Flame retardant polyamide composition, method, and article
View Patent ↗A composition is prepared by melt blending specific amounts of a polyamide, a flame retardant that includes brominated polystyrene, a polymeric flame retardant synergist, and a compatibilizing agent. The polymeric flame retardant synergist can be a poly(arylene ether), a poly(arylene ether)-polysiloxane block copolymer, or a mixture thereof. The composition is useful for molding automotive and electrical parts.
1. A composition comprising the product of melt blending:
about 30 to about 60 weight percent of a polyamide;
a flame retardant comprising about 10 to about 25 weight percent brominated polystyrene; and
about 5 to about 30 weight percent of a polymeric flame retardant synergist selected from the group consisting of mixtures of poly(arylene ether)s and poly(arylene ether)-polysiloxane block copolymers; and wherein the poly(arylene ether)-polysiloxane block copolymer is the product of a process comprising oxidatively copolymerizing a monomer mixture comprising a monohydric phenol and a hydroxyaryl-terminated polysiloxane;
wherein at least 80 weight percent of the hydroxyaryl-terminated polysiloxane in the monomer mixture is incorporated into the poly(arylene ether)-polysiloxane block copolymer;
wherein the composition comprises less than or equal to 0.1 weight percent of any polymer other than the polyamide, the brominated polystyrene, and the polymeric flame retardant synergist; and
wherein all weight percent are based on the total weight of the composition.
2. The composition of claim 1 , wherein the brominated polystyrene comprises an average of about 2 to about 4 bromine atoms per phenyl ring and less than or equal to 5 mole percent bromination of aliphatic carbon atoms.
3. The composition of claim 1 , wherein the monomer mixture comprises about 90 to about 99 parts by weight of the monohydric phenol and about 1 to about 10 parts by weight of the hydroxyaryl-terminated polysiloxane, based on the total weight of the monohydric phenol and the hydroxyaryl terminated polysiloxane.
4. The composition of claim 1 , wherein the hydroxyaryl-terminated polysiloxane comprises a hydroxyaryl-diterminated polysiloxane comprising
a plurality of repeating units having the structure
wherein each occurrence of R 7 is independently hydrogen, C 1 -C 12 hydrocarbyl or C 1 -C 12 halohydrocarbyl; and
two terminal units having the structure
wherein Y is hydrogen, C 1 -C 12 hydrocarbyl, C 1 -C 12 hydrocarbyloxy, or halogen, and wherein each occurrence of R 8 is independently hydrogen, C 1 -C 12 hydrocarbyl or C 1 -C 12 halohydrocarbyl.
5. The composition of claim 1 , wherein the monohydric phenol comprises 2,6-dimethylphenol, and the hydroxyaryl terminated polysiloxane has the structure
wherein n is, on average, about 5 to about 100.
6. The composition of claim 1 , comprising about 10 to about 25 weight percent of the poly(arylene ether)-polysiloxane block copolymer.
7. The composition of claim 1 , wherein the poly(arylene ether)-polysiloxane block copolymer provides about 0.5 to about 2 weight percent polysiloxane to the composition.
8. The composition of claim 1 , comprising less than or equal to 0.05 weight percent free polysiloxane.
9. The composition of claim 1 , further comprising about 2 to about 40 weight percent glass fibers.
10. The composition of claim 1 , further comprising about 5 to about 15 weight percent glass fibers.
11. The composition of claim 1 , further comprising about 20 to about 40 weight percent glass fibers.
12. The composition of claim 1 , wherein the polymeric flame retardant synergist is halogen free.
13. The composition of claim 1 , wherein the flame retardant further comprises about 1 to about 10 weight percent antimony trioxide.
14. The composition of claim 1 , further comprising the product of melt blending about 0.1 to about 1 weight percent of a compatibilizing agent with the polyamide, the brominated polystyrene, and the polymeric flame retardant synergist; wherein the compatibilizing agent is selected from the group consisting of quinones, organosilane compounds, maleic acid, maleic anhydride, fumaric acid, glycidyl acrylate, itaconic acid, aconitic acid, maleimide, maleic hydrazide, dichloro maleic anhydride, maleic acid amide, acrylic acid, butenoic acid, methacrylic acid, pentenoic acid, decenoic acids, undecenoic acids, dodecenoic acids, linoleic acid, crotyl alcohol, methyl vinyl carbinol, 4-pentene-1-ol, 1,4-hexadiene-3-ol, 3-butene-1,4-diol, 2,5-diol, and combinations thereof.
