Latent mercaptans as stabilizers for halogen-containing polymer compositions
View Patent ↗Compositions useful as heat stabilizers comprising at least one latent mercaptan-containing compound and at least one zinc compound are provided. Halogen-containing polymer compositions comprising such heat stabilizers are also provided.
1. A polymeric composition comprising
(a) a polymer component susceptible to heat-induced deterioration,
(b) degradation products of a blocked mercaptan present in an amount of from about 1 to about 3.5 parts per hundred parts of said polymer component during processing of said polymeric composition at an elevated temperature, wherein said degradation products comprise a free mercaptan, and wherein said blocked mercaptan has the structure:
wherein:
a is 0 or 1, m and n are 0 or 1; y=1 to 4; when y1, z is 1 to 4; when y is more than 1, z is 1;
R 1 is an alkoxycarbonylalkyl, alkoxycarbonylalkylenyl, hydroxyalkoxycarbonylalkyl, hydroxy(polyalkoxy)carbonylalkyl, alkoxy(polyalkoxy)carbonylalkyl, mercaptoalkoxycarbonylalkyl, mercaptoalkoxycarbonylalkylenyl, tetrahydropyranyloxycarbonylalkyl, tetrahydropyranyloxy(polyalkoxy)carbonylalkyl, or alkylcarbonyloxy(polyalkoxy)carbonylalkyl radical having from 1 to 22 carbon atom;
R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 , are independently hydrogen, a hydroxyl, mercapto, acyl, alkyl, alkylenyl, aryl, haloaryl, alkaryl, aralkyl, hydroxyalkyl, mercaptoalkyl, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, mercaptoalkylenyl, mercaptoalkoxycarbonylalkylenyl, hydroxyaryl, arylcarbonyl, mercaptoaryl, carboxyalkyl, or carboxyaryl radical having from 1 to 22 carbon atoms; and
X is aryl, haloaryl, alkaryl, hydroxyaryl, dihydroxyaryl, aralkyl, alkoxyaryl, arylcycloalkyl, or a heteroatom;
with the option that, when a is 1 and m is 0, one of the R 3 and R 5 radicals joins with R 7 and X to farm a heterocyclic moiety with X as a heteroatom selected from the group consisting of oxygen and sulfur;
with the further option that, when m is 1, R 6 and R 7 form a heterocyclic moiety in conjunction with X as a nitrogen atom;
with the proviso that, when R 6 is not a hydroxyl or mercapto, z is 1; and
(c) at least one zinc compound, wherein when both zinc chloride and zinc carboxylate are present, the ratio of zinc contributed by zinc carboxylate to zinc contributed by zinc chloride either is between 0:100 and 10:90 or is between 80:20 and 100:0.
2. The composition of claim 1 wherein said zinc compound is selected from the group consisting of zinc halides, zinc carboxylates, zinc β-diketones, and mixtures thereof.
3. The composition of claim 1 wherein X is oxygen, m is 0, R 5 and R 7 form a heterocyclic moiety in conjuction with X, and n is 0.
4. The composition of claim 1 wherein R 1 is alkoxycarbonylalkyl.
5. The composition of claim 1 wherein said polymeric composition comprises a halogen-containing polymer.
6. The composition of claim 5 wherein said halogen-containing polymer is a vinyl chloride polymer.
7. The composition of claim 1 wherein said composition further comprises at least one organotin compound.
8. A composition for stabilizing PVC comprising
(a) a zinc compound, wherein when both zinc chloride and zinc carboxylate are present, the ratio of zinc contributed by zinc carboxylate to zinc contributed by zinc chloride either is between 0:100 and 10:90 or is between 80:20 and 100:0, and
(b) a latent mercaptan having the formula
wherein
a is 0 or 1, m and n are 0 or 1; y=1 to 4; when y=1, z is 1 to 4 and when y is more than 1, z is 1;
R 1 is an alkoxycarbonylalkyl, alkoxycarbonylalkylenyl, hydroxyalkoxycarbonylalkyl, hydroxy(polyalkoxy)carbonylalkyl, alkoxy(polyalkoxy)carbonylalkyl, mercaptoalkoxycarbonylalkyl, mercaptoalkoxycarbonylalkylenyl, tetrahydropyranyloxycarbonylalkyl, tetrahydropyranyloxy(polyalkoxy)carbonylalkyl, or alkylcarbonyloxy(polyalkoxy)carbonylalkyl radical having from 1 to 22 carbon atoms;
R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , are independently hydrogen, a hydroxyl, mercapto, acyl, alkyl, alkylenyl, aryl, haloaryl, alkaryl, aralkyl, hydroxyalkyl, mercaptoalkyl, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, mercaptoalkylenyl, mercaptoalkoxycarbonylalkylenyl, hydroxyaryl, arylcarbonyl, mercaptoaryl, carboxyalkyl, or carboxyaryl radical having from 1 to 22 carbon atom; and
X is aryl, haloaryl, alkaryl, hydroxyaryl, dihydroxyaryl, aralkyl, alkoxyaryl, arylcycloalkyl, or a heteroatom;
with the option that, when a is 1 and m is 0, one of the R 3 and R 5 radicals joins with R 7 and X to form a heterocyclic moiety with X as a heteroatom selected from the group consisting of: oxygen and sulfur;
with the further option that, when m is 1, R 6 and R 7 form a heterocyclic moiety in conjunction with X as a nitrogen atom;
with the proviso that, when R 6 is not a hydroxyl or mercapto, z is 1.
9. The composition of claim 8 wherein said zinc compound is selected from the group consisting of zinc halides, zinc carboxylates, zinc β-diketones, and mixtures thereof.
10. The composition of claim 8 wherein X is oxygen, a is 1, m is 0, R 5 and R 7 form a heterocyclic moiety in conjuction with X, and n is 0.
11. The composition of claim 8 wherein R 1 is alkoxycarbonylalkyl.