# US 4,396,476 A · Blend of cross-linked polymer, swelling monomer and cross-linking agent and curing process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,396,476 A - Document ID: US4396476A - Status: Granted - Kind: A - Application number: 06/318,356 - Filed: 1981-11-05 - Granted: 1983-08-02 - Earliest claimed: 1979-02-01 - Assignees: Dentsply Research & Development Corp. - Inventors: Frederick D. Roemer; Louis H. Tateosian - Web page: https://patentgrep.com/patent/US4396476A ## CPC - C08F 265/06: Polymerisation of acrylate or methacrylate esters on to polymers thereof - A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds - C08F 291/00: Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 - Y10S 525/903: Interpenetrating network - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D) - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract Compositions hardenable by exposure to heat or electromagnetic radiation are provided by blending from about 0% to about 50% by weight of an uncrosslinked polymer, from about 20% to about 66% of a polymerizable monomer capable of dissolving said polymer, from about 10% to about 70% of a crosslinked polymer in the form of discrete particles having average diameters of from 0.001 micron to about 500 microns and being swellable by said monomer, and from about 0.25% to about 27% of a crosslinking agent for said monomer. Such compositions exhibit superior chemical and physical characteristics when hardened and are suitable in a wide variety of applications as construction media. In accordance with a preferred form of the invention, a precursor blend is formed from a mixture comprising (A) from 13 to 52 weight percent of a crosslinked polymer of an ester of a C.sub.1 -C.sub.6 alkyl acrylic acid and a C.sub.1 -C.sub.20 alkyl or cycloalkyl alcohol, said crosslinked polymer being in the form of fine particles at least 50% by weight of which have average diameters less than 150 microns; (B) from 13 to 34 weight percent of an uncrosslinked polymerized ester of a C.sub.1 -C.sub.6 alkyl acrylic acid and a C.sub.1 -C.sub.20 alkyl or cycloalkyl alcohol having an average molecular weight of from 500,000 to 900,000 g/mole; (C) from 25 to 55% by weight of a polymerizable monomeric ester of a C.sub.1 -C.sub.6 alkyl acrylic acid and a C.sub.1 -C.sub.20 alkyl or cycloalkyl alcohol, which monomeric ester is capable of dissolving said uncrosslinked polymerized ester and of swelling, or interpenetrating, said crosslinked polymer particles; and (D) from 7% to 22% by weight of a crosslinking agent for said polymerizable monomeric ester. Such precursor blends, after being aged for a time sufficient to insure that the crosslinked polymer particles have become substantially fully swollen with or interpenetrated by the mixture of monomeric ester and crosslinking agent, is especially suitable in the production of prosthetic dental appliances, such as, for example, prosthetic teeth. ## Claims ### Claim 1 A hardenable composition comprising a blend of: (A) from 0% to about 50% of an uncrosslinked polymer capable of dissolving in component (B); (B) from about 20% to about 66% of a monofunctional polymerizable monomer; (C) from about 10% to about 70% of a crosslinked polymer in the form of discrete particles having average diameters up to about 500 microns and being swellable in said monomer; and (D) from about 7% to about 27% of a di- or polyfunctional crosslinking agent reactive with said polymerizable monomer; said percentages being based upon the total weight of A, B, C and D in said composition, said composition being capable of being hardened into a water insensitive object. ### Claim 2 (depends on 1) The composition of claim 1 wherein said crosslinked polymer is present in an amount of from about 13% to about 52% by weight. ### Claim 3 (depends on 1) The composition of claim 1 wherein said uncrosslinked polymer is present in an amount of from about 13% to about 34% by weight. ### Claim 4 (depends on 1) The composition of claim 1 wherein said polymerizable monomer is present in an amount of from about 25% to about 55% by weight. ### Claim 5 (depends on 1) The composition of claim 1 wherein said crosslinking agent is present in amount of from about 7% to about 22% by weight. ### Claim 6 (depends on 1) The composition of claim 1 wherein at least about 50% by weight of said particles have average diameters below about 150 microns. ### Claim 7 (depends on 1) The composition of claim 1 wherein said crosslinked polymer is present in an amount of from about 13% to about 52% by weight, said crosslinked polymer is present in an amount of from about 13% to about 34% by weight, said polymerizable monomer is present in an amount of from about 25% to about 55% by weight, said crosslinking agent is present in an amount of from about 7% to about 22% by weight, and at least about 50% by weight of said particles have average diameters below about 150 microns. ### Claim 8 (depends on 1, 5, 6, 7) The composition of claims 1, 5, 6 or 7 wherein said