Chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymers and their preparation

Claim 2

AT LAST ONE COPOLYMERIZABLE NORMALLY HYDROPHOBIC MARCORMOLECULAR MONOMER HAVING A SUBSTANTIALLY UNIFORM MOLECULAR WEIGHT DISTRIBUTION, AND

Claim 3

A HYDROGEL COMPRISING A CHEMICALLY JOINED, PHASE SEPARATED SELF-CURED HYDROPHILIC THERMOPLASTIC GRAFT COPOLYMER IN THE FORM OF A HYDROGEL CONTAINING FROM ABOUT 10 TO ABOUT 95% BY WEIGHT OF AN AQUEOUS LIQUID BASED ON THE WEIGHT OF SAID GRAFT COPOLYMER, WHEREIN SAID GRAFT COPOLYMER IS COPOSED OF

Claim 4

A HYDROGEL COMPRISING A CHEMICALLY JOINED, PHASE SEPARATED SELF-CURED HYDROPHILIC THERMOPLASTIC GRAFT COPOLYMER IN THE FORM OF A HYDROGEL CONTAINING FROM ABOUT 10 TO ABOUT 95% BY WEIGHT OF AN AQUEOUS LIQUID BASED ON THE WEIGHT OF SAID GRAFT COPOLYMER, WHEREIN SAID GRAFT COPOLYMER IS COPOSED OF

Claim 5

A hydrogel comprising a chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymer in the form of a hydrogel containing from about 10 to about 95% by weight of an aqueous liquid based on the weight of said graft copolymer, wherein said graft copolymer is composed of:

Claim 6

A hydrogel comprising a chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymer in the form of a hydrogel containing from about 10 to about 95% by weight of an aqueous liquid based on the weight of said graft copolymer, wherein said graft copolymer is composed of:

Claim 7

at least one hydrophilic (water-soluble) copolymerizable comonomer or compound rendered hydrophilic forming the polymeric backbone of said copolymer, said copolymerizable normally hydrophobic macromolecular monomer forming linear polymeric sidechains of said graft copolymer, wherein: a. the polymeric backbones of the graft copolymer are comprised of polymerized units of said copolymerizable comonomers, said copolyMerizable comonomers being at least one ethylenically unsaturated monomer of a hydrophilic or water-soluble compound and mixtures thereof or a compound which can be rendered hydrophilic or water soluble; b. the linear polymeric sidechains of the graft copolymer consist essentially of a polymerized hydrophobic macromolecular monomer, said hydrophobic macromolecular monomer comprising a linear polymer or copolymer having a molecular weight of at least about 2,000 and having a substantially uniform molecular weight distribution, such that its ratio of Mw/Mn is not substantially above about 1.1, said macromolecular monomer being further characterized as having no more than one copolymerizable moiety per linear polymer or copolymer chain, said copolymerization occurring between the copolymerizable end group of said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer; and c. the linear polymeric sidechains of the graft copolymer which are copolymerized into the copolymeric backbone are separated by at least about 20 uninterrupted recurring monomeric units of said hydrophilic polymeric backbone, the distribution of the sidechains along the backbone and the copolymerization being controlled by the reactivity ratios of the copolymerizable end group on said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer.

Claim 8

at least one hydrophilic (water-soluble) copolymerizable comonomer or compound rendered hydrophilic forming the polymeric backbone of said copolymer, said copolymerizable normally hydrophobic macromolecular monomer forming linear polymeric sidechains of said graft copolymer, wherein: a. the polymeric backbones of the graft copolymer are comprised of polymerized units of said copolymerizable comonomers, said copolyMerizable comonomers being at least one ethylenically unsaturated monomer of a hydrophilic or water-soluble compound and mixtures thereof or a compound which can be rendered hydrophilic or water soluble; b. the linear polymeric sidechains of the graft copolymer consist essentially of a polymerized hydrophobic macromolecular monomer, said hydrophobic macromolecular monomer comprising a linear polymer or copolymer having a molecular weight of at least about 2,000 and having a substantially uniform molecular weight distribution, such that its ratio of Mw/Mn is not substantially above about 1.1, said macromolecular monomer being further characterized as having no more than one copolymerizable moiety per linear polymer or copolymer chain, said copolymerization occurring between the copolymerizable end group of said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer; and c. the linear polymeric sidechains of the graft copolymer which are copolymerized into the copolymeric backbone are separated by at least about 20 uninterrupted recurring monomeric units of said hydrophilic polymeric backbone, the distribution of the sidechains along the backbone and the copolymerization being controlled by the reactivity ratios of the copolymerizable end group on said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer.

