Thermosetting elastomers

 

(57) Abstract:

Describes a new thermosetting elastomer, comprising either (1) poperechnyy pseudostatic copolymer consisting of (a) 15-70 wt.% at least one of alphaolefin, (b) 30-70 wt.% at least one vinylaromatic connection and (C) 0-15 wt.% at least one diene, or (2) poperechnyy mostly static copolymer consisting of (a) 15-70 wt.% at least one of alphaolefin, (b) 30-70 wt.% at least one vinylaromatic connection and (C) 0-15 wt.% at least one diene. These materials have an excellent balance of properties compared to materials on the basis of ethylene-propylene-diene rubber. 7 C. and 24 C.p. f-crystals, 6 PL.

The object of the present invention comprises thermosetting elastomers, method of their production and products obtained from such elastomers.

Elastomers are defined as materials capable of large reversible deformations under the action of a relatively low voltage. Usually elastomers are characterized by the presence of structural irregularities, non-polar entities or flexible links in the polymer chain. Some examples of industrial elastomers vcltestoolglue copolymers, chlorinated polyethylene and silicon rubber.

Thermoplastic elastomers are elastomers having the properties of thermoplastics. That is, thermoplastic elastomers can be molded or shaped in another way and reprocessed at temperatures above their melting point or softening. One of the examples of thermoplastic elastomers is strabomantidae (SBS) block copolymer. SBS block copolymers have a two-phase morphology, including glassy polystyrene domains, interconnected koutsokoumnis butadiene segments. At temperatures between the glass transition temperature of butadiene units and styrene end blocks, i.e. at temperatures from -90oC to 116oC, SBS copolymers behave as Poperechnaya elastomers.

In the description of European Patent 416815 disclosed pseudotachylites Ethylenediamine copolymers. Unvulcanized pseudotachylites Ethylenediamine copolymers are characterized by low values of modules at temperatures above the melting temperature or softening of the copolymer.

The disadvantages of SBS copolymers and unvulcanized atransferrinemia destruction (to the extent they become places of unsaturation in the main polymer chain) and use only for the production of such products, which operate at temperatures not exceeding the melting point or softening of the elastomer.

In contrast, thermoset elastomers have the properties of thermoset materials. That is, thermosetting elastomers irreversibly otverzhdajutsja or "seize" when heated usually due to leakage of irreversible reactions vulcanization. Two examples of thermosetting elastomers are vulcanized ethylene-propylene (EPM) and the vulcanized ethylenepropylene (EPDM) rubbers. Materials based on EMF produced by copolymerization of ethylene and propylene. PEM materials usually vulcanized using peroxides, resulting in their cross-stitching and education as a consequence of the properties of thermoset materials. EPDM materials are linear copolymers of ethylene, propylene and a non-conjugate diene such as 1,4-hexadiene, Dicyclopentadiene or telenorba. EPDM materials usually vulcanized grey and achieve as a result of this property, thermoset materials, although they can be vulcanizate for production, operating at elevated temperatures, but the disadvantages of EPM and EPDM materials are their low cohesive strength (at low ethylene content), reduced the oil resistance of vulcanized elastomers compared to the oil resistance of rubber based on the best choice of rubbers and the resistance of the vulcanized elastomer surface modification.

There is a need in the elastomers suitable for use in a wide temperature range, and are less susceptible to ozone destruction. Especially necessary thermosetting elastomers obtained from elastomers with high cohesive strength (which provides greater flexibility when processing up to the stage vulcanization). In addition, the necessary thermosetting elastomers with oil resistance and intended for the manufacture of products, working in contact with oils, such as products for cars and gaskets. In addition, there is a need for thermosetting elastomers, for which it would be easy to carry out surface modification to increase surface adhesion of the elastomer and/or ionic places on the surface of the elastomer. In addition, it is necessary which have a crystalline polyolefin matrix, which usually evenly distributed thermosetting elastomers. Examples of thermoplastic vulcanizates are EPM and EPDM thermoset materials, distributed in a matrix of crystalline polypropylene. Such thermoplastic vulcanizates are disadvantageous materials, since they are subject to destruction under the action of oils. There is a need for thermoplastic vulcanizates with greater oil resistance. In addition, a method of obtaining such thermoplastic vulcanizates.

Summary of the invention.

The aim of the present invention is to develop a thermosetting elastomer containing vulcanized, almost a statistical copolymer based on (a) 15-70 wt.% at least one alpha-olefin, (b) 30-70 wt.% at least one vinyl or vinylidene aromatic compounds and (C) 0-15 wt.% at least one diene.

Further objective of the present invention includes a method of obtaining a thermosetting elastomer, comprising the following stages:

(a) the interaction of at least one alpha-olefin, at least one vinyl or vinylidene aromatic compound in the presence of a catalyst which (b) a vulcanization almost statistical copolymer with the formation of thermosetting elastomer.

Further, the purpose of the present invention includes thermoplastic vulcanizer, consisting of a mixture of (1) vulcanized almost statistical copolymer based on (a) 15-70 wt.%, at least one alpha-olefin, (b) 30-70 wt. % of at least one vinyl or vinylidene aromatic compounds and (C) 0-15 wt.%, at least one diene; and,

(2) at least one thermoplastic polyolefin.

Further, the purpose of the present invention includes a method of obtaining a thermoplastic vulcanizate comprising the following stages:

(a) the interaction of at least one alpha-olefin, at least one vinyl or vinylidene aromatic compound and optionally at least one diene in the presence of a catalyst with complicated geometry, which is formed almost a statistical copolymer;

(b) uniform mixture is almost a statistical copolymer of at least one thermoplastic polyolefin at a temperature above the melting temperature or softening of thermoplastic polyolefin;

(C) the introduction of a uniform mixture of the vulcanization agent is almost a statistical copolymer;

(g) of thermoplastic vulcanizate.

Further, the purpose of the present invention includes products derived from thermosetting elastomers or thermoplastic vulcanizates of the present invention.

These and other embodiments of the present invention is more fully described below in the full description of the invention.

Used in the present text, the term "polymer" refers to a polymer compound obtained by polymerization of monomers of the same or of different types. Thus, the generic term polymer covers the term homopolymer, usually used to refer to polymers derived from a monomer of the same type, and the term copolymer, as defined below.

Used in the present text, the term "copolymer" refers to polymers obtained by polymerization of at least two monomers of different types. Thus, the General term copolymer includes copolymers prepared from two different monomers, and polymers derived from more than two types of monomers.

The statement used in this text that the polymer or copolymer comprises or contains some monomers, means that the polymer or copolymer comprises or contains polymerized units of such a monomer. N is ergate in itself ethylene derivatives, that is,- CH2-CH2-.

Elastomeric thermosetting composition of the present invention preferably comprise mainly statistical, mostly linear or linear copolymers containing olefin and vinylidene aromatic monomer, where the copolymer vulcanized with the aim of achieving the properties of thermoset material. Used in the present text the term "mainly statistical" means that the distribution of monomers in the copolymer can be described by statistical Bernoulli model or statistical model of the first or second order, as described in the book by J. C. Randall in Polimer Sequence Determination, Carbon-13 NMR Method, Academic Press New York, 1977, pp. 71-78. Mainly statistical copolymers contain no more than 15 wt.% of the total number of vinyl or vinylidene aromatic monomer in blocks consisting of more than three vinyl and vinylidene aromatic Monomeric units.

Pseudotachylites copolymers represent a subclass of mainly statistical copolymers.

Pseudotachylites copolymers are characterized by a structure in which everything is phenyl (or substituted Fineline) group, placed at the side of the main polymer is the copolymer of the present invention in unstitched able to describe the following General formula (where used styrene as a vinyl or vinylidene aromatic monomer and ethylene as alpha-olefin, for example):

< / BR>
Unstitched pseudotachylites copolymers described in EP patent 416815, relevant portions of which are included in the description by reference.

