MXPA00002018A - Thermoset interpolymers and foams - Google Patents

Abstract

The subject invention provides a thermoset elastomer comprising a crosslinked pseudo-random or substantially random interpolymer of:(a) from 15 to 70 weight percent of at least one a-olefin, (b) from 30 to 70 weight percent of at least one vinylidene aromatic compound, and (c) from 0 to 15 weight percent of at least one diene. The subject invention further provides a thermoplastic vulcanizate comprising the thermoset elastomers of the invention as provided in a thermoplastic polyolefin matrix. The subject invention further provides processes for preparing the inventive thermoset elastomers and thermoplastic vulcanizates, as well as parts fabricated therefrom. The inventive materials have a superior balance of properties, as compared to EPM and EPDM based materials. The subject invention also pertains to foams and methods for their preparation.

Description

INTERPOLIMEROS AND FOAM SHOULDERS The present invention pertains to thermosetting interpolymers, to a process for their preparation, and to products made from said thermosetting interpolymers. In a preferred embodiment, the present invention further pertains to foams prepared from said thermosetting interpolymers and to methods for the preparation of interlaced α-olefin / vinyl or vinylidene aromatic ether copolymers and / or aliphatic vinyl monomer or vinylidene ether copolymers. hidden Elastomers are defined as materials that undergo large reversible deformations under relatively low stress. Elastomers are typically characterized by structural irregularities, non-polar structures, or flexible units in the polymer chain. Some examples of commercially available elastomers include natural rubber, ethylene / propylene copolymers (EPM), ethylene / propylene / diene copolymers (EPDM), styrene / butadiene copolymers, chlorinated polyethylene and silicone rubber. Thermoplastic elastomers are elastomers that have thermoplastic properties. That is, the thermoplastic elastomers can be molded, or otherwise formed and reprocessed at temperatures above their melting and softening point. An example of a thermoplastic elastomer is a styrene-butadiene-styrene (SBS) block copolymer. The block copolymers of SBS exhibit a two-phase morphology consisting of glassy polystyrene domains connected by rubber butadiene segments. At temperatures between the glass transition temperatures of the butadiene block medium and the styrene end blocks, ie, at temperatures of -90 ° C to 116 ° C, the SBS copolymer acts in a manner similar to the entangled elastomer. European Patent Application No. 416,815 discloses pseudo-random ethylene-styrene interpolymers. The non-interlaced pseudo-random ethylene / styrene interpolymers exhibit a decreased modulus at temperatures above the melting point and softening of the interpolymer. SBS copolymers and non-interlaced pseudo-random ethylene-styrene interpolymers suffer from the disadvantages of relatively low mechanical strength, susceptibility to ozone degradation (to the extent that they have sites of unsaturation in the polymeric column), and utility only in applications where the temperature of the elastomer may not exceed the melting or softening point of the elastomer. In contrast, thermosetting elastomers are elastomers that have thermosetting properties. That is, thermoset elastomers solidified irreversibly or "set" when heated, generally due to an irreversible entanglement reaction. Two examples of thermosetting elastomers are crosslinked ethylene-propylene monomer rubber (EPM) and rubber ethylene-propylene-diene interlaced monomer (EPDM). The EPM materials are made by the copolymerization of ethylene and propylene. EPM materials are usually cured with peroxides to raise the interlacing, and thus inducing thermosetting properties. The EPDM materials are linear ethylene, propylene and a non-conjugated diene ether polymers such as 1,4-hexadiene, dicyclopentadiene, or ethylidene norbornene. EPDM materials are usually vulcanized with sulfur to induce thermosetting properties, although alternatively they can be cured with peroxide. While the EPM and EPDM materials are advantageous in that they have applicability in applications at higher temperatures, EPM and EPDM elastomers suffer from the disadvantage of low green resistance (to lower ethylene content), of superior susceptibility of cured elastomer to attacks by oils of the characteristics of rubbers of styrene butadiene, and of the resistance of the cured elastomer for the modification of the surface. Suitable elastomers are desired for use over a wide range of temperatures and which are also less susceptible to ozone degradation. Thermosetting elastomers that are prepared from elastomers that have strong green resistance (which provide greater flexibility in handling before curing) are particularly desired. Also if desired, they are thermosetting elastomers that are resistant to. oil, which are useful in fabricated parts that normally contact oil, such as automotive parts and gaskets. Thermofixed elastomers are also desired which readily undergo surface modification, to promote adhesion of the elastomer surface and / or to provide ionic sites on the elastomeric surface. A process for the preparation of such thermosetting elastomers is also desired. Thermoplastic vulcanizates are crystalline polyolefin matrices through which thermosetting elastomers are generally distributed uniformly. Examples of thermoplastic vulcanizates include thermosetting materials of EPM and EPDM distributed in a crystalline polypropylene matrix. Such thermoplastic vulcanizates are disadvantageous in that they are susceptible to oil degradation. Thermoplastic vulcanizates that are more resistant to oil are desired. A process for the preparation of said vulcanizates is also desired. The interpolymers prepared from the aromatic monomer of α-olefin / vinylidene or hidden aliphatic vinylidene monomer having excellent properties; however, it may be convenient to make such polymers have improved properties. It has been discovered that the properties, such as the higher main service temperature, melt processability Improved and self-adhesion tendencies of such polymers can be improved via the interlacing of the interpolymers. The foams prepared from the interlaced interpolymers are thought to have one or more of the following improvements: improved main service temperatures, lower density, improved elastic recovery properties, improved mechanical properties as compared to non-interlaced interpolymer foams. The object of the invention provides a thermosetting product comprising a substantially interlaced intepolymer comprising: (1) from 1 to 65 mole percent of polymer units derived from: (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hidden aliphatic vinyl or vinylidene monomer, or (c) a combination of at least one vinyl aromatic or vinylidene monomer and at least one hidden aliphatic vinylidene vinylidene monomer; Y (2) from 35 to 99 mole percent of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms. Another aspect of the present invention relates to a foamable composition comprising (I) a partially or fully entangled composition comprising (A) from 2 to 100 weight percent based on the combined weight of the components (A) and (B) of at least one partially random or substantially interlaced interpolymer that comprises: (1) from 1 to 65 mole percent polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hidden aliphatic vinylidene vinylidene monomer, or (c) ) a combination of at least one aromatic vinyl or vinylidene monomer and at least one hidden aliphatic vinyl or vinylidene monomer, and (2) from 35 to 99 mole percent of polymer units derived from at least one α-olefin aliphatic of 2 to 20 carbon atoms; (B) from 0 to 98 weight percent based on the combined weight of components (A) and (B) of at least one of the following polymers (1) a partially or fully entangled homopolymer containing polymer units derived from one or more α-olefins having from 2 to 20 carbon atoms; (2) a copolymer containing (a) from 2 to 98 percent of polymer units derived from ethylene and (b) from 98 to 2 mole percent of polymer units derived from at least one of the α-olefins having from 3 to 20 carbon atoms; acrylic acid, methacrylic acid, vinyl alcohol, vinyl acetate, diene having from 4 to 20 carbon atoms; (3) a partially or fully entangled styrene block copolymer; (4) a partially random or partially intertwined substantially random interpolymer defined as in (1) wherein the interpolymers (1) and (4) are distinguished by: (i) the amount of aromatic monomer of vinylidene and / or aliphatic or cycloaliphatic vinylidene monomer in any interpolymer of component (1) differs from that the amount in any interpolymer of component (4) by at least 0.5 mole percent; and / or (ii) there is a difference of at least 20 percent between the number average molecular weight (Mn) in any interpolymer of component (1) and any interpolymer of component (4); and (ll) from 0.1 to 25 weight percent based on the combined weight of components (I) and (II) of at least one foaming agent.

Another aspect of the present invention pertains to a method for entangling a polymer composition comprising (A) from 2 to 100 weight percent based on the combined weight of the components (A) and (B) of at least one interpolymer substantially random partial or totally interlaced comprising: (1) from 1 to 65 mole percent of polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one vinyl or vinylidene monomer aliphatic, or (c) a combination of at least one vinyl or vinylidene aromatic monomer and at least one hidden aliphatic vinyl or vinylidene monomer, and (2) from 35 to 99 mole percent of polymer units derived from at least one aliphatic α-olefin of 2 to 20 carbon atoms; (B) from 0 to 98 weight percent based on the combined weight of components (A) and (B) of at least one of the following polymers (1) a homopolymer containing polymer units derived from one or more α-olefins having from 2 to 20 carbon atoms; (2) a copolymer containing (a) from 2 to 98 percent of polymer units derived from ethylene and (b) from 98 to 2 mole percent of polymer units derived from at least one of the α-olefins having from 3 to 20 carbon atoms; acrylic acid, methacrylic acid, vinyl alcohol, vinyl acetate, diene having from 4 to 20 carbon atoms; (3) a styrenic block copolymer; (4) a polymer defined as in (A) wherein the interpolymers (A) and (B4) are different in that: (i) the amount of the aromatic vinyl or vinylidene monomer and / or vinylidene or vinylidene monomer or aliphatic cycloaliphatic hidden in any interpolymer of component (A) that differs from the amount in any interpolymer of component (B4) by at least 0.5 mole percent; and / or (ii) there is a difference of at least 20 percent between the number average molecular weight (Mn) in any ether polymer of the component (A) and any interpolymer of the component (B4); whose process for entanglement comprises (a) subjecting the polymer composition to a sufficient amount of electron beam radiation to at least partially the entanglement of the polymer composition; or (b) contacting the polymer composition with a sufficient amount of at least one peroxide compound to at least partially the entanglement of the polymer composition; or (c) contacting the polymer composition with a sufficient amount of at least one silane compound for partial entanglement of the polymer composition; or (d) contacting the polymer composition with a sufficient amount of at least one azide compound for at least partial entanglement of the polymer composition; or (e) a combination of any of two or more of the above entanglement methods. Another aspect of the present invention pertains to foams that result from foamable polymer compositions mentioned above for foaming conditions. These and other embodiments are described more fully in the following detailed description. The term "polymer", as used herein, refers to a polymeric compound prepared by polymerization monomers whether of the same type or a different one. The generic term polymer, therefore, embraces the term homopolymer, usually used to refer to polymers prepared only from one type of monomer, and the term interpolymer is as defined below.

