Classifications

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  • 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
  • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
  • B32B5/022—Non-woven fabric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
  • B32B5/024—Woven fabric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
  • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
  • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
  • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
  • C08G65/44—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols by oxidation of phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
  • C08G65/485—Polyphenylene oxides
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
  • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C09D171/12—Polyphenylene oxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/101—Glass fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
  • B32B2262/10—Inorganic fibres
  • B32B2262/106—Carbon fibres, e.g. graphite fibres
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • 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
  • C08J2335/00—Characterised by the use of homopolymers or 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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
  • C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
• • 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
  • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08J2371/12—Polyphenylene oxides

Definitions

• This disclosure relates to an end-capped phenylene ether oligomer, a method of forming the same, a curable thermosetting composition including the same, and articles derived therefrom.
• Thermosetting resins are materials that cure to form extremely hard plastics. These materials that can be used in a wide variety of consumer and industrial products. For example, thermosets are used in protective coatings, adhesives, electronic laminates (such as those used in the fabrication of computer circuit boards), flooring, and paving applications, glass fiber-reinforced pipes, and automotive parts (including leaf springs, pumps, and electrical components). Poly(arylene ether) copolymers generally have good dielectric properties.
• curable thermosetting compositions including poly(arylene ether) copolymers with a lower viscosity while maintaining or improving the dielectric constant, dissipation factor, heat resistance, and water absorption.
• a linear bifunctional phenylene ether oligomer comprising repeating units derived from 2-methyl-6-cyclohexylphenol and having (meth) acrylate end groups.
• Also provided is a process for forming the linear bifunctional phenylene ether oligomer including oxidatively polymerizing 2-methyl-6-cyclohexyl phenol in the presence of a catalyst to provide a phenylene ether oligomer; and reacting the phenylene ether oligomer with a (meth)acrylate-containing compound to provide the linear bifunctional phenylene ether oligomer.
• curable thermosetting composition comprising the linear bifunctional phenylene ether oligomer and an article derived from the curable thermosetting composition.
• a phenylene ether oligomer derived from 2-methyl-6-cyclohexylphenol and end-capped with (meth)acrylate groups can be included in curable thermosetting compositions to achieve improved properties over thermosetting compositions that include a phenylene ether oligomer without repeating units derived from 2-methyl-6-cyclohexylphenol.
• a phenylene ether oligomer derived from 2-methyl-6-cyclohexylphenol can provide an improved combination of properties, such as solution viscosity, dissipation factor, resin flow, and dielectric constant.
• an aspect of the present disclosure is a linear bifunctional phenylene ether oligomer comprising repeating units derived from 2-methyl-6-cyclohexylphenol.
• the phenylene ether oligomer therefore comprises repeating units having the structure
• the oligomer can consist of the above repeating units derived from 2-methyl-6- cyclohexylphenol or can comprise repeating units derived from a monohydric phenol different from 2-methyl-6-cyclohexylphenol.
• the phenylene ether oligomer comprises less than 30 weight percent (based on the total weight of the phenylene ether oligomer) of repeating units derived from a monohydric phenol having identical substituents in the 2- and 6- positions (e.g., 2,6-dimethylphenol, 2,3,6-dimethylphenol, and the like, or combinations thereof).
• the phenylene ether oligomer comprises less than 20, or less than 15, or less than 10, or less than 5, or less than 2, or less than 1, or less than 0.5 or less than 0.1 weight percent of repeating units derived from a monohydric phenol having identical substituents in the 2- and 6- positions.
• the oligomer can comprise no repeating units derived from a monohydric phenol having identical substituents in the 2- and 6- positions.
• the phenylene ether oligomer of the present disclosure excludes repeating units derived from 2-cyclohexylphenol.
• the phenylene ether oligomer has a linear architecture and is bifunctional. “Bifunctional” as used herein means that the phenylene ether oligomer has functional groups at both termini of the oligomer chain. Bifunctional oligomers with functional groups at both termini of an oligomer chain are also referred to as “telechelic” oligomers.
• the phenylene ether oligomer therefore has, on average, 2 functional end groups (i.e., (meth) acrylate groups) per oligomer chain.
• the bifunctional oligomer has at least 1.5 to 2, or at least 1.70 to 2, or at least 1.8 to 2, or at least 1.9 to 2, or at least 1.95 to 2 (meth)acrylate groups per molecule, or up to 1.99 (meth) acrylate groups per molecule.
• the phenylene ether oligomer is of the structure wherein R 1 and R 2 are each independently halogen, unsubstituted or substituted C ⁇ -n primary or secondary hydrocarbyl, C ⁇ -n hydrocarbylthio, C ⁇ -n hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of R 3 and R 4 are each independently hydrogen, halogen, unsubstituted or substituted Ci-12 primary or secondary hydrocarbyl, Ci-12 hydrocarbylthio, Ci-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y are independently 0 to 30, preferably 0 to 20, more preferably 0 to 15, still more preferably 0 to 10, even more preferably 0 to 8, provided that the sum of x and y
• the phenylene ether oligomer is of the structure wherein R'-R 4 are as defined above.
• each occurrence of R 1 and R 2 is methyl
• each occurrence of R 3 and R 4 is hydrogen
• z is 1
• Y is an isopropylidene group
• the phenylene ether oligomer is of the structure
• each occurrence of R 1 and R 2 is methyl
• each occurrence of R 3 and R 4 is hydrogen
• z is 1
• Y is an isopropylidene group
• the phenylene ether oligomer is of the structure
• the phenylene ether oligomer of the present disclosure can be made by oxidatively polymerizing 2-methyl-6-cyclohexyl phenol in the presence of a catalyst to provide the phenylene ether oligomer.
• the phenylene ether oligomer can be formed by polymerization of monomers comprising 2-methyl-6-phenylphenol and a dihydric phenol by continuous addition of oxygen to a reaction mixture comprising the monomers, solvent, and polymerization catalyst.
• the dihydric phenol has the structure wherein R 1 to R 4 , Y 1 , and z are as defined above.
• the dihydric phenol can be l,l-bis(3,5-dimethyl-4-hydroxyphenyl) ethane, l,l-bis(3-chloro-4-hydroxyphenyl)ethane, l,l-bis(3-methyl-4-hydroxyphenyl)-ethane, l,2-bis(4-hydroxy-3,5-dimethylphenyl)-l,2-diphenylethane, l,2-bis(3-methyl-4-hydroxyphenyl)
• the molecular oxygen (O2) can be provided as air or pure oxygen.
• the polymerization catalyst is a metal complex comprising a transition metal cation.
• the metal cation can include ions from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. Of these, chromium, manganese, cobalt, copper, and combinations comprising at least one of the foregoing ions can be used.
• the metal ion is a copper ion (Cu + and Cu 2+ ).
• Metal salts which can serve as sources of metal cations include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cuprous sulfate, cupric sulfate, cuprous tetraamine sulfate, cupric tetraamine sulfate, cuprous acetate, cupric acetate, cuprous propionate, cupric butyrate, cupric laurate, cuprous palmitate, cuprous benzoate, and the corresponding manganese salts and cobalt salts.
• metal salts instead of use of any of the above-exemplified metal salts, it is also possible to add a metal or a metal oxide and an inorganic acid, organic acid or an aqueous solution of such an acid and form the corresponding metal salt or hydrate in situ.
• a metal or a metal oxide and an inorganic acid, organic acid or an aqueous solution of such an acid can be added to generate cuprous bromide in situ.
• cuprous oxide and hydrobromic acid can be added to generate cuprous bromide in situ.
