Polyolefin composition capable of crosslinking
(57) Abstract:Describes a bimodal polyolefin composition containing two olefinic polymer component, and this composition satisfies the following conditions: Mn1/Mn2>7,0, Mn2>3000 and 0.7(A1+A2)OF 0.15, A1+A2=1 and 0<<1, the total Mnis from 6950 to 29900, total Mwis 81000 to 124000 total Mw/Mn>4, where Mn1represents srednekamennogo the molecular weight of the first nakruchivayuschiysya component; Mn2represents srednekamennogo the molecular weight of the second nakruchivayuschiysya component; AND1and a2represent the relative amounts of the first and second components, and this polyolefin composition is characterized by the total density less than to 0.900 g/cm3. Also describes products made from these compositions, and methods of making such compositions, which have a good capacity for processing, and high speed curing. Described above polyolefin composition capable of crosslinking, are used to produce various products, such as the coating of wires and cables,einevoll patterns, having closed or open cells and/or their combination; a hollow containers, hollow vessels, medical devices, fabrics and coatings, personal care items and health; fibers, tapes, pipes and hoses, bellows, boots, socks and shoes. 5 C. and 18 h.p. f-crystals, 9 tab., 10 Il. The invention relates to polyolefins. In this aspect of the invention relates to polyolefin compositions capable of binding, in particular polyethylene compositions which have good processing and high speed curing. In another aspect this invention relates to bidisperse polyolefin compositions from the same family of polymers having different srednecenovogo molecular weight, which are used in a large set of production technologies, such as extrusion of cables, rotary molding, profile extrusion, injection molding, pneumotropica with extrusion, injection molding, injection blow, thermoforming, coating molding, Rostovka with the use of a press, slit extrusion, fabrication of sheet extrusion, fabrication film extrusion injection blow and powder coating. In another aspect invented is Lishou speed curing. In another aspect the invention relates to various products, for example the coating of wires and cables, sealing gaskets and seals, packings; products made of foam or sponge crosslinked polyolefin structure with closed or open cells and/or their combination; a hollow containers, hollow vessels, medical devices, fabrics and coatings, personal care items and health; fibers, tapes, pipes and hoses, bellows, boots, socks and shoes made from polyolefin compositions capable of stitching.Polyolefin compositions can be processed into molded articles using a variety of techniques. For many end use of these products should be made. Usually the stitching is at the stage of processing or after it.Generally such polyolefin compositions must be recycled relatively easily and should be crosslinked or cured relatively quickly. Usually consider that the rate of curing, i.e. the time required to achieve the desired or optimum state of cure will depend on a number of factors.It is generally accepted that the higher the temperature utverzhdeni what s happened in a short time, as it increases productivity and reduces costs of equipment at work." On the other hand, desirable less stringent (e.g., lower temperature) curing conditions in order to, for example, to reduce energy consumption or to expedite the processing of manufactured parts and semi-finished products.Another important aspect is the ability of the composition to processing. Have been proposed various indicators to assess the workability of the polymer composition. Among them the most famous is the melt index, the so-called2measured in accordance with the US standard ASTM D-1238 (Condition 190/2,16, first Condition E). The melt index is a useful indicator of processing AIDS in the comparison of the polymers belonging to the same family. In General, the lower the value of I2the tougher the conditions of processing of the polymer. In General polyolefins with high molecular weight have a lower melt index and, therefore, such polymers harder processed. For example, during injection molding at low values of melt index requires a higher pressure to fill the cavity of the mold, and in the case chrismer to consume excessive amounts of energy, to call for the polymer.Another measure of processing AIDS is the shear rate (or shear stress) at which a gap melt polyolefin composition during processing. Preferably, the shear rate (or shear stress), which begins the gap melt, would be the highest possible, in order to provide high speed production of finished products or semi-finished products. It is generally assumed that for a given distribution of molecular weight shear rate corresponding to the beginning of the rupture surface of the melt decreases when increasing the average molecular weight polyolefin composition.John Dilai in the book "the Rheology of melts and its role in plastics processing" (Melt Rheology and Its Role in Plastics Processing), published by the firm of van Nostrand country Director Mr Reinhold Co. in 1990, indicates on page 597 that the measurement of melt index in accordance with the US standard ASTM D-1238 using a variety of loads can assess the dependence of shear rate on the viscosity of the melt, which is sensitive to srednevekovoi molecular mass (Mwand to srednetsenovoj molecular mass (Mn). Most often as a measure of constirute 10 kg, the melt index, measured under the load of 2.16 kg is Usually this ratio is called the I10/I2.In the U.S. patents of Stehling etc. N N 5387630 and 5382631 (which corresponds to WO 90/03414) indicated that specific mixture of linear low density polyethylenes with a narrow molecular weight distribution, is substantially characterized in that the index value of polydispersity (Ww/Mn) more than three, provided that the value of Ww/Mnfor each component of the mixture is less than three, have high resistance to wear and low "extractibility" compared with compositions of the prior art. This publication describes the crosslinking of such compositions.Desirable commercial product is a polyolefin composition which has a high curing speed and excellent processability, and when there are conflicting requirements of low molecular weight (to improve processing AIDS) and high molecular weight (for speed curing) specialists in this field of technology has put a lot of effort trying to balance these conflicting demands or to optimize the hardware and the operating conditions of the processing SS="ptx2">Manufacturers of polyolefin compositions capable of crosslinking, has put a lot of effort, for example, selecting the exact dimensions of tooling in order to minimize the sharpness of a pressure jump when the polymer under the force flows through the forming hole. This makes it possible to use polyolefins with high molecular weight and are provided benefits by reducing the curing time. However, an optimal design of the forming device to one of the polyolefin composition is not necessarily best for another polyolefin composition and therefore there is a need to change the direction of flow and the structure forming the matrix for each change in the product, and in any case the benefits are negligible, even if the original design meets satisfactory industrial practice.Have been proposed various forms of "processing AIDS". Among such processing AIDS include, for example, cobalt stearate, zinc stearate, magnesium stearate, mineral oil with different viscosity (usually from 50 to 150 cSt), microcrystalline paraffin in the ü up to 10% of polyethylene wax in linear low density polyethylene (LLDPE) with the aim of improving processing AIDS LLDPE, stitched by silane and intended for the production of coatings and insulation of wires and cables. Generally aim to reduce the friction between the polymer melt and the inner surfaces of the forming matrix and the corresponding channels for the flow. Usually additive, at least partially migrates from the molten polymer composition to the surface of the partition matrix and thereby lubricates the surface. By their nature such lubricating additives dissolved at the interface polymer/metal in the course of their use and thus it is necessary to regularly update them continuously adding such an aid processing. This significantly increases the cost of the process. As derived adjuvant processing usually remains within the mass or associated with the surface of the polymer being processed, this leads to contamination that pose potential problems of use and durability of the obtained products, such as the deterioration of the sealing properties, difficulties when printing on the surface, deterioration of electrical properties.Varrall, etc. in