Polyethylene films

FIELD: packing industry.

SUBSTANCE: invention relates to polyethylene films and first of all to bimodal polyethylene compositions designed for the production of films with low impurities content and increased manufacturability. The film contains polyethylene composition with the density of 0.940-0.970 g/cm3 and melt index value (I21) measured according to ASTM-D-1238-F technique 190°C/21.6 kg, from 4 to 20 dg/min. The polyethylene composition contains a high-molecular component with the average molecular weight more than 50000 and a low-molecular component with the average molecular weight less than 50000.

EFFECT: definite combination of the composition polymer characteristics meets the commercial requirements to the production of polyethylene films suitable for manufacturing the films by moulding, blow formation and other methods, the films are characterised by improved operational parameters along with high film quality that is revealed by low gel fraction content and simultaneous retention of strength, flexibility and impact resistance values.

28 cl, 7 dwg, 6 tbl, 12 ex

 

The scope of the invention

The present invention relates to polyethylene films and above all to the bimodal polyethylene compositions, intended for the production of films with low impurity content and high manufacturability.

Background of invention

Bimodal composition of high density polyethylene and is primarily a "bimodal" or "multimodal" high density polyethylene ("bpmp") is used for films intended for some commercial products, such as films, pipes, castings, etc. However, the disadvantages of such compositions is the relatively high cost, since most bpmp get in 2 or more stages and/or in two - or multi-stage reactors on how Dow, Basell, Borealis and Mitsui. Such industrial polymerization system described in the book, for example, John Scheirs &W. Kaminsky, Metallocene-Based Polyolefins, 2, 366-378, Ed. by John Wiley & Sons, Ltd. (2000).

Moreover, processing PAIT associated with some commercial problems. For example, the cooling of the film after extrusion of the polyethylene is a limiting factor in the production of films, primarily in the extrusion of HDPE, as described in the book, Film Extrusion Manual, Process, Materials, Properties, cc.497, TAPPI, (1992). One solution to this problem is the process is possible at low temperature is of aspreva. However, given the bimodal nature of these resins, the melting may be heterogeneous and/or data resins it is necessary to maintain a relatively high temperature of the melt. To compensate, you can maintain a high magnitude of back pressure, but this causes other problems, as well as to increase the intensity of the process. In this regard, there is a need in the films of PMP, which can be obtained by extrusion at high speed at a relatively low temperature of the melt using a lower engine load of the extruder while maintaining the high quality of the obtained films.

Another advantage, which is of great importance in the production of bpmp is a low cost production process, which is achieved when using dorectory systems. Although dorectory systems are known as systems that receive bimodal polyethylene for the manufacture of films, as for example described in the article N.-T. Liu and others, MACROMOL. SYMP., 195, 309-316 (2003), quality and technological characteristics of such films should not yield the same properties of polyethylene films obtained in the two-stage reactors on an industrial scale. One object of the present invention relates to the creation of this film, because the authors set the network, when a certain combination of polymer properties are satisfied simultaneously as commercial requirements for obtaining polyethylene films, suitable for film casting, blow molding and other methods, and another object relates to the production of such films of polyethylene compositions obtained in the single-stage reactor.

A brief description of the invention

One object of the present invention offers a film comprising a polyethylene composition, preferably bimodal polyethylene, characterized by the density of 0,940 to 0,970 g/cm3and the value of the melt index (I21) less than 20 DG/min, and the polyethylene composition is subjected to extrusion at a melt temperature Tm, the value of which satisfies the following relationship: Tm≤235-3 .3 (I21), and specific performance from 1 (0,454 kg/h/rpm) up to 1.5 lb/HR/rpm (0,681 kg/h/rpm), and the film is characterized by a value of the content of the gel fraction is less than 100.

Another object of the present invention offers a film comprising a polyethylene composition, preferably bimodal polyethylene, and the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 50,000, and a low molecular weight component x is rasterizes mass-average molecular mass of less than 40000, or less than 20,000, or less than 15000, 12000 or less; and the density of the polyethylene composition is from 0,940 to 0,970 g/cm3the value of I21less than 20 DG/min, the value of Mw/Mn of more than 30, or 35, or 40, and the film is characterized by the size of the gel fraction is less than 100.

Another object of the present invention a polyethylene composition used to produce the films of the present invention, receive in a single reactor, preferably in one gas-phase reactor with continuous action.

Various objects of the present invention is described with reference to any option or combination of embodiments of the invention, which is described polymer composition, properties, extrusion of the polymer composition and film and which will be described in more detail below.

Brief description of figures

In figures 1 and 2 show diagrams of dependence of the melt index (I21) compositions of the present invention, described in examples 1 and 2 (◆) and the examples for comparison (Δ, □), engine load and pressure during extrusion with the formation of a film of 0.5 mil, performance extrusion is from 1,84 to 1.90 lb/HR/rpm

In figures 3,4 and 5 show graphs GPC to compare the profile of molecular weight compositions described in example 1 for comparisonwith each compositie the present invention, described in examples 3, 4 and 5 (-----).

In figures 6 and 7 show graphs of the values of melt index (I21) compositions of the present invention, described in examples 3 and 5-9 (◆) and the examples for comparison (numbered circles), engine load and pressure during extrusion with the formation of a film of 0.5 mil, performance extrusion is from 1.16 to 1.20 lb/HR/rpm

Detailed description of the present invention

In the present invention proposes a film comprising a polyethylene composition, and the polyethylene composition in one embodiment includes a high molecular weight component and a low molecular weight component and in the preferred embodiment, is characterized by a multimodal or bimodal GPC profile. The polyethylene composition is characterized by improved processing characteristics, namely the reduction of the engine load of the extruder (or energy consumption) in comparison with other plastic resins with similar density and melt index (I21). Another characteristic of the present invention is a high performance at extremely low temperatures of the melt. Described in this context, the films are characterized by improved processing characteristics while keeping a high quality film, which is about what is, for example, in a low maintenance gel-fraction while maintaining the values of strength, flexibility and toughness comparable to polyethylene with the same density and I21.

Used in this context, the term "film" or "film" includes a film, sheet or membrane thickness of less than 1000 microns, more preferably less than 500 μm, even more preferably less than 200 microns and most preferably less than 100 μm and includes film, obtained by any method known in the art, such as molding or blow molding, oriented or unoriented, obtained by extrusion or calandrinia, preferably by extrusion of polyethylene, as described in this context, and film for various purposes, such as screwing, protection, packaging, rasfasovyvanie, floor, coextrusion with other materials; as well as such films are characterized by any required dimensions: thickness, length, etc. of the Film of the present invention are not only transparencies, but also can be an opaque or translucent or transparent, preferably transparent film and are characterized by other properties, as described in this context. The film of the present invention is produced by coextruding or alternatively applied to other sheets/St is ucture etc. with the formation of structures with thickness of more than 1000 μm.

The advantages of the films of the present invention, namely the use of lower motor loads during extrusion of polymer compositions for the preparation of films and providing a lower melting temperatures in the provision of necessary on an industrial scale performance and high quality film that confirmed low levels of gel-fraction and/or high value FAR described with reference to any embodiment of the present invention, as described in this context.

One object of the present invention offers a film comprising a polyethylene composition, the density of which is 0,940 to 0,970 g/cm3and the value of I21from 4 to 20 DG/min, and the polyethylene composition is subjected to extrusion at a melt temperature Tm, the value of which satisfies the following relation (I):

and performance extrusion ranges from 1 (0,454 kg/h/rpm) up to 1.5 lb/HR/rpm (0,681 kg/h/rpm), and the content of the gel fraction in the film is less than 100. The value of I21should be multiplied by a factor of 3.3. In another embodiment, the ratio of (I) the temperature of the melt is determined by the equation Tm≤240-3,3 (I21), another version of the Tm≤240-3,5 (I21and in another embodiment, T m≤235-3,5 (I21). The melt temperature is the temperature in the lower section of the mixing zone of the extruder, which is used for processing polyethylene compositions in forming the film of the present invention. This object of the present invention the melting temperature determined in the system of the extruder, suitable for film, described in this context.

In one embodiment, the polyethylene composition is obtained by extrusion performance from 1.00 lb polyethylene/HR/rpm (0,454 kg/h/rpm) to 1.45 pounds of polyethylene/HR/rpm (0,648 kg/h/rpm) when the melt temperature Tm, the value of which satisfies the equation Tm≤235-3,3 (I21).

In another embodiment, the polyethylene composition is obtained by extrusion performance from 1.00 lb polyethylene/HR/rpm (0,454 kg/h/rpm) to 1.40 pounds of polyethylene/HR/rpm (0,636 kg/h/rpm) when the melt temperature Tm, the value of which satisfies the equation Tm≤235-3,3 (I21).

In yet another embodiment, the polyethylene composition is obtained by extrusion performance from 1.00 lb polyethylene/HR/rpm (0,454 kg/h/rpm) to 1.30 lb polyethylene/HR/rpm (0,590 kg/h/rpm) when the melt temperature Tm, the value of which satisfies the equation Tm≤235-3,3 (I21). In another embodiment, the bottom ol the Affairs of performance is 1.10 lb polyethylene/HR/rpm (0,499 kg/h/rpm).

Examples of the required temperature of the melt Tmthe polyethylene compositions of the present invention include less than 206°or 204°or 202°or 200°or 198°or 196°or 190°or 188°or 186°or 184°or 182°or 180°With or 179°and in another embodiment, the melt temperature is at least 170°or at least 175°C. In yet another embodiment, the lower limit of the temperature of the melt is equal to the minimum melt temperature required to obtain the films described in this context, under certain performance and speed at the exit of the head of the extruder described in this context.

In another variant embodiment of the present invention improved extrusion properties of the films described in this context, indicate in the form of a module of the extruder, in a preferred embodiment, the preferred speed at the exit of the head of the extruder, as described in the present invention, is provided in a screw extruder with a screw size of the channel 50 mm and L/D ratio (the relative length of the screw) 21:1. Thus, in one embodiment, the film of the present invention is obtained by extrusion of the polymer composition during the melt temperature Tmthat satisfies the relation of Tm≤235-3,3 (I21), with the speed o the de from the head of the extruder 10 to 20 lbs of polymer/HR/inch circumference head extruder (0,179 to 0,357 kg/h/mm), in another embodiment, with the velocity head of the extruder 10 to 15 lbs of polymer/HR/inch of the circumference of the head (0,179 to 0,268 kg/h/mm). This object of the present invention, the melt temperature is determined in the system of the extruder, suitable for film, described in this context.

Basically, the film of the present invention are characterized by superior temperatures of the melt compared with the known films of polyethylene bpmp, which are characterized by the value of I21from 4 to 20 DG/min, regardless of how they receive or the way of obtaining the above polyethylene compositions used to produce the films of the present invention. The above relation (I) holds for a given set of characteristics of the extruder. In one embodiment, the specified improvement in the more General form is expressed by the ratio of Tm≤TmX-3,3 (I21), where TmXmeans the melt temperature, linearly extrapolated to the value of I21=0 for any given set of characteristics of the extruder. In most cases, the melt temperature of the polyethylene compositions used to produce the films of the present invention, are the quantities below are for 2-20°compared with the corresponding values for bpmp described in predshestvuyuschee technique and characterized by similar values of I 21(in the interval from ±2 to ±3 units).

Another object of the present invention relates to a film comprising a polyethylene composition, the density of which is 0,940 to 0,970 g/cm3and the value of I21from 4 to 20 DG/min, and the polyethylene composition is subjected to extrusion at a melt temperature Tmvalue for 2-4 or 10-20°lower than the melt temperature of the polyethylene composition with the same density and the value of I21obtained using two - or multi-stage reactor and extrusion under the same conditions, the content of the gel fraction in the film is less than 100. Such two - or multi-stage processes and reactors known in the art, such as described in articles F.P.Alt and others, Macromol. Symp., 163. 135-143 (2001) and Metallocene-Based Polyolefins, 2, 366-378 (2000); and U.S. patent No. 6407185, 4975485, 4511704. Used in this context, the term "polyethylene composition obtained using a multistage reactor" means a polyethylene composition obtained using a multistage process that includes a series-connected two or more reactors, or one reactor operated in sequential mode, as described in the above references. This object of the present invention, the melt temperature of the film p is the present invention preferably are comparable with values polyethylene compositions obtained in a multistage reactor, i.e. above the melt temperature (the value of I21) are in the range ±3 DG/min, more preferably ±2 DG/min and even more preferably in the range of ±1 DG/min

Another object of the present invention offers a film comprising a polyethylene composition, and the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 50,000, and low-molecular component, characterized by a mass-average molecular mass of less than 40000, or less than 20,000, or less than 15000, 12000 or less; and the density of the polyethylene composition is from 0,940 to 0,970 g/cm3the value of I21less than 20 DG/min, the value of Mw/Mn of more than 30, or 35, or 40, and the film is characterized by the content of the gel fraction is less than 100. Other characteristics of the polyethylene composition described below in this context.

