Poly(phenylene ether)-polyvinyl thermosetting resin

• US 6,352,782 B2
• Filed: 12/01/1999
• Issued: 03/05/2002
• Est. Priority Date: 12/01/1999
• Status: Expired due to Term

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: General Electric Company
• Inventors: Yeager, Gary W., Colborn, Robert E.
• Primary Examiner(s): Short, Patricia A.
• Application Number:
  US09/452,733
• Publication Number:
  US 20010053450A1
• Time in Patent Office: 825 Days
• Field of Search: 525/391, 528/205, 428/458, 428/461, 428/457
• US Class Current: 428/461
• CPC Class Codes: C08G 65/485 Polyphenylene oxides
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/24 Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• CPC Class Codes: C08L 71/126 modified by chemical after-treatment
• CPC Class Codes: H05K 1/0326 containing O
• CPC Class Codes: Y10T 428/31678 Of metal
• CPC Class Codes: Y10T 428/31681 Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
• CPC Class Codes: Y10T 428/31692 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31696 Including polyene monomers [e.g., butadiene, etc.]
• CPC Class Codes: Y10T 428/31699 Ester, halide or nitrile of addition polymer

Abstract

A capped poly(phenylene ether) resin composition is formed from (1) a poly(phenylene ether) compound (PPE) in which at least a portion, preferably substantially all of the hydroxyl groups have been reacted with a compound containing ethylenic unsaturation (carbon-carbon double bonds) which is further reactive with unsaturated monomers (reactively endcapped PPE) and (2) a curable unsaturated monomer composition. The composition optionally contains a polymerization catalyst; a flame-retardant compound; and fibrous reinforcement. The composition can be cured to form a laminate, and clad with copper to form a circuit board.

Claims

1. A curable poly(phenylene ether) composition, which comprises:

(a) a poly(phenylene ether) containing hydroxyl groups that have been capped with a compound containing ethylenic unsaturation;

wherein the poly(phenylene ether) has the structure Q—

(J—

K)y

wherein Q has the structure

wherein X is hydrogen;

R^1-4 are independently hydrogen, C_1-100 alkyl, C_1-100 aryl, or C_1-100 mixed allyl-aryl hydrocarbon; and

n is 1;

wherein J has the structure

wherein R^5-8 are independently hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynoyl, unsubstituted or substituted aryl, or unsubstituted or substituted mixed alkyl-aryl hydrocarbons, wherein substituents may be selected from the group consisting of carboxylic acid, aldehyde, alcohol, and amino; and

m is 1-200;

wherein K has the structure

wherein Z is

and wherein R^9-11 is hydrogen, C_1-100 alkyl, C_1-100 aryl, or C_1-100 mixed alkyl-aryl; and

and wherein y is 1; and

(b) a curable unsaturated monomer composition.

2. The composition of claim 1, wherein the compound containing ethylenic unsaturation is selected from methacrylic anhydride and acrylic anhydride.

3. The composition of claim 1, wherein the number average molecular weight of said poly(phenylene ether) is less than about 5,000 g/mol.

4. The composition of claim 1, wherein the number average molecular weight of said poly(phenylene ether) is less than about 3,000 g/mol.

5. The composition of claim 1, wherein (b) is one or more of a mono functional styrenic compound, a monofunctional acrylic compound, a polyfunctional allylic compound, a polyfunctional acrylate, a polyfunctional acrylamide, or a polyfunctional styrenic compound.

6. The composition of claim 1, wherein (b) is a monofunctional styrenic compound.

7. The composition of claim 1 wherein (b) is comprises a mixture of (I) a mono-unsaturated compound and (II) a poly-unsaturated compound.

8. The composition of claim 7, wherein (I) is a styrenic compound and (II) is one or more of a polyfunctional allylic compound, a polyfunctional acrylate compound, a polyfunctional acrylamide, or a polyfunctional styrene compound.

