WO2022219427A1 - Compositions comprenant des oléfines cycliques et une charge thermoconductrice et un promoteur d'adhérence - Google Patents

Compositions comprenant des oléfines cycliques et une charge thermoconductrice et un promoteur d'adhérence Download PDF

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WO2022219427A1
WO2022219427A1 PCT/IB2022/052175 IB2022052175W WO2022219427A1 WO 2022219427 A1 WO2022219427 A1 WO 2022219427A1 IB 2022052175 W IB2022052175 W IB 2022052175W WO 2022219427 A1 WO2022219427 A1 WO 2022219427A1
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composition
thermally conductive
cyclic olefin
substrate
adhesion promoter
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Binhong Lin
Mario A. Perez
Ahmad Shaaban
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3M Innovative Properties Company
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    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
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    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3321—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclopentene
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Definitions

  • a composition comprising a cyclic olefin; a ring opening metathesis polymerization catalyst; thermally conductive particles; and an adhesion promoter having a number average molecular weight of at least 500 g/mole and one or more silicon- containing moieties, such an alkoxy silane.
  • the adhesion promoter comprises a polyolefin moiety.
  • the polyolefin moiety may comprise alkene moieties, such as in the case of polybutadiene.
  • the thermally conductive particles are selected such that the composition after curing has a thermal conductivity of greater than 1 W/M*K.
  • the composition comprises at least 20, 25, 30, 35, 40, 45, 50 wt.% of the thermally conductive particles having a particle size no greater than 5 or 10 microns. In some embodiments, the composition comprises at least 10 wt.% of thermally conductive particles having a particle size of at least 30, 40, or 50 microns.
  • the thermally conductive particle comprises a combination of smaller and larger thermally conductive particles.
  • the composition is an adhesive, film, or coating.
  • the adhesive composition is typically provided in two parts, wherein the catalyst is in a separate container (e.g. chamber of two-component dispensing system) than the cyclic olefin prior to use of the composition.
  • articles comprising a cured composition as described herein.
  • a method of bonding comprising providing a composition as described herein, applying the composition between a first and second substrate; and polymerizing the cyclic olefin.
  • the adhesive composition may be characterized as a thermoset, since the cyclic olefin is polymerized by exposure to heat.
  • the polymerizable compositions described herein comprise one or more cyclic olefins.
  • the cyclic olefins are generally mono-unsaturated (i.e. mono-olefin) or poly-unsaturated (i.e. comprising two or more carbon-carbon double bonds or in otherwords alkene groups).
  • the double bond or in otherwords ethylenic unsaturation is not part of a (meth)acrylate or vinyl ether group.
  • the cyclic olefin may be mono- or poly-cyclic (i.e. comprising two or more cyclic groups).
  • the cyclic olefin may generally be a strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition.
  • the polymerizable composition comprise cyclic diene monomers, including for example 1,3- cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-l,3-cyclohexadiene, 1,3- cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, norbomadiene, cyclohexenylnorbomene, including oligomers thereof such as trimers, tetramers, pentamers, etc.
  • the polyolefin cyclic materials are amenable to thermosetting.
  • the polymerizable composition comprises dicyclopentadiene (DCPD), depicted as follows:
  • DCPD suppliers and purities may be used such as Lyondell 108 (94.6% purity), Veliscol UHP (99+% purity), Cymatech Ultrene (97% and 99% purities), and Hitachi (99+% purity).
  • the composition comprises cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; depicted as follows: cyclopentadiene oligomers, n is typically 3, 4 or 5.
  • the composition comprises cyclic diene monomer in the absence of mono-olefins.
  • the composition further comprises a cyclic mono-olefin.
  • a cyclic mono-olefin examples include cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions thereof such as 1-methylcyclopentene, 1- ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4- methylcyclopentene, 4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol, cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3-
  • composition further comprises norbomene, depicted as follows:
  • Suitable norbomene monomers include substituted norbomenes such as norbomene dicarboxylic anhydride (nadic anhydride); and as well as alkyl and cycloalkyl norbomenes including butyl norbomene, hexyl norbomene, octyl norbomene, decyl norbomene, and the like.
  • the cyclic olefin monomers and oligomers may optionally comprise substituents provided the monomer, oligomer, or mixture is suitable for metathesis reactions.
  • the carbon atoms of the cyclic olefin moiety may optionally comprise substituents derived from radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphoms, antimony, or boron.
  • the olefin may be substituted with one or more groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carboiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
  • groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carboiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
  • the olefin may be substituted with one or more groups such as C1-C20 alkyl, aryl, acyl, C1-C20 alkoxide, aryloxide, C3-C20 alkyldiketonate, aryldiketonate, C1-C20 carboxylate, arylsulfonate, C1-C20 alkylsulfonate, C1-C20 alkylthio, arylthio, C1-C20 alkylsulfonyl, C1-C20 alkylsulfinyl, C-C20 alkylphosphate, and arylphosphate.
  • groups such as C1-C20 alkyl, aryl, acyl, C1-C20 alkoxide, aryloxide, C3-C20 alkyldiketonate, aryldiketonate, C1-C20 carboxylate, arylsulfonate, C1-C20 al
  • Preferred cyclic olefins can include dicyclopentadiene; tricyclopentadiene; dicyclohexadiene; norbomene; 5-methyl-2-norbomene; 5-ethyl-2-norbomene; 5-isobutyl-2-norbomene; 5,6- dimethyl-2-norbomene; 5-phenylnorbomene; 5-benzylnorbomene; 5-acetylnorbomene; 5- methoxycarbonylnorbomene; 5-ethoxycarbonyl-l-norbomene; 5-methyl-5-methoxy- carbonylnorbomene; 5-cyanonorbomene; 5,5,6-trimethyl-2-norbomene; cyclo-hexenylnorbomene; endo, exo-5,6-dimethoxynorbomene; endo, endo-5,6-dimethoxy
  • More preferred cyclic olefins include dicyclopentadiene, tricyclopentadiene, and higher order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like, tetracyclododecene, norbomene, and C2-C12 hydrocarbyl substituted norbomenes, such as 5-butyl- 2-norbomene, 5-hexyl-2-norbomene, 5-octyl-2-norbomene, 5-decyl-2-norbomene, 5-dodecyl-2- norbomene, 5 -vinyl -2 -norbomene, 5 -ethylidene-2 -norbomene, 5-isopropenyl-2-norbomene, 5- propenyl-2 -norbomene, 5 -but
  • the cyclic olefins may be used alone or mixed with each other in various combinations to adjust the properties of the olefin monomer composition.