the application WO 91/08262 suggested a way to improve the processing AIDS of polyethyleneimine low-density LLDPE for polyolefin compositions stitched by silane and intended for the production of insulation and coatings of wires and cables, in order to improve the ability of the LLDPE composition to extrusion.Another approach was the use of mixtures of high molecular weight and low molecular weight polyethylenes. For example, Worrall, etc. in the application WO 91/08262 mentioned that the mixture of the first LLDPE having a melt index from 0.2 to 10, and the second LLDPE having a melt index of from 20 to 50, most preferably in fractions of from 30 to 70% of the first component and from 70 to 30% of the second component, provides a good combination of speed curing and processing AIDS polyolefin compositions, stitched with silane and intended for the production of insulation and coatings of wires and cables. However, they failed to give an example of such a composition.Another example of attempts to determine the optimal composition of the mixture and the composition was proposed by Wong and others in Europatent 584927, in which they recommended to add a small amount of secondary polymer component, which crystallizes together with the main polymer component, which is derived from ethylene, and optionally at least one higher alpha-olefin in order) is on. However, they also recommend that it is preferable to add a polymer adjuvant treatment in the form of a fluorinated polymer and/or polymer derived from ethylene and at least one alafinova-unsaturated co monomer having a melt index of at least 5 g/10 min is greater than the melt index of the basic component.In spite of past attempts, it is desirable to provide polyolefin compositions capable of crosslinking, which have good processability and a high curing speed.The present invention provides a polyolefin compositions which have a good combination of processing AIDS and high speed curing. Polyolefin compositions of the invention contain at least one polymer, preferably a polymer of ethylene, and this composition satisfies the following conditions:
Mn1/Mn2> 7, Mn2> 3000;
0,7 (A1/(A1+A2)) 0,15,
where A1, A2, Mn1and Mn2are derived molecular mass distribution of the composition obtained by the method of gel permeation chromatography by scanning the relative response (RR) in zavisit a weighted sum of two functions lognormal distribution:
< / BR>using methods of nonlinear regression to obtain the parameters A1, A2,1,2,1and2in which
MW is the molecular weight according to gel permeation chromatography (GPC);
RR is the relative response, which for a set of individual data RR/MW is:
RR[i] = Normalized height [i]/(log(MW[i-1])-log(MW[i]))
where the Normalized height [i] is the output signal for the corresponding civil faction MW[i];
1and21represent the average and standard deviation of the first logarithmic normal distribution;
2and22represent the average and standard deviation of the second logarithmic normal distribution;
A1+A2= 1 and 0 < A1< 1;
The present invention also provides a method of obtaining a polyolefin composition, which includes:
a) preparation of the first olefin and the second olefin polymers;
b) mixing the first and second olefin polymers in such a way that satisfies the following conditions:
Mn1/Mn2> 7, Mn2> 3000;
0,7 (A1/(A1+A2)) 0,15,
where A1, A2, Mn1and Mn2are derived molecular mass distribution of the composition obtained by the method of gel permeation chromatography by scanning the relative response (RR) depending on the molecular weight (MW) to RR and MW satisfy the following dependencies, which is a weighted sum of two functions lognormal distribution:
< / BR>using methods of nonlinear regression to obtain the parameters A1, A2,1,2,1and2in which
MW is the molecular weight according to gel permeation chromatography (GPC);
RR is the relative response, which for a set of individual data RR/MW is:
RR[i] = Normalized height [i]/(log(MW[i-1])-log(MW[i]))
where normalized to a height [i] is the output signal for the corresponding civil faction MW[i];
1and21represent the average and standard deviation of the first logarithmic normal distribution;
2and22represent the average and the UB>1< 1;
Another aspect of the present invention is a product containing crosslinked polyolefin composition which is obtainable by curing the stitching polyolefin compositions of the present invention.An additional aspect of the invention is a method of stitching indicated stitched composition.In Fig. 1 shows the gel permeation chromatogram for polyethylene prior art TafmerTMPO480.In Fig. 2 shows the gel permeation chromatogram for polyethylene prior art, with the total value of Mn19400, the total value of Mw64100 and index polydispersity, 3,3.In Fig. 3 shows the gel permeation chromatogram for a typical olefin compositions of the present invention, corresponding to Example 2 and having a total value of Mn29900, the total value of Mw124,000 and index polydispersity equal to 4.14. Obvious bidisperse the nature of the molecular mass distribution.In Fig. 4 shows the gel permeation chromatogram for another typical olefin is RNA the value of Mw85000 and index polydispersity, equal to 12.2. Here presents an extreme case of bidisperse.In Fig. 5 presents the dependence of the shear rate at which begins the process of breaking up the surface of the melt, from the total of Mnfor polymer compositions of table 4.In Fig. 6 presents the dependence of the melt viscosity of the total Mnfor the compositions of table 5.In Fig. 7 shows the change of the curing time for a number of peroxide stitched compositions of table. 6 depending on the total Mn.In Fig. 8 shows the change of the curing time of the target to 175% thermal shrinkage for a number of curing in air for stapling the silane compositions are given in table. 7, depending on the total Mn.In Fig. 9 shows the effect of total Mnat the time of curing of the target to 175% thermal shrinkage for a number of curing in water at 60oC stitched the silane polyethylene compositions are given in table. 8.Experimental data corresponding to the present invention, indicated by arrows.In Fig. 10 graphically illustrates the difference between the compositions of the prior art and the present ptx2">When this application uses the terms Mwand Mnor the terms "total Mnand the total of Mw"they belong respectively to srednetsenovoj molecular weight and srednevekovoi molecular weight of the entire polyolefin compositions, in contrast to the Mn1and Mn2that represent characteristics of the polyolefin composition obtained using a special method scan.In accordance with the present invention it has been unexpectedly found that compositions of the invention exhibit a superior combination of processing AIDS and speed curing in comparison with compositions of the prior art with similar srednetsenovoj molecular mass Mnand the same density. The inventors have found that such improved properties are related to specific parameters of the molecular mass, which will be explained in more detail in the following.The parameters A1, A2, Mn1and Mn2used to describe these polyolefin compositions obtained by the method of gel permeation chromatography (GPC) of the samples of these compositions.In Fig. 1 and 2 show typical curves for civil polyolefin compositions according to the level of TM invention.These samples are analyzed by gel permeation chromatography at high temperature block waters 150oC, equipped with speakers with 3% mixed PI-e-gel 10 μm, operating at a system temperature of 140oC. the Solvent is 1,2,4-trichlorobenzene, from which is prepared 0.2 wt.% solutions of the samples for injection. The flow rate is 1.0 ml/min and the amount of injection of 200 μl.Molecular weight determinations carried out on the basis of standard polystyrene standards with a narrow distribution of molecular weight (from the firm Polymer laboratories) in combination with their eluruumina volumes. Equivalent molecular weight polyethylene determine, using the appropriate coefficients Brand-Houwink for polyethylene and polystyrene (as described by Williams and Ward in J. of Polymer Science, Polymer Lett., v. 6 (1968), p. 621), obtaining the following equation:
M(polyethylene) = aMb(polystyrene).In this equation a = 0,4316 and b = 1,0. Srednevekovoy molecular mass Mwexpect the usual manner, in accordance with the following formula:
Mw= Wi* Mi,
where wiand Mirepresent respectively the mass fraction and molecular weight of i-th fraction, elwira regression based on the dual function of a lognormal distribution, above, you can calculate the value of A1, A2,1,2,1and2for each gel permeation chromatogram. To calculate the values of Mn1and Mn2use the parameters accordingly 1,1and2,2.