The quality of the films according to the present invention is characterized by the content of gel-fraction, as described in this context. In one embodiment, the content of the gel fraction in the films is less than 100, in another embodiment, the content of the gel fraction is less than 60, in one embodiment, the content of the gel fraction is less than 50, in one embodiment, the content of the gel fraction is less than 40, and in yet another embodiment, the content of the W gel fraction is less than 35. Described in another embodiment of the film according to the present invention are characterized in one embodiment, a value FAR greater than +20, in another embodiment more than +30 and in yet another embodiment, more than +40. The thickness of the films of the present invention in one embodiment is less than 16% of the total film thickness, in another embodiment less than 13%, and in yet another embodiment, less than 10%.

A polyethylene composition used to produce the films of the present invention, can be processed by extrusion at lower power values and the pressure at given values of performance and the temperature of the melt compared with the previous conditions. For this extruder under the same conditions polyethylene compositions of the present invention is processed by extrusion at lower engine loads (1-10% lower) compared to the bimodal polyethylene compositions, which are characterized by a density of from 0,940 to 0,970 g/cm3and the value of I21less than 20 DG/min In another embodiment, the improvement is the reduction of the engine load of the extruder at a value of from 2 to 5% compared to the comparable bimodal polyethylene compositions.

In other words, for a given extruder polyethylene compositions of the present invention characterized by the above properties, in odnawiane extrusion process when the engine load is less than 80% of the maximum engine load, and in another embodiment less than 77% of the maximum engine load, and in another embodiment less than 75% of maximum engine load, and in another embodiment from 66 to 80% of the maximum engine load, and in another embodiment from 70 to 77% of the maximum engine load, and the desired interval in % includes any combination of any upper limit with any lower limit. These preferred properties are provided when the temperature of the melt and performance within the limits described in this context.

The film of the present invention are characterized by properties that are suitable for use in industry. For example, films of the present invention are characterized in one embodiment, the tensile strength in the longitudinal direction MD from 9,000 to 15,000 pounds per square inch and a tensile strength in the transverse direction TD from 9,000 to 15,000 psi, in another embodiment, a relative elongation at break MD from 200 to 350% and elongation at break TD from 200 to 350%, in another embodiment, the strength of raster on Elmendorf MD from 10 to 30 g/mil and strength of raster on Elmendorf TD from 20 to 60 g/mil; and in one embodiment, the resistance at the instant the shock (F50) more than 150 g, and more than 170 g in another embodiment. These values are determined by testing according to the methods described in this context is who.

In one embodiment, the films of the present invention the polyethylene composition used to produce films, practically does not contain solid materials, deteriorating the film quality". Such solid materials, deteriorating the film quality is a zone of material inhomogeneity in the structure of the polyethylene compositions which have different properties. In one embodiment, the solid gel component is characterized by a melting temperature according to differential scanning calorimetry (DSC) from 125°With up to 133°or in another embodiment from 126°With up to 132°With; in addition, in one embodiment, the solid gel component is characterized by a value of I21less than 0.5 DG/min, and in another embodiment less than 0.4 DG/min; and in one embodiment, the viscosity η (at shear rate of 0.1 rad/s at 200° (C) more than 1000 MP, and in another embodiment, more than 1200 MP, with solid gel component is characterized by the presence of any one or combination of the above properties. The term "containing no solid materials, deteriorating the film quality" means that the solid gel particles (if present at all) in one embodiment, present in an amount of not more than 1 wt.% calculated on the total weight of the polyethylene composition, and in another embodiment less than 0.01 wt.%, and in another the embodiment, less than 0.001 wt.%.

To obtain polyethylene compositions intended for the manufacture of films of the present invention, it is possible to use any desired ways polymerization of olefins, such as gas-phase, emulsion polymerization or polymerization in solution, which are known for the polymerization of olefins to form polyolefins. In one embodiment, the use of two or more series-connected reactors, such as, for example, serially arranged gas-phase and emulsion reactors, or two consecutive gas-phase reactor, or two consecutive emulsion reactor. In another embodiment, using a single reactor, preferably one gas-phase reactor. More preferably, in the latter case, high molecular weight (VM) polyethylene include low molecular weight (NM) polyethylene simultaneously in the same reactor with the formation of the polyethylene composition in the presence of polymerizable monomers and the bimetallic catalyst composition. In one embodiment, the polyethylene composition is a bimodal polyethylene composition comprising more than 80%, preferably more than 90% of the ethylene monomer unit, and the remaining monomer units are3-C13the olefins and diolefins, as described below.

In one var is antes BM and NM polyethylene include each other sequentially or simultaneously, preferably at the same time using one, two or more reactors of any suitable construction, or in the preferred embodiment, they include each other simultaneously using a single polymerization reactor. In a preferred variant embodiment of the present invention to obtain a polyethylene composition using gas-phase polymerization reactor with a fluidized bed as described in U.S. patent No. 4302566, 5834571 and 5352749, usually including at least one reactor, and in the preferred embodiment, only one reactor.

In one embodiment, the NM polyethylene is homopolymer or copolymer of polyethylene comprising from 0 to 10 wt.% With3-C10-α-olefinic monomer unit, especially homopolymers of ethylene or copolymer of ethylene and 1-butene, 1-pentene or 1-hexene. NM polyethylene is characterized by several properties. In one embodiment, the mass-average molecular mass NM polyethylene is less than 50000, and other options are described below.

In one embodiment, the VM polyethylene is homopolymer or copolymer of polyethylene comprising from 0 to 10 wt.% With3-C10-α-olefinic monomer unit, especially homopolymers of ethylene or copolymer of ethylene and 1-butene, 1-pentene or 1-hexene. In one embodiment, the bulk mole is alarna mass VM polyethylene is more than 50000, and other options are described below. The polyethylene composition of the present invention, including at least a BM and NM polymers are also characterized by a number of parameters described below.

To obtain a polyolefin by polymerization of olefins using the catalysts. The film of the present invention is obtained using any of the compositions of the catalysts, which is used to produce polyethylene compositions and films described in this context. In one embodiment, the film is produced from polyethylene compositions, which are formed by polymerization using a single class of catalysts, or in another embodiment, combinations of two or more catalysts of the same class, or in another embodiment, combinations of two or more different classes of catalysts. In a preferred embodiment, the film comprising a polyethylene composition described in this context, is produced by polymerization using a bimetallic composition of the catalysts. Such bimetallic catalytic compositions include at least two, preferably two compounds containing metals of group 3-10, while both metals are the same or different metals from the same or different coordination spheres, the composition of the substituents at the Central metal atom or ligand SV is related to the Central metal atom. Examples of suitable catalysts for the polymerization of olefins, which are mixed in any way with the formation of bimetallic catalytic compositions include, without limitation, metallocene, the catalysts of the Ziegler-Natta, metal amide catalysts described, for example, in U.S. patents№№ 6593438, 6380328, 6274684, 6333389, the applications WO 99/01460 and WO 99/46304, and catalysts based on chromium, as described in U.S. patent No. 3324095, including, for example, cyclopentadienyl chromium, chromium oxides, alkyl substituted derivatives of chromium, as well as their options, deposited on a substrate, and their modified versions. In another embodiment, the bimetallic catalyst composition is a combination of two or more catalytic compounds of the same class.

In a preferred embodiment, the bimetallic catalyst composition used to produce the polymer compositions described in this context, includes metallocene and titanium containing catalyst of the Ziegler-Natta, for example, described in U.S. patent No. 5539076 and in the application WO 02/090393, which is incorporated into this description by reference. The preferred catalytic compounds deposited on a substrate, and in the preferred embodiment, both the catalytic component deposited on a substrate in a mixture with primary activator, in the preferred embodiment, with alumoxanes, p and in this preferred embodiment, the substrate is an inorganic oxide.

In one embodiment, in the presence of the metallocene component of the catalyst composition of the bimetallic catalytic compositions have NM polyethylene to polyethylene composition, which is used to produce films. Metallocene catalyst compound, as described in this context include connection type "full sandwich"containing two ligand Withp(cyclopentadienyls ligands and isolable analogues of cyclopentadienyl)associated with at least one metal atom of groups 3 to 12, and one or more leaving groups associated with at least one metal atom. First of all, the ligand(s)pselected from the group comprising substituted and unsubstituted cyclopentadienyls ligands and isolable analogues of cyclopentadienyl, examples of which are, without limitation, include cyclopentadienyl, indenyl, fluorenyl and other structures. In this context, these connections are called "metallocene" or "metallocene components of the catalyst.

Used in this context, the system for determining the groups of elements in the Periodic table is the "new" numbering system groups of the Periodic table of elements, as described in the CRC Handbook of Chemistry and Physics, Ed. by David R.Lide, CRC Press, 81-oe ed. (2000).

The metal atom "M" of the metallocene catalyst compounds is tion is chosen from the group including in one embodiment, the atoms of groups 4, 5 and 6, and in the preferred embodiment, the atoms of Ti, Zr, Hf, and in an even more preferred embodiment, the Zr atom. The ligand(s) Cf form at least one chemical bond with the metal atom M with the formation of the "metallocene catalyst compounds. One object of the present invention metallocene catalyst components of the present invention characterized by formula (II):

where M has the values described above, each X is associated with M, each Cf group forms a chemical bond with M, and n is 0 or an integer from 1 to 4, or in a preferred embodiment, 1 or 2.

The ligands of CuAand SRBin the formula (II) mean the same or different cyclopentadienyls ligands or isolable analogues of cyclopentadienyl, each of which or both contain heteroatoms, and each of them is or both are substituted by a group R. In one embodiment, CuAand SRBindependently selected from the group comprising cyclopentadienyl, indenyl, tetrahydroindene, fluorenyl and their substituted derivatives.

Each of the ligands of CuAand SRBformula (II) independently is unsubstituted or substituted by any one substituent R or a combination of both. Examples of the substituents of group R in the formula (II), and the substituents in the ring of formula (II), without the OTF is the limit listed, include hydrogen, C1-C6alkyl, C2-C6alkenyl,3-C6cycloalkyl,6-C10aryl or alkylaryl and combinations thereof.

Each X in formulas (II) and (III) is independently chosen from the group, in the preferred embodiment, includes ions of Halogens (fluoride, chloride, bromide), hydrides, With1-C12alkyl, C2-C12alkenyl,6-C12aryl, C7-C20alkylaryl,1-C12alkoxy, C6-C16aryloxy,7-C18alkylacrylate,1-C12foralkyl,6-C12ferril and containing a heteroatom With1-C12hydrocarbons and their substituted derivatives, and in the most preferred embodiment, the fluoride.

Another object of the present invention metallocene component of the catalyst include compounds of formula (II), where CfAand SRBconnected to each other by at least one bridging group, (A), such as the structure of the formula (III):

Such bridging the compounds of formula (III) are called "bridging metallocene". CfA, CuB, M, X and n in the structure (III) have the meanings given above in the description of formula (II); and each ligand Cf is associated with M, and (A) forms a chemical bond with each group Wed. Examples of bridging group (A), without limitation, clucalc divalent hydrocarbon group, containing at least one atom of group 13-16, such as, without limitation, at least one of the carbon atoms, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin, and combinations thereof; heteroatom can contain substituents With1-C12alkyl or aryl, provided that the formation of neutral molecules that do not contain free valence. Bridging group (A) also contains the substituents R, described above (in the description of formula (II)), including halogen atoms and iron. First of all, examples of bridging group (A), without limitation, include C1-C6alkylene, substituted C1-C6alkylene, oxygen, sulfur, R'2C=, R'2Si=, -Si(R')2Si(R'2)-, R'2Ge=, R P= (where "=" means a double chemical bond, where R' is independently selected from the group including hydride, C1-C10alkyl, aryl and substituted aryl.

