is Applied a constant relative hencky strain and determine the time-dependent voltage from the measurement of time and time-dependent cross-section sample. Viscosity tensile or growth factor uniaxial tension get by dividing the voltage relative to the hencky strain.

Table 16
Data for strain control (Unbound)
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec)8109012430306000
Time (sec)0,130,312,71
The hencky strain at break (rate of strain hencky×time)2,63,12,71

Table 17
Data on deformation for D5110
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec)5070058660137100
Time (sec)0,10,171,35
The hencky strain at break (rate of strain hencky×time)21,71,35

Table 18
Data on strain for industrial polymer S
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec) 2970076730225800
Time (sec)0,070,21,89
The hencky strain at break (rate of strain hencky×time)1,421,89

Table 19
The data on strain for industrial polymer M
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec)290503857087630
Time (sec)0,080,161,03
The hencky strain at break (rate of strain hencky×time)1,61,61,03

Table 20
Data on the deformation for the example 1 (39,7 ppm azide)
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec)5174048940243700
Time (sec)0,10,162,52
The hencky strain at break (rate of strain hencky×time)21,62,52

Table 21
Data on deformation for example 2 (71,2 ppm azide)
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec)3654073700143900
Time (sec)0,080,211,94
The hencky strain at break (soon the be the hencky strain×time) 1,62,11,94

Table 22
Data on deformation for example 3 (of 101.7 ppm azide)
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec)5072049560220200
Time (sec)0,080,12of 1.34
The hencky strain at break (rate of strain hencky×time)1,61,2of 1.34

Table 23
Data on deformation for example 4 (137,4 ppm azide)
The speed of the hencky strain (s-1)20101
Viscosity tensile (PA·sec)39820 60700171800
Time (sec)0,070,141
The hencky strain at break (rate of strain hencky×time)1,41,41

Thermodormancy sheet - results in sagging

Samples of the sheets produced from polymer D5110, industrial polymer M and azide-linked polymer (Example 3 - scaled). Each polymer ekstragiruyut in the form of a sheet with the following dimensions: width 24 inches, length 36 inches, and the thickness 0,120 inches. Samples of the sheets produced on conventional lines for sheet extrusion using an extruder with a diameter of 2.5 inches with an aspect ratio of length to diameter of 30:1, and 2-stage auger-style double waves for plasticization of the polymer. Extrusion head width of 26 inches is used for molding the extrudate in the shape of a molten sheet, and horizontal 3-roll rolling mill is used for calibration and cooling of the sheet.

Then the samples of leaves thermoformed on the hook for thermoforming ZMD International Model V223. Each sheet is placed in the clamping frame device for thermoforming ZDM and rigidly secured on all four sides. Then squeezed listindexes on the heating station device for thermoforming ZMD, where the sheet is heated by quartz infrared radiator heaters. When the temperature of the sheet increases, the sheet begins to SAG below the clamping frame. The distance from the SAG of the sheet to the clamping frame is measured using an infrared profiling scanner (light curtains), which is located to detect the sagging of the sheet in the middle of the oven. The amount of sagging of the sheet is registered at the end of the heating cycle and before the clamping frame is indexed out of the oven, and in the molding station.

The results of the sagging sheet sheet heated for 150 seconds in a furnace, shown below in Table 24. Azide-linked polymer demonstrates a lower SAG than the polymer D5110 and industrial polymer M.

Table 24
Sagging sheet
D5110Comm. MAside-related
(Example 3)
The average measured SAG
in inches (cm)
2.5-inch (6,4)2,0 (5,1)1,5 (3,8)

Suddenly, as rheological kinematics sagging and stretching demonstrate that linked polymers for the present the invention are more favorable for the formation of the sheet, the industrial product and unmodified control product.

For azide-linked polymers from polymers catalyzed by Cr, as shown, the strength of the melt, as measured by sagging, improving to levels similar to or better than the control and industrial analogues, while the elongation, as measured by viscosity tensile retained. In addition, the viscous response to shear rate at high shear rates is very similar to that of control and industrial polymer, so that extraterrest should not deteriorate. This means that the polymers of the present invention will have improved response shift (SAG), without loss of response in tension, so that both the rheological response is improved in comparison with competing counterparts. This should lead to products that have superior rheological characteristics of the market thermoforming sheet. Thus, the products of the present invention have a preferred combination of rheological properties for applications in thermoforming for sheets. In the case of the azide modification, improvement, both in shear flow, and when the thread under tension, are unexpected preferential properties.