The method described above scanner provides two log-normal distributions, each of which is characterized by parameters Mn1,iandi. It was found that the advantages of the present invention are that determine when Mn1and Mn2satisfy the above relationship. We can assume that Mn1represents srednecenovogo the molecular weight of the log-normal distribution, corresponding to the fractions with high molecular weight, obtained by a special method scan. Similarly, Mn2represents srednecenovogo the molecular weight of the log-normal distribution, corresponding to the fractions with low molecular weight, obtained by a special method.The greater the ratio of Mn1/Mn2the higher the processability of the polyolefin composition. However, to maintain the desired speed curing HDMI and, it is impossible to realize the advantage of increasing the speed of cure.In accordance with the present invention it is preferable that the composition contained a mixture of components selected from the family of homogeneous linear polyethylenes or family of substantially linear ethylene polymers (SLEP). The most preferred compositions have from two SLAP.The value of Mn2is more than 3000, and more preferably 4000.In addition, the magnitude of the relations A1/(A1+A2), which can be viewed as the relative contribution of the first log-normal distribution (characterized by the coefficientsiandi) in a weighted sum of the first and second log-normal distribution obtained by applying the double lognormal function scanner described above, the gel-penetrating the chromatogram of the composition, must be enclosed within certain limits. The relation A1for (A1+A2must be greater than or equal to 0.15, and preferably greater than or equal to 0.2, and more preferably greater than or equal to 0.25. In addition, the relation A1/(A1+A2must be less than or equal to 0.7, and the preference is>) is outside the interval from 0.15 to 0.7, the curing speed will be lower than desired and, in addition, the effect of shear thinning associated with bimodal distribution of molecular weight of polymers will decrease, which will lead to the deterioration of processing AIDS.The parameters A1, A2, Mn1and Mn2obtained using nonlinear analysis using the least squares method series of experimental data obtained by gel permeation chromatography and expressed in the form of dependence of the logarithm of molecular mass from the relative response. The actual increase in the relative response (RR[i]), corresponding to a particular value of the logarithm of molecular weight (log(MW[i])), is expressed by the formula:
RR[i] = Normalized height [i]/(log(MW[i-1])-log(MW[i]))
where the Normalized height [i] , MW[i-l] and MW[i] determined according to GPC. For i=1 relative response equal to zero. The sum of all normalized heights [i] equal to 1.The numerical method used to approximate the curve is a method of decomposition of Holeckova with numerically determined first derivative with errors in all variables, as described in the publication of the Technical University of Eindhoven (the Netherlands) TUE-RC 68438, 1989, Ley & sons, Inc., 1978. This numerical analysis can be performed using commercially available software such as RRGraphTM(from the firm Reactor research Foundation), which is registered with the Chamber of Commerce, Delft, the Netherlands, N registration S145980. This non-linear least-squares method applied to the dual function of lognormal distribution for a set of experimental data, represented as the dependence of log(MW[i]) from the Relative response RR[i], in order to determine the parameters of A1, A2,1,2,1and2,which provide the best fit of log(MW[i]) from RR[i] with the experimental data. The initial (starting) values of the parameters A1, A2(equal to 1-A1),1,2,1and2 taken on the basis of knowledge of the composition and/or shape of the curve GPC. It turned out that the following initial values lead to a successful scan: A1= from 0.4 to 0.6;1about 5;2about 4; each of the1and2approximately 0,35. If the scan is unsuccessful, these initial values can be customized with regard to parachute of the compositions and in the case of real mixtures may differ from the actual relations of the components in the mixture and their srednekislyh molecular masses. Thus, the relation1for (A1+A2) do not necessarily correspond to the actual ratio in the mixture when the composition is produced by mixing one or more polymer components. Also the values of Mn1or Mn2not necessarily correspond to the actual values of Mnthat could be obtained by gel permeation chromatography of the individual components of the mixture prior to mixing. Compositions of the present invention may include more than two olefinic component, especially if they are prepared by mixing, under the condition that the total composition satisfies the above requirements.Polyolefin compositions of the present invention can be obtained by mixing two or more polyolefins, preferably selected from the same family. As such, the polyolefin compositions of this invention include a mixture of two or more linear polyethylene, or a mixture of two or more polyethylenes of low density, or two or more of the SLAP, but not a mixture of linear polyethylenes and low density polyethylenes.Low density polyethylene (LDPE) generally receive at high pressure, using freely the property is also known as "branched" polyethylene, because it has a relatively large number of long chain branches off from the main polymer chain. Low density polyethylene contains ethylene and optionally may include a small amount (for example, up to 5 wt.%) such comonomers as propylene, butene-1, vinyl acetate and butyl acrylate.The polymers and copolymers of ethylene, obtained using a coordination catalyst such as a Ziegler catalyst or a catalyst of the firm Phillips, generally known as linear polyethylene (let) in connection with the fact that they are practically absent blocks olefin polymer with a branched chain, branches off from the main chain.Linear polyethylene includes high density polyethylene (HDPE) and linear low density polyethylene (LLDPE), the latter being the term for the purposes of the present invention includes polyethylene, ultralow density (PAOP) and very low density (PMNP). High-density polyethylene (HDPE) has a density of from 941 to 967 kg/m3and usually is a linear homopolymer ethylene or interpolymers ethylene and a small amount of alpha-olefin, and it contains a relatively small number of side chains, branches off from the discrepancies between the measures of two or more comonomers, for example, a copolymer or ternary polymer.Linear low density polyethylene (LLDPE) is usually interpolymers ethylene and alpha-olefin containing from 3 to 12 carbon atoms, preferably from 4 to 8 Atmos carbon (for example, butene-1 or octene-1-), which has a sufficient content of alpha-olefin to reduce the density interpolymer to the value of the corresponding LDPE. LLDPE is a member of a family of linear polyethylenes. If interpolymer has a high content of alpha-olefin, the density is reduced below about 910 kg/m3and such interpolymer known as polyethylene, ultralow density (PAOP) or very low density (PMNP). These linear polymers typically have a density in the range from 856 to 910 kg/m3. As polyethylene, ultralow-density polyethylene and very low density are members of a family of linear polyethylenes.Linear interpolymer ethylene include homogeneous and heterogeneously branched LLDPE. Heterogeneous LLDPE typically have very broad inhomogeneous distribution of the content of comonomers, i.e., some of the polymer molecules have a relatively high content of alpha-olefin by somona is. the total polymer molecules with a relatively low content of co monomer have relatively high crystallinity and a high melting point, whereas the polymer molecules with a relatively high content of co monomer is more amorphous and melt at a lower temperature.Homogeneity-branched linear polyethylene, which can be used in the practical implementation of this invention (also referred to as "homogeneous linear polyethylene or homogeneous LLDPE"), the famous and the retrieval method described in U.S. patent 3645992. Examples of homogeneous LLDPE are polymers TafmerTM(Mitsui) and ExactTM(trade mark of the firm Exxon).Substantially linear polymers of olefins represent another family of olefin polymers. Substantially linear polymers of olefins, and more specifically substantially linear ethylene polymers (SLEP) and methods for their preparation are described in U.S. patents 5272236, 5278272 and 5380810. Polymers SLAP available on the DuPont Dau of Elastomers al-al-si as polyolefin elastomers Engageand the company the Dow chemical company, as the polyolefin plastomer Affinity.
