CN1098287C - Thermoset interpolymers and foams - Google Patents

Abstract

The present invention provides a thermoset elastomer comprising a crosslinked pseudorandom or substantially random interpolymer of (a) 15 to 70 wt% of at least one alpha-olefin, (b) 30 to 70 wt% and (c) 0 to 15 wt% of at least one diene. The invention also provides a thermoplastic vulcanizate (eg provided in a thermoplastic polyolefin matrix) comprising the thermoset elastomer of the invention. The invention also provides a process for preparing the thermoset elastomers and thermoplastic vulcanizates of the invention and parts processed therefrom. The material of the present invention has an excellent balance of properties compared to EPM and EPDM based materials. The invention also relates to foams and methods for their preparation.

Description

Thermoset Copolymers and Foams

This invention relates to thermosetting interpolymers, processes for their preparation and products processed from the thermosetting interpolymers.

In a preferred embodiment, the present invention further relates to foams prepared from these thermoset interpolymers and to the preparation of crosslinked alpha-olefin/vinyl or vinylidene aromatic monomers and/or hindered aliphatic vinyl or vinylidene Monomer interpolymer approach.

Elastomers are defined as materials that exhibit large reversible deformations under relatively low stresses. Elastomers are often characterized by structural irregularities, nonpolar structures, or soft units in the polymer chain. Some examples of commercially available elastomers include natural rubber, ethylene/propylene (EPM) copolymers, ethylene/propylene/diene (EPDM) copolymers, styrene/butadiene copolymers, chlorinated polyethylene, and silicone rubber.

A thermoplastic elastomer is an elastomer having thermoplasticity. In other words, thermoplastic elastomers can be molded or shaped and reprocessed at temperatures at or above their melting point. An example of a thermoplastic elastomer is a styrene-butadiene-styrene (SBS) block copolymer. SBS block copolymers exhibit a two-phase rheology consisting of a glassy polystyrene body linked by rubbery butadiene segments. At temperatures between the glass transition temperatures of the butadiene mid-block and the styrene end-blocks, ie between -90°C and 116°C, SBS copolymers resemble cross-linked elastomers.

EP 416,815 discloses pseudorandom ethylene-styrene interpolymers. Uncrosslinked pseudorandom ethylene-styrene interpolymers exhibit low modulus at temperatures above the melting or softening point of the interpolymer.

SBS copolymers and uncrosslinked ethylene-styrene pseudorandom interpolymers suffer from the following disadvantages: lower mechanical strength, susceptibility to ozone degradation (to the extent they have unsaturation sites in the polymer backbone), and only Can be used in fields where the temperature of the elastomer does not exceed the melting point or softening point of the elastomer.

In contrast, thermoset elastomers are elastomers that have thermosetting properties. In other words, thermoset elastomers generally irreversibly cure or "cure" upon heating due to irreversible crosslinking reactions. Two examples of thermoset elastomers are crosslinked ethylene-propylene monomer rubber (EPM) and crosslinked ethylene-propylene-diene monomer rubber (EPDM). EPM materials are prepared by copolymerization of ethylene and propylene. EPM materials are usually cross-linked with peroxide cure and thus introduce thermoset properties. EPDM materials are linear interpolymers of ethylene, propylene and non-conjugated dienes such as 1,4-hexadiene, dicyclopentadiene or vinylidene norbornene. EPDM materials are usually cured with sulfur to introduce thermoset properties, although they can also be cured with peroxides. Although EPM and EPDM materials have the advantage of being used in higher temperature applications, EPM and EPDM elastomers have low green strength (at low ethylene content), higher cured elastomers than styrene butadiene rubber, and are more susceptible to oil attack The susceptibility, and resistance of cured elastomers to surface modification properties have these disadvantages.

There is a need for elastomers suitable for wide temperature ranges and low susceptibility to ozone degradation. There is a particular need for thermoset elastomers prepared from elastomers with high green strength that provide greater flexibility in elastomer handling prior to curing. There is a need for thermoset elastomers that are resistant to oil and can be used in machined parts that typically come into contact with oil, such as automotive parts and gaskets. There is a need for elastomers that are readily surface-modified to promote surface bonding of the elastomer and/or to provide ionic sites on the surface of the elastomer. There is also a need for methods of making these thermoset elastomers.

Thermoplastic vulcanizates are a crystalline polyolefin matrix in which a thermoset elastomer is uniformly distributed. Examples of thermoplastic vulcanizates include EPM and EPDM thermosets distributed in a crystalline polypropylene matrix. A disadvantage of these thermoplastic vulcanizates is that they are susceptible to oil degradation. There is a need for more oil-resistant thermoplastic vulcanizates. There is also a need for methods of making these thermoplastic vulcanizates.

Interpolymers prepared from alpha-olefin/vinylidene arene monomers or hindered aliphatic vinylidene monomers have excellent properties; however, there is a need for these polymers with improved properties.

It has been found that the properties of these interpolymers, such as higher upper service temperature, improved melt processability and tendency to self-adhesive, can be improved by crosslinking these interpolymers.

Foams prepared from crosslinked interpolymers are believed to have one or more of the following improved properties compared to non-crosslinked interpolymer foams: improved upper service temperature, lower density, improved elastic recovery, improved mechanical performance.

The present invention provides a thermoset product comprising a crosslinked substantially random interpolymer comprising:

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

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

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

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

(2) 35 to 99 mol% of polymer units derived from at least one aliphatic α-olefin having 2 to 20 carbon atoms.

Another aspect of the present invention relates to a foamable composition comprising:

(I) Partially or fully crosslinked compositions comprising:

(A) 2 to 100% by weight (based on the total weight of components (A) and (B)) of at least one partially or fully crosslinked substantially random interpolymer comprising:

(1) 1 to 65 mol% of polymer units derived from (a) at least one vinyl or vinylene aromatic monomer, or (b) at least one hindered aliphatic vinyl or vinylidene monomer, or (c) a mixture of at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic vinyl or vinylidene monomer; and

(2) 35 to 99 mol% of polymer units derived from at least one aliphatic α-olefin having 2 to 20 carbon atoms.

(B) 0 to 98% by weight (based on the total weight of components (A) and (B)) of at least one of the following polymers:

(1) a partially or fully crosslinked homopolymer comprising polymer units derived from one or more α-olefins having 2 to 20 carbon atoms;

(2) A partially or fully crosslinked copolymer comprising (a) 2 to 98 mol% of polymer units derived from ethylene and (b) 98 to 2 mol% of polymer units derived from at least one compound having 3 to 20 polymer units of aliphatic alpha-olefins having 4 to 20 carbon atoms, acrylic acid, methacrylic acid, vinyl alcohol, vinyl acetate or dienes having 4 to 20 carbon atoms;

(3) A partially or fully crosslinked styrene block copolymer;

(4) A partially or fully crosslinked substantially random interpolymer as defined in (1), wherein the interpolymers (1) and (4) differ in that:

(i) the amount of vinylidene aromatic hydrocarbon monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer in any interpolymer of component (1) is different from that in any interpolymer of component (4) The amounts in differ by at least 0.5 mol %; and/or

(ii) the number average molecular weight (Mn) of any interpolymer of component (1) differs from the number average molecular weight (Mn) of any interpolymer of component (4) by at least 20%; and (II) 0.1 to 25 wt % (based on the total weight of components (I) and (II)) of at least one blowing agent.

Another aspect of the invention relates to a method of crosslinking a polymer composition comprising:

(A) 2 to 100% by weight (based on the total weight of components (A) and (B)) of at least one partially or fully crosslinked substantially random interpolymer comprising:

(1) 1 to 65 mol% of polymer units derived from (a) at least one vinyl or vinylene aromatic monomer, or (b) at least one hindered aliphatic vinyl or vinylidene monomer, or (c) a mixture of at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic vinyl or vinylidene monomer; and

(2) 35 to 99 mol % of polymer units derived from at least one aliphatic alpha-olefin having 2 to 20 carbon atoms;

(B) 0 to 98% by weight (based on the total weight of components (A) and (B)) of at least one of the following polymers:

(1) a homopolymer comprising polymer units derived from one or more α-olefins having 2 to 20 carbon atoms;

(2) A copolymer comprising (a) 2 to 98 mol% of polymer units derived from ethylene and (b) 98 to 2 mol% derived from at least one aliphatic α-olefin having 3 to 20 carbon atoms , polymer units of acrylic acid, methacrylic acid, vinyl alcohol, vinyl acetate or dienes having 4 to 20 carbon atoms;

(3) A styrene block copolymer;

(4) An interpolymer as defined in (A), wherein the interpolymers (A) and (B4) differ in that:

(i) The amount of vinyl or vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer in any interpolymer of component (A) is the same as that in component (B4 ) differ by at least 0.5 mol% in either interpolymer; and/or

(ii) the number average molecular weight (Mn) of any interpolymer of component (A) differs by at least 20% from the number average molecular weight (Mn) of any interpolymer of component (B4);

Described cross-linking method comprises the steps:

(a) subjecting the polymer composition to a sufficient amount of electron beam radiation to at least partially crosslink the polymer; or

(b) contacting the polymer composition with a sufficient amount of at least one peroxide to at least partially crosslink the polymer composition; or

(c) contacting the polymer composition with a sufficient amount of at least one silane compound to at least partially crosslink the polymer composition; or

(d) contacting the polymer composition with a sufficient amount of at least one azide to at least partially crosslink the polymer composition; or

(e) Combining two or more of the above crosslinking methods.

Another aspect of the present invention relates to foams obtained by subjecting the above-described foamable polymer composition to foaming conditions.

The invention further comprises fabricated parts comprising the thermoset elastomer or thermoplastic vulcanizate or partially or fully crosslinked foam of the invention.

These and other embodiments are described in more detail below.

As used herein, the term "polymer" refers to a polymeric substance prepared by polymerizing monomers of the same or different type. The generic term polymer thus includes the term homopolymer (which term refers to a polymer prepared from only one type of monomer), and the term interpolymer as defined below.

As used herein, the terms "crosslinked interpolymer" and "thermoset interpolymer" are used interchangeably and refer to interpolymers having greater than 10% gel (as determined by ASTM D-2765-84).

Any numerical value referred to herein includes all values from the lowest value to the highest value in increments of one unit, provided that there is a separation of at least two units between any lowest value and any highest value. For example, if the given component content or process parameters such as temperature, pressure, time, etc. are variable, such as from 1 to 90, preferably 20 to 80, especially 30 to 70, it actually means, for example, 15 to 85 , 22 to 68, 43 to 51, 30 to 32, etc. The numerical ranges have been specifically listed in this specification. For values less than 1, a unit at this time should be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of those values which are expressly indicated, and all possible combinations of values from the lowest value to the highest value enumerated are to be considered expressly expressed in the same manner in this specification.

As used herein, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. The generic term interpolymer thus includes copolymers (often used to refer to polymers prepared by making from two different monomers), and polymers made from more than two different types of monomers.

The description herein that polymers or interpolymers include or contain certain monomers means that these polymers or interpolymers include or contain polymerized units derived from the monomers. For example, if a polymer is described as containing ethylene monomer, then the polymer has incorporated ethylene derivatives, ie _-CH2 - _CH2- .

The term "hydrocarbyl" is intended to mean any aliphatic, cycloaliphatic, aromatic, aryl-substituted aliphatic, aryl-substituted cycloaliphatic, aliphatic-substituted aromatic, or cycloaliphatic-substituted aryl group. Aliphatic or cycloaliphatic groups are preferably saturated. Similarly, the term "hydrocarbyloxy" refers to a hydrocarbyl group having oxygen between the group and the carbon atom to which it is attached.

The terms "monomer residues" or "polymer units derived from these monomers" refer to polymerizable monomer molecules remaining in a polymer chain through polymerization with another polymerizable molecule from which the polymer chain was made part.

The elastomeric thermoset compositions of the present invention are preferably substantially random interpolymers comprising olefin and vinyl aromatic monomers which are crosslinked to impart thermoset properties.

The term "substantially random" as used herein is composed of one or more alpha-olefin monomers and one or more vinylidene aromatic monomers or hindered aliphatic or cycloaliphatic vinylidene monomers, and optionally with other polymerizable ethylenically unsaturated monomers to obtain substantially random interpolymers, referring to the distribution of monomers in said interpolymers can be obtained by Bernoulli statistical model or first order Or a second-order Markovian statistical model to describe, see "Polymer Sequence Determination, Carbon-13 NMR Method" (J.C.Randall, Polymer Sequence Determination, Carbon-13 NMR Method, Academic Press New Youk, 1977, pages 71-78). Substantially random The interpolymers preferably contain no more than 15% of the total amount of vinyl or vinylidene aromatic monomers in blocks containing more than 3 vinyl or vinylidene aromatic monomers. More preferably, the interpolymer is not structurally characterized by a high degree of isotactic or syndiotactic configuration. This means that in the carbon-13 NMR spectrum of an essentially random interpolymer, the methylene carbons and methine carbons of the main chain representing the meso dyad sequence or the racemic dyad sequence The corresponding peak area does not exceed 75% of the total peak area of the main chain methylene carbons and methine carbons.

Pseudorandom interpolymers are a branch of substantially random interpolymers. Pseudorandom interpolymers are characterized as having a structure in which all phenyl (or substituted phenyl) groups (pendent groups pendant from the polymer backbone) are separated by two or more carbon backbone units. In other words, the pseudorandom interpolymers of the present invention in the uncrosslinked state can be described by the following general formula (using styrene as the vinyl aromatic monomer and ethylene as the alpha-olefin for ease of illustration):

Non-crosslinked pseudorandom interpolymers are described in EP416815A.

While not wishing to be bound by any particular theory, it is believed that during the addition polymerization of, for example, ethylene with styrene in the presence of the constrained geometry catalyst described below, if styrene monomer is inserted into the growing polymer chain, the inserted lower One monomer is a vinyl monomer or a styrene monomer inserted in an upside-down or "tail-to-tail" fashion. It is believed that after the upside-down or "tail-to-tail" insertion of a styrene monomer, the next monomer is ethylene, since insertion of a second styrene monomer at this point would place it too close to the inverted styrene monomer, i.e. separated by no more than two carbon backbone units.

The substantially random interpolymer is preferably characterized in that it is substantially random by 13C-NMR spectroscopy, wherein the main chain methylene groups corresponding to the meso dyad sequence or the racemic dyad sequence and The peak area of methine carbon does not exceed 75% of the total peak area of main chain methylene and methine carbon.

Substantially random interpolymers suitable for use as components (A) and (B4) of the present invention include those obtained by polymerizing i) one or more alpha-olefin monomers and ii) one or more vinyl or vinylene groups Substantially random interpolymers prepared from aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionally iii) other polymerizable ethylenically unsaturated monomers .

Suitable α-olefins include, for example, α-olefins containing 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, particularly suitable are ethylene, propylene, butene-1,4 - methyl-1-pentene, hexene-1 or octene-1, or ethylene with propylene, butene-1, 4-methyl-1-pentene, hexene-1 or octene-1 One or more in combination. These alpha-olefins do not contain aryl moieties.

Other optional polymerizable ethylenically unsaturated monomers include norbornene and C _1-10 alkyl or C _6-10 aryl substituted norbornene, for example the interpolymer is ethylene/styrene/norbornene.

Suitable vinyl or vinylidene aromatic monomers useful in preparing the interpolymers include, for example, those represented by the formula:

wherein ^R is selected from H and an alkyl group containing 1 to 4 carbon atoms, preferably H or methyl; each ^R is independently selected from H and an alkyl group containing 1 to 4 carbon atoms, preferably H or methyl; Ar is phenyl or phenyl with 1 to 5 substituents selected from halogen, C _1-4 alkyl and C _1-4 haloalkyl; and n has a value of 0 to 4, preferably 0 to 2, most preferably 0. Examples of monovinylaromatic monomers include styrene, vinyltoluene, α-methylstyrene, t-butylstyrene and chlorostyrene, including all isomers of these compounds. Particularly suitable monomers of this type include styrene and its lower alkyl or halogen substituted derivatives. Preferred monomers include styrene, alpha-methylstyrene and lower alkyl (C _1-4 ) or phenyl ring substituted styrene derivatives such as o-, m- and p-methylstyrene, ring halogenated styrene, p-vinyltoluene or mixtures thereof. A more preferred aromatic vinyl monomer is styrene.