9. The composition of claim 8, wherein (I) is one or more bromostyrene, dibromostyrene, or tribromostyrene.

10. The composition of claim 7, wherein (I) is selected from the bromostyrene, dibromostyrene, and tribromostyrene.

11. The composition of claim 1, which further comprises one or more of a curing catalyst, a flame retardant, a flame retardant synergist, a fibrous reinforcement, a filler, a thermoset, and a thermoplastic additive.

12. The composition of claim 11, wherein said curing catalyst is one or more of 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butylperoxide, t-butylcumyl peroxide, α

,α

′

-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumylperoxide, di(t-butylperoxy isophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, and trimethylsilylphenyltriphenylsilyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, or 2,3-trimethylsilyloxy-2,3-diphenylbutane.

13. The composition of claim 11, wherein the flame retardant is a bromine or phosphorus containing flame retardant.

14. The composition of claim 13, wherein the bromine or phosphorus containing flame retardant is one or more of 1,3,5-tris(2,4,6-tribromophenoxy)triazine, polybrominated diphenyl ethers, poly(2,6-dibromophenylene ether), brominated polystyrene, brominated cyclododecane, brominated bisphenol-A diglycidyl ether, brominated bisphenol-A hydroxyethyl ether, brominated bisphenol-A diacrylate or dimethacrylate, brominated bisphenol-A ethoxylate diacrylate or dimethacrylate, triphenyl phosphate, tricresyl phosphate, tris(2-allylphenylphosphate), tris(2-methoxy-4-allylphosphate), tris(2-propenylphenyl)phosphate, bis(diphenylphosphate ester)s of bisphenol-A, the bis(diphenyl phosphoramide) of 1,6-hexanediamine or piperidine, or alkylated or substituted derivatives therefrom.

15. The composition of claim 11, comprising a fibrous reinforcement that is one or more of E-, NE-, S-, T- and D-type glass, or aramid fiber.

16. The composition of claim 15, wherein the glass is NE-type glass.

17. The composition of claim 15, comprising a fibrous reinforcement comprising about 12-30 parts Al₂O₃, about 45-70 parts SiO₂, about 0.3-32 parts CaO, and about 2-24 parts B₂O₃, all parts being parts by weight.

18. The composition of claim 15, comprising a fibrous reinforcement comprising about 15-20 parts Al₂O₃, about 50-64 parts SiO₂, about 5-10 parts CaO, and about 15-20 parts B₂O₃, all parts being parts by weight.

19. The composition of claim 1, which as been at least partially cured.

20. A laminate of the composition of claim 19.

21. The composition of claim 19, which is clad with copper foil to form a copper clad laminate.

22. The composition of claim 1, wherein (I) comprises a methacrylate capped poly(phenylene ether).

23. The composition of claim 22, wherein (II) comprises diallylphthalate.

24. The composition of claim 22, wherein (II) comprises at least one of t-butylstyrene and methylstyrene.

25. The composition of claim 22, wherein (II) comprises at least one of triallylcyanurate and triallylisocyanurate.

26. The composition of claim 22, wherein (II) comprises diallylphthalate and at least one of triallylcyanurate and triallylisocyanurate.

27. The composition of claim 22, wherein (II) comprises (a) at least one of t-butylstyrene and methylstyrene and (b) at least one of triallylcyanurate and triallylisocyanurate.

28. The composition of claim 22, wherein at least part of (I) is dispersed as a powder.

29. The composition of claim 28, wherein (II) comprises a halogenated styrene.

30. The composition of claim 29, further comprising a poly-unsaturated compound.

31. The composition of claim 28, wherein the powder has a particle size between about 0.05-300 microns.

32. The composition of claim 22, wherein (II) comprises a fluorine containing styrene.

33. The composition of claim 1, further comprising carbon fibrils.

34. The composition of claim 1, wherein the curable unsaturated monomer composition comprises (1) a monofunctional styrenic compound, and (2) a polyfunctional acrylate compound and/or a polyfunctional polyamide compound.

35. The composition of claim 34, wherein the monofunctional styrenic compound is selected from the group consisting of styrene, methylstyrene, ethylstyrene, isopropylstyrene, tertiary-butylstyrene, phenylstyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, bromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, difluorostyrene, trifluorostyrene, tetrafluorostyrene, pentafluorostyrene, chloromethylstyrene, methoxystyrene, ethoxystyrene, and combinations comprising at least one of the foregoing monofunctional styrenic compounds.

