WO2008033612A1 - Composition de poly(arylène éther), procédé et article - Google Patents

Composition de poly(arylène éther), procédé et article Download PDF

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Publication number
WO2008033612A1
WO2008033612A1 PCT/US2007/074436 US2007074436W WO2008033612A1 WO 2008033612 A1 WO2008033612 A1 WO 2008033612A1 US 2007074436 W US2007074436 W US 2007074436W WO 2008033612 A1 WO2008033612 A1 WO 2008033612A1
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Prior art keywords
arylene ether
curable composition
meth
bifunctional poly
weight
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PCT/US2007/074436
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English (en)
Inventor
Hua Guo
Edward N. Peters
Christina Louise Braidwood
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Sabic Innovative Plastics Ip B.V.
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Publication date
Priority claimed from US11/532,153 external-priority patent/US20080071034A1/en
Priority claimed from US11/532,164 external-priority patent/US20080071000A1/en
Application filed by Sabic Innovative Plastics Ip B.V. filed Critical Sabic Innovative Plastics Ip B.V.
Priority to JP2009528366A priority Critical patent/JP5237284B2/ja
Priority to CN2007800342488A priority patent/CN101516937B/zh
Priority to KR1020097005442A priority patent/KR101412865B1/ko
Publication of WO2008033612A1 publication Critical patent/WO2008033612A1/fr

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    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
    • 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
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
    • C08F283/085—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides on to unsaturated polyphenylene oxides
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • 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

Definitions

  • Circuit boards are used in virtually every electronic device today from computer equipment to cell phones to electronic toys and even watches. As the use of circuit boards has increased, their performance requirements also increased including better toughness, higher temperature resistance and better signal-to-noise ratios.
  • Circuit boards are commonly manufactured by coating a cloth made of glass fibers with a liquid resin that wets the cloth. Chemicals called hardeners or curing agents are added to the liquid resin to begin chemical reactions that convert the liquid resin into a solid. This chemical conversion is often referred to as curing.
  • the glass cloth that contains the liquid resin is often partially cured and is referred to a "prepreg" describing the preimpregnation of the glass cloth with the liquid resin.
  • prepreg During the manufacture of circuit boards, several layers of prepreg are often combined under pressure and allowed to fully cure into a solid circuit board.
  • Vinyl resins are one example of commonly used curable liquid resins in such processes.
  • the cured vinyl resins are generally too brittle and have insufficient heat resistance to be used in some circuit board applications.
  • the addition of various poly(arylene ether)s, for example poly(arylene ether)s terminally functionalized with polymerizable carbon-carbon double bonds, into vinyl resins has been proposed as a way to reduce their brittleness in circuit boards.
  • U.S. Patent No. 6,352,782 to Yeager et al. describes a resin composition comprising (1) a reactively end-capped poly(phenylene ether), and (2) a curable unsaturated monomer composition.
  • thermosetting composition comprising a capped poly(arylene ether), an alkenyl aromatic monomer, and an acryloyl monomer.
  • preparation of the curable compositions in the absence of added solvent requires heating to a temperature of about 80 to 14O 0 C. See U.S. 6,352,782 at col. 16, lines 42-45; and U.S. 6,627,704 at col. 28, lines 60-64.
  • a curable composition comprising: a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; and an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl
  • the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of at least 10 weight percent for at least seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; and wherein the curable composition has a viscosity less than or equal to 2000 centipoise at 23 0 C.
  • Another embodiment is a curable composition, consisting of: a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl; optionally, a filler; optionally, a crosslinker selected from the group consisting of divinylbenzenes, diallylbenzenes, trivinylbenzenes, triallylbenzenes, divinyl phthalates, diallyl phthalates, triallyl mesate, triallyl mesitate, ethoxylated bisphenol A dimethacrylates, and mixtures thereof; optionally, a curing initiator, a curing inhibitor, or a combination thereof; and optionally, an additive selected from the group consisting of dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, and combinations thereof; wherein
  • Another embodiment is a curable composition
  • a curable composition comprising: about 30 to about 90 parts by weight of a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C, wherein the bifunctional poly(arylene ether) has the structure
  • each occurrence of x is independently 1 to about 20; and about 10 to about 70 parts by weight of an alkyl styrene selected from the group consisting of 2- methylstyrene, 4-methylstyrene, 2-tert-butylstyrene, 4-tert-butylstyrene, and mixtures thereof; wherein the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of about 30 to about 60 weight percent for seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; and wherein the curable composition has a viscosity of about 50 to about 600 centipoise at 23 0 C; wherein all parts by weight are based on 100 parts by weight total of the bifunctional poly(arylene ether) and the alkyl styrene.