The term "hindered aliphatic or cycloaliphatic vinyl or vinylidene compound" refers to an addition polymerizable vinyl or vinylidene monomer represented by the formula:

Wherein A ¹ is a sterically hindered large aliphatic or cycloaliphatic substituent containing up to 20 carbon atoms, R ¹ is selected from H and an alkyl group containing 1 to 4 carbon atoms, preferably H or methyl; Each ^R2 is independently selected from H and an alkyl group containing 1 to 4 carbon atoms, preferably H or methyl; or ^R1 and ^A1 may also form a ring system. Preferred aliphatic or cycloaliphatic vinyl or vinylidene monomers are those in which one carbon atom bearing an ethylenically unsaturated bond is tertiary or quaternary substituted. Examples of such substituents include cycloaliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctyl, or ring alkyl- or aryl-substituted derivatives thereof, t-butyl and norbornyl. The most preferred sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene compounds are the various isomers of cyclohexene, substituted cyclohexene and 5-vinylidene-2- Norbornene, especially 1-, 3- and 4-vinylcyclohexene.

These substantially random interpolymers can be modified by typical grafting, hydrogenation, functionalization or other reactions well known to those skilled in the art. The polymers can be readily sulfonated or chlorinated according to the prior art to provide functionalized derivatives. These substantially random interpolymers can also be modified by various chain extension or crosslinking methods including, but not limited to, peroxide-, silane-, sulfur-, radiation- or azide-based cure systems. Various crosslinking techniques are described in detail in co-pending US Patent Application Serial Nos. 08/921,641 and 08/921,642 (both filed August 27, 1997), the entire contents of which are incorporated herein by reference. Dual-cure systems can be effectively used, ie using heat, moisture curing combined with a radiation step. Dual cure systems are disclosed and claimed in US Patent Application Serial No. 536,022, filed September 29, 1995, by K.L. Walton and S.V. Karande, incorporated herein by reference. For example, it may be appropriate to combine a peroxide crosslinker with a silane crosslinker, a peroxide crosslinker with radiation, a sulfur-containing crosslinker with a silane crosslinker, and the like. The substantially random interpolymers can also be modified by various cross-linking methods including, but not limited to, the introduction of the diene component as a third monomer in the preparation of the interpolymers, and then by the methods described above and including the use of Other methods such as sulfur as a crosslinking agent are crosslinked via vinyl vulcanization.

One or more α-olefin monomers and one or more vinyl or vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or Interpolymers of vinylidene monomers are substantially random polymers. These interpolymers generally contain from 0.5 to 65, preferably from 1 to 55, more preferably from 2 to 50 mole percent of at least one vinyl or vinylidene aromatic monomer and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers. vinyl monomers, and 35 to 99.5, preferably 45 to 99, more preferably 50 to 98 mole percent of at least one aliphatic alpha-olefin containing 2 to 20 carbon atoms.

Other optional polymerizable ethylenically unsaturated monomers include strained cyclic olefins such as norbornene and C _1-10 alkyl or C _6-10 aryl substituted norbornene, an example of an interpolymer is ethylene/benzene Ethylene/Norbornene.

The number average molecular weight (Mn) of the polymers and copolymers is generally greater than 5,000, preferably from 20,000 to 1,000,000, especially from 50,000 to 500,000.

Conducting the polymerization reaction at a temperature above the autopolymerization temperature of the respective monomers and removing unreacted monomers may result in some homopolymer product being formed by free radical polymerization. For example, in the preparation of substantially random interpolymers, there will be some atactic homopolymerization of the vinyl aromatic monomer due to the possible homopolymerization of the vinyl aromatic monomer at higher temperatures. Polymer formation. The presence of homopolymers of vinyl or vinylidene aromatic monomers generally does not affect the effect of the present invention and is therefore allowed. Homopolymers of vinyl or vinylidene aromatic monomers can be separated from interpolymers as desired by extraction, e.g. with either interpolymer or homopolymers of vinyl or vinylidene aromatic monomers Precipitating agents selectively precipitate from their solutions. It is preferred in the present invention that the homopolymer of vinyl or vinylidene aromatic monomer does not exceed 20%, preferably less than 15%, of the total weight of the interpolymer.

The conditions for polymerizing alpha-olefins, vinyl or vinylidene arenes, and optional dienes are generally those used in solution polymerization processes, although the invention is not limited thereto. It is also believed that high pressure, slurry and gas phase polymerization methods can be used, provided that suitable catalysts and polymerization conditions are used.

In general, the polymerizations used to practice the present invention can be carried out under polymerization conditions known to those skilled in the art for Ziegler-Natta or Kaminsky-Sinn type polymerizations.

The substantially random interpolymers are prepared by polymerizing a mixture of polymerizable monomers in the concomitant presence of one or more metallocene or tethered geometry catalysts and various cocatalysts, as described in James C. Stevens et al. EP- A-0,416,815 and US 5,703,187 to Francis J. Timmers, both of which are hereby incorporated by reference in their entirety. The process for preparing substantially random interpolymers involves polymerizing a mixture of polymerizable monomers in the simultaneous presence of one or more metallocene or constrained geometry catalysts and various cocatalysts. Preferred operating conditions for these polymerizations are pressures from 1 atmosphere to 3000 atmospheres and temperatures from -30°C to 200°C. Conducting the polymerization reaction at a temperature above the autopolymerization temperature of the respective monomers and removing unreacted monomers may result in some homopolymer product being formed by free radical polymerization.

Examples of suitable catalysts and methods for preparing substantially random interpolymers are disclosed in U.S. Patent Application No. 07/702,475 filed May 20, 1991 (corresponding to EP-A-514,828), and U.S. Patent No. 5,055,438 , 5,057,475, 5,096,867, 5,064,802, 5,132,380, 5,189,192, 5,321,106, 5,347,024, 5,350,723, 5,374,696, 5,399,635, 5,470,993, 5,703,187 and 5,72

Substantially random α-olefin/vinyl aromatic monomer interpolymers can also be prepared according to the method described in JP07/278230 using compounds described by the following general formula Wherein C _P ¹ and C _P ² are independently cyclopentadienyl, indenyl, fluorenyl or equivalent groups of these groups; R ¹ and R ² are independently hydrogen atoms, halogen atoms, having 1-12 A hydrocarbon group, alkoxy group or aryloxy group of 3 carbon atoms; M is a group IV metal, preferably Zr or Hf, most preferably Zr; R ³ is an alkylene group or silanedi for crosslinking C _P ¹ and C _p ² base.

Substantially random interpolymers of α-olefins/vinyl aromatic monomers can also be obtained as described in WO 95/32095 by John G. Bradfute et al. (WR Grace & Co.), and by RBPannell (Exxon Chemical Patents) in WO 94/ 00500 and the method described in "Plastics Technology" (Plastics Technology ) September 1992, page 25, the entire contents described in these references are incorporated herein.

Also applicable are U.S. No. 08/708,809 and WO 98/09999 filed September 4, 1996 by Francis J. Timmers et al. A substantially random interpolymer of aromatic monomer/α-olefin tetrads. These interpolymers contain additional signals with intensity peaks 3 times larger than the noise peaks. The chemical shifts of these signals are between 43.70 to 44.25 ppm and 38.0 to 38.5 ppm. More specifically, the chemical shifts of the main peaks are 44.1, 43.9 and 38.2 ppm. The NMR proton test shows that the signal with a chemical shift of 43.70 to 44.25ppm belongs to methine carbon, and the signal with a chemical shift of 38.0 to 38.5ppm belongs to methylene carbon.

The new signal is believed to be attributable to sequences formed by the insertion of at least one alpha-olefin before and after two vinylaromatic monomers connected head to tail, such as the ethylene/styrene/styrene/ethylene tetrad, where benzene Vinyl monomers are inserted into this tetrad only in a 1,2 fashion (head to tail). Those skilled in the art understand that for tetrads containing vinyl aromatic monomers other than styrene and alpha-olefins other than ethylene, such ethylene/vinyl aromatic monomer/vinyl aromatic monomer/ Ethylene tetrads will have similar carbon-13 NMR peaks, but slightly different chemical shifts.

These interpolymers are prepared by polymerization at temperatures from -30°C to 250°C in the presence of catalysts such as those shown in the formulas below, optionally if desired but preferably in the presence of an activating cocatalyst :

Wherein each Cp is a substituted cyclopentadienyl group connected to M by a π bond; E is C or Si; M is a metal element of Group IV, preferably Zr or Hf, most preferably Zr; each R is independently is H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms; each R' is independently H, halogen, hydrocarbyl, Hydrocarbyloxy, silahydrocarbyl or hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms or silicon atoms, or two R' groups together can constitute a C _1-10 hydrocarbyl substitution 1,3-butadiene; m is 1 or 2. In particular, suitable substituted cyclopentadienyl groups include those represented by the formula:

wherein each R is independently H, hydrocarbyl, silahydrocarbyl or hydrocarbylsilyl, containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms, or two R groups together can be Constituting a divalent derivative of this group. Preferably, each R group is independently (including all isomers where appropriate) H, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl, or (If appropriate) two R groups are joined to form a fused ring system, such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl or octahydrofluorenyl.

Particularly preferred catalysts include, for example, rac(dimethylsilyldiyl)-bis-(2-methyl-4-phenylindenyl))zirconium dichloride, rac(dimethylsilyldiyl) Base)-bis-(2-methyl-4-phenylindenyl))1,4-diphenyl-1,3-butadiene zirconium, racemic (dimethylsilyldiyl)-bis -(2-Methyl-4-phenylindenyl)) diC _1-4 alkyl zirconium, racemic (dimethylsilyl diyl)-bis-(2-methyl-4-phenylindene base)) two C _1-4 alkoxy zirconium, or any combination thereof and the like.

The following titanium-based bound geometry catalysts can also be used: [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η ( tert-butylamino)dimethylsilane dimethyltitanium, (3-tert-butyl)(1,2,3,4,5-η)-1-indenyl(tert-butylamino)dimethylsilane di Methyltitanium and ((3-isopropyl)(1,2,3,4,5-η)-1-indenyl)(tert-butylamino)dimethylsilanedimethyltitanium or mixtures thereof.

Other methods of preparation of the interpolymers useful in the present invention have been reported in the literature. Longo and Grassi ( Makromol. Chem. , 1990, Vol. 191, pp. 2387-2396) and D'Anniello et al. ( Journal of Applied Polymer Science , 1995, Vol. 58, pp. 1701-1706) The preparation of ethylene-styrene copolymers using a catalyst system based on methylaluminoxane (MAO) and cyclopentadienyl titanium trichloride (CpTiCl ₃ ) is reported. Xu and Lin ( American Chemical Society Polymer Chemistry Section, Polymer Preprints , Am. Chem. Soc., Div. Polym. Chem. , 1994, Vol. 35, pp. 686, 687) reported using MgCl ₂ /TiCl ₄ /NdCl ₃ /Al(iBu) ₃ catalysts were used for copolymerization to prepare random copolymers of styrene and propylene. Lu et al. ( Journal of Applied Polymer Science , 1994, Vol. 53, pp. 1453-1460) reported the copolymerization of ethylene and styrene using a _TiCl4 / _NdCl3 / _MgCl2 /Al(Et) ₃ catalyst. Sernetz and Mulhaupt ( Macromol.Chem.Phys. , 1997, Vol. 197, pp. 1071-1083) describe the effect of polymerization conditions on the use of Me ₂ Si(Me ₄ Cp)(N-tert-Bu) Effect of TiCl ₃ /methylaluminoxane Ziegler-Natta type catalysts on the copolymerization of styrene and ethylene. Arai, Toshiaki, and Suzuki describe the production of copolymers of ethylene and styrene by bridged metallocene catalysts (Polymer Preprints, Am. Chem. Soc., Div. . Polym. Chem.) , 1997, Vol. 38, 349, 350), and disclosed in US 5,652,315 to Mitsui Toatus Chemicals, Inc. The manufacture of alpha-olefin/vinyl aromatic monomer interpolymers such as propylene/styrene and butene/styrene interpolymers is disclosed in US 5,244,996 to Mitsui Petrochemical Industries Ltd., to Mitsubishi In US 5,652,315 to Mitsui Petrochemical Industries Ltd., DE 197 11 339 A1 to Denki Kagaku Kogyo KK. All above-disclosed methods of making interpolymers are hereby incorporated by reference into this application.

The amount of vinyl or vinylidene arene monomer incorporated into the thermoset elastomer of the present invention is at least 30 wt%, preferably at least 35 wt%, based on the weight of the interpolymer. The amount of vinyl or vinylidene arene monomer incorporated into the interpolymer of the present invention is generally less than 70 wt%, preferably less than 60 wt%, based on the total weight of the interpolymer.

The substantially random interpolymers of the present invention generally contain from 0.5 to 65, preferably from 1 to 55, more preferably from 2 to 50 mole percent of at least one vinyl or vinylidene aromatic hydrocarbon monomer and/or hindered aliphatic or cycloaliphatic vinyl groups or vinylidene monomers, and 35 to 99.5, preferably 45 to 99, more preferably 50 to 98 mol % of at least one aliphatic alpha-olefin having 2 to 20 carbon atoms.

One or more dienes may optionally be incorporated into the interpolymer to provide functional unsaturation on the interpolymer, thereby allowing the interpolymer to participate in, for example, crosslinking reactions. Although conjugated dienes such as butadiene, 1,3-pentadiene (ie, piperylene) or isoprene may be used for this purpose, non-conjugated dienes are preferred. Typical non-conjugated dienes include, for example, open-chain non-conjugated dienes such as 1,4-hexadiene (see US 2,933,480) and 7-methyl-1,6-octadiene (also known as MOCD); Dienes; bridged cyclic dienes such as dicyclopentadiene (see US 3,211,709); or alkylene norbornenes such as methylene norbornene or ethylidene norbornene (see US 3,151,173). Non-conjugated dienes are not limited to those having only two double bonds, but also include those having three or more double bonds.

The amount of diene incorporated into the elastomer of the invention is from 0 to 15% by weight (based on the total weight of the interpolymer). When a diene is used, it preferably comprises at least 2 wt%, more preferably at least 3 wt%, and most preferably at least 5 wt%, based on the total weight of the interpolymer. Likewise, when a diene is used, it does not exceed 15 wt%, preferably not more than 12 wt%, based on the total weight of the interpolymer.

The number average molecular weight (Mn) of the polymers and interpolymers is generally greater than 5,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000. Compounding and curing of substantially random interpolymers

The thermosetting elastomer of the present invention includes various additives, such as carbon black, silicon dioxide, titanium dioxide, coloring pigments, clay, zinc oxide, stearic acid, accelerators, curing agents, sulfur, stabilizers, antidegradants, processing aids additives, binders/tackifiers, plasticizers, waxes, pre-crosslinking inhibitors, discontinuous fibers (such as wood cellulose fibers) and extender oils. These additives can be added before, during or after curing of the substantially random interpolymer. Substantially random interpolymers are typically mixed with fillers, oils, and curing agents at elevated temperatures for compounding. The compound is then cured at a temperature higher than that normally employed during compounding.

Carbon black is preferably added to the substantially random interpolymer prior to curing. The added carbon black is usually used to improve the tensile strength or toughness of the compounded product, and it can also be used as an extender for the compounded product or to mask the color of the compounded product. The amount of carbon black used is generally 0 to 80 wt%, preferably 0.5 to 50 wt%, based on the total weight of the formulation. When carbon black is used for color masking, it is generally used in an amount of 0.5 to 10% by weight of the formulation. When carbon black is used to increase the toughness of the furnish and/or reduce the cost, it is generally used in an amount greater than 10 wt% of the total weight of the furnish.

More preferably one or more extender oils are added to the substantially random copolymer prior to curing. The addition of extender oils generally improves processability and low temperature flexibility and reduces cost. Suitable extender oils are listed in Rubber World Blue book 1975 Edition: Substances and Furnishing Components for Rubber, pp. 145-190. Typical classes of extender oils include aromatic, naphthenic, and paraffinic extender oils. Extender oils are generally used in amounts of 0 to 50% by weight. When extender oil is used, it is generally used in an amount of at least 5 wt%, more preferably 15 to 25 wt%, based on the total weight of the furnish.

The amount of curing agent used is generally 0.5 to 12 wt% of the total weight of the formulation.