• Suitable dialkylmonoamines include dimethylamine, di-n-propylaminc , di-n-butylaminc, di -sec- butyl amine, di-ieri-butylamine, dipentylamine, dihexylamine, dioctylamine, didecylamine , dibenzylamine, methylethylamine, methylbutylamine, dicyclohexylamine, N- phenylethanolamine, N-(/?-methyl)phenylethanolamine, N-(2,6-dimethyl)phenylethanolamine, N-(p-chloro)phenylethanolamine, N-ethylaniline, N-butyl aniline, N-methyl-2-methylaniline, N- methyl-2, 6-dimethylaniline, diphenylamine, and the like, or a combination thereof.
• Suitable trialkylmonoamines include trimethylamine, triethylamine, tripropylamine, tribu
• R d is a substituted or unsubstituted divalent residue; and each R d is independently hydrogen or Ci-s alkyl.
• R c is a substituted or unsubstituted divalent residue; and each R d is independently hydrogen or Ci-s alkyl.
• two or three aliphatic carbon atoms form the closest link between the two diamine nitrogen atoms.
• Specific alkylenediamine ligands include those in which R c is dimethylene (-CH 2 CH 2- ) or trimethylene (-CH 2 CH 2 CH 2- ).
• R d can be independently hydrogen, methyl, propyl, isopropyl, butyl, or a C 4-8 alpha-tertiary alkyl group.
• alkylenediamine ligands include N,N,N',N' tetramethylethylene diamine (TMED), N,N'-di-tert-butylethylenediamine (DBEDA), N,N,N',N'-tetramethyl-l,3- diaminopropane (TMPD), N-methyl-l,3-diaminopropane, N,N'-dimethyl-l,3-diaminopropane, N,N,N'-dimethyl- 1 ,3-diaminopropane, N-ethyl- 1 ,3-diaminopropane, N-methyl-l,4-diaminobutane, N,N'-trimethyl-l,4-diaminobutane, N,N,N'-trimethyl-l,4-diaminobutane, N,N,N'-trimethyl-l,4-diaminobutane,
• the amine ligand is di-n-butylaminc (DBA), N,N-dimethylbutylamine (DMBA), N,N'-di-/ ⁇ ?/7 - butylethylenediamine (DBEDA), or combinations thereof.
• the catalyst can be prepared in situ by mixing a metal ion source (e.g., cuprous oxide and hydrobromic acid) and amine ligands.
• a metal ion source e.g., cuprous oxide and hydrobromic acid
• the polymerization catalyst comprises copper ion, bromide ion, and N,N’-di-tert- buty lethy lenediamine .
• the phenylene ether oligomer can be obtained as a powder that is subsequently combined with the compound comprising a (meth) acrylate group and a solvent.
• the uncapped phenylene ether oligomer can be obtained as a solution from the oxidative polymerization reaction without removing the solvent, and the uncapped phenylene ether oligomer is not isolated as a powder from the solvent solution.
• the compound comprising a (meth) acrylate group can be added directly to a solution of the uncapped phenylene ether oligomer that is directly obtained from oxidatively polymerizing the 2-methyl-6-cyclohexylphenol and the dihydric phenol in a solvent, wherein the solvent is not removed from the reaction product before reacting with the compound comprising a (meth) acrylate group.
• An exemplary synthesis is further described in the working examples below. Suitable compounds comprising the (meth)acrylate group and a group reactive toward the hydroxyl-terminated phenylene ether oligomer can be readily determined by one skilled in the art.
• a curable thermosetting composition including the linear bifunctional phenylene ether oligomer having (meth)acrylate end groups.
• the bifunctional phenylene ether oligomer can be present in the curable thermosetting composition in an amount of 1 to 95 weight percent (wt%), or 5 to 95 wt%, or 10 to 85 wt%, or 20 to 80 wt%, 30 to 70 wt%, or 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable thermosetting composition.
• the curable thermosetting composition can further include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.
• the curable thermosetting composition can further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.
• the curable thermosetting composition can include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; and can further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.
• thermosetting resins there is considerable overlap among thermosetting resins, crosslinking agents, and coupling agents.
• crosslinking agent includes compounds that can be used as thermosetting resins, crosslinkers, coupling agents, or a combination thereof.
• a compound that is a thermosetting resin could also be used as a crosslinking agent, a coupling agent, or both.
• thermosetting resins are not particularly limited, and thermosetting resins can be used alone or in combinations of two or more thermosetting resins (e.g., including one or more auxiliary thermosetting resins).
• exemplary thermosetting resins include epoxy resins, cyanate ester resins, (bis)maleimide resins, (poly)benzoxazine resins, vinyl resins (e.g., a vinyl benzyl ether resin), phenolic resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers or polymers with curable unsaturation (e.g., a vinyl functionality), or the like, or a combination thereof.
• the epoxy resins can include bisphenol A type epoxy resins such as those obtained from bisphenol A and resins obtained by substituting at least one position of the 2-position, the 3-position and the 5-position of bisphenol A with a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; bisphenol F type epoxy resins such as those obtained from bisphenol F and a resin obtained by substituting at least one position of the 2-position, the 3-position and the 5-position of bisphenol F with a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; glycidyl ether compounds derived from bivalent or tri- or more-valent phenols such as hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane and l,l,2,2-tetrakis(4-hydroxyphenyl)ethane; a novolak type epoxy resin derived from a novolak resin which is a reaction product between
• cyanate ester resins include 2,2-bis(4-cyanatophenyl)- propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4- cyanatophenyl)- 1 , 1 , 1 ,3 ,3 ,3-hexafluoropropane, a,a'-bis(4-cy anatophenyl)-m-diisopropyl- benzene, cyanate ester resins prepared from dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers.
• a prepolymer is PRIMASET BA- 2308 (Lonza).
• the cyanate ester prepolymers can be homopolymers or can be copolymers that incorporate other monomers. Examples of such copolymers include BT resins available from Mitsubishi Gas Chemical, such as, BT 2160 and BT2170, which are prepolymers made with cyanate ester monomers and bismaleimide monomers.
• BT resins available from Mitsubishi Gas Chemical, such as, BT 2160 and BT2170, which are prepolymers made with cyanate ester monomers and bismaleimide monomers.
• Other cyanate esters polymers, monomers, prepolymers, and blends of cyanate ester monomers with other non-cyanate ester monomers are disclosed in US 7393904, US 7388057, US 7276563, and US 7192651.
• Bismaleimide resins can be produced by reaction of a monomeric bismaleimide with a nucleophile such as a diamine, aminophenol, or amino benzhydrazide, or by reaction of a bismaleimide with diallyl bisphenol A.
• a nucleophile such as a diamine, aminophenol, or amino benzhydrazide
• Exemplary bismaleimide resins include 1,2- bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1 ,4-bismaleimido- benzene, 2,4-bismaleimidotoluene, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimido- diphenylether, 3,3'-bismaleimidodiphenylsulfone, 4,4'-bismaleimido-diphenylsulfone, 4,4'- bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6-bismaleimido- pyridine, 1 ,3-bis(maleimidomethyl)cyclohexane, 1 ,3-bis(maleimidomethyl)benzene, l,l-bis(4-maleimidophenyl)cyclohexan
• Exemplary phenols for use in the preparation of benzoxazine monomers include phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydrooxynapthalene, 2-(diphenyl-phosphoryl)hydroquinone, 2,2’-biphenol, 4,4-biphenol, 4,4’-isopropylidenediphenol, 4,4’-isopropylidenebis(2-methyl- phenol), 4,4’-isopropylidenebis(2-allylphenol), 4,4’(l,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4’-isopropylidenebis(3-phenylphenol) 4,4’-(l,4-phenylenediisoproylidene)- bisphenol, 4,4’-ethylidenediphenol, 4,4
• the aldehydes used to form the benzoxazine can be any aldehyde, such as an aldehyde having 1 to 10 carbon atoms.
