CN1276801A

CN1276801A - Thermoset interpolymers and foams

Info

Publication number: CN1276801A
Application number: CN 98810339
Authority: CN
Inventors: K·W·麦凯; F·J·蒂默斯; E·R·费格; T·H·霍; S·V·卡兰德
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1997-08-27
Filing date: 1998-08-26
Publication date: 2000-12-13
Anticipated expiration: 2018-08-26
Also published as: ID28337A; CN1098287C; TR200000515T2; PL338893A1

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 .alpha.-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

Thermoset interpolymers and foam

The present invention relates to thermoset interpolymers, its preparation method and by this thermoset interpolymers product processed.

In a preferred embodiment, the invention further relates to foam for preparing by these thermoset interpolymers and the method for preparing crosslinked alpha-olefin/binyl or vinylidene aromatic monomer and/or hindered aliphatic vinyl or vinylidene/interpolymer.

Elastomerics is defined as the material that shows bigger reversible deformation under suitable low-stress.Elastomerics has these features of soft unit in structure irregularity, nonpolar structure or the polymer chain usually.Commercial more elastomeric examples comprise natural rubber, ethylene/propene (EPM) multipolymer, ethylene/propylene/diene hydrocarbon (EPDM) multipolymer, styrene/butadiene copolymers, chlorinatedpolyethylene and silicon rubber.

Thermoplastic elastomer is for having the thermoplastic elastomer body.In other words, thermoplastic elastomer can molding or moulding and reprocessing under the temperature that is higher than its fusing point or fusing point.An example of thermoplastic elastomer is styrene-butadiene-styrene (SBS) segmented copolymer.The SBS segmented copolymer shows the two phase flow sex change of being made up of the vitreous state polystyrene main body that connects by rubbery state divinyl segment.Under the temperature between the glass transition temp of butadiene midblock and styrene end block, promptly under the temperature between-90 ℃ to 116 ℃, the SBS copolymer analog is similar to cross-linked elastomer.

EP 416,815 discloses false random ethylene-styrene copolymer.Uncrosslinked false random ethylene-styrene copolymer is higher than under the fusing point of interpolymer or the softening temperature in temperature and shows low modulus.

There is following shortcoming in the false random copolymer of SBS multipolymer and uncrosslinked ethene-vinylbenzene: lower physical strength, to the ozone degradation sensitivity (to they in main polymer chain, have the degree of unsaturated position) and only can be used for the field that wherein elastomeric temperature is no more than elastomeric fusing point or softening temperature.

On the contrary, thermo-setting elastomer is the elastomerics with thermosetting performance.When in other words, thermo-setting elastomer is usually owing to irreversible crosslinking reaction irreversible curing of meeting or heating " curing ".Two examples of thermo-setting elastomer are cross-linked ethylene-propylene monomer rubber (EPM) and cross-linked ethylene-propylene-diolefinic monomer rubber (EPDM).The EPM material is by ethene and copolymerization of propylene preparation.The EPM material carries out crosslinked usually with peroxide cure, and introduces the thermosetting performance thus.The EPDM material be ethene, propylene and non-conjugated diene hydrocarbon as 1, the linear interpolymer of 4-hexadiene, Dicyclopentadiene (DCPD) or vinylidene norbornylene.The EPDM material uses sulfur vulcanization to introduce the thermoset performance, although their also available peroxide cures usually.Though EPM and EPDM material have the advantage that can be used for the comparatively high temps field, but EPM and EPDM elastomerics exist low green strength (when low ethylene content), the curing elastomer higher than styrene butadiene ribber to be subjected to susceptibility and anti-these shortcomings of surface modification performance of curing elastomer of oil immersion erosion.

Need be suitable for wide temperature range and to the elastomerics of ozone degradation Wheat Protein.Especially need be by the thermo-setting elastomer of elastomer production with high green strength (this green strength provides bigger snappiness before solidifying in the elastomerics operation).Need oil resistant and can be used for usually the processing component of contact oil such as the thermo-setting elastomer of trolley part and packing ring.Need carry out surface modification easily, to promote elastomeric surface adhesion and/or the elastomerics at ionic position is provided on surface of elastomer.Also need to prepare the method for these thermo-setting elastomers.

Thermoplastic Vulcanizate is for wherein being evenly distributed with the crystalline polyolefin matrix of thermo-setting elastomer.The example of Thermoplastic Vulcanizate comprises EPM and the EPDM thermosetting material that is distributed in the crystalline polypropylene base material.The shortcoming that these Thermoplastic Vulcanizate exist is that they are easy to the oil degraded.Need more grease-proof Thermoplastic Vulcanizate.Also need to prepare the method for these Thermoplastic Vulcanizate.

Interpolymer by alpha-olefin/vinylidene aromatic monomer or the preparation of hindered aliphatic vinylidene monomer has fabulous performance; Yet needs improve these polymkeric substance of performance.

Find, can improve the performance of these interpolymers by crosslinked these interpolymers, as higher upper limit use temperature, improved melt processability and self-adhesive trend.

Compare with non-crosslinked interpolymer foam, it is believed that the foam that is equipped with by the copolymerzation with cross-linking system has one or more following improvement performances: improved upper limit use temperature, lower density, improved elastic recovery, improved mechanical property.

The invention provides a kind of thermoset product that comprises crosslinked random basically interpolymer, described crosslinked random basically interpolymer comprises:

(1) 1 to 65mol% derived from following polymer of monomers unit,

(a) at least a vinyl or vinylidene aromatic monomer, or

(b) at least a hindered aliphatic vinyl or vinylidene monomer, or

(c) mixture of at least a vinyl or vinylidene aromatic monomer and at least a hindered aliphatic vinyl or vinylidene monomer; With

(2) 35 to 99mol% derived from least a polymer unit with aliphatic alpha-olefin of 2 to 20 carbon atoms.

The present invention relates to foamable composite on the other hand, comprising:

(I) partially or completely crosslinked composition comprises:

(A) at least a partially or completely crosslinked random basically interpolymer of 2 to 100wt% (by component (A) and gross weights (B)), this interpolymer comprises:

(1) 1 to 65mol% derived from following polymer of monomers unit, (a) at least a vinyl or vinylidene aromatic monomer, or (b) at least a hindered aliphatic vinyl or vinylidene monomer, or (c) mixture of at least a vinyl or vinylidene aromatic monomer and at least a hindered aliphatic vinyl or vinylidene monomer; With

(B) at least a following polymers of 0 to 98wt% (by component (A) and gross weight (B)):

(1) a kind of partially or completely crosslinked homopolymer, this homopolymer comprises the polymer unit derived from one or more alpha-olefins with 2 to 20 carbon atoms;

(2) a kind of partially or completely crosslinked copolymers, this multipolymer comprise (a) 2 to 98mol% derived from ethylene polymer unit and (b) 98 to 2mol% derived from least a aliphatic alpha-olefin with 3 to 20 carbon atoms, vinylformic acid, methacrylic acid, vinyl alcohol, vinyl-acetic ester or have the polymer unit of the diolefine of 4 to 20 carbon atoms;

(3) a kind of partially or completely crosslinked styrene block copolymer;

(4) the partially or completely crosslinked random basically interpolymer of definition in a kind of (1), wherein the difference of interpolymer (1) and (4) is:

(i) vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer amount in arbitrary interpolymer of component (1) and the amount in arbitrary interpolymer of component (4) differ 0.5mol% at least; And/or

(ii) the number-average molecular weight (Mn) of arbitrary interpolymer of component (1) differs at least 20% with the number-average molecular weight (Mn) of arbitrary interpolymer of component (4); (II) at least a whipping agent of 0.1 to 25wt% (by component (I) and gross weight (II)).

The present invention relates to the method for crosslinking polymer composition on the other hand, and described polymer composition comprises:

(2) 35 to 99mol% derived from least a polymer unit with aliphatic alpha-olefin of 2 to 20 carbon atoms;

(1) a kind of homopolymer that comprises derived from the polymer unit of one or more alpha-olefins with 2 to 20 carbon atoms;

(2) a kind of multipolymer, comprise (a) 2 to 98mol% derived from ethylene polymer unit and (b) 98 to 2mol% derived from least a aliphatic alpha-olefin with 3 to 20 carbon atoms, vinylformic acid, methacrylic acid, vinyl alcohol, vinyl-acetic ester or have the polymer unit of the diolefine of 4 to 20 carbon atoms;

(3) a kind of styrene block copolymer;

(4) interpolymer of definition in a kind of (A), wherein interpolymer (A) and difference (B4) are:

(i) vinyl or vinylidene aromatic monomer and/or hindered aliphatic or cyclic aliphatic vinyl or vinylidene monomer amount in arbitrary interpolymer of component (A) and the amount in arbitrary interpolymer of component (B4) differ 0.5mol% at least; And/or

(ii) the number-average molecular weight (Mn) of arbitrary interpolymer of component (A) differs at least 20% with the number-average molecular weight (Mn) of arbitrary interpolymer of component (B4);

Described cross-linking method comprises the steps:

(a) make this polymer composition bear the electron beam irradiation of q.s so that polymkeric substance is partial cross-linked at least; Or

(b) this polymer composition is contacted with at least a superoxide of q.s make polymer composition partial cross-linked at least; Or

(c) polymer composition is contacted with at least a silane compound of q.s make polymer composition partial cross-linked at least; Or

(d) this polymer composition is contacted with at least a trinitride of q.s make polymer composition partial cross-linked at least; Or

(e) above-mentioned two or more cross-linking methods are combined.

The present invention relates to the foam that obtains under the foaming condition by but above-mentioned foaming polymer composition is placed on the other hand.

The present invention further comprises and contains thermo-setting elastomer of the present invention or Thermoplastic Vulcanizate or partially or completely crosslinked foamy processing component.

These and other embodiment is described in greater detail below.

Term " polymer " used herein " be meant the polymeric material of the monomer preparation by the identical or different type of polymerization.Therefore general term polymer comprises term homopolymer (this term only refers to the polymkeric substance by a kind of monomer preparation) and the term interpolymer that defines below.

Term used herein " copolymerzation with cross-linking body " and " thermoset interpolymers " can exchange use mutually, and refer to have the interpolymer greater than 10% gel (measuring according to ASTM D-2765-84).

As long as the gap of at least two units is arranged between any Schwellenwert and any maximum, any quantized numerical value of being mentioned here be included under the unit increment from Schwellenwert to all numerical value between the maximum.For example, if component concentration that provides or processing parameter are variable as temperature, pressure, time or the like, for example from 1 to 90, preferred 20 to 80, particularly 30 to 70, for example be meant in fact that 15 to 85,22 to 68,43 to 51,30 to 32 or the like numerical range has specifically been enumerated in this manual.For less than 1 numerical value, the unit of this moment then suitably should be 0.0001,0.001,0.01 or 0.1.These are the example of those numerical value of clear and definite indication, for cited from Schwellenwert to all possible combinations of values between the maximum, should think that this specification sheets is clearly expressed in an identical manner.

Term used herein " interpolymer " is meant the polymkeric substance by at least two kinds of dissimilar monomer preparations of polymerization.Therefore general term interpolymer comprises multipolymer (be generally used for refer to by by two kinds of different monomers preparations polymkeric substance) and by the polymkeric substance of two or more dissimilar monomers preparations.

Here including or containing some monomeric description for polymkeric substance or interpolymer is meant and includes or contains in these polymkeric substance or the interpolymer derived from this monomeric polymerized unit.For example, contain vinyl monomer, then have the ethene derivatives of introducing in this polymkeric substance if describe a kind of polymkeric substance, promptly-CH ₂-CH ₂-.

Term " alkyl " is meant that any aliphatic series, cyclic aliphatic, aromatics, aryl replace aliphatic series, aryl substituted ring aliphatic series, fat base replacement aromatics or cycloaliphatic radical substituted aryl.Aliphatic series or cycloaliphatic groups are preferably saturated.Similarly, term "-oxyl " is meant the alkyl that has oxygen between this group and the carbon atom that is connected it.

Term " monomer residue " or " deutero-is from these polymer of monomers unit " are meant by what another polymerizable molecules polymerization with the preparation polymer chain brought and residue in polymerisable monomer molecular moiety in the polymer chain.

Elastomerics thermoset composition of the present invention is preferably the random basically interpolymer that comprises alkene and vinyl aromatic monomer, and this interpolymer obtains the thermoset performance after crosslinked.

Term " random basically ", here be used for by one or more 'alpha '-olefin monomers and one or more vinylidene aromatic monomers or hindered aliphatic or cycloaliphatic vinylidene monomer, carry out polymerization with non-essential and other polymerisable ethylenically unsaturated monomer and in the random interpolymer of being essentially of obtaining, the monomeric distribution that refers to said interpolymer can be described with Bai Nuli statistical model or one-level or secondary Markovian statistical model, referring to " polymer sequence is measured, the 13C nuclear magnetic resonance method " (J.C.Randall, Polymer Sequence Determination, Carbon-13 NMR Method, Academic Press New Youk, 1977, the 71-78 page or leaf).By one or more 'alpha '-olefin monomers and one or more vinylidene aromatic monomers with non-essentially carry out polymerization with other polymerisable ethylenically unsaturated monomer and being essentially of the obtaining vinyl that random interpolymer preferably contained or the total amount of vinylidene aromatic monomer are no more than 15% in the block that contains above 3 vinyl or vinylidene aromatic monomer.More preferably, interpolymer be not with height complete with or syndiotaxy be constitutional features.In other words in being essentially the carbon-13 nmr of random interpolymer, be no more than 75% of the total peak area of main chain mesomethylene carbon and methine carbon with the main chain mesomethylene carbon of representing meso diad sequence or racemize diad sequence and the corresponding peak area of methine carbon.

False random copolymer is a branch of random interpolymer basically.False random copolymer is characterised in that to have such structure: wherein all phenyl (or substituted-phenyl) (hanging on the side group on the main polymer chain) are separated by two or more carbon backbone chains unit.In other words, the false random copolymer of the present invention that is in the non-crosslinked attitude can describe by following general formula (for ease of explanation use vinylbenzene as vinyl aromatic monomer and ethene as alpha-olefin):

The false random copolymer of non-crosslinked is described among the EP416815A.

Though do not desire to be subjected to any particular theory constraint, but it is believed that during addition polymerization in the presence of the constraint geometry catalyst that for example ethene and vinylbenzene are described below, if styrene monomer inserts in the polymer chain growing, then the next monomer of Cha Ruing is a vinyl monomer or to put upside down the styrene monomer that mode or " the tail tail joins " mode are inserted.It is believed that and put upside down or after " the tail tail joins " mode inserted styrene monomer, next monomer was an ethene, can make its too close styrene monomer of putting upside down because insert second styrene monomer at this point that promptly being separated by is no more than two carbon backbone chain unit.

Basically random interpolymer is characterized in that preferably showing that by the 13C-NMR spectrum it is essentially random that wherein the peak area corresponding to the main chain methylene radical of representing meso diad sequence or racemize diad sequence and methine carbon is no more than 75% of main chain methylene radical and methine carbon total peak area.

Be suitable as component of the present invention (A) and random basically interpolymer (B4) comprises by polymerization i) one or more 'alpha '-olefin monomers and ii) one or more vinyl or vinylidene aromatic monomer and/or one or more hindered aliphatics or cyclic aliphatic vinyl or vinylidene monomer and the non-essential iii) random basically interpolymer of other polymerizable ethylenically unsaturated monomer preparation.

Suitable alpha-olefin for example comprises and contains 2 to 20 carbon atoms, preferred 2 to 12 carbon atoms, the more preferably alpha-olefin of 2 to 8 carbon atoms, specially suitable is ethene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1, or in ethene and propylene, butene-1,4-methyl-1-pentene, hexene-1 or the octene-1 one or more and use.These alpha-olefins do not contain aryl moiety.

Other non-essential polymerizable ethylenically unsaturated monomer comprises norbornylene and C _1-10Alkyl or C _6-10The norbornylene that aryl replaces, for example interpolymer is an ethylene/styrene/norbornene.

The vinyl or the vinylidene aromatic monomer that are fit to that can be used for preparing interpolymer comprise, for example by those monomers of following molecular formula representative:

R wherein ¹Be selected from H and the alkyl that contains 1 to 4 carbon atom, be preferably H or methyl; Each R ²Be selected from H and the alkyl that contains 1 to 4 carbon atom independently of one another, be preferably H or methyl; Ar is phenyl or has 1 to 5 and be selected from halogen, C _1-4Alkyl and C _1-4The substituent phenyl of haloalkyl; With the value of n be 0 to 4, be preferably 0 to 2, most preferably 0.The monomeric example of mono vinyl aromatics comprises vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene and chlorostyrene, comprises the isomer that these compounds are all.This class monomer of particularly suitable comprises the derivative that vinylbenzene and its low alkyl group or halogen replace.Preferred monomer comprises vinylbenzene, alpha-methyl styrene and low alkyl group (C _1-4) or the nuclear substituted styrene derivatives of phenyl, for example adjacent, and p-methylstyrene, ring by halogenated vinylbenzene, to Vinyl toluene or their mixture.Preferred aromatic vinyl monomer is a vinylbenzene.

Term " hindered aliphatic or cyclic aliphatic vinyl or vinylidene compound " but be meant vinyl or vinylidene monomer by the represented addition polymerization of following molecular formula:

A wherein ¹For containing the sterically hindered big aliphatic series or the cyclic aliphatic substituting group of 20 carbon atoms at the most, R ¹Be selected from H and the alkyl that contains 1 to 4 carbon atom, be preferably H or methyl; Each R ²Be selected from H and the alkyl that contains 1 to 4 carbon atom independently of one another, be preferably H or methyl; Or R ¹And A ¹Also can constitute member ring systems.Preferred aliphatic series or cyclic aliphatic vinyl or vinylidene monomer have ethylenic unsaturated bond for those one of them carbon atom is the monomer that replaces in uncle or season.The substituent example of this class comprises deriveding group, the tertiary butyl and the norcamphyl that alkyl or aryl replaces on cycloaliphatic radical such as cyclohexyl, cyclohexenyl, ring octyl group or their ring.Most preferred hindered aliphatic or cyclic aliphatic vinyl or vinylidene compound are gone up by the tetrahydrobenzene of the various isomer of the tetrahydrobenzene of vinyl substituted, replacement and 5-vinylidene-2-norbornylene for ring, particularly 1-, 3-and 4 vinyl cyclohexene.

These basic random copolymers can carry out modification with typical graft well-known to those skilled in the art, hydrogenation, functionalization or other reaction.According to prior art, can be at an easy rate with this polymkeric substance sulfonation or chlorination, so that the derivative of functionalization to be provided.These random basically interpolymers also can by various chain extensions or cross-linking method (include but not limited to superoxide-, silane-, sulphur-, radiation-or trinitride base curing system) modification.Various crosslinking technologicals are described in detail in the common unsettled U.S. Patent application 08/921,641 and 08/921,642 (applying date all is on August 27th, 1997), and the full content of these two applications is introduced as reference here.Can effectively use dual cure systems, promptly use heat, moisture-curable to combine with irradiation step.Open and claimed dual cure systems in U.S. Patent application serial number 536,022 that K.L.Walton and S.V.Karande1995 submitted at September 29 (here as with reference to introducing).For example, can suitably peroxide cross-linking agent be combined with silane crosslinker, peroxide cross-linking agent is combined with radiation, the linking agent of sulfur-bearing is combined with silane crosslinker etc.Described random basically interpolymer also can be by various cross-linking method modifications, these cross-linking methods include but not limited to introduce the diolefine component during interpolymer as the 3rd monomer in preparation, then by aforesaid method with comprise and use that for example sulphur is crosslinked through other methods of vinyl sulfurized as linking agent.

The interpolymer of one or more 'alpha '-olefin monomers of the present invention and one or more vinyl or vinylidene aromatic monomer and/or one or more hindered aliphatics or cyclic aliphatic vinyl or vinylidene monomer is random basically polymkeric substance.These interpolymers contain 0.5 to 65 usually, at least a vinyl preferred 1 to 55, more preferably 2 to 50 moles of % or vinylidene aromatic monomer and/or hindered aliphatic or cyclic aliphatic vinyl or vinylidene monomer and 35 to 99.5, preferred 45 to 99, more preferably 50 to 98 moles of at least a aliphatics alpha-olefins that contain 2 to 20 carbon atoms of %.

Other non-essential polymerisable ethylenically unsaturated monomer comprises tension link alkene such as norbornylene and C _1-10Alkyl or C _6-10The norbornylene that aryl replaces, an example of interpolymer is an ethylene/styrene/norbornene.

The number-average molecular weight of polymkeric substance and multipolymer (Mn) is preferably 20,000 to 1,000,000 usually greater than 5,000, and particularly 50,000 to 500,000.

Under the temperature on the monomer auto-polymerization temperature separately, carry out polyreaction and remove unreacted monomer causing some homopolymer products to generate by radical polymerization.For example, when preparation was essentially random interpolymer, because homopolymerization may take place vinyl aromatic monomers under higher temperature, the homopolymer that therefore has some atactic vinyl aromatic monomers generated.The existence of vinyl or vinylidene aromatic monomer homopolymer generally can not influence effect of the present invention, therefore is to allow its existence.The homopolymer of vinyl or vinylidene aromatic monomer can be as required separate from interpolymer by the method for extracting, and for example optionally precipitates from their solution with one of them precipitation agent of interpolymer or vinyl or vinylidene aromatic monomer homopolymer.The homopolymer of preferred vinyl of the present invention or vinylidene aromatic monomer be no more than interpolymer gross weight 20%, preferably less than 15%.