Conclusions - linked polymers, catalizer the s Cr

The polymer sheet and thermoforming require a balance of rheological properties. The balance is in shear flow, and flow under tension, since there are large and rapid shear and tensile deformation in the method of producing sheet and thermoforming. Responses to large and rapid deformation depend on the size and speed of deformation and kinematics of deformation or a warp. Thus, it is impossible to measure the response of one type of deformation, and use this result to predict other types of deformation. In this case, measure both shear and tensile threads make a significant contribution to the extrusion and thermoforming parts. The tensile flow is a deformation of the flow, which includes a stretch along the lines of flow that is not the case of shear flows.

Azide-linked polymers show superior resistance to sagging in shear flow, as measured by the viscosity at low shear rates. Linked polymers also keep extraterrest, as measured by the viscosity at shear rate 100 sec-1. When measuring the viscosity tensile improve the viscosity and rate of strain. This combination of superior resistance to sagging in shear flow and Ulu is suitable for high viscosity and strain rate during tensile threads are unexpected, since these properties are usually not related to each other. Thus, the polymers of the present invention are particularly preferred combination of rheological properties for applications for sheet and thermoforming. In the polymers of the present invention, improvement, both in shear flow and tensile represent unexpected results.

The uniqueness of the azide modification is that this technology even works on polymers, which have high melt strength in comparison with other polymers with low melt strength such as polypropylene. The effect is a significant change in viscosity at low shear rate, shear rate 10-4or 10-5s-1. Azide modification makes the response Cr polymers roughly equivalent competing counterparts. In addition, no significant reduction of the levels of active phosphite, so that the products remain very stable in the presence of a coupling reaction.

The smoothness of the surface of the extruded sheet and thermoformed parts equivalent to unbound polymer. Viscosity tensile improved compared to competing polymer Marlex. This viscosity is preferred for maintaining the thickness of the workpiece during the stretch and in the time of thermoforming operation. "The evaluation of the appearance of the film (FAR)for these sheets preferably equal to zero or above, more preferably ten or higher, and even more preferably 20 or higher.

1. Reologicheskie modified polyethylene composition suitable for the production of pipes, comprising the reaction product of:
(a) a mixture containing a low molecular weight component (LMW) polyethylene and high molecular weight component (HMW) polyethylene, and
(b) a coupling agent comprising polysulfones in the amount of at least 0,0025 wt.% on the total weight of the polymer, and where the blend has a single peak in the distribution curve of the thickness of the leafs (LTD), and
where the composition is research slow crack growth (PENT), more than 1000 h at 80°C and applied voltage of about 2.4 MPa, measured in accordance with ASTM F-1473-97,
where the HMW component has a flow rate of the melt I2from 0.001 to 1.0 g/10 min, measured in accordance with ASTM 1238-03, 190°C, 2,16 kg
where LMW component has a flow rate of the melt I2from 40 to 2000 g/10 min, measured in accordance with ASTM 1238-03, 190°C, 2,16 kg

2. The composition according to claim 1, where the LMW component has a density of from 0,940 to 0,980 g/cm3.

3. The composition according to claim 1, where the LMW component is a component with high density.

4. The composition according to claim 1, where the HMW component has a flow rate of the melt I21from 0.20 to 5.0 g/10 min, measured in accordance with ASTM 1238-03, 190°C, 21,6 kg

5. The composition according to claim 1, which is set to PENT, more roughly than 3000 hours, at about 80°C and about 3 MPa.

6. The composition according to claim 5, which is set to PENT, more roughly than 6500 hours, at about 80°C and about 3 MPa.

7. The composition according to claim 1, in which the composition has a density greater about than 0,940 g/cm3average molecular weight in the range from 200000 to 490,000 g/mol and the ratio of velocity of flow (I21/I5from 15 to 50.

8. The composition according to claim 1, in which the HMW polyethylene component contains comonomer selected from the group consisting of C3-C10alpha-olefins.

9. The composition according to claim 8, in which the content of the co monomer is in the range from greater than 0 to 6.0 wt.%.

10. The composition according to claim 1, in which LMW polyethylene component contains comonomer selected from the group consisting of C3-C10alpha-olefins.

11. The composition according to claim 10, in which the content of the co monomer is in the range from greater than 0 to 3.0 wt.%.

