Polymeric mixtures from ethylene/α-olefin interpolymers having improved compatibility

FIELD: chemistry.

SUBSTANCE: mixture contains two different polyolefin and ethylene/α-olefin copolymers. The ethylene/α-olefin copolymer is a block-copolymer containing at least one hard block and at least one soft block. The ethylene/α-olefin copolymer can function as a component which improves compatibility between two polyolefins which may be incompatible. The disclosed polymeric mixtures can be used in making various articles such as tyres, hoses, belts, linings, shoe soles, cast and moulded articles. Said mixtures are especially useful for applications requiring melt strength, such as big articles made by blow moulding, foam and bundled bars.

EFFECT: improved compatibility of mixtures.

27 cl, 10 dwg, 13 tbl, 40 ex

 

The technical FIELD

The present invention relates to polymer mixtures made from ethylene/α-olefin of interpolymer, and at least two polyolefins, to methods for producing mixtures, and products made from these mixtures.

The LEVEL of TECHNOLOGY

Multiphase polymer mixtures are of great economic importance in the polymer industry. Some examples of multiphase polymer blends are thermoplastic, modified for toughness due to dispersion of rubber modifiers in thermoplastic matrices. In General industrial polymer mixture composed of two or more polymers, combined with small amounts of combining agent / interfacial agent. Usually combining agents or interfacial agents represent a block - or graft-copolymers, which can encourage the formation of small domains of rubber in the polymer mixtures so that improved impact strength.

In many cases, a mixture of polypropylene (PP) and ethylene/α-olefin copolymers. The ethylene/α-olefin copolymer operates in mixtures as rubber modifier and provides strength and good toughness. In General impact the effectiveness of the ethylene/α-olefin copolymer may be a function of (a) glass transition temperature (Tarticle) mod is ficalora rubber, b) adhesion of the rubber modifier to interphase polypropylene and (C) the difference in viscosities of the rubber modifier and polypropylene. Tarticlerubber modifier can be improved in various ways, such as lowering of crystallinity α-olefin component. Similarly, the difference between the viscosities of the rubber modifier and polypropylene can be optimized using various techniques, such as the regulation of the molecular mass and molecular mass distribution of the rubber modifier. For copolymers of ethylene and higher alpha olefins (NAO) interfacial adhesion of the copolymer can be increased by increasing the number of the NAO. However, when the copolymer of ethylene/NAO amount of the NAO is more than 55 mol.%, the polypropylene becomes miscible with the copolymer of ethylene/NAO and they form a single phase, and a small rubber domains are missing. Therefore, the copolymer of ethylene/NAO with more than 55 mol.% NAO finds limited use as a modifier toughness.

For thermoplastic vulcanizates (TPV, TPV), in which the rubber domains of cross stitched, preferably improved properties, such as residual deformation under compression and ultimate tensile strength. The necessary properties can be improved by lowering the average particle size of the rubber. During stage d is namikoshi vulcanization ( containing polypropylene and a polyolefin interpolymer, such as terpolymer ethylene/α - olefin/diene (for example, terpolymer ethylene/propylene/diene (EPDM)), there must be a balance compatibility terpolymer with polypropylene. In General EPDM has good compatibility with polypropylene, but with higher levels of propylene EPDM compatibility can be improved only minimally.

Despite the availability of a number of polymer blends, there remains a need in the development of polymer blends with improved properties.

The INVENTION

The above needs are met by various aspects of the present invention. In one aspect the invention relates to polymer mixtures containing: (i) a first polyolefin; (ii) a second polyolefin; and (iii) the ethylene/α-olefin interpolymer, where the first polyolefin, the second polyolefin and the ethylene/α-olefin interpolymer are different. The definition of "different"when it refers to two polyolefins, means that the two polyolefin differ in composition (type of comonomers, the content of comonomers, etc.), structure, properties, or combinations of such parameters. For example, ethylene/octenoyl block copolymer differs from the statistical ethylene/actinophage copolymer, even if they have the same amount of comonomers. The ethylene/octenoyl block copolymer is different is raised from the ethylene/butenova copolymer regardless whether it is a statistical or block copolymer, or whether it has the same content of comonomers. Two polyolefin also are considered different if they have different molecular weight even with the same structure and the same composition. Moreover, statistical homogeneous ethylene/octenoyl copolymer differs from the statistical heterogeneous ethylene/actinophage copolymer, even if all other parameters can be the same.

The ethylene/α-olefin interpolymer used in polymer mixtures, has one or more of the following characteristics:

(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting temperature, TPLin degrees Celsius and density, d, in grams/cubic centimeter, where the numerical values of TPLand d correspond to the relationship:

TPL>-2002,9+4538,5(d)-2422,2(d)2or

(b) has a Mw/Mn from about 1.7 to about 3.5 and is characterized by a heat of fusion, ΔN, j/g, and the value of Delta, ΔT, in degrees Celsius defined as the temperature difference between the highest peak of the DSC and the highest CRYSTAF peak, where the numerical values of ΔT and ΔN are the following relations:

ΔT>-0,1299(ΔN)+62,81 for ΔN more than zero and up to 130 j/g,

ΔT≥48°C for ΔN more than 130 j/g,

where CRYSTAF peak is determined using at least 5% in aggregate what about the polymer, and, if less than 5% of the polymer have an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; or

(C) is characterized by an elastic recovery, Re, in percent at strain of 300% and 1 cycle measured using the direct compression molded film of the ethylene/α-olefin of interpolymer, and has a density, d, in grams/cubic centimeter, where the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin interpolymer essentially no cross-linked phase:

Re>1481-1629(d); or

(d) has a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF, characterized in that the fraction has a molar content of comonomers, at least 5% higher than the molar content of comonomers fraction of comparable statistical interpolymer ethylene, eluting between the same temperatures, where the specified comparable statistical interpolymer ethylene contains the same comonomer(s) and has a melt index, density, and molar fractions of the comonomers (based on the whole polymer) within 10% of the melt index, density, and molar content of comonomers the ethylene/α-olefin of interpolymer; or

(e) is characterized by a dynamic elastic modulus at 25°C., G'(25°C), and dynamic modulus of elasticity at 100°C., G'(100°C.), where the ratio of G'(25°C.)to G'(100°C.) is from about 1:1 to about 10:1.

In one of the embodiments, the ethylene/α-olefin interpolymer has a Mw/Mn from about 1.7 to about 3.5, at least one melting temperature, TPLin degrees Celsius and density, d, in grams/cubic centimeter, where the numerical values of TPLand d correspond to the relationship:

TPL≥858,91-1825,3(d)+1112,8(d)2.

In another embodiment of the invention, the ethylene/α-olefin interpolymer has a Mw/Mn from about 1.7 to about 3.5 and is characterized by a heat of fusion, ΔN in j/g and the value of Delta, ΔT, in degrees Celsius defined as the temperature difference between the highest peak of the DSC and the highest CRYSTAF peak, where the numerical values of ΔT and ΔN are the following relations:

ΔT>-0,1299(ΔN)+62,81 for ΔN more than zero and up to 130 j/g,

ΔT≥48°C for ΔN more than 130 j/g,

where CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5% of the polymer have an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C.

In one embodiment of the invention, the ethylene/α-olefin interpolymer characterized by an elastic recovery, Re, in percent at strain of 300% and 1 cycle measured using the direct pressing of a film of the ethylene/α-olefin of interpolymer, and has a density, d, in grams/cubic centimeter, where the numerical values of Re and d is udovletvoryaut following relationship, when the ethylene/α-olefin interpolymer essentially no cross-linked phase: Re>1481-1629(d), Re>1491-1629(d), Re>1501-1629(d), Re>1511-1629(d).

In some embodiments of the invention the polymer mixture contains (i) a first polyolefin; (ii) a second polyolefin; and (iii) the ethylene/α-olefin interpolymer, where the first polyolefin, the second polyolefin and the ethylene/α-olefin interpolymer are different. In one of the embodiments, the ethylene/α-olefin interpolymer has:

(a) at least one molecular fraction which aluinum from 40 to 130°C. fractionation using TREF, characterized in that the fraction has a blocking of at least 0.5 and up to about 1 and a molecular weight distribution Mw/Mn of more than about 1.3; or

(b) has an average deblocking more than zero and up to approximately 1.0 and a molecular weight distribution Mw/Mn of more than approximately 1.3.

In other embodiments of the invention, the ethylene/α-olefin interpolymer has a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF, characterized in that the fraction has a molar content of comonomers, at least 5% higher than the molar content of comonomers fraction of comparable statistical interpolymer ethylene, eluting between the same temperatures, where the specified FOSS is tamimy statistical interpolymer ethylene contains the same comonomer(s) and has a melt index, the density and molar fractions of the comonomers (based on the whole polymer) within 10% of the melt index, density, and molar content of ethylene/α-olefin of interpolymer.

In some embodiments of the invention, the ethylene/α-olefin interpolymer characterized by a dynamic elastic modulus at 25°C., G'(25°C), and dynamic modulus of elasticity at 100°C., G'(100°C.), where the ratio of G'(25°C.) to G'(100°C.) is from about 1:1 to about 10:1.

In one embodiment of the invention, the ethylene/α-olefin interpolymer is a statistical block copolymer containing at least a solid block and at least a soft block. In another embodiment, the ethylene/α-olefin interpolymer is a statistical block copolymer containing many solid blocks and a lot of soft blocks and hard blocks and soft blocks are statistically distributed in the polymer chain.

In one embodiment of the invention the α-olefin in the polymer mixture described is a4-40-α-olefin. In another embodiment of the invention the α-olefin is a styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-penten, norbornene, 1-mission 1,5-hexadiene or a combination of both.

In some embodiments of the invention, the ethylene/α-olefin interpolymer has a melt index in the range of from about 0.1 to arr is siteline 2000 g/10 min, from about 1 to about 1500 g/10 min, from about 2 to about 1000 g/10 min, or from about 5 to about 500 g/10 min when measured according to ASTM D-1238, condition 190°C/2,16 kg

In some embodiments of the invention, the amount of the ethylene/α-olefin of interpolymer in polymer mixtures proposed in the invention is from about 0.5 to about 99%, from about 1 to about 50%, from about 2 to about 25%, from about 3 to about 15% or from about 5 to about 10% based on the weight of the entire composition.

In other embodiments of the invention, the ethylene/α-olefin interpolymer contains soft segments having a content of α-olefin is more than 30 mol.%, more than 35 mol.%, more than 40 mol.%, more than 45 mol.% or more than 55 mol.% In one embodiment of the invention the elastomeric polymer contains soft segments having a content of α-olefin, more than 55 mol.%.

In some embodiments of the invention, the ethylene/α-olefin interpolymer in the polymer mixture contains an elastomeric polymer having an ethylene content of 5 to 95 mol.%, the content of diene from 5 to 95 mol.% and the content of α-olefin of 5 to 95 mol.%. the α-olefin in the elastomeric polymer may be a4-40-α-olefin.

In some embodiments of the invention the number of the first floor is the olefin in polymer blends is from about 0.5 to about 99 wt.% based on the total weight of the polymer mixture. In some embodiments of the invention, the amount of the second polyolefin in the polymer mixture is from about 0.5 to about 99 wt.% based on the total weight of the polymer mixture.

In one embodiment of the invention, the first polyolefin is an olefin Homo-polymer, such as polypropylene. The polypropylene for use in this case is up to, but not limited to, polypropylene, low density (LDPP), polypropylene, high-density (HDPP), polypropylene with high melt strength (HMS-PP), polypropylene with high toughness (HIPP), isotactic polypropylene (RR), syndiotactic polypropylene (sPP) and their combination. In one embodiment of the invention, the polypropylene is an isotactic polypropylene.

In another embodiment of the invention the second polyolefin is an olefin copolymer, the olefin terpolymer or a combination of both. Olefin copolymer may be derived from ethylene and monoene containing 3 or more carbon atoms. Examples of olefinic comonomers are ethylene/alpha-olefin (EAO) copolymers and ethylene/propylene copolymers (EPM). The olefinic terpolymer for use in polymer mixtures can be obtained from ethylene, monoene containing 3 or more carbon atoms and diene, and includes, but is not limited to, t is polymer ethylene/alpha-olefin/diene (DM) and terpolymer ethylene/propylene/diene (DM). In one embodiment of the invention the second polyolefin is a capable of vulcanization of rubber.

In some embodiments of the invention the polymer blend further comprises at least one additive, such as decreasing the friction additive-caking agent, plasticizer, antioxidant, UV stabilizer, a colorant or pigment, a filler, a lubricating substance, protivoukachiwauschee substance that increases the fluidity additive, a binder, a crosslinking agent, a nucleating agent, a surfactant, a solvent, a flame retardant, an antistatic agent or a combination of both. Also in the invention offers a molded product containing the polymer mixture. Examples of the molded products are tire, hose, belt, seals, Shoe soles, casting or molded part. Such molded articles can be obtained by injection molding, the molding extrusion blow or injection molding blow. In one embodiment of the invention is a molded product of foamed by chemical or physical blowing agent.

In addition, the invention provides a sheet products, profiled products and film products, including at least one layer containing the proposed polymer mixture. In one embodiment of the invention sheet product produces the t extrusion or calandrinia. In another embodiment of the invention the sheet product is foamed by chemical or physical blowing agent. Also the invention provides a thermoplastic molded product consisting of a sheet. In some embodiments of the invention profiled and film products can be obtained by extrusion.

Also the methods of obtaining a polymer mixture comprising blending a first polyolefin, the second polyolefin and the ethylene/α-olefin of interpolymer, where the first polyolefin, the second polyolefin and the ethylene/α-olefin interpolymer are different. The ethylene/α-olefin interpolymer used in the polymer mixture, is an ethylene/α-olefin interpolymer, which is described above and throughout the description.

Additional aspects of the invention and the characteristics and properties of various embodiments of the invention will be clear from the following description.

BRIEF DESCRIPTION of DRAWINGS

Figure 1 illustrates the ratio of the melting point/density for the inventive polymers (shown by diamonds) in comparison with traditional statistical copolymers (shown with circles) and copolymers of Ziegler-Natta (shown with triangles).

Figure 2 is a graphic Delta DSC-CRYSTAF as a function of enthalpy of melting in the DSC for different polymers. Ambani shows statistical copolymers, ethylene/octene; squares show the polymers of examples 1-4; triangles shows the polymers of examples 5-9; and circles shows the polymers of examples 10-19. The symbols "X" indicate the comparative polymers of examples A*-F*.

Figure 3 shows the effect of density on elastic recovery for unoriented films made from the claimed interpolymers (shown by squares and circles), and traditional copolymers (shown by triangles), which represent the various polymers Dow AFFINITY®. Squares presents the inventive ethylene/butenova copolymers; and circles presents the inventive ethylene/okanoya copolymers.

Figure 4 is a plot of octene content in separated by TREF fractions of the copolymer of ethylene/1-octene from the temperature of the elution fraction at TREF for the polymer of example 5 (shown by circles) and the polymer of comparative examples E* and F* (shown by symbols "X"). Diamonds shows traditional statistical copolymers, ethylene/octene.

Figure 5 is a plot of octene content in the fractions fractionated using TREF ethylene/1-actinophage copolymer to the temperature of the elution fraction at TREF for the polymer of example 5 (curve 1) and the polymer of comparative example F* (curve 2). Squares show the polymer of comparative example F*; and treugol what IKI 5 shows an example.

6 is a graph showing the log of the dynamic modulus of elasticity as a function of temperature for comparative ethylene/1-actinophage copolymer (curve 2), propylene/ethylene copolymer (curve 3) and for two ethylene/1-oktanovyh block copolymers of the present invention, made with different amounts of agent transfer chain (curve 1).

7 is a graph of data TMA (1 mm) from the modulus of elasticity in bending for some of the claimed polymers (shown by diamonds) in comparison with some well-known polymers. Triangles shows the different polymers Dow VERSIFY®; circles presents various statistical copolymers, ethylene/styrene; and squares show the different polymers Dow AFFINITY®.

Fig is a micrograph obtained with a transmission electron microscope, a mixture of polypropylene and ethylene/actinophage block copolymer of example 20.

Figure 9 is a micrograph obtained with a transmission electron microscope, a mixture of polypropylene and statistical ethylene/actinophage copolymer (comparative example a1).

Figure 10 is a micrograph obtained with a transmission electron microscope, a mixture of polypropylene, ethylene/actinophage block copolymer (example 20) statisticheskoe ethylene/actinophage copolymer (comparative example a 1).

DETAILED description of the INVENTION

Common definitions

"Polymer" means a polymer compound obtained by polymerization of the monomers, or the same or different type. A General definition of "polymer" encompasses the definition of "homopolymer", "copolymer", "terpolymer"and "interpolymer".

"Interpolymer" means a polymer obtained by polymerization of at least two different types of monomers. The General definition of "interpolymer" includes the term "copolymer" (which is typically used for polymer derived from two different monomers), as well as the definition of "terpolymer" (which is typically used for polymers derived from three different types of monomers). It also includes polymers made by the polymerization of four or more types of monomers.

The term "ethylene/α-olefin interpolymer" in General refers to polymers containing ethylene and α-olefin containing 3 or more carbon atoms. Preferably the ethylene constitutes a significant molar fraction of the total polymer, i.e. the ethylene is at least about 50 mol.% based on the entire polymer. More preferably, the ethylene is at least about 60 mol.%, at least about 70 mol.% or at least about 80 mol.%, the being is m a signicant balance of the total polymer is at least one other comonomer, which preferably is an α-olefin containing 3 or more carbon atoms. For many, the ethylene/oktanovyh copolymers, the preferred composition is characterized by an ethylene content of more than about 80 mol.% based on the entire polymer, and the content of octene from about 10 to about 15, preferably from about 15 to about 20 mol.% based on the entire polymer. In some embodiments, the ethylene/α-olefin interpolymer not include interpolymer produced with low output or in a small amount or as a by-product of a chemical process. Although the ethylene/α-olefin interpolymer can be mixed with one or more polymers, themselves obtained ethylene/α-olefin interpolymer are essentially pure and often contain as the main component is the reaction product of the polymerization process.

The ethylene/α-olefin interpolymer contain ethylene and one or more capable of copolymerization of α-olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties. That is, the ethylene/α-olefin interpolymer represent b is OK interpolymer, preferably the polyblock-interpolymer or copolymers. The definition of "interpolymer" and "copolymer" in this description are used interchangeably. In some embodiments of the invention, the polyblock copolymer can be represented by the following formula:

(AB)n,

where n has a value of at least 1, preferably is an integer more than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or more "A" represents a hard block or segment and "B" represents a soft block or segment. Preferably the blocks a and b are connected essentially in a linear scheme, in contrast, essentially, branched or, essentially, a star schema. In other embodiments of the invention blocks a and blocks In a statistically distributed along the polymer chain. In other words, the block copolymers do not usually have the following structure:

AAA-AA-BBB-CC.

In other embodiments of the invention block copolymers usually have no unit of the third type, which contains the other(s) comonomer(s). In yet another variant of the invention, each of block a and block b contains monomers or comonomers essentially statistically distributed within the block. In other words, neither the block a or the block does not contain two or more sub-segments (or sub-blocks) of the other part, such as the terminal segment, which has, essentially, on the natives of the composition, than the remainder of the block.

The polyblock-polymers usually contain different amounts of "hard" and "soft" segments. "Hard" segments indicate blocks of polymerized units in which ethylene is present in more than 95% and preferably more than about 98% based on weight of the polymer. In other words, the content of comonomers (content of monomers other than ethylene) in the hard segments is less than about 5 wt.% and preferably less than about 2 wt.% based on weight of the polymer. In some embodiments, the solid segments contain all or almost all of the ethylene. "Soft" segments, on the other hand, are blocks of polymerized units in which the content of comonomers (content of monomers other than ethylene) is more than about 5 wt.%, more than about 8 wt.%, preferably more than about 10 wt.% or more than about 15 wt.% based on weight of the polymer. In some embodiments, the content of comonomers in the soft segments can be more than about 20 wt.%, more than about 25 wt.%, more than about 30 wt.%, more than about 35 wt.%, more than about 40 wt.%, more than about 45 wt.%, more than about 50 wt.% or more than about 60 wt.%.

Soft semanticist may be present in the block-interpolymer in the amount of from about 1 to about 99 wt.% based on the total weight of the block interpolymer, preferably from about 5 to about 95 wt.%, from about 10 to about 90 wt.%, from about 15 to about 85 wt.%, from about 20 to about 80 wt.%, from about 25 to about 75 wt.%, from about 30 to about 70 wt.%, from about 35 to about 65 wt.%, from about 40 to about 60 wt.% or from about 45 to about 55 wt.% based on the total weight of the block interpolymer. And, on the contrary, the hard segments may be present in the same intervals. The mass percentage of the soft segment and the mass percentage of hard segment can be calculated on the basis of data obtained by DSC or NMR. Such methods and calculations are described in on the simultaneous consideration of the patent application U.S. registration No._______(to enter, when it becomes known), Attorney Docket No. 385063-999558, entitled "Ethylene/α-olefin block interpolymer"aimed for review March 15, 2006, on behalf of Colin L.P. Shan, Lonnie Hazlitt et al., and owned by Dow Global Technologies Inc., the description of which is incorporated in its entirety by reference.

The definition of "crystal", if it is used, refers to a polymer that has a transition point of the first order or crystalline melting temperature (TPL), about the certain using differential scanning calorimetry (DSC) or equivalent technique. The definition can be used interchangeably with the term "semi-crystalline". The definition of "amorphous" refers to a polymer that does not have a crystalline melting temperature, determined by differential scanning calorimetry (DSC) or equivalent technique.

The definition of "polyblock copolymer" or "segmented copolymer" means a polymer containing two or more chemically distinct regions or segments (referred to as "blocks")preferably joined at a linear pattern, i.e. the polymer contains chemically distinct units, which are connected end-to-end relative to the polymerized ethylene functionality, and not by the scheme with the side chain or by inoculation. In a preferred embodiment, the blocks differ in the amount or type of co monomer entered into them, density, crystallinity, size, crystallinity attributed to a polymer of such composition, the type or degree of regularity of the molecular structure (isotactic or syndiotactic), Regio-regularity or Regio-irregularity, the number of branches, including long chain branching or Hyper-branching, homogeneity, or any other chemical or physical properties. The polyblock copolymers are characterized by a unique index paid is sparsely (TTD (PDI or Mw/Mn), distribution blocks along the length and/or distribution of units by number due to the unique process of obtaining copolymers. More specifically, when receiving a continuous way the polymer in accordance with the need has TTD from 1.7 to 2.9, preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to 2.1. By periodic or properities process the polymer has a TTD from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to 1.8.

The definition of "combining agent" refers to a polymer which when added to immiscible polymer blends can improve the Miscibility of the two polymers, resulting in improved stability of the mixture. In some embodiments of the invention combining the agent can reduce the average size of the domain, at least 20%, more preferably at least 30%, at least 40% or at least 50%when added to the mixture to approximately 15 wt.% combining agent. In other embodiments of the invention combining the agent can increase the Miscibility of two or more polymers, at least 10%, more preferably at least 20%, at least 30%, at least 40% or at least 50%when added to the mixture about 1 wt.% combining agent.

The definition of "immiscible" refers to two polymers, when they do not form a homogeneous mixture after mixing. In other words, the mixture is phase separation. One of the methods for the quantitative determination of necesitamos two polymers is the use of the solubility parameter of Hildebrand, which is a measure of the total forces holding the molecules of solids and liquids together. Each polymer has a specific value of the solubility parameter, although this option is not always available. Polymers with similar solubility parameters tend to be mixed. On the other hand, polymers with widely differing solubility parameters tend not to mix, although there are many exceptions to this rule. Discussion of the concepts of solubility parameters presented in publications (1) Encyclopedia of Polymer Science and Technology, Interscience, New York (1965), Vol. 3, p. 833; (2) Encyclopedia of Chemical Technology, Interscience, New York (1971), Supp. Vol., p. 889; and (3) Polymer Handbook, 3-rd Ed., J. Brandup, E.H. Immergut (Eds.), (1989), John Wiley & Sons “Solubility Parameter Values”, pp. VII-519, which are included in the description by reference in their entirety.

The definition of "interfacial agent" refers to an additive that reduces the energy of the interface between the phase domains.

The term "olefin" refers to a hydrocarbon containing, hence, is her least one carbon-carbon double bond.

