GB865379A - Improved acrylate synthesis - Google Patents

Improved acrylate synthesis

Info

Publication number
GB865379A
GB865379A GB11038/57A GB1103857A GB865379A GB 865379 A GB865379 A GB 865379A GB 11038/57 A GB11038/57 A GB 11038/57A GB 1103857 A GB1103857 A GB 1103857A GB 865379 A GB865379 A GB 865379A
Authority
GB
United Kingdom
Prior art keywords
calcium
acid
catalyst
dehydrochlorination
bacl2
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.)
Expired
Application number
GB11038/57A
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.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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 Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of GB865379A publication Critical patent/GB865379A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form

Landscapes

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

Abstract

Acrylic acid or a lower alkyl ester thereof is prepared by contacting a -chloro propionic acid or a lower alkyl ester thereof at a temperature of from 300 DEG to 650 DEG C. with a dehydrochlorination catalyst comprising at least a poly basic phosphate, sulphate or halide of a metal of Group II of the Periodic Table and lying above cadmium in the Electromotive series and recovering the resulting acrylic acid or ester thereof from the reaction product. The term "lower" denotes not more than 4 carbon atoms. The process is suitably carried out by passing preheated vaporised a -chloro-propionic acid compound down a heated column of catalyst and condensing the products from the gaseous effluent and fractionating the condensate; suitable apparatus is described. Examples illustrate the dehydrochlorination of a -chloropropionic acid to acrylic acid admixed with b -chloropropionic acid, which may be converted to acrylic acid in known manner, the dehydrochlorination catalyst being Ca3(PO4)2, BaCl2, Ba3(PO4)2, Mg3(PO4)2, CaSO4, BaSO4, BaF2, ZnCl2 on silica gel, and also CaSO4, calcium pyrophosphate, calcium chloride or Ca3(PO4)2 promoted by one or more of various of these compounds: LaPO4,CsH2PO4, BaTiO3, CsRb HPO4, CsPO3, CsPO4, Rb2SO4, Th3(PO4)4, CaCl2, Li2SO4, SrSO4, CeSO4, KPO3, NaCl and BaCl2, some of which compounds are themselves dehydrochlorination catalysts (see Group III). Calcium meta-phosphate is stated to have negligible catalytic effect.ALSO:Dehydrochlorination catalysts for use in the conversion of a -chlorpropionic acid and its lower alkyl esters to the corresponding acrylic compounds (see Group IV(b)) include calcium sulphate, calcium pyrophosphate, calcium chloride or tribasic calcium phosphate each promoted by one or more of various of the following promotors: LaHPO4, CsH2PO4, BaTiO3, CsRbHPO4, CsPO3, CePO4, Rb2SO4, Th3(PO4)4, CaCl2, Li2SO4, SrSO4, Ce2(SO4)3, KPO3, NaCl and BaCl2, the promotors being present in amounts of about 1 mol per 25 moles of the principal component. A preferred catalyst is prepared by mixing phosphoric acid with a wet slurry of calcium sulphate and LaCl3 or CeCl3 washing free from chloride ions, drying at 138 DEG C. and then granulating; an additional promotor such as KPO3 may be added after the washing step. Tribasic barium phosphate, also utilizable as a catalyst may be prepared by adding an aqueous solution of BaCl2 to an aqueous ammoniacal solution of (NH4)2PO4, washing the precipitate free from chloride ions, drying and then granulating.
GB11038/57A 1956-04-04 1957-04-04 Improved acrylate synthesis Expired GB865379A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US865379XA 1956-04-04 1956-04-04

Publications (1)

Publication Number Publication Date
GB865379A true GB865379A (en) 1961-04-19

Family

ID=22199240

Family Applications (1)

Application Number Title Priority Date Filing Date
GB11038/57A Expired GB865379A (en) 1956-04-04 1957-04-04 Improved acrylate synthesis

Country Status (1)

Country Link
GB (1) GB865379A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013104924A1 (en) * 2012-01-13 2013-07-18 Lucite International Uk Limited A process for the production of ethylenically unsaturated carboxylic acids or esters and a catalyst therefor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013104924A1 (en) * 2012-01-13 2013-07-18 Lucite International Uk Limited A process for the production of ethylenically unsaturated carboxylic acids or esters and a catalyst therefor
CN104039751A (en) * 2012-01-13 2014-09-10 璐彩特国际英国有限公司 A process for the production of ethylenically unsaturated carboxylic acids or esters and a catalyst therefor
KR20140111329A (en) * 2012-01-13 2014-09-18 루사이트 인터내셔널 유케이 리미티드 A process for the production of ethylenically unsaturated carboxylic acids or esters and a catalyst therefor
US9199907B2 (en) 2012-01-13 2015-12-01 Lucite International Uk Limited Process for the production of ethylenically unsaturated carboxylic acids for esters and a catalyst therefor
CN104039751B (en) * 2012-01-13 2017-04-12 璐彩特国际英国有限公司 A process for the production of ethylenically unsaturated carboxylic acids or esters and a catalyst therefor
RU2621687C2 (en) * 2012-01-13 2017-06-07 ЛУСАЙТ ИНТЕРНЭШНЛ ЮКей ЛИМИТЕД Method of obtaining ethylene-unsaturated carboxylic acids or their complex ethers and catalyst for this

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