As used herein, the terms "interleaved interpolymers" and "thermoset interpolymers" are used interchangeably, and mean polymers having more than 10 percent gel as determined in accordance with ASTM D-2765-84. . Any numerical value recited herein, includes all values from the value below the upper value in increments of a provided unit having a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a variable process such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as from 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly listed in this specification. For values that are less than one, a unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lower value and the upper value listed can be considered to be expressly established in this application in a similar way. The term "interpolymer" as used herein, refers to polymers prepared by the polymerization of at least two different types of monomers. The generic term interpolymer, therefore, includes copolymers, usually used to refer to polymers prepared from two different monomers, and polymers prepared from more than two different types of monomers. The present deations that a polymer or interpolymer comprises or contains certain monomers, means that said polymer or interpolymer comprises or contains polymerized units of said monomer. For example, if a polymer is such that it contains the ethylene monomer, the polymer could be incorporated into an ethylene derivative, i.e., -CH2-CH2-. The term "hydrocarbyl" means any aliphatic, cycloaliphatic, aromatic, substituted aliphatic aryl, cycloaliphatic substituted with aryl, aromatic substituted with aliphatic, or aromatic substituted with cycloaliphatic groups. The aliphatic or cycloaliphatic groups are preferably saturated. In the same way, the term "hydrocarbyloxy" means a hydrocarbyl group having an oxygen bond between and in the carbon atom to which it is attached. The term "monomeric residue" or "polymer units derived from said monomer" means that portion of the polymerizable monomer molecule whose residues in the polymer chain result in being polymerized with another polymerizable molecule to label the polymer chain. The elastomeric thermosetting compositions of the invention, preferably the substantially random interpolymers comprising an olefin and an aromatic monomer of vinyl, whose interpolymers have been interlaced to give the thermofixed operation. The term "substantially random" in the substantially random interpolymer results from the polymerization of one or more α-olefin monomers and one or more vinyl aromatic or vinylidene monomers or hidden aliphatic or cycloaliphatic vinylidene or vinylidene monomers, and optionally, with others Polymerizable ethylenically unsaturated monomers, as used herein, means that the distribution of the monomers of said interpolymer can be described by the Bernoulli statistical model or by a first or second order of the Markovian statistical model, as described by JC Randall in POLYMER SEQUENCE DETERMINATION. Carbon-13 NMR Method. Academic Press New York, 1977, pages, 71-78. Preferably, the substantially random interpolymer resulting from the polymerization of one or more α-olefin monomers and one or more vinyl or vinylidene aromatic monomers, and optionally, with other polymerizable ethylenically unsaturated monomers that do not contain more than 15 percent of the total amount of vinyl aromatic vinylidene monomer residue in vinyl or vinylidene aromatic monomer blocks of more than 3 units. More preferably, the interpolymer is not characterized by a superior degree of sotacticity or syndiotacticity. This means that in the Carbon NMR spectrum13 of the substantially random interpolymer in peak areas corresponding to the main chain Methylene and methine carbons representing meso-diadal sequences or sequences of racemic dyads may not exceed 75 percent of the total peak area of the methylene backbone or methine carbons. Pseudo-random interpolymers are a subgroup of substantially random interpolymers. The pseudo-random interpolymers are characterized by an architecture in which all the phenyl (or substituted phenyl) groups that hang from the polymer column are separated by two or more units from the carbon column. In other words, the pseudo-random copolymers of the invention, in their non-interlaced state, can be described by the following general formula (using styrene as the vinyl aromatic monomer and ethylene as the α-olefin for illustration): The non-interlaced pseudo-random interpolymers are described in European Patent Publication 416,815-A. While not wishing to be bound by any particular theory, it is thought that during the addition of the polymerization reaction of, for example, ethylene and styrene, in the presence of a geometry constructed as described below, if a styrene monomer is inserted into the polymeric growth chain, the next inserted monomer should be an ethylene monomer or a styrene monomer inserted in an inverted or "end-to-end" form. It is thought that after the inverted or "end-to-end" styrene monomer is inserted, the next monomer that could be ethylene, since the insertion of a second styrene monomer at this point could be placed very close to the styrene monomer inverted, that is, less than two units of coal column. Preferably, the substantially random interpolymer could be characterized as largely atactic, as indicated by the 13 C-NMR spectrum, in which the peak areas corresponding to the methyl chains or major methine carbons, represent the meso diadas sequences or the sequences of racemic dyads do not exceed 75 percent of the total peak area of the methylene backbone and methine carbons. Substantially random interpolymers which are suitable as components (A) and (B4) of the present invention include, substantially random interpolymers prepared by the polymerization of i) one or more α-olefin monomers and ii) one or more vinyl monomers or aliphatic or hidden cycloaliphatic vinylidene, and optionally iii) other polymerizable ethylenically unsaturated monomers.

Suitable α-olefins include, for example, α-olefins containing from 2 to 20, preferably from 2 to 12, more preferably from 2 to 18 carbon atoms. Particularly suitable are ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 or ethylene in combination with one or more of propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1. These α-olefins do not contain an aromatic portion. Other optional polymerizable ethylenically unsaturated monomers include norbornene and C? _ Alquilo alquiloalkyl or C6-α o aryl-substituted norbornenes, with an illustrative interpolymer being ethylene / styrene / norbornene. Suitable vinyl or vinylidene aromatic monomers that can be used to prepare the interpolymers include, for example, those represented by the following formula: Ar I (CH 2) n R C = C (R 2) 2 wherein R1 is selected from the group consisting of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 independently is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with 1 to 5 substituents selected from the group consisting of halo, C? -4 alkyl, halo C? -4 alkyl; and n has a value from zero to 4, preferably from zero to 2, more preferably zero. Illustrative monovinyl aromatic monomers include styrene, vinyl toluene, α-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly, suitable monomers include styrene and lower alkyl or halogen-substituted derivatives thereof. Preferred monomers include styrene, α-methyl styrene, C alquilo-C - lower alkyl or substituted styrene phenyl ring derivatives, such as, for example, ortho-, meta and para-methylstyrene, the halogenated styrene rings, for -vinyl toluene or mixtures thereof. A most preferred aromatic vinyl monomer is styrene. By the term "sterically hidden aliphatic or cycloaliphatic vinylidene or vinylidene compounds" is meant the addition of the polymerizable vinyl or vinylidene monomers corresponding to the formula: A1 R1_C = C (R2) 2 wherein A1 is a sterically bulky aliphatic or cycloaliphatic substituent of up to 20 carbons, R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R2 independently is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; or alternatively R1 and A1 together form a ring system. Preferred aliphatic or cycloaliphatic vinylidene or vinylidene compounds are monomers in which one of the carbon atoms resists ethylenic unsaturation as a tertiary or quaternary substitution. Examples of such substituents include cycloaliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or an alkyl ring or aryl substituted derivatives thereof, tert-butyl, norbornyl. The most preferred aliphatic or cycloaliphatic vinylidene or vinylidene compounds are various derivatives substituted with isomeric vinyl ring of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene. In particular, 1-, 3-, and 4-vinylcyclohexene are suitable. Substantially random interpolymers can be modified by normal grafting, hydrogenation, functionalization, or other reactions well known to those skilled in the art. The polymers can be easily sulfonated or chlorinated to provide derivatives functionalized according to established techniques. The substantially random interpolymers can also be modified by various chain extension or chain interlacing processes including, but not limited to, peroxide, silane, sulfur, radiation, or azide-based healing systems. A complete description of various entanglement technologies are described in the U.S. Patent Applications. copendientes Nos. 08/921, 641 and 08/921, 642, both filed on August 27, 1997, the total content of both of which is incorporated herein by reference. Dual healing systems, which use a combination of heat, moisture cure and radiation steps, can be effectively employed. Dual cure systems are described and claimed in the patent application of E.U.A. Series No. 536, 022, filed on September 29, 1995, in the name of K. L. Walton and S.V. Karande, incorporated herein by reference. For example, it may be convenient to employ the peroxide crosslinking agents together with the silane crosslinking agents, peroxide crosslinking agents together with radiation, sulfur-containing crosslinking agents together with the silane crosslinking agents, etc. Substantially random interpolymers can be modified by various entanglement processes including, but not limited to, the incorporation of a diene component as a thermonomer in its preparation and subsequent entanglement by the methods mentioned above and additional methods including vulcanization via the vinyl group using sulfur for example as the entanglement agent. The interpolymers of one or more α-olefins and one or more aromatic vinyl or vinylidene monomers and / or one or more aliphatic or cycloaliphatic vinylidene or vinylidene monomers used in the present invention are substantially random polymers. These etherpolymers usually contain 0.5 to 65, preferably from 1 to 55, more preferably from 2 to 50 mole percent of at least one aromatic vinyl or vinylidene monomer and / or an aliphatic or cycloaliphatic vinylidene or cycloaliphatic monomer and from 35 to 99.5, preferably from 45 to 99 , more preferably from 50 to 98 mole percent of at least one aliphatic α-olefin having from 2 to 20 carbon atoms. Other polymerizable ethylenically unsaturated monomers include pressurized ring olefins such as norbornene and C -? - 10 alkyl or norbornenes substituted with C? -? Aryl or, with an illustrative interpolymer being ethylene / styrene / norbornene. The number average molecular weight (Mn) of the polymers and interpolymers is usually more than 5,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000. Polymerization and monomeric removal without reaction at temperatures above the auto-polymerization temperature of the respective monomers may result in the formation of some amounts of the homopolymer polymerization products resulting from free radical polymerization. For example, while preparing the substantially random interpolymer, an amount of atactic vinyl vinylidene homopolymer may be formed due to the homopolymerization of the aromatic vinyl vinylidene monomer at elevated temperatures. The presence of the aromatic vinyl or vinylidene homopolymer in general is not detrimental to the purposes of the present invention and can be tolerated. The aromatic homopolymer Vinyl or vinylidene can be separated from the interpolymers, if desired, by extraction techniques such as the selective precipitation of a solution with a non-solvent for the interpolymer or the aromatic vinyl or vinylidene homopolymer. For the purpose of the present invention it is preferred that no more than 20 weight percent, preferably less than 15 weight percent, is present based on the total weight of the vinyl aromatic vinylidene or vinylidene homopolymer interpolymers. The polymerization conditions of the α-olefin, aromatic vinyl or vinylidene, and optionally the diene, are generally those useful in the solution of the polymerization process, although the application of the present invention is not limited thereto. The upper pressure, slurry and gas phase polymerization processes are thought to be useful, provide the appropriate catalyst and polymerization conditions are employed. In general, the polymerization useful in practice of the object of the invention can be achieved under conditions well known in the prior art of Ziegler-Natta or Keminsky-Sinn type polymerizations. A method of preparing the substantially random interpolymers includes polymerizing a mixture of the polymerizable monomers in the presence of one or more geometric metallocene catalysts or constructed in combination with various co-catalysts, as described in EP-A-0,416,815 by James C. Stevens and others, and in the Patent of E.U.A. No. 5,703,187 by Francis J. Timmers, both of which are hereby incorporated by reference in their entirety. Said method of preparation of the substantially random interpolymers include the polymerization of a mixture of polymerizable monomers in the presence of one or more geometric metallocene catalysts or constructed in combination with several cocatalysts. The preferred operating conditions for the polymerization reactions are atmospheric pressures of up to 3000 atmospheres and temperatures of -30 ° C to 200 ° C. Polymerizations and removal of the unreacted monomer at temperatures above the self-polymerization temperature of the respective monomers may result in the formation of some amounts of the homopolymer polymerization products resulting from free radical polymerization. Examples of suitable catalysts and methods for the preparation of substantially random interpolymers are described in the application of E.U.A. Series No. 702,475. Submitted on May 20, 1991 (EP-A-514,828); as well as U.S. Patents: 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024, 5,350,723; 5,375,696; 5,399,635; 5,470,993; 5,703,187; and 5,721,185 all of which, patents and applications, are incorporated herein by reference.