The definition of "thermoplastic vulcanizer" (TPV, PV) refers to technical thermoplastic elastomer, in which the cured elastomeric phase dispersed in a thermoplastic matrix. TPV usually contains at least one thermoplastic material and at least one cured (i.e. cross-linked) of elastomeric material. In some embodiments of the invention thermoplastic material forms a continuous phase, and the cured elastomer forms a discrete phase; that is, the domains of the cured elastomer dispersed in a thermoplastic matrix. In other embodiments of the invention, the domains of the cured elastomer is completely and uniformly dispersed with an average domain size in the range of from about 0.1 to about 100 microns, from about 1 to about 50 microns, from about 1 to about 25 microns, from about 1 to about 10 microns, or from about 1 to about 5 microns. In some embodiments of the invention the matrix phase of the TPV is present in amount of less than about 50 vol.% based on TPV, and the dispersed phase is present in amounts of at least about 50 vol.% based on TPV. In other words, cross-linked elastomeric phase is in TPV main phase while thermoplastic polymer is a minor phase. TPV with such phase composition can have a good residual deformation under compression. However, it can also be obtained (with the main phase, representing a thermoplastic polymer and a minor phase is cross-linked elastomer. Typically, the cured elastomer has a portion which is insoluble in cyclohexane at 23°C. the Amount of the insoluble part is preferably more than about 75% or about 85%. In some cases, the amount of insoluble component is more than about 90%, about 93%, about 95% or about 97 wt.% based on the entire elastomer.

In the description below, disclosed all numbers are approximate values, regardless of whether used or not in connection with them the word "approximately" or "about". They can vary by 1%, 2%, 5% and sometimes up to 10-20%. Whenever describes the numeric interval with a lower bound of RLand upper bound RU, any number falling within the interval, is specified. In particular, the following numbers within the range are specifically disclosed: R=RL+k*(RU-RL), where k represents a variable, in the range from 1 to 100% with a 1%increase, that is, k is 1%, 2%, 3%, 4%, 5%, ..., 50%, 51%, 52%, ..., 95%, 96%, 97%, 98%, 99% or 100%. Bo is her, any numeric interval defined by two numbers R, as shown above, is also specifically disclosed. Embodiments of the present invention offer a polymer mixture containing at least one ethylene/α-olefin interpolymer and at least two polyolefin. Polymer blend with improved compatibility has unique physical and mechanical properties that are suitable for the manufacture of moulded products for various applications. The ethylene/α-olefin interpolymer can improve the compatibility of the two polyolefins, which otherwise can be relatively incompatible. In other words, interpolymer is combining agent between two or more polyolefins.

The ethylene/α-olefin interpolymer

The ethylene/α-olefin interpolymer used in embodiments implementing the present invention (also referred to as "claimed by interpolymer" or "inventive polymer"), contain ethylene and one or more capable of copolymerization of α-olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), preferably in the form of a polyblock-copolymerisation/α-olefin interpolymer are characterized by one or more aspects, below.

In one aspect, the ethylene/α-olefin interpolymer used in embodiments of the invention have a Mw/Mn from about 1.7 to about 3.5, at least one melting temperature, TPLin degrees Celsius and density, d, in grams/cubic centimeter, where the numerical values of the variables correspond to the relationship:

TPL>-2002,9+4538,5(d)-2422,2(d)2and preferably

TPL≥-6288,1+13141(d)-6720,3(d)2and more preferably

TPL≥858,91-1825,3(d)+1112,8(d)2.

The specified value melting point/density figure 1 illustrates. Unlike traditional random copolymers of ethylene/α-olefins whose melting points decrease with decreasing density, the claimed interpolymer (represented by diamonds) are the melting temperature is essentially independent of the density, particularly when the density is in the range of from about 0.87 for up to about 0.95 g/cm3. For example, the melting temperature of such polymers is in the range of from about 110 to about 130°C., when the density is in the range from 0,875 to approximately 0,945 g/cm3. In some embodiments of the invention, the melting point of these polymers is in the range of from about 115 to about 15°C, when the density is in the range from 0,875 to approximately 0,945 g/cm3.

In another aspect, the ethylene/α-olefin interpolymer contain in polymerized form ethylene and one or more α-olefins and are characterized by ΔT, in degrees Celsius defined as the temperature of the highest peak in differential scanning calorimetry (DSC, DCK) minus the temperature of the highest peak in the analysis fractionation by crystallization ("CRYSTAF"), and a heat of fusion, ΔN, j/g, ΔT and ΔN satisfy the following relations:

ΔT>-0,1299(ΔN)+62,81, and preferably

ΔT≥-0,1299(ΔN)+64,38, and more preferably

ΔT≥-0,1299(ΔN)+65,95,

for ΔN up to 130 j/g moreover, ΔT is equal to or greater than 48°C for ΔN more than 130 j/g CRYSTAF Peak is determined using at least 5% of the total polymer (that is, the peak must display at least 5% of the cumulative polymer, and if less than 5% of the polymer are determined by CRYSTAF peak, then the CRYSTAF temperature is 30°C., and ΔN represents the numerical value of the heat of fusion in j/g, More preferably, when the most high CRYSTAF peak contains, in least 10% of the total polymer. Figure 2 graphically illustrates data for the inventive polymers, as well as for the comparative examples. Integrated peak areas and peak temperatures calculated with whom utiliziruemoj program construction drawings, supplied by the equipment manufacturer. The diagonal line shown for statistical ethylene/oktanovyh comparative polymers corresponds to the equation ΔT=-0,1299(ΔN)+62,81.

In yet another aspect, the ethylene/α-olefin interpolymer have a molecular fraction which aluinum from 40 to 130°C. fractionation using the fractionation method elution with increasing temperature (TREF), characterized in that the fraction has a molar content of comonomers is preferably at least 5 percent higher, more preferably at least 10% higher than the molar content of comonomers fraction of comparable statistical interpolymer ethylene, eluting between the same temperatures, where the specified comparable statistical interpolymer ethylene contains the same comonomer(s) and has a melt index, density, and molar content of comonomers (based on the whole polymer) within 10% of the melt index, density, and molar content of comonomers block interpolymer. Preferably Mw/Mn of comparable interpolymer is also within 10% of Mw/Mn of block interpolymer and/or comparable interpolymer has a total content of comonomers is in the range of 10 wt.% from the total content of comonomers block interpolymer.

In yet another aspect, the ethylene/α-olei the marketing interpolymer characterized by an elastic recovery, Re, in percent at strain of 300% and 1 cycle measured using the direct pressing of a film of the ethylene/α-olefin of interpolymer, and has a density, d, in grams/cubic centimeter, where the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin interpolymer essentially no cross-linked phase:

Re>1481-1629(d); and preferably

Re≥1491-1629(d); and more preferably

Re≥1501-1629(d); and even more preferably

Re≥1511-1629(d).

Figure 3 illustrates the effect of density on elastic recovery for unoriented films made from the claimed interpolymers and traditional statistical copolymers. For the same values of density of the claimed interpolymer have significantly higher elastic recovery.

In some embodiments of the invention, the ethylene/α-olefin interpolymer have a limit of tensile strength of more than 10 MPa, preferably a tensile strength at elongation ≥11 MPa, more preferably limit tensile stress ≥13 MPa, and/or elongation at break of at least 600%, more preferably at least 700%, more preferably at least 800 percent, and most preferably at least 900%, at a speed of separation of the guide head 11 cm/min

In other in which the options for the implementation of the ethylene/α-olefin interpolymer are (1) the ratio of the dynamic modulus of elasticity G'(25°C.)/G'(100°C) from 1 to 50, preferably from 1 to 20, more preferably from 1 to 10; and/or (2) the residual deformation under compression at 70°C less than 80%, preferably less than 70%, in particular less than 60%, less than 50% or less than 40%, falling to the relative deformation in compression 0%.

In other embodiments, implementation of the ethylene/α-olefin interpolymer have residual deformation under compression at 70°C less than 80%, less than 70%, less than 60% or less than 50%. Preferably the residual deformation under compression at 70°C interpolymer is less than 40%, less than 30%, less than 20% and may drop to approximately 0%. In some embodiments, the implementation of the ethylene/α-olefin interpolymer have a heat of fusion of less than 85 j/g and/or the strength of adhesion of the pellets is equal to or less than 100 lb/ft2(4800 PA), preferably equal to or less than 50 lb/ft2(2400 PA), especially equal to or less than 5 lb/ft2(240 PA), and to 0 lb/ft2(0 PA).

In other embodiments of the invention, the ethylene/α-olefin interpolymer contain in polymerized form, at least 50 mol.% ethylene and have a residual deformation under compression at 70°C less than 80%, preferably less than 70% or less than 60%, most preferably less than 40-50% and falls to nearly zero percent.

In some embodiments of the invention the polyblock copolymers have a measure of polydispersity (TTD, PDI), satisfying the m distribution Schulz-Flora, instead of the Poisson distribution. The copolymers are also characterized as having as polydisperse distribution blocks and polydisperse distribution of units by size and with the probable distribution of block length. Preferred polyblock copolymers are copolymers containing 4 or more blocks or segments, including the end blocks. More preferably, the copolymers contain at least 5, 10 or 20 blocks or segments, including end blocks.

The content of comonomers can be measured using any suitable technique, preferably are methods based on nuclear magnetic resonance (NMR). Moreover, in the case of polymers or mixtures of polymers having relatively broad curves TREF, the polymer it is desirable to first fractionate using TREF fractions, each of which has a temperature range of elution of 10°C or less. That is, each allerona faction has a temperature window Assembly 10°C or less. When using such methods specified block interpolymer contain at least one fraction having a higher molar content of comonomers than the corresponding fraction of comparable interpolymer.

In yet another aspect, the inventive polymer is an olefin is th interpolymer, preferably contains ethylene and one or more capable of copolymerization of the comonomers in polymerized form, characterized by multiple blocks (i.e., at least two blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), most preferably in the form of a polyblock-copolymer; and the specified block interpolymer has a peak (and not just a molecular fraction)which aluinum from 40 to 130°C. (but without collecting and/or separation of individual fractions), characterized in that said peak, has a content of the comonomers, estimated using infrared spectroscopy, the extension using the area calculation all width/half maximum (FWHM) has an average molar content of the above comonomers, preferably at least 5 percent higher, more preferably at least 10% higher than the molar content of the copolymers peak comparable statistical interpolymer ethylene at the same temperature elution and expansion using the area calculation all width/half maximum (FWHM), where specified comparable statistical ethylene interpolymer contains the same comonomer(s) and has a melt index, the density and the molar content of comonomers (based on in the camping polymer) within 10 percent of the melt, density and molar content of comonomers block interpolymer. Preferably Mw/Mn of comparable interpolymer is also within 10% of the value of Mw/Mn of block interpolymer and/or comparable interpolymer has a total content of comonomers is in the range of 10 wt.% from the total content of comonomers block interpolymer. Calculation of all width/half maximum (FWHM) is based on the area ratio of the response of methyl to methylene [CH3/CH2] from the infrared detector ATREF, where the highest (largest) peak is determined from the zero line, then the area is calculated FWHM. For distribution, measured using ATREF peak, the FWHM area is defined as area under the curve between T1and T2where T1and T2are certain points on the left and right ATREF peak by dividing the peak height by two and then holding the line, horizontal zero line, which crosses the left and right side of the ATREF curve. Receive a calibration curve for the content of comonomers using statistical ethylene/α-olefin copolymers, causing the content of comonomers from the NMR data against space FWHM of the peaks TREF. In the case of an infrared method, a calibration curve is built for this type of co monomer. The content of comonomers for maximum TREF claimed is the iMER can be determined by correlating data from this calibration curve using his relationship areas FWHM methyl:methylene [CH 3/CH2] TREF peak.

The content of comonomers can be measured using any suitable technique, preferably the techniques based on spectroscopy nuclear magnetic resonance (NMR). When using this method, the specified block interpolymer have a higher molar content of comonomers than the corresponding comparable interpolymer.

Preferably in the case of interpolymers ethylene and 1-octene block interpolymer is the content of the comonomers of the TREF fraction, eluting between 40 and 130°C, more than or equal to the value

(-0,2013)T+20,07, more preferably more than or equal to the value (-0,2013)T+21,07, where T represents the numerical value of the temperature of the elution peak compared to the TREF fraction, measured in °C.

Figure 4 graphically shows a variant implementation of the block-interpolymers ethylene and 1-octene, where the graph of the content of comonomers relative to the temperature of the TREF elution for some comparable ethylene/1-oktanovyh of interpolymers (random copolymers) meets the line corresponding to the equation (-0,2013)T+20,07 (solid line). The line for the equation (-0,2013)T+21,07 are shown with dotted lines. Also presents the content of comonomers for fractions of some block interpolymers ethylene/1-octene of the present invention (polyblock copolymers). All factions BC is K-interpolymer have significantly higher content of 1-octene, than any line at equivalent temperatures elution. This result is characteristic of the claimed interpolymer and is believed due to the presence within the polymer chains of distinct blocks having crystalline and amorphous nature.

Figure 5 graphically displays the TREF curve and the content of comonomers polymer fractions for example 5 and comparative example F*, which are discussed below. The peak eluting between 40 and 130°C., preferably from 60 to 95°C, for both polymers is divided into three parts, with each part aluinum in the temperature interval of less than 10°C. the Actual data for example 5 represented by triangles. The person skilled in the art will understand that it can be constructed corresponding calibration curve for interpolymers containing various comonomers, and the line used for comparison, corresponds to TREF values obtained for comparable interpolymer from the same monomers, preferably for statistical copolymers obtained using metallocene or composition of another homogeneous catalyst. The claimed interpolymer different molar fractions of the comonomers more than the value determined from the calibration curve at the same temperature TREF elution, preferably at least 5% more, more preference is sustained fashion, at least 10% more.

In addition to the above aspects and properties described, the inventive polymers can be characterized using one or more additional characteristics. In one aspect of the inventive polymer is an olefin, interpolymer, preferably containing ethylene and one or more capable of copolymerization of the comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), most preferably in the form of a polyblock-copolymer; and the specified block interpolymer has a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF increments, characterized in that the fraction has a molar content of the above comonomers, preferably at least 5%, more preferably at least 10, 15, 20 or 25% higher than the molar content of comonomers fraction of comparable statistical ethylene of interpolymer, eluting between the same temperatures, where the specified comparable statistical ethylene interpolymer contains the same copolymer(s), preferably it represents the same comonomer(s)and has a melt index, latest and the molar content of comonomers (based on the whole polymer) within 10 percent of the melt, density and molar content of comonomers block interpolymer. Preferably Mw/Mn of comparable interpolymer is also within 10% of Mw/Mn of block interpolymer and/or comparable interpolymer has a total content of comonomers within 10% of the total content of comonomers block interpolymer.

Preferably the above interpolymer are interpolymer of ethylene and at least one α-olefin, in particular interpolymer, has a density of polymer from about 0,855 to about 0.935 g/cm3and more preferably in the case of polymers containing more than about 1 mol.% the co monomer, block-interpolymer is the content of the comonomers of the TREF fraction, eluting between 40 and 130°C, more than or equal to the value (-0,1356)T+13,89, more preferably more than or equal to the value

(-0,1356)T+14,93, and most preferably more than or equal to the value

(-0,2013)T+21,07, where T represents the numerical value of the temperature of the elution peak ATREF compare the TREF fraction, which is measured in °C.

Preferably in the case described above interpolymers of ethylene and at least one alpha-olefin, especially interpolymers, has a density of polymer from about 0,855 to about 0.935 g/cm3and more preferably for polymers, containing the more about 1 mol.% the co monomer, block interpolymer is the content of the comonomers of the TREF fraction, eluting between 40 and 130°C, more than or equal to the value (-0,2013)T+20,07, more preferably more than or equal to the value (-0,2013)T+21,07, where T represents the numerical value of the temperature of the elution peak compared to the TREF fraction, which is measured in °C.

In yet another aspect, the inventive polymer is an olefin, interpolymer, preferably containing ethylene and one or more capable of copolymerization of the comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), most preferably in the form of a polyblock-copolymer; and the specified block interpolymer has a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF increments, characterized in that every fraction that has the content of comonomers, at least about 6 mol.%, has a melting temperature of more than approximately 100°C. In the case of fractions with the content of comonomers from about 3 to about 6 mol.%, each faction has a melting point by DSC of about 110°C. or higher. More preferably, these polymeric fraction containing, for men is our least 1 mol.% the comonomers have a melting point by DSC, which corresponds to the equation:

TPL≥(-5,5926)(mol.% the comonomers in the faction)+135,90.

In yet another aspect, the inventive polymer is an olefin, interpolymer, preferably containing ethylene and one or more capable of copolymerization of the comonomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units differing in chemical or physical properties (block interpolymer), most preferably in the form of a polyblock-copolymer; and the specified block interpolymer has a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF increments, characterized in that every fraction that has a temperature ATREF elution of more than or equal to about 76°C has an enthalpy of melting (heat of fusion)as measured by DSC, corresponding to the equation:

The heat of melting (j/g)≤(3,1718)(temperature ATREF elution in °C)-136,58.

The inventive block interpolymer have a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF increments, characterized in that every fraction that has a temperature of ATREF elution from 40°C and less than about 76°C., has ental the Oia melting (heat of melting), measured by DSC, corresponding to the equation:

The heat of melting (j/g)≤(1,1312)(temperature ATREF elution in °C)+22,97.

Measurement comonomeric composition ATREF peak using an infrared detector

Comonomeric the composition of the TREF peak can be measured using an infrared detector IR4, supplied by Polymer Char, Valencia, Spain ().

"Composite type" detector equipped with a measuring sensor (CH2) and the sensor composition (CH3), which are fixed narrowband infrared filters in the region of 2800-3000 cm-1. The measuring sensor detects methylene (CH2) the carbon atoms on the polymer (which is directly related to the concentration of polymer in solution), whereas the sensor structure defines a methyl (CH3group in the polymer. Mathematical quotient of the signal composition (CH3) on the measuring signal (CH2) is sensitive to the content of comonomers measured polymer in the solution and its response is calibrated using known standards ethylene/alpha-olefin copolymers.

Detector when used with a device ATREF gives as concentration (CH2), and composite (CH3) signal response lirovannomu polymer during the process TREF. Specific calibration of the polymer can be obtained by measuring the relationship of the horses CH 3for CH2for polymers with known content of comonomers (preferably measured by means of NMR). The content of comonomers ATREF peak of the polymer can be estimated by applying the reference calibration relations of squares for the individual responses of CH3and CH2(that is, the relationship of the squares of CH3/CH2regarding the content of comonomers).

The area of the peaks can be calculated using the calculate all width/half maximum (FWHM) after application of the respective zero lines to integrate the responses of individual signals from TREF chromatogram. Calculation of all width/half maximum is based on the ratio of the areas of methyl and methylene responses [CH3/CH2] from ATREF infrared detector, where the zero line is determined by the highest (largest) peak, and then the area is calculated FWHM. For distribution, measured using ATREF peak, the FWHM area is defined as area under the curve between T1 and T2, where T1 and T2 represent certain points on the left and right ATREF peak by dividing the peak height by two and then holding the line horizontally to the zero line, which crosses the left and right side of the ATREF curve.

The use of infrared spectroscopy for measurement of the content of comonomers in the polymer in such a way ATREF - so on; product designs is owned spectroscopy, in principle, similar to the definition using system GPC/FTIR, which are described in the following publications: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley; “Development of gel-permeation chromatography-Fourier transform infrared spectroscopy for characterization of ethylene-based face copolymers”. Polymeric Materials Science and Engineering (1991), 65, 98-100; and Deslauriers P.J.; Rohlfing, D.C.; Shieh, E.T., “Quantifying short chain branching microstructures in ethylene-1-olefin copolymers using size exclusion chromatography and Fourier transform infrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, which are both included in the description in its entirety by reference.

In other embodiments of the invention the inventive ethylene/α-olefin interpolymer characterized by an average blocking, ABI, which has a value greater than zero and reaches approximately 1.0 and a molecular weight distribution, Mw/Mn, of more than approximately 1.3. The average blocking, ABI, is a weighted average of deblocking (BI) for each fraction of the polymer obtained in preparative fractionation using TREF from 20 to 110°C with increment of 5°With:

where BIithis is a measure of blocking for the i-th fraction of the claimed ethylene/α-olefin of interpolymer obtained in preparative fractionation using TREF, and wirepresents the mass percentage of the i-th fraction. For each fraction of polymer BI is determined by one of the following two equations, both of which give the same value BI):

or

where TXis the temperature of the elution preparative fractionation using TREF for the i-th fraction (preferably expressed in Kelvin), RXrepresents the molar fraction of ethylene for the i-th fraction, which can be measured by NMR or IR spectroscopy, which is described above. PABrepresents the molar fraction of ethylene only the ethylene/α-olefin of interpolymer (before fractionation), which can also be measured by NMR or IR spectroscopy. TAndand RAndrepresent the temperature of the ATREF elution and the molar proportion of ethylene to clean "hard segments" (which are crystalline segments interpolymer). As an approximation of the first order value of TAndand RAndlead to values for polyethylene homopolymer high density, if the actual values of TAndand RAndfor "hard segments" is not available. In the case of calculations conducted in this description, TAndequal K, RAndequal to 1.

TABis the ATREF temperature for a statistical copolymer of the same composition and having a molar fraction of ethylene in fraction RAB. TABcan be calculated from the following is about the equation:

LnAB=α/TAB+β,

where α and β are two constants which can be determined by calibration using a number of known statistical copolymers of ethylene. It should be noted that α and β can vary from device to device. Moreover, you must obtain your own standard curve using the considered polymer compositions and, in addition, with a similar range of molecular weights as fractions. There is a small influence of the molecular weight. If the calibration curve obtained for similar intervals molecular mass, this effect is essentially negligible. In some embodiments the invention, a random copolymer of ethylene satisfy the following relations:

Ln=-237,83/TATREF+0,639.

THOis the ATREF temperature for a statistical copolymer of the same composition and having a molar fraction of ethylene in fraction RX. THOcan be calculated from the equation: LnX=α/THO+β. On the other hand, RHOrepresents the molar fraction of ethylene in fraction for statistical copolymer of the same composition and having an ATREF temperature TXthat can be calculated from the equation: LnHO=α/TX+β.

After receiving the indicator of deblocking (BI) for each is racchi preparative fractionation using TREF can be calculated, the weighted average of deblocking, The abi, for the whole polymer. In some embodiments of the invention ABI has a value greater than zero but less than about 0.3 or from approximately 0.1 to approximately 0.3. In other embodiments, the ABI value is larger than about 0.3 and up to approximately 1.0. Preferably ABI should be in the range from approximately 0.4 to approximately 0.7, from about 0.5 to about 0.7 or from about 0.6 to ~ 0.9. In some embodiments of the invention ABI is in the range from approximately 0.3 to approximately to 0.9, from about 0.3 to about 0.8, or from approximately 0.3 to approximately 0.7, from approximately 0.3 to approximately 0.6, from about 0.3 to about 0.5, or from about 0.3 to about 0.4. In other embodiments of the invention the abi is in the range from approximately 0.4 to approximately 1.0, from about 0.5 to about 1.0, or from about 0.6 to approximately 1.0, from approximately 0.7 to approximately 1.0, from about 0.8 to about 1.0, or from about 0.9 to approximately 1.0.

Another feature of the inventive ethylene/α-olefin of interpolymer is that the inventive ethylene/α-olefin interpolymer contains at least one fraction of polymer that can be obtained using preparative practionier the project using TREF, where this fraction is a measure of the deblocking more than about 0.1 and up to approximately 1.0 and a molecular weight distribution, Mw/Mn, of more than approximately 1.3. In some embodiments of the invention the fraction of the polymer is the rate of deblocking more than approximately 0.6 to approximately 1,0, more than approximately 0.7 to approximately 1.0, the more approximate to 0.8 and about 1.0, or about 0.9 and up to approximately 1.0. In other embodiments of the invention the fraction of the polymer is the rate of deblocking more than about 0.1 and up to approximately 1.0, more than approximately 0.2 to approximately 1.0, more than about 0.3 and up to approximately 1.0, about 0.4 to about 1.0, or about 0.4 to about 1.0 in. In other embodiments of the invention the fraction of the polymer is the rate of deblocking more than about 0.1 and up to about 0.5, about 0.2 to about 0.5, more than about 0.3 and up to about 0.5 or about 0.4 to about 0.5. In other embodiments of the invention the fraction of the polymer is the rate of deblocking more about 0.2 to approximately 0,9, more than about 0.3 and up to about 0.8, about 0.4 to about 0.7 or more than about 0.5 and up to approximately 0.6.