  • mixtures of cyclopentadiene dimer and trimers offer a reduced melting point and yield cured olefin copolymers with increased mechanical strength and stiffness relative to pure poly-DCPD.
  • incorporation of norbomene, or alkyl norbomene comonomers tend to yield cured olefin copolymers that are relatively soft and rubbery.
  • the cyclic olefin material comprises a mixture of DCPD monomer and cyclopentadiene oligomer. In some embodiments, the mixture comprises at least 25, 30, 35, 40 or 45 wt.% DCPD based on the total amount a cyclic olefin monomer(s) and obgomer(s). In some embodiments, the mixture comprises no greater than 75, 70, 65, 60, 55, or 50 wt.% DCPD based on the total amount a cyclic olefin monomer(s) and oligomer(s).
  • the mixture comprises at least 15, 20, 25, 30, or 35 wt.% of cyclic olefin oligomers, such as cyclopentadiene trimer and/or tetramer based on the total amount a cyclic olefin monomer(s) and oligomer(s). In some embodiments, the mixture comprises no greater than 60, 55, 50, 45, or 40 wt.% of cyclic olefin oligomers, such as cyclopentadiene trimer and/or tetramer based on the total amount a cyclic olefin monomer(s) and oligomer(s).
  • the mixture comprises at least 2, 3, 4, or 5 wt.% of cyclic olefin oligomers having greater than four cyclopentadiene repeat units, such as cyclopentadiene pentamer. In some embodiments, the mixture comprises no greater than 10, 9, 8, 7, 6, or 5 wt.% of cyclic olefin oligomers having greater than four cyclopentadiene repeat units, such as cyclopentadiene pentamer.
  • the cyclic olefin material comprises a mixture of DCPD monomer and cyclopentadiene oligomer, in the absence of mono-olefins or in combination with a low concentration of mono-olefin.
  • the amount of mono-olefin is less than 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt.% based on the total amount a cyclic olefin monomer(s) and oligomer(s).
  • the mixture comprises at least 25, 30, 35, 40 or 45 wt.% of a mono- olefin such as a substituted norbomene, based on the total amount a cyclic olefin monomer(s) and oligomer(s).
  • a mono- olefin such as a substituted norbomene
  • the mixture comprises no greater than 75, 70, 65, 60, 55, or 50 wt.% mono-olefin (e.g. C4-C12 (e.g. C8) alkyl norbomene) based on the total amount a cyclic olefin monomer(s) and oligomer(s).
  • the mixture comprises at least 15, 20, 25, 30, or 35 wt.% of cyclic olefin oligomers, such as cyclopentadiene trimer and/or tetramer based on the total amount a cyclic olefin monomer(s) and oligomer(s). In some embodiments, the mixture comprises no greater than 60, 55, 50, 45, or 40 wt.% of cyclic olefin oligomers, such as cyclopentadiene trimer and/or tetramer based on the total amount a cyclic olefin monomer(s) and oligomer(s).
  • the mixture comprises at least 2, 3, 4, or 5 wt.% of cyclic olefin oligomers having greater than four cyclopentadiene repeat units, such as cyclopentadiene pentamer. In some embodiments, the mixture comprises no greater than 10, 9, 8, 7, 6, or 5 wt.% of cyclic olefin oligomers having greater than four cyclopentadiene repeat units, such as cyclopentadiene pentamer. In some embodiments, the mixture comprises no greater than 5, 4, 3, 2, or 1 wt.% of DCPD monomer. In other embodiments, the mixture comprises no greater than 25 or 20 wt.% of DCPD monomer.
  • the amount of cyclic olefin is typically at least 5, 6, 7, 8, 9, or 10 wt.% of the total composition. In some embodiments, the amount of cyclic olefin is at least 11, 12, 13, 14, or 15 wt.% of the total composition. In other embodiments, the amount of cyclic olefin is at least 16, 17, 18, 19, or 20 wt.% of the total composition.
  • the amount of cyclic olefin (i.e. polyolefin and optional mono-olefin) is typically no greater than 60 wt.% of the total composition. In some embodiments, the amount of cyclic olefin is no greater than 55, 50, 45, 40,
  • the amount of cyclic olefin is typically at least 25,
  • the amount of cyclic olefin is typically at least 35, 40,
  • the amount of cyclic olefin is typically no greater than 75, 74, 73, 72, 71, or 70 vol.% based on the total volume of the composition. In some embodiments, the amount of cyclic olefin (i.e. polyolefin and optional mono-olefin) is no greater than 65 or 60 vol.% based on the total volume of the composition.
  • compositions described herein are typically prepared by the metathesis of cyclic olefins polymerized with a metal carbene catalyst.
  • Group 8 transition metals, such as ruthenium and osmium, carbene compounds have been described as effective catalysts for ring opening metathesis polymerization (ROMP). See for example US 10,239,965; incorporated herein by reference.
  • the catalyst is a metal carbene olefin metathesis catalyst.
  • Such catalysts typically have the following structure:
  • M is a Group 8 transition metal
  • L 1 , L 2 , and L 3 are independently neutral electron donor ligands; n is 0 or 1; m is 0, 1, or 2; k is 0 or 1;
  • X 1 and X 2 are independently anionic ligands
  • R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
  • Typical metal carbene olefin metathesis catalysts contain Ru or Os as the Group 8 transition metal, with Ru being preferred.
  • a first group of metal carbene olefin metathesis catalysts are commonly referred to as First Generation Grubbs-type catalysts, and have the structure of formula (I).
  • M is a Group 8 transition metal
  • m is 0, 1, or 2
  • n is 0, 1, or 2
  • X 1 , X 2 , L 1 , L 2 , and L 3 are described as follows.
  • n is 0, and L 1 and L 2 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, (including cyclic ethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine and thioether.
  • Exemplary ligands are trisubstituted phosphines.
  • Typical trisubstituted phosphines are of the formula PR H1 R H2 R H3 , where R m , R m , and R H3 are each independently substituted or unsubstituted aryl or Cl -CIO alkyl, particularly primary alkyl, secondary alkyl, or cycloalkyl.
  • L 1 and L 2 are independently selected from the group consisting of trimethylphosphine (PMe 3 ), triethylphosphine (PEt3), tri-n-butylphosphine (PBU 3 ), tri(ortho-tolyl)phosphine (P-o-tolyF), tri-tert-butvlphosphine (P-tert-Bu 3 ), tricyclopentylphosphine (PCyclopentyF), tricyclohexylphosphine (PCy 3 ), triisopropylphosphine (P-i-Pr3), trioctylphosphine (POct 3 ), triisobutylphosphine, (P-1-BU3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(CgF5)3), methyldiphenylphosphine (PMcPlu).
