# US 8,771,815 B2 · Process for making triglyceride plasticizer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,771,815 B2 - Document ID: US8771815B2 - Status: Granted - Kind: B2 - Application number: 12/971,629 - Filed: 2010-12-17 - Published: 2011-06-23 - Granted: 2014-07-08 - Earliest claimed: 2009-12-17 - Assignees: ExxonMobil Research and Engineering Company - Applicants: Jihad Mohammed Dakka; Edmund John Mozeleski - Inventors: Jihad Mohammed Dakka; Edmund John Mozeleski - Web page: https://patentgrep.com/patent/US8771815B2 ## CPC - C07C 67/08: by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds - C08K 5/0016: {Plasticisers} - C08K 5/103: with polyalcohols - C08L 23/0853: Ethylene vinyl acetate copolymers - C08L 91/00: Compositions of oils, fats or waxes; Compositions of derivatives thereof - Y02P 20/582: Recycling of unreacted starting or intermediate materials - Y10T 428/1352: Polymer or resin containing [i.e., natural or synthetic] - Y10T 428/139: Open-ended, self-supporting conduit, cylinder, or tube-type article - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Provided are processes for making, and processes for using triglycerides as plasticizers. The process for making the triglyceride plasticizer includes: (i) recovering at least one linear C4 to C10 aldehyde, one branched C4 to C10 aldehyde, or a combination thereof from a hydroformylation product; (ii) oxidizing the linear, branched or combination thereof C4 to C10 aldehyde to form a linear, branched or combination thereof C4 to C10 acid; (iii) esterifying the linear, branched or combination thereof C4 to C10 acid with a polyol to yield a linear alkyl triglyceride, a branched alkyl triglyceride, or a combination thereof, and reaction byproducts; (iv) purifying the linear, branched or combination thereof alkyl triglyceride to form a plasticizer stream, a reaction byproduct stream, and an unreacted input stream, wherein the total carbon number of the triester groups ranges from 20 to 25 for greater than or equal to 45 wt % of the plasticizer; and (v) recycling from the purifying step back to the esterifying step the unreacted input stream and the reaction byproduct stream. ## Claims ### Claim 1 A process for producing a plasticizer comprising: (i) recovering at least one linear C4 to C10 aldehyde, one branched C4 to C10 aldehyde, or a combination thereof from a hydroformylation product; (ii) oxidizing the linear, branched or combination thereof C4 to C10 aldehyde to form a linear, branched or combination thereof C4 to C10 acid; (iii) esterifying the linear, branched or combination thereof C4 to C10 acid with a polyol to yield a linear alkyl triglyceride, a branched alkyl triglyceride, or a combination thereof, and reaction byproducts; (iv) purifying the linear, branched or combination thereof alkyl triglyceride to form a plasticizer stream, a reaction byproduct stream, and an unreacted input stream, wherein the total carbon number of the alkyl triester groups ranges from 20 to 25 for greater than or equal to 45 wt % of the plasticizer; and (v) recycling from the purifying step back to the esterifying step the unreacted input stream and the reaction byproduct stream. ### Claim 2 (depends on 1) The process of claim 1, wherein the at least one branched C4 to C10 aldehyde is characterized by a branching of from about 0.8 to about 3.0 branches per molecule. ### Claim 3 (depends on 1) The process of claim 1, wherein the oxidizing step is with oxygen and/or air. ### Claim 4 (depends on 1) The process of claim 1, further including recovering at least one linear C4 to C10 alcohol, one branched C4 to C10 alcohol, or a combination thereof from the hydroformylation product, oxidizing the linear, branched or combination thereof C4 to C10 alcohol to form a linear, branched or combination thereof C4 to C10 acid; and feeding the linear, branched or combination thereof C4 to C10 acid to step (iii) of claim 1. ### Claim 5 (depends on 1) The process of claim 1, wherein the hydroformylation product includes a mixture of at least one linear C4 to C10 aldehyde, one branched C4 to C10 aldehyde, or a combination thereof and at least one at least one linear C4 to C10 alcohol, one branched