# US 2014/0193629 A1 · Oxygen scavenging polyester composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0193629 A1 - Document ID: US20140193629A1 - Status: Published application - Kind: A1 - Application number: 14/193,162 - Filed: 2014-02-28 - Published: 2014-07-10 - Earliest claimed: 2009-05-07 - Assignees: Reliance Industries Limited - Applicants: Reliance Industries Limited - Inventors: Uday Shankar Agarwal; B. V. Venkatarishnan; Rajesh Jalan; Thaliyil Veedu Sreekumar; Srinivasacharya Ramacharya Ayodhya; Ashwin Kumar Jain; Shivamurthy Padadayya Jadimath; Pushap Sudan; Anant Gajanan KelKar - Web page: https://patentgrep.com/patent/US20140193629A1 ## CPC - B29D 22/003: {Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks} - A23B 2/717: Oxygen absorbent - C08G 63/6886: {Dicarboxylic acids and dihydroxy compounds} - C08L 67/02: Polyesters derived from dicarboxylic acids and dihydroxy compounds (C08L67/06 takes precedence) - B29D: PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE (making granules B29B9/00; making preforms B29B11/00) - A23B: PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract The present disclosure provides a polyester polymer product which contains partially or fully cobalt-neutralized organic sulphonic acid component and which is substantially free of ether and its preparation. The present disclosure also provides an oxygen scavenging composition made from a mixture of the polyester polymer product of the present disclosure, an organic oxidizable polymeric component and optionally at least one additional polyester component. The present disclosure further provides a packaging article defined by walls having an oxygen transmission rate (OTR) less than 0.2 cc·m−2 day−1 at 0.28 mm thickness and its preparation. ## Claims ### Claim 1 A process for preparing a polyester polymer product comprising at least partially cobalt-neutralized organic sulphonic acid component and having ether content less than 8 mole %, said process comprising the following steps: a. subjecting at least one dicarboxylic acid or mono-esters, di-esters or anhydrides thereof and at least one diol to esterification in a vessel by heating under pressure to obtain an esterified product; b. adding at least one at least partially cobalt-neutralized organic sulphonic acid to the esterified product to obtain a mixture; c. removing at least partially the diol from the esterified product or said mixture; and d. heating the mixture under reduced pressure to obtain the polyester polymer product. ### Claim 2 (depends on 1) The process as claimed in claim 1, wherein the step of removing the diol is carried out by at least one technique selected from the group consisting of depressurizing the vessel under heat and an inert gas sweep under heat. ### Claim 3 (depends on 1) The process as claimed in claim 1, wherein the dicarboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid and combinations thereof; the diol is selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 8-octanediol, 1,10 decanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexanediol, cyclobutanediol, cyclobutane dimethanol, tetramethane cyclobutanediol, combinations thereof; and the ether is selected from the group consisting of diethylene glycol, polyethylene glycol, polypropylene glycol, dipropylene glycol, polytetramethylene glycol and combinations thereof. ### Claim 4 (depends on 1) The process as claimed in claim 1, wherein the organic sulphonic acid is selected from the group consisting of sulfophthalic acid, dialkyl sulphopthalate, sulfoterephthalic acid, dialkyl sulfoterephthalate, sulfoisophthalic acid, dialkyl sulfoisophthalate, 4-sulfonaphthalene-2,7-dicarboxylic acid, dialkyl 4-sulfonaphthalene-2,7-dicarboxylate and organic sulfonic acids represented by the formula R—SO3H, wherein R is an alkyl, substituted alkyl, aryl or substituted aryl moiety. ### Claim 5 (depends on 1) The process as claimed in claim 1, wherein the at least partially cobalt-neutralized organic sulphonic acid is cobalt sulphonate of dimethylisophthalate (CoSIPM2). ### Claim 6 (depends on 1) The process as claimed in claim 1, wherein the at least partially cobalt-neutralized organic sulphonic acid is Co-pTSA. ### Claim 7 (depends on 1) The process as claimed in claim 1, includes a step of incorporation of at least one polymerization catalyst, said polymerization catalyst being selected from the