Modified polymer composition and stabilizer mixture for making the same

1. A stabilizer mixture for modifying an olefin-based polymer, the stabilizer mixture comprising:

at least one organic phosphorus-containing antioxidant represented by a formula selected from the group consisting of formulae (1), (2), (3), (4), (5), (6), (7), and (8):

wherein R 11 , R 12 , and R 13 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

wherein R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

wherein R 31 , R 32 , R 33 , R 34 , and R 35 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

wherein

R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , and R 48 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

Z 41 and Z 42 are independently selected from the group consisting of O, S, and a C 1 -C 4 alkylene group,

wherein

R 51 , R 52 , R 53 , R 54 , R 55 , and R 56 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

Z 51 is selected from the group consisting of O, S, and a C 1 -C 4 alkylene group,

wherein

R 61 , R 62 , R 63 , and R 64 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

T is selected from the group consisting of a C 1 -C 18 hydrocarbon group and a group represented by

 where R 65 , R 66 , and R 67 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

Z 61 is selected from the group consisting of O, S, and a C 1 -C 4 alkylene group,

wherein R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , and R 78 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

and

at least one sulfur-containing carboxylate salt represented by a formula selected from the group consisting of formulae (9), (10), (11), and (12):

wherein

R 91 is selected from the group consisting of hydrogen and a C 1 -C 18 alkyl group,

R 92 is selected from the group consisting of a C 1 -C 30 alkyl group and a C 6 -C 18 aryl group,

M q+ is selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , Zn 2+ , and Al 3+ ,

q is an integer of 2 or 3, and

t is an integer ranging from 0 to 6,

wherein

X 11 and X 12 are independently selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , and Zn 2+ ,

Y 11 and Y 12 are independently selected from the group consisting of a C 1 -C 30 alkyl group and a C 6 -C 18 aryl group, and

a and b are independently an integer ranging from 1 to 6,

wherein

X 21 is selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , and Zn 2+ ,

G 1 and G 2 independently represent

 where c and d are independently an integer ranging from 1 to 6, and

p is an integer ranging from 1 to 9 on the proviso that a plurality of G 1 are the same or different and a plurality of X 21 are the same or different when p is an integer equal to or larger than 2,

and

wherein

X 31 is selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , and Zn 2+ , and

Y 31 is selected from the group consisting of a C 1 -C 30 alkyl group, a C 6 -C 18 aryl group, and a group represented by R 93 OOC—(CH 2 ) k — where R 93 is selected from the group consisting of a C 1 -C 30 alkyl group and a C 6 -C 18 aryl group, and k is an integer ranging from 1 to 5.

2. The stabilizer mixture according to claim 1 , wherein R 91 represents hydrogen and R 92 is selected from the group consisting of a C 1 -C 18 alkyl group and a C 6 -C 18 aryl group.

3. The stabilizer mixture according to claim 2 , wherein R 92 is dodecyl.

4. The stabilizer mixture according to claim 1 , further comprising an antioxidant selected from the group consisting of a hindered phenolic antioxidant, a benzofuranone-based antioxidant, an amine oxide-based antioxidant, and combinations thereof.

5. The stabilizer mixture according to claim 4 , wherein the hindered phenolic antioxidant is selected from the group consisting of pentaerythritol-tetra-[β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate], ethylenebis(oxyethylene)bis[β-(3-tert-butyl-4-hydr-oxy-5-methylphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benze-ne, 1 ,3 ,5 -tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris(butylcresol)butane, 4,4′-butylidenebis(6-tert-butyl-3-methylphenol), N,N′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazide, N,N′-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylene diamine, 2,2′-methylenebis-(4-methyl-6-tert-butylphenol), octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, 1,2-di[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl-yl]hydrazide, 2,2′-oxamidobis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and combinations thereof.

6. The stabilizer mixture according to claim 4 , wherein the benzofuranone-based antioxidant is selected from the group consisting of xylyl dibutylbenzofuranone, 5-(tert-butyl)-3-[5-(tert-butyl)-2-hydroxyphenyl]benzofuran-2(3H)-one, 3-[3,5-bis(1,1-dimethylethyl)-2-hydroxyphenyl]-5,7-bis(1,1-dimethylethyl)-2(3H)-benzofuranone, and combinations thereof.

7. The stabilizer mixture according to claim 4 , wherein the amine oxide-based antioxidant is selected from the group consisting of oxidized bis(hydrogenated tallow alkyl)amine, bis(octadecyl)hydroxylamine, and a combination thereof.

8. The stabilizer mixture according to claim 1 , further comprising an additive selected from the group consisting of an antacid agent, a metal deactivating agent, and a combination thereof.

9. The stabilizer mixture according to claim 8 , wherein the antacid agent is a fatty acid salt.

10. The stabilizer mixture according to claim 8 , wherein the metal deactivating agent is oxalyl-bis(benzylidene)hydrazide.