12. The composition according to claim 1, in which the first composition is bimodal, as determined using GPC.

13. The composition according to claim 1, in which the first composition is multimodal, as determined using Gel Chromatography (GPC).

14. The composition according to claim 1, in which the HMW polyethylene component comprises from 48 to 67 wt.% from United m the ssy HMW component and the LMW component.

15. The composition according to claim 1, in which LMW polyethylene component comprises from 33 to 52 wt.% from the combined mass of the HMW component and the LMW component.

16. The composition according to claim 1, in which the composition has the following properties:
1) a density of at least 0,94 g/cm3as measured according to ASTM Method D-792-03 Method;
2) the flow rate of melt (I5from 0.2 to 1.5 g/10 min, measured in accordance with ASTM D-1238-03, 190°C, 5 kg;
3) the ratio of velocity of flow (I21/I5from 20 to 50; and
4) the distribution of molecular masses, Mw/Mnfrom 15 to 40; and
where component HMW polyethylene is from 30 to 70 wt.% composition;
has a density of at least 0,89 g/cm3as measured according to ASTM D-792-03 Method; is the flow rate of melt (I2) from 0.01 to 0.2 g/10 min and the ratio of velocity of flow (I21/I2) from 20 to 65; and where the component LMW polyethylene is from 30 to 70 wt.% composition;
has a density of at least 0,940 g/cm3as measured according to ASTM D-792-03 Method; is the flow rate of melt (I2from 40 to 2,000 g/10 min and has a ratio of flow rates (I21/I2) from 10 to 65.

17. The composition according to claim 1, in which the concentration polysulfonamide up to 200 mcg/g

18. The composition according to claim 1, in which the composition is associated with less than 200 µg/g polysulfonamide.

19. Reologicheskie modify the new polyethylene composition, suitable for film extrusion blown comprising the reaction product of:
(a) a mixture containing a low molecular weight component (LMW) polyethylene and high molecular weight component (HMW) polyethylene, and
(b) a coupling agent comprising polysulfones in the amount of at least 0,0025 wt.% on the total weight of the polymers, and
where the blend has a single peak in the distribution curve of the thickness of the leafs (LTD), and
where the composition is research slow crack growth (PENT), more than 1000 h at 80°C and applied voltage of about 2.4 MPa, measured in accordance with ASTM F-1473-97, and has a density greater about than 0/940 g/cm3average molecular weight in the range from 200000 to 490,000 g/mol and the ratio of velocity of flow (I21/I5from 15 to 50;
where the HMW component has a flow rate of the melt I21from 0.01 to 50.0 g/10 min, measured in accordance with ASTM 1238, 190°C. of 21.6 kg, where the LMW component has a flow rate of the melt I2from 0.5 to 3000 g/10 min, measured in accordance with ASTM 1238-03, 190°C, 2,16 kg

20. The composition according to claim 19, where the weight ratio of the component HMW to LMW component is from 30:70 to 70:30.

21. The composition according to claim 19, which is set to PENT, more roughly than 3000 hours, at about 80°C and about 3 MPa.

22. The composition according to item 21, which is set to PENT, more roughly than 6500 hours, at about 80°C and PR is about 3 MPa.

23. The composition according to claim 19, in which the HMW polyethylene component contains comonomer selected from the group consisting of C3-C10alpha-olefins.

24. The composition according to item 23, in which the content of the co monomer is in the range from greater than 0, up to 6.0 wt.%.

25. The composition according to claim 19, in which LMW polyethylene component contains comonomer selected from the group consisting of C3-C10alpha-olefins.

26. The composition according A.25, in which the content of the co monomer is in the range from greater than 0 to 3.0 wt.%.

27. The composition according to claim 19, in which the first composition is bimodal, as determined using Gel Chromatography (GPC).

28. The composition according to claim 19, in which the first composition is multimodal, as determined by GPC).

29. The composition according to claim 19, in which the HMW polyethylene component comprises from 48 to 67 wt.% from the combined mass of the HMW component and the LMW component.

30. The composition according to claim 19, in which LMW polyethylene component comprises from 33 to 52 wt.% from the combined mass of the HMW component and the LMW component.