As these copolymers is Jena and α-olefin of the inventive polymers preferably possess (1) TTD (PDI), at least 1.3, more preferably at least 1.5 times, at least 1.7 or at least a 2.0, and most preferably at least 2.6, up to a maximum value of 5.0, more preferably up to a maximum value of 3.5, and in particular up to a maximum of 2.7; (2) a heat of fusion of 80 j/g or less; (3) the ethylene content of at least 50 wt.%; (4) glass transition temperature, Tarticleless -25°C, more preferably less than -30°C., and/or (5) one and only one TPL.

In addition, the inventive polymers can be separately or in combination with any other properties described in this dynamic elastic modulus, G', that log(G') has a value greater than or equal to 400 kPa, preferably greater than or equal to 1.0 MPa, at a temperature of 100°C. moreover, the inventive polymers have relatively flat dynamic modulus as a function of temperature in the range from 0 to 100°C (as shown in Fig.6)that is characteristic of block copolymers, and was previously unknown to olefin copolymer, especially a copolymer ethylene and one or more3-8-aliphatic α-olefins. (Under the definition of "relatively flat" in this context means that logG' (PA) decreases less than one order of magnitude from 50 to 100°C., preferably from 0 to 100°C).

The claimed interp the materials can additionally be characterized by the penetration depth of 1 mm under thermomechanical analysis at a temperature at least 90°C., and a modulus of elasticity in bending from 3 to 13 cfont/inch2(from 20 to 90 MPa). On the other hand, the claimed interpolymer can have a penetration depth of 1 mm under thermomechanical analysis at a temperature of at least 104°C., and the modulus of elasticity in bending of at least 3 cfont/inch2(20 MPa). They can be characterized as having a resistance to wear or loss of volume) of less than 90 mm3. Figure 7 presents data TMA (1 mm) relative to the modulus of elasticity in bending for the inventive polymers in comparison with other known polymers. The inventive polymers have significantly more a good balance of flexibility-resistant than other polymers.

In addition, the ethylene/α-olefin interpolymer can have a melt index, I2from 0.01 to 2000 g/10 min, preferably from 0.01 to 1000 g/10 min, more preferably from 0.01 to 500 g/10 min and in particular from 0.01 to 100 g/10 minutes, In some embodiments of the invention, the ethylene/α-olefin interpolymer have a melt index, I2from 0.01 to 10 g/10 minutes, from 0.5 to 50 g/10 min, from 1 to 30 g/10 min, from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes, In some embodiments of the invention, the melt index of the ethylene/α-olefin polymer is equal to 1 g/10 min, 3 g/10 min, or 5 g/10 minutes

The polymers can have a molecular mass Mwfrom 1000 to 5000000 g/mol, suppose the equipment from 1000 to 1000000 g/mol, more preferably from 10,000 to 500,000 g/mol and especially from 10000 to 300000 g/mol. The density of the inventive polymers may be from 0.80 to 0.99 g/cm3and preferably in the case atlantageorgia polymers from 0.85 to 0.97 g/cm3. In some embodiments of the invention the density of the ethylene/α-olefin polymers is in the range from 0,860 to 0,925 g/cm3or from 0,867 to 0.910 g/cm3.

Methods of production of the polymers disclosed in the following patent applications: provisional application U.S. No. 60/553906, submitted March 17, 2004; provisional application U.S. No. 60/662937, sent for review March 17, 2005; provisional application U.S. No. 60/662939, sent for review March 17, 2005; provisional application U.S. No. 60/662938, sent for review March 17, 2005; PCT application number PCT/US2005/008916, sent for review March 17, 2005; PCT application number PCT/US2005/008915, sent for review March 17, 2005; and the PCT application number PCT/US2005/008917, sent for review March 17, 2005; all of which are included in the description in its entirety by reference. For example, one such method comprises introducing into contact with ethylene and, optionally, one or more capable of polymerization by the addition of monomers other than ethylene, in terms of speed of polymerization with a catalytic composition comprising a:/p>

a mixture or a reaction product obtained by mixing:

(A) a first catalyst for polymerization of olefin, having a high coefficient of introduction of co monomer,

(B) a second catalyst for polymerization of olefin, having a ratio of introduction of the co monomer less than 90%, preferably less than 50%, most preferably less than 5% of the ratio of introduction of the co monomer catalyst (A), and

(C) agent transfer chain.

Typical catalysts and agents of the transfer circuit is shown below.

The catalyst (A1)represents dimethyl-[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium obtained in accordance with the instructions of publications WO 03/40195, 2003US0204017, US reg. No. 10/429024 aimed for review may 2, 2003, and WO 04/24740:

The catalyst (A2)represents dimethyl-[N-(2,6-di(1-methylethyl)phenyl)amido)(2-were)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafnium obtained in accordance with the instructions of publications WO 03/40195, 2003US0204017, US reg. No. 10/429024 aimed for review may 2, 2003, and WO 04/24740:

The catalyst (A3)is dibenzyl-bis[N,N”'-(2,4,6-three(were)amido)Ethylenediamine]hafnium:

The catalyst (A4)is dibenzyl-bis((2-oxol-3-(dibenzo-1H-pyrrole-1-the l)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diizinkan (IV), obtained essentially in accordance with the instructions of the publication US-A-2004/0010103:

The catalyst (B1)is dibenzyl-1,2-bis(3,5-di-tert-butylphenyl)(1-(N-(1-methylethyl)imino)methyl)(2-oxol)zirconium:

The catalyst (B2)is dibenzyl-1,2-bis(3,5-di-tert-butylphenyl)(1-(N-(2-methylcyclohexyl)imino)methyl)-(2-oxol)zirconium:

The catalyst (C1)is a dimethyl-(tert-butylamide)dimethyl(3-N-pyrrolyl-1,2,3,3A,7a-η-inden-1-yl)selandian obtained in accordance with the directions publishing USP 6268444:

The catalyst (C2)is a dimethyl-(tert-butylamino)di(4-were)(2-methyl-1,2,3,3A,7a-η-inden-1-yl)selandian obtained in accordance with the instructions of the publication US-A-2003/004286:

The catalyst (C3)is a dimethyl-(tert-butylamino)di(4-were)(2-methyl-1,2,3,3A,8A-η-s-indocin-1-yl)selandian obtained in accordance with the instructions of the publication US-A-2003/004286:

The catalyst (D1)represents dichloride, bis(dimethylsiloxane)(inden-1-yl)zirconium, supplied by Sigma-Aldrich:

Agents transfer circuit. Used agents transfer chain are the FDS is th diethylzinc, di(isobutyl)zinc, di(n-hexyl)zinc, triethylaluminium, trioctylamine, triethylgallium, isobutylamine-bis(dimethyl(tert-butyl)siloxane), isobutylamine-bis(di(trimethylsilyl)amide), n-octylamine-di(pyridine-2-methoxide), bis(n-octadecyl)isobutylamine, isobutylamine-bis(di(n-pentyl)amide), n-octylamine-bis(2,6-di-tert-butylperoxide, n-octylamine-di(ethyl(1-naphthyl)amide), ethylaluminum-bis(tert-butyldimethylsiloxy), ethylaluminum-di(bis(trimethylsilyl)amide), ethylaluminum-bis(2,3,6,7-dibenzo-1-azacycloheptane), n-octylamine-bis(2,3,6,7-dibenzo-1-azacycloheptane), n-octylamine-bis(dimethyl(tert-butyl)siloxy), ethylzinc(2,6-diphenylphenol) and ethylzinc(tert-piperonyl).

Preferably, the following processes have the form of a continuous process in the solution for the formation of block copolymers, in particular the polyblock copolymers, preferably linear polyblock copolymers of two or more monomers, especially ethylene and C3-20-olefin or cycloolefin, and most preferably ethylene and C4-20-α-olefin, using a composite catalyst which is not capable of mutual transformation. That is, the catalyst is chemically individual. In continuous polymerization in solution, the process is ideally suited for the polymerization of mixtures of monomers at high CONV is rsii monomers. Under these conditions, polymerization moving from agent transfer circuit to the catalyst becomes predominant compared to chain growth and polyblock copolymers, in particular linear polyblock copolymers are formed with high efficiency.

The claimed interpolymer may differ from the usual statistical copolymers, physical blends of polymers and block copolymers obtained using a serial connection of monomer, fluidized catalysts, methods of anionic or cationic polymerization. In particular, compared with a statistical copolymer of the same monomers and with the same content of monomers at equivalent crystallinity or modules claimed interpolymer have better (higher) heat-defined melting temperature, higher temperature penetration with a TMA, a higher high-temperature limit of the tensile strength and/or higher high temperature dynamic modulus of elasticity in torsion, determined using dynamic mechanical analysis. Compared with the statistical copolymer containing the same monomers and having the same content of the monomers, the claimed interpolymer have lower residual deformation under compression, particularly at elevated temperatures, the lower curve is suciu stress higher creep resistance, higher tear resistance, higher resistance to adhesion, faster setting due to the higher temperature of crystallization (solidification), higher elastic recovery (particularly at elevated temperatures), higher abrasion resistance, higher return force, a better acceptance of oil and filler.

The claimed interpolymer also show the unique relationship between crystallization and distribution of branching. That is, the claimed interpolymer have a relatively large difference between the highest peaks of temperatures measured using CRYSTAF and DSC as a function of heat of fusion, especially in comparison with the statistical copolymers containing the same monomers and having the same content of monomers, or compared with physical mixtures of polymers, such as a mixture of high density polymer and copolymer of low density, equivalent to the total density. I believe that this unique characteristic of the proposed interpolymers due to the unique distribution of co monomer in blocks within the main chain of the polymer. In particular, the claimed interpolymer can contain alternating blocks with different content of comonomers (including homopolymer blocks). yavlenie interpolymer may also have a distribution in the number and/or size of the block polymer blocks with different density or content of comonomers, which corresponds to the distribution Shultz-Flora. In addition, the claimed interpolymer also have clearly defined peak of the melting temperature and the temperature profile of crystallization, which essentially does not depend on the density of the polymer, the modulus of elasticity and morphology. In a preferred embodiment, the microcrystalline order polymer demonstrates characteristic spherulite and lamellae, which can be distinguished from statistical or block copolymers, even when the TTD values that are less than 1.7 or even less than 1.5 to fall to less than 1.3.

In addition, the claimed interpolymer can be obtained using methods that affect the degree or level of deblocking. That is, the number of co monomer and the length of each polymer block or segment can be changed by controlling the ratio and type of catalyst and agent transfer chain, as well as the polymerization temperature and other process variables polymerization. An unexpected advantage of this phenomenon consists in the discovery that by increasing the degree of blocking, optical properties, tear resistance and characteristics of high-temperature elastic recovery of the final polymer are improved. In particular, the opacity decreases, whereas transparency, tear resistance and characteristics in comtemplating elastic recovery increases as the increase of the average number of blocks in the polymer. By choosing agents transfer chain and catalytic combinations having the desired ability of the transfer circuit (high speed transfer circuit with low open circuit), the other forms the end of the polymer is effectively suppressed. Thus, there is little, if at all it occurs, β-hydride elimination in the polymerization of ethylene/α-olefin comonomer mixtures in accordance with the variants of implementation of the present invention, and the final crystalline blocks are substantially or essentially completely linear, with very little branching or not having long chain branching.

In accordance with the variants of implementation of the present invention can be selectively obtained polymers with vysokobaricheskie terminal groups of the chain. In elastomer options for use of the decrease in the relative amount of polymer, which ends amorphous block, reduces the effect of intermolecular dilution in the crystalline regions. This result may be obtained by selecting agents transfer circuit and catalysts having an appropriate response to hydrogen or other regulators of molecular weight. Specifically, if the catalyst that produces vysokokritichnyh polymer is more sensitive to chain termination (such as for the odd use of hydrogen), what is the catalyst responsible for obtaining less crystalline polymer segments (for example, due to the higher injection comonomers, education irregular or atactic polymer), vysokobaricheskie polymer segments will be mainly to fill in an end part of the polymer. Not only derived end groups are crystalline, but at the end of the polymer site catalyst, forming vysokokritichnyh polymer, more time becomes available for re-initiating polymer formation. Educated at the initial stage of the polymer thus represents another vysokokritichnyh polymer segment. Thus, both the end received the polyblock-copolymer are preferably vysokobaricheskie.

The ethylene/α-olefin interpolymer used in the variants of implementation of the present invention, preferably are interpolymer ethylene, at least one With3-C20-α-olefin. Copolymers of ethylene and C3-C20α-olefins are particularly preferred. Interpolymer can also contain a4-C18-diolefin and/or alkenylphenol. Suitable unsaturated comonomers which can be used in the polymerization of ethylene, are, for example, ethylene-unsaturated monomial is s, paired or unpaired diene, polyene, alkenylbenzene and other Examples of such comonomers are3-C20α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-penten, 4-methyl-1-penten, 1-hepten, 1-octene, 1-none, 1-mission, etc. are Particularly preferred are 1-butene and 1-octene. Other suitable monomers are styrene, halogen - or alkyl-substituted styrene, vinylbenzoate, 1,4-hexadiene, 1,7-octadiene and naphthenes (for example, cyclopentene, cyclohexene, cyclooctene).

Although the ethylene/α-olefin interpolymer are the preferred polymers also can be used other ethylene/olefin polymers. The olefins used in this case, belong to the family of unsaturated hydrocarbon compounds, at least one carbon-carbon double bond. Depending on the choice of catalysts any olefin may be used in embodiments implementing the present invention. Preferably suitable olefins are3-C20-aliphatic and aromatic compounds containing vinyl unsaturation, as well as cyclic compounds, such as cyclobutene, cyclopentene, Dicyclopentadiene, and norbornene, including but not limited to, norbornene substituted in the 5 - and 6-position With1-C20is a hydrocarbon and is and Cyclopentanone group. In addition, a mixture of such olefins as well as mixtures of such olefins with4-C40-diolefine connections.

Examples of olefin monomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-penten, 1-hexene, 1-hepten, 1-octene, 1-none, 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1 achozen, 3-methyl-1-butene, 3-methyl-1-penten, 4-methyl-1-penten, 4,6-dimethyl-1-hepten, 4-vinylcyclohexane, vinylcyclohexane, norbornadiene, ethylidenenorbornene, cyclopentene, cyclohexene, Dicyclopentadiene, cyclooctene,4-C40-diene, including, but without limitation, 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other4-C40-α-olefins, etc. In some embodiments of the invention the α-olefin is a propylene, 1-butene, 1-penten, 1-hexene, 1-octene or a combination of both. Although any hydrocarbon containing a vinyl group, can potentially be used in embodiments of the invention, practical issues such as availability of monomer, cost and convenient removal of unreacted monomer from the polymer obtained may become more problematic when the molecular weight of the monomer becomes too high. The polymerization processes described in the invention are well suited for the production of olefin polymer is in, containing monolinoleate aromatic monomers including styrene, o-methylsterol, p-methylsterol, tert-butalbiral etc. In particular, interpolymer containing ethylene and styrene, can be obtained if you follow the invention shown in the instructions. Optional can be obtained having improved properties of copolymers containing ethylene, styrene and3-C20-α-olefin, optionally containing4-C20-diene.

Suitable non-conjugate diene monomers can be linear, branched or cyclic diene hydrocarbons containing from 6 to 15 carbon atoms. Examples of suitable non-conjugate dienes include, but are not limited to, linear acyclic diene, such as 1,4-hexadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, branched acyclic diene, such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 3,7-dimethyl-1,7-octadiene and mixed isomers dihydromyrcene and dihydroionone, alicyclic diene with one ring, such as 1,3-cyclopentadiene; 1,4-cyclohexadiene; 1, 5cyclooctadiene and 1.5-cyclododecatriene; and policyleve alicyclic condensed and bridge dieny such as tetrahydroindene, methyltetrahydrofuran, Dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkeneamine, alkylidene, cycloalkenyl and cycloalkylation norbornene, such as 5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5 - vinyl-2-norbornene and norbornadiene. Among dienes typically used to obtain EPDM, particularly preferred danami are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (NB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB) and Dicyclopentadiene (DCPD). Especially preferred danami are 5-ethylidene-2-norbornene (NB) and 1,4-hexadiene (HD).

One of the desired classes of polymers that can be obtained in accordance with the variants of implementation of the present invention are elastomeric interpolymer ethylene, With3-C20-olefin, in particular propylene, and optionally one or more diene monomers. Preferred α-olefins for use in this embodiment of the present invention are denoted by the formula CH2=R*, where R* is a linear or branched alkyl group containing from 1 to 12 carbon atoms. Examples of suitable α-olefins include, but are not limited to, propylene, isobutylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten and 1-octene. Particularly preferred α-olefin is propylene. Based polymers of propylene in the art commonly called EP or DM polymers. Suitable danami for use in receiving the AI of such polymers, especially polymers of type a polyblock-EPDM, are paired or non-paired, linear or branched, cyclic or polycyclic diene containing from 4 to 20 carbon atoms. The preferred danami are 1,4-pentadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene, Dicyclopentadiene, cyclohexadiene and 5-butylidene-2-norbornene. Especially preferred diene is 5-ethylidene-2-norbornene.

As diesterase polymers include alternating segments or blocks containing larger or smaller amounts of diene (including nesadurai Dien) and α-olefin (including nesadurai olefin), the total amount of the diene and the α-olefin may be reduced without loss of properties of the final polymer. That is because diene and α-olefin monomers are preferably introduced into one type of block polymer and not evenly or statistically throughout the polymer, they are used more effectively, and subsequently, the density of crosslinking of the polymer can be controlled more effectively. Such cross-linked elastomers and cured products have the preferred properties, including a higher ultimate tensile strength and better elastic recovery.

In some embodiments of the invention claimed interpolymer obtained using two catalysts, introducing different amounts with which anomura, have a mass ratio of educated so blocks from 95:5 to 5:95. Elastomeric polymers preferably have an ethylene content from 20 to 90%, the content of the diene from 0.1 to 10% and the content of α-olefin of 10 to 80% based on the total weight of the polymer. Also preferably, the elastomer polyblock-polymer had an ethylene content of 60 to 90%, the content of the diene from 0.1 to 10% and the content of α-olefin of 10 to 40% based on the total weight of the polymer. Preferred polymers are high molecular weight polymers having srednevekovoy molecular weight (Mw) from 10,000 to approximately 2500000, preferably from 20,000 to 500,000, more preferably from 20,000 to 350,000, a polydispersity less than 3.5, preferably less than 3.0 and a viscosity Mooney viscometer (ML (1+4) 125°C) from 1 to 250. More preferably, such polymers have an ethylene content from 65 to 75%, the content of the diene from 0 to 6% and the content of α-olefin of from 20 to 35%.

The ethylene/α-olefin interpolymer can be functionalized with at least one functional group in their polymeric structure. Examples of functional groups can be, for example, ethylene-unsaturated mono - and difunctional carboxylic acids, anhydrides, ethylene-unsaturated mono - and difunctional carboxylic acids, their salts and esters. Such functional groups can be grafted on the ethylene/is-the olefinic interpolymer or can be copolymerizable with ethylene and optionally additional co monomer to form interpolymer ethylene, functional co monomer and optionally other co monomer(s). Means the grafting of functional groups on the polyethylene described, for example, in U.S. patent No. 4762890, 4927888 and 4950541, descriptions of which are incorporated in their entirety by reference. One particularly useful functional groups is malic anhydride.

The number of functional groups present in the functional interpolymer may vary. Typically, the functional group may be present in the functionalized type interpolymer in the amount of at least 1.0 wt.%, preferably, at least about 5 wt.% and more preferably at least about 7 wt.%. Functional group typically will be present in the functionalized type interpolymer in the amount of less than about 40 wt.%, preferably less than about 30 wt.% and more preferably less than about 25 wt.%.

The amount of the ethylene/α-olefin of interpolymer in polymer mixtures described in the invention depends on several factors such as the type and number two polyolefins. Generally, the amount should be sufficient to interpolymer was effective as a combining agent, as described above. In some embodiments of the invention it should be present in sufficient quantity, the button to affect morphological changes between the two polymers in the final mixture. Generally, the amount may be from about 0.5 to about 99 wt.%, from about 5 to about 95 wt.%, from about 10 to about 90 wt.%, from about 20 to about 80 wt.%, from about 0.5 to about 50 wt.%, from about 50 to about 99 wt.%, from about 5 to about 50 wt.% or from about 50 to about 95 wt.% based on the weight of the polymer mixture. In some embodiments of the invention, the amount of the ethylene/α-olefin of interpolymer in polymer blends is from about 1 to about 30%, from about 2 to about 20%, from about 3 to about 15%, from about 4 to about 10 wt.% based on the weight of the entire polymer mixture. In some embodiments of the invention, the amount of the ethylene/α-olefin of interpolymer in polymer blends is less than about 50%, less than about 40%, less than about 30%, less than about 20%, less than about 15%, less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%, but more than about 0.1 wt.% based on abdulmassih polymer mixture.

Polyolefins

The polymer mixtures described in the invention can contain at least two polyolefin, in addition to at least one ethylene/α-olefin of interpolymer described above. The polyolefin is a polymer derived from two or more olefins (i.e. alkenes). Olefin (alkene) is a hydrocarbon that contains at least one carbon-carbon double bond. The olefin may be monorom (i.e. olefin containing one carbon-carbon double bond), diene (i.e. olefin containing two carbon-carbon double bond), triens (i.e. olefin containing three carbon-carbon double bond), tetraena (i.e. olefin containing four carbon-carbon double bonds) and other polirom. Olefin or alkene, such as moneen, diene, triene, terrain and other Polian may contain 3 or more carbon atoms of 4 or more carbon atoms of 6 or more carbon atoms of 8 or more carbon atoms. In some embodiments of the invention, the olefins contain from 3 to about 100 carbon atoms, from 4 to about 100 carbon atoms, from 6 to about 100 carbon atoms, from 8 to about 100 carbon atoms, from 3 to about 50 carbon atoms, from about 3 to about 25 carbon atoms, from 4 to about 25 carbon atoms, the t 6 to about 25 carbon atoms, from 8 to about 25 carbon atoms, or from 3 to about 10 carbon atoms. In some embodiments of the invention, the olefin is a linear or branched, cyclic or acyclic moneen containing from 2 to about 20 carbon atoms. In other embodiments of the invention, the alkene is a diene, such as butadiene and 1,5-hexadiene. In other embodiments of the invention, at least one hydrogen atom of the alkene substituted by alkyl or aryl. In specific embodiments of the invention, the alkene is an ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-mission 4-methyl-1-penten, norbornene, 1-mission, butadiene, 1,5-hexadiene, styrene, or a combination of both.

The amount of polyolefin in the polymer blend can be from about 0.5 to about 99 wt.%, from about 10 to about 90 wt.%, from about 20 to about 80 wt.%, from about 30 to about 70 wt.%, from about 5 to about 50 wt.%, from about 50 to about 95 wt.%, from about 10 to about 50 wt.% or from about 50 to about 90 wt.% based on the total weight of the polymer mixture. In some embodiments of the invention, the amount of polyolefin in the polymer mixture may be approximately 50%, 60%, 70% or 80% based on the weight of the polymer mixture. M is sawoe the ratio of the two polyolefins may be in the range from about 1:99 to about 99:1, preferably from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, from about 40:60 to about 60:40, from about 45:55 to about 55:45 to about 50:50.

Any polyolefin known to the person skilled in the art, may be used to obtain a polymer mixture described in the invention. The polyolefins can represent the olefin homopolymers, olefin copolymers, the olefin terpolymer, the olefinic terpolymer, etc. and combinations thereof.

In some embodiments of the invention, at least one of the two polyolefin is an olefin Homo-polymer. Olefin Homo-polymer can be obtained from a single olefin. Any homopolymer, known to the person skilled in the art, may be used. Non-limiting examples of olefin homopolymers include polyethylene (e.g., polyethylene, ultra-low and low density, linear low density polyethylene, polyethylene, medium, high and ultra-high density), polypropylene, polybutylene (e.g., polybutene-1), polypenco-1, polyhexes-1, policen-1, polydecene-1, poly-3-methylbutan-1, poly-4-methylpentene-1, polyisoprene, polybutadiene, poly-1,5-hexadien.

