Patent GB-684640-A (GB)
Title: Reaction products of n-acylated polyalkylenepolyamines with alkenyl succinic acids or anhydrides or derivatives thereof
IPC: C23F11/14
Filed: 1950-08-15
Abstract: Corrosion inhibiting compounds are manufactured by reacting one mole. of a polyalkylenepolyamine, containing x nitrogen atoms and x-1 alkylene groups per molecule, with from one to x-1 moles of a monocarboxylic acid or its anhydride or halide or a mixture of said compounds, and reacting the intermediate product with from one to x-1 moles of an alkenyl succinic acid anhydride or the corresponding acid or a compound obtained from either by saturation of the double bond by an addition reaction (e.g. with hydrogen, sulphur, bromine, chlorine or iodine), the sum of the number of moles. of the monocarboxylic acid or equivalent and of the alkenyl succinic acid anhydride or equivalent being not greater than x.  When the terminal nitrogen atom of the polyalkylenepolyamine is separated from the next nitrogen atom by two or three carbon atoms, the first molecule of monocarboxylic acid appears to react at both these points to form an imidazoline or D 2-tetrahydropyrimidine ring (e.g. one mole of caprylic acid with one mole of diethylene- or dipropylene-triamine yields respectively 1-b -aminoethyl - 2 - n - heptylimidazoline and 1 - g  - aminopropyl - 2 - n - heptyl - D 2 - tetrahydropyrimidine), and in these cases some or all of the alkenyl succinic acid anhydride will be present merely in physical admixture unless the number of moles of monocarboxylic acid is not more than x-2 and the sum of the number of moles of monocarboxylic acid and of alkenyl succinic acid anhydride is not more than x-1. The first stage of the reaction is preferably effected at 130-160 DEG  C., advantageously with removal of water liberated by azeotropic distillation with a hydrocarbon solvent (preferably aromatic), and the second stage preferably below 110 DEG  C., advantageously in the presence of a solvent, especially one which forms an azeotropic mixture with water, or a mineral oil. Preferably the polyalkylenepolyamine is a polyethylenepolyamine containing 2-6 ethylene groups per molecule, the monocarboxylic acid is aliphatic (especially with a chain length of 10-30 carbon atoms), and the alkenyl succinic acid anhydride contains 8-18 carbon atoms in the alkenyl radical.  Specified reactants, some of which are employed in examples, are: polyalkylene polyamines (obtainable by the action of ammonia on alkylene or substituted alkylene dihalides, especially ethylene bromide): diethylene-, di-(methylethylene)-, di-(1-methylbutylene)-, di-(1 - methylamylene) -, di - (1 - methyl - 4 - ethylbutylene)-, didodecylene-, dieicosylene-, di-(1 : 2 - dimethyl - 14 - nonyltetradecylene)- and di - (1 : 18 - dioctyloctadecylene) - triamine, triethylene-, tri-(ethylethylene)-, tri-(1 : 2 : 2-trimethylethylene)-, tri-(1 : 4-diethylbutylene)-, tridecylene-, tri-(1 : 15-dimethylpentadecylene)-, trioctadecylene- and tri-(1-methyl-1-phenyl-3-propylpropylene) - tetramine, tetraethylene-, tetrabutylene-, tetra-(1 : 3-dimethylpropylene)-, tetraoctylene-, tetra-(1 : 4-dipropylbutylene)-, tetratetradecylene-, tetra-(1 - methyl - 3 - benzylpropylene) - and tetra - (1 - ethyl - 2 - benzylethylene) - pentamine, penta - (1 - methylpropylene) -, penta-amylene -, penta - (1 : 5 - dimethylamylene)-, penta - (1 : 2 - dimethyl - 1 - isopropylethylene) -, penta - (1 - methyl - 4 - nonylbutylene)- and penta-(1-methyl-2-benzylethylene)-hexamine, hexapropylene- and hexa(1 : 1-dimethylethylene)-heptamine; monocarboxylic acids and equivalents; formic, acetic, fluoroacetic, bromacetic, propionic, b -chloropropionic, propiolic, isobutyric, a -bromobutyric, isocrotonic, b -ethylacrylic, valeric, a -bromoiso-valeric, allylacetic, hexanoic, sorbic and b , chloroacrylic acid, acetic, propionic, butyric, crotonic, acrylic and caproic anhydride, acetyl chloride and fluoride, propionyl bromide, crotonic acid chloride, hexanoyl chloride, nitrosobutyric acids, aminovaleric acids, aminohexanoic acids, heptanoic, octanoic, 2-ethylhexanoic, a -bromo-octanoic, decanoic, dodecanoic, undecylenic and tetradecanoic acid, heptanoic anhydride, myristoyl bromide, hexadecanoic, palmitic, oleic, heptadecanoic, stearic, linoleic and linolenic acid, phenylstearic acids, xylylstearic acids, a -dodecyltetradecanoic, arachidic, behenic, behenolic, erucic, cerutic, selacholeic, montanic, melissic and ketotriacontic