Hydroxyl-terminated thiocarbonate containing compounds, polymers, and copolymers, and polyurethanes and urethane acrylics made therefrom

A hydroxyl-terminated thiocarbonate represented by a compound of the formula:

• wherein R14 is a polyol residue, wherein said polyol is selected from a hydrocarbon polyol wherein R14 is selected from a substituted or unsubstituted alkylene group having from 2 to about 200 carbon atoms, and wherein said substituted alkylene group having a substituent selected from a halide and cyano;
• a polyester polyol, polyether polyol, polyhydroxy polyester amide, a polycaprolactone having a hydroxyl group, an epoxide having a hydroxyl group, polyhydroxy polycarbonate, polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylated polysiloxane polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyacrylate polyol, halogenated polyester polyol, halogenated polyether polyol, and combinations thereof;
• wherein said —R14-(TC)— of Formula 1 is represented by the formula:
• wherein a is from 1 to about 20, wherein R1 and R2, independently, are selected from substituted and unsubstituted linear and branched alkyl having from 1 to about 6 carbon atoms, and substituted or unsubstituted aryl having from 1 to 6 substituents on the aryl ring;
• wherein said substituents on said substituted alkyl and on said substituted aryl groups, independently, are selected from an alkyl having from 1 to 6 carbon atoms, aryl, halogen, cyano, an ether having a total of from 2 to about 20 carbon atoms, nitro, and combinations thereof;
• and R1 and R2 are part of a cyclic ring having from about 5 to about 12 total carbon atoms;
• or
• wherein said —R14-(TC)— of Formula 1 is represented by the formula:
• wherein c is from 1 to about 20;
• wherein R4 and R5, independently, are selected from substituted and unsubstituted linear and branched alkyl having from 1 to about 12 carbon atoms;
• substituted and unsubstituted aryl having from 6 to about 18 carbon atoms;
• R4 and R5 can form a substituted and unsubstituted cyclic ring having from 3 to about 12 carbon atoms;
• wherein when R4 and R5 are substituted said substituents, independently, are selected from an alkyl having from 1 to 6 carbon atoms, aryl, halogen, cyano, an ether having a total of from 2 to about 20 carbon atoms, nitro, and combinations thereof;
• and T is a divalent radical having a nitrogen atom directly connected to a thiocarbonyl group and is represented by the formula:
• wherein R8 and R9, independently, are selected from hydrogen, substituted and unsubstituted linear or branched alkyl having from 1 to about 18 carbon atoms, substituted and unsubstituted aryl having from about 6 to about 18 carbon atoms, substituted and unsubstituted arylalkyl having from 7 to about 18 carbon atoms, substituted and unsubstituted alkenealkyl having from 3 to about 18 carbon atoms, wherein when R8 and R9 are substituted the substituents are selected from an alkyl having, from 1 to 6 carbon atoms, aryl, halogen which can be the same or different, cyano, an ether having a total of from 2 to about 20 carbon atoms, nitro, and combinations thereof;
• wherein R10 is present or not present and is selected from a substituted and unsubstituted alkylene group having from 1 to about 18 carbon atoms, a substituted and unsubstituted polyalkylene glycol ether residue having from 3 to about 200 carbon atoms, wherein when R10 is substituted the substituents are selected from an alkyl having from 1 to 6 carbon atoms, aryl, halogen which can be the same or different, cyano, an ether having a total of from 2 to about 20 carbon atoms, nitro, and combinations thereof;
• and
• wherein R11 and R12, independently, are selected from a substituted and unsubstituted alkylene group having from 1 to 4 carbon atoms, with R11 and R12 having a total of from about 3 to about 5 carbon atoms, wherein when R11 and R12 are substituted the substituents are selected from an alkyl having from 1 to 6 carbon atoms, aryl, halogen which can be the same or different, cyano, an ether having a total of from 2 to about 20 carbon atoms, nitro, and combinations thereof;
• and
• wherein said —R14-(TC)— of Formula 1 is represented by the formula:
• wherein e is from 1 to about 20;
• wherein R4 and R5, independently, are defined as set forth above;