In other variants of the Ah invention olefinic Homo-polymer is a polypropylene. Any polypropylene, known to the person skilled in the art, can be used to produce the polymer mixtures described in the invention. Neorganicheskie examples of the polypropylene is a polypropylene low density (LDPP), polypropylene, high-density (HDPP), polypropylene with high melt strength (HMS-PP), polypropylene with high toughness (HIPP), isotactic polypropylene (RR), syndiotactic polypropylene (sPP) and others, and combinations thereof.

The amount of polypropylene in the polymer blend can be from about 0.5 to about 99 wt.%, from about 10 to about 90 wt.%, from about 20 to about 80 wt.%, from about 30 to about 70 wt.%, from about 5 to about 50 wt.%, from about 50 to about 95 wt.%, from about 10 to about 50 wt.% or from about 50 to about 90 wt.% based on the weight of the polymer mixture. In some embodiments of the invention, the amount of polypropylene in the polymer blend is about 50%, 60%, 70% or 80% based on the total weight of the polymer mixture.

In other embodiments of the invention, at least one of the two polyolefin is an olefin copolymer. Olefin copolymer can be obtained from two different olefins. The number on Edinboro copolymer in the polymer blend can be from about 0.5 to about 99 wt.%, from about 10 to about 90 wt.%, from about 20 to about 80 wt.%, from about 30 to about 70 wt.%, from about 5 to about 50 wt.%, from about 50 to about 95 wt.%, from about 10 to about 50 wt.% or from about 50 to about 90 wt.% based on the weight of the polymer mixture. In some embodiments of the invention, the amount of olefin copolymer in the polymer mixture is approximately 10%, 15%, 20%, 25%, 30%, 35%, 40% or 50% based on the weight of the polymer mixture.

Any olefin copolymer known to the person skilled in the art, may be used in the polymer mixtures described in the invention. Neorganicheskie examples of olefin copolymers are copolymers derived from ethylene and monoene containing 3 or more carbon atoms. Neorganicheskie examples of monoene containing 3 or more carbon atoms, are propene; butenes (e.g., 1-butene, 2-butene or isobutene) and the alkyl substituted butenes; pentane (for example, 1-penten and 2-penten) and the alkyl substituted pentane (for example, 4-methyl-1-penten); hexene (for example, 1-hexene, 2-hexene and 3-hexene) and alkyl substituted hexene; heptane (for example, 1-hepten, 2-hepten and 3-hepten) and the alkyl substituted Heptene; octene (for example, 1-octene, 2-octene, 3-octene and 4-octene) and alkyl substituted cheny; nonene (for example, 1-none, 2-nonen, 3 none and 4 nonen) and the alkyl substituted nonene; deceny (for example, 1-mission 2 mission 3 mission 4 mission 5-the mission) and the alkyl substituted decene; dodecene and alkyl substituted dodecene; and butadiene. In some embodiments of the invention the olefin copolymer is an ethylene/alpha-olefin (EAO) copolymer or ethylene/propylene copolymer (EPM). In some embodiments of the invention the olefin copolymer is an ethylene/octenoyl copolymer.

In other embodiments of the invention olefin copolymer derived from (i)3-20-olefins, substituted alkyl or aryl group (for example, 4-methyl-1-pentene and styrene) and (ii) diene (such as butadiene, 1,5-hexadiene, 1,7-octadiene and 1.9-decadiene). Non-limiting examples of such olefin copolymer is a styrene-butadiene-styrene (SBS) block copolymer.

In other embodiments of the invention, at least one of the two polyolefin is an olefin, terpolymer. The olefinic terpolymer can be obtained from three different olefins. The amount of olefin terpolymer in the polymer blend can be from about 0.5 to about 99 wt.%, from about 10 to about 90 wt.%, from about 20 to about 80 wt.%, from about 30 to about 70 wt.%, from about 5 to when listello 50 wt.%, from about 50 to about 95 wt.%, from about 10 to about 50 wt.% or from about 50 to about 90 wt.% based on the weight of the polymer mixture.

Any olefin terpolymer known to the person skilled in the art, may be used in the polymer mixtures described in the invention. Non-limiting examples of olefin terpolymers are terpolymers obtained from (i) ethylene, (ii) monoene containing 3 or more carbon atoms, and (iii) of the diene. In some embodiments of the invention the olefinic terpolymer is an ethylene/alpha-olefin/diene terpolymer (DM) and ethylene/propylene/diene terpolymer (EPDM).

In other embodiments of the invention the olefinic terpolymer obtained from (i) two different monoenes and (ii)3-20-olefins, substituted alkyl or aryl group. Non-limiting examples of such olefins terpolymer is a styrene-ethylene-(butene)-styrene (SEBS) block copolymer.

In other embodiments of the invention, at least one of the two polyolefins may be any capable of vulcanization of the elastomer or rubber, which is obtained from an olefin, provided that they are capable of vulcanization of the elastomer can be cross stitched (i.e. vulcanized) with a crosslinking agent. Capable of vulcanization of the elastomer and thermopl the stick, such as polypropylene, after stitching together may form a TPV. Capable of vulcanization of elastomers, for example, as a rule, and thermoplastic in the uncured state, are usually classified as thermosetting, because they are irreversible process of heat to an unhandled condition. Preferably capable of vulcanization of the elastomer are distributed in a matrix of thermoplastic polymer in the form of domains. The average size of the domain can be in the range from about 0.1 to about 100 microns, from about 1 to about 50 microns, from about 1 to about 25 microns, from about 1 to about 10 microns, or from about 1 to about 5 microns.

Non-limiting examples of suitable capable of vulcanization of elastomers or rubbers are terpolymer rubber ethylene/high alpha-olefin/Polian, such as EPDM. Suitable is any such terpolymeric rubber, which can be fully overiden (cross stitched) with phenolic hardener or other cross-linking agent. In some embodiments terpolymer rubbers can be an essentially non-crystalline koutsokoumnis terpolymer two or more alpha-olefins, preferably copolymerizing at least one of polie is ω (i.e. alkene, containing two or more carbon-carbon double bonds), usually with non-conjugate of the diene. Suitable terpolymer rubbers containing polymerization products of monomers comprising two olefin containing only one double bond, and small quantities of non-conjugate diene. The number of non-conjugate diene is usually from about 2 to about 10 wt.% based on the rubber. Any terpolymeric rubber that has sufficient reactivity in relation to phenolic hardener to achieve full curing is acceptable. Reactivity terpolymer rubber varies as the number of unsaturation, and the type of unsaturation present in the polymer. For example, terpolymer rubbers obtained from ethylidenenorbornene more reactive relative to the phenolic hardeners than terpolymer rubbers derived from Dicyclopentadiene and terpolymer rubbers derived from 1,4-hexadiene, less reactive in relation to phenolic hardeners than terpolymer rubbers derived from Dicyclopentadiene. However, the differences in reactivity can be overcome by polymerization of large quantities of less active diene in the molecule of rubber. For example, 2.5 wt.% ethylidenenorbornene or dizick is pentadiene can be sufficient to make terpolymer required reactivity, to make it completely cured with phenolic hardener containing conventional curing catalysts, whereas at least 3.0 wt.% or more is required to obtain sufficient reactivity in terpolymer rubber derived from 1,4-hexadiene. Varieties terpolymer rubbers, such as EPDM rubbers suitable for implementing the present invention are commercially available. Some of the EPDM rubbers is described in the publication Rubber World Blue Book, 1975 Edition, Materials and Compounding Ingredients for Rubber, pp. 406-410.

Usually terpolymer elastomer has an ethylene content from about 10 to about 90 wt.%, the high content of alpha-olefin from about 10 to about 80 wt.% and the content of polyene from about 0.5 to about 20 wt.%, all based on the total weight of the polymer. High alpha-olefin contains from about 3 to about 14 carbon atoms. Examples of alpha-olefins are propylene, isobutylene, 1-butene, 1-penten, 1-octene, 2 - ethyl-1-hexene, 1-dodecen etc. Polian can be paired diene, such as isoprene, butadiene, chloropren etc.; unpaired-diene; triens or polirom higher order. Examples of trienol are 1,4,9-decatriene, 5,8-dimethyl-1,4,9-decatriene, 4,9-dimethyl-1,4,9-decatriene etc. preferred unpaired diene. H is conjugate diene contain from 5 to about 25 carbon atoms. Examples are unpaired diolefin, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-octadiene etc.; cyclic diene, such as cyclopentadiene, cyclohexadiene, cyclooctadiene, Dicyclopentadiene and so on; vinyl cyclic enemy, such as 1-vinyl-1-cyclopentene, 1-vinyl-1-cyclohexen etc.; alkylbetaine, such as 3-methylbicyclo(4,2,1)Nona-3,7-diene, 3-activitynode etc.; indene, such as methyltetrahydrofuran and so; alkenylamine, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-Isopropenyl-5-norbornene, 5-(1,5-hexadienyl)-2-norbornene, 5-(3,7-octadiene)-2-norbornene, etc.; and tricyclodecane, such as 3-methyl-tricyclo-(5,2,1,02,6)-3,8-decadiene etc.

In some embodiments of the invention terpolymer rubbers contain from about 20 to about 80 wt.% ethylene, from about 19 to about 70 wt.% high alpha-olefin and from about 1 to about 10 wt.% non-conjugate diene. Preferred high alpha-olefins are propylene and 1-butene. The preferred polyene are ethylidenenorbornene, 1,4 - hexadiene and Dicyclopentadiene.

In other embodiments of the invention terpolymer rubbers are ethylene content from about 50 to about 70 wt.%, the content of the PCC is Lena from about 20 to about 49 wt.% and the content of non-conjugate diene is from about 1 to about 10 wt.% - all based on the total weight of the polymer.

Some non-limiting examples terpolymer rubbers for use in the invention are NORDEL®IP 4770R, NORDEL®3722 IP (DuPont Dow Elastomers, Wilmington, DE) and KELTAN®5636A (DSM Elastomers Americas, Addis, LA).

Other suitable elastomers are described in the following U.S. patents№№ 4130535, 4111897, 4311628, 4594390, 4645793, 4808643, 4894408, 5936038, 5985970 and 6277916, which are all included in the description in their entirety by reference.

Supplements

Optional polymer blends disclosed in the present invention may contain at least one additive to improve and/or control of workability, appearance, physical, chemical and/or mechanical properties of the polymeric composition. In some embodiments of the invention polymer compositions do not contain additives. Any polymer additive known to a person skilled in the art, may be used in the described polymeric compositions. Non-limiting examples of suitable additives are low-friction additives, plasticizers, oils, antioxidants, UV stabilizers, colorants or pigments, fillers, lubricants, protivoprilipajushchie substances that increase the fluidity of additives, binders, crosslinking agents, nucleating, surfactants, solvents, flame retardants, antistatic and and their combinations. The total amount of the additives may be in the range from about 0 to about 80%, from about 0.001 to about 70%, from about 0.01 to about 60%, from about 0.1 to about 50%, from about 1 to about 40%, or from about 10 to about 50% based on the total weight of the polymer composition. Some polymer additives described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, (2001), which is included in the description by reference.

In some embodiments of the invention the polymer mixture described in the invention contain an additive, reducing friction. In other embodiments of the invention described polymer blends do not contain the additive, reducing friction. The phenomenon of slip is a slip surface film on each other or on some other basis. The phenomenon of slide films can be measured using standard ASTM D 1894, Static and Kinetic Coefficients of Friction of Plastic Film and Sheeting, which is included in the description by reference. In the General case, decreasing the friction additive can give sliding properties through modification of the surface properties of the films and the reduction of friction between the layers of film and between the film and other surfaces with which they come in contact. Any lowering friction additive, know what percentage of the specialist in this field, can be added to polymeric compounds described in the invention. Non-limiting examples of decreasing friction additives are primary amides containing from about 12 to about 40 carbon atoms (for example, erucamide, oleamide, stearamide and beginnig); secondary amides containing from about 18 to about 80 carbon atoms (for example, stearinerie, beenreduced, metelerkamp and etilenoksid); secondary bis-amides containing from about 18 to about 80 carbon atoms (for example, ethylene-bis-stearamide and ethylene-bis-oleamide); and combinations thereof. In a specific embodiment, the invention lowers the friction additive described for polymer blends is an amide represented by the following formula (I):

where each of the substituents R1and R2independently represents H, alkyl, cycloalkyl, alkenyl, cycloalkenyl or aryl; and R3represents an alkyl or alkenyl, and each contains from about 11 to about 39 carbon atoms, from about 13 to about 37 carbon atoms, from about 15 to about 35 carbon atoms, from about 17 to about 33 carbon atoms, or from about 19 to about 33 carbon atoms. In some embodiments, R3PR is dstanley an alkyl or alkenyl, each of which contains at least from about 19 to about 39 carbon atoms. In other embodiments of the invention R3is pentadecyl, heptadecyl, Needell, heneicosanol, triazinyl, pentacosane, heptacosane, nonacosane, hentriacontanol, tritriacontane, entrycontrol or a combination of both. In other embodiments of the invention R3represents pentadecanol, heptadecanol, nonadecane, heneicosanol, trichosanthin, pentacosanoic, heptacosanoic, nonacosanol, hentriacontanol, tritriacontane, nonthreatening or a combination of both.

In some embodiments of the invention, decreasing the friction additive is a primary amide with a saturated aliphatic group containing from 18 to about 40 carbon atoms (for example, stearamide and beginnig). In other embodiments of the invention, decreasing the friction additive is a primary amide with unsaturated aliphatic group containing at least one carbon-carbon double bond and from 18 to about 40 carbon atoms (for example, erucamide, oleamide). In other embodiments of the invention, decreasing the friction additive is a primary amide containing at least 20 carbon atoms. In other embodiments of the invention, decreasing the friction additive is a e is UNAMID, oleamide, stearamide, beginnig, ethylene-bis-stearamide, ethylene-bis-oleamide, stearinerie, beenreduced or a combination of both. In other embodiments of the invention, decreasing the friction additive is erucamide. In other embodiments of the invention, decreasing the friction additive is commercially available under the trade name ATMERTMSA (Uniqema, Everberg, Belgium); ARMOSLIP®(Akzo Nobel Polymer Chemicals, Chicago, IL); KEMAMIDE®(Witco, Greenwich, CT); and CRODAMIDE®(Croda, Edison, NJ). The amount of reducing friction additives in the polymer blend can be from about 0 to about 3 wt.%, from about 0.0001 to about 2 wt.%, from about 0.001 to about 1 wt.%, from about 0.001 to about 0.5 wt.% or from about 0.05 to about 0.25 wt.% based on the total weight of the polymer mixture. Some low-friction additives described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 8, pp. 601-608 (2001), which is included in the description by reference.

Not necessarily described polymer mixture may contain the agent, caking. In some embodiments described polymer mixture does not contain-caking agent. - Caking agent can be used to prevent unwanted adhesion between soprikasalis the layers of products, made from polymer blends, especially under moderate pressure and heat during storage, production and application. Any caking agent known to a person skilled in the art may be added to the described polymer mixtures. Non-limiting examples caking agents are minerals (such as clay, chalk and calcium carbonate), synthetic silica gel (for example, SYLOBLOC®, Grace Davison, Columbia, MD), natural silicon dioxide (for example, SUPER FLOSS®, Celite Corporation, Santa Barbara, CA), talc (e.g., OPTIBLOC®, Luzenac, Centennial, CO), zeolites (e.g., SIPERNAT®, Degussa, Parsippany, NJ), silicates (for example, SILTON®, Mizusawa Industrial Chemicals, Tokyo, Japan), lime (for example, CARBOREX®, Omya, Atlanta, GA), spherical polymer particles (e.g., EPOSTAR®the particles of poly(methyl methacrylate) (Nippon Shokubai, Tokyo, Japan) and silicone particles TOSPEARL®(GE Silicones, Wilton, CN), waxes, amides (for example, erucamide, oleamide, stearamide, beginnig, ethylene-bis-stearamide, ethylene-bis-oleamide, stearinerie and other low-friction additives), molecular sieves, and combinations thereof. Mineral particles can reduce adhesion by creating a physical gap between products, while organic-caking agents can migrate to the surface, limiting surface adhesion. When prepa the corresponding caking agent used in the polymer mixture, its amount may be from about 0 to about 3 wt.%, from about 0.0001 to about 2 wt.%, from about 0.001 to about 1 wt.% or from about 0.001 to about 0.5 wt.% based on the total weight of the polymer mixture. Some caking agents described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 7, pp. 585-600 (2001), which is included in the description by reference.

Not necessarily described in the invention polymer mixture may contain a plasticizer. In General, the plasticizer is a chemical compound that can improve the elasticity and lower the glass transition temperature of polymers. Any plasticizer known to the person skilled in the art, may be added to those described in the invention polymer mixtures. Non-limiting examples of plasticizers are abietate, adipate, alkyl sulphonates, azelate, benzoate, chlorinated paraffins, citrates, epoxides, simple glycol ethers and their esters, glutarate, hydrocarbon oils, isobutyrate, oleates, derivatives of pentaerythritol, phosphates, phthalates, esters, polybutene, ricinoleate, sebacate, sulfonamides, three - and pyromellitate, biphenylene derivatives, stearates, complex diesters difuran, fluorinated place ifactory, esters of hydroxybenzoic acid, isocyanate adducts, polycyclic aromatic compounds, derivatives of natural products, NITRILES, plasticizers, based on the siloxane, the products on the basis of tar, thioethers and combinations thereof. When a plasticizer is used, its amount in the polymer blend can be from greater than 0 to about 15 wt.%, from about 0.5 to about 10 wt.% or from about 1 to about 5 wt.% based on the total weight of the polymer mixture. Some of the plasticizers described in the publication of George Wypych, ”Handbook of Plasticizers”, ChemTec Publishing, Toronto-Scarborough, Ontario (2004), which is included in the description by reference.

In some embodiments of the invention described polymer mixture optionally contain an antioxidant that prevents the oxidation of the polymer components and organic additives in polymer blends. Any antioxidant known to the person skilled in the art, may be added to the described polymer mixtures. Non-limiting examples of suitable antioxidants include aromatic or employed amines, such as alkyldiphenylamine, phenyl-α-naphtylamine, alkyl - or aralkyl-substituted phenyl-α-naphtylamine, alkylated p-phenylendiamine, tetramethylethylenediamine etc.; phenols, such as 2,6-di-tert-butyl-4-METHYLPHENOL; 1,3,5-trimethyl-2,4,6-Tris(3',5'-di-t is et-butyl-4'-hydroxybenzyl)benzene; tetrakis[(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (e.g., IRGANOXTM1010, Ciba Geigy, New York); modified acryloyl phenols; octadecyl-3,5-di-tert-butyl-4-hydroxycinnamic (for example, IRGANOXTM1076, commercially available product company Ciba Geigy), phosphites and phosphonite; hydroxyamine; derivatives of benzophenone; and combinations thereof. When the antioxidant is used, its amount in the polymer blend can be from about 0 to about 5 wt.%, from about 0.0001 to about 2.5 wt.%, from about 0.001 to about 1 wt.% or from about 0.001 to about 0.5 wt.% based on the total weight of the polymer mixture. Some antioxidants are described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 1, pp. 1-140 (2001), which is included in the description by reference.

In one embodiment described in the invention polymer mixture optionally contain a UV stabilizer that may prevent or reduce the degradation of polymer mixtures under the action of UV radiation. Any UV stabilizer known to the person skilled in the art, may be added to polymeric compounds described in the invention. Non-limiting examples of suitable UV stabilizers are benzophenone, benzotriazole, arrowie esters, oxamyl the water, acrylic esters, formamidines, soot, employed amines, Nickel extinguishers, phenolic antioxidants, metal salts, zinc compounds, and combinations thereof. When the UV stabilizer is used, its amount in the polymer blend can be from about 0 to about 5 wt.%, from about 0.01 to about 3 wt.%, from about 0.1 to about 2 wt.% or from about 0.1 to about 1 wt.% based on the total weight of the polymer mixture. Some UV stabilizers described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 2, pp. 141-426 (2001), which is included in the description by reference.

In other embodiments, the polymer mixture described in the invention optionally may contain a dye or pigment that can change the appearance of the polymer mixtures for the human eye. Any dye or pigment known to the person skilled in the art, may be added to the described polymer mixtures. Non-limiting examples of suitable dyes or pigments are inorganic pigments such as metal oxides, such as iron oxide, zinc oxide and titanium dioxide, mixed metal oxides, carbon black, organic pigments, such as anthraquinones, antandroy, azo - and monoethanolamine, arylamide, benzimidazolone, BONA l is CI, diketopiperazines, dioxazine, diazocompounds, dianiline connection flavanone, indanthrene, isoindoline, isoindoline, metal complexes, Monogatari, naftaly, β-Naftali, naphthol AS, naftalie lucky, perylenes, perinone, phthalocyanines, parentani, chinagreen and hinotori and combinations thereof. When the dye or pigment is used, its amount in the polymer blend can be from about 0 to about 10 wt.%, from about 0.1 to about 5 wt.% or from about 0.25 to about 2 wt.% based on the total weight of the polymer mixture. Some dyes described in publications Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 15, pp. 813-882 (2001), which is included in the description by reference.

Optional polymer mixture described in the invention may contain a filler, which can be used to regulate, among other things, volume, mass, cost and/or technical indicators. Any filler known to the person skilled in the art, may be added to polymeric compounds described in the invention. Non-limiting examples of suitable excipients are talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silicon dioxide, glass, colloidal silicon dioxide, mica, wollastonite, feldspar, aluminum is Silikat, calcium silicate, alumina, aluminum hydroxide, such as aluminum trihydrate, glass microspheres, ceramic microspheres, thermoplastic microspheres, barite, wood flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates, and combinations thereof. In some embodiments of the invention, the filler is a barium sulphate, talc, calcium carbonate, silicon oxide, glass, fiberglass, aluminum oxide, titanium dioxide or mixtures thereof. In other embodiments of the invention, the filler is a talc, calcium carbonate, barium sulfate, glass fiber, or a mixture thereof. When the filler is used, its amount in the polymer blend can be from about 0 to about 80 wt.%, from about 0.1 to about 60 wt.%, from about 0.5 to about 40 wt.%, from about 1 to about 30 wt.% or from about 10 to about 40 wt.% based on the total weight of the polymer mixture. Some fillers are described in U.S. patent No. 6103803 and publishing Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 17, pp. 901-948 (2001), which are both included in the description by reference.

Optional polymer mixture described in the image is the situation, may contain a lubricating substance. In General lubricating substance can be used, among other things, to modify the rheology of the molten polymer mixtures, to improve the surface finish of the molded product and/or to facilitate the formation of a dispersion of fillers or pigments. Any lubricating substance known to the person skilled in the art, may be added to polymeric compounds described in the invention. Non-limiting examples of suitable lubricants are fatty alcohols and their esters with dicarboxylic acids, esters of fatty acids and short-chain alcohols, fatty acids, amides of fatty acids, Soaps of metals, oligomeric esters of fatty acids, esters of fatty acids and long-chain alcohols, mountain waxes, polyethylene waxes, polypropylene waxes, natural and synthetic paraffin waxes, fluoropolymers, and combinations thereof. When grease is used, its amount in the polymer blend can be from about 0 to about 5 wt.%, from about 0.1 to about 4 wt.% or from about 0.1 to about 3 wt.% based on the total weight of the polymer mixture. Some suitable lubricants are described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 5, pp. 511-552(2001), which is included in the description by reference.

Optional polymer mixture described in the invention may contain an antistatic agent. In General, the antistatic agent may increase the conductivity of polymer blends and to prevent the accumulation of static charge. Any antistatic agent known to the person skilled in the art, may be added to polymeric compounds described in the invention. Non-limiting examples of suitable antistatic agents are conductive fillers (e.g. carbon black, metal particles and other conductive particles), fatty acid esters (for example, glycerol monostearate), the ethoxylated alkylamines followed, diethanolamide, ethoxylated alcohols, alkyl sulphonates, arylphosphate, Quaternary ammonium salts, dealkylation and combinations thereof. When the antistatic agent is used, its amount in the polymer blend can be from about 0 to about 5 wt.%, from about 0.01 to about 3 wt.% or from about 0.1 to about 2 wt.% based on the total weight of the polymer mixture. Some suitable antistatics are described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 10, pp. 627-646 (2001), which is included in the description by reference.