The condition of polymerization of Alpha-olefin, vinyl or vinylidene aromatic and non-essential diolefine is generally those that are used for solution polymerization process, although the invention is not restricted to this.It is believed that also and can use high pressure, slurry and gas phase polymerization process that condition is to use appropriate catalyst and polymerizing condition.

Usually, being used to implement polymerization of the present invention can finish under the used polymerizing condition of the known Z-N of those skilled in the art or the polymerization of Kaminsky-Sinn type.

Be essentially random interpolymer by one or more metalloceness or constraint geometry catalyst and various promotor simultaneously in the presence of the mixture preparation of polymerization polymerisable monomer, as be described in people's such as James C.Stevens EP-A-0,416,815 and the US 5 of Francis J.Timmers, 703, in 187, the full content of these two pieces of documents is introduced as reference here.This preparation method of random interpolymer basically is included in the mixture preparation that there are following polymerization polymerisable monomer simultaneously in one or more metalloceness or constraint geometry catalyst and various promotor.The preferred operational condition of these polyreactions is that pressure is from 1 normal atmosphere to 3000 normal atmosphere, and temperature is-30 ℃ to 200 ℃.Under the temperature on the monomer auto-polymerization temperature separately, carry out polyreaction and remove unreacted monomer causing some homopolymer products to generate by radical polymerization.

The example of the catalyzer that is suitable for is disclosed in the U.S. Patent application US No.07/702 that submitted on May 20th, 1991,475 (corresponding to EP-A-514,828), and United States Patent (USP) 5 with the method for preparing the interpolymer that is essentially random, 055,438,5,057,475,5,096,867,5,064,802,5,132,380,5,189,192,5,321,106,5,347,024,5,350,723,5,374,696,5,399,635,5,470,993,5,703,187 and 5, in 721,185, all patents and application are introduced as reference here.

Basically random alpha-olefin/binyl aromatic monomer interpolymer also can adopt the compound of following general formula description according to the method for describing among the JP07/278230

C wherein _P ¹And C _P ²Be the identical radicals of cyclopentadienyl, indenyl, fluorenyl or these groups independently of each other; R ¹And R ²Be hydrogen atom, halogen atom, alkyl, alkoxyl group or aryloxy independently with 1-12 carbon atom; M is an IV family metal, preferred Zr or Hf, most preferably Zr; R ³For being used for crosslinked C _P ¹And C _P ²Alkylidene group or silane two bases.

Basically the random interpolymer of alpha-olefin/binyl aromatic monomer also can be according to (W.R.Grace such as John G.Bradfute; Co.) at WO 95/32095, R.B.Pannell (Exxon Chemical Patents Inc) is at WO 94/00500 with in " plastics technology " (PlasticsTechnology) in September, 1992, the 25th page of described method is prepared, and the described full content of these reference is all incorporated this paper into.

The same Francis J.Timmers that also has that is suitable for equals the U.S. Patent application U.S.No.08/708 that submitted on September 4th, 1996,809 and WO98/09999 in the disclosed random interpolymer that is essentially that contains at least one alpha-olefin/binyl aromatic monomer/vinyl aromatic monomers/alpha-olefin four unit groups.These interpolymers contain intensity peak other signal bigger 3 times than noise peak.The chemical shift of these signals is between 43.70 to 44.25ppm and 38.0 to 38.5ppm.More specifically, the chemical shift of main peak is 44.1,43.9 and 38.2ppm.The nucleus magnetic resonance proton test shows that chemical shift belongs to methine carbon at 43.70 to 44.25ppm signal, and chemical shift belongs to mesomethylene carbon at 38.0 to 38.5ppm signal.

It is believed that new signal is to belong to the sequence of inserting at least one alpha-olefin in the front and back of two connected head-to-tail vinyl aromatic monomers and forming, ethylene/styrene/styrene/ethylene four unit groups for example, wherein styrene monomer only inserts in this Unit four group in 1,2 mode (connected head-to-tail mode).Those skilled in the art understand for containing vinyl aromatic monomers outside the vinylbenzene and four unit groups of the alpha-olefin outside the ethene, this ethylene/vinyl base aromatic monomer/vinyl aromatic monomers/ethene four unit groups will have similar 13C nuclear magnetic resonance peak, but small difference will be arranged in chemical shift.

These interpolymers are under-30 ℃ to 250 ℃ temperature, and in the presence of those catalyzer shown in following molecular formula, and selectivity adopts but the polyreaction preparation preferably carried out in the presence of active cocatalyst as required:

Wherein each Cp is the cyclopentadienyl of the replacement that links to each other with M with the π key; E is C or Si; M is an IV family metallic element, is preferably Zr or Hf, most preferably Zr; Each R is H, alkyl, sila alkyl or silicon alkyl alkyl independently of one another, contains 30 at the most, preferred 1 to 20, more preferably 1 to 10 carbon atom or Siliciumatom; Each R ' is H, halogen, alkyl,-oxyl, sila alkyl or silicon alkyl alkyl independently of one another, contain 30 at the most, preferred 1 to 20, more preferably 1 to 10 carbon atom or Siliciumatom, or two R ' bases can constitute C jointly _1-10The 1,3-butadiene that alkyl replaces; M is 1 or 2.Especially, the cyclopentadienyl of the replacement of Shi Yonging comprises those groups shown in the following molecular formula:

Wherein each R is H, alkyl, sila alkyl or silicon alkyl alkyl independently of one another, contains 30 at the most, preferred 1 to 20, more preferably 1 to 10 carbon atom or Siliciumatom, or two R bases can constitute the divalence deriveding group of this group jointly.Preferably, each R base is (if suitable independently of one another, comprise all isomer) H, methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, phenyl or silylation, or (if suitable) two R bases couple together and constitute a condensed ring system, as indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl or octahydrofluorenyl.

Particularly preferred catalyzer comprises for example racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl)) zirconium dichloride, racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl)) 1,4-phenylbenzene-1,3-butadiene zirconium, racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl)) two C _1-4Alkyl zirconium, racemize (dimethyl silyl base)-two-(2-methyl-4-phenyl indenyl)) two C _1-4Zirconium alkoxide, or their arbitrary combination or the like.

Can also use following titanium-Ji to fetter geometry catalyst: [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-s-cyclopenta indenes (indcen)-1-yl] silane amino (2-)-N] the dimethyl titanium, (1-indenyl) (tertiary butyl amino) dimethylsilane dimethyl titanium, (the 3-tertiary butyl) (1,2,3,4,5-η)-1-indenyl (tertiary butyl amino) dimethylsilane dimethyl titanium and ((3-sec.-propyl) (1,2,3,4,5-η)-the 1-indenyl) (tertiary butyl amino) dimethylsilane dimethyl titanium or its mixture.

The existing in the literature report of other preparation method that is used for interpolymer of the present invention.Longo and Grassi (macromolecular chemistry (Makromol.Chem.), nineteen ninety, the 191st volume, the 2387-2396 page or leaf) and (journal of applied such as D ' Anniello, nineteen ninety-five, the 58th volume, the 1701-1706 page or leaf) reported and adopted based on methylaluminoxane (MAO) and cyclopentadienyl titanous chloride (CpTiCl ₃) catalyst system prepare ethylene-styrene copolymer.Xu and Lin (polymer chemistry branch of American Chemical Society, polymkeric substance preprint collection (PolvmerPreprints, Am.Chem.Soc..Div.Polvm.Chem.) .1994. the 35th volume, 686,687 pages) report adopts MgCl ₂/ TiCl ₄/ NdCl ₃/ Al (iBu) ₃Catalyzer carries out the random copolymers of copolymerization with preparation vinylbenzene and propylene.People such as Lu (journal of applied,, the 53rd volume, 1453-1460 page or leaf in 1994) report adopts TiCl ₄/ NdCl ₃/ MgCl ₂/ Al (Et) ₃Catalyzer carries out copolymerization with ethene and vinylbenzene.Sernetz and Mulhaupt (macromolecular chemistry physics (Macromol.Chem.Phys.),, the 197th volume, 1071-1083 page or leaf in 1997) have described polymerizing condition to adopting Me ₂Si (Me ₄Cp) (the TiCl of uncle N--Bu) ₃The influence of the vinylbenzene of/methylaluminoxane Ziegler-natta catalyst and ethylene copolymerization reaction.Arai, Toshiaki and Suzuki have described method (the polymer chemistry branch of American Chemical Society by bridged metallocene Catalyst Production ethene and cinnamic multipolymer, polymkeric substance preprint collection (Polvmer Preprints, Am.Chem.Soc., Div.Polym.Chem.), 1997, the 38th volume, 349,350 pages), and be disclosed in and authorize Mitsui ToatusChemicals, among the US 5,652,315 of Inc.The manufacturing of the interpolymer of alpha-olefin/binyl aromatic monomer such as propylene/styrene and butylene/styrene interpolymer is disclosed in the US5 that authorizes petrochemical industry Co., Ltd. of Mitsubishi (Mitsui Petrochemical Industries Ltd.), 244,996, authorize the US 5 of petrochemical industry Co., Ltd. of Mitsubishi (Mitsui PetrochemicalIndustries Ltd.), 652,315, authorize among DE 197 11 339 A1 of Denki Kagaku Kogyo KK..All above-mentioned disclosed methods that prepare interpolymer are all incorporated this paper into as the application's reference.

The amount of introducing vinyl in the thermo-setting elastomer of the present invention or vinylidene aromatic monomer is 30wt% at least, preferably 35wt% (by interpolymer weight) at least.Introduce the vinyl in the interpolymer of the present invention or the amount of vinylidene aromatic monomer and be usually less than 70wt%, preferably be lower than 60wt% (by the gross weight of interpolymer).

The random basically interpolymer of the present invention contains 0.5 to 65 usually, preferred 1 to 55, more preferably 2 to 50mol% at least a vinyl or vinylidene aromatic monomer and/or hindered aliphatic or cyclic aliphatic vinyl or vinylidene monomer and 35 to 99.5, preferred 45 to 99, more preferably 50 to 98mol% at least a aliphatic alpha-olefin with 2 to 20 carbon atoms.

One or more diolefine optionally can be introduced in the interpolymer so that unsaturated sense position to be provided on interpolymer, be made this interpolymer can participate in for example crosslinking reaction thus.Although conjugated diene such as divinyl, 1,3-pentadiene (being piperylene) or isoprene can be used for this purpose, non-conjugated diene is preferred.Typical non-conjugated diene hydrocarbon for example comprises open chain non-conjugated diene hydrocarbon as 1,4-hexadiene (referring to US 2,933,480) and 7-methyl isophthalic acid, 6-octadiene (being called MOCD again); Cyclodiene; Bridged ring diolefine such as dicyclopentadiene (referring to US3,211,709); Or alkylidene group norbornylene such as methene norbornene or ethylidene norbornene (referring to US 3,151,173).The non-conjugated diene hydrocarbon is not limited to only to have those of two two keys, also comprises those with three or more pair key.

The amount of introducing the diolefine in the elastomerics of the present invention is 0 to 15wt% (by the gross weight of interpolymer).When using diolefine, it preferably accounts for the 2wt% at least of interpolymer gross weight, more preferably 3wt% and most preferably 5wt% at least at least.Equally, when using diolefine, it is no more than the 15wt% of interpolymer gross weight, preferably is no more than 12wt%.

The number-average molecular weight of polymkeric substance and interpolymer (Mn) is usually greater than 5,000, and is preferred 20,000 to 1,000,000, and more preferably 50,000 to 500,000.Compounding is also solidified random basically interpolymer

Thermo-setting elastomer of the present invention comprises various additives, as carbon black, silicon-dioxide, titanium dioxide, tinting pigment, clay, zinc oxide, stearic acid, promotor, solidifying agent, sulphur, stablizer, anti degradant, processing aid, tackiness agent/tackifier, softening agent, paraffin, precrosslink inhibitor, discontinuous fibre (as the wood cellulose fiber) and extending oil.These additives can be before solidifying random basically interpolymer, during or add afterwards.Basically random interpolymer at high temperature mixes so that its compounding with filler, oil and solidifying agent usually.Solidify under the temperature that mixing material adopts during temperature is higher than compounding subsequently usually.

Preferably before solidifying, carbon black is added in the random basically interpolymer.The carbon black that adds is generally used for improving the tensile strength or the toughness of compounding product, the color that also can be used as the extender of compounding product or shelter the compounding product simultaneously.The sooty consumption be generally the batching gross weight 0 to 80wt%, preferred 0.5 to 50wt%.When carbon black is used to shelter color, its consumption be generally ingredients by weight 0.5 to 10wt%.When carbon black was used to improve the toughness of batching and/or reduces expense, its consumption was usually greater than the 10wt% of batching gross weight.

More preferably before curing, one or more extending oils are added in the random basically multipolymer.Add extending oil and can improve processibility and low temperature flexibility usually, and with low cost.Suitable extending oil is listed in rubber world blue Book version (Rubber World Blue book 1975Edition) in 1975: be used for the material and the furnish component of rubber, in the 145-190 page or leaf.The extending oil of several quasi-representatives comprises aromatic hydrocarbons, cycloalkanes and alkane extending oil.The consumption of extending oil is generally 0 to 50wt%.When using extending oil, its consumption is generally the 5wt% at least of batching gross weight, and more preferably 15 to 25wt%.

The consumption of solidifying agent be generally the batching gross weight 0.5 to 12wt%.

Proper curing agents comprises superoxide, phenol, trinitride, aldehyde-amine reactor product, replaces urea, replaces guanidine, replace xanthogenate, replace dithiocar-bamate, the compound of sulfur-bearing such as thiazole, imidazoles, inferior yellow acid amides, thiuram disulphide, paraquinonedioxime, dibenzo paraquinonedioxime, sulphur and its mixture, referring to chemical industry technology complete works (Encyclopedia of ChemicalTechnology), the 17th volume, second edition, Interscience Publisher, nineteen sixty-eight; And organo-peroxide (Organic Peroxides, Daniel Seern), the 1st volume, Wiely-Interscience, 1970.

Suitable superoxide comprises the aromatics diacyl peroxide; The aliphatic series diacyl peroxide; The diprotic acid superoxide; Ketone peroxide; The alkyl peroxy esters; Alkyl peroxide (diacetyl peroxide base for example; Dibenzoyl peroxide; Peroxidation is two-the 2,4 dichloro benzene formyl; Di-t-butyl peroxide; Dicumyl peroxide; T-butylperoxyl benzoate; The tert-butyl peroxide cumyl; 2, two (the tert-butyl peroxy bases)-2 of 5-, 5-dimethylhexane; 2, two (the tert-butyl peroxy bases)-2 of 5-, 5-dimethyl hexin-3; 4,4,4 ', 4 '-four (tert-butyl peroxy bases)-2,2-dicyclohexyl propane; 1, two (the tert-butyl peroxy base sec.-propyl) benzene of 4-; 1, two (the tert-butyl peroxy bases)-3,3 of 1-, 5-trimethyl-cyclohexane; Lauroyl peroxide, succinic acid peroxide; Cyclohexanone peroxide; T-butyl peroxy-acetate; Tertbutyl peroxide etc.

Suitable phenol is disclosed in USP4, and in 311,628, the disclosed content of the document is here as with reference to introducing.An example of phenol solidifying agent is halogen fortified phenol or C ₁-C ₁₀Alkyl substituted phenol and the aldehyde condensed products in basic solvent, or the condensed products of difunctional phenol glycol.Wherein a class phenol solidifying agent is by C in contraposition ₅-C ₁₀The hydroxymethyl-phenol that alkyl replaces.Alkylhalide group fortified phenol solidifying agent and comprise that it also is suitable that resol resin, halogen are given the curing system of body and metallic compound.

Appropriate azide comprises triazo acid ester, as butylidene two (triazo acid esters) (also can be referring to USP3,284,421, Breslow, on November 8th, 1966); The many trinitride of aromatics, as 4,4 '-the ditan diazide (also can be referring to USP3,297,674, Breslow, on January 10th, 1967); With sulfuryl azide such as p, p '-oxygen connects two (benzenesulfonyl trinitride).

Many (sulfuryl azides) for have at least two can with the sulfuryl azide group (SO of random interpolymer reaction basically ₂N ₃) any compound.Many (sulfuryl azides) preferably have structure X-R-X, and wherein each X is-SO ₂N ₃R represents not replace or inertia replaces alkyl, hydrocarbyl ether or siliceous group; be enough to the sulfuryl azide group separated so that enough carbon, oxygen or the silicon that between polyolefine and sulfuryl azide, reacts easily preferably having between these functional groups; preferred carbon atom; more preferably have at least one 1, further more preferably at least 2, most preferably at least 3 carbon atoms, Sauerstoffatom or Siliciumatoms, preferred carbon atom.Term " inertia replacement " is meant that the atom of the desired properties that is not disturbed required reaction or gained cross-linked polymer or group replace.Suitable group comprises fluorine, aliphatic series or aromatic oxide, siloxanes and sulfuryl azide group (when needs connect random basically interpolymer chain more than two).Suitable structure comprises that R for example is aryl, alkyl, aralkyl, aralkyl silane or heterocyclic group and inert and other group of on demand the sulfuryl azide group being separated.R more preferably is included at least one aryl between the alkylsulfonyl, most preferably at least two aryl (as R be 4,4 '-diphenyl ether or 4,4 '-during xenyl).When R was an aryl, this group preferably had a plurality of rings, as naphthalene two (sulfuryl azide).Many (alkylsulfonyl) trinitride comprises that compound is as 1; 5-pentane two (sulfuryl azide); 1; 8-octane two (sulfuryl azide); 1; 10-decane two (sulfuryl azide); 1; 10-octadecane two (sulfuryl azide); 1-octyl group-2; 4; 6-benzene three (sulfuryl azide); 4; 4 '-diphenyl ether two (sulfuryl azide); 1; 6-pair (4 '-the alkylsulfonyl azidophenyl) hexane; 2; 7-naphthalene two (sulfuryl azides) and contain the mixing sulfuryl azide of the chloro aliphatic hydrocrbon of average 1 to 8 chlorine atom and 2 to 5 sulfuryl azide group/molecule, and composition thereof.Preferred many (sulfuryl azides) comprise that oxygen connects-two (4-alkylsulfonyl phenylazides), 2; 7-naphthalene two (sulfuryl azide), 4; 4 '-two (alkylsulfonyl azido-) biphenyl, 4,4 '-diphenyl ether two (sulfuryl azide) and two (4-alkylsulfonyl azido-phenyl) methane and its mixture.

Crosslinked for carrying out; use many (sulfuryl azides) of crosslinked amount; promptly compare and make the crosslinked significant quantity of random basically interpolymer with initial random basically interpolymer material; in other words; cause forming abundant (sulfuryl azide) of 10wt% gel (when testing, confirming) at least by insoluble gel in boiling toluene according to ASTMD-2765A-84.The amount of many (sulfuryl azides) is preferably at least 0.5 of random basically interpolymer gross weight, and more preferably at least 1.0,2.0wt% most preferably, these values depend on the molecular weight of trinitride and the molecular weight or the melt index of random interpolymer basically.For avoiding uncontrollable heating and unnecessary cost and/or physicals to reduce, the amount of many (sulfuryl azides) preferably is lower than 10wt%, more preferably less than 5wt%.

Crosslinked for carrying out, with sulfuryl azide and random interpolymer blending basically, and be heated to the decomposition temperature of sulfuryl azide (usually above 100 ℃, usually above 150 ℃) at least.Preferred temperature range depends on the performance of the trinitride of use.For example, for 4,4 '-disulfonyl base azido-diphenyl ether, preferred temperature range is preferably greater than 160 ℃ greater than 150 ℃, more preferably greater than 185 ℃, most preferably greater than 190 ℃.Ceiling temperature preferably is lower than 250 ℃.

Suitable aldehyde-amine reactor product comprises formaldehyde-ammonia; Formaldehyde-monochloroethane-ammonia; Acetaldehyde-ammonia; Formaldehyde-aniline; Butyraldehyde-aniline and enanthaldehyde-aniline.

Suitable replacement urea comprises trimethyl thiourea; Diethyl thiourea; Dibutyl thiourea; Three amyl group thiocarbamides; 1, two (the 2-[4-morpholinodithio base thiopurine methyltransferase) ureas of 3-; And N, the N-diphenyl thiourea.

Suitable replacement guanidine comprises diphenylguanidine; Two-o-tolyl guanidine; The diphenylguanidine phthalic ester; Two-o-tolyl guanidinesalt with two catechol boric acid.

Suitable replacement xanthogenate comprises zinc ethyl xanthate, Good-Rite Nix, butyl xanthic acid disulphide, potassium isopropyl xanthate and zinc butyl xanthate.

Suitable dithiocar-bamate comprises cupric dimethyldithiocarbamate, ziram, diethyldithiocar bamic acid thallium, dicyclohexyl dithiocarbamic acid cadmium, lead dimethyl dithiocarbamate, lead dimethyl dithiocarbamate, selenium dibutyldithiocarbamate, pentylidene zinc dithiocarbamate, didecyl zinc dithiocarbamate and sec.-propyl octyl group zinc dithiocarbamate.

Suitable thiazole comprises 2-mercaptobenzothiazole, thyroidan base mercaptan zinc, 2-[4-morpholinodithio base-N, and N-diethyl thiocarbamoyl sulfide and 2,2 '-two sulphur connect two (benzothiazoles).

Suitable imidazoles comprises 2-mercaptoimidazoline and 2-sulfydryl-4,4,6-trimethylammonium dihydro-pyrimidin.

Suitable sulfinyl amine comprises the N-tertiary butyl-2-[4-morpholinodithio sulfinyl amine, N-cyclohexyl benzo thiazole sulfinyl amine, N, N-di-isopropyl benzo thiazole sulfinyl amine, N-(2, the 6-thebaine)-and 2-[4-morpholinodithio sulfinyl amine and N, N-diethyl benzo thiazole sulfinyl amine.

