Patent GB-1028565-A (GB)
Title: Alkyldithiophosphoric acid salt of polymeric materials and manufacture and use thereof
Inventor: CYBA HENRY ANTONI
IPC: C07F9/17
Filed: 1963-01-21
Abstract: Oils are stabilized against deterioration by adding thereto agents made by reacting an alkyldithiophosphoric acid with a polymeric material containing a basic nitrogen atom and which is either (1) the condensation product of 1-2 mol proportions of an N-aliphatic dialkanolamine in which the N-aliphaticgroup contains 1-50 carbon atoms with 1 mol proportion of a polycarboxylic acid, or (2) the reaction product of equimolar proportions of an epihalohydrin with a primary or secondary alkylamine, or an ester of said product (see Division C3).  The oil may be either natural or synthetic, for example a mineral lubricating oil, fuel oil, diesel oil, gasoline, dialkyl sebacates, azelates, suberates, pimelates, adipates and glutarates, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, pentanediol-di-(2-ethylhexanoate) polypropylene oxide and its diethers and diesters, methyl and methylphenyl silicones, silicates, silanes, perfluorinated hydrocarbons, neopentyl glycol esters, trimethylol alkanes and esters thereof and phosphate esters.  The oils may also contain other additives, e.g. phenylarylamines, alkoxydiphenylamines, dihydroxy polyalkyldiphenyl methanes and sulphides, esters of orthophosphoric, pyrophosphoric, phosphonic and phosphinic acids and thio derivatives thereof, polyacrylates, polymethacylates, calcium and barium phenates, and the reaction product of sulphur dichloride and allyl phosphate.  The examples describe (4) the addition to paraffinic oil of a compound made by reacting hydrogenated tallow amine with epichlorohydrin, then reacting the product with diisoamyldithiophosphoric acid, and (9) the addition to dioctyl sebacate of a compound made by condensing N-soya-diethanolamine and maleic anhydride, and reacting the product with O,O-dicapryldithiophosphoric acid.ALSO:Oil stabilizing agents are prepared by reacting an alkyldithiophosphoric acid with a basic nitrogen containing polymeric reaction product of either (1) 1-2 mols. of an N-aliphatic-dialkanol-amin in which the aliphatic group contains 1-50 carbon atoms and 1 mol. of a polycarboxylic acid, or (2) equimolar proportions of an epihalohydrin and a primary or secondary alkylamine or an ester of (2).  The phosphoric acid may be of formula <FORM:1028565/C3/1> where R is alkyl and R1 is H, alkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl or a hydrocarbon group containing halogen substituants, e.g. Cl or Br. Both R and R1 may be long chain, i.e. C5- 20 alkyl.  For polymer (1) the alkanol group may contain 2-4 carbon atoms and may be substituted. The aliphatic group may be linear or branched and may contain N, O or a halogen, e.g. Cl or Br.  A mixture of alkanolamines may be used.  The polycarboxylic acid may contain 2,3,4 or more carboxyl groups and may be unsaturated.  A mixture of acids may be used and the acids may be replaced by their anhydrides. The polymerization may be at 80-204 DEG C. in the presence of a solvent and an alkylene diol.  Reduced pressure may be applied or the eliminated water may be removed by azeotropic distillation.  The phosphoric acid treatment may be at - 20 DEG  to 150 DEG  6. in the presence of a solvent and/or a catalyst; 0.25-2 equivalents of acid may be used per basic equivalent of polymer unless the polymer is unsaturated when the number of equivalents of acid may equal the total of basic equivalents and double bonds. The products may be mixed with oils, greases and gasolines. Materials specified include aliphatic esters, polyethers, silicones, esters of phosphoric and silicic acids, fluoro-hydrocarbons and compositions of these with metal soaps. These compositions may also contain antioxidants, antiscuff agents, anti-friction agents.  Many are specified.  The products may be marketed as 0.01-15% solutions in an organic solvent, examples of which are given. The examples describe (1) condensing N-tallow-diethanolamine with maleic anhydride in xylene and treating the product with O-capryl, O-hexyl-dithiophosphonic acid in benzene, (3) reacting hydrogenated tallow amine with epichlorohydrin, then reacting the product with diisoamyldithiophosphoric acid, (5) reacting the condensation product of (1) with O-stearyl, O-capryl-dithiophosphoric acid, (6) condensing N-tallow diethanolamine and ethyl-diethanolamine with maleic anhydride and reacting the product with distearyl-dithiophosphoric acid, (7) condensing N-tallow-diethanolamine with itaconic acid in toluene and reacting the product with disteuryldithio-phosphoric acid, (8) esterifying the condensation product of (3) with pelargonic acid and then reacting it with O-isopropyl-O-capryldithiophosphoric, and (9) condensing N-soya-diethanolamine and maleic anhydride and reacting the product with O,O-dicapryldithiophosphoric acid.