Patent GB-924623-A (GB)
Title: Preparation of copolymers
IPC: C10L1/14
Filed: 1959-05-20
Abstract: As additives to oils there are used copolymers made by a process which involves partially polymerizing an ethylenically unsaturated monomeric material, adding a nitrogen-containing ethylenically unsaturated monomer thereto, and then completing the polymerization, the monomer mixture being such as to provide an oil-soluble copolymer (see Group IV(a)).  Oils specified are fuel oils, mineral lubricating oils, kerosenes and synthetic lubricants, e.g. esters of sebacic and phosphoric acid.  As monomers for use in preparing the prepolymer there are specified esters of acrylic and substituted acrylic acids, esters of maleic, fumaric and itaconic acids, styrenes, unsaturated nitrites, ethers, thioethers and ketones and vinyl and vinylidene chlorides. Nitrogen-containing monomers specified are vinyl lactams, oxazolidones, unides, ureas and pyridines, aminoalkyl styrenes, acrylates, ethers and thioethers and unsaturated hydrazides.ALSO:Oil-soluble copolymers are obtained by: (A) forming a polymerizing mixture of (1) one or more ethylenically unsaturated monomers and (2) a prepolymer derived from one or more monoethylenically unsaturated monomers and which is present in an amount of from 40 to 85% by weight of the combined weight of monomer and prepolymer, the mixture undergoing polymerization under the influence of a free-radical initiator, (B) adding to the polymerizing mixture at least one monoethylenically unsaturated nitrogenous monomer which contains a trivalent nitrogen atom bonded to at least two atoms at least one of which is carbon, and which is either an imide having non-terminal unsaturation or is a compound containing a terminal methylene group, and (C) continuing polymerization of the resulting mixture, the monomer mixture being such as to provide an oil-soluble copolymer containing nitrogenous monomer in an amount between about 1% and 30% by weight of the final copolymer.  As monomers for forming the prepolymer there are listed alkyl acrylates, alkacrylates, phenacrylates and chloroacrylates, esters of acrylic and methacrylic acids in which the alcohol portion contains a hetero atom, e.g. oxygen, nitrogen, sulphur or phosphorus, vinyl esters of fatty acids, alkyl maleates, fumarates and itaconates, styrene, alkyl styrenes, p-chlorostyrene, acrylonitrile, methacrylonitrile, vinyl ethers, vinyl thioethers, vinyl ketones and vinyl and vinylidene chlorides.  Nitrogen containing monomers listed are N-vinyl lactams, N-vinyl oxazolidones, cyclic N-vinyl imides, N-vinyl ureas, N-vinyl carboxylic amides, N-acryloxy and N-methacryloxy lactams, N-acrylamido and N-methacrylamido lactams, N-alkyl acrylamides and methacrylamides, N-vinyl amines, vinyl pyridines, aminostyrenes, aminoalkyl vinyl ethers and thioethers, aminoalkyl acrylates and methacrylates, and unsaturated hydrazides. Free-radical initiators listed are azo compounds, peroxides, hydroperoxides, peresters and combinations of hydroperoxides and quaternary ammonium salts. Polymerization may be carried out in bulk or, preferably, in solution in an organic solvent.  The examples describe the application of the above process to the following combinations of monomers: (1) cetyl-stearyl methacrylate, lauryl-myristyl methacrylate, butyl methacrylate and N-vinyl pyrrolidinone; (2) stearyl methacrylate, styrene and N-vinyl pyrrolidinone; (3) vinyl stearate, vinyl-2-ethyl hexoate and N-vinyl pyrrolidinone; (4) vinyl stearate, dodecyl methacrylate and N-vinyl-5-methyl pyrrolidinone; (5) dilauryl fumarate, vinyl acetate and N-vinyl pyrrolidinone; (6) distearyl maleate and N-vinyl pyrrolidinone; (7) distearyl itaconate and N-vinyl pyrrolidinone; (8) cetyl-stearyl fumarate vinyl acetate and N-vinyl caprolactam; (9) lauryl-myristyl methacrylate and N-vinyl oxazolidone; (10) as in (9) but including also dimethaminoethyl methacrylate; (11) lauryl methacrylate and N-vinyl succinimide; (12) lauryl methacrylate and N-(8-methacryloxy-3,6-dioxaoctyl) pyrrolidinone; (13) lauryl methacrylate and N-n-butylacrylamide; (14) lauryl, stearyl, butyl and dimethylaminoethyl methacrylates; (15) lauryl and dimethylaminoethyl methacrylates and N-vinyl pyrrolidinone; (16) lauryl methacrylate and N-vinyl-N1-dimethylamino-ethylethyleneurea; (17) lauryl methacrylate and N-vinyl-N-methylacetamide; (18) lauryl methacrylate and 4-vinyl pyridine; (19) lauryl methacrylate and N-(2-methacryloxyethyl)-2-oxazolidone; (20) octyl methacrylate and 1-(2-methacryloxyethyl) - 2,4,4 - trimethylpyrrolidine; (21) lauryl methacrylate and diethylaminoethyl vinyl thioether; (22) dodecyl methacrylate and N-methacrylyl-N,N-dimethyl hydrazide; and (23) lauryl-myristyl methacrylate and N-methyl maleimide.ALSO:Ethylenically unsaturated nitrogen-containing compounds are prepared as follows:-  (a) N-acryloxyalkyl or N-methacryloxyalkyl lactams are prepared by reacting N-hydroxyalkyl lactams with lower alkyl methacrylates or acryloyl or methacryloyl halides, e.g. N-(2-hydroxyethyl)pyrrolidinone and methyl methacrylate are heated in the presence of sodium methoxide to produce N-(2-methacryloxyethyl)pyrolidinone;  (b) N-acrylamidoalkyl or N-methacrylamidoalkyl lactams are prepared by reacting acryloyl and methacryloyl halides with N-(aminoalkyl) lactams, e.g. methacryloyl chloride and N-2-aminoethyl-3,5.5-trimethylpyrrolidinone are heated together in the presence of sodium carbonate to produce 2-methacrylamidoethyl- 3,5.5-trimethyl pyrrolidinone;  (c) N-acryloyl or N-methacryloyl pyrrolidinones are prepared by reacting pyrrolidinone with acryloyl or methacryloyl halides;  (d) 1-(2-hydroxyethyl)- 2,4,4-trimethylpyrrolidine is reacted with methyl methacrylate in the presence of sodium methoxide to produce 1-(2-methacryloxyethyl)- 2,4,4-trimethylpyrrolidine.