EP1007577A1 - Thermohärtbare copolymere und schäume - Google Patents

Thermohärtbare copolymere und schäume

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Publication number
EP1007577A1
EP1007577A1 EP98941063A EP98941063A EP1007577A1 EP 1007577 A1 EP1007577 A1 EP 1007577A1 EP 98941063 A EP98941063 A EP 98941063A EP 98941063 A EP98941063 A EP 98941063A EP 1007577 A1 EP1007577 A1 EP 1007577A1
Authority
EP
European Patent Office
Prior art keywords
vinyl
inte
åolymer
monomer
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98941063A
Other languages
English (en)
French (fr)
Inventor
Kevin W. Mckay
Francis J. Timmers
Edwin R. Feig
Thoi H. Ho
Seema V. Karande
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/921,641 external-priority patent/US5869591A/en
Priority claimed from US08/921,642 external-priority patent/US5977271A/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP1007577A1 publication Critical patent/EP1007577A1/de
Withdrawn legal-status Critical Current

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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
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    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0838—Copolymers of ethene with aromatic monomers
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the subject invention pertains to thermoset interpolymers, to a process for their preparation, and to products fabricated from such thermoset interpolymers.
  • the present invention further pertains to foams prepared from such thermoset inte ⁇ olymers and to methods for the preparation of cross-linked ⁇ -olefin/vinyl or vinylidene aromatic monomer and/or hindered aliphatic vinyl or vinylidene monomer inte ⁇ olymers.
  • Elastomers are defined as materials which experience large reversible deformations under relatively low stress. Elastomers are typically characterized as having structural irregularities, non-polar structures, or flexible 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.
  • EPM ethylene/propylene
  • EPDM ethylene/propylene/diene copolymers
  • styrene/butadiene copolymers styrene/butadiene copolymers
  • chlorinated polyethylene and silicone rubber.
  • Thermoplastic elastomers are elastomers having thermoplastic properties. That is, thermoplastic elastomers may be molded or otherwise shaped and reprocessed at temperatures above their melting or softening point.
  • a thermoplastic elastomer is a styrene-butadiene-styrene (SBS) block copolymer.
  • SBS block copolymers exhibit a two phase mo ⁇ hology consisting of glassy polystyrene domains connected by rubbery butadiene segments. At temperatures between the glass transition temperatures of the butadiene midblock and the styrene endblocks, that is, at temperatures from -90°C to 116°C, the SBS copolymer acts like a crosslinked elastomer.
  • European Patent Publication 416,815 discloses pseudorandom ethylene-styrene inte ⁇ olymers. Uncrosslinked pseudorandom ethylene/styrene inte ⁇ olymers exhibit a decreased modulus at temperatures above the melting or softening point of the inte ⁇ olymer. SBS copolymers and uncrosslinked ethylene-styrene pseudorandom inte ⁇ olymers suffer the disadvantages of relatively low mechanical strength, susceptibility to ozone degradation (to the extent that they have sites of unsaturation in the polymer backbone), and utility only in applications where the temperature of the elastomer will not exceed the melting or softening point of the elastomer.
  • thermoset elastomers are elastomers having thermoset properties. That is, thermoset elastomers irreversibly solidify or "set” when heated, generally due to an irreversible crosslinking reaction.
  • Two examples of thermoset elastomers are crosslinked ethylene-propylene monomer rubber (EPM) and crosslinked ethylene- propylene-diene monomer rubber (EPDM).
  • EPM materials are made by the copolymerization of ethylene and propylene. EPM materials are typically cured with peroxides to give rise to crosslinking, and thereby induce thermoset properties.
  • EPDM materials are linear inte ⁇ olymers of ethylene, propylene, and a nonconjugated diene such as 1 ,4-hexadiene, dicyclopentadiene, or ethylidene norbornene. EPDM materials are typically vulcanized with sulfur to induce thermoset properties, although they alternatively may be cured with peroxides.
  • EPM and EPDM materials are advantageous in that they have applicability in higher temperature applications
  • EPM and EPDM elastomers suffer the disadvantages of low green strength (at lower ethylene contents), of a higher susceptibility of the cured elastomer to attack by oils than characteristic of styrene butadiene rubbers, and of resistance of the cured elastomer to surface modification.
  • thermoset elastomers suitable for use over a broad range of temperatures and which are also less susceptible to ozone degradation are desired.
  • Thermoset elastomers which are prepared from elastomers having high green strength (which provides greater flexibility in their handling prior to curing) are particularly desired.
  • thermoset elastomers which are resistant to oil, which are useful in fabricated parts which typically contact oil, such as automotive parts and gaskets.
  • thermoset elastomers which easily undergo surface modification, to promote surface adhesion of the elastomer and/or to provide ionic sites on the elastomer surface.
  • a process for preparing such thermoset elastomers are also desired.
  • Thermoplastic vulcanizates are crystalline polyolefinic matrices through which thermoset elastomers are generally uniformly distributed.
  • examples of thermoplastic vulcanizates include EPM and EPDM thermoset materials distributed in a crystalline polypropylene matrix.
  • Such thermoplastic vulcanizates are disadvantageous, in that they are susceptible to oil degradation.
  • Thermoplastic vulcanizates which are more resistant to oil are desired. Also desired is a process for preparing such thermoplastic vulcanizates.
  • Inte ⁇ olymers prepared from ⁇ -olelfin/vinylidene aromatic monomer or hindered aliphatic vinylidene monomer have excellent properties; however, it would be desirable to have such polymers with improved properties.
  • the foams prepared from the cross-linked inte ⁇ olyers are believed to have one or more of the following improvements: improved upper service temperature, lower density, improved elastic recovery properties, improved mechanical properties as compared to non-crosslinked inte ⁇ olymer foams.
  • thermoset product comprising a crosslinked substantially random inte ⁇ olymer comprising:
  • Another aspect of the present invention concerns a foamable compositon comprising
  • polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hindered aliphatic vinyl or vinylidene monomer, or (c) a combination of at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic vinyl or vinylidene monomer, and
  • the amount of vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinylidene monomer in any inte ⁇ olymer of component (1 ) differs from that amount in any inte ⁇ olymer of component (4) by at least 0.5 mole percent; and/or
  • Another aspect of the present invention pertains to a method for cross-linking a polymer composition
  • a method for cross-linking a polymer composition comprising
  • polymer units derived from (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one hindered aliphatic vinyl or vinylidene monomer, or (c) a combination of at least one vinyl or vinylidene aromatic monomer and at least one hindered aliphatic vinyl or vinylidene monomer, and
  • the amount of vinyl or vinylidene aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer in any inte ⁇ olymer of component (A) differs from that amount in any inte ⁇ olymer of component (B4) by at least 0.5 mole percent; and/or
  • Another aspect of the present invention pertains to foams resulting from subjecting the aforementioned foamable polymer compositions to foaming conditions.
  • the subject invention further comprises fabricated parts comprising the thermoset elastomers or thermoplastic vulcanizates or partially or totally crosslinked foams of the invention.
  • polymer refers to a polymeric compound prepared by polymerizing monomers whether of the same or a different type.
  • the generic term polymer thus embraces the term homopolymer, usually employed to refer to polymers prepared from only one type of monomer, and the term inte ⁇ olymer as defined hereinafter.
  • crosslinked inte ⁇ olymers and “thermoset inte ⁇ olymers” are used interchangeably, and mean inte ⁇ olymers which have greater than 10 percent gel as determined in accordance with ASTM D-2765-84.
  • any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value.
  • the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification.
  • one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate.
  • inte ⁇ olymer refers to polymers prepared by the polymerization of at least two different types of monomers.
  • the generic term inte ⁇ olymer thus includes copolymers, usually employed to refer to polymers prepared from two different monomers, and polymers prepared from more than two different types of monomers.
  • a polymer or inte ⁇ olymer comprises or contains certain monomers, mean that such polymer or inte ⁇ olymer comprises or contains polymerized therein units derived from such a monomer. For example, if a polymer is said to contain ethylene monomer, the polymer will have inco ⁇ orated in it an ethylene derivative, that is, -CH2-CH2-.
  • hydrocarbyl means any aliphatic, cycloaliphatic, aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or cycloaliphatic substituted aromatic groups.
  • the aliphatic or cycloaliphatic groups are preferably saturated.
  • hydrocarbyloxy means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached.
  • monomer residue or "polymer units derived from such monomer” means that portion of the polymerizable monomer molecule which resides in the polymer chain as a result of being polymerized with another polymerizable molecule to make the polymer chain.
  • the elastomeric thermoset compositions of the invention are preferably substantially random inte ⁇ olymers comprising an olefin and a vinyl aromatic monomer, which inte ⁇ olymers have been crosslinked to yield thermoset behavior .
  • substantially random in the substantially random inte ⁇ olymer resulting from polymerizing one or more ⁇ -olefin monomers and one or more vinyl or vinylidene aromatic monomers or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionally, with other polymerizable ethylenically unsaturated monomer(s) as used herein means that the distribution of the monomers of said inte ⁇ olymer can be described by the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J.
  • the substantially random inte ⁇ olymer resulting from polymerizing one or more ⁇ -olefin monomers and one or more vinyl or vinylidene aromatic monomer, and optionally, with other polymerizable ethylenically unsaturated monomer(s) does not contain more than 15 percent of the total amount of vinyl or vinylidene aromatic monomer residue in blocks of vinyl or vinylidene aromatic monomer of more than 3 units. More preferably, the inte ⁇ olymer is not characterized by a high degree of either isotacticity or syndiotacticity.
  • Pseudorandom inte ⁇ olymers are a subset of substantially random inte ⁇ olymers. Pseudorandom inte ⁇ olymers are characterized by an architecture in which all phenyl (or substituted phenyl) groups which are pendant from the polymer backbone are separated by two or more carbon backbone units.
  • the pseudorandom inte ⁇ olymers of the invention in their noncrosslinked state, can be described by the following general formula (using styrene as the vinyl aromatic monomer and ethylene as the ⁇ -olefin for illustration):
  • Noncrosslinked pseudorandom inte ⁇ olymers are described in European Patent Publication 416,815-A.
  • the substantially random inte ⁇ olymer will be characterized as largely atactic. as indicated by a 13C-NMR spectrum in which the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic diad sequences does not exceed 75 percent of the total peak area of the main chain methylene and methine carbons.
  • Substantially random inte ⁇ olymers which are suitable as components (A) and (B4) of the present invention include, substantially random inte ⁇ olymers prepared by polymerizing i) one or more ⁇ -olefin monomers and ii) one or more vinyl or vinylidene aromatic monomers and/or one or more sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionally iii) other polymerizable ethylenically unsaturated monomer(s)
  • Suitable ⁇ -olefins include for example, ⁇ -olefins containing from 2 to 20, preferably from 2 to 12, more preferably from 2 to 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1, 4-methyl-l-pentene, hexene-1 or octene-1 or ethylene in combination with one or more of propylene, butene-1, 4-methyl-l-pentene, hexene-1 or octene-1. These ⁇ -olefins do not contain an aromatic moiety.
  • ethylenically unsaturated monomer(s) include norbornene and C,. 10 alkyl or C 6 . 10 aryl substituted norbornenes, with an exemplary inte ⁇ olymer being ethylene/styrene/norbornene.
  • Suitable vinyl or vinylidene aromatic monomers which can be employed to prepare the inte ⁇ olymers include, for example, those represented by the following formula:
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C -alkyl, and C,_ 4 -haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero.
  • Exemplary monovinyl aromatic monomers include styrene, vinyl toluene, ⁇ -methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof.
  • Preferred monomers include styrene, ⁇ -methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof.
  • a more preferred aromatic vinyl monomer is styrene.
  • a 1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons
  • R 1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl
  • R 1 and A 1 together form a ring system.
  • Preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted.
  • substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, tert-butyl, norbornyl.
  • Most preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are the various isomeric vinyl- ring substituted derivatives of cyclohexene and substituted cyclohexenes, and 5-ethylidene-2-norbornene.
  • 1-, 3-, and 4- vinylcyclohexene are especially suitable.
  • the substantially random inte ⁇ olymers may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art.
  • the polymers may be readily sulfonated or chlorinated to provide functionalized derivatives according to established techniques.
  • the substantially random inte ⁇ olymers may also be modified by various chain extending or cross-linking processes including, but not limited to peroxide-, silane-, sulfur-, radiation-, or azide- based cure systems.
  • a full description of the various cross-linking technologies is described in copending U.S. Patent Application No's 08/921,641 and 08/921,642 both filed on August 27, 1997, the entire contents of both of which are herein inco ⁇ orated by reference.
  • Dual cure systems which use a combination of heat, moisture cure, and radiation steps, may be effectively employed. Dual cure systems are disclosed and claimed in U. S. Patent Application Serial No. 536,022, filed on September 29, 1995, in the names of K. L. Walton and S. V. Karande, inco ⁇ orated herein by reference. For instance, it may be desirable to employ peroxide crosslinking agents in conjunction with silane crosslinking agents, peroxide crosslinking agents in conjunction with radiation, sulfur-containing crosslinking agents in conjunction with silane crosslinking agents, etc.
  • the substantially random inte ⁇ olymers may also be modified by various cross-linking processes including, but not limited to the inco ⁇ oration of a diene component as a termonomer in its preparation and subsequent cross linking by the aforementioned methods and further methods including vulcanization via the vinyl group using sulfur for example as the cross linking agent.
  • the inte ⁇ olymers of one or more ⁇ -olefins and one or more vinyl or vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers employed in the present invention are substantially random polymers. These inte ⁇ olymers usually 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 hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer and from 35 to 99.5, preferably from 45 to 99, more preferably from 50 to 98 mole percent of at least one aliphatic ⁇ -olefin having from 2 to 20 carbon atoms.
  • strained ring olefins such as norbornene and C M0 alkyl or C 6 . 10 aryl substituted norbornenes, with an exemplary inte ⁇ olymer being ethylene/styrene/norbornene.
  • the number average molecular weight (Mn) of the polymers and inte ⁇ olymers is usually greater than 5,000, preferably from 20.000 to 1.000.000. more preferably from 50,000 to 500,000.
  • Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • an amount of atactic vinyl or vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinyl or vinylidene aromatic monomer at elevated temperatures.
  • the presence of vinyl or vinylidene aromatic homopolymer is in general not detrimental for the pu ⁇ oses of the present invention and can be tolerated.
  • the vinyl or vinylidene aromatic homopolymer may be separated from the inte ⁇ olymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the inte ⁇ olymer or the vinyl or vinylidene aromatic homopolymer.
  • extraction techniques such as selective precipitation from solution with a non solvent for either the inte ⁇ olymer or the vinyl or vinylidene aromatic homopolymer.
  • the conditions for polymerizing the ⁇ -olefm. vinyl or vinylidene aromatic, and optional diene are generally those useful in the solution polymerization process, although the application of the present invention is not limited thereto. High pressure, slurry and gas phase polymerization processes are also believed to be useful, provided the proper catalysts and polymerization conditions are employed.
  • the polymerization useful in the practice of the subject invention may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerizations.
  • One method of preparation of the substantially random inte ⁇ olymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts, as described in EP-A-0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers, both of which are inco ⁇ orated herein by reference in their entirety.
  • Such a method of preparation of the substantially random inte ⁇ olymers includes polymerizing a mixture of polymerizable monomers in the presence of one or more metallocene or constrained geometry catalysts in combination with various cocatalysts.
  • Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -30°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization.
  • Cp 1 and Cp 2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other;
  • R 1 and R 2 are hydrogen atoms, halogen atoms, hydrocarbon groups with carbon numbers of 1-12, alkoxyl groups, or aryloxyl groups, independently of each other;
  • M is a group IV metal, preferably Zr or Hf, most preferably Zr; and
  • R 3 is an alkylene group or silanediyl group used to crosslink Cp' and Cp 2 ).
  • the substantially random ⁇ -olefin/vinyl aromatic inte ⁇ olymers can also be prepared by the methods described by John G. Bradfute et al. (W.
  • inte ⁇ olymers which comprise at least one ⁇ -olefin/vinyl aromatic/vinyl aromatic/ ⁇ -olefin tetrad disclosed in U. S. Application No. 08/708,809 filed September 4, 1996 and WO 98/09999 both by Francis J. Timmers et al.
  • These inte ⁇ olymers contain additional signals in their carbon- 13 NMR spectra with intensities greater than three times the peak to peak noise. These signals appear in the chemical shift range 43.70 - 44.25 ppm and
  • these new signals are due to sequences involving two head-to- tail vinyl aromatic monomer insertions preceded and followed by at least one ⁇ -olefin insertion, for example an ethylene/styrene/styrene/ethylene tetrad wherein the styrene monomer insertions of said tetrads occur exclusively in a 1 ,2 (head to tail) manner.
  • inte ⁇ olymers can be prepared by conducting the polymerization at temperatures of from -30°C to 250°C in the presence of such catalysts as those represented by the formula
  • I0 hydrocarbyl substituted 1,3- butadiene; m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst.
  • suitable substituted cyclopentadienyl groups include those illustrated by the formula: wherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group.
  • R independently each occurrence is (including where appropriate all isomers) hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl or silyl or (where appropriate) two such R groups are linked together forming a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.
  • Particularly preferred catalysts include, for example, racemic-
  • racemic- (dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl))zirconium dichloride racemic- (dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl))zirconium 1 ,4-diphenyl-l ,3- butadiene, racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl))zirconium di- Cl-4 alkyl, racemic-(dimethylsilanediyl)-bis-(2-methyl-4-phenylindenyl))zirconium di- C 1 -4 alkoxide, or any combination thereof .
  • titanium-based constrained geometry catalysts [N-(l, l-dimethylethyl)-l,l -dimethyl- l -[( l ,2.3,4,5- ⁇ )-l ,5,6.7-tetrahydro-s- indacen- 1 -yl] silanaminato(2-)-N]titanium dimethy 1 ; ( 1 -indeny 1 )(tert- butylamido)dimethyl-silane titanium dimethyl; ((3-tert-butyl)(l , 2,3.4, 5- ⁇ )-l- indenyl)(tert-butylamido) dimethylsilane titanium dimethyl; and ((3-iso- propyl)(l,2,3,4,5- ⁇ )-l-indenyl)(tert-butyl amido)dimethylsilane titanium dimethyl, or any combination thereof.
  • the level of vinyl or vinylidene aromatic monomer inco ⁇ orated in the thermoset elastomers of the invention is at least 30, preferably at least 35 weight percent based on the weight of the inte ⁇ olymer.
  • the vinyl or vinylidene aromatic monomer is typically inco ⁇ orated in the inte ⁇ olymers of the invention in an amount less than 70, more typically less than 60 weight percent based on the weight of the inte ⁇ olymer.
  • the substantially random inte ⁇ olymers usually 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 hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer and from 35 to 99.5, preferably from 45 to 99, more preferably from 50 to 98 mole percent of at least one aliphatic ⁇ -olefin having from 2 to 20 carbon atoms.
  • One or more dienes can optionally be inco ⁇ orated into the inte ⁇ olymer to provide functional sites of unsaturation on the inte ⁇ olymer useful, for example, to participate in crosslinking reactions.
  • nonconjugated dienes While conjugated dienes such as butadiene, 1,3- pentadiene (that is, piperylene), or isoprene may be used for this purpose, nonconjugated dienes are preferred.
  • Typical nonconjugated dienes include, for example the open-chain nonconjugated diolefms such as 1 ,4-hexadiene (see U.S. Patent No. 2,933,480) and 7-methyl-l,6-octadiene (also known as MOCD); cyclic dienes; bridged ring cyclic dienes, such as dicyclopentadiene (see U.S. Patent No.
  • alkylidenenorbornenes such as methylenenorbornene or ethylidenenorbornene (see U.S. Patent No. 3,151,173).
  • the nonconjugated dienes are not limited to those having only two double bonds, but rather also include those having three or more double bonds.
  • the diene is inco ⁇ orated in the elastomers of the invention in an amount of from 0 to 15 weight percent based on the total weight of the inte ⁇ olymer.
  • a diene When a diene is employed, it will preferably be provided in an amount of at least 2 weight percent, more preferably at least 3 weight percent, and most preferably at least 5 weight percent, based on the total weight of the inte ⁇ olymer.
  • a diene when a diene is employed, it will be provided in an amount of no more than 15, preferably no more than 12 weight percent based on the total weight of the inte ⁇ olymer.
  • the number average molecular weight (Mn) of the polymers and inte ⁇ olymers is usually greater than 5,000, preferably from 20,000 to 1,000,000, more preferably from 50,000 to 500,000.
  • thermoset elastomers of the invention may include various additives, such as carbon black, silica, titanium dioxide, colored pigments, clay, zinc oxide, stearic acid, accelerators, curing agents, sulfur, stabilizers, antidegradants, processing aids, adhesives, tackifiers, plasticizers, wax, precrosslinking inhibitors, discontinuous fibers (such as wood cellulose fibers) and extender oils.
  • additives may be provided either prior to, during, or subsequent to curing the substantially random inte ⁇ olymers.
  • the substantially random inte ⁇ olymers are typically mixed with a filler, an oil, and a curing agent at an elevated temperature to compound them.
  • the compounded material is the subsequently cured at a temperature which is typically greater than that employed during compounding.
  • carbon black will be added to the substantially random inte ⁇ olymer prior to curing.
  • Carbon black is typically added to improve the tensile strength or toughness of the compounded product, but can also be used as an extender or to mask the color of the compounded product.
  • Carbon black will typically be provided in an amount from 0 to 80 weight percent, typically from 0.5 to 50 weight percent, based on the total weight of the formulation.
  • When the carbon black is employed to mask a color it is typically employed in the range of 0.5 to 10 weight percent, based on the weight of the formulation.
  • the carbon black is employed to increase toughness and/or decrease the cost of the formulation, it is typically employed in amounts greater than 10 weight percent based on the weight of the formulation.
  • one or more extender oils will be added to the substantially random inte ⁇ olymer prior to curing.
  • Extender oils are typically added to improve processability and low temperature flexability, as well as to decrease cost.
  • Suitable extender oils are listed in Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, pages 145-190.
  • Typical classes of extender oils include aromatic, naphthenic, and paraffinic extender oils.
  • the extender oil(s) will typically be provided in an amount from 0 to 50 weight percent. When employed, the extender oil will typically be provided in an amount of at least 5 weight percent, more typically in an amount of from 15 to 25 weight percent, based on the total weight of the formulation.
  • the curing agent(s) will typically be provided in an amount of from 0.5 to 12 weight percent, based on 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, sulfenamides, thiuramidisulfides, paraquinonedioxime, dibenzoparaquinonedioxime, sulfur; and combinations thereof. See Encyclopedia of Chemical Technology, Vol. 17, 2nd edition, Interscience Publishers, 1968; also Organic Peroxides, Daniel Seern, Vol. 1, Wiley-Interscience. 1970).
  • Suitable peroxides include aromatic diacyl peroxides; aliphatic diacyl peroxides; dibasic acid peroxides; ketone peroxides; alkyl peroxyesters; alkyl hydroperoxides (for example, diacetylperoxide; dibenzoylperoxide; bis-2,4- dichlorobenzoyl peroxide; di-tert-butyl peroxide; dicumylperoxide; tert- butylperbenzoate; tert-butylcumylperoxide; 2,5-bis (t-butylperoxy)-2,5- dimethylhexane; 2,5-bis (t-butylperoxy)-2,5-dimethylhexyne-3; 4,4,4',4'-tetra-(t- butylperoxy)-2,2-dicyclohexylpropane; l,4-bis-(t-butylperoxyisopropyl)-benz
  • Suitable phenols are disclosed in USP 4,31 1.628. the disclosure of which is inco ⁇ orated herein by reference.