A-olefin / vinyl aromatic interpolymers can also be prepared by the methods described in JP 07/278230 using the compounds shown in the general formula: Cp R1 XC ^ wherein Cp1 and Cp2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents thereof, independently of one another; R1 and R2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxy groups, or aryloxy groups, independently of one another; M is a group IV metal, preferably Zr or Hf, more preferably Zr; R3 is an alkylene group or silanodiyl group used for interlaced Cp1 and Cp2. A-olefin / vinyl aromatic interpolymers can be prepared by the methods described by John G. Bradfute et al. (W.R. Grace &Co.) in WO 95/32095; by R.B. Pannell (Exxon Chemical Patents, Inc.) in WO 94/00500, and in Plastics Technology, p. 25 (September 1992), all of which are incorporated herein by reference in their entirety. They are also substantially suitable interpolymers comprising at least one a-olefin / vinyl aromatic / vinyl aromatic / α-olefin tetrad described in the Application E.U.A .. No. 08 / 708,809 filed September 4, 1996 and WO 98/09999 both by Francis J. Timmers et al. These interpolymers contain additional signals in their carbon 13 NMR spectrum with intensities greater than three times the peak-to-peak interference. These signals appear on the chemical change scale 43.70-44.25 ppm and 38.0 - 38.5 ppm. Specifically, the main peaks were observed at 44.1, 43.9 and 38.2 ppm. A proton test NMR experiment indicated that the signals in the chemical change region 43.70-44.25 ppm are methine carbons and the signals in the 38.0-38.5 ppm region are methylene carbons. It is thought that these new signals are due to sequences involving two vinyl aromatic monomer insertions from head to tail preceded and followed by at least one α-olefin insert, for example ethylene / styrene / styrene tetrad. / ethylene wherein the styrene monomer insertions of said tetrads occur exclusively in a 1.2 form (head to tail). It should be understood by one skilled in the art that said tetradas involve a vinyl aromatic monomer other than styrene and a different ethylene α-olefin so that the ethylene tetrad / vinyl aromatic monomer / vinyl aromatic monomer / ethylene could rise to similar carbon 13 NMR peaks but with slightly different chemical changes.

These interpolymers can be prepared by conducting the polymerization at temperatures from -30 ° C to 250 ° C in the presence of such catalysts as those represented by the formula / \ wherein: each Cp is independently, each time it is presented, a group of substituted cyclopentadienyl p-linked to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, more preferably Zr; each R is independently, each time it occurs, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms; each R 'is independently, each time it occurs, H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl, containing up to 30 preferably from 1 to 20, more preferably from 1 to 10 carbon atoms or silicone or two R' groups together they can be 1, 3-butadiene substituted with Cl-10 hydrocarbyl; m is 1 or 2; and optionally, but preferably in the presence of an activating co-catalyst. Particularly, suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, each time it occurs, H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, which contains up to 30, preferably from 1 to 20, more preferably from 1 to 10 carbon atoms or silicone or two R groups together form a divalent derivative of said group. Preferably, r independently each time it is represented (including all the appropriate isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (when appropriate) two R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl. The particularly preferred catalyst includes, for example, racemic (dimethylsilanediyl) -bis) - (2-methyl-4-phenylindenyl) zirconium dichloride, 1,4-diphenyl-1,3-butadiene dimethylsilanediyl) -bis- ( Racemic 2-methyl-4-phenylindenyl) zirconium, C 1-4 alkyl of racemic (dimethylisilanodiyl) -bis- (2-methyl-4-phenylindenyl) zirconium, di (dimethylsilanediyl) -bis- di ( Racemic 2-methyl-4-phenylindenyl) zirconium, or any combination thereof. It is also possible to use the following geometric catalysts based on titanium, [N- (1,1-dimethylethyl) -1, 1-dimethyl-1 [(1,2,3,4,5-γ) -1.5, 6,7-tetrahydro-s-indacen-1-yl] silanaminate (2 -) - N] titanium; (1-indenyl) (tert-butylamido) dimethyl-silane titanium dimethyl; ((3-tert-butyl) (1, 2,3,4, 5 -?) - 1-indenyl) (tert-butylamido) dimethylsilane titanium dimethyl; and ((3-isopropyl) (1, 2,3,4, 5 -?) - 1-indenyl) (tert-butyl amido) dimethylsilane titanium dimethyl, or any combination thereof. Additional preparative methods for the interpolymers used in the present invention have been described in the literature. Longo and Grassi (Makromol, Chem., Volume 191, pages 2387 to 2396 [1990]) and D'Anniello and others (Journal of Applied Polymer Science, Volume 58, pages 1701-1706 [1995]) report the use of a system catalyst based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCh) to prepare the ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am. Chem. Soc. Div. Polym. Chem.) Volume 35, pages 686, 687 [1994]) have reported the copolymerization using a MgCl2 / TiCl4 / NdCI3 / AI (iBu) 3 to give random copolymers of styrene and propylene. Lu et al. (Journal of Applied Polymer Science, Volume 53, pages 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl 4 / NdCl 3 / MgCl 2 / AI (Et) 3 catalyst. Sernetz and Mulhaupt, (Macromol. Chem. Phvs., Volume 197, pages 1071-1083, 1997) have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Ziegler-Natta catalysts of Me2Si (Me4Cp) ( N-tert-butyl) TiCl 2) methylaluminoxane.

Ethylene-styrene copolymers produced by bridging metallocene catalysts have been described by Arai, Toshiaki and Suzuki (Polymer Preprints, Am. Chem. Soc. Div. Polym. Chem.) Volume 38, pages 349, 350 [1997]) and in U.S. Patent No. 5,652,315, filed by Mitsui Toatsu Chemical, Inc. The manufacture of the α-olefin / vinyl aromatic monomer interpolymers such as propylene / styrene and butene / styrene are described in U.S. Pat. 5,244,996, filed by Mitsui Petrochemical Industries Ltd, or U.S. Patent No. 5,652,315 also filed by Mitsui Petrochemical Industries Ltd or as described in DE 197 11 339 A1 of Denki Kagaku Kogyo KK. All the above methods described for the preparation of the interpolymer component are incorporated herein by reference. The level of aromatic vinyl or vinylidene monomer incorporated in the thermosetting elastomers of the invention are at least 30, preferably at least 35 weight percent based on the weight of the interpolymer. The aromatic vinyl vinylidene monomer is usually incorporated into the interpolymers of the invention in an amount less than 70, more preferably less than 60 weight percent based on the total weight of the interpolymer. Substantially random interpolymers contain from 0.5 to 65, preferably from 1 to 55, more preferably from 2 to 50 mole percent of at least one vinyl or vinylidene monomer aromatic and / or a hidden aliphatic or cycloaliphatic vinylidene or vinylidene monomer and from 35 to 99.5, preferably from 45 to 99, more preferably from 50 to 98 mole percent of at least one aliphatic α-olefin of 2 to 20 carbon atoms; carbon. One or more dienes may optionally be incorporated into the interpolymer to provide functional sites of unsaturation on the interpolymer useful, for example, to participate in the crosslinking reactions. While conjugated dienes such as butadiene, 1,3-pentadiene (ie, piperylene), or isoprene can be used for this purpose, non-conjugated dienes are preferred. Normal non-conjugated dienes include, for example, open chain unconjugated diolefins such as 1,4-hexadiene (see U.S. Patent No. 2,933,480) and 7-methyl-1,6-octadiene (also known as MOCD); cyclic dienes; diene ring bridged rings, such as dicyclopentadiene (see U.S. Patent No. 3,211,709); or alkylidene norbornenes, such as methylene norbornene or ethylidene norbornene (see U.S. Patent No. 3,151,173). Non-conjugated dienes are not limited to those that have only two double bonds, but instead also include those that have three or more double bonds. The diene is incorporated in the elastomers of the invention in a quantity of 0 to 15 weight percent based on the total weight of the interpolymer. When the diene is employed, it will preferably be provided in an amount of at least 2 weight percent, more preferably at least 3 weight percent, and even more preferably at least 5 weight percent, based on the total weight of the interpolymer. Likewise, when a diene is employed, it should be provided in an amount of not more than 15, preferably no more than 12 weight percent based on the total weight of the interpolymer. The number average molecular weight (Mn) of the polymers and interpolymers is usually greater than 5., 000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000. Composition and Healing of Substantially Random Interpolymers The thermosetting elastomers of the invention may include various additives, such as carbon smoke, silica, titanium dioxide, color pigments, clay, zinc oxide, stearic acid, accelerators, curing agents , sulfur, stabilizers, antidegradants, processing assistants, adhesives, thickeners, plasticizers, wax, pre-entanglement inhibitors, staple fibers (such as wood cellulose fibers) and extender oils. Said additives may be provided before, during or subsequent to the curing of the substantially random interpolymers. Substantially random interpolymers are usually mixed with a filler, an oil, and a curing agent at an elevated temperature for a compound thereof. The composite material is subsequently cured at a temperature which is usually higher than that used during the composition.

