Patent GB-779216-A (GB)
Title: Process for the production of polymerization products
IPC: C08F4/34
Filed: 1955-05-27
Abstract: Ethylenically unsaturated monomers are polymerized, e.g. in bulk, in the presence of a catalyst of the formula <FORM:0779216/IV(a)/1> in which R is an organic group, X a sulphur atom or a SO2 group, R1 and R2 are hydrogen or an organic group, and R3 and R4 each represent a negative group by means of which the hydrogen atom of the neighbouring carbon atom is activated, such as -COR, -COOR, -CN and -SO2R groups, and further R3 and R4 may form a ring system such as a cyclohexanedione or a cyclopentanedione ring.  The polymerization may also be effected in the presence of an inorganic or organic basically reacting substance, compounds which increase the velocity of the reaction such as water, methanol, mercaptans, beta-dicarbonyl compounds such as dimedone, carboxylic acids such as methacrylic or stearic, imides such as succinimides, or phthalimides, or acrylic acid amides, preformed polymers, e.g. polymethyl methacrylate, and peroxy catalysts, e.g. benzoyl peroxide or tert.-butyl permaleic acid.  Monomers mentioned are styrene, acrylic and methacrylic acids and their methyl, butyl, or dodecyl esters, acrylonitrile, vinyl acetate, butadiene, esters of polyhydric alcohols, e.g. ethylene glycols, and alpha, beta unsaturated carboxylic acids, e.g. maleic or fumaric acid, and mixtures.  Catalysts mentioned are alpha-methylene acetoacetic acid ethyl ester, ethyl sulphide; tolyl, or methoxy methyl, 2-methylene 5,5-dimethyl-cyclohexane-1,3-dione sulphide; bis-(2-methylene 5,5 - dimethyl - cyclohexane - 1,3 - dione) - sulphide; tolyl, 2 - isopropyl 5,5 - dimethyl - cyclohexane-1,3-dione sulphide; tolyl, methyl cyano acetic ester sulphide; tolyl, alpha-methylene acetothioacetic acid methyl ester; tolyl, 2 - ethylidene 5,5 - dimethyl - cyclohexane 1,3-dione sulphone; tolyl, ethylidene acetoacetic acid ethyl ester sulphone; ethyl, 2-methylene-5,5 - dimethyl - cyclohexane - 1,3 - dione sulphide, dodecyl, 2-methylene-5,5-dimethyl-cyclohexane-1,3-dione sulphide; tolyl, cyclohexane-1,3-sulphone; tolyl, isopropylidene acetoacetic acid ethyl ester sulphone; tolyl, ethylidene malonitrile sulphone; tolyl, ethylidene cyanoacetic acid methyl ester; bis-(ethylidene acetoacetic acid methyl ester) sulphone; and b -propionitrile, ethylidene acetoacetic acid ethyl ester sulphone.  Specified basically reacting substances are morpholine, diethylamine, diethanolamine, triethanolamine, tert. - butylamine, benzyltrimethylammonium hydroxide, ammonium methacrylate, and the ammonium salt of maleic monododecyl ester.  The process may be used in dentistry.ALSO:Compounds of the formula: <FORM:0779216/IV(b)/1> in which R is an organic group, X a sulphur atom or a SO2 group, R1 and R2 are hydrogen or an organic group, and R3 and R4 each represent a negative group which activates the hydrogen atom of the neighbouring carbon atom or R3 and R4 together form a ring system may be made by (1) the addition of mercaptans to alpha-methylene-acetoacetic acid ester or ethylidene-cyano-acetic ester and oxidizing the product to the corresponding sulphone; (2) the addition of hydroxy-methyl alkyl sulphides to compounds having a mobile hydrogen atom such as acetoacetic acid esters, dimedone, or cyclopentanone carboxylic acid esters in the presence of an acid such as hydrochloric acid; or (3) by reacting a sulphinic acid with an alpha-methylene-acetoacetic acid ester or ethylidene-cyanoacetic ester.  The preparation of the following compounds is described: <FORM:0779216/IV(b)/2> by reacting 5.5-dimethyl-1.3-cyclohexanedione and p-toluyloxymethylsulphone in the presence of metallic sodium: <FORM:0779216/IV(b)/3> by reacting formaldehyde, a semi-mercaptal of p-thio-cresol and the sodium salt of dimedone: <FORM:0779216/IV(b)/4> by reacting p-toluenesulphinic acid and ethylidene-acetoacetic acid ethyl ester: <FORM:0779216/IV(b)/5> by reacting formaldehyde, dimethyl-cyclohexane-1.3-dione and ethylmercaptan: <FORM:0779216/IV(b)/6> from dodecyl mercaptan, formaldehyde and dimedone: <FORM:0779216/IV(b)/7> from p-toluyl-hydroxymethyl-sulphone and dihydroresorcinol in the presence of metallic sodium: <FORM:0779216/IV(b)/8> from isopropylidene acetoacetic acid ethyl ester, p-toluene sulphinic acid and the sodium salt of p-toluene sulphinic acid: <FORM:0779216/IV(b)/9> by reacting ethylidene malonitrile and p-toluene sulphinic acid: <FORM:0779216/IV(b)/100> from ethylidene cyanoacetic acid methyl ester and p-toluene sulphinic acid: <FORM:0779216/IV(b)/111> by reacting the methyl ester of ethylidene acetoacetic acid with hydroxy methyl sulphinic acid in the presence of sulphuric acid, and: <FORM:0779216/IV(b)/122> by reacting a mixture of the sodium salts of cyanoethylsulphinic acid and cyano ethyl sulphonic acid with ethylidene acetacetic acid ethyl ester in the presence of sulphuric acid.  The compounds are used as polymerization catalysts.