  • Pe 3 trimethylpho
  • L 1 and L 2 may be independently selected from phosphabicycloalkane (e.g., monosubstituted 9- phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1]nonane] such as cyclohexylphoban, isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphoban and the like.
  • phosphabicycloalkane e.g., monosubstituted 9- phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1]nonane
  • X 1 and X 2 are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring.
  • X 1 and X 2 may be substituted with one or more moieties selected from Cl -Cl 2 alkyl, Cl -Cl 2 alkoxy, C5-C24 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, C1-C6 alkyl, C1-C6 alkoxy, and phenyl.
  • X 1 and X 2 are halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylsulfanyl, aryl, or C1-C6 alkylsulfonyl.
  • X 1 and X 2 are each halide, CF3CO2, CH3CO2, CFH2CO2, (CH 3 ) CO, (CF 3 )2(CH 3 )CO, (CF 3 )(CH 3 ) 2 C0, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane -sulfonate.
  • X 1 and X 2 are each chloride.
  • R 1 and R 2 are independently selected from hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6- C24 alkaryl, C6-C24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom- containing C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl (e.g., substituted hetero
  • R 1 and R 2 may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and/or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ring atoms.
  • R 1 is C1-C6 alkyl, C2-C6 alkenyl, and C5-C14 aryl.
  • R 2 is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl, and a functional group Fn.
  • Suitable functional groups include phosphonato, phosphoryl, phosphanyl, phosphino, sulfonato, C1-C20 alkylsulfanyl, C5-C20 arylsulfanyl, C1-C20 alkylsulfonyl, C5-C20 arylsulfonyl, C1-C.20 alkylsulfmyl, C5-C20 arylsulfmyl, sulfonamido, amino, amido, imino, nitro, nitroso, hydroxyl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxy carbonyl, C5-C20 aryloxy carbonyl, carboxyl, carboxylato, mercapto, formyl, C1-C20 thioester, cyano, cyanato, thiocyanato, isocyanate, thioiso
  • R 2 is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl.
  • R 1 and R 2 may have the structure -(W) n -U + V , wherein W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counterion; and n is zero or 1.
  • R 1 and R 2 may be taken together to form an indenylidene moiety, such as phenylindenylidene.
  • any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 and R 2 may be attached to a support or two or more (e.g. three or four) of said groups can be bonded to one another to form one or more cyclic groups, including bidentate or multidentate ligands, as disclosed, for example, in U.S. Pat. No. 5,312,940, incorporated herein by reference.
  • those cyclic groups may contain 4 to 12, preferably 4,
  • the cyclic groups may be aliphatic or aromatic, and may be heteroatom-containing and/or substituted.
  • the cyclic group may, in some cases, form a bidentate ligand or a tridentate ligand.
  • bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.
  • a second group of metal carbene olefin metathesis catalysts commonly referred to as Second Generation Grubbs-type catalysts, have the structure of formula (I), wherein L 1 is a carbene ligand having the structure of formula (II) wherein M, m, n, X 1 , X 2 , L 2 , L 3 , R 1 and R 2 are as previously defined Formula I;
  • X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, q is necessarily zero when Y is O or S, and k is zero or 1. However, when X is N or P, then p is 1, and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N;
  • Q 1 , Q 2 , Q 3 , and Q 4 are linkers, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and/or heteroatom-containing alkylene) or -(CO)-, and w, x, y, and z are independently zero or 1, meaning that each linker is optional. Preferably, w, x, y, and z are all zero. Further, two or more substituents of adjacent atoms within Q 1 , Q 2 , Q 3 , and Q 4 may be linked to form an additional cyclic group;
  • R 3 , R 3A , R 4 , and R 4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl.
  • X and Y may be independently selected from carbon and one of the heteroatoms mentioned above, preferably no more than one of X or Y is carbon.
  • L 2 and L 3 may be taken together to form a single bindentate electron-donating heterocyclic ligand.
  • R 1 and R 2 may be taken together to form an indenylidene moiety, preferably phenylindenylidene.
  • X 1 , X 2 , L 2 , L 3 , X and Y may be further coordinated to boron or to a carboxylate;
  • Any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , R 2 R 3 , R 3A , R 4 , R 4A , Q 1 , Q 2 , Q 3 , and Q 4 can be bonded to one another to form one or more cyclic groups or can also be taken to be -A-Fn, wherein "A" is a divalent hydrocarbon moiety and Fn is a functional group as previously described.
  • Such groups may be bonded to a support.
  • N-heterocyclic carbene (NHC) ligands A particular class of such carbene are commonly referred to as N-heterocyclic carbene (NHC) ligands.
  • N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as LI thus include, but are not limited to, the following where DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6-trimethylphenyl:
  • Representative metal carbene olefin metathesis catalysts include for example bis(tricyclohexylphosphine) benzylidene ruthenium dichloride, bis(tricyclohexylphosphine) dimethylvinylmethylidene ruthenium dichloride, bis(tricyclopentylphosphine) dimethylvinylmethylidene ruthenium dichloride, (tricyclohexylphosphine)(l,3-dimesityl-4,5- dihydroimidazol-2-ylidene) benzylidene ruthenium dichloride, (tricyclopentylphosphine)(l,3- dimesityl-4,5 -dihydroimidazol-2-ylidene) dimethylvinylmethylidene ruthenium dichloride, (tricyclohexylphosphine)(l,3-dimesityl-4,5-dihydroimidazol-2-ylid
  • the composition typically comprises the metathesis catalyst in an amount ranging from about 0.0001 wt.% to 2 wt.% catalyst based on the total weight of the composition. In some embodiments, the composition typically comprises at least 0.0005, 0.001, 0.005, 0.01, 0.05, 0.10, 0.15 or 0.20 wt.% catalyst. In some embodiments, the composition typically comprises no greater than 1.5, 1, or 0.5 wt.% catalyst.
  • the composition may optionally further comprise a rate modifier such as, for example, triphenylphosphine (TPP), tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites, triarylphosphites, mixed phosphites, pyridine, or other Lewis base.
  • TPP triphenylphosphine
  • the rate modifier may be added to the cyclic olefin component to retard or accelerate the rate of polymerization as required.