In one embodiment, in the presence of a component of a catalyst of Ziegler-Natta in the composition of the bimetallic catalytic compositions have VM polyethylene to polyethylene composition, which is used to produce films of the present invention. The catalysts of the Ziegler-Natta described in the book Ziegler Catalysts 363-386, G.Fink, R.Mulhaupt and H.H.Brintzinger, eds., Springer-Verlag (1995) and RE 33683. Examples of such catalysts include the oxides, alkoxides and halides of transition IU allow groups 4, 5 or 6, especially oxides, alkoxides and halides of titanium, zirconium or vanadium in combination with compounds of magnesium, internal and/or external electron donors (alcohols, ethers, siloxanes and the like), alkylamines or alkylboron and alkylhalogenide, as well as substrates of inorganic oxides.

In one embodiment, the catalyst of the Ziegler-Natta used in combination with the substrate, and in the presence or in the absence of the metallocene component of the catalyst. Component of the catalyst of the Ziegler-Natta mixed with the substrate, put on it or otherwise fixed to the substrate using a number of methods. One such method involves contacting a suspension of the substrate in a suitable non-polar hydrocarbon diluent with magnetogenesis connection, which then dissolves in non-polar hydrocarbon diluent for suspension, thereby forming a solution from which magyarkanizsa compound forms a layer on the substrate. Magyarkanizsa compound characterized by the formula RMgR', where R' and R denote identical or different groups With2-C12alkyl or C4-C10alkyl or C4-C8alkyl. In at least one specific embodiment, magnetogenesis connection is dibutylamine.

In one embodiment, maniola the economic connection and processed by the alcohol suspension is in contact with the transition metal compound. Suitable transition metal compounds include compounds of metals of groups 4 and 5, which are soluble in non-polar hydrocarbon, which is used to obtain a suspension of silica. Examples of suitable compounds of transition metals of groups 4, 5 or 6, without limitation, include, for example, the halides of titanium and vanadium, oxychloride or alkoxylated, such as titanium tetrachloride (TiCl4), vanadium tetrachloride (VCl4and oxytrichloride vanadium (VOCl3), and alkoxides of titanium and vanadium, which alkoxide residue contains a branched or unbranched alkyl group containing from 1 to 20 carbon atoms, in the preferred embodiment, from 1 to 6 carbon atoms. Also use a mixture of such compounds of transition metals. In the preferred embodiment, to obtain a magnesium-containing catalyst of the Ziegler-Natta as a source of transition metal compounds using TiCl4or TiCl3.

In one embodiment, the catalyst of the Ziegler-Natta contact with the electron donor, such as tetraethylorthosilicate (TEOS), simple ether, such as tetrahydrofuran, or an organic alcohol of the formula R"OH, where R indicates the group With1-C12alkyl or C1-C8alkyl or C2-C4alkyl and/or a simple ester or cyclic ether, such as tetrahydrofuran.

Metallocene component and a component of the catalyst of the Ziegler-Natta contact with the substrate in any order. In a preferred embodiment of the present invention the first component of the first catalyst is in contact with the substrate, as described above, and then the first component of the catalyst on the substrate in contact with the second component of the catalyst.

When mixing with formation of bimetallic component of the catalyst, the molar ratio of the second catalyst component and the first component of the catalyst (for example, the molar ratio of Ti:Zr) in one embodiment is from 0.1 to 100; in another embodiment from 1 to 50, in another embodiment from 2 to 20 alternatively from 3 to 12; in yet another embodiment, from 4 to 10, in another embodiment, from 4 to 8; however, the required molar ratio of the component Ti and Zr component is any combination of any upper limit with any lower limit specified in the given context.

The method of polymerization used to produce polyethylene compositions suitable for producing films of the present invention, preferably includes an introduction to the composition of the catalyst on the substrate in a polymerization reactor. The catalytic components and the activator(s) (metallocene and components of the catalyst of the Ziegler-Natta) is mixed with the substrate by any method, Izv the STN in the art. Preferably the catalytic components is applied onto the substrate in the presence of at least one activator, preferably alumoxane. In another embodiment, in a polymerization reactor introduce another activator, preferably alkylamine, in the form of a separate component. In the most preferred embodiment, the bimetallic catalyst composition, preferably including metallocene and component of the catalyst of the Ziegler-Natta injected in one reactor, preferably a gas phase reactor with a fluidized bed of catalyst, under the conditions of polymerization, suitable for the production of bimodal polyethylene compositions described in this context.

Substrate, methods of coating substrates, modification and activation of substrates for catalysts with one active site, such as metallocene described, for example, article G.G.Hlatky, Chem. Rev., 100 (4), 1347-1374 (2000). Used in this context, the term "substrate" means any material of the substrate, in one embodiment, the porous substrate material including inorganic or organic substrate materials. In one embodiment, the most preferred substrate materials include silicon dioxide, aluminum oxide, aluminum silicate, magnesium chloride, graphite, and mixtures thereof. The most preferred substrate is silicon dioxide. In a preferred embodiment, vile who ICOI is an inorganic oxide, preferably silicon dioxide, characterized by an average particle size of less than 50 microns, or less than 35 μm, and a pore volume from 0.1 to 1 or 2 or 5 cm3/year

The substrate is preferably annealed. Suitable interval temperature calcination in one embodiment, is between 500°1500°With, in another embodiment from 600°With up to 1200°in another embodiment from 700°With up to 1000°With, in another embodiment from 750°900°and in an even more preferred embodiment, from 800°900°when this required interval includes any combination of any upper limit and any lower limit specified in this context. The calcination is carried out in the absence of oxygen and moisture when using, for example, an atmosphere of dry nitrogen. In another embodiment, the calcination is carried out in the presence of moisture and air.

The substrate is in contact with the other components of the catalytic system in any way. In one embodiment, the substrate is in contact with the activator with the formation of associates of activator and substrate, or associated activator". In another embodiment, a component of the catalyst is in contact with the substrate with the formation of a linked component of the catalyst. In yet another embodiment, the substrate is in contact with the activator component of the catalyst simultaneously or in part with each of them in any order. Contacting the components of the clients perform any suitable means, for example, in solution, in suspension or in solid form or in the form of their combinations, and when contacting the components are heated at a temperature of from 25°, 250°C.

In one embodiment, the bimetallic catalyst composition comprises an activator of at least one, preferably of the same type. Used in this context, the term "activator" refers to any compound or combination of compounds is applied or not applied on the substrate, which can activate the catalyst with one active site (for example, metallocene, metallogeny catalysts and the like), for example, in the formation of cationic derivative component of the catalyst. Examples of such activators include Lewis acid, such as cyclic or oligomeric poly(gidrokarbonatnye oxides). The preferred activator is alumoxane, and more preferred alumoxane on a substrate of an inorganic oxide, and before contacting with alumoxane substrate calcined.

In one embodiment, as the activator component of the Ziegler-Natta in the composition of the bimetallic catalyst system in a polymerization reactor, it is preferable to add alkylamine. Alkylamines activator represented by the formula AlR§3where R§selected from the group including1-C20alkyl, C -C20alkoxy, halogen (chlorine, fluorine, bromine), C6-C20aryl, C7-C25alkylaryl and C7-C25arylalkyl. Examples of compounds alkylamine, without limitation, include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylamine, tri-n-octylamine etc. Alkylamino preferably not deposited on a substrate, which is applied to the components of the catalytic system and primary activator (for example, alumoxane), and represents a separate component, which is added to the reactor(s).

Connection alkylamine or mixture of compounds, such as trimethylaluminum or triethylaluminum, in one embodiment, served in the reactor at a rate from 10 miscast./million to 500 miscast./million (feed rate alkylamine mass parts per million compared with the feed rate of ethylene), in another embodiment from 50 miscast./million to 400 miscast./million, in yet another embodiment, from 60 miscast./million to 300 miscast./million, in another embodiment from 80 miscast./million to 250 miscast./million and in another embodiment from 75 miscast./million to 150 miscast./million, and the desired interval includes any combination of any upper and any lower limit.

For the bimetallic catalyst compositions described in this context, use of other primary or separately introduced activators, reinforcement of the local in the art. Ionizing activators known in the art and described, for example, in the book Eugene You-Xian Chen & Tobin J. Marks, Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure-Activity Relationships 100(4) Chemical Reviews 1391-1434 (2000). Examples of ionizing ionic activators, without limitation, include trialkylamine ammonium salts, such as triethylammonium(phenyl)boron and the like, salts of N,N-dialkylanilines, such as N,N-dimethylanilinium(phenyl)boron and the like; salts of dialkylamino, such as di(isopropyl)ammoniate(pentafluorophenyl)boron and the like; salts triarylamine (triteleia salt), such as triphenylcarbenium(pencil)boron and the like, salts triarylphosphine, such as triphenylphosphine(phenyl)boron and the like, and similar aluminum compounds.

When used as an activator of cyclic or oligomeric poly(carbylamines), i.e., "alumoxane", such as metallocen "MAO", the molar ratio of activator and catalyst component is in one embodiment from 2:1 to 100000:1, in another embodiment from 10:1 to 10000:1 and in yet another embodiment, from 50:1 to 2000:1; most preferably alumoxane deposited on a substrate of the inorganic oxide so that during the simultaneous application to the substrate with metallocene molar ratio of aluminum (alumoxane)/metal of group 4, 5 or 6 (metallocene) is from 500:1 to 10:1 and more PR is doctitle from 200:1 to 50:1.

To obtain polyethylene with the characteristics described in this context, using any suitable method of polymerization of olefin (type polymerization reactor and reactor process, for example, polymerization in the gas phase, slurry, solution, under high pressure, and so on). The performance of the reactor(s)in which the use of the catalytic system described in this context, in one embodiment is more than 500 lb/h (230 kg/h), in another embodiment, more than 1000 lbs/HR (450 kg/HR)in yet another variant, more than 2,000 lb/h (910 kg/h), in another embodiment, more than 10,000 lb/h (4500 kg/HR)in yet another variant, more than 20,000 lb/h (9100 kg/h) and in another embodiment, more than 500,000 lb/h (over 230,000 kg/h).

The film of the present invention is preferably produced by extrusion, molding or casting with a blown polyethylene composition obtained using a gas-phase reactor with a fluidized bed continuous action, and primarily using one gas-phase reactor with a fluidized bed continuous action in one stage. A reactor of this type and its equipment are known and fully described, for example, in U.S. patent No. 4003712, 4588790, 4302566, 5834571 and 5352749. In another embodiment, the process is carried out in a single gas phase reactor, as described in U.S. patent No. 5352749 and 5462999. In the last two patents epicaricacy gas-phase polymerization, using a fluidized bed polymerization medium in a continuous stream of gaseous monomers and optional "condensing agent".

Variant of the reactor with a fluidized bed used to obtain the polyethylene of the present invention, typically includes a reaction zone and a so-called zone speed reduction. The reaction zone comprises a layer of growing particles of polyethylene, formed of particles of polyethylene and a minor amount of catalyst particles fluidized in a continuous stream of gaseous monomer and optional diluent for heat removal from the polymerization mixture through the reaction zone. Not necessarily, some of the recycle gas is cooled and compressed with the formation fluids, which increase the heat capacity of the circulating gas stream during the second passage through the reaction zone. Suitable rate of replenishment of the gas flow can be determined by simple experiment. Adding gaseous monomer in the circulating gas stream is conducted at a speed equal to the speed of removal of the product in the form of particles of polyethylene in the mixture with the monomer from the reactor, and the composition of the gas passing through the reactor is adjusted so that basically to maintain the equilibrium state of the gas composition in the pre is Elah the reaction zone. The gas coming from the reaction zone passes through the zone speed reduction, which removes the captured particles. The smaller the captured particles and dust is removed using a cyclone and/or a fine filter. The gas passes through the recirculation line and then through the heat exchanger, in which the removal of heat of polymerization, the gas is then compressed in the compressor and returned to the reaction zone. The so-called "monitoring agents" (e.g., tetrahydrofuran, isopropyl alcohol, molecular oxygen, phenolic compounds, ethoxylated amines, and the like) is added to any area of the reactor, as described in this context, and in a particular embodiment, they are administered in the recirculation line, preferably in quantities of from 0.1 to 50 miscast./million, and in yet another variant is introduced into the recirculation line, located above the heat exchanger. It is known that such agents lead to the reduction of electrostatic charge and/or contamination of the reactor on large surfaces, recirculation lines, the plate in the bottom of the reactor, etc.

