Hydroxyl-Terminated Thiocarbonate Containing Compounds, Polymers, and Copolymers, and Polyurethanes and Urethane Acrylics Made Therefrom

A hydroxyl-terminated compound, comprising:

• a polymer or copolymer having the formula
• wherein, in the above formulas:
• each 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 one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring;
• wherein said one or more substitutents, independently, comprise 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 combinations thereof;
• or wherein R1 and R2 are part of a cyclic ring having from about 5 to about 12 total carbon atoms;
• each R3, independently, is benzyl, a C1 through C18 alkyl, or a substituted C1 to C18 alkyl wherein said substituted group is halogen, hydroxyl, or alkoxy, or a C1 to C18 hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl, carboalkoxyalkyl, or mercaptoalkyl,
• each R4 and R5, independently, is optionally substituted, and is a linear or branched alkyl having from 1 to about 12 carbon atoms;
• or an aryl having from 6 to about 18 carbon atoms, optionally containing heteroatoms;
• or wherein said R4 and said R5 substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20 carbon atoms, a nitro, or combinations thereof, or R4 and R5 can form a substituted or unsubstituted cyclic ring having from 3 to about 12 carbon atoms;
• wherein R6 and R7, independently, is optionally substituted and optionally contains heteroatoms;
• and is hydrogen;
• a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl having from 6 to about 18 carbon atoms optionally saturated or unsaturated;
• an arylalkyl having from about 7 to about 18 carbon atoms;
• an alkenealkyl having from 3 to about 18 carbon atoms;
• or is derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms;
• or is derived from 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, phenoxazine, N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivatives thereof;
• 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 said substituents, independently, are the same as R13;
• each R13, independently, is optionally substituted, and is a linear or branched alkyl or alkylene having from 1 to about 12 carbon atoms, an aryl optionally saturated or unsaturated;
• an arylalkyl having from about 7 to about 18 carbon atoms;
• an acyl;
• an alkene group;
• an alkenealkyl having from 3 to about 18 carbon atoms;
• an alkylene group;
• an alkoxyalkyl derived from a polyalkylene glycol or derived from a polyalkylene glycol monoalkyl ether having from about 3 to about 200 carbon atoms or derived from a polyalkylene glycol monoaryl ether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;
• a phosphorous containing alkyl;
• or a substituted or unsubstituted aryl ring containing heteroatoms;
• or
• wherein the R13 substituents comprise an alkyl having from 1 to 6 carbon atoms;
• an aryl;
• a halogen such as fluorine or chlorine;
• 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;
• sulfur;
• phosphorous;
• a carboalkoxy group;
• a heterocyclic group containing one or more sulfur, oxygen or nitrogen atoms, or combinations thereof;
• each R14 is derived from a polyol, wherein said polyol comprises a hydrocarbon polyol wherein R14 comprises an alkyl or an alkylene group, or a substituted alkyl or alkylene group having from 2 to about 200 carbon atoms, and wherein said substituted alkyl or alkylene group comprises oxygen, or a halogen;
• a polyester polyol, polyether polyol, polyhydroxy polyester amide, polyolefin, hydroxyl-containing polycaprolactone, hydroxyl-containing acrylic interpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate, polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylated polysiloxane polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyacrylate polyol, halogenated polyester polyol, or halogenated polyether polyol, or combinations thereof;
• wherein said m and said n, independently, is from about 1 to about 10,000;
• wherein said T is
• wherein R8 and R9, independently, is optionally substituted and is hydrogen, a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl group having from about 6 to about 18 carbon atoms, an arylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl having from 3 to about 18 carbon atoms, wherein the substituents can be the same as described herein for R1 and R2;
• wherein R10 is optionally substituted, and is non-existent, or an alkylene group having from 1 to about 18 carbon atoms with about 1 to about 6 carbon atoms preferred, or derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms, wherein the substituents can be the same as described herein for R1 and R2 or are hereroatoms such as oxygen, nitrogen, sulfur or phosphorous;
• and
• wherein R11 and R12, independently, is an 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 R11 and R12, independently, is optionally substituted and wherein said substituted are, independently, R1 and R2.