31. The composition according to claim 19, in which the composition has the following properties:
1) a density of at least 0,94 g/cm3as measured according to ASTM Method D-792-03 Method;
2) the flow rate of melt (I5from 0.2 to 1.5 g/10 min, measured in accordance with ASTM D-1238-03, 190°C, 5 kg;
3)the ratio of velocity of flow (I 21/I5from 20 to 50; and
4) the distribution of molecular masses, Mw/Mnfrom 15 to 40; and
where component HMW polyethylene is from 30 to 70 wt.% composition;
has a density of at least 0,89 g/cm3as measured according to ASTM D-792-03 Method; is the flow rate of melt (I2) from 0.01 to 0.2 g/10 min and the ratio of velocity of flow (I21/I2) from 20 to 65; and where the component LMW polyethylene is from 30 to 70 wt.% composition;
has a density of at least 0,940 g/cm3as measured according to ASTM D-792-03 Method;
has the flow velocity of the melt (I2from 40 to 2,000 g/10 min and has a ratio of flow rates (I21/I2) from 10 to 65.

32. The composition according to claim 19, in which the concentration polysulfonamide up to 200 mcg/g

33. The composition according to claim 19, in which the composition is associated with less than 200 µg/g polysulfonamide.

34. Reologicheskie modified polyethylene composition suitable for obtaining molded products blown comprising the reaction product of:
(a) a mixture containing a low molecular weight component (LMW) polyethylene and high molecular weight component (HMW) polyethylene, and
(b) a coupling agent comprising polysulfones in the amount of at least 0,0025 wt.% on the total weight of the polymer, and where the blend has a single peak in the distribution curve of the thickness of the leafs, LTD.), and
where the composition is research slow crack growth (PENT), more than 1000 h at 80°C and applied voltage of about 2.4 MPa, measured in accordance with ASTM F-1473-97,
where the HMW component has a flow rate of the melt I21from 0.01 to 50.0 g/10 min, measured in accordance with ASTM 1238, 190°C. of 21.6 kg,
where LMW component has a flow rate of the melt I2from 40 to 2000 g/10 min, measured in accordance with ASTM 1238-03, 190°C, 2,16 kg

35. The composition according to clause 34, where the LMW component is a component with high density.

36. The composition according to clause 34, which is set to PENT, more roughly than 3000 hours, at about 80°C and about 3 MPa.

37. The composition according to p that matters PENT, more roughly than 6500 hours, at about 80°C and about 3 MPa.

38. The composition according to clause 34, in which the composition has a density greater about than 0,940 g/cm3average molecular weight in the range from 200000 to 490,000 g/mol and the ratio of velocity of flow (I21/I5from 15 to 50.

39. The composition according to clause 34, in which the HMW polyethylene component contains comonomer selected from the group consisting of C3-C10alpha-olefins.

40. The composition according to § 39, in which the content of the co monomer is in the range from greater than 0 to 6.0 wt.%.

41. The composition according to clause 34, in which LMW polyethylene component contains comonomer selected from GRU the dust, consisting of C3-C10alpha-olefins.

42. The composition according to paragraph 41, in which the content of the co monomer is in the range from greater than 0 to 3.0 wt.%.

43. The composition according to clause 34, in which the first composition is bimodal, as determined using Gel Chromatography (GPC).

44. The composition according to clause 34, in which the first composition is multimodal, as determined by GPC).

45. The composition according to clause 34, in which the HMW polyethylene component comprises from 48 to 67 wt.% from the combined mass of the HMW component and the LMW component.

46. The composition according to clause 34, in which LMW polyethylene component comprises from 33 to 52 wt.% from the combined mass of the HMW component and the LMW component.

47. The composition according to clause 34, in which the composition has the following properties:
1) a density of at least 0,94 g/cm3as measured according to ASTM Method D-792-03 Method;
2) the flow rate of melt (I5from 0.2 to 1.5 g/10 min, measured in accordance with ASTM D-1238-03, 190°C, 5 kg;
3) the ratio of velocity of flow (I21/I5from 20 to 50; and
4) the distribution of molecular masses, Mw/Mnfrom 15 to 40; and where the component HMW polyethylene is from 30 to 70 wt.% composition; has a density of at least 0,89 g/cm3as measured according to ASTM D-7 92-03 Method; is the flow rate of melt (I2) from 0.01 to 0.2 g/10 min and the ratio of speeds is Otok (I 21/I2) from 20 to 65; and where the component LMW polyethylene is from 30 to 70 wt.% composition; has a density of at least 0,940 g/cm3as measured according to ASTM D-792-03 Method; is the flow rate of melt (I2from 40 to 2,000 g/10 min and has a ratio of flow rates (I21/I2) from 10 to 65.