Used here, the term "substantially linear" is preferably from 0.1 to 1 long chain branch per 1000 carbon atoms, and more preferably from 0.05 to 1 long chain branch per 1000 carbon atoms. In contrast, the term "simple linear" means that the main chain of the polymer is substituted by less than 0.01 long chain branch per 1000 carbon atoms.Used herein, the term "polymer block polymerization" means a polymer obtained by the polymerization process, and for substantially linear polymers includes molecules without long chain branching, as well as with long-chain branches. Thus, the term "polymer block polymerization" includes any molecule, obtained in the course of polymerization. Assume that for substantially linear polymers, not all molecules have long chain branching, however, a significant number of molecules have branches, so that the average content of long chain branches in the polymer block polymerization has a positive effect on the rheology of the melt (i.e., break properties of the melt).Long chain branching is defined here as the length of the chain, at least one carbon atom less than the number of carbon atoms in the co monomer, whereas short-chain branching is defined here as the length is likely. For example, substantially linear polymer of ethylene/octene-1 has a main chain with long-chain branches, containing at least 7 carbon atoms in length, but also has a short chain branch length to 6 carbon atoms.Long chain branching can be distinguished from short-chain branches, using spectroscopy 13C-NMR (nuclear magnetic resonance), and with some restriction, it can be quantified, for example, homopolymers of ethylene, using the method of Randall (Rev. Macromol. Chem. Phys., v. C29 (2& 3), p. 285-297). In practice, however, existing spectroscopy12C-NMR spectroscopy cannot determine the length of long-chain branches, containing more than about 6 carbon atoms, and for this analytical technique, as such, cannot be distinguished branches 7 and 70 carbon atoms. Long chain branching can be the same length or about the same length as the main chain of the polymer.In U.S. patent 4500648 indicated that the frequency of long chain branches (CDO) can be represented by the equation
CDO = b/MW,
in which b is srednevekovym number of long chain branches per molecule and MW is the middleweights, is the quiet determined by using gel permeation chromatography and the method of characteristic viscosity.Used here, the term "homogeneous-branched" means that comonomer statistically distributed within a given molecule and that virtually all of the copolymer molecules have the same ratio of ethylene/comonomer. Distribution or homogeneity comonomeric branches for the substantially linear ethylene interpolymers and homopolymers is characterized by the index of distribution of short chain branches or index of compositional distribution of the branches and are defined as the mass percentage of polymer molecules having a content of co monomer within 50% of the average total molar content of co monomer. The composite index of the distribution of branches in the polymer is readily calculated from data obtained by methods known from the prior art, such as, for example, elsinoe fractionation with increasing temperature (here we use the abbreviation "APPT"), as described, for example, Wilde and others in the journal J. Pol. Sci., Polymer Phys. Ed. v. 20, (1982), p. 441, or in U.S. patent 4798081. The index of distribution of short chain branches or composite index distribution is provided in accordance with the present invention generally exceeds 30%, preferably more than 50%, and especially greater than 80%.As a linear homogeneous-branched polymers, and SLAP used in this invention have a single melting peak as measured using differential scanning calorimetry (DSC), in contrast to linear heterogeneously branched polymers of ethylene, which have two (or more) melting peak due to the wide distribution of branches.The unique property of the SLAP is a very obvious feature of the flow where I10/I2polymer does not depend on index polydispersity (i.e., the relationship of Mw/Mnof the polymer. This distinguishes the SLAP from the traditional linear homogeneous-branched and linear heterogeneously branched polyethylene resins having rheological properties, which to increment the value of I10/I2it is also necessary to increase the index polydispersity. Preferably the index melt flow, measured as the I10/I2(US standard ASTM D-1238), is greater than or equal 5,63, and preferably equal to at least about 6.5, and more preferably equal to at least 7, and can reach values up to 20, preferably 15, and more pre what ametria, moreover, they are characterized by a narrow distribution of molecular weight, and if they are interpolymers, are characterized by a narrow and homogeneous distribution of co monomer. Preferably the molecular weight distribution (Mw/Mn), measured by gel permeation chromatography, is determined by the equation:
(Mw/Mn) (I10/I2) - 4,63,
and usually it is less than five, preferably between 1.5 and 2.5, and especially from 1.7 to 2.3.Preferably the melt index, measured as the I2(ASTM D-1238, condition 190/2.16, first, the condition (E) is from 0.1 to 100 g/10 min, more preferably from 1 to 20 g/10 min Typical preferred substantially linear ethylene polymers used in the practical implementation of this invention are homogeneous-branched and do not contain any appreciable fraction with a high density (i.e., according to lucynova fractionation with increasing temperature), for example, they do not contain any polymer fraction has a degree of branching less than or equal to two methyl groups per 1000 carbon atoms.Other key features of these substantially linear polymers of ethylene include small collesuem to obtain polymer, unreacted comonomers (or they are) and low molecular weight oligomers, obtained in the course of polymerization) and regulated molecular structure that provides good processability, even if the molecular weight distribution is narrow compared to conventional olefin polymers.Substantially linear polymers of the olefins used in the preparation of the polymer compositions of this invention preferably contain substantially linear ethylene polymers, such as Homo-and interpolymer. Preferably the substantially linear ethylene polymers contain from 50 to 95 wt.% ethylene and from 5 to 50 wt.%, at least one alpha-olefin co monomer, more preferably from 10 to 25 wt.%, at least one alpha-olefin co monomer. The content of the co monomer is measured by the method of infrared (IR) spectroscopy according to ASTM D-2238, method B. Typically, these substantially linear ethylene polymers and homogeneous linear polyethylene are copolymers of ethylene and alpha-olefin co monomer having from 3 to 20 carbon atoms (e.g. propylene, butene-1, hexene-1, 4-methyl-pentan-1, hepten-1, octene-1 and styrene) with a density of 850 to USIM from 4 to 10 carbon atoms, more preferably from 5 to 10 carbon atoms. Especially preferred are 4-methyl-penten-1-, hepten-1 and octene-1.For the substantially linear polymers of ethylene ratio I10/I2indicates the intensity of long-chain branching, i.e., the higher the ratio of I10/I2the higher the intensity of long-chain branching in the polymer."Rheological index processing is observed viscosity (cropwatch, KP) of the polymer measured using a gas extrusion rheometer, which is described M Sidom, R. N. Sraffa and L. C. Cancio in Polymer journal Engng. Sci. v. 17, N 11, p. 770 (1977) and in the book.Dilai "Rheometers for molten plastics", published by the firm of van Nostrand country Director Mr Reinhold Co. (1982), S. 97-99. Experiments with gas extrusion rheometer was carried out at a temperature of 190oC, the nitrogen pressure between 250 and 5500 psi (1,75-to 38.5 MPa), using the matrix in diameter 75,4 mm, ratio of length/diameter of 20:1, with an entrance angle of 180o. For the preferred substantially linear polymers of ethylene, described here for the polymer compositions of the present invention, the rheological index processing is observed viscosity (in CP) of a material measured by gas EC interpolymer and homopolymers of ethylene preferably have an index value processing in the range of from 0.01 to 50 CP, preferably 15 CP or less, or 70% or less of the value of the index processing comparative linear polymer of ethylene (or ziperovich polymer, or a linear uniformly branched polymer as described by Alsthom in U.S. patent 3645992) with almost identical values of I2and Mw/Mn.To identify the phenomena of rupture of the melt using the graphical dependence of the observed shear stress from the observed shear rate. According to ramamurti (J. of Rheology, v. 30 (2), p. 337-357, 1986), above a certain critical value of the flow velocity of the observed extrudate irregularities may be broadly classified into two main groups: divide the melt surface and a gap weight of the melt.Break the surface of the melt is obvious when the steady state flow and detail changes from the loss of gloss of the film to the more rigid types of skins sharks. In this description of the beginning of the rupture surface of the melt is characterized visually by the appearance of the surface roughness of the extrudate from the capillary rheometer. Critical shear rate at the beginning of the rupture surface of the melt to the preferred substantially Lina is 50% more than the critical shear rate at the beginning of the rupture surface of the melt for comparative linear polymer of ethylene with almost identical values of I2and Mw/Mn.The destruction of the mass of the melt is in non-stationary conditions of the extrusion flow and detail changes from regular (for example, alternating smooth and sharp or coil current) to random distortions. For industrial application (for example, blown films and bags of these films), it is necessary that the surface defects were minimal or absent, to ensure good quality and properties of the film. Critical voltage
