Patent GB-768701-A (GB)
Title: Copolymeric dispersants and lubricant compositions containing them
IPC: C08F8/32
Filed: 1954-05-25
Abstract: Copolymers of (A) an olefinically-unsaturated compound preferably containing an oil-solubilizing group of from 4 to 30 aliphatic carbon atoms, and (B) an alpha-beta-unsaturated carboxylic acid, in which some of the carboxyl groups are ester-linked to a poly-(1,2-alkylene oxide) glycol, and some are linked to a nitrogen-containing compound to form either of the radicals <FORM:0768701/IV(a)/1> and <FORM:0768701/IV(a)/2> where R1 is hydrogen or an organic radical and R2 an organic radical are made (1) by partially hydrolysing a homopolymer of an ester of an unsaturated acid and reacting the free carboxyl groups with the desired polyglycol and nitrogen-containing compound; (2) partially esterifying a copolymer of an olefinically-unsaturated monomer of an alpha, beta-unsaturated acid or anhydride with a polyglycol and nitrogen-containing compound; or (3) polymerizing an appropriate monomer mixture.  (A) may be selected from an extensive list including ethylene, hexene-1, cyclohexene and substituted cyclohexenes, p-octylstyrene, 2-hexadecylbutadiene-1,3, vinyl n-butyl ether, allyl cyclohexyl ether, methallyl n-hexyl ether, vinyl p-octylphenyl ether, 1-decenyl-2-phenylbutyl ether, vinyl caproate, allyl stearate, methallyl palmitate, dodecyl acrylate, cyclohexyl methacrylate, decyl vinyl acetate, p-tert. amylphenyl octadecyl maleate, di-2-ethylhexyl maleate, di-dodecyl mesaconate and citraconate, and 1-hexadecenyl myristate.  The alpha, beta-unsaturated acid may be acrylic, methacrylic, crotonic, tiglic, angelic, alpha-ethylacrylic, beta-ethyl crotonic, maleic, fumaric, itaconic, glutaconic, citraconic, mesaconic or aconitic. The poly-(1,2-alkylene oxide) glycol may be diethylene glycol, pentaethylene glycol, nonaethylene glycol, tetra-1,2-propylene glycol, the monobutyl ether of heptaethylene glycol or a polymer of one or more 1,2-alkylene oxides of molecular weight up to 10,000 in which, if desired, at least one of the end groups is replaced by alkoxy or acyloxy groups.  In the case of the nitrogen containing compound the organic radical may be methyl to heptadecyl, phenyl, tolyl, xylyl, benzyl, naphthyl, 2-hydroxyethyl, 4 - hydroxycyclohexyl, 3 - azapentyl, 4-amonohexyl, 2-mercaptoethyl, 3-aza-5 - hydroxypentyl, 2 - ethyl - 6 - aminohexyl, 2-nitrohexyl, p-aminophenyl, or 2-hydroxy-6-phenylhexyl.  An extensive list of monomeric nitrogen-containing compounds is given including methacrylamide, N - ethylmethacrylamide, N-phenyl methacrylamide, N,N-di-(2-hydroxyethyl)-methacrylamide, the ethylamine or ethanolamine salt of methacrylic acid, acrylamide, N,N - di - (2 - ethylhexyl) - acrylamide, crotonamide, N - (2 - nitroethyl)-crotonamide, tiglamide, maleamic acid, maleamide, N,N1 - diethylmaleamide, N - phenylmaleamic acid, lauryl N-(2-hydroxyethyl)-malemate, tetraethylene pentamine salt of lauryl maleate, N,N1 - di - (2 - mercaptoethyl)-maleamide, dodecyl N-(p-aminophenyl)-malemate, fumaramic acid, erythritol monofumaramate, dodecyl N - (2 - hydroxyethyl) - citraconamate. The copolymers may be prepared by bulk, solution or emulsion techniques in the presence of a catalyst.  The copolymerization is preferably effected in an inert solvent such as benzene, toluene, xylene, or petroleum naphtha.  Catalysts mentioned are benzoyl, acetyl, di-tert. butyl, and di-tert. amyl peroxides, 1,11-azodicyclohexanecarbonitrile, and alpha, alpha1 - azodiisobutyronitrile.  