48. The composition according to clause 34, in which the concentration polysulfonamide up to 200 mcg/g

49. The composition according to clause 34, in which the composition is associated with less than 200 µg/g polysulfonamide.

50. Pipe made from the composition according to any one of claims 1 to 18.

51. Pipe on item 50, where the pipe has a wall thickness up to 4 inches (10.2 cm).

52. The film made from the composition according to any one of p-33.

53. The film according to paragraph 52, in which the composition is associated with less than 150 μg/g polysulfonamide.

54. The film according to item 53, where the film has a higher strength when tested for impact strength falling sharpened cargo than film made from otherwise identical polymer composition in which no bonding agent.

55. The film according to item 53, where the film has a higher lateral stability sleeve film than film made from otherwise identical polymer composition in which no bonding agent.

56. The film according to item 53, where the film has a higher tensile strength test impact PR is knosti pointed falling cargo, and higher lateral stability sleeve film than film made from otherwise identical polymer composition in which no bonding agent.

57. Products, blow molded, made from the composition according to any one of p-49.

58. The product, molded blown, § 57, where the product has a higher value through the gap and through the gap according to Izod measured in accordance with ASTM D 256-03 way In and at least the same value of resistance to cracking under the action of the environment (ESCR), measured according to ASTM D 1693-01 method as articles, blow molded, made from otherwise identical polymer composition in which no bonding agent.

59. The product, molded blown by § 57, where the product is a bottle, a cylindrical barrel or part of the car.

60. The way to improve the behavior of creeping deformation of the polymer that includes the interaction polysulfonamide with a composition which contains a low molecular weight component (LMW) polyethylene, having Mwfrom 10 000 to 40 000 g/mol, and high molecular weight component (HMW) polyethylene, having Mwfrom 100 000 to 600 000 g/mol, and where the composition has a single peak in the distribution curve of the thickness of the leafs (LTD), and
where interactive composition is set to study the Oia slow crack growth (PENT), more than 1000 h at 80°C and applied voltage of about 2.4 MPa, measured in accordance with ASTM F-1473-97.

61. The method according to p, in which the composition, after binding assays, has a melt viscosity, at a shear rate of 1·10-5rad/s, which is 2 times greater than the melt viscosity of the composition of the polymer under the same shear rate.

62. The method according to p, in which the composition, after binding assays, has a melt viscosity, at a shear rate of 1·10-5rad/s, which is 5 times greater than the melt viscosity of the composition of the polymer under the same shear rate.

63. The method according to p, in which the composition, after binding assays, has a melt viscosity, at a shear rate of 1·10-5rad/s, which is 10 times greater than the melt viscosity of the composition of the polymer under the same shear rate.

64. A method of manufacturing a pipe, including:
(a) selecting a polymeric composition according to any one of claims 1 to 18;
(b) extruding the polymer composition with the formation of the pipe.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: film is made from a composition having multi-modal molecular-weight distribution and density between 0.940 and 0.948 g/cm3. The composition contains 40-60 wt % of a first fraction of an ethylene polymer made from a homopolymer A, 25-45 wt % of a second fraction of ethylene polymer made from a first copolymer B of ethylene and at least one first comonomer from a group of olefins having 4-8 carbon atoms and 10-30 wt % of a third fraction of ethylene polymer made from a second copolymer C of ethylene and at least one second comonomer from a group of olefins having 4-8 carbon atoms. The first copolymer B of ethylene has molecular weight which is less than that of the second copolymer C of ethylene, but greater than that of homopolymer A.

EFFECT: disclosed thin films have improved mechanical properties, particularly impact resistance when testing the films using a falling pointed load, with high rate of collection without deterioration of stability of the molten bubble.

12 cl, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyethylene moulding composition having multi-modal molecular-weight distribution, especially suitable for films made via extrusion blowing, having thickness between 8 and 200 mcm. The polyethylene moulding composition has density between 0.953 and 0.960 g/cm3 and MFR190/5 of the end product after extrusion between 0.10 and 0.50 dg/min. The composition contains 42-52 wt % of a first fraction of ethylene polymer made from a homopolymer A, having a first molecular weight, 27-38 wt % of a second fraction of ethylene polymer made from another homopolymer or a first copolymer B of ethylene and at least one first comonomer from a group of olefins having 4-8 carbon atoms,whereby the first copolymer B has a second molecular weight greater than the said first molecular weight, and 15-25 wt % of a third fraction of ethylene polymer made from a second copolymer C having a third molecular weight greater than the second molecular weight.