  • a phenolic cure agent is the condensation product of a halogen substituted phenol or a C]-C ⁇ o alkyl substituted phenol with an aldehyde in an alkaline medium, or by condensation of bifunctional phenoldialcohols.
  • One such class of phenolic cure agents is dimethylol phenols substituted in the para position with C5-C10 alkyl group(s).
  • halogenated alkyl substituted phenol curing agents and cure systems comprising methylol phenolic resin, a halogen donor, and a metal compound.
  • Suitable azides include azidoformates, such as tetramethylenebis(azidoformate) (see, also, USP 3,284,421, Breslow, Nov. 8, 1966); aromatic polyazides, such as 4,4'- diphenylmethane diazide (see, also, USP 3,297,674, Breslow et al., Jan. 10, 1967); and sulfonazides, such as p,p'-oxybis(benzene sulfonyl azide).
  • azidoformates such as tetramethylenebis(azidoformate) (see, also, USP 3,284,421, Breslow, Nov. 8, 1966); aromatic polyazides, such as 4,4'- diphenylmethane diazide (see, also, USP 3,297,674, Breslow et al., Jan. 10, 1967); and sulfonazides, such as p,p'-oxybis(benzene
  • the poly(sulfonyl azide) is any compound having at least two sulfonyl azide groups (-SO 2 N 3 ) reactive with thesubstantially random inte ⁇ olymer.
  • the poly(sulfonyl azide)s have a structure X-R-X wherein each X is SO 2 N 3 and R represents an unsubstituted or inertly substituted hydrocarbyl, hydrocarbyl ether or silicon- containing group, preferably having sufficient carbon, oxygen or silicon, preferably carbon, atoms to separate the sulfonyl azide groups sufficiently to permit a facile reaction between the substantially random inte ⁇ olymer and the sulfonyl azide, more preferably at least 1, more preferably at least 2, most preferably at least 3 carbon, oxygen or silicon, preferably carbon, atoms between functional groups.
  • inertly substituted refers to substitution with atoms or groups which do not undesirably interfere with the desired reaction(s) or desired properties of the resulting crosslinked polymers.
  • groups include fluorine, aliphatic or aromatic ether, siloxanes, as well as sulfonyl azide groups when more than two substantially random inte ⁇ olymer chains are to be joined.
  • Suitable structures include R as aryl. alkyl, aryl alkaryl, arylalkyl silane, or heterocyclic, groups and other groups which are inert and separate the sulfonyl azide groups as described.
  • R includes at least one aryl group between the sulfonyl groups, most preferably at least two aryl groups (such as when R is 4,4' diphenylether or 4,4'-biphenyl).
  • R is one aryl group, it is preferred that the group have more than one ring, as in the case of naphthylene bis(sulfonyl azides).
  • Poly(sulfonyl)azides include such compounds as 1, 5-pentane bis(sulfonyl azide), 1,8-octane bis(sulfonyl azide), 1,10-decane bis(sulfonyl azide), 1,10-octadecane bis(sulfonyl azide), l-octyl-2,4,6-benzene tris(sulfonyl azide), 4,4'-diphenyl ether bis(sulfonyl azide), l,6-bis(4'-sulfonazidophenyl)hexane, 2,7-naphthalene bis(sulfonyl azide), and mixed sulfonyl azides of chlorinated aliphatic hydrocarbons containing an average of from 1 to 8 chlorine atoms and from 2 to 5 sulfonyl azide groups per molecule, and mixtures thereof.
  • Preferred poly(sulfonyl azides) include oxy-bis(4- sulfonylazidobenzene), 2,7-naphthalene bis(sulfonyl azido), 4,4'-bis(sulfonyl azido)biphenyl, 4,4'-diphenyl ether bis(sulfonyl azide) and bis(4-sulfonyl azidophenyl)methane, and mixtures thereof
  • the poly(sulfonyl azide) is used in a crosslinking amount, that is an amount effective to crosslink the substantially random inte ⁇ olymer as compared with the starting material substantially random inte ⁇ olymer, that is sufficient poly(sulfonyl azide) to result in the formation of at least 10 weight percent gels as evidenced by insolubility of the gels in boiling xylene when tested according to ASTM D-2765A-84.
  • the amount is preferably at least 0.5, more preferably at least 1.0, most preferably 2.0 weight percent poly(sulfonyl azide) based on total weight of substantially random inte ⁇ olymer, with these values depending on the molecular weight of the azide and the molecular weight or melt index of the substantially random inte ⁇ olymer.
  • the amount of poly(sulfonyl azide) is preferably less than 10 weight percent, more preferably less than 5.
  • the sulfonyl azide is admixed with the substantially random inte ⁇ olymer and heated to at least the decomposition temperature of the sulfonyl azide, that is usually greater than 100°C and most frequently greater than 150°C.
  • the preferred temperature range depends on the nature of the azide that is used. For example, in the case of 4,4'-disulfonylazidediphenylether 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 temperature is less than 250°C.
  • Suitable aldehyde-amine reaction products include formaldehyde-ammonia; formaldehyde-ethylchloride-ammonia; acetaldehyde-ammonia; formaldehyde-aniline; butyraldehyde-aniline; and heptaldehyde-aniline.
  • Suitable substituted ureas include trimethylthiourea; diethylthiourea; dibutylthiourea; tripentylthiourea; l,3-bis(2-benzothiazolylmercaptomethyl)urea; and N,N-diphenylthiourea.
  • Suitable substituted guanidines include diphenylguanidine; di-o-tolylguanidine; diphenylguanidine phthalate; and the di-o-tolylguanidine salt of dicatechol borate.
  • Suitable substituted xanthates include zinc ethylxanthate; sodium isopropylxanthate; butylxanthic disulfide; potassium isopropylxanthate; and zinc butylxanthate.
  • Suitable dithiocarbamates include copper dimethyl-, zinc dimethyl-, tellurium diethyl-, cadmium dicyclohexyl-, lead dimethyl-, lead dimethyl-, selenium dibutyl-, zinc pentamethylene-, zinc didecyl-, and zinc isopropyloctyl-dithiocarbamate.
  • Suitable thiazoles include 2-mercaptobenzothiazole, zinc mercaptothiazolyl mercaptide, 2-benzothiazolyl-N,N-diethylthiocarbamyl sulfide, and 2,2 ' -dithiobis(benzothiazole) .
  • Suitable imidazoles include 2-mercaptoimidazoline and 2-mercapto-4,4,6- trime hyldihydropyrirnidine.
  • Suitable sulfenamides include N-t-butyl-2-benzothiazole-, N- cyclohexylbenzothiazole-, N.N-diisopropylbenzothiazole-, N-(2,6- dimethylmo ⁇ holino)-2-benzothiazole-, and N,N-diethylbenzothiazole-sulfenamide.
  • Suitable thiuramidisulfides include N,N'-diethyl-, tetrabutyl-, N,N'- diisopropyldioctyl-, tetramethyl-, N,N'-dicyclohexyl-, and N,N'-tetralauryl- thiuramidisulfide.
  • dicumyl peroxide when the substantially random inte ⁇ olymer is characterized as having less than 35 weight percent styrene, dicumyl peroxide will typically be provided in an amount of at least 0.1 weight percent, preferably at least 1 weight percent, more preferably at least 2 weight percent based on the combined weight of polymer and peroxide.
  • dicumyl peroxide when the substantially random inte ⁇ olymer is characterized as having from at least 35 to 60 weight percent styrene, dicumyl peroxide will typically be provided in an amount of at least 0.3 weight percent, preferably at least 3 weight percent, more preferably at least 4 weight percent based on the combined weight of polymer and peroxide.
  • dicumyl peroxide when the substantially random inte ⁇ olymer is characterized as having greater than 60 weight percent styrene, dicumyl peroxide will typically be provided in an amount of at least 1 weight percent, preferably at least 6 weight percent, more preferably at least 9 weight percent based on the combined weight of polymer and peroxide.
  • the amount of crosslinking agent employed will not exceed that which is required to effect the desired level of crosslinking.
  • dicumyl peroxide will typically not be employed in an amount greater than 15 weight percent, preferably no more than 12 weight percent based on the combined weight of polymer and peroxide.
  • silane crosslinking agents may be employed.
  • any silane that will effectively graft to and crosslink the substantially random interpolymers can be used in the practice of this invention.
  • Suitable silanes include unsaturated silanes that comprise an ethylenically unsaturated hydrocarbyl group, such as a vinyl, allyl, isopropenyl, butenyl, cyclohexenyl or ⁇ -(meth)acryloxy allyl group, and a hydrolyzable group, such as, for example, a hydrocarbyloxy, hydrocarbonyloxy, or hydrocarbylamino group.
  • hydrolyzable groups include methoxy, ethoxy, formyloxy, acetoxy, proprionyloxy, and alkyl or arylamino groups.
  • Preferred silanes are the unsaturated alkoxy silanes which can be grafted onto the polymer. These silanes and their method of preparation are more fully described in USP 5,266,627 to Meverden, et al. Vinyl trimethoxy silane, vinyl triethoxy silane, ⁇ -(meth)acryloxy propyl trimethoxy silane and mixtures of these silanes are the preferred silane crosslinkers for use in this invention.
  • the amount of silane crosslinking agent used in the practice of this invention can vary widely depending upon the nature of the substantially random inte ⁇ olymer, the silane employed, the processing conditions, the amount of grafting initiator, the ultimate application, and similar factors.
  • VTMOS vinyltrimethoxysilane
  • the VTMOS will typically be provided in an amount of at least 0.1 weight percent, preferably at least 1 weight percent, more preferably at least 3 weight percent based on the combined weight of polymer and silane.
  • VTMOS vinyltrimethoxysilane
  • the maximum amount of silane crosslinker used in the practice of this invention are usually the two principal limitations on the maximum amount of silane crosslinker used in the practice of this invention. For instance, when VTMOS is employed, the maximum amount of VTMOS employed will typically not exceed 10 weight percent, and more preferably does not exceed 8, and most preferably does not exceed 6 weight percent based on the combined weight of polymer and silane.
  • the silane crosslinking agent is grafted to the substantially random inte ⁇ olymer by any conventional method, typically in the presence of a free radical initiator for example peroxides and azo compounds, or by ionizing radiation, etc.
  • Organic initiators are preferred, such as any one of the peroxide initiators, for example, dicumyl peroxide, di-tert-butyl peroxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide, t- butyl peroctoate, methyl ethyl ketone peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, lauryl peroxide, and tert-butyl peracetate.
  • a suitable azo compound is azobisisobutyl nitrite.
  • the amount of initiator will depend upon the percent of vinyl or vinylidene aromatic or hindered aliphatic or cycloaliphatic comonomer present in the substantially random inte ⁇ olymer. For instance, in the case of crosslinking using VTMOS, when the substantially random inte ⁇ olymer is characterized as having less than 35 weight percent styrene, dicumyl peroxide will typically be provided in an amount of at least 250 ppm, preferably at least 500 ppm, more preferably at least 1,500 ppm based on the combined weight of polymer, silane and initiator.
  • dicumyl peroxide when the substantially random inte ⁇ olymer is characterized as having from at least 35 to 60 weight percent styrene, dicumyl peroxide will typically be provided in an amount of at least 400 ppm, preferably at least 1 ,000 ppm, more preferably at least 2,000 ppm based on the combined weight of polymer, silane and initiator.
