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 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. The phosphite preferably is a liquid phosphite composition comprising two or more alkylated aryl phosphites.
1. A stabilizing composition for polyolefins, comprising:
(1) a sterically hindered phenol; and
(2) a phosphite composition comprising at least two different phosphites selected from:
(i) a tris(dialkylaryl)phosphite,
(ii) a tris(monoalkylaryl)phosphite,
(iii) a bis(diakylaryl)monoalkylaryl phosphite, and
(iv) a bis(monoalkylaryl)dialkylaryl phosphite; wherein the phosphite composition is a liquid at ambient conditions,
wherein the sterically hindered phenol has the structure of compound 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.
2. The composition 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.
3. The composition of claim 1 , wherein the sterically hindered phenol has the structure of compound I.
4. The composition of claim 1 , wherein the sterically hindered phenol has the structure of compound II.
5. The composition of claim 1 , wherein the phosphite composition comprises:
from 0.1 to 20 wt. % of the tris(dialkylaryl)phosphite;
from 20 to 70 wt. % of the tris(monoalkylaryl)phosphite;
from 2 to 20 wt. % of the bis(dialkylaryl)monoalkylaryl phosphite, and
from 15 to 60 wt. % of the bis(monoalkylaryl)dialkylaryl phosphite, based on the total weight of the phosphite composition.
6. The composition of claim 1 , wherein the tris(dialkylaryl)phosphite is tris(2,4-di-tert-amyl-phenyl)phosphite or tris(2,4-di-tert-butyl-phenyl)phosphite.
7. The composition of claim 1 , wherein the tris(monoalkylaryl)phosphite is tris(4-t-amyl-phenyl)phosphite or tris(4-t-butyl-phenyl)phosphite.
8. The composition of claim 1 , wherein the bis(dialkylaryl)monoalkylaryl phosphite is bis(2,4-di-tert-amyl-phenyl)-4-t-amyl-phenyl phosphite or bis(2,4-di-tert-butyl-phenyl)-4-t-butyl-phenyl phosphite.
9. The composition of claim 1 , wherein the bis(monoalkylaryl)dialkylaryl phosphite is bis(4-t-amyl-phenyl)-2,4-di-t-amyl-phenyl)phosphite or bis(4-t-butyl-phenyl)-2,4-di-t-butyl-phenyl)phosphite.
10. The composition of claim 1 , wherein he composition is substantially free of anti-gel agents.
11. The composition of claim 1 , wherein the weight ratio of the sterically hindered phenol to the phosphite composition is from 1:1 to 1:20.
12. The composition of claim 1 , wherein the polyolefin is produced by free-radical polymerization, Ziegler-Natta catalysts, Phillips-type catalysts, single-site catalysts, and metaliocene catalysts.
13. The composition of claim 1 , wherein the polyolefin is linear low density polyethylene produced from a metallocene catalyst.
14. An article, 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; and
(2) a phosphite composition comprising at least two different phosphites selected from:
(i) a tris(dialkylaryl)phosphite,
(ii) a tris(monoalkylaryl)phosphite,
(iii) a bis(dialkylaryl)monoalkylaryl phosphite, and
(iv) a bis(monoalkylaryl)dialkylaryl phosphite; wherein the phosphite composition is a liquid at ambient conditions,
wherein the sterically hindered phenol has the structure of compound 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.
15. The article of claim 14 , 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 film.
16. The article of claim 14 , wherein the article has no detectable gel sized formations that are greater than 400 μm.
17. The article of claim 14 , wherein the article 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.
18. The article of claim 14 , wherein the article comprises the stabilizing composition in an amount from 250 to 5000 wppm.
19. The article of claim 14 , wherein the phosphite composition comprises:
from 0.1 to 20 wt. % of the tris(dialkylaryl)phosphite;
from 20 to 70 wt. % of the tris(monoalkylaryl)phosphite;
from 2 to 20 wt. % of the bis(dialkylaryl)monoalkylaryl phosphite, and
from 15 to 60 wt. % of the bis(monoalkylaryl)dialkylaryl phosphite, based on the total weight of the phosphite composition.