Granted Patent B2

US 7,329,708 · App. 10/920,744 · Granted Feb 12, 2008

Abstract

Claims (70)

1. A curable composition, comprising:

a difunctionalized poly(arylene ether) having an intrinsic viscosity of about 0.05 to about 0.30 deciliter per gram at 25° C.; wherein the difunctionalized poly(arylene ether) has the structure

wherein each occurrence of Q 1 is independently selected from halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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 from the halogen and oxygen atoms; each occurrence of Q 2 is independently selected from hydrogen, halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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; each occurrence of x is independently 1 to about 100; each occurrence of R 2 –R 4 is independently hydrogen of C 1 –C 18 hydrocarbyl; and L has the structure

wherein each occurrence of R 5 and R 6 is independently selected from hydrogen, halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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; z is 0 or 1 ; and Y has a structure

wherein each occurrence of R 8 and R 9 is independently selected from hydrogen and C 1 –C 12 hydrocarbyl;

an olefinically unsaturated monomer; and

a cure inhibitor.

2. The curable composition of claim 1 , wherein the difunctionalized poly(arylene ether) has the structure

wherein Q 1 is methyl; each occurrence of Q 2 is independently hydrogen or methyl; each occurrence of R 2 is independently hydrogen or methyl; R 3 and R 4 are hydrogen; each occurrence of R 5 and R 6 is independently selected from hydrogen, halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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; R 8 and R 9 are independently hydrogen or C 1 –C 6 hydrocarbyl; and each occurrence of x is 1 to about 100.

3. The curable composition of claim 1 , wherein the difunctionalized poly(arylene ether) has the structure

wherein each occurrence of x is 1 to about 100.

4. The curable composition of claim 3 , wherein the difunctionalized poly(arylene ether) is the product of oxidative copolymerization of a monohydric phenol and a dihydric phenol.

5. The curable composition of claim 4 , wherein the monohydric phenol is selected from 2,6-dimethylphenol, 2,3,6-trimethylphenol, and mixtures thereof; and wherein the dihydric phenol is selected from 3,3′,5,5′-tetramethyl-4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane 2,2-bis(4-hydroxyphenyl)butane, 2,2bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-n-butane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-1-methylphenyl)propane, 1,1-bis(4-hydroxy-t-butylphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and mixtures thereof.

6. The curable composition of claim 1 , wherein the difunctionalized poly(arylene ether) has an intrinsic viscosity of about 0.08 to about 0.20 deciliters per gram.

7. The curable composition of claim 1 , wherein the difunctionalized poly(arylene ether) was isolated by devolatilization extrusion.

8. The curable composition of claim 1 , wherein the difunctionalized poly(arylene ether) the difunctionalized poly(arylene ether) has a number average molecular weight of about 1,000 to about 10,000 atomic mass units (AMU), with the provisos that less than 10 weight percent of the difunctionalized poly(arylene ether) has a number average molecular weight less than 500 AMU, and less than 25 weight percent of the difunctionalized poly(arylene ether) has a number average molecular weight less than 1,000 AMU.

9. The curable composition of claim 1 , wherein the difunctionalized poly(arylene ether) has a number average molecular weight of at least 10,000 AMU, with the provisos that less than 2 weight percent of the difunctionalized poly(arylene ether) has a number average molecular weight less than 500 AMU, and less than 5 weight percent of the difunctionalized poly(arylene ether) has a number average molecular weight less than 1,000 AMU.

10. The curable composition of claim 1 , comprising about 5 to about 90 parts by weight of the difunctionalized poly(arylene ether) per 100 parts by weight total of the difunctionalized poly(arylene ether) and the olefinically unsaturated monomer.

11. The curable composition of claim 1 , wherein the olefinically unsaturated monomer is selected from alkenyl aromatic monomers, allylic monomers, acryloyl monomers, vinyl ethers, maleimides, and mixtures thereof.

12. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises an acryloyl monomer having at least two acryloyl moieties.