• the aldehyde can be formaldehyde.
• the amine used to form the benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl substituted aromatic, or an aromatic substituted alkyl amine.
• the amine can be a polyamine, for example to prepare polyfunctional benzoxazine monomers for crosslinking.
• the amines for forming benzoxazines have 1 to 40 carbon atoms unless they include aromatic rings, and then they can have 6 to 40 carbon atoms.
• the amine of di- or polyfunctional can be a branch point to connect one polybenzoxazine to another.
• thermal polymerization at 150 to 300° C can be used for polymerizing benzoxazine monomers.
• the polymerization can be done in bulk, from solution, or otherwise.
• Catalysts, such as carboxylic acids, can be used to reduce the polymerization temperature or accelerate the polymerization rate at the same temperature.
• Exemplary vinyl benzyl ethers can include those vinylbenzyl ethers produced from reaction of a vinylbenzyl halide with resorcinol, catechol, hydroquinone, 2,6- dihydroxynaphthalene, 2,7 -dihydroxynaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, bis(2,6-dimethylphenol) 2,2’ -biphenol, 4,4-biphenol, 2,2’,6,6’-tetramethylbiphenol, 2,2’,3,3’,6,6’-hexamethylbiphenol, 3,3’,5,5’-tetrabromo-2,2’6,6’-tetramethylbiphenol, 3,3’- dibromo-2,2’,6,6’-tetramethylbiphenol, 2,2’,6,6’-tetramethyl-3,3’5-dibromobiphenol, 4,4’-iso- propylidenediphenol, 4,4’-isopropylid
• Arylcyclobutenes include those derived from compounds of the structure wherein B is an organic or inorganic radical of valence n (including carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidene dialkylsilanyl, arylalkylsilanyl, diarylsilanyl and C6-20 phenolic compounds); each occurrence of X is independently hydroxy or Ci-24 hydrocarbyl (including linear and branched alkyl and cycloalkyl); and each occurrence of Z is independently hydrogen, halogen, or Ci-12 hydrocarbyl; and n is 1 to 1000 ,or 1 to 8, or n is 2, 3, or 4.
• valence n including carbonyl, sulfonyl, sul
• Perfluorovinyl ethers are typically synthesized from phenols and bromotetrafluoroethane followed by zinc catalyzed reductive elimination producing ZnFBr and the desired perfluorovinylether. By this route bis, tris, and other polyphenols can produce bis-, tris- and poly(perfluorovinylether)s.
• Phenols useful in their synthesis include resorcinol, catechol, hydroquinone, 2,6-dihydroxy naphthalene, 2,7-dihydroxynapthalene, 2-(diphenyl- phosphoryl)hydroquinone, bis(2,6-dimethylphenol) 2,2’-biphenol, 4,4-biphenol, 2, 2’, 6,6’- tetramethylbiphenol, 2,2’,3,3’,6,6’-hexamethylbiphenol, 3,3’,5,5’-tetrabromo-2,2’6,6’-tetra- methylbiphenol, 3,3’-dibromo-2,2’,6,6’-tetramethylbiphenol, 2,2’,6,6’-tetramethyl-3,3’5- dibromobiphenol, 4,4’-isopropylidenediphenol (bisphenol A), 4,4’-isopropylidenebis(2,6- dibromophenol), 4,4’
• the crosslinking agents which also include auxiliary crosslinking agents, are not particularly limited.
• the crosslinking agents can be used alone or in combinations of two or more different crosslinking agents.
• Exemplary crosslinking agents and auxiliary crosslinking agents include oligomers or polymers with curable vinyl functionality. Such materials include oligomers and polymers having crosslinkable unsaturation.
• SBR styrene butadiene rubber
• BR butadiene rubber
• NBR nitrile butadiene rubber
• natural rubber NR
• IR isoprene rubber
• CR chloroprene rubber
• HR butyl rubber
• halogenated butyl rubber having unsaturated bonding based on isoprene
• ethylene-a-olefin copolymer elastomers having unsaturated bonding based on dicyclopentadiene (DCPD), ethylidene norbomene (ENB), or 1,4-dihexadiene (1,4-HD)
• DCPD dicyclopentadiene
• EMB ethylidene norbomene
• 1,4-dihexadiene 1,4-HD
• Examples also include hydrogenated nitrile rubber, fluorocarbon rubbers such as vinylidenefluoride-hexafluoropropene copolymer and vinylidenefluoride-pentafluoropropene copolymer, epichlorohydrin homopolymer (CO), copolymer rubber (ECO) prepared from epichlorohydrin and ethylene oxide, epichlorohydrin allyl glycidyl copolymer, propylene oxide allyl glycidyl ether copolymer, propylene oxide epichlorohydrin allyl glycidyl ether terpolymer, acrylic rubber (ACM), urethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T) and ethylene acrylic rubber.
• fluorocarbon rubbers such as vinylidenefluoride-hexafluoropropene copolymer and vinylidenefluoride-pent
• liquid rubbers for example several types of liquid butadiene rubbers, and the liquid atactic butadiene rubber that is butadiene polymer with 1,2-vinyl connection prepared by anionic living polymerization. It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc. by Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene type hydrocarbon polymer, and polynorbomene (for example, as sold by Elf Atochem).
• liquid styrene butadiene rubber liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc. by Ube Industries, Ltd.)
• liquid chloroprene rubber liquid polyisoprene
• dicyclopentadiene type hydrocarbon polymer for example, as sold by Elf Atochem.
• Polybutadiene resins containing elevated levels of 1,2 addition are desirable for thermosetting matrices.
• examples include the functionalized polybutadienes and poly(butadiene- styrene) random copolymers sold by Ricon Resins, Inc. under the trade names RICON, RICACRYL, and RICOBOND resins.
• butadienes containing both low vinyl content such as RICON 130, 131, 134, 142
• polybutadienes containing high vinyl content such as RICON 150, 152, 153, 154, 156, 157, and P30D
• random copolymers of styrene and butadiene including RICON 100, 181, 184, and maleic anhydride grafted polybutadienes and the alcohol condensates derived therefrom such as RICON 130MA8, RICON MA13, RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA17, RICON MA20, RICON 184MA6 and RICON 156MA17.
• polybutadienes that can be used to improve adhesion including RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500; the polybutadienes RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene); (meth)acrylic functionalized polybutadienes such as polybutadiene diacrylates and polybutadiene dimethacrylates. These materials are sold under the tradenames RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. Also are included are powder dispersions of functional polybutadiene derivatives including, for example, RICON 150D,
• butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as those with molecular weights from 3,000 to 50,000 g/mol and polybutadiene homopolymers having molecular weights from 3,000 to 50,000 g/mol. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride functions, 2- hydroxyethylmaleic functions, or hydroxylated functionality.
• oligomers and polymers with curable vinyl functionality include unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid and citraconic acid; unsaturated epoxy (meth)acrylate resins containing acryloyl groups, or methacryloyl group; unsaturated epoxy resins containing vinyl or allyl groups, urethane (meth) acrylate resin, polyether (meth) acrylate resin, polyalcohol (meth) acrylate resins, alkyd acrylate resin, polyester acrylate resin, spiroacetal acrylate resin, diallyl phthalate resin, diallyl tetrabromophthalate resin, diethyleneglycol bisallylcarbonate resin, and polyethylene polythiol resins.
• crosslinking agent further include polyfunctional crosslinking monomers such as (meth) acrylate monomers having two or more (meth) acrylate moieties per monomer molecule.