EFFECT: disclosed polyethylene moulding composition enables to obtain thin films with improve processing properties without deterioration of mechanical properties.

12 cl, 2 tbl, 3 ex

Polyethylene tubes // 2394052

FIELD: chemistry.

SUBSTANCE: method involves preparation of a mixture containing 5-50 wt % filler and 95-50 wt % low density polyethylene and 0-3 wt % of one or more stabilisers.The obtained mixture and high density polyethylene containing at least one low-molecular component which is a copolymer of ethylene and C3-C10 α-olefin are mixed in a molten mass until the end product is obtained at drop point of 165-185°C. The obtained composition for making tubes contains 1-20 wt % filler in terms of mass of the composition.

EFFECT: composition has better balance of properties and can be extruded with sufficiently high efficiency at optimal low melt temperature.

19 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a polyethylene composition with multimodal molecular weight distribution for blow moulding canisters with volume ranging from 2 to 20 dm3 and a method of preparing the said composition. The composition has density ranging from 0.950 to 0.958 g/cm3 at 23°C and melt flow rate (MFR190/5) from 0.30 to 0.50 dg/min. The composition also contains 40 to 50 wt % low molecular weight ethylene homopolymer A and 25 to less than 30 wt % high molecular weight copolymer B obtained from ethylene and another 1-olefin containing 4 to 8 carbon atoms, and 24 to 28 wt % ethylene copolymer C having ultra-high molecular weight.

EFFECT: obtained composition has good resistance to chemical effect, especially high mechanical strength, high corrosion resistance and is a naturally light material; high melt strength of the composition enables prolonged extrusion without breaking the workpiece, and an accurately selected swelling index of the composition enables optimisation of controlling thickness of the wall of the article.

10 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: polyethylene in form of ethylene homopolymers and copolymers of ethylene with α-olefins and having molecular weight distribution range Mw/Mn from 6 to 100, density from 0.89 to 0.97 g/cm3, weight-average molecular weight Mw from 5000 g/mol to 700000 g/mol and from 0.01 to 20 branches/1000 carbon atoms and at least 0.5 vinyl groups/1000 carbon atoms, where the fraction of polyethylene with molecular weight less than 10000 g/mol has degree of branching from 0 to 1.5 branches on the side chains, longer than CH3/1000 carbon atoms. The catalyst composition for synthesis of polyethylene in paragraph 1 consists of at least two different polymerisation catalysts, from which A) is at least one polymerisation catalyst based on monocyclopentadienyl complex of a group IV-VI metal, in which the cyclopentadienyl system is substituted by an uncharged donor (A1) of formula Cp-Zk-A-MA (II), where variables assume the following values: Cp-Zk-A is , MA is a metal which is selected from a group consisting of titanium (III), vanadium, chromium, molybdenum and tungsten, and k equals 0 or 1, or with hafnocene (A2), and B) is at least one polymerisation catalyst based on a ferrous component with a tridentate ligand containing at least two ortho-, ortho-disubstituted aryl radicals (B).

EFFECT: obtaining polyethylene with good mechanical properties, possibility for processing and high content of vinyl groups.

27 cl, 12 ex, 2 tbl, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to high-strength bimodal polyethylene compositions which are meant for preparing compositions for pipes, particularly high-strength compositions for pipes. The composition has density equal to or greater than 0.940 g/cm3, overall polydispersity index equal to or greater than 25 and contains a high-molecular polyethylene component and a low-molecular polyethylene component. The ratio of weight-average molecular weight of the high-molecular component to the weight-average molecular weight of the low-molecular component of the composition is equal to or greater than 30. The weight-average molecular weight of the low-molecular polyethylene component ranges from 5000 to 30000. The composition is classified as PE 100 material, has proper balance of properties such as strength and hardness, as well as good processing properties. A pipe made from the composition which has undergone internal strength tests has extrapolated stress equal to or greater than 10 MPa when the internal strength curve of the pipe is extrapolated to 50 or 100 years in accordance with ISO 9080:2003(E).

EFFECT: increased strength of products.