  • the amount of rate modifier can be the same amounts just described for the catalyst. Typically, the amount of rate modifier is less than 0.01 or 0.005 wt.% based on the total amount of cyclic olefin.
  • the composition further comprises an adhesion promoter.
  • the composition comprises one or more polymeric adhesion promoters.
  • Polymeric adhesion promoters have a number average molecular weight of at least 500 g/mole and comprise silicon-containing moieties.
  • the silicon- containing functional groups may be present as terminal groups, pendent groups or in other words side chains, or a combination thereof.
  • the adhesion promoter comprises a polymeric group that may be characterized as a polyolefin.
  • the polyolefins may be unsaturated, comprising alkene moieties, such as polybutadiene.
  • the polyolefin (e.g. polybutadiene) of the adhesion promoter has a (e.g. 1,2) vinyl content of at least 10, 15 or 20 wt.%.
  • the polymeric (e.g. polyolefin adhesion promoter has a (e.g. 1,2) vinyl content of no greater than 40, 35, or 30 wt.%.
  • the polyolefin e.g.
  • polybutadiene) of the adhesion promoter may further comprise a similar amount of polymerized cis-butadiene as vinyl -butadiene.
  • the polyolefin (e.g. polybutadiene) of the adhesion promoter may contain 50-60 wt.% of trans-butadiene.
  • the adhesion promoter lacks polystyrene blocks.
  • the polyolefin may comprise other moieties provided the inclusion of such does not detract from the adhesion improvement.
  • the polymeric (e.g. polyolefin) adhesion promoters have an average silicon-containing moiety functionality of 1 or greater than 1 or greater than 1.5. In some embodiments, the average silicon-containing moiety functionality ranges up to 2.5.
  • the silicon (i.e. atom)-containing moiety may be an alkoxy silane moiety comprising one or more (Cl, C2, C3, or C4) alkoxy groups bonded to the silicon atom. In some embodiments, Cl is preferred.
  • the adhesion promoters may be characterized as an alkoxysilane terminated polyolefin such as di or tri (Cl-C4)alkoxysilane-terminated polybutadiene.
  • Trialkoxysilane- terminated liquid polybutadiene are commercially available from Evonik and Ricon.
  • One representative structure is as follows: wherein R’ is independently ethoxy or methoxy and x, y, and n are the number of repeat units such that the adhesion promoter has a particular molecular weight range, as described as follows.
  • the adhesion promoter is polymeric i.e. having a backbone with polyolefin repeat units.
  • the polymeric adhesion promoter has a number average molecular weight (Mn) of no greater than 10,000; 9,000; 8,000; 7,000; or 6,000 g/mole.
  • the polymeric adhesion promoter has a molecular weight (Mn) of no greater than 5,000; 4,500; 4,000; 3,500; or 3,000 g/mole.
  • the polymeric adhesion promoter has a molecular weight (Mn) has a molecular weight of at least 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, or 2000 g/mole.
  • the adhesion promoter has a Tg less than 0, -20, -40, -60, or -80°C.
  • the adhesion promoter is typically a liquid, having a viscosity at 20 or 25°C of at least 2000, 3000, 4000, or 5000 mPas. (DIN EN ISO 3219). In some embodiments, the viscosity at 20 or 25°C is no greater than 75,000 mPas. In some embodiments, the viscosity is no greater than 30,000, 25,000, 20,000, or 15,000 or 10,000 mPas. In some embodiments, the viscosity is less than 1000 or 500 mPas. In other embodiments, the adhesion promoter may have a viscosity of at least 50,000; 75,000; 100,000; 125,000 or 150,000 mPas at 45, 50, or 55°C.
  • the viscosity is indicative of the molecular weight.
  • Liquid adhesion promoters can be combined with the liquid unpolymerized cyclic olefin more easily than solids, resulting in the adhesion promoter being more uniformly dispersed within the mixture.
  • adhesion promoter polymers as described herein can be used independently or in combination with additional or in other words a second adhesion promoters, as described in the art.
  • the adhesion promoter and overall composition may be free of isocyanate moieties.
  • the additional adhesion promoter is a compound containing at least two isocyanate groups.
  • the adhesion promoter may be a diisocyanate, triisocyanate, or polyisocyanate (i.e., containing four or more isocyanate groups).
  • the adhesion promoter may be a mixture of at least one diisocyanate, triisocyanate, or polyisocyanate.
  • the adhesion promoter is a diisocyanate compound, or mixtures of diisocyanate compounds.
  • the additional adhesion promoter is an aliphatic diisocyanate.
  • Aliphatic diisocyanates comprise a linear, branched, or cyclic saturated or unsaturated hydrocarbon group typically containing 1 to about 24 carbon atoms.
  • the alkyl diisocyanate contains at least 2, 3, 4, 5, or 6 carbon atoms.
  • the aliphatic diisocyanate contains no greater than 22, 20, 18, 16, 14, or 12 carbon atoms.
  • Representative examples include hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like.
  • the aliphatic diisocyanate comprises a cycloaliphatic (e.g. cyclcoalkyl) moiety, typically having 4 to 16 carbon atoms, such as cyclohexyl, cyclooctyl, cyclodecyl, and the like.
  • the cycloalkyl diisocyanate is isophorone diisocyanate (IPDI) and the isomers of isocyanato-[(isocyanatocyclohexyl) methyl] cyclohexane (H12MDI).
  • the additional adhesion promoter is an aromatic diisocyanate.
  • Aromatic diisocyanates include one or more aromatic rings that are fused together or covalently bonded with an organic linking group such as an alkylene (e.g. methylene or ethylene) moiety.
  • aromatic moieties include phenyl, tolyl, xylyl, napthyl, biphenyl, diphenylether, benzophenone, and the like.
  • Suitable aromatic diisocyanates contain 6 to 24 carbon atoms, such as toluene diisocyanates, xylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI), that may comprise any mixture of its three isomers, 2.2'-MDI, 2,4'-MDI, and 4,4'-MDI.
  • the adhesion promoters is a polymeric polyisocyanate (e.g. diisocyanate).
  • Polymeric isocyanates include for example PM200 (poly MDI), LupranateTM (poly MDI from BASF), various isocyanate terminated polybutadiene prepolymers available from Cray Valley including KrasolTM LBD2000 (TDI based), KrasolTM LBD3000 (TDI based), KrasolTM NN- 22 (MDI based), KrasolTM N -23 (MDI based), KrasolTM N -25 (MDI based); as well as polyisocyanate prepolymers available from Convestro including the trade designations DESMODUR E-28 (MDI based) and Baytec ME-230 (modified MDI based on polytetramethylene ether glycol (PTMEG).