In one embodiment, the bulk density of fluidized plastic compositions obtained in the reactor(s), ranges from 16 to 24 lb/ft3and in another embodiment from 16.5 to 20 lb/ft3. Volumetric capacity of the reactor(s)used to obtain polyethylene HDMI the Nations of the present invention, is preferably from 5 to 20 lb/h/ft3and more preferably from 6 to 15 lb/h/ft3. Moreover, the contact time in the reactor(s), preferably in a single reactor is from 1 to 7 hours, more preferably from 1.2 to 6 h, and most preferably from 1.3 to 4 hours

In the variation of gas-phase reactor with a fluidized bed temperature of the fluidized bed in the reactor is in the range from 70°75°S, 80°to 90°or 95°or 100°or 110°s, and the desired temperature range comprises any combination of any upper temperature limit with any lower limit temperature. Basically the temperature in the reactor is equal to the maximum usable temperature taking into account the sintering temperature of the polyethylene product in the reactor and the formation of impurities in the reactor or recirculation lines.

In the variation of gas-phase reactor with a fluidized bed pressure of the gas phase in the reactor, which includes hydrogen, ethylene, higher comonomers and other gases, in one embodiment, ranges from 1 (101 kPa) to 100 ATM (10132 kPa), in another embodiment from 5 (506 kPa) to 50 bar (5066 kPa), and in another embodiment from 10 (1013 kPa) to 40 MPa (4050 kPa).

The method according to the present invention is intended to obtain homopolymers comprising units of ethylene and/or copolymers comprising units of ethylene and jingle is at least one or more other olefins. Preferably the ethylene will copolymerized with α-olefins, containing in one embodiment, from 3 to 12 carbon atoms, in another embodiment, from 4 to 10 carbon atoms, and in yet another embodiment, from 4 to 8 carbon atoms. More preferably, the ethylene will copolymerized with 1-butene or 1-hexene, and most preferably ethylene will copolymerized with 1-butene with the formation of the polyethylene compositions intended for obtaining films of the present invention.

Comonomer is present in any quantity corresponding to the desired mass percentage of co monomer in the final polymer. In one embodiment, the receiving PE product comonomer is present in a mixture with ethylene in the circulating gaseous stream in a molar ratio of 0.005 (comonomer/ethylene) to 0,100, in another embodiment from 0,0010 to 0,050, in another embodiment from 0,0015 to 0.040, and in another embodiment from 0,018 to 0,035.

Hydrogen gas is added to the polymerization reactor(s) to regulate the properties of the resulting polyethylene composition (for example, the values of I21and/or I2, bulk density). In one embodiment, the molar ratio of hydrogen to the total amount of ethylene monomer (H2/S2) in the circulating gas stream is the interval of 0.001, or from 0.002, or 0.003 to 0.014, or 0,016, or 0,018, or 0,024, and the desired interval for the ratio includes any combination of any upper limit of the molar ratios with any lower limit of the molar ratio, described in this context. In other words, the amount of hydrogen in the reactor at any point in time in one embodiment ranges from 1000 ppm million to 20,000 ppm million, in another embodiment from 2000 ppm million to 10000 ppm million, in another embodiment from 3000 ppm million to 8000 ppm million and in another embodiment from 4000 ppm million to 7000 ppm million, and the desired interval includes any combination of any upper limit of hydrogen content with any lower limit of the amount of hydrogen that is described in this context.

Bimetallic catalytic composition is introduced into the polymerization reactor by any suitable means, regardless of the type used in the polymerization reactor. In one embodiment, the bimetallic catalyst composition fed into the reactor in a practically dry condition, and a solid form of the catalyst is not diluted or not mixed with diluent prior to feeding into the reactor. In another embodiment, Catholic composition is mixed with a diluent, and fed into the reactor, and in one embodiment, the diluent are alkanes, such as C4-C20alkanes, toluene, xylene, mineral or silicone oil, or a combination of these substances, as described, for example, in U.S. patent No. 5290745.

In one embodiment, the bimetallic catalyst composition is mixed with not more than 2.5 wt.% metal salt and fatty key is lots such as, for example, aluminum stearate, based on the weight of the catalytic system (or its components), as described in U.S. patent No. 6608153. Other suitable metals, used in combination with a fatty acid include other metals of group 2 and group 5-13. In yet another embodiment, a solution of metal salt and fatty acid fed into the reactor. In another embodiment, a metal salt and a fatty acid mixed with catalyst and fed into the reactor separately. Such agents are mixed with the catalyst or fed into the reactor in the form of a solution or in suspension in the presence or in the absence of a catalyst system or its components.

In another embodiment, the catalyst(s) is mixed with activators and mixed, for example, in the drum or using another machine with no more than 2.5 wt.% (calculated on the weight of the catalytic composition) of an antistatic agent such as ethoxylated or methoxycarbonyl amine, such as Kemamine AS-990 (company ICI Specialties, Bloomington Delaware).

Polyethylene compositions described in this context, in one embodiment, are multi-modal and bimodal, preferably bimodal, and include in one embodiment, the at least one VM polyethylene and at least one NM polyethylene. The term "bimodal"used in the description of the polyethylene composition, means "bimodal (bimodal) moleculae-passoveraustralia", this term is used more broadly in this context compared to the term used in the published papers and patents granted. For example, in this description one of a polyethylene composition comprising a polyolefin with at least one identifiable high-molecular mass distribution and polyolefins with at least one identifiable low molecular mass distribution, referred to as "bimodal" polyolefin. Such high and low molecular weight polymers identified using the method of treatment of a convolution, which allows to establish the existence of two polymers by GPC curve with a wide peaks or GPC curve with peaks and a shoulder for bimodal polyolefins of the present invention, and in another embodiment, the curve is bimodal GPC of polymers according to the present invention contains a separate peaks with area of overlap, as shown in figures 3-5. The polyethylene compositions of the present invention are characterized by a combination of properties.

In one embodiment, the polyethylene composition comprises poly(ethylene-co-1-butene) or poly(ethylene-co-1-hexene), preferably poly(ethylene-co-1-butene), and the number of co monomer is from 0.1 to 5 mol.% based on the weight of the polymeric composition, mainly on the mass NM polyethylene plastic bag is Oh compositions.

The polyethylene compositions of the present invention in one embodiment is characterized by a density in the range from 0,940 g/cm3to 0,970 g/cm3in another embodiment, from 0,942 g/cm3to 0,968 g/cm3in yet another variant from 0,943 g/cm3to 0,965 g/cm3and in another embodiment from 0,944 g/cm3to 0,962 g/cm3and the desired interval density polyethylene compositions include any combination of any upper density limit with any lower limit of the density is described in this context.

The polyethylene compositions of the present invention are characterized by the molecular-mass characteristics, which determine, for example, by GPC method described in this context. The polyethylene compositions of the present invention in one embodiment is characterized by the value srednetsenovoj molecular weight (Mn) of from 2,000 to 70,000, in another embodiment from 10000 to 50000, and in yet another embodiment, the size of the mass-average molecular weight (Mw) from 50,000 to 2000000, in another embodiment from 70000 to 100000, and in another embodiment from 80,000 to 800000. Bimodal polyolefins of the present invention in one embodiment are also characterized by the value of the z-average molecular weight (Mz) in the range of more than 200,000, in another embodiment, more than 800000, in another embodiment, more than 900000, in another embodiment, more than 1,000,000, in another embodiment, more than 1100000, in others the d variant more than 1200000 and in another embodiment less than 1,500,000, when the desired interval of values of Mn, Mw or Mz includes any combination of any upper limit with any lower limit, as described in this context.

The polyethylene compositions of the present invention are characterized by a molecular weight distribution or, in other words, the ratio of mass-average molecular weight to srednetsenovoj molecular mass (Mw/Mn) or "index polydispersity" from more than 30 or 40 in the preferred embodiment, and in one embodiment in the range from 30 to 250, in another embodiment from 35 to 220 in one embodiment, from 40 to 200, with the desired option includes any combination of any upper limit with any lower limit, as described in this context. Polyethylene compositions are also characterized by the "z-average" molecular weight distribution (Mz/Mwin one embodiment, from 2 to 20 alternatively from 3 to 20, in another embodiment, from 4 to 10, in another embodiment from 5 to 8, and in yet another embodiment, from 3 to 10, with the desired interval value includes any combination of any upper limit with any lower limit, as described in this context.

The polyethylene compositions of the present invention in one embodiment are characterized by a melt index (MI or I2measured by method ASTM-D-1238-E 190°C/2,16 kg) in one embodiment in the range from 0.01 the g/min to 50 DG/min, in another embodiment, from 0.02 DG/min to 10 DG/min in yet another variant from 0.03 DG/min to 2 DG/min, while the desired interval value includes any combination of any upper limit with any lower limit, as described in this context. The polyethylene compositions of the present invention in one embodiment is characterized by the flow index (FI or I21measured by method ASTM-D-1238-F, 190°C/21,6 kg) in one embodiment in the range from 4 DG/min to 20 DG/min in another embodiment, from 4 DG/min to 18 DG/min in yet another embodiment, from 5 DG/min to 16 DG /min in another embodiment, from 6 DG/min to 14 DG/min, while the desired interval of values of I21includes any combination of any upper limit with any lower limit, as described in this context. In some embodiments, the polyethylene composition according to the present invention is characterized by the ratio of melt index (I21/I2from 80 to 400, in another embodiment from 90 to 300, and in one embodiment from 100 to 250, and in another embodiment from 120 to 220, and the desired interval of values of I21/I2includes any combination of any upper limit with any lower limit, as described in this context.

In another embodiment, the polyethylene compositions include more than 50 wt.% VM polyethylene based on the total weight of the composition, in another embodiment, more than 55 wt.%, in yet another variant 50 is about 80 wt.%, in another embodiment, from 55 to 75 wt.% and in another embodiment from 55 to 70 wt.% the content in wt.% determined by the GPC method.

Moreover, the polyethylene compositions of the present invention in one embodiment is characterized by a dynamic viscosity η 200°and 0.1/s from 100 CP to 3000 CP, in another embodiment from 300 to 1400 KP KP, in another embodiment from 350 CP to 1000 CP, in another embodiment from 400 to 800 KP KP and in another embodiment from about 500 CP to about 700 CP. Values of dynamic viscosity specified in the Examples in the present description, was measured by the method ASTM D4440-95 in nitrogen atmosphere (the head clearance viscometer 1.5 mm parallel plates of 25 mm at 200°and 0.1/s).

Another object of the present invention the polyethylene composition designed to produce films, characterized by an elasticity of more than 0.60, in another embodiment, more 0,61, in another embodiment, more than 0.62 in another embodiment, more 0,63.

The individual components of the polyethylene composition described with reference to certain embodiments of the invention, and in one embodiment, the polyethylene composition comprises one VM polyethylene and one NM polyethylene; and in another embodiment, the polyethylene composition includes mainly one VM polyethylene and one NM polyethylene.

In one embodiment, the molecular weight distribution (Mw/Mn) VM polyethylene is interval is 3 to 24, in another embodiment, from 4 to 24, in another embodiment, from 6 to 18, in another embodiment from 7 to 16, and in one embodiment from 8 to 14, with the desired interval value includes any combination of any upper limit with any lower limit, as described in this context. VM polyethylene in one embodiment, is characterized by a mass-average molecular weight in the range of more than 50,000, in another embodiment from 50000 to 1000000, in another embodiment from 80,000 to 900000, in another embodiment from 100000 to 800000 and in one embodiment from 250,000 to 700,000, with the desired interval value includes any combination of any upper limit with any lower limit, as described in this context. Mass fraction VM polyethylene in the polyethylene compositions varies depending on the desired properties of the polyethylene compositions, in one embodiment, the mass fraction VM polyethylene is the interval from 0.3 to 0.7, in another preferred embodiment, from 0.4 to 0.6, and in another preferred embodiment, from 0.5 to 0.6.