15 cl, 6 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of preparing an ethylene polymer composition. Described is a method of preparing an ethylene polymer composition in a multistage process. The said method involves polymerisation of only one of ethylene or ethylene with a comonomer to obtain ethylene polymer at the first stage, supply of the polymer obtained at the first stage to the second stage, where at the second stage only one of ethylene or ethylene with a comonomer is polymerised in the presence of the polymer obtained at the first stage, and where the first stage is a suspension polymerisation stage, and polymerisation at the first stage is carried out in the presence of a catalyst system containing: (a) a precursor solid catalyst containing a transition metal selected from titanium and vanadium; magnesium, haloid, electron donor and solid dispersion material containing inorganic oxide, and (b) organoaluminium compound; and where the average diametre of particles of the precursor solid catalyst obtained per total volume of the precursor solid catalyst, D50, ranges from 1 to 13 micrometres. Also described is an ethylene polymer composition obtained using the said method, having density in the range 0.915-0.970 g/cm3 and MI5 in the range 0.02-3.5 dg/min and less than 6 regions of gel per m2 with size greater than 800 micrometres, and less than 100 regions of gel per m2 with size ranging from 400 to 800 micrometres, where the amount and size of gel is determined for a 5 m2 cast film sample with thickness of 50 micrometres, obtained from the ethylene polymer composition; also described is an industrial product made from the said composition. Described is an ethylene polymer composition obtained using the said method, having density in the range 0.915-0.970 g/cm3 and MI5 in the range 0.02-3.5 dg/min, where the composition has Young's modulus during bending, measured using an Instron device in accordance with ISO 178, exceeding 1340*{1-exp[-235*(density-0.9451)]}; ethylene polymer composition having density in the range 0.915-0.970 g/cm3 and MI5 in the range 0.02-3.5 dg/min, where the composition has Young's modulus during bending which exceeds 1355*{1-exp[-235*(density-0.9448)]}. Described is a composition obtained using the said method and containing bimodal polyethylene resin, and where the bimodal polyethylene resin contains high-molecular ethylene polymer and low-molecular ethylene polymer, and where the low-molecular ethylene polymer has MI2 ranging from 10 g/10 min to 1000 g/10 min and density of at least 0.920 g/cm3, and where the composition has density ranging from 0.915 g/cm3 to 0.970 g/cm3.

EFFECT: improved mechanical properties of products made from the compositions, reduced amount of gel in the compositions.

20 cl, 38 ex, 1 dwg, 4 tbl

FIELD: chemistry.

SUBSTANCE: thermoplastic elastomer material contains: (a) from 10 to 100 wt % of at least one thermoplastic elastomer based on styrene; (b) from 0 to 90 wt % of at least one thermoplastic homopolymer or copolymer of α-olefin, different from (a); where amount of (a)+(b) equals 100; (c) from 2 to 90 pts. wt of vulcanised rubber in crushed state; (d) from 0.01 to 10 pts. wt of at least one coupling agent which contains at least one unsaturated ethylene; where amounts (c) and (d) are expressed in ratio to 100 pts. wt of (a)+(b).

EFFECT: improved mechanical properties, specifically breaking stress and breaking elongation, increased wear resistance.

60 cl, 6 tbl, 6 ex

FIELD: process engineering.

SUBSTANCE: invention relates to techniques of producing high-strength thermosetting films. Proposed method comprises mechanical missing of granules of several types of polyethylene and film extrusion with its subsequent pneumatic expansion. Extrusion rate makes over 18 m/min. Mix of granules contains unimodal low-pressure polyethylene and bimodal high-pressure polyethylene.

EFFECT: optimum ratio of components allow optimum physicochemical parametres and increased strength.

2 dwg, 2 tbl

FIELD: chemistry.

SUBSTANCE: polyethylene composition is intended for formation with blowing of barrels with 2 discharge holes with volume ranging from 50 to 250 dm3(l). Composition has density within the range from 0.950 to 0.956 g/cm3 at 23°C, value of index of melt flow rate MFR190/21.6 within the range from 1.5 to 3.5 dg/min and multimodal molecular-weight distribution. It includes from 35 to 45 wt % of homopolymer of ethylene A with low molecular weight, from 34 to 44 wt % of copolymer B with high molecular weight, representing copolymer of ethylene and 1-olefin, containing from 4 to 8 carbon atoms, and from 18 to 26 wt % of copolymer of ethylene C with superhigh molecular weight. Copolymer B contains less than 0.1 wt % of comonomer calculating on copolymer B weight, and copolymer C contains comonomers in amount from 0.1 to 0.6 wt % calculating on copolymer C weight.