  • PM200 poly MDI
  • LupranateTM poly MDI from BASF
  • various isocyanate terminated polybutadiene prepolymers available from Cray Valley including Krasol
  • the polymeric isocyanate adhesion promoter is typically the reaction product of a polyol and MDI.
  • the polyol typically has one or more oxygen atoms in the backbone such as in the case of polytetramethylene ether glycol and polypropylene oxide.
  • the additional adhesion promoter is a maleic-anhydride polyolefin lacking styrene moieties.
  • the additional adhesion promoter is a maleic- anhydride grafted styrene-ethylene/butylene-styrene hydrogenated copolymer, typically comprising at least 0.1, 0.2, 0.3, 0.4 or 0.5 wt.% of grafted maleic anhydride.
  • the amount of grafted maleic anhydride is typically no greater than 7, 6, 5, 4, 3, or 2 wt. %.
  • Maleic-anhydride grafted styrene-ethylene/butylene-styrene hydrogenated copolymers typically comprise at least 10 and no greater than 60, 50, or 40% polystyrene.
  • Suitable functional elastomers are commercially available from Kraton Performance Polymers as the trade designations “Kraton FG1901G” and “Kraton FG1924G”.
  • the amount of (e.g. functional) elastomer when present in typically at least 0.001, 0.05, or 0.1 wt.% based on the weight of the cyclic olefin.
  • the composition typically comprises at least 0.005, 0.010, 0.050, 0.10, 0.50, or 1 wt.% of polymeric adhesion promoter(s) having one or more silicon-containing moieties based on the total weight of the composition.
  • the amount of polymeric adhesion promoter(s) having one or more silicon-containing moieties is no greater than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt.% of the total weight of the composition.
  • the amount of each adhesion promoter is typically less than 5, 4, 3, 2, or 1 wt.% of the total weight of the composition.
  • the composition comprises thermally conductive inorganic particles.
  • the particle size and loading levels of the inorganic particles are selected to provide the desired thermal conductivity.
  • the thermal conductivity of the cured composition (as determined by the test method described in the examples) of greater than 1 W/m*K.
  • the thermal conductivity of the cured composition is at least 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 W/m*K.
  • the thermal conductivity of the cured composition is no greater than 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.3, 2.1 or 2.0 W/m*K.
  • the composition typically comprises thermally conductive particles in an amount of at least 40 wt.% based on the total weight of the composition.
  • the amount of thermally conductive particles can vary depending on the density of the thermally conductive particles.
  • the amount of thermally conductive inorganic fdlers is at least 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 wt.% of the composition.
  • the amount of thermally conductive inorganic fdlers is typically no greater than 95, 94, 93, 92, 91, or 90 wt.% of the composition.
  • the amount of thermally conductive fdler is no greater than 89, 88, 87, 86, 85, 84, 83, 82, 81, or 80 wt.% of the composition. In some embodiments, the amount of thermally conductive fdler is no greater than 79, 78, 75, 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, or 60 wt.% of the composition.
  • the composition typically comprises at least 25, 26, 27, 28, 29, or 30 vol.% thermally conductive particles.
  • the thermally conductive particles comprise a mixture of lower density particles and high density particles (at least 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, or 3.2 g/cc)
  • the composition typically comprises at 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 vol.% thermally conductive particles.
  • the composition typically comprises at least 41, 42, 43, 44, or 45 vol.% thermally conductive particles.
  • the vol.% of thermally conductive particles is typically no greater than 70, 69, 68, 67, or 65 vol.%.
  • the vol.% is no greater than 64, 63, 62, 61, 60, 59, 58, 57, 56, or 55 vol.%.
  • the vol.% is no greater than 54, 53, 52, 51, 50, 49, 48, 47, 46, 45 vol.%.
  • the vol.% is no greater than 44, 43, 42, 41, 40, 39, 38, 37, 36, or 35 vol.%. of the composition.
  • the thermally conductive inorganic particles are preferably an electrically non-conductive material.
  • Suitable electrically non-conductive, thermally conductive materials include ceramics such as metal oxides, hydroxides, oxyhydroxides, silicates, borides, carbides, and nitrides.
  • Suitable ceramic fdlers include, e.g., silicon oxide, zinc oxide, alumina trihydrate (ATH) (also known as hydrated alumina, aluminum oxide, and aluminum trihydroxide), aluminum nitride, boron nitride, silicon carbide, and beryllium oxide.
  • Other thermally conducting fdlers include carbon-based materials such as graphite and metals such as aluminum and copper. Combinations of different thermally conductive materials may be utilized.
  • Such materials are not electrically conductive, i.e. have an electronic band gap greater than 0 eV and in some embodiments, at least 1, 2, 3, 4, or 5 eV. In some embodiments, such materials have an electronic band gap no greater than 15 or 20 eV.
  • the composition may optionally further comprise a small concentration of thermally conductive particles having an electronic band gap of less than 0 eV or greater than 20 eV. In some embodiments, such as when the composition comprises alumina trihydrate, the composition can pass the UL94 V-0 flammability standard.
  • the thermally conductive particles comprise a material having a bulk thermal conductivity > 10 W/m*K.
  • the thermal conductivity of some representative inorganic materials is set forth in the following table.
  • the thermally conductive particles comprise material(s) having a bulk thermal conductivity of at least 15 or 20 W/m*K. In other embodiments, the thermally conductive particles comprise material(s) having a bulk thermal conductivity of at least 25 or 30 W/m*K. In yet other embodiments, the thermally conductive particles comprise material(s) having a bulk thermal conductivity of at least 50, 75 or 100 W/m*K. In yet other embodiments, the thermally conductive particles comprise material(s) having a bulk thermal conductivity of at least 150 W/m*K. In typical embodiments, the thermally conductive particles comprise material(s) having a bulk thermal conductivity of no greater than about 350 or 300 W/m*K.
  • Thermally conductive particles are available in numerous shapes, e.g. spheres and acicular shapes that may be irregular or plate like.
  • the thermally conductive particles are crystals, typically have a geometric shape.
  • boron nitride hexagonal crystals are commercially available from Momentive.
  • alumina trihydrate is described as a hexagonal platelet. Combinations of particles with different shapes may be utilized.
  • the thermally conductive particles generally have an aspect ratio less than 100: 1, 75:1, or 50: 1.
  • the thermally conductive particles have an aspect ratio less than 3:1, 2.5: 1, 2: 1, or 1.5: 1.