  • dicumyl peroxide when the substantially random inte ⁇ olymer is characterized as having greater than 60 weight percent styrene, dicumyl peroxide will typically be provided in an amount of at least 500 ppm, preferably at least 1,500 ppm, more preferably at least 3000 ppm based on the combined weight of polymer, silane and initiator.
  • the amount of initiator employed will not exceed that which is required to effect grafting.
  • dicumyl peroxide will typically not be employed in an amount greater than 20,000 ppm, preferably not greater than 10,000 ppm based on the combined weight of polymer, silane and initiator.
  • one preferred method is blending the two with the initiator in the first stage of a reactor extruder, such as a Buss kneader.
  • the grafting conditions can vary, but the melt temperatures are typically between 160°C and 260°C C, preferably between 190°C and 230°C, depending upon the residence time and the half life of the initiator.
  • Cure is promoted with a crosslinking catalyst, and any catalyst that will provide this function can be used in this invention.
  • These catalysts generally include organic bases, carboxylic acids, and organometallic compounds including organic titanates and complexes or carboxylates of lead, cobalt, iron, nickel, zinc and tin.
  • Tin carboxylate, especially dibutyltindilaurate and dioctyltinmaleate are particularly effective for this invention.
  • the catalyst (or mixture of catalysts) is present in a catalytic amount, typically between 0.015 and 0.035 weight percent based on the combined weight of polymer, silane, initiator and catalyst.
  • crosslinking may be effected by use of radiation.
  • Useful radiation types include electron beam or beta ray, gamma rays, X-rays, or neutron rays. Radiation is believed to effect crosslinking by generating polymer radicals which may combine and crosslink. Additional teachings concerning radiation crosslinking are seen in C. P. Park, "Polyolefin Foam” Chapter 9, Handbook of Polymer Foams and Technology, D. Klempner and K. C. Frisch, eds., Hanser Publishers, New York (1991), pages 198 - 204, which is inco ⁇ orated herein by reference.
  • Radiation dosage depends upon the composition of the substantially random inte ⁇ olymer. Generally speaking, as the amount of the vinyl or vinylidene aromatic or hindered aliphatic or cycloaliphatic comonomer increases, greater dosages will be required to cause the desired level of crosslinking, that is, to lead to compositions exhibiting at least 10 percent gel, preferably at least 20 percent gel, and more preferably at least 30 percent gel.
  • typical radiation dosages will be greater than 5 Mrad, preferably greater than 10 Mrad, more preferably greater than 15 Mrad.
  • Electronic radiation dosages are referred to herein in terms of the radiation unit "RAD", with one million RADs or a megarad being designated as "Mrad.”
  • typical radiation dosages will be greater than 5 Mrad, preferably greater than 15 Mrad, more preferably greater than 20 Mrad.
  • typical radiation dosages will be greater than 10 Mrad, preferably greater than 15 Mrad, more preferably greater than 20 Mrad.
  • the dosage will not exceed that which is required to effect the desired level of crosslinking. For instance, dosages above 80 Mrad are not typically employed.
  • substantially random inte ⁇ olymers not including the optional diene component peroxide or azide cure systems are preferred; in the case of inte ⁇ olymer with high styrene content (> than 50 wt. percent) azide cure systems are preferred; in the case of substantially random inte ⁇ olymers including the optional diene component, sulfur-based (for example, containing sulfur, a dithiocarbamate, a thiazole, an imidazole, a sulfenamide, a thiuramidisulfide or combinations thereof) and phenolic cure systems are preferred.
  • sulfur-based for example, containing sulfur, a dithiocarbamate, a thiazole, an imidazole, a sulfenamide, a thiuramidisulfide or combinations thereof
  • phenolic cure systems are preferred.
  • dual cure systems which use a combination of heat, moisture cure, and radiation steps, may be effectively employed.
  • Dual cure systems are disclosed and claimed in U. S. Patent Application Serial No. 536,022, filed on September 29, 1995, in the names of K. L. Walton and S. V. Karande, inco ⁇ orated herein by reference.
  • peroxide crosslinking agents in conjunction with silane crosslinking agents, peroxide crosslinking agents in conjunction with radiation, sulfur-containing crosslinking agents in conjunction with silane crosslinking agents, etc.
  • Olefinic polymers suitable for use as components (Bl. B2 and B3) employed in the present invention are aliphatic ⁇ -olefin homopolymers or inte ⁇ olymers, or inte ⁇ olymers of one or more aliphatic ⁇ -olefins and one or more non-aromatic monomers inte ⁇ olymerizable therewith such as C 2 -C 20 ⁇ -olefins or those aliphatic ⁇ - olefins having from 2 to 20 carbon atoms and containing polar groups.
  • Suitable aliphatic ⁇ -olefin monomers which introduce polar groups into the polymer 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 (both mono- and difunctional) such as acrylic acid and methacrylic acid, etc.; esters (especially lower, for example C,-C 6 , alkyl esters) of ethylenically unsaturated carboxylic acids such as methyl methacrylate, ethyl acrylate, hydroxyethylacrylate, n-butyl acrylate or methacrylate.
  • ethylenically unsaturated nitriles such as acrylonit
  • 2-ethyl-hexylacrylate etc. ethylenically unsaturated vinyl alcohols, such as ethylene vinyl alcohol (EVOH); ethylenically unsaturated dicarboxylic acid imides such as N-alkyl or N-aryl maleimides such as N-phenyl maleimide, etc.
  • ethylenically unsaturated vinyl alcohols such as ethylene vinyl alcohol (EVOH)
  • ethylenically unsaturated dicarboxylic acid imides such as N-alkyl or N-aryl maleimides such as N-phenyl maleimide, etc.
  • monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride and acrylonitrile.
  • Halogen groups which can be included in the polymers from aliphatic ⁇ -olefin monomers include fluorine, chlorine and bromine; preferably such polymers are chlorinated polyethylenes (CPEs).
  • Preferred olefinic polymers for use in the present invention are homopolymers or inte ⁇ olymers of an aliphatic, including cycloaliphatic, ⁇ -olefin having from 2 to 18 carbon atoms. Suitable examples are homopolymers of ethylene or propylene, and inte ⁇ olymers of two or more ⁇ -olefin monomers. Other preferred olefinic polymers are inte ⁇ olymers of ethylene and one or more other ⁇ - olefins having from 3 to 8 carbon atoms.
  • Preferred comonomers include 1-butene, 4- methyl-1-pentene, 1-hexene, and 1-octene.
  • the olefinic polymer blend component (B) may also contain, in addition to the ⁇ -olefin, one or more non-aromatic monomers inte ⁇ olymerizable therewith.
  • additional inte ⁇ olymerizable monomers include, for example, C 4 -C 20 dienes, preferably, butadiene or 5-ethylidene-2-norbornene.
  • the olefinic polymers can be further characterized by their degree of long or short chain branching and the distribution thereof.
  • LDPE long chain branched low density polyethylene
  • ASTM Test Method D 1238, condition I One class of olefinic polymers is generally produced by a high pressure polymerization process using a free radical initiator resulting in the traditional long chain branched low density polyethylene (LDPE).
  • LDPE employed in the present composition usually has a density of less than 0.94 g/cc (ASTM D 792) and a melt index of from 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes (as determined by ASTM Test Method D 1238, condition I).
  • linear olefin polymers which have an absence of long chain branching, as the traditional linear low density polyethylene polymers (heterogeneous LLDPE) or linear high density polyethylene polymers (HDPE) made using Ziegler polymerization processes (for example, U.S. Patent No. 4,076,698 (Anderson et al.), sometimes called heterogeneous polymers.
  • heterogeneous polymers for example, U.S. Patent No. 4,076,698 (Anderson et al.
  • HDPE consists mainly of long linear polyethylene chains.
  • the HDPE employed in the present composition usually has a density of at least 0.94 grams per cubic centimeter (g/cc) as determined by ASTM Test Method D 792, and a melt index (ASTM-1238, condition I) in the range of from 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes.
  • the heterogeneous LLDPE employed in the present composition generally has a density of from 0.85 to 0.94 g/cc (ASTM D 792), and a melt index (ASTM-1238, condition I) in the range of from 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes.
  • the LLDPE is an inte ⁇ olymer of ethylene and one or more other ⁇ -olefins having from 3 to 18 carbon atoms, more preferably from 3-8 carbon atoms.
  • Preferred comonomers include 1-butene, 4-methyl-l-pentene, 1-hexene, and 1- octene.
  • a further class is that of the uniformly branched or homogeneous ethylene polymers.
  • the homogeneous linear ethylene polymers contain no long chain branches and have only branches derived from the monomers (if having more than two carbon atoms).
  • Homogeneous linear ethylene polymers include those made as described in
  • U.S. Patent 3,645,992 (Elston), and those made using so-called single site catalysts in a batch reactor having relatively high olefin concentrations (as described in U.S. Patent Nos. 5,026,798 and 5,055,438 (Canich).
  • the uniformly branched/homogeneous linear ethylene polymers are those polymers in which the comonomer is randomly distributed within a given inte ⁇ olymer molecule and wherein the inte ⁇ olymer molecules have a similar ethylene/comonomer ratio within that inte ⁇ olymer.
  • the homogeneous linear ethylene polymer employed in the present composition generally has a density of from 0.85 to 0.94 g/cc (ASTM D 792), and a melt index (ASTM-1238, condition I) in the range of from 0.01 to 100, and preferably from 0.1 to 50 grams per 10 minutes.
  • the homogeneous linear ethylene polymer is an inte ⁇ olymer of ethylene and one or more other ⁇ -olefins having from 3 to 18 carbon atoms, more preferably from 3-8 carbon atoms.
  • Preferred comonomers include 1- butene, 4-methyl-l-pentene, 1-hexene, and 1-octene.
  • substantially linear olefin polymers that may advantageously be used in component (B) of the blends of the present invention.
  • SLOP substantially linear olefin polymers
  • these polymers have a processability similar to LDPE, but the strength and toughness of LLDPE.
  • the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers have only a single melting peak, as opposed to traditional Ziegler polymerized heterogeneous linear ethylene/ ⁇ -olefin inte ⁇ olymers which have two or more melting peaks (determined using differential scanning calorimetry).
  • Substantially linear olefin polymers are disclosed in U.S. Patent Nos. 5,272,236 and 5,278,272 which are inco ⁇ orated herein by reference.
  • the density of the SLOP as measured in accordance with ASTM D-792 is generally from 0.85 g/cc to 0.97 g/cc, preferably from 0.85 g/cc to 0.955 g/cc, and especially from 0.85 g/cc to 0.92 g/cc.
  • the melt index, according to ASTM D-l 238, Condition 190°C/2.16 kg (also known as I 2 ), of the SLOP is generally from 0.01 g/10 min. to 1000 g/10 min., preferably from 0.01 g/10 min. to 100 g/10 min., and especially from 0.01 g/10 min. to 10 g/10 min. Also, included are the ultra low molecular weight ethylene polymers and ethylene/ ⁇ -olefin inte ⁇ olymers described in the patent application entitled Ultra-low Molecular Weight Polymers, filed provisionally on January 22, 1996 in the names of M. L. Finlayson, C. C. Garrison, R. E. Guerra, M. J. Guest, B. W. S. Kolthammer, D. R.
  • the SLOP can be a homopolymer of a C 2 -C 20 olefin. such as ethylene, propylene, 4-methyl-l-pentene, etc., or it can be an inte ⁇ olymer of ethylene with at least one C 3 -C 20 ⁇ -olefin and/or C,-C 20 acetylenically unsaturated monomer and/or C 4 - C lg diolefin.
  • the SLOP can also be an inte ⁇ olymer of ethylene with at least one of the above C 3 -C 20 ⁇ -olefins, diolefins and/or acetylenically unsaturated monomers in combination with other unsaturated monomers.