• polyfunctional monomers include di(meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, or the like
• the crosslinking agent can be included in an amount of 1 to 60 wt%, or 5 to 45 wt%, or 10 to 30 wt%, based on total weight of the curable thermosetting composition.
• the curable thermosetting composition can include one or more curing agents.
• curing agent includes compounds that are variously described as curing agents, hardeners, or the like, or as both.
• Exemplary curing agents and hardeners include amines, alcohols, phenols, carboxylic acids, acid anhydrides, and the like.
• phenolic hardeners include novolac type phenol resins, resole type phenol resins, cresol novolac resins, aralkyl type phenol resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene type phenol resins, terpene modified phenol resins, biphenyl type phenol resins, biphenyl-modified phenol aralkyl resins, bisphenols, triphenylmethane type phenol resins, tetraphenylol ethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, amino triazine modified phenol resin
• anhydride hardeners examples include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymers (SMA), and olefin- maleic anhydride copolymers such as maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination thereof.
• MHHPA methylhexahydrophthalic anhydride
• SMA styrene-maleic anhydride copolymers
• olefin- maleic anhydride copolymers such as maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination thereof.
• curing agents and hardeners include compounds such as dicyandiamides, polyamides, amidoamines, phenalkamines, Mannich bases, anhydrides, phenol-formaldehyde resins, amine-formaldehyde resins, phenol-formaldehyde resins, carboxylic acid functional polyesters, polysulfides, polymercaptans, isocyanates, cyanate ester compounds, or any combination thereof.
• Other exemplary curing agents include tertiary amines, Lewis acids, and oligomers or polymers with unsaturation.
• the curing agent can be included in an amount of 0.01 to 50 wt%, or 0.1 to 30 wt%, or 0.1 to 20 wt%, based on total weight of the curable thermosetting composition.
• the curable thermosetting composition can include a curing catalyst.
• curing catalyst includes compounds that are variously described as curing accelerators, curing promoters, curing catalysts, and curing co-catalysts.
• Exemplary curing accelerators include heterocyclic accelerators such as a substituted or unsubstituted C3-6 heterocycle comprising 1 to 4 ring heteroatoms, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon, or sulfur.
• heterocyclic accelerators such as a substituted or unsubstituted C3-6 heterocycle comprising 1 to 4 ring heteroatoms, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon, or sulfur.
• Heterocyclic accelerators include benzotriazoles; triazines; piperazines such as aminoethylpiperazine, N-(3-aminopropyl)piperazine, or the like; imidazoles such as 1- methylimidazole, 2-methylimidazole, 3 -methyl imidazole, 4-methylimidazole, 5- methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5- ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2- isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2- isobutylimidazole, 2-undecyl-lH-imidazole, 2-h
• Amine curing accelerators include isophoronediamine, triethylenetetraamine, diethylenetriamine, 1,2- and 1,3-diaminopropane, 2,2-dimethylpropylenediamine, 1.4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane,
• the curing accelerator can be a latent cationic cure catalyst including, for example, diaryliodonium salts, phosphonic acid esters, sulfonic acid esters, carboxylic acid esters, phosphonic ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, or the like, or a combination thereof.
• a latent cationic cure catalyst including, for example, diaryliodonium salts, phosphonic acid esters, sulfonic acid esters, carboxylic acid esters, phosphonic ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts,
• the diaryliodonium salt can have the structure [(R 10 )(R U )I] + X , wherein R 10 and R 11 are each independently a Ce-i A monovalent aromatic hydrocarbon radical, optionally substituted with from 1 to 4 monovalent radicals selected from Ci-20 alkyl, Ci-20 alkoxy, nitro, and chloro; and wherein X- is an anion.
• the curing accelerator can be a metal salt complex, such as a copper (II) aluminum (III), zinc, cobalt, tin salt of an aliphatic or aromatic carboxylic acid selected from copper (II), tin (II), and aluminum (III) salts of acetate, stearate, gluconate, citrate, benzoate, and mixtures thereof.
• a metal salt complex such as a copper (II) aluminum (III), zinc, cobalt, tin salt of an aliphatic or aromatic carboxylic acid selected from copper (II), tin (II), and aluminum (III) salts of acetate, stearate, gluconate, citrate, benzoate, and mixtures thereof.
• the cure accelerator can be a copper (II) or aluminum (III) salts of b-diketonates; copper (II), iron (II), iron (III), cobalt (II), cobalt (III), or aluminum (III) salts of acetylacetonates; zinc (II), chromium (II), or manganese (II) salts of octoates; or a combination thereof.
• the curable thermosetting composition can optionally include a curing initiator, such as a peroxide compound.
• a curing initiator such as a peroxide compound.
• exemplary peroxide curing initiators can include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate, t- butylperoxybenzoate, t-butylperoxy 2-ethylhexyl carbonate, 2,4-dichlorobenzoyl peroxide, 2,5- dimethylhexane-2, 5-dihydroperoxide, butyl-4, 4-bis(tert-butyldioxy)valerate, 2,5-dimethyl-2,5- di(t-butylperoxy)-hex-3
• the curing initiator can be included in an amount of 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, based on total weight of the curable thermosetting composition.
• Flame retardants include, for example, organic compounds that comprise phosphorus, bromine, or chlorine.
• Non-brominated and non-chlorinated phosphorus -containing flame retardants can be preferred in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus-nitrogen bonds.
• Examples of phosphorous flame retardants include phosphates, phosphazenes, phosphite esters, phosphines, phosphinates, polyphosphates, and phosphonium salts.
• Phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl) p- tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, bis(d
• Examples of the phosphazene compounds include cyclic and chain phosphazene compounds.
• the cyclic phosphazene compounds (cyclophosphazenes) have a cyclic structure in which phosphorus -nitrogen double bonds are present in the molecule.
• Examples of phosphinate compounds include aluminum dialkylphosphinate, aluminum tris-(diethylphosphinate), aluminum tris-(methylethylphosphinate), aluminum tris-(diphenylphosphinate), zinc bis- (diethylphosphinate), zinc bis-(methylphosphinate), zinc bis-(diphenylphosphinate), titanyl bis- (diethylphosphinate), titanyl bis-(methylethylphosphinate), and titanyl bis- (diphenylphosphinate).
• Examples of polyphosphate compounds include melamine polyphosphate, melam polyphosphate, and melem polyphosphate.
• Examples of phosphonium salt compounds include tetraphenylphosphonium tetraphenylborate.
• Examples of the phosphite ester compounds include trimethylphosphite and triethylphosphite.
• Flame retardant compounds containing phosphorus -nitrogen bonds include phosphonitrilic chloride, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl) phosphine oxide.
• Halogenated materials can also be used as flame retardants, for example bisphenols such as 2,2-bis-(3,5-dichlorophenyl)-propane; bis-(2-chlorophenyl)-methane; bis(2,6- dibromophenyl) -methane; l,l-bis-(4-iodophenyl)-ethane; l,2-bis-(2,6-dichlorophenyl)-ethane; l,l-bis-(2-chloro-4-iodophenyl)ethane; l,l-bis-(2-chloro-4-methylphenyl)-ethane; l,l-bis-(3,5- dichlorophenyl)-ethane; 2,2-bis-(3-phenyl-4-bromophenyl)-ethane; 2,6-bis-(4,6- dichloronaphthyl)-propane; and 2,2-bis-(3,5-dich
• halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, l,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'- dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'- dichlorobiphenyl as well as decabromobiphenyl ether, decabromodiphenylethane, as well as oligomeric and polymeric halogenated aromatic compounds, such as brominated styrene, 4,4- dibromobiphenyl, ethylene-bis(tetrabromophthalimide), or a copolycarbonate of bisphenol A and tetrabromobisphenol A and a carbonate precursor, e.g., phosgene.
