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(12) United States Patent (10) Patent No.: US 9,464,024 B2 Le Notre Et Al

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(12) United States Patent (10) Patent No.: US 9,464,024 B2 Le Notre Et Al USOO9464024B2 (12) United States Patent (10) Patent No.: US 9,464,024 B2 Le Notre et al. (45) Date of Patent: Oct. 11, 2016 (54) PROCESS FOR THE PRODUCTION OF (52) U.S. Cl. METHACRYLIC ACID CPC ..................................... C07C 51/38 (2013.01) (58) Field of Classification Search (71) Applicant: Stichting Dienst Landbouwkundig CPC ...................................................... CO7C 51/38 Onderzoek, Wageningen (NL) USPC .......................................................... 562/598 See application file for complete search history. (72) Inventors: Jerome Emile Lucien Le Notre, Arnhem (NL); Elinor Lindsey Scott, (56) References Cited Amersfoort (NL); Roeland Leo Croes, U.S. PATENT DOCUMENTS Nijmegen (NL); Jacobus Van Haveren, Ede (NL) 2012/0178961 A1* 7, 2012 Sanders .................... CO7C 604 560,205 (73) Assignee: Stichting Dienst Landbouwkundig Onderzoek, Wageningen (NL) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO WO 2012O698.13 A1 * 5, 2012 ............. CO7C 51.38 patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS Carlsson et al. Study of the Sequential Conversion of Citric to (21) Appl. No.: 14/913,833 Itaconic to Methacrylic Acid in Near-Critical and Supercritical (22) PCT Filed: Aug. 26, 2014 Water. Ind. Eng. Chem. Res., vol. 33, 1994, 1989-1996.* (86). PCT No.: PCT/NL2014/050575 * cited by examiner S 371 (c)(1), Primary Examiner — Sikarl Witherspoon (2) Date: Feb. 23, 2016 (74) Attorney, Agent, or Firm — William B. Miller (87) PCT Pub. No.: WO2015/030580 (57) ABSTRACT Disclosed is a method of making methacrylic acid, or a PCT Pub. Date: Mar. 5, 2015 carboxylic derivative thereof, from itaconic acid, isomers, or precursors thereof. A starting material comprising an acid (65) Prior Publication Data selected from the group consisting of itaconic acid, citra US 2016/02O7867 A1 Jul. 21, 2016 conic acid, mesaconic acid, citric acid, aconitic acid, isoc itric acid and mixtures thereof, is subjected to contact with (30) Foreign Application Priority Data 0.1 eq. to 3.0 eq. of a base, at a temperature of 150° C. to 350° C., under the influence of a transition metal-containing Aug. 26, 2013 (EP) ..................................... 13181709 heterogeneous catalyst. A better yield at lower temperatures is achieved. (51) Int. Cl. C07C 5 L/38 (2006.01) 14 Claims, No Drawings US 9,464,024 B2 1. 2 PROCESS FOR THE PRODUCTION OF by reference. Herein a process is described by which MMA METHACRYLIC ACID can be produced by Successive reactions (dehydration, form aldehyde aldol condensation, esterification) starting from CROSS-REFERENCE TO RELATED biobased glycols such as ethylene glycol and propylene APPLICATIONS glycol. Another reference relating to such a route is WO 2012/ This application is a national stage entry of International 0898.13, the disclosure of which is hereby incorporated by Application No. PCT/NL2014/050575, filed Aug. 26, 2014, reference. Herein a process is described by which MAA can which itself claims priority to EP Patent Application No. be produced from the decarboxylation of itaconic acid or a 13181709.0, filed Aug. 26, 2013, each of the contents of the 10 Source thereof in the presence of base catalysts. Although entirety of which are incorporated by this reference. this process is interesting, the yield of MAA is far below a value that would render the process of commercial interest. FIELD OF THE INVENTION Whilst the yield can be increased by raising the reaction temperature, this goes with a dramatic reduction of selec The invention pertains to the synthesis of methacrylic acid 15 tivity. Also, the high temperatures per se, and the high (MAA), or a carboxylic derivative thereof from, itaconic pressures applied, make the process less interesting, if not acid, or a precursor or isomer thereof. Particularly, the plainly prohibitive, for economic application. invention pertains to a route to MAA from bio-based, It would be desired to provide a process that allows to non-fossil resources. produce MAA in a good yield, yet with a high selectivity. Also, it would be desired to provide a process that is BACKGROUND OF THE INVENTION economically more attractive by allowing lower energy input, e.g. by requiring a lower reaction temperature, and MAA, and methyl methacrylate (MMA) are widely used without applied pressure. in industry, mainly as monomers to make polymers having Further, the known process is applicable to itaconic acid, a variety of uses, such as acrylate fibers (polyMAA), cement 25 its isomers. The reference mentioned that the process is also in total hip or knee replacements (MMA), various optical applicable to a source of these acids. However, from the glasses and lenses (PMMA). MAA can be used as a co disclosure itself it is clear that the actual process far making monomer together with MMA or ethyl acrylate to produce MAA is not directly applied on precursors of itaconic acid, polymers used in coatings and slow release applications. Such as citric acid. Background art on making methacrylic MMA can also be used as co-monomer to produce polymers 30 acid from citric acid is Carlsson et al., Ind. Eng. Chem. Res. such as methyl methacrylate-butadiene-styrene (MBS). 