US 4,408,008 AGranted

Stable, colloidal, aqueous dispersions of cross-linked urea-urethane polymers and their method of production

AssigneeMobay Chemical Corporation

InventorPeter Markusch

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Abstract

The present invention relates to a process for the preparation of stable, colloidal, aqueous dispersions of cross-linked urea-urethanes which comprises reacting (a) an aqueously dispersed, substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 and containing (i) about 0 to 120 milliequivalents of ionic groups per 100 grams of prepolymer, and (ii) about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units wherein components (i) and (ii) are present in an amount sufficient to provide a stable dispersion of the prepolymer in the aqueous medium, with (b) polyfunctional amine chain extenders having an average functionality between about 2.2 and 6.0. The present invention additionally relates to the aqueous dispersions produced by the above process and to the films, coatings or adhesives produced from these dispersions.

Claims69

Dependent claims

A process for the preparation of a stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which comprises

(a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 by reacting
(i) an organic polyisocyanate which contains at least two aliphatically or cycloaliphatically bound isocyanate groups,
(ii) an organic compound which has at least two isocyanate-reactive groups,
(iii) an organic compound which comprises a member selected from the group consisting of diisocyanates which contain lateral, hydrophilic ethylene oxide units;
compounds which are difunctional in the isocyanate-polyaddition reaction and contain lateral, hydrophilic ethylene oxide units;
monoisocyanates which contain terminal, hydrophilic ethylene oxide units;
compounds which are monofunctional in the isocyanate-polyaddition reaction and contain terminal, hydrophilic ethylene oxide units, and mixtures thereof;
and optionally,
(iv) an organic compound which comprises a member selected from the group consisting of monoisocyanates or diisocyanates which contain ionic group(s) or potential ionic group(s);
and compounds which are monofunctional or difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s),
wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.1 to 3.0 on an equivalent basis;
component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units;
and component (iv) is treated with a neutralizing agent either before, during or after formation of the prepolymer in an amount sufficient to provide up to about 120 milliequivalents of ionic groups per 100 grams of said prepolymers, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer;
(b) forming a dispersion of said prepolymer in water;
and subsequently
(c) chain extending said prepolymer to form said cross-linked urea-urethane with a sufficient amount of a polyfunctional amine chain extender having an average functionality (number of amine nitrogens per molecule) between about 2.2 and 6.0 to provide a ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine of between about 1.0:0.6 and 1.0:1.1.

13 more elements

A process for the preparation of a stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which comprises

(a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 by reacting
(i) an organic diisocyanate which contains aliphatically or cycloaliphatically bound isocyanate groups,
(ii) an organic dihydroxy compound with a molecular weight from about 300 to 6,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates,
(iii) an organic compound which is monofunctional or difunctional in the context of the isocyanatepolyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and optionally,
(iv) an organic compound comprising a member selected from the group consisting of sulfonic acid-containing diols, tertiary nitrogen-containing diols and hydroxy-carboxylic acids of the formula
(HO).sub.x Q(COOH).sub.y
wherein
Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and
x and y represent values from 1 to 3,
wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis;
component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units;
and component (iv) is treated with a neutralizing agent either before, during or after formation of said prepolymer in an amount sufficient to provide about 0 to 120 milliequivalents of ionic groups per 100 grams of said prepolymer, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer;
(b) forming a dispersion of said prepolymer in water;
and subsequently,
(c) chain-extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) of about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:0.6 and 1.0:1.1.

12 more elements

A process for the preparation of stable, colloidal, aqueous dispersions of cross-linked urea-urethanes which comprises

(a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight between about 600 and 12,000 by reacting
(i) an organic diisocyanate comprising a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane,
(ii) an organic dihydroxy compound with a molecular weight from about 300 to 3,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates,
(iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-poly-addition reaction and contains lateral or terminal, hydrophilic ethylene oxide units and
(iv) a dihydroxy alkanoic acid of the formula ##STR32## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, and
wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis;
component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units;
and component (iv) is neutralized with a tertiary amine either before, during or after formation of said prepolymer in an amount sufficient to provide about 10 to 60 milliequivalents of ionic groups per 100 grams of prepolymer, the amount of component (iii) and the neutralized amount of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer;
(b) forming a dispersion of said prepolymer in water and;
subsequently,
(c) chain extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogen of the polyfunctional amine is between about 1.0:0.8 and 1.0:0.98.