• Metal synergists e.g., antimony oxide, can also be used with the flame retardant.
• the flame retardant can be included in an amount of greater than 1 wt%, or 1 to 20 wt%, or 5 to 20 wt%, based on total weight of the curable thermosetting composition.
• the curable thermosetting composition can further include inorganic or organic fillers, such as a particulate filler, a fibrous filler, or the like, or a combination thereof. Any inorganic and organic fillers, including those known in the art, can be used without limitation.
• Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate; alumina, thiourea, glass powder, B- or Sn-based fillers such as zinc borate, zinc stannate and zinc hydroxy stannate; metal oxides such as zinc oxide and tin oxide alumina, silica (including fused silica, fumed silica, spherical silica, and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, antimony trioxide, glass fibers (chopped, milled, or cloth), glass mat, glass bubbles, hollow glass microspheres, aramid fibers, quartz, or the like, or a combination thereof.
• silica including fused silica, fumed silica, spherical silica, and crystalline
• inorganic fillers include powdered titanium ceramics such as any one of the titanates of barium lead, strontium, calcium, bismuth, magnesium, or the like. Inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolite, and hydrotalcite. In some aspects, the filler can be treated with a coupling agent as disclosed herein.
• Glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as quartz.
• the glass fiber can have any suitable diameter, such as from 2 to 30 micrometers (mhi), or 5 to 25 mhi, or 5 to 15 mhi.
• the length of the glass fibers before compounding are not limited and can be 2 to 7 millimeters (mm), or 1.5 to 5 mm. Alternatively, longer glass fibers or continuous glass fibers can be used. Suitable glass fiber is commercially available from suppliers such as Owens Coming, Nippon Electric Glass, PPG, and Johns Manville.
• the organic filler can be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder, and poly(ether sulfone) powder, poly(phenylene ether) powder, polystyrene, divinylbenzene resin, or the like, or a combination thereof.
• the filler can be selected based on the thermal expansion coefficient (CTE) and thermal conductivity requirements.
• CTE thermal expansion coefficient
• AI 2 O 3 , BN, AIN, or a combination thereof can be used for an electronics module with high thermal conductivity.
• MgO can be used for increased thermal conductivity and increased CTE.
• S1O 2 e.g., amorphous S1O 2
• a lightweight module having a low CTE and a small dielectric constant can be used for a lightweight module having a low CTE and a small dielectric constant.
• the filler can be included in an amount of greater than 1 wt%, or 1 to 50 wt%, or 1 to 30 wt%, or 10 to 30 wt%, based on total weight of the curable thermosetting composition.
• Coupling agents also referred to as adhesion promoters, include chromium complexes, silanes, titanates, zircon-aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, and the like.
• Exemplary olefin-maleic anhydride copolymers can include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination thereof.
• Exemplary silanes can include epoxysilane compound, aminosilane compounds methacryloxysilane compounds, vinylsilane compounds, or a combination thereof.
• aminosilane coupling agents are g -aminopropyltrimethoxy- silane, g-aminopropyltriethoxysilane, N-beta(aminoethyl) g-aminopropylmethyl-dimethoxysilane, N- beta(aminoethyl) g -aminopropyltrimethoxysilane, and N- bet a( a m i noct h y 1 )g- aminopropyltriethoxy silane.
• silane coupling agents include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2- triethoxysilylethyl) tetrasulfide, bis(3-trimethoxysilylpropyl) tetrasulfide, bis(2- trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3- mercaptopropyltriethoxy silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltri- ethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3- triethoxysilylpropyl-N
• the silane coupling agent can be a polysulfide silane coupling agent having 2 to 4 sulfur atoms forming a polysulfide bridge.
• the coupling agent can be a bis(3-triethoxysilylpropyl) di-, tri-, or tetrasulfide.
• the coupling agent can be included in an amount of 0.01 to 5 wt%, or 0.05 to 5 wt%, or 0.1 to 5 wt%, based on total weight of the curable thermosetting composition.
• Specific C4-8 N,N- dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, /V-methyl- 2-pyrrolidone, or a combination thereof.
• Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethylether, dioxane, or a combination thereof.
• Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylenes, styrene, divinylbenzenes, or a combination thereof. The aromatic hydrocarbon solvent can be non- halogenated.
• Specific C3-6 alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or a combination thereof.
• Specific C2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof.
• Specific C2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof.
• the solvent can be N,N-dimethylformamide, N,N- dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxy acetamide, N-methyl-2- pyrrolidone, N-cyclohexylpyrrolidinone, N-methylcaprolactam, l,3-dimethyl-2-imidazolidone, 1,2-dimethoxy ethane, 1,3 -dioxane, 1,4-dioxane, tetrahydrofuran, g-butyrolactone, g- caprolactone, dimethylsulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diglyme, triglyme, tetraglyme, N,N-dimethylethyleneurea, N,N- dimethylpropyleneurea, tetramethylurea, propylene glyco
• the curable thermosetting composition can include 2 to 99 wt% of the solvent, based on weight total of the curable thermosetting composition.
• the solvent amount can be 5 to 80 wt%, or 10 to 60 wt%, or 20 to 50 wt%, based on weight total of the curable thermosetting composition.
• the solvent can be chosen, in part, to adjust the viscosity of the curable thermosetting composition.
• the solvent amount can depend on variables including the type and amount of capped poly(arylene ether) copolymer, the type and amount of other components such as curing additive, the type and amount of any auxiliary thermosetting resin(s), and the processing temperature used for any subsequent processing of the curable thermosetting composition, for example, impregnation of a reinforcing structure with the curable thermosetting composition for the preparation of a composite.
• the solvent can be anhydrous.
• the solvent can include less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water based on total weight of the solvent.
• 6,627,704 to Yeager et ah include (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidone, and vinylazalactones as disclosed in U.S. Pat. No. 4,304,705 of Heilman et al.
• Exemplary monofunctional monomers include mono(meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isooctyl (meth)acrylate, isobomyl (meth)acrylate, (meth)acrylic acid, n-hexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, or the like, or a combination thereof.
• mono(meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isooctyl (meth)acrylate, isobomyl (meth)acrylate, (meth)acrylic acid, n-hexyl (meth)acrylate, tetrahydr
• the curable thermosetting composition can, optionally, further include one or more additional additives.
• Additional additives include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoaming agents, lubricants, dispersants, flow modifiers, drip retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, or the like, or a combination thereof.
• the additional additives can be included in any effective amount, for example in an amount of 0.01 to 20 wt%, or 0.01 to 10 wt%, or 0.01 to 5 wt%, or 0.01 to 1 wt%, based on the total weight of the curable thermosetting composition.
• the curable thermosetting composition can be prepared by combining the bifunctional phenylene ether oligomer and the other optional components disclosed herein using any suitable method.
• the curing can be staged to produce a partially cured and often tack- free resin, which then is fully cured by heating for longer periods or temperatures within the aforementioned ranges.
• cured encompasses products that are partially cured or fully cured.
• the cured thermoset composition can have one or more desirable properties.
• the thermoset composition can have a glass transition temperature of greater than or equal to 165°C, preferably greater than or equal to 170°C, more preferably 165 to 180°C.
• the thermoset composition can also advantageously exhibit a low dielectric constant (Dk), a low dissipation factor (Df), and reduced moisture absorption.
• the thermoset composition can have a dielectric constant of less than 3.0, preferably less than 2.75, more preferably less than 2.6 at a frequency of 10 GHz.
