EP3008035A1 - Synthèse de (méth)acrylates d'acides carboxyliques alpha, bêta-insaturés à partir d'oléfines et de co2 - Google Patents

Synthèse de (méth)acrylates d'acides carboxyliques alpha, bêta-insaturés à partir d'oléfines et de co2

Info

Publication number
EP3008035A1
EP3008035A1 EP14725662.2A EP14725662A EP3008035A1 EP 3008035 A1 EP3008035 A1 EP 3008035A1 EP 14725662 A EP14725662 A EP 14725662A EP 3008035 A1 EP3008035 A1 EP 3008035A1
Authority
EP
European Patent Office
Prior art keywords
formula
unsaturated carboxylic
halide
composition
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14725662.2A
Other languages
German (de)
English (en)
Inventor
Benjamin SCHÄFFNER
Matthias Blug
Dieter Vogt
Coen HENDRIKSEN
Evgeny PIDKO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP3008035A1 publication Critical patent/EP3008035A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Definitions

  • the present invention is a process for the preparation of ⁇ , ⁇ -unsaturated carboxylic acids (for example acrylic or methacrylic acid) or a salt of ⁇ , ⁇ -unsaturated carboxylic acids, which comprises a process step in which a complex in a solvent in the presence of a halide is reacted, a composition comprising ⁇ , ⁇ -unsaturated carboxylic acid or its salt and halide ions, and the use of these compositions for the production of superabsorbent materials or as a monomer composition for the preparation of polymers, such as. B. polymethylmethacrylate.
  • ⁇ , ⁇ -unsaturated carboxylic acids for example acrylic or methacrylic acid
  • a salt of ⁇ , ⁇ -unsaturated carboxylic acids which comprises a process step in which a complex in a solvent in the presence of a halide is reacted, a composition comprising ⁇ , ⁇ -unsaturated carboxylic acid or its salt and
  • C0 2 is used as a raw material for the production of popular chemical products.
  • One method is z.
  • the preparation of acrylates by reacting carbon dioxide with olefins in the presence of a nickel bisphosphine catalyst and a base, as described by Michael L. Lejkowski et al., The First Catalytic Synthesis of acrylates from C0 2 and to alkenes - A Rational Approach ", Chem. Eur. J. 2012; Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; Wiley Online Library; DOI: 10.1002 / chem.201201757.
  • the established catalytic cycle involves the steps of converting an olefin complex with C0 2 to the lactone complex, converting the lactone complex to the acrylate complex, and then exchanging the acrylate ligand with the olefin ligand to give the olefin complex.
  • strong bases such as sodium butanolate or NaOH are used.
  • a disadvantage of the use of these strong bases is that in a CO2 atmosphere they tend to react with the carbon dioxide to form carbonates and thus no longer be available for the catalytic conversion. To avoid this
  • anion bases such as. Salts with inorganic or organic ammonium ions or alkali or alkaline earth metals, or neutral bases, inorganic anion bases including carbonates, phosphates, nitrates or halides and organic anion bases including phenolates, carboxylates, sulfates organic molecular units, sulfonates, phosphates, phosphonates can be and organic neutral bases may be, inter alia, primary, secondary or tertiary amines, furthermore ethers, esters, imines, amides, carbonyl compounds, carboxylates or carbon monoxide.
  • the auxiliary base used is preferably a primary, secondary or tertiary amine, more preferably a tertiary amine.
  • a disadvantage of using the amines as auxiliary bases is that the auxiliary bases must be removed again in one or more steps. This is preferably done using alkali metal carbonates, hydroxides or oxides, preferably sodium hydroxide.
  • simple ammonium iodides such as tetrabutylammonium iodide are also suitable for the reaction.
  • sodium iodide as a salt and Lewis acid can lead directly to the formation of sodium acrylate, a precursor for the synthesis of superabsorbents.
  • the process according to the invention has the particular advantage that the synthesis of ⁇ , ⁇ -unsaturated carboxylic acids or their salts can be carried out directly from the starting materials of an olefin and C0 2 without isolation of special intermediates.
  • the process according to the invention, the composition according to the invention and the use thereof are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be.
  • (meth) acrylic acid or ( Meth) acrylate is to be understood as meaning both methacrylic acid and acrylic acid or both methacrylate and acrylate
  • the process according to the invention for the production of ⁇ , ⁇ -unsaturated carboxylic acids or a salt of the ⁇ , ⁇ -unsaturated carboxylic acid, preferably (meth) acrylic acid or a salt of (meth) acrylic acid, preferably acrylic acid or a salt of acrylic acid is characterized in that it comprises a process step in which, preferably intermediately (or in the meantime), a substance of the formula (I)
  • E element of groups 4, 6, 7, 8, 9 or 10 of the Periodic Table of the Elements, preferably nickel,
  • R is H or an aryl or alkyl radical, preferably H or a branched or unbranched alkyl radical having 1 to 10 carbon atoms, particularly preferably H or a methyl group and very particularly preferably H,
  • L is preferably a ligand selected from phosphanes or phosphonates, preferably bisphosphanes or bisphosphonates, preferably selected from trialkyl, dialkyl-aryl, alkyl-diaryl and triaryl-bisphosphane ligands.
  • L is selected from bis (dicyclohexylphosphino) ethane (Dcpe), bis (di-tert-butylphosphino) ethane and bis (diphenylphosphino) ethane.
