Patent GB-1068133-A (GB)
Title: Nitrogen-containing derivatives of substituted succinic acids
Inventor: NORMAN GEORGE RUSSELL
IPC: C08G69/26
Filed: 1965-02-04
Abstract: Lubricating oil, gasoline and fuel oil additives are products obtained by reacting 1 equivalent of a hydrocarbon-substituted succinic acid producing compound having at least 50 aliphatic carbon atoms in the substituent with at least 0.5 equivalent of an alkylene amine of the formula <FORM:1068133/C4-C5/1> where n is an integer preferably less than 10, A is H or a substantially hydrocarbon radical preferably having up to 30 C atoms, and the alkylene radical is preferably a lower alkylene radical of less than 8 C atoms, cyclic derivatives thereof such as piperazines, pyrimidine, and imidazolines, or alkylene amines having one or more hydroxyalkyl substituents on the nitrogen atoms, and at least 0.1 equivalent of an alkenyl or aryl-substituted alkenyl cyanide.  Cyanides specified are acrylonitrile and methacrylonitrile; 1-butyl-, 1-hexyl-, 1-cyclohexyl-, 1-t-butyl-and 1-isopropyl-vinyl cyanide; crotonitrile; 2 - dodecyl -, 2,21 - didodecyl -, 2-cyclopentyl -, 2 - octyl - 2 - methyl -, 2 - decyl-2 - hexyl -, and 2 - t - pentyl - vinyl cyanide; 3 - hexenyl - and 2 - octenyl - cyanide; and 1-phenyl-, 2-phenyl-, 1-tolyl-, and 2-phenethylvinyl cyanide.  Higher homologues of the alkylene amines or hydroxyalkyl substituted alkylene amines obtained by condensation through amino or hydroxy radicals may be employed. The hydrocarbon radical may be derived from a polyolefin, such as a polymer of e.g. ethylene, 1-butene, isobutene, 2-butene, 1-octene, 4-octene, 2-methyl-1-heptene, 3-cyclohexyl - 1 - butene, 3 - pentene, or a copolymer e.g. of isobutene/styrene, isobutene/butadiene, propene/isoprene, ethylene/piperylene, isobutene/chloroprene, 1 - hexene/1,3 - hexadiene, or isobutene/styrene/piperylene, or may be derived from high molecular weight white oils or synthetic alkanes obtained by hydrogenating high molecular weight polyolefines or olefinic substances.  More than one succinic group can be attached to a single substantially hydrocarbon radical.  In Example 1, polyisobutene-substituted succinic anhydride, tetraethylene pentamine, crotonitrile, and mineral oil are mixed and heated at 100-200 DEG  C. for 7 hours.  Example 2 reacts a mixture of diethylene triamine and triethylene tetramine, and acrylonitrile first, and then reacts with the substituted succinic anhydride. Example 9 reacts the substituted succinic anhydride with an ethylene amine mixture having an average composition corresponding to tetraethylene pentamine and then reacts the product in oil with acrylonitrile. Example 13 reacts ethylene diamine, 2,2-dimethylvinyl cyanide, and polypropene-substituted succinic anhydride in oil. Example 14 uses polyethylene-substituted succinic anhydride. Example 17 first reacts 1-methyl-2-dodecylvinyl cyanide and octamethylene diamine, and then reacts with an isobutene/ piperylene copolymer substituted succinic anhydride in oil.  The products may be added in amounts from 0.1-10% by weight to gasolines, to hydraulic fluids, and to burner fuel, cutting and lubricating oils, including synthetic oils such as didodecyl adipate and di-2-octyl sebacate.  The products impart oxidation- and corrosion-inhibiting and detergent properties to oils.  A test lubricant contains mineral oil, polyacrylic acid ester V.I. improver, polyacrylic acid ester pour-point depressant, zinc dialkylphosphorodithioate, and the product of the invention. Ash-containing detergents such as the Na, K, Li, Ca, Mg, Sr and Ba salts of sulphonic, carboxylic and organic phosphorus acids containing at least one direct C-to-P linkage, e.g. a phosphorized polyolefine, may be present and may have been prepared using a promoter (many specified).  Polyamines acylated with high molecular weight hydrocarbon-substituted succinic acid or anhydride may also be present.  Other additives are chlorinated wax, organic sulphides and polysulphides (many specified), phosphosulphurized hydrocarbons, phosphorus esters such as phosphites (many specified), zinc dioctyl and barium heptylphenyl dithiocarbamates; and Group II metal phosphorodithioates (many specified). In examples: (I) S.A.E. 20 oil contains 0.5% of the product of Example 1; (II) S.A.E. 30 oil contains 0.75% of the product of Example 2 and the Ba salt of di-n-nonylphosphorodithioic acid; (III) S.A.E. 30 oil, a product according to the invention, the zinc salt of a mixture of diisopropylphosphorodithioic and di - n - decylphosphorodithioic acids, and the product obtained by carbonating at 150 DEG  C. mineral oil, barium didodecylbenzenesulphonate and barium hydroxide in the presence of water and octylphenol; (IV) S.A.E. 10W-30 oil, a product according to the invention, zinc di-n-octylphosphorodithioate, and the steam-hydrolyzed reaction product of polyisobutene with P2S5; and (V) S.A.E. 20 oil, the product of Example 1, the reaction product of polyisobutene-substituted succinic anhydride and an ethylene amine mixture having an average composition corresponding to tetraethylene pentamine, and zinc dioctylphosphorodithioate.ALSO:A nitrogen-containing composition is obtained by reacting 1 equivalent of a hydrocarbon-substituted succinic acid-producing compound having at least 50 aliphatic carbon atoms in the hydrocarbon substituent with at least 0.5 equivalents of an alkylene amine or a hydroxyalkyl substituted alkylene amine and at least 0.1 equivalents of an alkenyl or aryl-substituted alkenyl cyanide.  The alkylene amines have the general formula <FORM:1068133/C3/1> where n is an integer preferably less than 10, A is hydrogen or a substantially hydrocarbon radical preferably having up to 30 carbon atoms, and the alkylene radical is preferably a lower alkylene radical having less than 8 carbon atoms. Cyclic and higher homologues of such amines such as piperazines may also be used. The substantially hydrocarbon-substituted succinic acid producing compounds include succinic acids, anhydrides, halides and esters and they may be derived from homo- or co-polymers of olefines having 2 to 30 C atoms (e.g. ethylene, 1-butene, isobutene, 2-butene, 1-octene, 4-octene, 3 - cyclohexyl - 1 - butene, propene/isoprene, ethylene/piperylene, isobutene/chloroprene, 1 - hexene/1,3 - hexadiene, and isobutene/styrene/piperylene) by heating the polymer or copolymer with maleic anhydride at 100 DEG -200 DEG  C.  More than one succinic group can be attached to a single substantially hydrocarbon radical, and the hydrocarbon radical may also be derived from high molecular weight white oils or synthetic alkanes obtained by hydrogenating high molecular weight polyolefines or olefinic substances.  The alkenyl cyanides are preferably vinyl cyanides having the general formula <FORM:1068133/C3/2> where R1 and R2 are H or hydrocarbon radicals. Alternatively, the cyanide group may be separated from the olefinic group by one or more methylene radicals. Preferably the alkylene amine is reacted with the alkenyl cyanide and the product then reacted with the succinic reactant.  Numerous examples are given, and the products are used as lubricating oil additives.