Phosphorus containing flame retardants

Patent metadata

Field	Value
Publication number	US-9752011-B2
Application number	US-201514592472-A
Country	US
Kind code	B2
Filing date	Jan 8, 2015
Priority date	Jul 24, 2013
Publication date	Sep 5, 2017
Grant date	Sep 5, 2017

Abstract

Certain phosphonic acid salts heated at temperatures over 200° C. generate thermally stable, highly efficient flame retardant materials well suited for use as flame retardant additives in polymers. Various methods for preparing flame retardant materials from more than one phosphonic acid salts are provided, wherein each method can generate different flame retardant materials from the same mixture of starting phosphonic acids. The flame retardants of the invention can be used as the sole flame retardant in a composition or in combination with other flame retardants, synergists or adjuvants.

First claim

What is claimed:

1. A flame retardant polymer composition prepared by compounding a mixture comprising:
a) a thermoset or thermoplastic polymer,
b) from 1% to 50%, by weight based on the total weight of the flame retardant polymer composition, of a flame retardant material comprising a mixture of compounds of empirical formula (IV)

wherein R is C 1-12 alkyl, C 6-10 aryl, C 7-8 alkylaryl, or C 7-8 arylalkyl, wherein said alkyl, aryl, alkylaryl, or arylalkyl are unsubstituted or are-substituted by halogen, hydroxyl, amino, C 1-4 alkylamino, di-C 1-4 alkylamino, C 1-4 alkoxy, carboxy or C 2-5 alkoxycarbonyl;
M is a metal,
y is a number of from 1 to 4, and
q is 1, 2 or 3, n is 1 or 2, r is 0, 1 or 2 provided that 2(q)+r=n(y) which mixture of compounds comprise more than one R group and/or more than one metal;

wherein the flame retardant material is obtained by a process comprising heating in the absence of other materials at temperatures higher than 200° C. from about 0.01 hour to about 20 hours more than one phosphonic acid salt of formula (I)

wherein R, M and y are as defined above and
M (+) Y is a metal cation where (+)y represents the
charge formally assigned to the cation, and p is a number of from 1 to 4, to form a different chemical species comprising at least one compound of formula (IV), wherein the process for obtaining the flame retardant material comprises:
i) preparing an intermediate salt complex by treating one or more phosphonic acid compound with one or more appropriate metal compound to give an intermediate salt complex corresponding to formula (I) comprising multiple values for R and/or M, and then heating the intermediate salt complex in the absence of other materials at temperatures higher than 200° C. for about 0.01 hour to about 20 hours;
or
ii) preparing an intimate salt mixture by combining two or more individual metal phosphonic acid salts of formula (I) which have differing values for R and/or M, and then heating the intimate salt mixture in the absence of other materials at temperatures higher than 200° C. for about 0.01 hour to about 20 hours;
or
(iii) heating in the absence of other materials at temperatures higher than 200° C. for about 0.01 hour to about 20 hours two or more separate metal phosphonic acid salts of formula (I), which differ by having different values for R and/or M to form individual flame retardant materials that are subsequently mixed together to form a blended flame retardant material,
wherein the phosphonic acid salt of formula (I) is thermally transformed into a different more thermally stable flame retardant material before it is incorporated into the polymer composition.

2. The flame retardant polymer composition according to claim 1 wherein M in formula (I) is selected from Li, K, Na, Mg, Ca, Ba, Zn, Zr, B, Al, Si, Ti, Sn or Sb.

3. The flame retardant polymer composition according to claim 1 wherein in at least one phosphonic acid salt of formula (I), M is Al, Zn or Ca.

4. The flame retardant polymer composition according to claim 1 wherein in formula (I) R is unsubstituted C 1-6 alkyl.

5. The flame retardant polymer composition according to claim 1 wherein in at least one phosphonic acid salt of formula (I) R is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl,.

6. The flame retardant polymer composition according to claim 4 wherein in at least one phosphonic acid salt of formula (I) M is Al, Zn or Ca.