acid, erucic and heptacosanoic anhydride, hexahydrobenzoic acid, hexahydrobenzoyl bromide, furoic acid, chlorofuroic acids, thiophenecarboxylic acids, picolinic, nicotinic and benzoic acid, benzoic anhydride, benzoyl chloride and iodide, toluic acids and anhydrides, xylic acids, chloranthranilic acids, chlorodinitrobenzoic acids, cinnamic acid and anhydride, aminocinnamic acids, salicylic acid, hydroxytoluic acids, iodosalicylic acids, naphthoyl chlorides and naphthoic acids, and mixtures of oleic acid with decanoic or dodecanoic acid; alkenylsuccinic acid anhydrides and equivalents: ethenylsuccinic acid and anhydride, ethylsuccinic anhydride, propenylsuccinic anhydrides and their sulphurized derivatives, butenylsuccinic acids, 2-methylbutenylsuccinic anhydrides, 1 : 2-dichloropentylsuccinic anhydride, hexenylsuccinic anhydrides, hexylsuccinic acid, sulphurized 3 - methylpentenylsuccinic anhydrides, 2 : 3- and 3 : 3-dimethylbutenylsuccinic anhydrides, 1 : 2 - dibromo - 2 - ethylbutylsuccinic acid, heptenylsuccinic anhydrides, 1 : 2 - di-iodo-octylsuccinic acid, octenylsuccinic anhydrides, 2 - methylheptenylsuccinic anhydrides, 4 - ethylhexenylsuccinic acids, 2 - isopropylpentenylsuccinic anhydrides, nonenylsuccinic anhydrides, 2-propylhexenylsuccinic anhydrides, decenylsuccinic acids, and anhydrides, 5 - methyl - 2 - isopropylhexenylsuccinic anhydrides, 1 : 2 - dibromo - 2 - ethyloctenylsuccinic anhydrides, decylsuccinic anhydride, undecenylsuccinic anhydrides, 1 : 2-dichloroundecylsuccinic acid, 3 - ethyl - 2 - tert. - butylpentenylsuccinic anhydrides, dodecenylsuccinic acids and anhydrides, 2-propylnonenylsuccinic anhydrides, 3-butyloctenyl - succinic anhydrides, tridecenylsuccinic anhydrides, tetradecenylsuccinic anhydrides, hexadecenylsuccinic anhydrides, sulphurized octadecenylsuccinic acids, octadecylsuccinic anhydride, 1 : 2 - dibromo - 2 - methylpentadecylsuccinic anhydrides, 8-propylpentadecylsuccinic anhydride, eicosenylsuccinic anhydrides, 1 : 2-dichloro - 2 - methylnonodecenylsuccinic anhydrides, 2-octyldodecenylsuccinic acids, 1 : 2-diiodotetracosenylsuccinic anhydrides, hexacosenylsuccinic acids and anhydrides, hentriacontenylsuccinic anhydrides, triisobutenylsuccinic anhydride, and commercial mixtures of alkenylsuccinic anhydrides containing 6-8, 8-10 or 10-12 carbon atoms in the alkenyl groups.ALSO:Oils, fats and waxes.-Corrosion inhibitors, suitable for addition to mineral lubricating oils, light petroleum products such as fuel oils, petroleum waxes such as slack wax and paraffin wax, natural waxes such as carnauba wax, Japan wax and beeswax, natural fats and oils such as sperm oil, tallow, cottonseed oil, castor oil, linseed oil, tung oil, soya bean oil, oiticica oil and oleo oil, and greases, consist of reaction products of one mole of a polyalkylene-polyamine, containing x nitrogen atoms and x-1 alkylene groups per molecule, with from one to x-1 moles of a monocarboxylic acid or its anhydride or halide or a mixture of said compounds, and with from one to x-1 moles of an alkenyl succinic acid anhydride or the corresponding acid or a compound obtained from either by saturation of the double bond by an addition reaction, the sum of the number of moles of the monocarboxylic acid or equivalent and of the alkenyl succinic acid anhydric or equivalent being not greater than x.  In some cases the preparation of the corrosion inhibitors, or especially the second stage thereof, is advantageously carried out in solution or dispersion in a mineral oil.  In an example, the reaction product of 1.5 moles of triethylenetetramine with 2 moles of oleic acid is heated with 3.4 moles of triisobutenyl succinic acid anhydride in a furfural-refined Midcontinent (Rodessa) distillate mineral lubricating oil; the product may be added to a leaded, catalytically cracked gasoline.  Tables show the rust inhibiting properties of this and other products in the said oil and in a blend of solvent refined Midcontinent residual stock and solvent refined Midcontinent (Rodessa) distillate stock, both oils in most cases containing as antioxidants 2 : 6-di-tert.-butyl-4-methylphenol and phenyl-a-naphthylamine. Other additives specified are pour point depressants, V.I. improvers, antidetonants, cetane number improvers, emulsifiers and thinners.  Coating compositions.-The same corrosion inhibitors may be incorporated in paints, varnishes and lacquers, suitable vehicles including water, drying oils and asphalt roofing compositions.