A process for forming a hydroxyl-terminated thiocarbonate, comprising the step of:

• reacting a thiocarbonate compound with a polyol;
• said thiocarbonate 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 one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring;
• wherein said one or more substituents, independently, comprise 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 combinations thereof;
• or wherein R1 and R2 are part of a cyclic ring having from about 5 to about 12 total carbon atoms;
• or
• said thiocarbonate has the formula
• wherein R3 is benzyl, a C1 through C18 alkyl, or a substituted C1 to C18 alkyl wherein said substituted group is halogen, hydroxyl, or alkoxy, or a C1 to C18 hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl, carboalkoxyalkyl, or mercaptoalkyl, and
• wherein R1 and R2, independently, are as set forth above;
• or
• said thiocarbonate has the formula
• wherein R4 and R5, independently, is optionally substituted, and is a linear or branched alkyl having from 1 to about 12 carbon atoms;
• or an aryl having from 6 to about 18 carbon atoms, optionally containing heteroatoms;
• or wherein said R4 and said R5 substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20 carbon atoms, a nitro, or combinations thereof, or R4 and R5 can form a substituted or unsubstituted cyclic ring having from 3 to about 12 carbon atoms;
• or
• wherein R6 and R7, independently, is optionally substituted and optionally contains heteroatoms;
• and is hydrogen;
• a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl having from 6 to about 18 carbon atoms optionally saturated or unsaturated;
• an arylalkyl having from about 7 to about 18 carbon atoms;
• an alkenealkyl having from 3 to about 18 carbon atoms;
• or is derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms;
• or is derived from 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, phenoxazine, N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivatives thereof;
• 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 said substituents, independently, are the same as R13;
• wherein said thiocarbonate is
• wherein R4 and R5, independently, is as set forth above;
• wherein said T is
• wherein R8 and R9, independently, is optionally substituted and is hydrogen, a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl group having from about 6 to about 18 carbon atoms, an arylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl having from 3 to about 18 carbon atoms, wherein the substituents can be the same as described herein for R1 and R2;
• wherein R10 is optionally substituted, and is non-existent, or an alkylene group having from 1 to about 18 carbon atoms with about 1 to about 6 carbon atoms preferred, or derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms, wherein the substituents can be the same as described herein for R1 and R2 or are hereroatoms such as oxygen, nitrogen, sulfur or phosphorous;
• and
• wherein R11 and R12, independently, is an 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 R11 and R12, independently, is optionally substituted and wherein said substituted are, independently, R1 and R2;
• wherein said thiocarbonyl has the formula
• wherein j=1, wherein R4 and R5 are as defined hereinabove, and wherein R13, is optionally substituted, and is a linear or branched alkyl or alkylene having from 1 to about 12 carbon atoms, an aryl optionally saturated or unsaturated;
• an arylalkyl having from about 7 to about 18 carbon atoms;
• an acyl;
• an alkene group;
• an alkenealkyl having from 3 to about 18 carbon atoms;
• an alkylene group;
• an alkoxyalkyl derived from a polyalkylene glycol or derived from a polyalkylene glycol monoalkyl ether having from about 3 to about 200 carbon atoms or derived from a polyalkylene glycol monoaryl ether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;
• a phosphorous containing alkyl;
• or a substituted or unsubstituted aryl ring containing heteroatoms;
• or
• said thiocarbonyl compound has the formula
• wherein R4 and R5, independently, are as set forth above, and wherein R13, independently, is as set forth above;
• and
• wherein said polyol comprises a hydrocarbon polyol of the formula HO—R14—(OH)n and wherein R14 comprises an alkyl or an alkylene group, or a substituted alkyl or alkylene group having from 2 to about 200 carbon atoms, wherein n is 1 to about 7, and wherein said substituted alkyl or alkylene group comprises oxygen;
• a polyester polyol, polyether polyol, polyhydroxy polyester amide, polyolefin, hydroxyl-containing polycaprolactone, hydroxyl-containing acrylic interpolymer, hydroxyl-containing epoxide, polyhydroxy polycarbonate, polyhydroxy polyacetal, polyhydroxy polythioether, polysiloxane polyol, ethoxylated polysiloxane polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyacrylate polyol, halogenated polyester polyol, or halogenated polyether polyol, or combinations thereof.

