Polymer blends with improved impact resistance

• US 20030088027A1
• Filed: 07/10/2002
• Published: 05/08/2003
• Est. Priority Date: 08/12/1999
• Status: Active Grant

• Current Assignee: Francesco Fuso, Hui Chin, James Botkin, Wiebke Wunderlich
• Original Assignee: Francesco Fuso, Hui Chin, James Botkin, Wiebke Wunderlich
• Inventors: Chin, Hui, Botkin, James, Wunderlich, Wiebke, Fuso, Francesco
• Granted Patent: US 6,765,062 B2
• Time in Patent Office: Days
• US Class Current: 525/132
• CPC Class Codes: C08L 25/00 Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 71/123 not modified by chemical after-treatment
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/06 Polyamides derived from polyamines and polycarboxylic acids C08L77/10 takes precedence

Abstract

Polymer blends, in particular polyphenylene ether-polyamide blends, are effectively compatibilized by incorporating under blending conditions certain oligomers, cooligomers, polymers and copolymers of narrow molecular weight distribution that are prepared under free radical polymerization conditions with glycidyl-functionalized nitroxyl initiators. The oligomers, cooligomers, polymers and copolymers contain at least one oxyamine group and at least one glycidyl-containing initiator group. The polymer blends have excellent mechanical properties.

Claims

1. A composition comprising

i.) a polymer selected from the group consisting of polyphenylene ether and polystyrene,

ii.) at least one other polymer containing amine or carboxylic acid end groups, and

iii.) an oligomer, polymer, cooligomer or copolymer prepared by free-radical polymerization of at least one ethylenically unsaturated monomer or oligomer in the presence of a glycidyl-functionalized nitroxyl initiator.

2. A composition according to claim 1 in which the polyphenylene ether comprises a plurality of structural units having the formula

3. A composition according to claim 2 in which the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether).

4. A composition according to claim 1 in which component ii.) is selected from the group consisting of polyamide and polyester.

5. A composition according to claim 4 in which the polyamide is a polyamide-6 or polyamide-6,6.

6. A composition according to claim 4 in which the polyester is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polycyclohexane-1,4-dimethyleneterephthalate, polyethylene terephthalate/polycyclohexane-1,4-dimethyleneterephthalate copolymer, polyethylene 2,6-naphthalate and polyethylene terephthalate/polyethylene 2,6-naphthalate copolymer.

7. A composition according to claim 1 wherein the glycidyl-functionalized nitroxyl initiator is of the formula

8. A composition according to claim 7 wherein the glycidyl-functionalized nitroxyl initiator is of the formula (Ib) wherein

R₂ are independently CH₃ or C₂H₅;

A is —

CH₂OC(O)—

, —

OCH₂—

, C₂-C₃alkylene, C₂-C₃alkenylene, or 1,2-phenylene, or said C₂-C₃alkylene, C₂-C₃alkenylene and 1,2-phenylene groups substituted by hydroxy, C₁-C₁₈alkylcarboxy, C₁-C₁₈alkoxy, benzyloxy, C₁-C₁₈alkanoyloxy, benzoyloxy, C₁-C₁₈alkylamino or di(C₁-C₁₈alkyl)amino; and

R₃ is a radical of formula (II)

X is phenylene, naphthylene or biphenylene;

one R₁₂ is H and the other R₁₂ is CH₃;

D is a group

and

m is a number from 1 to 2.

9. A composition according to claim 8 wherein the glycidyl-functionalized nitroxyl initiator is of the formula

10. A composition according to claim 9 wherein the glycidyl-functionalized nitroxyl initiator is of the formula (III) wherein

11. A composition according to claim 10 wherein the glycidyl-functionalized nitroxyl initiator is of the formula

12. A composition according to claim 1 in which the ethylenically unsaturated monomer is selected from the group consisting of styrene, α

-methylstyrene, p-methylstyrene, isoprene and butadiene.

