Polyurea-polyurethane acrylate polymer dispersions

Claim 2

A process for preparing a polymerizable ethylenically unsaturated urea-urethane polymer dispersed in a polymerizable ethylenically unsaturated compound, which comprises reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of: (a) a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation, (b) a diluent which is an ethylenically unsaturated compound free of active hydrogens, and (c) an active hydrogen-containing polymerizable ethylenically unsaturated compound, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form a polymerizable ethylenically unsaturated urea-urethane polymer dispersed in a polymerizable ethlenically unsaturated compound.

Claim 3

A process for preparing a polymerizable ethylenically unsaturated urea-urethane polymer dispersed in a polymerizable ethylenically unsaturated compound, which comprises the sequential steps of: (a) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound, followed by (b) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion.

Claim 4

A process for preparing a polymerizable ethylenically unsaturated urea-urethane polymer dispersed in a polymerizable ethylenically unsaturated compound, which comprises the sequential steps of: (a) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound, followed by (b) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion.

Claim 5

The process of claim 1 or 2 wherein the ethylenic unsaturation in the polymerizable ethylenically unsaturated urea-urethane polymer is in the terminal position.

Claim 6

The process of claim 2 wherein the polyfunctional amine and polyol are premixed before being contacted with the polyisocyanate.

Claim 7

The process of claim 1 or 2 wherein the organic polyisocyanate is selected from the group consisting of aliphatic polyisocyanates and aromatic polyisocyanates.

Claim 8

The process of claim 5 wherein the organic polyisocyanate is a diisocyanate.

Claim 9

The process of claim 1 or 2 wherein the polyol is a diol.

Claim 10

The process of claim 7 wherein the diol is selected from the group consisting of polyether diols, polyester diols both of which have a molecular weight of 500 or more and mixtures of said polyether diols or polyester diols with diols having a molecular weight of 250 or less.

Claim 11

The process of claim 8 wherein the diol is a polyether diol.

Claim 12

The process of claim 8 wherein the diol is a polyester diol.

Claim 13

The process of claim 8 wherein the diol is a mixture of a polyether diol or a polyester diol, both of which have a molecular weight of 500 or more, with a diol having a molecular weight of 250 or less.

Claim 14

The process of claim 1 or 2 wherein the active hydrogen-containing ethylenically unsaturated compound is a hydroxyalkyl acrylate or methacrylate.

Claim 15

A process of claim 1 wherein the ethylenically unsaturated compound free of active hydrogens is selected from the group consisting of vinyl aromatic compounds and alkyl acrylates or methacrylates.

Claim 16

The process of claim 1 or 2 wherein the polyfunctional amine is a diamine.

Claim 17

The process of claim 14 wherein the diamine is a cyclic diamine.

Claim 18

The process of claim 15 wherein the diamine is isophoronediamine.

Claim 19

The process of claim 2 wherein a portion of the active hydrogen-containing polymerizable ethylenically unsaturated compound is present in Step (a).

Claim 20

The process of claim 17 wherein a portion of the diol is present in Step (b).

Claim 21

A polymerizable ethylenically unsaturated urea-urethane polymer dispersed in a polymerizable ethylenically unsaturated compound prepared by a process, which comprises (a) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound; followed by (b) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion.

Claim 22

A polymerizable ethylenically unsaturated urea-urethane polymer dispersed in a polymerizable ethylenically unsaturated compound prepared by a process, which comprises (a) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound; followed by (b) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion.

Claim 23

An in-mold coating composition, which comprises a dispersion of the following ingredients in an ethylenically unsaturated monomer: (a) a polymerizable ethylenically unsaturated urea-urethane polymer prepared by a process, which comprises: (i) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound; followed by (ii) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion. (b) a catalyst, and (c) a mold release agent; said coating composition capable of being applied to the outer surface of a molded article while still in the mold such that when the mold is closed and sufficient pressure applied the coating composition substantially and uniformly covers and penetrates the article surface.

Claim 24

An in-mold coating composition, which comprises a dispersion of the following ingredients in an ethylenically unsaturated monomer: (a) a polymerizable ethylenically unsaturated urea-urethane polymer prepared by a process, which comprises: (i) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound; followed by (ii) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion. (b) a catalyst, and (c) a mold release agent; said coating composition capable of being applied to the outer surface of a molded article while still in the mold such that when the mold is closed and sufficient pressure applied the coating composition substantially and uniformly covers and penetrates the article surface.

