Stabilization of vinyl halide polymers
View Patent ↗The heat and light stability imparted to vinyl halide polymers by metal compounds conventionally employed for this purpose is considerably improved by the presence of a mercapto ester such as 2-mercaptoethyl stearate. The esters can replace a substantial portion of the metal compound with no significant reduction in stability.
1. A method of stabilizing a vinyl halide resin comprising the steps of:
adding to the vinyl halide resin
(a) a metal containing stabilizer corresponding to formula I
RSn(S)(SR″) (I)
in which,
R represents an alkyl group, and
SR″ represents a mercaptide ligand; and
(b) a mercapto alkanol ester of a carboxylic acid which is added to said resin in an amount from about 2 to 25 times the amount of the Sn in said metal containing stabilizer,
wherein said mercapto alkanol ester of a carboxylic acid has the formula:
R a COOR b SH
where R a is a linear or branched alkyl or alkenyl, aryl or aralkyl; and
R b represents a C 2 to C 18 alkylene, and replaces from about 20% to about 90% by weight of the metal containing stabilizer and wherein said composition has a heat or light stability at least comparable to a composition where said mercapto alkanol ester does not replace about 20% to about 90% by weight of the metal containing stabilizer.
2. The method of claim 1 , wherein said mercaptide ligand is a derivative of a carboxylic acid, a polycarboxylic acid, a mercaptan, a mercaptoacid, a mercaptoalcohol, a mercaptoacid ester, or a mercaptoalcohol ester.
3. The method of claim 1 , wherein said mercaptide ligand is an ester of mercaptocarboxylic acid, a 2-mercaptoalkanol ester of a carboxylic acid, a 2-mercaptoalkanol, or an alkyl thiol.
4. The method of claim 1 , where the carboxylic acid is at least one chosen from caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, 2-ethylhexanoic, neodecanoic, oleic, or linoleic.
5. The method of claim 1 , wherein the mercapto alkanol ester of a carboxylic acid is at least one chosen from mercapto ethyl stearate, 3-thio-glyceryl myristate, mercapto ethyl palmitate, mercaptoethyl oleate, or mercapto ethyl myristate.
6. The method of claim 1 , wherein the mercapto alkanol ester of a carboxylic acid is present in the range of 0.01% wt. to 5.0% wt of the vinyl halide resin.
7. The method of claim 1 , wherein the mercapto alkanol ester of a carboxylic acid is present in the range of 0.1% wt. to 1.0% wt. of the vinyl halide resin.
8. The method of claim 1 , wherein the vinyl halide resin is polyvinyl chloride.
9. The method of claim 1 , where the carboxylic acid comprises at least one natural fatty acid present in peanut oil, tall oil, safflower oil, soybean oil, tallow, lanolin, palm oil, or coconut oil.
10. A method of stabilizing a vinyl halide resin comprising the steps of:
adding to the vinyl halide resin (a) a metal containing stabilizer of formula II
R n Sn(SR″) x (II)
in which,
R represents an alkyl group
SR″ represents a mercaptide ligand
n=1 or 2, and
x=4−n, wherein x is an integer; and
(b) a mercapto alkanol ester of a carboxylic acid which is added to said resin in an amount from about 2 to 25 times the amount of the Sn in said metal containing stabilizer,
wherein said mercapto alkanol ester of a carboxylic acid has the formula:
R a COOR b SH
where R a is a linear or branched alkyl or alkenyl, aryl or aralkyl; and
R b represents a C 2 to C 18 alkylene, and replaces from about 20% to about 90% by weight of the metal containing stabilizer and wherein said composition has a heat or light stability at least comparable to a composition where said mercapto alkanol ester does not replace about 20% to about 90% by weight of the metal containing stabilizer.
11. The method of claim 10 , wherein said mercaptide ligand is a derivative of a carboxylic acid, a polycarboxylic acid, a mercaptan, a mercaptoacid, a mercaptoalcohol, a mercaptoacid ester, or a mercaptoalcohol ester.
12. The method of claim 10 , wherein said mercaptide ligand is an ester of mercaptocarboxylic acid, a 2-mercaptoalkanol ester of a carboxylic acid, a 2-mercaptoalkanol, or an alkyl thiol.
13. The method of claim 10 , where the carboxylic acid is at least one chosen from caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, 2-ethylhexanoic, neodecanoic, oleic, or linoleic.