In other embodiments, the polymer mixture described in the invention, it is not necessarily which may contain a crosslinking agent, which can be used to increase the density of crosslinking of the polymer mixtures. Any crosslinking agent known to the person skilled in the art, may be added to polymeric compounds described in the invention. Non-limiting examples of suitable crosslinking agents are organic peroxides (for example, alkylperoxide, allproxy, paroxetine, peroxocarbonate, diazepamonline, peroxyketal and cyclic peroxides) and silanes (for example, VINYLTRIMETHOXYSILANE, vinyltriethoxysilane, vinyltris(2 methoxyethoxy)silane, vinyltriethoxysilane, wikimediamessages and 3-methacryloxypropyltrimethoxysilane). When a crosslinking agent is used, its amount in the polymer blend can be from about 0 to about 20 wt.%, from about 0.1 to about 15 wt.% or from about 1 to about 10 wt.% based on the total weight of the polymer mixture. Some suitable cross-linking agents described in the publication Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, Cincinnati, Ohio, 5-th edition, Chapter 14, pp. 725-812 (2001), which is included in the description by reference.

Cross-linking of polymer blends can also be initiated by any means exposure, known in this field, including, but without limiting them, electron-beam irradiation, beta irradiation is s, gamma radiation, the radiation of corona discharge and UV radiation, with or without the use of a catalyst for cross-linking. In the patent application U.S. No. 10/086057 (published as US2002/0132923 A1) and U.S. patent No. 6803014 disclosed methods of electron-beam irradiation, which can be used in embodiments implementing the present invention.

Obtaining polymer blends

Ingredients polymer mixtures, i.e. the ethylene/α-olefin interpolymer, polyolefins (i.e. the first polyolefin and the second polyolefin) and optional additives can be mixed or blended using methods known to the person skilled in the art, preferably methods that can provide essentially homogeneous distribution of the polyolefin and/or additives in the ethylene/α-olefins interpolymer. Non-limiting examples of suitable methods of mixing are mixing in the melt, mixing in a solvent, extruding, etc.

In some embodiments of the invention, the ingredients of the polymer mixtures are mixed in the melt using the method described in U.S. patent No. 4152189 (Guerin et al.). First of all solvents, if present at all, removed from the ingredients by heating to a suitable elevated temperature from about 100 to about 200°C. or from about 150 to bring the flax 175°C at a pressure of from about 5 to about 10 mm Hg (667-1333 PA). Then the ingredients are weighed in a vessel in the required proportions and polymer mixture is produced by heating of the tank's contents to the molten state under stirring.

In other embodiments of the invention, the ingredients of the polymer mixtures are processed using a mixture in a solvent. First, the ingredients of the desired polymer mixture is dissolved in a suitable solvent, and then the mixture is stirred or mixed. Then the solvent is removed and receive a polymer mixture.

In other embodiments of the invention in obtaining homogeneous mixtures can be used in the device physical mixing, which provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing. Can be used both periodic and continuous methods of physical mixing. Non-limiting examples of periodic ways are ways of mixing using a BRABENDER mixing equipment®(for example, BRABENDER PREP CENTER®, C.W. Brabender Instruments, Inc., South Hackensack, N.J.) or equipment of the closed mixing and roller grinding BANBURY®(Farrel Company, Ansonia, Conn.). Non-limiting examples of continuous methods are single-screw extrusion, twin screw extrusion, disc extrusion, return the but-progressive-screw extrusion and single screw extrusion with a pin camera. In some embodiments of the invention, additives can be added to the extruder through the hopper or the receiving hole while extruding the ethylene/α-olefin of interpolymer, polyolefin or polymer mixture. The blending or mixing of the polymers by extrusion process described in the publication of C. Rauwendaal, “Polymer Extrusion”, Hanser Publishers, New York, NY, pp. 322-334 (1986), which is included in the description by reference.

When in polymer mixtures necessary, one or more additives, the required amount of additives can be added to a single load or multiple downloads to the ethylene/α-olefin to interpolymer, polyolefins or polymeric mixture. Furthermore, the addition can be performed in any order. In some embodiments of the invention, first add additives and mixed or blended with the ethylene/α-olefin by interpolymers, and then containing additives interpolymer mixed with polyolefins. In other embodiments of the invention, first add additives and mixed or blended with polyolefins and then with ethylene/α-olefin by interpolymers. In other embodiments of the invention, the ethylene/α-olefin interpolymer mixed with polyolefins and then additives are mixed with the polymer mixture.

On the other hand, you can use the original mixture containing a high concentration of additives. In the General case, the original mixture m which may be prepared by mixing or ethylene/α-olefin of interpolymer, or one of polyolefin or polymer mixture with additives in high concentrations. The initial mixture may have additive concentration from about 1 to about 50 wt.%, from about 1 to about 40 wt.%, from about 1 to about 30 wt.% or from about 1 to about 20 wt.% based on the total weight of the polymer mixture. Then the mixture can be added to polymer mixtures in a quantity determined so as to obtain the desired concentration of additives in the final product. In some embodiments of the invention the mixture to contain lower friction additive-caking agent, plasticizer, antioxidant, UV stabilizer, a colorant or pigment, a filler, a lubricating substance, protivoukachiwauschee substance that increases the fluidity additive, a binder, a crosslinking agent, a nucleating agent, a surfactant, a solvent, a flame retardant, an antistatic agent or a combination of both. In another embodiment, the initial mixture contains a lower friction additive-caking agent, or a combination of both. In another embodiment, the initial mixture contains a lower friction additive.

In some embodiments of the invention, the first polyolefin and the second polyolefin together comprise thermoplastic vulcanizer, where the first polyolefin made the focus of a thermoplastic such as polypropylene, and the second polyolefin is a cured vulcanized rubber, such as EPDM. Thermoplastic vulcanizates are usually obtained by mixing thermoplastic and cured vulcanized rubber by dynamic vulcanization. The composition can be obtained by any suitable method of mixing kauchukopodobnoe polymers, including mixing mill for rubber or a closed rubber mixer, such as mixer Bunbury. In the process of mixing, you can enter one or more additives described above. It is generally preferable to add a crosslinking or curing agent in the second stage of mixing, which can take place in the mill for rubber or rubber mixer in a closed, operating typically at a temperature not exceeding about 60°C.

Dynamic vulcanization is a process in which a mixture of thermoplastic, rubber and rubber hardener frays as curing rubber. The definition of "dynamic" indicates that the mixture is subjected to shear stress during stage vulcanization, in contrast to "static" vulcanization, when a vulcanized composition stationary (in a fixed relative space) during the stage of vulcanization. One of the advantages of dynamic vulcanization one is camping, what elastoplastic (thermoplastic elastomer) compositions can be obtained when the mixture contains appropriate proportions of plastic and rubber. Examples of dynamic vulcanization is described in U.S. patent№№ 3037954, 3806558, 4104210, 4116914, 4130535, 4141863, 4141878, 4173556, 4207404, 4271049, 4287324, 4288570, 4299931, 4311628 and 4338413, which are all included in the description by reference.

Any mixer capable of creating a shear rate of 2000 sec-1or higher is acceptable for the process. Usually the necessary high-speed closed rubber having a narrow clearance between the working heads kneading elements and the wall. Shear rate is the velocity gradient in the space between the head and the wall. Depending on the clearance between the working cylinder and the wall of the rotation of the kneading elements from approximately 100 to approximately 500 revolutions per minute (rpm) is usually sufficient to develop the required shear rate. Depending on the number of working heads on this kneading element and depending on the rotation speed of the number of times that the composition mesida each item ranges from approximately 1 to approximately 30 times per second, preferably from about 5 to about 30 times per second and more preferably from approximately 10 to approximately 30 times per second. This means the AET, during the vulcanization of the material is usually mesida from approximately 200 to approximately 1800 times. For example, in a typical process using a rotor with three working heads rotate at approximately 400 rpm in a mixer with a residence time of approximately 30 seconds, the material is kneaded approximately 600 times.

Mixer, suitable for carrying out such a process represents the extruder mixing with a high shear produced by Werner &Pfleiderer, Germany. The extruder Werner &Pfleiderer (W&P) is a biaxial screw extruder in which two screws are engaged, rotate in the same direction. The details of such extruders are described in U.S. patent No. 3963679 and 4250292; and in patents Germany No. 2302546, 2473764 and 2549372, descriptions of which are included as references. The diameters of the screws vary from about 53 to about 300 mm; the length of the drum varies, but typically the maximum drum length corresponds to the length necessary to maintain the ratio of the length to the diameter is approximately 42. The axis of the screw such extruders are usually made of alternating series of sections of the movement and mixing sections. Section move forcing the material to move in the direction of travel from each section of the mixing extruder. Usually there is an approximately equal number of sections per the placement and mixing, relatively evenly distributed along the length of the drum. Kneading elements, containing one, two, three or four working heads are acceptable, but preferable kneading elements with a width of approximately 5 to approximately 30 mm, with three working heads. At the recommended speed of the auger from approximately 100 to approximately 600 rpm and a radial clearance from approximately 0.1 to approximately 0.4 mm such mixing extruders provide a shear rate of at least from about 2000 to about 7500 sec-1or more. Useful power mixing spent in the process, including homogenization and dynamic vulcanization, is usually from about 100 to about 500 watt-hours per 1 kg of product produced; and usually from about 300 to about 400 watt-hours per 1 kg

The process is illustrated using a twin-screw extruder W&P, model ZSK-53 or ZSK-83. Unless otherwise noted, plastic, rubber and mix all other ingredients, except the catalyst, served in the inlet of the extruder. In the first third of the extruder composition fray to melt the plastic and to get essentially homogeneous mixture. The catalyst for curing (vulcanization accelerator) to add che is another ez inlet, located approximately one third of the length of the drum downstream from the primary inlet. The last two-thirds of the extruder (from the inlet of the catalyst to the exit of the extruder) is considered as an area of dynamic vulcanization. The air valve operating at reduced pressure, is located near the exit to remove volatile by-products. Sometimes additional oil for filling or plasticizer and colorants is added through another entrance hole located approximately in the middle zone of vulcanization.

The residence time within the zone of vulcanization represents the time during which this quantity is within the specified zone vulcanization. As extruders usually work in conditions of incomplete filling, usually from about 60 to about 80% of full load, time, essentially directly proportional to the feed speed. Therefore, the residence time in the zone of vulcanization is calculated by multiplying the total area of vulcanization on the fill factor and dividing by the volumetric rate of flow. The shear rate calculated by dividing the works of the circumference of the circle described by the working head of the screw, the number of rotations of the auger in a second, in the light of the working th is ovci. In other words, the panning speed is a speed of the working head, divided into the lumen of the working head.

To obtain compositions can be used in ways different from the dynamic curing of a mixture of rubber/thermoplastic polymer resin. For example, the rubber can be fully overiden in the absence of a thermoplastic polymer resin, or dynamically or statically crushed to powder and mixed with a thermoplastic polymer resin at a temperature higher than a melting temperature or softening resin. If particles cross-linked rubber are small, well dispersed and are in a suitable concentration, the composition is easily obtained by mixing the cross-linked rubber and thermoplastic polymer resin. Preferably, to form a mixture containing well-dispersed fine particles of cross-linked rubber. The mixture, which contains poorly dispersed or too large rubber particles may be crushed by cold milling to reduce the particle size to a value below about 50 microns, preferably below about 20 microns and more preferably below about 5 microns. After sufficient grinding or transferring the powder get the TPV composition. Often poor dispersion or too large particles couch the spacecraft visible to the naked eye and visible in the moulded sheet. This is particularly noticeable in the absence of pigments and fillers. In this case, grinding into a powder and re-molding give the canvas, in which the agglomerates of particles of rubber or large particles imperceptible or nearly imperceptible to the naked eye, and the mechanical properties are significantly improved.

The use of polymer blends

The polymer mixtures described in the invention can be used for the manufacture of various products, such as tires, hoses, belts, gaskets, Shoe soles, castings and molded parts. They are particularly useful for applications requiring high melt strength, such as large parts manufactured by blow molding, foam and reinforcing beams. Additional applications are described in U.S. patents№№ 6329463, 6288171, 6277916, 6270896, 6221451, 6174962, 6169145, 6150464, 6147160, 6100334, 6084031, 6069202, 6066697, 6028137, 6020427, 5977271, 5960977, 5957164, 5952425, 5939464, 5936038, 5869591, 5750625, 5744238, 5621045 and 4783579, which are all included in the description by reference.

Polymer blends can be used to produce various products using known processes, polymer processing, such as extrusion (for example, the receiving sheet extrusion and extrusion of profiled products), injection molding, casting, centrifugal moulding and blow moulding. In General, the extrusion is a process through which Yu which the polymer is driven continuously along the auger through the field of high temperature and high pressure, where it is melted and compacted, and finally pressed firmly across the head of the extruder. The extruder may be a single screw extruder, mnogoshagovyi extruder, disk or piston extruder extruder. The head of the extruder may be film head, cylinder for blowing film, listovalnogo head, head for the extrusion of pipes, the sleeve cylinder and head for the extrusion of profiled products. Extrusion of the polymers described in the publications of C. Rauwendaal, “Polymer Extrusion”, Hanser Publishers, New York, NY, (1986), and M.J. Stevens, “Extruder Principals and Operation”, Ellsevier Applied Science Publishers, New York, NY (1985), which are both included in the description by reference in their entirety.

Injection molding is widely used for produce various plastic parts for different applications. In General injection molding is a process by which the polymer is melted and pumped at high pressure into the mold, which has the opposite configuration relative to the desired configuration, with the receipt of the items desired shape and size. Mold can be made of metal, such as steel and aluminum. Injection molding of polymers described in the publication Beaumont et al., “Successful Injection Molding: Process, Design and Simulation”, Hanser Gardner Publications, Cincinnati, Ohio (2002), which is included in the description as a reference throughout her the note.

Casting is usually a process by which the polymer is melted and served in the mold, which has the opposite configuration relative to the desired configuration, with the receipt of the items desired shape and size. Casting can be carried out in the absence of pressure or under pressure. Casting polymers described in the publication by Hans-Georg Elias “An Introduction to Plastics”, Wiley-VCH, Weinhei, Germany, pp. 161 to 165 (2003), which is included in the description by reference.

Centrifugal molding is a process commonly used for the production of hollow plastic products. Through the use of secondary operations after molding complex parts can be produced as efficiently as other technologies moulding and extrusion. Centrifugal molding differs from other methods of processing the fact that all stages of heating, melting, shaping and cooling flow after placing the polymer into the mold, resulting in the molding process no external pressure is not applied. Centrifugal molding of the polymers described in the publication Glenn Beall, “Potational Molding: Design, Materials and Processing, Hanser Gardner Publications, Cincinnati, Ohio (1998), which is included in the description by reference in its entirety.

The blow molding can be used for the manufacture of hollow plastic containers. The process VK is uchet download the softened polymer in the center of the mold, swelling of the polymer to the walls of the mold with a needle for blowing and curing of the product cooling. There are three General types of blow molding: pneumotropica with extrusion, injection molding, by extrusion and pneumotropica with hood. Injection molding, blow can be used for polymer processing, which cannot be extruded. Pneumotropica with extractor can be used in case it is difficult blown crystal and prone to crystallization of polymers, such as polypropylene. The blow molding of the polymers described in the publication of Norman C. Lee, “Understanding Blow Molding”, Hanser Gardner Publications, Cincinnati, Ohio (2000), which is included in the description by reference in its entirety.

The following examples are given to illustrate embodiments of the invention. All numeric values are approximate. When numerical interval, it should be understood that embodiments of beyond established boundaries, can still fall under the scope of the invention. The specific details described in each example, should not be considered mandatory features of the invention.

EXAMPLES

Test methods

The examples below use the following analytical methods:

Method GPC (GPC) for samples 1-4 and a-C

Robototehnicheskogo automated liquid supply, equipped with a heated needle set to 160°C, is used to add a sufficient amount of 1,2,4-trichlorobenzene stabilized with 300 ppm Ionol, to each sample of the dried polymer to obtain a final concentration of 30 mg/ml Small glass rod for stirring placed in each tube, and samples heated to 160°C for 2 hours, heated orbital vibrator, rotating at 250 Rev/min Concentrated polymer solution is then diluted to a concentration of 1 mg/ml using a robotic device of the automated fluid and the heated needle set to 160°C.

System Symyx Rapid GPC is used to determine the molecular weight of each sample. Pump Gilson 350 mounted on a flow rate of 2.0 ml/min, used for force feeding purged with helium 1,2-dichlorobenzene stabilized with 300 ppm Ionol, as mobile phase, three columns Plgel 10 micrometers (μm) Mixed B (300 mm × 7.5 mm), placed in series and heated to 160°C. Use the detector Polymer Labs ELS 1000 evaporator set at 250°C, nebulizer set at 165°C., and the flow rate of nitrogen is set at 1.8 tbsp/min at a pressure of N260-80 lbs/inch2(400-600 kPa). Samples of the polymer is heated to 160°C., and each sample is injected into a 250-ál loop using rabotat khnichenkova device of the automated fluid and the heated needle. Used serial analysis of polymer samples using two switched circuits and overlapping injections. Collect data for the samples and analyzed using software Symyx EpochTM. Peaks manually integrate and information molecular weight provide without regard to the amendments concerning the calibration curve for polystyrene standards.

The standard method of fractionation CRYSTAF

The distribution of branching is determined using the fractionation method of crystallization (CRYSTAF) using installation CRYSTAF 200, commercially available from the company PolymerChar, Valencia, Spain. Samples are dissolved in 1,2,4-trichlorobenzene at 160°C (0,66 mg/ml) for 1 hour and stabilized at 95°C for 45 minutes. The temperature of the samples are in the range from 95 to 30°C during cooling at a rate of 0.2°C/min To measure the concentration of polymer in the solution using an infrared detector. The total concentration of dissolved substances is measured when the polymer solidifies as the temperature drops. The analytical derivative of the total profile reflects the distribution of short-chain branching of the polymer.

Temperature CRYSTAF peak, and the area identified using the peak analysis module included in the CRYSTAF software (Version 2001.b, PolymerChar, Valencia, Spain). From the established practice of discovery CRYSTAF peak determines the peak temperature as a maximum on the curve dW/dT and the area between the largest positive points of inflection on either side of the identified peak on the curve derivatives. To calculate the CRYSTAF curve are preferred processing parameters with a temperature limit of 70°C and with smoothing parameters above the temperature limit of 0.1 and below the temperature limit of 0.3.

The standard method of DSC (DSC) (excluding samples 1-4 and a-C)

Data of differential scanning calorimetry to determine whether use of the device TAI model Q1000 DSC equipped with an auxiliary cooling unit RCS and an automatic sampler. Use the flow of purge gas of nitrogen 50 ml/min Sample is pressed into a thin film and melted in the press at about 175°C and then cooled down to room temperature (25°C). Then 3-10 mg of material is cut into disks with a diameter of 6 mm, accurately weighed, placed in a light aluminum pan (approximately 50 mg) and then press lid. Thermal properties of the sample are examined using the following temperature profile. The sample is rapidly heated to 180°C and held isothermal for 3 minutes to remove any thermal history. The sample was then cooled to -40°C at a cooling rate of 10°C/min and kept at -40°C for 3 minutes. The sample was then heated to 150°C at a heating rate of 10°C/min Recording cooling curves and the second heat.

Melting peak by DSC measured at a maximum speed of heat flow (W/g) on the relatively linear zero line, carried out between -30°C and the end of melting. The heat of fusion is measured as the area under the melting curve between

-30°C and the end of melting using linear zero line.

Method GPC (GPX) (excluding samples 1-4 and a-C)

System gel permeation chromatography is or from the device Polymer Laboratories Model PL-210 or device Polymer Laboratories Model PL-220. Column and rotating offices are at 140°C. Using three columns Polymer Laboratories 10-micron Mixed-b Solvent is 1,2,4-trichlorobenzene. Samples are prepared at a concentration of 0.1 g polymer in 50 ml of solvent containing 200 ppm of butylated of hydroxytoluene (OSH, BHT). Samples are prepared by lightly stirring for 2 hours at 160°C. Using the injection amount of 100 μl and a flow rate of 1.0 ml/min

Calibration kit columns GPC is carried out with the help of 21 standard polystyrene with narrow molecular weight distribution with molecular masses in the range from 580 to 8400000, distributed in a mixture of 6 "cocktails", at least with the decimal separation between individual molecular weights. Standards delivers Polymer Laboratories (Shropshire, UK). The polystyrene standards are prepared at a concentration of 0.025 g in 50 ml of solvent for molecular weights equal to or more than 1000000, and 0.05 g in 50 ml of solvent for molecular weights less than 1000000. Polystyrene standard is dissolved at 80°C with gentle stirring for 30 minutes. A mixture of narrow standards have first and in order of decreasing component with the highest molecular weight, in order to minimize decomposition. The peak molecular weights of polystyrene standards was transferred to the molecular weight polyethylene using the following equation (described in the publication of Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

MPE=0,431(Mpolystyrene).

Equivalent molecular weight polyethylene calculated using software Viscotek TriSEC, Version 3.0.

The residual deformation under compression

Residual strain in compression is measured in accordance with ASTM D 395. The sample is prepared by blending in a stack of circular disks with a diameter of 25.4 mm, thickness 3.2 mm, 2.0 mm and 0.25 mm, until it reaches the total thickness of 12.7 mm Discs cut from the plates with dimensions of 12.7×12.7 cm, obtained by direct pressing with a hot press under the following conditions: zero pressure for 3 minutes at 190°C, then 86 MPa for 2 minutes at 190°C, followed by cooling inside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared in accordance with ASTM D 1928. The measurements are carried out within one hour after pressing the sample using ASTM D792, method C.

Mod is any elasticity in bending/secant modulus/dynamic modulus of elasticity

Samples receive direct compaction using ASTM D 1928. The modulus of elasticity in bending and 2% secant modulus, measured in accordance with ASTM D-790. The dynamic modulus is measured in accordance with ASTM D 5026-01 or using equivalent methods.

Optical properties

Direct pressing get a film thickness of 0.4 mm using a hot press (Carver Model #4095-4PR1001R). The pellets are placed between the plates of polytetrafluoroethylene, and heated at 190°C. under a pressure of 55 lbs/inch2(380 kPa) for 3 minutes, then at 1.3 MPa for 3 minutes and then to 2.6 MPa for 3 minutes. Then the film is cooled in the press with running cold water at 1.3 MPa for 1 minute. Obtained by direct pressing of the film used to determine optical properties, behavior, tensile, elastic recovery and stress relaxation.

Transparency is measured using turbidimeter BYK Gardner Haze-gard, as defined in ASTM D 1746.

Shine with the reflection angle of 45° measured by using a gloss BYK Gardner Glossmeter Microgloss 45°, as defined in ASTM D-2457.

Internal turbidity is measured using turbidimeter BYK Gardner Haze-gard based on the standard ASTM D 1003, method A. To remove the surface scratches on the surface of the film put mi is eraline oil.

Mechanical properties - tensile strength, hysteresis, tear resistance

The deformation under uniaxial tension is measured using samples for microbacteria ASTM D 1708. The sample is pulled through the machine Instron at a speed of 500%/min at 21°C. the ultimate tensile strength and elongation at break is determined from the average values for the 5 samples.

Hysteresis 100% and 300% is determined from cyclic application of load to deformation of 100% and 300% using samples for microbacteria ASTM D 1708 using the Instron machineTM. Samples load and unload at 267%/min for 3 cycles at 21°C. Cyclic experiments at 300% and at 80°C, make use of a climatic chamber. In the experiments at 80°C before testing the samples provide an opportunity to balanced within 45 minutes at the test temperature. At 21°C in cyclic experience with the strain of 300% write voltage reduction in deformation of 150% in the first cycle unloading. The percentage of elastic recovery for all experiments, counting from the first unloading cycle using a strain in which the load is assigned to the zero line. The percentage of elastic recovery is defined as:

where εfrepresents the deformation, perceived the cycle load, and εsis the strain where the load is given to the zero line in the first cycle unloading.

The stress relaxation is measured at a strain of 50% and at 37°C for 12 hours by using the Instron machineTMequipped with a climate chamber. The geometry of the standard 76 mm × 25 mm × 0,4 mm After equilibration at 37°C for 45 minutes in a climate chamber where the sample is pulled up to a strain of 50% at 333%/min Voltage is recorded as a function of time for 12 hours. The percentage of stress relaxation after 12 hours should be calculated using the formula:

where L0represents the load at the deformation of 50% at time 0 and L12represents the load at the deformation of 50% after 12 hours.