C4 to C10 alcohol, or a combination thereof. ### Claim 6 (depends on 1) The process of claim 1, further including purifying the linear, branched or combination thereof C4 to C10 acid of step (ii) from the unreacted branched or combination thereof C4 to C10 aldehyde via distillation before the esterifying step (iii). ### Claim 7 (depends on 1) The process of claim 1, wherein the polyol is selected from glycerol, ethylene glycol, and propylene glycol, and mixtures thereof. ### Claim 8 (depends on 7) The process of claim 7, wherein the polyol comprises glycerol. ### Claim 9 (depends on 1) The process of claim 1, further comprising providing a feed for the hydroformylation process from dimerization of a feedstock. ### Claim 10 (depends on 9) The process of claim 9, wherein the feedstock comprises an olefin selected from propylene, butenes, pentenes and mixtures thereof. ### Claim 11 (depends on 9) The process of claim 9, wherein the hydroformylation reaction is catalyzed by a metal selected from Groups 8-10 according to the new notation for the Periodic Table as set forth in Chemical Engineering News, 63(5), 27 (1985). ### Claim 12 (depends on 11) The process of claim 11, wherein the hydroformylation reaction is catalyzed by a metal selected from Rh, Co, and mixtures thereof. ### Claim 13 (depends on 12) The process of claim 12, wherein the hydroformylation reaction is catalyzed by a metal selected from Rh, Co, and mixtures thereof including an organic ligand. ### Claim 14 (depends on 1) The process of claim 1, wherein the total carbon number of the triester groups ranges from 20 to 25 for greater than or equal to 75 wt % of the plasticizer. ### Claim 15 (depends on 14) The process of claim 14, wherein the total carbon number of the triester groups ranges from 20 to 25 for greater than or equal to 95 wt % of the plasticizer. ### Claim 16 (depends on 1) The process of claim 1, wherein the oxidizing step is catalyzed. ### Claim 17 (depends on 1) The process of claim 1, wherein the oxidizing step is not catalyzed. ### Claim 18 (depends on 1) The process of claim 1, wherein the esterifying step is catalyzed by at least one metal selected from Ti, Zr or Sn, or a mixture thereof, or catalyzed by an organic acid. ### Claim 19 (depends on 1) The process of claim 1, further comprising dimerizing a feedstock selected from propylene, butenes, pentenes and mixtures thereof by solid phosphoric acid or a zeolite dimerization to provide a feed for the hydroformylation process. ### Claim 20 (depends on 1) A plasticizer made by the process of claim 1, wherein the average branching of the alkyl triester groups ranges from about 1.2 to about 3.0 and with the proviso that the plasticizer is substantially free of aryl triglyceride. ### Claim 21 (depends on 20) The plasticizer of claim 20 characterized as being phthalate-free. ### Claim 22 (depends on 20) A resin composition comprising the plasticizer of claim 20 and a resin. ### Claim 23 (depends on 22) The resin composition of claim 22, wherein the resin is selected from vinyl chloride resins, polyesters, polyurethanes, ethylene-vinyl acetate copolymer, rubbers, acrylics, and mixtures thereof. ### Claim 24 (depends on 22) The resin composition of claim 22, further comprising stabilizers, fillers, pigments, biocides, carbon black, adhesion promoters, viscosity reducers, thixotropic agents, thickening agents, blowing agents, and mixtures thereof. ### Claim 25 (depends on 22) The resin composition of claim 22, further comprising at least one plasticizer selected from phthalates, adipates, trimellitates, cyclohexanoates, benzoates, and combinations thereof. ### Claim 26 (depends on 20) A plastisol comprising the plasticizer of claim 20. ### Claim 27 (depends on 20, 22, 26) An article comprising the plasticizer of claim 20, the resin composition of claim 22, or the plastisol of claim 26. ### Claim 28 (depends on 27) The article of claim 27, wherein the article is selected from toys, films and sheets, tubing, coated fabrics, wire and cable insulation and jacketing, flooring materials, adhesives, sealants, inks, and medical products. ### Claim 29 (depends on 28) The article of claim 28, made by a process including steps