Suitable curing agents include peroxides, phenols, azides, aldehyde-amine reaction products, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, sulfur-containing compounds such as thiazoles, imidazoles , xanthamide, thiuram disulfide, p-quinone dioxime, dibenzoquinone dioxime, sulfur and mixtures thereof, see Encyclopedia of Chemical Technology , Volume 17, Second Edition, Interscience Publisher, 1968; and Organic Peroxides (Daniel Seern), Vol. 1, Wiely-Interscience, 1970.

Suitable peroxides include aromatic diacyl peroxides; aliphatic diacyl peroxides; dibasic acid peroxides; ketone peroxides; alkyl peroxyesters; Acetyl; Dibenzoyl peroxide; Bis-2,4-dichlorobenzoyl peroxide; Di-tert-butyl peroxide; Dicumyl peroxide; Tert-butyl perbenzoate; Tert-butylcumyl peroxide 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane; 2,5-bis(tert-butylperoxy)-2,5-dimethylhexyne-3; 4,4,4',4'-tetra(tert-butylperoxy)-2,2-dicyclohexylpropane; 1,4-bis(tert-butylperoxyisopropyl)benzene; 1,1-bis (tert-butylperoxy)-3,3,5-trimethylcyclohexane; lauroyl peroxide, succinic acid peroxide; cyclohexanone peroxide; tert-butyl peracetate; tert-butyl peroxide Hydrogen etc.

Suitable phenols are disclosed in USP 4,311,628, the disclosure of which is incorporated herein by reference. An example of a phenolic curing agent is the condensation product of a halogen-substituted phenol or a C ₁ -C ₁₀ alkyl-substituted phenol with an aldehyde in a basic solvent, or a condensation product of a difunctional phenolic diol. One class of phenolic curing agents is dimethylol phenol substituted by C ₅ -C ₁₀ alkyl in the para position. Haloalkyl substituted phenol curing agents and curing systems including methylol phenolic resins, halogen donors and metal compounds are also suitable.

Suitable azides include azidoformates such as butylene bis(azidoformate) (see also USP 3,284,421, Breslow, Nov. 8, 1966); aromatic polyazides, such as 4,4'-diphenylmethanediazide (see also USP 3,297,674, Breslow, January 10, 1967); and sulfonyl azides such as p,p'-oxybis(benzenesulfonate acyl azides).

A poly(sulfonyl azide) is any compound having at least two sulfonyl azide groups (SO ₂ N ₃ ) that are reactive with the substantially random interpolymer. The poly(sulfonyl azide) preferably has the structure XRX, wherein each X is -SO ₂ N ₃ , R represents an unsubstituted or inertly substituted hydrocarbyl, hydrocarbyl ether or silicon-containing group, preferably with sufficient Sufficient carbon, oxygen or silicon, preferably carbon atoms, to space the sulfonyl azide group for ease of reaction between the polyolefin and the sulfonyl azide, more preferably with at least one 1, still more preferably at least 2 one, most preferably at least three carbon atoms, oxygen atoms or silicon atoms, preferably carbon atoms. The term "inertly substituted" refers to substitution with atoms or groups that do not interfere with the desired reaction or the desired properties of the resulting crosslinked polymer. Suitable groups include fluorine, aliphatic or aromatic ether, siloxane, and sulfonyl azide groups when it is desired to link more than two substantially random interpolymer chains. Suitable structures include R, for example, an aryl, alkyl, aralkyl, aralkylsilane, or heterocyclic group, and other groups that are inert and space the sulfonyl azide group as desired. R more preferably includes at least one aryl group between the sulfonyl groups, most preferably at least two aryl groups (eg when R is 4,4'-diphenyl ether or 4,4'-biphenyl). When R is an aryl group, the group preferably has multiple rings, such as naphthalene bis(sulfonyl azide). Poly(sulfonyl)azides include compounds such as 1,5-pentanebis(sulfonylazide), 1,8-octanebis(sulfonylazide), 1,10-decanebis(sulfonylazide), acyl azide), 1,10-octadecanebis(sulfonyl azide), 1-octyl-2,4,6-benzenetri(sulfonyl azide), 4,4′-diphenyl Base ether bis(sulfonyl azide), 1,6-bis(4′-sulfonyl azidophenyl)hexane, 2,7-naphthalene bis(sulfonyl azide), and containing an average of 1 to 8 Chlorine atoms and 2 to 5 sulfonyl azide groups/molecule of mixed sulfonyl azides of chlorinated aliphatic hydrocarbons, and mixtures thereof. Preferred poly(sulfonyl azides) include oxo-bis(4-sulfonyl azide), 2,7-naphthalene bis(sulfonyl azide), 4,4'-bis(sulfonyl azide base) biphenyl, 4,4'-diphenyl ether bis(sulfonyl azide) and bis(4-sulfonyl azidophenyl)methane and mixtures thereof.

For crosslinking, a crosslinking amount of poly(sulfonyl azide) is used, i.e. an effective amount to crosslink the substantially random interpolymer compared to the starting substantially random interpolymer material, in other words, to result in the formation of at least 10% by weight gel (as evidenced by insoluble gel in boiling toluene when tested according to ASTM D-2765A-84) is sufficient (sulfonyl azide). The amount of poly(sulfonyl azide) is preferably at least 0.5, more preferably at least 1.0, and most preferably 2.0 wt%, based on the total weight of the substantially random interpolymer, these values depending on the molecular weight of the azide and the substantially random copolymer The molecular weight or melt index of the body. To avoid uncontrolled heating and unnecessary cost and/or reduction in physical properties, the amount of poly(sulfonyl azide) is preferably less than 10 wt%, more preferably less than 5 wt%.

To effect crosslinking, the sulfonyl azide is blended with the substantially random interpolymer and heated to at least the decomposition temperature of the sulfonyl azide (usually above 100°C, most often above 150°C). The preferred temperature range depends on the properties of the azide used. For example, for 4,4'-disulfonyl azidodiphenyl ether, the preferred temperature range is greater than 150°C, preferably greater than 160°C, more preferably greater than 185°C, most preferably greater than 190°C. The upper limit temperature is preferably lower than 250°C.

Suitable aldehyde-amine reaction products include formaldehyde-ammonia; formaldehyde-ethyl chloride-ammonia; acetaldehyde-ammonia; formaldehyde-aniline; butyraldehyde-aniline and heptanal-aniline.

Suitable substituted ureas include trimethylthiourea; diethylthiourea; dibutylthiourea; tripentylthiourea; 1,3-bis(2-benzothiazolylmercaptomethyl)urea; N-Diphenylthiourea.

Suitable substituted guanidines include diphenylguanidine; di-o-tolylguanidine; diphenylguanidine phthalate; and di-o-tolylguanidine salt of catecholboronic acid.

Suitable substituted xanthates include zinc ethyl xanthate, sodium isopropyl xanthate, butyl xanthate disulfide, potassium isopropyl xanthate, and zinc butyl xanthate.

Suitable dithiocarbamates include copper dimethyldithiocarbamate, zinc dimethyldithiocarbamate, thallium diethyldithiocarbamate, cadmium dicyclohexyldithiocarbamate, Lead Dimethyl Dithiocarbamate, Lead Dimethyl Dithiocarbamate, Selenium Dibutyl Dithiocarbamate, Zinc Pentylene Dithiocarbamate, Zinc Didecyl Dithiocarbamate and Zinc isopropyloctyldithiocarbamate.

Suitable thiazoles include 2-mercaptobenzothiazole, zinc mercaptothiazolyl thiol, 2-benzothiazolyl-N,N-diethylthiocarbamoyl sulfide and 2,2'-dithiobis( benzothiazole).

Suitable imidazoles include 2-mercaptoimidazoline and 2-mercapto-4,4,6-trimethyldihydropyrimidine.

Suitable sulfenamides include N-tert-butyl-2-benzothiazole sulfenamide, N-cyclohexylbenzothiazole sulfenamide, N,N-diisopropylbenzothiazole sulfenamide, N-( 2,6-Dimethylmorpholine)-2-benzothiazole sulfenamide and N,N-diethylbenzothiazole sulfenamide.

Suitable thiuram disulfides include N,N'-diethylthiuram disulfide, tetrabutylthiuram disulfide, N,N'-diisopropyldioctylthiuram disulfide Sulfide, tetramethylthiuram disulfide, N,N'-dicyclohexylthiuram disulfide and N,N'-tetralaurylthiuram disulfide.

Those skilled in the art will be able to select the amount of cross-linking agent based on the properties of the substantially random interpolymer or blends comprising the substantially random interpolymer such as molecular weight, molecular weight distribution, comonomer content, presence of Selection of cross-linking enhancing aids and additives (such as oil). Since it is possible to blend substantially random interpolymers with other polymers prior to crosslinking, one skilled in the art can use the following rules as refer to.

For example, for crosslinking using dicumyl peroxide, when the substantially random interpolymer is characterized by less than 35 wt% styrene, the amount of dicumyl peroxide is based on the total weight of polymer and peroxide The weight is usually at least 0.1 wt%, preferably at least 1 wt%, more preferably at least 2 wt%.

Additionally, for crosslinking with dicumyl peroxide, when the substantially random interpolymer is characterized by at least 35 to 60 wt% styrene, the amount of dicumyl peroxide is based on the total weight of polymer and peroxide The weight is usually at least 0.3 wt%, preferably at least 3 wt%, more preferably at least 4 wt%.

In addition, for crosslinking with dicumyl peroxide, when the substantially random interpolymer is characterized by greater than 60% by weight of styrene, the amount of dicumyl peroxide used is generally based on the total weight of polymer and peroxide It is at least 1 wt%, preferably at least 6 wt%, more preferably at least 9 wt%.

Generally, the amount of cross-linking agent used is no more than that required to effect a suitable degree of cross-linking. For example, the amount of dicumyl peroxide is not more than 15 wt%, preferably not more than 12 wt%, based on the total weight of polymer and peroxide.

Additionally, silane crosslinkers may be used. In this case, any silane that can effectively graft on and crosslink the substantially random interpolymer can be used in the practice of this invention. Suitable silanes include unsaturated silanes containing ethylenically unsaturated hydrocarbon groups such as vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or gamma-(meth)acryloyloxyallyl , and hydrolyzable groups such as alkoxy, alkyloxy or alkamino. Examples of hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, propionyloxy, and alkylamino or arylamino groups. Preferred silanes are unsaturated alkoxy groups that can be grafted onto the polymer. These silanes and their method of preparation are fully described in USP 5,266,627 to Meverden et al. Vinyltrimethoxysilane, vinyltriethoxysilane, gamma-(meth)propionyloxypropyltrimethoxysilane, and mixtures of these silanes are preferred silane crosslinkers for use in the present invention.

The amount of silane crosslinker used in the practice of this invention can vary widely depending on the properties of the substantially random interpolymer, the silane used, the processing conditions, the amount of grafting initiator, the end use, and the like. factor. Typically, when using vinyltrimethoxysilane (VTMOS) for crosslinking, the amount of VTMOS used is usually at least 0.1 wt%, preferably at least 1 wt%, more preferably at least 3 wt%, based on the total weight of polymer and silane.

Convenience and economical considerations are generally the two major limitations on the maximum amount of silane crosslinker used in the practice of this invention. For example, when using VTMOS, the maximum amount of VTMOS used is generally no more than 10 wt%, more preferably no more than 8 wt%, most preferably no more than 6 wt%, based on the combined weight of polymer and silane.

The silane crosslinker is grafted to the substantially random interpolymer generally by any conventional method in the presence of free radical initiators such as peroxides and azo compounds, or by ionizing radiation or the like. Organic initiators are preferred, such as any peroxide initiator such as dicumyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, peroxide tert-butyl octanoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, lauroyl peroxide and tert-butyl peracetate. A suitable azo compound is azobisisobutyronitrile.

A person skilled in the art can readily select the amount of initiator used, which amount depends on the characteristics of the substantially random interpolymer such as molecular weight, molecular weight distribution, comonomer content, presence of crosslinking enhancing aids, additives (such as oils), etc. select.

The amount of initiator depends on the % of vinyl or vinylidene aromatic or hindered aliphatic or cycloaliphatic comonomer present in the substantially random interpolymer. For example, for crosslinking using VTMOS, when the substantially random interpolymer is characterized by less than 35 wt% styrene, dicumyl peroxide is typically used in an amount of at least 250 ppm, preferably at least 500 ppm, more preferably at least 1500 ppm.

In addition, for crosslinking with VTMOS, when the substantially random interpolymer is characterized by at least 35 to 60 wt% styrene, dicumyl peroxide is typically used in amounts based on the total weight of polymer, silane and initiator At least 400 ppm, preferably at least 1,000 ppm, more preferably at least 2000 ppm.

In addition, for crosslinking with VTMOS, when the substantially random interpolymer is characterized by greater than 60 wt% styrene, the amount of dicumyl peroxide used is generally at least 500 ppm based on the total weight of polymer, silane and initiator , preferably at least 1,500 ppm, more preferably at least 3000 ppm.

Generally, no more initiator is used than is needed to effect effective grafting. For example, the amount of dicumyl peroxide is generally no greater than 20,000 ppm, preferably no greater than 10,000 ppm, based on the total weight of polymer, silane, and initiator.

Although any conventional method can be used to graft the silane crosslinker onto the substantially random interpolymer, a preferred method is to combine the two components in the first stage of a reactor extruder such as a Buss kneader. Blend with initiator. Grafting conditions can vary, but the melt temperature is typically 160°C to 260°C, preferably 190°C to 230°C, depending on residence time and half-life of the initiator.

Curing is accelerated with a crosslinking catalyst. Any catalyst that provides this function can be used in the present invention. These catalysts generally include organic bases, carboxylic acids, and organometallic compounds, including organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc, and tin. Dibutyltin dilaurate, Dioctyltin maleate, Dibutyltin diacetate, Dibutyltin dioctoate, Stannous acetate, Stannous octoate, Lead naphthenate, Zinc caprylate, Cobalt naphthenate. Tin carboxylates, especially dibutyltin dilaurate and dioctyltin maleate are particularly preferred in the present invention. The catalyst (or mixture of catalysts) is present in a catalytic amount, typically 0.015 to 0.035% by weight of the total weight of polymer, silane, initiator and catalyst

Instead of using chemical crosslinking agents, crosslinking can be performed by using radiation. Useful radiation types include electron beams or beta rays, gamma rays, X-rays or neutron rays. The radiation is believed to effect crosslinking by generating free radicals of the polymer which can bind and crosslink. Additional teachings related to radiation crosslinking are found in "Polyolefin Foam" in "Handbook of Polymer Foams and Technology" (C.P. Park, "Polyolefin Foam", Chapter 9, Handbook of Polymer Foams and Technology, edited by D. Klempner and K.C. Frisch, Hanser Press, New York (1991)), the contents of which are incorporated herein by reference in this application.

The radiation dose depends on the composition of the substantially random interpolymer. In general, as the amount of vinyl or vinylidene aromatic or hindered aliphatic or cycloaliphatic interpolymer increases, greater dosages are required to obtain the desired degree of crosslinking, i.e., resulting in the composition exhibiting at least 10% Gel, preferably at least 20% gel, more preferably at least 30% gel. Those skilled in the art depend on variables such as the thickness and structure of the article to be irradiated, and the characteristics of the substantially random interpolymers such as molecular weight, molecular weight distribution, comonomer content, presence of crosslinking enhancing aids, additives such as Oil), etc., can easily and appropriately select the radiation dose.

For example, for an 80 mil thick plate crosslinked by electron beam radiation, when the substantially random interpolymer is characterized by less than 35 wt% styrene, the typical radiation dose is greater than 5 Mrad, preferably greater than 10 Mrad, more preferably greater than 15 Mrad. Electron beam radiation dose is expressed here in the radiation unit "rad (RAD)", where one million rad is called "Mrad".

Furthermore, for crosslinking 80 mil thick plates by electron beam radiation, when the substantially random interpolymer is characterized by 35 to 60 wt% styrene, the typical radiation dose is greater than 5 Mrad, preferably greater than 15 Mrad, more preferably greater than 20 Mrad.

Furthermore, for crosslinking 80 mil thick plates by electron beam radiation, when the substantially random interpolymer is characterized by greater than 60 wt% styrene, the typical radiation dose is greater than 10 Mrad, preferably greater than 15 Mrad, more preferably greater than 20 Mrad.

Generally, the dosage will be no more than that necessary to cause the appropriate degree of crosslinking. For example, doses greater than 80 Mrad are generally not employed.

