Patent GB-985989-A (GB)
Title: Addition polymers and compositions containing them
IPC: C08F28/00
Filed: 1961-05-24
Abstract: Ethylsulphinylethyl methacrylate and bis-(ethylsulphinylethyl) fumarate are made by oxidizing the corresponding ethylthioethyl esters with hydrogen peroxide.  Bis-(ethylthioethyl) fumarate is made by transesterification of dimethyl fumarate with ethylthioethanol.ALSO:Oil-soluble polymers are made which contain at least 0.5% by weight of recurring units corresponding to at least one of the following sulphur-containing monomers:  (a) acrylic and methacrylic acid in which the hydrogen atoms of the carboxyl groups have been replaced by groups <FORM:0985989/C3/1> and (b) maleic, fumaric, itaconic and aconitic acids in which at least one of the hydrogen atoms of the carboxyl groups has been replaced by a group <FORM:0985989/C3/2> and the remaining hydrogen atoms have been replaced by alkyl, aryl or aralkyl groups, A in the above formula representing a divalent aliphatic or aromatic hydrocarbon group, or an alkylene group containing one or more interrupting ether oxygen atoms in the chain, and R represents an alkyl, aryl or aralkyl group. The polymers are typically those of alkylsulphinyl-alkyl esters of the specified acids, and may be homopolymers, ifoil-soluble, or copolymers with vinyl esters, acrylic, methacrylic, itaconic and fumaric acids, and esters and amides thereof, vinyl ethers and thioethers, acrylonitrile, vinylidene chloride, styrene, vinyl lactams, vinyl pyridines, vinyl succinimide and N-dimethylaminoethyl acrylamide.  Polymerization is preferably carried out in solution in an organic solvent in the presence of an initiator, e.g. an organic peroxide or azo compound, or an organic peroxide activated with a quaternary ammonium salt.  The examples describe the solution copolymerization of:  (1) 2-ethylsulphinylethyl methacrylate and lauryl-myristyl methacrylate, (2) 2-ethylsulphinylethyl acrylate and lauryl-stearyl methacrylate, (3) n-butylsulphinylmethyl acrylate, octyl acrylate and N-vinyl-2-pyrrolidinone, (4) 2-n-dodecyclsulphinylethyl methacrylate and butyl methacrylate, (5) 2-ethylsulphinylethyl acrylate and lauryl methacrylate, (6) 2-ethylsulphinylethyl methacrylate, and mixed stearyl, lauryl and methyl methacrylates, (7) 2-ethylsulphinylethyl methacrylate and decyl-octyl and lauryl-myristyl methacrylates, (8) di-lauryl-myristyl fumarate, vinyl acetate and 2-ethylsulphinylethyl methacrylate, (9) 2-ethylsulphinylethyl methacrylate and di-cetyl-stearyl itaoconate, (10) 2-ethylsulphinylethyl methacrylate, lauryl-myristyl methacrylate and styrene, and (13) 2-ethylsulphinylethyl methacrylate and lauryl methacrylate.ALSO:The properties of lubricating and fuel oils are improved by incorporating therein a polymer derived from at least one of the following sulphur-containing monomers:  (a) acrylic and methacrylic acid in which the hydrogen atoms of the carboxyl groups have been replaced by groups <FORM:0985989/C4-C5/1> and (b) maleic, fumaric, itaconic and aconitic acids in which at least one of the hydrogen atoms of the carboxyl groups has been replaced by the group <FORM:0985989/C4-C5/2> and the remaining hydrogen atoms have been replaced by alkyl, aryl or aralkyl groups, A in the above formula representing a divalent aliphatic or aromatic hydrocarbon group containing one or more interrupting ether oxygen atoms in the chain, and R represents an alkyl, aryl or aralkyl group.  The polymers are typically derived from alkylsulphinylalkyl esters of the specified acids, e.g. 2-ethylsulphinylethyl acrylate and methacrylate.  The polymer may be a homopolymer, or a copolymer with comonomers such as vinyl esters, styrene, esters of unsaturated carboxylic acids, and vinyl lactams.  The oil to which the polymer is added may be a mineral lubricating oil, diesel oil, gasoline, kerosene, jet-engine fuel, or a synthetic lubricant, e.g. butyl stearate, dodecyl pelargonate, di-2-ethylhexyl sebacate and azelate, dioctyl adipate, bis-(2,2,4-trimethylpentyl) sebacate, tributyl, trioctyl, tricyclohexyl, triphenyl, and tricresyl phosphates, phosphites and phosphonates, diethyl, dibutyl and dioctyl silicates, and polyesters derived from ethylene glycol and adipic, sebacic and phthalic acids. Also present in the oil compositions may be zinc dialkyl dithiophosphate, phenol sulphonates, alkylaryl sulphonates, petroleum sulphonates, polybutenes, silicones, phosphate esters, and polymers of alkyl esters of unsaturated acids.