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

A block copolymer dispersion, comprising:

• at least one polyurethane block polymer comprising at least one repeat unit derived from a monoisocyanate or a polyisocyanate, at least one repeat unit derived from active hydrogen compound capable of reacting with said isocyanate, and optionally at least one repeat unit derived from a dispersant;
• and
• at least one thiocarbonate block polymer derived from a thiocarbonate compound 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;
• 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,
• 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;
• 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;
• 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 substantial hydrocarbon polyol 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, and wherein said substituted alkyl or alkylene group comprises oxygen, or a halogen;
• 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 T is a divalent radical having a nitrogen atom directly attached to a carbon atom of the thiocarbonyl group, and
• wherein said m and said n, independently, is from about 1 to about 10,000;
• wherein said conjugated diene monomer has a total of from 4 to about 12 carbon atoms;
• wherein said vinyl monomer has the formula
• where R15 comprises hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR17), carboxy, metal carboxylate (COOM) with M being sodium, potassium, calcium, zinc, or an ammonium salt, acyloxy, aroyloxy(O2CR17), alkoxy-carbonyl(CO2R17), or aryloxy-carbonyl;
• wherein R16 comprises hydrogen, R17, CO2H, CO2R17, COR17, CN, CONH2, CONHR17, O2CR17, OR17, or halogen;
• R17, independently, comprises C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently comprise 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 vinyl containing monomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;
• styrene, α methyl styrene, C1, —C12 alkyl styrenes with substitute groups either on the chain or on the ring, or combinations thereof;
• and
• wherein said thiocarbonate block copolymer is connected to said mono or polyisocyanate of said polyurethane block.

A process for forming a polyurethane comprising the steps of:

• (a) adding to a reaction vessel an isocyanate compound, a hydroxyl-terminated thiocarbonate compound, optionally an active hydrogen compound, and optionally a chain extender;
• said hydroxyl-terminated thiocarbonate compound 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;
• 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,
• 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;
• 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;
• 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 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, and wherein said substituted alkyl or alkylene group comprises oxygen, or a halogen;
• polyester polyol, polyether polyol, polyhydroxy polyester amide, 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 T is a divalent radical having a nitrogen atom directly attached to a carbon atom of a thiocarbonyl group, and
• wherein said m and said n, independently, is from about 1 to about 10,000;
• wherein said conjugated diene monomer has a total of from 4 to about 12 carbon atoms;
• wherein said vinyl monomer has the formula
• where R15 comprises hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR17), carboxy, metal carboxylate (COOM) with M being sodium, potassium, calcium, zinc, or an ammonium salt, acyloxy, aroyloxy(O2CR17), alkoxy-carbonyl(CO2R17), or aryloxy-carbonyl;
• wherein R16 comprises hydrogen, R17, CO2H, CO2R17, COR17, CN, CONH2, CONHR17, O2CR17, OR17, or halogen;
• R17, independently, comprises C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently comprise 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 vinyl containing monomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;
• styrene, α methyl styrene, C1, —C12 alkyl styrenes with substitute groups either on the chain or on the ring, or combinations thereof;
• and
• reacting said compounds to form a thermoplastic polyurethane.

A process for forming a polyurethane dispersion comprising the steps of:

• (a) reacting an isocyanate compound, a dispersant, and a hydroxyl-terminated thiocarbonate compound containing repeat groups therein derived from at least one conjugated diene, or at least one vinyl monomer, or combinations thereof, and forming a polyurethane, said thiocarbonate compound having the following formula:
• optionally an active hydrogen compound and optionally a chain extender;
• (b) neutralizing said polyurethane and forming a polyurethane dispersion in water;
• 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;
• 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,
• 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;
• 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 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 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, and wherein said substituted alkyl or alkylene group comprises oxygen, or a halogen;
• polyester polyol, polyether polyol, polyhydroxy polyester amide, 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 T is a divalent radical having a nitrogen atom directly attached to a carbon atom of the thiocarbonyl group;
• and
• wherein said m and said n, independently, is from about 1 to about 10,000;
• wherein said conjugated diene monomer has from 4 to about 12 carbon atoms;
• wherein said vinyl monomer has the formula
• where R15 comprises hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR17), carboxy, metal carboxylate (COOM) with M being sodium, potassium, calcium, zinc, or an ammonium salt, acyloxy, aroyloxy(O2CR17), alkoxy-carbonyl(CO2R17), or aryloxy-carbonyl;
• wherein R16 comprises hydrogen, R17, CO2H, CO2R17, COR17, CN, CONH2, CONHR17, O2CR17, OR17, or halogen;
• R17, independently, comprises C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently comprise 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 vinyl containing monomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;
• styrene, α methyl styrene, C1, —C12 alkyl styrenes with substitute groups both either on the chain or on the ring, or combinations thereof.