Irrespective of any specific theory believe that during the polymerization reaction, for example, ethylene and styrene in the presence of a catalyst complicated geometry, as described above, if the styrene monomer is introduced into the growing polymer chain, the next monomer introduced into the circuit, be ethylene monomer or styrene monomer, acceding reverse or "tail-to-tail" manner. Consider that after the reverse or "tail-to-tail joining of styrene monomer as the monomer is ethylene, since the accession of the second styrene monomer at this point would cause its too close to reverse the styrene monomer, i.e. less than two carbon atoms of the main chain.

Preferably, mainly statistical/pseudotachylites copolymer is characterized as substantially atactic, as shown by the spectrum of 13C-NMR, in which the area of the peaks corresponding to the methylene and methine bond breaking carbon atoms of the main chain, which represents either a sequence of meso dyads Piot carbon main chain.

Next, mainly statistical/pseudotachylites copolymers can be characterized as linear or substantially linear. Used in this text, the term "mostly linear" means that the copolymer has a long chain branching. In contrast, the term "linear" means that the copolymer does not contain long chain branching.

Mainly linear copolymers are characterized by the fact that the relevant indexes melt 120/12(as determined by ASTM D-1238) 5,63, molecular weight distribution (determined by using gel permeation chromatography Mw/Mn(110/12) - 4,63 and a critical shear rate of the beginning of the destruction of the melt surface is not less than 50% larger than the critical shear rate start breaking the surface of the melt of a linear olefin polymer having about the same 12and Mw/Mnor critical shear rate beginning total destruction of the melt more about 4x106Dean/see

To identify the phenomenon of melt fracture, you can use the dependence of the apparent shear stress of the apparent shear rate. According to Ramamurthy in Journal of Rheoloqy, 30(2), 337-357,main type: the destruction of the surface of the melt and the total destruction of the melt.

The destruction of the surface of the melt occurs in the context of a seemingly constant flow and is in the range from loss of gloss to a more rigid form of "shark skin". Under used in this text the concept of the beginning of the fracture surface of the melt is assumed loss of the extrudate gloss at which the surface roughness of extrudate can only be detected with magnification of 40 times. The total destruction of the melt occurs in the conditions of unstable flow and minutely subdivided from regular (alternating rough and smooth parts, the spiral surface, etc.,) to statistical irregularities. The critical shear rate at the beginning of the destruction of the surface of the melt and the beginning of the destruction of the melt used in this description, based on the changes of surface roughness and configurations of the extrudates emerging from the extruder GER.

Mainly linear copolymers of ethylene and styrene are disclosed in U.S. patent 5272236 and patent application U.S. N 08/166789 in the name of Lai et al., submitted December 13, 1993, and 08/166412 in the name of Lai et al., submitted December 13, 1993, which are used here as references.

Alpha-olefin monomer

Acceptable alpha-olefins oical, containing from one to twenty carbon atoms. Typical alphaolefin include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-penten, 4-methyl-1-penten, 1-hexene, 5-methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-dodecene, 3 phenylpropan and mixtures thereof. Preferably the alpha-olefin will include ethylene, or a mixture of ethylene with another alpha-olefin such as 1-butene, 1-penten, 4-methyl-1-penten, 1-hexene or 1-octene.

Vinyl or vinylidene aromatic monomer

Acceptable to use vinyl or vinylidene aromatic monomers are described by the following formula:

< / BR>
where R1choose from the group of radicals consisting of hydrogen atom and alkyl radicals containing three carbons or less, and the radical Ar is chosen from the group of radicals consisting of phenyl, halophenol, alkylphenyl and alkylhalogenide. Examples of vinyl or vinylidene aromatic monomers include styrene, alpha-methylsterol; C1-C4alkyl - or phenylsilane styrene, such as ortho-, meta - and parameterstyle, mixtures thereof, halogenated on the ring sterols, such as chloresterol; vinylbenzoate and divinylbenzene. Styrene is particularly desirable vinylidene aromaticheski the th or vinylidene aromatic monomer, introduced in thermosetting elastomers of the present invention is at least 30, preferably at least 35 wt.% based on the weight of the copolymer. Vinyl or vinylidene aromatic monomer is usually injected in the copolymers of the present invention in amounts of less than 70, more typically less than 60 wt.% based on the weight of the copolymer.

Dien

One or more dienes can be optionally incorporated into the copolymer to provide functional sites of unsaturation in the copolymer that are involved, for example, in the vulcanization reactions. Although for these purposes can be mated diene, such as butadiene, 1,3-pentadiene (i.e. piperylene) or isoprene, but preferred are unpaired diene. Typical unpaired diene include, for example, unpaired diolefine with open ring, such as 1,4-hexadiene (see U.S. patent N 2933480) and 7-methyl - 1,6-octadiene (also known as MACD); cyclic diene; colophony ring cyclic diene, such as Dicyclopentadiene (see U.S. patent 3211709); or alcaligenaceae, such as methylindoline or ethylidenenorbornene (see U.S. patent N 3151173).

Unpaired dieny not limited to those, sod the ptx2">

Dieny inserted into the elastomers of the present invention in amounts of from 0 to 15 wt.% calculated on the total weight of the copolymer. When using a diene, it is preferable to take at least 2 wt.%, more preferably at least 3 wt. % and most preferably at least 5 wt.% calculated on the total weight of the copolymer. Similarly, when using a diene, it take not more than 15, preferably not more than 12 wt.% calculated on the total weight of the copolymer.

Obtaining mainly statistical/pseudotachylites copolymers.

Mainly statistical/pseudotachylites copolymers can be obtained by solution, suspension or gas-phase copolymerization of alpha-olefin, vinyl or vinylidene aromatic compounds and optionally a diene in the presence of a catalyst for olefin polymerization containing a coordination complex of a metal and activating socialization, such as described in EP patent 416815, 468651, 514828 and 520732, in the patent application U.S. N 8003, filed January 21, 1993, and U.S. patent NN 5055438, 5057475, 5096867, 5064802 and 5132380, the essence of which is referred to in this application as references. Also acceptable for savannahlander, disclosed in U.S. patent 5026798, and the catalysts disclosed in publication EP 572990-A2, the essence of which is mentioned here as a reference.

The foregoing catalysts may be further described as containing a coordination complex of a metal containing a metal of groups III or IV, or metal of some lanthanides of the Periodic Table of the Elements and a delocalized-attached residue substituted causing difficulty with balance, this complex has zatrudnieniu geometry on the metal atom, so that the angle at the metal between the centroid of delocalized, substituted, attached balance and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar-attached residue without causing shortness Deputy, and further, for such complexes, containing more than one delocalized, substituted --attached balance, only one of them for each metal atom in the complex is a cyclic, delocalized, substituted X-attached residue. Further, the catalyst preferably contains activating socializaton.