11. A modified polymer composition, comprising:

an olefin-based polymer selected from the group consisting of polyolefin, ethylene-vinyl acetate copolymer, and a combination thereof; and

a stabilizer mixture containing:

at least one organic phosphorus-containing antioxidant represented by a formula selected from the group consisting of formulae (1), (2), (3), (4), (5), (6), (7), and (8):

wherein R 11 ,R 12 , and R 13 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

wherein R 21 , R 22 , R 23 , R 24 , and R 25 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

wherein R 31 , R 32 , R 33 , R 34 , and R 35 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

wherein

R 41 , R 42 , R 43 , R 44 , and R 45 , R 46 , R 47 , and R 48 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

Z 41 and Z 42 are independently selected from the group consisting of O, S, and a C 1 -C 4 alkylene group,

wherein

R 51 , R 52 , R 53 , R 54 , R 55 , and R 56 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

Z 51 is selected from the group consisting of O, S, and a C 1 -C 4 alkylene group,

wherein

R 61 , R 62 , R 63 , and R 64 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group,

T is selected from the group consisting of a C 1 -C 18 hydrocarbon group and a group represented by

 where R 65 , R 66 , and R 67 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

Z 61 is selected from the group consisting of O, S, and a C 1 -C 4 alkylene group,

wherein R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , and R 78 are independently selected from the group consisting of hydrogen, a tert-butyl group, an isopropylphenyl group, and a linear C 1 -C 8 alkyl group, and

and

at least one sulfur-containing carboxylate salt represented by a formula selected from the group consisting of formulae (9), (10), (11), and (12):

wherein

R 91 is selected from the group consisting of hydrogen and a C 1 -C 18 alkyl group,

R 92 is selected from the group consisting of a C 1 -C 30 alkyl group and a C 6 -C 18 aryl group,

M q+ is selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , Zn 2+ , and Al 3+ ,

q is an integer of 2 or 3, and

t is an integer ranging from 0 to 6,

wherein

X 11 and X 12 are independently selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , and Zn 2+ ,

Y 11 and Y 12 are independently selected from the group consisting of a C 1 -C 30 alkyl group and a C 6 -C 18 aryl group, and

a and b are independently an integer ranging from 1 to 6,

wherein

X 21 is selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , and Zn 2+ ,

G 1 and G 2 independently represent

 where c and d are independently an integer ranging from 1 to 6, and

p is an integer ranging from 1 to 9 on the proviso that a plurality of G 1 are the same or different and a plurality of X 21 are the same or different when p is an integer equal to or larger than 2,

and

wherein

X 31 is selected from the group consisting of Ca 2+ , Ba 2+ , Mg 2+ , and Zn 2+ , and

Y 31 is selected from the group consisting of a C 1 -C 30 alkyl group, a C 6 -C 18 aryl group, and a group represented by R 93 OOC—(CH 2 ) k — where R 93 is selected from the group consisting of a C 1 -C 30 alkyl group and a C 6 -C 18 aryl group, and k is an integer ranging from 1 to 5.

12. The modified polymer composition according to claim 11 , wherein said stabilizer mixture is present in an amount ranging from 0.01 to 2.2 parts by weight based on 100 parts by weight of said olefin-based polymer.

13. The modified polymer composition according to claim 11 , wherein said polyolefin is selected from the group consisting of polyethylene, polypropylene, and a combination thereof.

14. The stabilizer mixture according to claim 1 , wherein:

when the at least one organic phosphorus-containing antioxidant is represented by a formula selected from the group consisting of formulae (2), (3), (4), (5), (6), (7), and (8), the at least one sulfur-containing carboxylate salt is represented by a formula selected from the group consisting of formulae (9), (10), (11), and (12); and

when the at least one organic phosphorus-containing antioxidant is represented by a formula (1), the at least one sulfur-containing carboxylate salt is represented by a formula selected from the group consisting of formulae (10) and (12).

15. The stabilizer mixture according to claim 14 , wherein R 91 represents hydrogen, and R 92 is selected from the group consisting of a C 1 -C 18 alkyl group and a C 6 -C 18 aryl group.

16. The stabilizer mixture according to claim 15 , wherein R 92 is dodecyl.

17. The modified polymer composition according to claim 11 , wherein:

when the at least one organic phosphorus-containing antioxidant is represented by a formula selected from the group consisting of formulae (2), (3), (4), (5), (6), (7), and (8), the at least one sulfur-containing carboxylate salt is represented by a formula selected from the group consisting of formulae (9), (10), (11), and (12); and

when the at least one organic phosphorus-containing antioxidant is represented by a formula (1), the at least one sulfur-containing carboxylate salt is represented by a formula selected from the group consisting of formulae (9), (10), and (12).

18. The modified polymer composition according to claim 17 , wherein said stabilizer mixture is present in an amount ranging from 0.01 to 2.2 parts by weight based on 100 parts by weight of said olefin-based polymer.

19. The modified polymer composition according to claim 17 , wherein said polyolefin is selected from the group consisting of polyethylene, polypropylene, and a combination thereof.