Suitable thiuram disulphide comprises N, N '-diethyl thiuram disulphide, tetrabutyl thiuram disulphide, N, N '-di-isopropyl dioctyl thiuram disulphide, tetramethyl thiuram disulfide, N, N '-dicyclohexyl thiuram disulphide and N, N '-four lauryl thiuram disulphide.

Those skilled in the art can choose the amount of linking agent, and this amount is according to random interpolymer basically or comprise that characteristic of the blend of random interpolymer such as molecular weight, molecular weight distribution, co-monomer content, the crosslinked reinforcing aids of existence, additive (as oil) are chosen basically for these.Owing to may make random basically interpolymer and other polymer blending before crosslinked, so those skilled in the art can use following rule as a reference when optimization is preferred for the amount of linking agent of above-mentioned specific blends.

For example, the superoxide dicumyl is crosslinked for using, and when random interpolymer had this feature of vinylbenzene that is lower than 35wt% basically, the consumption of dicumyl peroxide was generally 0.1wt% at least by the gross weight of polymkeric substance and superoxide, preferred 1wt% at least, more preferably 2wt% at least.

In addition, for crosslinked with dicumyl peroxide, when random interpolymer had this feature of vinylbenzene of at least 35 to 60wt% basically, the consumption of dicumyl peroxide was generally 0.3wt% at least by the gross weight of polymkeric substance and superoxide, preferred 3wt% at least, more preferably 4wt% at least.

In addition, for crosslinked with dicumyl peroxide, when random interpolymer basically had this feature of vinylbenzene greater than 60wt%, the consumption of dicumyl peroxide was generally 1wt% at least by the gross weight of polymkeric substance and superoxide, preferred 6wt% at least, more preferably 9wt% at least.

Usually, the amount of the linking agent of use is no more than the crosslinked required amount of carrying out appropriate level.For example, the amount of dicumyl peroxide is not more than the 15wt% of polymkeric substance and superoxide gross weight, preferably is no more than 12wt%.

In addition, can use silane crosslinker.In the case, can grafting on also effectively, any silane of crosslinked random copolymer basically can be used for implementing the present invention.Suitable silane comprises unsaturated silane, these silane contain ethylenically unsaturated hydrocarbons base such as vinyl, allyl group, pseudoallyl, butenyl, cyclohexenyl or γ-(methyl) acryloxy allyl group and hydrolyzable group such as-oxyl, alkylacyloxy or hydrocarbon amino.The example of hydrolysable group comprises methoxyl group, oxyethyl group, methanoyl, acetoxyl group, propionyloxy and alkylamino or virtue amino.Preferred silane is for being grafted to the unsaturated alkoxyl group on the polymkeric substance.These silane and its preparation method fully are described in the USP5 that authorizes people such as Meverden, in 266,627.The mixture of vinyltrimethoxy silane, vinyltriethoxysilane, γ-(methyl) propionyloxy propyl trimethoxy silicane and these silane is to be used for preferred silane linking agent of the present invention.

The amount that is used to implement silane crosslinker of the present invention can change in wide range, depends on the silane, processing conditions, the amount of grafting initiator, final purposes and similar factor of performance, the use of random interpolymer basically.Usually, when using vinyltrimethoxy silane (VTMOS) crosslinked, the consumption of VTMOS is generally 0.1wt% at least by the gross weight of polymkeric substance and silane, preferred 1wt% at least, more preferably 3wt% at least.

Convenience and economic consideration are normally to two major limitation of the maximum consumption that is used to implement silane crosslinker of the present invention.For example, when using VTMOS, the maximum of the VTMOS of use is no more than the 10wt% of polymkeric substance and silane gross weight usually, more preferably no more than 8wt%, is most preferably not exceeding 6wt%.

Silane crosslinker usually in the presence of free-radical initiator such as superoxide and azo-compound by any ordinary method, or by ionizing radiation etc. and random interpolymer grafting basically.Preferably have organic initiators, as arbitrary peroxide initiator, for example superoxide dicumyl, di-t-butyl peroxide, t-butylperoxyl benzoate, benzoyl peroxide, hydroperoxide cumene, cross the sad tert-butyl ester, methylethyl ketone peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxy base) hexane, lauroyl peroxide and t-butyl peroxy-acetate.Suitable azo compound is a Diisopropyl azodicarboxylate.

Those skilled in the art choose the amount of the initiator of use easily, and this amount is chosen according to the crosslinked reinforcing aids of the characteristic of random interpolymer basically such as molecular weight, molecular weight distribution, co-monomer content, existence, additive (as oil) etc.

The amount of initiator depends on the vinyl that exists in the random basically interpolymer or the % of vinylidene aromatic or hindered aliphatic or cyclic aliphatic comonomer.For example, VTMOS is crosslinked for using, and when random interpolymer had this feature of vinylbenzene that is lower than 35wt% basically, the consumption of dicumyl peroxide was generally 250ppm at least by the gross weight of polymkeric substance, silane and initiator, preferred 500ppm at least, more preferably 1500ppm at least.

In addition, for crosslinked, when random interpolymer has this feature of vinylbenzene of at least 35 to 60wt% basically with VTMOS, the consumption of dicumyl peroxide is generally 400ppm at least by the gross weight of polymkeric substance, silane and initiator, preferably at least 1,000ppm, more preferably 2000ppm at least.

In addition, for crosslinked, when random interpolymer basically has this feature of vinylbenzene greater than 60wt% with VTMOS, the consumption of dicumyl peroxide is generally 500ppm at least by the gross weight of polymkeric substance, silane and initiator, preferably at least 1,500ppm, more preferably 3000ppm at least.

Usually, the amount of the initiator of use is no more than and carries out the required amount of effective grafting.For example, the amount of dicumyl peroxide is not more than 20 of polymkeric substance, silane and initiator gross weight usually, and 000ppm preferably is not more than 10,000ppm.

Although any ordinary method can be used for silane crosslinker is grafted on the random basically interpolymer, a kind of preferable methods is that at reactor forcing machine (as the Buss kneader) first section is with this two component and initiator blend.The grafting condition can change, but melt temperature is generally 160 ℃ to 260 ℃, preferred 190 ℃ to 230 ℃, depends on transformation period of the residence time and initiator.

Promote to solidify with crosslinking catalyst.The present invention can use any catalyzer that this function is provided.These catalyzer generally include organic bases, carboxylic acid and organometallic compound, comprise organic titanate and the title complex or the carboxylate salt of lead, cobalt, iron, nickel, zinc and tin.Dibutyl tin laurate, dioctyl tin maleate, dibutyltin diacetate, two sad dibutyl tins, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, cobalt naphthenate.Carboxylic acid tin, especially dibutyl tin laurate and dioctyl tin maleate are particularly preferred among the present invention.The amount of catalyzer (or catalyst mixture) is a catalytic amount, be generally polymkeric substance, silane, initiator and total catalyst weight 0.015 to 0.035wt%

Except using chemical cross-linking agent, crosslinked can being undertaken by using radiation.The available emission types comprises electron beam or β ray, gamma-rays, X-ray or neutron ray.It is believed that radiation by generate can in conjunction with and crosslinked free polymer readical carry out crosslinked.Other instruction that relates to radiation crosslinking is referring to " foam of polymers and technical manual " the 9th chapter " expanded polyolefin " (C.P.Park, " Polyolefin Foam ", Chapter 9, Handbook of Polymer Foams and Technology, D.Klempner and K.C.Frisch edit, Hanser press, New York (1991)), this chapters and sections content is incorporated this paper in this application as a reference into.

Radiation dose depends on the composition of random interpolymer basically.Generally speaking, along with vinyl or vinylidene aromatic or hindered aliphatic or the rising of the cyclic aliphatic copolymerization scale of construction, need bigger dosage to obtain required crosslinking degree, promptly cause said composition to show at least 10% gel, preferably at least 20% gel, more preferably at least 30% gel.Those skilled in the art are according to thickness and the structure of various variablees as wanting the radiating goods, and crosslinked reinforcing aids of the feature of random interpolymer such as molecular weight, molecular weight distribution, co-monomer content, existence basically, additive (as oil) etc., can choose radiation dose easily suitably.

For example, for by the thick plate of crosslinking electron beam irradiation 80mil, when random interpolymer had this feature of the 35wt% of being lower than vinylbenzene basically, typical radiation dose was preferably greater than 10Mrad, more preferably greater than 15Mrad greater than 5Mrad.Doses of electron beam radiation is used radiation unit " rad (RAD) " expression here, and wherein 1,000,000 rads are called " Mrad ".

In addition, for by the thick plate of crosslinking electron beam irradiation 80mil, when random interpolymer had 35 to 60wt% these features of vinylbenzene basically, typical radiation dose was preferably greater than 15Mrad, more preferably greater than 20Mrad greater than 5Mrad.

In addition, for by the thick plate of crosslinking electron beam irradiation 80mil, when random interpolymer had greater than this feature of 60wt% vinylbenzene basically, typical radiation dose was preferably greater than 15Mrad, more preferably greater than 20Mrad greater than 10Mrad.

Usually, this dosage is no more than the amount that causes suitable crosslinking degree required.For example, the common dosage that does not adopt greater than 80Mrad.

For the random basically interpolymer that does not comprise non-essential diolefine component, superoxide or trinitride curing system are preferred; (＞50wt%) interpolymer, the trinitride curing system is preferred for having high-phenylethylene content.For the random basically interpolymer that comprises non-essential diolefine component, sulfenyl (as sulfur-bearing, dithiocar-bamate, thiazole, imidazoles, sulfinyl amine, thiuram disulphide or its mixture) and phenol curing system are preferred.

In some preferred embodiment of the present invention, can effectively use dual cure systems (using heat, moisture-curable and irradiation step to combine).Open and claimed dual cure systems in U.S. Patent application serial number 536,022 (September 29 nineteen ninety-five applying date, applicant K.L.Walton and S.V.Karande), the document is introduced as reference here.For example, peroxide cross-linking agent can be used in combination or the like with silane crosslinker with the linking agent of radiation, sulfur-bearing with silane crosslinker, peroxide cross-linking agent.The preparation blend polymer

Being adapted at the present invention is aliphatic alpha-olefin homopolymer or interpolymer as the olefin polymer of component (B1, B2 and B3), or one or more aliphatics alpha-olefins and one or more non-aromatic monomer such as the C of copolymerization with it _2-20Alpha-olefin or contain 2 to 20 carbon atoms and contain polar group the interpolymer of those aliphatics alpha-olefins.The aliphatics 'alpha '-olefin monomers that is suitable for of introducing polar group in polymkeric substance for example comprises: olefinically unsaturated nitriles, as vinyl cyanide, methacrylonitrile, ethyl acrylonitrile etc., the ethylenic unsaturated acid acid anhydride is as maleic anhydride, the olefinic unsaturated amides is as acrylamide, Methacrylamide etc.; Ethylenically unsaturated carboxylic acids (single acid and diacid) is as vinylformic acid and methacrylic acid etc.; (lower member ester particularly is as C for the ester of ethylenically unsaturated carboxylic acids ₁-C ₆Alkyl ester), as the positive butyl ester of methyl methacrylate, ethyl propenoate, Hydroxyethyl acrylate, acrylic or methacrylic acid, 2-EHA etc.; Olefinic unsaturated ethylene enol such as ethylene-vinyl alcohol (EVOH); The imide of the unsaturated diacid of olefinic is as N-alkyl or N-aryl maleimide (as N-phenylmaleimide) etc.This kind monomer that contains polar group is preferably vinylformic acid, vinyl acetate, maleic anhydride and vinyl cyanide.Can comprise fluorine, chlorine and bromine by the halogen that the aliphatics 'alpha '-olefin monomers is introduced in the polymkeric substance, this kind polymkeric substance is preferably chlorinatedpolyethylene (CPEs).Be used for preferred olefin polymer of the present invention and be containing the homopolymer or the interpolymer of 'alpha '-olefin monomers of the aliphatics (comprising cyclic aliphatic) of 2 to 18 carbon atoms.The example that is suitable for has the homopolymer of ethene or propylene and the interpolymer of two or more alpha-olefin.Other preferred olefin polymer is that ethene contains the interpolymer of other alpha-olefin of 3 to 8 carbon atoms with one or more.Preferred comonomer comprises 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.Olefin polymer blend components (B) also can contain one or more the non-aromatic monomers of copolymerization with it except that alpha-olefin.This other copolymerizable monomer for example comprises C ₄-C ₂₀Diene, preferred divinyl or 5-ethylidene-2-norbornene.Olefin polymer further can also be different with the distribution characteristics that how much reaches them of their long or short branched chains.

A kind of olefin polymer can adopt radical initiator to pass through high-pressure polymerization process to prepare, and what obtain is the new LDPE (film grade) (LDPE) of traditional long chain branching.Usually less than 0.94 gram/cubic centimetre (ASTM D 792), melt index is 0.01 to 100 to the density of the LDPE that is adopted in the present composition, is preferably 0.1 to 50 gram/10 minutes (according to ASTM D1238, the standard method of test of condition I is measured).

Another kind is to adopt the Ziegler polymerization technique (U.S. Patent No. 4 of invention such as Anderson for example, 076,698) Zhi Bei the polymer of linear olefin that does not contain long chain branching, be called as linear, low density polyethylene polymerization thing (heterogeneous LLDPE) or line style high density polyethylene polyethylene polymers (HDPE) traditionally, be called as multiphase polymer sometimes.

HDPE mainly is made of the polyethylene long-chain of line style.The density of the HDPE that is adopted in the present composition is generally at least 0.94 gram/cubic centimetre (g/cc, standard method of test according to ASTM D 792 is measured), melt index is 0.01 to 100, is preferably/10 minutes (ASTM D-1238, condition I) of 0.1 to 50 gram.

The density of the heterogeneous LLDPE that is adopted in the present composition is generally 0.85 to 0.94 gram/cubic centimetre (ASTM D 792), and melt index is 0.01 to 100, is preferably/10 minutes (ASTM D 1238, condition I) of 0.1 to 50 gram.Preferred LLDPE is that ethene contains the interpolymer of other alpha-olefin of 3 to 18 carbon atoms, preferred 3-8 carbon atom with one or more.Preferred comonomer comprises 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.

Also have a kind of polymkeric substance be even branching or the homogeneous polymkeric substance.Homogeneous polymer does not contain long branched chain, and its branched chain only derives from monomeric polymerization (if containing the monomeric words that surpass two carbon atoms).The homogenous linear ethylene polymkeric substance comprises according to US 3,645, those polymkeric substance of the described method preparation of 992 (Elston), with according to US 5,026,798 and 5,055,438 (Canich) described method adopts those polymkeric substance of so-called single-point catalyst preparation in batch reactor and under the higher concentration of olefin.Evenly branching/homogeneous phase linear polymer is meant wherein the comonomer random distribution in given interpolymer molecule, and those polymkeric substance that interpolymer molecule has similar ethene/comonomer ratio in this kind interpolymer.

The density of the homogenous linear ethylene polymkeric substance that is adopted in the present composition is generally 0.85 to 0.94 gram/cubic centimetre (ASTM D 792), and melt index is 0.01 to 100, is preferably/10 minutes (ASTM D 1238, condition I) of 0.1 to 50 gram.Preferred homogenous linear ethylene polymkeric substance is that ethene contains the interpolymer of other alpha-olefin of 3 to 18 carbon atoms, preferred 3-8 carbon atom with one or more.Preferred comonomer comprises 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.

Further, the component (B) that a kind of olefin polymer (SLOP) that is essentially line style is used as blend of the present invention is favourable.These polymkeric substance have the processing characteristics similar to LDPE, but have intensity and the toughness of LLDPE simultaneously.Similar to traditional homogeneous polymer, the interpolymer that is essentially the ethylene/alpha-olefin of line style has only a single melting peak, different with the resulting heterogeneous linear ethylene/alpha-olefin interpolymer of traditional Ziegler polyreaction, the latter has two or more melting peaks (measuring with differential scanning calorimetry).The olefin polymer that is essentially line style is at US5, open report arranged in 272,236 and 5,278,272, and these patents are incorporated herein as a reference.

The density of SLOP is generally 0.85 to 0.97 gram/cubic centimetre, is preferably 0.85 to 0.955 gram/cubic centimetre, particularly 0.85 to 0.92 gram/cubic centimetre (measuring according to ASTM D 792 standard method of test).

The melt index of SLOP be 0.01 the gram/10 minutes to 1000 the gram/10 minutes, be preferably 0.01 the gram/10 minutes to 100 the gram/10 minutes, particularly 0.1 gram/10 minutes to 10 grams (according to ASTM D 1238, (also were called condition I in/10 minutes under 190 ℃/2.16 kilograms condition ₂) standard method of test measure).

In addition, also comprise M.L.Finlayson, C.C.Garrison, R.E.Guerra, M.J.Guest, B.W.S.Kolthammer, ultra-low molecular amount ethene polymers and the ethylene/alpha-olefin interpolymer of denomination of invention that D.R.Parikin and S.M.Ueligger submitted on January 22nd, 1996 for describing in the temporary patent application of " ultra-low molecular weight polymers ", this paper is incorporated in this patent application as a reference into.The I that these ethylene/alpha-olefin interpolymers have ₂Melt index restrains/10 minutes greater than 1000, or number-average molecular weight (Mn) is less than 11000.

SLOP can be C ₂-C ₂₀Alkene is the homopolymer of ethene, propylene, 4-methyl isophthalic acid amylene etc. for example, maybe can be ethene and at least a C ₃-C ₂₀Alpha-olefin and/or C ₂-C ₂₀Acetylene series unsaturated monomer and/or C ₄-C ₁₈The interpolymer of diolefine.SLOP also can be ethene and at least a above-mentioned C ₃-C ₂₀The interpolymer of alpha-olefin, diolefine and/or acetylene series unsaturated monomer and other unsaturated monomer.

The particularly preferred olefin polymer that is suitable for use as component (B) comprises LDPE, HDPE, heterogeneous LLDPE, homogenous linear ethylene polymkeric substance, SLOP, polypropylene (PP), especially isotactic polyprophlene and rubber toughened polypropylene, or ethylene-propylene copolymer body (EP), or chlorinatedpolyolefins (CPE), or ethylene-vinyl acetate copolymer (EVA), or ethylene-acrylic acid copolymer (EAA), or their mixture.

Term " segmented copolymer " is used to represent to have the elastomerics of unitary block segments of at least one hard polymer and the unitary block segments of at least one rubber monomer here.Yet this term does not comprise the thermoelastic ethylene interpolymer that is generally unregulated polymer.Preferred segmented copolymer contains the hard segment and the saturated or unsaturated rubber monomer segment of styrenic polymer.The structure that is used for segmented copolymer of the present invention is unimportant, can be linear or radial diblock or three blocks, or its arbitrary combination.Preferred primary structure is three blocks, more preferably linear three blocks.

Here the preparation method of the block interpolymers of Shi Yonging is not a theme of the present invention.The preparation method of these segmented copolymers is known in the art.Be used to prepare the suitable catalyst that available has the segmented copolymer of unsaturated rubber monomeric unit and comprise that lithium is catalyst based, particularly lithium alkylide.US3,595,942 have described hydrogenation has the method for the segmented copolymer of unsaturated rubber monomeric unit, has the segmented copolymer of saturated rubber monomer units with formation.The structure of these polymkeric substance is determined by its polymerization process.For example, such as lithium alkylide or dithio stilbene required rubber monomer is added in the reactor in proper order by adopting, or by two multipolymer segment blocks are obtained linear polymer with the coupling of difunctionality coupling agent.On the other hand, branched structure can obtain by the suitable coupling agent that use has corresponding to the functional group of the segmented copolymer that contains three or more unsaturated rubber monomeric unit.Coupling can be carried out with the ester of multifunctional coupling agent such as dihalo alkane or alkene and Vinylstyrene and some polar compound such as silicon halide, siloxanes or monohydroxy-alcohol and carboxylic acid.The various coupling residues that exist in the polymkeric substance can be ignored for the segmented copolymer that abundant description forms a present composition part.

Suitable block copolymers with unsaturated rubber monomeric unit include but not limited to styrene butadiene (SB), styrene-isoprene (SI), styrene-butadiene-styrene (SBS), styrene-isoprene-phenylethene (SIS), vinyl toluene-divinyl-vinyl toluene and-vinyl toluene-isoprene-vinyl toluene.

The vinylbenzene of segmented copolymer partly is preferably the polymkeric substance or the interpolymer of vinylbenzene and analogue and its homologue (vinylbenzene that comprises alpha-methyl styrene and ring substituted phenylethylene, particularly ring-methylated).Preferred styrene monomer is vinylbenzene and vinyl toluene, and vinylbenzene is particularly preferred.

Block interpolymers with unsaturated rubber monomeric unit comprises in the homopolymer of divinyl or isoprene and these monomers one or both and the monomeric multipolymer of small amounts of styrene class.When the monomer that uses during as divinyl, 35 to 55mol% condensed butadiene unit in the butadiene polymer block has 1, and the 2-configuration is preferred.Therefore, when a block is hydrogenated, products obtained therefrom for or be similar to the regular copolymer block (EB) of ethene and 1-butylene.If the conjugated diene that uses is during as isoprene, gained hydrogenation product is or is similar to the regular copolymer block (EP) of ethene and propylene.Preferred block copolymer with saturated rubber monomer units comprises at least one styrene units segment and at least one ethene-butylene or ethylene-propylene copolymer segment.These preferred example with segmented copolymer of saturated rubber monomer units comprise styrene/ethylene-butylene copolymer, styrene/ethylene-propylene copolymer, styrene/ethylene-butylene/styrene (SEBS) multipolymer and styrene/ethylene-propylene/styrene (SEPS) multipolymer.