For substantially random interpolymers that do not include the optional diene component, peroxide or azide cure systems are preferred; for interpolymers with high styrene content (>50 wt%), azide cure system is preferred. For substantially random interpolymers including an optional diene component, sulfur groups (such as sulfur-containing, dithiocarbamate, thiazole, imidazole, sulfenamide, thiuram disulfide, or mixtures thereof) And phenolic cure systems are preferred.

In certain preferred embodiments of the present invention, dual cure systems (using a combination of heat, moisture curing and radiation steps) can be effectively used. Dual cure systems are disclosed and claimed in US Patent Application Serial No. 536,022 (filed September 29, 1995 to applicants K.L. Walton and S.V. Karande), which is incorporated herein by reference. For example, peroxide crosslinkers can be used in combination with silane crosslinkers, peroxide crosslinkers with radiation, sulfur-containing crosslinkers with silane crosslinkers, and the like. Preparation of polymer blends

Olefin polymers suitable for use as components (B1, B2 and B3) in the present invention are aliphatic α-olefin homopolymers or interpolymers, or one or more aliphatic α-olefins and one or more optional Copolymerized with non-aromatic monomers such as C _2-20 α-olefins or those aliphatic α-olefins containing 2 to 20 carbon atoms and containing polar groups. Suitable aliphatic α-olefin monomers for introducing polar groups into polymers include, for example, ethylenically unsaturated nitriles such as acrylonitrile, methacrylonitrile, ethacrylonitrile, etc., ethylenically unsaturated anhydrides such as Maleic anhydride, ethylenically unsaturated amides, such as acrylamide, methacrylamide, etc.; ethylenically unsaturated carboxylic acids (mono- and di-acids), such as acrylic acid and methacrylic acid, etc.; esters of ethylenically unsaturated carboxylic acids (especially lower esters, such as C ₁ -C ₆ alkyl esters), such as methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate or methacrylate, 2-ethylhexyl acrylate etc.; ethylenically unsaturated vinyl alcohols such as ethylene vinyl alcohol (EVOH); imides of ethylenically unsaturated diacids such as N-alkyl or N-arylmaleimides (such as N-phenylmaleimide imide), etc. Such monomers containing polar groups are preferably acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile. Halogens which may be introduced into polymers from aliphatic alpha-olefin monomers include fluorine, chlorine and bromine, such polymers being preferably chlorinated polyethylenes (CPEs). Preferred olefin polymers for use in the present invention are homopolymers or interpolymers of aliphatic (including cycloaliphatic) alpha-olefin monomers containing from 2 to 18 carbon atoms. Suitable examples are homopolymers of ethylene or propylene, and copolymers of two or more α-olefins. Other preferred olefin polymers are interpolymers of ethylene and one or more other alpha-olefins containing from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. The olefin polymer blend component (B) may also contain one or more non-aromatic monomers other than alpha-olefins which are copolymerizable therewith. Such other copolymerizable monomers include, for example, C ₄ -C ₂₀ dienes, preferably butadiene or 5-ethylidene-2-norbornene. Olefin polymers can furthermore differ in the number of their long or short chain branches and their distribution characteristics.

An olefinic polymer can be prepared by a high-pressure polymerization process using a free radical initiator, resulting in traditional long-chain branched low-density polyethylene (LDPE). The LDPE employed in the compositions of the present invention typically has a density of less than 0.94 g/cm3 (ASTM D 792) and a melt index of 0.01 to 100, preferably 0.1 to 50 g/10 min (according to ASTM D1238, condition I standard test method).

The other is a linear olefin polymer without long chain branching prepared by Ziegler polymerization process (such as U.S. Patent No. 4,076,698 invented by Anderson et al.), traditionally known as linear low density polyethylene polymer (heterophasic LLDPE) or linear high-density polyethylene polymer (HDPE), sometimes called heterophasic polymers.

HDPE is mainly composed of linear polyethylene long chains. The HDPE employed in the compositions of the present invention typically has a density of at least 0.94 grams per cubic centimeter (g/cc, as determined by ASTM D 792) and a melt index of 0.01 to 100, preferably 0.1 to 50 g/cc. 10 minutes (ASTM D-1238, condition I).

The heterophasic LLDPE employed in the compositions of the present invention typically has a density of 0.85 to 0.94 g/cm3 (ASTM D 792) and a melt index of 0.01 to 100, preferably 0.1 to 50 g/10 min (ASTM D 1238, Condition I). A preferred LLDPE is an interpolymer of ethylene and one or more other alpha-olefins containing from 3 to 18 carbon atoms, preferably from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.

Yet another polymer is a homogeneously branched or homogeneous polymer. Homogeneous polymers do not contain long chain branches, the branching of which originates only from the polymerization of monomers (if the monomers contain more than two carbon atoms). Homogeneous linear ethylene polymers include those prepared as described in US 3,645,992 (Elston), and in batch reactors and at higher olefin concentrations as described in US 5,026,798 and 5,055,438 (Canich) Below are those polymers prepared using so-called single-site catalysts. Homogeneously branched/homogeneously linear polymers are those in which the comonomers are distributed randomly within a given interpolymer molecule and where the interpolymer molecules have similar ethylene/comonomer ratios .

The homogeneous linear ethylene polymers employed in the compositions of the present invention typically have a density of 0.85 to 0.94 g/cm3 (ASTM D 792) and a melt index of 0.01 to 100, preferably 0.1 to 50 g/10 min (ASTM D 792). D 1238, condition I). Preferred homogeneous linear ethylene polymers are interpolymers of ethylene and one or more other alpha-olefins containing from 3 to 18 carbon atoms, preferably from 3 to 8 carbon atoms. Preferred comonomers include 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.

Further, it is advantageous to use a substantially linear olefin polymer (SLOP) as component (B) of the blend of the invention. These polymers have similar processability to LDPE, but have the strength and toughness of LLDPE. Similar to traditional homogeneous polymers, the essentially linear ethylene/α-olefin interpolymer has only a single melting peak, unlike the heterogeneous linear ethylene/α-olefin obtained by traditional Ziegler polymerization Interpolymers differ, which have two or more melting peaks (determined by differential scanning calorimetry). Substantially linear olefin polymers are disclosed in US 5,272,236 and 5,278,272, which patents are incorporated herein by reference.

The density of SLOP is generally 0.85 to 0.97 g/cm3, preferably 0.85 to 0.955 g/cm3, especially 0.85 to 0.92 g/cm3 (determined according to ASTM D 792 standard test method).

The melt index of SLOP is 0.01 g/10 min to 1000 g/10 min, preferably 0.01 g/10 min to 100 g/10 min, especially 0.1 g/10 min to 10 g/10 min (according to ASTM D 1238 , determined by the standard test method under the condition of 190°C/2.16 kg (also known as condition I ₂ ).

Also included are ultra-low molecular weight ethylene polymers and Ethylene/α-Olefin Interpolymers, this patent application is incorporated herein by reference. These ethylene/α-olefin interpolymers have an _I2 melt index of greater than 1000 g/10 minutes, or a number average molecular weight (Mn) of less than 11,000.

SLOP may be a homopolymer of C ₂ -C ₂₀ olefins such as ethylene, propylene, 4-methyl-1 pentene, etc., or may be ethylene with at least one C ₃ -C ₂₀ α-olefin and/or C ₂ - Interpolymers of C ₂₀ acetylenically unsaturated monomers and/or C ₄ -C ₁₈ dienes. SLOP may also be an interpolymer of ethylene with at least one of the aforementioned C ₃ -C ₂₀ α-olefins, dienes and/or acetylenically unsaturated monomers and other unsaturated monomers.

Particularly preferred olefinic polymers suitable for use as component (B) include LDPE, HDPE, heterophasic LLDPE, homogeneous linear ethylene polymers, SLOP, polypropylene (PP), especially isotactic polypropylene and rubber Toughened polypropylene, or ethylene-propylene copolymer (EP), or chlorinated polyolefin (CPE), or ethylene-vinyl acetate copolymer (EVA), or ethylene-acrylic acid copolymer (EAA), or mixtures thereof .

The term "block copolymer" is used herein to denote an elastomer having at least one block segment of hard polymer units and at least one block segment of rubber monomer units. However, the term excludes thermoelastic ethylene interpolymers, which are generally random polymers. Preferred block copolymers contain hard segments of styrenic polymers and segments of saturated or unsaturated rubber monomers. The structure of the block copolymers used in the present invention is not critical and can be linear or radial diblock or triblock, or any combination thereof. Preferably the main structure is triblock, more preferably linear triblock. The preparation of the block interpolymers suitable here is not the subject-matter of the present invention. Methods for the preparation of these block copolymers are known in the art. Suitable catalysts for preparing useful block copolymers having unsaturated rubber monomer units include lithium-based catalysts, especially alkyl lithiums. US 3,595,942 describes a process for hydrogenating block copolymers having unsaturated rubber monomer units to form block copolymers having saturated rubber monomer units. The structure of these polymers is determined by their method of polymerization. For example, by sequentially adding the required rubber monomers into the reactor using, for example, alkyllithium or dithiostilbene, or by coupling two copolymer segments with a bifunctional coupling agent A linear polymer is obtained. On the other hand, a branched structure can be obtained by using a suitable coupling agent having a functional group corresponding to a block copolymer containing three or more unsaturated rubber monomer units. Coupling can be carried out with polyfunctional coupling agents such as dihaloalkanes or alkenes and divinylbenzene, as well as certain polar compounds such as silicon halides, siloxanes or esters of monoalcohols and carboxylic acids. The presence of various coupling residues in the polymer is negligible for adequate description of the block copolymers forming part of the compositions of the invention.

Suitable block copolymers with unsaturated rubber monomer units include, but are not limited to, styrene-butadiene (SB), styrene-isoprene (SI), styrene-butadiene-styrene (SBS) , styrene-isoprene-styrene (SIS), methylstyrene-butadiene-methylstyrene and -methylstyrene-isoprene-methylstyrene.

The styrene portion of the block copolymer is preferably a polymer or interpolymer of styrene and its analogs and homologues, including alpha-methylstyrene and ring-substituted styrenes, especially ring-methylated styrenes . Preferred styrenic monomers are styrene and methylstyrene, with styrene being particularly preferred.

Block interpolymers having unsaturated rubber monomer units include homopolymers of butadiene or isoprene and copolymers of one or both of these monomers with small amounts of styrenic monomers. When the monomer used is butadiene, it is preferred that 35 to 55 mole percent of the condensed butadiene units in the butadiene polymer block have the 1,2-configuration. Thus, when one block is hydrogenated, the resulting product is or resembles a regular copolymer block of ethylene and 1-butene (EB). If the conjugated diene used is isoprene, the resulting hydrogenated product is or is similar to a regular copolymer block (EP) of ethylene and propylene. Preferred block copolymers having saturated rubber monomer units include at least one segment of styrene units and at least one segment of ethylene-butylene or ethylene-propylene copolymers. Preferred examples of these block copolymers having saturated rubber monomer units include styrene/ethylene-butylene copolymers, styrene/ethylene-propylene copolymers, styrene/ethylene-butylene/styrene (SEBS) copolymers , and styrene/ethylene-propylene/styrene (SEPS) copolymers.

Hydrogenation of block copolymers with unsaturated rubber monomer units, preferably by use of reaction products comprising alkylaluminum compounds with nickel or cobalt carboxylates or alkoxides, such as at least 80% substantially complete hydrogenation of at least 80% of the aliphatic double bonds , Under the condition that hydrogenation does not exceed 25% of styrene aromatic double bonds. Preferred block copolymers are those in which at least 99% of the aliphatic double bonds are hydrogenated while less than 5% of the aromatic double bonds are hydrogenated.

The proportion of styrene blocks is generally 8 to 65% by weight of the total weight of the block copolymer. The block copolymer preferably contains 10 to 35% by weight of styrenic block segments and 90 to 65% by weight of rubber monomer block segments (based on the total weight of the block copolymer).

The average molecular weight of each block can vary within a certain range. In many cases, the styrenic block segment has a number average molecular weight of 5,000 to 125,000, preferably 7,000 to 60,000, and the rubber monomer block segment has a number average molecular weight of 10,000 to 300,000, preferably 30,000 to 150,000. The total number average molecular weight of the block copolymer is usually 25,000 to 250,000, preferably 35,000 to 200,000. These molecular weights are measured very accurately by deuterium counting methods or osmolarity measurements.

In addition, various block copolymers suitable for use in the present invention may be grafted with minor functional groups by any means known in the art, such as modification with maleic anhydride.

Block copolymers useful in the present invention are commercially available from Shell Chemical Corporation under the tradename KRATON and from Dexco Polymers under the tradename VECTOR.

Additionally, blends of substantially random interpolymers with polyvinyl chloride (PVC) or ethylene vinyl alcohol (EVOH) may suitably be used. Preparation of thermoplastic vulcanizates

The thermosetting compositions of the present invention can be incorporated into polyolefins to form thermoplastic vulcanizates. The proportions of the components employed will vary somewhat depending upon the particular polyolefin employed, the intended use, and the nature of the crosslinked substantially random interpolymer and the formulation components. In general, as the amount of crosslinked substantially random interpolymer increases, the stiffness of the resulting thermoplastic vulcanizate decreases. The thermoplastic vulcanizates of the present invention generally comprise 10 to 90 weight percent polyolefin and 10 to 90 weight percent crosslinked substantially random interpolymer.

Suitable polyolefins include thermoplastic, crystalline high molecular weight polymers prepared by polymerizing one or more monoolefins. Examples of suitable polyolefins include ethylene and isotactic and syndiotactic polymer resins, examples of such monoolefins are propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl - 1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof. The thermoplastic vulcanizates of the present invention most preferably employ isotactic polypropylene as the polyolefin component.

The thermoplastic vulcanizates of the present invention are preferably prepared by dynamic vulcanization in which a mixture of uncrosslinked substantially random interpolymers is mixed with a polyolefin resin and a suitable curing agent to form a blend which is then masticated at the vulcanization temperature. In particular, the non-crosslinked substantially random interpolymer is blended with the polyolefin at a temperature above the melting point of the polyolefin. After the substantially random interpolymer has been thoroughly mixed with the polyolefin, a suitable curing agent is added, such as those described above corresponding to compounding and curing the substantially random interpolymer. The blend is then masticated using conventional masticating equipment such as a Banbury mixer, Brabender mixer or mixing extruder. The temperature of the blend during mastication should be sufficient to effectively vulcanize the substantially random interpolymer. Suitable vulcanization temperatures range from the melting temperature of the polyolefin (120°C for polyethylene and 175°C for polypropylene) to the temperature at which the substantially random interpolymer, polyolefin or curing agent degrades. Typical temperatures are from 180°C to 250°C, preferably from 180°C to 200°C.

Other methods than the substantially random interpolymer/polyolefin dynamic vulcanization method are also suitable. For example, substantially random interpolymers can be crosslinked prior to incorporation into the polyolefin. The crosslinked substantially random interpolymer can be pulverized and mixed with the polyolefin at a temperature above the melting or softening point of the polyolefin. The thermoplastic vulcanizates of the present invention are readily obtainable if the particles of the crosslinked substantially random interpolymer are small, well dispersed and of suitable concentration (i.e. if a mixture of the crosslinked substantially random interpolymer and polyolefin is achieved) . If such an intimately mixed mixture is not obtained, the resulting product will contain observable islands of cross-linked substantially random interpolymers. In this case, the fraction can be pulverized or cold ground to reduce the particle size to below 50 μm. With proper comminution, these pellets can be remolded into parts exhibiting a more uniform composition and exhibiting the enhanced properties of the thermoplastic vulcanizates of the present invention.

The thermoplastic vulcanizate of the present invention may include various additives such as carbon black, silica, titanium dioxide, coloring pigments, clay, zinc oxide, stearic acid, accelerators, vulcanizing agents, sulfur, stabilizers, antidegradants, processing aids , adhesives, tackifiers, plasticizers, waxes, premature vulcanization inhibitors, discontinuous fibers (such as lignocellulosic fibers) and extender oils. These additives can be added before, during or after vulcanization. Prepare foam:

The foam structures of the present invention may take any physical form known in the art, such as sheets, slabs, injection molded articles or blocks. Other useful forms are expandable particles, moldable foamed particles, or beads, and articles made from the expansion and/or coalescence or welding of those particles.