Preferably, the carbon smoke can be added to a substantially random interpolymer before curing. Carbon smoke is usually added to improve the tensile strength or hardness of the compound product, but can also be used as an extender or to hide the color of the product of the composition. Carbon smoke is usually provided in an amount of 0 to 80 percent, usually 0.5 to 50 percent by weight, based on the total weight of the formulation. When carbon smoke is used to hide the color, it will normally be used on the scale of 0.5 to 10 percent by weight, based on the weight of the formulation. When the carbon smoke is used to increase the hardness and / or decrease the cost of the formulation, it will normally be used in amounts greater than 10 weight percent based on the weight of the formulation. In addition, preferably, one or more extender oils can be added to the substantially random interpolymer prior to curing. Extender oils are usually added to improve the processability and flexibility of the lower temperature, as well as to decrease the cost. Suitable oils are listed in Rubber World Blue Book 1975 Edition, Materials and Componding Ingredients for Rubber, pages 145-190. Normal classes of extender oils include aromatic, naphthenic and paraffin extender oils. The extender oils would normally provide in an amount of 0 to 50 weight percent.

When employed, more normal in an amount of 15 to 25 percent by weight, based on the total weight of the formulation. The curing agents could normally be provided in an amount of 0.5 to 12 weight percent, based on the total weight of the formulation. Suitable curing agents include peroxides, phenols, azides, reaction production of aldheidoamine, substituted ureas, substituted guanidines, substituted xantanes, substituted dithiocarbamates; sulfur-containing compounds, such as thiazoles, imidazoles, sulfenamides, thiuramide sulfides, paraquinone dioxime, dibenzoparaquinone dioxime, sulfur; and combinations thereof. See Encyclopedia of Chemical Technology, Vol. 17, 2a. edition, Interscience Publisher, 1968; also Organic Peroxides, Daniel Seern, Vol. 1, Wiley-lnterscience, 1970). Suitable peroxides include aromatic diacyl peroxides; aliphatic diacyl peroxide; dibasic acid peroxides; ketone peroxide; alkyl peroxyesters; alkyl hydroperoxides (e.g., diacetyl peroxide; dibenzoyl peroxide; bis-2,4-dichlorobenzoyl peroxide; di-tert-butyl peroxide; dicumyl peroxide; tert-butylperbenzoate; dicumyl tert-peroxide; 2,5-bis (t -butylperoxy) -2,5-dimethylhexane; 2,5-bis (t-butylperoxy) -2,5-dimethylhexine-3; 4,4,4 ', 4'-tetra- (t-butylperoxy) -2.2 -dicyclohexylpropane; 1,4-bis- (t-butylperoxyisopropyl) -benzene; 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane; lauroyl peroxide; succinic acid peroxide; cyclohexanone peroxide; t-butyl paracetate; butyl hydroperoxide; etc. Suitable phenols are described in USP 4,311,628, the disclosure of which is incorporated herein by reference. An example of a phenolic curing agent is the condensation product of a halogen substituted with phenol or a phenol substituted with d-Cι alkyl with an aldehyde in an alkaline medium, or by the condensation of bifunctional phenol dialcohols. One such class of phenolic curing agents are dimethylol phenols substituted at the para position with C5-C10 alkyl groups. They are also suitable halogenated alkyl substituted with phenol curing agents, and curing systems comprising methylol phenolic resin, or a halogen donor, and a metal compound. Suitable azides include azidoformates, such as tetramethylenebis (azidoformate) (see, also, USP 3,284,421, Breslow, Nov. 8, 1966); aromatic polyazides, such as 4,4'-diphenylmethane diazide (see, also, USP 3,297,674, Breslow et al., January 10, 1967); and sulfonazides, such as p, p'-oxybis (benzene sulfonyl azide). The poly (sulfonyl azide) is any compound having at least two sulfonyl azide (-SO2N3) groups reactive with the substantially random interpolymer. Preferably the poly (sulfonyl azide) has a structure X-R-X wherein each x is SO2N3 and R represents a group containing hydrocarbyl, hydrocarbyl unsubstituted or inertly substituted ether or silicone, preferably having enough carbon, oxygen or silicone, preferably carbon, the atoms to separate the sulfonyl azide groups sufficiently to allow an easy reaction between the substantially random interpolymer and the sulfonyl azide, more preferably by at least 1, more preferably at least 2, still more preferably at least 3 carbon atoms, oxygen or silicone, preferably carbon, between the functional groups. The term "inertly substituted" refers to the substitution with atoms or groups that do not undesirably interfere with the desired reactions or desired properties of the resulting entangled polymers. Such groups include fluoride, aliphatic or aromatic ether, siloxanes, as well as sulfonyl azide groups when more than two substantially random interpolymer chains are joined. Suitable structures include R as aryl, alkyl, aryl alkaryl, arylalkyl, silane or heterocyclic groups, and other groups which are inert and are separated into the sulfonyl azide groups as described. More preferably R includes at least one aryl group between the suphonyl groups, more preferably at least two aryl groups (if preferred, the group has more than one ring, as in the case of naphthalene bis (sulfonyl azides). (sulfonyl) azides include compounds such as 1,5-pentane bis (sulfonyl azide), 1,8-octane bis (sulfonyl azide), 1,10-decane bis (sulfonyl azide), 1, 10-octadecane bis (sulfonyl) azide), 1-octyl-2,4,6-benzene tris (sulfonyl azide), 4,4'-diphenyl ether bis (sulfonyl azide), 1,6- bis (4'-sulfonazidophenyl) hexane. 2,7-naphthalene bis (sulfonyl azide), and mixed sulfonyl azides of chlorinated aliphatic hydrocarbons containing an average of 1 to 8 chloride atoms and 2 to 5 sulfonyl azide groups per molecule, and mixtures thereof. Preferred poly (sulfonyl azides) include oxy-bis (4-sulfonylazidobenzene), 2,7-naphthalene bis (sulfonyl azido), 4,4'-bis (sulfonyl azido) biphenyl, 4,4'-diphenyl ether bis (sulfonyl) azide) and bis (4-sulfonyl azidophenyl) methane, and mixtures thereof For entanglement, the poly (sulfonyl azide) is used in an amount of entanglement, ie an effective amount for interlacing the substantially random interpolymer compared to the starting material of the substantially random interpolymer, ie sufficient poly (sulfonyl azide) to result in the formation of at least 10 weight percent of gels as evidenced by the insolubility of the genes in the boiling of xylene when tested in accordance with ASTM D-2765A-84.The amount is preferably at least 0.5, more preferably at least 1.0, still more preferably 2.0 weight percent poly (sulfonyl azide) based on the total weight of substantially random interpolymer, with these values depending on the molecular weight of the azide and the molecular weight or melt index of the substantially random interpolymer. To avoid uncontrolled heating and unnecessary cost, and / or degradation of physical properties, the amount of poly (sulfonyl) azide) is preferably less than 10 weight percent, more preferably less than 5. For crosslinking, the sulfonyl azide is mixed with the substantially random interpolymer and heated to at least the decomposition temperature of the sulfonyl azide, i.e. usually more than 100 ° C and more frequently more than 150 ° C. The preferred temperature scale depends on the nature of the azide, ie used. For example, in the case of 4,4'-disulfonylaziphenylether, the preferred temperature scale is greater than 150 ° C, preferably more than 160 ° C, still more preferably greater than 185 ° C, even more preferably more than 190 ° C. Preferably, the upper temperature is less than 250 ° C. Suitable aldehyde-amine reaction products include formaldehyde-ammonia; formaldehyde, ethylchloride-ammonia; acetaldehyde-ammonia, formaldehyde-aniline; butyraldehyde-aniline; and heptaldehyde-aniline. Suitable substituted ureas include trimethyl thiourea, diethyl thiourea; dibutylthiourea; tripentylthiourea, 1,3-bis (2-benzothiazolylmercapomethyl) urea; and N, N-diphenylthiourea. Suitable substituted guanidines include diphenylguanidine; di-o-tolylguanidine; phenylguanidine phthalate; and the di-o-tolylguanidine salt of dicatecol borate. Suitable substituted xanthans include zinc ethylxanthate; sodium isopropylxantate, butylxantic disulfide; potassium isopropylxanthate; and zinc butylxanthate.

