S,S′-bis-(α, α′—disubstituted—α″—acetic acid)—trithiocarbonates and polymers thereof for toughening thermosetting resins

A composition, comprising:

• the reaction product of a polymer with an epoxy resin in the presence of an acid anhydride curing agent, wherein said polymer is represented by the formula
• wherein R1 and R2, independently, is a linear or branched alkyl having from 1 to about 6 carbon atoms, or a substituted C1 to about C6 alkyl having one or more substituents, or aryl, or a substituted aryl having from 1 to 6 substituents on the aryl ring;
• wherein said one or more substituents, independently, represent an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atom, or a nitro;
• or wherein R1 and R2 are part of a ring having from about 5 to about 12 total carbon atoms;
• and
• wherein said (polymer), independently, is derived from a conjugated diene monomer containing from 4 to about 12 carbon atoms, or is derived from a vinyl monomer having the formula
• where R3 is selected from hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR5), carboxy, acyloxy, aryloxy(O2CR5), alkoxy-carbonyl(CO2R5), or aryloxy-carbonyl;
• wherein R4 is selected from hydrogen, R5, CO2H, CO2R5, COR5, CN, CONH2, CONHR5, O2CR5, OR5, or halogen;
• wherein R5 is selected from C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently are selected from one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato, cyano, silyl, halo and dialkylamino;
• or wherein said polymer is derived from maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate a cyclo-polymerizable monomer, styrene, α-methyl styrene, C1-C12 alkyl styrene with substituent groups both either on the chain or on the ring, N,N-alkylacrylamide, or combinations thereof.

A composition comprising:

• the reaction product of a polymer with an epoxy resin in the presence of a curing agent, wherein said polymer is represented the formula
• wherein R1 and R2, independently, is a linear or branched alkyl having from 1 to about 6 carbon atoms, or a substituted C1 to about C6 alkyl having one or more substituents, or aryl, or a substituted aryl having from 1 to 6 substituents on the aryl ring;
• wherein said one or more substituents, independently, represent an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or wherein R1 and R2 are part of a ring having from about 5 to about 12 total carbon atoms;
• wherein said (polymer), independently, is derived from a conjugated diene monomer containing from 4 to about 12 carbon atoms, or is derived from a vinyl monomer having the formula
• where R3 is selected from hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR5), carboxy, acyloxy, aryloxy(O2CR5), alkoxy-carbonyl(CO2R5), or aryloxy-carbonyl;
• wherein R4 is selected from hydrogen, R5, CO2H, CO2R5, COR5, CN, CONH2, CONHR5, O2CR5, OR5, or halogen;
• wherein R5 is selected from C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently are selected from one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato, cyano, silyl, halo and dialkylamnino;
• or wherein said (polymer), independently, is derived from maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate a cyclo-polymerizable monomer;
• styrene, α-methyl styrene, C1-C12 alkyl styrene with substituent groups both either on the chain or on the ring, N,N-alkylacrylamide, or combinations thereof;
• wherein said EPOXY is derived from glycidyl ethers of novolae resins;
• glycidyl ethers of mononuclear di- and trihydric phenols;
• glycidyl ethers of bisphenols;
• glycidyl ethers of polynuclear phenols;
• epoxy resin from diphenolic acid;
• glycidyl ethers of aliphatic polyols;
• glycidyl esters;
• glycidyl epoxies containing nitrogen;
• glycidyl derivatives of cyanuric acid;
• glycidyl amines;
• thioglycidyl resins;
• silicon-glycidyl resins;
• fluorine glycidyl resins;
• epoxy resins where are synthesized from monoepoxies other than epihalohydrins including epoxy resins from unsaturated monoepoxies;
• epoxy resins from monoepoxy alcohols;
• epoxy resins from monoepoxies by ester interchange;
• epoxy resins from glycidaldehyde;
• polyglycidyl compounds containing unsaturation epoxy resins which are synthesized from olefins and chloroacetyls;
• or epoxy-resin adducts of the above, or combinations thereof.

A process for forming a thermoset composition, comprising the steps of:

• mixing a polymer and an epoxy resin, said polymer having the formula
• wherein R1 and R2, independently, is a linear or branched alkyl having from 1 to about 6 carbon atoms, or a substituted C1 to about C6 alkyl having one or more substituents, or aryl, or a substituted aryl having from 1 to 6 substituents on the aryl ring;
• wherein said one or more substituents, independently, represent an alkyl having from 1 to 6 carbon atoms, or an aryl, or a halogen which can be the same or different, or a cyano, or an ether having a total of from 2 to about 20 carbon atoms, or a nitro, or wherein R1 and R2 are part of a ring having from about 5 to about 12 total carbon atoms;
• wherein said (polymer), independently, is derived from a conjugated diene monomer containing from 4 to about 12 carbon atoms, or is derived from a vinyl monomer having the formula
• where R3 is selected from hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR5), carboxy, acyloxy, aryloxy(O2CR5), alkoxy-carbonyl(CO2R5), or aryloxy-carbonyl;
• wherein R4 is selected from hydrogen, R5, CO2H, CO2R5, COR5, CN, CONH2, CONHR5, O2CR5, OR5, or halogen;
• wherein R5 is selected from C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently are selected from one or more epoxy, hydroxy, alkoxy, acyl, acyloxy, carboxy (and salts), sulfonic acid (and salts), alkoxy- or aryloxy-carbonyl, dicyanato, cyano, silyl, halo and dialkylamino;
• or wherein said (polymer), independently, is derived from maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate a cyclo- polymerizable monomer;
• styrene, α-methyl styrene, C1-C12 alkyl styrene with substitute groups both either on the chain or on the ring, N,N-alkylacrylamide, or combinations thereof;
• wherein said EPOXY is derived from glycidyl ethers of novolac resins;
• glycidyl ethers of mononuclear di- and trihydric phenols;
• glycidyl ethers of bisphenols;
• glycidyl ethers of polynuclear phenols;
• epoxy resin from diphenolic acid;
• glycidyl ethers of aliphatic polyols;
• glycidyl esters;
• glycidyl epoxies containing nitrogen;
• glycidyl derivatives of cyanuric acid;
• glycidyl amines;
• thioglycidyl resins;
• silicon-glycidyl resins;
• fluorine glycidyl resins;
• epoxy resins where are synthesized from monoepoxies other than epihalohydrins including epoxy resins from unsaturated monoepoxies;
• epoxy resins from monoepoxy alcohols;
• epoxy resins from monoepoxies by ester interchange;
• epoxy resins from glycidaldehyde;
• polyglycidyl compounds containing unsaturation;
• epoxy resins which are synthesized from olefins and chloroacetyls;
• or epoxy-resin adducts of the above, or combinations thereof.