Patent GB-796820-A (GB)
Title: Manufacture of esters of ª‡:ª‰-ethylenically unsaturated acids
IPC: C07C51/00
Filed: 1955-06-27
Abstract: An ester of an a  : b -ethylenically unsaturated carboxylic acid is obtained by reacting a ketone and an aldehyde in the vapour phase at an elevated temperature and subjecting the esterifiable fraction of the products obtained to esterification with an alcohol while it is still in admixture with other products of the reaction.  The products from the reaction between the ketene and the aldehyde are preferably rapidly cooled by quenching with a liquid, e.g. a liquid alcohol.  In the latter case the resulting mixture may be heated in the presence of an esterification catalyst to yield the unsaturated ester. Specified aldehydes are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, unsaturated aldehydes, e.g. acrolein and crotonaldehyde, and aromatic aldehydes, e.g. benzaldehyde. Specified ketenes are ketene itself, methyl ketene, ethyl ketene, benzyl ketene, phenyl ketene, dimethyl ketene, and diethyl ketene. It is preferred to use ketene itself and formaldehyde in which case an ester of acrylic acid is obtained on esterification with the alcohol. If ketene and acetaldehyde are used the corresponding acid is b -methyl acrylic acid and if methyl ketene and formaldehyde are used the corresponding acid will be a -methyl acrylic acid.  In one method of operation the aldehyde and the ketene are fed continuously into a reaction zone heated to above 100 DEG  C., preferably 100-300 DEG C., and it is desirable to maintain the molar ratio of ketene to aldehyde in the feed at 1 : 1 at least and preferably at 1 : 1 to 3 : 1 and to feed an inert gas, e.g. nitrogen into the reaction zone which may, if desired, contain suitable packing, e.g. glass or ceramic beads, helices, rings, or saddles, but an unpacked reaction zone is preferred. The vapour phase reaction between the ketene and the aldehyde is preferably carried out under substantially anhydrous conditions and in the presence of a Friedel-Crafts catalyst, e.g. a volatile chloride, bromide, or fluoride of boron, aluminium, ferric iron, stannic tin, titanium, or arsenic, e.g. boron trifluoride, titanium tetrachloride, aluminium chloride and ferric chloride. It is preferred to inject a solution of the catalyst into a stream of inert gas, e.g. nitrogen which is fed into the reaction zone. The catalyst solution may be made up with an inert volatile solvent, e.g. pentane or diethyl ether.  Suitable space velocities are above 200 hour-1, e.g. about 700 to 1000 hour-1. Esterification of the hot gaseous product is preferably effected by quenching the gas stream with a liquid alcohol, distilling off the uncondensed gases and subjecting the resulting liquid to distillation in the presence of an esterification catalyst to recover the ester product.  Specified alcohols are methanol, ethanol, propanol, n-butanol, decanol, 2-ethyl hexanol, benzyl alcohol, and polyhydric alcohols, e.g. ethylene glycol, diethylene glycol, glycerol and pentaerythritol.  Suitable esterification catalysts are sulphuric acid, p-toluene sulphonic acid, benzene sulphonic acid, and hydrochloric acid.  The reaction product may also be esterified by vaporizing the alcohol and feeding it into the gaseous product stream instead of quenching the latter with the alcohol.  Examples are given for the production of methyl acrylate and n-butyl acrylate respectively by reacting ketene with formaldehyde at 250-260 DEG  C. in the presence of nitrogen and of a solution of boron trifluoride in diethyl ether as catalyst and then quenching the gaseous product in liquid methanol or n-butanol, cooling the mixture to 0 DEG  to 5 DEG  C., distilling off any uncondensed gas and then esterifying the mixture by distilling in the presence of concentrated sulphuric acid.