  • olefin polymers suitable for use as component (B) comprise LDPE, HDPE, heterogeneous LLDPE, homogeneous linear ethylene polymers, SLOP, polypropylene (PP), especially isotactic polypropylene and rubber toughened polypropylenes, or ethylene-propylene inte ⁇ olymers (EP). or chlorinated polyolefins (CPE), or ethylene-vinyl acetate copolymers (EVA), or ethylene-acrylic acid copolymers (EAA), or any combination thereof.
  • block copolymer is used herein to mean elastomers having at least one block segment of a hard polymer unit and at least one block segment of a rubber monomer unit. However, the term is not intended to include thermoelastic ethylene inte ⁇ olymers which are, in general, random polymers.
  • Preferred block copolymers contain hard segments of styrenic type polymers in combination with saturated or unsaturated rubber monomer segments.
  • the structure of the block copolymers useful in the present invention is not critical and can be of the linear or radial type, either diblock or triblock, or any combination of thereof. Preferably, the predominant structure is that of triblocks and more preferably that of linear triblocks.
  • the preparation of the block copolymers useful herein is not the subject of the present invention. Methods for the preparation of such block copolymers are known in the art. Suitable catalysts for the preparation of useful block copolymers with unsaturated rubber monomer units include lithium based catalysts and especially lithium-alkyls. U.S. Pat. No. 3,595,942 describes suitable methods for hydrogenation of block copolymers with unsaturated rubber monomer units to from block copolymers with saturated rubber monomer units. The structure of the polymers is determined by their methods of polymerization.
  • linear polymers result by sequential introduction of the desired rubber monomer into the reaction vessel when using such initiators as lithium-alkyls or dilithiostilbene, or by coupling a two segment block copolymer with a difunctional coupling agent.
  • Branched structures may be obtained by the use of suitable coupling agents having a functionality with respect to the block copolymers with unsaturated rubber monomer units of three or more.
  • Coupling may be effected with multifunctional coupling agents such as dihaloalkanes or alkenes and divinyl benzene as well as with certain polar compounds such as silicon halides, siloxanes or esters of monohydric alcohols with carboxylic acids.
  • the presence of any coupling residues in the polymer may be ignored for an adequate description of the block copolymers forming a part of the composition of this invention.
  • Suitable block copolymers having unsaturated rubber monomer units includes, but is not limited to, styrene-butadiene (SB), styrene-isoprene(SI), styrene-butadiene- styrene (SBS), styrene-isoprene-styrene (SIS), -methylstyrene-butadiene-methylstyrene and -methylstyrene-isoprene-methylstyrene.
  • SB styrene-butadiene
  • SI styrene-isoprene
  • SI styrene-butadiene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • the styrenic portion of the block copolymer is preferably a polymer or inte ⁇ olymer of styrene and its analogs and homologs including ⁇ -methylstyrene and ring-substituted styrenes, particularly ring-methylated styrenes.
  • the preferred styrenics are styrene and methylstyrene, and styrene is particularly preferred.
  • Block copolymers with unsaturated rubber monomer units may comprise homopolymers of butadiene or isoprene and copolymers of one or both of these two dienes with a minor amount of styrenic monomer.
  • the monomer employed is butadiene, it is preferred that between 35 and 55 mol percent of the condensed butadiene units in the butadiene polymer block have 1 ,2 configuration.
  • the resulting product is, or resembles a regular copolymer block of ethylene and 1-butene (EB).
  • the conjugated diene employed is isoprene
  • the resulting hydrogenated product is or resembles a regular copolymer block of ethylene and propylene (EP).
  • Preferred block copolymers with saturated rubber monomer units comprise at least one segment of a styrenic unit and at least one segment of an ethylene- butene or ethylene-propylene copolymer.
  • Preferred examples of such block copolymers with saturated rubber monomer units include styrene/ethylene-butene copolymers, styrene/ethylene-propylene copolymers, styrene/ethylene-butene/styrene (SEBS) copolymers, and styrene/ethylene-propylene/styrene (SEPS) copolymers.
  • Hydrogenation of block copolymers with unsaturated rubber monomer units is preferably effected by use of a catalyst comprising the reaction products of an aluminum alkyl compound with nickel or cobalt carboxylates or alkoxides under such conditions as to substantially completely hydrogenate at least 80 percent of the aliphatic double bonds while hydrogenating no more than 25 percent of the styrenic aromatic double bonds.
  • Preferred block copolymers are those where at least 99 percent of the aliphatic double bonds are hydrogenated while less than 5 percent of the aromatic double bonds are hydrogenated.
  • the proportion of the styrenic blocks is generally between 8 and 65 percent by weight of the total weight of the block copolymer.
  • the block copolymers contain from 10 to 35 weight percent of styrenic block segments and from 90 to 65 weight percent of rubber monomer block segments, based on the total weight of the block copolymer.
  • the average molecular weights of the individual blocks may vary within certain limits.
  • the styrenic block segments will have number average molecular weights in the range of 5,000 to 125,000, preferably from 7,000 to 60,000 while the rubber monomer block segments will have average molecular weights in the range of 10,000 to 300,000, preferably from 30,000 to 150,000.
  • the total average molecular weight of the block copolymer is typically in the range of 25,000 to 250,000, preferably from 35,000 to 200,000. These molecular weights are most accurately determined by tritium counting methods or osmotic pressure measurements.
  • block copolymers suitable for use in the present invention may be modified by graft inco ⁇ oration of minor amounts of functional groups, such as, for example, maleic anhydride by any of the methods well known in the art.
  • Block copolymers useful in the present invention are commercially available, such as, for example, supplied by Shell Chemical Company under the designation of KRATON and supplied by Dexco Polymers under the designation of VECTOR.
  • blends of the substantially random inte ⁇ olymer with polyvinylchloride (PVC) or ethylene vinyl alcohol (EVOH) may be suitably employed.
  • thermoset compositions of the invention may be inco ⁇ orated into polyolefms to form thermoplastic vulcanizates.
  • the proportions of ingredients utilized will vary somewhat with the particular polyolefin employed, with the desired application, as well as with the character of the crosslinked substantially random inte ⁇ olymer and compounding ingredients. Typically, as the amount of the crosslinked substantially random inte ⁇ olymer increases, the stiffness of the resultant thermoplastic vulcanizate decreases.
  • the thermoplastic vulcanizates of the invention will typically comprise from 10 to 90 weight percent of the polyolefin and from 10 to 90 weight percent of the crosslinked substantially random inte ⁇ olymer.
  • Suitable polyolefms include thermoplastic, crystalline, high molecular weight polymers prepared by the polymerization of one or more monoolefins.
  • suitable polyolefms include ethylene and the isotactic and syndiotactic monoolefin polymer resins, such as propylene, 1-butene, 1-pentene, 1-hexene, 2-methyl-l-propene, 3-methyl-l-pentene, 4-methyl-l-pentene, 5 -methyl- 1-hexene and mixtures thereof.
  • the thermoplastic vulcanizates of the invention will utilize isotactic polypropylene as the polyolefin component.
  • thermoplastic vulcanizates of the invention are preferably prepared by dynamic vulcanization, wherein a mixture of the noncrosslinked substantially random inte ⁇ olymer is mixed with the polyolefin resin and an appropriate curing agent to form a blend, which is then masticated at vulcanization temperature.
  • the noncrosslinked substantially random inte ⁇ olymer is blended with a polyolefin at a temperature above the melting point of the polyolefin.
  • an appropriate curing agent is added, such as are described above with respect to the compounding and curing of the substantially random inte ⁇ olymers.
  • the blend is subsequently masticated using conventional masticating equipment, such as a Banbury mixer. Brabender mixer, or a mixing extruder.
  • the temperature of the blend during mastication is that sufficient to effect vulcanization of the substantially random inte ⁇ olymer.
  • a suitable range of vulcanization temperatures is from the melting temperature of the polyolefin resin (120°C in the case of polyethylene and 175°C in the case of polypropylene) to the temperature at which the substantially random inte ⁇ olymer. the polyolefin, or the curing agent degrades. Typical temperatures are from 180°C to 250°C, preferably from 180°C to 200°C.
  • the substantially random inte ⁇ olymer may be crosslinked prior to introduction to the polyolefin.
  • the crosslinked substantially random inte ⁇ olymer may then be powdered and mixed with the polyolefin at a temperature above the melting or softening point of the polyolefin.
  • the crosslinked substantially random inte ⁇ olymer particles are small, well-dispersed, and in an appropriate concentration, (that is, provided an intimate mixture of the crosslinked substantially random inte ⁇ olymer and polyolefin is achieved), the thermoplastic vulcanizates of the invention may be readily obtained.
  • the resultant product will contain visually observable islands of the crosslinked substantially random inte ⁇ olymer.
  • the part may be comminuted by pulverizing or by cold milling to reduce particle size to below 50 microns. Upon adequate comminution, the particles may be remolded into a part exhibiting more uniform composition and the enhanced properties characteristic of the thermoplastic vulcanizates of the invention.
  • thermoplastic vulcanizates of the invention may include various additives, such as carbon black, silica, titanium dioxide, colored pigments, clay, zinc oxide, stearic acid, accelerators, vulcanizing agents, sulfur, stabilizers, antidegradants, processing aids, adhesives, tackifiers, plasticizers, wax, prevulcanization inhibitors, discontinuous fibers (such as wood cellulose fibers) and extender oils.
  • additives such as carbon black, silica, titanium dioxide, colored pigments, clay, zinc oxide, stearic acid, accelerators, vulcanizing agents, sulfur, stabilizers, antidegradants, processing aids, adhesives, tackifiers, plasticizers, wax, prevulcanization inhibitors, discontinuous fibers (such as wood cellulose fibers) and extender oils.
  • additives may be provided either prior to, during, or subsequent to vulcanization.
  • the foam structure of the present invention may take any physical configuration known in the art, such as sheet, plank,injection molded articles, or bun stock.
  • Other useful forms are expandable or foamable particles, moldable foam particles, or beads, and articles formed by expansion and/or coalescing and welding of those particles.
  • the present foam structure may be prepared by blending and heating a polymer material comprising at least one substantially random inte ⁇ olymer and a decomposable chemical blowing agent to form a foamable plasticized or melt polymer material, extruding the foamable melt polymer material through a die, inducing cross- linking in the melt polymer material, and exposing the melt polymer material to an elevated temperature to release the blowing agent to form the foam structure.
  • the polymer material and the chemical blowing agent may be mixed and melt blended by any means known in the art such as with an extruder, mixer, or blender.
  • the chemical blowing agent is preferably dry -blended with the polymer material prior to heating the polymer material to a melt form, but may also be added when the polymer material is in melt phase.
  • Cross-linking may be induced by addition of a cross-linking agent or by radiation. Induction of cross-linking and exposure to an elevated temperature to effect foaming or expansion may occur simultaneously or sequentially. If a cross-linking agent is used, it is inco ⁇ orated into the polymer material in the same manner as the chemical blowing agent. Further, if a cross-linking agent is used, the foamable melt polymer material is heated or exposed to a temperature of preferably less than 150°C to prevent decomposition of the cross-linking agent or the blowing agent and to prevent premature cross-linking. If radiation cross-linking is used, the foamable melt polymer material is heated or exposed to a temperature of preferably less than 160°C to prevent decomposition of the blowing agent.
  • the foamable melt polymer material is extruded or conveyed through a die of desired shape to form a foamable structure.
  • the foamable structure is then cross-linked and expanded at an elevated or high temperature (typically, 150°C-250°C) such as in an oven to form a foam structure.
  • an elevated or high temperature typically, 150°C-250°C
  • the foamable structure is irradiated to cross-link the polymer material, which is then expanded at the elevated temperature as described above.