7. The flame retardant polymer composition according to claim 5 wherein in at least one phosphonic acid salt of formula (I) M is Al, Zn or Ca.

8. The flame retardant polymer composition according to claim 5 wherein in each phosphonic acid salt of formula (I) M is Al, Zn or Ca.

9. The flame retardant polymer composition according to claim 7 wherein the flame retardant material b) is obtained by a process comprising first preparing an intermediate salt complex by treating in a single vessel one or more phosphonic acid compound with one or more appropriate metal compound to give an intermediate salt complex corresponding to formula (I) comprising multiple values for R and/or M, and then heating the intermediate salt complex, in the absence of other components, at temperatures higher than 200° C. for about 0.01 hour to about 20 hours.

10. The flame retardant polymer composition according to claim 7 wherein the flame retardant material b) is obtained by a process comprising preparing an intimate salt mixture by combining two or more individual metal phosphonic acid salts of formula (I) having different values for R and/or M, and then heating the intimate salt mixture, in the absence of other components, at temperatures higher than 200° C. for about 0.01 hour to about 20 hours.

11. The flame retardant polymer composition according to claim 5 wherein the flame retardant material b) is obtained by a process comprising heating, in the absence of other components, at temperatures higher than 200° C. from about 0.01 hour to about 20 hours two or more separate metal phosphonic acid salts of formula (I), which differ by having different values for R and/or M to form individual flame retardant materials that are subsequently mixed together to form a blended flame retardant material.

12. The flame retardant polymer composition according to claim 1 wherein the thermoset or thermoplastic polymer comprises one or more of a polyolefin homopolymer, polyolefin copolymer, rubber, epoxy resin, polyester, polyurethane, polysulfone, polyimide, polyphenylene ether, styrenic polymer, styrenic copolymer, polycarbonate, acrylic polymer, polyamide, polyacetal or a blend thereof.

13. The flame retardant polymer composition according to claim 1 wherein the thermoset or thermoplastic polymer comprises one or more of a polyphenylene ether/styrenic resin blend, ABS, polyvinyl chloride/ABS blend, methacrylonitrile containing ABS, α-methylstyrene containing ABS, polyester/ABS, polycarbonate/ABS, impact modified polyester or impact modified polystyrene.

14. The flame retardant polymer composition according to claim 12 wherein the thermoset or thermoplastic polymer comprises one or more of a styrenic polymer, polyolefin, polyalkylene terephthalate, epoxy resin, polycarbonate, polyamide, or polyurethane.

15. The flame retardant polymer composition according to claim 14 wherein the thermoset or thermoplastic polymer further comprises a reinforcing agent.

16. The flame retardant polymer composition according to claim 14 wherein the thermoset or thermoplastic polymer comprises a polyalkylene terephthalate, HIPS, epoxy resin or polyamide, and wherein the thermoset or thermoplastic polymer optionally further comprises a reinforcing agent.

17. The flame retardant polymer composition according to claim 16 wherein the thermoset or thermoplastic polymer comprises polybutylene terephthalate, polyethylene terephthalate, glass filled polybutylene terephthalate, glass filled polyethylene terephthalate, a glass reinforced epoxy resin, a thermoplastic polyamide or a glass filled thermoplastic polyamide.

18. The flame retardant polymer composition according to claim 17 , wherein the polyamide or glass filled polyamide comprises nylon 66.

19. The flame retardant polymer composition according to claim 1

Assignees

• Chemtura Corp
• Lanxess Solutions Us Inc

Inventors

• Stockdale Zachary
• Hanson Mark V
• Timberlake Larry D
• Narayan Subramaniam
• Fielding William R

Classifications

• C08K5/5317 Primary

  Phosphonic compounds, e.g. R—P(:O)(OR')2 · CPC title

• C08K5/0066

  Flame-proofing or flame-retarding additives · CPC title

• C08K2003/329

  Phosphorus containing acids · CPC title

• C08K3/016

  Flame-proofing or flame-retarding additives · CPC title

• C08K5/3495

  condensed with carbocyclic rings · CPC title