Claim 9

AT LEAST ONE HYDROPHILIC (WATER-SOLUBLE) COPOLYMERIZABLE COMONOMER OR COMPOUND RENDERED HYDROPHILIC FORMING THE POLYMERIC BACKBONE OF SAID COPOLYMER, SAID COPOLYMERIZABLE NORMALLY HYDROPHOBIC MACROMOLECULAR MONOMER FORMING LINEAR POLYMERIC SIDECHAINS OF SAID GRAFT COPOLYMER, WHEREIN: A. THE POLYMERIC BACKBONES OF THE GRAFT COPOLYMER ARE COMPRISED OF POLYMERIZED UNITS OF SAID COPOLYMERIZABLE COMONOMERS, SAID COPOLYMERIZABLE COMONOMERS BEING AT LEAST ONE ETHYLENICALLY UNSATURATED MONOMER OF A HYDROPHILIC OR WATER-SOLUBLE COMPOUND AND MIXTURES THEREOF OR A COMPOUND WHICH CAN BE RENDERED HYDROPHILIC OR WATER SOLUBLE, B. THE LINEAR POLYMERIC SIDECHAINS OF THE GRAFT COPOLYMER CONSIST ESSENTIALLY OF A POLYMERIZED HYDROPHOBIC MACROABOVE ABOUT 1.1, SAID MACROMOLECULAR MONOMER BEING MONOMER COMPRISING A LINEAR POLYMER OR COPOLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST ABOUT 2,000 AND HAVING A SUBSTANTIALLY UNIFORM MOLECULAR WEIGHT DISTRIBUTION, SUCH THAT ITS RATIO OF MW/MN IS NOT SUBSTANTIALLY ABOVE ABOUT 1.1, SAID MACROMOLECULAR MONOMER BEING FURTHER CHARACTERIZED AS HAVING NO MORE THAN ONE COPOLYMERIZABLE MOIETY PER LINEAR POLYMER OR COPOLYMER CHAIN, SAID COPOLYMERIZATION OCCURRING BETWEEN THE COPOLYMERIZABLE END GROUP OF SAID HYDROPHOBIC MACROMOLECULAR MONOMER AND SAID COPOLYMERIZABLE HYDROPHILIC COMONOMER, AND C. THE LINEAR POLYMERIC SIDECHAINS OF THE GRAFT COPOLYMER WHICH ARE COPOLYMERIZED INTO THE COPOLYMERIC BACKBONE ARE SEPARATED BY AT LEAST ABOUT 20 UNINTERRUPTED RECURRING MONOMERIC UNITS OF SAID HYDROPHILIC POLYERIC BACKBONE, THE DISTRIBUTION OF THE SIDECHAINS ALONG THE BACKBONE AND THE COPOLYMERIZATION BEING CONTROLLED BY THE REACTIVITY RATIOS OF THE COPOLYMERIZABLE END GROUP ON SAID HYDROPHOBIC MACROMOLECULAR MONOMER AND SAID COPOLYMERIZABLE HYDROPHILIC COMONOMER.