In examples: (a) a copolymer of dodecyl methacrylate, polyethylene glycol methacrylate, N-octyl-methacrylamide and methacrylic acid is made by partially hydrolysing a homopolymer of dodecyl methacrylate and reacting with a mixture of polyethylene glycols which includes a major proportion of nonaethylene glycol and then with n-octylamine; (b) a copolymer of dodecyl methacrylate, polyethylene glycol monoether methacrylate and N - (2 - hydroxyethyl) - methacrylamide is similarly made; (c) a copolymer of vinyl 2-ethyl hexyl ether, acrylic acid, methacrylamide, and polypropylene glycol acrylate is made by copolymerizing the ether, acid, and amide in bulk, and esterifying the product with 2-propylene glycol; (d) a copolymer of dodecyl methacrylate, the methacrylate of a polyglycol mono-octyl ether and maleic anhydride is reacted first with pentaerythritol and then with isooctadecylamine; (e) a copolymer of tridecyl acrylate, the methacrylate of polyethylene glycol monoethyl ether and methacrylic acid is treated with p-nitroaniline; (f) the copolymer of (e) is reacted first with glycerol and then with n-octylamine.ALSO:A lubricant composition comprises a major proportion of an oil of lubricating viscosity and a minor proportion of an oil-soluble copolymer (see Group IV(a)) of (A) an olelinically-unsaturated compound, and (B) an alpha, betaunsaturated carboxylic acid, in which a portion of the carboxylic groups of the acid are ester-linked to a poly-(1, 2-alkylene oxide) glycol and another portion of the carboxyl groups are linked to a nitrogen-containing compound to form radicals selected from <FORM:0768701/III/1> or <FORM:0768701/III/2> where R1 is hydrogen or an organic radical and R2 an organic radical.  The compositions may also contain pour point depressants, oiliness and extreme pressure agents, antioxidants corrosion inhibiting agents, blooming agents, thickening agents, detergents, anti-wear agents or compounds for enhancing the temperature-viscosity characteristics of oils.  Oils mentioned are refined Pennsylvania or other paraffin base oil, a refined naphthenic base oil, alkylated waxes, hydrogenated hydrocarbon polymers, the condensation products of chlorinated alkyl hydrocarbons with aryl compounds, polymers of propylene and/or ethylene oxide and acetates of these polymers, di - (2 - ethylhexyl) sebacate, tricresyl phosphate, silicate esters, or a mixture of a mineral oil and a synthetic oil.  Polymers exemplified in oil compositions are (1) a copolymer of dodecyl methacrylate/polyethylene glycol methacrylate/N - octyl - methacrylamide (2) a copolymer of dodecyl methacrylate/polyethylene glycol monoether methacrylate/N - (2 - hydroxyethyl) methacrylamide, (3) a copolymer of vinyl 2 - ethyl-hexyl ether/methacrylamide/acrylic acid/polypropylene glycol acrylate (4) a copolymer of dodecyl methacrylate/polyglycol ether methacrylate/pentaerythritol maleate/maleic acid amine salt (5) a copolymer of allyl stearate/di - tridecyl maleate-mono - tridecyl polyglycol maleate/ethanolamine salt of mono-tridecyl maleate-monotridecyl maleate, (6) a copolymer of tridecyl acrylate-polyethylene glycol ether methacrylate/N - (p - nitrophenyl) methacrylamide-methacrylic acid, and (7) a copolymer of tridecyl acrylate/polyethylene glycol ether methacrylate/glycerol monomethacrylate/octyl amine salt of methacrylic acid.  The function of the copolymer in the oil is that of a detergent.