Hydrogenation has the segmented copolymer of unsaturated rubber monomeric unit, the reactor product that preferably comprises alkyl aluminum compound and nickel or cobalt carboxylate salt or alkoxide by use is such as fully hydrogenation at least 80% aliphatic double bond, hydrogenation simultaneously are no more than under the condition of 25% two keys of styrenic aromatics and carry out basically.Preferred segmented copolymer is that wherein at least 99% aliphatic double bond is hydrogenated and is lower than those polymkeric substance that 5% two keys of aromatics are hydrogenated simultaneously.

The ratio of styrene block be generally the segmented copolymer gross weight 8 to 65wt%.This segmented copolymer preferably contains the rubber monomer block segments (by the gross weight of segmented copolymer) of 10 to 35wt% styrenic block segments and 90 to 65wt%.

The molecular-weight average of each block can change within the specific limits.Under many circumstances, the styrenic block segment has number-average molecular weight 5,000 to 125,000, and is preferred 7,000 to 60,000, and the rubber monomer block segments has number-average molecular weight 10,000 to 300,000, and preferred 30,000 to 150,000.Total number-average molecular weight of segmented copolymer is generally 25,000 to 250,000, and preferred 35,000 to 200,000.These molecular weight are very accurately measured by deuterium method of counting or osmolarity measuring value.

In addition, be applicable to that various segmented copolymer of the present invention can be by going into a small amount of functional group with any method grafting well known in the art, as with maleic anhydride modified.

Be used for segmented copolymer of the present invention can trade(brand)name KRATON available from shell chemical company and with trade(brand)name VECTOR available from Dexco Polymer Company.

In addition, can use the blend of random basically interpolymer and polyvinyl chloride (PVC) or ethylene-vinyl alcohol (EVOH) suitably.The preparation Thermoplastic Vulcanizate

Thermoset composition of the present invention can be introduced and form Thermoplastic Vulcanizate in the polyolefine.The ratio of the component of using can be carried out some variation according to the special polyolefins that adopts, required purposes and crosslinked random basically interpolymer and the characteristics of furnish component.Usually, the amount along with crosslinked random interpolymer basically increases the stiffness reduction of gained Thermoplastic Vulcanizate.Thermoplastic Vulcanizate of the present invention generally includes 10 to 90wt% polyolefine and 10 to 90wt% crosslinked random basically interpolymer.

Suitable polyolefine comprises thermoplasticity, the crystalline polymer weight polymers by one or more monoolefine preparations of polymerization.Suitable polyolefinic example comprises ethene and isotaxy and syndiotactic polymer resin, the example of described monoolefine such as propylene, 1-butylene, 1-amylene, 1-hexene, 2-methyl isophthalic acid-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene and its mixture.Thermoplastic Vulcanizate of the present invention most preferably uses isotactic polyprophlene as polyolefin component.

Thermoplastic Vulcanizate of the present invention is preferably by the dynamic vulcanization preparation, and wherein the mixture with uncrosslinked random interpolymer basically mixes formation blend, mastication under curing temperature then with polyolefin resin and proper curing agents.Particularly, noncrosslinking random basically interpolymer and polyolefine are higher than blending under the polyolefine fusing point in temperature.Will be basically behind random interpolymer and the polyolefine thorough mixing, add proper curing agents, as above-mentioned corresponding to compounding and curing those solidifying agent of random interpolymer basically.Then with this blend with conventional mastication device such as Banbury mixer, Bradley Bender mixing roll or mix the forcing machine mastication.The temperature of blend should be enough to the random basically interpolymer of efficient vulcanization during mastication.Suitable sulfurizing temperature range for from polyolefine temperature of fusion (for polyethylene is 120 ℃, is 175 ℃ for polypropylene) to random interpolymer basically, the temperature of polyolefine or solidifying agent degraded.Typical temperature is 180 ℃ to 250 ℃, preferred 180 ℃ to 200 ℃.

Other method except that random interpolymer/polyolefine dynamic vulcanization method basically also is suitable.For example, random basically interpolymer is crosslinked before can be in adding polyolefine.Can be higher than under polyolefinic fusing or the softening temperature in temperature with crosslinked random basically interpolymer efflorescence and with polyolefine and mix.If crosslinked random basically interpolymer particles is very little, fully disperse and have suitable concentration (even realizing crosslinked random basically interpolymer and polyolefinic mixture), then can obtain Thermoplastic Vulcanizate of the present invention easily.If can not obtain well-mixed mixture like this, then products obtained therefrom can contain observable crosslinked random basically interpolymer island.In the case, can be with this part pulverizing or cold grinding so that particle size reduce to below the 50 μ m.Under suitable pulverizing, these particles can be molded as again the parts of strengthening the property that present more even composition and present Thermoplastic Vulcanizate of the present invention.

Thermoplastic Vulcanizate of the present invention can comprise various additives such as carbon black, silicon-dioxide, titanium dioxide, tinting pigment, clay, zinc oxide, stearic acid, promotor, vulcanizing agent, sulphur, stablizer, anti degradant, processing aid, tackiness agent, tackifier, softening agent, paraffin, scorching inhibitor, discontinuous fibre (as lignocellulose fiber) and extending oil.These additives can before the sulfuration, during or add afterwards.The preparation foam:

Foamy structure of the present invention can adopt physical aspect arbitrarily known in the art, for example thin slice, sheet, injection-molded item or block.Other useful form has foamable particle, mouldable foam beads, or pearl, and the goods of being made by those particulate foaming and/or coalescent or welding.

C.P.Park has fabulous description for method for preparing the vinyl polymer foamy structure and working method thereof, referring to " foam of polymers and technical manual " the 9th chapter " expanded polyolefin " (C.P.Park, " Polyolefin Foam ", Chapter 9, Handbook of PolymerFoams and Technology, D.Klempner and K.C.Frisch edit, Hanser press, Munich, vienna, New York, Barcelona (1991)), this chapters and sections content is incorporated this paper as a reference into.

Foamy structure of the present invention can prepare by the following method: foamable plastifying or melt polymer material are made in the polymer materials heating that will comprise at least a random basically interpolymer and decomposable chemical foaming agent, extrude foamable melt polymers material through die head, induced cross-linking in the melt polymers material, and the polymer materials that will melt is exposed under the high temperature to discharge whipping agent and forms foamy structure thus.Polymer materials and whipping agent can be by any way well known in the art as adopting forcing machine, mixing machine or blender and mix and melt mixed.Chemical foaming agent preferably mixed with polymer materials is dried before heated polymerizable thing material is melt form, also can be the melt phase time at polymer materials and add.Can be by adding linking agent or radiation-initiated crosslinking.Induced cross-linking foams under the high temperature and can carry out simultaneously or sequentially with being exposed to.If use linking agent, then add in the polymer materials by the mode identical with chemical foaming agent.In addition, if use linking agent,, thereby prevent crosslinked too early then with foamable melt polymers material heating or be exposed under the temperature that preferably is lower than 150 ℃ preventing that linking agent or whipping agent from decomposing.If use radiation crosslinking, the melt polymers material that then can foam is heated to or is exposed under the temperature that preferably is lower than 160 ℃ to prevent that whipping agent from decomposing.Foamable melt polymers material is extruded by a die head with desired shape or transmits to form foamable structure.Then should foamable structure crosslinked and under high temperature (being generally 150 ℃-250), in such as baking oven, form foamy structure.As use radiation crosslinking, then with foamable structure radiation so that polymer materials is crosslinked, under above-mentioned high temperature, foam then.Foamy structure of the present invention can use linking agent or radiation advantageously to make sheet material or sheet form according to aforesaid method.

Foamy structure of the present invention also can be used as GB2 by extrusion method, and 145, the long profiled section die head of describing among the 961A is made continuous thick plate structure.In the method, polymkeric substance, decomposable whipping agent and linking agent mixed in forcing machine, this mixture heating up made crosslinked polymer and whipping agent is decomposed in long profiled section die head; Through the die head moulding and draw off from die head, described die head is lubricated contact with the proper lubrication material.

Foamy structure of the present invention also can be shaped to the crosslinked foams bead that is suitable for being molded as goods.In order to prepare this foam beads, discrete resin particle for example is suspended in them through the resin beads of granulation is insoluble to wherein liquid medium basically for example in the water, in autoclave or other pressure vessel under higher pressure and temperature with linking agent and whipping agent dipping, and fast resin particle is discharged in air or the low pressure area and makes foam beads to foam.Another kind method is that polymer beads is flooded, cools off, takes out from container, foams by heating or with steam then with whipping agent.Whipping agent can be immersed in the resin beads in suspension or under non-water state.Foamable bead is passed through with the steam heating foaming then, and by being used for the conventional molding methods moulding of expandable polystyrene (EPS) foam beads.

Foam beads can adopt any method known in the art to carry out molding subsequently, for example foam beads is put into mould, mould is exerted pressure with the die casting bead, and the mode that adopts water vapor for example with the bead heating so that bead is bonding and bonding mutually, thereby the formation goods.Optionally, bead can carry out preheating with air or other whipping agent before putting into mould.The fabulous instruction of aforesaid method and molding methods is referring to C.P.Park, quote from the same, the 227-229 page or leaf, US3 is in 886,100, US3,959,189, US4,168,353 and US4,429,059.This foam beads also can prepare by the following method: but in suitable mixing equipment or forcing machine, prepare the mixture of polymkeric substance, linking agent and decomposition of the mixture, and be bead with this mixture forming, then with this bead heat cross-linking and foaming.

Be fit to be molded as in the method for crosslinked foams bead of goods in another preparation, this random basically interpolymer material is melted in conventional foam extrusion device and and physical foaming agent and mixing, form successive foam yarn material basically thus.This foam yarn material granulation is formed foam beads.Then with this foam beads radiation crosslinking, make subsequently this crosslinked foam beads according to the above-mentioned method bonding that is used for other foam beads and molding with the formation goods.The further instruction of this method can be referring to US3,616,365 and C.P.Park, quote from the same, the 224-228 page or leaf.

Foamy structure of the present invention can be made foam bulk blank form by two kinds of different methods.A kind of method relates to uses linking agent or radiation.

Foam of the present invention can be made foam bulk blank by the following method, basically random interpolymer material, linking agent and chemical foaming agent mix the formation foam block, this mixture of heating in mould, linking agent can make the crosslinked and whipping agent of polymer materials decompose like this, then by the foaming of relief pressure in mould.Optionally, can heat once more with further foaming through the bulk blank that relief pressure forms.

The cross-linked polymer sheet material can be by with high energy beam radio polymerization thing sheet material or contain the polymer sheet preparation of chemical cross-linking agent by heating.This cross-linked polymer sheet material is cut into required shape and under temperature is higher than the softening temperature of polymkeric substance, is flooding under the elevated pressures with nitrogen; Relief pressure is so that abscess coring and generation foaming to a certain degree in sheet material.This sheet material is being higher than heating once more under the fusing point under the lower pressure, relief pressure makes foam expansion then.

The whipping agent that is used to prepare foamy structure of the present invention comprises decomposable chemical foaming agent.Some chemical foaming agent at high temperature is decomposed to form gas or steam, makes polymer foaming form form of foam thus.This reagent is preferably solid form, so that do mixed with polymer materials.Chemical foaming agent comprises azodicarboamide, Diisopropyl azodicarboxylate, benzol sulfohydrazide, 4,4-oxybenzene sulphonyl semicarbazides, tolysulfonyl semicarbazides, azoformic acid barium, N, N '-dimethyl-N, N '-dinitrosoterephthalamine, N, N '-dinitrosopentamethylene tetramine, 4,4-oxygen connect two (benzol sulfohydrazide) and three hydrazine triazines.Azodicarboamide is preferred.To the further instruction of chemical foaming agent referring to C.P.Park, quote from the same, the 205-208 page or leaf, and F.A.Shutov, " expanded polyolefin ", " foam of polymers and technical manual " (" Polyolefin Foam ", Handbookof Polymer Foams and Technology) 382-402 page or leaf, D.Klempner and K.C.Frisch edit, Hanser press, Munich, vienna, New York, Barcelona (1991).

Chemical foaming agent to be enough to discharging 0.2 to 5.0, is preferably the amount and the mixed with polymers of 0.5 to 3.0, most preferably 1.0 to 2.50mol gases or steam/kg polymkeric substance.

In some method of preparation foamy structure of the present invention, can use pneumatogen.Pneumatogen comprises organic and inorganic foaming agent.The inorganic foaming agent that is suitable for comprises carbonic acid gas, nitrogen, argon gas, water, air, nitrogen and helium.Organic blowing agent comprises the aliphatic hydrocarbon that contains 1 to 9 carbon atom, contains the Fatty Alcohol(C12-C14 and C12-C18) of 1 to 3 carbon atom and contains 1 to 4 complete and partially halogenated aliphatic hydrocarbon of carbon atom.Aliphatic hydrocarbon comprises methane, ethane, propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane and neopentane.Fatty Alcohol(C12-C14 and C12-C18) comprises methyl alcohol, ethanol, n-propyl alcohol and Virahol.Complete and partially halogenated aliphatic hydrocarbon comprises hydrofluoric ether, hydrochloric ether and Chlorofluorocarbons (CFCs).The example of hydrofluoric ether comprises fluoromethane, perfluoromethane, fluoroethane, 1,1-C2H4F2 C2H4F2 (HFC-152a), 1,1,1-Halothane (HFC-143a), 1,1,1,2-Tetrafluoroethane (HFC-134a), pentafluoride ethane, methylene fluoride, R 116,2,2-difluoropropane, 1,1,1-trifluoro propane, perfluoropropane, propylene dichloride, difluoropropane, perfluorinated butane, perfluorocyclobutane.Partially halogenated hydrochloric ether and Chlorofluorocarbons (CFCs) that the present invention adopts comprise methyl chloride, methylene dichloride, monochloroethane, 1,1,1-trichloroethane, 1,1-two chloro-1-fluoroethanes (HCFC-141b), 1-chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b), 1,1-two chloro-2,2,2-Halothane (HCFC-123) and 1-chloro-1,2,2,2-Tetrafluoroethane (HCFC-124).Complete halogenated Chlorofluorocarbons (CFCs) comprises Trichloromonofluoromethane (CFC-11), Refrigerant 12 (CFC-12), Refrigerant R 113 (CFC-113), 1,1,1-Halothane, pentafluoride ethane, dichloro tetrafluoro ethane (CFC-114), a chlorine heptafluoro-propane and a dichlorohexafluoropr.pane.

For preparation forms the foamy polymer gel, the amount of the whipping agent that adds in every kg of polymer melting material is 0.2 to 5.0, is preferably 0.5 to 3.0, most preferably 1.0 to 2.50mol.

Various additives can add in the foamy structure of the present invention, and the example of these additives is stability control agent, nucleator, mineral filler, pigment, oxidation inhibitor, acid scavenger, UV light absorber, fire retardant, processing aid and extrusion aid.

Can add stability control agent in the foam of the present invention to improve dimensional stability.Preferred stability control agent comprises C _10-24The acid amides of lipid acid and ester.This analog assistant can be referring to US3, and 644,230 and 4,214,054, these patents are incorporated herein as a reference.Most preferred auxiliary agent comprises octadecyl stearylamide, glyceryl monostearate, single behenic acid glyceryl ester and monooctadecyl acid sorbitol ester.The amount ranges of this type of stability control agent is generally per 100 parts of polymkeric substance with 0.1 to 10 part.

In addition, the size for the control foam abscess can add nucleator.Preferred nucleator comprises the mixture of inorganic substance such as lime carbonate, talcum, clay, titanium dioxide, silicon-dioxide, barium sulfate, diatomite, citric acid and sodium bicarbonate.The consumption of nucleator is per 100 parts by weight polymer, 0.01 to 5 weight part.

The density of foamy structure is less than 250, preferably less than 100, most preferably 10 to 70 kilograms per cubic meter.The mean sizes of foam abscess is 0.05 to 5.0, preferred 0.2 to 2.0, most preferably 0.3 to 1.8 millimeter (measuring) according to ASTM D3576.

Foamy structure can have any physical form known in the art, for example the sheet of extrusion moulding, bar-shaped, tabular and section bar.Foamy structure also can be shaped to above-mentioned arbitrarily shape or other Any shape by foamable bead being carried out molding.

Foamy structure can be open cell type or obturator-type according to ASTM D2856-A.

In one embodiment of the invention, composition of the present invention can be used for cable insulation and/or cable jacket.Cable insulation material of the present invention can be filling or unfilled.If fill, then the amount of filler of Cun Zaiing should be no more than the amount that causes interpolymer electricity and/or mechanical property to reduce.Usually, the amount of filler of existence is 20 to 80, preferred 50 to 70wt% (by polymer weight).Representational filler comprises kaolin, magnesium hydroxide, silicon-dioxide, lime carbonate.Exist therein in the preferred embodiment of the invention of filler, filler is applied with a kind of like this material, promptly this material can prevent or postpone the trend that filler may disturb curing reaction.An example of this filler coatings is a stearic acid.Other additive can be used for preparation and is present in the isolator of the present invention, and these fillers comprise oxidation inhibitor, processing aid, pigment and lubricant.

In another embodiment of the present invention, the random basically interpolymer of composition of the present invention, particularly silane grafted is formed as weather strip for automobile, liner or sealing member.Sealed strip is as the sealing system of door, luggage, belt lining, stink cupboard and like.These materials can be processed on conventional thermoplasticity processing units.The goods that are equipped with by the copolymerzation with cross-linking system should have than the good sound-proofing properties of conventional sulfur curable EPDM sealed strip.

In another embodiment of the present invention, can prepare crosslinkable fiber.In a specific embodiments, random interpolymer is basically mixed with the superoxide or the trinitride of significant quantity as herein described.The gained mixture extruded make fiber, heating makes it crosslinked then.

In another embodiment, will be basically random interpolymer extrude and make fiber, then according to described herein by under the radiation of significant quantity, carrying out radiation crosslinking.

In another embodiment, the random basically interpolymer of silane grafted is shaped to fiber, this fiber shows improved thermotolerance.These fibers are being exposed under the moisture crosslinkedly easily, and this can be undertaken by immersing in the water or by being exposed in the ambient moisture.

The gained cross filament can be used for Woven fabric and nonwoven fabric (heat-resisting rinsable cloth), elasticity cord (for example weaving flexible tie), is used for water/airfiltering flexible filter (for example nonwoven air freshener), and fibrefelt (for example nonwoven carpet bottom).

For thermo-setting elastomer of the present invention, preferably before sulfuration, carbon black is added in random basically interpolymer and the polyolefinic blend.The carbon black that adds is generally 0 to 50wt% by total dosage, and preferred 0.5 to 50wt%.When carbon black is used to cover color, its consumption be generally the batching total amount 0.5 to 10wt%.When carbon black is used to improve toughness and/or reduces cost, its consumption usually greater than the batching total amount 10wt%.

In addition, for thermo-setting elastomer of the present invention, preferably before sulfuration, one or more extending oils are added in random basically interpolymer and the polyolefinic blend.Suitable extending oil is listed in rubber world blue Book version in 1975, be used in the material and compounding component (RubberWorld Blue Book 1975 Edition, Materials and CompoundingIngredients for Rubber) 145-190 page or leaf of rubber.More typical extending oils comprise aromatic hydrocarbon oil, naphthenic oil and alkane extending oil.The consumption of extending oil be generally the batching gross weight 0 to 50wt%.When using extending oil, its consumption is generally the 5wt% at least of batching gross weight, and preferred 15 to 25wt%.

Additive such as oxidation inhibitor are (for example, hindered phenol such as Irganox  1010), phosphinate (as Irgafos  168), ultra-violet stabilizer, cling additives (as polyisobutene), anti-caking agent, tinting material, pigment and filler also can be included in the used interpolymer of blend of the present invention and/or be used for the present invention, and condition is the improvement performance that should not disturb the applicant to find.

Additive uses by the amount that works on the function known in the art.For example, the consumption of oxidation inhibitor is to prevent that polymkeric substance or blend polymer from the amount of oxidation taking place under polymkeric substance storage and temperature between the last usage period and environment.The amount of these oxidation inhibitor is generally 0.01 to 10wt%, and preferred 0.05 to 5wt%, more preferably 0.1 to 2wt% (by the gross weight of polymkeric substance or blend polymer).Similarly, the amount of arbitrary other additive of enumerating is the amount that works on the function, as make polymkeric substance or blend polymer agglomeration resistance, the filler load that produces aequum to be to obtain required result, to use tinting material or pigment to make to have required color.The suitable amounts of these additives is 0.05 to 50wt%, and preferred 0.1 to 35wt%, more preferably 0.2 to 20wt% (by the weight of polymkeric substance or blend polymer).Yet for filler, their consumption can be the 90wt% at the most of polymkeric substance or blend polymer gross weight.

In a preferred embodiment, Thermoplastic Vulcanizate of the present invention can comprise 30 to 60wt% random basically interpolymer, 15 to 55wt% TPO and 15 to 30wt% extending oil.These Thermoplastic Vulcanizate especially can be used as car molding spare.

In a particularly preferred embodiment of the present invention, Thermoplastic Vulcanizate of the present invention can be lower than 60% by ASTM#2 oil swelling and characterize (measuring by ASTM D-471).Testing method

Monomer content is composed mensuration by carbon-13NMR.

Stress-strain property is measured down at 5 inches/min of rate of extension (12.7cm/min) with 0.870 inch (2.2cm) little stretching sample on Instron 1122 load framves.Fracture stretching, extension at break and 100% modulus are measured according to ASTM D-412.