crosslinking agent is selected from the group consisting of 2,2-bis(methacryloxyphenyl)propane; ethylene "glycol" dimethacrylate; ethylene "glycol" diacrylate; 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane; and the reaction product of either hydroxyethyl acrylate or hydroxyethyl methacrylate with 2,2,4-trimethylhexyl-1,6-diisocyanate. ### Claim 9 (depends on 1, 6, 7) The composition of claims 1, 6 or 7 further comprising one or more members selected from the group consisting of free radical initiators, photochemical initiators, activators, pigments, fillers, adhesion modifiers and radiopaquing agents. ### Claim 10 (depends on 1) The composition of claim 1 wherein said polymerizable monomer comprises an ester of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl alcohols having from 1 to about 20 carbon atoms, cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituents thereof. ### Claim 11 (depends on 1) The composition of claim 1 wherein said crosslinking agent comprises an ester of at least two moles of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids reacted with one mole of an alcohol having at least two hydroxylic functionalities, said alcohol having from 2 to about 30 carbon atoms. ### Claim 12 (depends on 1) The composition of claim 1 wherein said polymerizable monomer is selected from the group consisting of methyl-, ethyl-, trifluoroethyl-, propyl-, butyl-, pentyl-, and hexyl-, acrylate and methacrylate. ### Claim 13 (depends on 1) The composition of claim 1 wherein said uncrosslinked polymer comprises a polymerized mixture of two or more monomers. ### Claim 14 (depends on 1) The composition of claim 1 wherein said uncrosslinked polymer comprises a polymerized ester of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl and cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituents thereof. ### Claim 15 (depends on 1) The composition of claim 1 wherein said uncrosslinked polymer is selected from the group consisting of polymerized methyl-, ethyl-, propyl-, isopropyl- and butyl-acrylate and methacrylate and mixtures thereof. ### Claim 16 (depends on 1) The composition of claim 1 where said crosslinked polymer comprises a polymerized mixture of from about 70% to about 99.99% monomer and from about 0.01% to about 30% crosslinking agent for said monomer. ### Claim 17 (depends on 16) The composition of claim 16 wherein said polymerizable monomer comprises an ester of an acid selected from the group consisting of acrylic acid, and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl alcohols having from 1 to about 20 carbon atoms, cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituents thereof. ### Claim 18 (depends on 17) The composition of claim 17 wherein said crosslinking agent comprises an ester of at least two moles of said acid reacted with one mole of an alcohol having at least two hydroxylic functionalities and having from 2 to about 30 carbon atoms. ### Claim 19 (depends on 16) The composition of claim 16 wherein said crosslinking agent comprises an ester of at least two moles of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids, reacted with one mole of an alcohol having at least two hydroxylic functionalities and having from 2 to about 30 carbon atoms. ### Claim 20 A process for producing a hard, water insensitive shaped article comprising: mixing together a blend comprising: (A) from 0 to about 50% of an uncrosslinked polymer capable of dissolving in component (B); (B) from about 20% to about 66% of a monofunctional polymerizable monomer; (C) from about 10% to about 70% of a crosslinked polymer in the form of discrete particles having average diameters up to about 500 microns and being swellable by said monomer; and (D) from about 7% to about 27% of a di- or polyfunctional crosslinking agent reactive with said polymerizable monomer; said percentages being based upon the total weight of A, B, C and D; maintaining said components in association with one another in said blend for a period of time sufficient to substantially swell said particles with the mixture of said monomer having said crosslinking agent dissolved therein; shaping said blend; and exposing said blend to heat or to electromagnetic radiation to harden said blend and to provide said shaped article. ### Claim 21 (depends on 20) The process of claim 20 wherein said crosslinked polymer is present in an amount of from about 13% to about 52% by weight. ### Claim 22 (depends on 20) The process of claim 20 wherein said uncrosslinked polymer is present in an amount of from about 13% to about 34% by weight. ### Claim 23 (depends on 20) The process of claim 20 wherein said polymerizable monomer is present in an amount of from about 25% to about 55% by weight. ### Claim 24 (depends on 20) The process of claim 20 wherein said crosslinking agent is present in amount of from about 7% to about 22% by weight. ### Claim 25 (depends on 20) The process of claim 20 wherein at least about 50% by weight of said particles have average diameters below about 