shift at the beginning of volume destruction of the melt substantially linear interpolymers and homopolymers of ethylene, used in obtaining the preferred polymer compositions of the present invention, approximately more than 4 Mdina/cm2. Critical shear rate at the beginning of surface melt fracture and at the beginning of volume destruction of the melt will be used here based on the changes of surface roughness and configurations of the extrudates obtained from gas extrusion rebate rheological index Dow (REED), which expresses the "normalized relaxation time as the result of long-chain branches" of the polymer (see , for example, C. Lai, and C. knight, Proceedings of the ANTEC '93: "INSITE technology polyolefins (Ah-Tee-Pee)-New rules on the structure and rheology of copolymers of ethylene and alpha-olefins, new Orleans, PCs Louisiana, may, 1993). The value of the rheological index Dow varies from 0 to polymers in which there are no noticeable long-chain branching (e.g., products TafmerTMavailable in firm Mitsui Petrochemical industries, and ExactTMavailable on the company Exxon chemical company), 15 and does not depend on the melt index. Generally in the field of low to medium pressure for polymers of ethylene (especially at low densities) rheological index Dow provides the best correlation with the elasticity of the melt and flow at high shear compared with the same correlation properties with relative fluidity of the melt. For the substantially linear polymers of ethylene used in this invention, REID preferably equal at least to 0.1, and more preferably equal at least to 0.8, and most preferably at least -0,8. Rheological index Dow can be calculated by equation (1):0is the viscosity at zero shear. As0and0are the values obtained by the method of nonlinear regression in best accordance between experimental data and cross-equation (2), i.e.:
/0= 1/(1+(0)n), (2)
where n represents the index of the power law for the material, and and are the measured values of viscosity and shear rate (rad/s), respectively. Baseline determination of viscosity and shear rate is done using rheometrics mechanical spectrometer (AP-GM-es-800) under dynamic fashion sweep from 0.1 to 100 rad/s at 190oC and gas extrusion rheometer when the extrusion pressure from 1000 to 5000 psi (6,89 to 34.5 MPa), which corresponds to shear stress from 0,086 to 0.43 MPa, using the matrix in diameter 0,754 mm, with a ratio of length/diameter of 20:1, at 190oC, as required to match the changes of the melt index.The mixture can be prepared by physically mixing two or more of these polyolefins, or by mixing in the reactor. The preparation of these compositions by physical mixing includes dry mixing, blending in RASplus removal of solvent or solvents. Mixing in the reactor typically includes the components are mixed in the polymerization reactor during or after receiving one or both components. Both types of mixing, i.e., physical mixing and mixing in the reactor, is well known. Preferably these compositions are obtained by mixing in the reactor using two reactors operating in series or in parallel, or using two or more catalysts in a single reactor, or a combination of several catalysts and several reactors. The General principle of polymeric mixtures by mixing in the reactor using two or more catalysts in a single reactor, or a combination of several catalysts and several reactors described in applications WO 93/13143, EP-A-619827 and in U.S. patent 3914342. Polyolefin compositions of the present invention can be obtained by selection of the appropriate catalyst and process conditions based on the characteristics of the final composition.Polyolefin compositions of the present invention can be sewn or solidified in accordance with any known method stitching saturated polyolefin compositions. Suitable methods for the introduction of cross-links between different chains moremodest polyethylene with peroxide or other free radical initiator, and optionally with a suitable auxiliary reagent and/or catalyst and/or a combination of activator and/or catalyst and/or promoter, such as treelistener or elemental sulfur. Usually this reaction is initiated by heating the molded part.In General, the desired melt index will depend on the intended final use of products made from this composition, and method of producing articles of the stitching composition and can range from 0.01 to 100 g per 10 minutes for Example, the amount of melt index from about 0.2 to 5 g for 10 min is preferred for products that will be manufactured using extrusion processes, such as the technique of blowing films. In General, lower values of melt index will be required for products that require high resistance to misuse, or require resistance to cracking under the action of the environment. Products that will be manufactured by injection molding, can usually be obtained from the compositions of the invention with a melt index of from 4 to 100 g for 10 min, and most preferably from about 5 to 25 g for 10 min Professionals in this area of RASPLAV for compositions intended application.Compositions of the present invention preferably have an overall density of at least 0,850 g/cm3preferably, at least 0,855 g/cm3more preferably, at least 0,860 g/cm3. Usually values of total density is less than 0,907 g/cm3preferably less than to 0.900 g/cm3more preferably less 0,890 g/cm3most preferably less 0,885 g/cm3. Compositions having densities less to 0.900 g/cm3very convenient for use as a coating or insulation of wires and cables, especially for flexible coatings and insulation.In the United Kingdom patent 1286460 Scott (corresponding to U.S. patent 3646155) indicated that the main chain of the polymer can impart chemically reactive substances so that could occur subsequent reaction between the grafted substances associated with different chains of polymer molecules. An example of such method is the so-called process of crosslinking the silane, in which the grafted polymer ninasimone silanes, which subsequently interact with water in the presence of a catalyst with the formation of cross-links between polymer CEPA is/BR> in which R' represents a hydrogen atom or methyl group; x and y are 0 or 1 provided that when x is 1, y = 1; n is an integer from 1 to 12 inclusive, preferably from 1 to 4; and each of the radicals R independently is a hydrolyzable organic group such as CNS group having from 1 to 12 carbon atoms (e.g. methoxy, ethoxy or butoxy), aryloxy group (for example, phenoxy-), arakaki- (for example, benzyloxy-), aliphatic, acyloxy group having from 1 to 12 carbon atoms (for example, formyloxy, atomic charges or propenyloxy-), oxime or substituted amino group (alkylamino or arylamino-), or a lower alkyl group having from 1 to 6 carbon atoms, inclusive, provided that not more than one radical R of the three is alkyl. Such silanes can be grafted to the polyolefin composition either before or during forming operations or pressing. This silane can be grafted to the polymer by any conventional method, typically in the presence of a free radical initiator, such as organic initiator, or by ionizing irradiation. Organic initiators are preferred, such as organic peroxides, such as Dicumyl-lane is ticketone. The amount of initiator can vary, but usually it is present in amount of at least 0,04 h 100 h (es) per polyolefin composition (parts by 100 g polymer), preferably at least 0,06 h per 100 g polymer. Generally, the amount of initiator does not exceed 0.15 hours per 100 g polymer, and preferably does not exceed about 0.10 to hours 100 hours of the polymer. The ratio of silane to the initiator may also vary widely, but typically the ratio of silane to initiator is between 10:1 and 30:1, preferably between 18:1 and 24:1.The crosslinking of the composition with the grafted silane is carried out by contacting such compositions with water or any other compound with an active hydrogen. Such connection or water has the ability to prodifferentiating in the polymer from the atmosphere or from water bath, or sauna, or by incorporating in the polymer substance, which is able to allocate water under suitable conditions, for example by heating the polymer containing the hydrated filler, such as trihydroxide aluminum. Typically, the crosslinking reaction requires a catalyst for the crosslinking, which may contain a crosslinking agent, activator, promoter and/or accelerator, or a combination thereof. These catalysts in common with the e titanates and complexes or carboxylates of lead, cobalt, iron, Nickel, zinc and tin; dilaurate dibutylamine, maleate dactylology, diacetate dibutylamine, diktat dibutylamine, tin acetate, octoate tin, lead naphthenate, kaprilat zinc and cobalt naphthenate. Particularly effective for this invention, the tin carboxylates and especially dilaurate dibutylamine and maleate dactylology. The catalyst (or mixture of catalysts) are present in small amounts, typically from about 0.01 to 1.0, preferably between 0.015 to 0.10 weight. hours at 100 weight. including the polymer, i.e., parts per hundred parts of polymer.You can use other methods of crosslinking polyolefin compositions of the invention. For example, you can use the combined effect of the electron beam and a crosslinking activator, or a multifunctional monomer, such as of ethylene glycol dimethacrylate, dimethacrylate of tetraethyleneglycol, trimethacrylate of trimethylolpropane, triacrylate of trimethylolpropane, diacrylate diethylene glycol, diallylphthalate, treelistener or tetraacrylate pentaerythritol, in order to perform a reliable staple products of the present invention. Such details technology of radiation crosslinking published in Radiation Processing of Polymers", publisher Hanser Publishers of Munic, Vienna, New York and Barcelona, posmatrivat as illustrative and but not as limiting. Stage of the process, which creates cross-links between the different chains of the polymer molecules, typically called the "stage of curing, and the process is normally also referred to as "curing".This olefin composition may optionally contain additives, such as, for example, thermal stabilizers, such as stabilizers, ultraviolet radiation, pigments, dyes, extenders, fillers or technological means. Mostly they are introduced into the composition to the stage stitching.The compositions of this invention can be used in a variety of applications and, in particular, they are effective in those applications where it is required or is desirable short time of curing. Illustrative applications include films, extrusion coated or laminated foil, extruded or calendered sheets and foil, the coating of wires and cables, sealing gaskets and seals, oil seals; products made of foam or sponge crosslinked polyolefin structure with closed or open cells and/or their combination; a hollow container, a hollow tanks, medical propositon, boots, socks and shoes, soles and uppers made from stitched polyolefin compositions. Compositions of the present invention can be converted into final products or companysee parts intended for the introduction of other products during their manufacture, using well-known methods of polymer processing, such as extrusion of cables, rotary extrusion, profile extrusion, injection molding, press-moulding, injection moulding, extrusion with pereformuliruem, blow molding, injection molding, blow, thermal pressing, surface finishing, extrusion blow, slit extrusion, fabrication of sheet extrusion, extrusion foam, making film extrusion injection blow, extrusion of monolete and monofilament and powder coating.Examples