Melt index is measured according to ASTM D-1238.

Molecular weight and molecular weight distribution are measured by gel permeation chromatography.

ASTM#2 and #3 oil swelling are measured according to ASTM D-471.

Shore " A " hardness is measured according to ASTM D-2240.

Compressive set is measured according to ASTM D-395.

Gel content % (crosslinked %) uses the xylene extraction method to measure according to ASTM D-2765-84.Take by weighing about 1g polymer samples, in these sample transfer networking baskets, put into ebullient dimethylbenzene then 12 hours.After 12 hours, take out the sample basket and be positioned in the baking oven under 150 ℃ and 28 inch of mercury vacuum 12 hours.After 12 hours, take out sample, make its at 1 hour internal cooling to room temperature, weigh then.The polymkeric substance % of extraction calculates with following formula:

The polymkeric substance %=((initial weight-final weight)/initial weight) * 100 of extraction.

The gel % numerical value of record is calculated as follows:

The polymkeric substance % of gel %=100-extraction

Upper limit use temperature is measured in order to trade(brand)name Perkin Elmer TMA7 type thermodynamic analyzer.Use 102g probe power and 5 ℃/min of heating rate.Each sample is suppressed also air cooling to the disk of thick about 2mm diameter of room temperature preparation for passing through 205 ℃ of following fusions.Embodiment 1

Preparation ethene-styrene copolymer and thermo-setting elastomer

The following method of root a tree name (tertiary butyl amino) dimethyl (tetramethyl--η of 1: 1 of mol ratio ⁵-cyclopentadienyl) silane dimethyl titanium (+4) catalyzer and three (pentafluorophenyl group) borine promotor prepare the ethylene/styrene multipolymer.In 2 liters of reactors, add 360g (500ml) ISOPAR ^TMThe styrene copolymerized monomer of E combination chain alkane solvents (available from exxon chemical company) and aequum.In reactor, add hydrogen by the 75ml coppers by the pressure reduction expansion.Reactor is heated to operating temperature and under required pressure, uses ethene saturated.In-loft drier by ISOPAR with aequum ^TMThe 0.005M solution of three in E combination chain alkane solvents or the toluene (pentafluorophenyl group) borine promotor moves at ISOPAR ^TM(tertiary butyl amino) dimethyl (tetramethyl--η in E combination chain alkane solvents or the toluene ⁵-cyclopentadienyl) in silane dimethyl titanium (IV) catalyzer, makes (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-cyclopentadienyl) silane dimethyl titanium (IV) catalyzer and three (pentafluorophenyl group) borine promotor mix.In gained catalyst solution enter catalyst coppers and injecting reactor.

Feed ethene on demand and carry out polyreaction.If desired, prepare other catalyzer and promotor raw material with the same manner and periodically join in the reactor.The total amount of used catalyzer is listed in the table 1.In each case, the amount of listed three (pentafluorophenyl group) borine promotor (by mole) equals (tertiary butyl amino) dimethyl (tetramethyl--η in the table 1 ⁵-cyclopentadienyl) amount of silane dimethyl titanium (IV) catalyzer.After the running once, from reactor, draw off polymers soln and use the isopropyl alcohol quenching.In polymkeric substance, add hindered phenol antioxygen (IRGANOX ^TM1010 (available from Ciba Geigy companies)).In the reduced vacuum baking oven, under 135 ℃, from this polymkeric substance, removed volatile matter 20 hours.

Table 1 is listed in the preparation condition of random interpolymer basically.

Table 1

Sample	Catalytic amount (μ-mol)	ISOPAR ^TM-E(mL)	Vinylbenzene (mL)	Ethene (psig)	Hydrogen (Δ psi)	Temperature of reaction (℃)	Reaction times (min)	Yield (g)
Sample	Catalytic amount (μ-mol)	ISOPAR ^TM-E(mL)	Vinylbenzene (mL)	Ethene (psig)	Hydrogen (Δ psi)	Temperature of reaction (℃)	Reaction times (min)	Yield (g)	??ES-1	????2.5	????250	????750	????300	????0	????80	????10	??32.3
??ES-2	????3.8	????500	????500	????200	????0	????80	????10	??28.8	??ES-1	????2.5	????250	????750	????300	????0	????80	????10	??32.3
??ES-2	????3.8	????500	????500	????200	????0	????80	????10	??28.8	??ES-3	????15.0	????500	????500	????200	????100	????60	????30	??166

The random basically interpolymer that obtains is characterised in that it is false random and linear.

According to following method this interpolymer is carried out compounding and curing.60g Bradley Bender PS-2 Banbury mixer barrel is preheated to 120 °F.In plastics or paper container with 100pph carbon black N550 (available from Cabot company), 50pph SUNPAR ^TM2280 oil (available from Sun Oil), 5pph paraffin, 1pph stearic acid, 8pphVul-Cup 40KE superoxide (available from Hercules) and 1.5pph cyanuric acid triallyl ester auxiliary agent (available from American Cyanamide) premix.The gained blend is added in the 60g barrel.In this barrel, add the required as above random basically interpolymer of preparation of 100pph again.Piston fallen put to Banbury mixer, and mix to temperature reaches 220 °F (about 5 minutes).Drawing off mixing material from Banbury mixer also optionally is rolled.

Sample is obtained uncured (raw material) test block 260 following compression moulding.Uncured (raw material) test block was solidified 20 minutes 340 following compression moulding, obtain crosslinked thermo-setting elastomer composition.

The stress-strain property of clean interpolymer, uncured (raw material) test block and crosslinked thermo-setting elastomer composition is listed in the table 2.Wherein, the specified performance of mark " ND " expression undetermined.

Table 2

	????ES-1	????ES-2	????ES-3	?C1 ^*(Tafmer ????680-P) ¹	????C2 ??(V-457) ²	????C3 ?(V-707) ³
	????ES-1	????ES-2	????ES-3	?C1 ^*(Tafmer ????680-P) ¹	????C2 ??(V-457) ²	????C3 ?(V-707) ³	Co-monomer content (measuring) by NMR
Wt% ethene	????67.5	????56.8	????48.0		????51.0	????70.0	Co-monomer content (measuring) by NMR
Wt% ethene	????67.5	????56.8	????48.0		????51.0	????70.0	Wt% vinylbenzene	????32.5	????43.2	????52.0		????0	????0
The wt% propylene	????0	????0	????0		????49.0	????30.0	Wt% vinylbenzene	????32.5	????43.2	????52.0		????0	????0
The wt% propylene	????0	????0	????0		????49.0	????30.0	The stress-strain property of clean no cross-linked polymer
Fracture stretching (psi)	????3200	????2156	????1390	????668	????243	????887	The stress-strain property of clean no cross-linked polymer
Fracture stretching (psi)	????3200	????2156	????1390	????668	????243	????887	100% modulus (psi)	????759	????445	????256	????170	????75	????205
Extension at break (%)	????395	????420	????518	????1115	????1780	????1336	100% modulus (psi)	????759	????445	????256	????170	????75	????205
Extension at break (%)	????395	????420	????518	????1115	????1780	????1336	Melt index in the time of 190 ℃ (g/10 minute)	????0.8	????0.8	????10.2	????4.0	????7.1	????3.9
Mw/Mn	????2.07	????2.14	????3.50	????21.8	????3.07	????4.59	Melt index in the time of 190 ℃ (g/10 minute)	????0.8	????0.8	????10.2	????4.0	????7.1	????3.9
Mw/Mn	????2.07	????2.14	????3.50	????21.8	????3.07	????4.59	The stress-strain property of raw material
Fracture stretching (psi)	????ND	????ND	????594	????460	????70	????459	The stress-strain property of raw material
Fracture stretching (psi)	????ND	????ND	????594	????460	????70	????459	100% modulus (psi)	????ND	????ND	????315	????264	????52	????231
Extension at break (%)	????ND	????ND	????453	????476	????84	????685	100% modulus (psi)	????ND	????ND	????315	????264	????52	????231
Extension at break (%)	????ND	????ND	????453	????476	????84	????685
	????ES-1	????ES-2	????ES-3	?C1 ^*(Tafmer ??680-P) ¹	??C2 ^*(V- ??457) ²	????C3 ^*(V- ????707) ³
	????ES-1	????ES-2	????ES-3	?C1 ^*(Tafmer ??680-P) ¹	??C2 ^*(V- ??457) ²	????C3 ^*(V- ????707) ³	The stress-strain property of cross-linked polymer
Fracture stretching (psi)	????3156	????ND	????1005	????1994	????1236	????1569	The stress-strain property of cross-linked polymer
Fracture stretching (psi)	????3156	????ND	????1005	????1994	????1236	????1569	100% modulus (psi)	????1076	????ND	????532	????506	????276	????674
Extension at break (%)	????300	????ND	????297	????383	????409	????292	100% modulus (psi)	????1076	????ND	????532	????506	????276	????674

* not embodiments of the invention

As shown in table 2, cross-linked thermal set elastic composition of the present invention presents comparison than material C 1 (Tafmer ^TM680-P (available from mitsui petrochemical industry)) and C2 (Vistalon ^TM457 (available from exxon chemical companies)) high 100% modulus.This shows that than material 100% high modulus is consistent with clean interpolymer comparison.Embodiment 2

Preparation ethylene/styrene/ethylidene norbornene interpolymer and thermo-setting elastomer

The following method of root a tree name (tertiary butyl amino) dimethyl (tetramethyl--η of 1: 1 of mol ratio ⁵-cyclopentadienyl) silane dimethyl titanium (+4) catalyzer and three (pentafluorophenyl group) borine promotor prepare ethylene/styrene/ethylidene norbornene interpolymer.In 2 liters of reactors, add 360g (500ml) ISOPAR ^TMThe styrene copolymerized monomer of E combination chain alkane solvents (available from exxon chemical company) and aequum.Ethylidene norbornene is conveyed in the reactor.In reactor, add hydrogen by the 75ml coppers by the pressure reduction expansion.Reactor is heated to operating temperature and under required pressure, uses ethene saturated.In a loft drier, pass through ISOPAR with aequum ^TMThe 0.005M solution of three in E combination chain alkane solvents or the toluene (pentafluorophenyl group) borine promotor moves at ISOPAR ^TM(tertiary butyl amino) dimethyl (tetramethyl--η in E combination chain alkane solvents or the toluene ⁵-cyclopentadienyl) in silane dimethyl titanium (IV) catalyzer, makes (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-cyclopentadienyl) silane dimethyl titanium (IV) catalyzer and three (pentafluorophenyl group) borine promotor mix.In gained catalyst solution enter catalyst coppers and injecting reactor.

Feed ethene on demand and carry out polyreaction.If desired, prepare other catalyzer and promotor raw material with the same manner and periodically join in the reactor.The total amount of used catalyzer is listed in the table 3.In each case, the amount of listed three (pentafluorophenyl group) borine promotor (by mole) equals (tertiary butyl amino) dimethyl (tetramethyl--η in the table 3 ⁵-cyclopentadienyl) amount of silane dimethyl titanium (IV) catalyzer.After the running once, from reactor, draw off polymers soln and use the Virahol quenching.In polymkeric substance, add hindered phenol antioxygen (IRGANOX ^TM1010 (available from Ciba Geigy companies .)).In the reduced vacuum baking oven, under 135 ℃, from this polymkeric substance, removed volatile matter 20 hours.

The condition of preparation ethylene/styrene/ethylidene norbornene interpolymer is listed in the table 3.Table 3

Sample	Catalytic amount (mol)	ISOPAR -E (ml)	Vinylbenzene (mL)	ENB measures (mL)	Ethylene pressure (psig)	Hydrogen (psi)	Temperature of reaction (C)	Reaction times (min)	Yield (g)
Sample	Catalytic amount (mol)	ISOPAR -E (ml)	Vinylbenzene (mL)	ENB measures (mL)	Ethylene pressure (psig)	Hydrogen (psi)	Temperature of reaction (C)	Reaction times (min)	Yield (g)	ES-1	????15	??500	??500	??50	??250	??100	??65	??20	?149.9
ES-2	????12.5	??500	??500	??75	??300	??100	??65	??30	?120.7	ES-1	????15	??500	??500	??50	??250	??100	??65	??20	?149.9
ES-2	????12.5	??500	??500	??75	??300	??100	??65	??30	?120.7	ES-3	????10	??500	??500	??25	??200	??100	??65	??30	?135.1

According to following method this interpolymer is carried out compounding and curing.60g Bradley Bender PS-2 Banbury mixer barrel is preheated to 120 °F.In plastics or paper container with 100pph carbon black N550 (available from Cabot company), 50pph SUNPAR ^TM2280 oil (available from Sun Oil), 5pph paraffin, 1pph stearic acid, 5pph zinc oxide, 1.5pph sulphur and 0.5pph Captax 2-mercaptobenzothiazole (available from R.T.Vanderbilt) premix.The gained blend is added in the 60g barrel.In this barrel, add the required as above random basically interpolymer of preparation of 100pph again.Piston fallen put to Banbury mixer, and mix to temperature reaches 220 °F (about 5 minutes).Drawing off mixing material from Banbury mixer also optionally is rolled.

For ESDM1 (a)-(d), ESDM1 is according to above-mentioned formulation.ESDM1 (b)-(d) is also according to above-mentioned formulation, and different is for ESDM1 (b), to replace SUNPAR oil with 50pph SUNDEX750T oil (available from Sun Oil), for ESDM1 (c), with 50pph trioctyl trimellitate replacement SUNPAR oil; For ESDM1 (d), use 0.75pph (but not 1.5pph).

As for contrast material,, wherein use Vistalon 6505EPDM (available from the Exxon) to replace random basically interpolymer with the formulation C4 that provides above.With the formulation C5 that provides above, wherein use EPSyn 70A EPDM (available from the DSM multipolymer) to replace the random basically interpolymer that uses among the present invention.With the formulation C6 that provides above (a), wherein replace random basically interpolymer and replace SUNPAR oil with Sundex 750 T oil (available from Sun oil) with SBR 1500 styrene butadiene ribbers.With the formulation C6 that provides above (b), but replace random basically interpolymer, use 50pph (but not 100pph) N550 carbon black, use 7pph Sundex 750 T oil (but not 50pph SUNPAR 2280 oil) with the SBR1500 styrene butadiene ribber.

The stress-strain property of clean interpolymer, uncured (raw material) test block and crosslinked thermo-setting elastomer composition is listed in the table 4.Wherein, the specified performance of mark " ND " expression undetermined.

Table 4

	?ESDM-1	?ESDM-2	?ESDM-3	?C4	?C5	?C6
	?ESDM-1	?ESDM-2	?ESDM-3	?C4	?C5	?C6	Co-monomer content is measured by C-NMR
Wt% ethene	?50.9	??46.7	??49.4	?50	?50	?0	Co-monomer content is measured by C-NMR
Wt% ethene	?50.9	??46.7	??49.4	?50	?50	?0	Wt% vinylbenzene	?35.3	??43.7	??44	?0	?0	?24
The wt% diolefine	?13.8	??9.6	??6.6	?12	?10	?0	Wt% vinylbenzene	?35.3	??43.7	??44	?0	?0	?24
The wt% diolefine	?13.8	??9.6	??6.6	?12	?10	?0	The wt% propylene		??0	??0	?38	?40	?0
The wt% divinyl		??0	??0	?0	?0	?76	The wt% propylene		??0	??0	?38	?40	?0
The wt% divinyl		??0	??0	?0	?0	?76	The stress-strain property of clean no cross-linked polymer
Fracture stretching (psi)	?1884	?1345	?1021	?83	?80	?31	The stress-strain property of clean no cross-linked polymer
Fracture stretching (psi)	?1884	?1345	?1021	?83	?80	?31	100% modulus (psi)	?319	?212	?242	?81	?75	?30
	?ESDM-1	?ESDM-2	?ESDM-3	?C4	?C5	?C6	100% modulus (psi)	?319	?212	?242	?81	?75	?30
	?ESDM-1	?ESDM-2	?ESDM-3	?C4	?C5	?C6	Extension at break (%)	?513	?566	?505	?288	?300	?＞400
Melt index (g/10 minute)	?1.6	?8.0	?4.6	?＜2.0	?＜0.5	?ND	Extension at break (%)	?513	?566	?505	?288	?300	?＞400
Melt index (g/10 minute)	?1.6	?8.0	?4.6	?＜2.0	?＜0.5	?ND	The stress-strain property of raw material
	?a????b???c????d	?ND	?ND	?ND	?ND	?a????b	The stress-strain property of raw material
	?a????b???c????d	?ND	?ND	?ND	?ND	?a????b	Fracture stretching (psi)	?869?723?859??932	?ND	?ND	?78	?80	?3????61
100% modulus (psi)	?570?457?606??469	?ND	?ND	?32	?67	?14???51	Fracture stretching (psi)	?869?723?859??932	?ND	?ND	?78	?80	?3????61
100% modulus (psi)	?570?457?606??469	?ND	?ND	?32	?67	?14???51	Extension at break (%)	?338?395?276??369	?ND	?ND	?250	?130	?2129??300

Table 4 (continuing)

The stress-strain property and the oil resistance of the copolymerzation with cross-linking body of compounding
								?a????b????c????d					?a?????b
Fracture stretching (%)	2379?2279?2451?2033	?ND	?ND	?2044	?2399	?1575??1475		?a????b????c????d					?a?????b
Fracture stretching (%)	2379?2279?2451?2033	?ND	?ND	?2044	?2399	?1575??1475	100% modulus	1455?1395?1539?1018	?ND	?ND	?598	?533	?295???386
Extension at break (%)	188??219??183??246	?ND	?ND	?318	?401	?277???392	100% modulus	1455?1395?1539?1018	?ND	?ND	?598	?533	?295???386
Extension at break (%)	188??219??183??246	?ND	?ND	?318	?401	?277???392	ASTM#2 oil swell (@ was 212 in 70 hours)	54???55???54???62	?ND	?ND	?93	?100	?57????49
	ESDM-1	?ESDM-2	?ESDM-3	?C4 ^*	?C5 ^*	?C6 ^*	ASTM#2 oil swell (@ was 212 in 70 hours)	54???55???54???62	?ND	?ND	?93	?100	?57????49
	ESDM-1	?ESDM-2	?ESDM-3	?C4 ^*	?C5 ^*	?C6 ^*	Aging stress-strain property after 70 hours in 250 baking oven
	?a????b????c???d					?a?????b
	?a????b????c???d					?a?????b	Fracture stretching (psi)	2697?2907?ND??2507	?ND	?ND	?ND	?ND	?663???1352
100% modulus (psi)	2143??ND??ND??1401	?ND	?ND	?ND	?ND	?ND????1326	Fracture stretching (psi)	2697?2907?ND??2507	?ND	?ND	?ND	?ND	?663???1352
100% modulus (psi)	2143??ND??ND??1401	?ND	?ND	?ND	?ND	?ND????1326	Extension at break (%)	34????84??ND??199.6	?ND	?ND	?ND	?ND	?93????103
Aging stress-strain property after 70 hours in 250 baking oven							Extension at break (%)	34????84??ND??199.6	?ND	?ND	?ND	?ND	?93????103
								?a????b????c???d					?a?????b
Fracture stretching (%)	+15??+28??ND??+24	?ND	?ND	?ND	?ND	?-58???-8		?a????b????c???d					?a?????b
Fracture stretching (%)	+15??+28??ND??+24	?ND	?ND	?ND	?ND	?-58???-8	100% modulus (%)	-47??ND???ND??+38	?ND	?ND	?ND	?ND	?ND????+378
Extension at break (%)	-29??-62??ND??-19	?ND	?ND	?ND	?ND	?-76???-74	100% modulus (%)	-47??ND???ND??+38	?ND	?ND	?ND	?ND	?ND????+378

^*Not embodiments of the invention

As shown in table 4, cross-linked thermal set elastomerics of the present invention presents comparison than material C 4 (Vistalon TM 6505 EPDM (available from the Exxon)), C5 (EPSyn 70 A EPDM (available from DSM Copolymer, Inc.)) and significantly improved 100% modulus of C6 (SBR1500 styrene butadiene rubbers).

Further specify as table 4, the similar oil resistant swelling property of cross-linked thermal set elastomer display of the present invention and styrene butadiene rubbers, but be better than the EPDM material.

Table 4 illustrates that also cross-linked thermal set elastomer display of the present invention is better than the ageing-resistant performance of styrene butadiene rubbers.For example, after under 250 °F aging 70 hours, cross-linked ethylene/vinylbenzene/ethylidene norbornene interpolymer shows the extension at break value of high fracture tension values and appropriateness in air oven.On the contrary, after wearing out under the same conditions, styrene butadiene rubbers shows low fracture tension values and the obvious extension at break value that reduces.

Therefore, as can be seen from Table 4, cross-linked ethylene/vinylbenzene of the present invention/diene thermo-setting elastomer presents the oil resistant swelling property of styrene butadiene rubbers, and does not sacrifice heat aging property.Embodiment 3: the preparation Thermoplastic Vulcanizate

Bradley Bender PS-2 or Haake torque Banbury mixer are preheated to 350 ℃.Pro-fax 6524 isotactic polyprophlenes (available from Himont Incorporated) of aequum are added in the mixing roll, and make its fusing and homogenizing.After 1 minute, add the uncrosslinked random basically interpolymer of aequum.Then, add treated oil, oxidation inhibitor, stearic acid and carbon black and mixed 1 minute.Add zinc oxide, sulphur, benzothiazole based bisulfide and methyl tuads.Be mixed to torque and reach maximum value, and make total mixing time reach at least 10 minutes.From Banbury mixer, draw off Thermoplastic Vulcanizate.