EFFECT: polyethylene composition possesses increased impact viscosity and has high degree of blowing 180-220%.

9 cl, 1 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a rubber mixture for filling sides and tyres with a side filler made from the said rubber mixture. The said rubber mixture contains the following: 5-25 pts. wt phenol resin and/or modified phenol resin; 5.1-7.0 pts wt sulphur; 0.5-2.5 pts. wt hexamethylenetetramine; 2.0-5.0 pts. wt sulfenamide vulcanisation accelerator and/or thiazole vulcanisation accelerator; 0.1-5 pts. wt of at least one auxiliary substances for accelerating vulcanisation selected from a group consisting of citraconimide based compounds, a product of condensation of alkylphenol and sulphur chloride, an organic thiosulphate compound and a compound of the following basic formula: R'-S-S-A-S-S-R2, where A is an alkylene group containing 2-10 carbon atoms, and each of R1 and R2 is a univalent organic group containing a nitrogen atom per 100 pts. wt of diene rubber.

EFFECT: higher technological effectiveness of extrusion through optimisation of the rate of vulcanisation, improved hardness, stability of controlling an automobile and reduced specific fuel consumption.

6 cl, 6 ex, 2 tbl, 5 dwg

FIELD: production of tires and mechanical rubber goods; activation of vulcanization of rubber on base of non-saturated rubbers.

SUBSTANCE: rubber vulcanization activator contains the following components, parts by mass: zinc oxide, 5.90-20.0; stearine, 27.40-46.50; ε-caprolactam, 11.60-26.60 and N-(cyclohelxylthio)phthalimide-36. Proposed activator increases rate of vulcanization in main period without reducing the time of beginning of pre-vulcanization - reduction of induction period at retained physical-mechanical parameters of vulcanizers at required level.

EFFECT: enhanced efficiency.

3 tbl, 6 ex

The invention relates to inhibitors of podocarpaceae used in tire and rubber industry for rubber mixtures based on natural and synthetic rubbers

Polymer composition // 2165440
The invention relates to polymeric compositions that can be used for the manufacture of rubber products such as o-rings to field pipelines

The invention relates to composite materials based on high-molecular compounds, and in particular to compositions for the preparation of foam-based phenol-formaldehyde resins, and can be used in aviation, shipbuilding, machine building, transport and industry, as well as in the field of industrial and civil construction

The rubber mixture // 2125066

Polymer composition // 2084474
The invention relates to polymer compositions based (co)polymer of vinyl chloride and can be used to obtain non-toxic materials with different degree of plasticization for food packaging, cosmetics, medical devices and drugs, as well as various consumer goods

Polymer composition // 2084473
The invention relates to polymeric compositions based on unplasticized polyvinyl chloride (PVC), used, for example, to obtain a molding products (Windows and doors) with high resistance to fracture and lightfastness

The invention relates to a stabilizer for chlorine-containing polymers and can be used in the processing compositions of chlorine-containing polymers such as polyvinyl chloride, copolymers of vinyl chloride etc. in various products (film materials, bottles, profiles, pipes and so on)

FIELD: chemistry.

SUBSTANCE: invention relates to polymeric intermediate layers used in multilayer glass panels The intermediate layer contains a polymeric stack having a first polyvinylbutyral sheet without anti-adhesives, tightly attached to a polyvinylbutyral sheet with anti-adhesives.

EFFECT: invention presents adhesion of polyvinylbutyral sheets while preserving optical purity of the ready laminated glass and the acceptable level of adhesion between a polyvinylbutyral sheet and glass.

11 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: film is made from a composition having multi-modal molecular-weight distribution and density between 0.940 and 0.948 g/cm3. The composition contains 40-60 wt % of a first fraction of an ethylene polymer made from a homopolymer A, 25-45 wt % of a second fraction of ethylene polymer made from a first copolymer B of ethylene and at least one first comonomer from a group of olefins having 4-8 carbon atoms and 10-30 wt % of a third fraction of ethylene polymer made from a second copolymer C of ethylene and at least one second comonomer from a group of olefins having 4-8 carbon atoms. The first copolymer B of ethylene has molecular weight which is less than that of the second copolymer C of ethylene, but greater than that of homopolymer A.

EFFECT: disclosed thin films have improved mechanical properties, particularly impact resistance when testing the films using a falling pointed load, with high rate of collection without deterioration of stability of the molten bubble.

12 cl, 2 tbl, 3 ex

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