Polymers with low gel content and enhanced gas-fading
View Patent ↗A polymer stabilizing composition comprising a sterically hindered phenol and a phosphite that provides low gel content and enhanced resistance to gas-fading. The stabilizer composition is particular useful for stabilizing polyethylene homopolymers and copolymers, such as linear low density polyethylenes produced from metallocene catalyst. The sterically hindered phenol is, for example, selected from the group consisting of 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-Triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene.
1. A polyolefin film, comprising:
a) a polyolefin selected from the group consisting of polyethylene homopolymers, polyethylene copolymers, polypropylene homopolymers, and polypropylene copolymers; and
b) an effective amount of a stabilizing composition, comprising:
(1) a sterically hindered phenol of formula I or II:
wherein: x is independently 0, 1, 2, or 3; R 1 , R 2 , and R 3 is independently hydrogen, and C 1 -C 12 alkyl, and C 5 -C 10 cycloalkyl, provided that at least one of R 1 , R 2 , and R 3 is not hydrogen; and R 4 is independently C 1 -C 6 alkyl; and
(2) a phosphite selected from the group consisting of triphenyl phosphite, tris(nonyl-phenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tris(dipropyleneglycol)phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite, and mixtures thereof;
wherein the article has a gel content of 200 to 400 μm gel sized formations of from 0.01 to 0.5 gel per square meter (gel/m 2 ) of the article.
2. The film of claim 1 , wherein the film has no detectable gel sized formations that are greater than 400 μm.
3. The film of claim 1 , wherein the film has a yellowness index after exposure to NOx for 7 days of less than 0, for 18 days of less than 0.7, for 25 days of less than 1.1, for 33 days of less than 1.7 or for 41 days of less than 2.5.
4. The film of claim 1 , wherein the article comprises the stabilizing composition in an amount from 250 to 5000 wppm.
5. The film claim 1 , wherein the sterically hindered phenol is of formula I.
6. The film claim 1 , wherein the sterically hindered phenol is of formula II.
7. The film of claim 1 , wherein the sterically hindered phenol is selected from the group consisting of 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-Triazine-2,4,6-(1H,3H,5H)-trione, and 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene.
8. The film of claim 7 , wherein the sterically hindered phenol is selected from the group consisting of 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.
9. The film of claim 1 , wherein the composition is substantially free of anti-gel agents.
10. The film of claim 1 , wherein the weight ratio of the sterically hindered phenol to the phosphite composition is from 1:1 to 1:20.
11. The film of claim 1 , wherein the polyolefin is produced by free-radical polymerization, Ziegler-Natta catalysts, Phillips-type catalysts, single-site catalysts, and metallocene catalysts.
12. The film of claim 1 , wherein the polyolefin is linear low density polyethylene produced from a metallocene catalyst.
13. A polyolefin film, comprising:
a) a polyolefin selected from the group consisting of polyethylene homopolymers, polyethylene copolymers, polypropylene homopolymers, and polypropylene copolymers: and
b) an effective amount of a stabilizing composition, comprising:
(1) a sterically hindered phenol selected from the group consisting of 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; and
(2) a liquid tris(mono-alkyl)phenyl phosphite ester or a liquid mixture of liquid tris(mono-alkyl)phenyl phosphite esters;
wherein the article has a gel content of 200 to 400 μm gel sized formations of from 0.01 to 0.5 gel per square meter (gel/m 2 ) of the article.
14. The film of claim 13 , wherein b) comprises a mixture of two phosphites selected from tris(3-t-butylphenyl)phosphite, tris(2-sec-butylphenyl)phosphite, and tris(4-sec-butylphenyl)phosphite, or a mixture of a phosphite selected from tris(3-t-butylphenyl)phosphite, tris(2-sec-butylphenyl)phosphite, and tris(4-sec-butylphenyl)phosphite with a phosphite selected from tris(2-t-butylphenyl)phosphite, tris(4-t-butylphenyl)phosphite, or tris(2,4-di-t-butylphenyl)phosphite.
15. The film of claim 13 , wherein the film has no detectable gel sized formations that are greater than 400 μm.
16. The film of claim 13 , wherein the article comprises the stabilizing composition in an amount from 250 to 5000 wppm.
17. The film of claim 13 , wherein the composition is substantially free of anti-gel agents.
18. The film of claim 13 , wherein the weight ratio of the sterically hindered phenol to the phosphite composition is from 1:1 to 1:20.
19. The film of claim 13 , wherein the polyolefin is produced by free-radical polymerization, Ziegler-Nitta catalysts, Phillips-type catalysts, single-site catalysts, and metallocene catalysts.
20. The composition of claim 13 , wherein the polyolefin is linear low density polyethylene produced from a metallocene catalyst.