When stating step on the implementation, the prescription that provides in the use table 5.Except as otherwise noted, all amounts all are based on 100 parts of elastomeric umbers.

Table 5

Elastomerics	????TPV-1	????TPV-2	????C-TPV-1	??C-TPV-2
Elastomerics	????TPV-1	????TPV-2	????C-TPV-1	??C-TPV-2		????ESDM-2	????ESDM-3	????C-4	????C-5
Wt% ethene	????46.7	????49.4	????50	????50		????ESDM-2	????ESDM-3	????C-4	????C-5
Wt% ethene	????46.7	????49.4	????50	????50	Wt% vinylbenzene	????43.7	????44	????0	????0
The wt% diolefine	????9.6	????6.6	????12	????10	Wt% vinylbenzene	????43.7	????44	????0	????0
The wt% diolefine	????9.6	????6.6	????12	????10	Wt ﹠ propylene	????0	????0	????38	????40
TPV prepare burden (all by pph)		????A????B????C????D			Wt ﹠ propylene	????0	????0	????38	????40
TPV prepare burden (all by pph)		????A????B????C????D			Basically random interpolymer	????100	????100?100??100??100	????100	????100
Isotactic polyprophlene	????67	????67???33???67???100	????67	????67	Basically random interpolymer	????100	????100?100??100??100	????100	????100
Isotactic polyprophlene	????67	????67???33???67???100	????67	????67	Treated oil	????50	????50???100??100??100	????50	????50
IRGANOX 1010 oxidation inhibitor (available from Ciba Geigy Corp.)	????3	????3????3????3????3	????3	????3	Treated oil	????50	????50???100??100??100	????50	????50
	????3	????3????3????3????3	????3	????3	Stearic acid	????1	????1????1????1????1	????1	????1
Elastomerics	????TPV-1	????TPV-2	????C-TPV-1	????C-PTV-2	Stearic acid	????1	????1????1????1????1	????1	????1
Elastomerics	????TPV-1	????TPV-2	????C-TPV-1	????C-PTV-2	The N550 carbon black is available from Cabot	????1	????1????1????1????1	????1	????1
Zinc oxide	????5	????5????5????5????5	????5	????5	The N550 carbon black is available from Cabot	????1	????1????1????1????1	????1	????1
Zinc oxide	????5	????5????5????5????5	????5	????5	Sulphur	????1.5	????1.5??1.5??1.5??1.5	????1.5	????1.5
Benzothiazole based bisulfide (available from Altax)	????0.38	????0.38?0.38?0.38?0.38	????0.38	????0.38	Sulphur	????1.5	????1.5??1.5??1.5??1.5	????1.5	????1.5
Benzothiazole based bisulfide (available from Altax)	????0.38	????0.38?0.38?0.38?0.38	????0.38	????0.38	Methyl tuads	????0.75	????0.75?0.75?0.75?0.75	????0.75	????0.75

Except that TPV1 (b), SunParTM 2280 (available from Sun Oil) is used as treated oil.For TPV1 (b), trioctyl trimellitate is used as treated oil.

With the gained Thermoplastic Vulcanizate 380 following compression moulding.The representative physicals of this Thermoplastic Vulcanizate and contrast Thermoplastic Vulcanizate C-TPV1 (by Vistalon 6505 EPDM (available from the Exxon) preparation) and C-TPV2 (by EPSyn 70A EPDM (available from DSM rubber company) preparation) is listed in the table 6.Wherein, be called for short " ND " expression performance undetermined of giving.

Table 6

	????TPV1	????TPV2	????C-TPV-1	????C-TPV-2
	????TPV1	????TPV2	????C-TPV-1	????C-TPV-2	Stress-strain property	????A?????B	????A????B???????C?????D
Fracture stretching (psi)	????1507??1589	???1621??515????1549??1436	????1520	????1787	Stress-strain property	????A?????B	????A????B???????C?????D
Fracture stretching (psi)	????1507??1589	???1621??515????1549??1436	????1520	????1787	100% modulus (psi)	????1375??1307	???951???327????691???1008	????759	????889
Extension at break (%)	????132???164	???251???192????336???247	????322	????344	100% modulus (psi)	????1375??1307	???951???327????691???1008	????759	????889
Extension at break (%)	????132???164	???251???192????336???247	????322	????344	ASTM #2-70 hour 212 °F (% swelling)	????ND????ND	???109.5?133.8??89.3??68.2	????ND	????ND
Hardness Shore " A "	????88????86	???86????63?????77????83	????90	????88	ASTM #2-70 hour 212 °F (% swelling)	????ND????ND	???109.5?133.8??89.3??68.2	????ND	????ND

TPV1 (a) and TPV2 (a) and contrast material C-TPV1 (by Vistalon 6505 EPDM (available from the Exxon) preparation) and C-TPV2 (by EPSyn 70 A EPDM (available from DSM rubber company) preparation) comparative descriptions are not reducing the oil-proofness (measuring according to ASTM#2) that Thermoplastic Vulcanizate demonstration of the present invention is bigger under the hardness (Shore " A " hardness).Contrast these materials and further specify, Thermoplastic Vulcanizate of the present invention is compared with contrast material, shows improved 100% modulus value and analogous fracture tension values.

Contrast TPV-2 (b), TPV-2 (c) and TPV-2 (d) illustrate, can by the adjusting polypropylene and basically the ratio of random interpolymer regulate anti-ASTM#2 oil swell and hardness value.In other words, along with the polypropylene ratio raises, anti-ASTM#2 oil swell and hardness also raise.In addition, confirmed to add the effect of random interpolymer basically.Particularly, the extension at break % of Thermoplastic Vulcanizate of the present invention is big doubly more a lot of than unmodified isotactic polyprophlene (its extension at break value is 13%).Embodiment 4: the polymer reactor that peroxide modified ESI preparation is used is described

6 gallons of (22.7L) oil jacket autoclave continuously stirring jar reactors (CSTR) are used as reactor.To have the angle of rake magnetic coupling agitator of Ligtning A-320 is used for mixing.With this reactor full of liquid under 475psig (3275kPa).Process fluid is gone into and is flowed out from reactor top from the reactor underflow.Thermal oil circulates to remove some reaction heat through reactor jacket.Flow out back fine motion flowmeter survey fluid and solution density from reactor.All pipelines that are connected with reactor outlet are all used 50psi (344.7kPa) steam flush and insulation.Step:

Ethyl benzene solvent is descended in the input packaged unit at 30psig (207kPa).By the charging in fine motion (Micor-motion) the streams flowmeter measurement adding reactor.With speed change surge pump control feed rate.In the solvent pump exit, an effluent is set so that (1lb/hr (0.45kg/hr) and reactor agitator (0.75lb/hr (0.34kg/hr)) provide flushing flow to the catalyst injection pipeline.These fluids are by the differential pressure flowmeter survey and by the control of hand adjustment joint miniflow needle type valve.The styrene monomer that does not suppress is dropped in the reactor down at 30psig (308kPa).Drop into the material microfauna materials flow flowmeter measurement of reactor.With speed change surge pump control feed rate.Styrene stream is mixed with remaining solvent streams.With ethene 600psig (4,137kPa) down in the feeding packaged unit.With the microfauna materials flow flowmeter measurement ethene flow that was right after before control fluidic Reserach valve.With Brooks under meter/controller hydrogen is imported in the ethylene stream in ethene control valve exit.Ethene/hydrogen mixture is at room temperature mixed with solvent/styrene stream.Before solvent/monomer enters reactor its temperature is reduced to 5 ℃ with heat exchanger, described heat exchanger is equipped with-5 ℃ ethylene glycol in its chuck.Enter at the bottom of this logistics autoreactor.Three component catalyst systems and its rinse solvent are also from the bottom but enter reactor from the inlet different with monomer stream.Catalyst component prepares in the glove box under the inert atmosphere.The component input of having diluted is full of in the steel cylinder of nitrogen and adds in the catalyzer operation jar of process island.With piston pump with catalyzer from this operation jar pressurization and with fine motion flowmeter survey flow.These logistics just will before entering reactor, mixed single injection pipeline mutually with the catalyzer rinse solvent.

By the position of catalyst deactivation agent (being mixed with the water of solvent) after the under meter of measuring solution density added in this reactor product pipeline, polymerization is stopped.Can add other polymeric additive with the catalyst deactivation agent.Static mixer in the pipeline disperses catalyst deactivation agent and additive in reactor effluent stream.Then in the well heater after this logistics inflow reactor, this well heater is provided for flash distillation and removes the other energy that desolvates.Well heater after the logistics outflow reactor and pressure from 475psig (3,275kPa) reduce to reactor pressure control valve place-carry out this flash distillation during 250mmHg (33kPa).This polymkeric substance of flash distillation enter in the hot-oil jacket devolatilization device.In this devolatilization device, about 85% volatile compound (being called volatile matter) is removed from polymkeric substance.Volatile matter is emitted from devolatilization device top.The volatilization logistics spent glycol chuck interchanger of emitting is cooled off, enters vacuum pump to be aspirated and is discharged in the solvent and styrene/ethylene separation vessel that has the glycol chuck.Solvent and vinylbenzene are removed from reactor head from reactor bottom, ethene.Measure ethylene stream and analyze its composition with the fine motion under meter.The emptying ethene of measuring is added that the dissolved gases in solvent/vinylbenzene of calculating is used to calculate conversion of ethylene.Isolated polymkeric substance in the devolatilization device is used in the toothed gear pump suction ZSK-30 devolatilization vacuum-extruder.This exsiccant polymkeric substance flows out forcing machine with the single line material.This wire rod cools off by water-bath.Excessive water is blown out from the line material with air and this line material is cut into pellet with line material cutting machine.

The catalyzer that uses

	Titanium compound	Boron compound		????MMAO ^e
	Titanium compound	Boron compound		????MMAO ^e		Type	Type	Boron/Ti ratio	The A1/T1 ratio
????ESI-4	????A ^a	????A ^c	????1.25∶1	????12.0∶1		Type	Type	Boron/Ti ratio	The A1/T1 ratio
????ESI-4	????A ^a	????A ^c	????1.25∶1	????12.0∶1	????ESI-5	????B ^b	????A ^c	????1.26∶1	????8.0∶1
????ESI-6	????B ^b	????A ^c	????1.25∶1	????10.0∶1	????ESI-5	????B ^b	????A ^c	????1.26∶1	????8.0∶1
????ESI-6	????B ^b	????A ^c	????1.25∶1	????10.0∶1	????ESI-7	????B ^b	????A ^c	????1.25∶1	????10.0∶1
????ESI-8	????B ^b	????A ^c	????1.24∶1	????10.0∶1	????ESI-7	????B ^b	????A ^c	????1.25∶1	????10.0∶1
????ESI-8	????B ^b	????A ^c	????1.24∶1	????10.0∶1	????ESI-9	????A ^a	????A ^c	????1.251	????10.01
????ESI-10	????B ^b	????B ^d	????2.98∶1	????7.0∶1	????ESI-9	????A ^a	????A ^c	????1.251	????10.01
????ESI-10	????B ^b	????B ^d	????2.98∶1	????7.0∶1	????ESI-11	????B ^b	????B ^d	????3.011	????7.01
????ESI-12	????B ^b	????B ^d	????3.491	????9.01	????ESI-11	????B ^b	????B ^d	????3.011	????7.01
????ESI-12	????B ^b	????B ^d	????3.491	????9.01	????ESI-13	????B ^b	????A ^c	????1.25∶1	????10.0∶1
????ESI-14	????A ^a	????A ^c	????1.25∶1	????9.9∶1	????ESI-13	????B ^b	????A ^c	????1.25∶1	????10.0∶1
????ESI-14	????A ^a	????A ^c	????1.25∶1	????9.9∶1	????ESI-15	????A ^a	????A ^c	????1.24∶1	????12.0∶1

A (tertiary butyl amino) dimethyl (tetramethyl-ring pentadienyl) silane titanium (II) 1,3-pentadiene.The b dimethyl [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-3-phenyl-s-encircles luxuriant diene and indenes-1-yl] silane ammino (2-)-N]-titanium.C four (pentafluorophenyl group) boric acid is two-hydrogenated tallow alkyl methyl ammonium.D three (pentafluorophenyl group) borine.The e modified methylaluminoxane, with MMAO-3A available from Akzo Nobel.Reactor data

Polymkeric substance	Temperature of reactor ℃	Solvent flow rate		The ethene flow velocity		Hydrogen flow rate SCCM	Vinylbenzene		Transformation efficiency %
		Solvent flow rate		The ethene flow velocity			Vinylbenzene			lb/hr	??kg/hr	????lb/hr	??kg/hr	??lb/hr	??kg/hr
		??ESI-4	????65.5	??8.8	????3.99		????0.81	??0.37		lb/hr	??kg/hr	????lb/hr	??kg/hr	??lb/hr	??kg/hr	??4.5	??13.0	??5.90	??87.26
??ESI-5	????71.4	??ESI-4	????65.5	??8.8	????3.99	??11.4	????0.81	??0.37	????5.17	????1.21	??0.55	??9.0	??14.0	??6.35	??87.79	??4.5	??13.0	??5.90	??87.26
??ESI-5	????71.4	??ESI-6	????80.3	??18.6	????8.44	??11.4	????1.69	??0.77	????5.17	????1.21	??0.55	??9.0	??14.0	??6.35	??87.79	?12.0	??12.0	??5.44	??88.18
??ESI-7	????86.7	??ESI-6	????80.3	??18.6	????8.44	??28.9	????1.69	??0.77	???13.11	????2.48	??1.12	?17.0	???9.7	??4.40	??92.43	?12.0	??12.0	??5.44	??88.18
??ESI-7	????86.7	??ESI-8	????90.4	??30.1	???13.66	??28.9	????2.90	??1.32	???13.11	????2.48	??1.12	?17.0	???9.7	??4.40	??92.43	?21.0	???8.9	??4.04	??92.06
??ESI-9	???101.9	??ESI-8	????90.4	??30.1	???13.66	??19.2	????2.90	??1.32	????8.72	????1.99	??0.90	??4.0	???7.0	??3.18	??87.72	?21.0	???8.9	??4.04	??92.06
??ESI-9	???101.9	??ESI-10	????90.9	??40.0	???18.16	??19.2	????3.13	??1.42	????8.72	????1.99	??0.90	??4.0	???7.0	??3.18	??87.72	?16.0	???5.3	??2.41	??95.72
??ESI-11	????89.9	??ESI-10	????90.9	??40.0	???18.16	??25.6	????3.13	??1.42	???11.62	????2.06	??0.94	??9.0	???4.3	??1.95	??96.71	?16.0	???5.3	??2.41	??95.72
??ESI-11	????89.9	??ESI-12	????79.4	??41.0	???18.61	??25.6	????2.18	??0.99	???11.62	????2.06	??0.94	??9.0	???4.3	??1.95	??96.71	??6.0	??16.5	??7.49	??94.91
??ESI-13	????79.7	??ESI-12	????79.4	??41.0	???18.61	??18.6	????2.18	??0.99	????8.44	????1.70	??0.77	??11.7	??12.0	??5.44	??88.6	??6.0	??16.5	??7.49	??94.91
??ESI-13	????79.7	??ESI-14	????69.2	??2.92	????1.32	??18.6	?????1.0	??0.45	????8.44	????1.70	??0.77	??11.7	??12.0	??5.44	??88.6	????0	??20.0	??9.07	??86.3
??ESI-15	????65.0	??ESI-14	????69.2	??2.92	????1.32	???8.8	?????1.0	??0.45	????3.99	?????0.80	??0.36	??4.5	??13.0	??5.90	??88.7	????0	??20.0	??9.07	??86.3

Table 7 is generally listed the characteristic of the polymkeric substance that uses in this research.

The polymkeric substance that table 7 uses

???Lot?No.	Describe	I ₂ ^a(g/10min)	?I ₁₀/I ₂	Total vinylbenzene amount (%)	Atactic PS (%)
???Lot?No.	Describe	I ₂ ^a(g/10min)	?I ₁₀/I ₂	Total vinylbenzene amount (%)	Atactic PS (%)	????ESI-4	????74％S?ESI	????1.44	????8.8	????58.4	????15.5
????ESI-5	????67％S?ESI	????1.10	????9.0	????51.2	????15.3	????ESI-4	????74％S?ESI	????1.44	????8.8	????58.4	????15.5
????ESI-5	????67％S?ESI	????1.10	????9.0	????51.2	????15.3	????ESI-6	????60％S?ESI	????1.11	????7.5	????56.4	????3.4
????ESI-7	????54％S?ESI	????1.72	????6.6	????52.3	????1.5	????ESI-6	????60％S?ESI	????1.11	????7.5	????56.4	????3.4
????ESI-7	????54％S?ESI	????1.72	????6.6	????52.3	????1.5	????ESI-8	????45％S?ESI	????1.08	????7.7	????43.4	????1.3
????ESI-9	????33％S?ESI	????1.22	????7.6	????26.4	????6.2	????ESI-8	????45％S?ESI	????1.08	????7.7	????43.4	????1.3
????ESI-9	????33％S?ESI	????1.22	????7.6	????26.4	????6.2	????ESI-10	????41	????1.3	?????-	????41.0	????0.3
????ESI-11	????51	????1.2	?????-	????50.0	????0.6	????ESI-10	????41	????1.3	?????-	????41.0	????0.3
????ESI-11	????51	????1.2	?????-	????50.0	????0.6	????ESI-12	????73	????1.2	?????-	????69.1	????1.7
????ESI-13	????58％S?ESI	????1.0	?????-	??????-	????3	????ESI-12	????73	????1.2	?????-	????69.1	????1.7
????ESI-13	????58％S?ESI	????1.0	?????-	??????-	????3	????ESI-14	????73.4％S?ESI	????5.0	?????-	??????-	????8.6
????ESI-15	????68.5％S?ESI	????1.05	????9.0	??????-	????16.9	????ESI-14	????73.4％S?ESI	????5.0	?????-	??????-	????8.6
????ESI-15	????68.5％S?ESI	????1.05	????9.0	??????-	????16.9	????POE	?Affinity-EG?8100 ^b	????1	?????-	??????-	??????-

A measures by ASTM D 1238 condition I.B ethylene-octene copolymer has melt index 1g/10min. (measuring by ASTM D 1238 condition I) and density 0.870g/cc (measuring by ASTM D 792), available from Dow Chemical.The batching processing conditions

With 3,6 and the dicumyl peroxide of 9wt% (DiCup is made by Hercules company) preparation have the batching of above-mentioned polymkeric substance.This batching is preparation under the following conditions in the HakkeRheocord 9000 that 50g mixing barrel is housed: 120 ℃, 50RPM, 10-12 minute mixing time.The batching condition of cure:

Sample was descended crosslinked 20 minutes at 170 ℃ with 200 ft lbfs in plasticator (tetrahedral press MTP-8 type).The result

Table 8 is generally listed the gel content and the upper limit use temperature of peroxide crosslinking ESI sample.Presentation of results superoxide in the table 8 can be used for crosslinked ESI.Degree of crosslinking is by analyzing gel content determining.All peroxide modified samples have gel content greater than 60%.Upper limit use temperature raises when sample is used peroxide treatment.Fig. 1 provides expection and gel content reality and vinylbenzene composition diagram with the ESI sample of 9% peroxide treatment.The gel content of measuring is big more a lot of than desired value.Owing to the reactivity of ESI and superoxide is similar to the multipolymer that polyethylene is different from vinylbenzene and ethene, so this is unexpected result.