• the thermoset composition can have a dissipation factor of less than 0.01, or less than 0.005 at a frequency of 10 GHz.
• thermoset compositions comprising the phenylene ether oligomer of the present disclosure can be particularly well suited for use in electronics applications.
• the curable thermosetting compositions and cured thermoset compositions can be used in a variety of applications and uses, including any applications where conventional thermosetting compositions are used.
• useful articles including the curable thermosetting composition or the cured thermoset composition can be in the form of a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a laminate, a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.
• Exemplary uses and applications include coatings such as protective coatings, sealants, weather resistant coatings, scratch resistant coatings, and electrical insulative coatings; adhesives; binders; glues; composite materials such as those using carbon fiber and fiberglass reinforcements.
• the disclosed compounds and compositions can be deposited on a surface of a variety of underlying substrates.
• the compositions can be deposited on a surface of metals, plastics, glass, fiber sizings, ceramics, stone, wood, or any combination thereof.
• the disclosed compositions can be used as a coating on a surface of a metal container (e.g., aluminum or steel), such as those commonly used for packaging and containment in the paint and surface covering industries.
• Methods of forming a composite can include impregnating a reinforcing structure with a curable thermosetting composition; partially curing the curable thermosetting composition to form a prepreg; and laminating a plurality of prepregs.
• the reinforcing structure can be a porous base material such as a fibrous preform or substrate, or other porous material comprising a ceramic, a polymer, a glass, carbon, or a combination thereof.
• the porous base material can be woven or non-woven glass fabric, a fiberglass fabric, or carbon fiber.
• the method of manufacturing the article can include forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition.
• the impregnated fibrous preform can optionally be shaped before or after removing the solvent.
• the curable thermosetting composition layer can further comprise a woven or nonwoven glass fabric.
• the curable layer can be prepared by impregnating the glass fabric with a curable composition and removing the solvent from the impregnated glass fabric. Exemplary reinforcing structures are described, for example, in Anonymous (Hexcel Corporation), “Prepreg Technology”, March 2005, Publication No.
• the weight and thickness of the reinforcing structure are chosen according to the intended use of the composite using criteria well known to those skilled in the production of fiber reinforced resin composites.
• the reinforced structure can contain various finishes suitable for the thermosetting components of the curable thermosetting composition.
• the method of manufacturing the articles from the curable thermosetting composition can include partially curing the curable thermosetting composition to form a prepreg, or fully curing the curable thermosetting composition to form a composite article.
• References herein to properties of the “cured composition” refer to a composition that is substantially fully cured.
• the resin in a laminate formed from prepregs is typically substantially fully cured.
• One skilled in the thermoset arts can determine whether a sample is partially cured or substantially fully cured without undue experimentation.
• the curing can be before or after removing the solvent from the curable composition.
• the article can be further shaped before removal of the solvent or after removal of the solvent, before curing, after partial curing, or after full curing, for example by thermoforming.
• the article is formed, and the solvent is removed; the article is partially cured (B -staged); optionally shaped; and then further cured.
• Articles include those comprising printed circuits as used in medical or aerospace industries. Still other articles include antennae and like articles. Articles such as printed circuit boards are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile telephones, electronic notepads, and similar devices, or office automation equipment. For example, electrical parts can be mounted on printed circuit boards comprising a laminate.
• Other exemplary articles prepared from the curable composition for various applications can include copper clad laminates (CCL), for example, metal core copper clad laminates (MCCCL), composite articles, and coated articles, for example multilayer articles.
• Dielectric layer can be prepared from the curable thermosetting composition can be useful in a circuit assembly, for example, in a metal-clad laminate such as a copper clad laminate.
• a laminate can comprise a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally, a heat dissipating metal matrix layer disposed on the dielectric layer on a side opposite the conductive metal layer.
• the dielectric layer can optionally include a fibrous preform (e.g., a fabric layer).
• the dielectric layer can further include a glass fabric layer.
• the conductive metal layer can be in the form of a circuit, and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, or the like, or a combination thereof.
• Other metals include a copper molybdenum alloy, a nickel-cobalt iron alloy such as KOVAR, available from Carpenter Technology Corporation, a nickel-iron alloy such as INVAR, available from National Electronic Alloys, Inc., a bimetal, a trimetal, a trimetal derived from two-layers of copper and one layer of INVAR, and a trimetal derived from two layers of copper and one layer of molybdenum.
• Exemplary metal layers comprise copper or a copper alloy.
• wrought copper foils can be used.
• Conductive metal layers can have a thickness of 2 to 200 micrometers (Em), or 5 to 50 Em, or 5 to 40 Em.
• a heat dissipating metal matrix layer can be a thermally conductive metal such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or the like, or a combination thereof.
• a thermally conductive, electrically conductive metal can be used provided that the metal is electrically isolated from the metal circuit layer.
• Preferred supporting metal matrix layers can have a thickness of 0.1 to 20 millimeters (mm), or 0.5 to 10 mm, or 0.8 to 2 mm.
• the conductive metal layer and the supporting metal matrix layers can be pretreated to have high surface roughness for enhanced adhesion to the dielectric layer.
• Treatment methods include washing, flame treatment, plasma discharge, corona discharge, or the like, for example to enhance adhesion of the metal layer.
• the dielectric layer can adhere firmly to the conductive metal layer or the heat dissipation layer without using an adhesive, or an adhesive can be used to improve adhesion of the dielectric layer to the conductive metal layer or the heat dissipation layer.
• Exemplary adhesives used to bond the composite sheet to a metal include polyimide adhesives, acrylic adhesives, epoxies, or the like, or a combination thereof.
• the copper clad laminates can be made by thermal lamination of one or more dielectric layers, one or more conductive metal layers, and a supporting metal matrix layer, under pressure without using thermosetting adhesives.
• the dielectric layer can be prepared from the curable thermosetting composition and can be prepared prior to the thermal lamination step by a solvent casting process to form a layer.
• the dielectric layer, the conductive metal layer, and the thermal dissipation layer can be thermally laminated together by an adhesive-free process under pressure to form a laminate.
• the electrically conductive metal layer can optionally be in the form of a circuit before laminating, or the conductive metal layer can optionally be etched to form the electrical circuit following lamination.
• the laminating can be by hot press or roll calendaring methods, for example, a roll-to-roll method.
• the conductive metal layer in a copper clad laminate can further be patterned to provide a printed circuit board.
• the copper clad laminates can be shaped to provide a circuit board having the shape of a sheet, a tube, or a rod.
• laminates for a circuit assembly can be made by a solution casting method in which the curable thermosetting composition is cast directly onto the electrically conductive metal layer, followed by lamination to the heat dissipating metal matrix layer.
• the curable thermosetting composition can be cast directly onto the heat dissipating metal matrix layer, followed by lamination to the electrically conductive metal layer.
• Multilayer laminates including additional layers can also be made by thermal lamination in one step or in two or more consecutive steps by such processes as hot press or roll calendaring methods. For example, seven layers or fewer can be present in the laminate, or sixteen layers or fewer.
• a laminate can be formed in one step or in two or more consecutive steps with sequential layers of fabric-thermoset-metal-thermoset-fabric-thermoset- metal foil or a sub-combination thereof with fewer layers, such that the laminate comprises a layer of thermoset film between any layer of metal foil and any layer of fabric.
• a first laminate can be formed in one step or in two or more consecutive steps with a layer of fabric between two layers of the thermoset, such as a layer of woven glass fabric between two layers of the thermoset.
• a second laminate can then be prepared by laminating a metal foil to a thermoset side of the first laminate.
• the curable thermosetting composition can be used as a coating, for example in the preparation of a multilayer article.