8 more elements

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by

(a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 from the reaction product of
(i) an organic polyisocyanate which contains at least two aliphatically or cycloaliphatically bound isocyanate groups,
(ii) an organic compound which has at least two isocyanate-reactive groups,
(iii) an organic compound which comprises a member selected from the group consisting of diisocyanates which contain lateral, hydrophilic ethylene oxide units;
compound which are difunctional in the isocyanate-polyaddition reaction and contain lateral, hydrophilic ethylene oxide units;
monoisocyanates which contain terminal, hydrophilic ethylene oxide units;
compounds which are monofunctional in the iso- cyanate-polyaddition reaction and contain terminal, hydrophilic ethylene oxide units, and mixtures thereof;
and optionally,
(iv) an organic compound whch comprises a member selected from the group consisting of monoisocyanates or diisocyanates which contain ionic group(s) or potential ionic group(s);
and compounds which are monofunctional or difunctional in the isocyanate-polyaddition reaction and contain ionic group(s) or potential ionic group(s),
wherein components (i), (ii), (iii) and (iv) and reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.1 to 3.0 on an equivalent basis;
component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units;
and component (iv) is treated with a neutralizing agent either before, during or after formation of the prepolymer in an amount sufficient to provide up to about 120 milliequivalents of ionic groups per 100 grams of said prepolymers, the amount of component (iii) and the neutralized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer;
(b) forming a dispersion of said prepolymer in water;
and subsequently
(c) chain extending said prepolymer to form said cross-linked urea-urethane with a sufficient amount of a polyfunctional amine chain extender having an average functionality (number of amine nitrogens per molecule) between about 2.2 and 6.0 to provide a ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine of between about 1.0:0.6 and 1.0:1.1.

13 more elements

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by

(a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight of up to about 25,000 from the reaction product of
(i) an organic diisocyanate which contains aliphatically or cycloaliphatically bound isocyanate groups,
(ii) an organic dihydroxy compound with a molecular weight from about 300 to 6,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates,
(iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-polyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and optionally,
(iv) an organic compound comprising a member selected from the group consisting of sulfonic acid-containing diols, tertiary nitrogen-containing diols and hydroxy-carboxylic acids of the formula
(HO).sub.x Q(COOH).sub.y
wherein
Q represents a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and
x and y represent values from 1 to 3,
wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis;
component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units;
and component (iv) is treated with a neutralizing agent either before, during or after formation of said prepolymer in an amount sufficient to provide about 0 to 120 milliequivalents of ionic groups per 100 grams of said prepolymer, the amount of component (iii) and the neutalized portion of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer;
(b) forming a dispersion of said prepolymer in water and;
subsequently,
(c) chain-extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amines is between 1.0:0.6 and 1.0:1.1.

12 more elements

A stable, colloidal, aqueous dispersion of cross-linked urea-urethanes which is prepared by

(a) forming a substantially linear, isocyanate-terminated prepolymer having a molecular weight between about 600 and 12,000 from the reaction product of
(i) an organic diisocyanate comprising a member selected from the group consisting of bis-(4-isocyanatocyclohexyl)-methane and 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane,
(ii) an organic dihydroxy compound with a molecular weight from about 300 to 3,000 comprising a member selected from the group consisting of polyesters, polyethers and polycarbonates,
(iii) an organic compound which is monofunctional or difunctional in the context of the isocyanate-polyaddition reaction and contains lateral or terminal, hydrophilic ethylene oxide units, and
(iv) a dihydroxy alkanoic acid of the formula ##STR36## wherein Q' represents hydrogen or an alkyl group containing 1 to 8 carbon atoms, and
wherein components (i), (ii), (iii) and (iv) are reacted in the presence of excess isocyanate groups and are chosen to provide a ratio of isocyanate groups to isocyanate-reactive groups of about 1.2 to 2.0 on an equivalent basis;
component (iii) is present in an amount sufficient to provide about 0.35 to 10% by weight, based on the weight of the prepolymer, of lateral and/or terminal, hydrophilic ethylene oxide units;
and component (iv) is neutralized with a tertiary amine either before, during or after formation of said prepolymer in an amount sufficient to provide about 10 to 60 milliequivalents of ionic group per 100 grams of prepolymer, the amount of component (iii) and the neutralized amount of component (iv) being present in an amount sufficient to provide a stable, aqueous dispersion of the prepolymer;
(b) forming a dispersion of said prepolymer in water;
and subsequently,
(c) chain extending said prepolymer to form said cross-linked urea-urethane with a polyfunctional amine comprising a member selected from the group consisting of ethylene diamine, bis-(4-aminocyclohexyl)-methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, diethylene triamine, triethylene tetramine, and mixtures thereof, wherein said polyfunctional amine has an average functionality (number of amine nitrogens per molecule) between about 2.2 and 4.0 and wherein the ratio of the terminal isocyanate groups of the prepolymer to the amino hydrogens of the polyfunctional amine is between about 1.0:0.8 and 1.0:0.98.

8 more elements

Dependencies are inferred from the claim text.