Impact modified polyphenylene ether interpolymer resins

• US 4,816,515 A
• Filed: 04/13/1987
• Issued: 03/28/1989
• Est. Priority Date: 04/13/1987
• Status: Expired due to Term

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Weiss, Kurt A.
• Primary Examiner(s): Ziegler, Jacob
• Application Number:
  US07/037,763
• Time in Patent Office: 715 Days
• Field of Search: 525/68, 525/905
• US Class Current: 525/68
• CPC Class Codes: C08G 65/485 Polyphenylene oxides
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 51/04 grafted on to rubbers
• CPC Class Codes: C08L 71/126 modified by chemical after-treatment
• CPC Class Codes: Y10S 525/905 Polyphenylene oxide

Abstract

Compositions with enhanced impact strength, solvent and thermal aging resistance are prepared by interpolymerizing polyphenylene ether resins functionalized with acids or anhydrides, e.g., fumaric acid, and rubbers, e.g., EPDM rubbers, grafted with glycidyl acrylates or methacrylates.

Claims

1. A composition comprising the interpolymerization product of:

(a) a polyphenylene ether resin functionalized with a reactive compound selected from the group consisting of a dicarboxylic acid, the corresponding anhydride, and a mixture thereof; and

(b) an effective amount of an impact improving rubbery polymer grafted with (i) a compound selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, and a mixture thereof, or

(ii) a compound selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, and a mixture thereof in further combination with a compound selected from the group consisting of a C₁ -C₁₈ alkyl methacrylate, a C₁ -C₁₈ alkyl acrylate and a mixture thereof said interpolymerization comprises melt blending the functionalized polyphenylene ether resin component (a) and the rubbery polymer (b) unitl the reaction is substantially complete.

2. A composition as defined in claim 1 wherein said dicarboxylic acid or anhydride is selected from the group consisting of fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and a mixture of any of the foregoing.

3. A composition as defined in claim 1 wherein said rubbery polymer is selected from the group consisting of natural rubber, synthetic rubber and a mixture thereof.

4. A composition as defined in claim 3 wherein said rubbery polymer is a synthetic terpolymer comprising units of ethylene, propylene and a diene.

5. A composition as defined in claim 1, wherein the polyphenylene ether resin (a) is a homopolymer or copolymer containing structural units of the formula:

##STR8## in which for each of these units independently each Q¹ is hydrogen, halogen, primary or secondary lower alkyl having up to seven carbon atoms, phenyl, aminoalkyl or haloalkyl wherein at least two carbon atoms separate the halogen atom from the benzene ring, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and

each Q² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹.

6. A composition as defined in claim 1, wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene ether).

7. A composition as defined in claim 6, wherein the poly(2,6-dimethyl-1,4-phenylene ether) has an intrinsic viscosity of about 0.4 to 0.6 deciliters per gram in chloroform at 25°

C.

8. A composition as defined in claim 1, wherein said dicarboxylic acid or anhydride comprises fumaric acid.

9. A composition as defined claim 4, wherein the grafted terpolymer is derived from approximately 45 to 70 mole percent ethylene, approximately 30-55 mole percent propylene and a minor amount of 5-ethylidene-2-norbornene.

10. A composition as defined in claim 1, wherein said acid, anhydride or mixture thereof comprises from about 0.1 to 2.5% by weight based on the weight of the polyphenylene ether resin (a).

11. A composition as defined in claim 10, wherein said acid, anhydride or mixture thereof comprises from about 0.5 to 1.25% by weight based on the weight of the polyphenylene ether resin (a).

12. A composition as defined in claim 1 wherein the glycidyl ester grafted rubbery polymer (b) comprises from about 5 to about 20 percent by weight based on the total of (a) and (b).

13. A composition as defined in claim 12 wherein the grafted rubbery polymer (b) comprises from about 7.5 to about 15.0 percent by weight based on the total of (a) and (b).

27. An article thermoformed from the composition of claim 1.

14. A method for providing a composition adapted to produce a thermoshaped article having high impact strength and improved solvent resistance comprising

(a) a polyphenylene ether resin functionalized with a reactive compound selected from a dicarboxylic acid or the corresponding anhydride or a mixture thereof, said method comprising adding

(b) an effective amount of an impact improving rubbery polymer grafted with (i) a compound selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, and a mixture thereof, or

(ii) a compound selected from the group consisting of a glycidyl methacrylate, glycidyl acrylate, and a mixture thereof in further combination with a compound selected from the group consisting of a C₁ -C₁₈ alkyl methacrylate, a C₁ -C₁₈ alkyl acrylate and a mixture thereof said method comprises melt blending the functionalized polyphenylene ether resin component (a) and the rubbery polymer (b) until the reaction is substantially complete.

15. A composition as defined in claim 14 wherein said dicarboxylic acid or anhydride is selected from fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, trimellitic acid, trimellitic anhydride, trimellitic anhydride acid chloride, or a mixture of any of the foregoing.

16. A composition as defined in claim 14 wherein said rubbery polymer is selected from natural rubber, synthetic rubber or a mixture thereof.

17. A composition as defined in claim 16 wherein said rubbery polymer is a synthetic rubber terpolymer comprising units of ethylene, propylene and a diene.

18. A method as defined in claim 14, wherein the polyphenylene ether resin (a) is a homopolymer or copolymer containing structural units of the formula:

##STR9## in which for each of these units independently each Q¹ is hydrogen, halogen, primary or secondary lower alkyl having up to seven carbon atoms, phenyl, aminoalkyl or haloalkyl wherein at least two carbon atoms separate the halogen atom from the benzene ring, hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and

each Q² is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹.

19. A method as defined in claim 14, wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4phenylene ether).

20. A method as defined in claim 19, wherein the poly(2,6-dimethyl-1,4-phenylene ether) has an intrinsic viscosity of about 0.4 to 0.6 deciliters per gram in chloroform at 25°

C.

21. A method as defined in claim 14, wherein said dicarboxylic acid or anhydride comprises fumaric acid.

22. A method as defined claim 17 wherein the grafted terpolymer is derived from approximately 45 to 70 mole percent ethylene, approximately 30-55 mole percent propylene and a minor amount of 5-ethylidene-2-norbornene.

23. A method as defined in claim 14, wherein said acid, anhydride or mixture thereof comprises from about 0.1 to 2.5% by weight based on the weight of the polyphenylene ether resin (a).

24. A method as defined in claim 23, wherein said acid, anhydride or mixture thereof comprises from about 0.5 to 1.25% by weight based on the weight of the polyphenylene ether resin (a).

25. A method as defined in claim 14 wherein the glycidyl ester grafted rubbery polymer (b) comprises from about 5 to about 20 percent by weight based on the total of (a) and (b).

26. A method as defined in claim 25 wherein the grafted rubbery polymer (b) comprises from about 7.5 to about 15.0 percent by weight based on the total of (a) and (b).

28. A composition comprising the interpolymerization product of:

(a) a polyphenylene ether resin functionalized with a reactive compound selected from the group consisting of fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and a mixture of any of the following; and

(b) an effective amount of an impact improving rubbery terpolymer having rubber diene segments grafted with (i) a compound selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, and a mixture thereof, or

(ii) a compound selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, and a mixture thereof, in further combination with compound selected from the group consisting of a C₁ -C₁₈ alkyl methacrylate, a C₁ -C₁₈ alkyl acrylate, and a mixture thereof.

29. A composition as defined in claim 28 wherein said rubbery terpolymer comprises units of ethylene, propylene and a diene.

30. A composition as defined in claim 29 wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene ether).

31. A composition as defined in claim 30 wherein said reactive compound comprises fumaric acid.