Tensile test at break notched carried out on samples having a density of 0.88 g/cm3or less using the Instron machineTM. The geometry includes a plot of the standard 76 mm × 13 mm × 0.4 mm to 2-mm incisions in the sample half the length of the sample. The sample is pulled at a speed of 508 mm/min at 21°C before breaking. The energy of the tear is calculated as the area under the curve of the stress-elongation to deformation at maximum load. Determine the average value of at least 3 samples.

TMA

Thermomechanical analysis (temperature Prony the breath) is performed on the received direct pressing of the discs with a diameter of 30 mm and a thickness of 3.3 mm, molded at 180°C and at a pressure molding 10 MPa for 5 minutes, followed by quenching air. Use TMA 7 trademarks of the company Perkin-Elmer. When the test probe with a tip radius of 1.5 mm (P/N N519-0416) is applied to the surface of the sample disc with a force of 1 N. The temperature was raised at 5°C/min from 25°C. the Distance of penetration of the probe is measured as a function of temperature. Experiments completed when the probe penetrates the sample at 1 mm.

DMA

Dynamic mechanical analysis (DMA) is performed on the received direct pressing of the discs are molded in a hot press at 180°C and at a pressure of 10 MPa for 5 minutes with subsequent cooling water in the press with a speed of 90°/min. Testing is carried out using controlled strain rheometer ARES (TA Instruments)equipped with a dual cantilever clamps for torsion tests.

Pressed for 1.5-mm plate and cut out a block of size 32×12 mm, the Sample is clamped at both ends between the clamps, separated by 10 mm (separation capture ΔL), and is exposed to successive temperature stages from -100 to 200°C (5°C on the stage). At each temperature is measured modulus of elasticity in torsion G' at an angular frequency of 10 rad/s, and the amplitude of deformation is maintained between 0.1 and 4%, to ensure that torque is DOS is enough and that measurements remain in the linear mode.

Support initial static force of 10 g (model samaritaine)to prevent sagging in the sample, when there is thermal stretching. As a consequence, the separation capture ΔL increases with temperature, especially above the melting temperature or softening of the polymer sample. The test is stopped when the maximum temperature, or when the gap between the clamp reaches 65 mm

The rate of melt

The melt index or I2measured in accordance with ASTM D 1238, condition 190°C/2,16 kg Rate of the melt or I10measured in accordance with ASTM D 1238, condition 190°C./10 kg

ATREF

Analytical analysis by fractionation by elution with increasing temperature (ARTEF) is carried out in accordance with the method described in U.S. patent No. 4798081 and in the publication of Wilde, L.; Ryle T.R., Knobeloch D.C., Peat I.R., “Determination of Branching Distributions in Polyethylene and Ethylene Copolymers”, J. Polym. Sci., 20, 441-455 (1982), which are included in the description by reference in their entirety. The analyzed composition is dissolved in trichlorobenzene and allow it to crystallize in a column containing an inert support (bullet stainless steel), by slowly lowering the temperature to 20°C at a cooling rate of 0.1°C/min, the Column is equipped with an infrared detector. Then get an ATREF chromatogram of the elution of sacristan isovalerate polymer sample from the column by slowly increasing the temperature of the eluting solvent (trichlorobenzene) from 20 to 120°C at a rate of 1.5°C/min

Analysis13C-NMR

Samples are prepared by adding approximately 3 g of a mixture of tetrachlorethane-d2/ortho-dichlorobenzene (50:50) to 0.4 g sample in a 10-mm vials for NMR. The samples are dissolved and homogenized by heating the tube and its contents to 150°C. the Data obtained using the spectrometer JEOL ECLIPSETM400 MHz or Varian Unity spectrometer PLUSTM400 MHz, corresponding to a resonance frequency of the atom13With 100,5 MHz. Data obtained using 4000 short single pulses on the data file with 6-second delay pulse repetition. To achieve a minimum ratio of signal to noise ratio for the quantitative analysis of duplicate data files add to each other. The spectrum width is 25000 Hz with a minimum file size of the data points 32 K. the Samples assayed at 130°C in a 10 mm probe with a wide range of frequencies. The introduction of comonomers determined using the method of triads Randall (Randall, J.C., JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which is included in the description by reference in its entirety).

Fractionation of the polymer using TREF

Fractionation using TREF in a large volume is carried out by dissolving 15-20 g of polymer in 2 liters of 1,2,4-trichlorobenzene (TCB) under stirring for 4 hours at 160°C. the polymer Solution is forcibly fed through the nitrogen is (15 lb/in 2, 100 kPa) on a steel column with dimensions of 3 inches × 4 ft (7.6 cm × 12 cm)filled with a mixture (60:40, vol/about.) spherical glass beads of the technical quality of 30-40 mesh (600-425 μm) (Potters Industries, HC 30 Box 20, Brownwood, TX 76801) and cut wire pellets stainless steel diameter 0,028” (0.7 mm) (Pellets, Inc., 63 Industrial Drive, North Tonawanda, NY, 14120). The column is immersed in a temperature controlled oil-shirt, set initially at 160°C. the Column is cooled first ballisticheskih to 125°C, then slowly cooled to 20°C at a rate of 0.04°C per minute and allowed to stand for 1 hour. Enter fresh TCB at a rate of about 65 ml/min, while the temperature increase speed 0,167°C/min

A portion of the eluate volume of approximately 2000 ml of preparative TREF column is collected in a 16-way heated collector fractions. The polymer in each fraction concentrated using a rotary evaporator until there is approximately 50 to 100 ml of polymer solution. Concentrated solutions are allowed to stand over night, then add an excess of methanol, filtered and washed (about 300-500 ml of methanol, including the final rinse). Stage filtering is performed on a 3-point vacuum filtration unit using polytetrafluoroethylene-coated filter paper (5.0 µm) (Osmonics Inc., Cat# Z50WP04750). Filtered fractions are dried over night is in a vacuum oven at 60°C and before the subsequent test is weighed on an analytical balance.

The strength of the melt

The melt strength (PR, MS) is measured using a capillary rheometer equipped with a head diameter of 2.1 mm, 20:1, with an entrance angle of about 45 degrees. After equilibration of the samples at 190°C for 10 minutes, the plunger is moved with a speed of 1 inch/minute (2.54 cm/min). The standard test temperature is 190°C. the Sample is uniaxial stretch to a set of accelerating gaps, located 100 mm below the head, with an acceleration of 2.4 mm/s2. Write the desired tensile stress as a function of the velocity of the exciting winding rolls. The maximum tensile stress reached during the test, defined as the strength of the melt. In the case of a polymer melt, showing the resonance phenomenon in the hood, the tensile stress before the resonance phenomenon is taken for the strength of the melt. The strength of the melt record in centinewton (SN).

Catalysts

The definition of "overnight", if used, refers to a time of approximately 16-18 hours, "room temperature" means a temperature of 20-25°C, and the definition of "mixed alkanes" means a commercially obtained mixture With6-9-aliphatic hydrocarbons available under the trade name Isopar E®(ExxonMobil Chemical Company). When the connection name does not prove that he is strukturnoi view structural representation will be checked. The synthesis of all the metal complexes and all screening experiments carried out in dry nitrogen atmosphere using a box with purified and dried up atmosphere. All used solvents are as HPLC and before applying them dry.

MMOmeans modified methylalumoxane-modified triisobutylaluminum methylalumoxane, commercially available from Akzo-Noble Corporation.

The catalyst (B1) was prepared as follows:

a) Obtaining (1-methylethyl)(2-hydroxy-3,5-di(tert-butyl)phenyl)methylamine

3,5-di-tert-butylsilane aldehyde (3.00 g) are added to 10 ml of Isopropylamine. The solution quickly becomes bright yellow. After stirring at ordinary temperature for 3 hours, the volatile components are removed under vacuum, get a bright yellow crystalline solid (yield 97%).

b) Receiving dibenzyl-1,2-bis(3,5-di-tert-butylphenyl)(1-(N-(1-methylethyl)imino)methyl)(2-oxol)zirconium

A solution of (1-methylethyl)(2-hydroxy-3,5-di(tert-butyl)phenyl)imine (605 mg, 2.2 mmol) in 5 ml of toluene is added slowly to a solution of Zr(CH2Ph)4(500 mg, 1.1 mmol) in 50 ml of toluene. The obtained dark-yellow solution is stirred for 30 minutes. The solvent is removed under reduced pressure to obtain the target product as a reddish brown solid.

The catalyst (B2) which are square as follows:

a) Obtaining (1-(2-methylcyclohexyl)ethyl)(2-oxol-3,5-di(tert-butyl)phenyl)imine

Dissolve 2-methylcyclohexylamine (8,44 ml, 64,0 mmol) in methanol (90 ml) and added dropwise di-tert-butylsilane aldehyde (10,00 g, 42,67 mmol). The reaction mixture is stirred for 3 hours and then cooled to -25°C within 12 hours. The precipitate yellow solid is filtered off and washed with cold methanol (2×15 ml), then dried under reduced pressure. The output is 11,17 g yellow solid. Range1H-NMR corresponds to the target product as a mixture of isomers.

b) Receiving dibenzyl-bis-(1-(2-methylcyclohexyl)ethyl)(2-oxol-3,5-di(tert-butyl)phenyl)immino)zirconium

A solution of (1-(2-methylcyclohexyl)ethyl)(2-oxol-3,5-di(tert-butyl)phenyl)imine (7,63 g, 23.2 mmol) in 200 ml of toluene is added slowly to a solution of Zr(CH2Ph)4(5,28 g, 11.6 mmol) in 600 ml of toluene. The obtained dark-yellow solution is stirred for 1 hour at 25°C. the Solution was diluted with another 680 ml of toluene, to obtain a solution having a concentration 0,00783 M

Acetalization 1. A mixture of methyldi(C14-18-alkyl)ammonium salts of tetrakis(pentafluorophenyl)borate (hereinafter called Borat), obtained by the interaction of long chain trialkylamine (ArmeenTMMNT, Akzo-Nobel, Inc.), HCl and Li[B(C6F5)4]essentially, in accordance with the description of U.S. patent No. 5919883, example 2.

Acetalization 2. Mixed With14-18-alkyldimethylammonium salt of bis(Tris(pentafluorophenyl)-Allman)-2-undeterminated received in accordance with U.S. patent No. 6395671, example 16.

Agents transfer circuit. Used agents transfer chain, which include diethylzinc (DEZ, SA1), di(isobutyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminium (tea, SA4), trioctylamine (SA5), triethylgallium (SA6), isobutylamine-bis(dimethyl(tert-butyl)siloxane) (SA7), isobutylamine-bis(di(trimethylsilyl)amide) (SA8), n-octylamine-di(pyridine-2-methoxide) (SA9), bis(n-octadecyl)isobutylamine (SA10), isobutylamine-bis(di(n-pentyl)amide) (SA11), n-octylamine-bis(2,6-di-tert-butyl)phenoxide (SA12), n-octylamine-di(ethyl(1-naphthyl)amide) (SA13), ethylaluminum-bis(tert-butyldimethylsiloxy) (SA14), ethylaluminum-di(bis(trimethylsilyl)amide) (SA15), ethylaluminum-bis(2,3,6,7-dibenzo-1-azacycloheptane) (SA16), n-octylamine-bis(2,3,6,7-dibenzo-1-azacycloheptane) (SA17), n-octylamine-bis(dimethyl(tert-butyl)siloxy (SA18), ethylzinc(2,6-diphenylphenol) (SA19) and ethylzinc(tert-piperonyl) (SA20).

Examples 1-4. Comparative examples a-C

General conditions of high-performance parallel polymerization

The polymerization is carried out with the use of high-performance parallel polymerization reactor (PPR)supplied by the company Symyx Technlogies, Inc. and working essentially in accordance with U.S. patent No. 6248540, 6030917, 6362309, 6306658 and 6316663. The copolymerization of ethylene is carried out at 130°C and a pressure of 200 lb/in2(1.4 MPa) with ethylene supplied on demand, using 1.2 equivalents of catalyst 1 is based on all the used catalyst (1.1 equivalent, when present MMAO). A series of polymerization reactions carried out in a parallel pressure reactor (PPR), containing 48 individual reactor cells arranged in the order of 6×8, which is equipped with a pre-weighed glass vials. The working volume of each reactor cell is 6000 mm. The temperature and pressure of each cell is controlled by mixing, provide a separate mixing blades. Gas monomer and gas to stop the polymerization reaction proceed directly to the installation of PPR and regulated by automatic valves. Liquid reagents using a robotic device added to each reactor cell using a syringe and the solvent in the reactor is a mixed alkanes. Use the following order of addition: solvent-based mixed alkanes (4 ml), ethylene, 1-octenoyl comonomer (1 ml), acetalization 1 or a mixture of acetalization 1/MAO agent transfer circuit and the catalyst or catalytic the Kaya mixture. When a mixture of catalyst 1 and MAO or a mixture of two catalysts, reagents are pre-mixed in a small vessel immediately before adding to the reactor. When the reagent is expelled from experience, the above procedure of adding in the rest of the remains. The polymerization is conducted for about 1-2 minutes, until it reaches a certain consumption of ethylene. After stopping the reaction with assistance FROM the reactor is cooled and the glass tube is unloaded. The tubes are transferred into the installation centrifuge/vacuum drying, dried for 12 hours at 60°C. the Tubes containing the dry polymer weighed, and the difference between their weight and tare weight gives a net yield of polymer. The results are shown in table 1. In table 1 and throughout the application of the compounds of the comparison are shown with an asterisk (*).

Examples 1-4 illustrate the synthesis of linear block copolymers with the present invention, as evidenced by the formation of very narrow MWD, in particular modal copolymer, when present DEZ, and bimodal product with a wide molecular weight distribution (mixture of separately derived polymers) in the absence of DEZ. Due to the fact that the catalyst (A1), as is known, introduces more octene than the catalyst (B1), different blocks or segments of the obtained copolymers of the invention is izlecimi, on the basis of branching or density.

Table 1
ExampleThe catalyst (A1) (µmol)The catalyst (B1) (µmol)Socialization (µmol)MAO (µmol)Agent transfer chain (µmol)Output (g)MnMw/MnSexily1
A*0,06-of 0.0660,3-0,13633005023,32-
In*-0,10,1100,5-0,1581369571,222,5
S*0,060,10,1760,8 -0,2038455265,3025,5
10,060,10,192-DEZ (8,0)0,1974287151,194,8
20,060,10,192-DEZ (80,0)0,146821611,1214.4V
30,060,10,192-TEA (8,0)0,208226751,714,6
40,060,10,192-TEA (80,0)0,18793338 1,549,4
1Content6or higher chains per 1000 carbon atoms
2Bimodal molecular weight distribution

You can see that the polymers produced in accordance with the present invention have a relatively narrow polydispersity (Mw/Mn) and a higher content of block copolymers (trimer, tetramer or higher)than the polymers obtained in the absence of the agent transfer chain.

Other characteristic data for the polymers of table 1 is determined with reference to the drawings. More specifically, the data of DSC and ATREF show the following.

The DSC curve for the polymer of example 1 shows the melting point by 115.7°C (TPL) with a heat of fusion 158,1 j/g Corresponding CRYSTAF curve shows the tallest peak at 34.5°C with the peak area of 52.9%. The difference between TPLby DSC and Tcrystafis 81,2°C.

The DSC curve for the polymer of example 2 shows the peak melting temperature 109,7°C (TPL) with a heat of fusion 214,0 j/g Corresponding CRYSTAF curve shows the tallest peak at 46,2°C With peak area to 57.0%. The difference between TPLby DSC and Tcrystafis 63,5°C.

The DSC curve for the polymer of example 3 shows the peak melting temperature of 120.7°C (TPL) with a heat of fusion 160,1 the W/G. The corresponding CRYSTAF curve shows the tallest peak at 66,1°C With peak area 71,8%. The difference between TPLby DSC and Tcrystafis the 54.6°C.

The DSC curve for the polymer of example 4 shows the peak with a melting point of 104.5°C (TPL) with a heat of fusion 170,7 j/g Corresponding CRYSTAF curve shows the tallest peak at 30°C with the peak area of 18.2%. The difference between TPLby DSC and Tcrystafis 74,5°C.

The DSC curve for the polymer of comparative example A* indicates the melting temperature of 90.0°C (TPL) with a heat of fusion 86,7 j/g Corresponding CRYSTAF curve shows the tallest peak at 48,5°C with the peak area of 29.4%. Both of these values are consistent with data for resins with low density. The difference between TPLby DSC and Tcrystafis 41,8°C.

The DSC curve for the polymer of comparative example* shows the melting temperature 129,8°C (TPL) with a heat of fusion 237,0 j/g Corresponding CRYSTAF curve shows the tallest peak at 82,4°C With peak area 83,7%. Both of these values are consistent with data for resins with high density. The difference between TPLby DSC and Tcrystafis 47.4°C.

The DSC curve for the polymer of comparative example* shows the melting point to 125.3°C (TPL) with a heat of fusion 143,0 j/, Correspond to the th CRYSTAF curve shows the tallest peak at 81,8°C with the peak area of 34.7%, as well as lower peak crystallization at a 52.4°C. the Distance between two peaks is consistent with the presence of vysokobarotermicheskogo and nizkochastotnogo polymer. The difference between TPLby DSC and Tcrystafis 43.5°C.

Examples 5-19. Comparative examples D*-F*.

Continuous polymerization in solution, catalyst A1/B2+DEZ

Continuous polymerization in solution is carried out in a controlled using the computer autoclave with a stirrer. The purified solvent-based mixed alkanes (ISOPARTME, ExxonMobil Chemical Company), ethylene at a speed 2,70 lb/HR (1.22 kg/hour), 1-octene, and hydrogen (if used) is served in a reactor with a volume of 3.8 l, equipped with a jacket for temperature control and an internal thermocouple. The solvent is fed to the reactor, metered using mass flow controller. Diaphragm pump with variable speed controls the flow of solvent and the pressure in the reactor. During the unloading of the pump is withdrawn side stream to provide flushing flows to the input lines of the catalyst and socializaton 1 and mixer reactor. These threads are dosed using mass flowmeters Micro-Motion and regulated by control valves or by manual adjustment of needle valves. The rest of the solvent is mixed with 1-octene, ethylene and hydrogen(if used), and fed into the reactor. The mass flow controller is used to feed the reactor with hydrogen, if necessary. The temperature of the solvent/monomer solution is controlled by using a heat exchanger before entering the reactor. This stream flows through the lower part of the reactor. The solutions of the catalyst components measure using pumps and mass flow meters, mixed with fresh solvent for the catalyst and is introduced into the lower part of the reactor. The reactor operates in full filling liquid at 500 lb/in2(3,45 MPa) under vigorous stirring. The product removed through the output line in the upper part of the reactor. All the output line from the reactor are piping with steam companion and thermally insulated. The polymerization is stopped by adding a small amount of water in the output line, together with any stabilizers or other additives and passing the mixture through a stationary mixer. Then before removing the volatile components of the product stream is heated, flowing through the heat exchanger. The polymer product produce by extrusion using an extruder to remove volatile components and water-cooled pelletizer. Process details and results are presented in table 2. Selected properties of the polymers are shown in table 3.

Table 3
The typical properties of polymers
ExampleDensity (g/cm3)I2I10I10/I2Mw (g/mol)Mn (g/mol)Mw/MnThe heat of melting (j/g)TPL(C)Twith(C)Tcrystaf(C)TPL-Tcrystaf(C)The CRYSTAF peak area (%)
D*0,86271,510,06,5110000558002,032374530799
E*0,93787,039,05,6 65000333002,0183124113794595
F*0,88950,912,5the 13.4137300998013,890125111784720
50,87861,59,86,7104600532002,055120101487260
60,87851,17,56,5109600of 53,3002,1 5511594447163
70,88251,07,27,1118500531002,269121103497229
80,88280,96,87,7of 129,000401003,268124106804313
90,88361,1the 9.79,1129600287004,574125109 814416
100,87841,27,56,5113100582001,95411692417552
110,88189,159,26,566200365001,86311493407425
120,87002,113,26,4101500551001,84011380308391
130,87180,74,46,5132100636002,1421148030818
140,91162,6the 15.66,081900436001,9123121106734892
150,87196,041,66,979900401002,03311491328210
160,87580,57,1148500749002,04311796486965
170,87571,711,36,8107500540002,04311696437357
180,91924,124,96,172000379001,9136120106705094
190,93443,420,36,076800 394001,9169125112804588
* Comparative example, not an example of the present invention

The resulting polymers are tested using DSC and ATREF, as the previous examples. The following results are obtained.

The DSC curve for the polymer of example 5 shows the peak melting temperature 119,6°C (TPL) with a heat of fusion 60,0 j/g Corresponding CRYSTAF curve shows the tallest peak at 47,6°C with the peak area of 59.5%. The Delta between TPLby DSC and Tcrystafis 72,0°C.

The DSC curve for the polymer of example 6 shows the peak melting temperature 115,2°C (TPL) with a heat of fusion 60,4 j/g Corresponding CRYSTAF curve shows the tallest peak at 44,2°C With peak area 62,7%. The Delta between TPLby DSC and Tcrystafis 71.0°C.

The DSC curve for the polymer of example 7 shows the peak melting temperature 121,3°C (TPL) with a heat of fusion 69,1 j/g Corresponding CRYSTAF curve shows the tallest peak at 49,2°C with the peak area of 29.4%. The Delta between TPLby DSC and Tcrystafis 72,1°C.

The DSC curve for the polymer of example 8 which shows the peak melting temperature to 123.5°C (T PL) with a heat of fusion 67,9 j/g Corresponding CRYSTAF curve shows the tallest peak at 80,1°C with the peak area of 12.7%. The Delta between TPLby DSC and Tcrystaf$ 43.4°C.

The DSC curve for the polymer of example 9 shows the peak melting temperature of 124.6°C (TPL) with a heat of fusion of 73.5 j/g Corresponding CRYSTAF curve shows the tallest peak at 80,8°C with the peak area of 16.0%. The Delta between TPLby DSC and Tcrystafis 43.8°C. the DSC Curve for the polymer of example 10 shows the peak melting temperature 115,6°C (TPL) with a heat of fusion of 60.7 j/g Corresponding CRYSTAF curve shows the tallest peak at 40,9°C With peak area to 52.4%. The Delta between TPLby DSC and Tcrystafaccounts for 74.7°C.

The DSC curve for the polymer of example 11 shows the peak melting temperature 113,6°C (TPL) with a heat of fusion of 70.4 j/g Corresponding CRYSTAF curve shows the tallest peak at 39,6°C with the peak area of 25.2%. The Delta between TPLby DSC and Tcrystafis 74,1°C.

The DSC curve for the polymer of example 12 shows the peak melting temperature of 113.2°C (TPL) with a heat of fusion 48,9 j/g Corresponding CRYSTAF curve has a peak equal to or higher than 30°C. (Tcrystaffor the subsequent calculation, therefore, set at 30°C). The Delta between TPLon Dsci T crystafis 83,2°C.

The DSC curve for the polymer of example 13 shows the peak melting temperature to 114.4°C (TPL) with a heat of fusion of 49.4 j/g Corresponding CRYSTAF curve shows the tallest peak at 33,8°C with the peak area of 7.7%. The Delta between TPLby DSC and Tcrystaf84.4°C.

The DSC curve for the polymer of example 14 shows the peak melting temperature 120,8°C (TPL) with a heat of fusion 127,9 j/g Corresponding CRYSTAF curve shows the tallest peak at 72,9°C with the peak area of 92.2%. The Delta between TPLby DSC and Tcrystafis 47.9°C.

The DSC curve for the polymer of example 15 shows the peak melting temperature of 114.3°C (TPL) with a heat of fusion of 36.2 j/g Corresponding CRYSTAF curve shows the tallest peak at 32,3°C with the peak area of 9.8%. The Delta between TPLby DSC and Tcrystafis 82,0°C.

The DSC curve for the polymer of example 16 shows the peak melting temperature 116,6°C (TPL) with a heat of fusion of 44.9 j/g Corresponding CRYSTAF curve shows the tallest peak at 48,0°C with the peak area of 65.0%. The Delta between TPLby DSC and Tcrystafis 68,6°C.