1994, 33, 1989. Herein a low yield, 6%, of methacrylic acid Materials can be obtained by blending PMMA with other is obtained, via a dehydration reaction and two decarboxy polymers such as polyvinylchloride (PVC). lation reactions. It would be desired to provide a process that MAA is currently produced from petrochemical would be directly applicable to itaconic acid precursors, resources. It would be desired to find a route by which it can 35 particularly to citric acid, and by which methacrylic acid can be produced from bio-based, renewable, non-fossil be produced in better yield. SOUCS. A reference relating to such a route is WO 2009/ SUMMARY OF THE INVENTION 135074A2, the disclosure of which is hereby incorporated by reference. Herein a process is described by which MAA 40 In order to address one or more of the foregoing desires, can be produced by fermentation of a renewable Sugar the invention, in one aspect, provides a method, of making feedstock of non-natural micro-organisms. methacrylic acid, or a salt thereof, by Subjecting a starting Another reference relating to such a route is US 2010/ material comprising an acid selected from the group con 0035314A1, the disclosure of which is hereby incorporated sisting of itaconic acid, citraconic acid, mesaconic acid, by reference. Herein a process is described by which MAA 45 citric acid, aconitic acid, isocitric acid and mixtures thereof can be produced by catalytic dehydration of 2-hydroxy-2- to contact with 0.1 eq. to 3.0 eq. of a base, at a temperature methylcarboxylic acid obtained by fermentation, of a renew of 150° C. to 350° C., under the influence of a transition able Sugar feedstock of non-natural micro-organisms. metal-containing catalyst. Another reference relating to such a route is the work In another aspect, the invention pertains to the use of a described by Pyo et al. (Green Chem. 2012, 14, 1942), the 50 transition metal catalyst for the purpose of increasing the disclosure of which is hereby incorporated by reference. yield and selectivity of the synthesis of methacrylic acid, or Herein a process is described by which MAA can be a salt thereof, from a starting material comprising an acid produced by a consecutive microbial conversion and cata selected from the group consisting of itaconic acid, citra lytic dehydration of 2-methyl-1-3-propanediol, potentially conic acid, mesaconic acid, citric acid, isocitric acid, aco obtained by fermentation of biobased glycerol. 55 nitic acid, and mixtures thereof. Another reference relating to such a route is WO 2010/ 058119A1, the disclosure of which is hereby incorporated DETAILED DESCRIPTION OF THE by reference. Herein a process is described by which MMA INVENTION can be produced by reaction of methyl propionate and formaldehyde. Methyl propionate is produced by carbo 60 In a broad sense, the invention is based on the judicious nylation of ethylene in the presence of methanol where at insight to add a transition metal catalyst to the base-cata least one of the three reactants used are obtained from lyzed process of decarboxylating itaconic acid or a precursor biomass: ethylene by dehydration of bio-ethanol and/or or isomer thereof. The use of the catalyst allows to obtain a carbon monoxide and methanol obtained by biobased syn dramatic increase in yield and/or selectivity, in a reaction gas. Formaldehyde can be produced from biobased syngas. 65 conducted under much milder conditions than available in Another reference relating to such a route is WO 2012/ the art. Also, the use of the catalyst in accordance with the 154450A2, the disclosure of which is hereby incorporated invention allows a feasible process to produce methacrylic US 9,464,024 B2 3 4 acid from citric acid, isocitric acid, itaconic acid, citraconic homogeneous catalysis include PdCl2, PdBr, PdL, acid, mesaconic acid, aconitic acid, and mixtures thereof. Pd(OAc), Pd(CN), PdO, PtC1, PtBr, PtI, PtC1, PtC), Therewith, the invention provides a process wherein citric RuCls, Rul, RuO, RuO, NiCl, NiBr. NiI2. NiF. acid, and preferably a bio-based source thereof, can be itself Ni(OH), Ni(OAc), Ni(CO), AuCl, AuCl, AuBr, AuO used, as a starting material for the direct synthesis of the 5 RhCls, RhBr. RhI, and RhC). valuable chemical methacrylic acid. In addition to producing Heterogeneous catalysts are preferred. Therewith a pro methacrylic acid, the process of the invention also allows the cess advantage can be attained, in the sense that separation direct production of salts of methacrylic acid, with the base of catalysts and products is easier. Also, heterogeneous forming the counterion of the salt.
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