AQUEOUS POLYURETHANEUREA COMPOSITIONS INCLUDING DISPERSIONS AND FILMS
Included are polyurethaneurea compositions include polyurethaneurea aqueous dispersions. The dispersions may be prepared with solvent or in the absence of any added solvent. Films and other shaped articles may be prepared from the dispersions by a casting a drying method and optionally included with a substrate including paper, fabric or garments.
1 . A composition comprising a polyurethaneurea aqueous dispersion; said dispersion comprising a polymer which is the reaction product of:
(a) at least one polyol selected from polyethers, polyesters, polycarbonates, and combinations thereof, wherein the polyol has a number average molecular weight of 600 to 4000;
(b) a polyisocyanate comprising a member selected from the group consisting of aromatic diisocyantes, aliphatic diisocyanates, cycloaliphatic diiosocyanates, and combinations thereof;
(c) at least one diol compound comprising: (i) hydroxy groups capable of reacting with polyisocyanate, and (ii) at least one carboxylic acid group capable of forming a salt upon neutralization, wherein said at least one carboxylic acid group is incapable of reacting with the polyisocyanate;
(d) a neutralizing agent;
(e) a chain extender;
(f) a blocking agent for isocyanate groups comprising at least one mono-functional alcohol; and
at least one surface active agent.
2 . The composition of claim 1 , wherein said dispersion is substantially free of added solvent.
3 . The composition of claim 1 , wherein said polyol has a number average molecular weight of 600 to 3500;
4 . The composition of claim 1 , wherein said mono-functional alcohol comprises at least one member selected from the group consisting of aliphatic and cycloaliphatic primary and secondary alcohols with 1 to 18 carbons, phenol, substituted phenols, ethoxylated alkyl phenols and ethoxylated fatty alcohols with molecular weight less than 750, hydroxyamines, hydroxymethyl and hydroxyethyl substituted tertiary amines, hydroxymethyl and hydroxyethyl substituted heterocyclic compounds, and combinations thereof.
5 . The composition of claim 1 , wherein said mono-functional alcohol comprises at least one member selected from the group consisting of furfuryl alcohol, tetrahydrofurfuryl alcohol, N-(2-hydroxyethyl)succinimide, 4-(2-hydroxyethyl)morpholine, methanol, ethanol, butanol, neopentyl alcohol, hexanol, cyclohexanol, cyclohexanemethanol, benzyl alcohol, octanol, octadecanol, N,N-diethylhydroxylamine, 2-(diethylamino)ethanol, 2-dimethylaminoethanol, and 4-piperidineethanol, and combinations thereof.
6 . The composition of claim 1 , wherein the polyol comprises a poly(tetramethylene ether) glycol having a number average molecular weight of 1400 to 2400.
7 . The composition of claim 1 , wherein the chain extender is selected from water, a diamine chain extender and combinations thereof.
8 . The composition of claim 1 , wherein said polyisocyanate comprises a mixture of 4,4′- and 2,4′-methylene bis(phenyl isocyanate) (MDI) isomers, wherein the ratio of 4,4′-MDI to 2,4′-MDI isomers ranges from 65:35 to 35:65.
9 . The composition of claim 1 , wherein the diol is selected from the group consisting of 2,2-dimethylopropionic acid (DMPA), 2,2-dimethylobutanoic acid, 2,2-dimethylovaleric acid, and combinations thereof.
10 . The composition of claim 1 , wherein said dispersion comprises a polyurethaneurea polymer having a weight average molecular weight from about 40,000 to about 250,000.
11 . The composition of claim 1 , wherein said dispersion comprises a polyurethaneurea polymer having a weight average molecular weight from about 40,000 to about 150,000.
12 . The composition of claim 1 , wherein the neutralizing agent comprises at least one member selected from the group consisting of tertiary amines and alkali metal hydroxides; and the at least one blocking agent is selected from the group consisting of N,N-diethylamine, N-ethyl-N-propylamine, N,N-diisopropylamine, N-tert-butyl-N-methylamine, N-tert-butyl-N-benzylamine, N,N-dicyclohexylamine, N-ethyl-N-isopropylamine, N-tert-butyl-N-isopropylamine, N-isopropyl-N-cyclohexylamine, N-ethyl-N-cyclohexylamine, N,N-diethanolamine, and 2,2,6,6-tetramethylpiperidine.
