POLY (PHENYLENE ETHER) - POLYVINYL THERMOSETTING RESIN

• US 20010053450A1
• Filed: 12/01/1999
• Published: 12/20/2001
• Est. Priority Date: 12/01/1999
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: General Electric Company
• Inventors: YEAGER, GARY W., COLBURN, ROBERT E.
• Granted Patent: US 6,352,782 B2
• Time in Patent Office: Days
• 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; and

(b) a curable unsaturated monomer composition.

2. The composition of

claim 1

, wherein said poly(phenylene ether) of (a) is of the general structure, 1:

Q—

(J—

K)_y 

 

1

wherein Q is the residuum of a phenol;

y ranges from about 1-100,

J comprises recurring units of the following structure, 3;

wherein, for structure 3, R^5-8 independently is selected from hydrogen, alkyl, alkenyl, alkynoyl, aryl, mixed alkyl-aryl hydrocarbons, wherein such groups may contain a substituent selected from carboxylic acid, aldehyde, alcohol, and amino functionality;

K has the following structure;

wherein X is O, S, or two hydrogens, and wherein R^9-11 is a hydrogen or C_1-100 alkyl or aryl or mixed alkyl or aryl group; and

m ranges from 1-200.

3. The composition of

claim 2

, wherein Q is a radical of the following structure, 2:

4. A composition of

claim 2

, wherein K has the following structure:

5. The composition of

claim 1

, wherein the compound containing ethylenic unsaturation is selected from methacrylic anhydride and acrylic anhydride.

6. The composition of

claim 1

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

7. The composition of

claim 1

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

8. The composition of

claim 1

, wherein (b) is one or more of a monofunctional styrenic compound, a monofunctional acrylic compound, a polyfunctional allylic compound, a polyfunctional acrylate, a polyfunctional acrylamide, a polyfunctional styrenic compound, or an unsaturated polymer.

9. The composition of

claim 1

, wherein (b) is a monofunctional styrenic compound.

10. The composition of

claim 1

wherein (b) is comprises a mixture of (I) a mono- unsaturated compound and (II) a poly-unsaturated compound.

11. The composition of

claim 10

, wherein (I) is a styrenic compound and (II) is one or more of a polyfunctional allylic compound, a polyunsaturated polymer, a polyfunctional acrylate compound, a polyfunctional acrylamide, or a polyfunctional styrene compound.

12. The composition of

claim 10

, wherein (I) is selected from the bromostyrene, dibromostyrene, and tribromostyrene.

13. The composition of

claim 11

, wherein (I) is one or more bromostyrene, dibromostyrene, or tribromostyrene.

14. 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.

15. The composition of

claim 14

, 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.

18. The composition of

claim 14

, wherein the fibrous reinforcement is one or more of E-, NE-, S-, T- and D-type glass, or aramid fiber.

19. The composition of

claim 18

, wherein the glass is NE-type glass

20. The composition of

claim 18

, wherein the fibrous reinforcement comprises 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.

21. The composition of

claim 18

, wherein the fibrous reinforcement comprises 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.

22. The composition of

claim 1

, which as been at least partially cured.

23. A laminate of the composition of

claim 22

.

24. The composition of

claim 22

, which is clad with to form a copper clad laminate.

25. The composition of

claim 1

, wherein (I) comprises a methacrylate capped poly(phenylene ether).

26. The composition of

claim 25

, wherein (II) comprises diallylphthalate.

27. The composition of

claim 25

, wherein (II) comprises at least one of t-butylstyrene and methylstyrene.

28. The composition of

claim 25

, wherein (II) comprises at least one of triallylcyanurate and triallylisocyanurate.

29. The composition of

claim 25

, wherein (II) comprises diallylphthalate and at least one of triallylcyanurate and triallylisocyanurate.

30. The composition of

claim 25

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

31. The composition of

claim 25

, wherein at least part of (I) is dispersed as a powder.

32. The composition of

claim 31

, wherein (II) comprises a halogenated styrenic resin.

33. The composition of

claim 32

, further comprising a poly-unsaturated compound.

34. The composition of

claim 31

, wherein the powder has a particle size between about 0.05-300 microns.

35. The composition of

claim 25

, wherein (II) comprises a fluorine containing styrene.

36. The composition of

claim 1

, further comprising carbon fibrils.

16. The composition of 14, wherein the flame retardant is a bromine or phosphorus containing flame retardant.

17. The composition of

claim 16

, 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.

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.

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) a compound or compounds containing one polymerizable carbon-carbon double bond and (b) a compound or compounds containing greater than one polymerizable carbon-carbon double bond.

42. The method of

claim 37

, further comprising carbon fibrils.