Patent GB-900573-A (GB)
Title: Preparation of thiolacrylic esters
IPC: C08F28/00
Filed: 1958-09-26
Abstract: Thiolacrylates of the general formula CH2=CHCOSR wherein R is the residue of a thiol are polymerized or copolymerized with the aid of a free radical initiator.  Copolymerization of a small proportion of the thiolacrylate with a monovinylidene compound yields a copolymer of improved thermal stability.  R may represent an alkyl group which may be substituted, e.g. by a hydroxy or ether substituent, a cycloalkyl group or an aralkyl group. Numerous thiolacrylates are specified including the methyl, sec.butyl, tertiary-dodecyl, n-octadecyl, hydroxyethyl, methoxy or butoxy ethyl, ethoxy ethoxy ethyl, cyclohexyl, phenethyl and phen-propyl esters.  The thiolacrylates are prepared in specified manner (see Group IV(b)). Specification 708,007 is referred to.ALSO:A thiol acrylic acid is prepared by initially reacting at 20 DEG -75 DEG C., an aliphatic monocarboxylic acid containing not more than 4 carbon atoms, nickel carbonyl and acetylene and then introducing into the reacting mixture of monocarboxylic acid, nickel carbonyl and acetylene, a thiol, carbon monoxide and, if not already present, acrylic acid, the temperature of the reacting mixture of monocarboxylic acid (including acrylic acid), nickel carbonyl, acetylene, thiol and carbon monoxide being from about 20 DEG  to about 80 DEG C., and the carbon monoxide supplying less than 70 mole per cent of the total CO available from both carbon monoxide and nickel carbonyl.  The mono carboxylic acid used in the initial reaction may be acetic, propionic or, preferably, acrylic acid and an inert organic solvent may be present.  The process may be made continuous by continuing to bring together in the reacting mixture, acrylic acid, thiol, carbon monoxide, acetylene and nickel carbonyl.  Preferably, the monocarboxylic acid is used in an amount about equivalent to the nickel present and acetylene and the thiol are used in slight excess over that equivalent to the total CO. The reaction is preferably carried out under an inert gas.  The flow of carbon monoxide may be begun before or after the addition of the thiol.  Reaction mixture may be withdrawn as by overflow and worked up to recover the thiolacrylate ester.  Any nickel carbonyl therein is removed by reacting with a thiol, acrylic acid and acetylene and then washing with dilute hydrochloric acid.  The organic layer is thereafter washed, dried and finally distilled, preferably in the presence of a polymerization inhibitor e.g., di-b -naphthol. Suitable thiols include alkane thiols, cycloalkane thiols and aralkyl mercaptans and substituted thiols such as hydroxyalkane thiols, alkoxyalkane thiols and thiols containing more than one ether linkage e.g., ethoxy ethoxy ethane thiol.  Examples describe the preparation of thiol acrylic esters using as the thiol:-(1) methane thiol, yielding some methyl methylthio thiol propionate as by-product; (3) ethane thiol with ethyl ethylthio thiol propionate formed as byproduct; (4) propane thiol; (5) sec.-butane thiol or cyclohexane thiol; (6) tert.-butane thiol; (7) a crude lauryl mercaptan comprising C8-16 alkyl mercaptans; (8) tert.-dodecane thiol; (9) hydroxy ethane thiol.  Numerous other thiols are specified including butoxy ethane thiol, n-octadecane thiol, phenyl ethane thiol and 2- and 3-phenyl propane thiols. The thiol acrylates may be polymerized (see Group IV(a)). Specification 708,007 is referred to.