Stabilized polyolefin compositions comprising benzofuranones and hindered phenolic antioxidants

Patent metadata

Field	Value
Publication number	US-10913841-B2
Application number	US-201816026288-A
Country	US
Kind code	B2
Filing date	Jul 3, 2018
Priority date	Jul 6, 2017
Publication date	Feb 9, 2021
Grant date	Feb 9, 2021

Abstract

Polyolefin compositions comprising i) a polyolefin, ii) one or more phosphorus-containing benzofuranone compounds and iii) one or more hindered phenolic antioxidants are provided excellent protection against discoloration and enhanced thermal stability during melt processing as exhibited by improved retention of molecular weight and maintenance of polymer molecular architecture.

First claim

The invention claimed is:

1. A composition comprising
i) a polyolefin,
ii) one or more benzofuranone compounds selected from the group consisting of formula (I-p2), (I-o2) and (I-m2):

wherein X and Z are independently P or P═O; with the proviso that when X or Z is P, X and Z are not the same;
R 1p , represents one of subformulae (II-p), (II-o) or (II-m)

or
R 1o represents one of subformulae (II-o) or (II-m),
R 1m represents subformula (II-m), or
R 1p , R 1o and R 1m independently represent a C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom; R 4 , R 5 , R 6 and R 7 are each independently hydrogen or C 1 -C 8 -alkyl, R p2 , R p3 , R p5 and R p6 are each independently hydrogen or C 1 -C 8 -alkyl, R o1 , R o2 , R o5 and R o6 are each independently hydrogen or C 1 -C 18 -alkyl, R m1 , R m3 , R m5 and R m6 are each independently hydrogen or C 1 -C 8 -alkyl, R a1 , R a2 , R a3 and R a4 are each independently hydrogen or C 1 -C 8 -alkyl, R 1b , R b2 , R b3 , R b4 , R b5 and R b6 are each independently hydrogen or C 1 -C 8 -alkyl and R c1 , R c2 , R c3 and R c4 are each independently hydrogen or C 1 -C 8 -alkyl, and iii) one or more hindered phenolic antioxidants.

2. The composition according to claim 1 , wherein the polyolefin comprises polypropylene.

3. The composition according to claim 1 , wherein the polyolefin comprises polyethylene.

4. The composition according to claim 1 , wherein the hindered phenolic antioxidants are selected from the group consisting of tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, the calcium salt of the monoethylester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,2′-methylenebis(4-methyl-6-tert-butylphenol)monoacrylate and alpha-tocopherol.

5. The composition according to claim 1 , comprising one or more hindered phenolic antioxidants selected from the group consisting of tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, alpha-tocopherol, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

6. The composition according to claim 1 , comprising pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and/or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

7. The composition according to claim 1 , further comprising one or more organophosphorus stabilizers.

8. The composition according to claim 1 , further comprising one or more organophosphorus stabilizers selected from the group consisting of tris-nonylphenyl phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2′,2″-nitrilo[triethyltris(3,3′5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl) phosphite], bis(2,4-di-α-cumylphenyl) pentaerythrtitol diphosphite and tris(2,4-di-tert-butylphenyl) phosphite.

9. The composition according to claim 1 , wherein the one or more benzofuranone compounds are present from about 20 ppm to about 1000 ppm by weight, based on the weight of the polyolefin.

10. The composition according to claim 1 , wherein the one or more hindered phenolic antioxidants are present from about 20 ppm to about 1000 ppm by weight, based on the weight of the polyolefin.

11. The composition according to claim 1 , wherein a weight/weight ratio of the one or more benzofuranone compounds to the one or more hindered phenolic antioxidants is from about 0.05 to about 1.0.

12. The composition according to claim 1 , wherein the benzofuranone compounds are selected from the group consisting of formula (I-p2).

13. The composition according to claim 1 , wherein
R 4 and R 6 are hydrogen,
R 5 and R 7 are each independently hydrogen or C 1 -C 8 -alkyl,
R p2 and R p6 are each independently hydrogen or C 1 -alkyl,
R p3 and R p5 are each independently hydrogen or C 1 -C 4 -alkyl,
R o1 and R o6 are each independently hydrogen or C 1 -C 8 -alkyl,
R o2 is hydrogen or C 1 -alkyl,
R o5 is hydrogen or C 1 -C 4 -alkyl, R m1 is hydrogen or C 1 -alkyl,
R m3 and R m5 are each independently hydrogen or C 1 -C 4 -alkyl,
R m6 is hydrogen or C 1 -C 8 -alkyl,
R a1 , R a2 , R a3 and R a4 are each independently hydrogen or C 1 -C 4 -alkyl,
R b1 , R b2 , R b3 , R b4 , R b5 and R b6 are each independently hydrogen or C 1 -C 4 -alkyl and
R c1 , R c2 , R c3 and R c4 are each independently hydrogen or C 1 -C 4 -alkyl.

14. The composition according to claim 1 , wherein the benzofuranones are of formula (I-p2) or (I-o2).

15. The composition according to claim 1 , wherein the benzofuranones are of formula (I-p2) or (I-o2), wherein R 4 , R 5 , R 6 and R 7 are each independently hydrogen or C 1 -C 8 -alkyl, R p2 , R p3 , R p5 and R p6 are each independently hydrogen or C 1 -C 8 -alkyl, R o1 , R o2 , R o5 and R o6 are each independently hydrogen or C 1 -C 8 -alkyl, R a1 , R a2 , R a3 and R a4 are each independently hydrogen or C 1 -C 8 -alkyl, R b1 , R b2 , R b3 , R b4 , R b5 and R b6 are each independently hydrogen or C 1 -C 8 -alkyl R c1 , R c2 , C c3 and R c4 are each independently hydrogen or C 1 -C 8 -alkyl.

16. A composition comprising:
i) a polyolefin,
ii) one or more benzofuranone compound; and
iii) one or more hindered phenolic antioxidants, wherein the one or more benzofuranone compound is selected from the group consisting of compounds of formula (125)-(132):

17. A shaped article comprising the composition according to claim 1 .

18. A method of preparing the shaped article according to claim 17 , the method comprising melt blending the composition.

19. An additive composition comprising ii) one or more benzofuranone compounds selected from the group consisting of formula (I-p2), (I-o2) and (I-m2) of claim 1 and iii) one or more hindered phenolic antioxidants.

20. The additive composition according to claim 19 , wherein a weight/weight ratio of the one or more benzofuranone compounds to the one or more hindered phenolic antioxidants is from about 0.05 to about 1.0.

21. A method of stabilizing a polyolefin against deleterious effects of heat, light and oxygen, the method comprising incorporating into the polyolefin ii) one or

Assignees

• Basf Se

Inventors

• King Iii Roswell E
• Hoelzl Werner

Classifications

• C08K5/3492 Primary

  Triazines · CPC title

• C08K5/529

  Esters containing heterocyclic rings not representing cyclic esters of phosphoric or phosphorous acids · CPC title

• C08K2003/2224

  Magnesium hydroxide · CPC title

• C08K5/1535

  Five-membered rings · CPC title

• C07F9/6552

  the oxygen atom being part of a six-membered ring · CPC title