  • generally symmetrical (e.g., spherical, semi-spherical) particles may be employed.
  • the thermally conductive particles comprise a combination of smaller particles and larger particles.
  • the combination of particle sizes can provide higher thermal conductivity, than thermally conductive particles having an intermediate median particle size and a normal particle size distribution. Without intending to be bound by theory it is surmised that including a sufficient amount of smaller particles of the proper particle size improves the thermal conductivity between the larger particles.
  • At least 20, 25, 30, 35, 40, 45, 50 vol.% of the thermally conductive particles have a particle size no greater than 5 or 10 microns. In some embodiments, at least 10, 15, 20, 25 30, 35, 40, 45, 50, 55 or 60 vol.% of the thermally conductive particles have a particle size less than 5 microns. In some embodiments, at least 10 % of the thermally conductive particles have a particle size less than 1 or 2 microns. In some embodiments, at least 20, 25, or 30 vol.% of the thermally conductive particles have a particle size less than 1 or 2 microns. In other embodiments, less than 10 vol.% of the thermally conductive particles have a particle size less than 1 or 2 microns.
  • particles at least 10, 15, 20, 25 or 30 vol.% of the thermally conductive particles have a particle size of at least 30, 40, or 50 microns.
  • the larger thermally conductive particles have a particle size of at least 55, 60, 65, 70, 75, 80, 85, 90 or 100 microns.
  • the larger particles typically have a particle size of no greater than 200, 190, 180 microns.
  • the larger thermally conductive particles have a particle size of no greater than 170, 160, 150, 140 microns.
  • the larger thermally conductive particles have a particle size of no greater than 130, 120, 110 microns.
  • the larger thermally conductive particles have a particle size of no greater than 100, 90, 80 microns. In some embodiments, 5 vol.% of the particles have a particle size greater than 55, 60, 65, 70, 75, 80, 85, 90 or 100 microns. In some embodiments, 5 vol.% of the particles have a particle size greater than 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 166, 170, 175, 180, or 185 microns.
  • the combination of smaller particles and larger particles can be obtained by selection of certain (e.g. commercially available) thermally conductive particles having at least a bimodal particle size distribution.
  • the combination of smaller particles and larger particles can also be obtained by combining two or more (e.g. commercially available) thermally conductive particles having a normal particle size distribution, but sufficiently different median particles sizes.
  • the thermally conductive particles further comprises particle having an intermediate particle size.
  • the thermally conductive particles further comprise particles ranging from greater than 10 to less than 30 microns.
  • the sum of the smaller particles (i.e. no greater than 10 microns), larger particles (at least 30 microns) and intermediate particles is typically 95, 96, 97, 98, 99, or 100% of the thermally conductive particles.
  • the thermally conductive particles may optionally comprise 1, 2, 3, 4, or 5% of (e.g. extra-large) particles, having a particle size greater than 200 microns.
  • the particle size of the thermally conductive particle can be determined utilizing the test method described in the examples.
  • particle size refers to the "primary particle size", meaning the diameter of a single (non-aggregate, non-agglomerate) particle.
  • the primary particles can form an "agglomerate”, i.e. a weak association between primary particles which may be held together by charge or polarity and can be broken down into smaller entities. These weakly bound agglomerates would typically break down during high energy mixing processes.
  • the particle size may be the particle size of an aggregate, i.e. two or more primary particles bonded to each other. Depending on the viscosity and mixing technique, the aggregates may break down into smaller entities during mixing.
  • thermally conductive fdler is not exclusively alumina abrasive particles. Due to the specific chemical composition, and/or particle shape, and/or particle size distribution alumina abrasive particles do not provide high thermal conductivity.
  • the composition comprises one or more dispersants.
  • the dispersants can reduce the viscosity and stabilize the inorganic filler particles in the composition such that the thermally conductive particles are uniformly dispersed in the cyclic olefin.
  • the dispersant may be pre-mixed with the thermally conductive particles prior to combining with the cyclic olefin component.
  • suitable dispersants include a binding group and a compatibilizing segment. The binding group may be ionically bonded to the particle surface. Examples of binding groups for alumina particles include phosphoric acid, phosphonic acid, sulfonic acid, carboxylic acid, and amine.
  • the compatibilizing segment may be selected to be miscible with the cyclic olefin.
  • Useful compatibilizing agents may include polyalkylene oxides, e.g., polypropylene oxide, polyethylene oxide, as well as polycaprolactones, polyimines and combinations thereof.
  • Various dispersants for thermoset composites are commercially available such as from Lubrizol under the trade designation SolplusTM
  • dispersant(s) may be present in the composition in an amount of at least 0.1, 0.2, 0.3, or 0.4 wt.% ranging up to 5 wt.-%, based on the total weight of the composition. In some embodiments, the amount of dispersant(s) is no greater than 4, 3, 2 or 2 wt.%.
  • the composition may be optionally comprise various additives.
  • Suitable additives include, but are not limited to, gel modifiers, hardness modulators, antioxidants, stabilizers, crosslinkers, non- thermally conductive fillers, binders, coupling agents, thixotropes, wetting agents, biocides, plasticizers, pigments, flame retardants (other than alumina trihydrate), dyes, and fibers.
  • the amount of additives present in the compositions may vary depending on the particular type of additive used.
  • the total concentration of such additives in the compositions is typically no greater than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 wt.% of the composition. Due to the high concentration of thermally conductive particles, the compositions are typically pastes at room temperature.
  • the viscosity of the composition is typically at least 100,000;
  • the viscosity of the composition is typically no greater than 750,000; 700,000; 650,000; 600,000; 550,000 or 500,000 cps at a shear rate of 1 1/second and at 25°C.
  • the compositions are provided as a two-part composition.
  • the catalyst is provided in a separate container (e.g. chamber of a two-component dispensing system) than the cyclic olefin.
  • the volume ratio of the first cyclic olefin part to catalyst part is typically in the range of 10: 1 to 100: 1.
  • a portion of the filler and/or dispersant is included with the catalyst part in order that the first and second part have sufficiently similar viscosities.
  • the separate parts are mixed prior to use.
  • curable compositions described herein are suitable for use as a (e.g. structural) adhesive.
  • a method of bonding comprising providing a composition as described herein; providing the composition between a first and second substrate; and polymerizing the cyclic olefin.
  • the cyclic olefin is typically polymerized by exposure to heat.
  • the substrates may comprise an organic polymer or an inorganic material (e.g. aluminum).
  • compositions described herein are also suitable for molded articles.