C.P. Park has an excellent description of methods for preparing olefinic polymer foam structures and their processing methods, see "Polyolefin Foam" in "Polyolefin Foam" in "Handbook of Polymer Foams and Technology" (C.P. Park, "Polyolefin Foam", Chapter 9 , Handbook of PolymerFoams and Technology, edited by D.Klempner and K.C.Frisch, Hanser Verlag, Munich, Vienna, New York, Barcelona (1991)), the content of this chapter is incorporated herein by reference.

The foam structures of the present invention can be prepared by heating a polymeric material comprising at least one substantially random interpolymer and a decomposable chemical blowing agent to form a foamable plasticized or molten polymeric material , extruding a foamable molten polymeric material through a die, inducing crosslinking in the molten polymeric material, and exposing the molten polymeric material to an elevated temperature to release a blowing agent thereby forming a foamed structure. The polymeric material and blowing agent can be mixed and melt-blended by any means known in the art such as using an extruder, mixer or blender. The chemical blowing agent is preferably dry blended with the polymeric material prior to heating the polymeric material in melt form, and may also be added while the polymeric material is in the melt phase. Crosslinking can be induced by addition of crosslinking agents or radiation. Induction of crosslinking and exposure to high temperature for foaming can be performed simultaneously or sequentially. If a crosslinking agent is used, it is added to the polymeric material in the same manner as a chemical blowing agent. Additionally, if a crosslinking agent is used, the foamable melt polymer material is heated or exposed to a temperature preferably below 150° C. to prevent decomposition of the crosslinking agent or blowing agent, thereby preventing premature crosslinking. If radiation crosslinking is used, the foamable melt polymer material is heated or exposed to a temperature preferably below 160°C to prevent decomposition of the blowing agent. The foamable molten polymer material is extruded or conveyed through a die having a desired shape to form a foamable structure. The foamable structure is then cross-linked and formed into a foam structure at elevated temperature (typically 150° C. to 250° C.), such as in an oven. If radiation crosslinking is used, the foamable structure is irradiated to crosslink the polymeric material and then foamed at the elevated temperature described above. The foam structures of the present invention can advantageously be produced in sheet or sheet form using crosslinking agents or radiation according to the methods described above.

The foam structures of the present invention can also be made into continuous slab structures by extrusion processes using long-form dies as described in GB 2,145,961A. In this process, a polymer, a decomposable blowing agent, and a cross-linking agent are mixed in an extruder, the mixture is heated to cross-link the polymer and decompose the blowing agent in a long forming section die; The die is formed and discharged from the die, which is brought into lubricated contact with a suitable lubricating material.

The foam structures of the present invention may also be formed into cross-linked foam beads suitable for molding into articles. To prepare the foam beads, discrete resin particles, such as pelletized resin globules, are suspended in a liquid medium, such as water, in which they are substantially insoluble, in an autoclave or other pressure-resistant vessel at elevated pressure and temperature. Next, it is impregnated with crosslinking agent and blowing agent, and the resin particles are quickly discharged into the air or low-pressure area for foaming to make foam beads. Another method is to impregnate the polymer beads with a blowing agent, cool, remove from the container, and expand by heating or steam. The blowing agent can be impregnated into the resin beads in suspension or in a non-aqueous state. The expandable beads are then expanded by heating with steam and shaped by conventional molding methods for expandable polystyrene foam beads.

The foam beads can then be molded by any method known in the art, such as placing the foam beads in a mold, applying pressure to the mold to die cast the beads, and heating the beads, for example with steam, to cause the beads to The particles adhere and bond to each other to form the article. Optionally, the beads can be preheated with air or other blowing agent before being placed into the mold. Excellent teachings of the above methods and molding methods are found in C.P. Park, cited above, pp. 227-229, US 3,886,100, US 3,959,189, US 4,168,353 and US 4,429,059. The foam beads can also be prepared by preparing a mixture of polymer, crosslinker and decomposable compound in a suitable mixing device or extruder and forming the mixture into beads and then heating the beads Cross-linked and foamed.

In another method of making crosslinked foam beads suitable for molding into articles, the substantially random interpolymer material is melted in conventional foam extrusion equipment and mixed with a physical blowing agent, thereby forming a substantially continuous foam strands. The foam strands are pelletized to form foam beads. The foam beads are then radiation crosslinked, and the crosslinked foam beads are subsequently bonded and molded as described above for other foam beads to form articles. Further teaching of this method can be found in US 3,616,365 and C.P. Park, cited above, pp. 224-228.

The foam structures of the present invention can be produced in the form of foam slabs by two different methods. One method involves the use of crosslinking agents or radiation.

The foam of the present invention can be formed into a foam block stock by combining a substantially random interpolymer material, a crosslinking agent, and a chemical blowing agent to form a foam block, and heating the mixture in a mold so that the crosslinking agent can The polymer material is cross-linked and the blowing agent can be decomposed, and then foamed by releasing the pressure in the mold. Optionally, the pressure-releasing formed bulk can be reheated for further foaming.

Crosslinked polymer sheets can be prepared by irradiating a polymer sheet with a high energy beam or by heating a polymer sheet containing a chemical crosslinking agent. The cross-linked polymer sheet is cut into the desired shape and impregnated with nitrogen at elevated pressure at a temperature above the softening point of the polymer; the pressure is released to allow cell nucleation and some degree of of foaming. The sheet is reheated above the melting point under lower pressure, and the pressure is released to expand the foam.

Blowing agents useful in preparing the foam structures of the present invention include decomposable chemical blowing agents. Certain chemical blowing agents decompose at high temperatures to form gases or vapors, thereby expanding the polymer into foam form. The agent is preferably in solid form to facilitate dry mixing with the polymeric material. Chemical blowing agents include azodicarbonamide, azobisisobutyronitrile, benzenesulfonyl hydrazide, 4,4-hydroxybenzenesulfonyl semicarbazide, p-toluenesulfonyl semicarbazide, barium azodicarboxylate, N , N'-dimethyl-N, N'-dinitrosoterephthalamide, N,N'-dinitrosopentamethylenetetramine, 4,4-oxobis(benzenesulfonyl hydrazine) and trihydrazine triazine. Azodicarbonamide is preferred. Further teaching on chemical blowing agents is found in CP Park, cited above, pp. 205-208, and FA Shutov, " Polyolefin Foams", "Polyolefin Foam", Handbook of Polymer Foams and Technology 382- 402 pp., edited by D. Klempner and KC Frisch, Hanser Verlag, Munich, Vienna, New York, Barcelona (1991).

The chemical blowing agent is mixed with the polymer in an amount sufficient to release 0.2 to 5.0, preferably 0.5 to 3.0, most preferably 1.0 to 2.50 mol gas or vapor per kg polymer.

In some of the methods of making the foam structures of the present invention, physical blowing agents may be used. Physical blowing agents include organic and inorganic blowing agents. Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, nitrogen and helium. Organic blowing agents include aliphatic hydrocarbons containing 1 to 9 carbon atoms, aliphatic alcohols containing 1 to 3 carbon atoms, and fully and partially halogenated aliphatic hydrocarbons containing 1 to 4 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and neopentane. Fatty alcohols include methanol, ethanol, n-propanol and isopropanol. Fully and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorinated hydrocarbons and chlorofluorocarbons. Examples of fluorocarbons include fluoromethane, perfluoromethane, fluoroethane, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1 , 1,2-tetrafluoroethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane , Dichloropropane, Difluoropropane, Perfluorobutane, Perfluorocyclobutane. Partially halogenated chlorinated hydrocarbons and chlorofluorocarbons used in the present invention include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane ( HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and 1-chloro- 1,2,2,2-Tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane alkanes, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane and dichlorohexafluoropropane.

To prepare foam-forming polymer gels, blowing agent is added in an amount of 0.2 to 5.0, preferably 0.5 to 3.0, most preferably 1.0 to 2.50 mol per kg of polymer melt.

Various additives can be added to the foam structure of the present invention, examples of these additives are stability control agents, nucleating agents, inorganic fillers, pigments, antioxidants, acid scavengers, ultraviolet absorbers, flame retardants, processing aids and extrusion Auxiliary.

Stability control agents may be added to the foams of the present invention to enhance dimensional stability. Preferred stability control agents include amides and esters of C _10-24 fatty acids. Such adjuvants are described in US 3,644,230 and 4,214,054, which are incorporated herein by reference. Most preferred adjuvants include stearyl stearamide, glyceryl monostearate, glyceryl monobehenate and sorbitan monostearate. Such stability control agents are generally used in amounts ranging from 0.1 to 10 parts per 100 parts of polymer.

In addition, nucleating agents can be added to control the size of the foam cells. Preferred nucleating agents include mixtures of inorganic substances such as calcium carbonate, talc, clay, titanium dioxide, silicon dioxide, barium sulfate, diatomaceous earth, citric acid and sodium bicarbonate. The nucleating agent is used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of polymer.

The density of the foam structure is less than 250, preferably less than 100, most preferably 10 to 70 kg/m3. The foam cells have an average size of 0.05 to 5.0, preferably 0.2 to 2.0, most preferably 0.3 to 1.8 mm (measured according to ASTM D3576).

The foam structure can have any physical shape known in the art, such as extruded sheets, rods, plates, and profiles. The foam structure can also be formed into any of the above shapes or any other shape by molding the expandable beads.

Foam structure can be open cell or closed cell according to ASTM D2856-A.

In one embodiment of the invention, the composition of the invention can be used for cable insulation and/or cable jackets. The cable insulation material of the present invention may be filled or unfilled. If filled, the amount of filler present should not exceed that which would result in a reduction in the electrical and/or mechanical properties of the interpolymer. Typically, the filler is present in an amount of from 20 to 80, preferably from 50 to 70 wt%, based on the weight of the polymer. Representative fillers include kaolin, magnesium hydroxide, silica, calcium carbonate. In preferred embodiments of the invention in which fillers are present, the fillers are coated with a material which prevents or delays the tendency of the fillers to interfere with the curing reaction. An example of such a filler coating is stearic acid. Other additives may be used to prepare and be present in the insulation of the present invention, such fillers include antioxidants, processing aids, pigments and lubricants.

In another embodiment of the invention, the compositions of the invention, in particular the silane-grafted substantially random interpolymers, are formed into automotive weather strips, gaskets or seals. Weatherstrips are used as sealing systems for doors, trunks, belt liners, fume hoods and similar components. These materials can be processed on conventional thermoplastic processing equipment. Articles made from cross-linked interpolymers should have better sound insulation properties than conventional sulfur-cured EPDM weatherstrips.

In another embodiment of the invention, crosslinkable fibers can be prepared. In a specific embodiment, the substantially random interpolymer is mixed with an effective amount of a peroxide or azide as described herein. The resulting mixture is extruded into fibers, which are then heated to crosslink.

In another embodiment, the substantially random interpolymer is extruded into fibers and then crosslinked by radiation under an effective amount of radiation as described herein.

In another embodiment, the silane-grafted substantially random interpolymer is formed into fibers that exhibit improved heat resistance. These fibers are readily crosslinked upon exposure to moisture, either by immersion in water or by exposure to ambient moisture.

The resulting cross-linked fibers can be used in woven and non-woven fabrics (heat resistant washable cloths), elastic strings (e.g. woven elastic belts), elastic filters for water/air filtration (e.g. non-woven air fresheners), and fiber mats (such as non-woven carpet underlays).

For the thermoset elastomers of the present invention, carbon black is preferably added to the blend of the substantially random interpolymer and polyolefin prior to vulcanization. The carbon black added is usually 0 to 50 wt%, preferably 0.5 to 50 wt%, based on the total ingredient amount. When carbon black is used for color shading, it is generally used in an amount of 0.5 to 10% by weight of the total formulation. When carbon black is used to improve toughness and/or reduce cost, its usage is usually greater than 10wt% of the total amount of ingredients.

Additionally, for the thermoset elastomers of the present invention, it is preferred that one or more extender oils be added to the blend of the substantially random interpolymer and polyolefin prior to vulcanization. Suitable extender oils are listed in Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, pp. 145-190. Typical extender oils include aromatic oils, naphthenic oils and paraffinic extender oils. Extender oils are generally used in amounts of 0 to 50% by weight based on the total weight of the furnish. When extender oil is used, it is generally used in an amount of at least 5 wt%, preferably 15 to 25 wt%, based on the total weight of the furnish.

Additives such as antioxidants (eg hindered phenols such as Irganox® 1010), phosphonites (eg Irgafos® 168), UV stabilizers, adhesion additives (eg polyisobutylene), anti-blocking agents, colorants, pigments and fillers They may also be included in the interpolymers used in the blends of the present invention and/or used in the present invention, provided they do not interfere with the improved properties discovered by applicants.

Additives are used in functionally effective amounts known in the art. For example, an antioxidant is used in an amount that prevents oxidation of the polymer or polymer blend at the temperature and environment during storage and final use of the polymer. These antioxidants are generally present in amounts of 0.01 to 10 wt%, preferably 0.05 to 5 wt%, more preferably 0.1 to 2 wt% (based on the total weight of the polymer or polymer blend). Similarly, the amounts of any other additives recited are those that function functionally, such as to render the polymer or polymer blend resistant to caking, to produce the desired amount of filler loading to achieve the desired result, to use colorants or Pigments give the desired color. Suitable amounts of these additives are from 0.05 to 50 wt%, preferably from 0.1 to 35 wt%, more preferably from 0.2 to 20 wt%, based on the weight of the polymer or polymer blend. However, for fillers, they may be used in amounts up to 90% by weight of the total weight of the polymer or polymer blend.

In a preferred embodiment, the thermoplastic vulcanizate of the present invention may comprise 30 to 60 wt% substantially random interpolymer, 15 to 55 wt% thermoplastic polyolefin, and 15 to 30 wt% extender oil. These thermoplastic vulcanizates are especially useful as automotive moldings.

In a particularly preferred embodiment of the invention, the thermoplastic vulcanizates of the invention can be characterized by ASTM #2 oil swell of less than 60% (as determined by ASTM D-471). Test Methods

Monomer content was determined by carbon-13 NMR spectroscopy.

Stress-strain properties were measured on an Instron 1122 load frame with 0.870 inch (2.2 cm) microtensile samples at a tensile rate of 5 inches/min (12.7 cm/min). Tensile at break, elongation 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 swells are measured according to ASTM D-471.

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

Compression set is measured according to ASTM D-395.

Gel content % (crosslinking %) is measured using the xylene extraction method according to ASTM D-2765-84. About 1 g of polymer samples were weighed, these samples were transferred into mesh baskets, and placed in boiling xylene for 12 hours. After 12 hours, the sample baskets were removed and placed in an oven at 150°C and 28 inches of mercury vacuum for 12 hours. After 12 hours, the samples were removed, allowed to cool to room temperature within 1 hour, and weighed. The % polymer extracted was calculated using the following formula:

% polymer extracted = ((initial weight - final weight)/initial weight) x 100.

The recorded gel% value is calculated according to the following formula:

Gel % = 100 - Extracted polymer %

The upper limit service temperature is measured with a thermodynamic analyzer named Perkin Elmer TMA7. A probe force of 102 g and a heating rate of 5°C/min was used. Each sample was a disc of approximately 2 mm in diameter prepared by melt pressing at 205°C and air cooling to room temperature.

Example 1

Preparation of ethylene-styrene copolymers and thermoset elastomers

According to the following method, (tert-butylamino) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane dimethyl titanium (+4) catalyst and tris(pentafluorobenzene) in a molar ratio of 1:1 base) borane cocatalysts for the preparation of ethylene/styrene copolymers. To a 2 liter reactor was charged 360 g (500 ml) of ISOPAR ^™ E mixed paraffinic solvent (available from Exxon Chemical Company) and the required amount of styrene comonomer. Hydrogen was added to the reactor by differential pressure expansion from a 75ml addition kettle. The reactor is heated to operating temperature and saturated with ethylene at the desired pressure. In a dry box by pipetting the required amount of a 0.005 M solution of tris(pentafluorophenyl)borane cocatalyst in ISOPAR ^™ E mixed paraffinic solvent or toluene into ISOPAR ^™ E mixed paraffinic solvent or toluene In (tert-butylamino) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane dimethyl titanium (IV) catalyst, (tert-butylamino) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)silane dimethyl titanium(IV) catalyst mixed with tris(pentafluorophenyl)borane cocatalyst. The resulting catalyst solution was fed into the catalyst feed tank and injected into the reactor.