1. The coordination complex of the metal. Who/BR>< / BR>
where R' in each case independently selected from the group comprising a hydrogen atom, hydrocarbon, silyl, germyl, cyano, halo and combinations thereof, each of these radicals R' contains up to 20 non-hydrogen atoms, and two R' groups (where R' is a hydrogen atom, halogen or cyano) optionally joined together with formation of divalent derivative, United adjacent to the provisions of cyclopentadienyls ring with the formation of condensed nuclear structure;

the radical X in each case independently of one another selected from the group including hydride, halo, hydrocarbon, silyl, germyl, hydrocarbonate, amido, siloxy groups and their combinations, each of these radicals X contains up to 20 non-hydrogen atoms; or when M is in oxidation state +3, X preferably represents a stabilised ligand containing amine, phosphine, ether or thioester functional group capable of forming a coordination-covalent bond or chelating bond with the radical M, or (when X is hydrocarbon) ethylene unsaturated group, can form a 3-link with the radical M;

the radical Y is a divalent anionic gigantosaurus up to 20 non-hydrogen atoms, the specified radical Y is connected to Z and M heart these atoms of nitrogen, phosphorus, oxygen or sulfur, and the radicals Y and Z is not necessarily connected to each other to form a condensed nuclear system;

M represents a metal atom 4 Groups, especially the titanium atom;

Z represents SiR2x, CR2x, SiR2x, CR2xCR2x, CRx=CRx, CR2xSiR2x,

GeR2x, BRxor BR2x; where

the radical Rxin each case, independently selected from the group including a hydrogen atom, hydrocarbon, silyl, halogenated gidrolabilna group containing up to 20 non-hydrogen atoms, and combinations thereof, and two Rxfrom the group Z (when Rxis not a hydrogen atom) or a group Rxfrom the group (when Rxis not a hydrogen atom) and Rxfrom the group of Y (when Rxis not a hydrogen atom) optionally joined together with formation of condensed nuclear systems; and

n = 1 or 2.

Preferred coordination complexes of metal are aminosilane or aminoalkylsilane compounds described by the following formula:

R' in each case independently of one another selected from the group including a hydrogen atom, silyl, hydrocarbon and their combinations, each of these radicals R' has up to 10 carbon atoms or silicon, or two R' groups (when R' is not hydrogen) together with the education of their divalent derivative attached at adjacent positions cyclopentadienyls ring with the formation of condensed nuclear structure;

E represents a silicon atom or carbon;

X is independently in each case is a hydride, halo, hydrocarbon or hydrocarbonate, each of these radicals X has up to 10 carbon atoms or, when M is in oxidation state +3, X preferably represents a stabilizing ligand, such as hydrocarbon, silyl, amido or hospitalised substituted by one or more aliphatic or aromatic ether, thioester, amine or phosphine functional groups, especially such amine or phosphine groups are tert-substituted specified stabilizing ligand has from 3 to 30 non-hydrogen atoms, or X represents a C3-15hydrocarbonous group containing ethylene transition metal complexes include compounds in which R' aminogroup represents methyl, ethyl, propyl, butyl, pentyl or hexyl (including isomers of these Akilov), norbornyl, benzyl, phenyl, etc; cyclopentadienyls group is a cyclopentadienyl, indenyl, tetrahydroindene, fluorenyl, octahydronaphthalene, tetrahydrofluorene, etc.,; R' on the above cyclopentadienyls groups independently of one another represent in each case hydrogen atom, methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers of these Akilov), norbornyl, benzyl, phenyl, etc.,, or when M represents a metal atom with oxidation number +3, X most preferably represents 2-dialkylamino-benzyl or 2-(dialkyl-aminomethyl/a phenyl group containing from 1 to 4 carbon atoms in the alkyl groups, or allyl, 1-methylallyl, 2-methylallyl, 1,1-dimethylallyl, 1,2,3-trimethylsilyl, 1-phenyl-3-basilaris or 1,1-diphenyl-3-(diphenylmethyl) allyl group.

Specific options such preferred coordination complexes of metals include (tert-butylamide) (tetramethyl-5 - cyclopentadienyl)-1,2-tenderloi chloride; (tert-butylamide) (tetramethyl-5 - cyclopentadienyl)-1,2 - attendeestatus dichloride; (methylamide) (tetramethyl-5-chlorid; (tert-butylamino/dimethyl/tetramethyl-5 - cyclopentadienyl)selandian dimethyl; (tert-butylamino/dimethyl/tetramethyl-5 - cyclopentadienyl) silenzione dibenzyl; (benzylamino/dimethyl/tetramethyl-5 - cyclopentadienyl/selandian dichloride and (phenylphosphino)-dimethyl/tetramethyl-5 - cyclopentadienyl/silenzione dibenzyl.

Other preferred monosyllabically coordination metal complexes suitable for obtaining copolymers of the present invention will include a titanium or zirconium in the oxidation States +2 and will correspond to the following formula:

< / BR>
the radical R' in each case, independently of one another, are selected from the group including a hydrogen atom, hydrocarbon, silyl, germyl, cyano, geograpy and their combinations, each of these radicals R' contains up to 20 non-hydrogen atoms, and two R' groups (when R' is not hydrogen, halo or cyano) is not necessarily connected with the education of their divalent derivative that is attached adjacent to the provisions of cyclopentadienyls ring with the formation of condensed nuclear structure;

X is a neutral 4-connected diene group containing up to 30 non-hydrogen atoms, Kotor is., or application N 267993, filed in the U.S. Office on June 28, 1994, the essence of which is included in this text as a reference),

Y represents-O-, -S-, -NRx-, -PRx-;

M is an atom of titanium or zirconium in the oxidation state +2;

the radical Zxrepresents SiR2x, CR2x, SiR2xSiR2x, CR2xCR2x, CRx= CRx, CR2xSiR2xor GeR2xwhere the radical Rxin each case, independently of one another, represents a hydrogen atom or a group selected from among the following radicals: hydrocarbon, silyl, halogenated hydrocarbon and their mixture, each of these radicals Rxcontains up to 20 non-hydrogen atoms, and two groups of Rxfrom the Zx(where Rxis not a hydrogen atom) or Rxa group of Zx(where Rxis not a hydrogen atom) and Rxfrom Y (where Rxis not a hydrogen atom) is not necessarily connected to each other to form a condensed nuclear system. They are disclosed in the application N 82197, filed in the U.S. Office on June 24, 1993, and the corresponding parts of it are included in this description as with the coordination complex of a metal as a catalyst of polymerization, or to balance the ionic charge of catalytically activated coordination complexes of metal. Acceptable socializaton for use in this invention include polymeric or oligomeric alumoxanes, especially methylalumoxane and modified methylalumoxane; polymeric, oligomeric or Monomeric carnivoran, especially Tris/pentafluorophenyl/borane; aluminiumgie; aluminosiloxane, haloaluminate; other strong Lewis acid; ammonium salt; oxidizing agents, such as salts of silver ions ferrocene and so forth; and mixtures of such socialization. The preferred socialization are not interact and do not form coordination bonds, but ion forming the boron compounds, such as Tris/pentafluorophenyl/borane.

Alumoxane can be obtained, as disclosed in U.S. patents NN 5542199; 4544762; 5015749 and 5041585, the essence of which is included in this description by reference. The so-called modified methylalumoxane (MMAO) also suitable for use as socializaton. One method of obtaining such a modified alumoxane disclosed in U.S. patent N 5041584, the essence of which is referred to in this description as a reference.

3. Getting active coordination complexes of metals. The active catalytic sistematizadora, can be obtained by any of the following methods.

A. As shown in U.S. patents 5064802 and 513238 included in this description as a reference, the coordination complex of a metal containing at least one substituent (preferably, at least one hydrocarbon or substituted hydrocarbonous group), connected with the cation of the second component, which is a Bronsted acid, and not forming coordination bonds with a compatible anion, such as substituted ammonium salts, for example N,N-dimethylanilinium tetrakis/pentafluorophenyl/Borat.

B. As shown in the PCT application 93/23412 mentioned here as a reference, the coordination complex of a metal is connected at least with the second component, which is the salt of the vinylcarbene and not forming a coordination compatible anion.

C. As shown in PCT application 93/23412 included in this description as a reference, the coordination complex of a metal is connected to at least one second component which is a salt of carbene and forming complexes compatible anion.

, As shown in the application N 08/34434, filed in the U.S. Office on March 19, 1993, the relevant part of which was complex metal in which the metal is in the oxidation degree is one less than the metal in the finished complex, connected, at least one second component, which is a neutral oxidizing agent (such as quinone compounds, especially bichinho), in combination with an agent that weakens the Lewis acid (such as tripartition).