13. The curable composition of claim 1 , wherein the olefinically unsaturated monomer comprises an acryloyl monomer selected from trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl 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)acrylate, methacryloxypropyl trimethoxysilane, ethoxylated (2) bisphenol A di(meth)acrylate, and mixtures thereof.

14. The curable composition of claim 1 , comprising about 10 to about 95 parts by weight of the olefinically unsaturated monomer per 100 parts by weight total of the difunctionalized poly(arylene ether) and the olefinically unsaturated monomer.

15. The curable composition of claim 1 , further comprising a cure initiator.

16. The curable composition of claim 1 , further comprising an adhesion promoter selected from metal (meth)acrylate salts, combinations of an aromatic epoxy compound and an aromatic amine, copolymers of a vinyl aromatic compound and an α,β-unsaturated cyclic anhydride, partially (meth)acrylated epoxy compounds, and mixtures thereof.

17. The curable composition of claim 16 , wherein the adhesion promoter comprises a styrene-maleic anhydride copolymer.

18. The curable composition of claim 16 , comprising about 0.1 to about 20 parts by weight of the adhesion promoter per 100 parts by weight total of the difunctionalized poly(arylene ether) and the olefinically unsaturated monomer.

19. The curable composition of claim 1 , further comprising about 2 to about 95 weight percent of a filler, based on the total weight of the composition.

20. 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.

21. The curable composition of claim 1 , having a spiral flow of at least about 50 centimeters measured at a temperature in the range of about 130 to about 180° C. and a pressure in the range of about 3 to about 7 megapascals.

22. A cured composition, comprising the reaction products obtained by curing the curable composition of claim 1 .

23. A curable composition, comprising:

a difunctionalized poly(arylene ether) having an intrinsic viscosity of about 0.08 to about 0.25 deciliter per gram at 25° C.; wherein the difunctionalized poly(arylene ether) has the structure

wherein Q 1 is methyl; each occurrence of Q 2 is independently hydrogen or methyl; each occurrence of R 2 is independently hydrogen or methyl; R 3 and R 4 are hydrogen; each occurrence of R 5 and R 6 is independently selected from hydrogen, halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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; R 8 and R 9 are independently hydrogen or C 1 –C 6 hydrocarbyl; and each occurrence of x is 1 to about 100;

an olefinically unsaturated monomer comprising an acryloyl monomer comprising at least two acryloyl moieties;

a cure initiator 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, 2,5-dimethyl-2,5-di(t-butylperoxy)-hex-3-yne, di-t-butylperoxide, t-butylcumyl peroxide, α,α′-bis(t-butylperoxy-m-isopropyl)benzene, 2,5dimethyl-2,5-di(t-butylperoxy)hexane, di(t-butylperoxy) isophthalate, tbutylperoxy 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; and

a curing inhibitor selected from diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensates, N,N′-dibutyl-o-phenylenediamine, N-butyl-p-aminophenol, 2,4,6-triphenyiphenoxyl, pyrogallol, catechol, hydroquinone, monoalkyihydroquinones, p-methoxyphenol, t-butylhydroquinone, C 1 –C 6 -alkyl-substituted catechols, 4-t-butylcatechol, dialkylhydroquinone, 2,4,6-dichloronitrophenol, halogen-ortho-nitrophenols, alkoxyhydroquinones, mono- and di- and polysulfides of phenols and catechols, thiols, oximes and hydrazones of quinone, phenothiazine, dialkylhydroxylamines, and mixtures thereof.