Ethylene was introduced to carry out the polymerization reaction as needed. Additional catalyst and cocatalyst feedstocks were prepared in the same manner and periodically added to the reactor, if necessary. The total amount of catalyst used is listed in Table 1. In each case, the amount of tris(pentafluorophenyl)borane cocatalyst listed in Table 1 (on a molar basis) was equal to (tert-butylamino)dimethyl(tetramethyl-η ⁵ -cyclopenta The amount of dienyl)silane dimethyl titanium(IV) catalyst. After one run, the polymer solution was discharged from the reactor and quenched with isopropyl alcohol. A hindered phenol antioxidant (IRGANOX ^™ 1010 (available from Ciba Geigy)) was added to the polymer. Volatiles were removed from the polymer in a reduced pressure vacuum oven at 135°C for 20 hours.

The conditions for the preparation of substantially random interpolymers are listed in Table 1.

Table 1 sample Catalyst amount (μ-mol) ISOPAR ^™ -E (mL) Styrene (mL) Ethylene (kPa) Hydrogen (kPa) Reaction temperature (°C) Response time (min) Yield (g) ES-1 2.5 250 750 2068 0 80 10 32.3 ES-2 3.8 500 500 1379 0 80 10 28.8 ES-3 15.0 500 500 1379 689 60 30 166

The resulting substantially random interpolymers are characterized as pseudorandom and linear.

The interpolymers were compounded and cured as follows. A 60 g Brabender PS-2 internal mixer barrel was preheated to 49°C. 100pph carbon black N550 (available from Cabot Corporation), 50pph SUNPAR ^™ 2280 oil (available from Sun Oil), 5pph paraffin, 1pph stearic acid, 8pph Vul-Cup 40KE peroxide (available from Hercules) in a plastic or paper container Premixed with 1.5pph triallyl cyanurate additive (purchased from American Cyanamide). The resulting blend was added to a 60 g cartridge. To the barrel was added another 100 pph of the desired substantially random interpolymer prepared above. Lower the plunger onto the internal mixer and mix the ingredients until the temperature reaches 104°C (approximately 5 minutes). Rolling is not necessary for discharging the compound from the internal mixer.

The samples were compression molded at 127°C to obtain uncured (green) test pieces. The uncured (green) test pieces were compression molded and cured at 171° C. for 20 minutes to obtain a crosslinked thermosetting elastomer composition.

The stress-strain properties of neat interpolymer, uncured (green) coupons, and crosslinked thermoset elastomer compositions are listed in Table 2. Here, the mark "ND" indicates that the specified property has not been determined.

Table 2 ES-1 ES-2 ES-3 C1 ^* (Tafmer680-P) ¹ C2(V-457) ² C3(V-707) ³ Comonomer content (determined by NMR) wt% ethylene 67.5 56.8 48.0 51.0 70.0 wt% styrene 32.5 43.2 52.0 0 0 wt% propylene 0 0 0 49.0 30.0 Stress-strain properties of neat uncrosslinked polymers Tensile at break (psi) 3200 2156 1390 668 243 887 100% modulus (psi) 759 445 256 170 75 205 Elongation at break (%) 395 420 518 1115 1780 1336 Melt index at 190°C (g/10min) 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 Stress-strain properties of raw meal Tensile at break (psi) ND ND 594 460 70 459 100% modulus (psi) ND ND 315 264 52 231 Elongation at break (%) ND ND 453 476 84 685 ES-1 ES-2 ES-3 C1 ^* (Tafmer680-P) ¹ C2 ^* (V-457) ² C3 ^* (V-707) ³ Stress-strain properties of crosslinked polymers Tensile at break (psi) 3156 ND 1005 1994 1236 1569 100% modulus (psi) 1076 ND 532 506 276 674 Elongation at break (%) 300 ND 297 383 409 292 *Not an example of the invention

As shown in Table 2, the cross-linked thermosetting elastomer composition of the present invention exhibits a better performance than the comparative materials C1 (Tafmer ^TM 680-P (purchased from Mitsui Petrochemical)) and C2 (Vistalon ^TM 457 (purchased from Exxon Chemical Company)) High 100% modulus. This is consistent with the neat interpolymer showing a higher 100% modulus than the comparative material.

Example 2

Preparation of ethylene/styrene/ethylene norbornene interpolymers and thermoset elastomers

According to the following method, (tert-butylamino) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane dimethyl titanium (+4) catalyst and tris(pentafluorobenzene) in a molar ratio of 1:1 Preparation of ethylene/styrene/ethylene norbornene copolymers with borane cocatalysts. To a 2 liter reactor was charged 360 g (500 ml) of ISOPAR ^™ E mixed paraffinic solvent (available from Exxon Chemical Company) and the required amount of styrene comonomer. Ethylene norbornene is fed into the reactor. Hydrogen was added to the reactor by differential pressure expansion from a 75ml addition kettle. The reactor is heated to operating temperature and saturated with ethylene at the desired pressure. In a dry box by pipetting the required amount of a 0.005 M solution of tris(pentafluorophenyl)borane cocatalyst in ISOPAR ^™ E mixed paraffinic solvent or toluene into ISOPAR ^™ E mixed paraffinic solvent or toluene In (tert-butylamino) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane dimethyl titanium (IV) catalyst, (tert-butylamino) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)silane dimethyl titanium(IV) catalyst mixed with tris(pentafluorophenyl)borane cocatalyst. The resulting catalyst solution was fed into the catalyst feed tank and injected into the reactor.

Ethylene was introduced to carry out the polymerization reaction as needed. Additional catalyst and cocatalyst feedstocks were prepared in the same manner and periodically added to the reactor, if desired. The total amount of catalyst used is listed in Table 3. In each case, the amount of tris(pentafluorophenyl)borane cocatalyst listed in Table 3 (on a molar basis) was equal to (tert-butylamino)dimethyl(tetramethyl-η ⁵ -cyclopenta The amount of dienyl)silane dimethyl titanium(IV) catalyst. After one run, the polymer solution was discharged from the reactor and quenched with isopropanol. A hindered phenol antioxidant (IRGANOX ^™ 1010 (available from Ciba Geigy Co.)) was added to the polymer. Volatiles were removed from the polymer in a reduced pressure vacuum oven at 135°C for 20 hours.

The conditions for the preparation of ethylene/styrene/ethylidene norbornene interpolymers are listed in Table 3.

table 3 sample Catalyst amount (-mol) ISOPAR-E (ml) Styrene (mL) Amount of ENB (mL) Ethylene pressure (psig) Hydrogen (psi) Reaction temperature (C) Response time (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-3 10 500 500 25 200 100 65 30 135.1

The resulting substantially random interpolymers are characterized as pseudorandom and linear.

The interpolymers were compounded and cured as follows. A 60 g Brabender PS-2 internal mixer barrel was preheated to 49°C. 100pph carbon black N550 (available from Cabot Corporation), 50pph SUNPAR ^™ 2280 oil (available from Sun Oil), 5pph paraffin, 1pph stearic acid, 5pph zinc oxide, 1.5pph sulfur and 0.5pph Captax 2 in a plastic or paper container - Mercaptobenzothiazole (from RTVanderbilt) premixed. The resulting blend was added to a 60 g cartridge. To the barrel was added another 100 pph of the desired substantially random interpolymer prepared above. Lower the plunger onto the internal mixer and mix the ingredients until the temperature reaches 104°C (approximately 5 minutes). Rolling is not necessary for discharging the compound from the internal mixer.

The samples were compression molded at 127°C to obtain uncured (green) test pieces. The uncured (green) test pieces were compression molded and cured at 171° C. for 20 minutes to obtain a crosslinked thermosetting elastomer composition.

For ESDM1(a)-(d), ESDM1 was prepared according to the above recipe. ESDM1(b)-(d) were also prepared according to the above recipe, except that, for ESDM1(b), 50pph SUNDEX750T oil (purchased from Sun Oil) was used instead of SUNPAR oil, and for ESDM1(c), 50pph trimellitic acid was used Trioctyl ester was substituted for SUNPAR oil; for ESDM1(d), 0.75pph (instead of 1.5pph) was used.

As for the comparative material, C4 was prepared using the recipe provided above, substituting Vistalon 6505EPDM (ex Exxon) for the substantially random interpolymer. C5 was prepared using the recipe provided above, wherein EPSyn 70A EPDM (available from DSM Copolymers) was used in place of the substantially random interpolymer used in the present invention. C6(a) was prepared using the formulation provided above, substituting SBR 1500 styrene butadiene rubber for the substantially random interpolymer and Sundex 750T oil (available from Sunoil) for the SUNPAR oil. C6(b) was prepared using the recipe provided above, but substituting SBR1500 styrene butadiene rubber for the essentially random interpolymer, using 50pph (instead of 100pph) N550 carbon black, using 7pph Sundex 750 T oil (instead of 50pph SUNPAR 2280 oil).

The stress-strain properties of neat interpolymer, uncured (green) coupons, and crosslinked thermoset elastomer compositions are listed in Table 4. Here, the mark "ND" indicates that the specified property has not been determined.

Table 4 ESDM-1 ESDM-2 ESDM-3 C4 C5 C6 Comonomer content, determined by C-NMR wt% ethylene 50.9 46.7 49.4 50 50 0 wt% styrene 35.3 43.7 44 0 0 twenty four wt% dienes 13.8 9.6 6.6 12 10 0 wt% propylene 0 0 38 40 0 wt% butadiene 0 0 0 0 76 Stress-strain properties of neat uncrosslinked polymers Tensile at break (psi, Kpa) 1884, 12990 1345, 9273 1021, 7040 83,572 80,552 31,214 100% modulus (psi, kPa) 319, 2199 212, 1462 242, 1668 81,558 75,517 30, 207 ESDM-1 ESDM-2 ESDM-3 C4 C5 C6 Elongation at break (%) 513 566 505 288 300 >400 Melt index (g/10min) 1.6 8.0 4.6 <2.0 <0.5 ND Stress-strain properties of raw meal a b c d ND ND ND ND a b Tensile at break (kPa) 5991 4985 5923 6426 ND ND 538 552 21 421 100% modulus (kPa) 3930 3151 4178 3234 ND ND 221 462 96 352 Elongation at break (%) 338 395 276 369 ND ND 250 130 2129 300

Table 4 (continued) Stress-strain properties and oil resistance properties of compounded cross-linked interpolymers a b c d a b Elongation at break (%) 2379 2279 2451 2033 ND ND 2044 2399 1575 1475 100% modulus 1455 1395 1539 1018 ND ND 598 533 295 386 Elongation at break (%) 188 219 183 246 ND ND 318 401 277 392 ASTM #2 Oil Swell (70 hours @ 212°F) 54 55 54 62 ND ND 93 100 57 49 ESDM-1 ESDM-2 ESDM-3 C4 ^* C5 ^* C6 ^* Stress-Strain Properties After Oven Aging at 250°F for 70 Hours a b c d a b Tensile at break (kPa) 18595 20043 ND 17285 ND ND ND ND 4571 9322 100% modulus (kPa) 14775 ND ND 9659 ND ND ND ND ND 9146 Elongation at break (%) 34 84 ND 199.6 ND ND ND ND 93 103 Stress-Strain Properties After Oven Aging at 250°F for 70 Hours a b c d a b Elongation at break (%) +15 +28 ND +24 ND ND ND ND -58 -8 100% modulus (%) -47 ND ND +38 ND ND ND ND ND +378 Elongation at break (%) -29 -62 ND -19 ND ND ND ND -76 -74

^* Not an example of the invention

As shown in Table 4, the cross-linked thermosetting elastomer of the present invention exhibits a higher performance than the comparative materials C4 (Vistalon™ 6505 EPDM (available from Exxon)), C5 (EPSyn 70 A EPDM (available from DSM Copolymers)) and C6 (SBR1500 Styrene-Butadiene Rubber) Significantly improved 100% modulus.

As further illustrated in Table 4, the crosslinked thermoset elastomers of the present invention exhibit oil swelling resistance similar to that of styrene-butadiene rubber, but superior to EPDM materials.

Table 4 also illustrates that the cross-linked thermoset elastomers of the present invention exhibit superior aging properties over styrene-butadiene rubber. For example, crosslinked ethylene/styrene/ethylene norbornene interpolymers exhibit high tensile at break values and moderate elongation at break values after aging in an air oven at 250°F for 70 hours. In contrast, styrene-butadiene rubbers show low tensile values at break and significantly reduced elongation at break values after aging under the same conditions.

Therefore, it can be seen from Table 4 that the crosslinked ethylene/styrene/diene thermosetting elastomer of the present invention exhibits the oil swelling resistance of styrene-butadiene rubber without sacrificing heat aging resistance. Embodiment 3: Preparation thermoplastic vulcanizate

Preheat a Brabender PS-2 or Haake Torque Internal Mixer to 350°C. The required amount of Pro-fax 6524 isotactic polypropylene (available from Himont Incorporated) was added to the mixer and allowed to melt and homogenize. After 1 minute, the desired amount of uncrosslinked substantially random interpolymer was added. Then, process oil, antioxidant, stearic acid and carbon black were added and mixed for 1 minute. Add zinc oxide, sulfur, benzothiazolyl disulfide and methyl tuads. Mix until torque is at maximum and allow a total mixing time of at least 10 minutes. Unload the thermoplastic vulcanizate from the internal mixer.

In carrying out the above steps, the recipe given in Table 5 was used. All amounts are in parts per 100 parts of elastomer unless otherwise indicated.

table 5 elastomer TPV-1 TPV-2 C-TPV-1 C-TPV-2 PSDM-2 ESDM-3 C-4 C-5 wt% ethylene 46.7 49.4 50 50 wt% styrene 43.7 44 0 0 wt% dienes 9.6 6.6 12 10 wt% propylene 0 0 38 40 TPV ingredients (all in pph) A B C D essentially random copolymer 100 100 100 100 100 100 100 isotactic polypropylene 67 67 33 67 100 67 67 processing oil 50 50 100 100 100 50 50 IRGANOX 1010 antioxidant (available from Ciba Geigy Corp.) 3 3 3 3 3 3 3 stearic acid 1 1 1 1 1 1 1 elastomer TPV-1 TPV-2 C-TPV-1 C-PTV-2 N550 carbon black, purchased from Cabot 1 1 1 1 1 1 1 Zinc oxide 5 5 5 5 5 5 5 sulfur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Benzothiazolyl disulfide (purchased 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 for TPV1(b), SunParTM2280 (available from Sun Oil) was used as the processing oil. For TPV1(b), trioctyl trimellitate was used as the processing oil.

The resulting thermoplastic vulcanizate was compression molded at 380°F. The representative physical properties of this thermoplastic vulcanizate and comparative thermoplastic vulcanizates C-TPV1 (prepared by Vistalon 6505 EPDM (available from Exxon)) and C-TPV2 (prepared by EPSyn 70A EPDM (available from DSM Rubber Company)) are listed in the table 6 in. Among them, the abbreviation "ND" indicates that the given property has not been determined.

Table 6 TPV1 TPV2 C-TPV-1 C-TPV-2 Stress-strain properties A B A B C D Tensile at break (psi) 1507 1589 1621 515 1549 1436 1520 1787 00% modulus (psi) 1375 1307 951 327 691 1008 759 889 Elongation at break (%) 132 164 251 192 336 247 322 344 ASTM #2 - 70 hours 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

TPV1(a) and TPV2(a) compared with comparative materials C-TPV1 (prepared by Vistalon 6505 EPDM (purchased from Exxon)) and C-TPV2 (prepared by EPSyn 70 A EPDM (purchased from DSM Rubber Company)) , the thermoplastic vulcanizates of the present invention exhibit greater oil resistance (measured according to ASTM #2) without loss of hardness (Shore "A" hardness). Comparing these materials further illustrates that the thermoplastic vulcanizates of the present invention exhibit improved 100% modulus values and comparable tensile at break values compared to the comparative materials.