  • an alkyl styrene selected from the
  • Another embodiment is a curable composition, consisting of: about 30 to about 90 parts by weight of a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C, wherein the bifunctional poly(arylene ether) has the structure
  • each occurrence of x is independently 1 to about 20; and about 10 to about 70 parts by weight of an alkyl styrene selected from the group consisting of 2- methylstyrene, 4-methylstyrene, 2-tert-butylstyrene, 4-tert-butylstyrene, and mixtures thereof; optionally, about 2 to about 95 weight percent of a filler, based on the total weight of the composition; optionally, about 4 to about 16 parts by weight of divinylbenzene; optionally, a curing initiator, a curing inhibitor, or a combination thereof; and optionally, an additive selected from the group consisting of dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-re
  • Another embodiment is a curable composition, comprising: about 40 to about 70 parts by weight of a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.12 deciliter per gram, measured in chloroform at 25 0 C, wherein the bifunctional poly(arylene ether) has the structure
  • each occurrence of x is independently 1 to about 20; and about 30 to about 60 parts by weight of an alkyl styrene selected from the group consisting of 2-methylstyrene, 4-methylstyrene, 2-te/t-butylstyrene, 4-te/t-butylstyrene, and mixtures thereof; wherein the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of about 30 to about 60 weight percent for seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; and wherein the curable composition has a viscosity of about 50 to about 600 centipoise at 23 0 C; wherein all parts by weight are based on 100 parts by weight total of the bifunctional poly(arylene ether) and the alkyl styrene.
  • an alkyl styrene
  • Another embodiment is a curable composition, consisting of: about 40 to about 70 parts by weight of a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.12 deciliter per gram, measured in chloroform at 25 0 C, wherein the bifunctional poly(arylene ether) has the structure
  • each occurrence of x is independently 1 to about 20; about 30 to about 60 parts by weight of an alkyl styrene selected from the group consisting of 2- methylstyrene, 4-methylstyrene, 2-tert-butylstyrene, 4-tert-butylstyrene, and mixtures thereof; optionally, about 2 to about 95 weight percent of a filler, based on the total weight of the composition; optionally, about 4 to about 16 parts by weight of divinylbenzene; optionally, a curing initiator, a curing inhibitor, or a combination thereof; and optionally, an additive selected from the group consisting of dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relie
  • Another embodiment is a curable composition
  • a curable composition comprising: a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl; and glass beads having a density less than or equal to 0.5 gram per milliliter and an isostatic crush strength of at least 10 megapascals, wherein 95 volume percent of beads have a diameter less than or equal to 200 micrometers; wherein the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of at least 10 weight percent for seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; wherein the curable composition in the absence of the glass beads has a viscosity less than or equal to 2000 centipoise at 23 0 C; and wherein the composition after curing has a density less than or equal to 0.9 gram per milliliter at
  • Another embodiment is a method of preparing a curable composition, comprising: blending a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; and an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl
  • the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of at least 10 weight percent for at least seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; and wherein the curable composition has a viscosity less than or equal to 2000 centipoise at 23 0 C.
  • the present inventors have conducted research on curable poly(arylene ether) compositions with more convenient processing characteristics and improved thermal, physical, and dielectric properties in the cured state.
  • the present inventors have discovered that the use of particular alkyl styrene compounds in combination with particular low molecular weight bifunctional poly(arylene ether)s allows the formulation of curable compositions that exhibit substantially improved properties relative to prior art compositions.
  • the curable compositions described here exhibit markedly improved solubility of the bifunctional poly(arylene ether) in the composition, which allows solvent-free preparation and processing of the composition at substantially lower temperatures than those used in the prior art.
  • the curable compositions exhibit solubility and viscosity properties that allow them to be stored and handled at room temperature without phase separation of the bifunctional poly(arylene ether).
  • the compositions also exhibit an excellent balance of impact resistance, heat resistance, and dielectric properties after curing.
  • one embodiment is a curable composition, comprising: a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; and an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl
  • the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of at least 10 weight percent for at least seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; and wherein the curable composition has a viscosity less than or equal to 2000 centipoise at 23 0 C.
  • the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of at least 10 weight percent for at least seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene.
  • the bifunctional poly(arylene ether) solubility is at least 20 weight percent, or at least 30 weight percent, or at least 40 weight percent, or at least 50 weight percent.
  • the bifunctional poly(arylene ether) solubility is up to about 80 weight percent, or up to about 70 weight percent, or up to about 60 weight percent. A specific procedure for conducting the solubility test is described in the working examples below.
  • the bifunctional poly(arylene ether) remains soluble in the alkyl styrene for seven days, or fourteen days, or one month, or even three months at 23 0 C.
  • the curable composition has a viscosity less than or equal to 2000 centipoise at 23 0 C. In some embodiments, the curable composition has viscosity of at least about 10 centipoise, or at least about 20 centipoise, or at least about 50 centipoise. In some embodiments, the curable composition has viscosity less than or equal to 1000 centipoise, or less than or equal to 800 centipoise, or less than or equal to 600 centipoise.
  • the curable composition comprises a bifunctional poly(arylene ether).
  • bifunctional means that the molecule has two polymerizable groups selected from aliphatic carbon-carbon double bonds and aliphatic carbon-carbon triple bonds.