The following examples are an illustration of some special variants of the embodiment of this invention. Unless otherwise indicated, all parts and percentages are massive.Was made a number of substantially linear ethylene polymers (SLEP) in solution using the mini-setup with two reactors, which are referred to here as the "Pern polymerization of the initial mixture, containing a mixture of ethylene/octene-1/solvent and hydrogen gas, in the presence of a metallocene catalyst, such as described in U.S. patents NN 5272236, 5278272 and 5380810. Partially reacted product of the primary reactor is continuously fed to the secondary reactor through a series of sequential connections between these reactors, where the product is subjected to interaction with an additional quantity of ethylene again in the presence of the same metallocene catalyst, under such reaction conditions under which the result is a polymer with a different value srednetsenovoj molecular weight, usually with a value of Mnless srednetsenovoj molecular weight of the polymer obtained in the primary reactor. Generally, such conditions include operation of the secondary reactor at a higher temperature than in the primary reactor. Polymer mixture, corresponding to Examples 1-4, obtained by variation of the reaction parameters in the primary and secondary reactors.For example, the mixture of Example 1 is obtained by introducing into the primary reactor mixture containing ethylene (C2), octene-1 (C8) and gaseous hydrogen (H2), with velocities presented in table.1aat the end of the description.Temperature is origny reactor with a speed of 23.6 kg/h, along with a stream of ethylene 7,71 kg/h; the temperature in the secondary reactor support 120oC and get the final product at 36.5 kg/hComparative Examples C-1 to C-14 are examples of comparison SLAP, C-15 is an example of a homogeneous polymer of ethylene, in examples from C-16 to C-19 compares the polymer is linear low density polyethylenes (LLDPE), and C-20 and C-21 are examples of comparative polymers - polyethylene low density (PMNP).In comparative examples C-11 to C-20 industrial use available ethylene polymers, polyolefin elastomers Engageand the polyolefin plastomer Affinityboth are a SLAP. Polymers Dowlexand Attaneare LLDPE resins and PAWN respectively, which are produced and sold by the firm Jo Dow chemical company. TafmerTMa homogeneous linear polyethylene interpolymer supplied by the company Mitsui (Japan).In addition, there were comparative examples DR-A - DR-M by mixing different pairs SLAP and extrusion of this mixture. The extrudate is cooled and granularit and then with these tablets spend extrasmall mixture.When each polymer mixture is subjected to analysis by gel permeation chromatography, get the chromatogram with a double peak. These results and other characteristics are given in table. 1-3 and 9 at the end of the description.Data from table. 4 at the end of the description show that the processability of stitched plastic composition is connected with the total srednekislovsky moment of its molecular mass Mn. In table. 4 shows the dependence of the shear rate at which begins the process of destruction of the surface of the melt, of the total value of Mnfor a number of substantially linear compositions of polymers of ethylene. In Fig. 5 shows the dependence of the shear rate for the onset of the process of destruction of the surface of the melt from the total values of Mnfor a number of substantially linear ethylene polymers (SLEP).In table. 5 at the end of the description shows the dependence of melt viscosity, which begins the process of destruction of the surface of the melt, measured at 220oC and speed of 1800 s-1on the total value of Mnfor polymers of the prior art and examples of this invention. In Fig. 6 shows this dependence, from which it is clear that the viscosity of the melt depends substantially on Sal. 6 at the end of the description, compounding stitched together with compounds in accordance with Formula 1 by the following procedure: add 85 wt.% polymer in a two-liter internal mixer Farrell M and stirred until a temperature load equal to 80oC (approximately 2 min). Use the total load in the mixer weight 1335 Then add other ingredients and mix further, so that the total cycle time from start time is 5 min, and then the load is removed from the mixer. Typical temperature paged product is from 100 to 110oC. the mixture is Then milled on the sliding mill Farrell 6"X13" for 2 min at 60oC, using the friction ratio between the speeds of the front and rear roller from 1.5 to 1 when the gap is equal to about 0.5 mm, to rolling sheets of 4 mm, which stand for vacation stress) 2 h at 20oC before the test.Formula 1
Component - Quantity, part 100 including the resin (PC)
Polymer - 100,0
Perkadox 14/40 K*- 2,00
Benefit TAC/S**- 0,5
Vulkanox HS/LG***- 1,00
Total - 103,50
*Perkadox 14/40 K is bis(tert-butylperoxyisopropyl)benzene peroxide (aktivnosti TAC/S is a mixed agent 70% of cialiscanada and 30% silicon dioxide, supplied by the company Rhein Chemie Rheinau, GmbH, Mannheim, Germany.***Vulkanox HS/LG is polymerized 2,2,4-trimethyl-1,2-dihydroquinoline antioxidant supplied by Bayer AG, Leverkusen, Germany.The optimum cure time for the stitching peroxides compositions determined at 160oC, using a vibratory disc rheometer Zwick 4308 (angle of the rotor 1othe vibration frequency of 100 min-1). The value of the optimal cure time is expressed as T90calculate directly using software Zwick ODR, model 7049 3-2, version 06.07.89/07.07.89, in accordance with the procedure described in DIN 53529/T2.In table. 6 shows the dependence of the optimal curing time, which is determined using a vibrating disk rheometer and the above-described method, the total values of Mnfor a number of stitched peroxides compositions SLAP, as described in Recipe 1. Samples identified by referring to the original polymer, which is made of stitched composition. This dependence is illustrated in Fig. 7, from which it is clear that the rate of curing of the compositions of the invention above the expected rate of curing otnositel what I 160oC for 46,2 min, whereas for this srednetsenovoj molecular weight expected curing time is approximately 54 minutes Similar to the composition of Example 3 is cured at 160oC during 47.3 min, whereas the expected curing time 60 min, and the composition of Example 1 is cured at 160oC for 48 minutes at the expected time of curing, equal to 56 minutes estimated time of curing estimate based on extrapolation of data for compositions of the prior art, i.e. on the basis of extrapolation of the correlation time of the curing of the total Mnfor compositions of the prior art.Examples of compositions crosslinked silane
A number of plastic resins and substantially linear ethylene polymers are subjected to interaction with the composition for vaccination, consisting of 1,519 wt.% VINYLTRIMETHOXYSILANE, of 0.075 wt. % dicumylperoxide as an initiator vaccinations, and 0.025 wt. % of dilaurate dibutylamine as a catalyst for crosslinking, based on the weight of a polyethylene resin or a SLAP. For the preparation of the grafting mix 10 ml Dynasylan Silvina 12, consisting of 92.5% VINYLTRIMETHOXYSILANE and 7.5% dicumylperoxide from 6.67 ml Dynasylan Silvina 21, consisting of 96,2% VINYLTRIMETHOXYSILANE available on the company Huls). This mixture was added to 985 g of a polymer sample in a closed drum. The contents of the drum mix by rocking for 1 h and then fed to a single screw 16 mm extruder with the ratio of length/diameter = 28/1. Extruder equipped with a screw with a compression ratio of 2.5:1 and is equipped with a "Mixer with moving cavity" feeding the ribbon matrix. Such equipment is produced in the center of the extrusion company Plasticizers Engineering Ltd. (United Kingdom).In addition, it is possible to apply a pre-prepared mixture of silane/peroxide/catalyst directly into the hopper of the extruder, although this method is not used for the purposes of the present invention. The speed of rotation of the extruder is such that the residence time of the mixture was between 3 and 7 minutes, and the melt temperature of the resin was about 220oC. When using this technique all resins are imparted equally. Tapes from the extruder is cut pneumatic cutter, using a blow dry with compressed air to prevent premature curing due to contact with moisture. Compression molded plates extrudates receive, selecting dry granules and placing them in the mold with a nominal PAA pressure 15 bar for 6 min, then increase the pressure up to 150 bar for 3 min and then give the form to cool to 20oC with a cooling rate of 15 degrees per minute, using a hydraulic press type of Paid Press 200, produced by Collins. Then pressed plates utverjdayut at the 23oC in air with a relative humidity of 80% or utverjdayut, placing them in a temperature-controlled water bath, heated to 