D. As shown in the application EP 520732, relevant portions of which are incorporated in this description by reference, a coordination complex of a metal (preferably containing at least one hydride, hidrocarburos or substituted hydrocarbones group capable of removal under the action of the Lewis acid) is connected with a Lewis acid, with sufficient activity to cause the removal of anionic ligands of the coordination complex of a metal and form, so its cationic derivative (such as Tris/perftoralkil/-borane).

4. The reaction of polymerization. Conditions for the polymerization of alpha-olefin, aromatic vinylidene and optional diene is usually the same as for the process of solution polymerization, although the application for the invention and is not limited to them. Suppose that processes high-pressure suspension the ditch and the conditions of the polymerization process.

In General, the polymerization used in the practice of the present invention, can be held in conditions that are well known and used for polymerization type Ziegler-Natta or Kaminsky-Sinn. In particular, such a polymerization process usually requires pressures from atmospheric to 1000 atmospheres (100 MPa) and temperatures from 0oC to 250oC.

In the polymerization process and the allocation of mainly statistical/pseudotachylites copolymer can form a small amount of atactic homopolymer aromatic vinyl or vinylidene due process of homopolymerization vinyl or vinylidene aromatic monomer. In General, the higher the polymerization temperature, the higher the number of the resulting homopolymer. If necessary, a homopolymer of an aromatic vinyl or vinylidene may be at least partially separated from the largely statistical/pseudotachylites copolymer, for example, the extraction method suitable solvent extraction.

Mainly statistical/pseudotachylites copolymers can be modified by conventional methods vaccinations, vulcanization, hydrogenation, the introduction of the function is not significantly impaired. Such polymers can be easily sulfonated or chlorinated order to obtain derivatives containing functional groups, using established methods.

The preparation of compositions and vulcanization mainly statistical/pseudotachylites copolymers.

Thermosetting elastomers of the present invention may include various additives such as carbon black, silicon dioxide, titanium dioxide, colored pigments, clay, zinc oxide, accelerators, vulcanizing agents, sulfur, stabilizers, antioxidants, processing AIDS, adhesives, povysili stickiness, plasticizers, wax inhibitors preliminary vulcanization, continuous fibers (such as fibers of wood pulp and filling oil. Such additives can be introduced before, during or after vulcanization mainly statistical/ pseudotachylites copolymers. Usually mainly statistical/pseudotachylites copolymers mixed with a filler, oil and curing agent at an elevated temperature for the preparation of compositions of them. Then the prepared composition vulcanized at a temperature which is usually higher than the temperature used in the ical/pseudotachylites copolymer prior to vulcanization. Typically, carbon is injected to improve the tensile strength at break, or hardness of the product, but also it can be used as filler or to disguise the color of the finished product. Usually, carbon black is used in amounts of from 0 to 80 wt.%, usually from 0.5 to 50 wt.%, calculated on the total weight of the composition. In the case where carbon black is used for masking color, its amount is usually from 0.5 to 10 wt. % (based on the weight of the composition. When carbon black is used to increase the rigidity and/or reduce the cost of the composition, it is usually used in an amount more than 10 wt.% based on the weight of the composition.

In addition, it is preferable to introduce mainly statistical/pseudotachylites copolymer filling oil to the stage of vulcanization. Filling oil is usually added to improve processing AIDS and flexibility at low temperatures, as well as to reduce costs. Acceptable filling oils are listed in the reference Rubber World Blue Book 1975 Edition, Materials and Compounding Indredients for Rubber, paqes 145-190. Typical classes are filling oils include aromatic, naphthenic and paraffinic napolo included in the recipe this amount will usually be not less than 5 wt.%, more usually from 15 to 25 wt.%, calculated on the total weight of the composition.

Vulcanizing agents are typically used in amounts of from 0.5 to 12 wt.% calculated on the total weight of the composition.

Acceptable curing agents include peroxides, phenols, azides, the interaction products of aldehydes with amines, substituted urea, substituted guanidine, substituted xanthate, substituted dithiocarbamate, thiazole, imidazoles, sulfenamide, turangalila, parakinetic, dibenzobarrelenes, sulfur, and combinations thereof. See Encyclopedia of chemical technoloqy, vol. 17, 2nd edition, interscience publishers, 1968; also Organic Peroxides, Daniel Seeru, vol.1, Wiley-interscience, 1970.

Acceptable peroxides include aromatic diazepamonline; aliphatic diazepamonline; peroxides duotronic acid; ketone peroxides; complex alkylperoxide; alkylhydroperoxide (for example, diacetyltartaric; Dibenzoyl peroxide; bis-2,4-dichlorobenzophenone; di-tert-butylperoxide; dicumylperoxide; tert-butylperbenzoate; tert-butylcumylperoxide; 2,5-bis/tert-BUTYLPEROXY/-2,5-dimethylhexane; 2,5-bis/tert-BUTYLPEROXY/-2,5-dimethylhexane-3; 4,4,4', 4'- Tetra/tert-BUTYLPEROXY/-2.2-dicyclohexylurea; 1,4-shall eroxia actionboy acid; peroxide, cyclohexanone; peracetic tert-butyl; butylhydroperoxide etc.

Acceptable phenols are disclosed in U.S. patent 4311628, which is included in this description by reference. One of the examples of the phenolic curing agent is the condensation products of halogen-substituted phenol or1-C10-alkyl substituted phenol and an aldehyde in an alkaline medium, or condensation products of bifunctional fieldsports. One such class of phenolic curing agents is dimethylamino substituted in paraprotein5-C10alkyl groups. Also acceptable are halogenated alkyl substituted phenolic curing agents and curing system that includes methylol-phenolic resin, a halogen donor and a metal connection.

Acceptable azides include azithromyci, such as tetramethylenebis(acidform) (see also U.S. patent 3284421, Breslow, Nov. 8, 1966); aromatic Polizei, such as 4,4'-diphenylmethane (see also U.S. patent 3297674, Breslow et al., Jan.10, 1967); and sulfonated, such as p,p'-oxybis/benzosulfimide.

Acceptable for use interaction products of aldehydes and amines include formaldehyde-ammonia; formalin.

Acceptable for use substituted urea include trimethylammonio; diethyltoluamide; dibutylamine; triphenylamine; 1,3-bis/2-benzothiazolylsulfenamide/urea and N,N-definitionaudio.

Acceptable for use substituted guanidine include diphenylguanidine; di-o-tolylguanidine; diphenylguanidine-phthalate and di-o-tolylguanidine salt dietechinacea.

Acceptable for use substituted xanthates include ethylxanthate zinc, isopropylxanthate sodium; builtexercise; isopropylxanthate potassium and zinc butyl xanthate.

Acceptable for use dithiocarbamate include copper dimethyldithiocarbamate, zinc dimethyldithiocarbamate, tellurium diethyldithiocarbamate, dicyclohexylthiourea cadmium, lead dimethyldithiocarbamate, dibutyldithiocarbamate selenium, pentametilenditiokarbamata zinc, dodecyldimethylamine zinc and isopropylaminocarbonyl zinc.

Acceptable for use thiazole include 2-mercaptobenzothiazoles, mercaptothiazoline zinc, 2-benzothiazolyl-, N,N-diethylthiocarbamoyl sulfide and 2,2'-dithiobis(benzothiazole).

Acceptable for use imidazoles wkly sulfenamide include N-t-butyl-2 - benzothiazole-, N-cyclohexylbenzothiazole-, N,N-diisopropylbenzamide-, N-(2,6-dimethylmorpholine)-2-benzothiazole and N,N-diethylbenzimidazolium.

Acceptable for use turangalila include N,N'-diethyl-, tetrabutyl-, N', N'-diisopropylphenyl-, tetramethyl-, N,N'-DICYCLOHEXYL - N,N'-tetrafluoropyridine.