Comparing TPV-2(b), TPV-2(c) and TPV-2(d) demonstrates that ASTM #2 oil swell resistance and hardness values can be tuned by adjusting the ratio of polypropylene to substantially random interpolymer. In other words, as the proportion of polypropylene increases, the resistance to ASTM #2 oil swelling and hardness also increase. Furthermore, the effect of adding a substantially random interpolymer was confirmed. In particular, the % elongation at break of the thermoplastic vulcanizate of the present invention is many times greater than that of unmodified isotactic polypropylene, which has an elongation at break of 13%. Example 4: Description of the polymer reactor used in the preparation of peroxide modified ESI

A 6 gallon (22.7 L) oil jacketed autoclave continuous stirred tank reactor (CSTR) was used as the reactor. A magnetically coupled stirrer with a Ligtning A-320 propeller was used for mixing. The reactor was filled with liquid at 475 psig (3275 kPa). The process fluid flows in from the bottom of the reactor and out from the top of the reactor. Heat transfer oil is circulated through the reactor jacket to remove some of the heat of reaction. Fluid and solution densities were measured with micro-motion flowmeters after exiting the reactor. All lines connected to the reactor outlet were flushed and insulated with 50 psi (344.7 kPa) steam. step:

Ethylbenzene solvent was fed into the small apparatus at 30 psig (207 kPa). The feed to the reactor was measured by a Micor-motion material flow meter. The feed rate was controlled with a variable speed diaphragm pump. At the outlet of the solvent pump, a side stream is provided to provide a flush flow to the catalyst injection line (1 lb/hr (0.45 kg/hr) and the reactor agitator (0.75 lb/hr (0.34 kg/hr)). The pressure flow meter is measured and controlled by a hand-adjusted micro-flow needle valve. The uninhibited styrene monomer is dropped into the reactor at 30 psig (308kPa). The material put into the reactor is measured with a micro-material flow meter. With a variable speed diaphragm The pump controls the feed rate. The styrene stream is mixed with the remaining solvent stream. Ethylene is fed into the small unit at 600 psig (4,137 kPa). The ethylene flow is measured with a micro-material flow meter immediately before the Reserach valve controlling the fluid .Hydrogen is fed into the ethylene stream at the outlet of the ethylene control valve using a Brooks flow meter/controller.The ethylene/hydrogen mixture is mixed with the solvent/styrene stream at room temperature.The temperature of the solvent/monomer is adjusted before it enters the reactor with The heat exchanger was cooled to 5°C, and said heat exchanger contained ethylene glycol at -5°C in its jacket. This stream entered from the bottom of the reactor. The three-component catalyst system and its flushing solvent also came from the bottom but from the The different inlets of the monomer stream enter the reactor. The catalyst components are prepared in a glove box under an inert atmosphere. The diluted components are put into a cylinder filled with nitrogen and added to the catalyst operating tank in the process area. The catalyst is pumped by a piston pump Pressurize from the operating tank and measure the flow with a micro-motion flow meter.These streams are intermixed with the catalyst flush solvent just before entering the reactor through a single injection line.

Polymerization was stopped by adding a catalyst kill (water mixed with solvent) into the reactor product line at a point after a flow meter to measure the density of the solution. Other polymer additives may be added along with the catalyst kill. An in-line static mixer disperses the catalyst kill and additives in the reactor effluent stream. This stream then flows into a heater after the reactor which provides additional energy for flash removal of the solvent. This flash occurs as the stream exits the heater after the reactor and the pressure drops from 475 psig (3,275 kPa) to -250 mmHg (33 kPa) at the reactor pressure control valve. The flashed polymer enters a hot oil jacketed devolatilizer. About 85% of the volatile compounds, called volatiles, are removed from the polymer in the devolatilizer. Volatiles are vented from the top of the devolatilizer. The evolved volatile stream was cooled with a glycol-jacketed exchanger, drawn into a vacuum pump and discharged into a glycol-jacketed solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of the reactor and ethylene was removed from the top of the reactor. The ethylene flow was measured with a micro-motion flowmeter and its composition analyzed. The measured vented ethylene plus the calculated gas dissolved in solvent/styrene was used to calculate the ethylene conversion. The polymer separated from the devolatilizer is pumped into the ZSK-30 devolatilization vacuum extruder with a gear pump. The dried polymer exits the extruder as a single strand. The wire is cooled by a water bath. Excess water was blown out of the strand with air and the strand was cut into pellets with a strand cutter.

catalyst used Titanium compound boron compound ^MMAO type type Boron/Ti ratio A1/T1 ratio ESI-4 A ^{a Ac} 1.25:1 12.0:1 ESI-5 B ^{b Ac} 1.26:1 8.0:1 ESI-6 B ^{b Ac} 1.25:1 10.0:1 ESI-7 B ^{b Ac} 1.25:1 10.0:1 ESI-8 B ^{b Ac} 1.24:1 10.0:1 ESI-9 A ^{a Ac} 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-13 B ^{b Ac} 1.25:1 10.0:1 ESI-14 A ^{a Ac} 1.25:1 9.9:1 ESI-15 A ^{a Ac} 1.24:1 12.0:1

a Titanium(II) 1,3-pentadiene (tert-butylamino)dimethyl(tetramethylcyclopentadienyl)silane.

b Dimethyl[N-(1,1-dimethylethyl)-1,1-dimethyl-1[(1,2,3,4,5-η)-1,5,6,7 -tetrahydro-3-phenyl-s-cycloceneinden-1-yl]silaneammine(2-)-N]-titanium.

c Bis-hydrogenated tallow alkylmethylammonium tetrakis (pentafluorophenyl) borate.

d Tris(pentafluorophenyl)borane.

e Modified methylalumoxane, available from Akzo Nobel as MMAO-3A. Reactor data polymer Reactor temperature °C Solvent flow rate Ethylene flow rate Hydrogen flow rate SCCM Styrene Conversion rate% lb/hr kg/hr lb/hr kg/hr lb/hr kg/hr ESI-4 65.5 8.8 3.99 0.81 0.37 4.5 13.0 5.90 87.26 ESI-5 71.4 11.4 5.17 1.21 0.55 9.0 14.0 6.35 87.79 ESI-6 80.3 18.6 8.44 1.69 0.77 12.0 12.0 5.44 88.18 ESI-7 86.7 28.9 13.11 2.48 1.12 17.0 9.7 4.40 92.43 ESI-8 90.4 30.1 13.66 2.90 1.32 21.0 8.9 4.04 92.06 ESI-9 101.9 19.2 8.72 1.99 0.90 4.0 7.0 3.18 87.72 ESI-10 90.9 40.0 18.16 3.13 1.42 16.0 5.3 2.41 95.72 ESI-11 89.9 25.6 11.62 2.06 0.94 9.0 4.3 1.95 96.71 ESI-12 79.4 41.0 18.61 2.18 0.99 6.0 16.5 7.49 94.91 ESI-13 79.7 18.6 8.44 1.70 0.77 11.7 12.0 5.44 88.6 ESI-14 69.2 2.92 1.32 1.0 0.45 0 20.0 9.07 86.3 ESI-15 65.0 8.8 3.99 0.80 0.36 4.5 13.0 5.90 88.7 Table 7 summarizes the properties of the polymers used in this study.

Table 7 Polymers used Lot No. describe I ₂ ^a (g/10min) I ₁₀ /I ₂ Total styrene content (%) 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-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-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-14 73.4% S ESI 5.0 - - 8.6 ESI-15 68.5% S ESI 1.05 9.0 - 16.9 POE Affinity EG ^8100b 1 - - - a Measured by ASTM D 1238 Condition I. b An ethylene-octene copolymer having a melt index of 1 g/10 min. (by ASTM D 1238 condition I) and a density of 0.870 g/cc (by ASTM D 792), available from The Dow Chemical Company. Ingredients Processing Conditions

Formulations with the above polymers were prepared with 3, 6 and 9% by weight of dicumyl peroxide (DiCup, manufactured by Hercules Corporation). The batch was prepared in a Hakke Rheocord 9000 equipped with a 50 g mixing cartridge under the following conditions: 120°C, 50 RPM, 10-12 minutes mixing time. Ingredients curing conditions:

The samples were crosslinked in a compression molding machine (tetrahedral press MTP-8 model) with 200 pounds force at 170°C for 20 minutes. result

Table 8 summarizes the gel content and upper use temperature of the peroxide crosslinked ESI samples. The results in Table 8 demonstrate that peroxides can be used to crosslink ESI. The degree of crosslinking was determined by analyzing the gel content. All peroxide modified samples had a gel content greater than 60%. The upper limit use temperature increases when the sample is treated with peroxide. Figure 1 presents a plot of expected and actual gel content versus styrene composition for ESI samples treated with 9% peroxide. The measured gel content was much greater than expected. This is an unexpected result since the reactivity of ESI with peroxides is similar to that of polyethylene and different from that of styrene and ethylene copolymers.

Table 8 peroxide crosslinked ethylene styrene copolymers sample number polymer describe %gel Upper limit use temperature (C) ESI-9 33% S ESI - 0% Peroxide 0 86.0 B ESI-8 45% S ESI - 0% Peroxide 0 50.0 C ESI-7 54% S ESI - 0% Peroxide 0 50.0 D. ESI-6 60% S ESI - 0% Peroxide 0 50.0 E. ESI-5 67% S ESI - 0% Peroxide 0 60.0 f ESI-4 74% S ESI - 0% Peroxide 0 68.0 G POE Affinity EG8100-0% peroxide 0 68.0 h x-LINKEDESI-9 33% S ESI - 3% peroxide 88.6 >185 I x-LINKEDESI-8 45% S ESI-3% peroxide 93.0 165.0 J x-LINKEDESI-7 54% S ESI - 3% Peroxide 79.3 >185 K x-LINKEDESI-6 60% S ESI-3% peroxide 82.2 179.0 L x-LINKEDESI-5 67% S ESI - 3% peroxide 68.6 170.0 m x-LINKEDESI-4 74% S ESI - 3% peroxide 63.5 97.0 N ^* x-LINKED POE AffinityO EG8100-3% peroxide 97.3 >185 o x-LINKEDESI-9 33% S ESI-6% peroxide 94.6 >185 P x-LINKEDESI-8 45% S ESI-6% peroxide 90.5 >185 Q x-LINKEDESI-7 54% S ESI-6% peroxide 92.0 >185 R x-LINKEDESI-6 60% S ESI - 6% peroxide 92.6 >185 S x-LINKEDESI-5 67% S ESI - 6% peroxide 85.5 >185 T x-LINKEDESI-4 74% S ESI - 6% peroxide 75.3 >185 U ^* x-LINKED POE AffinityO EG8100-6% peroxide 99.4 >185 V x-LINKEDESI-9 33% S ESI-9% peroxide 94.9 >185 W x-LINKEDESI-8 45% S ESI-9% peroxide 93.6 >185 x x-LINKEDESI-7 54% S ESI-9% peroxide 92.6 >185 Y x-LINKEDESI-6 60% S ESI-9% peroxide 91.5 >185 Z x-LINKEDESI-5 67% S ESI-9% peroxide 89.0 >185 AAA x-LINKEDESI-4 74% S ESI-9% peroxide 80.7 >185 AB ^* x-LINKED POE AffinityO EG8100-9% peroxide 97.8 >185 ^* Not the polymer used in the peroxide-modified ESI blends of the examples of the present invention

Table 9 summarizes the ESI samples used for this study.

Table 9 Polymers used polymer describe ESI-9 33% S ESI ESI-4 74% S ESI POE affinity EG 8100 SBS Vector 2518 Styrenic Block Copolymer ^* *A styrene-butadiene-styrene block copolymer containing 30 wt% styrene and having a melt index of 1 g/10 min. (measured by ASTM D1238 condition I), available from Dexco. Ingredients Processing Conditions

A formulation having the above polymer was prepared using 4% by weight of dicumyl peroxide (DiCup, manufactured by Hercules Corporation). The batch was prepared in a Hakke Rheocord 9000 equipped with a 50 g mixing cartridge under the following conditions: 120°C, 50 RPM, 10-12 minutes mixing time. Ingredients curing conditions:

The samples were crosslinked in a compression molding machine (tetrahedral press MTP-8 model) with 200 pounds force at 170°C for 20 minutes. result

Table 10 summarizes the blends prepared with AFFINITY EG 8100 and SBS to determine the effect of blending polyolefin elastomers or styrene/butadiene/styrene polymers on the crosslinking efficiency of ESI copolymers. Table 10

Table 10 Blend Properties sample number describe gel% 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 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 *Not an example of the invention

The addition of SBS increased the amount of gelling of the studied ethylene/styrene interpolymers. Substantially random interpolymers irradiated by electron beams

The same polymers as listed in Table 7 were used for this study. Batch Preparation and Curing Conditions

Compression molded specimens were treated with 5, 10, 15 and 20 Mrad electron beam radiation. result

The results in Table 11 demonstrate that electron beam radiation can be used to crosslink ESI, in other words, the radiation increases the gel content and upper use temperature. Note that the e-beam irradiated samples (R, Q and P) are much less viscous than the unmodified samples (C, D and E). The effect of low radiation dose on I ₁₀ /I ₂ ratio was measured on 74% S ESI samples irradiated with 5 Mrad dose: the I ₁₀ /I ₂ ratio of the untreated sample was 8.8, and it was 12.3 after treatment with 5 Mrad dose.

Table 11 Electron Beam Crosslinked Ethylene Styrene Interpolymers sample number describe gel% Upper limit use temperature (°C) A ESI-9(33%S)-0Mrad 0 86 B ESI-8(45%s)-0Mrad 0 50 C ESI-7(54%S)-0Mrad 0 50 D. ESI-6(60%S)-0Mrad 0 56 E. ESI-5(67%S)-0Mrad 0 60 f ESI-4(74%S)-0Mrad 0 68 G ^{* AffinityTM} EG 8100-0Mrad 0 68 h 33%S ESI-5Mrad 0.1 88 I 45%S ESI-5Mrad 0 56 J 54%S ESI-5Mrad 1.8 56 K 60%S ESI-5Mrad 0.3 60 L 67%S ESI-5Mrad 0.4 64 m 74%S ESI-5Mrad 0.4 72 N ^{* AffinityTM} EG 8100-5Mrad 0.3 73 o ESI-9(33%S)-10Mrad - - P ESI-8(45%s)-10Mrad 1.3 62 Q ESI-7(54%S)-10Mrad 0.1 64 R ESI-6(60%S)-10Mrad 0.4 68 S ESI-5(67%S)-10Mrad 0.1 74 T ESI-4(74%S)-10Mrad 0.2 80 U ^{* AffinityTM} EG 8100-10Mrad 76.3 77 V ESI-9(33%S)-15Mrad 62.2 98 W ESI-8(45%s)-15Mrad 68 80 x ESI-7(54%S)-15Mrad 65 72 Y ESI-6(60%S)-15Mrad 44.6 70 Z ESI-5(67%S)-15Mrad 8.2 74 AAA ESI-4(74%S)-15Mrad 1.2 77 AB ^{* AffinityTM} EG 8100-15Mrad 82.3 96 AC ESI-9(33%S)-20Mrad 70 125 AD ESI-8(45%s)-20Mrad 70.4 94 AE ESI-7(54%S)-20Mrad 75.2 92 AF ESI-6(60%S)-20Mrad 67.1 80 AG ESI-5(67%S)-20Mrad 55.3 80 AH ESI-4(74%S)-20Mrad 21.2 80 AI ^{* AffinityTM} 8100-20Mrad 90.2 186 *Not the material used for the silane-modified substantially random interpolymers of the examples of the present invention

Table 12 summarizes the substances used in this study

Table 12 Polymers used Polymer No. describe ESI-10 41% S ESI ESI-11 51% S ESI ESI-12 73% S ESI POE Affinity 8100 Ingredients Preparation Conditions

Table 13 shows the ingredients prepared for the silane crosslinking studies

Table 13 Ingredients used for ESI silane crosslinking studies 41% Styrene ESI-10wt% 51% Styrene ESI-11wt% 73% Styrene ESI-12wt% AffinityEG 8100wt% Trimethoxyvinylsilane wt% Dicumyl peroxide wt% Dibutyltin dilaurate wt% 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 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 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 0 97.85 2 0.15 0.02 0 0 0 95.85 4 0.15 0.02

Samples were extruded on a Haake Polylab polymer processing unit with an air jet knife equipped with a 18 mm twin screw extruder, pelletizer and water bath. Samples were prepared in two steps:

Step 1: Graft silane onto the polymer as follows:

·Inject the appropriate proportion of vinyltrimethoxysilane and dicumyl peroxide solution together with the polymer into the barrel of the extruder in liquid form.

·Conditions: 200°C melt temperature, 50rpm.

Step 2: Add dibutyltin dilaurate catalyst

· A 2% masterbatch of the catalyst in each polymer studied was prepared. The catalyst masterbatch pellets were dry blended with the silane grafted material from step 1 and extruded at 200°C, 50 rpm.