13. A composition according to claim 1 in which the ethylenically unsaturated monomer is styrene.

14. A composition according to claim 7 in which the oligomer, polymer, cooligomer or copolymer prepared by free-radical polymerization of at least one ethylenically unsaturated monomer or oligomer in the presence of a glycidyl-functionalized nitroxyl initiator contains at least one initiator group —

R₃ and at least one oxyamine group of formula

15. A composition according to claim 1 which further comprises an elastomeric impact modifier.

16. A composition according to claim 15 in which the impact modifier is a triblock copolymer wherein the end-blocks are polystyrene and the mid-block is selected from the group consisting of polyisoprene, polybutadiene, poly(ethylene/butylene) and poly(ethylene/propylene).

17. A composition according to claim 16 in which the mid-block has been hydrogenated.

18. A composition according to claim 16 in which the triblock copolymer is functionalized with maleic anhydride.

33. A method according to claim 18 which component iv.) is an elastomeric impact modifier.

34. A composition according to claim 33 in which the impact modifier is a triblock copolymer wherein the end-blocks are polystyrene and the mid-block is selected from the group consisting of polyisoprene, polybutadiene, poly(ethylene/butylene) and poly(ethylene/propylene).

35. A method according to claim 34 in which the mid-block has been hydrogenated.

36. A composition according to claim 34 in which the triblock copolymer is functionalized with maleic anhydride.

19. A method for preparing highly compatible polyphenylene ether-polyamide mixtures which comprises blending under intimate blending conditions

i.) a polymer selected from the group consisting of polyphenylene ether and polystyrene,

ii.) at least one other polymer containing amine or carboxylic acid end groups,

iii.) an oligomer, polymer, cooligomer or copolymer prepared by free-radical polymerization of at least one ethylenically unsaturated monomer or oligomer in the presence of a glycidyl-functionalized nitroxyl initiator, and

iv.) optional further additives.

20. A method according to claim 19 in which the polyphenylene ether comprises a plurality of structural units having the formula

21. A method according to claim 20 in which the polyphenylene ether is a poly(2,6-dimethyl-1,4-phenylene ether).

22. A method according to claim 19 in which component ii.) is selected from the group consisting of polyamide and polyester.

23. A method according to claim 22 in which the polyamide is a polyamide-6 or polyamide-6,6.

24. A method according to claim 22 in which the polyester is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polycyclohexane-1,4-dimethyleneterephthalate, polyethylene terephthalate/polycyclohexane-1,4-dimethyleneterephthalate copolymer, polyethylene 2,6-naphthalate and polyethylene terephthalate/polyethylene 2,6-naphthalate copolymer.

25. A method according to claim 19 wherein the glycidyl-functionalized nitroxyl initiator is of the formula

26. A method according to claim 25 wherein the glycidyl-functionalized nitroxyl initiator is of the formula (Ib) wherein

R₂ are independently CH₃ or C₂H₅;

A is —

CH₂OC(O)—

, —

OCH₂—

, C₂-C₃alkylene, C₂-C₃alkenylene, or 1,2-phenylene, or said C₂-C₃alkylene, C₂-C₃alkenylene and 1,2-phenylene groups substituted by hydroxy, C₁-C₁₈alkylcarboxy, C₁-C₁₈alkoxy, benzyloxy, C₁-C₁₈alkanoyloxy, benzoyloxy, C₁-C₁₈alkylamino or di(C₁-C₁₈alkyl)amino; and

R₃ is a radical of formula (II)

X is phenylene, naphthylene or biphenylene;

one R₁₂ is H and the other R₁₂ is CH₃;

D is a group

m is a number from 1 to 2.

27. A method according to claim 26 wherein the glycidyl-functionalized nitroxyl initiator is of the formula

28. A method according to claim 27 wherein the glycidyl-functionalized nitroxyl initiator is of the formula (III) wherein

29. A method according to claim 28 wherein the glycidyl-functionalized nitroxyl initiator is of the formula

30. A method according to claim 19 in which the ethylenically unsaturated monomer is selected from the group consisting of styrene, α

-methylstyrene, p-methylstyrene, isoprene and butadiene.

31. A method according to claim 19 in which the ethylenically unsaturated monomer is styrene.

32. A method according to claim 25 in which the oligomer, polymer, cooligomer or copolymer prepared by free-radical polymerization of at least one ethylenically unsaturated monomer or oligomer in the presence of a glycidyl-functionalized nitroxyl initiator contains at least one initiator group —

R₃ and at least one oxyamine group of formula