150 microns. ### Claim 26 (depends on 20) The process of claim 20 wherein said crosslinked polymer is present in an amount of from about 13% to about 52% by weight, said uncrosslinked polymer is present in an amount of from about 13% to about 34% by weight, said polymerizable monomer is present in an amount of from about 25% to about 55% by weight, said crosslinking agent is present in an amount of from about 7% to about 22% by weight, and at least about 50% by weight of said particles have average diameters below about 150 microns. ### Claim 27 (depends on 20, 24, 25) The process of claims 20, 24, 25, or 26 wherein said crosslinking agent is selected from the group consisting of 2,2-bis(methacryloxyphenyl)propane; ethylene "glycol" dimethacrylate; ethylene "glycol" diacrylate; 2,2-bis [4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane; and the reaction product of either hydroxyethyl acrylate or hydroxyethyl methacrylate with 2,2,4-trimethylhexyl-1,6-diisocyanate. ### Claim 28 (depends on 20, 25) The process of claims 20, 25, or 26 further comprising one or more members selected from the group consisting of free radical initiators, photochemical initiators, activators, pigments, fillers, adhesion modifiers and radiopaquing agents. ### Claim 29 (depends on 20) The process of claim 20 wherein said polymerizable monomer comprises an ester of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl alcohols having from 1 to about 20 carbon atoms, cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituents thereof. ### Claim 30 (depends on 20) The process of claim 20 wherein said crosslinking agent comprises an ester of at least two moles of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids reacted with one mole of an alcohol having at least two hydroxylic functionalities said alcohol having from 2 to about 30 carbon atoms. ### Claim 31 (depends on 20) The process of claim 20 wherein said polymerizable monomer is selected from the group consisting of methyl-, ethyl-, trifluoroethyl-, propyl-, butyl-, pentyl-, and hexyl-, acrylate and methacrylate. ### Claim 32 (depends on 20) The process of claim 20 wherein said uncrosslinked polymer comprises a polymerized mixture of two or more monomers. ### Claim 33 (depends on 20) The process of claim 20 wherein said uncrosslinked polymer comprises a polymerized ester of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl and cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituents thereof. ### Claim 34 (depends on 20) The process of claim 20 wherein said uncrosslinked polymer is selected from the group consisting of methyl-, ethyl-, propyl-, isopropyl- and butyl-acrylate and methacrylate and mixtures thereof. ### Claim 35 (depends on 20) The process of claim 20 where said crosslinked polymer comprises a polymerized mixture of from about 70% to about 99.99% monomer and from about 0.01% to about 30% crosslinking agent for said monomer. ### Claim 36 (depends on 35) The process of claim 35 wherein said monomer comprises an ester of an acid selected from the group consisting of acrylic acids, and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl alcohols having from 1 to about 20 carbon atoms, cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituients thereof. ### Claim 37 (depends on 36) The process of claim 36 wherein said crosslinking agent comprises an ester of at least two moles of said acid reacted with one mole of an alcohol having at least two hydroxylic functionalities and having from 2 to about 30 carbon atoms. ### Claim 38 (depends on 35) The process of claim 35 wherein said crosslinking agent comprises an ester of at least two moles of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids, reacted with one mole of an alcohol having at least two hydroxylic functionalities and having from 2 to about 30 carbon atoms. ### Claim 39 A process for producing a hard, water insensitive shaped article comprising: forming a first component from a mixture comprising: (a) a monofunctional polymerizable monomer, (b) a di- or polyfunctional crosslinking agent for said monomer, and (c) a crosslinked polymer in the form of discrete particles having average diameters up to about 500 microns and being swellable by said monomer; maintaining (a), (b), and (c) in association with one another in said mixture for a period of time sufficient to substantially swell said particles with the mixture of said monomer having said crosslinking agent dissolved therein; blending said first component with additional monofunctional polymerizable monomer, additional di-or polyfunctional crosslinking agent for said monomer, and an uncrosslinked polymer, to form a blend comprising from 0% to about 50% of said uncrosslinked polymer, from about 20% to about 66% of said monomer, said monomer being capable of dissolving said uncrosslinked polymer, from about 10% to about 70% of said crosslinked polymer and from about 7% to about 27% of said crosslinking agent, said percentages being based upon the total weight of said uncrosslinked