  • poly(arylene ether) resin the term “bifunctional” means that the resin comprises, on average, 1.6 to 2.4 of such polymerizable groups per poly(arylene ether) molecule.
  • the bifunctional poly(arylene ether) comprises, on average, 1.8 to 2.2 of such polymerizable groups per poly(arylene ether) molecule.
  • nuclear magnetic resonance spectroscopy can be used to determine whether a poly(arylene ether) is bifunctional.
  • the bifunctional poly(arylene ether) has an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C. Within this range, the intrinsic viscosity may be at least about 0.06 deciliter per gram. Also within this range, the intrinsic viscosity may be up to about 0.15 deciliter per gram, or up to about 0.12 deciliter per gram. In some embodiments, the bifunctional poly(arylene ether) has an intrinsic viscosity of about 0.06 deciliter per gram. In some embodiments, the bifunctional poly(arylene ether) has an intrinsic viscosity of about 0.09 deciliter per gram.
  • the bifunctional poly(arylene ether) has the structure
  • each occurrence of Q 1 is independently halogen, unsubstituted or substituted C1-C12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
  • each occurrence of Q 2 is independently hydrogen, halogen, unsubstituted or substituted Ci -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
  • each occurrence of x is independently 1 to about 100;
  • each occurrence of R 1 is independently C 1
  • each occurrence of R 5 and R 6 is independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted Ci -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, Ci -C 12 hydrocarbylthio, C1-C12 hydrocarbyloxy, and C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; z is 0 or 1; and Y has a structure selected from the group consisting of
  • each occurrence of R is independently selected from the group consisting of hydrogen and C 1 -C 12 hydrocarbyl
  • each occurrence of R 8 and R 9 is independently selected from the group consisting of hydrogen, Ci-Ci 2 hydrocarbyl (including, for example, C 3 -Cs cycloalkyl and phenyl), and Ci-C 6 hydrocarbylene wherein R 8 and R 9 collectively form a C 4 -C 12 alkylene group.
  • the term "hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term refers to a residue that contains only carbon and hydrogen.
  • the residue may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
  • the hydrocarbyl residue when so stated however, may contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically noted as containing such heteroatoms, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it may contain heteroatoms within the backbone of the hydrocarbyl residue.
  • the bifunctional poly(arylene ether) has the structure
  • each occurrence of R 10 and R 11 and R 12 and R 13 is independently hydrogen, C 1 -C 12 hydrocarbyl or C 1 -C 12 halohydrocarbyl; wherein each occurrence of m is independently 0, 1, 2, 3, 4, 5, or 6; and wherein each occurrence of Y 1 and Y 2 and Y 3 and Y 4 is independently hydrogen, C 1 -C 12 hydrocarbyl, C 1 -C 12 hydrocarbyloxy, or halogen; and wherein n is 5 to about 200.
  • Q 1 is methyl
  • each occurrence of Q 2 is independently hydrogen or methyl.
  • n is 0, R 3 and R 4 are hydrogen, and each occurrence of R 2 is independently hydrogen or methyl.
  • Y 1 is methoxy
  • Y 2 and Y 3 and Y 4 are hydrogen
  • m is 3
  • n is 5 to about 50
  • R 6 , R 7 , R 8 , and R 9 are methyl.
  • the bifunctional poly(arylene ether) has the structure
  • the bifunctional poly(arylene ether) has the structure
  • the bifunctional poly(arylene ether) may be produced by a process comprising oxidative copolymerization of a monohydric phenol and a dihydric phenol, followed by capping of the phenolic hydroxy groups by reaction with an unsaturated acid anhydride such as acrylic anhydride or methacrylic anhydride.
  • Suitable monohydric phenols include, for example, 2,6-dimethylphenol, 2,3,6- trimethylphenol, and mixtures thereof.
  • Suitable dihydric phenols include, for example, 3 ,3 ' ,5 ,5 ' -tetramethyl-4,4 ' -biphenol, 2,2-bis(3-methyl-4- hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, l,l-bis(4- hydroxyphenyl)methane, 1 , 1 -bis(4-hydroxyphenyl)ethane, 2,2-bis(4- hydroxyphenyl)propane 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)octane, 1 , 1 -bis(4-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)- n-butane, bis(4-hydroxyphenyl)phenylmethane, 1 , 1 -bis(4-hydroxy-3 - methylphenyl)cyclohexane
  • the monohydric phenol is 2,6-dimethylphenol
  • the dihydric phenol is 2,2-bis(3,5- dimethyl-4-hydroxyphenyl)propane.
  • the monohydric phenol is 2,6-dimethylphenol
  • the dihydric phenol is selected from 2,2-bis(3-methyl-4- hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cycloheptane, 1 , 1 -bis(4- hydroxy-3,5-dimethylphenyl)cycloheptane, and mixtures thereof.
  • Procedures for capping poly(arylene ether)s with reactive groups are known in the art. One example of such a procedure is the reaction of the uncapped poly(arylene ether) with methacrylic anhydride in the presence of 4-(N,N-dimethylamino)pyridine as catalyst.
