Patent GB-1081330-A (GB)
Title: Stabilization of organic substances
IPC: C10L1/222
Filed: 1964-12-11
Abstract: An additive for stabilizing organic substances such as oils, fuels, waxes, greases, synthetic resins and rubber comprises the reaction product of an amine and either a polyhalopolyhydroalkanonaphthalene dicarboxylic acid of formula <FORM:1081330/C4-C5/1> where X and Y are halogen, hydrogen, or an alkyl radical having 1 to 10 carbon atoms, at least two X's being halogen, m is 1 to 4 and n is 0 to 4, or the anhydride or an ester of such an acid. The acid may be prepared by condensing a cyclohexenedicarboxylic acid, prepared by a Diels-Alder reaction, with a halocycloalkadiene. For example 1,3-butadiene is condensed with maleic acid to form 1,2,3,5-tetrahydrophthalic acid, which is then condensed with hexachlorocyclopentadiene to form 5,6,7,8,9,9 - hexachloro - 1,2,3,4,4a,5,8,8a - octahydro - 5,8 - methano - 2,3 - naphthalene dicarboxylic acid.  The anhydride is formed by starting with maleic anhydride.  The ester is formed by reaction of the product with an alcohol having 1 to 25 carbon atoms. The amine may be a mono- or polyamine and may have 2 to 50 carbon atoms.  Amines mentioned include the series from octyl to eicosyl amine, tallow amine, stearyl amine, coconut amine, N-alkyldiaminoalkanes, particularly N-alkyl-1,3-diaminopropane, alkylene diamines and polyalkylene polyamines, the latter preferably being N-alkyl substituted, aromatic amines, amino phenyl ethers, sulphides and substituted methanes and other alkanes, and cycloalkyl amines.  A sulphur-containing amine, which may be desirable when the eventual additive is to be incorporated in a lubricating oil, may also be formed by reacting an N-alkylated or N,N-dialkylated alkylene polyamine with carbon disulphide.  The reaction product of the acid, anhydride or ester with the amine may be a salt, including the half salt, or a condensation product.  To form the salt, the reactants preferably dissolved in a solvent, are mixed and left at up to 66 DEG C. under up to 34 atmospheres for up to 12 hours.  To form the condensation product, the reactants are refluxed in a solvent at a temperature at which water is eliminated, suitably azeotropically. The product may be an imide, or imide-amine, but is ill-defined and mixtures, possibly including heterocyclic rings, are thought to be formed.  The additive may be used in the reaction solvent, or this may be removed and the additive redissolved in an alkyl or polyalkylphenol.  Lubricating oils stabilized by the additive include mineral oils, oils of animal, marine or vegetable origin and synthetic oils, e.g. aliphatic esters, polyalkylene oxides, silicones, phosphoric and silicic acid esters, fluorinated hydrocarbons, neopentyl glycol esters and trimethylol alkanes. Greases stabilized may be whale grease, wool grease, those made from inedible fats, tallow, butcher's waste and synthetic greases. The additive is used in proportions of 0.01 to 25%.ALSO:Additives for stabilizing organic compounds (see Division C5) are made by reacting an amine with an acid of formula <FORM:1081330/C2/1> wherein X = Cl, m = 1 and either n = 0 (I) or n = 1, Y = H (II), or with an anhydride of such acid.  In examples, (a) salts are made from I and oleylamine, N-alkyl (C12- 20)-1,3,-diamino-propane (III), or NH(CH2CH2NHCHEtCH2CHMeEt)2/CS2 reaction product; (b) cyclic imides are made from I-anhydride with NH(CH2CH2NH2)2, and II-anhydride with III; (c) a product, apparently an amidic acid, is made by reacting in a 1:1 molar ratio, II anhydride with N,N1-di-secoctyl-p-phenylenediamine.