The ethylene styrene interpolymer of table 8 peroxide crosslinking

Sample number	Polymkeric substance	Describe	The % gel	Upper limit use temperature (C)
Sample number	Polymkeric substance	Describe	The % gel	Upper limit use temperature (C)		?ESI-9	33%S ESI-0% superoxide	????0	????86.0
????B	?ESI-8	45%S ESI-0% superoxide	????0	????50.0		?ESI-9	33%S ESI-0% superoxide	????0	????86.0
????B	?ESI-8	45%S ESI-0% superoxide	????0	????50.0	????C	?ESI-7	54%S ESI-0% superoxide	????0	????50.0
????D	?ESI-6	60%S ESI-0% superoxide	????0	????50.0	????C	?ESI-7	54%S ESI-0% superoxide	????0	????50.0
????D	?ESI-6	60%S ESI-0% superoxide	????0	????50.0	????E	?ESI-5	67%S ESI-0% superoxide	????0	????60.0
????F	?ESI-4	74%S ESI-0% superoxide	????0	????68.0	????E	?ESI-5	67%S ESI-0% superoxide	????0	????60.0
????F	?ESI-4	74%S ESI-0% superoxide	????0	????68.0	????G	?POE	Affinity EG8100-0% superoxide	????0	????68.0
????H	?x-LINKEDESI-9	33%S ESI-3% superoxide	????88.6	????＞185	????G	?POE	Affinity EG8100-0% superoxide	????0	????68.0
????H	?x-LINKEDESI-9	33%S ESI-3% superoxide	????88.6	????＞185	????I	?x-LINKEDESI-8	45%S ESI-3% superoxide	????93.0	????165.0
????J	?x-LINKEDESI-7	54%S ESI-3% superoxide	????79.3	????＞185	????I	?x-LINKEDESI-8	45%S ESI-3% superoxide	????93.0	????165.0
????J	?x-LINKEDESI-7	54%S ESI-3% superoxide	????79.3	????＞185	????K	?x-LINKEDESI-6	60%S ESI-3% superoxide	????82.2	????179.0
????L	?x-LINKEDESI-5	67%S ESI-3% superoxide	????68.6	????170.0	????K	?x-LINKEDESI-6	60%S ESI-3% superoxide	????82.2	????179.0
????L	?x-LINKEDESI-5	67%S ESI-3% superoxide	????68.6	????170.0	????M	?x-LINKEDESI-4	74%S ESI-3% superoxide	????63.5	????97.0
????N ^*	?x-LINKED?POE	AffinityO EG8100-3% superoxide	????97.3	????＞185	????M	?x-LINKEDESI-4	74%S ESI-3% superoxide	????63.5	????97.0
????N ^*	?x-LINKED?POE	AffinityO EG8100-3% superoxide	????97.3	????＞185	????O	?x-LINKEDESI-9	33%S ESI-6% superoxide	????94.6	????＞185
????P	?x-LINKEDESI-8	45%S ESI-6% superoxide	????90.5	????＞185	????O	?x-LINKEDESI-9	33%S ESI-6% superoxide	????94.6	????＞185
????P	?x-LINKEDESI-8	45%S ESI-6% superoxide	????90.5	????＞185	????Q	?x-LINKEDESI-7	54%S ESI-6% superoxide	????92.0	????＞185
????R	?x-LINKEDESI-6	60%S ESI-6% superoxide	????92.6	????＞185	????Q	?x-LINKEDESI-7	54%S ESI-6% superoxide	????92.0	????＞185
????R	?x-LINKEDESI-6	60%S ESI-6% superoxide	????92.6	????＞185	????S	?x-LINKEDESI-5	67%S ESI-6% superoxide	????85.5	????＞185
????T	?x-LINKEDESI-4	74%S ESI-6% superoxide	????75.3	????＞185	????S	?x-LINKEDESI-5	67%S ESI-6% superoxide	????85.5	????＞185
????T	?x-LINKEDESI-4	74%S ESI-6% superoxide	????75.3	????＞185	????U ^*	?x-LINKED?POE	AffinityO EG8100-6% superoxide	????99.4	????＞185
????V	?x-LINKEDESI-9	33%S ESI-9% superoxide	????94.9	????＞185	????U ^*	?x-LINKED?POE	AffinityO EG8100-6% superoxide	????99.4	????＞185
????V	?x-LINKEDESI-9	33%S ESI-9% superoxide	????94.9	????＞185	????W	?x-LINKEDESI-8	45%S ESI-9% superoxide	????93.6	????＞185
????X	?x-LINKEDESI-7	54%S ESI-9% superoxide	????92.6	????＞185	????W	?x-LINKEDESI-8	45%S ESI-9% superoxide	????93.6	????＞185
????X	?x-LINKEDESI-7	54%S ESI-9% superoxide	????92.6	????＞185	????Y	?x-LINKEDESI-6	60%S ESI-9% superoxide	????91.5	????＞185
????Z	?x-LINKEDESI-5	67%S ESI-9% superoxide	????89.0	????＞185	????Y	?x-LINKEDESI-6	60%S ESI-9% superoxide	????91.5	????＞185
????Z	?x-LINKEDESI-5	67%S ESI-9% superoxide	????89.0	????＞185	????AA	?x-LINKEDESI-4	74%S ESI-9% superoxide	????80.7	????＞185
????AB ^*	?x-LINKED?POE	AffinityO EG8100-9% superoxide	????97.8	????＞185	????AA	?x-LINKEDESI-4	74%S ESI-9% superoxide	????80.7	????＞185

^*It or not the polymkeric substance of the ESI blend use of embodiments of the invention peroxide modified

Table 9 is generally listed and is used for the ESI sample that this research is used.

The polymkeric substance that table 9 uses

Polymkeric substance	Describe
Polymkeric substance	Describe	????ESI-9	????33％S?ESI
????ESI-4	????74％S?ESI	????ESI-9	????33％S?ESI
????ESI-4	????74％S?ESI	????POE	????affinity?EG?8100
????SBS	Vector 2518 styrene block copolymers ^*	????POE	????affinity?EG?8100

* a styrene-butadiene-styrene block copolymer contains 30wt% vinylbenzene, has melt index 1g/10min.(measuring by ASTM D1238 condition I) is available from Dexco.The batching processing conditions

Dicumyl peroxide (DiCup is made by Hercules company) preparation with 4wt% has the batching of above-mentioned polymkeric substance.This batching is preparation under the following conditions in the HakkeRheocord 9000 that 50g mixing barrel is housed: 120 ℃, 50RPM, 10-12 minute mixing time.The batching condition of cure:

Table 10 is generally listed the blend of usefulness AFFINITY EG 8100 and SBS preparation to measure the influence to the cross-linking efficiency of ESI multipolymer of blend polyolefin elastomer or styrene/butadiene/styrene polymkeric substance.Table 10

Table 10 blend performance

Sample number	Describe	Gel %
Sample number	Describe	Gel %	????A	????ESI-9(33％S)	????0
????B	????ESI-9(33％S)+4％DCP	????83.8	????A	????ESI-9(33％S)	????0
????B	????ESI-9(33％S)+4％DCP	????83.8	????C	????ESI-9(33％S)+10％SBS+4％DCP	????87
????D	????ESI-9(33％S)+10％POE+4％DCP	????81.1	????C	????ESI-9(33％S)+10％SBS+4％DCP	????87
????D	????ESI-9(33％S)+10％POE+4％DCP	????81.1	????E	????ESI-4(74％S)	????0
????F	????ESI-4(74％S)+4％DCP	????64.5	????E	????ESI-4(74％S)	????0
????F	????ESI-4(74％S)+4％DCP	????64.5	????G	????ESI-4(74％S)+10％SBS+4％DCP	????71.5
????H	????ESI-4(74％S)+10％POE+4％DCP	????59.6	????G	????ESI-4(74％S)+10％SBS+4％DCP	????71.5

* not embodiments of the invention

The SBS that adds raises the gel content of the ethylene/styrene interpolymer of research.Basically the random interpolymer of electron beam irradiation

Will with listed polymer phase in the table 7 with polymkeric substance be used for this research.Batching preparation and condition of cure

With 5,10,15 and the 20Mrad electron beam irradiation handle compression molding sample.The result

Presentation of results in the table 11, electron beam irradiation can be used for crosslinked ESI, and in other words, this radiation improves gel content and SC service ceiling temperature.Notice that electron beam irradiation sample (R, Q and P) is more much lower than unmodified sample (C, D and E) viscosity.To using 5Mrad dosage radiating 74%S ESI sample measurement low radiation dose to I ₁₀/ I ₂The influence of ratio: the I of untreated sample ₁₀/ I ₂Ratio is 8.8, is 12.3 after handling with the 5Mrad metering.

Table 11 electron beam crosslinking ethylene styrene interpolymer

Sample number	Describe	Gel %	Upper limit use temperature (℃)
Sample number	Describe	Gel %	Upper limit use temperature (℃)	????A	?ESI-9(33％S)-0?Mrad	????0	????86
????B	?ESI-8(45％s)-0?Mrad	????0	????50	????A	?ESI-9(33％S)-0?Mrad	????0	????86
????B	?ESI-8(45％s)-0?Mrad	????0	????50	????C	?ESI-7(54％S)-0?Mrad	????0	????50
????D	?ESI-6(60％S)-0?Mrad	????0	????56	????C	?ESI-7(54％S)-0?Mrad	????0	????50
????D	?ESI-6(60％S)-0?Mrad	????0	????56	????E	?ESI-5(67％S)-0?Mrad	????0	????60
????F	?ESI-4(74％S)-0?Mrad	????0	????68	????E	?ESI-5(67％S)-0?Mrad	????0	????60
????F	?ESI-4(74％S)-0?Mrad	????0	????68	????G ^*	?Affinity ^TMEG?8100-0?Mrad	????0	????68
????H	?33％S?ESI-5?Mrad	????0.1	????88	????G ^*	?Affinity ^TMEG?8100-0?Mrad	????0	????68
????H	?33％S?ESI-5?Mrad	????0.1	????88	????I	?45％S?ESI-5?Mrad	????0	????56
????J	?54％S?ESI-5?Mrad	????1.8	????56	????I	?45％S?ESI-5?Mrad	????0	????56
????J	?54％S?ESI-5?Mrad	????1.8	????56	????K	?60％S?ESI-5?Mrad	????0.3	????60
????L	?67％S?ESI-5?Mrad	????0.4	????64	????K	?60％S?ESI-5?Mrad	????0.3	????60
????L	?67％S?ESI-5?Mrad	????0.4	????64	????M	?74％S?ESI-5?Mrad	????0.4	????72
????N ^*	?Affini?ty ^TMEG?8?100-5?Mrad	????0.3	????73	????M	?74％S?ESI-5?Mrad	????0.4	????72
????N ^*	?Affini?ty ^TMEG?8?100-5?Mrad	????0.3	????73	????O	?ESI-9(33％S)-10?Mrad	????-	????-
????P	?ESI-8(45％s)-10?Mrad	????1.3	????62	????O	?ESI-9(33％S)-10?Mrad	????-	????-
????P	?ESI-8(45％s)-10?Mrad	????1.3	????62	????Q	?ESI-7(54％S)-10?Mrad	????0.1	????64
????R	?ESI-6(60％S)-10?Mrad	????0.4	????68	????Q	?ESI-7(54％S)-10?Mrad	????0.1	????64
????R	?ESI-6(60％S)-10?Mrad	????0.4	????68	????S	?ESI-5(67％S)-10?Mrad	????0.1	????74
????T	?ESI-4(74％S)-10?Mrad	????0.2	????80	????S	?ESI-5(67％S)-10?Mrad	????0.1	????74
????T	?ESI-4(74％S)-10?Mrad	????0.2	????80	????U ^*	?Affinity ^TMEG?8100-10?Mrad	????76.3	????77
????V	?ESI-9(33％S)-15?Mrad	????62.2	????98	????U ^*	?Affinity ^TMEG?8100-10?Mrad	????76.3	????77
????V	?ESI-9(33％S)-15?Mrad	????62.2	????98	????W	?ESI-8(45％s)-15?Mrad	????68	????80
????X	?ESI-7(54％S)-15?Mrad	????65	????72	????W	?ESI-8(45％s)-15?Mrad	????68	????80
????X	?ESI-7(54％S)-15?Mrad	????65	????72	????Y	?ESI-6(60％S)-15?Mrad	????44.6	????70
????Z	?ESI-5(67％S)-15?Mrad	????8.2	????74	????Y	?ESI-6(60％S)-15?Mrad	????44.6	????70
????Z	?ESI-5(67％S)-15?Mrad	????8.2	????74	????AA	?ESI-4(74％S)-15?Mrad	????1.2	????77
????AB ^*	?Affinity ^TMEG?8100-15?Mrad	????82.3	????96	????AA	?ESI-4(74％S)-15?Mrad	????1.2	????77
????AB ^*	?Affinity ^TMEG?8100-15?Mrad	????82.3	????96	????AC	?ESI-9(33％S)-20?Mrad	????70	????125
????AD	?ESI-8(45％s)-20?Mrad	????70.4	????94	????AC	?ESI-9(33％S)-20?Mrad	????70	????125
????AD	?ESI-8(45％s)-20?Mrad	????70.4	????94	????AE	?ESI-7(54％S)-20?Mrad	????75.2	????92
????AF	?ESI-6(60％S)-20?Mrad	????67.1	????80	????AE	?ESI-7(54％S)-20?Mrad	????75.2	????92
????AF	?ESI-6(60％S)-20?Mrad	????67.1	????80	????AG	?ESI-5(67％S)-20?Mrad	????55.3	????80
????AH	?ESI-4(74％S)-20?Mrad	????21.2	????80	????AG	?ESI-5(67％S)-20?Mrad	????55.3	????80
????AH	?ESI-4(74％S)-20?Mrad	????21.2	????80	????Al ^*	?Affinity ^TM8100-20?Mrad	????90.2	????186

* not the material that the silane-modified random basically interpolymer of embodiments of the invention uses

Table 12 is generally listed the material that is used for this research

The polymkeric substance that table 12 uses

Polymkeric substance number	Describe
Polymkeric substance number	Describe	????ESI-10	????41％S?ESI
????ESI-11	????51％S?ESI	????ESI-10	????41％S?ESI
????ESI-11	????51％S?ESI	????ESI-12	????73％S?ESI
????POE	????Affinity?8100	????ESI-12	????73％S?ESI

The batching preparation condition

Table 13 provides the batching that is used for crosslinked with silicane research of preparation

Table 13 is used for the batching of ESI crosslinked with silicane research

41% vinylbenzene ESI-10 wt%	51% vinylbenzene ESI-11 wt%	73% vinylbenzene ESI-12 wt%	Affinity ?EG?8100 ???wt％	Trimethoxy vinyl silanes wt%	Dicumyl peroxide wt%	Dibutyl tin laurate wt%
41% vinylbenzene ESI-10 wt%	51% vinylbenzene ESI-11 wt%	73% vinylbenzene ESI-12 wt%	Affinity ?EG?8100 ???wt％	Trimethoxy vinyl silanes wt%	Dicumyl peroxide wt%	Dibutyl tin laurate wt%	????97.85	????0	????0	????0	????2	????0.15	????0.02
????97.7	????0	????0	????0	????2	????0.30	????0.02	????97.85	????0	????0	????0	????2	????0.15	????0.02
????97.7	????0	????0	????0	????2	????0.30	????0.02	????95.85	????0	????0	????0	????4	????0.15	????0.02
????95.7	????0	????0	????0	????4	????0.30	????0.02	????95.85	????0	????0	????0	????4	????0.15	????0.02
????95.7	????0	????0	????0	????4	????0.30	????0.02	????0	????97.85	????0	????0	????2	????0.15	????0.02
????0	????97.7	????0	????0	????2	????0.30	????0.02	????0	????97.85	????0	????0	????2	????0.15	????0.02
????0	????97.7	????0	????0	????2	????0.30	????0.02	????0	????95.85	????0	????0	????4	????0.15	????0.02
????0	????95.7	????0	????0	????4	????0.30	????0.02	????0	????95.85	????0	????0	????4	????0.15	????0.02
????0	????95.7	????0	????0	????4	????0.30	????0.02	????0	????0	????97.85	????0	????2	????0.15	????0.02
????0	????0	????97.7	????0	????2	????0.30	????0.02	????0	????0	????97.85	????0	????2	????0.15	????0.02
????0	????0	????97.7	????0	????2	????0.30	????0.02	????0	????0	????95.85	????0	????4	????0.15	????0.02
????0	????0	????95.7	????0	????4	????0.30	????0.02	????0	????0	????95.85	????0	????4	????0.15	????0.02
????0	????0	????95.7	????0	????4	????0.30	????0.02	????0	????0	????0	????97.85	????2	????0.15	????0.02
????0	????0	????0	????95.85	????4	????0.15	????0.02	????0	????0	????0	????97.85	????2	????0.15	????0.02

Sample is extruded being equipped with on the Haake Polylab polymer processing device that has jet scraper of 18mm twin screw extruder, tablets press and water-bath.Sample prepares by two-step approach:

Step 1: silane is grafted on the polymkeric substance by following technology:

The vinyltrimethoxy silane and the dicumyl peroxide solution of proper ratio are injected in the extruder barrel with liquid form with polymkeric substance.

Condition: 200 ℃ of melt temperatures, 50rpm.

Step 2: add dibutyltin dilaurate catalyst

2% masterbatch of preparation catalyzer in each polymkeric substance of research.This catalyst masterbatch pellet is mixed and extrudes under 200 ℃, 50rpm with doing from the silane grafting material of step 1.

Presentation of results in the table 14, silane reagent can be used to prepare crosslinked ESI by the moisture-curable method.With the vinylsiloxane grafting ESI that plays the moisture-curable active sites.Form 41 to 51% ESI for having vinylbenzene, obtain 40 to 65% gel content.

Table 14 crosslinked with silicane ethylene styrene interpolymer

Sample number	Describe	Gel %	Upper limit use temperature (℃)
Sample number	Describe	Gel %	Upper limit use temperature (℃)	????A	??ESI-10(41％S)，1500ppm?DCP、2％VTMOS	??45.6	????55.2
????B	??ESI-10(41％S)，3000ppm?DCP、2％VTMOS	??65.3	????55.1	????A	??ESI-10(41％S)，1500ppm?DCP、2％VTMOS	??45.6	????55.2
????B	??ESI-10(41％S)，3000ppm?DCP、2％VTMOS	??65.3	????55.1	????C	??ESI-10(41％S)，1500ppm?DCP、4％VTMOS	??57.0	????55.1
????D	??ESI-10(41％S)，3000ppm?DCP、4％VTMOS	??44.3	????55.1	????C	??ESI-10(41％S)，1500ppm?DCP、4％VTMOS	??57.0	????55.1
????D	??ESI-10(41％S)，3000ppm?DCP、4％VTMOS	??44.3	????55.1	????E	??ESI-11(51％S)，1500ppm?DCP、2％VTMOS	??45.8	????47.3
????F	??ESI-11(51％S)，3000ppm?DCP、2％VTMOS	??57.6	????49.3	????E	??ESI-11(51％S)，1500ppm?DCP、2％VTMOS	??45.8	????47.3
????F	??ESI-11(51％S)，3000ppm?DCP、2％VTMOS	??57.6	????49.3	????G	??ESI-11(51％S)，1500ppm?DCP、4％VTMOS	??64.8	????49.5
????H	??ESI-11(51％S)，3000ppm?DCP、4％VTMOS	??46.8	????49.3	????G	??ESI-11(51％S)，1500ppm?DCP、4％VTMOS	??64.8	????49.5
????H	??ESI-11(51％S)，3000ppm?DCP、4％VTMOS	??46.8	????49.3	????I	??ESI-12(73％S)，1500ppm?DCP、2％VTMOS	??0.4	????59.7
????J	??ESI-12(73％S)，3000ppm?DCP、2％VTMOS	??0.3	????61.6	????I	??ESI-12(73％S)，1500ppm?DCP、2％VTMOS	??0.4	????59.7
????J	??ESI-12(73％S)，3000ppm?DCP、2％VTMOS	??0.3	????61.6	????K	??ESI-12(73％S)，1500ppm?DCP、4％VTMOS	??0.1	????61.4
????L	??ESI-12(73％S)，3000ppm?DCP、4％VTMOS	??1.0	????59.9	????K	??ESI-12(73％S)，1500ppm?DCP、4％VTMOS	??0.1	????61.4
????L	??ESI-12(73％S)，3000ppm?DCP、4％VTMOS	??1.0	????59.9	????M ^*	??Affinity?EG?8100?8100、1500ppm?DCP、2％VTMOS	??87.5	????92.4
????N ^*	??Affinity?8100EG?8100、1500ppm?DCP、4％VTMOS	??93.9	????＞185	????M ^*	??Affinity?EG?8100?8100、1500ppm?DCP、2％VTMOS	??87.5	????92.4

* not embodiments of the invention trinitride modification ESI

Be used to prepare and test testing method and the device test method of following sample 1-10:

The kinetics spectrometer of the RAD-II of rheometer company (Rheometric Inc.) is used to obtain the DMS data.Temperature scanning is scanned up to 300 ℃ by the 5 ℃/step (having delay in 30 seconds in each step) from about-70 ℃.Oscillation frequency is 1 radian/s, and wherein just starting from function of strain is 0.1% strain, and when torque is reduced to all forward raisings 100% of 4g-cm.Maximum strain is set at 26%.Use 7.9-mm parallel plate anchor clamps, its initial gap in the time of 160 ℃ is 1.5mm (sample is inserted among the RAD-II 160 ℃ the time)." anchor clamps " are cooled to instrument-70 ℃ 160 ℃ of lower tooths merging.(effect of anchor clamps is thermal expansion or the contractions when being used to proofread and correct heating or cooling test cabinet).In whole experiment, keep nitrogen environment minimum so that oxidative degradation is reduced to.

DSC (differential scanning calorimetric) data obtain with Perkin-Elmer DSC-7.Sample melted is compressed to thin slice and puts into the aluminium dish.This sample is heated to 180 ℃ and keep 4min to melt fully guaranteeing therein in DSC.Then sample is cooled to-30 ℃ and be heated to 140 ℃ with 10 ℃/min with 10 ℃/min.

Perkin Elmer TMA 7 type thermodynamic analyzers are used to measure upper limit use temperature.Use 102g probe power and 5 ℃/min of heating rate.Sample is for by 205 ℃ of following compression moulding and be cooled to the about 2mm of thickness of heating mode preparation and the disk of diameter in air.

The general approach of measuring compressive set is described among the ASTM D395-89.Sample is cut into the disk of 1.14 inches of diameters, this disk is accumulated to thickness up to 0.5 inch.Under 70 ℃, measure sample 22 hours with constant strain 25%.This sample wearing out 22 hours under 70 ℃, is cooled to 22 ℃ under 25% compression.

Xylene extraction is undertaken by taking by weighing the 1g polymer samples.In these sample transfer networking baskets, put into ebullient dimethylbenzene then 12 hours.After 12 hours, take out the sample basket and be positioned in the baking oven under 150 ℃ and 28 inch of mercury vacuum 12 hours.After 12 hours, take out sample, make its at 1 hour internal cooling to room temperature, weigh then.The polymkeric substance % of extraction calculates with following formula:

The polymkeric substance %=((initial weight-final weight)/initial weight) of extraction.

Tensile property is measured by 1/16 inch sample of compression moulding.From these samples, cut out tension specimen then and in Instron tension test aircraft measurements.