13 . The composition of claim 1 , wherein the surface active agent comprises at least one member selected from the group consisting of sodium dodecyl sulfate, sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, ethoxylated alkylphenols, lauryl pyridinium bromide, ethoxylated fatty alcohols, polyether phosphates, phosphate esters modified al.
14 . A composition comprising a polyurethaneurea aqueous dispersion, said dispersion comprising a polymer which is the reaction product of a composition comprising a prepolymer composition, a neutralizing agent and a chain extender;
wherein said prepolymer composition is the reaction product of a composition comprising a polyol, a polyisocyanate, a diol, and a blocking agent.
15 . The composition of claim 14 , wherein said polyol is selected from polyethers, polyesters, polycarbonates, and combinations thereof, wherein the polyol has a number average molecular weight of 600 to 4000.
16 . The composition of claim 14 , wherein said polyol is selected from polyethers, polyesters, polycarbonates, and combinations thereof, wherein the polyol has a number average molecular weight of 600 to 3500.
17 . The composition of claim 14 , wherein said polyisocyanate comprises a member selected from the group consisting of aromatic diisocyantes, aliphatic diisocyanates, cycloaliphatic diiosocyanates, and combinations thereof.
18 . The composition of claim 14 , wherein said diol compound comprises: (i) hydroxy groups capable of reacting with the polyisocyanate, and (ii) at least one carboxylic acid group capable of forming a salt upon neutralization, wherein said at least one carboxylic acid group is incapable of reacting with the polyisocyanate.
19 . The composition of claim 14 wherein said blocking agent for isocyanate groups comprises at least one mono-functional alcohol.
20 . The composition of claim 14 , wherein the prepolymer composition has a bulk viscosity from 500 to 6,000 poises, measured by the falling ball method at 40° C.
21 . The composition of claim 14 , wherein the prepolymer composition is prepared in the absence of added solvent.
22 . A method of preparing a polyurethaneurea aqueous dispersion comprising
(a) preparing a prepolymer composition comprising the reaction product of
(i) at least one polyol selected from polyethers, polyesters, polycarbonates, and combinations thereof, wherein the polyol has a number average molecular weight of 600 to 4000;
(ii) a polyisocyanate comprising a member selected from the group consisting of aromatic diisocyantes, aliphatic diisocyanates, cycloaliphatic diiosocyanates, and combinations thereof;
(iii) at least one diol compound comprising: (i) hydroxy groups capable of reacting with polyisocyanate, and (ii) at least one carboxylic acid group capable of forming a salt upon neutralization, wherein said at least one carboxylic acid group is incapable of reacting with the polyisocyanate
(b) dispersing the prepolymer in an aqueous composition comprising a neutralizing agent and a surfactant;
(c) chain extending the prepolymer to form the polyurethaneurea dispersion wherein the polyurethaneurea polymer has a weight average molecular weight from about 40,000 to about 250,000; and
(d) controlling the molecular weight of the polymer through the use of a blocking agent for isocyanate groups.
23 . The method of claim 22 , wherein said controlling the molecular weight includes controlling the weight average molecular weight and controlling the polymer molecular weight distribution.
24 . The method of claim 22 , wherein said blocking agent is selected from a mono-functional alcohol, a mono-functional amine, and combinations thereof.
25 . The method of claim 22 , wherein said blocking agent is added to said prepolymer composition, said aqueous composition or both.
26 . The method of claim 22 , wherein said blocking agent is at least one mono-functional alcohol and said blocking agent is added to said prepolymer composition at a time selected from (a) before formation of said prepolymer, (b) after formation of said prepolymer, (c) during formation of said prepolymer, and combinations thereof.
27 . A composition comprising a polyurethaneurea aqueous dispersion and a substrate; said dispersion comprising a polymer which is the reaction product of:
(a) at least one polyol selected from polyethers, polyesters, polycarbonates, and combinations thereof, wherein the polyol has a number average molecular weight of 600 to 4000;
(b) a polyisocyanate comprising a member selected from the group consisting of aromatic diisocyantes, aliphatic diisocyanates, cycloaliphatic diiosocyanates, and combinations thereof;
(c) at least one diol compound comprising: (i) hydroxy groups capable of reacting with polyisocyanate, and (ii) at least one carboxylic acid group capable of forming a salt upon neutralization, wherein said at least one carboxylic acid group is incapable of reacting with the polyisocyanate;
(d) a neutralizing agent;
(e) a chain extender;
(f) a blocking agent for isocyanate groups comprising at least one mono-functional alcohol; and
at least one surface active agent.