In the case of mainly statistical/pseudotachylites copolymers not containing optional diene component, preferred are peroxide vulcanizing system; in the case of mainly statistical/pseudotachylites copolymers containing optional diene component, preferred are sulfur-containing (for example, sulphur-containing dithiocarbamate, thiazole, imidazole, sulfenamid, turondale or combinations thereof) and the phenolic curing system.

Getting thermoplastic vulcanizates

Thermosetting compositions of the present invention can be introduced into the polyolefin and get thermoplastic vulcanizates. The ratio of ingredients used will change somewhat depending on the particular polyolefin, scope, purpose, and nature Poperechnaya mainly statistical/pseudostatic the nom statistical/pseudotachylites copolymer rigidity of the obtained thermoplastic vulcanizate is reduced. Thermoplastic vulcanizates of the present invention will generally contain from 10 to 90 wt.% polyolefin and 10 to 90 wt.% Poperechnaya mainly statistical/pseudotachylites copolymer.

Acceptable for use polyolefins include thermoplastic, crystallizable, high molecular weight polymers obtained by polymerization of one or more monoolefins. Examples of acceptable use of polyolefins include polymeric resins based on ethylene and isotactic and syndiotactic of monoolefins, such as propylene, 1-butene, 1-penten, 1-hexene, 2-methyl-1-propene, 3-methyl-1-penten, 4-methyl-1-penten, 5-methyl-1-hexene and mixtures thereof. Most characteristically, thermoplastic vulcanizates of the present invention will provide for the use as the polyolefin components isotactic polypropylene.

Thermoplastic vulcanizates of the present invention is preferably produced by the method of dynamic vulcanization, in which a mixture of unvulcanized mainly statistical/pseudotachylites copolymer is mixed with a polyolefin resin and an appropriate curing agent, resulting in compositio the Ohm statistical/predestinatione copolymer is mixed with the polyolefin at a temperature above the melting temperature of the polyolefin. After mainly statistical/pseudotachylites copolymer and the polyolefin thoroughly mixed, add the appropriate curing agent, such as described above in the section dealing with receptorsare and vulcanization mainly statistical/pseudotachylites copolymers. The mixture is then plasticity using traditional plasticise equipment such as mixer, Banbury, Brabender mixer, or a mixing extruder. The temperature of the mixture during its plastilinovaya is that sufficient for the reactions vulcanization mainly statistical/pseudotachylites copolymer. The acceptable range of temperature vulcanization is the melting temperature of the polyolefin resin (120oC in the case of polyethylene and 175oC in the case of polypropylene) to a temperature at which destruction occurs mainly statistical/pseudotachylites copolymer, polyolefin and vulcanizing agent. Typically, these temperatures range from 180oC to 250oC, preferably from 180oC to 200oC.

For the use of acceptable and distinct from the dynamic vulcanization mainly statistical/pseudotachylites with vulcanized to the stage of entering into the polyolefin. Then vulcanized mainly statistical/pseudotachylites copolymer can be crushed and mixed with the polyolefin at a temperature above the melting temperature or softening of the polyolefin. Provided that the particles of vulcanized mainly statistical/pseudotachylites copolymer is small and contained in the appropriate concentration (that is, upon achieving a uniform mixture of vulcanized mainly statistical/pseudotachylites copolymer and polyolefin), you can easily get thermoplastic vulcanizates of the present invention. If such a uniform mixture is achieved, the final product will contain visible to the naked eye include vulcanized mainly statistical/pseudotachylites copolymer. In this case, the product may be converted into a powder by spraying or cold crushing to reduce the particle size below 50 microns. After proper grinding particles can be re-molded into a product, characterized by a more uniform structure and superior properties typical for thermoplastic vulcanizates of the present invention.

Thermoplastic vulcanizates of the present of the coloring pigments, kaolin, zinc oxide, stearic acid, accelerators, vulcanizing agents, sulfur, stabilizers, antioxidants, processing AIDS, adhesives, povysili stickiness, plasticizers, wax, inhibitors of premature vulcanization, endless fibers (such as fibers of wood pulp and filling oil. Such additives can be introduced either before or during or after vulcanization.

As in the case of thermosetting elastomers of the present invention, carbon black is preferably introduced into the mixture in the main statistical/pseudotachylites copolymer and polyolefin to the stage of vulcanization. Usually, carbon black is used in amounts of from 0 to 50 wt. %, typically from 0.5 to 50 wt.% calculated on the total weight of the composition. When carbon black is used to mask the color, its content is usually from 0.5 to 10 wt.% calculated on the total weight of the composition. When carbon black is used to increase the stiffness and/or cost reduction, its content is usually more than 10 wt.% calculated on the total weight of the composition.

In addition, as in the case of thermosetting elastomers of the present isopropamide one or more filling oils to the stage of vulcanization. Acceptable for use oils listed in the directory Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, paqes 145-190. Typical classes are filling oils include aromatic, naphthenic and paraffin filling oil. Usually filling oil used in amounts of from 0 to 50 wt.% calculated on the total weight of the recipe. In that case, when filling oil included in the composition, its amount is usually at least 5 wt. percent, more usually from 15 to 25 wt.% calculated on the total weight of the composition.

In one of the preferred embodiments of the present invention thermoplastic vulcanizates of the present invention will include from 30 to 60 wt.% mainly statistical/pseudotachylites copolymer, from 15 to 55 wt.% thermoplastic polyolefin and from 15 to 30 wt.% filling oil. Such thermoplastic vulcanizates preferably used for the manufacture of automobile parts.

In a particularly preferred embodiment of the present invention thermoplastic vulcanizates of the present invention are characterized by swelling in oil S N 2 less than 60% in accordance with the method S D-471.

Test methods

the properties are defined at Instron model 1122 on microbranch to determine the strength of a size of 2.2 cm at a speed of stretching of 12.7 cm/min Tensile strength at break, elongation at break

and voltage when the elongation of 100% measured according to method ASTM D-412.

The melt index is determined in accordance with the method of ASTM D-1238.

Molecular weight and molecular weight distribution determined by gel permeation chromatography.

Swelling in oil ASTM No. 2 and No. 3 is determined according to ASTM D-471.

Hardness shore "A" is determined according to method ASTM D-2240.

Residual strain in compression is measured in accordance with the method S D-395.

EXAMPLE 1

Getting Ethylenediamine copolymer and thermosetting elastomers

Ethylenediamine copolymers were obtained when using /tert-butylamide/dimethyl/tetramethyl-5 - cyclopent-dienyl/silane of dimethylsilane (+4) as the catalyst and Tris/pentafluorophenyl/borane as socializaton in the ratio of 1:1 by the following method. In a two-liter reactor was loaded 360 grams (500 ml) ISOPARTME - mixed alkaline solvent (supplied by the firm "echop Chemicals Inc.) and the required amount of co monomer styrene. The hydrogen introduced into the reactor by way of expanding under the action of differential pressure of 75 ml capacity for Grail-/tetramethyl-5 - cyclopentadienyl/silane dietitian (1V), used as a catalyst, and bis/ pentafluorophenyl/bananowy socialization mixed in a dry glass, having measured pipette the required amount of 0.005 M solution of Tris/pentafluorophenyl/boranova of socializaton mixed alkaline solvent ISOPARTME or toluene in the solution /tert-butylamide/dimethyl/tetramethyl-5 - cyclopentadienyl/silane of dimethylsilane (1V) used as a catalyst in the mixed alkaline solvent ISOPARTME or toluene. The resulting solution of catalyst was transferred to a container for the introduction of catalyst and injectively in the reactor.

Ensured the course of the polymerization reaction by introducing additional ethylene.