• a method of manufacturing the coating can include combining the curable thermosetting composition and optionally a fluoropolymer and forming a coating on a substrate.
• a multilayer article can be manufactured by forming a layer including the curable thermosetting composition, removing the solvent from the layer and optionally curing to provide a primer layer, forming a second layer comprising a ceramic (e.g., AI2O3, Ti0 2 , Zr0 2 , Cr 2 0 3 , Si0 2 , MgO, BeO, Y 2 0 3 , Al 2 0 3 -Si0 2 , MgO-Zr0 2 , SiC, WC, B 4 C, TiC, Si 3 N 4 , TiN, BN, AIN, TiB, ZrB 2 , or the like), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinylether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers , polychlorotrifluoroethylene
• Additional applications for the curable thermosetting compositions include, for example, acid bath containers; neutralization tanks; aircraft components; bridge beams; bridge deckings; electrolytic cells; exhaust stacks; scrubbers; sporting equipment; stair cases; walkways; automobile exterior panels such as hoods and trunk lids; floor pans; air scoops; pipes and ducts, including heater ducts; industrial fans, fan housings, and blowers; industrial mixers; boat hulls and decks; marine terminal fenders; tiles and coatings; building panels; business machine housings; trays, including cable trays; concrete modifiers; dishwasher and refrigerator parts; electrical encapsulants; electrical panels; tanks, including electrorefining tanks, water softener tanks, fuel tanks, and various filament-wound tanks and tank linings; furniture; garage doors; gratings; protective body gear; luggage; outdoor motor vehicles; pressure tanks; optical waveguides; radomes; railings; railroad parts such as tank cars; hopper car covers; car doors; truck bed liners; satellite dishes; signs;
• Processes useful for preparing the articles and materials include those generally known to the art for the processing of thermosetting resins. Such processes have been described in the literature as in, for example, Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987 Cyril A. Dostal Senior Ed, pp. 105-168 and 497-533, and “Polyesters and Their Applications” by Bjorksten Research Laboratories, Johan Bjorksten (pres.) Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956.
• Processing techniques include resin transfer molding; sheet molding; bulk molding; pultmsion; injection molding, including reaction injection molding (RIM); atmospheric pressure molding (APM); casting, including centrifugal and static casting open mold casting; lamination including wet or dry lay up and spray lay up; also included are contact molding, including cylindrical contact molding; compression molding; including vacuum assisted resin transfer molding and chemically assisted resin transfer molding; matched tool molding; autoclave curing; thermal curing in air; vacuum bagging; pultmsion; Seeman's Composite Resin Infusion Manufacturing Processing (SCRIMP); open molding, continuous combination of resin and glass; and filament winding, including cylindrical filament winding.
• an article can be prepared by a resin transfer molding process.
• an article derived from the curable thermosetting composition wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof; or, wherein the article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.
• Articles can be manufactured as disclosed herein, for example by casting, molding, extruding, or the like, and removing the solvent from the formed article.
• the article can be a layer, and can be formed by casting the curable composition onto a substrate to form a cast layer.
• articles prepared by the above-described methods can include adhesives, packaging material, capacitor films, or circuit board layers.
• articles prepared from the curable composition can be a dielectric layer, or a coating disposed on a substrate, for example a wire or cable coating.
• the article can be a dielectric layer in a circuit material, for example in a printed circuit board, used, for example, in lighting or communications applications.
• Other exemplary articles prepared from the curable composition can be one or more painted layers.
• the curable compositions can be used to prepare articles as disclosed herein for other curable thermosetting compositions.
• Oxidative coupling polymerization reactions were carried out in a bubbling reactor, a 500 ml jacketed glass reactor charged with an overhead agitator, a thermocouple, nitrogen pad and a dip tube for oxygen bubbling.
• the derivatization or end capping reaction was carried out in a 500 ml glass reactor equipped with a heating mantle, a dean stark condenser, a thermocouple, and an additional funnel.
• Casting of the curable compositions for subsequent curing was carried out using a manual hydraulic press from Specac.
• PPE-CMP oligomers were synthesized according to the following procedure. Toluene (42.45 grams), CMP (42.3 grams), TMBPA (5.76 grams), DMBA (4.32 grams), DBA (0.28 grams), and a mixture of DBEDA (0.075 grams), PTC-1 (0.04 grams), and toluene (0.13 grams) were charged to a 500 ml bubbling polymerization vessel and stirred under nitrogen. Catalyst solution (0.02 grams CU2O and 0.33 grams of 48% HBr) was added to the above reaction mixture. After the addition of catalyst solution, oxygen flow was started. The temperature was ramped from 25°C to 32°C in 15 minutes, and at 115 minutes it was increased to 49°C.
• Oxygen flow was maintained for 1500 minutes, at which point the flow was stopped, and 0.46 grams NTA and 5.68 grams water were added to the reaction mixture.
• the resulting mixture was stirred at 60°C for 2 hours.
• the layers were separated by centrifugation and the light phase was isolated by removal of toluene.
• the oligomer was obtained after drying in a vacuum oven at 110°C under nitrogen overnight.
• PPE-CMP-2MA oligomers were synthesized according to the following procedure.
• PPE-CMP oligomer 36 grams was dissolved in toluene (75 grams) in a 500 ml 3-neck round bottom flask equipped with a heating mantle, dean-stark condenser, agitator and thermocouple. The solution was heated to 120°C to remove water by azeotropic distillation. After the removal of water, the reaction mixture was cooled to 85°C and DMAP (0.36 grams) was added. After complete dissolution of DMAP, MAA (6.63 grams) was added over 20 minutes using an addition funnel. The reaction temperature was raised to 110°C, and the reaction was stirred for 4 hours. PPE-CMP-2MA was isolated by precipitation into methanol. The powder was further dried under vacuum and nitrogen at 110°C overnight.
• Curable compositions were prepared by dissolving the PPE-CMP-2MA in chloroform. Chloroform was removed under vacuum and nitrogen until a dried powder was obtained. The dried powder was used for chemorheology and further cured for performance evaluation. Cured castings were prepared by curing the compositions partially (e.g., to the gel time). The partially cured compositions were transferred to a 40 millimeter-diameter die and the die was placed in a hot die press. The samples were cured by increasing the temperature to 150°C under pressure (1 ton). Once the temperature reaches 150°C, the sample was then cooled to 70°C and the die was transferred to an oven and the sample was cured at 200°C for 120 minutes under vacuum.
• compositions were characterized using the following testing procedures.
• Nuclear Magnetic Resonance (NMR) Spectroscopy Analysis The chemical structure and composition of the oligomers were determined by NMR analysis. All 1 H NMR spectra were acquired on a Varian Mercury Plus 400 instrument operating at an observe frequency of 400.14 MHz.
• Solution Viscosity Measurements DV2+ pro Brookfield viscometer equipped with an UL adaptor for low viscosity materials was used. The measurements were conducted to determine the solution viscosity of the 50 wt.% oligomers in MEK using spindle 00 at 25 °C controlled by a water jacket.
• DSC Differential scanning calorimetry
• the heat of exotherm and extent of cure were also determined using DSC with a temperature ramp from 25°C to 300°C at a 10°C/min temperature ramp. All sample weights were in the range of 8 to 11 milligrams.
• the extent of cure was determined by the ratio of the heat of exotherm from the uncured composition and partially cured (B -stage) composition.
• Viscosity measurements (referred to as “resin flow” in the tables that follow) were carried out using an Ares G2 Rheometer from TA Instruments under a nitrogen atmosphere using 25 mm parallel plates with a target gap of 1 mm. An oscillation temperature ramp was used with a starting temperature of 80°C and a ramp rate of 3°C/minute with a constant strain of 1% and an angular frequency of 10 Rad/s.