60oC.The rate of crosslinking is determined by the periodic removal of plates and selection of the sample in the form of a dog bone for analysis of thermal shrinkage. In this analysis placed the "dog bone" standard (ASTM) sizes in the oven at 200oC and attach to sample the goods, the equivalent stress of 20 N/cm2. Write the resulting elongation of the sample. With the strengthening of state of cure of the sample measured elongation decreases. Thus, reducing the degree of elongation is a measure of the speed of curing. This method is described in the publication 811-2-1 Standard of the international electrotechnical Commission, edition 1986, According to the industrial standard, consider that achieved a satisfactory state of cure, if thermal shrinkage of the sample (elongation at the I-cured, corresponding to this value of thermal shrinkage (175% after 15 min at 200oC and a load of 20 N/cm2), thermal shrinkage is measured using different samples in the form of a dog bone at each value of the curing time, then build a graph of thermal shrinkage from the curing time in logarithmic coordinates. At a very short time curing the value of thermal shrinkage can be very high, and the sample may be destroyed before the expiration of 15 minutes In this case, the elongation under load is measured directly before the rupture of the sample. The experimental data is plotted, the line of best fit, the intersection of which with the amount of thermal shrinkage 175% gives the curing time target for the evaluation task.In table. 7 at the end of the data according to the curing time of the target for a number of linear low density polyethylenes (including PAWN and PAOP) and a comparative SLAP on srednetsenovoj molecular weight cross-linking in the air with a relative humidity of 80% at 23oC, in accordance with the above methodology. This dependence is illustrated in Fig. 8, where it is clearly visible that the curing time of the target increases dramatically when slimming is diolefines.In accordance with the methods described above was prepared with a number of stitched the silane compositions with the difference that these songs were made during curing molded plates in water at a temperature of 60oC. This number included compositions on the basis of the substantially linear polymers of ethylene, mixtures of substantially linear polymers of ethylene and traditional homogeneous polyethylene.In table. 8 at the end of the data according to the curing time of the target for this series polymer stitched the silane compositions of Mnwhen stitching using water at 60oC, in accordance with the above method.At that time, as in Fig. 5 and 6 it is obvious that the processability of the compositions is improved by the reduction of size Mnpolyethylene, of Fig. 8 and 9 clearly shows that the curing time targets for stapling the silane compositions according to the prior art increases sharply with decreasing primary Mnsample of polyethylene. In addition, Fig. 9 clearly demonstrates that the formulations proposed by Wong with employees, characterized by the same regularities that can be expected on the basis of their values of Mn.In table. 8 also shows the data on salicylideneaniline, processing AIDS that are associated with the curing time of the respective formulations of the prior art. In Fig. 9 examples of the invention are presented in the form of squares, highlighted by arrows. The axis scale is "hardening the target" is logarithmic in order to more clearly demonstrate the unexpected and significant improvement in performance speed curing, which can be obtained without whosane processing AIDS, through the use of this invention.For example, the composition of the invention on the basis of example 1 overiden for 2,79 h, compared with 31,35 h for comparative example DR-B and 104,3 h for comparative example C-14, with close values of srednetsenovoj molecular weight. The composition of example 2 overiden in water at 60oC in 3.67 h compared with curing time 9,82 h under the same conditions for comparative compositions DR-C with a close value srednetsenovoj molecular weight. The composition of example 3 under the same conditions overiden for 17,43 h compared with the expected curing time more than 1000 h, similar to the composition of example 4 overiden for 31,16 h compared with the expected curing time more than 1000 hoursThe composition of the invention in example 1, Koversada in 3.67 h 2,40 h, respectively. In example 1, the polymer melt has a viscosity of 112 Pass at a speed of 1800 cm-1and a temperature of 220oC compared with the viscosity values for the compositions of examples DR F and DR-E-163 Pas and 185 Pass. Thus, the processability of the composition of the invention according to example 4, which overiden for 31,16 h, may be correlated with the processability of the comparative composition of example, DR-B, which also cures for 31,35 o'clock In example 4, the polymer melt has a viscosity of 44 Pass at a speed of 1800 s-1and a temperature of 220oC compared with the value of viscosity for the composition of example, DR-B - 72 Pass and therefore the processability of the composition of the invention will be significantly better.In table. 9 at the end of the description summarizes the values of Mn1/Mn2and A1/(A1+A2for compositions of the invention and comparative compositions. In Fig. 10 the same data are presented graphically, and they illustrate the combination of parameters Mn1/Mn2and A1/(A1+A2), which provide the advantages according to the invention.Although this invention has been described in great detail through the preceding specific variants of embodiment of the invention, it should be understood that these variants of the embodiment shown tol the th of this invention, without deviation from his plan and volume. 1. Bimodal polyolefin composition containing two olefinic polymer component, and this composition satisfies the following conditions:
nis from 6950 to 29900, total Mwis 81000 to 124000 total Mw/Mn>4, where Mn1represents srednekamennogo the molecular weight of the first nakruchivayuschiysya component, Mn2represents srednekamennogo the molecular weight of the second nakruchivayuschiysya component, AND1and a2represents the relative amounts of the first and second components, and this polyolefin composition is characterized by the total density less than to 0.900 g/cm3.2. The composition according to p. 1, having a total density of less than 0,890 g/cm3.3. Composition under item 1 or 2, in which Mn2more than 4000.4. Composition according to any one of paragraphs.1 to 3, in which the relation of a1/(A1+A2) is equal to or less than 0,65.5. Composition according to any one of paragraphs.1 to 4, in which the relation of the polymer component, of ethylene.7. The composition according to p. 6, in which both the polymer component, of ethylene selected from substantially linear polymers of ethylene.8. The composition according to p. 7, in which the substantially linear ethylene polymers include comonomers of ethylene and alpha-olefin having from 4 to 10 carbon atoms.9. The composition according to p. 8, in which each of the substantially linear polymers of ethylene has a molecular weight distribution (Mw/Mn) defined by the formula
where the ratio of the indices of melt flow (l10/l2) is equal to or greater 5,63.10. The composition according to p. 7, having a density in the range from 0,850 to 0,890 g/cm3.11. Composition under item 1, which further comprises a crosslinking agent, activator, promoter or accelerator and is suitable for stitching.12. The composition according to p. 11, in which the crosslinking agent is an unsaturated silane grafted to the composition.13. The composition according to p. 12, in which the unsaturated silane represented by the formula
< / BR>in which R' represents a hydrogen atom or methyl group, x and y are zero or 1, provided that when x is 1, y=1; n is an integer from 1 to 12, including, predpochtitel is the SCP, having from 1 to 12 carbon atoms, alloctype, alexikoua, the aliphatic alloctype having from 1 to 12 carbon atoms, oxime or substituted amino group, or a lower alkyl group having from 1 to 6 carbon atoms, inclusive, provided that not more than one of the three R groups is an alkyl.14. The composition according to p. 11, in which Mn2more than 4000 and a1(A1+A2) is equal to or greater than 0.2 and equal to or less than 0,65.15. Product comprising crosslinked polyolefin composition obtained by curing the composition under item 11.16. Product comprising crosslinked polyolefin composition obtained by curing the composition under item 14.17. A method of obtaining a polyolefin composition, which comprises: a) preparing a first olefinic polymer and a second olefinic polymer; b) mixing the first and second olefin polymers so that the first and second olefin polymers homogeneous mixed with the formation of the polyolefin composition, which satisfies the following requirements:
n1represents srednekamennogo the molecular weight of the first nakruchivayuschiysya component, Mn2represents srednekamennogo the molecular weight of the second nakruchivayuschiysya component, AND1and a2represent the relative amounts of the first and second components, and this polyolefin composition is characterized by the total density less than to 0.900 g/cm3.18. The method according to p. 17, in which the olefin polymer is an ethylene polymer obtained in the first reactor and the second olefin polymer is an ethylene polymer obtained in the second reactor.19. The method according to p. 18, in which the ethylene polymer obtained in the first reactor is transferred to the second reactor, in which the second olefinic polymer is produced in the presence of the first ethylene polymer.20. The method according to p. 18 or 19, which is carried out in a slurry phase, solution phase or in the gas phase.21. The method according to any of paragraphs.17 - 20, in which the composition additionally add a crosslinking agent.22. The method of stitching the stitching composition on p. 11, which comprises adding a crosslinking agent in the composition.23. The method according to p. 22, the cat is the product or after it.
