Poly(arylene ether) compositions and articles
View Patent ↗A curable composition includes a functionalized poly(arylene ether), a vinyl thermoset resin, and a flame retardant composition. The flame retardant composition includes a trihydrocarbylphosphine oxide and a nitrogen-containing flame retardant that may be melamine phosphate, melamine pyrophosphate, or melamine polyphosphate. The combination of the trihydrocarbylphosphine oxide and the nitrogen-containing flame retardant is particularly effective at improving the flame retardancy of the cured composition at relatively low levels of total flame retardant. A method of preparing the curable composition and articles including the cured composition are also described.
1. A curable composition, comprising:
a functionalized poly(arylene ether);
a vinyl thermoset; and
a flame retardant composition consisting of a trihydrocarbylphosphine oxide and a nitrogen-containing flame retardant selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphates, and mixtures thereof.
2. The curable composition of claim 1 , wherein the functionalized poly(arylene ether) is a capped poly(arylene ether) having the structure
wherein each occurrence of Q 1 and Q 2 is independently halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q 3 and Q 4 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; p is 1 to about 100; R 1 is C 1 -C 12 hydrocarbylene; n is 0 or 1; and R 2 and R 3 and R 4 are each independently hydrogen or C 1 -C 18 hydrocarbyl; wherein the capped poly(arylene ether) has an intrinsic viscosity of about 0.03 to about 0.20 deciliter per gram, measured at 25° C. in chloroform.
3. The curable composition of claim 1 , wherein the functionalized poly(arylene ether) is a capped poly(arylene ether) having the structure
wherein Q 5 and Q 6 are each independently methyl or di-n-butylaminomethyl; s is 1 to about 20; and the capped poly(arylene ether) has an intrinsic viscosity of about 0.03 to about 0.20 deciliter per gram, measured at 25° C. in chloroform.
4. The curable composition of claim 1 , wherein the functionalized poly(arylene ether) is a capped poly(arylene ether) having the structure
wherein each occurrence of Q 1 and Q 2 is independently halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q 3 and Q 4 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of x and y is independently 0 to about 100 with the proviso that the sum of x and y is 2 to about 100; each occurrence of R 1 is independently C 1 -C 12 hydrocarbylene; each occurrence of n is independently 0 or 1; each occurrence of R 2 -R 4 is independently hydrogen or C 1 -C 18 hydrocarbyl; and L has the structure
wherein each occurrence of Q 3 is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12 hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12 hydrocarbylthio, C 1 -C 12 hydrocarbyloxy, or C 2 -C 12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; z is 0 or 1; and X 1 has a structure selected from the group consisting of
wherein each occurrence of R 14 is independently selected from the group consisting of hydrogen and C 1 -C 12 hydrocarbyl and each occurrence of R 15 and R 16 is independently selected from the group consisting of hydrogen, C 1 -C 12 hydrocarbyl, and C 1 -C 6 hydrocarbylene wherein R 15 and R 16 collectively form a C 4 -C 12 alkylene group; wherein the capped poly(arylene ether) has an intrinsic viscosity of about 0.03 to about 0.20 deciliter per gram, specifically about 0.06 to about 0.15 deciliter per gram, more specifically about 0.06 to about 0.12 deciliter per gram, even more specifically about 0.06 to about 0.09 deciliter per gram, measured at 25° C. in chloroform.
5. The curable composition of claim 1 , wherein the functionalized poly(arylene ether) is a capped poly(arylene ether) having the structure
wherein each occurrence of Q 5 and Q 6 is independently methyl or di-n-butylaminomethyl; each occurrence of x and y is independently 0 to about 100 with the proviso that the sum of x and y is 2 to about 100.
6. The curable composition of claim 1 , wherein the functionalized poly(arylene ether) is a capped poly(arylene ether) having the structure
wherein U is a C 6 -C 18 aryl group optionally substituted with one or more C 1 -C 6 alkyl groups; V is a phenylene ether group; k is 1 to about 100; r is 1 to 6; W is a phenylene group or an oxygen atom; each occurrence of R 17 , R 18 , and R 19 is independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, and C 2 -C 6 alkynyl; and q is 1, 2, 3, or 4.