group consisting of salts and oxides of antimony, tin and titanium. ### Claim 8 (depends on 1) The process as claimed in claim 1, include steps of extrusion of the polymer product, converting into chips, crystallization and solid state polymerization. ### Claim 9 (depends on 1) A process for preparing an intermediate product made from the polymer product as claimed in claim 1; said process comprising mixing said polyester polymer product of claim 1, at least one organic oxidizable polymer and optionally a second polyester component to obtain a mass followed by drying and molding said mass to obtain an intermediate product, wherein the organic oxidizable polymer is at least one selected from the group consisting of: (i) a copolymer of m-xylenediamine and adipic acid (MXD6); (ii) an aliphatic poly-amide comprising repeating units of the general formula CO(CH2)nCONH(CH2)mNH— or (CH2)pCONH—, wherein any of n, m or p is an integer between 3 and 7; and (iii) a co-polyester, derived from hydroxyl- or carboxyl-terminated monomeric, oligomeric or polymeric olefin or olefin oxide segments capable of oxygen scavenging, constituted by at least one member selected from the group consisting of a dicarboxylic, hydroxy-carboxylic or dihydroxy compound comprising at least one olefinic unsaturation, wherein the second polyester component comprises: (i) at least one member selected from the group of dicarboxylic acids comprising terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid and cyclohexane dicarboxylic acid or anhydrides or diesters or monoesters thereof with a lower alcohol; and (ii) at least one member selected from the group of diols comprising ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane diol, 8-octanediol, 1,10 decanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexanediol, cyclobutanediol, cyclobutane dimethanol, tetramethane cyclobutanediol and their ester forming derivatives. ### Claim 10 (depends on 1, 9) The process as claimed in claim 9, further comprises a step of adding at least one at least partially cobalt-neutralized organic sulphonic acid during mixing the polyester polymer product of claim 1, the at least one organic oxidizable polymer and optionally the second polyester component. ### Claim 11 (depends on 9) The process as claimed in claim 9, wherein the organic oxidizable polymer is poly (m-xylene adipamide. ### Claim 12 (depends on 9) The process as claimed in claim 9, wherein the second polyester component comprises a copolymeric condensate of ethylene terephthalate and ethylene isophthalate, the amount of ethylene isophthalate being <2.5 mole %. ### Claim 13 (depends on 1) A process for preparing a packaging article defined by walls having an oxygen transmission rate (OTR) less than 0.2 cc·m−2 day−1 at 0.28 mm thickness, said process comprising: i) mixing said polyester polymer product of claim 1, at least one organic oxidizable polymer and optionally a second polyester component to obtain a mass; and ii) drying and molding said mass to obtain an intermediate product followed by converting said intermediate product into the packaging article, wherein the organic oxidizable polymer is at least one selected from the group consisting of: (i) a copolymer of m-xylenediamine and adipic acid (MXD6); (ii) an aliphatic poly-amide comprising repeating units of the general formula CO(CH2)nCONH(CH2)mNH— or (CH2)pCONH—, wherein any of n, m or p is an integer between 3 and 7; and (iii) a co-polyester, derived from hydroxyl- or carboxyl-terminated monomeric, oligomeric or polymeric olefin or olefin oxide segments capable of oxygen scavenging, constituted by at least one member selected from the group consisting of a dicarboxylic, hydroxy-carboxylic or dihydroxy compound comprising at least one olefinic unsaturation, wherein the second polyester component comprises: (i) at least one member selected from the group of dicarboxylic acids comprising terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid and cyclohexane dicarboxylic acid or anhydrides or diesters or monoesters thereof with a lower alcohol; and (ii) at least one member selected from the group of diols comprising ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane diol, 8-octanediol, 1,10 decanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexanediol, cyclobutanediol, cyclobutane dimethanol, tetramethane cyclobutanediol and their ester forming