In one embodiment, the molecular weight distribution (Mw/Mn) of the polyethylene is the interval from 1.8 to 6, alternatively from 2 to 5 and in another embodiment from 2.5 to 4, wherein the desired interval value includes any combination of any upper limit with any lower limit, as described in this context. In one embodiment, the mass-average molecular mass N the polyethylene is in the range from 2000 to 50000, in another embodiment, from 3000 to 40000, in another embodiment from 4,000 to 30,000, while the desired interval of values of the NM content of polyethylene in the polyethylene composition comprises any combination of any upper limit with any lower limit, as described in this context. In another embodiment, the medium-mass molecular mass NM polyethylene is less than 50,000, in another embodiment less than 40000, in another embodiment less than 30,000, in another embodiment less than 20,000, in one embodiment, less than 15,000, and in another embodiment less than 13000. In one embodiment, the value of I2for NM polyethylene is from 0.1 DG/min to 10,000 DG/min, alternatively from 1 DG/min to 5000 DG/min in yet another variant from 100 DG/min to 3000 DG/min, and the value of I21is from 2.0 DG/min up to 300,000 DG/min in another embodiment, from 20 DG/min up to 150,000 DG/min in one embodiment, from 30 DG/min to 15,000 DG/min, while the desired interval of values of I2and I21includes any combination of any upper limit with any lower limit, as described in this context. The value of I2and I21for NM polyethylene determined using any techniques known in the art, and in one embodiment, the determine method of treatment convolution on the GPC curve.

Granules of plastic material produced by the methods described in this context to obtain polyethylene HDMI is tion. Optionally, the polyethylene composition is mixed with one or more additives. Depending on the physical method of producing a plastic mixture with one or more additives before turning the mixture in the final film product spend quite intensive mixing to form a homogeneous mixture. One way of mixing additives with the polyolefin is in the contacting of the components in the drum or other devices for physical mixing, and the polyolefin get in the reactor in the form of granules. If necessary, this stage is followed by mixing in the melt in the extruder. Another way of mixing is the mixing in the melt polyolefin granules with the additives directly into the extruder, brabender or other device for mixing the melt, preferably in the extruder. Examples of suitable extruders include extruders design Farrel and Kobe. Because it is not supposed that mixing with additives affect the defined properties of the polyethylene compositions described in the Examples, density, rheological and other properties of the polyethylene compositions was determined after mixing the compositions with additives.

Examples of additives include, without limitation, processing additives, such as forecaster, glycols and polika nolactone, antioxidants, nucleation agents, absorbents acids, plasticizers, stabilizers, anticorrosion agents, pore substances, other adsorbents ultraviolet radiation, such as antioxidants, leading to rupture of the chains and the like, extinguishers, antistatics, glidant, pigments, dyes and fillers and curing agents, such as peroxide.

First of all, the content of antioxidants and stabilizers such as organic phosphites, amines retarded conformation, finasteride antioxidants in the polyolefin compositions of the present invention is in one embodiment from about 0.001 to 2 wt.%, in another embodiment, from 0.01 to 1 wt.% in one embodiment, from 0.05 to 0.8 wt.%; in other words, from 1 to 5000 ppm million calculated on the total weight of the polymer composition, and in a more preferred embodiment, from 100 to 3000 ppm million Examples of suitable organic phosphites, without limitation, include Tris(2,4-di-tert-butylphenyl)fosfat (IRGAFOS 168) and diphosphite, di(2,4-di-tert-butylphenyl)pentaerythritol (ULTRANOX 626). Examples of amines with inhibited conformation, without limitation, include poly[2-N,N'-di(2,2,6,6-tetramethyl-4-piperidinyl)hexanediamine-4-(1-amino-1,1,3,3-TETRAMETHYLBUTYL)centresin] (CHIMASORB 944) and bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN 770). Examples of the phenolic antioxidant is in, without limitation, include pentaerythrityl ether of tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (IRGANOX 1010), 1,3,5-three(3,5-di-tert-butyl-4-hydroxybenzenesulfonate (IRGANOX 3114), Tris(nonylphenyl)fosfat (TNPP) and octadecyl-3,5-di-(tert)-butyl-4-hydroxyhydrocinnamate (IRGANOX 1076), other additives include zinc stearate and zinc oleate.

In one embodiment, the filler content is from 0.1 to 5 wt.%, in another embodiment, from 0.1 to 2 wt.%, in yet another embodiment, from 0.2 to 1 wt.% and most preferably from 0.02 to 0.8 wt.%. The required fillers include, without limitation, titanium dioxide, silicon carbide, silicon dioxide (and other besieged or neozhidannye silicon oxides, antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, Apatite, powdered barite, barium sulphate, magnesium oxide, carbon black, acetylene black, dolomite, calcium carbonate, talc and connection hydrotalcite ions Mg, CA, or Zn with Al, Cr or Fe and CO3and/or HPO4, hydrated or non hydrated, powdered quartz, carbonate-magnesium chloride, fiberglass, clay, aluminum oxide and other oxides and metal carbonates, metal hydroxides, chromium, phosphorus and brominated flame retardants, antimony trioxide, silicon dioxide, silicone, and mixtures of the above compounds. Such fillers primarily on the receive any other fillers and pore-forming fillers and the substrate, known in this technical field.

Basically fillers, antioxidants and other additives included in the composition of the polyethylene compositions of the present invention in amounts of less than 2 wt.%, preferably less than 1 wt.% and more preferably less than 0.8 wt.% calculated on the total weight of the composition.

In one embodiment, during the formation of pellets in a plastic composition also add the oxidizing agent as a reactive component. This object polyethylene compositions of the present invention is extruded in the presence of an oxidant, preferably oxygen, as described in the application WO 03/047839. In one embodiment, the extrusion process in the formation of the film in the polyethylene composition is added from 0.01 or 0.1 or 1 to 14 or 16 SCFM (standard cubic feet per minute) of oxygen, and the exact number depends on the type of extruder used and other conditions. In other words, in one embodiment, during extrusion of polymer composition add from 10 to 21 vol.% oxygen in the atmosphere of inert gas, such as nitrogen. In one embodiment, the extruder add a sufficient amount of oxygen for increasing values of I21/I2polyethylene compositions produced in the reactor(s), i.e. from 1 to 40% and in another embodiment from 5 to 25%. Thus obtained pellets used in isout then for the extrusion of films of the present invention in a separate installation, for example, to install Alpine.

The obtained pellets of the polyethylene composition, in the presence or in the absence of additives formed by any means in the film: forming blown or cast films or any other means for obtaining films, for example, odnosno or dvuhstoechnye film, as described in the book of Plastics Processing (Radian Corporation, Noyes Data Corp. 1986). In the most preferred embodiment, the polyethylene compositions of the present invention formed into a film as described in the book, Film Extrusion Manual, Process, Materials, Properties (TAPPI, 1992). Even more preferred films of the present invention is a film obtained by extrusion-blow process, the ways of getting mainly described, for example, in book, Film Extrusion Manual, Process, Materials, Properties, cc.16-29.

To obtain films of the present invention may use any extruders suitable for the extrusion of HDPE (density more 0,940 g/cm3)operated in any of the required conditions for the polymer compositions described in this context. Such extruders are known to experts in the art and include extruders in one embodiment with a screw diameter of 30 to 150 mm and in another embodiment from 35 to 120 mm, and the performance of such extruders is in one embodiment from 100 to 1500 lb/h, and in another embodiment from about 200 to 1000 pounds/hour In one of the variations is the use of a screw extruder, the relative length L/D of the extruder is in one embodiment from 80:1 to 2:1, in another embodiment, from 60:1 to 6:1, in another embodiment from 40:1 to 12:1 and in another embodiment from 30:1 to 16:1.

You can use a single-layer or multi-layer cylinder. In one embodiment, the use of single-layer head size from 50 to 200 mm, in another embodiment using a single-layer head size from 90 to 160 mm, and in yet another variant uses a single layer head size from 100 mm to 140 mm; in one embodiment, use a cylinder with a nominal gap of 0.6 to 3 mm, in another embodiment from 0.8 to 2 mm and in another embodiment from 1 to 1.8 mm, and the required head can include a combination of any of the options described in this context. In a preferred embodiment, the preferred performance is achieved when using a screw extruder of 50 mm and L/D ratio of 21:1.

The temperature in the zones of the extruder, cap and adapter of the extruder is in the range in one embodiment from 150°230°With, in another embodiment from 160°210°and in another embodiment from 170°190°C. In one embodiment, the temperature in the cylinder is the interval from 160°, 250°With, in another embodiment from 170°to 230°and in yet another variant of 180°210°C.

Thus, the film of the present invention in another embodiment may include l the specific variants of the present invention or a combination of any of the options described in this context. Embodiments of the present invention without limitation illustrated by the following examples without limiting the scope of the invention.

Examples

The following examples relate to gas-phase methods of polymerization, which is carried out in a reactor with a fluidized bed of catalyst, the performance of which is more than 500 lb/h (230 kg/h) product speeds ranging from 8 to 40 t/h or more, with the use of co monomer of ethylene and 1-butene, you get a plastic composition. The tables show the different samples of polymers and films obtained from these samples, as well as reaction conditions, during which selected samples ("samples"). Also described various properties of the obtained polymer products and films. The products described in examples 1 and 2, was obtained by extrusion in the absence of oxygen (without specified property), as described below, while the products described in examples 3-9 were obtained by extrusion in the presence of oxygen (with the desired properties, as described in the application WO 03/047839 included in the present description by reference. In the examples described the standard composition of the film by standard methods.

Fluidized bed reactor includes granules of polyethylene. The reactor was passivatable alkylamines, suppose the equipment with trimethylaluminum. In each cycle gazoobraznye streams of ethylene and hydrogen was admitted into the gas recirculation line, located above the fluidized bed. Gases fed into the area below the line recirculation heat exchanger and compressor. Liquid 1-butenova comonomer was introduced into the zone above the fluidized bed reactor. Control agent (if it is used, in most cases, isopropyl alcohol), which affect the cleavage of the resin and reduces pollution, especially pollution of the lower plate, served in gaseous or liquid form into the zone above the fluidized bed reactor in the gas recirculation line. Separate streams of ethylene, hydrogen and co monomer of 1-butene was regulated in such a way as to ensure the final conditions in the reactor, as indicated in each example. The gas concentration was measured using chromatograph, a built-in system of the reactor.

In examples 1 and 2 were sampled after polymerization, which was carried out for 3-4 days in one gas-phase reactor with a fluidized bed with a diameter of 8 feet and a catalyst bed height (from the bottom plate of the distributor prior to the beginning of zone expansion) 38 feet. In examples 3-9 were sampled after another cycle of polymerization, which was carried out for 3-4 days in one gas-phase reactor with a fluidized bed of catalyst diameter 11cm,3 feet and a catalyst bed height (from the bottom plate of the distributor prior to the zone extension) 44,6 feet.

In each cycle of polymerization, as described in the examples of the present invention, the bimetallic catalyst on the substrate was injected directly into the fluidized bed using purified nitrogen. The feed rate of the catalyst is regulated in such a way as to provide approximately constant level of performance. In each cycle, the catalyst was obtained in the presence of silicon dioxide, digidratirovannogo at 875°and metallocene compounds Cf2MX2where Cf denotes the n-butylsilane cyclopentadienyls ring, M stands for zirconium, and X is fluorine. The source of the titanium component of the Ziegler-Natta was TiCl4.

In each cycle of the reactive layer growing polyethylene particles maintained in a fluidized state by means of a continuous feed stream and a recycle gas that passed through the reaction zone. As indicated in the tables, in each cycle of polymerization in examples of the present invention utilized a particular temperature in the reactor and the temperature of the catalyst layer"), namely approximately 95°C. during each cycle the temperature in the reactor was maintained at approximately a constant level by increasing or decreasing the temperature of the recirculating gas to compensate for any changes in the rate of heat generation is the process of polymerization.