polymer, monomer, crosslinked polymer and crosslinking agent, shaping said blend, and exposing said blend to heat or to electromagnetic radiation to cause a hardening of said blend and to provide said shaped article. ### Claim 40 (depends on 39) The process of claim 39 wherein said crosslinked polymer is present in an amount of from about 13% to about 52% by weight. ### Claim 41 (depends on 39) The process of claim 39 wherein said uncrosslinked polymer is present in an amount of from about 13% to about 34% by weight. ### Claim 42 (depends on 39) The process of claim 39 wherein said polymerizable monomer is present in an amount of from about 25% to about 55% by weight. ### Claim 43 (depends on 39) The process of claim 39 wherein said crosslinking agent is present in amount of from about 7% to about 22% by weight. ### Claim 44 (depends on 39) The process claim 39 wherein at least about 50% by weight of said particles have average diameters below about 150 microns. ### Claim 45 (depends on 39) The process of claim 39 wherein said crosslinked polymer is present in an amount of about 13% to about 52% by weight, said uncrosslinked polymer is present in an amount of from about 13% to about 34% by weight, said polymerizable monomer is present in an amount of from about 25% to about 55% by weight, said crosslinking agent is present in an amount of from about 7% to about 22% by weight, and at least 50% by weight of said particles have average diameters below about 150 microns. ### Claim 46 (depends on 39, 43, 44, 45) The process of claims 39, 43, 44 or 45 wherein said crosslinking agent is selected from the group consisting of 2,2-bis(methacryloxyphenyl)propane; ethylene "glycol" dimethacrylate; ethylene "glycol" diacrylate; 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane; and the reaction product of either hydroxyethyl acrylate or hydroxyethyl methacrylate with 2,2,4-trimethylhexyl-1,6-diisocyanate. ### Claim 47 (depends on 39, 44, 45) The process of claims 39, 44 or 45 further comprising one or more members selected from the group consisting of free radical initiators, photochemical initiators, activators, pigments, fillers, adhesion modifiers and radiopaquing agents. ### Claim 48 (depends on 39) The process of claim 39 wherein said polymerizable monomer comprises an ester of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl alcohols having from 1 to about 20 carbon atoms, cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituents thereof. ### Claim 49 (depends on 39) The process of claim 39 wherein said crosslinking agent comprises an ester of at least two moles of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids reacted with one mole of an alcohol having at least two hydroxylic functionalities said alcohol having from 2 to about 30 carbon atoms. ### Claim 50 (depends on 39) The process of claim 39 wherein said polymerizable monomer is selected from the group consisting of methyl-, ethyl-, trifluoroethyl-, propyl-, butyl-, pentyl-, and hexyl-, acrylate and methacrylate. ### Claim 51 (depends on 39) The process of claim 39 wherein said uncrosslinked polymer comprises a polymerized mixture of two or more monomers. ### Claim 52 (depends on 39) The process of claim 39 wherein said uncrosslinked polymer comprises a polymerized ester of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl and cycloalkyl alcohols having from 1 to about 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituents thereof. ### Claim 53 (depends on 39) The process of claim 39 wherein said uncrosslinked polymer is selected from the group consisting of polymerized methyl-, ethyl-, propyl-, isopropyl- and butyl-acrylate and methacrylate and mixtures thereof. ### Claim 54 (depends on 39) The process of claim 39 where said crosslinked polymer comprises a polymerized mixture of from about 70% to about 99.99% monomer and from about 0.01% to about 30% crosslinking agent for said monomer. ### Claim 55 (depends on 54) The process of claim 54 wherein said monomer comprises an ester of an acid selected from the group consisting of acrylic acids, and C.sub.1 to C.sub.6 alkyl acrylic acids and an alcohol selected from the group consisting of alkyl alcohols having from 1 to about 20 carbon atoms, cycloalkyl alcohols having from 1 to 20 carbon atoms, phenol, and alkyl substituted phenol having from 1 to about 6 carbon atoms in the alkyl substituients thereof. ### Claim 56 (depends on 55) The process of claim 55 wherein said crosslinking agent comprises an ester of at least two moles of said acid reacted with one mole of an alcohol having at least two hydroxylic functionalities and having from 2 to about 30 carbon atoms. ### Claim 57 (depends on 54) The process of claim 54 wherein said crosslinking agent comprises an ester of at least two moles of an acid selected from the group consisting of acrylic acid and C.sub.1 to C.sub.6 alkyl acrylic acids, reacted with one mole of an alcohol having at least two hydroxylic functionalities and having from 2 to about 30 carbon atoms.