derivatives. ### Claim 14 (depends on 1, 13) The process as claimed in claim 13, further comprises a step of adding at least one at least partially cobalt-neutralized organic sulphonic acid during mixing the polyester polymer product of claim 1, the at least one organic oxidizable polymer and optionally the second polyester component. ### Claim 15 (depends on 13) The process as claimed in claim 13, wherein the molding is carried out by using an injection molding technique in a molding machine operated at 270 to 310° C. ### Claim 16 (depends on 13) The process as claimed in claim 13, wherein the step of converting said intermediate product into the oxygen barrier packaging article includes blowing of said intermediate product, said oxygen barrier packaging article is a bottle. ### Claim 17 A polyester polymer product comprising at least partially cobalt-neutralized organic sulphonic acid component and having ether content less than 8 mole %, wherein the organic sulphonic acid is selected from the group consisting of sulfophthalic acid, dialkyl sulphopthalate, sulfoterephthalic acid, dialkyl sulfoterephthalate, sulfoisophthalic acid, dialkyl sulfoisophthalate, 4-sulfonaphthalene-2,7-dicarboxylic acid, dialkyl 4-sulfonaphthalene-2,7-dicarboxylate and organic sulfonic acids represented by the formula R—SO3H, wherein R is an alkyl, substituted alkyl, aryl or substituted aryl moiety. ### Claim 18 (depends on 17) The product as claimed in claim 17, wherein the at least partially cobalt-neutralized organic sulphonic acid is selected from the group consisting of cobalt sulphonate of dimethylisophthalate (CoSIPM2) and Co-pTSA. ### Claim 19 An oxygen scavenging composition comprising: A) a polyester polymer product comprising at least partially cobalt-neutralized organic sulphonic acid component and having ether content less than 8 mole %; B) optionally a polyester component comprising (i) at least one member selected from the group of dicarboxylic acids comprising terephthalic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, naphthalene dicarboxylic acid and cyclohexane dicarboxylic acid or anhydrides or diesters or monoesters thereof with a lower alcohol; and (ii) at least one member selected from the group of diols comprising ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexane diol, 8-octanediol, 1,10 decanediol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexane dimethanol, 1,4-cyclohexanediol, cyclobutanediol, cyclobutane dimethanol, tetramethane cyclobutanediol and their ester forming derivatives; and C) an organic oxidizable polymeric component selected from the group consisting of: (i) a copolymer of m-xylenediamine and adipic acid (MXD6); (ii) an aliphatic poly-amide comprising repeating units of the general formula CO(CH2)nCONH(CH2)mNH— or (CH2)pCONH—, wherein any of n, m or p is an integer between 3 and 7; and (iii) a co-polyester, derived from hydroxyl- or carboxyl-terminated monomeric, oligomeric or polymeric olefin or olefin oxide segments capable of oxygen scavenging, constituted by at least one member selected from the group consisting of a dicarboxylic, hydroxy-carboxylic or dihydroxy compound comprising at least one olefinic unsaturation, wherein the organic sulphonic acid is selected from the group consisting of sulfophthalic acid, dialkyl sulphopthalate, sulfoterephthalic acid, dialkyl sulfoterephthalate, sulfoisophthalic acid, dialkyl sulfoisophthalate, 4-sulfonaphthalene-2,7-dicarboxylic acid, dialkyl 4-sulfonaphthalene-2,7-dicarboxylate and organic sulfonic acids represented by the formula R—SO3H, wherein R is an alkyl, substituted alkyl, aryl or substituted aryl moiety. ### Claim 20 (depends on 19) The composition as claimed in claim 19, wherein the at least partially cobalt-neutralized organic sulphonic acid is selected from the group consisting of cobalt sulphonate of dimethylisophthalate (CoSIPM2) and Co-pTSA. ### Claim 21 (depends on 19) The composition as claimed in claim 19, wherein the organic oxidizable polymer is poly(m-xylene adipamide) and the polyester component comprises a copolymeric condensate of ethylene terephthalate and ethylene isophthalate, the amount of ethylene isophthalate being <2.5 mole %. ### Claim 22 (depends on 19) A packaging article defined by walls having an oxygen transmission rate (OTR) less than 0.2 cc·m−2 day−1 at 0.28 mm thickness made from the composition as claimed in claim 19.