  • the curable composition comprises an alkyl styrene having the structure
  • Ci-C 6 primary or tertiary alkyl Suitable Ci-C 6 primary or tertiary alkyl groups include, for example, methyl, ethyl, 1 -propyl (n-propyl), 1,1-dimethylethyl (tert-butyi), 1-methylcyclopropyl, 2 -methyl- 1 -butyl, 3-methyl-l -butyl, 2-methyl-2- butyl, 2,2-dimethyl-l -propyl (neopentyl), 1-methylcyclobutyl, 1,2- dimethylcyclopropyl, 1-hexyl, 2-methyl-l-pentyl, 3 -methyl- 1-pentyl, 4-methyl-l- pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-l -butyl, 3,3-dimethyl-l-butyl, 2,3-dimethyl- 1-butyl, 2,3-dimethyl-2-butyl, 1,
  • the alkyl styrene is 3-methylstyrene, 4-methylstyrene, 3-tert- butylstyrene, 4-tert-butylstyrene, or a mixture thereof. In some embodiments, the alkyl styrene is 3-methylstyrene, 4-methylstyrene, or a mixture thereof. In some embodiments, the alkyl styrene is 4-methylstyrene. In some embodiments, the alkyl styrene is 3-tert-butylstyrene, 4-tert-butylstyrene, or a mixture thereof. In some embodiments, the alkyl styrene is 4-te/t-butylstyrene.
  • the composition may comprise the bifunctional poly(arylene ether) and the alkyl styrene in widely varying amounts.
  • the composition comprises about 1 to about 90 parts by weight of the bifunctional poly(arylene ether) and about 10 to about 99 parts by weight of the alkyl styrene, based on 100 parts by weight total of the bifunctional poly(arylene ether) and the alkyl styrene.
  • the bifunctional poly(arylene ether) amount may be at least about 10 parts by weight, or at least 20 parts by weight, or at least about 30 parts by weight, or at least about 40 parts by weight.
  • the bifunctional poly(arylene ether) amount may be up to about 80 parts by weight, or up to about 70 parts by weight, or up to about 60 parts by weight.
  • the alkyl styrene amount may be at least about 20 parts by weight, or at least about 30 parts by weight, or at least about 40 parts by weight.
  • the alkyl styrene amount may be up to about 90 parts by weight, or up to about 80 parts by weight, or up to about 70 parts by weight, or up to about 60 parts by weight.
  • the curable composition may, optionally, further comprise styrene.
  • the styrene may be used in an amount of about 1 to about 99 parts by weight based on 100 parts by weight of the alkyl styrene.
  • the curable composition may, optionally, further comprise a crosslinker.
  • a crosslinker is defined as a compound comprising at least two polymerizable groups selected from carbon-carbon double bonds, carbon-carbon triple bonds, and combinations thereof.
  • the crosslinker comprises at least three polymerizable groups, or at least four polymerizable groups, or at least five polymerizable groups.
  • Suitable crosslinkers include, for example, divinylbenzenes, diallylbenzenes, trivinylbenzenes, triallylbenzenes, divinyl phthalates, diallyl phthalates, triallyl mesate, triallyl mesitate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, isobornyl (meth)acrylate, methyl (meth)acryl
  • the crosslinker is divinylbenzene.
  • the composition is free of (meth)acrylate crosslinkers, where "(meth)acrylate” includes acrylate, methacrylate, and combinations thereof.
  • the curable composition as a whole is free of polymerizable groups such as acrylate and methacrylate, where an aliphatic carbon-carbon double bond and a carbonyl group are covalently linked by a single bond.
  • the crosslinker may be used in an amount of about 1 to about 50 parts by weight, based on 100 parts by weight total of the bifunctional poly(arylene ether) and the alkyl styrene. Within this range, the crosslinker amount may be at least about 3 parts by weight, or at least about 6 parts by weight. Also within this range, the crosslinker amount may be up to about 40 parts by weight, or up to about 30 parts by weight.
  • the curable composition may, optionally, further comprise a curing initiator, a curing inhibitor, or a combination thereof.
  • curing initiators include those described in U.S. Patent Nos. 5,407,972 to Smith et al., 5,218,030 to Katayose et al., and 7,067,595 to Zarnoch et al.
  • the curing initiator may include any compound capable of producing free radicals at elevated temperatures.
  • Such curing initiators may include both peroxy and non-peroxy based radical initiators.
  • peroxy initiators examples include, for example, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t- butyl peroctoate, 2,5-dimethylhexane-2,5-dihydroperoxide,
  • Suitable non-peroxy initiators include, for example, 2,3-dimethyl-2,3-diphenylbutane, 2,3-trimethylsilyloxy-2,3-diphenylbutane, and the like, and mixtures thereof.
  • the curing initiator may further include any compound capable of initiating anionic polymerization of the unsaturated components.