  • the present structure can advantageously be made in sheet or thin plank form according to the above process using either cross-linking agents or radiation.
  • the present foam structure may also be made into a continuous plank structure by an extrusion process utilizing a long-land die as described in GB 2,145,961 A.
  • the polymer, decomposable blowing agent and cross-linking agent are mixed in an extruder, heating the mixture to let the polymer cross-link and the blowing agent to decompose in a long-land die; and shaping and conducting away from the foam structure through the die with the foam structure and the die contact lubricated by a proper lubrication material.
  • the present foam structure may also be formed into cross-linked foam beads suitable for molding into articles.
  • discrete resin particles such as granulated resin pellets are: suspended in a liquid medium in which they are substantially insoluble such as water; impregnated with a cross-linking agent and a blowing agent at an elevated pressure and temperature in an autoclave or other pressure vessel; and rapidly discharged into the atmosphere or a region of reduced pressure to expand to form the foam beads.
  • a version is that the polymer beads is impregnated with blowing agent, cooled down, discharged from the vessel, and then expanded by heating or with steam. Blowing agent may be impregnated into the resin pellets while in suspension or, alternately, in non-hydrous state. The expandable beads are then expanded by heating with steam and molded by the conventional molding method for the expandable polystyrene foam beads.
  • the foam beads may then be molded by any means known in the art, such as charging the foam beads to the mold, compressing the mold to compress the beads, and heating the beads such as with steam to effect coalescing and welding of the beads to form the article.
  • the beads may be pre-heated with air or other blowing agent prior to charging to the mold.
  • Excellent teachings of the above processes and molding methods are seen in CP. Park, above publication, pp. 227-233, U.S. Patent No. 3,886,100, U.S. Patent No. 3,959,189, U.S. Patent No. 4,168,353, and U.S. Patent No. 4,429,059.
  • the foam beads can also be prepared by preparing a mixture of polymer, cross-linking agent, and decomposable mixtures in a suitable mixing device or extruder and form the mixture into pellets, and heat the pellets to cross-link and expand.
  • the substantially random inte ⁇ olymer material is melted and mixed with a physical blowing agent in a conventional foam extrusion apparatus to form an essentially continuous foam strand.
  • the foam strand is granulated or pelletized to form foam beads.
  • the foam beads are then cross-linked by radiation.
  • the cross- linked foam beads may then be coalesced and molded to form various articles as described above for the other foam bead process. Additional teachings to this process are seen in U.S. Patent No. 3,616,365 and CP. Park, above publication, pp. 224-228.
  • the present foam structure may be made in bun stock form by two different processes. One process involves the use of a cross-linking agent and the other uses radiation.
  • the present foam structure may be made in bun stock form by mixing the substantially random inte ⁇ olymer material, a cross-linking agent, and a chemical blowing agent to form a slab, heating the mixture in a mold so the cross-linking agent can cross-link the polymer material and the blowing agent can decompose, and expanding by release of pressure in the mold.
  • the bun stock formed upon release of pressure may be re-heated to effect further expansion.
  • Cross-linked polymer sheet may be made by either irradiating polymer sheet with high energy beam or by heating a polymer sheet containing chemical cross-linking agent.
  • the cross-linked polymer sheet is cut into the desired shapes and impregnated with nitrogen in a higher pressure at a temperature above the softening point of the polymer; releasing the pressure effects nucleation of bubbles and some expansion in the sheet.
  • the sheet is re-heated at a lower pressure above the softening point, and the pressure is then released to allow foam expansion.
  • Blowing agents and foaming agents as employed herein are interchangeable and have the same meaning.
  • Blowing agents useful in making the present foam structure include decomposable chemical blowing agents. Such chemical blowing agents decompose at elevated temperatures to form gases or vapors to blow the polymer into foam form.
  • the agent preferably takes a solid form so it may be easily dry-blended with the polymer material.
  • Chemical blowing agents include azodicarbonamide, azodiisobutyro-nitrile, benzenesulfonhydrazide, 4,4-oxybenzene sulfonyl- semicarbazide, p-toluene sulfonyl semi-carbazide, barium azodicarboxylate, N,N'- dimethyl-N,N ' -dinitrosoterephthalamide, N,N ' -dinitrosopentamethylenetetramine, 4-4- oxybis (benzenesulfonylhydrazide), and trihydrazino triazine. Azodicarbonamide is preferred. Additional teachings to chemical blowing agents are seen in CP.
  • the chemical blowing agent is blended with the polymer material in an amount sufficient to evolve 0.2 to 5.0, preferably from 0.5 to 3.0, and most preferably from 1.0 to 2.50 moles of gas or vapor per kilogram of polymer.
  • a physical blowing agent may be used.
  • Physical blowing agents include organic and inorganic agents. Suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, nitrogen, and helium.
  • Organic blowing agents include aliphatic hydrocarbons having 1 -9 carbon atoms, aliphatic alcohols having 1-3 carbon atoms, and fully and partially halogenated aliphatic hydrocarbons having 1-4 carbon atoms.
  • Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, and neopentane.
  • Aliphatic alcohols include methanol, ethanol, n-propanol. and isopropanol.
  • Fully and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chloro fluorocarbons.
  • fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1.1-difluoroethane (HFC- 152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoro-ethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane.
  • Partially halogenated chlorocarbons and chlorofluorocarbons for use in this invention include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-l-fluoroethane (HCFC-141b), 1 -chloro- 1,1- difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), l,l-dichloro-2,2,2- trifluoroethane (HCFC-123) and 1 -chloro- 1,2,2,2-tetrafluoroethane (HCFC-124).
  • Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC- 11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane.
  • the amount of blowing agent inco ⁇ orated into the polymer melt material to make a foam-forming polymer gel is from 0.2 to 5.0, preferably from 0.5 to 3.0, and most preferably from 1.0 to 2.50 moles per kilogram of polymer.
  • additives may be inco ⁇ orated in the present foam structure such as stability control agents, nucleating agents, inorganic fillers, pigments, antioxidants, acid scavengers, ultraviolet absorbers, flame retardants, processing aids and extrusion aids.
  • a stability control agent may be added to the present foam to enhance dimensional stability.
  • Preferred agents include amides and esters of CI Q-24 fatty acids. Such agents are seen in U. S. Pat Nos. 3,644,230 and 4,214,054, which are inco ⁇ orated herein by reference. Most preferred agents include stearyl stearamide, glycerol monostearate, glycerol monobehenate, and sorbitol monostearate. Typically, such stability control agents are employed in an amount ranging from 0.1 to 10 parts per hundred parts of the polymer.
  • nucleating agent may be added in order to control the size of foam cells.
  • Preferred nucleating agents include inorganic substances such as calcium carbonate, talc, clay, titanium oxide, silica, barium sulfate, diatomaceous earth, mixtures of citric acid and sodium bicarbonate.
  • the amount of nucleating agent employed may range from 0.01 to 5 parts by weight per hundred parts by weight of a polymer resin.
  • the foam structure has density of less than 250, more preferably less than 100 and most preferably from 10 to 70 kilograms per cubic meter.
  • the foam has an average cell size of from 0.05 to 5.0, more preferably from 0.2 to 2.0, and most preferably 0.3 to 1.8 millimeters according to ASTM D3576.
  • the foam structure may take any physical configuration known in the art, such as extruded sheet, rod, plank, and profiles.
  • the foam structure may also be formed by molding of expandable beads into any of the foregoing configurations or any other configuration.
  • the foam structure may be closed-celled or open-celled according to ASTM D2856-A.
  • the compositions of the invention will be utilized in cable insulation and/or cable jacketing.
  • the cable insulation of this invention can be filled or unfilled. If filled, then the amount of filler present should not exceed an amount that would cause degradation of the electrical and/or mechanical properties of the inte ⁇ olymers.
  • the amount of filler present is between 20 and 80, preferably between 50 and 70, weight percent (wt percent) based on the weight of the polymer.
  • Representative fillers include kaolin clay, magnesium hydroxide, silica, calcium carbonate.
  • the filler is coated with a material that will prevent or retard any tendency that the filler might otherwise have to interfere with the cure reactions. Stearic acid is illustrative of such a filler coating.
  • Other additives can be used in the preparation of and be present in the insulation of this invention, and include antioxidants, processing aids, pigments and lubricants.
  • compositions of the invention are shaped into automotive weatherstripping, gaskets or seals.
  • This weatherstripping is useful as a sealing system for doors, trunks, belt lines, hoods, and similar items.
  • These materials can be processed on conventional thermoplastic equipment.
  • the articles made from crosslinked inte ⁇ olymers should have better sound insulation than conventional sulfur- cured EPDM weatherstripping.
  • crosslinkable fibers may be prepared.
  • a substantially random inte ⁇ olymer is provided with an effective amount of a peroxide or an azide compound, as described herein.
  • the resultant mixture is extruded into fibers, which are then heated to cause crosslinking.
  • the substantially random inte ⁇ olymer is extruded into fibers, which are then crosslinked by irradiation with an effective amount of radiation, such as is described herein.
  • silane-grafted substantially random inte ⁇ olymers are shaped into fibers, which exhibit improved heat resistance. These fibers are readily crosslinked upon exposure to moisture which can be affected by immersion in water or by exposure to atmospheric moisture.
  • the resultant crosslinked fibers are usefully employed in woven and non-woven fabric (for example washable clothing), elastic string (for example woven elastic strap), elastic filters for air/water filtration (for example non- woven air cleaners), and fiber mats (for example non-woven ca ⁇ et underlayment).
  • woven and non-woven fabric for example washable clothing
  • elastic string for example woven elastic strap
  • elastic filters for air/water filtration for example non- woven air cleaners
  • fiber mats for example non-woven ca ⁇ et underlayment
  • carbon black will preferably be added to the blend of the substantially random inte ⁇ olymer and polyolefin prior to vulcanization.
  • Carbon black will typically be provided in an amount from O to 50 weight percent, typically from 0.5 to 50 weight percent, based on the total formulation weight.
  • one or more extender oils will preferably be added to the blend of the substantially random inte ⁇ olymer and polyolefin prior to vulcanization.
  • Suitable extender oils are listed in Rubber World Blue Book 1975 Edition, Materials and Compounding Ingredients for Rubber, pages 145-190.
  • Typical classes of extender oils include aromatic, naphthenic, and paraffinic extender oils.
  • the extender oil(s) will typically be provided in an amount from 0 to 50 weight percent based on the total formulation weight. When employed, the extender oil will typically be provided in an amount of at least 5 weight percent, more typically in an amount of from 15 to 25 weight percent, based on the total weight of the formulation.
  • Additives such as antioxidants (for example, hindered phenols such as, for example, Irganox® 1010), phosphites (for example, Irgafos® 168)), U. V. stabilizers, cling additives (for example, polyisobutylene), antiblock additives, colorants, pigments, fillers, can also be included in the inte ⁇ olymers employed in the blends of and/or employed in the present invention, to the extent that they do not interfere with the enhanced properties discovered by Applicants.
  • antioxidants for example, hindered phenols such as, for example, Irganox® 1010), phosphites (for example, Irgafos® 168)
  • U. V. stabilizers for example, polyisobutylene
  • antiblock additives for example, colorants, pigments, fillers
  • the additives are employed in functionally equivalent amounts known to those skilled in the art.
  • the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers.
  • Such amounts of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend.
  • the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend antiblocking, to produce the desired amount of filler loading to produce the desired result, to provide the desired color from the colorant or pigment.
  • Such additives can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the polymer or polymer blend.
  • fillers they could be employed in amounts up to 90 percent by weight based on the weight of the polymer or polymer blend.
  • the thermoplastic vulcanizates of the invention will comprise from 30 to 60 weight percent of the substantially random inte ⁇ olymer, from 15 to 55 weight percent of the thermoplastic polyolefin, and from 15 to 30 weight percent of the extender oil.
