摘要 |
1,235,530. Polymerization initiator combination. ELEKTROCHEMISCHE WERKE MUNCHEN A.G. 24 Dec., 1968 [28 Dec., 1967], No. 61300/68. Heading C3P. Olefinically unsaturated compounds are polymerized using a polymerization initiator comprising, in combination, an organic peroxide compound having the formula wherein R 1 is a hydroxy or alkoxy radical and R 2 is an alkyl radical, or a radical of formula and one or more reductive compounds, capable of addition to a carbon-carbon double bond activated by adjacent C=O groups, selected from (a) aliphatic, aromatic or alicyclic compounds having a thiol group together with one ore more oxygen, nitrogen or sulphur containing groups, except compounds falling within classes (b) to (e); (b) salts of thiocyanic acid which are soluble in organic media; (c) thiocarboxylic acids and thiocarbonamides of formula HSCOR, HSCSR, HSC(NH)R or HSC(NR)R where R is alkyl or aromatic; (d) dithiocarbamate and mercaptothiazole compounds of formula or salts thereof, where R is alkyl or cycloalkyl and may form part of a ring structure and A<SP>1</SP> is hydride or links the SCN structure; (e) compounds of structure wherein R a and R b are hydrogen or alkyl or are linked to form a ring structure; (f) dithiophosphoric acid esters or dithiophosphinic acids and salts thereof having the structure HS-PS(OR) 2 or HSPSR 2 where R is alkyl or aryl; (g) alkyl and aryl sulphonyl hydrazides; (h) 4 - hydroxypyridine and derivatives thereof and (i) tertiary phosphines i.e. trialkyl and triarylphosphines and tertiary phosphites i.e. trialkyl phosphites. In a modification the peroxide compound is the reaction product of 2,5 - dimethyl 2,5 - dihydroperoxy hexane with anα,# - unsaturated dicarboxylic acid or semiester thereof. In the examples polyester resins are polymerized with t-butyl permaleinate, tbutyl perethyl fumarate, bis ethyl fumaroyl peroxide, various compounds of classes (a) to (i) and tri-isopropanolamine in isopropanol as base. Methyl methacrylate, styrene, acrylonitrile and vinyl acetate are bulk polymerized, acrylonitrile polymerized in solution and vinyl chloride polymerized in aqueous suspension.
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