A process for forming a polyurethane dispersion comprising the steps of:

• (a) reacting an isocyanate;
• a dispersant;
• and a hydroxyl-terminated thiocarbonate compound;
• and optionally an active hydrogen compound;
• and forming a polyurethane in the presence of at least one diluent monomer, said diluent monomer comprising at least conjugated diene, or at least one vinyl monomer, or combinations thereof;
• wherein said thiocarbonate compound has the formula
• (b) neutralizing said polyurethane and forming a dispersion in water;
• and
• reacting said conjugated diene or vinyl monomer into said thiocarbonate compound;
• 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;
• 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,
• 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;
• 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;
• 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 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, and wherein said substituted alkyl or alkylene group comprises oxygen, or a halogen;
• polyester polyol, polyether polyol, polyhydroxy polyester amide, 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 T is a divalent radical having a nitrogen atom directly attached to a carbon atom of a thiocarbonyl group;
• and
• wherein said m and said n, independently, is from about 1 to about 10,000;
• wherein said conjugated diene monomer has from 4 to about 12 carbon atoms;
• wherein said vinyl monomer has the formula
• where R15 comprises hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR17), carboxy, metal carboxylate (COOM) with M being sodium, potassium, calcium, zinc, or an ammonium salt, acyloxy, aroyloxy(O2CR17), alkoxy-carbonyl(CO2R17), or aryloxy-carbonyl;
• wherein R16 comprises hydrogen, R17, CO2H, CO2R17, COR17, CN, CONH2, CONHR17, O2CR17, OR17, or halogen;
• R17, independently, comprises C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently comprise 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 vinyl containing monomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;
• styrene, α methyl styrene, C1, —C12 alkyl styrenes with substitute groups both either on the chain or on the ring, or combinations thereof.

A process for forming a neutralized block copolymer dispersion, comprising the steps of:

• reacting at least one polyurethane block polymer with at least one thiocarbonate block polymer, said polyurethane block comprising at least one repeat unit derived from an mono-isocyanate or a polyisocyanate, at least one repeat unit derived from an active hydrogen compound, and at least one repeat unit derived from a dispersant;
• said at least one thiocarbonate block copolymer containing repeat units derived from a hydroxyl terminated thiocarbonate containing compound, 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;
• 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,
• 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;
• 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;
• 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 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, and wherein said substituted alkyl or alkylene group comprises oxygen, or a halogen;
• polyester polyol, polyether polyol, polyhydroxy polyester amide, 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 T is a divalent radical having a nitrogen atom directly attached to a carbon atom of a thiocarbonyl group, and
• wherein said m and said n, independently, is from about 1 to about 10,000;
• wherein said conjugated diene monomer has a total of from 4 to about 12 carbon atoms;
• wherein said vinyl monomer has the formula
• where R15 comprises hydrogen, halogen, C1 to C4 alkyl, or substituted C1-C4 alkyl wherein the substituents, independently, comprise one or more hydroxy, alkoxy, aryloxy(OR17), carboxy, metal carboxylate (COOM) with M being sodium, potassium, calcium, zinc, or an ammonium salt, acyloxy, aroyloxy(O2CR17), alkoxy-carbonyl(CO2R17), or aryloxy-carbonyl;
• wherein R16 comprises hydrogen, R17, CO2H, CO2R17, COR17, CN, CONH2, CONHR17, O2CR17, OR17, or halogen;
• R17, independently, comprises C1-C18 alkyl, substituted C1-C18 alkyl, C2-C18 alkenyl, aryl, heterocyclyl, aralkyl, or alkaryl, wherein the substituents independently comprise 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 vinyl containing monomer is maleic anhydride, N-vinyl pyrrolidone, N-alkylmaleimide, N-arylmaleimide, dialkyl fumarate and cyclo-polymerizable monomers;
• styrene, α methyl styrene, C1, —C12 alkyl styrenes with substitute groups either on the chain or on the ring, or combinations thereof;
• and reacting said thiocarbonate block copolymer with said polyurethane block.