| 摘要 |
Vinyl compounds are polymerized using as catalyst an unsymmetrical peroxide of formula: RCO-O-O-COR1, wherein R is a hydrocarbon radical, e.g. C1-10 alkyl, cycloalkyl or aryl, and R1 is a halogen-substituted hydrocarbon radical which may contain 1-5 halogen substituents. A number of such peroxides are listed. Generally, the pure peroxide is not isolated but use is made of the mixture of peroxides resulting from reaction of the corresponding acid chlorides with aqueous sodium peroxide in a solvent such as heptane or ethylene dichloride. In the examples, a mixture of 95% vinyl chloride-5% vinyl acetate is polymerized, the catalyst being of the above formula, wherein R is methyl or ethyl and R1 is dichloroor trichloro-methyl. Other specified monomers are styrene, p a -chlorostyrene; acrylic and a -substituted acrylic acids, esters, nitriles and amides, such as acrylic acid, acrylonitrile, a -methacrylonitrile, methyl and ethyl acrylate and methylacrylamide; vinyl esters such as the acetate, propionate and butyrate; vinyl ethers and ketones, vinyl chloride and mixtures of any two or more of the foregoing monomers. Vinyl chloride, which is preferred, may contain minor proportions of, e.g. vinyl bromide or acetate, vinylidene chloride, methyl acrylate or methacrylate, or ethylene.ALSO:Unsymmetrical peroxides of formula RCO-O-O-COR1, wherein R is a hydrocarbon radical such as C1-10 alkyl (e.g. Me, Et, Pr, i-Pr, hexyl or octyl), a cycloaliphatic radical such as cyclopentyl or-hexyl or an aryl radical such as phenyl or naphthyl, and R1 is a halogen-substituted hydrocarbon radical containg 1-5 halogen substituents, are prepared by reacting the acid chlorides RCOCl and R1COCl with aqueous Na2O2 in a solvent such as heptane or ethylene dichloride; the pure peroxides are not isolated as such, the reaction mixture in the solvent layer being used directly as a polymerisation catalyst. In examples, peroxides used have R1=Me or Et and R1=dichloro- or trichloro-acetyl. Other specified peroxides are acetyl-tetrachlorobutyl and -dichlorophenyl; propionyl-tribromovaleryl and -pentachlorovaleryl; butyryl-di- and -tri-chloroacetyl and -alphachloronaphthoyl; valeryl-dibromobutyryl and capryl-trichlorovaleryl.
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