Suitable dithiocarbamates include dimethyl, zinc dimethyl, tellurium diethyl, cadmium dicyclohexyl, lead dimethyl, lead dimethyl, selenium dibutyl, zinc pentamethylene, zinc didecyl, and zinc isopropyloctyl dithiocarbamate. Suitable thiazoles include 2-mecaptobenzothiazole, zinc mercaptothiazolyl mecaptide, 2-benzothiazoyl-N, N-diethylthiocarbamyl sulfide and 2,2'-dithiobis (benzothiazole). Suitable imidazoles include 2-mercaptoimidazoline and 2-mercapto-4,4,6-trimethyldihydropyridine. Suitable sulfenamides include N-t-butyl-2-benzothiazole, N-cyclohexylbenzothiazole, N, N-diisopropylbenzothiazole, N- (2,6-di methyl morpholino) -2-benzothiazole, and N, N-diethylbenzothiazole-sulfenamide.

Suitable thiouramide sulfides include N, N'-diethyl, tetrabutyl, N, N'-diisopropyldioctyl, tetramethyl, N, N'-dicylohexyl and N, N'-tetra uryl-thiuram id sulfide. Those skilled in the art will be able to readily select amount of the entanglement t, with the selected amount taking the explanation characteristics of the substantially random interpolymer or the mixture comprising said substantially random interpolymer, such as molecular weight, molecular weight distribution, content of comonomer, the presence of cots that increase entanglement, additives (such as oil), etc. Since the substantially random interpolymer is expressly contemplated it can be mixed with other polymers before the interleaving, those skilled in the art can use the following guidelines as a reference point by optimizing the amount of the preferred entanglement t for the particular blends in question. For example, in the case of entanglement using dicumyl peroxide, when the substantially random interpolymer is characterized as having less than 35 weight percent styrene, the dicumyl peroxide would normally be provided in an amount of at least 0.1 percent by weight. weight, preferably at least 1 weight percent, even more preferably at least 2 weight percent based on the combined weight of the polymer and peroxide. In addition, in the case of entanglement using dicumyl peroxide, when the substantially random interpolymer is characterized as having at least 35 to 60 weight percent styrene, dicumyl peroxide could normally be provided in an amount of at least 0.3. percent by weight, preferably at least 3 percent by weight, more preferably at least 4 percent by weight based on the combined weight of the polymer and the peroxide. Further, in the case of entanglement using dicumyl peroxide, when the substantially random interpolymer is characterized as having more than 60 weight percent styrene, the dicumyl peroxide will normally be provided in an amount of at least 1 weight percent , preferably at least 6 weight percent, more preferably at least 9 weight percent based on the combined weight of the polymer and peroxide. Normally, the amount of the entanglement t employed can not exceed such that when it is required to effect the desired level of entanglement. For example, dicumyl peroxide will normally not be used in an amount greater than 15 weight percent, preferably not more than 12 weight percent based on the combined weight of the polymer and the peroxide. Alternatively, silane crosslinking ts may be employed. In this case, any silane that can be effectively inserted and the entanglement of the substantially random interpolymers can be used in the practice of this invention. Suitable silanes include unsaturated silanes comprising an ethylenically unsaturated hydrocarbyl group, such as vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or α-methacryloxy allyl and a hydrolyzable group, such as, for example, a hydrocarbyloxy, hydrocarbonyloxy or hydrocarbylamino group. Examples of the hydrolysable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkyl or arylamino groups. Preferred silanes are unsaturated alkoxy silanes that can be inserted into the polymer. These silanes and their method of preparation are described more fully in USP 5,266,627 to Meverden, et al. Vinyl trimethoxy silane, vinyl triethoxy silane,? - (meth) acryloxypropyl silane trimethoxy and mixtures of these silanes are the preferred silane crosslinkers for use in this invention. The amount of the silane crosslinking agent used in the practice of this invention can vary widely depending on the nature of the substantially random interpolymer, the silane employed, the processing conditions, the amount of the graft initiator, the last application and the like. Typically, in the case of entanglement using vinyltrimethoxysilane (VTMOS), the VTMOS could normally be provided in an amount of at least 0.1 percent by weight, preferably at least 1 percent by weight, more preferably at least 3 percent by weight. percent by weight based on the combined weight of the polymer and silane. Considerations of convenience and economy are usually two main limitations on the maximum amount of the silane interleaver used in the practice of this invention. For example, when VTMOS is employed, the maximum amount of VTMOS normally employed could not exceed 10 percent by weight, and more preferably does not exceed 8, and even more preferably does not exceed 6 percent by weight based on the combined weight of the polymer and silane. The silane crosslinking agent is grafted to a substantially random interpolymer by any conventional method, usually in the presence of a free radical initiator by examples of peroxides and azo compounds, or by radiation from ionization, etc. Organic initiators are preferred, such as any of one of the peroxide initiators, for example, dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, eumenohydroperoxide, t-butyl octoate. butyl, methyl ethyl ketone peroxide, 2,5-diethyl-2,5-di (t-butyl peroxy) hexane, lauryl peroxide and tert-butyl peracetate. A suitable azo compound is azobisisobutyl nitrite. Those skilled in the art are able to widely select amounts of the initiator employed, with the amount selected taking into account the characteristics of the substantially random interpolymer, such as molecular weight, molecular weight distribution, comonomer content, as well as the presence of coagents. which improve entanglement, additives (such as oil), etc. The amount of the initiator could depend on the percentage of aliphatic or cycloaliphatic aromatic or occult vinyl or vinylidene comonomer present in the substantially random interpolymer. For example, in the case of entanglement using VTMOS, when the substantially random interpolymer is characterized as having less than 35 weight percent styrene, the dicumyl peroxide will normally be provided in an amount of at least 250 ppm, preferably at at least 500 ppm, more preferably at least 1,500 ppm based on the combined weight of the polymer, silane and initiator.