  • Such anionic polymerization initiators include, for example, alkali metal amides such as sodium amide (NaNH 2 ) and lithium diethyl amide (LiN(C 2 Hs) 2 ), alkali metal and ammonium salts of C 1 -C 10 alkoxides, alkali metal hydroxides, ammonium hydroxides, alkali metal cyanides, organometallic compounds such as the alkyl lithium compound n-butyl lithium, Grignard reagents such as phenyl magnesium bromide, and the like, and combinations thereof.
  • the curing initiator may comprise t-butylperoxy benzoate or dicumyl peroxide.
  • the curing initiator may promote curing at a temperature in a range of about O 0 C to about 200 0 C.
  • the curing initiator is typically used in an amount of about 0.005 to about 1 part by weight per 100 parts by weight total of bifunctional poly(arylene ether) and alkyl styrene.
  • Suitable curing inhibitors include, for example, diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensates, N,N'-dibutyl-o-phenylenediamine, N-butyl-p-aminophenol, 2,4,6- triphenylphenoxyl, pyrogallol, catechol, hydroquinone, monoalkylhydroquinones, p- methoxyphenol, t-butylhydroquinone, Ci-C ⁇ -alkyl-substituted catechols (such as 4-te/t-butylcatechol), dialkylhydroquinone, 2,4,6-dichloronitrophenol, halogen-ortho- nitrophenols, alkoxyhydroquinones, mono- and di- and polysulfides of phenols and catechols, thiols,
  • Suitable curing inhibitors further include poly(arylene ether)s having free hydroxyl groups.
  • the curing inhibitor amount may be about 0.001 to about 10 parts by weight per 100 parts by weight total of bifunctional poly(arylene ether) and alkyl styrene.
  • the curable composition may, optionally, further comprise an inorganic filler.
  • suitable inorganic fillers include, for example, alumina, silica (including fused silica and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, glass fibers, glass mat, and the like, and combinations thereof.
  • the inorganic filler may be used in an amount of about 2 to about 95 weight percent, based on the total weight of the curable composition.
  • the curable composition comprises less than 50 weight percent filler, or less than 30 weight percent filler, or less than 10 weight percent filler.
  • the curable composition is free of inorganic filler (that is, no inorganic filler is intentionally added).
  • composition may, optionally, further comprise one or more additives such as, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, and combinations thereof.
  • additives such as, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, and combinations thereof.
  • One embodiment is a curable composition, consisting of: a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl; optionally, a filler; optionally, a crosslinker selected from the group consisting of divinylbenzenes, diallylbenzenes, trivinylbenzenes, triallylbenzenes, divinyl phthalates, diallyl phthalates, triallyl mesate, triallyl mesitate, ethoxylated bisphenol A dimethacrylates, and mixtures thereof; optionally, a curing initiator, a curing inhibitor, or a combination thereof; and optionally, an additive selected from the group consisting of dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, and combinations thereof; wherein
  • One embodiment is a curable composition
  • a curable composition comprising: about 30 to about 90 parts by weight of a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C, wherein the bifunctional poly(arylene ether) has the structure
  • each occurrence of x is independently 1 to about 20; and about 10 to about 70 parts by weight of an alkyl styrene selected from the group consisting of 2- methylstyrene, 4-methylstyrene, 2-tert-butylstyrene, 4-tert-butylstyrene, and mixtures thereof; wherein the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of about 30 to about 60 weight percent for seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; wherein the curable composition has a viscosity of about 50 to about 600 centipoise at 23 0 C; wherein all parts by weight are based on 100 parts by weight total of the bifunctional poly(arylene ether) and the alkyl styrene.
  • an alkyl styrene selected from the group
  • One embodiment is a curable composition, consisting of: about 30 to about 90 parts by weight of a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C, wherein the bifunctional poly(arylene ether) has the structure
  • each occurrence of x is independently 1 to about 20; and about 10 to about 70 parts by weight of an alkyl styrene selected from the group consisting of 2- methylstyrene, 4-methylstyrene, 2-tert-butylstyrene, 4-tert-butylstyrene, and mixtures thereof; optionally, about 2 to about 95 weight percent of a filler, based on the total weight of the composition; optionally, about 4 to about 16 parts by weight of divinylbenzene; optionally, a curing initiator, a curing inhibitor, or a combination thereof; and optionally, an additive selected from the group consisting of dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-re
  • the curable composition may be used in the preparation of syntactic foams.
  • a curable composition comprising: a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl; and glass beads having a density less than or equal to 0.5 gram per milliliter and an isostatic crush strength of at least 10 megapascals, wherein 95 volume percent of beads have a diameter less than or equal to 200 micrometers; wherein the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of at least 10 weight percent for seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; and wherein the curable composition in the absence of the glass beads has a viscosity less than or equal to 2000 centipoise at 23 0 C; and wherein the composition after curing has a density less than or equal to 0.9 gram per milliliter at 23 0 C.
  • the density of the glass beads may be less than or equal to 0.4 gram per milliliter, or less than or equal to 0.35 gram per milliliter at 25 0 C.
  • the isostatic crush strength of the glass beads is at least 20 megapascals, or at least 30 megapascals, measured at 25 0 C.