Additional loading of the catalyst and socializaton, if used, was prepared in the same manner and periodically brought them into the reactor. The total amount of used catalyst are shown in table 1. In each case, the number of Tris/pentafluorophenyl/boranova of socializaton (per mole) is equal to the number (tert-butylamino/dimethyl-/ -5 - cyclopentadienyl)silane of dimethylsilane (1V) used as the catalyst specified in table 1. After the experience of the polymer solution was removed from the reactor and smeshivateley company "Ciba Gigy Corp"). Volatile compounds were removed from the polymer in a vacuum thermostat at a temperature of 135oC for 20 hours.

Conditions for obtaining mainly statistical copolymers are presented in table 1.

Obtained mainly statistical copolymers were characterized as pseudotachylites and linear.

Mixing and vulcanization of the copolymer was carried out by the following method. 60-gram camera closed mixer, Brabender PS-2 is pre-heated to 49oC. In a plastic or paper container of pre-mixed 100 wt. parts carbon black 550 (supplied by company "Cabot Corporation"), 50 wt. including oil SUNPARTM2280 (supplied by company "Sun OiL"), 5 wt.h. paraffin wax, 1 wt.h. stearic acid, 8 wt.h. peroxide Vul-Cup KE (supplied by the company "Hercules") and 1.5 wt.h. realizeanything of Magenta (supplied by American Cyanamid"). The resulting mixture was loaded into a 60-gram camera. Then the camera was introduced 100 wt.h. required mainly statistical/pseudotachylites copolymer obtained as described above. The plunger was lowered into the rubber mixer, and the mixture was stirred until then, until the temperature reached 104,5oC (approximately five minutes). Setelem at 127oC chain obtain unvulcanized (raw) plates for testing. Unvulcanized (raw) plate test was subjected to vulcanization in the forms under pressure at a temperature of 171oC for 20 minutes and got vulcanized compositions based on thermosetting elastomer.

Deformation-strength properties of the crude copolymer, unvulcanized (raw) plates for testing and vulcanized compositions based on thermosetting elastomers are presented in table 2. In table designation ND " means that the given property is not defined.

As shown in table 2, compositions based on vulcanized elastomer of the present invention are characterized by large values of voltage when the elongation of 100% compared with the compared materials C1 (TafmerTM680-R supplied by the company "Mitsui Petrochemical) and C2 (VistalonTM457 supplied by the company Exxon Chemical). This is consistent with the significantly higher values of stress at elongation of 100% defined for crude copolymers, compared to the compared materials.

EXAMPLE 2

Obtaining ethylene (styrene) ethylidenenorbornene copolymer and thermosetting elastomers

Nozzles - up/dimethyl/tetramethyl-5 - cyclopent-dienyl/silane of dimethylsilane (+4) and Tris/pentafluorophenyl/borane as socializaton at a ratio of 1:1 by the following method. In a two-liter reactor was loaded 360 grams (500 ml) mixed alkaline solvent ISOPARTME (supplied by the firm "echop Chemicals Inc.) and the required amount of styrene as a co monomer. Ethylidenenorbornene transferred into the reactor. The hydrogen introduced into the reactor by way of expanding under the action of differential pressure of 75-ml capacity for storage. Then the reactor was heated to the temperature of the experience and saturated with ethylene at the desired pressure. Used as a catalyst (tert-butyl amido/dimethyl- /tetramethyl-5 - cyclopentadienyl/silane dietitian (1V) and socializaton Tris/pendaftar-phenyl/borane mixed in a dry glass, having measured pipette the required amount of 0.005 M solution of Tris/pentafluorophenyl/borane as socializaton mixed alkaline solvent ISOPARTME or toluene in the solution of (tert-butylamino)of dimethyl-/tetramethyl-5 - cyclopentadienyl/silane of dimethyltin (IV) used as a catalyst in the mixed alkaline solvent ISOPARTME or toluene. The resulting solution of catalyst was transferred to a container for the introduction of catalyst and injectively in the reactor.

Ensured the course of the polymerization reaction by introducing additional ethylene. To download katal is the actor. The total amount of used catalyst are presented in table 3. In each case, the number used as socializaton Tris/pendaftar-phenyl/borane (per mole) was equal to the number used as the catalyst (tert-/butylamide/dimethyl-/tetramethyl-5 - cyclopentadienyl/silane of dimethyltin (IV), as shown in table 3. At the end of the experiment the solution of the polymer removed from the reactor and mixed with isopropyl alcohol. In the polymer added antioxidant based on the difficulty of phenol (IRGANOXTM1010 supplied by the company "Ciba Geigy Corp."). Volatile compounds were removed from the polymer in a vacuum unit 135oC for 20 hours.

Conditions for obtaining copolymers of ethylene, styrene and ethylidenenorbornene presented in table 3.

Obtained mainly statistical copolymers were characterized as pseudotachylites and linear.

Mixing and vulcanization of the copolymer was carried out by the following method. 60-gram camera closed rubber mixer, Brabender PS-2 was pre-heated to 49oC. In a plastic or paper container of pre-mixed 100 wt. including carbon black N 550 (supplied by company "Cabot"), 50 wt.XID zinc, 1.5 wt.h. sulfur and 0.5.h. 2-mercaptobenzothiazoles aptax (supplied by the firm of R. T. Vanderbilt"). The resulting mixture was loaded into a 60-gram camera. Then the camera was introduced 100 wt. including the desired copolymer obtained as described above. The plunger was lowered into the rubber mixer, and the mixture was stirred until then, until the temperature reached 104,5oC (approximately five minutes). The mixture was removed from the rubber mixer and optional propulsively.

The samples were othermobile under pressure at 127oC in order to obtain unvulcanized (raw) plates for testing. Unvulcanized (raw) plate test was subjected to vulcanization in the forms under pressure at a temperature of 171oC for 20 minutes and got vulcanized compositions based on thermosetting elastomer.

As samples ESD1(a)-(g), the sample ESDM1(a) was prepared in accordance with the above recipe. Samples ESDM1(b)-(g) were also prepared in accordance with the above recipe, except that in the case of ESDM1(b) instead of oil SUNPAR was used SUNDEX oil T (supplied by company "Sun Oil"); if SDM () instead of butter SUPAR was used 50 wt.h. trioctyltrimellitate and if ESDM1(g) was used 0,75 recipe with EPDM brand Vistalon 6505 (supplied by the firm "echop") instead of mainly statistical/pseudotachylites copolymer. C5 was prepared according to the same recipe as above, with EPDM brand EPSyn 70A (supplied by the company DSM lymer) instead of mainly statistical/ pseudotachylites copolymer used in the present invention. C6(a) was prepared according to the recipe given above, with the best choice rubber stamps SBR 1500 instead of mainly statistical/pseudotachylites copolymer and Sundex oil T (supplied by company Sun Oil instead of oil SUNPAR. C6(b) prepared according to the recipe above, except that instead of mainly statistical/pseudotachylites copolymer used the best choice rubber SBR 1500; 50 wt.h. (not 100 wt.h.) carbon black N 550, 7 wt.h. oil Sundex 750T (instead of 50 wt.h. oil SUNPAR 2280).

Deformation-strength properties of the crude copolymer, unvulcanized (raw) plates for testing and vulcanized compositions based on thermosetting elastomer are shown in table 4. Here the reduction ND " means that the given property is not defined.

As shown in table 4, vulcanized thermoset elastomers of the present invention are usually characterized by a much higher voltage when the elongation of 100% srai firm "DS Copolymer") and C6 (the best choice rubber SBR 1500).

As further can be seen from table 4, vulcanized thermoset elastomers of the present invention typically have a resistance to swelling in oils, similar to this index to the best choice of rubber, but are superior in this regard, the materials on the basis of EPDM.

As further can be seen from table 4, the resistance to aging of vulcanized thermoset elastomers of the present invention are superior rubber-based best choice of rubber. For example, after aging at a temperature of 121oC for 70 hours in an air thermostat vulcanized copolymer of ethylene/styrene and ethylidenenorbornene had higher values of strength at break and the relatively lower values of the relative elongation at break. In contrast, after aging in an incubator under the same conditions rubber based on the best choice of rubber was characterized by reduction of tensile strength at break and a significant fall in the relative elongation at break.

