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

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

wherein R 14 is a polyol residue, wherein said polyol is selected from a hydrocarbon polyol wherein R 14 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 —R 14 -(TC)— of Formula 1 is represented by the formula:

wherein a is from 1 to about 20, wherein R 1 and R 2 , 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 R 1 and R 2 are part of a cyclic ring having from about 5 to about 12 total carbon atoms; or

wherein said —R 14 -(TC)— of Formula 1 is represented by the formula:

wherein c is from 1 to about 20; wherein R 4 and R 5 , 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; R 4 and R 5 can form a substituted and unsubstituted cyclic ring having from 3 to about 12 carbon atoms; wherein when R 4 and R 5 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 R 8 and R 9 , 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 R 8 and R 9 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 R 10 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 R 10 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 R 11 and R 12 , independently, are selected from a substituted and unsubstituted alkylene group having from 1 to 4 carbon atoms, with R 11 and R 12 having a total of from about 3 to about 5 carbon atoms, wherein when R 11 and R 12 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 —R 14 -(TC)— of Formula 1 is represented by the formula:

wherein e is from 1 to about 20; wherein R 4 and R 5 , independently, are defined as set forth above; wherein R 13 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 R 13 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 R 3 is selected from benzyl, a substituted and unsubstituted C 1 through C 18 alkyl, wherein said substituent when present is selected from halogen, hydroxyl, alkoxy, a C 1 to C 18 hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl, carboalkoxyalkyl, and mercaptoalkyl; and wherein R 1 and R 2 , independently, are defined as set forth above; or

wherein TC of Formula 2 is represented by the formula:

wherein R 4 and R 5 , independently, are defined as set forth above; and wherein R 6 and R 7 , 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 R 6 and R 7 can form a substituted or unsubstituted cyclic ring having a total of from 4 to about 12 carbon atoms; and wherein when said R 6 and R 7 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 R 4 and R 5 , independently, are defined as set forth above; and wherein R 13 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 R 13 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.

2. The hydroxyl-terminated thiocarbonate according to claim 1 , wherein R 1 and R 2 , independently, are selected from methyl, and phenyl, wherein R 3 is an alkyl having from 1 to about 18 carbon atoms; wherein R 4 and R 5 , independently, are selected from methyl and phenyl.

3. The hydroxyl-terminated thiocarbonate according to claim 2 , wherein R 6 and R 7 , independently, are selected from a phenyl, an alkyl, and a substituted alkyl having from 1 to about 18 carbon atoms.

4. The hydroxyl-terminated thiocarbonate according to claim 3 , wherein R 6 and R 7 are selected from methylene and hexamethylene.

5. The hydroxyl-terminated thiocarbonate according to claim 1 , wherein said polyol is said hydrocarbon polyol.

6. The hydroxyl-terminated thiocarbonate according to claim 2 , wherein said polyol is said hydrocarbon polyol and wherein said alkyl or alkylene group, or said substituted alkyl or alkylene group has from 2 to about 10 carbon atoms.

7. The hydroxyl-terminated thiocarbonate according to claim 4 , wherein said polyol is selected from ethylene glycol, diethylene glycol, propylene glycol, trimethyloipropane, butylene glycol, hexane diol, neopentyl glycol, polytetrahydrafuran, and combinations thereof.

8. The hydroxyl-terminated thiocarbonate according to claim 1 , wherein said TC of Formula 2 is represented by the formula:

and wherein said polyol is said hydrocarbon polyol and wherein said alkylene group, or said substituted alkylene group has from 2 to about 10 carbon atoms.

9. The hydroxyl-terminated thiocarbonate according to claim 7 , wherein said TC of Formula 2 is represented by the formula:

and wherein said polyol is selected from ethylene glycol, diethylene glycol, propylene glycol, trimethylolpropane, butylene glycol, hexane diol, neopentyl glycol, polytetrahydrafuran, and combinations thereof.