  • the solvent is selected from halogenated hydrocarbons, halogenated aromatics and cyclic ethers, preferably chlorobenzene or dichloromethane or tetrahydrofuran. Chloroform, dichloromethane or chlorobenzene, preferably chlorobenzene, is particularly preferably used as the solvent.
  • the reaction can be carried out at atmospheric pressure or elevated pressure.
  • the reaction of the compound of the formula (I) (of the nickelalactone) is preferably carried out at partial pressures of from 1 to 50 bar C0 2 and from 1 to 50 bar of the corresponding olefin.
  • the reaction can be carried out at any temperature.
  • the reaction is carried out at a temperature of 0 to 150 ° C, preferably 15 to 100 ° C and more preferably at a temperature of 25 to 60 ° C.
  • the molar ratio of halide ions to element E is preferably from 0.1 to 1 to 50 to 1, preferably from 1 to 1 to 20 to 1.
  • the olefins used are preferably hydrocarbons which have at least one unsaturated carbon-carbon bond.
  • Preferred olefins are those Hydrocarbons used which have 1 to 10 carbon atoms.
  • Particular preference is given to using ethene or propene as olefins, ethene being very particularly preferred.
  • This implementation can z. Example, as in Michael L. Lejkowski et al., "The First Catalytic Synthesis of an acrylate from C0 2 and to alkenes - A Rational Approach", Chem. Eur. J. 2012; Wiley-VCH Verlag GmbH & Co.
  • nickel (1, 5-cyclooctadiene) 2 (Ni (cod) 2) is used for the preparation of the compound of formula (I) and ligand L, preferably 1, 2-bis (dicyclohexylphosphino) ethane, bis (di-) tert-butylphosphino) ethane or
  • C0 2 / olefin atmosphere preferably a C0 2 / ethene or C0 2 / propene atmosphere, preferably prepared in a C0 2 / ethene atmosphere.
  • the inventive compositions are obtainable, the halide ions and ⁇ , ⁇ -unsaturated carboxylic acid, preferably (meth) acrylic acid, particularly preferably acrylic acid or its salts (with alkali, alkaline earth metal ammonium), in particular the inventive compositions described below ,
  • compositions according to the invention containing the ⁇ , ⁇ -unsaturated carboxylic acid or its salt are characterized in that they have halide ions, preferably iodide ions.
  • the proportion of halide ions, preferably iodide ions is preferably from 20 to 1000 mol%, preferably from 50 to 500 mol%, based on the substance of the formula (I).
  • compositions according to the invention obtained by a process according to the invention in which the substance of the formula (I) is not isolated, the compositions according to the invention have .alpha.,. Beta.-unsaturated carboxylic acid or a salt thereof and a halide ion, preferably iodide ions , on.
  • the proportion of halide ions, preferably iodide ions, is preferably 50 to 5000 mol%, preferably 100 mol% to 500 mol%, based on E before.
  • E is selected from the group comprising bis (dicyclohexylphosphino) ethane and bis (di-tert-butylphosphino) ethane (d'Bupe).
  • the determination of the content of E can be carried out by known suitable analytical methods. Represents E z. As nickel, the nickel content z. B. by atomic absorption spectrometry (AAS) at 232.0 nm, z. As in Welz, B .; Sperling, M., atomic absorption spectrometry, Wiley-VHC: Weinheim, (1997); P. 565, described.
  • the halide determination can be carried out by known suitable analytical methods. The determination of chloride, iodide and bromide is preferably carried out by the method "Titration Volhard", as in known
  • compositions according to the invention in particular those which contain acrylic acid or salts thereof, may, for.
  • superabsorbent materials or as monomer compositions for the preparation of polymers.
  • compositions of the invention in particular those containing methacrylic acid or salts thereof, may, for. B. for the production of polymethylmethacrylates and semifinished products or plates produced therefrom.
  • the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.
  • reaction was stopped by the addition of 0.02 ml of trifluoroacetic acid and converted unreacted Nickelalacton in free propionic acid.
  • the reaction mixture was dissolved in 1.0 mL of tetrahydrofuran and treated with 1 mg of acetic acid in 0.5 mL of tetrahydrofuran (internal standard). The mixture was filtered through silica gel and analyzed by GC and NMR.
  • Example 3 Reaction of a substance of the formula (I) in a solvent in the presence of a halide
  • DCM dichloromethane
  • I diphenylphosphinoethane Ni
  • I became 5 , 3 mg (0.125 mmol) of lithium chloride.
  • the mixture was stirred at 22 ° C for 20 hours.
  • the substance mixture was worked up and analyzed according to Example 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'acides carboxyliques a,ß-insaturés ou de leurs sels. Ledit procédé comporte une étape du procédé dans laquelle on fait réagir une métallalactone dans un solvant en présence d'un halogénure. L'invention concerne une composition qui comporte des acides carboxyliques a,ß-insaturés ou leurs sels et des ions halogénure, ainsi que l'utilisation de cette composition pour la production de matériaux super-absorbants ou comme composition monomère pour la production de polymères.
EP14725662.2A 2013-06-11 2014-05-12 Synthèse de (méth)acrylates d'acides carboxyliques alpha, bêta-insaturés à partir d'oléfines et de co2 Withdrawn EP3008035A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013210840.0A DE102013210840A1 (de) 2013-06-11 2013-06-11 Synthese von a,ß-ungesättigten Carbonsäuren (Meth)acrylaten aus Olefinen und CO2
PCT/EP2014/059596 WO2014198469A1 (fr) 2013-06-11 2014-05-12 Synthèse de (méth)acrylates d'acides carboxyliques alpha, bêta-insaturés à partir d'oléfines et de co2