Thus, as shown in table 4, vulcanized thermoset elastomers based on copolymers of ethylene, styrene and diene of the present invention showed resistance to swelling in oils who I am.

EXAMPLE 3

Getting thermoplastic vulcanizates

Brabender PS-2 or an indoor rubber mixer Haake pre-heated to 350oC. In the mixer have entered the required amount of isotactic polypropylene Pro-6524 fax (supplied by company "Himont Incorporated"), gave him the opportunity to melt and gomogeniziruetsya. After one minute, added the required amount of unvulcanized mainly statistical/pseudotachylites copolymer. Then added a process oil, an antioxidant, stearic acid, and carbon black and mixed for one minute. Added zinc oxide, sulfur, benzothiadiazole and metalloid. Mixing was carried out until such time as the torque not reached a maximum and not less than 10 minutes total time of mixing. The obtained thermoplastic vulcanizer removed from the mixer.

When implementing the above methods were used in the formulations listed in table 5. Except where otherwise noted, all quantities are in parts per 100 parts per 100 parts of elastomer.

With the exception of the composition TPV1(b) as process oil used oil Sun Par TM 2280. For the TPV composition(b) in cachesentry was subjected to compression molding at 193,4oC. table 6 presents the physico-mechanical properties of thermoplastic vulcanizates and comparative thermoplastic vulcanizates WITH-TPV1 (prepared on the basis of EPDM brand Vistalon 6505 (supplied by the firm "echop")) and C-TPV2 (prepared on the basis of EPDM brand EPSyn 70A (supplied by the company DSM Rubber")). Here the abbreviation ND " means that the given property is not defined.

Comparison of TPV1(a) and TPV2(a) with comparative materials-TPV1 (made from EPDM brand Vistalon 6505 (supplied by the firm "echop")) and C-TPV2 (prepared on the basis of EPDM brand EPSyn 70A (supplied by the company DSM Rubber") suggests that thermoplastic vulcanizates of the present invention have a significantly higher resistance to swelling in oils (test method STM N 2) than comparative materials without compromising the hardness (shore hardness "A"). Further comparison of these materials suggests that thermoplastic vulcanizates of the present invention have a superior measure voltage when the elongation of 100% and a comparable value of tensile strength at break relative to the comparative materials.

Comparison TPV-2(b), TPV-(2B) and TPV-2(g) indicates that you can adjust soprotivlenie statistical/pseudotachylites copolymer. Namely, by increasing the proportion of polypropylene is an increase in the resistance to swelling in ASTM oil No. 2. In addition, the apparent effect of the additive mainly statistical/pseudotachylites copolymer. In particular, the percentage of relative elongation at rupture declared thermoplastic vulcanizates many times more than the figure for unmodified isotactic propylene, which is characterized by relative elongation of 13%.

Thermosetting elastomers of the present invention can be used in various purposes. Examples of applications include sleeves, ducts, brake caps, roofing materials, as well as components in mixtures as modifiers impact resistance and molded products for General use.

Thermoplastic vulcanizates can also be used in various fields, especially in the products obtained by molding, injection molding and compression molding. One fundamentally important area of use Tpov of the present invention is a manufacturer of automotive engine parts such as grille and dust covers, pouches nodes topl the details of beauty (such as upholstery, dashboards covers air safety bag, door seals, control buttons, molded products and components of the fastening seat belts) and outer parts (such as tires and moldings).

1. Thermosetting elastomer, comprising either (1) poperechnyy pseudotachylites copolymer consisting of (a) 15-70 wt.% at least one of alphaolefin, (b) 30-70 wt.% at least one vinylaromatic connection and (C) 0-15 wt.% at least one diene; or (2) poperechnyy mainly statistical copolymer consisting of (a) 15-70 wt. % of at least one of alphaolefin, (b) 30-70 wt.% at least one vinylaromatic connection and (C) 0-15 wt.% at least one diene.

2. Thermosetting elastomer under item 1, comprising either (1) poperechnyy pseudotachylites copolymer consisting of (a) 25-60 wt.% at least one of alphaolefin, (b) 35-60 wt.% at least one vinylaromatic connection and (in) 3-15 wt.% at least one diene, or (2) poperechnyy mainly statistical copolymer consisting of (a) 25-60 wt. % of at least one of alphaolefin, (b) 35-60 wt.% at least one vinylaromatic connection and

4. Thermosetting elastomer under item 1, 2 or 3, where (a) alphaolefin chosen from the group comprising ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-penten, 4-methyl-1-penten, 1-hexene, 5-methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-to milliron, metamathematical, parameterstyle, chloresterol, vinylbenzoate and divinylbenzene, and mixtures thereof, and (b) a diene, if present, is chosen from the group comprising butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl-1,6-octadiene, Dicyclopentadiene, methylindoline, ethylidenenorbornene and methyltetrahydrofuran and mixtures thereof.

5. Thermosetting elastomer under item 4, where alphaolefin is ethylene, vinylaromatic compound is styrene and the diene, if present, is ethylidenenorbornene.

6. A method of obtaining a thermosetting elastomer, comprising the following stages: (a) the interaction of at least one of alphaolefin with at least one vinylaromatic connection and possibly at least one diene in the presence of a catalyst with complicated geometry, resulting in a primarily statistical or pseudotachylites copolymer, (b) a vulcanization primarily statistical or pseudotachylites copolymer, which is formed thermosetting elastomer, and the catalyst complicated geometry includes a coordination complex of a metal containing metal III or group IV metal, a lanthanide is OneNote balance, this complex contains a metal atom of the complicated geometry, so that the angle at the metal between the centroid delocalized substituted-linked residue and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar bound residue and does not contain such causes shortness Deputy, and further provided that for such complexes comprising more than one delocalized substituted-linked residue, only one of them for each metal atom of the complex is a cyclic delocalized substituted-linked residue.

7. The method according to p. 6, in which the catalyst of the complicated geometry chosen from the group comprising /tert-butylamide/-/tetramethyl--5-cyclopentadienyl/-1,2-tenderloi dichloride; /tert-butylamide//tetramethyl-5-cyclopentadienyl/1,2-attendeestatus dichloride; /tert-butylamide/dimethyl/-tetramethyl-5-cyclopentadienyl/-selandian dimethyl; /tert-butylamide/dimethyl/tetramethyl-5-indanyl/selandian dimethyl; /tert-butylamide/dimethyl/-tetramethyl-5-tetrahydroindene/selandian dimethyl; /tert-butylamide/dimethyl/tetramethyl-5-fluorenyl/selandian dimethyl; /tert-butylamide refloored/selandian dimethyl; /tert-butylamide/dimethyl/tetramethyl-5-cyclopentadienyl/-selandian dibenzyl; /tert-butylamide/dimethyl/tetramethyl-5-cyclopentadienyl/silenzione dibenzyl, and mixtures thereof.

8. The method according to p. 6, in which the catalyst of the complicated geometry activate using socializaton selected from the group comprising polymeric alumoxane, oligomeric alumoxane, polymer carnivoran, oligomeric carnivoran, Monomeric carnivoran, aluminiumgie, aluminosiloxane, haloaluminate, substituted ammonium salts, salts of silver ions ferrocene, and mixtures thereof.

9. The method according to p. 6, in which the catalyst of the complicated geometry activate using Tris(pentafluorophenyl)borane.

10. The method according to p. 6, in which the vulcanization is carried out with the help of a vulcanization agent selected from the group comprising peroxides, phenols, azides, the interaction products of aldehydes and amines, substituted urea, substituted guanidine, substituted xanthogenate, substituted dithiocarbamate, thiazole, imidazoles, sulfenamide, terminaology, parakinetic, dibenzodioxin and sulfur.