14. The method of claim 10 , wherein the mercapto alkanol ester of a carboxylic acid is at least one chosen from mercapto ethyl stearate, 3-thio-glyceryl myristate, mercapto ethyl palmitate, mercaptoethyl oleate, or mercapto ethyl myristate.
15. The method of claim 10 , wherein the mercapto alkanol ester of a carboxylic acid is present in the range of 0.01% wt. to 5% wt. of the vinyl halide resin.
16. The method of claim 10 , wherein the mercapto alkanol ester of a carboxylic acid is present in the range of 0.1% wt. to 1.0% wt. of the vinyl halide resin.
17. The method of claim 10 , wherein the vinyl halide resin is polyvinyl chloride.
18. The method of claim 10 , where the carboxylic acid comprises at least one natural fatty acid present in peanut oil, tall oil, safflower oil, soybean oil, tallow, lanolin, palm oil, or coconut oil.
19. A method of stabilizing a vinyl halide resin comprising:
adding to the vinyl halide resin
(a) at least two metal containing stabilizers chosen from formulas I, II, and III, wherein
formula I is:
RSn(S)(SR″) (I)
in which,
R represents an alkyl group, and
SR″ represents a mercaptide ligand,
formula II is:
R n Sn(SR′) x (II)
in which,
R represents an alkyl group
SR″ represents a mercaptide ligand,
n=1 or 2, and
x=4−n, wherein x is an integer, and
formula III is:
in which,
A and A 1 represent at least one alkyl of 1 to 12 carbon atoms, where A and A 1 can be the same or different;
A 2 , A 3 , A 4 , and A 5 represent at least one lower alkylene;
D, D 1 , D 2 , and D 3 represent at least one of OH; —(C 6 -C 18 alkyl); or
and
(b) a mercapto alkanol ester of a carboxylic acid having the formula:
R a COOR b SH
where R a is a linear or branched alkyl or alkenyl, aryl or aralkyl; and
R b represents a C 2 to C 18 alkylene, and which is present in an amount by weight from about 2 to about 25 times the amount by weight of the Sn in said metal containing stabilizers.
20. The method of claim 19 , where the carboxylic acid is at least one chosen from caprylic, pelargonic, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic, 2-ethylhexanoic, neodecanoic, oleic, or linoleic.
21. The method of claim 19 , wherein the mercapto alkanol ester of a carboxylic acid is at least one chosen from mercapto ethyl stearate, 3-thio-glyceryl myristate, mercapto ethyl palmitate, mercaptoethyl oleate, or mercapto ethyl myristate.
22. The method of claim 21 , wherein the mercapto alkanol ester of a carboxylic acid is present in the range of 0.01% wt. to 5% wt of the vinyl halide resin.
23. The method of claim 22 , wherein the mercapto alkanol ester of a carboxylic acid is present in the range of 0.1% wt. to 1.0% wt. of the vinyl halide resin.
24. The method of claim 23 , wherein the vinyl halide resin is polyvinyl chloride.
25. The method of claim 19 , where the carboxylic acid comprises at least one natural fatty acid present in peanut oil, tall oil, safflower oil, soybean oil, tallow, lanolin, palm oil, or coconut oil.
26. The method of claim 19 , wherein A and A 1 comprise at least one of methyl, butyl or octyl.
27. The method of claim 19 , wherein at least one of A 2 , A 3 , A 4 , and A 5 is ethylene.
28. The method of claim 19 , wherein said metal containing stabilizer of formula III is:
where
A and A 1 represent methyl, butyl or octyl and can be the same or different, and
ME represents a mercaptoethyl stearate, a mercaptoethyl oleate, or a mercaptoethyl linoleate and can be the same or different.
29. The method of claim 28 , wherein A and A 1 are both butyl and ME is mercaptoethyl oleate.
30. The method of claim 19 , wherein the combination of D and D 1 or the combination of D 2 and D 3 form the group
where m is an integer from 0 to 8.
31. The method of claim 19 , wherein said mercaptide ligand of formulas I and II is a derivative of carboxylic acid, a polycarboxylic acid, a mercaptan, a mercaptoacid, a mercaptoalcohol, a mercaptoacid ester, or a mercaptoalcohol ester.
32. The method of claim 31 , wherein said mercaptide ligand is an ester of mercaptocarboxylic acid, a 2-mercaptoalkanol ester of a carboxylic acid, a 2-mercaptoalkanol, or an alkyl thiol.
33. The method of claim 19 , where R a in formulas I and II contains 6 to 38 carbon atoms.
34. The method of claim 33 , where R a contains 8 to 18 carbon atoms.