  • 95 volume percent of beads have a diameter less than or equal to 150 micrometers, or less than or equal to 100 micrometers.
  • Suitable glass beads include the hollow glass beads available from 3M as Glass Bubbles D32/4500 having a density of 0.32 gram per milliliter, an isostatic crush strength of 31 megapascals (4,500 pounds per square inch), and 95 volume percent of beads with a diameter less than or equal to 85 micrometers.
  • the composition after curing has a density less than or equal to 0.8 gram per milliliter at 23 0 C.
  • the curable composition can be prepared and handled at temperatures lower than those used for prior art compositions.
  • one embodiment is a method of preparing a curable composition, comprising: blending a bifunctional poly(arylene ether) having an intrinsic viscosity of about 0.03 to about 0.2 deciliter per gram, measured in chloroform at 25 0 C; and an alkyl styrene having the structure
  • R' is Ci-C 6 primary or tertiary alkyl
  • the bifunctional poly(arylene ether) has a solubility in the alkyl styrene of at least 10 weight percent for at least seven days at 23 0 C, wherein the weight percent is based on the total weight of the bifunctional poly(arylene ether) and the alkyl styrene; and wherein the curable composition has a viscosity less than or equal to 2000 centipoise at 23 0 C.
  • blending is conducted at a temperature less than or equal to 7O 0 C, or less than or equal to 6O 0 C, or less than or equal to 5O 0 C, or less than or equal to 4O 0 C, or less than or equal to 3O 0 C. In some embodiments, blending is conducted in the absence of solvent. In some embodiments, the blending is conducted at a temperature less than or equal to 7O 0 C and in the absence of a reactive (polymerizable) solvent comprising an aliphatic carbon-carbon double bond or an aliphatic carbon-carbon triple bond.
  • a solvent is defined as a compound lacking polymerizable functionality and used primarily to facilitate dissolution of the bifunctional poly(arylene ether) in the curable composition.
  • the composition may, for example, be cured thermally or by using irradiation techniques, including radio frequency heating, UV irradiation, and electron beam irradiation.
  • the composition may be cured by initiating chain-reaction curing with 10 seconds of radio frequency heating.
  • the temperature selected may be about 80° to about 300 0 C, and the heating period may be about 5 seconds to about 24 hours.
  • Curing may be conducted in multiple steps using different times and temperatures for each step. For example, curing may be staged to produce a partially cured and often tack-free resin, which then is fully cured by heating for longer periods or at higher temperatures.
  • thermoset arts is capable of determining suitable curing conditions without undue experimentation.
  • the composition may be partially cured.
  • references herein to properties of the "cured composition” or the “composition after curing” generally refer to compositions that are substantially fully cured.
  • One skilled in the thermoplastic arts may determine whether a sample is substantially fully cured without undue experimentation. For example, one may analyze the sample by differential scanning calorimetry to look for an exotherm indicative of additional curing occurring during the analysis. A sample that is substantially fully cured will exhibit little or no exotherm in such an analysis.
  • the invention includes articles comprising the partially or fully cured composition.
  • the heat resistance, impact resistance, and excellent dielectric properties of the composition make it particularly useful for fabricating electronic components.
  • the compositions described herein are also useful in the manufacture of syntactic foams such as those used as insulation materials and various fiber reinforcing applications such as bulk molding compounds and sheet molding compounds.
  • M n number average molecular weight
  • M w weight average molecular weight
  • M w /M n polydispersity
  • the sample solutions were filtered through a Gelman 0.45 micrometer syringe filter before GPC analysis; no additional sample preparation was performed.
  • the injection volume was 50 microliters and the eluent flow rate was set at 1 milliliter/minute.
  • Two Polymer Laboratories GPC columns (Phenogel 5 micron linear(2), 300 x 7.80 millimeters) connected in series were used for separation of the sample.
  • the detection wavelength was set at 280 nanometers.
  • the data were acquired and processed using an Agilent ChemStation with integrated GPC data analysis software. The molecular weight distribution results were calibrated with polystyrene standards. The results are reported without any correction as "M n (AMU)" and "M w (AMU)".
  • the uncapped poly(arylene ether)s were analyzed by proton nuclear magnetic resonance spectroscopy ( 1 H NMR) to determine the concentration of hydroxyl end groups (in parts per million by weight).
  • Values of number average molecular weight were then calculated based on the relative amounts of internal units and total terminal units.
  • Values of hydroxyl end group content were calculated based on the relative amounts of terminal phenolic groups and total terminal and internal units.
  • Values of hydroxyl (OH) group content are expressed in parts per million by weight (ppm), where the hydroxyl groups were assigned a molecular weight of 17 grams per mole. "Functionality” is the average number of hydroxyl groups per molecule of poly(arylene ether). Functionality is calculated according to the formula
  • mol OH-endgroups is the moles of hydroxyl endgroups
  • mol of all endgroups is the moles of all endgroups, which includes hydroxyl endgroups and so- called “tail groups” which in this case are 2,6-dimethylphenyl groups.
