Patent GB-1074948-A (GB)
Title: Lubricating oil compositions and additives therefor
IPC: C08L33/10
Filed: 1964-08-21
Abstract: Polymeric ash-free lubricating oil additives having dispersing and detergent properties are prepared by reacting together a lubricating oil-soluble polymeric compound and an oligomeric or macromolecular oleophobic compound containing (a) cyclic or acyclic acid amide groups; (b) amino groups whose nitrogen atoms are situated in side chains of the oleophobic compound; or (c) nitrile groups, the said compounds containing mutually reactive groups.  The oil-soluble component is preferably a polymer or copolymer of an ester of an unsaturated mono- or di-carboxylic acid with an alcohol containing 8-18 carbon atoms or a polymer or copolymer of a C2-5 olefine.  The oleophobic compound preferably has a molecular weight of 500 to 50,000 and may be a polymer or copolymer of a vinyl pyrrolidone, a polyamide condensation polymer, a polymer of acrylamide or methacrylamide, a polymer of an unsaturated amino compound (e.g. amino-alkyl ester), a polyacrylonitrile or polymthacrylonitrile having some of the -CN groups reduced to -CH2NH2 groups, or a copolymer of acrylonitrile or methacrylonitrile.  In examples, some illustrative polymeric additives are incorporated in a mineral oil and subjected to a motor oil test.  The additives are particularly suitable for use in diesel engine lubricating oils.ALSO:Polymeric ash-free oil additives soluble in lubricating oil are prepared by reacting, in the substantial absence of a free radical polymerization catalyst, a lubricating oil-soluble polymeric compound with an oligomeric or macromolecular oleophobic compound containing (a) cyclic or acylic acid amide groups; (b) amino groups whose nitrogen atoms are situated in side chains of the oleophobic compound; or (c) nitrile groups, the said polymeric and oleophobic compounds containing reactive groups selected to react together to form chemical bonds between the said polymeric and oleophobic compounds, and the reaction conditions being such that the said reactive groups do so react.  The oil-soluble polymeric compound is preferably a polymer or copolymer of a mono- or di-ester of an alpha, beta-ethylenically unsaturated carboxylic acid (e.g. acrylic, methacrylic, fumaric or maleic acid) with an alcohol containing 8-18 carbon atoms (e.g. lauryl), stearyl or coconut oil alcohols), or a polymer or copolymer of an olefine containing 2-5 carbon atoms (e.g. isobutylene).  The oleophobic compound may have a molecular weight of 500 to 50,000.  Those having the amide groups (a) include polymers and copolymers of N - vinyl - 2 - pyrrolidone or an alkyl - substituted derivative thereof, condensation polymers of C6- 10 dicarboxylic acids or functional derivatives thereof with C2- 6 diamines (e.g. dimethy adipate-ethylene diamine polycondensation product), poly - e  - aminocaprolactam, and polymers of acrylamide or methacrylamide. Oleophobic compounds with amino groups (b) include oligomers and polymers of olefinically unsaturated amino compounds such as aminoalkyl acrylates and methacrylates, e.g. b  - dimethylaminoethyl acrylate or methacrylate and 1 - (b  - methacrylyloxyethyl) - 2 - methyl - D 2 - imidazoline. Oleophobic compounds having nitrile groups include polyacrylonitrile and polymethacrylonitrile, in which some of the -CN groups may be reduced to -CH2NH2 groups, and copolymers of acrylonitrile or methacrylonitrile with, e.g., monomers as described above containing groups (a) or (b). Generally, the molar ratio of oil-soluble compound to oleophobic compound is from 3:1 to 30:1, and the reaction between the compounds is preferably effected by heating in solution.  The reactive groups referred to may be anhydride, epoxy, isocyanate or 1-aziridinyl groups and these can be incorporated into either the oil-soluble compound or the oleophobic compound.  For example, where the oil-soluble compound is a copolymer of an unsaturated ester, the ester monomer may be copolymerized with maleic or itaconic anhydride, glycidyl acrylate or methacrylate, vinyl glycidyl ether, b -isocyanatoethyl acrylate or methacrylate, N-methacrylylaziridine or N-acrylaziridine; alternatively, compounds containing the reactive groups can be introduced by addition to polymeric compounds having residual unsaturation or terminal double bonds, e.g. maleic anhydride added to a copolymer of oleyl methacrylate or polyisobutylene. Reactive groups may be introduced terminally into the oleophobic compound by effecting oligimerization or polymerization of an appropriate monomer in the presence of chain transfer agents and/or accelerators, e.g. N-vinyl-pyrrolidene can be polymerized in the presence of N-(dialkylaminoalkyl) - amines and azobisisobutyronitrile. Reactive groups may also be introduced by copolymerizing a monomer such as N-vinyl pyrrolidone with suitable comonomers. In examples, oil additives are prepared by reacting (1) polyvinylpyrrolidone with lauryl/stearyl methacrylate-maleic anhydride copolymer; (2) vinylpyrrolidone-acrylonitrile copolymer (having -CN groups reduced to -CH2NH2 groups) with lauryl/stearyl methacrylate-maleic anhydride copolymer; (3) polyisobutylene-maleic anhydride adduct with ethylene diamine-dimethyl adipate polycondensation product; and (4) lauryl/stearyl methacrylate-methyl methacrylate-itaconic anhydride copolymer with poly-e -caprolactam; the preparation of the parent polymer reactants is also described.