Phosphite ester additive compositions
The invention relates to liquid polymer additive compositions comprising blends of phosphite esters selected from the group consisting of aryl phosphites, alkyl phosphites, aryl/alkyl phosphites, bisphenol-A phosphites, dialkylene glycol phosphites and polydialkylene glycol phosphites, pentaerythritol phosphites, p-cumyl phenol phosphites with from 50 to 800 ppm inclusive of zinc per 100 parts resin. The stabilizer is used as either a complete or a partial replacement of toxic-metal containing antioxidant stabilizer additives.
1. A vinyl resin stabilizer additive composition which consists of:
at least two phosphite esters selected from the group consisting of alkyl bisphenol-A phosphites and pentaerythritol phosphites; and
a zinc additive wherein a molar ratio of P/Zn is from about 80:1 to 4:1, and further wherein said additive composition is free of calcium, cadmium, barium and tin; and further wherein
said alkyl bisphenol-A phosphite is of formula (IV)
wherein
R 1 is independently selected from the group consisting of H, C 1-18 alkyl, C 1-18 alkoxy, halogens and
R 3 is C 10-15 alkyl, and
m is an integral value from 0 to 5 inclusive, and wherein
said pentaerythritol phosphite is of formula (VI)
wherein
R 4 is selected from the group consisting of C 8-18 alkyl, C 6-30 aryl, C 6-30 fused aryl rings, C 7-35 alklylaryl, C 7-35 arylalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of halogens, hydroxyl, C 1-4 alkyl and C 1-4 alkoxy.
2. The composition of claim 1 wherein
said ratio is from about 75:1 to 6:1.
3. The composition of claim 2 wherein
said ratio is from about 73:1 to 8:1.
4. The composition of claim 1 wherein a percentage weight loss of said additive composition as measured as a difference between a start and an end weight of said composition as measured after exposure to two hours at 110° C., is less than 1% by weight.
5. The composition of claim 4 wherein a percentage weight loss is less than 0.5% by weight.
6. The composition of claim 1 wherein
a first phosphite ester is C 10-15 alkyl bisphenol-A phosphites of formula (IV)
at least one second phosphite ester is selected from the group consisting of
C 10-15 alkyl bisphenol-A phosphites of formula (IV)
pentaerythritol phosphites of formula (VI)
and wherein R 1 , R 3 and R 4 are as previously defined.
7. The composition of claim 1 wherein said bisphenol-A phosphite ester is selected from the group consisting of
C 12-15 bisphenol-A phosphite of formula (VIII)
C 10 bisphenol-A phosphite of formula (IX)
8. The composition of claim 1 wherein a level of zinc is approximately 50 to 800 ppm zinc per 100 parts resin.
9. The composition of claim 8 wherein said level of zinc is approximately 100 to 500 ppm zinc per 100 parts resin.
10. The composition of claim 9 wherein said level of zinc is approximately 100 to 250 ppm zinc per 100 parts resin.
11. The composition of claim 8 wherein said resin is flexible polyvinyl chloride.
12. A halogenated vinyl resin stabilizer additive composition which consists of:
at least two phosphite esters wherein a first phosphite ester is an alkyl bisphenol-A phosphite of formula (IV)
at least one second phosphite ester which is selected from the group consisting of
alkyl bisphenol-A phosphites of formula (IV)
pentaerythritol phosphites of formula (VI)
and wherein
R 1 is independently selected from the group consisting of H, C 1-18 alkyl, C 1-18 alkoxy, halogens and
R 3 is C 10-15 alkyl, and
R 4 is selected from the group consisting of C 8-18 alkyl, C 6-30 aryl, C 6-30 fused aryl rings, C 7-35 alklylaryl, C 7-35 arylalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of halogens, hydroxyl, C 1-4 alkyl and C 1-4 alkoxy, and
m is an integral value from 0 to 5 inclusive, and
a zinc additive for said additive composition wherein a molar ratio of P/Zn is from about 80:1 to 4:1; and
said additive composition is free of calcium, cadmium, barium and tin.
13. The composition of claim 12 wherein a level of zinc is approximately 50 to 800 ppm zinc per 100 parts resin.
14. The composition of claim 13 wherein said level of zinc is approximately 100 to 500 ppm zinc per 100 parts resin.
15. The composition of claim 14 wherein said level of zinc is approximately 100 to 250 ppm zinc per 100 parts resin.
16. The composition of claim 12 wherein said resin is flexible polyvinyl chloride.
17. An essentially toxic-metal free liquid additive composition for use as at least a partial replacement of toxic metal stabilizer additive compositions for use in vinyl-containing resins, wherein the essentially toxic-free composition consists of:
at least two phosphite esters selected from the group consisting of alkyl bisphenol-A phosphite esters and alkyl substituted derivatives thereof, and pentaerythritol phosphite esters; and
a zinc additive wherein a molar ratio of P/Zn is from about 80:1 to 4:1; and further wherein
said alkyl bisphenol-A phosphite is of formula (IV)
Wherein
R 1 is independently selected from the group consisting of H, C 1-18 alkyl, C 1-18 alkoxy, halogens and
R 3 is C 10-15 alkyl, and
m is an integral value from 0 to 5 inclusive, and
said pentaerythritol phosphite is of formula (VI)
wherein
R 4 is selected from the group consisting of C 8-18 alkyl, C 6-30 aryl, C 6-30 fused aryl rings, C 7-35 alklylaryl, C 7-35 arylalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of halogens, hydroxyl, C 1-4 alkyl and C 1-4 alkoxy.