  • composition components and amounts are presented in Table 2, where amounts are expressed in parts by weight (pbw).
  • the monofunctional poly(arylene ether) (designated "PPE monofxl. 0.12" in Tables 2 and 3) was a methacrylate-capped poly(2,6-dimethyl-l,4-phenylene ether) resin, prepared by oxidative polymerization of 2,6-dimethylphenol followed by methacrylate capping using methacrylic anhydride; it had an intrinsic viscosity of 0.12 deciliter per gram (dL/g) measured at 25 0 C in chloroform.
  • dL/g deciliter per gram
  • the bifunctional poly(arylene ether)s were prepared by oxidative copolymerization of 2,6-dimethylphenol and 2,2-bis(4- hydroxy-3,5-dimethylphenyl)propane followed by methacrylate capping using methacrylic anhydride. They had intrinsic viscosities of 0.12 dL/g (designated "PPE bifxl. 0.12" in Tables 2 and 3) and 0.09 dL/g (designated "PPE bifxl. 0.09” in Tables 2 and 3).
  • the polymerization inhibitor 4-te/t-butylcatechol was obtained from Aldrich Chemical Co.
  • the alkyl styrene monomers 4-te/t-butylstyrene and 4-methylbutylstyrene were supplied by Deltech Corporation.
  • the crosslinker ethoxylated bisphenol A dimethacrylate was obtained from Sartomer Company under the designation SR-348, and the internal mold release from Stepan Company under the designation Zelec UN.
  • the polymerization initiator 2,5-dimethyl-2,5-di(te/t- butylperoxy)hexane was obtained from Akzo-Nobel under the designation Trigonox 101.
  • compositions were prepared according to the following general procedure.
  • the poly(arylene ether) and 4-te/t-butylcatechol were dissolved in 4-te/t-butylstyrene or 4-methylbutylstyrene at 9O 0 C.
  • the ethoxylated bisphenol A dimethacrylate was added to the mixture, followed by the addition of the internal mold release.
  • the mixture was degassed in a vacuum oven at 100 0 C and 25 inches of mercury vacuum, and then it was poured into the mold that had been preheated to 100 0 C.
  • the filled mold was then placed in an oven at 100 0 C for 90 minutes.
  • the oven temperature was then increased to HO 0 C where it was kept for 60 minutes.
  • the oven temperature was then raised to 15O 0 C where it was kept for another 10 minutes.
  • the oven was subsequently turned off and the mold was allowed to cool to room temperature inside the oven.
  • the cured plaque was removed from the mold and cut into test specimens.
  • the specimen thickness is 3.175 millimeters (1/8 inch).
  • the cutter make is a diamond-wheeled wet saw obtained as 158189 MK- 100 Tile Saw from MK Diamond Products, Inc.
  • the Blade is a MK-225, 25.4 centimeter (10 inch) diameter diamond blade with a thickness of 1.27 millimeters (0.05 inches).
  • the samples were placed on a plastic or wood backing material when cutting.
  • the poly(arylene ether) could be dissolved at 16O 0 C, when the mixture was cooled to below 100 0 C in order to add the peroxide, there was a substantial increase in viscosity that prevented effective mixing and degassing.
  • Density values expressing in grams per milliliter (g/mL), were measured according to ASTM D 792-00 in water. Glass transition temperature values, expressed in degrees centigrade ( 0 C), were measured by differential scanning calorimetry.
  • Heat deflection temperature values were measured automatically according to ASTM D 648-06, Method B, using a 0.45 megapascal force on samples having a width of 1.27 centimeters (0.5 inch) and a depth of 3.175 millimeters (0.125 inch).
  • the immersion medium was silicone fluid. Tests were conducted by heating the immersion medium, initially at a temperature of 23 0 C, at a rate of 2 0 C per minute.
  • Unnotched Izod impact strength values were measured at 23 0 C according to ASTM D 4812-06, using samples having a width of 1.27 centimeters (0.5 inch) and a depth of 3.175 millimeters (0.125 inch). The samples were cut from the molded bars described above. The apparatus used a 0.907 kilogram (2.00 pound) hammer.
  • Notched Izod impact strength values were measured according to ASTM D 256-06, Method A, at 23 0 C using a 0.907 kilogram (2.00 pound) hammer, and specimens having a notch such that at least 1.02 centimeter (0.4 inch) of the original 1.27 centimeter (0.5 inch) depth remained under the notch. The specimens were conditioned for 24 hours at 23 0 C after notching.
  • Dielectric constant (“Dk”) values and dissipation factor (“Df”) values were measured at 23 0 C according to IPC-TM-650-2.5.5.9. Samples were rectangular prisms having dimensions 5 centimeters by 5 centimeters by 3.5 millimeters. Samples were conditioned at 23 0 C and 50% relative humidity for a minimum of 24 hours before testing.
  • the measuring cell was a Hewlett-Packard Impedance Material Analyzer model 4291B and had a width of 27.5 centimeters, a height of 9.5 centimeters, and a depth of 20.5 centimeters.
