# US 4,397,996 A · Process for preparing polymeric oximes and compositions containing same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,397,996 A - Document ID: US4397996A - Status: Granted - Kind: A - Application number: 06/266,364 - Filed: 1981-05-22 - Granted: 1983-08-09 - Earliest claimed: 1981-05-22 - Assignees: Polaroid Corporation - Inventors: Charles K. Chiklis; Alan N. Schuler - Web page: https://patentgrep.com/patent/US4397996A ## CPC - C08F 8/32: by reaction with amines - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract A process for preparing polymeric oximes and photographic processing compositions containing polymeric oximes are described. The polymeric oximes are prepared by a process which comprises: introducing into an aqueous polymerization medium a portion of a polymerizable monomer to be polymerized, said polymerizable monomer having the formula ##STR1## wherein R is hydrogen or methyl, R.sup.1 is hydrogen, alkyl of from 1 to 4 carbon atoms, benzyl or phenyl, R.sup.2 is alkyl of from 1 to 4 carbon atoms, benzyl or phenyl, alkylene is a divalent alkylene radical having 1 or 2 carbon atoms, and R.sup.3 is hydrogen, alkyl of from 1 to 4 carbon atoms or phenyl; initiating the emulsion polymerization of said monomer, and while maintaining said polymerization, introducing substantially uniformly over the course of the polymerization, the remaining polymerizable monomer to be polymerized, thereby to provide a polymeric latex of polymeric particles of said polymerizable monomer in a water medium; contacting said polymeric latex with an organic solvent for said latex particles in an amount sufficient to effect swelling of the polymeric particles in said medium; and oximating the swollen polymeric particles by reaction with hydroxylamine salt and an amount of alkalinity sufficient to provide free hydroxylamine for said oximation but insufficient to effect alkali solubilization of the resulting oximated polymeric particles. ## Claims ### Claim 1 A process for preparing a polymeric oxime which comprises the steps of introducing into an aqueous polymerization medium a portion of a polymerizable monomer to be polymerized, said polymerizable monomer having the formula ##STR9## wherein R is hydrogen or methyl, R.sup.1 is hydrogen, alkyl of from 1 to 4 carbon atoms, benzyl or phenyl, R.sup.2 is alkyl of from 1 to 4 carbon atoms, benzyl or phenyl, alkylene is a divalent alkylene radical having 1 to 2 carbon atoms, and R.sup.3 is hydrogen, alkyl of from 1 to 4 carbon atoms or phenyl; initiating the emulsion polymerization of said monomer, and while maintaining said polymerization, introducing substantially uniformly over the course of the polymerization, the remaining polymerizable monomer to be polymerized, thereby to provide a polymeric latex of polymeric particles of said polymerizable monomer in a water medium; contacting said polymeric latex with an organic solvent for said latex particles in an amount sufficient to effect swelling of the polymeric particles in said medium; and oximating the swollen polymeric particles by reaction with hydroxylamine salt and an amount of alkalinity sufficient to provide free hydroxylamine for said oximation but insufficient to effect appreciable alkali solubilization of the resulting oximated polymeric particles. ### Claim 2 (depends on 1) The process of claim 1 wherein said portion of polymerizable monomer introduced into said aqueous polymerization medium comprises from about 1% to about 15% by weight of the polymerizable monomer to be polymerized. ### Claim 3 (depends on 2) The process of claim 2 wherein said remaining polymerizable monomer introduced substantially uniformly over the course of said polymerization is introduced over a period of up to about 6 hours. ### Claim 4 (depends on 1) The process of claim 1 wherein said amount of organic solvent contacted with said polymeric latex is in the range of from about 60% to about 150% by weight of the polymeric latex. ### Claim 5 (depends on 4) The process of claim 4 wherein said organic solvent is a lower alkanol. ### Claim 6 (depends on 1) The process of claim 1 wherein said organic solvent is