Rubber-modified cyanate ester resins and polytriazines derived therefrom

• US 5,079,294 A
• Filed: 11/13/1989
• Issued: 01/07/1992
• Est. Priority Date: 07/30/1987
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Yang, Philip C., Pickelman, Dale M.
• Primary Examiner(s): Bleutge, John C.
• Assistant Examiner(s): Hamilton, III, Thomas
• Application Number:
  US07/434,220
• Time in Patent Office: 785 Days
• Field of Search: 525/64, 525/66
• US Class Current: 525/66
• CPC Class Codes: C08G 73/0655 from polycyanurates
• CPC Class Codes: C08L 79/04 Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: H05K 1/0353 consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• CPC Class Codes: H05K 1/0373 containing additives, e.g. fillers H05K1/036 takes precedence

Abstract

Polytriazines exhibiting improved toughness without sacrificing heat resistance are prepared by curing a cyanate ester resin having dispersed therein resin-insoluble rubber particles grafted with a resin-soluble polymer. The resin-soluble polymer stabilizes the rubber particles and maintains the particles in an essentially discrete, nonagglomerated form.

Claims

1. A rubber-modified cyanate ester resin comprising a major portion of cyanate ester resin and a minor portion of grafted rubber additive which contains:

1. resin-insoluble rubber particles;

2. resin-soluble polymer moieties grafted to the resin-insoluble rubber particles; and

3. optionally ungrafted resin-soluble polymer moieties

wherein the concentration of grafted rubber additive and the ratio of components is such that;

the concentration of resin-insoluble rubber particles in the rubber-modified cyanate ester resin is at least about 6 weight percent,

the concentration of ungrafted resin-soluble polymer in the rubber-modified cyanate ester resin is at most about 10 weight percent,

the rubber particles are maintained in a discrete spaced apart relationship to each other, and

the grafted rubber additive and cyanate ester resin can be dispersed in a compatible solvent.

2. The rubber-modified cyanate ester resin of claim 1 wherein the cyanate ester resin is a difunctional or polyfunctional aromatic polycyanate.

3. The rubber-modified cyanate ester resin of claim 2 wherein the aromatic polycyanate is prepared from a polyhydric phenol selected from the group consisting of bisphenol A, bisphenol S, a halogenated or alkylated analog of bisphenol A or bisphenol S, a novolak resin, polyphenol bridged by at least one polycyclic aliphatic group or an alkylated variation thereof.

4. The rubber-modified cyanate ester resin of claim 3 wherein the cyanate ester resin has the formula:

##STR2## wherein the average value of n is about 0.2.

5. The rubber-modified cyanate ester resin of claim 1 wherein the grafted rubber additive comprises between at least 45 weight percent cross-linked rubber copolymer, between 5 and 50 weight percent grafted resin-soluble polymer, and no more than about 30 weight percent ungrafted resin-soluble polymer.

6. The rubber-modified cyanate ester resin of claim 5 wherein the rubber particles have diameters of about 300 Å

to about 20,0000 Å

.

7. The rubber-modified cyanate ester resin of claim 6 wherein rubber particles make up at least about 7 weight percent of the rubber-modified cyanate ester resin.

8. The rubber-modified cyanate ester resin of claim 6 wherein rubber particles make up at least about 8 weight percent of the rubber-modified cyanate ester resin.

9. The rubber-modified cyanate ester resin of claim 8 wherein grafted resin-soluble polymer makes up between 10 and 30 weight percent of the grafted rubber additive.

10. The rubber-modified cyanate ester resin of claim 9 wherein grafted resin-soluble polymer makes up between 15 and 20 percent of the grafted rubber additive.

11. The rubber-modified cyanate ester resin of claim 10 wherein the rubber particles make up at least about 60 percent of the grafted rubber additive.

12. The rubber-modified cyanate ester resin of claim 11 wherein the rubber particles make up at least about 80 percent of the grafted rubber additive.

13. The rubber-modified cyanate ester resin of claim 9 wherein the concentration of ungrafted resin-soluble polymer is no more than about 7 weight percent of the rubber-modified cyanate ester resin.

14. The rubber-modified cyanate ester resin of claim 13 wherein the concentration of ungrafted resin-soluble polymer is no more than about 5 weight percent of the rubber-modified cyanate ester resin.

15. The rubber-modified cyanate ester resin of claim 9 wherein the rubber-modified cyanate ester resin contains between 10 and 30 weight percent grafted rubber additive.

16. The rubber-modified cyanate ester resin of claim 9 wherein the rubber-modified cyanate ester resin is a concentrate comprising at least about 10 weight percent rubber particles.