• TGA Thermal gravimetric analysis
• Dielectric measurements were conducted using an Agilent Technologies E5071C network analyzer equipped with split post dielectric resonator (SPDR) fixture for the measurements of dielectric constant (Dk) and dissipation factor (Df) at 10 GHz.
• SPDR split post dielectric resonator
• Dk dielectric constant
• Df dissipation factor
• Moisture absorption was characterized by placing castings in a water bath at 50°C. Samples were removed from the bath, damp dried, and weights were measured every 24 hours.
• PPE-CMP-2MA was prepared according to the above-described synthesis.
• the structure of the PPE-CMP-2MA was confirmed by solution NMR spectroscopy. 1 H NMR spectroscopy also confirmed that the end groups of the oligomer were methacrylate units resulting in a bi-functional oligomer with an average functionality of 2.
• Curable compositions were prepared according to Table 3. The rheological and curing behavior of the formulations was measured following solvent removal. Performance of the cured materials are also shown in Table 3. The performance of the composition comprising the oligomer of Example 1 was compared to a bifunctional PPE-methacrylate oligomer comprising repeating units derived from 2,6-dimethylphenol (shown as Comparative Example 1).
• CP-PPE oligomers were synthesized according to the following procedure for comparison to the CMP-PPE oligomers described above. Toluene (168 grams), CP (49 grams), TMBPA (6.40 grams), DMBA (1.68 grams), DBA (0.56 grams), and a mixture of 0.088 grams DBEDA, 0.047 grams PTC-1, and 0.15 grams toluene were charged to a 500 milliliter bubbling polymerization vessel and stirred under nitrogen. Catalyst solution (0.42 grams; 0.03 grams Cu 2 0 and 0.39 grams (48%) HBr) was added to the above reaction mixture. After the addition of catalyst solution, oxygen flow was started.
• the temperature was ramped from 25°C to 39.4°C in 15 minutes, and at 70 minutes it was increased to 48.9°C.
• Oxygen flow was maintained for 130 minutes, at which point the flow was stopped, and 1.0 grams NTA and 6.0 grams water were added to the reaction mixture.
• the resulting mixture was stirred at 60°C for 2 hours.
• the layers were separated by centrifugation and the light phase was isolated by precipitation into methanol.
• the precipitated particles were filtered and analyzed after drying in a vacuum oven at 110°C under nitrogen overnight.
• CP-PPE oligomers were characterized by 1 H and 31 P NMR spectroscopy.
• 31 P-NMR spectroscopy was used for the identification and quantification of phenolic functionality in various polymer samples.
• This technique involves the derivatization of the polymer phenolic residues with 2-chloro-l,3,2-dioxaphospholane. This reaction produces a variety of structurally similar 2-aryloxy-l,3,2-dioxaphospholanes differing only in aromatic ring substitution.
• various phenolic endgroups can be identified from 31 P-chemical shifts of their corresponding phosphate derivatives.
• this method can also quantify alcohol and acidic functionalities in many resins. Through the use of the internal standard, 2,4-dibromophenol, quantification of the hydroxyl end-group functionality of polymeric resins can be determined.
• the decoupler was gated off during the pulse delay to eliminate NOE and to ensure complete relaxation of phosphorus nuclei between scans.
• Acquisition parameters included a pulse delay of 3s and a 45° flip angle.
• a 23.6 kHz spectral width (100 to 200 ppm region) and 32 K data points resulted in a 1.39s acquisition time.
• 1024 scans were required for adequate signal-to-noise.
• Broadband proton decoupling was carried out using the Waltz- 16 pulse sequence.
• CP-PPE cyclohexyl phenol and tetramethyl bisphenol A copolymer
• a linear bifunctional phenylene ether oligomer comprising repeating units derived from 2-methyl-6-cyclohexylphenol and having (meth) acrylate end groups.
• Aspect 2 The bifunctional phenylene ether oligomer of aspect 1, wherein the phenylene ether oligomer comprises less than 30 weight percent of repeating units derived from a monohydric phenol having identical substituents in the 2- and 6- positions.
• Aspect 3 The phenylene ether oligomer of aspect 1 or 2, wherein the repeating units derived from 2-methyl-6-cyclohexylphenol are of the structure
• Aspect 4 The phenylene ether oligomer of any of aspects 1 to 3, wherein the phenylene ether oligomer is of the structure wherein R is methyl or hydeogen; x and y are independently 0 to 30, provided that the sum of x and y is at least 2; each occurrence of R 1 , R 2 , R 3 , and R 4 independently comprises hydrogen, halogen, unsubstituted or substituted C ⁇ -n primary or secondary hydrocarbyl, C ⁇ -n hydrocarbylthio, Ci-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; z is 0 or 1; Y has a structure comprising wherein each occurrence of R 7 independently comprises hydrogen and Ci-12 hydrocarbyl, and each occurrence of R 8 and R 9 is each independently hydrogen, Ci-12 hydrocarbyl, or C 1-6 hydrocarbylene wherein R 8
• Aspect 5 A method of making the linear bifunctional phenylene ether oligomer of any of aspects 1 to 4, the method comprising oxidatively polymerizing 2-methyl-6-cyclohexyl phenol in the presence of a catalyst to provide a phenylene ether oligomer; and reacting the phenylene ether oligomer with a (meth)acrylate-containing compound to provide the linear bifunctional phenylene ether oligomer.
• Aspect 6 The method of aspect 5, wherein the oxidatively polymerizing is further in the presence of a bisphenol, preferably tetramethyl bisphenol A.
• a curable thermosetting composition comprising the linear bifunctional phenylene ether oligomer of any of aspects 1 to 4.
• Aspect 8 The curable thermosetting composition of aspect 7, further comprising one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.
• Aspect 9 The curable thermosetting composition of aspect 7 or 8, further comprising one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.
• Aspect 10 A cured thermoset composition, comprising a cured product of the curable thermosetting composition of any one or more of aspects 7 to 9, preferably wherein the thermoset composition has a glass transition temperature of greater than or equal to 165°C, preferably greater than or equal to 170°C, more preferably 165 to 180°C, as determined using differential scanning calorimetry; wherein the thermoset composition has a dielectric constant of less than 3.0, preferably less than 2.75, more preferably less than 2.6 at a frequency of 10 GHz; and wherein the thermoset composition has a dissipation factor of less than 0.01, or less than 0.005 at a frequency of 10 GHz.
• Aspect 12 An article comprising the cured thermoset composition of aspect 10, preferably wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof; or wherein the article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.
• a varnish composition comprising the curable thermosetting composition of any one of aspects 7 to 9; and a solvent.
• Aspect 14 An article manufactured from the varnish composition of aspect 13, preferably wherein the article is a fiber, a layer, a coating, a cast article, a prepreg, a composite, a laminate, or a metal clad laminate.
• Aspect 15 A method for the manufacture of the article of aspect 14, comprising impregnating the varnish composition into a substrate to form a prepreg; and curing the varnish composition.
• test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
• hydrocarbyl refers to a residue that contains only carbon and hydrogen.
• the residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
• the hydrocarbyl residue when described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
• the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue.
• alkyl means a branched or straight chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n- pentyl, s-pentyl, and n- and s-hexyl.
• Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
• Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH 2 -) or, propylene (-(CH 2 ) 3 -)).
• Cycloalky lene means a divalent cyclic alkylene group, -C n th n-x , wherein x is the number of hydrogens replaced by cyclization(s).
• Cycloalkenyl means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
• Aryl means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.
• Arylene means a divalent aryl group.
• hetero means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.
• a heteroatom e.g., 1, 2, or 3 heteroatom(s)

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