contacted with said polymeric latex by uniformly adding said solvent to said polymeric latex over a period of from about 0.5 to 2 hours. ### Claim 7 (depends on 1) The process of claim 1 wherein said amount of hydroxylamine salt corresponds to the stoichiometric amount required to react with the carbonyl groups of the polymeric particles of said latex. ### Claim 8 (depends on 1) The process of claim 1 wherein the amount of hydroxylamine salt is an amount of about 15% in excess of the stoichiometric amount required to react with the carbonyl groups of the polymeric particles. ### Claim 9 (depends on 8) The process of claim 8 wherein said hydroxylamine salt is hydroxylamine hydrochloride. ### Claim 10 (depends on 1) The process of claim 1 wherein said oximation reaction is conducted within a temperature range of about 25.degree. C. to about 60.degree. C. and over a period of from about 3 to 10 hours. ### Claim 11 (depends on 1) The process of claim 1 wherein said alkalinity is provided by an amount of alkali of up to about 20% in excess of that stoichiometrically required to provide free hydroxylamine from said hydroxylamine salt. ### Claim 12 (depends on 1) The process of claim 1 wherein the oximation product is neutralized with acid to recover the polymeric oxime. ### Claim 13 (depends on 1) The process of claim 1 wherein said emulsion polymerization is initiated with ammonium persulfate. ### Claim 14 (depends on 1) The process of claim 1 wherein the steps of introducing said portion of monomer into said polymerization medium and initiating said emulsion polymerization are conducted substantially simultaneously. ### Claim 15 (depends on 1) The process of claim 1 wherein said polymerization medium includes an emulsifying agent bis-tridecyl sodium sulfosuccinate. ### Claim 16 (depends on 1) The process of claim 1 wherein said polymerization medium includes a hydrocolloid stabilizer. ### Claim 17 (depends on 16) The process of claim 16 wherein said stabilizer is hydroxyethyl cellulose. ### Claim 18 (depends on 1) The process of claim 1 wherein said polymerizable monomer has the formula ##STR10## wherein R is hydrogen or methyl; each of R.sup.1 and R.sup.2 is alkyl of from 1 to 4 carbon atoms; and R.sup.3 is hydrogen or alkyl of from 1 to 4 carbon atoms. ### Claim 19 (depends on 18) The process of claim 18 wherein R is hydrogen and each of R.sup.1, R.sup.2 and R.sup.3 is methyl. ### Claim 20 (depends on 1) The process of claim 1 wherein said polymerizable monomer to be polymerized includes in an amount corresponding to about 1 to 10% by weight of the polymer of an ionizable monomer selected from the group consisting of acrylic acid, methyacrylic acid and 2-acrylamido-2-methylpropane sulfonic acid. ### Claim 21 A process for preparing a polymeric oxime which comprises introducing into an aqueous polymerization medium about 1% to about 15% by weight of an amount of diacetone acrylamide to be polymerized; initiating the emulsion polymerization of said diacetone acrylamide, and while maintaining said polymerization, adding uniformly over a period of about 2 to 6 hours the remaining diacetone acrylamide to be polymerized; thereby to provide in an aqueous latex polymeric particles comprising recurring units from said diacetone acrylamide; contacting the polymeric latex with from about 60% to about 150% by weight of the latex of a lower alkanol to effect swelling of the polymeric particles; and oximating the swollen polymeric particles by reaction with hydroxylamine hydrochloride and alkali, said hydroxylamine hydrochloride being in at least stoichiometric amount required to react with the carbonyl groups of the polymeric particles and said alkali being at least the stoichiometric amount required to provide free hydroxylamine from said hydroxylamine hydrochloride. ### Claim 22 (depends on 21) The process of claim 21 wherein there is introduced into said polymerication medium about 1% to about 10% by weight of the polymer to be formed of acrylic acid. ### Claim 23 (depends on 22) The process of claim 22 wherein said polymerization medium includes hydroxycellulose stabilizer and wherein the lower alkanol is methanol.