Furthermore, in the case of entanglement using VTMOS, when the substantially random interpolymer is characterized as having at least 35 to 60 weight percent styrene, the dicumyl peroxide is usually provided in an amount of at least 400 ppm, preferably at least 1,000 ppm, more preferably at least 2,000 ppm based on the combined weight of the polymer, silane and initiator. Further, in the case of entanglement using VTMOS, when the substantially random polymer is characterized as having more than 60 weight percent styrene, the dicumyl peroxide will normally be provided in an amount of at least 500 ppm, preferably at least Worms 1,500 ppm, more preferably at least 3000 ppm based on the combined weight of the polymer, silane and initiator. Normally, the amount of the initiator used will not exceed more than what is required to perform the graft. For example, dicumyl peroxide would not normally be employed in an amount greater than 20,000 ppm, preferably not more than 10,000 ppm based on the combined weight of the polymer, silane and initiator. While any conventional method can be used to graft the entangled silane into a substantially random interpolymer, a preferred method is mixed in two with the initiator in the first stage of a reactor extruder, such as a Buss kneader. The graft conditions may vary, but the melting temperatures are usually between 160 ° C and 260 ° C, preferably between 190 ° and 230 ° C, depending on the residence time and the half-life of the initiator. Healing is promoted with an entanglement catalyst, and any catalyst that could provide this function can be used in this invention. These catalysts generally include organic bases, carboxylic acids and organometallic compounds including organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin. Dibutyltindilaurate, dioctyltin maleate, dibutyltin diacetate, dibutyltinodioctoate, stannous acetate, stannous octoate, lead naphthenate, zinc caprylate, cobalt naphthenate. Tin carboxylate, especially dibutyltindilaurate and dioctyl tinomamaleate, are particularly effective for this invention. The catalyst (or catalyst mixtures) is present in a catalytic amount, usually between 0.015 and 0.035 weight percent based on the combined weight of the polymer, silane, initiator and catalyst. Instead of employing a chemical entanglement agent, entanglement can be effected by the use of radiation. Useful types of radiation include electron beam or beta rays, gamma rays, X-rays or neutron rays. The radiation is thought to effect entanglement by generating polymeric radicals that can be combined and interlaced. Additional teachings refer to the entanglement of radiation seen in C.P. Park, "Poiyolefin Foam" Chapter 9, Handbook of Polymer Foams and Technology, D. Klempner and K.C. Frisch, eds., Hanser Publishers, New York (1991), pages 198-204, which is incorporated herein by reference. The radiation dose depends on the composition of the substantially random interpolymer. Generally speaking, as the amount of aliphatic or aromatic cycloaliphatic or hidden vinyl vinylidene cycloaliphatic comonomer is increased, higher doses may be required to produce the desired level of entanglement, ie, to charge the compositions exhibiting at least 10 percent gel, preferably at least 20 percent gel, and more preferably at least 30 percent gel. Those skilled in the art will be able to easily select the appropriate radiation levels, taking into account the variables such as thickeners and geometry of the articles that will be irradiated, as well as the characteristics of the substantially random interpolymer, such as molecular weight, weight distribution. molecular, comonomer content, the presence of coagents that improve entanglement, additives (such as oil), etc. For example, in the case of the interlacing of 80,000 plates by the E-beam radiation, when the substantially random interpolymer is characterized as having less than 35 weight percent styrene, the normal radiation doses could be greater than 5 Mrad , preferably greater than 10 Mrad, more preferably greater than 15 Mrad. The doses of electronic radiation are referred in the present in terms of the radiation unit "RAD", with one million RAD or one megarad being designated as "Mrad". Furthermore, in the case of entanglement of 80,000 plates by E-beam radiation, when the substantially random interpolymer is characterized as having at least 35 to 60 percent styrene, radiation doses could normally be greater than 5. Mrad, preferably greater than 15 Mrad, more preferably greater than 20 Mrad. Furthermore, in the case of the interlacing of 80,000 plates by the E-beam radiation, when the substantially random interpolymer is characterized as having more than 60 weight percent styrene, the normal radiation doses could be greater than 10 Mrad, preferably greater than 15 Mrad, more preferably greater than 20 Mrad. Normally, the dose could not exceed more than required to effect the desired level of entanglement. For example, doses above 80 Mrad are not normally used. In the case that substantially random interpolymers do not include the optional diene component, peroxide or azide curing systems are preferred; in the case of the interpolymer with high styrene content (> 50 weight percent), azide curing systems are preferred; in case the substantially random interpolymers include the optional diene component, sulfur-based systems are preferred (eg, containing sulfur, a dithiocarbamate, a thiazole, an imidazole, a sulfenamide, a thiuramidisulfide or combinations thereof) and phenolic cure. In certain embodiments of the claimed invention, double curing systems, which use a combination of heat, moisture cure and radiation steps, can be effectively employed. The dual cure systems are described and claimed in the U.S. Patent Application. Series No. 536,022, filed on September 29, 1995, in the name of K.L. Walton and S.V. Karande, incorporated herein by reference. For example, it may be convenient to employ peroxide entangling agents in conjunction with the silane crosslinking agents, the peroxide crosslinking agents together with the radiation, the sulfur-containing crosslinking agents together with the silane crosslinking agents, etc. . Preparation of Polymeric Mixtures The olefinic polymers suitable for use as components (B1, B2 and B3) employed in the present invention are homopolymers or interpolymers of α-olefin, or ether polymers of one or more aliphatic α-olefins and one or more non-monomers. aromatics interpolymerizable therewith, such as the C2-C20 α-olefins or those aliphatic α-olefins having from 2 to 20 carbon atoms and containing polar groups. Suitable aliphatic α-olefin monomers that introduce the polar groups into the polymer include, for example, ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile, acetonitrile, etc .; ethylenically unsaturated anhydrides such as maleic anhydride, ethylenically unsaturated amides such as acrylamide, methacrylamide, etc .; ethylenically unsaturated carboxylic acids (both mono and difunctional) such as acrylic acid and methacrylic acid, etc .; esters (especially lower esters, for example C -C6 alkyl esters) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate, such as ethylene vinyl alcohol (EVOH); ethylenically unsaturated dicarboxylic acid imides such as N-alkyl or N-aryl maleimides such as N-phenyl maleimide, etc. Preferably, the monomers containing polar groups are acrylic acids, vinyl acetate, maleic anhydride and acrylonitrile. Halogen groups that can be included in the polymers of aliphatic α-olefin monomers include fluoride, chloride and bromide; preferably the polymers are chlorinated polyethylenes (CPE). Preferred olefinic polymers for use in the present invention are homopolymers or interpolymers of an aliphatic, which includes cycloaliphatic α-olefin having from 2 to 18 carbon atoms. Suitable examples are homopolymers of ethylene or propylene, and interpolymers of ethylene and one or more other α-olefins having from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene. The olefin polymer blend component (B) can also contain, in addition to an α-olefin, one or more non-monomers aromatics interpolymerizable with it. Such additional interpolymerizable monomers include, for example, C4-C2o dienes, preferably butadiene or 5-ethylidene-2-norbornene. The olefinic polymers can also be characterized by their degree of long or short chain branching and the distribution thereof. A class of olefinic polymers is generally produced by a high pressure polymerization process using a free radical initiator resulting in the traditional long chain branched low density polyethylene (LDPE). The LDPE employed in the present composition usually has a density of less than 0.94 g / cc (ASTM D 792) and a melt index of 0.001 to 100, and preferably 0.1 to 50 grams for 10 minutes (as determined by the Method). of Test ASTM D 1238, condition I). Another class is linear olefin polymers that have an absence of long chain branching, such as traditional low density polyethylene (PEBDL heterogeneous) polymers or high density polyethylene (HDPE) polymers made using the Ziegler polymerization process (e.g., U.S. Patent No. 4,076,698 (Anderson et al.), sometimes called heterogeneous polymers, HDPE consists mainly of large linear polyethylene chains.The HDPE used in the present composition usually has a density of at least 0.94 grams per cubic centimeter (g / cc) as determined by Test Method D 792 of ASTM, and a melt index (ASTM-1238, condition I) on the scale of 0.01 to 100, and preferably 0.1 to 50 grams for 10 minutes The heterogeneous LDPE used in the present composition generally has a density of 0.85 to 0.94 g / cc (ASTM D 792) and a melt index (ASTM-1238, condition I) on the scale of 0.01 to 100, and preferably 0.1 to 50 grams for 10 minutes. Preferably PEBDL is an interpolymer of ethylene and one or more different α-olefins having from 3 to 18 carbon atoms, more preferably 3-8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. An additional class is branching uniformly or homogeneous ethylene polymers. The linear homogeneous ethylene polymers do not contain chain branches and have only branches derived from the monomers (if they have more than two carbon atoms). Homogeneous linear ethylene polymers include those made as described in the U.S. Patent. 3,694,992 (Elston) and those made using so-called single-site catalysts in a batch reactor having relatively high olefin concentrations (as described in U.S. Patent Nos. 5,026,798 and 5,055,438 (Canich). Linear ethylene uniformly branched / homogeneous are those polymers in which the comonomer is randomly distributed within a given interpolymer molecule and wherein the interpolymer molecules have a similar ethylene / comonomer ratio within the interpolymer. The homogeneous linear ethylene polymer employed in the present composition generally has a density of 0.84 to 0.94 g / cc (ASTM D792) and a melt index (ASTM-1238, condition I) on the scale of 0.01 to 100, and preferably of 0.1 to 50 grams for 10 minutes. Preferably the homogeneous linear ethylene polymer is an interpolymer of ethylene and one or more α-olefins having from 3 to 18 carbon atoms, more preferably 3-8 carbon atoms. Preferred comonomers include -butene, 4-methyl-1-pentene, 1-hexene and 1-octene. In addition, there is the class of substantially linear olefin polymers (POSL) which can be advantageously used in the component (B) of the mixtures of the present invention. These polymers have a processability similar to that of LDPE, but the strength and hardness of PEBDL. Similar to traditional homogeneous polymers, the substantially linear ethylene / α-olefin interpolymers have only one melting peak, in opposite manner for the traditional Ziegler polymerized heterogeneous linear ethylene / α-olefin interpolymers having two or more peaks of fusion (determined using differential scanning calorimetry). The olefin polymers substantially linear are described in the Patents of E.U.A. Nos. 5,272,236 and 5,278,272 which are incorporated herein by reference. The density of the POSL as measured according to ASTM D-792 is generally from 0.85 g / cc to 0.97 g / cc, preferably from 0.85 g / cc to 0.955 g / cc, and especially from 0.85 g / cc to 0.92 g / cc. DC. The melt index, according to ASTM D-1238, Condition 190 ° C / 2.16 kg. (also known as l2), the POSL is usually 0.01 g / 10 min. at 1000 g / 10 minutes, preferably 0.01 g / 10 min. at 100 g / 10 minutes, and especially from 0.01 g / 10 minutes at 10 g / 10 minutes. Also, including the ultra low molecular weight ethylene polymers and ethylene / α-olefin interpolymers described in the patent application entitled Ultra-Low Molecular Weight Polymers, provisionally filed on January 22, 1996 with the names of M.L. Finlayson, C.C. Garrison, R.E. Guerra, M. J. Guest, B.W.S. Klthammer, D. R. Parikh, and S.M. Ueligger, which are incorporated here by reference. These ethylene / α-olefin interpolymers have l2 fusion rates greater than 1, 000 g / 10 minutes or a number average molecular weight (Mn) less than 11,000. The POSL can be a homopolymer of a C2-C2o olefin, such as ethylene, propylene, 4-methyl-1-pentene, etc., or it can be an interpolymer of ethylene with at least one C3-C20 α-olefin and / or C2-C20 acetynically unsaturated monomer and / or C-C18 diolefin. The POSL can be a polymer of ethylene with at least one of the above C3-C2o α-olefins, diolefins and / or monomers acetylenically unsaturated in combination with other unsaturated monomers. Especially preferred olefin polymers suitable for use as component (B) comprise PEBD, HDPE, heterogeneous PEBDL, homogeneous linear ethylene polymers, POSL, polypropylene (PP), especially isotactic polypropylene and rubber-resistant polypropylenes or ethylene-propylene intepolymers ( EP); or chlorinated polyolefins (CPE), or ethylene vinyl acetate copolymers (EVA), or ethylene-acrylic acid copolymers (EAA), or any combination thereof. The term "block copolymer" is used herein to mean elastomers having at least one block segment of a hard polymer unit and at least one block segment of a rubber monomer unit. However, the term is not intended to include thermoplastic ethylene interpolymers that are, in general, random polymers. Preferred block copolymers contain hard segments of styrene-type polymers in combination with saturated or unsaturated rubber monomer segments. The structure of the block copolymers useful in the present invention is not critical and may be of the linear or radial type, of diblock or triblock or any combination thereof. Preferably, the predominant structure is that of the triblocks and more preferably of the linear triblocks. The preparation of block copolymers useful herein is not subject to the present invention. The methods for Preparation of said block copolymers are known in the art. Said catalysts for the preparation of the useful block copolymers are unsaturated rubber monomer units include lithium based catalysts and especially lithium alkyls. The Patent of E.U.A. No. 3,595,942 discloses suitable methods for the hydrogenation of block copolymers with unsaturated rubber monomer units to form block copolymers with saturated rubber monomer units. The structure of the polymers was determined by their polymerization methods. For example, the linear polymers result from the sequential introduction of the desired rubber monomer into the reaction vessel when the initiators are used as lithium alkyls or dilithiostylebene, or by coupling a two-segment block copolymer with a difunctional coupling agent. Branched structures, on the other hand, can be obtained by their use of suitable coupling agents having a functionality with respect to block copolymers with unsaturated rubber monomer units of three or more. The coupling can be affected with multifunctional coupling agents such as dihaloalkanes or alkenes and divinyl benzene as well as with certain polar compounds such as silicon halides, siloxanes or esters of monohydric alcohols with carboxylic acids. The presence of any coupling residues in the polymer can be ignored for a proper description of the block copolymers that form a part of the composition of this invention.