24. A cured composition, comprising the reaction products obtained by curing the curable composition of claim 23 .

25. An article comprising the cured composition of claim 24 .

26. A curable composition, comprising:

about 5 to about 90 parts by weight of a difunctionalized poly(arylene ether) having an intrinsic viscosity of about 0.08 to about 0.20 deciliter per gram at 25° C.; wherein the difunctionalized poly(arylene ether) has the structure

wherein each occurrence of x is 1 to about 50;

about 5 to about 90 parts by weight of an acryloyl monomer selected from trimethyloipropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl 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, isobomyl (meth)acrylate, methyl (meth)acrylate, methacryloxypropyl trimethoxysilane, ethoxylated (2) bisphenol A di(meth)acrylate, and mixtures thereof;

about 0.2 to about 5 part by weight of a curing initiator 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, 2,5-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, 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; and

about 0.005 to about 1 part by weight of a curing inhibitor selected from diazoaminobenzene, phenylacetylene, sym-trinitrobenzene, p-benzoquinone, acetaldehyde, aniline condensates, N,N′-dibutybo-phenylenediamine, N-butyl-p-aminophenol, 2,4,6-triphenyiphenoxyl, pyrogallol, catechol, hydroquinone, monoalkyihydroquinones, p-methoxyphenol, t-butylhydroquinone, C 1 –C 6 -alkyl-substituted catechols, 4-t-butylcatechol, dialkyihydroquinone, 2,4,6-dichioronitrophenol, halogen-ortho-nitrophenols, alkoxyhydroquinones, mono- and di- and polysulfides of phenols and catechols, thiols, oximes and hydrazones of quinone, phenothiazine, dialkylhydroxylamines, and mixtures thereof;

wherein all parts by weight are based on 100 parts by weight total for the difunctionalized poly(arylene ether) and the acryloyl monomer.

27. A cured composition, comprising the reaction products obtained by curing the curable composition of claim 26 .

28. An article comprising the cured composition of claim 27 .

29. A curable composition, comprising:

about 5 to about 90 parts by weight of a difunctionalized poly(arylene ether) having an intrinsic viscosity of about 0.08 to about 0.20 deciliter per gram at 25° C.; wherein the difunctionalized poly(arylene ether) has the structure

wherein each occurrence of x is 1 to about 50, and z is 1;

about 5 to about 90 parts by weight of an acryloyl monomer comprising ethoxylated (2) bisphenol A di(meth)acrylate;

about 0.2 to about 5 part by weight of a curing initiator comprising dicumyl peroxide; and

about 0.005 to about 1 part by weight of a curing inhibitor comprising 4-t-butylcatechol;

wherein all parts by weight are based on 100 parts by weight total for the difunctionalized poly(arylene ether) and the acryloyl monomer.

30. A cured composition, comprising the reaction products obtained by curing the curable composition of claim 29 .

31. An article comprising the cured composition of claim 30 .

32. The article of claim 31 , further comprising a metallic substrate, wherein the article is formed by curing the curable composition in contact with the metallic substrate.

33. A method of forming a curable composition, comprising:

blending

a difunctionalized poly(arylene ether) having an intrinsic viscosity of about 0.05 to about 0.30 deciliter per gram at 25° C., wherein the difunctionalized poly(arylene ether) has the structure

wherein each occurrence of Q 1 is independently selected from halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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; each occurrence of Q 2 is independently selected from hydrogen, halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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; each occurrence of x is independently 1 to about 100; each occurrence of R 1 is C 1 –C 12 hydrocarbylene; each occurrence of n is 0 or 1; each occurrence of R 2 –R 4 is independently hydrogen of C 1 –C 18 hydrocarbyl; and L has the structure

wherein each occurrence of R 5 and R 6 is independently selected from hydrogen, halogen, primary or secondary C 1 –C 12 alkyl, C 2 –C 12 alkenyl, C 2 –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; z is 0 or 1; and Y has the structure

wherein each occurrence of R 8 and R 9 is independently selected from hydrogen and C 1 –C 12 hydrocarbyl;

an olefinically unsaturated monomer, and

a cure inhibitor

to form an intimate blend.

34. The cured composition of claim 22 , exhibiting a flexural strength of at least about 90 megapascals, measured according to ASTM D790.

35. The cured composition of claim 22 , exhibiting a break energy of at least 0.8 joules, measured according to ASTM D790.

36. The cured composition of claim 22 , exhibiting a poly(arylene ether) dispersed phase particle size of about 50 nanometers to about 1 micrometer.

37. An article comprising the cured composition of claim 22 .

Assignments (6)