A process for producing a hydroxyl-terminated thiocarbonate polymer or copolymer, comprising the steps of:

• reacting a thiocarbonate polymer or copolymer with a polyol,
• said thiocarbonate polymer or copolymer having the formula
• wherein, in the above formulas:
• each 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 one or more aryls, or a substituted aryl having from 1 to 6 substituents on the aryl ring;
• wherein said one or more substituents, independently, comprise 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 combinations thereof;
• or wherein R1 and R2 are part of a cyclic ring having from about 5 to about 12 total carbon atoms;
• each R3, independently, is benzyl, a C1 through C18 alkyl, or a substituted C1 to C18 alkyl wherein said substituted group is halogen, hydroxyl, or alkoxy, or a C1 to C18 hydroxyalkyl, aralkyl, cyanoalkyl, aminoalkyl, carboxylalkyl, carboalkoxyalkyl, or mercaptoalkyl,
• each R4 and R5, independently, is optionally substituted, and is a linear or branched alkyl having from 1 to about 12 carbon atoms;
• or an aryl having from 6 to about 18 carbon atoms, optionally containing heteroatoms;
• or wherein said R4 and said R5 substituents, independently, comprise an alkyl having from 1 to 6 carbon atoms, an aryl, a halogen, a cyano, an ether having from 2 to about 20 carbon atoms, a nitro, or combinations thereof, or R4 and R5 can form a substituted or unsubstituted cyclic ring having from 3 to about 12 carbon atoms;
• and T is a divalent radical having a nitrogen atom directly connected to a thiocarbonyl groups;
• wherein R6 and R7, independently, is optionally substituted and optionally contains heteroatoms;
• and is hydrogen;
• a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl having from 6 to about 18 carbon atoms optionally saturated or unsaturated;
• an arylalkyl having from about 7 to about 18 carbon atoms;
• an alkenealkyl having from 3 to about 18 carbon atoms;
• or is derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms;
• or is derived from 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, phenoxazine, N,N′-diphenyl-1,4-phenylenediamine, dicyclohexylamine, or derivatives thereof;
• 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 said substituents, independently, are the same as R13;
• each R13, independently, is optionally substituted, and is a linear or branched alkyl or alkylene having from 1 to about 12 carbon atoms, an aryl optionally saturated or unsaturated;
• an arylalkyl having from about 7 to about 18 carbon atoms;
• an acyl;
• an alkene group;
• an alkenealkyl having from 3 to about 18 carbon atoms;
• an alkylene group;
• an alkoxyalkyl derived from a polyalkylene glycol or derived from a polyalkylene glycol monoalkyl ether having from about 3 to about 200 carbon atoms or derived from a polyalkylene glycol monoaryl ether having from about 3 to about 200 carbon atoms, a polyfluoroalkyl;
• a phosphorous containing alkyl;
• or a substituted or unsubstituted aryl ring containing heteroatoms;
• or
• wherein the R13 substituents comprise an alkyl having from 1 to 6 carbon atoms;
• an aryl;
• a halogen such as fluorine or chlorine;
• 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;
• sulfur;
• phosphorous;
• a carboalkoxy group;
• a heterocyclic group containing one or more sulfur, oxygen or nitrogen atoms, or combinations thereof;
• wherein said T is
• wherein R8 and R9, independently, is optionally substituted and is hydrogen, a linear or branched alkyl having from 1 to about 18 carbon atoms, an aryl group having from about 6 to about 18 carbon atoms, an arylalkyl having from 7 to about 18 carbon atoms, an alkenealkyl having from 3 to about 18 carbon atoms, wherein the substituents can be the same as described herein for R1 and R2;
• wherein R10 is optionally substituted, and is non-existent, or an alkylene group having from 1 to about 18 carbon atoms with about 1 to about 6 carbon atoms preferred, or derived from a polyalkylene glycol ether having from 3 to about 200 carbon atoms, wherein the substituents can be the same as described herein for R1 and R2 or are hereroatoms such as oxygen, nitrogen, sulfur or phosphorous;
• and
• wherein R11 and R12, independently, is an 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 R11 and R12, independently, is optionally substituted and wherein said substituted are, independently, R1 and R2;
• wherein said m and said n, independently, is from about 1 to about 10,000.