Suitable block copolymers having unsaturated rubber monomer units include, but are not limited to, styrene-butadiene (SB); styrene-isoprene (SI), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), methylstyrene-butadiene-methylstyrene and methylstyrene-isoprene-methylstyrene. The styrenic portion of the block copolymer is preferably a styrene polymer or interpolymer and its analogs and homologs include α-methylstyrene and ring substituted styrenes, particularly methylated ring styrenes. The preferred styrenes are styrene and methylstyrene, and styrene is particularly preferred. Block copolymers with unsaturated rubber monomer units may comprise butadiene or isoprene homopolymers and copolymers of one or both of these two dienes with a minor amount of styrenic monomer. When the monomer used is butadiene, it is preferred that between 35 and 55 mole percent of the butadiene units condensed in the butadiene polymer block having the 1,2 configuration be included. Therefore, when said block is hydrogenated, the resulting product is a regular copolymer block reassembly of ethylene and 1-butene (EB). If the conjugated diene is used is isoprene, the resulting hydrogenated product is a reassembly of the regular ethylene-propylene copolymer block (EP). Preferred block copolymers with saturated rubber monomer units comprise at least one styrenic unit segment and at least one segment of an ethylene-butene or ethylene-propylene copolymer. Preferred examples of such block copolymers with saturated rubber monomer units include styrene / ethylene-butene copolymers, styrene / ethylene-propylene copolymers, styrene / ethylene-butene / styrene copolymers (SEBS) and styrene / ethylene copolymers -propylene / styrene (SEPS). The hydrogenation of the block copolymers with unsaturated rubber monomer units is preferably affected by the use of a catalyst comprising the reaction products of an aluminum alkyl compound with nickel or cobalt carboxylates or alkoxides under such conditions as substantially hydrogenated complete of at least 80 percent of the aliphatic double bonds while hydrogenation not more than 25 percent of the styrenic double aromatic ligatures. Preferred block copolymers are those in which at least 99 percent of the aliphatic double bonds were hydrogenated while less than 5 percent of the aromatic double bonds were hydrogenated. The proportion of the stretched blocks are generally between 8 and 65 weight percent of the total weight of the block copolymer. Preferably, the block copolymers contain from 10 to 35 weight percent of the styrenic block segments and from 90 to 65 weight percent of rubber monomer block segments, based on the total weight of the block copolymer.

The average molecular weights of the individual blocks may vary within certain limits. In many cases, the styrenic block segments could have number average molecular weights on the scale of 5,000 to 125,000, preferably 7,000 to 60,000 while the rubber monomer block segments could have average molecular weights on the scale of 10,000 to 300,000 , preferably from 30,000 to 150,000. The total average molecular weight of the block copolymer is usually in the range of 25,000 to 250,000, preferably from 35,000 to 200,000. These molecular weights are more accurately determined by tritium counting methods or osmotic pressure measurements. In addition, various block copolymers suitable for use in the present invention can be modified by grafting incorporation of minor amounts of functional groups, such as, for example, maleic anhydride by any of the methods well known in the art. The block copolymers useful in the present invention are commercially available, for example, supplied by Shell Chemical Company under the designation KRATON and supplied by Dexco Polymers under the designation VECTOR. Similarly, mixtures of substantially random interpolymers with polyvinylchloride (PVC), or ethylene vinyl alcohol (EVOH) can be suitably employed. Preparation of Thermoplastic Vulcanized The thermosetting compositions of the invention can be incorporated into polyolefins to form thermoplastic vulcanizates. The proportions of the ingredients used can sometimes vary with the particular polyolefin employed, with the desired application, as well as with the substantially random interlacing interpolymer character and ingredients of the composition. Normally, as the amount of substantially interlaced interpolymer increases, the softness of the resulting thermoplastic vulcanizate decreases. The thermoplastic vulcanizates of the invention could normally comprise from 10 to 90 weight percent of the polyolefin and from 10 to 90 weight percent of the substantially random interlaced interpolymer. Suitable polyolefins include thermoplastic, high molecular weight crystalline polymers prepared by the polymerization of one or more mono-olefins. Examples of suitable polyolefins include ethylene and the syndiotactic mono-olefin polymer resins, such as propylene., 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof. More typically, the thermoplastic vulcanizates of the invention could utilize isotactic polypropylene as the polyolefin component. The thermoplastic vulcanizates of the invention are preferably prepared by dynamic vulcanization, wherein a mixture of the substantially random non-interlacing interpolymer is mixed with the polyolefin resin and an agent of proper cure to form a mixture. Which is then chewed at a vulcanization temperature. In particular, the substantially random non-interlaced interpolymer is mixed with a polyolefin at a temperature above the diffusion point of the polyolefin. After the substantially random interpolymer and the polyolefin are intimately mixed, an appropriate curing agent is added. As described above with respect to the composition and cure of the substantially random interpolymers. The mixture is subsequently chewed using conventional chewing equipment, such as a Banbury mixer, Brabender mixer, or a mixing extruder. The temperature of the mixture during mastication is sufficient to effect vulcanization of the substantially random interpolymer. An adequate scale of

Claims (20)

