EP1071650A1 - Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete - Google Patents

Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete

Info

Publication number
EP1071650A1
EP1071650A1 EP99901641A EP99901641A EP1071650A1 EP 1071650 A1 EP1071650 A1 EP 1071650A1 EP 99901641 A EP99901641 A EP 99901641A EP 99901641 A EP99901641 A EP 99901641A EP 1071650 A1 EP1071650 A1 EP 1071650A1
Authority
EP
European Patent Office
Prior art keywords
meth
acrylate
iii
reaction
chloroformate
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Withdrawn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
EP99901641A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jean-Michel Paul
Alain Riondel
Frédéric FABIS
Sylvain Rault
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.)
Arkema France SA
Original Assignee
Atofina SA
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 Atofina SA filed Critical Atofina SA
Publication of EP1071650A1 publication Critical patent/EP1071650A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates

Definitions

  • the present invention relates to a process for the manufacture of mixed anhydrides represented by the general formula (I):
  • R 1 represents H or CH-; and - R represents an al yl, alkenyl, aryl, alkaryl or aralkyl residue, according to which an alkali (meth) acrylate of general formula (II) is reacted:
  • mixed anhydrides of formula (I) generate as by-products in acylation reactions only CO- and alcohol R OH, easier to remove than (meth) acrylic acid or HCl.
  • the processes for the synthesis of non-acrylic mixed anhydrides which have been described in the literature are, for the most part, based on the method described by Vaughan in J. AI ⁇ . Chem. Soc. 22.
  • mixed anhydride is synthesized by equi-olecular reaction between an alkyl chloroformate and a tertiary amine carboxylate, at low temperature (generally less than 0 ° C), in a solvent medium (tetrahydrofuran, acetone, toluene, chloroform, etc.).
  • a solvent medium tetrahydrofuran, acetone, toluene, chloroform, etc.
  • methacrylic carboethoxy anhydride is also described in French patent application FR-A-2 212 340, starting from triethylammonium methacrylate and ethyl chloroformate in solvent medium (acetonitrile).
  • R 1 mixed (eth) acrylic anhydride HC CC-0-C-0-R 2 containing
  • the present invention therefore relates to a process for the preparation of a mixed (meth) acrylic anhydride (I) of high purity, by reaction between the aforementioned compounds (II) and (III), characterized in that one carries out said reaction in an aqueous medium and in the absence of amines, the chloroformate (III) / (meth) acrylate (II) molar ratio being at least equal to 1.15.
  • reaction is performed with compounds (II) and (III) in which: - R 2 is selected from alkyl radicals c ⁇ ⁇ 0 -C 4 alkenyl, C 2 -C 40, phenyl, phenyl (C 1 ⁇ C 40) and alkyl (C ⁇ -C ⁇ ) -phenyl; and M represents Na or K.
  • the mixed anhydrides of formula (I) wherein alkyl is C ⁇ ⁇ C 40, such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and are of particular interest are a family of preferred mixed anhydrides the invention. They are mild acylating agents which can very advantageously replace methacrylic anhydride or (meth) acryloyl chloride which generate methacrylic acid or hydrochloric acid in acylation reactions.
  • the chloroformate (III) / (meth) acrylate (II) molar ratio can be between 1.15 and 2, preferably between 1.5 and 1.7, in order to limit the formation from R 1 R 1
  • the reaction according to the present invention is advantageously carried out at a temperature between -10 and + 30 ° C, preferably between +10 and + 20 ° C.
  • the (meth) acrylate is prepared alkali (II) in aqueous solution by neutralization of (meth) acrylic acid with hydroxide MOH, the molar ratio MOH / (meth) acrylic acid being between 1 and 1.5, in particular between 1 and 1.1 , and the weight ratio water / alkali (meth) acrylate (II) being between 1.5 and 7, in particular between 1.5 and 2, then reacting the chloroformate (III) on the alkali (meth) acrylate ( II).
  • the reaction is carried out between the alkali (meth) acrylate (II) and the chloroformate (III) in the presence of a phase transfer catalyst, dissolved or fixed on a polymeric support such a ⁇ tyrene-divinylbenzene copolymer or a crosslinked polyvinylpyridine resin used in particular at a rate of 0.001 to 0.02 mole, in particular from 0.005 to 0.01 mole, per mole of alkali (meth) acrylate (II),
  • the phase transfer catalyst is advantageously chosen from quaternary ammonium salts, phosphonium salts and crown ethers.
  • - R 4 to R each represent C 1 -C 40 alkyl, such as CH 3 , C 2 H 5 , C 4 H g , C g H 17 , C 16 H 33 , or aryl such as phenyl, or aralkyl such as benzyl;
  • - X represents one of Cl, Br, I, OH and HS0 4 ; and, in particular, tetramethyla monium chloride, benzyltrimethylammonium chloride, benzyltri-n-butylammonium chloride, tetra-n-butyl ammonium chloride, tetra-n-butylammonium bromide, methyltrioctylammonium bromide and l tetra-n-butylammonium hydrogen sulfate;
  • phosphonium salts we can quote (C 4 H g ) 4 P * C1 ⁇ , (C 4 H 9 ) 4 P ⁇ Br
  • crown ethers examples include 18-crown-6 and dibenzoyl-18-crown-6.
  • the reaction according to the invention is generally carried out with stirring in a thermostatic jacketed reactor while strictly controlling the temperature.
  • the crude reaction mixture settles in two phases if the stirring is stopped (or in three phases if a phase transfer catalyst is used, fixed on a polymeric support).
  • the progress of the reaction is monitored by regularly taking samples of the aqueous phase and by measuring the residual alkali (meth) acrylate (II).
  • the reaction is considered complete when the conversion rate of the alkali (meth) acrylate (II) is greater than 95%.
  • the two-phase or three-phase reaction mixture is decanted at room temperature, advantageously washed with water (amount 20 to 100% of the weight of the organic phase, preferably 30 to 40%) at room temperature, the organic phase containing the mixed anhydride (I) and the excess of chloroformate (III) then being topped under vacuum at a temperature less than or equal to 35 ° C.
  • the mixed anhydride is thus obtained with very high purity.
  • At least one polymerization inhibitor it is necessary to introduce into the reaction medium at least one polymerization inhibitor, at a rate of 500 to 5000 pp, in particular from 500 to 1000 ppm, relative to the alkali (meth) acrylate (II) - or to its acid precursor. (meth) acrylic - to over-stabilize the latter.
  • polymerization inhibitors mention may be made of the methyl ether of hydroquinone, hy dro qu ino ne, pheno thiazi ne, ditertiobutylparacresol.
  • the heterogeneous mixture is left under stirring for 15 hours. It is then decanted at room temperature.
  • the organic phase is dried over calcium sulphate, then topped under vacuum at a temperature below 35 "C, in order to get rid of the excess of chloroformate.
  • Example 1 is repeated while varying the temperature and the ethyl chloroformate / sodium methacrylate molar ratio. 8 The results are reported in Table 1.
  • composition of the decanted organic phase (% by weight)
  • composition of the topped anic gold phase (% by weight) • Carboethoxy anhydride-
  • the reaction mixture is left under stirring while controlling the temperature at 20 ° C.
  • the progress of the reaction is monitored by measuring the residual sodium methacrylate in the aqueous decantation phase (the mixture settles as soon as the stirring is stopped). After 3 hours of reaction, the conversion rate of sodium methacrylate is greater than 99%.
  • the reactor is then drained, decanted at room temperature, the organic phase is washed with 57 g of water and the washed organic phase is decanted.
  • Example 6 is repeated while varying the molar ratio of ethyl chloroformate / sodium methacrylate.
  • the crude product is then decanted but not washed and topped under vacuum at a temperature below 35 ° C.
  • the yield of methacrylic carboethoxy anhydride is 87.5%.
  • Example 6 is repeated using potassium methacrylate in place of sodium methacrylate and operating at 10 "C. 11
  • composition of the final product (in% by weight) is as follows:
  • Example 6 is repeated, operating at 10 ° C. and varying the nature of the phase transfer catalyst which is introduced in an amount of 0.01 mole / mole of sodium methacrylate.
  • composition of the final product (% by weight)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP99901641A 1998-02-02 1999-01-28 Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete Withdrawn EP1071650A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9801155A FR2774375B1 (fr) 1998-02-02 1998-02-02 Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete
FR9801155 1998-02-02
PCT/FR1999/000164 WO1999038837A1 (fr) 1998-02-02 1999-01-28 Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete

Publications (1)

Publication Number Publication Date
EP1071650A1 true EP1071650A1 (fr) 2001-01-31

Family

ID=9522463

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99901641A Withdrawn EP1071650A1 (fr) 1998-02-02 1999-01-28 Procede perfectionne de fabrication d'anhydrides (meth)acryliques mixtes de haute purete

Country Status (11)

Country Link
US (1) US6346650B1 (cs)
EP (1) EP1071650A1 (cs)
JP (1) JP3533178B2 (cs)
KR (1) KR20010040542A (cs)
CN (1) CN1135219C (cs)
AU (1) AU2167799A (cs)
CA (1) CA2319673C (cs)
CZ (1) CZ296363B6 (cs)
FR (1) FR2774375B1 (cs)
ID (1) ID26417A (cs)
WO (1) WO1999038837A1 (cs)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2799753B1 (fr) * 1999-10-19 2002-01-04 Atofina Procede perfectionne de fabrication d'anhydrides symetriques
JP2007039345A (ja) * 2005-08-01 2007-02-15 Sumitomo Chemical Co Ltd 混合酸無水物の製造方法
DE102006009973A1 (de) * 2006-03-03 2007-09-06 Cognis Ip Management Gmbh Bei Raumtemperatur flüssige Verbindungen
CN103588635A (zh) * 2013-10-11 2014-02-19 青岛文创科技有限公司 一种 2-甲基丙烯酸酐的制备方法
CN108191643A (zh) * 2018-01-18 2018-06-22 上海仁实医药科技有限公司 一种氯乙酸酐的合成工艺

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1133727B (de) * 1960-11-08 1962-07-26 Bayer Ag Verfahren zur Herstellung gemischter Carbonsaeure-kohlensaeure-monoester-anhydride
US3718675A (en) * 1970-06-18 1973-02-27 Stevens & Co Inc J P Carbonic carboxylic anhydrides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9938837A1 *

Also Published As

Publication number Publication date
JP3533178B2 (ja) 2004-05-31
CN1289320A (zh) 2001-03-28
CA2319673A1 (fr) 1999-08-05
KR100401241B1 (cs) 2003-10-17
US6346650B1 (en) 2002-02-12
FR2774375B1 (fr) 2000-03-24
FR2774375A1 (fr) 1999-08-06
CZ296363B6 (cs) 2006-02-15
CN1135219C (zh) 2004-01-21
CA2319673C (fr) 2005-03-22
JP2002501940A (ja) 2002-01-22
KR20010040542A (ko) 2001-05-15
CZ20002145A3 (cs) 2000-09-13
AU2167799A (en) 1999-08-16
ID26417A (id) 2000-12-21
WO1999038837A1 (fr) 1999-08-05

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