of dryblending and extrusion. ### Claim 30 (depends on 1) The process of claim 1, wherein the ratio of alcohol groups from the polyol to acid groups from the C4 to C10 acid in the esterifying step ranges from 1 to 1.1 to 1 to 10 to provide an excess of acid groups to alcohol groups. ### Claim 31 (depends on 30) The process of claim 30, wherein the unreacted input stream includes unreacted C4 to C10 acid. ### Claim 32 (depends on 30) The process of claim 30, wherein the reaction byproduct stream includes alkyl triglyceride with a total carbon number of the triester groups less than 20, and triglyceride with a total carbon number of the triester groups greater than 25. ### Claim 33 (depends on 30) The process of claim 30, wherein the reaction rate of the esterifying step is substantially similar to the reaction rate without the recycle of the unreacted C4 to C10 acid. ### Claim 34 (depends on 1) The process of claim 1, wherein the ratio of alcohol groups from the polyol to acid groups from the C4 to C10 acid in the esterifying step ranges from 1 to 1 to 10 to 1. ### Claim 35 (depends on 34) The process of claim 34, wherein the unreacted input stream includes unreacted polyol. ### Claim 36 (depends on 34) The process of claim 34, wherein the reaction byproduct stream includes monoglyceride, diglyceride, alkyl triglyceride with a total carbon number of the triester groups less than 20, and triglyceride with a total carbon number of the triester groups greater than 25. ### Claim 37 (depends on 36) The process of claim 36, wherein the reaction byproduct stream of the esterifying step also includes olefins, aldehydes, ketones, ethers and combinations thereof. ### Claim 38 A process for producing a plasticizer comprising: (i) recovering an aldehyde/alcohol mixture including at least one linear C4 to C10 aldehyde, one branched C4 to C10 aldehyde, or a combination thereof and at least one linear C4 to C10 alcohol, one branched C4 to C10 alcohol, or a combination thereof from a hydroformylation process; (ii) oxidizing the aldehyde/alcohol mixture to fbrm a linear, branched or combination thereof C4 to C10 acid; (iii) esterifying the linear, branched or combination thereof C4 to C10 acid with a polyol to yield a linear alkyl triglyceride, a branched alkyl triglyceride or a combination thereof, and reaction byproducts; (iv) purifying the linear, branched or combination thereof alkyl triglyceride to form a plasticizer stream, a reaction byproduct stream and an unreacted input stream, wherein the total carbon number of the alkyl triester groups ranges from 20 to 25 for greater than or equal to 45 wt % of the plasticizer; and (v) recycling from the purifying step back to the esterifying step the unreacted input stream and the reaction byproduct stream. ### Claim 39 (depends on 38) The process of claim 38, further including purifying the aldehyde/alcohol mixture of step (i) via distillation before the oxidizing step (ii). ### Claim 40 (depends on 38) The process of claim 38, wherein the at least one branched C4 to C10 aldehyde is characterized by a branching of from about 0.8 to about 3.0 branches per molecule. ### Claim 41 (depends on 38) The process of claim 38, wherein the oxidizing step is with oxygen and/or air. ### Claim 42 (depends on 38) The process of claim 38, further including purifying the linear, branched or combination thereof C4 to C10 acid of step (ii) from the unreacted aldehyde/alcohol mixture via distillation before the esterifying step (iii). ### Claim 43 (depends on 38) The process of claim 38, wherein said polyol is selected from glycerol, ethylene glycol, and propylene glycol, and mixtures thereof. ### Claim 44 (depends on 38) The process of claim 38, further comprising providing a feed for the e hydroformylation process from dimerization of a feedstock. ### Claim 45 (depends on 44) The process of claim 44, wherein the feedstock comprises an olefin selected from propylene, butenes, pentenes and mixtures thereof. ### Claim 46 (depends on 45) The process of claim 45, wherein the hydroformylation reaction is catalyzed by a metal selected from Groups 8-10 according to the new notation fbr the Periodic Table as set forth in Chemical Engineering