17. The rubber-modified cyanate ester resin of claim 9 wherein the rubber-modified cyanate ester resin comprises no more than about 25 weight percent rubber particles.

18. The rubber-modified cyanate ester resin of claim 9 wherein the rubber particles of the grafted rubber additive are cross-linked styrene-butadiene rubber copolymer and the resin-soluble polymer is styrene-acrylonitrile copolymer.

19. A rubber-modified polytriazine polymer comprising a continuous polytriazine phase and a discontinuous grafted rubber additive phase which contains:

1. resin-insoluble rubber particles;

2. resin-soluble polymer moieties grafted to the resin-insoluble rubber particles; and

3. optionally ungrafted resin-soluble polymer moieties

wherein the concentration of grafted rubber additive and the ratio of components is such that;

the concentration of resin-insoluble rubber particles in the rubber-modified polytriazine is at least about 6 weight percent,

the concentration of ungrafted resin-soluble polymer in the rubber-modified polytriazine is at most about 10 weight percent, and

the rubber particles are maintained in a discrete spaced apart relationship to each other by the resin-soluble polymer.

20. The rubber-modified polytriazine of claim 19 wherein the polytriazine is the product of a difunctional or polyfunctional aromatic polycyanate.

21. The rubber-modified polytriazine of claim 20 wherein the polytriazine is the product of an aromatic polycyanate prepared from a polyhydric phenol selected from the group consisting of bisphenol A, bisphenol S, a halogenated or alkylated analog of bisphenol A or bisphenol S, a novolak resin, a cresol, a polyphenol bridged by at least one polycyclic aliphatic group, or an alkylated variation of one of those groups.

22. The rubber-modified polytriazine of claim 21 wherein the polytriazine is the product of a cyanate ester resin which has the formula:

##STR3## wherein the average value of n is about 0.2.

23. The rubber-modified polytriazine of claim 19 wherein the grafted rubber additive comprises between at least 45 weight percent cross-linked rubber copolymer, between 5 and 50 weight percent grafted resin-soluble polymer, and no more than about 30 weight percent ungrafted resin-soluble polymer.

24. The rubber-modified polytriazine of claim 23 wherein the rubber particles have diameters of about 300 Å

to about 20,0000 Å

.

25. The rubber-modified polytriazine of claim 24 wherein rubber particles make up between about 7 and about 25 weight percent of the rubber-modified polytriazine.

26. The rubber-modified polytriazine of claim 25 wherein rubber particles make up at least about 8 weight percent of the rubber-modified polytriazine.

27. The rubber-modified polytriazine of claim 26 wherein grafted resin-soluble polymer makes up between 10 and 30 weight percent of the grafted rubber additive.

28. The rubber-modified polytriazine of claim 27 wherein grafted resin-soluble polymer makes up between 15 and 20 percent of the grafted rubber additive.

29. The rubber-modified polytriazine of claim 28 wherein the rubber particles make up at least about 60 percent of the grafted rubber additive.

30. The rubber-modified polytriazine of claim 29 wherein the rubber particles make up at least about 80 percent of the grafted rubber additive.

31. The rubber-modified polytriazine of claim 27 wherein the concentration of ungrafted resin-soluble polymer is no more than about 7 weight percent of the rubber-modified polytriazine.

32. The rubber-modified polytriazine of claim 31 wherein the concentration of ungrafted resin-soluble polymer is no more than about 5 weight percent of the rubber-modified polytriazine.

33. The rubber-modified polytriazine of claim 27 wherein the rubber-modified polytriazine contains between 10 and 30 weight percent grafted rubber additive.

34. The rubber-modified polytriazine of claim 27 wherein the rubber particles of the grafted rubber additive are cross-linked styrene-butadiene rubber copolymer and the resin-soluble polymer is styrene-acrylonitrile copolymer.

35. A process for creating a uniform dispersion of grafted rubber additive in cyanate ester resin, said process comprising the steps of:

1. contacting a grafted rubber additive, which contains a cross-linked rubber core having grafted thereto a resin-soluble polymer which is compatible with the cyanate ester resin, with an organic solvent, which can form a stable dispersion of the graft rubber additive without dissolving the rubber core or causing substantial swelling of the rubber core and can disperse uniformly with a cyanate ester resin or solution containing cyanate ester resin, under conditions such that a stable dispersion of the grafted rubber additive in the solvent is formed;

2. contacting the stable dispersion from step (1) with a cyanate ester resin and/or an organic solution containing a cyanate ester resin under conditions such that a uniform stable dispersion is formed; and

3. removing the solvent in a manner such that the grafted rubber additive remains uniformly dispersed throughout the cyanate ester resin.