The DSC curve for the polymer of example 17 shows the peak melting temperature 116,0°C (TPL) with a heat of fusion of 47.0 j/g Corresponding CRYSTAF curve shows the most high is the cue peak at 43,1°C with the peak area of 56.8%. The Delta between TPLby DSC and Tcrystafis 72.9°C.

The DSC curve for the polymer of example 18 shows a peak with a melting point of 120.5°C (TPL) with a heat of fusion 141,8 j/g Corresponding CRYSTAF curve shows the tallest peak at 70,0°C With peak area 94,0%. The Delta between TPLby DSC and Tcrystafis a 50.5°C.

The DSC curve for the polymer of example 19 shows the peak melting temperature of 124.8°C (TPL) with a heat of fusion 174,8 j/g Corresponding CRYSTAF curve shows the tallest peak at 79,9°C With peak area to 87.9%. The Delta between TPLby DSC and Tcrystafis 45.0°C.

The DSC curve for the polymer of comparative example D* shows the peak melting temperature of 37.3°C (TPL) with a heat of fusion of 31.6 j/g Corresponding CRYSTAF curve has a peak equal to and above 30°C. Both of these values are consistent with data for resins with low density. The Delta between TPLby DSC and Tcrystafis 7.3°C.

The DSC curve for the polymer of comparative example E* shows the peak temperature of the melting 124,0°C (TPL) with a heat of fusion 179,3 j/g Corresponding CRYSTAF curve shows the tallest peak at 79,3°C with the peak area of 94.6%. Both of these values are consistent with data for resins with high density. The Delta between TPLby DSC and TcrystafSOS is to place 44,6°C.

The DSC curve for the polymer of comparative example F* shows the peak temperature of melting of 124.8°C (TPL) with a heat of fusion 90,4 j/g Corresponding CRYSTAF curve shows the tallest peak at 77,6°C with the peak area of 19.5%. The distance between two peaks is consistent with the presence of vysokobarotermicheskogo and nizkochastotnogo polymer. The Delta between TPLby DSC and Tcrystafis to 47.2°C.

Testing of the physical properties

Samples of the polymers evaluated for their physical properties, such as high temperature stability, which is confirmed by the temperature test of the TMA, the strength of adhesion of the pellets, high-temperature elastic recovery, high temperature residual deformation under compression and the ratio of the dynamic moduli, G'(25°C.)/G'(100°C.). Several commercially available polymers included in the tests: comparative example G* represents an essentially linear ethylene/1-octenoyl copolymer (AFFINITY®, The Dow Chemical Company), comparative example H* is an elastomeric, essentially linear ethylene/1-octenoyl copolymer (AFFINITY®EG8100, The Dow Chemical Company), comparative example I* is an essentially linear ethylene/1-octenoyl copolymer (AFFINITY®PL1840, The Dow Chemical Company), comparative example J* is a hydrogenated tribes is OK-copolymer of styrene/butadiene/styrene (KRATON TMG1652, KRATON Polymers), comparative example K* is a thermoplastic vulcanizer (TPV, polyolefin mixture containing dispersed therein poperechnyy elastomer). The results obtained are presented in table 4.

Table 4
High-temperature mechanical properties
ExampleTMA - penetration of 1 mm (°C)The strength of adhesion of the pellets lb/ft2(kPa)G'(25°C.)/ G'(100°C)Recovery after deformation 300% (80°C) (%)The residual strain in compression (70°C) (%)
D*51-9Failed-
E*130-18--
F*70141 (6,8)9Failed100
5 1040 (0)68149
6110-5-52
7113-48443
8111-4Failed41
997-4-66
10108-58155
11100-8-68
1288-8 -79
1395-68471
14125-7--
1596-5-58
16113-4-42
171080 (0)48247
18125-10--
19133-9--
G*463 (22,2)89Failed100
H*70213 (10,2)29Failed100
I*111-11--
J*107-5Failed100
K*152-3-40

In table 4, the polymer of comparative example F* (which is a physical mixture of two polymers, obtained by simultaneous polymerization using catalyst A1 and B1) has a temperature of penetration of 1 mm to approximately 70°C, whereas the polymers of examples 5-9 are temperature penetration of 1 mm to 100°C or higher. In addition, the polymers of examples 10-19 - all have a temperature of penetration of 1 mm more than 85°C, and most which has a temperature of penetration of 1 mm TMA more than 90°C., and even more than 100°C. The data obtained show that the new polymers have higher dimensional stability at higher temperatures compared with the physical mixture. The polymer of comparative example J* (commercial SBS) has a good temperature penetration of 1 mm, approximately 107°C, but has a very bad (at high temperature 70°C) residual strain in compression is approximately 100%, and not restored (the sample is destroyed during a high temperature (80°C) recovery after 300%strain. Therefore, given as examples of the polymers have a unique combination of properties not available in some equivalent commercially available high-performance thermoplastic elastomers.

Similarly, table 4 shows that the inventive polymers have a low (good) the ratio of the dynamic modulus of elasticity G'(25°C.)/G'(100°C.) of 6 or less, while the physical mixture (comparative example F*) is the ratio of the dynamic modulus of elasticity 9, and statistical ethylene/octenoyl copolymer (comparative example G*) is similar to the density is the ratio of the dynamic modulus of elasticity substantially higher (89). It is desirable that the ratio of the dynamic moduli of elasticity of the polymer was as close as possible to 1. Such polymers will not be exposed to temperature, izgotovlenie of such polymer products can be successfully used in a wide temperature range. This lack of relationship dynamic modulus of elasticity and temperature independence is particularly useful when using elastomers, for example, in the case of formulations sensitive in the short-term pressing of adhesives.

The data of table 4 also show that the polymers of the present invention have improved strength of adhesion of the pellets. In particular, the polymer of example 5 has the strength of adhesion of the pellets 0 MPa, which means free flowing test conditions compared to the polymers of comparative examples F* and G*, which demonstrate the significant sticking. The strength of adhesion is important, because the volumetric batch of polymers having high strength adhesion, can lead to the product, seized or stuck together during storage or during transportation, resulting in poor machinability. High temperature (70°C) residual strain in compression in the case of the inventive polymers is generally good, with a value of in General less than about 80%, preferably less than about 70% and in particular less than approximately 60%. In contrast, the polymers of comparative examples F*, G*, H* and J* - all have residual deformation under compression at 70°C 100% (maximum possible value, including the lack of elastic recovery). Good high-temperature residual deformation of priiatii (lowest numerical value) is especially necessary in this application, as gaskets, window profiles, o-rings, etc.

Table 5 shows data on the mechanical properties of new polymers, and various comparative polymers at room temperature. You can see that the inventive polymers have good abrasion resistance when tested in accordance with ISO 4649, usually showing a loss of less than approximately 90 mm3, preferably less than about 80 mm3and in particular less than approximately 50 mm3. In this test, a higher numerical values indicate higher volume loss and therefore lower abrasion resistance.

Tear resistance, as measured by tensile strength at elongation at break notched, the inventive polymers is usually 1000 MJ or higher, as shown in table 5. The tear resistance of the inventive polymers can be up to 3000 MJ or even up to 5000 MJ. Comparative polymers generally have a tear resistance of not higher than 750 MJ.

Table 5 also shows that the polymers of the present invention have better voltage reduction in deformation of 150% (illustrated by the higher values of voltage reduction)than some comparative examples. The polymer is sravnitelnyh examples F*, G* and H* are the value of the voltage reduction at 150%strain 400 kPa or less, while the claimed polymers have values of voltage reduction at 150%strain 500 kPa (example 11) and up to about 1100 kPa (example 17). The polymers having higher values of voltage reduction in deformation of 150%would be especially useful when applied to an elastic product, such as elastic fibers and fabrics, especially woven materials. Other applications include wipes, hygiene items and medical items of clothing, such as loops and elastic waist.

In addition, the data of table 5 show that the stress relaxation (at 50%deformation) also improved (to a lesser extent) for the inventive polymers in comparison with, for example, the polymer of comparative example G*. Lower stress relaxation means that the polymer is better retains its force in such applications as napkins and other items of clothing where it is desirable to preserve the elastic properties over a long period of time when the temperature of the body.

Optical test

Transparency (%)
Table 6
Optical properties of polymers
ExampleInternal turbidity (%)The gloss at an angle of 45°(%)
F*842249
G*57356
5137260
6336953
7285759
8206562
9613849
10157367
11136967
1287572
13 77469
14591562
15117466
16397065
17297366
18612260
19741152
G*57356
H*127659
I*207559

Optical properties are presented in table 6, obtained by obtained by direct pressing of the films, essentially having no orientation. Optical properties is of polimerov can vary in a wide range due to changes in the size of the crystallite, what is the effect of changing the number of agent transfer circuit used in the polymerization.

Extraction of the polyblock copolymers

A study of extraction of the polymers of examples 5, 7 and comparative example E*. While conducting experiments, the polymer sample is weighed into the extraction Cup of mitterolang glass, and the glass is set in the extractor type Kumagawa. The extractor with the sample rinsed with nitrogen in a round bottom flask 500 ml load 350 ml of diethyl ether. Then the flask is set in the extractor. The ether is heated under stirring. Note the time when the air begins to condense in the glass, and give the possibility of leaking of extraction in nitrogen atmosphere for 24 hours. Through this period of time the heating is stopped and the solution is allowed to cool down. Any number of ester remaining in the extractor, return to the flask. The air in the flask was evaporated in vacuum at room temperature and the remaining solid substance is blown dry with nitrogen. Any residue is transferred into a weighed container using a sequential washes with hexane. The combined washings are then evaporated by additional purging with nitrogen, and the residue is dried in vacuum overnight at 40°C. Any remaining amount of the air extractor is blown dry with nitrogen.

Then the second is a clean round bottom flask, containing 350 ml of hexane, attached to the extractor. Hexane is heated to boiling under reflux with stirring and maintained at the boil under reflux for 24 hours after first observed the condensation of hexane in a glass. The heating is stopped and the flask is allowed to cool down. Any amount of hexane remaining in the extractor, return to the flask. Hexane is removed by evaporation in vacuo at room temperature and any residue remaining in the flask is transferred into a weighed container using a sequential washes with hexane. Hexane in the flask is evaporated by blowing with nitrogen, and the residue is dried in vacuum overnight at 40°C.

A sample of polymer remaining in the glass after extraction, are transferred from the glass in a suspended container and dried in vacuum overnight at 40°C. the results Obtained are presented in table 7.

Table 7
SampleWeight (g)Soluble in ether components (g)Soluble in ether components (%)With8(mol.%)1Soluble in hexane components (g)Soluble in hexane components (%) With8(mol.%)1Balance With8(mol.%)1
Comparative example F*1,0970,0635,6912,20,245to 22.3513,66,5
Example 51,0060,0414,08-0,0403,9814,2the 11.6
Example 71,0920,0171,5913,30,0121,1011,79,9
1Specified by using the13C-NMR

Additional polymers of examples 19A-F

Continuous polymerization in solution, catalyst A1/B2+DEZ

Continuous polymerization in solution is carried out in a controlled using the computer reactor intensive mixing. Cleaned will dissolve the al-based mixed alkanes (ISOPAR TME, ExxonMobil Chemical Company), ethylene, 1-octene, and hydrogen (if used) are mixed and fed into the reactor with a volume of 27 gallons. Fed to the reactor raw measure using mass flow controllers. The temperature of the flow of raw materials are controlled by a cooled glycol heat exchanger before entering the reactor. The solutions of the catalyst components is metered by means of pumps and mass flow meters. The reactor operates in full filling with fluid at a pressure of approximately 550 lb/in2. When you exit the reactor in the polymer solution injected water and additive. Water hydrolyzes the catalyst and stop the reaction of polymerization. The solution after the reactor is then heated to prepare for the two-stage removal of volatile components. During the stage of removal of volatile components remove the solvent and unreacted monomers. The polymer melt is served by the pump to the head for cutting into pellets under water.

The details of the process and the results are shown in table 8A. Selected properties of the polymers are given in tables 8B and 8C.

Table 8B
Physical properties of polymers
The polymer of example No.Density (g/is m 3)I2I10I10/I2Mw (g/mol)Mn (g/mol)Mw/MnThe heat of melting (j/g)TPL(C)Twith(C)Tcrystaf(C)TPL-Tcrystaf(C)The CRYSTAF peak area (wt.%)
19g0,86490,96,47,1135000648002,12612092309090
19h0,86541,07,07,1131600669002,02611888-- -

Table 8C
The average blocking for typical polymers1
ExampleZn/C22The average PB (BI)
Polymer F00
Polymer 80,560,59
The polymer 19a1,30,62
Polymer 52,40,52
The polymer 19b0,560,54
The polymer 19h3,150,59

1Additional information related to the calculation of indicators blocking for various polymers described in patent application U.S. reg. No. 11/376835, entitled "Ethylene/α-olefin block interpolymer"aimed for review March 15, 2006, under the name of Colin L.P. Shan, Lonnie Hazlitt et al., and owned by Dow Global Technologies Inc., description of which is incorporated in its entirety by reference.

2Zn/C2*1000 = (consumption Zn raw materials*the concentration of Zn/1000000/Mm Zn)/total flow rate of the ethylene raw materials*(1-fractional rate of conversion of ethylene)/Mm ethylene)*1000. Please note that "Zn" in "Zn/C2*1000" refers to the amount of zinc in diethylzinc ("DEZ")used in the polymerization process, and "C2" refers to the amount of ethylene used in the polymerization process.

The method of obtaining the polymer of example 20.

The following methods get the polymer of example 20 used in the examples below. Use the autoclave continuously stirred-tank reactor (CSTR) with a volume of one gallon. The reactor operates in full filling the liquid at approximately 540 lbs/inch2moreover , the process stream enters the lower portion and out of the upper part. The reactor has an oil jacket to drain a certain amount of heat of reaction. Primary temperature control is achieved using two heat exchangers on the line adding the solvent/ethylene. ISOPAR®E, hydrogen, ethylene and 1-octene are served in the reactor at controlled flow rates.

The catalytic components are diluted in the camera with gloves that do not contain air. Two catalyst is served separately if desired ratio of the various modular containers. To prevent clogging of the supply line is utilizator, line catalyst and socializaton disconnected and the flow in the reactor is carried out separately. Socialization mixed with agent transfer circuit diethylzinc before entering the reactor.

The main product is collected under steady-state operating conditions of the reactor. After a few hours product samples indicate no significant changes in the melt flow index or density. The product is stabilized with a mixture of IRGANOX®1010, IRGANOX®1076 and IRGAFOS®176.

The conversion From8(%)
DensityI2I10/I2Temperature (°C)Consumption2(kg/h)Consumption8(kg/h)The consumption of H2(LSM3/min)
0,85401,0537,90120,00,6005,3740,9
The conversion From2(%)The hardness of the substance (%)Performance polymer (kg/h)Catalyst efficiency (kg of polymer/g of total metal)The flow of catalyst A1 (kg/h)The concentration of catalyst A1 (h/m)
to 89.920,26310,01,632870,04388,099
The flow of catalyst A2 (kg/h)The concentration of catalyst A2 (h/m)A2 (mol.%)Consumption RIBS-2 (kg/h)The concentration of the RIBS-2 (h/m)Consumption DEZ (kg/h)Concentration DEZ (ppm Zn)
0,1969,81950,0390,0631417strength of 0.159 348

The structure of the two catalysts used in the method described above (i.e. catalysts A1 and A2), is presented below:

Examples of mixtures

Prepared and evaluated in a mixed composition containing the polymer of example 20, a statistical ethylene/1-octenoyl copolymer and the polypropylene (PP1), and tested their properties.

The polymer of example 20 is an ethylene/1-octenoyl block copolymer having a composite content of 1-octene 77 wt.%, composite density 0,854 g/cm3the peak melting temperature by DSC 105°C, the content of hard segments on the basis of DSC measurements of 6.8%, the crystallization temperature of the ATREF 73°C, srednekamennogo molecular weight 188254 Yes, srednevekovoy molecular weight 329600 Yes, the rate of melt under the conditions of 190°C/2,16 kg of 1.0 DG/min and a melt index under conditions of 190°C./10 kg 37,0 DG/min, the Polymer of example 20 is obtained, as described above.

Comparative example a1is a statistical ethylene/1-octenoyl copolymer, having a density of 0.87 g/cm3the content of 1-octene 38 wt.%, the peak melting temperature 59,7°C, srednekamennogo molecular weight 59000 Yes, srednevekovoy molecular weight 121300 Yes, the melt index of 1.0 DG/min under the conditions of 190°C/2,16 kg and the melt index under conditions of 190°C./10 kg of 7.5 DG/min is, the product is commercially available under the trade name Engage ®8100 (The Dow Chemical Company).

The above polymers are mixed in the melt with PP1, polypropylene homopolymer having a melt index under conditions of 230°C/2,16 kg to 2.0 DG/min, a melting point by DSC of 161°C. and a density of 0.9 g/cm3. The product is a commercially available product of The Dow Chemical Company under the trade name Dow Polypropylene H110-02N. In the case of all compounds per 100 parts total polymer added 0.2 parts of a mixture of phenol/Fofanova antioxidant (1:1), available under the trade name Irganox®V, for thermal stability. The additive indicated in table 9 as AO.

Use the following method of mixing. Mixing drum Haake periodic operation with a capacity of 69 cm3equipped with roller blades, heated to 200°C in all zones. The rotor speed of the mixing drum set at 30 rpm and load PP1, allow to drain for 1 minute, then download AO and allow to drain for a further 2 minutes. Then in a mixing drum load the polymer of example 20, the polymer of comparative example a1or a mixture of the polymer of example 20 and the polymer of comparative example a1(1:1). After adding the elastomer, the rotor speed of the mixing drum is increased to 60 rpm and conduct stirring for another 3 minutes. The mixture is then removed from the mixing drum and prijymayutsia leaves of Milara (Mylar), placed between the metal plates, and pressed in a car direct pressing Carver installed on cooling to 15°C at a pressure of 20 lb/in2. The cooled mixture was then subjected to direct pressed into plates with dimensions of 2 inches × 2 inches × 0.06 inch by direct pressing for 3 minutes at 190°C. under a pressure of 2 lb/in2within 3 minutes, at 190°C. under a pressure of 20 lb/in2within 3 minutes, then cooled at 15°C, 20 lb/in2within 3 minutes. The mixture obtained according to the described method, is shown below in table 9.

Table 9
Comparative mixture with RRA mixture of 1Mix 2A mixture of 3
IngredientPartPartPart
PP1707070
The polymer of example 2030015
The polymer of comparative example a10 3015
JSC0,20,20,2

Obtained by direct pressing plate is cut so that the sections could be collected from the middle. Cut plate before contrast criobolium by removing sections from billets at -60°C in order to prevent erosion of the elastomeric phase. Tripolitania billet is then contrasted with the vapor phase of a 2%aqueous solution of ruthenium tetroxide for 3 hours at room temperature. Contrasting solution was prepared by weighing 0.2 g of the hydrate of ruthenium chloride (III) (RuCl3·H2O) in a glass flask with screw cap and add 10 ml of 5.25%aqueous sodium hypochlorite solution in a wide-mouthed vessel. The sample is placed in wide-mouthed glass vessel using glass slides with double-sided tape. A glass slide is placed in the flask to suspend the procurement of approximately 1 inch above contrasting solution. Slices with a thickness of approximately 100 nanometers get at ambient temperature using a diamond knife on a Leica EM UC6 microtome and placed for observation in the free mesh for applying a sample of 400 mesh TEM (THEMES).

Svetopoli image recip who have a transmission electron microscope JEOL JEM 1230, operating at an accelerating voltage of 100 kV, and recorded using a digital camera Gatan 791 and Gatan 794. Further images processed using Adobe Photoshop 7.0.

Fig and 9 is a micrograph obtained with a transmission electron microscope, mixture 1 and mixture 2, respectively. Dark domains are contrastirovania using RuCl3·H2O ethylene/1-okanoya polymers. You can see that the domains containing the polymer of example 20, much less than in the case of the comparative example And1. The size of the domains in the case of the polymer of example 20 is in the range from approximately 0.1 to approximately 2 μm, whereas the size of the domains in the case of the comparative example And1leave from approximately 0.2 to more than 5 μm. Mixture 3 contains a mixture of the polymer of example 20 and the polymer of comparative example a1in the ratio of 1:1. You can see that the visual observation of the size of the domains of the mixture 3 is significantly below the size of the domains of the mixture 2, which indicates that the polymer of example 20 improves the compatibility of the polymer of comparative example a1c PP1.

Image analysis of mixtures 1, 2 and 3 are performed using the software Leica Qwin Pro V2.4 on 5kX the TEM images. The magnification of selected for image analysis depends on the number and size of particles, which is s are analyzed. To provide a duplex image formation, the markup elastomeric particles from photocopies PAM carried out manually using a black Sharpie marker. Tagged TEM image scan using the scanner Hewlett Packard Scan Jet 4c, in order to obtain a digital image. Digital images are imported into the software Leica Qwin Pro V2.4 and turn in the duplex image by thresholding of the grey levels to include items of interest. After forming duplex images using other processing tools for editing images before image analysis. Some of these elements include contour deleted items, accept or exclude items cutoff manually the items that you want to separate. After measuring the particles in the image sizes data export into an Excel pivot table, which is used to create intervals coded signals for particles of rubber. Data on the dimensions of the feature in the corresponding intervals coded signals and get a histogram of the lengths of the particles (the maximum length of particles) relative percent repeatability. Indicate the minimum, maximum, average particle size and standard deviation. Table 10 presents the results of image analysis.

Table 10
Image analysis of the sizes of the domains mixtures
The number of mixture123
The number of estimates718254576
The maximum domain size, mm5,115,32,9
The minimum domain size, mm0,30,30,3
The average domain size, mm0,81,90,8
The standard deviation, mm0,52,20,4

The results show that as the mixture 1 and mixture 2 have a lower average size of the elastomeric domain and a narrower distribution of domain sizes. Positive interfacial effect of the polymer of example 20 can be seen on the mixture of the polymer of comparative example a1(1:1) mixture 3. Recip is config the average size of the domain and the interval is nearly identical to a mixture of 1, which contains only the polymer of example 20 as elastomer.

As shown above, embodiments of the present invention offer various polymer blends with improved compatibility. Improved compatibility obtained by adding the inventive block interpolymer to a mixture of two or more polyolefins, who otherwise are relatively immiscible. Improved compatibility is confirmed by the reduction in the average size of the domain and a more homogeneous mixture. Such mixtures should show synergistic effects in the physical properties of mixtures.

Although the invention is described using a limited number of embodiments, the specific characteristics of one option should not be attributed to other variants of the invention. Neither option does not provide all the aspects of the invention. In some embodiments, compositions or methods may include numerous compounds or stage that is not mentioned in the invention. In other embodiments, the compositions or methods may not contain or, essentially, not to include any compound or stage described in the invention. There are changes and modifications of the described embodiments. And finally, any number, disclosed in the invention, should be interpreted as the average approximation, regardless of the use of the described or used the word "approximately" or "about" when describing numbers. Appended claims, is meant to encompass all such modifications and changes as fall within the scope of invention.

1. Polymer blend with improved compatibility, designed for the manufacture of moulded articles containing
(i) a first polyolefin;
(ii) a second polyolefin; and
(iii) the ethylene/α-olefin copolymer,
where the first polyolefin, the second polyolefin and the ethylene/α-olefin copolymer are different and where the ethylene/α-olefin copolymer is a block intercooler and:
(a) has a molecular weight distribution (Mw/Mn) from about 1.7 to about 3.5, at least one melting temperature, TPLin degrees Celsius and density, d, in grams/cubic centimeter, where the numerical values of TPLand d correspond to the relationship:
TPL>-2002,9+4538,5(d)-2422,2(d)2or
(b) has a molecular weight distribution (Mw/Mn) from about 1.7 to about 3.5 and is characterized by a heat of fusion, ΔN, j/g, and the value of Delta, ΔT, in degrees Celsius defined as the temperature difference between the temperature of the highest peak in the differential scanning calometry (DSC) and temperature of the highest peak in the analysis fractionation by crystallization (CRYSTAF), where the numerical values of ΔT and ΔN are the following relations
ΔT>-0,1299(ΔN)+62,81 for ΔN more than zero and up to 130 j/g, '
ΔT>48°C for ΔN more than 130 j/g, where the CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5% of the polymer have an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; or
(c) is characterized by an elastic recovery, Re, in percent at strain of 300% and 1 cycle measured using the direct pressing of a film of the ethylene/α-olefin copolymer, and has a density, d, in grams/cubic centimeter, where the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin copolymer, essentially, has no poperechnogo phase:
Re>1481-1629(d); or
(d) has a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF, characterized in that the fraction has a molar content of comonomers, at least 5% higher than the molar content of comonomers fraction of comparable statistical copolymer of ethylene, eluting between the same temperatures, where the specified comparable statistical copolymer of ethylene contains the same comonomer(s) and has a melt index, density, and molar content of comonomers (based on the whole polymer) within 10% of the melt index, density, and molar content of comonomers the ethylene/α-olefin copolymer; or
(e) has the dynamic modulus of elasticity at 25°C, G'(25°C), and dynamic modulus of elasticity at 100°C., G'(100°C), where the ratio of G'(25°C.) to G'(100°C) is in the range from about 1:1 to about 9:1.

2. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer has a Mw/Mn from about 1.7 to about 3.5, at least one melting temperature, TPLin degrees Celsius and density, d, in grams/cubic centimeter, where the numerical values of TPLand d correspond to the relationship:
MP≥858,91-1825,3(d)+1112,8(d)2.

3. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer has a Mw/Mn from about 1.7 to about 3.5 and is characterized by a heat of fusion, ΔN, j/g, and the value of Delta, ΔT, in degrees Celsius defined as the temperature difference between the highest peak of the DSC and the highest CRYSTAF peak, where the numerical values of ΔT and ΔN are the following relations:
ΔT>-0,1299(ΔN)+62,81 for ΔN more than zero and up to 130 j/g, '
ΔT>48°C for ΔN more than 130 j/g, '
where CRYSTAF peak is determined using at least 5 percent of the cumulative polymer, and if less than 5% of the polymer have an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C.

4. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is characterized by an elastic recovery, Re, in percent at strain of 300% and 1 cycle measured using the direct pressing of the film ethyl is/α-olefin copolymer, and has a density, d, in grams/cubic centimeter, where the numerical values of Re and d satisfy the following relationship when ethylene/α-olefin copolymer, essentially, has no poperechnogo phase:
Re>1481-1629(d).

5. The polymer mixture according to claim 4, where the numerical values of Re and d satisfy the following relations:
Re>1491-1629(d).

6. The polymer mixture according to claim 4, where the numerical values of Re and d satisfy the following relations:
Re>1501-1629(d).

7. The polymer mixture according to claim 4, where the numerical values of Re and d satisfy the following relations:
Re>1511-1629(d).

8. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer has a molecular fraction which aluinum from 40 to 130°C. fractionation using TREF, characterized in that the fraction has a molar content of comonomers, at least 5% higher than the molar content of comonomers fraction of comparable statistical copolymer of ethylene, eluting between the same temperatures, where the specified comparable statistical copolymer of ethylene contains the same comonomer(s) and has a melt index, density, and molar content of comonomers (based on the whole polymer) within 10 percent from melt index, density, and molar content of comonomers ethylene/α-olefin copolymer.

9. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer has the dynamic modulus of elasticity at 25°C, G'(25°C), and dynamic modulus of elasticity at 100°C., G'(100°C), where the ratio of G'(25°C.) to G'(100°C) is in the range from about 1:1 to about 9:1.

10. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is an elastomeric polymer having an ethylene content of 5 to 95 mol.%, the content of diene from 5 to 95 mol.% and the content of α-olefin of 5 to 95 mol.%.

11. The polymer mixture according to claim 1, where the first polyolefin is an olefin Homo-polymer.

12. The polymer mixture according to claim 11, where the olefin Homo-polymer is a polypropylene.

13. The polymer mixture according to item 12, where the polypropylene is a polypropylene low density (LDPP), polypropylene, high-density (HDPP), polypropylene with high melt strength (HMS-PP), polypropylene with high toughness (HIPP), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP) or a combination of both.

14. The polymer mixture according to 14, where the polypropylene is an isotactic polypropylene.

15. The polymer mixture according to claim 1, where the second polyolefin is an olefin copolymer, the olefin terpolymer or a combination of both.

16. The polymer mixture according to § 15, where the olefinic copolymer is an ethylene/propylene copolymer (EPM).

17. The polymer mixture according to § 15, where the olefinic terpolymer derived from ethylene, monoene, soda is containing 3 or more carbon atoms, or diene.

18. The polymer mixture according to claim 1, where the second polyolefin is a capable of vulcanization of rubber.

19. The polymer mixture according to claim 1, where the first polyolefin is a polypropylene and the second polyolefin is an ethylene/propylene copolymer (EPM).

20. The polymer mixture according to claim 1, where the first polyolefin is a polypropylene and the second polyolefin is terpolymer derived from ethylene, monoene containing 3 or more carbon atoms, or diene.

21. The polymer mixture according to claim 1, where the first polyolefin is a polypropylene and the second polyolefin is a capable of vulcanization of rubber.

22. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is a component that improves the compatibility.

23. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is contained in an amount of from about 0.5 to 99 wt.% from the whole composition.

24. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is contained in an amount of from about 0.5 to 50 wt.% from the whole composition.

25. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is contained in an amount of from about 2 to 25 wt.% from the whole composition.

26. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is contained in an amount of from about 3 to 15 wt.% from usecompatible.

27. The polymer mixture according to claim 1 where the ethylene/α-olefin copolymer is contained in an amount of from about 5 to 10 wt.% from the whole composition.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: description is given of an olefin polymer composition used in pressure moulding and in hot moulding equipment, containing the following (in terms of weight): A) 60-85% crystalline propylene homopolymer characterised by polydispersity index (P.I) value ranging from 4.5 to 6 and content of isotactic pentades (mmmm) of over 96%, measured from 13C NMR in a fraction which is insoluble in xylene at 25°C; B) 15-40% partially amorphous ethylene copolymer containing from 35% to 70% propylene; the said olefin polymer composition has breaking stretching, in accordance with ISO 527, ranging from 150% to 600%. Also described is a method of preparing an olefin polymer composition through polymerisation in paragraph 1, involving at least two successive steps on which components (A) and (B) are obtained at different successive steps, carrying out each step, except the first, in the presence of the obtained polymer and the catalyst used at the previous step, and in the presence a Ziegler-Natta polymerisation catalyst containing a solid catalyst component which contains: a) Mg, Ti and a halogen and at least two electron donor compounds, said catalyst component is characterised by that, at least one of the electron donor compounds, present in amount ranging from 15 to 50 mol % of the total amount of donors, is selected from a class of succinates which are not extractable above 20 mol % and at least another electron donor compound which is extracted above 30 mol %; b) alkyl aluminium and optionally, c) one or more electron donor compounds.

EFFECT: highly elastic olefin polymer composition with high breaking elongation value is obtained.

5 cl, 3 tbl, 3 ex

Additive mixture // 2374277

FIELD: chemistry.

SUBSTANCE: invention relates to mixtures of additives to polymers, specifically to additive mixtures which are used as clarifiers for propylene homo- or copolymers. According to this invention, additive mixtures contain components (A), (B), (C) and (D). Component (A) is at least one compound of formula (I-1) , ,

and , component (B) is a compound of formula (II-1)

and component (D) is a compound of formula (III-1)

EFFECT: use of the additive mixture in accordance with this invention improves the processed propylene homo- or copolymers.

13 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin compositions with good balance of hardness and impact-resistance and high elongation rating. A hetero-phase polyolefin composition is described, containing (wt %): (A) from 50 to 80 wt % crystalline propylene polymer with polydispersity index from 5.2 to 10 and isotactic pentad (mmmm) content over 97.5 mol %, determined by 13C-NMR spectroscopy in a fraction which is insoluble in xylene at 25°C; wherein the said polymer is chosen from a propylene homopolymer or propylene copolymer and at least a comonomer, chosen from ethylene and α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical, containing at least 95 % repeating units derived from propylene; (B) from 5 to 20 % of the first elastomeric ethylene copolymer with at least a comonomer chosen from propylene and another α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical; wherein the said first elastomeric copolymer contains from 25 to less than 40% ethylene and is soluble in xylene at room temperature in amount ranging from over 85 wt % to 95 wt %, where characteristic viscosity [η] of the fraction soluble in xylene ranges from 2.5 to 4.5 dl/g; and (C) from 10 to 40% of a second elastomeric ethylene copolymer with at elast a comonomer, chosen from propylene and another α-olefin with formula H2C=CHR, where R is a linear or branched C2-6-alkyl radical; wherein the said second elastomeric copolymer contains 50 to 75% ethylene and is soluble in xylene at room temperature in amount ranging from 50 wt % to 85 wt %, where characteristic viscosity [η] of the fraction which is soluble in xylene ranges from 1.8 to 4.0 dl/g; in which total amount of copolymer (B) and copolymer (C) ranges from 20 to 45 % of the total amount of components (A)-(C), total amount of ethylene with respect to total amount of components (A)-(C) is 23 wt %, and the ratio of ethylene content in the fraction which is insoluble in xylene at room temperature, (C2xif), multiplied by the weight percent content of the fraction which is insoluble in xylene at room temperature, (%XIF), and ethylene content in the fraction which is soluble in xylene at room temperature, (C2xsf), multiplied by weight percent content of the fraction which is soluble in xylene at room temperature (%SXF), i.e. C2xif x % XIF)/(C2xsf x % SXF), satisfies the following relationship (I): (C2xif x % XIF)/(C2xsf x % SXF)>0.01 x + 0.261, where x is total amount of ethylene. Described also is a method of polymerisation of the polyolefin composition described above, involving at least three consecutive steps, where components (A), (B) and (C) are obtained on separate consecutive steps, where operations on each step, except the first step, take place in the presence the polymer formed in the previous step and catalyst used in the previous step.

EFFECT: obtaining polyolefin compositions with high hardness, without reducing impact resistance, especially impact resistance at low temperatures and elastic properties.

2 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin composition which are resistant to dynamic loading and to the method of producing said composition. The composition contains A) 60 to 95 wt % propylene (co)polymer of with polydispersity index (P.I) from 4.6 to 10 and isotactic pentad content (mmmm) over 98 mol %, determined using 13C-NMR spectroscopy for a fraction which is insoluble in xylene at 25°C and B) 5 to 40 wt % ethylene copolymer, containing 40 to 70 wt % propylene or C4-C10 α-olefins or their combination and, optionally, small diene proportions. The composition has temperature rising elution fractionation (TREF) profile, obtained through fractionation in xylene with tapping fractions at temperature 40°C, 80°C and 90°C, in which ethylene content Y in the fraction tapped at 90°C satisfies relationship (I): Y≤-0.8+0.035X+0.0091X2, where X is ethylene content in the fraction tapped at 40°C, and both values of X and Y are expressed in weight percent, and value of intrinsic viscosity [η] of the fraction which is soluble in xylene at 25°C ranges from 1.8 to 4.2 dl/g.

EFFECT: obtaining olefin polymer with good balance of properties, more specifically with high hardness and good resistance to dynamic loading.

3 cl, 3 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: rubber composition consists of, wt %: polypropylene - 3-21, butadiene-nitrile rubber - 22-55, olefin rubber - 2.5 -9.5, modificator, cross-linking agent for rubbers - 1.5-3.5, activator - 0.18-0.3, plasticiser - 3.0-7.5, mineral oil - 8-40. The composition contains polyisocyanate containing not less than two isocyanate groups (0.05-2.3 wt %) as a modificator and polypropylene with 1-6% of grafted maleic anhydride or maleic acid - 6-20 wt %. Plasticiser solubility parametre of is not less than 18 (kJ/m3)1/2.

EFFECT: oil resistance enhancing, decrease of relative residual elongation and melt flow index.

1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polypropylene polymer composition, which has improved balance "impact resistance-rigidity" and suitable for formed products manufacturing. Composition contains a) from 50 to 90 wt % of propylene homopolymer or propylene copolymer, containing to 5% molar links, derivatives of C2-C20-alfa-olefins, b) from 5 to 25 wt % of ethylene copolymer and one or several links, derivatives of C4-C20-alfa-olefins, with content of links, derivatives of C4-C20-alfa-olefins, from 50 mol% to 92 mol % and c) from 5 to 25 wt % of copolymer of propylene and ethylene, with content of links, derivatives of propylene more than 50 mol % and less than 92 mol %. Weight ratio between ethylene copolymer(component b) and sum of component b and component c) is equal or is larger than 0.5 and smaller or equal 0.9. And component a) has polydispersibility index (PI) larger than 3, melt flow rate (MFR) larger than 1dg/min, measured at 230° C under loading 2.16 kg, and fraction, soluble in xylol at 25° C, more than 1%, it also does not contain 2,1-disturbances of location. Component b) has characteristic viscosity higher than 1.2 dl/g and lower than 6 dl/g, density within interval from 0.850 to 0.890 g/ cm3, crystallinity, expressed through melting enthalpy, lower than 25 J/g and value of copolymerisation constants product r1x r2 lower than 5. Component c) has characteristic viscocity higher than 2 dl/g and lower than 6 dl/g, density within interval from 0.850 to 0.890 g/ cm3, value of copolymerisation constants product r1xr2 lower than 1.8 and crystallinity, expressed through melting enthalpy, lower than 30 J/g.

EFFECT: creation of polypropylene composition possessing excellent rigidity, thermal stability and impact strength.

9 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: proposed composition contains a) synthetic polymer and b) one or several compounds of formula or where R1, R2 and R3 or Y1, Y2 and Y3, or Z1, Z2 and Z3 represent, for example branched C3-C20alkyl.

EFFECT: possibility of significantly reducing blushing of polymers.

41 cl, 10 tbl, 90 ex

FIELD: chemistry.

SUBSTANCE: composition contains propylene polymer 60 to 85 % with wide chain-length distribution of polydispersity index 5 to 15 and melt flow rate speed 40 to 75 g/10 min, specified according to ASTM-D 1238, provision L, at 230°C under load 2.16 kg and partially xylene-soluble polyolefin rubber 15 to 40 % containing ethylene propylene copolymer containing at least ethylene 65 wt % and xylene-insoluble components approximately 25-40 wt % specified at 25°C. Polyolefin composition is characterised with good balance of mechanical properties, particularly improved balance of bending elastic modulus and impact strength even at low temperatures, e.g., at -30°C, and also low heat settings.

EFFECT: specified property ensures high dimensional stability to the products made of polyolefin composition according to the present invention.

5 cl, 2 tbl, 2 ex

Polyolefin articles // 2342411

FIELD: chemistry.

SUBSTANCE: present invention pertains to the chemical industry and can be used for making articles from a polyolefin composition, obtained through extrusion, moulding and a combination of both. The composition contains (wt %) (1) 65-95% crystalline propylene polymer, insoluble in xylene at ambient temperature in quantity of over 85% and with heterogeneity index ranging from 4.5 to 13 and viscosity index of over 2.2 dl/g; and (2) 5-35% elastomer olefin polymer of ethylene and propylene, with ethylene content ranging from 15% to 85% and viscosity index of not less than 1.4 dl/g. The ratio of the viscosity index of component (1) to the viscosity index of component (2) ranges from 0.45 to 1.6. Single and/or multilayered pipes, films or sheets, made from the given composition can be used at relatively low pressure, have the best resistance to stretching and shock resistance at low temperature without reduction in rigidity.

EFFECT: obtaining materials with the best resistance to stretching and shock resistance at low temperature without reduction in rigidity.

13 cl, 4 tbl

FIELD: chemistry.

SUBSTANCE: composition of mother mixture has value of characteristic viscosity [η] of fraction, soluble in xilol at room temperature, equal or higher than 3,5 dl/g and contains 50-90 wt % of crystalline polypropylene and 10-50 wt % of ethylene copolymer and, at least, one C3-C10 α-olefin, which contains from 15 to 50 % of ethylene. Crystalline polypropylene contains two fractions with melt flow rate at 230°C and loading 2.16 kg from 0.1 to 10 g/10min (MFRI) and from 10 to 68 g/min (MFRII), respectively. Ratio MFRI/MFRII is from 5 to 60.

EFFECT: obtaining end polyolefin composition, ready for manufacturing by casting under pressure of large products, which have excellent surface appearance due to reduction of tiger stripes and absence of gels.

7 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: composition with multimodal distribution of molecular weight has density between 0.94 and 0.95 g/cm3 at 23°C and melt flow index (MFI190/5) between 1.2-2.1 dg/min in accordance with ISO 1133. The composition contains 45-55 wt % low molecular weight homopolymer A of ethylene, 30-40 wt % high molecular weight copolymer B of ethylene and another olefin containing 4-8 carbon atoms, and 10-20 wt % ultrahigh molecular weight copolymer C of ethylene and another olefin containing 4-8 carbon atoms. The composition has high processibillity and resistance to mechanical loads and breaking, especially at temperatures below 0°C.

EFFECT: flawless coating for steel pips has mechanical strength properties combined with high hardness.

10 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polymer moulding compositions meant for moulding screw fitments. The composition contains a copolymer of ethylene and 1-hexene with density between 0.947 and 0.962 g/cm3 and melt index between 2 and 8 g/10 min and another copolymer of ethylene and 1-hexene with density between 0.912 and 0.932 g/cm3 and melt index between 0.25 and 6 g/10 min. Difference in density of the two polyethylenes is equal to or greater than 0.03 g/cm3. Selection of the components enables to obtain polymer compositions which have sufficient resistance to cracking and impact strength at low production expenses and without loss of other necessary operational properties.

EFFECT: screw fittings made from the said composition have strength which conforms to requirements for maintaining pressure, particularly in bottles with carbonated drinks, as well as plasticity for providing an airtight seal without need for lining and without change in taste or smell of the contents of the bottle.

9 cl, 4 ex, 6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polyethylene and articles made by injection moulding polyethylene. Polyethylene contains homopolymers of ethylene and/or copolymers with ethylene with molecular weight distribution Mw/Mn between 3 and 30, density of 0.945 - 0.965 g/cm3, average molecular weight Mw between 50000 g/mol and 200000 g/mol, high-load melt index (HLMI) between 10 and 300 g/10 min. The polymer contains 0.1-15 branches/1000 carbon atoms, where 1-15 wt % polyethylene with the highest molecular weight has degree of branching greater than 1 branch of side chains with length greater than CH3/1000 carbon atoms.The polyethylene is obtained using a catalyst composition which contains at least two different polymerisation catalysts, where A) is at least one hafnocene-based polymerisation catalyst (A2), and B) is at least one polymerisation catalyst based on an iron component, having a tridentate ligand which contains at least two ortho-, ortho-disubstituted aryl radicals (B). The disclosed polyethylene can be subjected to processing treatment on standard injection moulding apparatus.

EFFECT: articles obtained through injection moulding is uniform and can further be improved by increasing rate of injection moulding or high melting point.

9 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyolefin compositions which have high decolouration and impact resistance. The composition contains from 50 to less than 70 wt % crystalline propylene homopolymer, 13-28 wt % elastomeric ethylene and propylene copolymer and 10-22 wt % polyethylene. Total amount of the elastomeric copolymer and polyethylene in the composition is more than 30 wt %. The crystalline propylene homopolymer has polydispersity index ranging from 4 to 10 and amount of isotactic pentades (mmmm) measured using 13C-NMR method on a fraction which is insoluble in xylene at 25°C more than 97.5 mol %. The elastomeric ethylene copolymer is partially soluble in xylene at ambient temperature. The polymer fraction which is soluble in xylene has value of inherent viscosity, measured in tetrahydronaphthalene at 135°C, which ranges from 2 to 4 dl/g. Polyethylene has inherent viscosity ranging from 1 to 3 dl/g.

EFFECT: obtained polypropylene compositions have relatively low hardness, high impact resistance and high resistance to decolouration, which enables their use in the motor car industry, particularly in bumpers and interior finishing, packaging and household objects.

5 cl, 4 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: composition contains at least one high-molecular polyethylene and at least one low-molecular polyethylene component. The high-molecular polyethylene component of the composition has molecular weight distribution of approximately 6 to 9, content of short-chain branches less than approximately 2 branches per 1000 carbon atoms of the main chain and Mz - approximately 1100000 or greater. The ratio of weight-average molecular weight of the high-molecular polyethylene component to the weight-average molecular weight of the low-molecular polyethylene component is less than 20. The disclosed composition has density greater than 0.94 g/cm3, resistance to cracking under the influence of the surrounding medium greater than 600 hours and percentage swelling greater than 70%.

EFFECT: improved mechanical strength characteristics, suitable for blow moulding.

22 cl, 1 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: resin has melt index MI5 from 0.40 to 0.70 g/10 min and contains from 47 to 52 wt % low-molecular polyethylene fraction and from 48 to 53 wt % high-molecular polyethylene fraction, where the high-molecular polyethylene fraction includes a copolymer of ethylene and 1-hexene and 1-octene.

EFFECT: improved hydrostatic properties.

5 cl, 3 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyethylene mixed compositions, intended for film manufacturing, which include two or more different ethylene polymers, each of which has different degree of complexity of long chain branching. Polyethylene composition is practically linear and has average index of branching constituting 0.85 or less. In addition, composition has density 0.935 g/cm3 or less, dullness - 10% or less and stability to falling load impact - 100g/mm or more, determined according to ASTM D-1709 methodology.

EFFECT: polyethylene compositions possess definite combination of required properties and characteristics, good optic properties and strengthening characteristics.

15 cl, 1 dwg, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention refers to making a moulded product for handling clean-room materials, intermediate products or end products, such as a container, a tray and a tool. The moulded product is made of resin compound prepared by mixing in melt cycloolefine polymer (A) 100 weight fractions chosen from the group including bicyclo[2.2.1]-2-heptene and its derivatives, tricyclo [4,3,0,12,5]-3-decene and its derivatives, and tetracyclo[4,4,0,12,5,17,10]-3-dodecene and its derivatives of vitrification temperature within 60 to 200°C, and amorphous or low-crystalline elastic copolymer (B(b1)) 1 to 150 weight fractions. Copolymer (B(b1)) is polymerised from at least two monomers chosen from the group including ethylene and a-olefin with 3 to 20 carbon atoms and vitrification temperature 0°C or lower. The compound contains radical polymerisation initiator 0.001 to 1 weight fractions containing peroxide, and polyfunctional compound (D) 0 to 1 weight fractions. The compound (D) has at least two radical-polymerised functional groups chosen from the group including vinyl group, allylic group, acrylic group and methacrylic group in a molecule.

EFFECT: clean-room moulded product is characterised with good chemical stability, heat resistance and dimensional accuracy, it prevents volatile component release in the surrounding space, has good abrasion resistance and prevents particle formation.

19 cl, 1 tbl, 2 dwg, 12 ex

Polyethylene films // 2349611

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

FIELD: chemistry.

SUBSTANCE: invented here is a copolymer of ethylene with α-olefins, with molecular weight distribution Mw/Mn from 1 to 8, density from 0.85 to 0.94 g/cm3 , molecular weight Mn from 10000 g/mol to 4000000 g/mol, not less than 50% distribution width index of the composition, and at least, bimodal distribution of branching of side chains. Branching of side chains in maximums of separate peaks of distribution of branching of side chains in all cases is larger than 5 CH3/1000 carbon atoms. Ethylene copolymers are obtained in the presence of a catalyst system, comprising at least, one monocyclopentadienyl complex A) or A'), optionally an organic or inorganic substrate B), one ore more activating compounds C) and optionally one or more compounds, containing group 1, 2 or 13 metals of the periodic system D).

EFFECT: invented compounds have bimodal distribution of short-chain branching and narrow molecular weight distribution, as well as high impact property.

11 cl, 1 tbl, 3 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: composition with multimodal distribution of molecular weight has density between 0.94 and 0.95 g/cm3 at 23°C and melt flow index (MFI190/5) between 1.2-2.1 dg/min in accordance with ISO 1133. The composition contains 45-55 wt % low molecular weight homopolymer A of ethylene, 30-40 wt % high molecular weight copolymer B of ethylene and another olefin containing 4-8 carbon atoms, and 10-20 wt % ultrahigh molecular weight copolymer C of ethylene and another olefin containing 4-8 carbon atoms. The composition has high processibillity and resistance to mechanical loads and breaking, especially at temperatures below 0°C.

EFFECT: flawless coating for steel pips has mechanical strength properties combined with high hardness.

10 cl, 1 tbl, 1 ex

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