  • Such thermoplastic vulcanizates are particularly useful as moldings for automotive applications.
  • the thermoplastic vulcanizates of the invention are characterized by an ASTM #2 oil swell of less than 60 percent, as determined by ASTM D-471.
  • Monomer contents are determined by carbon- 13 NMR spectroscopy.
  • ASTM #2 and #3 oil swells are measured in accordance with ASTM D-471.
  • Hardness shore "A” is measured in accordance with ASTM D-2240.
  • Compression set is measured in accordance with ASTM D-395.
  • Percent gel content (% crosslinking) is measured in accordance with ASTM D- 2765-84, using a xylene extraction method. Approximately 1 gram of sample is weighed out and was transferred to a mesh basket which is then placed in boiling xylene for 12 hours. After 12 hours, the sample baskets are removed and placed in a vacuum oven at 150 °C and 28 in. of Hg vacuum for 12 hours. After 12 hours, the samples are removed, allowed to cool to room temperature over a 1 hour period, and then weighed. The percent polymer extracted is calculated as:
  • Percent polymer extracted ((initial weight - final weight) / initial weight) x 100
  • the upper service temperature is determined using a Perkin Elmer model TMA 7 thermo-mechanical analyzer (TMA). Probe force of 102 g and heating rate of 5°C/min were used. The test specimen was a disk with thickness of about 2 mm in diameter, prepared by melting pressing at 205 °C and air-cooling to room temperature.
  • TMA 7 thermo-mechanical analyzer TMA 7 thermo-mechanical analyzer
  • Ethylene/styrene copolymers were made using (tert- butylamido)dimethyl(tetramethyl- ⁇ 5 -cyclopenta-dienyl)silane dimethyltitanium(+4) catalyst and tris(pentafluorophenyl)borane cocatalyst in a one to one molar ratio according to the following procedure.
  • a two liter reactor was charged with 360 grams ( 500 mL) of ISOPARTM E mixed alkane solvent (available from Exxon Chemicals Inc.) and the desired amount of styrene comonomer. Hydrogen was added to the reactor by differential pressure expansion from a 75 mL addition tank.
  • the reactor was heated to the run temperature and was saturated with ethylene at the desired pressure.
  • (Tert- butylamido)dimethyl-(tetramethyl- ⁇ 5 -cyclopentadienyl)silane dimethyltitanium (IV) catalyst and tris(pentafluorophenyl)borane cocatalyst were mixed in a dry box by pipeting the desired amount of a 0.005 M solution of the tris(pentafluorophenyl)borane cocatalyst in ISOPARTM E mixed alkane solvent or toluene into a solution of the (tert- butylamido)dimethyl-(tetramethyl- ⁇ 5 -cyclo ⁇ entadienyl)silane dimethyl-titanium (IV) catalyst in ISOPARTM E mixed alkane solvent or toluene.
  • the resulting catalyst solution was transferred to a catalyst addition tank and was injected into the reactor.
  • the polymerization was allowed to proceed, with ethylene being introduced on demand. Additional charges of catalyst and cocatalyst, if used, were prepared in the same manner and were added to the reactor periodically.
  • the total amount of catalyst employed was set forth in Table One. In each instance, the amount of tris(pentafluorophenyl)borane cocatalyst (on a molar basis) equals the amount of (tert- butylamido)dimethyl-(tetramethyl- ⁇ 5 -cyclopentadienyl)silane dimethyltitanium (IV) catalyst indicated in Table One.
  • the polymer solution was removed from the reactor and quenched with isopropyl alcohol.
  • a hindered phenol antioxidant IRGANOXTM 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 resultant substantially random inte ⁇ olymers were characterized as being pseudorandom and linear.
  • the inte ⁇ olymers were compounded and cured according to the following procedure.
  • the 60 gram bowl of a Brabender PS-2 internal mixer was preheated to 120°F. 100 pph carbon black N550 (available from Cabot Co ⁇ oration), 50 pph SUNPARTM 2280 oil (available from Sun Oil), 5 pph paraffin wax, 1 pph stearic acid, 8 pph Vul-Cup 40KE peroxide (available from Hercules) and 1.5 pph triallyl cyanurate coagent (available from American Cyanamid) were premixed in a plastic or paper container. The resultant blend was loaded into the 60 gram bowl.
  • thermoset elastomer compositions of the invention exhibit a higher 100 % modulus than the comparative materials Cl (TafmerTM 680-P (available from Mitsui Petrochemical)) and C2 (VistalonTM 457 (available from Exxon Chemical Co.)). This was consistent with the significantly higher 100 % modulus exhibited by the neat inte ⁇ olymers as compared to the comparative materials.
  • Ethylene/styrene/ethylidene norbornene inte ⁇ olymers were made using (tert- butylamido)dimethyl(tetramethyl- ⁇ :> -cyclopentadienyl)silane dimethyltitanium(+4) catalyst and tris(pentafluorophenyl)borane cocatalyst in a one to one molar ratio according to the following procedure.
  • a two liter reactor was charged with 360 grams (500 mL) of ISOPARTM E mixed alkane solvent (available from Exxon Chemicals Inc) and the desired amount of styrene comonomer. Ethylidene norbornene was transferred to the reactor.
  • (IV) catalyst as indicated in Table Three. After the run time, the polymer solution was removed from the reactor and quenched with isopropyl alcohol. A hindered phenol antioxidant (IRGANOXTM 1010 (available from Ciba Geigy Co ⁇ .) was added to the polymer. Volatiles were removed from the polymer in a reduced pressure vacuum oven at l35°C for 20 hours.
  • IRGANOXTM 1010 available from Ciba Geigy Co ⁇ .
  • the resultant substantially random inte ⁇ olymers were characterized as being pseudorandom and linear.
  • the inte ⁇ olymers were compounded and cured according to the following procedure.
  • the 60 gram bowl of a Brabender PS-2 internal mixer was preheated to 120°F. 100 pph carbon black N550 (available from Cabot), 50 pph SUNPARTM 2280 oil (available from Sun Oil), 5 pph paraffin wax. 1 pph stearic acid, 5 pph zinc oxide, 1.5 pph sulfur, and 0.5 pph Captax 2-mercaptobenzothiazole (available from R. T. Vanderbilt) were premixed in a plastic or paper container. The resultant blend was loaded into the 60 gram bowl. To the bowl was further added 100 pph of the desired inte ⁇ olymer as prepared above. The ram was lowered on the internal mixer, and the compound was allowed to mix until a temperature of 220°F was reached (approximately five minutes). The compound was removed from the mixer and was optionally roll-milled.
  • the samples were compression molded at 260°F to obtain uncured (green) test plaques.
  • the uncured (green) test plaques were compression mold cured at 340°F for 20 minutes to obtain crosslinked thermoset elastomer compositions.
  • ESDMl(a) was prepared in accordance with the above formulation.
  • ESDMl(b)-(d) were likewise prepared in accordance with the above formulation, except that in the case of ESDMl(b), 50 pph SUNDEX 750T oil (available from Sun Oil), was used in place of the SUNPAR oil; in the case of
  • ESDMl(c) 50 pph trioctyltrimelliate was used in place of the SUNPAR oil; and in the case of ESDMl(d), 0.75 pph (rather than 1.5 pph) sulfur was employed.
  • C4 was prepared using the formulation provided above, with Vistalon 6505 EPDM (available from Exxon) being used in place of the substantially random inte ⁇ olymer.
  • C5 was prepared using the formulation provided above, with EPSyn 70A EPDM (available from DSM Copolymer) being used in place of the substantially random inte ⁇ olymer used in the present invention.
  • C6(a) was prepared using the formulation provided above, with SBR 1500 styrene butadiene rubber being used in place of the substantially random inte ⁇ olymers and Sundex 75 OT oil (available from Sun Oil) being used in place of the SUNPAR oil.
  • C6(b) was prepared using the formulation provided above, except that SBR 1500 styrene butadiene rubber was used in place of the substantially random inte ⁇ olymer, 50 pph (rather than 100 pph) N550 carbon black was employed, 7 pph Sundex 750T oil (rather than 50 pph SUNPAR 2280 oil) was employed.
  • the crosslinked thermoset elastomers of the invention typically exhibit a highly improved 100% modulus, as compared to comparative materials C4 (VistalonTM 6505 EPDM (available from Exxon)), C5 (EPSyn 70A EPDM (available from DSM Copolymer)) and C6 (SBR 1500 styrene-butadiene rubber).
  • the crosslinked thermoset elastomers of the invention typically exhibit a resistance to oil swell similar to that of styrene-butadiene- rubber, but superior to that of EPDM materials.
  • the crosslinked thermoset elastomers of the invention exhibit aging properties superior to those of styrene-butadiene rubber. For instance, upon aging at 250°F for 70 hours in an air oven, the crosslinked ethylene/styrene/ethylidene norbornene inte ⁇ olymer exhibited increased tensile at break values and moderately decreased elongation at break values. In contrast, upon oven aging under the same conditions, the styrene-butadiene rubbers exhibited decreased tensile at break values and significantly decreased elongation at break values.
  • the crosslinked ethylene/styrene/diene thermoset elastomers of the invention exhibit a resistance to oil swell characteristic of styrene- butadiene rubber without suffering the concomitant negative effects of heat aging.
  • the Brabender PS-2 or Haake internal torque mixer was preheated to 350°C.
  • Pro-fax 6524 isotactic polypropylene available from Himont Inco ⁇ orated
  • the desired amount of Pro-fax 6524 isotactic polypropylene was added to the mixer, and was allowed to melt and to homogenize. Over one minute, the desired amount of the noncrosslinked substantially random inte ⁇ olymer was added. Thereafter, the process oil, antioxidant, stearic acid, and carbon black were added and mixed for one minute. The zinc oxide, sulfur, benzothiazyldisulfide and methyl tuads were added. Mixing occurs until the torque reaches a maximum and for at least 10 minutes total mix time. The resultant thermoplastic vulcanizate was removed from the mixer.
  • thermoplastic vulcanizates were compression molded at 380°F.
  • Representative physical properties of the thermoplastic vulcanizates and of comparative thermoplastic vulcanizates C-TPVl (made with Vistalon 6505 EPDM (available from Exxon)) and C-TPV2 (made with EPSyn 70A EPDM (available from DSM Rubber)) were set forth in Table 6. Therein, the abbreviation "ND" means that a given property was not determined.
  • thermoplastic vulcanizates of the invention exhibit a much greater resistance to oil swell (under the ASTM #2 test method) than the comparative materials without sacrificing hardness (Hardness Shore "A").
  • thermoplastic vulcanizates of the invention exhibit improved 100% modulus values and comparable tensile at break values, with respect to the comparative materials.
  • TPV -2(b), TPV-2(c), and TPV-2(d) indicates that one can adjust resistance to ASTM #2 oil swell and hardness values by adjusting the ratio between the polypropylene and the substantially random interpolymer. Namely, as the proportion of the polypropylene increases, the resistance to ASTM #2 oil swell and hardness likewise increase. Moreover, the effect of the added substantially random inte ⁇ olymer was evident. In particular, the percent elongation at break of the inventive thermoplastic vulcanizates was many times greater than that of unmodified isotactic polypropylene, which exhibits a percent elongation at break of 13 percent.
  • CSTR CSTR
  • a magnetically coupled agitator with Lightning A-320 impellers provided the mixing.
  • the reactor ran liquid full at 475 psig (3,275 kPa).
  • Process flow was in the bottom and out the top.
  • a heat transfer oil was circulated through the jacket of the reactor to remove some of the heat of reaction.
  • After the exit from the reactor was a micromotion flow meter that measured flow and solution density. All lines on the exit of the reactor were traced with 50 psi (344.7 kPa) steam and insulated.
  • Ethylbenzene solvent was supplied to the mini-plant at 30 psig (207 kPa).