7. The curable composition of claim 1 , wherein the functionalized poly(arylene ether) is a ring-functionalized poly(arylene ether) comprising repeating structural units of the formula
wherein each L 1 -L 4 is independently hydrogen, a C 1 -C 12 alkyl group, an alkenyl group, or an alkynyl group; wherein the alkenyl group is represented by
wherein L 5 , L 6 , and L 7 are each independently hydrogen or methyl, and c is 0, 1, 2, 3, or 4; wherein the alkynyl group is represented by
wherein L 8 is hydrogen, methyl, or ethyl, and d is 0, 1, 2, 3, or 4; and wherein about 0.02 mole percent to about 25 mole percent of the total L 1 -L 4 substituents in the ring-functionalized poly(arylene ether) are alkenyl and/or alkynyl groups.
8. The curable composition of claim 1 , wherein the vinyl thermoset is selected from the group consisting of maleimide resins, benzoxazine resins, vinylbenzyl ether resins, alkene-containing monomers alkyne-containing monomers, arylcyclobutene resins, perfluorovinyl ether resins, oligomers and polymers with curable vinyl functionality, and combinations thereof.
9. The curable composition of claim 1 , wherein the vinyl thermoset is triallyl cyanurate, triallyl isocyanurate, or a combination thereof.
10. The curable composition of claim 1 , wherein the vinyl thermoset is triallyl isocyanurate.
11. The curable composition of claim 1 , wherein the trihydrocarbylphosphine oxide has the structure
wherein R 20 , R 21 , and R 22 are each independently C 1 -C 12 hydrocarbyl, with the proviso that the trihydrocarbylphosphine oxide has at least six carbon atoms.
12. The curable composition of claim 1 , wherein the trihydrocarbylphosphine oxide is selected from the group consisting of triphenylphosphine oxide, allyldiphenylphosphine oxide, diallylphenylphosphine oxide, triallylphosphine oxide, bis(1-naphthyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(1-naphthyl)phosphine oxide, tris(4-hydroxyphenyl)phosphine oxide, tris(1-naphthyl)phosphine oxide, tris(2-naphthyl)phosphine oxide, bis(4-phenoxyphenyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(4-phenoxyphenyl)phosphine oxide, tris(4-phenoxyphenyl)phosphine oxide, bis(2,4,5-trimethylphenyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxyphenyl)(2,4,5-trimethylphenyl)phosphine oxide, tris(2,4,5-trimethylphenyl)phosphine oxide, bis(tert-butyl)(4-hydroxyphenyl)phosphine oxide, bis(4-hydroxy-phenyl)(tert-butyl)phosphine oxide, tris(tert-butyl)phosphine oxide, and the like, and combinations thereof.
13. The curable composition of claim 1 , wherein the trihydrocarbylphosphine oxide is triphenylphosphine oxide.
14. The curable composition of claim 1 , wherein the nitrogen-containing flame retardant is melamine pyrophosphate, melamine polyphosphate or a mixture thereof.
15. The curable composition of claim 1 , wherein the nitrogen-containing flame retardant is a melamine polyphosphate.
16. The curable composition of claim 1 , wherein the nitrogen-containing flame retardant is a melamine polyphosphate represented by the formula
wherein g has an average value of greater than 2 to about 500; and the ratio of f to g is about 0.5:1 to about 1.7:1.
17. The curable composition of claim 1 , wherein the nitrogen-containing flame retardant exhibits less than 1 percent weight loss by thermogravimetric analysis when heated from 25° C. to 280° C. at a rate of 20° C. per minute.
18. The curable composition of claim 1 , comprising
about 5 to about 70 parts by weight of the functionalized poly(arylene ether);
about 30 to about 95 parts by weight of the vinyl thermoset; and
about 5 to about 50 parts by weight a flame retardant composition consisting of about 2 to about 48 parts by weight triphenylphosphine oxide, and about 2 to about 48 parts by weight of melamine polyphosphate;
wherein all parts by weight are based on 100 parts by weight total of the functionalized poly(arylene ether) and the vinyl thermoset.
19. A curable composition, consisting of:
a functionalized poly(arylene ether);
a vinyl thermoset;
a flame retardant composition consisting of a trihydrocarbylphosphine oxide and a nitrogen-containing flame retardant;
optionally, a filler;
optionally, a curing initiator, a curing inhibitor, or a combination thereof; and
optionally, an additive selected from the group consisting of 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.