The results in Table 14 demonstrate that silane reagents can be used to prepare cross-linked ESI by moisture curing. ESI was grafted with vinyl siloxanes serving as moisture curing active sites. For ESIs with a styrene composition of 41 to 51%, gel contents of 40 to 65% were obtained.

Table 14 Silane crosslinked ethylene styrene copolymer sample number describe gel% Upper limit use temperature (°C) 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 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 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 M ^* Affinity EG 8100 8100, 1500ppm DCP, 2% VTMOS 87.5 92.4 N ^* Affinity 8100EG 8100, 1500ppm DCP, 4% VTMOS 93.9 >185 *Not an example of the present invention Azide modified ESI

The test methods and apparatus test methods used to prepare and test the following samples 1-10:

A RAD-II kinetic spectrometer from Rheometric Inc. was used to obtain DMS data. The temperature sweep was from about -70°C to 300°C at 5°C/step (with a 30 second delay in each step). The oscillation frequency is 1 rad/s with an initial self-strain function of 0.1% strain and a positive increase of 100% whenever the torque is reduced to 4 g-cm. The maximum strain was set at 26%. A 7.9-mm parallel plate fixture was used with an initial separation of 1.5 mm at 160°C (sample was inserted into the RAD-II at 160°C). The "jig" was toothed at 160°C and the instrument was cooled to -70°C. (The fixture is used to correct for thermal expansion or contraction when heating or cooling the test chamber). A nitrogen atmosphere was maintained throughout the experiment to minimize oxidative degradation.

DSC (Differential Scanning Calorimetry) data were acquired with a Perkin-Elmer DSC-7. The samples were melt pressed into thin sheets and placed in aluminum pans. The sample was heated to 180°C in the DSC and held there for 4 min to ensure complete melting. The sample was then cooled to -30°C at 10°C/min and heated to 140°C at 10°C/min.

A Perkin Elmer TMA 7 thermodynamic analyzer was used to measure the upper service temperature. A probe force of 102 g and a heating rate of 5°C/min was used. The test specimens were discs of about 2 mm in thickness and diameter prepared by compression molding at 205° C. and cooling in air to elevated temperature.

A general method for determining compression set is described in ASTM D395-89. Samples were cut into 1.14 inch diameter discs which were stacked up to 0.5 inch in thickness. Samples were tested at 70°C for 22 hours at a constant strain of 25%. The sample was aged at 70°C for 22 hours under 25% compression and cooled to 22°C.

Xylene extraction was performed by weighing 1 g of polymer sample. These samples were transferred into mesh baskets and placed in boiling xylene for 12 hours. After 12 hours, the sample baskets were removed and placed in an oven at 150°C and 28 inches of mercury vacuum for 12 hours. After 12 hours, the samples were removed, allowed to cool to room temperature within 1 hour, and weighed. The % polymer extracted was calculated using the following formula:

% polymer extracted = ((initial weight - final weight)/initial weight).

Tensile properties were determined by compression molding 1/16 inch test specimens. Tensile specimens were then cut from these specimens and tested on an Instron tensile testing machine.

These samples used a HaakeBunchler Rheomix 600 mixer with roller paddles connected to a HaakeBuchler Rheocord 9000 torque rheometer, or a Brabender mixer with a 50 g mixing barrel (Model: R.E.E.No.A- 19/S.B) Preparation. Preparation of 4,4'-disulfonyl azidophenyl ether

4,4'-Bis(chlorosulfonyl)phenyl ether (10 g, 0.027 mol) was dissolved in 100 mL of acetone, and 4.426 g (0.06808 mol) of solid sodium azide was added in portions within 15 minutes. The reaction mixture was stirred at room temperature for 26 hours, then filtered to remove sodium chloride. The filter cake was washed with acetone and the combined filtrates were evaporated to give a white solid which was washed twice with 20 mL of water and dried under vacuum at room temperature. The resulting white solid (7.3 g, 70%) was 4,4'-disulfonyl azidophenyl ether, as confirmed by 1H and 13C NMR spectroscopy. Cross-linked ethylene-styrene copolymer

Ethylene-styrene copolymer (40 g) containing 58 wt % styrene (ESI-3831-960921-1100) (3 wt % atactic polystyrene, 1.0 MI) was mixed with 0.2 g (0.5 wt %, 0.55 mmol) 4,4'-Disulfonyl azidobiphenyl was dry blended in a plastic bag. The blend was fed into a Brabender mixer (Model: R.E.E. No. A-19/S.B) with a 40 g mixing bowl at 120°C (60 rpm). The mixture was blended at 120° C. for 3 minutes, then removed from the mixer and allowed to cool, yielding 38.9 g of Blend 1 .

Repeat the above blending experiment with 0.4g (1.0wt%, 1.1mmol) 4,4'-disulfonyl azidobiphenyl to obtain blend 2, with 0.8g (2.0wt%, 2,2mmol) 4, 4'-Disulfonyl azidobiphenyl The above blending experiment was repeated to obtain blend 3.

The above blending experiment was repeated with 0.8 g (2 wt%) of 1,3-disulfonyl azidobenzene to obtain 39.3 g of blend 4, and with 0.8 g (2.0 wt%) of 1,3,5-trisulfonyl azide Benzene The above blending experiment was repeated to obtain 39.1 g of Blend 5.

Blends 1-5 and uncrosslinked ESI-13 (which was the untreated starting material) were pressed at 120° C. and 20,000 pounds force for 3 minutes, followed by curing at 190° C. and 20,000 pounds for 10 minutes, then Cool to 80° C. within 5 minutes while maintaining the pressure. All these samples were characterized by TMA analysis and selected samples were characterized by xylene extraction and DMS determination. The data demonstrate that in the presence of 2% sulfonyl azide, the sample is fully crosslinked. Crosslinked Blends 1-5 are referred to as Samples 1-5, respectively. sample UST(TMA)℃ %Xylene Extraction G'(20℃) G'(200℃) ESI-13 52 99 3.0E ^-07 3.0E ⁺⁰³ 1 64 12 Data not measured 2 106 2 Data not measured 3 >190 2 Data not measured 4 >190 0 8.0E ^-∞ 3.0E ^-∞ 5 >190 2 Data not measured sample Toughness (In-Lb/Cu.In) Fracture Stress (PSI) %elongation Compression set (70℃) ESI-13 2450 411 900 64% 3 4000 1700 650 17% 4 4700 2000 630 7% 5 4300 1700 630 16%

The experiments below demonstrate that crosslinking has high styrene ESI (St wt% > 50%), which is important to demonstrate that bifunctional azide crosslinking is superior to peroxide crosslinking.

A Haake Rheocord 9000 fitted with a 50 g mixing cartridge was heated to 120°C. 40.0 g of ESI (3831-960710-1500) (73.4% styrene copolymer, 8.6% atactic polystyrene @ 5.0MI) was added to the mixing bowl. After 1 minute, 0.8 g (2.0 wt %) of 1,3-disulfonylazidebenzene was added to the mixing bucket and the sample was compounded for 3 minutes. The polymer was removed from the Haake and pressed at 120°C and 20,000 pounds force for 3 minutes. The sample was then cured at 180°C and 20,000 lbs for 10 minutes, followed by cooling to 80°C over 5 minutes to yield Sample 6. Untreated ESI-14 was not treated with poly(sulfonyl azide), but was molded and cured as in sample 6. sample UST(TMA)℃ Compression set (70℃) ESI-14 60 97% 6 >190 15%

The results for samples 1-6 illustrate that disulfonyl azides can be used to prepare coupled, partially cross-linked and fully cross-linked ESIs. Samples 2-4 are fully crosslinked polymers. The toughness and upper service temperature of ESI crosslinked with disulfonyl azide are better than those of uncrosslinked ESI. Preparation of peroxide cross-linked ESI to compare samples 7 & 8 with azide cross-linked ESI

A Haake Rheocord 9000 fitted with a 50 g mixing cartridge was heated to 120°C. 48.5 g of ESI 6 (57.7% styrene copolymer, 3.3% homopolystyrene, 1.02 Mi, 7.8 I ₁₀ /I ₂ ) was added and mixed at 50 RPM. After 6 minutes, 1.5 g (3.0 wt %) of dicumyl peroxide (Hercules Inc.) was added and the sample was compounded for 6 more minutes. Samples were removed from the Haake and pressed in a compression molding machine (Tetrahedron Press Model MTP-8) at 120°C and 20,000 lbs force for 3 minutes, then cured at 170°C and 200 lbs (90.78 kg) force for 20 minutes. This is sample 7. For Sample 8, the process was repeated with 47.0 g of ESI-6 and 3.0 g of dicumyl peroxide (6 wt%). Tensile properties, compression set and UST were measured by TMA. Sample 9&10

A Haake Rheocord 9000 fitted with a 50 g mixing cartridge was heated to 120°C. 48.5 g of ESI-15 (68.5% styrene copolymer, 16.9% homopolystyrene, 1.05 Mi, 9.0 I ₁₀ /I ₂ ) was added and mixed at 50 RPM. After 6 minutes, 1.5 g (3.0 wt %) of dicumyl peroxide (Hercules Inc.) was added and the sample was compounded for 6 more minutes. Samples were removed from the Haake and pressed in a compression molding machine (Tetrahedron Press MTP-8 model) at 120°C and 20,000 lb (9078.48kg) force for 3 minutes, then cured at 170°C and 200 lb (90.78kg) force 20 minutes. This is sample 9. For Sample 10, the process was repeated with 47.0 g of ESI-15 and 3.0 g of dicumyl peroxide (6 wt%). Tensile properties, compression set and UST (by TMA) were measured by TMA. sample Peroxide wt% Azide wt% %elongation Fracture stress (psi) Compression set (70℃) UST(TMA-℃) gel% 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 9 3 - 320 1800 64% 97 64 10 6 - 310 1300 32% >190 81

Samples 3 and 6 illustrate that ESI crosslinked with difunctional sulfonyl azides represents an improvement over peroxide crosslinked ESI (Samples 7, 8, 9 and 10).

Claims (19)

1. one kind comprises component (A) and partially or completely crosslinked polymer blend composition (B), comprising:

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

(1) 35 to 60wt% polymer unit derived from least a vinyl aromatic monomer; With

(2) the remaining polymer unit that has the aliphatic alpha-olefin of 2 to 20 carbon atoms derived from least a that comprises;

(B) by component (A) and gross weight (B), at least a following polymers of 98wt% at the most:

(1) contains homopolymer derived from the polymer unit of the alpha-olefin 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) amount of vinyl aromatic monomer 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);

(C) by component (A), (B), (C), (D) and gross weight (E), from least 0.1 to the linking agent that is less than or equal to 10wt%, this linking agent includes the silane of ethylenically unsaturated hydrocarbons base;

(D) in component (A), (B), (C), (D) and gross weight (E), the cross-linked evocating agent of 250ppm at least; With

(E) randomly in component (A), (B), (C), (D) and gross weight (E), crosslinking catalyst from 0.015 to 0.035wt%.

2. the composition of claim 1, wherein

(1) described vinyl aromatic monomer is a vinylbenzene,

(2) described alpha-olefin is the mixture of ethene or ethene and propylene,

(3) described linking agent component C is unsaturated organoalkoxysilane and counts from 1wt% at least to less than 8wt% with the gross weight of component A, B and C;

(4) described cross-linked evocating agent component D is superoxide and counts 500ppm at least with the gross weight of component A, B, C, D and E; With

(5) described crosslinking catalyst component E if exist, is a carboxylic metallic salt.

3. the composition of claim 2, wherein

(1) described linking agent component C is vinyltrimethoxy silane and counts from 3wt% at least to being less than or equal to 6wt% with component A, B, C, D and E gross weight;

(2) described cross-linked evocating agent component D is dicumyl peroxide and counts 1500ppm at least with component A, B and C gross weight; With

(3) described crosslinking catalyst component E if having, is dibutyl tin laurate or dioctyl tin maleate.

4. the composition of claim 1, wherein the amount of cross-linked evocating agent is counted 400ppm at least with the gross weight of component A, B, C, D and E.

5. the composition of claim 1, wherein the amount of cross-linked evocating agent is counted 1000ppm at least with the gross weight of component A, B and C.

6. the composition of claim 3, wherein said cross-linked evocating agent component D is that dicumyl peroxide and its amount are counted 2000ppm at least with component A, B and C gross weight.

7. the composition of claim 1, the amount of wherein said cross-linked evocating agent is counted 500ppm at least with the gross weight of component A, B, C, D and E.

8. the composition of claim 1, wherein the amount of cross-linked evocating agent is counted 1500ppm at least with the gross weight of component A, B, C.

9. the composition of claim 6, wherein said cross-linked evocating agent component D is that dicumyl peroxide and its amount are counted 3000ppm at least with the gross weight of component A, B and C.

10. one kind by each the processing component of partially or completely crosslinked preparation of compositions of claim 1-9.

11. each partially or completely crosslinked composition of a claim 1-9, it is foam, 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.

12. the foam composition of claim 11 is sole, pipe thermally-insulated body, furniture, motion sponge pad, acoustical panel and thermally-insulated body form.

13. one kind prepares and comprises component (A) and partially or completely crosslinked polymer blend method for compositions (B), comprises

(A) reaction in the presence of the constraint geometry catalyst forms a kind of random basically interpolymer with at least a alpha-olefin and at least a vinyl aromatic (co) hydrocarbon compound, and this interpolymer comprises:

(1) 35 to 60wt% polymer unit derived from least a vinyl aromatic monomer; With

(2) the remaining polymer unit that has the aliphatic alpha-olefin of 2 to 20 carbon atoms derived from least a that comprises;

(B) with described random basically interpolymer and at least a following polymers blending

(1) contains homopolymer derived from the polymer unit of the alpha-olefin 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 the difference of interpolymer steps A and B4 is:

(a) amount of vinyl aromatic monomer in arbitrary interpolymer of steps A and the amount in arbitrary interpolymer of step B4 differ 0.5mol% at least; And/or

(b) number-average molecular weight of arbitrary interpolymer of steps A (Mn) differs at least 20% with the number-average molecular weight (Mn) of arbitrary interpolymer of step B4; Wherein in component (A) and (B) amount of gross weight component (A) be 1wt% at least, the amount of component (B) is at most 99wt%,

(C) usefulness comprises the blend of the solidifying agent curing schedule B of following component:

(i) from least 0.1 to the linking agent that is less than or equal to 10wt%, this linking agent includes the silane of ethylenically unsaturated hydrocarbons base,

The (ii) cross-linked evocating agent of 250ppm at least; With

(iii) randomly, 0.015 to 0.035wt% crosslinking catalyst.

14. the method for claim 13, wherein solidifying agent comprises the cross-linked evocating agent of 400ppm at least.

15. the method for claim 13, wherein solidifying agent comprises in the gross weight of component A, B, C, D and the E cross-linked evocating agent of 500ppm at least.

16. each method of claim 13-15, wherein

(1) described random substantially interpolymer is ethylene/styrene or ethylene/propene/styrene copolymer;

(2) described linking agent is a vinyltrimethoxy silane;

(3) described cross-linked evocating agent is a dicumyl peroxide; With

(4) described crosslinking catalyst if having, is dibutyl tin laurate or dioctyl tin maleate.

17. each method of claim 13-16 is wherein solidified with the random substantially interpolymer of compounding and is carried out simultaneously.

18. a method for preparing Thermoplastic Vulcanizate comprises:

(a) interpolymer that will be random substantially and at least a TPO temperature be higher than that TPO melts or the temperature of softening temperature under thorough mixing;

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

(c) be cured random basically interpolymer and this uniform mixture of compounding simultaneously, form Thermoplastic Vulcanizate thus; Wherein solidifying agent comprises

(i) by component (A), (B), (C), (D) and gross weight (E), from least 0.1 to the linking agent that is less than or equal to 10wt%, this linking agent includes the silane of ethylenically unsaturated hydrocarbons base;

(ii) in component (A), (B), (C), (D) and gross weight (E), the cross-linked evocating agent of 250ppm at least; With

(iii) randomly in component (A), (B), (C), (D) and gross weight (E), crosslinking catalyst from 0.015 to 0.035wt%.

19. the method for claim 18

(1) described random basically interpolymer is ethylene/styrene or ethylene/propene/styrene copolymer;

(2) described linking agent is a vinyltrimethoxy silane;

(3) described cross-linked evocating agent is a dicumyl peroxide; With

(4) described crosslinking catalyst is if having the dibutyl tin laurate of being or dioctyl tin maleate.