News, 63(5), 27 (1985). ### Claim 47 (depends on 46) The process of claim 46, wherein the hydroformylation reaction is catalyzed by a metal selected from Rh, Co, and mixtures thereof. ### Claim 48 (depends on 47) The process of claim 47, wherein the hydroformylation reaction is catalyzed by a metal selected from Rh, Co, and mixtures thereof including an organic ligand. ### Claim 49 (depends on 38) The process of claim 38, wherein the total carbon number of the triester groups ranges from 20 to 25 for greater than or equal to 75 wt % of the plasticizer. ### Claim 50 (depends on 49) The process of claim 49, wherein the total carbon number of the triester groups ranges from 20 to 25 for greater than or equal to 95 wt % of the plasticizer. ### Claim 51 (depends on 38) The process of claim 38, wherein the oxidizing step is catalyzed. ### Claim 52 (depends on 38) The process of claim 38, wherein the oxidizing step is not catalyzed. ### Claim 53 (depends on 38) The process of claim 38, wherein the esterifying step is catalyzed by at least one metal selected from Ti, Zr or Sn, or a mixture thereof, or catalyzed by an organic acid. ### Claim 54 (depends on 38) The process of claim 38, further comprising dimerizing feedstock selected from propylene, butenes, pentenes and mixtures thereof by solid phosphoric acid or a zeolite dimerization to provide a feed for the hydroformylation process. ### Claim 55 (depends on 38) A plasticizer made by the process of claim 38, wherein the average branching of the alkyl triester groups ranges from about 1.2 to about 3.0 and with the proviso that the plasticizer is substantially free of aryl triglyceride. ### Claim 56 (depends on 55) The plasticizer of claim 55 characterized as being phthalate-free. ### Claim 57 (depends on 55) A resin composition comprising the plasticizer of claim 55 and a resin. ### Claim 58 (depends on 57) The resin composition of claim 57, wherein the resin is selected from vinyl chloride resins, polyesters, polyurethanes, ethylene-vinyl acetate copolymer, rubbers, acrylics, and mixtures thereof. ### Claim 59 (depends on 55) A plastisol comprising the plasticizer of claim 55. ### Claim 60 (depends on 55, 57, 59) An article comprising the plasticizer of claim 55, the resin composition of claim 57, or the plastisol of claim 59. ### Claim 61 (depends on 60) The article of claim 60, wherein the article is selected from toys, films and sheets, tubing, coated fabrics, wire and cable insulation and jacketing, flooring materials, adhesives, sealants, inks, and medical products. ### Claim 62 (depends on 38) The process of claim 38, wherein the ratio of alcohol groups from the polyol to acid groups from the C4 to C10 acid in the esterifying step ranges from 1 to 1.1 to 1 to 10 to provide an excess of acid groups to alcohol groups. ### Claim 63 (depends on 61) The process of claim 61, wherein the unreacted input stream includes unreacted C4 to C10 acid. ### Claim 64 (depends on 61) The process of claim 61, wherein the reaction byproduct stream includes alkyl triglyceride with a total carbon number of the triester groups less than 20, and triglyceride with a total carbon number of the triester groups greater than 25. ### Claim 65 (depends on 61) The process of claim 61, wherein the reaction rate of the esterifying step is substantially similar to the reaction rate without the recycle of the unreacted C4 to C10 acid. ### Claim 66 (depends on 38) The process of claim 38, wherein the ratio of alcohol groups from the polyol to acid groups from the C4 to C10 acid in the esterifying step ranges from 1 to 1 to 10 to 1. ### Claim 67 (depends on 65) The process of claim 65, wherein the unreacted input stream includes unreacted polyol. ### Claim 68 (depends on 65) The process of claim 65, wherein the reaction byproduct stream includes monoglyceride, diglyceride, alkyl triglyceride with a total carbon number of the triester groups less than 20, and triglyceride with a total carbon number of the triester groups greater than 25. ### Claim 69 (depends on 67) The process of claim 67, wherein the reaction byproduct stream of the esterifying step also includes olefins, aldehydes, ketones, ethers and combinations thereof.