  • a method of making an article comprising providing a composition as described herein; dispensing the composition into a mold; and polymerizing the cyclic olefin.
  • the cyclic olefin is typically polymerized by exposure to heat.
  • composition described herein can have various physical properties in addition to high thermal conductivity. Such physical properties can be determined by the test methods describe in the forthcoming examples.
  • the cured composition has a glass transition temperature (Tg) of at least -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, or 70°C (as determined by the DMA test method described in the examples).
  • Tg glass transition temperature
  • the Tg is typically no greater than 185°C.
  • the Tg is no greater than 175, 170, 165, 160, 155, 150, 145, 140, 135, 130, 125, or 120°C.
  • the composition can be (heat) cured under various conditions such as temperatures of 130, 140, 150, 160, 170, 180, 190, or 200° for 2 hours prior to determining the Tg.
  • the cured composition exhibits an overlap shear adhesion to aluminum greater than 1, 2, 3, 4, or 5 MPa when tested at temperature of 25°C.
  • the composition can be (heat) cured at 80°C for 1 hour or 130°C for 2 hours prior to testing.
  • the overlap shear adhesion to aluminum is typically no greater than 10 or 15 MPa
  • the cured composition exhibits a dielectric constant of less than or equal to 4, 3.5 or 3.
  • the dielectric constant is typically at least 2.5.
  • the tan delta is less than or equal to 0.005 for frequencies ranging from 1 X 10 3 to IX 10 6 .
  • the tan delta is typically at least 0.001 or 0.0015.
  • the cured composition can be characterized as radio frequency transparent.
  • the cured composition has a maximum tensile strength of at least 1, 2,
  • the cured composition has a tensile strength less than 4, 3, 2, or 1 MPa. In some embodiments, the cured composition has an elongation at break of at least 1, 2, 3, 4, or 5% ranging up to 50, 60, 70, 80, 90 or 100%.
  • the cohesive strength e.g. tensile strength and modulus
  • the elongation can be higher.
  • the cured composition exhibits good hydrolytic stability after aging as evidenced by the tensile strength staying the same or increasing after aging. Further the elongation typically also stays the same or decreases with aging. In some embodiments, the tensile strength may decrease, but no greater than 25, 20, 15 or 10%. Likewise, in some embodiments, the elongation may decrease, but no greater than 25, 20, 15 or 10%.
  • the dielectric breakdown is at least 2, 3, 4, 5, 6, 7, 8, 9, or 10 kV/mm ranging up to 35, 40, 45, 50, 55, 60, 65, or 70 kV/mm.
  • the volume resistivity is at least 1 X 10 12 , 1 X 10 13 , 1 X 10 14 ohm-cm ranging up to 1 X 10 15 or 1 X 10 16 ohm-cm.
  • the composition has a low density, as compared to other (e.g. epoxy) thermosetting compositions having the same thermally conductive filler at the same concentration. Since the density increases with increasing filler concentration, the density can be expressed based on a ratio of density/volume % filler.
  • the density/volume % filler can be less than 5.5, 5.4, 5.3, 5.2, 5.1, 5.0, 4.9, 4.8, 4.7, 4.6 or 4.5. In some embodiments, the density/volume % filler is less than 4.4, 4.3, 4.2, 4.1, 4.0, 3.9, 3.8, 3.7, 3.6 or 3.5. In some embodiments, the density/volume % filler is less than 3.4, 3.3, 3.2, 3.1, 3.0, 2.9, 2.8, 2.7, 2.6 or 2.5.
  • the curable and cured compositions described herein are useful for coatings, shaped (e.g. molded) articles, adhesives (including structural and semi-structural adhesives), magnetic media, filled or reinforced composites, caulking and sealing compounds, casting and molding compounds, potting and encapsulating compounds, impregnating and coating compounds, conductive adhesives for electronics, protective coatings for electronics, as primers or adhesion-promoting layers, and other uses wherein thermally conductivity is of importance.
  • an article is described comprising a substrate, having a cured coating composition as described herein disposed on a surface of the substrate.
  • the curable composition may function as a structural adhesive, i.e.
  • the curable composition is capable of bonding a first substrate to a second substrate, after curing.
  • the bond strength e.g. peel strength, overlap shear strength, or impact strength
  • an article is described comprising a first substrate, a second substrate and a cured composition disposed between and adhering the first substrate to the second substrate, wherein the cured composition is the reaction product of the curable composition described herein.
  • the first and/or second substrate may be at least one of a metal, a ceramic and a polymer, e.g. a thermoplastic.
  • the curable compositions may be coated onto substrates at useful thicknesses ranging from 5 microns to 10000 microns, 25 micrometers to 10000 micrometers, 100 micrometers to 5000 micrometers, or 250 micrometers to 1000 micrometers.
  • Useful substrates can be inorganic, organic, or combinations thereof.
  • useful substrates include ceramics, siliceous substrates including glass, metal (e.g., aluminum or steel), natural and man-made stone, woven and nonwoven articles, polymeric materials, including thermoplastic and thermosets, (such as polymethyl (meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), silicones, paints (such as those based on acrylic resins), powder coatings (such as polyurethane or hybrid powder coatings), and wood; and composites of the foregoing materials.
  • thermoplastic and thermosets such as polymethyl (meth)acrylate, polycarbonate, polystyrene, styrene copolymers, such as styrene acrylonitrile copolymers, polyesters, polyethylene terephthalate), silicones, paints (such as those based on acrylic resins), powder coatings (such as poly
  • a coated article comprising a metal substrate comprising a coating of the uncured, partially cured or fully cured curable composition on at least one surface thereof.
  • the coating can be coated on one or both major surfaces of the metal substrate and can comprise additional layers, such as bonding, tying, protective, and topcoat layers.
  • the metal substrate can be, for example, at least one of the inner and outer surfaces of a pipe, vessel, conduit, rod, profile shaped article, sheet or tube.
  • the composition is useful for thermal management in electronics such as, for example, electric vehicle (EV) battery assembly, power electronics, electronic packaging, LED, solar cells, electric grid, and the like.
  • a battery module is described comprising a plurality of battery cells connected to a (e.g. first) base plate by a (e.g. first) layer of a composition as described herein, such as described in WO 2019/070819; incorporated herein by reference.
  • A1 coupons (1 inch by 4 inches by 0.08 inch (2.54 centimeters (cm) by 10.16 cm by 0.20 cm)) were used. At the tip of one coupon, a 1 inch by 0.5 inch (2.54 cm by 1.27 cm) area was coated with a thin layer of the prepared formulation with a tongue depressor, and then contacted with another coupon in the opposite tip direction. Paper clamps were used to hold the two halves together during the curing process. The samples were then cured in an oven at 100 °C for 30 minutes then at 120 °C for overnight.