These samples use HaakeBunchler Rheomix 600 mixing rolls with roll shape blade that are connected with HaakeBuchler Rheocord 9000 torque rheometers, or use the Bradley Bender mixing roll (model: R.E.E.No.A-19/S.B) preparation with 50g mixing barrel.Preparation 4,4 '-disulfonyl base azido-phenyl ether

With 4,4 '-(10g 0.027mol) is dissolved in the 100mL acetone two (chlorosulfonyl) phenyl ether, and adds 4.426g (0.06808mol) solid sodiumazide in 15 minutes in batches.This reaction mixture was at room temperature stirred 26 hours, remove by filter sodium-chlor then.With the filter cake washing with acetone, and, obtain white solid, with 20mL water washing 2 times of this white solid, vacuum-drying at room temperature then with the filtrate evaporation that merges.Confirming by 1H and 13CNMR spectrum, gained white solid (7.3g, 70%) is 4,4 '-disulfonyl azido-phenyl ether.Cross-linked ethylene-styrene copolymer

To contain 58wt% vinylbenzene (ESI-3831-960921-1100) (the 3wt% random isotactic polystyrene, ethylene-styrene copolymer 1.0MI) (40g) and 0.2g (0.5wt%, 0.55mmol) 4,4 '-disulfonyl base azido-biphenyl does in plastics bag and mixes.The adding under 120 ℃ (60rpm) of this blend had the Bradley Bender mixing roll (model: R.E.E.No.A-19/S.B) of 40g mixing barrel.This mixture 120 ℃ of following blend 3 minutes, is taken out from mixing tank then and makes its cooling, obtain 38.9g blend 1.

With 0.4g (1.0wt%, 1.1mmol) 4,4 '-disulfonyl base azido-biphenyl repeats above-mentioned blend experiment, obtains blend 2, with 0.8g (2.0wt%, 2,2mmol) 4,4 '-disulfonyl base azido-biphenyl repeats above-mentioned blend experiment and obtains blend 3.

With 0.8g (2wt%) 1,3-disulfonyl base triazobenzene repeats above-mentioned blend experiment and obtains 39.3g blend 4, and with 0.8g (2.0wt%) 1,3,5-three alkylsulfonyl triazobenzenes repeat above-mentioned blend experiment and obtain 39.1g blend 5.

Blend 1-5 and uncrosslinked ESI-13 (it is untreated initial substance) in the compacting 3 minutes down of 120 ℃ and 20,000 ft lbfs, were then solidified 10 minutes down at 190 ℃ and 20,000 pounds, then under keep-uping pressure at 5 minutes internal cooling to 80 ℃.All these samples all pass through the TMA analysis and characterization, and the sample of choosing is measured sign by xylene extraction and DMS.This data declaration, in the presence of 2% sulfuryl azide, sample is crosslinked fully.Crosslinked blends 1-5 is called sample 1-5.

Sample	??UST(TMA)℃	The % xylene extraction	????G’(20℃)	??G’(200℃)
Sample	??UST(TMA)℃	The % xylene extraction	????G’(20℃)	??G’(200℃)	????ESI-13	????52	????99	????3.0E ^-07	????3.0E ⁺⁰³
????1	????64	????12	Data are not measured		????ESI-13	????52	????99	????3.0E ^-07	????3.0E ⁺⁰³
????1	????64	????12	Data are not measured		????2	????106	????2	Data are not measured
????3	????＞190	????2	Data are not measured		????2	????106	????2	Data are not measured
????3	????＞190	????2	Data are not measured		????4	????＞190	????0	????8.0E ^-∞	????3.0E ^-∞
????5	????＞190	????2	Data are not measured		????4	????＞190	????0	????8.0E ^-∞	????3.0E ^-∞

Sample	Toughness (In-Lb/Cu.In)	Rupture stress (PSI)	The % elongation	Compressive set (70 ℃)
Sample	Toughness (In-Lb/Cu.In)	Rupture stress (PSI)	The % elongation	Compressive set (70 ℃)	????ESI-13	????2450	????411	??900	????64％
????3	????4000	????1700	??650	????17％	????ESI-13	????2450	????411	??900	????64％
????3	????4000	????1700	??650	????17％	????4	????4700	????2000	??630	????7％
????5	????4300	????1700	??630	????16％	????4	????4700	????2000	??630	????7％

Following description of test, crosslinked high-phenylethylene ESI (St wt%＞50%), this is important for the crosslinked peroxide crosslinking that is better than of explanation difunctionality trinitride.

The Haake Rheocord 9000 that 50g mixing barrel is housed is heated to 120 ℃.40.0gESI (3831-960710-1500) (73.4% styrol copolymer, 8.6% random isotactic polystyrene) is added in the mixing barrel.After 1 minute, with 0.8g (2.0wt%) 1,3-disulfonyl base triazobenzene adds and mixes in the charging basket and with sample compounding 3 minutes.From Haake, take out polymkeric substance, and in the compacting 3 minutes down of 120 ℃ and 20,000 ft lbfs.Then this sample was solidified 10 minutes down 180 ℃ and 20,000 pounds, then ℃ obtain sample 6 at 5 minutes internal cooling to 80.Untreated ESI-14 need not many (sulfuryl azide) be handled, but press sample 6 moldings and curing.

Sample	????UST(TMA)℃	Compressive set (70 ℃)
Sample	????UST(TMA)℃	Compressive set (70 ℃)	????ESI-14	????60	????97％
????6	????＞190	????15％	????ESI-14	????60	????97％

The presentation of results of sample 1-6, disulfonyl base trinitride can be used for preparing link coupled, partial cross-linked and complete crosslinked ESI.Sample 2-4 is complete crosslinked polymkeric substance.Use toughness and the upper limit use temperature of the crosslinked ESI of disulfonyl base trinitride better than uncrosslinked ESI.The preparation peroxide crosslinking ESI, with the crosslinked ESI comparative sample 7﹠amp of trinitride; 8

The Haake Rheocord 9000 that 50g mixing barrel is housed is heated to 120 ℃.With 48.5g ESI6 (57.7% styrol copolymer, 3.3% homopolystyrene, 1.02Mi, 7.8I ₁₀/ I ₂) add and under 50RPM, mix.After 6 minutes, add 1.5g (3.0wt%) dicumyl peroxide (Hercules Inc.) and with the sample compounding more than 6 minutes.From Haake, take out sample, and in plasticator (Tetrahedron Press MTP-8 type) in the compacting 3 minutes down of 120 ℃ and 20,000 ft lbfs, curing 20 minutes under 170 ℃ and 200 pounds of (90.78kg) power then.This is a sample 7.For sample 8, repeat this technology with 47.0g ESI-6 and 3.0g dicumyl peroxide (6wt%).Measure tensile property, compressive set and UST by TMA.Sample 9﹠amp; 10

The Haake Rheocord 9000 that 50g mixing barrel is housed is heated to 120 ℃.With 48.5gESI-15 (68.5% styrol copolymer, 16.9% homopolystyrene, 1.05Mi, 9.0I ₁₀/ I ₂) add and under 50RPM, mix.After 6 minutes, add 1.5g (3.0wt%) dicumyl peroxide (Hercules Inc.) and with the sample compounding more than 6 minutes.From Haake, take out sample, and compacting 3 minutes under 120 ℃ and 20,000 pounds of (9078.48kg) power in plasticator (Tetrahedron Press MTP-8 type), curing 20 minutes under 170 ℃ and 200 pounds of (90.78kg) power then.This is a sample 9.For sample 10, repeat this technology with 47.0gESI-15 and 3.0g dicumyl peroxide (6wt%).Measure tensile property, compressive set and UST (passing through TMA) by TMA.

Sample	Superoxide wt%	Trinitride wt%	The % elongation	Rupture stress (psi)	Compressive set (70 ℃)	?UST(TMA ???-℃)	Gel %
Sample	Superoxide wt%	Trinitride wt%	The % elongation	Rupture stress (psi)	Compressive set (70 ℃)	?UST(TMA ???-℃)	Gel %	????3	????-	????2.0	??650	????2000	????17％	??＞190	????98
????7	????3	?????-	??630	????890	????33％	????179	????82	????3	????-	????2.0	??650	????2000	????17％	??＞190	????98
????7	????3	?????-	??630	????890	????33％	????179	????82	????8	????6	?????-	??360	????880	????8％	??＞190	????93
????6	????-	????2.0	??310	????2300	????17％	??＞190	????98	????8	????6	?????-	??360	????880	????8％	??＞190	????93
????6	????-	????2.0	??310	????2300	????17％	??＞190	????98	????9	????3	?????-	??320	????1800	????64％	????97	????64
????10	????6	?????-	??310	????1300	????32％	??＞190	????81	????9	????3	?????-	??320	????1800	????64％	????97	????64

A kind of improvement of the crosslinked ESI representative of difunctionality sulfuryl azide to the ESI (sample 7,8,9 and 10) of peroxide crosslinking used in sample 3 and 6 explanations.

Claims

1. product that comprises partially or completely crosslinked random basically interpolymer, described crosslinked random basically interpolymer comprises:

(1) 1 to 65mol% derived from following polymer of monomers unit,

(a) at least a vinyl or vinylidene aromatic monomer, or

(b) at least a hindered aliphatic vinyl or vinylidene monomer, or

2. partially or completely crosslinked composition comprises:

(A) (by component (A) and gross weight (B)) 1 to 100wt% at least a random basically interpolymer, this interpolymer comprises:

(1) 1 to 65mol% derived from following polymer of monomers unit: (a) at least a vinyl or vinylidene aromatic monomer, or (b) at least a hindered aliphatic vinyl or vinylidene monomer, or (c) mixture of at least a vinyl or vinylidene aromatic monomer and at least a hindered aliphatic vinyl or vinylidene monomer; With

(B) at least a following polymers of (by component (A) and gross weight (B)) 0 to 99wt%:

(1) contains homopolymer derived from the polymer unit of one or more alpha-olefins with 2 to 20 carbon atoms, aryl substituted alpha-alkene or halogen substituted alpha-alkene;

(2) interpolymer, contain (a) 2 to 98mol% derived from ethylene polymer unit and (b) 98 to 2mol% derived from least a alpha-olefin with 3 to 20 carbon atoms, vinylformic acid, methacrylic acid, vinyl alcohol, diolefine, the polymer unit of vinyl-acetic ester with 4 to 20 carbon atoms;

(3) styrene block copolymer;

(4) (A) in the definition random basically interpolymer, wherein interpolymer (A) and difference (B4) are:

(a) vinyl or vinylidene aromatic monomer and/or hindered aliphatic or cyclic aliphatic vinyl or vinylidene monomer amount in arbitrary interpolymer of component (1) and the amount in arbitrary interpolymer of component (4) differ 0.5mol% at least; And/or

(b) number-average molecular weight (Mn) of arbitrary interpolymer of component (I) differs at least 20% with the number-average molecular weight (Mn) of arbitrary interpolymer of component (4).

3. processing component by the partially or completely crosslinked preparation of compositions of claim 2.

4. the partially or completely crosslinked composition of a claim 2, it is fiber, electric wire and cable insulating material, liner, flexible pipe, the boots that at high temperature uses and footwear, and trolley part and automobile decoration form.

5. foamable composite comprises:

(I) partially or completely crosslinked composition comprises:

(2) interpolymer, this interpolymer comprise (a) 2 to 98mol% derived from ethylene polymer unit and (b) 98 to 2mol% derived from least a alpha-olefin with 3 to 20 carbon atoms, vinylformic acid, methacrylic acid, vinyl alcohol, diolefine and the polymer unit of vinyl-acetic ester with 4 to 20 carbon atoms;

(3) styrene block copolymer;

(b) number-average molecular weight (Mn) of arbitrary interpolymer of component (1) differs at least 20% with the number-average molecular weight (Mn) of arbitrary interpolymer of component (4); (II) at least a whipping agent of (by component (I) and gross weight (II)) 0.1 to 25wt%.

6. a foam composition places acquisition under the foaming condition by the foamable composite with claim 5.

7. the foam composition of claim 6 is sole, pipe thermally-insulated body, furniture, motion sponge pad, acoustical panel and thermally-insulated body form.

8. a method for preparing thermo-setting elastomer comprises

(a) with at least a alpha-olefin and at least a vinyl or vinylidene aromatic compound and non-essential at least a diolefine in the presence of the constraint geometry catalyst reaction false random copolymer of formation and

(b) should solidify to form thermo-setting elastomer by the vacation random copolymer; Wherein solidify by the solidifying agent that is selected from silane compound, the initiator that is used for silane compound and the non-essential catalyzer that is used for silane compound; Carry out with radiation.

9. the method for claim 8, wherein alpha-olefin is selected from ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenyl propylene and its mixture;

Vinyl or vinylidene aromatic compound are selected from vinylbenzene, alpha-methyl styrene, o-methyl styrene, a vinyl toluene, p-methylstyrene, chloro-styrene, vinyl benzo tetramethylene, Vinylstyrene and its mixture; With

Diolefine is selected from divinyl, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl isophthalic acid, 6-octadiene, Dicyclopentadiene (DCPD), methene norbornene, ethylidene norbornene and its mixture.

10. the method for claim 8, wherein fetter geometry catalyst and comprise metal and the delocalization π-key bonding metal complexes partly of inducing part to replace in bond that contains periodic table of elements III-th family or IV family or lanthanon, described title complex has the constraint geometry around atoms metal, be lower than at the angle that delocalized replaces metal place between π-key bonding part branch center and at least one residue substituting group center like this and containing no this constraint and induce angle in substituent π-key bonding similar title complex partly, further condition is for containing these title complexs that an above delocalized replaces the part of x-key bonding, and wherein it only has one to be cyclic delocalized replacement π-bonding part for each atoms metal of ligand.

11. the method for claim 8 wherein fetters geometry catalyst and is selected from (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl)-1,2-ethane two basic zirconium dichlorides, (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl)-1,2-ethane two basic titanium dichloride, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-cyclopentadienyl) silane dimethyl titanium, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-indenyl) silane dimethyl titanium, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-tetrahydro indenyl) silane dimethyl titanium, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-fluorenyl) silane dimethyl titanium, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-tetrahydrofluorenyl) silane dimethyl titanium, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-octahydrofluorenyl) silane dimethyl titanium, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-cyclopentadienyl) silane dibenzyl titanium, (tertiary butyl amino) dimethyl (tetramethyl--η ⁵-cyclopentadienyl) silane dibenzyl zirconium and its mixture.

12. the method for claim 10 wherein fetters geometry catalyst by being selected from the promotor activation of polymerization aikyiaiurnirsoxan beta, oligomeric aikyiaiurnirsoxan beta, polymerization carbyl borine, oligomeric carbyl borine, monomer carbyl borine, aluminum alkyls, aluminum halide, aikyl aluminum halide, substituted ammonium salt, silver salt, ferricinium ion and its mixture.

13. the method for claim 10 wherein fetters geometry catalyst by the activation of three (pentafluorophenyl group) borine.

14. the method for claim 10 is wherein solidified by the solidifying agent that is selected from silane compound, the initiator that is used for silane compound and the non-essential catalyzer that is used for silane compound; Electron beam irradiation and its combination are carried out.

15. the method for claim 10 is wherein solidified with the false interpolymer of compounding and is carried out simultaneously.

16. a method for preparing Thermoplastic Vulcanizate comprises:

(a) at least a alpha-olefin and at least a vinyl or vinylidene aromatic compound and the polymerization in the presence of the constraint geometry catalyst of non-essential at least a diolefine are formed false random copolymer;

(b) should the vacation interpolymer and at least a TPO be higher than thorough mixing under the temperature of TPO fusing or softening temperature in temperature;

(c) in this uniform mixture, add the reagent that is used to solidify false random copolymer;

(d) be cured this uniform mixture of false random copolymer and compounding simultaneously, form Thermoplastic Vulcanizate thus; Be used to wherein solidify basically that the reagent of random interpolymer is selected from silane compound, be used for the initiator and the non-essential catalyzer that is used for silane compound of silane compound; Radiation and its combination.

17. the method for claim 16, wherein (a) alpha-olefin is selected from ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenyl propylene and its mixture; (b) vinyl or vinylidene aromatic compound are selected from vinylbenzene, alpha-methyl styrene, o-methyl styrene, a vinyl toluene, p-methylstyrene, chloro-styrene, vinyl benzo tetramethylene, Vinylstyrene and its mixture; (c) non-essential diolefine is selected from divinyl, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl isophthalic acid, 6-octadiene, Dicyclopentadiene (DCPD), methene norbornene, ethylidene norbornene, methyltetrahydro indenes and its mixture.

18. the method for claim 16, wherein fetter geometry catalyst and comprise metal and the delocalization π-key bonding metal complexes partly of inducing part to replace in bond that contains periodic table of elements III-th family or IV family or lanthanon, described title complex has the constraint geometry around atoms metal, be lower than at the angle that delocalized replaces metal place between π-key bonding part branch center and at least one residue substituting group center like this and containing no this constraint and induce angle in substituent π-key bonding similar title complex partly, further condition is for containing these title complexs that an above delocalized replaces the part of x-key bonding, and wherein it only has one to be cyclic delocalized replacement π-bonding part for each atoms metal of ligand.

19. the method for claim 18 wherein fetters geometry catalyst by being selected from the promotor activation of polymerization aikyiaiurnirsoxan beta, oligomeric aikyiaiurnirsoxan beta, polymerization carbyl borine, oligomeric carbyl borine, monomer carbyl borine, aluminum alkyls, aluminum halide, aikyl aluminum halide, ammonium salt, silver salt, ferricinium ion and its mixture.

20. the method for claim 18, wherein TPO contain derived from ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 2-methyl isophthalic acid-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene,, the monomeric unit of 5-methyl isophthalic acid-hexene and its mixture.

21. a method for preparing Thermoplastic Vulcanizate comprises:

(a) with at least a alpha-olefin and at least a vinyl or vinylidene aromatic compound and the polymerization in the presence of the constraint geometry catalyst of non-essential at least a diolefine, form random basically interpolymer;

(b) this random basically interpolymer and at least a TPO are higher than thorough mixing under the temperature of TPO fusing or softening temperature in temperature;

(c) adding is used to solidify this reagent of random interpolymer basically in this uniform mixture;

(d) be cured this random basically interpolymer and this uniform mixture of compounding simultaneously, form Thermoplastic Vulcanizate thus; Be used to wherein solidify basically that the reagent of random interpolymer is selected from silane compound, be used for the initiator and the non-essential catalyzer that is used for silane compound of silane compound; And composition thereof.

22. the method for claim 21, wherein (a) alpha-olefin is selected from ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene, 4-ethyl-1-hexene, 1-octene, 3-phenyl propylene and its mixture; (b) vinyl or vinylidene aromatic compound are selected from vinylbenzene, alpha-methyl styrene, o-methyl styrene, a vinyl toluene, p-methylstyrene, chloro-styrene, vinyl benzo tetramethylene, Vinylstyrene and its mixture; (c) non-essential diolefine is selected from divinyl, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,4-hexadiene, 7-methyl isophthalic acid, 6-octadiene, Dicyclopentadiene (DCPD), methene norbornene, ethylidene norbornene, methyltetrahydro indenes and its mixture.

23. the method for claim 21, wherein fetter geometry catalyst and comprise metal and the delocalization π-key bonding metal complexes partly of inducing part to replace in bond that contains periodic table of elements III-th family or IV family or lanthanon, described title complex has the constraint geometry around atoms metal, be lower than at the angle that delocalized replaces metal place between π-key bonding part branch center and at least one residue substituting group center like this and containing no this constraint and induce angle in substituent π-key bonding similar title complex partly, further condition is for containing these title complexs that an above delocalized replaces the part of x-key bonding, and wherein it only has one to be cyclic delocalized replacement π-bonding part for each atoms metal of ligand.

24. the method for claim 21 wherein fetters geometry catalyst by being selected from the promotor activation of polymerization aikyiaiurnirsoxan beta, oligomeric aikyiaiurnirsoxan beta, polymerization carbyl borine, oligomeric carbyl borine, monomer carbyl borine, aluminum alkyls, aluminum halide, aikyl aluminum halide, ammonium salt, silver salt, ferricinium ion and its mixture.

25. the method for claim 21, wherein TPO contains the monomeric unit that is selected from derived from ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 2-methyl isophthalic acid-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl isophthalic acid-hexene and its mixture.

26. the method for a crosslinking polymer composition, described polymer composition comprises:

(A) (by component (A) and gross weight (B)) 2 to 100wt% at least a random basically interpolymers, this interpolymer comprises:

(B) at least a following polymers of (by component (A) and gross weight (B)) 0 to 98wt%:

(1) contains polymkeric substance derived from the polymer unit of alpha-olefin with 2 to 20 carbon atoms or aryl substituted alpha-alkene;

(2) multipolymer, comprise (a) 2 to 98mol% derived from ethylene polymer unit and (b) 98 to 2mol% derived from least a alpha-olefin with 3 to 20 carbon atoms, vinylformic acid, methacrylic acid, vinyl alcohol, vinyl-acetic ester or have the polymer unit of the diolefine of 4 to 20 carbon atoms;

(3) styrene block copolymer;

(4) (A) in the definition interpolymer, wherein interpolymer (A) and difference (B4) are:

(b) number-average molecular weight (Mn) of arbitrary interpolymer of component (1) differs at least 20% with the number-average molecular weight (Mn) of arbitrary interpolymer of component (4); Described cross-linking method comprises the steps:

Make this polymer composition bear the electron beam irradiation of q.s so that polymkeric substance is partial cross-linked at least; Or

This polymer composition contacted with at least a superoxide of q.s make polymer composition partial cross-linked at least; Or

This polymer composition contacted with at least a trinitride of q.s make polymer composition partial cross-linked at least; Or

This polymer composition contacted with at least a silane compound, initiator and the non-essential catalyzer of q.s make polymer composition partial cross-linked at least; Or

Above-mentioned two or more cross-linking methods are combined.