Claim 10

AT LEAST ONE HYDROPHILIC (WATER-SOLUBLE) COPOLYMERIZABLE COMONOMER OR COMPOUND RENDERED HYDROPHILIC FORMING THE POLYMERIC BACKBONE OF SAID COPOLYMER, SAID COPOLYMERIZABLE NORMALLY HYDROPHOBIC MACROMOLECULAR MONOMER FORMING LINEAR POLYMERIC SIDECHAINS OF SAID GRAFT COPOLYMER, WHEREIN: A. THE POLYMERIC BACKBONES OF THE GRAFT COPOLYMER ARE COMPRISED OF POLYMERIZED UNITS OF SAID COPOLYMERIZABLE COMONOMERS, SAID COPOLYMERIZABLE COMONOMERS BEING AT LEAST ONE ETHYLENICALLY UNSATURATED MONOMER OF A HYDROPHILIC OR WATER-SOLUBLE COMPOUND AND MIXTURES THEREOF OR A COMPOUND WHICH CAN BE RENDERED HYDROPHILIC OR WATER SOLUBLE, B. THE LINEAR POLYMERIC SIDECHAINS OF THE GRAFT COPOLYMER CONSIST ESSENTIALLY OF A POLYMERIZED HYDROPHOBIC MACROABOVE ABOUT 1.1, SAID MACROMOLECULAR MONOMER BEING MONOMER COMPRISING A LINEAR POLYMER OR COPOLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST ABOUT 2,000 AND HAVING A SUBSTANTIALLY UNIFORM MOLECULAR WEIGHT DISTRIBUTION, SUCH THAT ITS RATIO OF MW/MN IS NOT SUBSTANTIALLY ABOVE ABOUT 1.1, SAID MACROMOLECULAR MONOMER BEING FURTHER CHARACTERIZED AS HAVING NO MORE THAN ONE COPOLYMERIZABLE MOIETY PER LINEAR POLYMER OR COPOLYMER CHAIN, SAID COPOLYMERIZATION OCCURRING BETWEEN THE COPOLYMERIZABLE END GROUP OF SAID HYDROPHOBIC MACROMOLECULAR MONOMER AND SAID COPOLYMERIZABLE HYDROPHILIC COMONOMER, AND C. THE LINEAR POLYMERIC SIDECHAINS OF THE GRAFT COPOLYMER WHICH ARE COPOLYMERIZED INTO THE COPOLYMERIC BACKBONE ARE SEPARATED BY AT LEAST ABOUT 20 UNINTERRUPTED RECURRING MONOMERIC UNITS OF SAID HYDROPHILIC POLYERIC BACKBONE, THE DISTRIBUTION OF THE SIDECHAINS ALONG THE BACKBONE AND THE COPOLYMERIZATION BEING CONTROLLED BY THE REACTIVITY RATIOS OF THE COPOLYMERIZABLE END GROUP ON SAID HYDROPHOBIC MACROMOLECULAR MONOMER AND SAID COPOLYMERIZABLE HYDROPHILIC COMONOMER.

Claim 11

at least one copolymerizable comonomer which is rendered hydrophilic forming the polymeric backbone of said copolymer, said copolymerizable normally hydrophobic macromolecular monomer forming linear polymeric sidechains of said graft copolymer, wherein: a. the polymeric backbone of the graft copolymer is comprised of polymerized units of said copolymerizable comonomers, wherein the copolymerizable comonomers are selected from the group consisting of vinyl esters of monocarboxylic acids which are rendered hydrophilic by hydrolysis of said vinyl esters subsequent to copolymerization, and mixtures thereof; b. the linear polymeric sidechains of the graft copolymer consist essentially of a polymerized hydrophobic macromolecular monomer, said hydrophobic macromolecular monomer comprising a linear polymer or copolymer having a molecular weight of at least about 2,000 and having a substantially uniform molecular weight distribution, such that its ratio of Mw/Mn is not substantially above about 1.1, said macromolecular monomer being further characterized as having no more than one copolymerizable moiety per linear polymer or copolymer chain, said copolymerization occurring between the copolymerizable end group of said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer; and c. the linear polymeric sidechains of the graft copolymer which are copolymerized into the copolymeric backbone are separated by at least about 20 uninterrupted recurring monomeric units of said hydrophilic polymeric backbone, the distribution of the side-chains along the backbone and the copolymerization being controlled by the reactivity ratios of the copolymerizable end group on said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer.