Polymer compositions described in the examples were subjected to extrusion in a 4-inch mixers, Farrel (or Kobe) continuous (4UMSD) at a speed of 500 lb/h, consumption specific power input 0,125 PS-h/lb, while the received pellets. We also added a set of agents, for example, polymeric compositions described in examples 1-9, included 800 ppm million product IRGANOX 1010 (pentaerythritoltetranitrate-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 200 ppm million product IRGAFOS 168 (Tris(2,4-di-tert-butylphenyl)FOSFA) and 1500 ppm million of zinc stearate. The compositions described in examples 1 and 2 were subjected to extrusion in an atmosphere of nitrogen (0% oxygen), the compositions described in examples 3-9, were subjected to extrusion in the presence of a certain amount of oxygen, as described in the application WO 03/047839.

The properties of the polymer compositions described in tables. The ratio of I21:HMW:MFR was calculated using the I21high molecular weight component and the values of I21and I2using the following empirical equation (IV):

where I21and I21determine by the method of ASTM described in this context. The ratio of I21:HMW:DSR was calculated using the I21high molecular weight component and the determined values of the dynamic viscosity using the following levels of the I (V):

where

η*x(poiz) means the complex viscosity, determined at 200°frequency x,

G'x(Dyne/cm2) is the real component of the shear modulus determined at 200°frequency x, and

G"x(Dyne/cm2) is the imaginary component of the shear modulus determined at 200°frequency (rad/s) X.

These values were determined using a dynamic rheometer Rheometrics Dynamic Stress parallel plates with a length of 25 mm, a head clearance of approximately 1.4 mm, at a voltage of 10,000 Dyne/cm2according to the method described in ASTM D4440-01, "Standard test method for plastics: Dynamo-mechanical properties, the determination of the rheological properties of the melt".

The samples described in examples 1 and 2 were processed by extrusion installation for blow molding (conditions described in table 2), the size of the screws (21 d) of the extruder is 50 mm and the extruder includes a feeding Assembly of LLDPE (catalog number Alpine 171764). The melting temperature Tmwas measured using immersion thermocouple in the host adapter near the outlet of the extruder. For cooling of the extruder used the cooled air (on the outer surface of the bladder).

The following are other methods of analysis:

The thickness of the films was measured according to the SNO method ASTM D374-94, method C.

FI (I21): flow index (I21) was measured according to ASTM D 1238 at 190°, 21,6 kg

MI (I2): melt index (I2) was measured according to ASTM D 1238 at 190°, 21,6 kg

MFR: ratio of indices of turnover and the melt was determined as the ratio of I21/I21.

Density (g/cm3) was determined using samples cut from compressed layers, which were formed according to the method ASTM D-4703-00, in the conditions of ASTM D618, methodology, and measurement was performed according to ASTM D1505-03.

Elasticity was determined by a special method on the ratio G'/G", measured at 0.1 rad/S. G' and G" were measured on the Stress rheometer Rheometer (200°With dynamic rheometer Dynamic Stree Rheometer) in oscillatory shear and constant voltage 1000 PA. The magnitude of G' and G" at 0.1 rad/s was chosen to determine the elasticity.

Complex viscosity η* measured on the Stress rheometer Rheometer at 0.1 rad/s and 200°C.

FAR: "the appearance of the films was determined by a special method, according to which the polymer was subjected to extrusion under standard conditions and the resulting film was examined visually for the presence of surface defects. The film was compared with a set of standard films and value FAR was assessed on a scale with the participation of the operator. Standard films are characterized by a magnitude FAR in the range from -50 to +50, and films with value FAR +0 and more suitable for commercial use.

The content of the gel fraction was determined using the following equipment: extruder firms Optical Control Systems GmbH (OCS), model BF-20, the system for forming films OCS, model CR-8, and a device for determination of gel OCS, model FS-5. The extruder MECHANISM 20 includes a standard screw 3/4" compression ratio 3:1) and the relative length L/D 25:1, and also includes the area of the feed zone, compression zone and the dosage. In the extruder used all solid controls, a motor for driving the screw at a variable frequency, AC, 5 zone heat, 3 zone for drum, 1 zone for measuring the melting temperature and pressure and 1 zone for the head. The head of the extruder is a cylinder-type "fish tail" with locking jaws 4" with a head clearance of approximately 20 mils. Test specimens were prepared by the company Southern Analytical, Inc., Houston TX.

System for casting films includes stainless steel dual chrome-plated and polished cooling rolls machined exact the air knife, clamping rubber rolls, push through the film determinant of the content of gel-fraction, and a device for winding film into a roll. Clamping rollers rotate separately from the cooling rolls and the rotation speed or the tension is adjustable. The system also includes a cooling unit/load the provision for cooling rollers, in which use ethylene glycol. The system also includes steel runners, sensors rupture and other nodes. Films prepared as described in examples 3-9, characterized by a thickness of 1 mil (25 microns), and the films described in the examples, comparison, C2, C3 and C5 thickness of 2 mils (50 microns).

The determinant of the content of gel-fraction includes a digital camera at 2048 pixels, halogen lamp, a computer for image processing and software Windows NT4. System camera/lamp built into the system for forming films between cooling rolls and crimping rollers, and the degree of resolution of this system is 50 μm. Such systems allow to detect the smallest defects size of 50 microns by 50 microns.

Pelleted samples were subjected to extrusion at constant temperature extrusion (180°in the feed area, 190°in other zones) and constant temperature of the cooling roll 40°C. the Speed of the extruder and the cooling rolls slightly changed depending on the sample to ensure that the education of each sample films with optimal properties. When conducting additional experiments, it was determined one set of operating conditions suitable for the extrusion of all samples. The parameters of the determinant of the content of the gel fraction was determined as follows: 10 different sizes ranging from 50-mm in increments of 100 μm, 4 different forms of the correct round shape to a more elongated shape and two levels of sensitivity (one for gels and one for black spots). Detection of gels or sensitivity was 35 on a scale from 0 to 100.

After setting the camera in the extruder filed the first sample (in most cases within about 20 min or until a stable or equilibrium conditions. Equilibrium was determined by the trend line content of the gel on the y-axis and time on the axis X. Then conducted tests on 3 m film when it is moving through the camera. To determine the repeatability of the tests were carried out in 3 successful repetitions for each sample. At the end of the assessment every 3 m2the results were printed in the form of a table. After cleaning for the first sample were testing 3 m2film of the second sample in three iterations and print the results.

All other gel samples were tested on the content of the gel in the same way, but for some specimens slightly changed the speed of the extruder, the speed of the cooling rolls and the thickness of the obtained film. During the tests were viewing the real image films (in the form of a "mosaic" images)to verify the correctness of the analysis, to avoid the repeated identification of the same gel or not to miss g who do. For granular samples was set one set of operating conditions, suitable for all samples, including film thickness, in order to compare all the results.

Tabular data of the determinant of gel-fraction normalized by the thickness. Each sample was measured in three repetitions. The data obtained in the tests used to calculate the sum of all of the gels with a size of 200 microns or less. Data from three repetitions for each sample were averaged, then the average value was divided by the thickness in mils. The results of the determinant of gel-fraction were expressed as the number of gels with a size less than 200 microns in the sample film 3 m2or a 7.62×10-5m3.

Voltage instant hit F50measured on the film by the method of ASTM D 1709, method A.

Gap Elmendorf was measured on the film by the method of ASTM D 1922.

The secant modulus 1% is measured on the film by the method of ASTM D 882.

Helpanimals chromatography (GPC). The value of Mw/Mn, Mz/Mw, Mw (AVG non-mass molecular weight) and Mn (Brednikova molecular weight) and the content of the VM component in%, etc. was determined by GPC method on columns with crosslinked polystyrene using a sequence of columns with different pore size: 1 column less than 1000, 3 columns with different pore size 5×10(7); the solvent is 1,2,4-trichlorobenzene at 145°C, detection of the refractive index. According to Sporadicaly content of high-molecular and low-molecular components by the method of treatment convolution using models Wesslau, where the value of P is reduced to a low molecular weight peak to 1.4, as described in article Ewghaweh & R.F.Abbott, Analysis of molecular weight distribution using multicomponent models, ACS Symp. Ser., 197 (Comput. Appl. Appl. Polym. Sci.), 45-64 (1982).

In the example for comparison 2 ("C2") described bimodal poly(ethylene-co-1-butene) Dow UNIPOL™ II 2100 obtained in two-stage gas-phase reactor in the presence of a catalyst of Ziegler-Natta.

In example 3 for comparison ("C3") described bimodal poly(ethylene-co-1-butene) Mitsui HD7960 obtained in the two-stage emulsion method (company ExxonMobil Chemical Co).

In the example for comparison 4 (C4) described a bimodal poly(ethylene-co-1-butene) Mitsui HD7755 obtained two-stage emulsion method (company ExxonMobil Chemical Co).

In the example for comparison 5 (C5) described a bimodal poly(ethylene-co-1-butene) Alathon™ L5005, received a two-step method (company Equistar Chemicals).

Described in examples 1 and 2 polymer compositions obtained in one gas-phase reactor in the presence of a bimetallic catalyst, as described in this context, characterized by unexpected superior technological characteristics in comparison with the well-known bimodal polymers obtained in the two reactors. Lower power, as shown in figures 1 and 2, represents a significant advantage for p is izvodstva films, because the compositions of the present invention can be obtained in a simple way, which leads to a decrease in their market value. These results are indeed surprising, since the value of I21for the samples described in examples 1 and 2, compared with values for the samples obtained in the examples for comparison, and, therefore, the amount of consumed power for forming films through the head of the extruder should increase and not decrease.

Another advantage is the significantly lower melt temperature of the samples described in examples 1 and 2, compared with the samples in the examples for comparison, which leads to the improvement of their technological characteristics. In the examples of the present invention described melt temperature of less than 180°and in one preferred embodiment, less than 179°while maintaining a high specific speed at the exit of the extruder crosshead at least 10 lbs of polymer/HR/inch circumference head and high performance. Thus, when equal loads of the engine and/or the pressure in examples 1 and 2 compared with example C4 performance should be higher by at least 1,90 pounds of polyethylene/HR/rpm (0.83 kg/h/rpm) at equal temperatures of the melt.

Conditions for obtaining polyethylene compositions in the reactor, relevant is the context for the films in examples 3-9, shown in table 3 below. The properties of the polyethylene compositions in the respective examples are shown in table 4. To obtain the films described in examples 3-9, to determine the ratio Tm≤235-3,3 (I21) and other variants used the following apparatus and conditions: extrusion system with Alpine screw extruder of 50 mm, the relative length L/D 21:1, the temperature profile in the extruder 180°and in the area of the head of the extruder 190°ratio BUR 4:1 ratio (when blown, i.e. the ratio of the diameter of the original bubble to the diameter of the head of the extruder), the output capacity 200 lb/HR and head size of 120 mm with a gap of 1.4 mm using auger design high density, one air clamping ring (with chilled air) and internal stabilizer bubble, the size of the screw 21 d of 50 mm HDPE and site supply of HDPE (catalog number Alpine 116882). The melt temperature Tmwas measured with the use of an immersion thermocouple in the host adapter near the outlet of the extruder. The samples described in examples 3-9, were treated in the presence of oxygen (films with the desired properties). The extrusion conditions and properties of the films obtained in examples 3-9, described in tables 5 and 6.

Samples obtained in examples 3-9, characterized by the absence of smell. Despite sample processing, opisannyh examples 3-9, oxygen (which, thus, are characterized by the average large values of I21and I2), they have the advantages of the present invention, since such polymers can be processed in an easier way compared with polymers known in the prior art.

Table 3.

The conditions of polymerization of the samples described in examples 3-9
DescriptionUnits3456789
Qty PE within 24 hourstons156156156156156156156
H2/C2mol/mol0,00850,00850,0090,0090,0090,0090,009
With4/S2mol/mol0,02720,02720,0210,0210,0210,01830,0183
Relationship With4/S2in the streamkg/kg0,01660,01660,01220,01220,01220,0122 0,0122
The partial pressure2kPa1400140014001400140014001400
Activity Tikg PE/kg of catalyst6766*53275927676258195915
The amount of TMA in the reactorwt. part./million103*96102107101123
The temperature in the reactor°95959595959595
* the amount was not determined, it is assumed to be approximately equal to the previously obtained data

td align="center"> 26
Table 4.

