Capped poly(arylene ether) composition and process
View Patent ↗A thermoset composition exhibiting reduced water absorption in the cured state includes an olefinically unsaturated monomer and a capped poly(arylene ether) prepared by the reaction of an uncapped poly(arylene ether) with an anhydride capping agent. The capped poly(arylene ether) is isolated and/or purified by methods that reduce the concentrations of polar impurities that contribute to water absorption by the cured composition.
1. A curable composition, comprising:
a capped poly(arylene ether) prepared by the reaction of an uncapped poly(arylene ether) with an anhydride capping agent; wherein the uncapped poly(arylene ether) comprises poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether-co-2,3,6-trimethyl-1,4-phenylene ether), or a mixture thereof; and wherein preparing the capped poly(arylene ether) further comprises precipitating the capped poly(arylene ether) by adding a solution of the poly(arylene ether) to isopropanol; and
an olefinically unsaturated monomer;
wherein the composition after curing absorbs less than 1 weight percent water after 7 days at 85° C. and 85% relative humidity.
2. The curable composition of claim 1 , wherein the composition comprises less than 50 parts per million by weight of the anhydride capping agent, based on the weight of the capped poly(arylene ether).
3. The curable composition of claim 2 , wherein the composition comprises less than 1 weight percent. based on the weight of the capped poly(arylene ether), of a free acid obtained on hydrolysis of the anhydride capping agent.
4. The curable composition of claim 2 , wherein the reaction of the uncapped poly(arylcne ether) with the anhydride capping agent is performed in the presence of an organic amine catalyst, and wherein the composition comprises less than 1,000 parts per million by weight of the organic amine catalyst, based on the weight of the capped poly(arylene ether).
5. The curable composition of claim 4 , wherein the organic amine catalyst comprises a tertiary alkylmmine, a tertiary mixed alkyl-aryl amine, or a heterocyclic amine.
6. The curable composition of claim 4 , wherein the organic amine catalyst comprises a 4-dialkylaminopyridine having the structure
wherein R 23 and R 24 are each independently hydrogen or C 1 –C 6 alkyl,and R 25 and R 26 are each independently C 1 –C 6 alkyl.
7. The curable composition of claim 4 , wherein the organic amine catalyst comprises 4-dimethylaminopyridine.
8. The curable composition of claim 1 , wherein the capped poly(arylene ether) comprises at least one capping group having the structure
wherein each occurence of R 6 –R 8 is independently selected from hydrogen, C 1–C 18 hydrocarbyl, C 2 –C 12 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, and thiocarboxylic acid.
9. The curable composition of claim 1 , wherein the capped poly(arylene ether) comprises a metbacrylate-capped poly(2,6-dlmethyl-1,4-phenylene ether).
10. The curable composition of claim 1 , comprising about 5 to about 90 parts by weight of the capped poly(arylene ether) per 100 parts by weight total of the capped poly(arylene ether) and the olefinically unsaturated monomer.
11. The curable composition of claim 1 , wherein the uncapped poly(arylenc ether) further comprises an uncapped poly(arylene ether) comprising repeating structural units having the formula
wherein for each structural unit, R 1 and R 3 are each independently selected from hydrogen halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C2–C 12 alkynyl, C 1 –C 12 aminoalkyl, C 1 –C 12 hydroxyalkyl, phenyl, C 1 –C 12 haloalkyl, C 1 –C 12 hydrocarbyloxy, and C 2 –C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and for each structural unit, R 2 and R 4 are each independently selected from halogen, primary or secondary C 1 –C 12 allyl, C 2 –C 12 alkenyl, C 2 –C 12 alkynyl, C 1 –C 12 aminoalkyl, C 1 –C 12 hydroxyalkyl, phenyl, C 1 –C 2 haloalkyl, C 1 –C 12 hydrocarbyloxy, and C 2 –C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms.
12. The curable composition of claim 1 , wherein the anhydride capping agent has the structure
wherein each occurrence of V is independently selected from
wherein R 5 is C 1 –C 12 hydrocarbyl optionally substituted with one or two carboxylic acid groups; R 6 –R 8 are each independently hydrogen, C 1–C 18 hydrocarbyl optionally substituted with one or two carboxylic acid groups, C 2 –C 18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; and R 9 –R 13 are each independently hydrogen, halogen, C 1 –C 12 alkyl, hydroxy, amino, or carboxylie acid.
13. The curable composition of claim 1 , wherein the anhydride capping agent has the structure
wherein each occurrence of R 5 –R 8 is independently selected from hydrogen, C 1 –C 18 hydrocarbyl, C 2 –C 12 hydrocarbyloxycarboflyl, nitrile, forniyl, carboxylic acid, imidate, and thiocarboxylic acid.
14. The curable composition of claIm 1 , wherein the anhydride capping agent comprises acrylic mnhydride, moth acrylic mnhydride, or a mixture thereof.
15. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises an alkenyl aromatic monomer, an aflylie monomer, an acryloyl monomer, or a mixture thereof.
16. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises an ulkenyl rain antic monomer having the formula
wherein each occurrence of R 16 is independently hydrogen or C 1 –C 18 hydrocarbyl; each occurrence of R 17 is independently halogen. C 1 –C 12 alkyl, C 1 –C 12 alkoxyl, or C 6 –C 18 aryl; p is 1 to 4; and q is 0 to 5.
17. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises an alkenyl aromatic monomer selected from styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, 1,3 -divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, styrenes having from 1 to 5 halogen substituents on the aromatic ring, and combinations thereof.
18. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises styrene.
19. The curable composition of claIm 1 , wherein the olefinically unsaturated monomer comprises an allylic monomer selected from diallyl phthalate, diallyl isophthalate, triallyl mellitate, triallyl mesate, triallyl benzenes, triallyl cyanucrate, triallyl isocyanurate, mixtures thereof, and partial polymerization products prepared therefrom.
20. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises an acryloyl monomer comprising least one acryloyl moiety having the structure
wherein R 20 –R 22 are each independently selected from hydrogen, C 1 –C 12 hydrocarbyl, C 2 –C 18 hydrocarbyloxycarbonyl, nitric, forinyt carboxylic acid, jirildate, and thiocarboxylic acid.
21. The curable composition of claim 20 , wherein the acryloyl monomer comprises at least two acryloyl moieties.
22. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises an acryloyl monomer selected from trimethylolpropane poly(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)aerylate, 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)acrylatc, isobomyl (meth)acrylate, methyl (meth)acrylate, methacryloxypropyl trimethoxysilane, ethoxylated (2) bisphenol A di(meth)acrylate, and mixtures thereof.
23. The curable composition of claIm 1 , comprising about 10 to about 95 parts by weight of the olefmically unsaturated monomer per 100 parts by weight total of the capped poly(arylene ether) and the olefinically unsaturated monomer.
24. The curable composition of claim 1 , further comprising about 5 to about 95 weight percent of a particulate filler, based on the total weight of the composition.
25. The curable composition of claim 24 , wherein the particulate filler amount is about 75 to about 95 weight percent, based on the total weight of the composition.
26. The curable composition of claim 24 , wherein the particulate filler is fused silica.
27. The curable composition of claim 1 , further comprising a curing catalyst.
28. The curable composition of claim 27 , wherein the curing catalyst is selected from 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, 2,5dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butylperoxide, t-butylcumyl peroxide, αα-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di(t-butylperoxy) isophthalate, t-butylperoxy benzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilyl peroxide, and mixtures thereof.
29. The curable composition of claim 1 , further comprising a curing inhibitor.
30. The curable composition of claim 1 , further comprising an additive selected from 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.
31. A cured composition comprising the reaction products obtained on curing the curable composition of claim 1 .
32. An article comprising the cured composition of claim 31 .
33. A curable composition comprising:
a capped poly(arylonc ether) prepared by the reaction of an uncapped poly(arylene ether) with an anhydride capping agent; wherein the uncapped poly(arylene ether) comprises poly(2.6-dimethyl-1,4-phenylene ether), poly(2,6-dimethyl-1,4-phenylene ether-co-2,3,6-trimethyl-1,4-phenylene ether), or a mixture thereof; and wherein preparing the capped poly(arylene ether) futher comprises precipitating the capped poly(arylene ether) by adding a solution of the poly(arylene ether) to isopropanol;
an oleflnlcaXly unsaturated monomer; and
a curing inhibitor; wherein the curing inhibitor is selected from diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensates, N,N′-dibutyl-o-phenylenediamine, N-butyl-p-aminophenol, p-methoxyphenol, 2,4,6-triphenylphenoxyl, pyrogallol, catechol, hydroquinone, monoalkylhydroquinones, t-butylhydroquinone, C 1 –C 6 -alkyl-substituted catechols, t-butyleatechol, dialkylhydroquinones, 2,4,6-dichloronitrpphenol, halogen-ortho-nitrophenols, alkoxyhydroquinones, mono- and di- and polysulfides of phenols and catechols, thiols, oximes and hydrazones of quinone, phenothiazine, dialkylhydroxylamines, poly(arylene ether)s having free hydroxyl groups, and combinations thereof;
wherein the composition after curing absorbs less than 1 weight percent water after 7 days at 85° C. and 85 percent relative humidity.
34. A curable composition, comprising:
about 1 to about 23 weight percent of a methacrylate-capped poly(2,6dimethyl-1,4-phenylene ether) prepared by the reaction of an uncapped poly(2,6dimethyl -1,4-phenylene ether) with methacrylic anhydride; wherein the methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) is isolated by a procedure comprising precipitation with isopropanol;
about 1 to about 23 weight percent of an acryloyl monomer comprising at least two acryloyl moieties;
about 1 to about 23 weight percent of an alkenyl aromatic monomer selected from styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, styrenes having from 1 to 5 halogen substituents on the aromatic ring, and combinations thereof; and
about 75 to about 95 weight percent of fused silica;
wherein all weight percents are based on the total weight of the composition; and
wherein the composition after curing absorbs less than 0.2 weight percent water after 7 days at 85° C. and 85 percent relative humidity.
35. The curable composition of claim 34 , wherein the alkenyl aromatic monomer comprises styrene and the acryloyl monomer comprises trimethylolpropane trimethacrylate or ethoxylated (2) bisphenol A dimethacrylate.
36. A cured composition comprising the reaction products obtained on curing the curable composition of claim 34 .
37. An article comprising the cured composition of claim 36 .