  • the OLS test samples were tested (MTS, crosshead speed of 0.1 inch/minute (0.25 cm/minute)).
  • the reported values are the “peak stress” in MPa of the average of at least three samples tested.
  • the thermal conductivity of the fdms was measured according to ASTM D5470 (“Standard Test Method for Thermal Transmission Properties of Thermally Conductive Electrical Insulation Materials”) using the Thermal Interface Material Tester Model TIM 1300 from AnalysisTech (Wakefield, MA). 33 millimeter (mm) discs were cut out of the densified squares using a hole punch. The test temperature was 50 °C and the applied test pressure was set to 1 MPa. The thickness of the samples was measured by a caliper.
  • Particle size analysis was performed using a three laser diffraction analyzer (Microtrac S3500). The particles were first dispersed in a 2% solution of sodium hexametaphosphate and water to approximately 10% particles by mass. A standard protocol for measuring particle size was used on the S3500 - SOP settings were the following: a transparent particle with refractive index of 1.58, an irregular shape, and the dispersal media was water (1.33 RI). Particles were loaded to the correct concentration in the instrument via the built in loading calculator on the Microtrac software. Prior to measuring the particle distribution the particle dispersion was ultrasonicated for 10 seconds with the built in ultrasonic generator on the analyzer to break up any large agglomerates. Three 30 second sequential measurements were taken of the particles and the average particle size distribution was reported.
  • the particle size of the thermally conductive particles was determined according to the test method just described. Following are the test results:
  • FORMULATION PREPARATION The components of the formulation were weighed out in a speedmixer cup, before being speedmixed at 1000 revolutions per minute (rpm) under vacuum for 2 minutes. After speedmixing, the formulations became a paste.
  • the mixed thermal interface materials (TIMs) formulations were placed in between two PET liners, before being pulled through a knife coater with a set spacing of 400 micrometers to create a film.
  • the films were cured in an oven at 100 °C for 30 minutes, and then at 120 °C overnight.
  • CE-3* is EX-104 of serial no. 63/112,898 filed November 12, 2020 (Docket No. 83433US002)
  • ST-M is needed to make a strong film with good cohesive and adhesive strength.
  • CE-1 no surface coupling agent added
  • CE-2 with an isocyanate surface coupling agent
  • ST-M can be also used for not only alumina fillers-only formulations (i.e. EX-1), but also AIN- and ZnO- containing formulations (i.e. EX-2).
  • Example 3 of international application no. PCT/IB2020/059215 (Docket No. 82235WO003) had the following composition:
  • Example 3 was reported as having a thermal conductivity of 1.39 W/mK and that it passed the flame retardancy test described below.
  • This same example can be prepared replacing the E-28 adhesion promoter with ST-M adhesion promoter. Such example would be expected to have similar thermal conductivity, pass the flame retardancy test, and exhibit improved overlap shear strength.
  • strip samples were made by pressing the mixed uncured paste into strip-shaped silicone rubber molds, and were then laminated with release liner on both sides.
  • the resulting samples had a length of about 5 inch (12.7 cm), a width of 0.5 inch (1.27 cm), and a thickness of 0.06 inch (1.52 mm).
  • Samples were then cured at 90°C for 1 hour prior to flame retardancy testing. Both horizontal and vertical testing configurations were conducted using a burner with methane gas, in accordance with the procedures outlined in UL94 “Tests for Flammability of Plastic Materials for Parts in Devices and Appliances.”

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Abstract

L'invention concerne une composition comprenant une oléfine cyclique ; un catalyseur de polymérisation par métathèse avec ouverture de cycle ; des particules thermoconductrices et un promoteur d'adhérence contenant des fragments contenant du silicium. Les particules thermoconductrices sont sélectionnées de telle sorte que la composition après durcissement présente une conductivité thermique supérieure à 1W/M*K. Dans un mode de réalisation, la particule thermoconductrice comprend une combinaison de particules thermoconductrices plus petites et plus grosses. L'invention concerne également des substrats revêtus, des procédés de collage et des articles.
PCT/IB2022/052175 2021-04-14 2022-03-10 Compositions comprenant des oléfines cycliques et une charge thermoconductrice et un promoteur d'adhérence WO2022219427A1 (fr)

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Citations (8)

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US20040068036A1 (en) * 2002-10-07 2004-04-08 Halladay James R. Flexible emissive coatings for elastomer substrates
EP2982709A1 (fr) * 2014-08-07 2016-02-10 Telene SAS Composition durcissable et article moulé comprenant la composition
US10239965B2 (en) 2015-02-12 2019-03-26 Materia, Inc. Cyclic olefin resin compositions comprising functional elastomers
WO2019070819A1 (fr) 2017-10-06 2019-04-11 3M Innovative Properties Company Compositions durcissables, articles obtenus à partir de celles-ci, et leurs procédés de préparation et d'utilisation
WO2020059215A1 (fr) 2018-09-19 2020-03-26 日立化成株式会社 Procédé de déplacement d'article, procédé de transport de minerai et dispositif de transport de minerai
WO2020123946A1 (fr) * 2018-12-13 2020-06-18 Materia, Inc. Compositions de revêtement
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US5312940A (en) 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
US20040068036A1 (en) * 2002-10-07 2004-04-08 Halladay James R. Flexible emissive coatings for elastomer substrates
EP2982709A1 (fr) * 2014-08-07 2016-02-10 Telene SAS Composition durcissable et article moulé comprenant la composition
US10239965B2 (en) 2015-02-12 2019-03-26 Materia, Inc. Cyclic olefin resin compositions comprising functional elastomers
WO2019070819A1 (fr) 2017-10-06 2019-04-11 3M Innovative Properties Company Compositions durcissables, articles obtenus à partir de celles-ci, et leurs procédés de préparation et d'utilisation
WO2020059215A1 (fr) 2018-09-19 2020-03-26 日立化成株式会社 Procédé de déplacement d'article, procédé de transport de minerai et dispositif de transport de minerai
WO2020123946A1 (fr) * 2018-12-13 2020-06-18 Materia, Inc. Compositions de revêtement
WO2021074749A1 (fr) * 2019-10-14 2021-04-22 3M Innovative Properties Company Procédés, articles et composition adhésive comprenant une oléfine cyclique non polymérisée, un catalyseur et un polymère promoteur d'adhérence

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