• wherein R13 is selected from a substituted or unsubstituted linear or branched alkylene having from 1 to about 12 carbon atoms, aryl, a polyalkylene glycol residue;
• wherein when R13 substituted said substituents are selected from an alkyl having from 1 to 6 carbon atoms, aryl, halogen, a cyano group, an amino group, an alkene group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, an acyloxy group, a carbarnoyl group, an alkylcarbonyl group, an alkylarylcarbonyl group, an arylcarbonyl group, an arylalkylcarbonyl group, a phthalimido group, a maleimido group, a succinimido group, amidino group;
• guanidimo group, allyl group, epoxy group, alkoxy group, an alkali metal salt, a quaternary ammonium salt, a hydroxyl group, nitro, a carboalkoxy group and combinations thereof;
• or
• wherein said TC of Formula 2 is represented by the formula:
• wherein R3 is selected from benzyl, a substituted and unsubstituted C1 through C18 alkyl, wherein said substituent when present is selected from halogen, hydroxyl, alkoxy, a C1 to C18 hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl, carboalkoxyalkyl, and mercaptoalkyl;
• and wherein R1 and R2, independently, are defined as set forth above;
• or
• wherein TC of Formula 2 is represented by the formula:
• wherein R4 and R5, independently, are defined as set forth above;
• and wherein R6 and R7, independently, are selected from hydrogen, a substituted and unsubstituted linear and branched alkyl having from 1 to about 18 carbon atoms, a substituted and unsubstituted aryl having from 6 to about 18 carbon atoms optionally saturated or unsaturated, a substituted and unsubstituted arylalkyl having from about 7 to about 18 carbon atoms, a substituted and unsubstituted alkenealkyl having from 3 to about 18 carbon atoms, a polyalkylene glycol ether residue having from 3 to about 200 carbon atoms, piperazine, morpholine, pyrrolidone, piperidine, 4-alkyl amino-2,2,6,6-tetramethyl piperidine, 1-alkylamioalkyl-3,3,5,5-tetramethyl-2-piperazinone, hexamethyleneimine, phenothiazine, iminodibenzyl, phehoxazine, N,N′-diphenyl-1,4-phenylenediarnine, and dicyclohexylamine, or R6 and R7 can form a substituted or unsubstituted cyclic ring having a total of from 4 to about 12 carbon atoms;
• and wherein when said R6 and R7 are substituted said substituents, independently, are selected from an alkyl having from 1 to 6 carbon atoms, aryl, halogen, a cyano group, an amino group, an alkene group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, an acyloxy group, a carbamoyl group, an alkylcarbonyl group, an alkylarylcarbonyl group, an arylcarbonyl group, an arylalkylcarbonyl group, a phthalimido group, a maleimido group, a succinimido group, amidino group;
• guanidimo group, allyl group, epoxy group, alkoxy group, an alkali metal salt, a quaternary ammonium salt, a hydroxyl group, an ether having a total of from 2 to about 20 carbon atoms, a nitro, a carboalkoxy group, and combinations thereof;
• or
• wherein said TC of Formula 2 is represented by the formula:
• wherein R4 and R5, independently, are defined as set forth above;
• and wherein R13 is optionally substituted and is selected from a linear and branched alkyl having from 1 to about 12 carbon atoms, aryl, arylalkyl having from about 7 to about 18 carbon atoms, acyl, alkenealkyl having from 3 to about 18 carbon atoms, a polyalkylene glycol residue, a polyalkylene glycol monoalkyl ether residue having from about 3 to about 200 carbon atoms, a polyalkylene glycol monoaryl ether residue having from about 3 to about 200 carbon atoms;
• wherein when said R13 is substituted said substituents, independently, are selected from an alkyl having from 1 to 6 carbon atoms, aryl, halogen, a cyano group, an amino group, an alkene group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, an acyloxy group, a carbamoyl group, an alkylcarbonyl group, an alkylarylcarbonyl group, an arylcarbonyl group, an arylalkylcarbonyl group, a phthalimido group, a maleimido group, a succinimido group, amidino group;
• guanidimo group, allyl group, epoxy group, alkoxy group, an alkali metal salt, a quaternary ammonium salt, a hydroxyl group, an ether having a total of from 2 to about 20 carbon atoms, a nitro, a carboalkoxy group, and combinations thereof.