  • the feed to the reactor was measured by a Micro-Motion mass flow meter.
  • a variable speed diaphragm pump controlled the feed rate.
  • a side stream was taken to provide flush flows for the catalyst injection line (1 lb/hr (0.45 kg/hr)) and the reactor agitator (0.75 lb/hr ( 0.34 kg/ hr)). These flows were measured by differential pressure flow meters and controlled by manual adjustment of micro-flow needle valves.
  • Uninhibited styrene monomer was supplied to the mini-plant at 30 psig (207 kpa).
  • the feed to the reactor was measured by a Micro-Motion mass flow meter. A variable speed diaphragm pump controlled the feed rate. The styrene streams was mixed with the remaining solvent stream. Ethylene was supplied to the mini-plant at 600 psig (4,137 kPa). The ethylene stream was measured by a Micro- Motion mass flow meter just prior to a Research valve controlling flow. A Brooks flow meter/controller was used to deliver hydrogen into the ethylene stream at the outlet of the ethylene control valve. The ethylene/hydrogen mixture combines with the solvent/styrene stream at ambient temperature. The temperature of the solvent/monomer as it enters the reactor was dropped to ⁇ 5 °C by an exchanger with -5°C glycol on the jacket.
  • This stream entered the bottom of the reactor.
  • the three component catalyst system and its solvent flush also entered the reactor at the bottom but through a different port than the monomer stream.
  • Preparation of the catalyst components took place in an inert atmosphere glove box.
  • the diluted components were put in nitrogen padded cylinders and charged to the catalyst run tanks in the process area. From these run tanks the catalyst was pressured up with piston pumps and the flow was measured with Micro-Motion mass flow meters.
  • the stream was condensed with a glycol jacketed exchanger, entered the suction of a vacuum pump and was discharged to a glycol jacket solvent and styrene/ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene from the top.
  • the ethylene stream was measured with a Micro-Motion mass flow meter and analyzed for composition. The measurement of vented ethylene plus a calculation of the dissolved gasses in the solvent/styrene stream was used to calculate the ethylene conversion.
  • the polymer separated in the devolatilizer was pumped out with a gear pump to a ZSK-30 devolatilizing vacuum extruder.
  • This strand was cooled as it was pulled through a water bath. The excess water was blown from the strand with air and the strand was chopped into pellets with a strand chopper.
  • Table 7 lists the characteristics of the polymers used in this study. Table 7 Polymers Used
  • Formulations with above polymers were prepared with 3, 6 and 9 wt % dicumyl peroxide (DiCup manufactured by Hercules Inc.). Formulations were prepared in a Hakke Rheocord 9000 equipped with a 50 g mixing bowl under the following conditions: 120°C, 50 RPM, 10-12 minutes mixing time.
  • Samples were crosslinked at 170°C for 20 minutes, using 200 pounds of force in a compression molding press (Tetrahedron Press Model-MTP-8).
  • Table 8 summarizes results for gel content and upper service temperature for the peroxide crosslinked ESI samples.
  • the results in Table 8 indicate that peroxide can be used to crosslink ESI.
  • the degree of crosslinking was measured by gel content analysis. All the peroxide modified samples have gel content greater than 60%.
  • the upper service temperature increased significantly when the samples were treated with peroxide.
  • Figure 1 shows the graph of expected and actual gel content vs. styrene composition for the ESI samples treated with 9% peroxide. The measured gel content is much higher than the expected value.
  • Table 9 summarizes ESI samples used for this study.
  • Formulations with the above polymers were prepared with 4 wt % dicumyl peroxide (DiCup manufactured by Hercules Inc.). Formulations were prepared in a Haake Rheocord 9000 equipped with a 50 g mixing bowl under the following conditions: 120°C, 50 RPM, 10-12 minutes mixing time.
  • Table 10 summarizes the blends of ESI prepared with AFFINITY EG 8100 and SBS to determine the effect of blending a polyolefin elastomer or a styrene/butadiene/styrene polymer on the crosslinking efficiency of ESI copolymers.
  • Compression molded plaques were treated with 5, 10, 15 and 20 Mrad of e- beam radiation.
  • Table 13 shows formulations prepared for the silane crosslinking study.
  • Samples were extruded on a Haake Polylab Polymer Processing unit equipped with a 18 mm twin screw extruder, pelletizer and water bath with air knife. Samples were prepared in a two step process:
  • Step 1 Silane was grafted onto the polymer using the following procedure:
  • a 2% concentrate of the catalyst was made in each of the polymers studied.
  • the catalyst concentrate pellets were dry blended with silane grafted material from Step 1 and extruded at 200°C at 50 rpm.
  • the results in Table 14 indicates that silane chemistry can be used to prepare crosslinked ESI by a moisture cured process.
  • ESI was grafted with vinyl siloxane which acts as a moisture cured reactive site.
  • the Gel content in the range of 40 to 65 % was achieved for ESI with the styrene compositions from 41 to 51%.
  • a Rheometrics Inc. RDA-II dynamic mechanical spectrometer was used to obtain DMS data. A temperature sweep was run from approximately -70°C to 300°C at 5°C/step with 30 s equilibration delay at each step. The oscillatory frequency was 1 radian/s with an autostrain function of 0.1% strain initially, increasing in positive 100% adjustments whenever the torque decreased to 4 g-cm. The maximum strain was set at 26%.
  • the 7.9-mm parallel plate fixtures were used with an initial gap of 1.5 mm at 160°C (the sample was inserted into the RDA-II at 160°C). The "Hold" function was engaged at 160°C and the instrument was cooled to -70°C and the test started. (The Hold function corrects for the thermal expansion or contraction as the test chamber is heated or cooled.) A nitrogen environment was maintained throughout the experiment to minimize oxidative degradation.
  • Test specimen was a disk with thickness of about 2mm and diameter, prepared by compression molding at 205 °C and air-cooling to room temperature.
  • Xylene Extraction was performed by weighing out 1 gram samples of the polymer. The samples were transferred to a mesh basket which was then placed in boiling xylene for 12 hours. After 12 hours, the sample baskets were removed and placed in a vacuum oven at 150°C and 28 in. of Hg vacuum for 12 hours. After 12 hours, the samples were removed, allowed to cool to room temperature over a 1 hour period, and then weighed. The results were reported as percent polymer extracted.
  • % extracted (initial weight-final weight)/initial weight.
  • Samples were prepared using either a HaakeBuchler Rheomix 600 mixer with roller style blades, attached to a HaakeBuchler Rheocord 9000 Torque rheometer, or using a Brabender mixer (Type R.E.E. No. A-19/S.B) with a 50 g mixing bowl.
  • Ethylene-styrene copolymer 40 g containing 58 wt % styrene (ESI-3831- 960921-1100) (3 wt % atactic polystyrene, 1.0 MI) was dry blended with 0.2 g (0.5 weight percent, 0.55 mmole) of 4,4'-disulfonylazidobiphenyl in a plastic bag. The blend was added to a Brabender mixer (Type R.E.E. No. A-19/S.B) at 120°C (60 rpm) with a 40 g mixing bowl. The mixture was blended at 120°C for 3 minutes and then removed from the mixer and allowed to cool yielding 38.9 g of blend 1.
  • a Brabender mixer Type R.E.E. No. A-19/S.B
  • Blends 1-5 and uncrosslinked ESI- 13 which is the untreated starting material were then compression molded at 120°C and 20,000 lb force for 3 minutes, followed by curing at 190°C and 20,000 lb for 10 minutes, followed by cooling to 80°C over 5 minutes while still under pressure. All of the samples were characterized by TMA analysis and select samples were characterized by xylene extraction and DMS measurements. This data shows that at 2% sulfonyl azide, the samples are completely crosslinked. Crosslinked Blends 1-5 are referred to as Samples 1-5 respectively.
  • Samples 1-6 demonstrate that disulfonyl azide can be used to prepare coupled, partially crosslinked, and fully crosslinked ESI.
  • Samples 2-4 are fully crosslinked polymers.
  • the toughness and the upper service temperature of crosslinked ESI using the disulfonyl azide are much better than that of the uncrosslinked ESI.
  • a Haake Rheocord 9000 equipped with a 50 g mixing bowl was heated to 120°C. 48.5 g of ESI 6 (57.7% copolymer styrene, 3.3% homopolymer Polystyrene, 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 Dicumylperoxide (Hercules Inc.) was added and the sample was compounded for 6 more minutes.
  • ESI 6 57.7% copolymer styrene, 3.3% homopolymer Polystyrene, 1.02 Mi, 7.8 I 10 /I 2
  • a Haake Rheocord 9000 equipped with a 50 g mixing bowl was heated to 120°C. 48.5 g of ESI-15 (68.5% copolymer styrene, 16.9% homopolymer Polystyrene, 1.05 Mi, 9.0 110/12) was added and mixed at 50 RPM. After 6 minutes, 1.5 g (3.0 wt%) of Dicumylperoxide (Hercules Inc.) was added and the sample was compounded for 6 more minutes.
  • ESI-15 68.5% copolymer styrene, 16.9% homopolymer Polystyrene, 1.05 Mi, 9.0 110/12
  • the sample was removed from the Haake and compression molded at 120°C and 20,000 lb (9078.48 kg)force for 3 minutes and then cured at 170°C for 20, 200 lb (90.78 kg) force in a compression molding press (Tetrahedron Press Model- MTP-8).
  • the procedure was repeated using 47.0 g of ESI- 15 and 3.0 g of dicumylperoxide (6 wt%).
  • Tensile properties, compression set and UST by TMA were measured.

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US08/921,641 US5869591A (en) 1994-09-02 1997-08-27 Thermoset interpolymers and foams
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US6709742B2 (en) 1998-05-18 2004-03-23 Dow Global Technologies Inc. Crosslinked elastic fibers
AR018359A1 (es) 1998-05-18 2001-11-14 Dow Global Technologies Inc Articulo resistente al calor , configurado, irradiado y reticulado, libre de un agente de reticulacion de silano
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US6613811B1 (en) 1999-06-03 2003-09-02 Trexel, Inc. Microcellular thermoplastic elastomeric structures
US6365658B1 (en) * 1999-08-12 2002-04-02 The Dow Chemical Company Polymer compositions
US6239242B1 (en) * 1999-08-21 2001-05-29 Nova Chemicals Corporation Vinylaromatic and olefin pseudoblock polymers
US20080011194A1 (en) * 2004-12-03 2008-01-17 Dow Global Technologies Inc. Wood Fiber Plastic Composites
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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1004558B (it) * 1972-08-31 1976-07-20 Ppg Industries Inc Agente copulante silanato per gomma
JPS6011329A (ja) * 1983-07-01 1985-01-21 Mitsubishi Petrochem Co Ltd 架橋発泡体の連続製造方法
NZ235032A (en) * 1989-08-31 1993-04-28 Dow Chemical Co Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component
EP0737694B1 (de) * 1993-12-28 2001-06-06 Idemitsu Kosan Company Limited Verfahren zur herstellung eines olefinpolymers und eines ethylenpolymers
BR9509193A (pt) * 1994-09-02 1997-10-21 Dow Chemical Co Elastômero termofixo processo para preparar um elastômero termofixo vulcanizado termoplástico processo para fazer um vulcanizado termoplástico e peça fabricada

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9910395A1 *

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BR9814448A (pt) 2001-11-06
KR20010023264A (ko) 2001-03-26
NO20000963L (no) 2000-04-26
NO20000963D0 (no) 2000-02-25
JP2001514275A (ja) 2001-09-11
WO1999010395A1 (en) 1999-03-04
AU8920998A (en) 1999-03-16
HUP0004824A3 (en) 2004-04-28
CA2300062A1 (en) 1999-03-04
HUP0004824A2 (hu) 2001-04-28

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