Publications (1)

Publication Number Publication Date
EP3008035A1 true EP3008035A1 (fr) 2016-04-20

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP14725662.2A Withdrawn EP3008035A1 (fr) 2013-06-11 2014-05-12 Synthèse de (méth)acrylates d'acides carboxyliques alpha, bêta-insaturés à partir d'oléfines et de co2

Country Status (8)

Country Link
US (1) US20160130208A1 (fr)
EP (1) EP3008035A1 (fr)
JP (1) JP2016523855A (fr)
CN (1) CN105517986A (fr)
BR (1) BR112015031158A2 (fr)
CA (1) CA2913520A1 (fr)
DE (1) DE102013210840A1 (fr)
WO (1) WO2014198469A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014203951A1 (de) * 2014-03-05 2015-09-10 Evonik Degussa Gmbh Synthese von alpha,beta-ungesättigten Carbonsäuren (Meth)acrylaten aus Olefinen
US9416087B2 (en) 2014-10-08 2016-08-16 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
US9725393B2 (en) 2014-10-08 2017-08-08 Chevron Phillips Chemical Company Lp Methods for the production of α,β-unsaturated carboxylic acids and salts thereof
CN108368017B (zh) 2015-12-15 2021-07-09 切弗朗菲利浦化学公司 由金属内酯和阴离子聚电解质形成α,β-不饱和羧酸和其盐
JP6814573B2 (ja) * 2016-08-26 2021-01-20 株式会社日本触媒 不飽和カルボン酸塩の製造方法
US10544080B2 (en) 2017-06-14 2020-01-28 Chevron Phillips Chemical Company Lp Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor
US10550061B2 (en) 2017-06-14 2020-02-04 Chevron Phillips Chemical Company Lp Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide
JP7065654B2 (ja) * 2018-03-15 2022-05-12 積水化学工業株式会社 α，β－不飽和カルボン酸の合成方法
WO2019188507A1 (fr) * 2018-03-28 2019-10-03 積水化学工業株式会社 PROCÉDÉ DE PRODUCTION D'UN CARBOXYLATE α, β-INSATURÉ
US11174213B2 (en) 2018-10-12 2021-11-16 Chevron Phillips Chemical Company, Lp Effects of catalyst concentration and solid activator on nickel-mediated olefin/carbon dioxide coupling to acrylates
CN111068789B (zh) * 2019-12-31 2021-10-08 中国科学院过程工程研究所 一种用于co2参与的烯烃羰基酯化反应的催化剂
FR3110570B1 (fr) * 2020-05-19 2022-05-20 Commissariat Energie Atomique PROCEDE DE PREPARATION D’ACIDE ACRYLIQUE A PARTIR DE β-PROPIOLACTONE
DE202021100428U1 (de) 2021-01-28 2021-02-08 Certoplast Technische Klebebänder Gmbh Klebeband

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DE805641C (de) * 1948-10-02 1951-05-25 Basf Ag Verfahren zur Herstellung ª‡,ª‰-ungesaettigter Carbonsaeuren und ihrer Abkoemmlinge
KR0144567B1 (ko) * 1989-03-03 1998-07-15 오노 알버어스 카르보닐화촉매시스템
CN101745428B (zh) * 2009-12-30 2011-09-28 山东大学 一种二氧化碳催化转化为甲基丙烯酸的催化剂与应用
CN102884025A (zh) * 2010-03-03 2013-01-16 巴斯夫欧洲公司 通过链烯的羧基化制备烯属不饱和羧酸盐的方法

Non-Patent Citations (2)

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Also Published As

Publication number Publication date
CA2913520A1 (fr) 2014-12-18
US20160130208A1 (en) 2016-05-12
DE102013210840A1 (de) 2014-12-11
WO2014198469A1 (fr) 2014-12-18
BR112015031158A2 (pt) 2017-07-25
JP2016523855A (ja) 2016-08-12
CN105517986A (zh) 2016-04-20

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