Functional phenylene ether oligomer, curable and thermoset compositions prepared therefrom
A functional phenylene ether oligomer of the structure wherein Q 1 , Q 2 , Q 3 , Q 4 , x, y, and R are as defined herein. A curable composition includes the functional phenylene ether oligomer, and a thermoset composition includes a cured product derived from the curable composition.
1. A functional phenylene ether oligomer of the structure
wherein
Q 1 and Q 2 are each independently halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
Q 3 and Q 4 are each independently hydrogen, halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;
Q 5 , Q 6 and Q 7 are each independently halogen, unsubstituted or substituted C 1-12 primary or secondary hydrocarbyl, C 1-12 hydrocarbylthio, C 1-12 hydrocarbyloxy, or C 2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably wherein Q 5 , Q 6 and Q 7 are each methyl;
x and y are each independently 0-30, provided that the sum of x and y is at least 2; and
R is independently at each occurrence a group containing unsaturation, an epoxy, a benzoxazine, an isocyanate, a cyanate ester, a melamine, a cyanophenyl, a maleimide, a phthalonitrile, a cycloalkylphenyl, an ethoxylate, a urethane, an anhydride, or an allylhydroxypropyl.
2. The functional phenylene ether oligomer of claim 1 , wherein each occurrence of R is independently a vinyl benzyl group, an allyl group, a nitrile group, an acrylate group, or a methacrylate group.
3. The functional oligomer of claim 1 , wherein the oligomer has an intrinsic viscosity of 0.04-0.2 deciliter per gram.
4. The functional oligomer of claim 1 , wherein the oligomer has a number average molecular weight of 600-4,500 grams per mole, determined by gel permeation chromatography relative to polystyrene standards in chloroform.
5. The functional phenylene ether oligomer of claim 1 , wherein each occurrence of Q 5 , Q 6 and Q 7 are methyl and the phenylene ether oligomer is of the structure
wherein Q 1 , Q 2 , Q 3 , Q 4 , R, x and y are as defined in claim 1 .
6. The functional phenylene ether oligomer of claim 1 , wherein each occurrence of Q 1 Q 2 , Q 5 , Q 6 and Q 7 are methyl and each occurrence of Q 3 and Q 4 are hydrogen and the phenylene ether oligomer is of the structure
wherein R, x and y are as defined in claim 1 .
7. A method of making the functional phenylene ether oligomer of claim 1 , the method comprising
oxidatively polymerizing a monohydric phenol in the presence of a catalyst and trisubstituted resorcinol to provide a phenylene ether oligomer; and
combining the phenylene ether oligomer with a compound comprising unsaturation, an epoxy, a benzoxazine, an isocyanate, a cyanate ester, a melamine, a cyanophenyl, a maleimide, a phthalonitrile, a cycloalkylphenyl, an ethoxylate, a urethane, an anhydride, or an allylhydroxypropyl to provide the functional phenylene ether oligomer.
8. A curable composition comprising
the functional phenylene ether oligomer of claim 1 ; and
a curing promoter.
9. The curable composition of claim 8 , further comprising an auxiliary curable resin, a curable unsaturated monomer composition, or both.
10. A thermoset composition comprising a cured product of the composition of claim 8 .
11. The thermoset composition of claim 10 , having a glass transition temperature of greater than or equal to 180° C.
12. An article comprising the thermoset composition of claim 10 .
13. The article of claim 12 , wherein the article is 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, or a combination comprising at least one of the foregoing.
14. A method for the manufacture of a thermoset composition, the method comprising curing the curable composition of claim 8 .
15. The method of claim 14 , wherein the curing comprises injecting the curable composition into a mold, and curing the injected composition at 150-250° C. in the mold.