20. A curable composition, comprising:
a capped poly(arylene ether);
triallyl cyanurate, triallyl isocyanurate, or a combination thereof; and
a flame retardant composition consisting of triphenylphosphine oxide and melamine polyphosphate.
21. A curable composition, consisting of:
a capped poly(arylene ether);
triallyl cyanurate, triallyl isocyanurate, or a combination thereof;
a flame retardant composition consisting of triphenylphosphine oxide and melamine polyphosphate;
optionally, a filler;
optionally, a curing initiator, a curing inhibitor, or a combination thereof; and
optionally, an additive selected from the group consisting of 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.
22. A curable composition, comprising:
about 10 to about 60 parts by weight of a methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin having an intrinsic viscosity of about 0.03 to about 0.30 deciliter per gram, measured in chloroform at 25° C.;
about 40 to about 90 parts by weight of triallyl isocyanurate; and
about 10 to about 40 parts by weight a flame retardant composition consisting of about 2 to about 38 parts by weight triphenylphosphine oxide, and about 2 to about 38 parts by weight of melamine polyphosphate;
wherein all parts by weight are based on 100 parts by weight total of the methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin and the triallyl isocyanurate.
23. A curable composition, consisting of:
about 10 to about 60 parts by weight of a methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin having an intrinsic viscosity of about 0.03 to about 0.30 deciliter per gram, measured in chloroform at 25° C.;
about 40 to about 90 parts by weight of triallyl isocyanurate; and
about 10 to about 40 parts by weight a flame retardant composition consisting of about 2 to about 38 parts by weight triphenylphosphine oxide, and about 2 to about 38 parts by weight of melamine polyphosphate;
optionally, up to 900 parts by weight of a filler;
optionally, a curing initiator, a curing inhibitor, or a combination thereof; and
optionally, an additive selected from the group consisting of 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;
wherein all parts by weight are based on 100 parts by weight total of the methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin and the triallyl isocyanurate.
24. A curable composition, comprising:
about 10 to about 60 parts by weight of a methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin having an intrinsic viscosity of about 0.03 to about 0.30 deciliter per gram, measured in chloroform at 25° C.;
about 40 to about 90 parts by weight of triallyl isocyanurate; and
about 15 to about 30 parts by weight a flame retardant composition consisting of about 2 to about 28 parts by weight triphenylphosphine oxide, and about 2 to about 28 parts by weight of melamine polyphosphate;
wherein all parts by weight are based on 100 parts by weight total of the methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin and the triallyl isocyanurate.
25. A curable composition, consisting of:
about 10 to about 60 parts by weight of a methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin having an intrinsic viscosity of about 0.03 to about 0.30 deciliter per gram, measured in chloroform at 25° C.;
about 40 to about 90 parts by weight of triallyl isocyanurate; and
about 15 to about 30 parts by weight a flame retardant composition consisting of about 2 to about 28 parts by weight triphenylphosphine oxide, and about 2 to about 28 parts by weight of melamine polyphosphate;
optionally, up to 900 parts by weight of a filler;
optionally, a curing initiator, a curing inhibitor, or a combination thereof; and
optionally, an additive selected from the group consisting of 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;
wherein all parts by weight are based on 100 parts by weight total of the methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin and the triallyl isocyanurate.
26. A method of preparing a curable composition, comprising:
blending
a functionalized poly(arylene ether);
a vinyl thermoset; and
a flame retardant composition consisting of a trihydrocarbylphosphine oxide and a nitrogen-containing flame retardant selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphates, and mixtures thereof.
27. A cured composition, comprising a reaction product obtained on curing the curable composition of claim 1 .
28. The cured composition of claim 27 , exhibiting a UL 94 Vertical Burning Flame Test rating of V-0.
29. An article comprising the cured composition of claim 27 .
30. A prepreg comprising the cured composition of claim 27 .
31. A circuit board comprising the cured composition of claim 27 .
32. A curable composition, comprising:
19.12 to 22.13 weight percent of a methacrylate-capped poly(2,6-dimethyl-1,4-phenylene ether) resin;
33.38 to 38.64 weight percent of triallyl isocyanurate;
17.78 to 20.58 weight percent of glass fibers; and
a flame retardant composition consisting of
5.88 to 16.02 weight percent triphenylphosphine oxide, and
11.76 to 12.82 weight percent melamine polyphosphate;
wherein all weight percents are based on the total weight of the composition.