Patent GB-652753-A (GB)
Title: Manufacture of esters of acrylic acid and manufacture and application of polymerisates thereof
IPC: D06M15/267
Filed: 1948-02-20
Abstract: Esters of acrylic acid, prepared by reacting acetylene, nickel carbonyl, an acid, and a hydroxy compound containing at least one alcoholic hydroxy group and at least one carbon chain with at least 12 carbon atoms or containing at least one hydroxy group bound to an aliphatic carbon atom, the 3 remaining valencies of which are bound to carbon, are polymerized on heating, especially with accelerators such as benzoyl peroxide, to yield products for coating textiles, for adhesives and lacquer ingredients.  Textiles may be impregnated with solutions of the polymers in organic solvents or aqueous dispersions and/or polymerization may be effected on the fibres.  Mixtures of the esters may be used.  In examples, polymers are made from the triacrylic acid esters of (hydrogenated) castor oil, acrylic ester of stearic acid diglyceride, acrylic ester of the diglyceride prepared from linseed oil and glycerine, acrylic ester of glycerol mono-stearate, acrylic ester of ricinoleic acid octadecyl-cetyl alcohol ester, acrylic ester of ricinoleic acid isopropyl ester, stearic acid acrylic acid ethylene glycol ester, montanic acid acrylic acid glycol ester, acrylic ester of ricinoleic acid, tertiary butyl acrylate, the acrylic ester from acetylene and acetoacetic ester, and dodecyl acrylate.  The Specification as open to inspection under Sect. 91 comprises also esters of olefin carboxylic esters generally by reacting acetylenic compounds, nickel or cobalt carbonyl, an acid, and an alcohol containing an unsaturated bond in an open carbon chain, at least 2 hydroxy groups or a tertiary carbon atom or of which the molecular weight is above 75, many examples of such acetylenic compounds and alcohols being furnished.  This subject-matter does not appear in the Specification as accepted.ALSO:Esters of acrylic acid are prepared by reacting acetylene with nickel carbonyl, an acid, and a hydroxy compound containing at least one alcoholic hydroxy group and at least one carbon chain with at least 12 carbon atoms or containing at least one hydroxy group bound to an aliphatic carbon atom, the three remaining valencies of which are bound to carbon.  The hydroxy compounds include alcohols, e.g. dodecyl, cetyl, octadecyl, and montanyl, hydroxy-acids, e.g. ricinoleic or hydroxystearic, obtainable by hydrogenation thereof, esters and amides of hydroxy-acids, e.g. octadecyl glycolate or ricinoleate, methyl ricinoleate, castor oil, hardened or not, 11-hydroxy-stearic acid amide or cetyl ester, polyhydric alcohols partially esterified, especially with higher fatty acids, and hydroxyalkyl amides of higher fatty acids, tertiary aliphatic alcohols, carbonyl compounds capable of reacting in the enol form, e.g. acetoacetic ester and a -substituted esters, acetyl-acetone, oxalacetone or oxalacetic esters.  The acid used may be hydrohalic, phosphoric or acetic. Reaction may be effected at ordinary or elevated temperature and pressure.  The nickel carbonyl may be formed during the reaction using nickel or a salt thereof and excess of carbon monoxide. Free acrylic acid present in the product may be esterified.  The esters polymerize on heating, especially with accelerators such as benzoyl peroxide, to give polymers for coating textiles, and for use as adhesives or in lacquers.  The esters containing an aliphatic residue of at least 16 carbon atoms can be used, in monomeric or polymeric form for dressing and waterproofing textiles.  In examples: (1) hardened castor oil is dissolved in benzene and benzine, hydrochloric acid and nickel carbonyl added, the mixture agitated with acetylene, and the triacrylic acid ester of the hydrogenated oil recovered.  This is polymerized by heating on the water bath with benzoyl peroxides; (2) castor oil is converted in similar manner; (3) stearic acid diglyceride is similarly treated in benzene at 50-60 DEG  C.; (4) a diglyceride obtained from linseed oil and glycerine reacts similarly; (5) glycerine monostearate is converted in like manner into the diacrylate; (6) ricinoleic acid, commercial octadecyl alcoholcetyl alcohol, benzene and sulphuric acid are refluxed and the ester obtained heated to 50-60 DEG  C. with hydrochloric acid, nickel carbonyl, and acetylene; (7) ricinoleic acid isopropyl ester is similarly acrylated; (8) sodium stearate is converted with ethylene chlorhydrin into the monostearic ester which is then acrylated; (9) sodium montanate is similarly converted with ethylene chlorhydrin and the monomontanic ester acrylated; (10) a commercial octadecyl-cetyl alcohol mixture is similarly reacted with acetylene and nickel carbonyl; (11) ricinoleic acid is similarly converted to an acrylic ester; (12) tertiary butanol is converted to the acrylate by reaction with acetylene and nickel carbonyl in presence of hydrochloric acid or of acetic acid or phosphoric acid and hydroquinone; (13) acetoacetic ester is converted with acetylene and nickel carbonyl; (4) a mixture of the ester products of (9) and (3) is heated at 95-100 DEG  C. with benzoyl peroxide and the polymerizate used in benzene solution to impregnate cotton fabric, after-polymerization by heating giving a water-repellent dressing.  A similar result is obtained using the products of (8) and (1); (15) dodecyl alcohol is reacted with acetylene and nickel carbonyl.  The Specification as open to inspection under Sect. 91 comprises also the preparation of olefin carboxylic esters generally by reacting an acetylenic compound with nickel or cobalt carbonyl, an acid, and alcohol containing an unsaturated bond in an open carbon chain, at least two hydroxy groups or a tertiary carbon atom or of which the molecular weight is above 75.  Acetylenic compounds include substituted acetylenes, alkinols, alkine-diols and their ethers or esters, ketones, and acetylene carboxylic acid esters. Alcohols include unsaturated aliphatic, saturated aliphatic of at least 5 carbon atoms, glycols, glycerols, sorbitol, polyvinyl alcohol, aromatic, cycloaliphatic, terpene, and heterocyclic alcohols, mono- or poly-saccharides, and tert.-hydroxyalkylamines or their esters with polyhydric alcohols.  Additional examples use di-ethylene glycol or 2-methyl - 3 - butine - ol - 2 (which apparently constitutes both the acetylenic compound and the alcohol) as a reactant.  This subject-matter does not appear in the Specification as accepted.