Claim 12

at least one copolymerizable comonomer which is rendered hydrophilic forming the polymeric backbone of said copolymer, said copolymerizable normally hydrophobic macromolecular monomer forming linear polymeric sidechains of said graft copolymer, wherein: a. the polymeric backbone of the graft copolymer is comprised of polymerized units of said copolymerizable comonomers, wherein the copolymerizable comonomers are selected from the group consisting of vinyl esters of monocarboxylic acids which are rendered hydrophilic by hydrolysis of said vinyl esters subsequent to copolymerization, and mixtures thereof; b. the linear polymeric sidechains of the graft copolymer consist essentially of a polymerized hydrophobic macromolecular monomer, said hydrophobic macromolecular monomer comprising a linear polymer or copolymer having a molecular weight of at least about 2,000 and having a substantially uniform molecular weight distribution, such that its ratio of Mw/Mn is not substantially above about 1.1, said macromolecular monomer being further characterized as having no more than one copolymerizable moiety per linear polymer or copolymer chain, said copolymerization occurring between the copolymerizable end group of said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer; and c. the linear polymeric sidechains of the graft copolymer which are copolymerized into the copolymeric backbone are separated by at least about 20 uninterrupted recurring monomeric units of said hydrophilic polymeric backbone, the distribution of the side-chains along the backbone and the copolymerization being controlled by the reactivity ratios of the copolymerizable end group on said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer.

Claim 13

at least one hydrophilic (water-soluble) copolymerizable comonomer or compound rendered hydrophilic forming the polymeric backbone of said copolymer, said copolymerizable normally hydrophobic macromolecular monomer forming linear polymeric sidechains of said graft copolymer, wherein: a. the polymeric backbones of the graft copolymer are comprised of polymerized units of said copolymerizable comonomers, wherein the copolymerizable comonomers are selected from the group consisting of acrylic acid, methacrylic acid, amides of acrylic and methacrylic acids, N-alkyl and N,N-dialkyl amides of acrylic and methacrylic acids, hydroxyalkyl and hydroxyalkoxyalkyl esters of acrylic and methacrylic acids, N-hydroxyalkyl and N,N-bis-hydroxyalkyl amides of acrylic and methacrylic acids, vinyl esters of monocarboxylic acids which are rendered hydrophilic by hydrolysis of said vinyl esters subsequent to copolymerization, N-vinyl pyrrolidone, N-vinyl piperidone, N-acrylylpyrrolidone, N-acrylylpiperidine, N-acrylylmorpholine, quaternary ammonium salts of ethylenically unsaturated compounds, and mixtures thereof; b. the linear polymeric sidechains of the graft copolymer consist essentially of a polymerized hydrophobic macromolecular monomer, said hydrophobic macromolecular monomer comprising a linear polymer or copolymer having a molecular weight of at least about 2,000 and having a substantially uniform molecular weight distribution, such that its ratio of Mw/Mn is not substantially above about 1.1, said macromolecular monomer being further characterized as having no more than one copolymerizable moiety per linear polymer or copolymer chain, said copolymerization occurring between the copolymerizable end group of said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer; and c. the linear polymeric sidechains of the graft copolymer which are copolymerized into the copolymeric backbone are separated by at least about 20 uninterrupted recurring monomeric units of said hydrophilic polymeric backbone, the distribution of the sidechains along the backBone and the copolymerization being controlled by the reactivity ratios of the copolymerizable end group on said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer.

Claim 14

at least one hydrophilic (water-soluble) copolymerizable comonomer or compound rendered hydrophilic forming the polymeric backbone of said copolymer, said copolymerizable normally hydrophobic macromolecular monomer forming linear polymeric sidechains of said graft copolymer, wherein: a. the polymeric backbones of the graft copolymer are comprised of polymerized units of said copolymerizable comonomers, wherein the copolymerizable comonomers are selected from the group consisting of acrylic acid, methacrylic acid, amides of acrylic and methacrylic acids, N-alkyl and N,N-dialkyl amides of acrylic and methacrylic acids, hydroxyalkyl and hydroxyalkoxyalkyl esters of acrylic and methacrylic acids, N-hydroxyalkyl and N,N-bis-hydroxyalkyl amides of acrylic and methacrylic acids, vinyl esters of monocarboxylic acids which are rendered hydrophilic by hydrolysis of said vinyl esters subsequent to copolymerization, N-vinyl pyrrolidone, N-vinyl piperidone, N-acrylylpyrrolidone, N-acrylylpiperidine, N-acrylylmorpholine, quaternary ammonium salts of ethylenically unsaturated compounds, and mixtures thereof; b. the linear polymeric sidechains of the graft copolymer consist essentially of a polymerized hydrophobic macromolecular monomer, said hydrophobic macromolecular monomer comprising a linear polymer or copolymer having a molecular weight of at least about 2,000 and having a substantially uniform molecular weight distribution, such that its ratio of Mw/Mn is not substantially above about 1.1, said macromolecular monomer being further characterized as having no more than one copolymerizable moiety per linear polymer or copolymer chain, said copolymerization occurring between the copolymerizable end group of said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer; and c. the linear polymeric sidechains of the graft copolymer which are copolymerized into the copolymeric backbone are separated by at least about 20 uninterrupted recurring monomeric units of said hydrophilic polymeric backbone, the distribution of the sidechains along the backBone and the copolymerization being controlled by the reactivity ratios of the copolymerizable end group on said hydrophobic macromolecular monomer and said copolymerizable hydrophilic comonomer.