18. The composition of claim 17 wherein
said ratio is from about 75:1 to 6:1.
19. The composition of claim 18 wherein
said ratio is from about 73:1 to 8:1.
20. The composition of claim 17 wherein a percentage weight loss of said additive composition as measured as a difference between a start and an end weight of said composition as measured after exposure to two hours at 110° C., is less than 1% by weight.
21. The composition of claim 20 wherein a percentage weight loss is less than 0.5% by weight.
22. The composition of claim 17 wherein
a first phosphite ester is C 10-15 alkyl bisphenol-A phosphites of formula (IV)
at least one second phosphite ester is selected from the group consisting of
alkyl bisphenol-A phosphites of formula (IV)
C 8-15 pentaerythritol phosphites of formula (VI)
and wherein R 1 , R 3 and R 4 are as previously defined.
23. The composition of claim 17 wherein said bisphenol-A phosphite ester is selected from the group consisting of
C 12-15 bisphenol-A phosphite of formula (VIII)
C 10 bisphenol-A phosphite of formula (IX)
24. The composition of claim 17 wherein a level of zinc is approximately 50 to 800 ppm zinc per 100 parts resin.
25. The composition of claim 24 wherein said level of zinc is approximately 100 to 500 ppm zinc per 100 parts resin.
26. The composition of claim 25 wherein said level of zinc is approximately 100 to 250 ppm zinc per 100 parts resin.
27. The composition of claim 24 wherein said resin is flexible polyvinyl chloride.
28. An additive composition for polyvinyl chloride resin which consists of:
at least two phosphite esters wherein a first phosphite ester is an alkyl bisphenol-A phosphite ester of formula (IV)
at least one second phosphite ester which is selected from the group consisting of
alkyl bisphenol-A phosphite ester of formula (IV)
pentaerythritol phosphite esters of formula (VI)
and wherein
R 1 is independently selected from the group consisting of H, C 1-18 alkyl, C 1-18 alkoxy, halogens and
R 3 is C 10-15 alkyl, and
R 4 is selected from the group consisting of C 8-18 alkyl, C 6-30 aryl, C 6-30 fused aryl rings, C 7-35 alklylaryl, C 7-35 arylalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of halogens, hydroxyl, C 1-4 alkyl and C 1-4 alkoxy, and
m is an integral value from 0 to 5 inclusive, and
a zinc additive for said additive composition wherein a molar ratio of P/Zn is from about 80:1 to 4:1.
29. The composition of claim 28 wherein a level of zinc is approximately 50 to 800 ppm zinc per 100 parts resin.
30. The composition of claim 29 wherein said level of zinc is approximately 100 to 500 ppm zinc per 100 parts resin.
31. The composition of claim 30 wherein said level of zinc is approximately 100 to 250 ppm zinc per 100 parts resin.
32. The composition of claim 29 wherein said resin is flexible polyvinyl chloride.
33. The composition of claim 28 wherein said at least two phosphite esters are selected from the group consisting of
C 10-15 alkyl bisphenol-A phosphites of formula (IV)
wherein
R 1 is independently selected from the group consisting of H, C 1-18 alkyl, C 1-18 alkoxy, halogens and
R 3 is C 10-15 alkyl, and
m is an integral value from 0 to 5 inclusive, and
pentaerythritol phosphites of formula (VI)
wherein
R 4 is selected from the group consisting of C 8-18 alkyl, C 6-30 aryl, C 6-30 fused aryl rings, C 7-35 alklylaryl, C 7-35 arylalkyl and substituted derivatives thereof wherein the substituents are selected from the group consisting of halogens, hydroxyl, C 1-4 alkyl and C 1-4 alkoxy.
34. The composition of claim 33 wherein a percentage weight loss of said additive composition as measured as a difference between a start and an end weight of said composition as measured after exposure to two hours at 110° C., is less than 1% by weight.
35. The composition of claim 34 wherein a percentage weight loss is less than 0.5% by weight.
36. The composition of claim 33 wherein
a first phosphite ester is C 10-15 alkyl bisphenol-A phosphites of formula (IV)
at least one second phosphite ester is selected from the group consisting of
C 10-15 alkyl bisphenol-A phosphites of formula (IV)
C 8-15 pentaerythritol phosphites of formula (VI)
and wherein R 1 , R 3 and R 4 are as previously defined.
37. The composition of claim 36 wherein said bisphenol-A phosphite ester is selected from the group consisting of
C 12-15 bisphenol-A phosphite of formula (VIII)
C 10 bisphenol-A phosphite of formula (IX)