  • the electrodes were Hewlett-Packard Model 16453 A and had a diameter of 7 millimeters.
  • Measurements were conducted using a capacitance method sweeping a range of frequency when DC voltage was applied to the dielectric materials.
  • the applied voltage was 0.2 millivolt to 1 volt at the frequency range of 1 megahertz to 1 gigahertz.
  • Table 3 provides values for dielectric constants and dissipation factors at frequencies of 100 megahertz, 500 megahertz, and 1 gigahertz.
  • Examples 1-7 and Comparative Examples 1-7 illustrate the effect of poly(arylene ether) type in compositions comprising 4-tert-butylstyrene.
  • the data show that the resins that contain the bifunctional poly(arylene ether) (Examples 1-7) exhibit superior property values, such as higher heat deflection temperatures, and higher unnotched and notched Izod impact strength values, compared to corresponding compositions using the monofunctional poly(arylene ether) (Comparative Examples 1-5).
  • the heat deflection temperatures and the notched and unnotched Izod impact strengths increase with increasing levels of poly(arylene ether).
  • the dielectric constant and dissipation factor decrease with increasing poly(arylene ether) levels.
  • Comparative Examples 6 and 7 could not be made due to viscosity limitations.
  • Examples 8-11 and Comparative Examples 8-11 illustrate the effect of poly(arylene ether) type in compositions comprising 4-methylstyrene.
  • the data show that the resins that contain bifunctional poly(arylene ether) (Examples 8-11) exhibit superior properties, such as higher heat deflection temperatures and higher unnotched and notched Izod impact strengths, compared to Comparative Examples 8 and 9 made using the monofunctional poly(arylene ether).
  • Comparative Examples 10 and 11 could not be made due to viscosity limitations.
  • compositions comprising bifunctional poly(arylene ether) with intrinsic viscosity of 0.06 dL/g, measured at 25 0 C in chloroform, are shown in Table 4.
  • This poly(arylene ether) was prepared by oxidative copolymerization of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane followed by methacrylate capping using methacrylic anhydride.
  • bifunctional poly(arylene ether)/4-te/t-butylstyrene examples have higher ductility, and lower dielectric constants and dissipation factors than the bifunctional poly(arylene ether)/triallyl isocyanurate (TAIC) example (Example 15 versus Comparative Example 13) or the t-butylstyrene/triallyl isocyanurate example (Example 15 versus Comparative Example 14).
  • Examples 16-30 illustrate additional compositions with a bifunctional poly(arylene ether) having an intrinsic viscosity of 0.09 dL/g.
  • Viscosity values for the curable (uncured) compositions were measured using a Brookfield digital Viscometer, Model DV-II, following the procedure in accompanying Manufacturing Operation Manual No: m/85-160-G.
  • Compression strength values and compression modulus values both expressed in megapascals (MPa), were measured for the cured compositions at 23 0 C according to ASTM D4762-04 on samples having dimensions 1.25 centimeters by 1.25 centimeters by 5.08 centimeters.
  • Shore D hardness values were measured for the cured compositions at 23 0 C according to ASTM D2240-05. The data in Table 5 show that glass transition temperature and compression strength values increase with increasing poly(arylene ether) content.
  • a curable composition was prepared by methacrylate-capping a poly(arylene ether) in 4-tert-butylstyrene, then adding additional components.
  • the bifunctional poly(arylene ether) starting material was a copolymer of 2,6- dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane having an intrinsic viscosity of 0.09 dL/g, measured at 25 0 C in chloroform.
  • the curable composition was used to prepare a syntactic foam.
  • the syntactic foam was made by mixing the resin with hollow glass beads. Hollow glass beads having a density of 0.32 gram per milliliter, an isostatic crush strength of 31 megapascals (4,500 pounds per square inch), and 95 volume percent of beads with a diameter less than or equal to 85 micrometers were obtained as Glass Bubbles D32/4500 from 3M.
  • the cured neat resin (without glass beads) had a density of 1.024 grams per milliliter. Syntactic foam with 50 percent by volume glass beads was prepared. Properties of the syntactic foam appear in Table 6.
  • compositions and properties are summarized in Table 7, where the term "vinyl toluene” refers to a mixture of 3-methylstyrene and 4-methylstyrene.

Abstract

L'invention concerne une composition durcissable comprenant un alkylestyrène et un poly(arylène éther) bifonctionnel de bas poids moléculaire. La composition peut être préparée et traitée à des températures sensiblement inférieures à celles des thermodurcis de poly(arylène éther) de l'art antérieur. Après durcissement, la composition présente une équilibre amélioré de résistance à la chaleur, de résistance aux impacts et de propriétés diélectriques, ce qui la rend particulièrement adaptée à la fabrication de composants électroniques.
PCT/US2007/074436 2006-09-15 2007-07-26 Composition de poly(arylène éther), procédé et article WO2008033612A1 (fr)

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JP5237284B2 (ja) 2013-07-17

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