Claim 25

The composition of claim 20 wherein it additionally contains a pigment.

Claim 26

The coating composition of claim 20 wherein the ethylenic unsaturation in the polymerizable ethylenically unsaturated urea-urethane polymer is in the terminal position.

Claim 27

The coating composition of claim 20 wherein it contains as an additional ingredient an ethylenically unsaturated polyurethane free of urea linkages.

Claim 28

The coating composition of claim 20 wherein the catalyst is a free radical generating catalyst.

Claim 29

The coating composition of claim 21 wherein the pigment is an electroconductive pigment.

Claim 30

The coating composition of claim 20 wherein the ethylenically unsaturated monomer is a vinyl aromatic compound.

Claim 31

The coating composition of claim 20 in which the mold release agent is a phosphate ester.

Claim 32

The coating composition of claim 24 in which (a) the polymerizable ethylenically unsaturated urea-urethane polymer is present in amounts of from about 5 to about 50 percent by weight, (b) the catalyst is present in amounts of from about 0.5 to about 3 percent by weight, and (c) the mold release agent is present in amounts of from about 0.01 to about 5 percent by weight; the percentages by weight being based on total weight of the composition.

Claim 33

An injection molding composition, which comprises a dispersion of the following ingredients in an ethylenically unsaturated monomer: (a) a polymerizable ethylenically unsaturated urea-urethane polymer prepared by a process, which comprises: (i) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound; followed by (ii) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion. (b) a mold release agent, and (c) reinforcements; said molding composition capable of being injected into a mold in a smooth even flow and cured therein.

Claim 34

An injection molding composition, which comprises a dispersion of the following ingredients in an ethylenically unsaturated monomer: (a) a polymerizable ethylenically unsaturated urea-urethane polymer prepared by a process, which comprises: (i) reacting a polyisocyanate, at least a portion of which is a diisocyanate, with a polyfunctional amine containing primary and/or secondary amino groups in the presence of a polyol, at least a portion of which is a polymeric polyol, free of ethylenic unsaturation and a diluent which is an ethylenically unsaturated compound free of active hydrogens, the equivalent ratio of isocyanate to active hydrogen in said polyol and said polyfunctional amine being within the range of 1.1 to 2.0/1 and the equivalent ratio of polyol to polyfunctional amine being within the range of 0.75 to 20/1, under conditions sufficient to form an NCO group-containing polyurea-polyurethane dispersed in an ethylenically unsaturated compound; followed by (ii) reacting the NCO group-containing polyurea-polyurethane dispersion with an active hydrogen containing polymerizable ethylenically unsaturated compound under conditions sufficient to react the NCO-functionality with the active hydrogens thereby forming the polymerizable ethylenically unsaturated urea-urethane polymer dispersion. (b) a mold release agent, and (c) reinforcements; said molding composition capable of being injected into a mold in a smooth even flow and cured therein.

Claim 35

The composition of claim 29 wherein the reinforcements are fillers.

Claim 36

The molding composition of claim 29 wherein the ethylenic unsaturation in the polymerizable ethylenically unsaturated urea-urethane polymer is in the terminal position.

Claim 37

The molding composition of claim 29 wherein it contains as an additional ingredient an ethylenically unsaturated polyurethane which is free of urea linkages and which is formed from reacting an organic polyisocyanate with an active hydrogen-containing unsaturated compound.

Claim 38

The molding composition of claim 29 which contains a free radical generating catalyst.

Claim 39

The molding composition of claim 29 which contains a surfactant.

Claim 40

The molding composition of claim 29 in which the ethylenically unsaturated monomer comprises at least in part a vinyl aromatic compound.

Claim 41

The molding composition of claim 29 in which the mold release agent is a phosphate ester.

Claim 42

The molding composition of claim 29 in which the reinforcement is fibrous.

Claim 43

The molding composition of claim 37 wherein the fibrous reinforcement is milled fiber glass.

Claim 44

The molding composition of claim 37 in which (a) the polymerizable ethylenically unsaturated urea-urethane polymer is present in amounts of from about 10 to about 85 percent by weight, (b) the mold release agent is present in amounts of from about 0.01 to about 5 percent by weight, and (c) the fibrous reinforcement is present in amounts of from about 0.5 to about 75 percent by weight; the percentage by weight being based on the total weight of the molding composition.