11. The method according to p. 6, in which the vulcanization is carried out using a vulcanizing agent, VDI, turangalila, sulfur and mixtures thereof with sulfur.

12. The method according to p. 6, in which the vulcanization is carried out simultaneously with the mixture of primarily statistical or pseudotachylites copolymer.

13. The method according to PP.6-12, according to which (1) alphaolefin chosen from the group comprising ethylene, propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 5-methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenylpropan and mixtures thereof, (II) vinylaromatic compound selected from the group including styrene, aromatisation, metamathematical, parameterstyle, chloresterol, vinylbenzoate and divinylbenzene, and mixtures thereof, and (III) a diene, if used, chosen from the group comprising butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl-1,6-octadiene, Dicyclopentadiene, methylindoline, ethylidenenorbornene and mixtures thereof.

14. Thermoplastic vulcanizer, comprising: (a) poperechnyy primarily statistical or pseudotachylites copolymer based on (I) 15-70 wt. % of at least one of alphaolefin, (II) 30-70 wt.% at least one vinylaromatic connections, and (III) 0-15 wt.% at least one diene, and (b) at least one thermoplastic polyolefin.

15. Thermoplastic in which copolymer and 10-90 wt.% thermoplastic polyolefin.

16. Thermoplastic vulcanizer under item 14, optionally containing 0-50 wt. % oil softener selected from the group including aromatic, naphthenic and paraffinic oils.

17. Thermoplastic vulcanizer under item 14, where Poperechnaya primarily statistical or pseudotachylites copolymer is a copolymer of (a) 40-65 wt.% at least one of alphaolefin and (b) 35-60 wt.% at least one vinylaromatic connection.

18. Thermoplastic vulcanizer according to p. 16, where Poperechnaya primarily statistical or pseudotachylites copolymer is a copolymer of (a) 25-60 wt.% at least one of alphaolefin and (b) 35-60 wt.% at least one vinylaromatic connection and (in) 3-15 wt.% at least one diene.

19. Thermoplastic vulcanizer under item 14, containing 30-60 wt.% Poperechnaya primarily statistical or pseudotachylites copolymer, 15-55 wt.% thermoplastic polyolefin and 15-30 wt.% oil softener.

20. Thermoplastic vulcanizer on PP.14-19, where (a) the alpha-olefin is chosen from the group comprising ethylene, propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 5-methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenylpropan and the Tyrol, parameterstyle, chloresterol, vinylbenzoate, divinylbenzene and mixtures thereof, and (C) the optional diene is chosen from the group comprising butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl-1,6-octadiene, Dicyclopentadiene, methylindoline, ethylidenenorbornene, methyltetrahydrofuran and mixtures thereof.

21. Thermoplastic vulcanizer according to p. 20, where thermoplastic polyolefin is chosen from the group comprising ethylene, propylene, 1-butene, 1-penten, 1-hexene, 2-methyl-1-propene, 3-methyl-1-penten, 4-methyl-1-penten, 5-methyl-1-hexene and mixtures thereof.

22. Thermoplastic vulcanizer according to p. 20, where alphaolefin is ethylene, vinylaromatic compound is styrene and the diene, when present, is ethylidenenorbornene.

23. Thermoplastic vulcanizer according to p. 21, where alphaolefin is ethylene, vinylaromatic compound is styrene and the diene, when present, ethylidenenorbornene.

24. Thermoplastic vulcanizer containing poperechnyy mainly statistical copolymer of at least one of alphaolefin at least one vinylaromatic compounds and, optionally, at least one diene, distributed in a matrix of thermoplastic polyolefin, MSD ASTM D-471.

25. A method of obtaining a thermoplastic vulcanizate comprising the following stages: (a) the interaction of at least one of alphaolefin with at least one vinylaromatic compound and, optionally, with at least one diene in the presence of a catalyst with complicated geometry, which is formed mainly statistical or pseudotachylites copolymer, (b) mixing until smooth mainly statistical or pseudotachylites copolymer with at least one thermoplastic polyolefin at a temperature above the melting temperature or softening of thermoplastic polyolefin, (b) introduction to mixed until homogeneous mixture agent for vulcanization primarily statistical or pseudotachylites copolymer, (d) simultaneous vulcanization primarily statistical or pseudotachylites copolymer and mixed until a homogeneous mixture with the formation of thermoplastic vulcanizate, and the catalyst with complicated geometry includes a coordination complex of a metal containing metal III or group IV metal of some lanthanides of the Periodic table of the elements and a delocalized-connected the pattern geometry, so the angle at the metal between the centroid delocalized substituted-linked residue and the center of at least one remaining substituent is less than such angle in a similar complex containing a similar bound residue that does not contain such causes shortness Deputy, and further provided that for such complexes comprising more than one delocalized substituted-linked residue, only one of them for each metal atom of the complex is a cyclic delocalized substituted-linked residue.

26. The method according to p. 25, by which (I) alphaolefin chosen from the group comprising ethylene, propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 5-methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenylpropan and their mixture, (II) vinylaromatic compound selected from the group including styrene, aromatisation, metamathematical, parameterstyle, chloresterol, vinylbenzoate, divinylbenzene and mixtures thereof, and (III) optional diene is chosen from the group comprising butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl-1,6-octadiene, Dicyclopentadiene, methylindoline, ethylidenenorbornene, methyltetrahydrofuran and mixtures thereof.

27. With the-penten, 1-hexene, 2-methyl-1-propene, 3-methyl-1-penten, 4-methyl-1-penten, 5-methyl-1-hexene and mixtures thereof.

28. The method according to p. 25, in which the vulcanization agent mainly statistical copolymer chosen from the group comprising peroxides, phenols, azides, the reaction products of aldehydes and amines, substituted urea, substituted guanidine, substituted xanthate, substituted dithiocarbamate, thiazole, imidazoles, sulfenamide, turangalila, parakinetic, dibenzobarrelenes, sulfur and mixtures thereof.

29. The method according to p. 25, in which the catalyst with complicated geometry activate using socializaton selected from the group comprising polymeric alumoxane, oligomeric alumoxane, polymer carnivoran, oligomeric carnivoran, Monomeric carnivoran, aluminiumgie, aluminosiloxane, haloaluminate, ammonium salts, salts of silver ions ferracina and mixtures thereof.

30. The finished product containing poperechnyy pseudotachylites copolymer of (a) 15-70 wt.% at least one of alphaolefin selected from the group comprising ethylene, propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 5-methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenylpropan and mixtures thereof, (b) 30-70 wt.% at least one is, parameterstyle, chloresterol, vinylbenzoate, divinylbenzene and mixtures thereof, (C) 0-15 wt.% at least one diene selected from the group comprising butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl-1,6-octadiene, Dicyclopentadiene, methylindoline, ethylidenenorbornene, methyltetrahydrofuran and mixtures thereof.

31. The finished product containing thermoplastic vulcanizer comprising 10-90 wt. % Poperechnaya mainly statistical copolymer of (I) 15-70 wt.% at least one of alphaolefin selected from the group comprising ethylene, propylene, 1-butene, 1-penten, 1-hexene, 4-methyl-1-penten, 5-methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenylpropan and mixtures thereof, (II) 30-70 wt.% at least one vinylaromatic compounds selected from the group including styrene, aromatisation, metamathematical, parameterstyle, chloresterol, vinylbenzoate, divinylbenzene and mixtures thereof, and (III) 0-15 wt. % of at least one diene selected from the group comprising butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl-1,6-octadiene, Dicyclopentadiene, methylindoline, ethylidenenorbornene, methyltetrahydrofuran and mixtures thereof, and (b) 10-90 wt.% at least one thermoplastic polyolefin, ethyl-1-penten, 5-methyl-1-hexene and mixtures thereof.

 

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