Properties of polyethylene films obtained as described in examples 3-9, and the examples for comparison
ExampleDensity (g/cm3)I21(°C/min)I21/I2Mw/Mnelasticity
C20,94910,381600,68
C30,95211,9133-0,60
C50,9508,6152-0,64
30,9498,39137840,62
40,9499,38157830,65
50,94911,12168900,62
60,9488,09146820,61
70,9478,61146810,61
80,95010,01174910,64
90,95111,51961100,65

C5
Table 5.

Other properties of the polyethylene obtained as described in examples 3-9, and the examples for comparison
St-inEd.3456709C2C3
The properties of the polymer
HM Mw782386208644869887097959638921454--
BM Mw444443480543505190539136456299494016493254481868--
BM MWD8,57,37,27,66,57,0to 12.04,3--

212
Table 6.

Properties and conditions of extrusion films obtained as described in examples 3-9, and the examples for comparison
St-inEd.3456789C2C3C5
The conditions of extrusion
The pace. repl.°201196195,5206204194193209200,5
PressurePound/square inch8550820082508980878082108110820079608450
Engine load%77%71%74%78%77%75%74%82%77%80%
Performance.lb/HR/rpm1,161,171,181,171,171,181,181,181,191,19
Thicknessmil0,50,50,50,50,50,50,50,50,50,5
BUR4:14:14:14:14:14:14:14:14:14:1
FAR40/5040/5040/5040/5040/5040/5050505040
Content. gelȀ 19934362932,53128-21833
DDIg182-201178180194-219270166
Gap MDg/mil21-24202225-241722
Gap TDg/mil30-31322731-415327
Limit durable. at break MDpound/square inch11632-11389123241115611140-122281101911406
Limit durable. at break TDpound/square inch11639-10942104041227510863-127461178410816
Rel. UDL. when Rast. MD%278%-251%252%275%-299%408%279%
TD Rel. udlp Rast.%278%-273%304%288%259%-322%356%385%
Before. fluent. MDpound/square inch5840-5376600957865374-518653255293
Before. fluent. TDpound/square inch4697-4575454847254568--43354627
Bit. UDL. MD%3%-4%5%5%5%--8%5%
Bit. UDL. TD%6%-4%4%4%4%--5%6%

The films described in examples 3-9 are of high quality, as evidenced by high values of FAR and low maintenance gel-f the shares. When equal quantities FAR the samples described in examples 1 and 2, they are also characterized by the same low content of gel-fraction. Therefore, treatment with oxygen does not affect the quality of the film.

Moreover, the advantages of the films of the present invention is confirmed by the following data. Especially when relatively high performance is significantly reduced engine load, a certain percentage of the maximum possible for this device to engine load, i.e. the load is less than 77-78% for examples 3-9 compared with each sample obtained in the examples for comparison, for which the load is much higher. In addition, the melt temperature for the samples obtained in examples of the present invention, is significantly lower as compared with examples for comparison. The samples described in examples 3-9, subject also to the ratio of Tm≤235-3,3 (I21), while the polyethylene composition is extruded with capacity from 1 to 1.5 lb/HR/inch, as shown on the graph of figure 6. Moreover, a more General expression Tm≤Tmx-3,3 (I21also occurs when comparing examples 1 and 2 and examples 3 to 9, although each set of samples was subjected to extrusion in different conditions and with different designs of screw extruders.

First of all the advantages to the society of the present invention are obvious when comparing loads of engines (%) and temperature of the melt samples described in examples 3-9 and the examples for comparison, as indicated in table 5, and graphs in Fig.6 and 7. While for the samples described in the examples of the present invention, there is a tendency to reduce the temperature of the melt and load of the engine when the magnitude of I21for comparative samples these values increase.

As follows from comparison of the values of performance, melt temperature and engine load, the present invention offers a significant improvement over the prior art, even in comparison with the prior art, in which is described a bimodal products obtained in a single reactor, as described in the article N.-T. Liu and others, Macromol. Symp.195, 309-316 (July, 2003). Films prepared as described in the work of Liu and others, of polymers characterized by technological parameters: the value of I216,2°C/min and a density of 0.95 g/cm3not have such advantages as film of the present invention. Therefore, the present invention offers a significant improvement over the prior art, i.e. compared to the bimodal polymers with values of I21less than 20 and a density in the range from 0,930 to 0,970 g/cm3and this merit is quite significant given the large to the richest polymers, recyclable industrial extruders.

Although the present invention is described and illustrated with reference to certain variations in its implementation, specialists in the art should understand that there are many possible modifications not described in this context. In this regard, the scope of the invention is only defined in the attached claims. Moreover, certain features of the present invention is indicated at intervals from a number of upper limits to the number of lower limits. It should be understood that all of the intervals obtained by any combination of these limits is included in the scope of the present invention, unless otherwise indicated.

1. Film comprising a polyethylene composition, which is characterized by the density of 0,940 to 0,970 g/cm3, the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 50,000, and low-molecular component, characterized by a mass-average molecular weight of less than 50,000; and the value of the melt index (I21)measured by method ASTM-D-1238-F, 190°C/21,6 kg, from 4 to 20 DG/min, and the polyethylene composition is subjected to extrusion at a melt temperature Tm, the value of which satisfies the following relationship:

Tm≤235-3,3 (I21/sub> ),

moreover, the polyethylene composition is subjected to extrusion performance from 1 to 1.5 lb/HR/rpm, and the resulting polyethylene composition film is characterized by a value of the content of the gel fraction is less than 100.

2. The film according to claim 1, characterized in that the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 50,000, and low-molecular component, characterized by a mass-average molecular mass of less than 40000.

3. The film according to claim 1, characterized in that the value of Mw/Mn of the polyethylene composition is more than 35.

4. The film according to claim 1, characterized in that the value of Mw/Mn of the polyethylene composition is more than 50.

5. The film according to claim 1, characterized in that the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 150,000, and low-molecular component, characterized by a mass-average molecular mass of less than 35000.

6. The film according to claim 1, characterized in that the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 250,000, and a low molecular weight component, characterized by a mass-average molecular mass of less than 35000.

7. The film according to claim 1, characterized in that the elasticity of the polyethylene is howl song is more than 0.60.

8. The film according to claim 1, characterized in that the polyethylene composition does not contain solid substances that can impair the quality of the film.

9. The film according to claim 1, characterized in that the film will receive a multistage method, including:

(a) obtaining a polyethylene composition comprising the inclusion of a high molecular weight polymer to low molecular weight polymer when contacting ethylene and C3-C12-α-olefins, alkylamine and bimetallic catalytic composition,

(b) extrusion of the polyethylene composition with the formation of granules with the optional addition of oxygen, thus obtain pellets of the polyethylene composition,

(C) isolation of the pellets of the polyethylene composition,

(g) the extrusion of the pellets of the polyethylene composition in the extruder to form a film.

10. The film according to claim 9, characterized in that in stage (b) in the polyethylene composition is added from 0.01 to 14 standard cubic feet per minute (SCFM) of oxygen.

11. The film according to claim 1, characterized in that the polyethylene composition was prepared in the same gas-phase reactor with continuous action.

12. The film according to claim 1, characterized in that the content of the gel fraction in the film is less than 50.

13. The film according to claim 1, characterized in that the content of the high molecular weight component according to gel chromatography GPC) is more than 50 wt.% calculated on the total weight of the polyethylene composition.

14. The film according to claim 1, characterized in that the extrusion of polyethylene compositions performed when the engine load is less than 80% of the maximum possible load on the engine.

15. Film comprising a polyethylene composition, which is characterized

a) density of 0,940 to 0,970 g/cm3,

b) the value of Mw/Mn, making up more than 35;

the value of the melt index (I21)measured by method ASTM-D-1238-F, 190°C/21,6 kg, from 4 to 20 DG/min;

and additionally characterized by the fact that the polyethylene composition is subjected to extrusion at a melt temperature Tm, the value of which satisfies the following relationship:

Tm≤235-3,3 (I21),

moreover, the polyethylene composition is subjected to extrusion performance from 1 to 1.5 lb/HR/rpm, and the resulting polyethylene composition film is characterized by a value of the content of the gel fraction is less than 100.

16. The film according to item 15, wherein the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 50,000, and low-molecular component, characterized by a mass-average molecular mass of less than 40000.

17. The film according to item 15, wherein the value of Mw/Mn of the polyethylene composition is more than 35.

18. The film according to item 15, great is the rpm die, what is the value of Mw/Mn of the polyethylene composition is more than 50.

19. The film according to item 15, wherein the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 150,000, and low-molecular component, characterized by a mass-average molecular mass of less than 35000.

20. The film according to item 15, wherein the polyethylene composition comprises high molecular weight component, characterized by a mass-average molecular weight of more than 250,000, and a low molecular weight component, characterized by a mass-average molecular mass of less than 35000.

21. The film according to item 15, wherein the elasticity of the polyethylene composition is more than 0.60.

22. The film according to item 15, wherein the polyethylene composition does not contain solid substances that can impair the quality of the film.

23. The film according to item 15, wherein the film get multistage method, including:

(a) obtaining a polyethylene composition comprising the inclusion of a high molecular weight polymer to low molecular weight polymer when contacting ethylene and C3-C12-α-olefins, alkylamine and bimetallic catalytic composition,

(b) extrusion of the polyethylene composition with the formation of granules with the optional addition of oxygen is, thus obtain pellets of the polyethylene composition,

(C) isolation of the pellets of the polyethylene composition,

(g) the extrusion of the pellets of the polyethylene composition in the extruder to form a film.

24. The film according to item 23, wherein in stage (b) in the polyethylene composition is added from 0.01 to 14 standard cubic feet per minute (SCFM) of oxygen.

25. The film according to item 15, wherein the polyethylene composition was prepared in the same gas-phase reactor with continuous action.

26. The film according to item 15, wherein the content of the gel fraction in the film is less than 50.

27. The film according to item 15, wherein the content of the high molecular weight component according to gel chromatography (GPC) is more than 50 wt.% calculated on the total weight of the polyethylene composition.

28. The film according to item 15, wherein the extrusion of the polyethylene compositions performed when the engine load is less than 80% of the maximum possible load on the engine.



 

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37 cl, 5 dwg, 3 tbl, 7 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to soft polymer compositions containing large amount of inorganic fillers. Composition according to invention contains 20-60% heterophase polyolefin composition (I) and 40-80% inorganic filler (II) selected from fire-retardant inorganic fillers and inorganic oxides or salts. Moreover, heterophase polyolefin composition I includes 8 to 25% crystalline polymer component (A) selected from propylene homopolymer, propylene copolymers, and mixtures thereof, and 75 to 92% elastomer fraction (B) composed of at least elastomeric propylene 04 ethylene copolymer with 15-45% of at least one α-olefin. Heterophase polyolefin composition I is characterized by solubility in xylene at room temperature above 50%, while intrinsic viscosity of xylene-soluble fraction ranges between 3.0 and 6.5 dL/g. Polyolefin compositions of invention find their use as substitute of plasticized polyvinylchloride.

EFFECT: increased plasticity of materials at the same good thermoplastic properties.

15 cl, 1 dwg, 2 tbl, 10 ex

FIELD: biopolymers.

SUBSTANCE: invention relates to production of plastic masses based on ethylene and vinylacetate copolymer for mould products useful in food processing industry and agriculture. Claimed composition contains 50-68.7 mass % of ethylene and vinylacetate copolymer, biologically degradable filler containing rye flour in amount of 30-48,7 mass % and additives such as surfactant in amount of 0.1 mass %, maize amylacetate in amount of 1 mass %, and 0.2 mass % of methylcellulose.

EFFECT: new biologically degradable composition.

2 tbl

FIELD: polymeric materials.