Claim 15

A hydrogel comprising a chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymer in the form of a hydrogel containing from about 10 to about 95% by weight of an aqueous liquid based on the weight of said graft copolymer, wherein said graft copolymer is composed of:

Claim 16

A hydrogel comprising a chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymer in the form of a hydrogel containing from about 10 to about 95% by weight of an aqueous liquid based on the weight of said graft copolymer, wherein said graft copolymer is composed of:

Claim 17

The graft copolymer of claim 2, wherein said copolymerizable comonomer which forms said hydrophilic copolymeric backbone is selected from the group consisting of acrylic acid and methacrylic acid.

Claim 18

The graft copolymer of claim 2, wherein said copolymerizable comonomer which forms said hydrophilic copolymeric backbone is selected from the group consisting of hydroxyalkyl and hydroxyalkoxyalkyl esters of acrylic and methacrylic acids.

Claim 19

The graft copolymer of claim 5, wherein said monoester is selected from the group consisting of 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.

Claim 20

The graft copolymer of claim 2, wherein said copolymerizable comonomer which forms the hydrophilic copolymeric backbone is a water-soluble vinyl monomer having at least one nitrogen atom in the molecule.

Claim 21

The graft copolymer of claim 7, wherein said water-soluble vinyl monomer is N,N-dimethylacrylamide.

Claim 22

The graft copolymer of claim 1, wherein said normally hydrophobic macromolecular monomer which is copolymerized with said copolymerizable comonomer forming the hydrophilic copolymeric backbone is derived from a monofunctional copolymerizable macromolecular monomer represented by the formula:

Claim 23

The graft copolymer of claim 9, wherein said copolymerizable hydrophobic macromolecular monomer is represented by the structural formula:

Claim 24

The graft copolymer of claim 9, wherein said copolymerizable hydrophobic macromolecular monomer is represented by the structural formula:

Claim 25

The graft copolymer of claim 9, wherein said copolymerizable hydrophobic macromolecular monomer is represented by the structural formula:

Claim 26

The graft copolymer of claim 3, wherein said vinyl ester is vinyl acetate.

Claim 27

The graft copolymer of claim 1, wherein the graft copolymer hydrogel is a porous membrane.

Claim 28

The graft copolymer according to claim 2, wherein the copolymerizable comonomers are selected from the group consisting of vinyl pyridine quaternary ammonium salts and dimethylaminoethyl methacrylate quaternary ammonium salts.

Claim 29

The graft copolymer of claim 2, wherein said hydrophilic copolymerizable comonomer is copolymerized in admixture with a hydrophobic copolymerizable comonomer.

Claim 30

The graft copolymer of claim 16, wherein the hydrophobic copolymerizable comonomer is selected from the group consisting of alkyl acrylates and methacrylates, vinyl esters of monocarboxylic acids, vinyl aromatic compounds including styrene and alpha-methylstyrene, vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinylidene cyanide and maleic anhydride.

Claim 31

The graft copolymer of claim 16, wherein said hydrophilic copolymerizable comonomer is N,N-dimethylacrylamide and said hydrophobic copolymerizable comonomer is butylacrylate.