36. The composition of claim 34, wherein the polyfunctional acrylate compound is selected from the group consisting of 1,4-butanediol diglycidylether dimethacrylate, bisphenol A diglycidylether dimethacrylate, neopentylglycol diglycidylether dimethacrylate, neopentylglycol diglycidylether diacrylate, ethylene glycol di(methacrylate), diethylene glycol di(methacrylate), tetraethylene glycol di(meth)acrylate, glycerol di(methacrylate), glycerol tri(methacrylate), 1,3-propylene glycol di(methacrylate), dipropyleneglycol di(methacrylate), 1,4-butanediol di(methacrylate), 1,2,4-butanetriol tri(methacrylate), 1,6-hexanedioldi(methacrylate), 1,4-cyclohexanediol di(methacrylate), 1,4-benzenediol di(methacrylate), pentaerythritoltetra(methacrylate), 1,5-pentanediol di(methacrylate), trimethylolpropane di(meth)acrylate, trimethylolpropane tri(methacrylate), 1,3,5-triacryloylhexahydro-1,3,5-triazine, 2,2-bis(4-(2-acryloxyethoxy)phenyl)propane, 2,2-bis(4-(2-acryloxyethoxy)-3-5-dibromophenyl)propane, 2,2-bis(4-(2-methacryloxy-ethoxy)phenyl)propane, 2,2-bis(4-(2-methacryloxyethoxy)-3-5-dibromophenyl)propane), 2,2-bis((4-acryloxy)phenyl)propane, 2,2-bis((4-methacryloxy)phenyl)propane, 2,2-bis((4-methacryloxy)-3,5-dibromophenyl)propane, 2,2-bis((4-methacryloxy)-3,5-dibromophenyl)propane, and mixtures comprising at least one of the foregoing polyfunctional acrylate compounds;

and wherein the polyfunctional polyamide compound is selected from the group consisting of N,N-bis(beta-hydroxyethyl)methacrylamide, methylenebismethacrylamide, 1,6-hexamethylenebis(methacrylamide), diethylenetriamine tris(methacrylamide), bis(gamma-(methacrylamide)propoxy) ethane, beta-(methacrylamide) ethylacrylate, and mixtures comprising at least one of the foregoing polyfunctional acrylamides.

37. A method for making curable poly(phenylene ether) composition, which comprises:

reacting (a) poly(phenylene ether) containing hydroxyl groups that have been capped with a compound containing ethylenic unsaturation with (b) a curable unsaturated monomer composition capable of reacting with said ethylenically unsaturated compound;

wherein the poly(phenylene ether) has the structure Q—

(J—

K)y

wherein Q has the structure

wherein X is hydrogen;

R^1-4 are independently hydrogen, C_1-100 alkyl, C_1-100 aryl, or C_1-100 mixed alkyl-aryl hydrocarbon; and

n is 1;

wherein J has the structure

wherein R^5-8 are independently hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynoyl, unsubstituted or substituted aryl, or unsubstituted or substituted mixed alkyl-aryl hydrocarbons, wherein substituents may be selected from the group consisting of carboxylic acid, aldehyde, alcohol, and amino; and

m is 1-200;

wherein K has the structure

wherein Z is

and wherein R^9-11 is hydrogen, C_1-100 alkyl, C_1-100 aryl, or C_1-100 mixed alkyl-aryl; and

and wherein y is 1.

38. The method of claim 37, wherein (b) comprises a styrenic compound.

39. The method of claim 37, wherein (b) comprises a brominated styrenic compound.

40. The method of claim 37, wherein (b) comprises a fluorinated styrenic compound.

41. The method of claim 37, wherein (b) comprises a monomer or monomers selected from the group consisting of a compound or compounds containing one polymerizable carbon-carbon double bond, and a compound or compounds containing greater than one polymerizable carbon-carbon double bond.

42. The method of claim 37, further comprising carbon fibrils.