SUBSTANCE: invention relates to polymeric composition materials, namely, to composition of polymeric composition of multifunctional modifying agent. Proposed multifunctional modifying agent comprises the following components, wt.-%: copolymer of ethylene with vinyl acetate, 2-20; calcium carbonate, 2-25; oleic acid amide, 2-20, and high pressure polyethylene, up to 100. Invention provides expanding functional properties of modifying agent and enhancing technological tasks in processing polymers. Invention can be used in making articles by extrusion or under pressure in casting machines of auger type and nontoxic materials using for package of foodstuffs an/or medicinal preparations.

EFFECT: valuable properties of modifying agent.

6 tbl, 6 ex

FIELD: chemical industry; metal working industry; methods of production of the adhesive composition used for deposition of the coatings on the metal surfaces.

SUBSTANCE: the invention is pertaining to the methods of production of the adhesive composition intended for deposition on the steel surface as the primer of the adhesive intermediate layer deposited on the steel surfaces under the polyolefin protecting coatings. The technical problem of the invention is the reduced duration of the contact of the adhesive composition melt with the surface of the metal at conservation of the high adhesive strength. The technical problem is being solved by that the method provides for the combined mixing of the ethylene copolymer and vinyl acetate or the combination of the copolymers of the ethylene and vinyl acetate differing in the contents of the vinyl acetate groups with polyisocyanate, caoutchouc and the filling agent. Premix the polyisocyanate containing of no less than two isocyanate groups with the filling agent consisting of the talcum or the mica in the conditions, when the polyisocyanate is in the liquid state, with the subsequent joint mixing of all the components. At that select the copolymer of ethylene and vinyl acetate with the contents of the vinyl acetate groups from 10 up to 45 %.

EFFECT: the invention ensures the reduced duration of the contact of the adhesive composition melt with the surface of the metal at conservation of the high adhesive strength.

1 tbl, 10 ex

Medical container // 2311165

FIELD: medical facilities.

SUBSTANCE: invention provides medical container, which is used to fill with blood, drug, and the like. Container is manufactured from film or sheet having at least one high-density polyethylene layer and polymer layer containing polyolefin composition, wherein said polyolefin composition comprises (A) at least one propylene-containing polymer selected from group consisting of (A1) propylene-containing polymer composition in the form of mixture of (A11) propylene polymer and (Q12) elastomeric ethylene-propylene copolymer and (A12) propylene-containing block-copolymer; and (B) ethylene-containing copolymer containing ethylene and at least one α-olefin having 4 or more carbon atoms and characterized by refractory index of xylene-soluble fraction of this polyolefin composition equal to 1.480-1.495; said high-density polyethylene containing 70% or more high-density polyethylene having density 0.950 g/cc or higher, while high-density polyethylene layer being disposed on at least one (inner or outer) side of container.

EFFECT: achieved temperature resistance high enough to enable sterilization at 121°C or higher and manifested excellent clearness, shock strength, elasticity, and resistance to conglomeration.

5 cl, 3 tbl, 14 ex

FIELD: rubber industry, in particular polymer composition.

SUBSTANCE: claimed composition contains (mass %): rubber 100; sulfur vulcanizating agent 2.5-3.5; promoter group 0.8-2.0; vulcanization activator 10-20; filler such as carbon black 50-70; plasticizer 2-3; anti-aging agent 3-6; ethylene/vinyl acetate copolymer containing 26-30 % of vinyl acetate 3-5.

EFFECT: copolymer with increased tear resistance.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to structural polymer compositions based on ultra-high molecular polyethylene and fibrous fillers and may be used to manufacture plain bearings, seals, gear wheels and other structural machinery. Composition contains ultra-high molecular polyethylene and 5 to 25 wt % of fibrous filler. A blend of fibers 2-3 mm long is used as fibrous filler. It consists of 70 wt % of polyoxadiazole fiber and 30 wt % of cotton yarn.

EFFECT: improved compression strength, impact strength and antifriction properties.

5 ex

FIELD: chemistry.

SUBSTANCE: thermoplastic elastomeric composition contains polypropylene, polyethylene, triple ethylene-propylene-diene copolymer, sulfur, primary and secondary vulcanisation accelerators, stearic acid and zinc oxide. Rubber crumb and bitumen are introduced into composition additionally. Combination of components in definite ratio improves rheological properties of composition and, correspondingly its processability.

EFFECT: high-strength products, of high ozone and atmosphere stability, resistance, can be practically fully utilised after expiry of product life.

5 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: method of production of polydisulfides of aromatic series, applied as stabilisers of oxidation processes in thermoplastic polymers by dissolution of initial products (for instance, resorcin, gallic acid, hydroquinone, etc.) and possibly dissolution of obtained polymer, containing disulfide groups by carrying out reaction in two stages: 1-st stage is carried out at room temperature and finish after introduction of sulfur monochloride solution into reaction medium during 15-30 minutes, 2-nd stage is carried out in process of reaction medium heating, but not higher than solvent boiling temperature, until complete stop of hydrogen chloride formation, then precipitator is added, precipitated product is washed with water, then dried. Polysulfides obtained by said method can be applied for inhibiting oxidation processes in thermoplastic polymers in concentration 0.15-1.50 wt % under service conditions. Application of said compounds allows 1.5 time reducing of rate of oxidation processes in thermoplastic polymers in comparison with known stabilisers (for instance, phenosane). Advantages of claimed method lie in the following: time of reaction of synthesis is reduced more than 10 times; reaction temperature is reduced, heating of reaction medium being carried out only in conducting second stage of synthesis; reaction output increases and makes not less than 85%; amount of solvent is reduced, ration of the latter to initial substances being not more than 4 to 1.

EFFECT: reduction of reaction time, reaction temperature, increase of reaction output.

7 cl, 17 tbl, 23 ex

FIELD: chemistry.

SUBSTANCE: invention refers to rubber-processing industry, in particular to development of thermoplastic elastomeric rubber materials that can be used for manufacturing of various extrusion profiles and moulded flexible parts for automotive, cable, light industry and construction engineering. Thermoplastic elastomeric material is made of composition including, wt. fraction: rubber - 100, polyolefin - 2-150, vulcanising agent 1-15, vulcanisation activator 3-10, stearic acid - 0.75-2.0, oil - 25-500 and bulk additive - 1-100, modified diene-containing thermoplastic elastomer, such as hydrooxylated, halogenated, hydrogenated or hydrohalogenated dienevinylaromatic thermoplastic elastomer - 5-150, release agent - zinc stearate, calcium stearate or their mixture - 0.1-2.0. As oil additive the material contains paraffine-naphthene oils, as bulk additive is contains powder filler with particle size 100 nanometers to 20 microns, selected from the group: schungite, kaolin, chalk, talcum powder or carbon white, as well as mixed mineral additive with 0.04-4.0 mass % of industrial carbon. Thus as rubber thermoplastic elastomeric material contains ethylene-propylene-diene rubber with propylene chains 27 to 40 mass %, and as the third comonomer is contains ethylidene norbornene or dicyclopentadiene in amount 2-10 mass %, as well as butyl rubber, chlorbutyl rubber, brominated butyl rubber, polyisoprene rubber, butadiene-styrene rubber, or polybutadiene rubber. As polyolefin it contains isotactic polypropylene, polyethylene or their mixture at ratio of polyethylene mixed with isotactic polypropylene in amount of 5-95 mass %.

EFFECT: production of material possessing high technological and physical-mechanical properties, melt processability to products without vulcanisation by moulding under pressure or extrusion, low density, high fullness by oil.

5 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to foam composition for cables and to telecommunications cable containing foam composition. Foam composition of density 85 kg/m3 to 120 kg/m3 is produced by heating up the olefin polymer, mainly, with foaming initiator added to molten state. Molten mixture is extruded under pressure through draw plate using foaming agent containing atmospheric gas, e.g. carbon dioxide, nitrogen or air, and additional foam-blowing agent of boiling point within -65°C to +50°C, selected from hydrofluorocarbons, hydrochlorofluorocarbons or perfluoro compounds. As olefin polymer mixture contains high density polyethylene, average density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene or their combinations. Cable is produced by extruding foam composition to signal-carrying conductor and coating signal-carring conductor embedded in foam material with suitable conducting screen.

EFFECT: produce telecommunication cable of low-loss signal; mixture of foaming agents is ecologically comprehensible, not inflammable and nontoxic and allows for considerable reduction of foam density maintaining number of open pores at comprehensible level.

15 cl, 9 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to compositions of high-molecular compounds, in particular, to compositions of homopolymers of vinyliden fluoride. Description is given of the composition based on polyvinyliden fluoride, containing polyvinyliden fluoride, as well as an elastomer, in the form of butadiene-styrene thermoplastic elastomer, in quantity of 15-30% of the mass, and extra 3-8% mass of high pressure dispersed polyethylene, irradiated in an oxygen containing medium, to an absorbed dose of 100-400 kGY.

EFFECT: increased tribotechnica characteristics, reduction of frictional coefficient and increased wear resistance of the composition based on polyvinyliden fluoride.

1 cl, 2 tbl, 7 ex

FIELD: chemistry; insulation.

SUBSTANCE: invention pertains to a cable with a coating layer, made from waste materials. The cable consists of at least, one conductor with at least one transfer element and at least one layer of coating. The coating material contains between 30 mass % and 90 mass % of the overal mass of the coating material, at least, first polyethylene with density not more than 0.940 g/cm3 and melt flow index from 0.05 g/10 min. to 2 g/10 min., measured at 190°C and a load of 2.16 kg in accordance with standard ASTM D1238-00, and quantity from 10 mass % to 70 mass % of the overall mass of the coating material, at least, second polyethylene with density of more than 0.940 g/cm3. The first polyethylene is obtained from waste material. Use of at least, one polyethylene with density of more than 0.940 g/cm3 in the recycled polyethylene allows for obtaining a layer of coating, capable of providing for mechanical characteristics, in particular, breaking stress and tensile strength, comparable to characteristics of primordial polyethylene. The stated coating layer is preferably used as an external protective coating.

EFFECT: obtaining of a new type of cable insulation.

43 cl, 9 dwg, 4 tbl, 10 ex

FIELD: construction.

SUBSTANCE: invention uses unsorted waste of thermoplastic polymers LDPE, HDPE, in an amount of 10-50 % weight. The waste is crushed in advance and mixed with clay with a humidity of 8-12 %. The product is formed and pressed at a specific pressure of 10MPa. After that, heat treatment is carried out at a temperature increase rate of 20°C/min. The duration of soaking at the polymer melting temperature is 90-180 minutes.

EFFECT: decreased energy consumption, simplification of method, and production of material with high technical performance.

1 tbl

FIELD: chemistry.

SUBSTANCE: polymer composition contains low- and high-molecular polyethylene components, the composition basically having a single peak of lamella width percentile curve and PENT greater than 1000 hours at 80°C and 2.4 MPa according to ASTM F1473. The process has several variants allowing production of tubes with enough viscosity to resist shock during laying or afterward; and with extra long working life under gas or water pressure, especially resistant to environmental stress cracking and to creep under internal pressure.

EFFECT: higher impact elasticity and longer working life of tubes.

37 cl, 5 dwg, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: rubber contains 17-23 mass % of acrylic acid nitrile. Rubber mix contains sulfur, zinc oxide, N,N-diphenylguanidine, carbon black "П803". In addition, 10.5-32.0 mass % of a polymer composition of ultra-high molecular weight polyethylene with natural zeolite in the mass ratio of 10-30:0.5-2.0 is inserted into the rubber mix. Natural zeolite undergoes mechanical activation beforehand.

EFFECT: higher frost and oil resistance of rubbers.

2 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns polymer film production technology, particularly polyethylene films with improved balanced physical and mechanical properties. Method of obtaining film involves obtaining ethylene-based polymer by reaction of links derived from ethylene and co-monomer in the presence of hafnium-based metallocene at 70 to 90°C, under absolute partial ethylene pressure of 120 to 260 pounds per square inch at co-monomer to ethylene ratio of 0.01 to 0.02 and obtained polymer melt extrusion under conditions sufficient for obtaining polyethylene film with 1% secant modulus over 25000 pounds per square inch, load hit resistance over 500 g/mm and longitudinal tear resistance over 500 g/mm.

EFFECT: obtaining polymer films, particularly polyethylene films with improved balanced physical and mechanical properties.

7 cl, 3 tbl, 17 ex

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