1. CLAIMS 1. A partially or fully entangled composition comprising: (A) from 1 to 99 weight percent based on the combined weight of components (A) and (B) of at least one substantially random interpolymer comprising: ( 1) from 1 to 65 mole percent of polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hidden aliphatic vinyl or vinylidene monomer, or (c) a combination of at least one aromatic vinyl or vinylidene monomer and at least one hidden aliphatic vinyl or vinylidene monomer; and (2) from 35 to 99 mole percent polymer units derived from at least one aliphatic α-olefin of 2. to 20 carbon atoms;
2. (B) from 0 to 98 weight percent based on the combined weight of components (A) and (B) of at least one of the following polymers (1) a partially or fully entangled homopolymer containing polymeric units derived from an α-olefin, aromatic substituted α-olefin, α-olefin substituted with halogen have from 2 to 20 carbon atoms; (2) a copolymer containing (a) from 2 to 98 percent of polymer units derived from ethylene and (b) from 98 to 2 mole percent of polymer units derived from at least one of the α-olefins having 3 to 20 carbon atoms; acrylic acid, methacrylic acid, vinyl alcohol, vinyl acetate, diene having from 4 to 20 carbon atoms; (3) a styrenic block copolymer; (4) a substantially random interpolymer defined as in (A) and (B4) are distinguished by: (a) the amount of aromatic monomer of vinylidene and / or aliphatic or cycloaliphatic vinylidene monomer in any interpolymer of component (1) differs from that amount in any interpolymer of component (4) by at least 0.5 mole percent; and / or (b) there is a difference of at least 20 percent between the number average molecular weight (Mn) in any interpolymer of component (1) and any interpolymer of component (4); 2. A prepared fabricated part of the fully entangled partial composition of claim 1.
3. 3. A partially or totally interlaced composition of claim 1, in the form of fiber, wire and insulation of cables, gasket, hose, boots and shoes for use at high temperatures, and automotive parts and belts.
4. 4. A foamable composition comprising: (I) a partially or fully entangled composition comprising (A) from 1 to 100 weight percent based on the combined weight of components (A) and (B) of at least one substantially random interpolymer comprising: (1) from 1 to 65 mole percent of polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hidden aliphatic vinyl or vinylidene monomer , or (c) a combination of at least one vinyl aromatic monomer or vinylidene and at least one hidden aliphatic vinyl or vinylidene monomer, and (2) from 35 to 99 mole percent polymer units derived from at least one an aliphatic α-olefin of 2 to 20 carbon atoms; (B) from 0 to 98 weight percent based on the combined weight of components (A) and (B) of at least one of the following polymers (1) a partially or fully entangled homopolymer containing polymeric units derived from an olefin, aromatic substituted-olefin, or a halogen-substituted olefin has from 2 to 20 carbon atoms; (2) a copolymer containing (a) from 2 to 98 percent of polymer units derived from ethylene and (b) from 98 to 2 mole percent of polymer units derived from at least one of the α-olefins having 3 to 20 carbon atoms; acrylic acid, methacrylic acid, vinyl alcohol, vinyl acetate, diene having from 4 to 20 carbon atoms; (3) a styrenic block copolymer; (4) a substantially random interpolymer defined as in (1) wherein the interpolymers (A) wherein the interpolymers (A) and (B4) are distinguished by: (a) the amount of vinylidene aromatic monomer and / or aliphatic or cycloaliphatic vinylidene monomer in any ether polymer of component (1) differs from that amount in any interpolymer of component (4) by at least 0.5 mole percent; and / or (b) there is a difference of at least 20 percent between the average molecular weight in number (Mn) in any interpolymer of component (1) and any interpolymer of component (4); and (II) from 0.1 to 25 weight percent based on the combined weight of the components (I) and (II) of at least one foaming agent.
5. 5. A foam composition resulting in subjecting the foamable composition of claim 4 to the foaming conditions.
6. 6. The foam composition of claim 5, in the form of shoe soles, pipe insulation, bonded materials, athletic sponge pads, sound-treated shock absorbing panels and heat insulation. The process for preparing a thermosetting elastomer comprising: (a) reacting at least one α-olefin with at least one aromatic vinyl or vinylidene compound and optionally at least one diene, in the presence of a catalyst constructed geometric, to form a pseudo-random interpolymer; and (b) curing the pseudo-random interpolymer to form a thermosetting elastomer wherein the cure is effected by a curing agent selected from the group consisting of silane compounds, initiator for silane compounds, and optional catalyst for silane compounds; and radiation. The process of claim 7, wherein the α-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 5-methyl- 1-hexene, 4-eti I-1-hexen, 1-octene, 3-phenylpropene, and mixtures thereof; the vinyl or vinylidene compound is selected from the groups consisting of styrene, α-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, chlorostyrene, vinylbenzocyclobutane, divinylbenzene and mixtures thereof; and the diene is selected from the group consisting of butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, methylene norbornene, norbornene ethylidene, and mixtures thereof. The process of claim 7, wherein the constructed geometry catalyst comprises a metal coordination complex comprising a Group III or IV metal or the Lanthanide series of the Periodic Table of the Elements and a p-linked portion. delocalized substituted with a restricting-inducing portion, the complex having a restriction geometry around the metal atom such as the elemental angle between the center of the substituted and delocalised p-linked portion in the center of at least one remaining substituent is less than the angle in a similar complex containing a similar p-linked portion lacking the substituent that induces the restriction, and it also provides complexes comprising one or more delocalized substituted x-linked portions, only for each metal atom of the complex which is a cyclical, delocalised, substituted p-linked potion. The process of claim 7, wherein the restricted geometrical catalyst is selected from the group consisting of (tert-butylamino) (tetramethyl-? 5-cyclopentadienyl) -1,2-ethanediylcircityl dichloride; (tert-buti lido) d i met I (tetra m eti l-? 5-cyclopentadienyl) siiototitanium dimethyl; (tert) -butylamido) d, methyl (tetramethyl-? 5- indenyl) silanetitanium dimethyl; (tert-butylamido) dimethyl (tetramethyl-? 5-tetrahydroindenyl) silanetitanium di methyl; (tert-buti lido) dimethyl (tetramethyl-5-fluorenyl) silanetitanium dimethyl; (tert-butylamido) dimethyl (tetramethyl-? 5-tetrahydrofluorenyl) silanetitanium dimethyl; (tert-butylamido) dimethyl (tetramethyl-? 5-tetrahydrofluorenyl) silanetitanium di methyl; (tert-butylamido) dimethyl (tetramethyl-? 5-octahydrofluorenyl) silanetitanium dimethyl; (tert-butylamido) dimethyl (tetramethyl-? 5-cyclopentadienyl) silanetitanium dibenzyl; (tert-butylamido) dimethyl (tetramethyl-? 5-cyclopentadienyl) silanozirconium dibenzyl; and mixtures thereof. The process of claim 9, wherein the constrained geometry catalyst is activated by a co-catalyst selected from the group consisting of polymeric alumoxanes, oligomeric alumoxanes, polymeric carbyborans, carbil boranes oligomers, monomeric carbilboranes, aluminum alkyls, aluminum halides, haloaluminium alkyls, substituted ammonium salts, plant salts, ferrocenium ions, and mixtures thereof. The process of claim 9, wherein the constrained geometry catalyst is activated by tris (pentafluorophenyl) borane. The process of claim 9, wherein the cure is effected when an agent selected from the group consisting of silane compounds, initiators for silane compounds and optional catalyst for silane compounds, electron beam radiation and mixtures of the same. The process of claim 9, wherein the cure is carried out simultaneously with the composition of the pseudo-random interpolymer. 15. The process for forming a thermoplastic vulcanizate comprising: (a) polymerizing at least one α-olefin with at least one aromatic vinyl or vinylidene compound and optionally at least one diene in the presence of a catalyst of restricted geometry for form a pseudo-random interpolymer; (b) intimately mixing the pseudo-random interpolymer with at least one thermoplastic polyolefin at a temperature above the melting or softening point of the thermoplastic polyolefin; (c) providing the intimate mixture with a healing agent of the pseudo-random interpolymer; (d) simultaneously curing the pseudo-random interpolymer and the composition of the intimate mixture to form a thermoplastic vulcanizate; wherein the substantially random interpolymer curing agent is selected from the group consisting of silane compounds, initiator for silane compounds, and optional catalyst for silane compounds, radiation and mixtures thereof. The process of claim 15, wherein (a) the α-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, - methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenylpropene, and mixtures thereof; (b) the vinyl or vinylidene compounds are selected from the groups consisting of styrene, α-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, chlorostyrene, vinylbenzocyclobutane, divinylbenzene and mixtures thereof; and (c) the diene is selected from the group consisting of butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7- methyl-1,6-octadiene, dicyclopentadiene, methylene norbornene , ethylidene norbornene, and mixtures thereof. 1
7. 7. The process of claim 15, wherein the constructed geometry catalyst comprises a complex of coordination of metals comprising a Group III or IV metal or the Lanthanide series of the Periodic Table of the Elements and a delocalised p-linked portion substituted with a restriction-inducing portion, the complex having a restriction geometry around the atom of metal such that the angle in elemental between the center of the substituted and delocalised p-joined portion in the center of at least one remaining substituent is less than the angle in a similar complex containing a similar p-linked portion lacking the substituent that induces the restriction, and further provides the complexes comprising one or more delocalized substituted x-linked portions, only for each metal atom of the complex which is a cyclical, delocalised, substituted p-linked potion. The process of claim 17, wherein the constrained geometry catalyst is activated by a co-catalyst selected from the group consisting of polymeric alumoxanes, oligomeric alumoxanes, polymeric carbylborans, oligomeric carbil boranes, monomeric carbilborans, aluminum alkyls, halides of aluminum, haloaluminum alkyls, substituted ammonium salts, plant salts, ferrocenium ions, and mixtures thereof. The process of claim 17, wherein the thermoplastic polyolefin is selected from the group consisting of monomer units derived from ethylene, propylene, 1-butene, 1-pentene, 1- hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. A process for forming a thermoplastic vulcanizate comprising: (a) polymerizing at least one α-olefin with at least one aromatic vinyl or vinylidene compound and optionally at least one diene in the presence of a catalyst of restricted geometry for form a pseudo-random interpolymer; (b) intimately mixing the pseudo-random polymer with at least one thermoplastic polyolefin at a temperature above the melting or softening point of the thermoplastic polyolefin; (c) providing the intimate mixture with a healing agent of the pseudo-random interpolymer; (d) simultaneously curing the pseudo-random interpolymer and the composition of the intimate mixture to form a thermoplastic vulcanizate; wherein the substantially random interpolymer curing agent is selected from the group consisting of silane compounds, initiator for silane compounds, and optional catalyst for silane compounds, radiation and mixtures thereof. The process of claim 20, wherein (a) the α-olefin is selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 5- methyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenylpropene, and mixtures thereof; (b) the vinyl or vinylidene compounds are selected from the groups consisting of styrene, α-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, chlorostyrene, vinylbenzocyclobutane, divinylbenzene and mixtures thereof; and (c) the diene is selected from the group consisting of butadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7- methyl-1,6-octadiene, dicyclopentadiene, methylene norbornene , ethylidene norbornene, and mixtures thereof. The process of claim 20, wherein the constructed geometry catalyst comprises a metal coordination complex comprising a Group III or IV metal or the Lanthanide series of the Periodic Table of the Elements and a p-linked portion delocalized substituted with a restricting inducing portion, the complex having a restriction geometry around the metal atom such as the elemental angle between the center of the substituted and delocalised p-linked portion in the center of at least one remaining substituent is less than the angle in a similar complex containing a similar p-linked portion that lacks the substituent that induces the restriction, and further provides the complexes comprising one or more delocalized substituted x-linked portions, only for each atom of complex metal that is a cyclical, delocalised, substituted p-linked potion. 23. The process of claim 20, wherein the constrained geometry catalyst is activated by a co-catalyst selected from the group consisting of polymeric alumoxanes, oligomeric alumoxanes, polymeric carbylborans, carborine oligomeric borane, monomeric carbylborane, aluminum alkyl, halide. of aluminum, haloaluminum alkyls, substituted ammonium salts, plant salts, ferrocenium ions, and mixtures thereof. The process of claim 20, wherein the thermoplastic polyolefin is selected from the group consisting of monomer units derived from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. 25. A method for the entanglement of a polymer composition comprising: (A) from 2 to 99 weight percent based on the combined weight of the components (A) and (B) of at least one partial substantially random interpolymer or fully entangled comprising: (1) from 1 to 65 mole percent polymeric units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hidden aliphatic vinylidene vinylidene monomer, or (c) a combination of at least one aromatic vinyl or vinylidene monomer and at least one hidden aliphatic vinyl or vinylidene monomer, and (2) from 35 to 99 mole percent polymeric units derived from at least one aliphatic α-olefin of 2 to 20 carbon atoms; (B) from 1 to 98 weight percent based on the combined weight of components (A) and (B) of at least one of the following polymers (1) a homopolymer containing polymer units derived from one or more α-olefins having from 2 to 20 carbon atoms; (2) a copolymer containing (a) from 2 to 98 percent of polymer units derived from ethylene and (b) from 98 to 2 mole percent of polymer units derived from at least one of the α-olefins having 3 to 20 carbon atoms; acrylic acid, methacrylic acid, vinyl alcohol, vinyl acetate, diene having from 4 to 20 carbon atoms; (3) a styrenic block copolymer; (4) an interpolymer defined as in (A) wherein the interpolymers (A) and (B4) are distinguished in that: (i) the amount of the aromatic monomer of vinyl or vinylidene and / or vinyl monomer or vinylidene aliphatic or cycloaliphatic hidden in any interpolymer of component (1) that differs from the amount in any interpolymer of component (B4) by at least 0.5 mole percent; and / or (ii) there is a difference of at least 20 percent between the number average molecular weight (Mn) in any interpolymer of component (1) and any interpolymer of component (4); whose process for entanglement comprises subjecting the polymer composition to a sufficient amount of electron beam radiation to at least partially the entanglement of the polymer composition; or contacting the polymer composition with a sufficient amount of at least one peroxide compound to at least partially the entanglement of the polymer composition; or contacting the polymer composition with a sufficient amount of at least one silane compound for partial entanglement of the polymer composition; or contacting the polymer composition with a sufficient amount of at least one azide compound for at least partial entanglement of the polymer composition; or a combination of any of two or more of the above entanglement methods.