FIELD: polymer materials.
SUBSTANCE: invention relates to stabilizer mixture used for stabilizing polyolefin against destruction initiated by visible light, heat, or oxidation and to thus stabilized polyolefin. Stabilizer mixture comprises spatially hindered amine compound and polymer containing polar residues, weight ratio of the two compounds being between 20:1 and 1:20, respectively, provided that (i) polymer cannot be the same compound as hindered amine compound and does not contain groups of formula (1) or (II): . Where G represents hydrogen atom or methyl and G1 and G2, independently of each other, each represents hydrogen atom or methyl or they together form =O; and (ii) polymer cannot contain acidic hydrogen atom.
EFFECT: considerable increased efficiency of stabilizer composition.
22 cl, 4 tbl, 4 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to compositions of polymer materials, which can be used to mold cutouts, fibers, tubes, films, and insulating coating on electric cable. Thermoplastic polymer material comprises polyolefin and additive for improving extrusion processing in amounts from 0.001 to 10 wt parts per 100 wt parts material. Additive is block copolymer based on diisocyanates with softening temperature below thermoplastic molding temperature.
EFFECT: improved appearance and mechanic characteristics and reduced price of manufactured products.
4 cl, 8 dwg, 1 tbl, 4 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to polymer material science and can be used to manufacture structural elements of various functional destinations. Composite thermoplastic polyolefin-based material contains filler and fire-retardant additive, the former being thermally treated silicate, namely product of treatment of naturally occurring silicates by heat stroke with gradient 800-1000°C, and the latter being halogen-containing oligomer selected from group including chloroparaffin and fluorine-containing oligomer ("Foleoks"), whereas above-mentioned polyolefin is selected from group including polypropylene, low-pressure polyethylene, high-pressure polyethylene, ethylene/vinyl acetate copolymer, and thermomechanically combined mixture of polyolefins with polyolefins, polyacetals, or styrene-containing plastics.
EFFECT: improved physico-mechanical characteristics of composite polyolefin-based material and increased resistance to burning and to action of negative temperatures.
FIELD: manufacture of building materials.
SUBSTANCE: material is made from principal composition containing polyethylene (mixtures of polyethylenes) and rubber crumb and, additionally, ethylene/vinyl acetate copolymer with vinyl acetate content 10-24% and characterized by melt flowability 10-18 g/10 min. Rubber crumb represents vulcanized waste with particle size 1.0-1.4 mm, which allows obtaining rubber-polymer material capable of being processed into granules and designed to be processed via jet molding into building materials such as large-size tile sheets.
EFFECT: enlarged choice of inexpensive building materials.
13 cl, 2 tbl, 6 ex
FIELD: polymer production.
SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.
EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.
26 cl, 8 tbl, 14 ex
SUBSTANCE: biodegradable granular polyolefin blend represents antimisting granules sized 2-8 mm of apparent bulk density 530-630 kg/m3, granule density less than 920-1300 kg/m3. Herewith melt flow index (MFI) of the parent polyolefin is MFI=2.5-25.0 g/10 minutes. Processing and relevant aid concentrate contains at least one biodegradable additive, thermostabilisers, antioxidants, lubricants, antistatic aids, pigments, fillers etc. The granular polymer blend is produced within a number of stages to ensure uniform distribution of all the aids in polyolefin. Four powder material flows are used. Three aid compositions are mixed with three parts of parent powder polyolefin in ratio 1:4, 1:3 and 1:2 respectively. Prepared concentrate mother stocks are supplied to the fourth combined mixer with residual part of polyolefin. If required, necessary liquid biodegradable additive. The blend is stirred and homogenised at 150-250°C.
EFFECT: underwater granulation and drying result in prepared antimisting and uncompressible sustained granular product characterised by good processing behaviour and performance attributes, easy-processed with the common equipment to make various products of controlled biodegradability.
3 cl, 5 tbl, 8 ex
SUBSTANCE: invention relates to fire-resistant compositions which are used for making various products, for example in form of films, fibre, tape, moulding compositions, section materials or as binders for coating materials, adhesives or filler. This composition contains (a) polyolefin and (b) at least one compound of formula I: R4R3R2C-Z1-Z2-Z3(R2)rR3R4 (I).
EFFECT: use of non-halogenated compounds of general formula (I) in the composition as antipyrene for polyolefins and is an industrially and environmentally necessary alternative to halogenated antipyrene compounds, resulting in excellent combustion slowing down, excellent initial colouring, weak yellowing and self-extinction of such compositions.
20 cl, 4 ex, 2 tbl
SUBSTANCE: thermoplastic polymer material is described, which contains an organic thermoplastic polymer and a complex additive for improving moulding in amount of 0.02-1 wt %. The complex additive used is a composition which contains polyester with melting temperature ranging from 35 to 120°C and molecular weight of 1000-10000 Da, and thickeners, selected from polymers with molecular weight ranging from 100000 to 20000000 Da which are soluble in polyesters, finely dispersed powders of oxides of silicon and titanium with particle size ranging from 1 to 1000 nm and phosphorus-containing organic compounds.
EFFECT: proposed thermoplastic polymer material allows for reducing energy consumption and moulding temperature during its processing, and reducing loss of polymer during moulding.
9 cl, 16 dwg, 16 ex
SUBSTANCE: composite additive contains particles of fibrous polytetrafluoroethylene and an effective amount of a fluorine-containing thermoplastic for preventing agglomeration of said particles of fibrous polytetrafluoroethylene.
EFFECT: improved processing of molten polymer, increased strength of basic polymer in molten mass.
10 cl, 2 tbl, 2 ex
SUBSTANCE: moulding method involves heating thermoplastic material higher than melting point, forcing the obtained melt through a die at 10-100°C higher than melting point of the thermoplastic material and cooling the product to temperature lower than melting point. The composition of thermoplastic material includes a thermoplastic polymer and a complex additive for improving moulding. The complex additive used is a reactive composition containing at least one polyether polyol and at least one thickening component selected from a group comprising polybasic organic acids, anhydrides of polybasic organic acids, fatty acids containing 8-18 carbon atoms, as well as mixtures thereof.
EFFECT: method cuts on induction time, increases rate of flawless moulding thermoplastic material, reduces power consumption and moulding temperature, lowers pressure in the equipment when moulding high molecular weight polymers, simplifies and lowers the cost of moulding articles from thermoplastic polymer materials.
12 cl, 11 dwg, 14 ex