Chain expended or branched copolymers of vinylidene aromatic monomer and unsaturated compounds with electrophilic groups
Disclosed are such co-polymers of vinylidene substituted aromatic monomers and unsaturated compounds containing nucleophilic groups chain extended by a copolymer of one or more vinylidene aromatic monomers and one or more unsaturated compounds having pendant electrophilic groups which copolymerize with the one or more vinylidene aromatic monomers. Disclosed are compositions comprising vinylidene substituted aromatic monomers and unsaturated compounds containing nucleophilic groups and a copolymer of one or more vinylidene aromatic monomers and one or more unsaturated compounds having pendant electrophilic groups, which may optionally, contain salts of alkaline earth metals, alkali metals, transition metals, post transition metals or metalloids. Disclosed are methods of preparing such chain-extended and/or branched copolymers.
1. A composition comprising one or more chain extended and/or branched copolymers which is the product of
one or more first copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing on average about 0.02 to about 3.0 percent by weight of nucleophilic groups pendant from the first copolymer, and
one or more second copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups,
wherein the one or more first copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups are chain extended and/or branched by the one or more second copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups as a result of formation of bonds by all or a portion of the nucleophilic groups of the first copolymer with all or a portion of the electrophilic groups of the second copolymer,
wherein the one or more chain extended and/or branched copolymers are soluble in methylene chloride at 23° C. and exhibit a polydispersity of 2.5 or greater.
2. The composition according to claim 1 wherein the one or more chain extended and/or branched copolymers contain from about 0.1 to about 0.5 percent by weight of the one or more second copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups, wherein the electrophilic groups are pendant from the one or more second copolymers.
3. The composition of claim 1 wherein the nucleophilic groups are carboxylate, carboxylic acid, alcohol, phenol, amine, aniline, imidazole, tetrazole, thiol, boronic acid, glycol, hydrazine and hydroxyl amine groups and the electrophilic groups are one or more of epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate and isothiocyanate groups.
4. The composition of claim 1 , wherein the nucleophilic groups are carboxylic acid groups and the electrophilic groups are one or more of epoxide groups.
5. The composition of claim 1 , wherein the Mz of the one or more chain extended and/or branched copolymers is from about 300 kg/mole to about 1,000 kg/mole and the Mw is from about 100 kg/mole to about 400 kg/mole.
6. The composition of claim 1 , wherein the one or more first copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing a nucleophilic group contains from about 0.5 to about 1.5 percent by weight nucleophilic groups.
7. The composition of claim 1 , wherein the melt viscosity at 0.314 s −1 angular frequency of the one or more chain extended and/or branched copolymers is at least 10 percent higher than the melt viscosity of one or more first copolymers without branching and chain extension when measured at 220° C.
8. The composition of claim 1 , wherein the nucleophilic groups are carboxylic acid groups.
9. A method of preparing a composition according to claim 1 , comprising:
melt blending one or more first copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.02 to about 3.0 percent by weight of nucleophilic groups pendant from the copolymer, with one or more second copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups; at a temperature of about 200° C. to about 300° C. for a time period of about 0.5 to about 5 minutes wherein the first copolymer of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups is chain extended and/or branched by the second copolymer of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups to form the one or more chain extended and/or branched copolymer which is soluble in methylene chloride at 23° C. and exhibits a polydispersity of 3.0 or greater.
10. The method of claim 9 , wherein the one or more first copolymers and one or more second copolymers are melt blended at a temperature of about 200° C. to about 260° C. for a time period of about 0.5 to about 3.0 minutes to form a melt blend, and a metalloid or a metal salt is added to the melt blend at a concentration of about 50 ppm to about 5000 ppm based on the weight of the copolymers and the copolymers are reacted under conditions such that the specific energy values are greater than 400 J/g.
11. The composition of claim 1 , wherein the polydispersity is about 3.2 or greater.
12. The composition of claim 1 , wherein the composition comprises a continuous matrix containing the chain extended and/or branched copolymer and a dispersed phase comprising an impact modifier.
13. The composition of claim 12 , wherein the dispersed phase comprises particles of about 0.05 to about 6.0 microns.
14. A composition comprising:
a) from about 90 to about 99.9 weight percent of one or more first copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.02 to about 3.0 percent by weight of nucleophilic groups pendant from the copolymer; and
b) from about 0.1 to about 10.0 weight percent of one or more second copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups.
15. The composition of claim 14 comprising:
from about 0.1 to about 0.5 percent of one or more second copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having pendant electrophilic groups.
16. The composition of claim 14 , wherein the nucleophilic groups are one or more of carboxylic acid, carboxylate, alcohol, phenol, amine, aniline, imidazole, tetrazole, thiol, boronic acid, glycol, hydrazine and hydroxyl amine groups and the electrophilic groups are one or more of epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate and isothiocyanate groups.
17. The composition of claim 14 , wherein the composition contains a metal salt comprises a salt of a transition metal, an alkali metal, an alkaline earth metal, or a post transition metal.
18. The composition of claim 17 , wherein the mole ratio of metal salts to nucleophilic groups on the first copolymer of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups is about 20:1 to about 1:20.
19. The composition of claim 14 , comprising one or more impact modifiers.
20. The composition of claim 14 , wherein the electrophilic groups are one or more of epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate and isothiocyanate groups.