15. The composition of claim 1 ,
wherein the composition comprises the product of melt blending
about 30 to about 40 weight percent of the polyamide,
about 15 to about 30 weight percent of the flame retardant, and
about 12 to about 25 weight percent of the polymeric flame retardant synergist;
wherein the polyamide comprises polyamide-6,6;
wherein the flame retardant comprises about 12 to about 25 weight percent of the brominated polystyrene;
wherein the flame retardant further comprises about 3 to about 8 weight percent of antimony trioxide; and
wherein the composition further comprises about 20 to about 30 weight percent glass fibers.
16. The composition of claim 1 , exhibiting a flame retardancy rating of V-1 or V-0 at a thickness of 3 millimeters, measured according to Underwriter's Laboratory Bulletin 94, “Tests for Flammability of Plastic Materials, UL 94”, Vertical Burning Flame Test.
17. The composition of claim 1 , exhibiting a flame retardancy rating of V-1 or V-0 at a thickness of 2 millimeters, measured according to Underwriter's Laboratory Bulletin 94, “Tests for Flammability of Plastic Materials, UL 94”, Vertical Burning Flame Test.
18. The composition of claim 1 , exhibiting a flame retardancy rating of V-1 or V-0 at a thickness of 1 millimeter, measured according to Underwriter's Laboratory Bulletin 94, “Tests for Flammability of Plastic Materials, UL 94”, Vertical Burning Flame Test.
19. The composition of claim 1 ,
wherein the composition comprises the product of melt blending
about 35 to about 45 weight percent of the polyamide,
about 15 to about 25 weight percent of the flame retardant, and
about 10 to about 20 weight percent of the polymeric flame retardant synergist;
wherein the polyamide comprises polyamide-6,6;
wherein the flame retardant comprises about 15 to about 25 weight percent of the brominated polystyrene;
wherein the flame retardant further comprises less than or equal to 1 weight percent of antimony trioxide; and
wherein the composition further comprises about 20 to about 30 weight percent glass fibers.
20. An article comprising the composition of claim 1 .
21. The composition of claim 1 , wherein at least 95 weight percent of the hydroxyaryl-terminated polysiloxane is incorporated into the poly(arylene ether)-polysiloxane block copolymer.
22. A method of forming a composition, comprising:
melt blending
about 30 to about 60 weight percent of a polyamide,
a flame retardant comprising about 10 to about 25 weight percent brominated polystyrene, and
about 5 to about 30 weight percent of a polymeric flame retardant synergist selected from the group consisting of mixtures of poly(arylene ether)s and poly(arylene ether)-polysiloxane block copolymers to form a composition;
wherein the poly(arylene ether)-polysiloxane block copolymer is the product of a process comprising oxidatively copolymerizing a monomer mixture comprising a monohydric phenol and a hydroxyaryl-terminated polysiloxane;
wherein at least 80 weight percent of the hydroxyaryl-terminated polysiloxane in the monomer mixture is incorporated into the poly(arylene ether)-polysiloxane block copolymer;
wherein the composition comprises less than or equal to 0.1 weight percent of any polymer other than the polyamide, the brominated polystyrene, and the polymeric flame retardant synergist; and
wherein all weight percent are based on the total weight of the composition.
23. The method of claim 22 , further comprising melt blending about 0.1 to about 1 weight percent of a compatibilizing agent with the polyamide, the brominated polystyrene, and the polymeric flame retardant synergist; wherein the compatibilizing agent is selected from the group consisting of quinones, organosilane compounds, maleic acid, maleic anhydride, fumaric acid, glycidyl acrylate, itaconic acid, aconitic acid, maleimide, maleic hydrazide, dichloro maleic anhydride, maleic acid amide, acrylic acid, butenoic acid, methacrylic acid, pentenoic acid, decenoic acids, undecenoic acids, dodecenoic acids, linoleic acid, crotyl alcohol, methyl vinyl carbinol, 4-pentene-1-ol, 1,4-hexadiene-3-ol, 3-butene-1,4-diol, 2,5-dimethyl-3-hexene-2,5-diol, and combinations thereof.
24. The method of claim 23 , wherein the polymeric flame retardant synergist and the compatibilizing agent are melt blended with each other prior to melt blending with the polyamide and the brominated polystyrene.
25. The method of claim 23 , wherein the polyamide and the flame retardant are melt blended with each other prior to melt blending with the polymeric flame retardant synergist and the compatibilizing agent.
26. The method of claim 22 , wherein at least 95 weight percent of the hydroxyaryl-terminated polysiloxane is incorporated into the poly(arylene ether)-polysiloxane block copolymer.