Patent GB-816337-A (GB)
Title: Preparation of hydrophobic siliceous material
IPC: B01J13/00
Filed: 1956-02-28
Abstract: Silica or silica-containing material is surface esterified by heating with alcohol in the presence of a hydrohalic acid, e.g. hydrochloric, hydrobromic or hydriodic acid, in an amount of at least 1.4 X 10-3 mole., preferably 3-6 X 10-3 mole., of hydrohalic acid per 100 grams of alcohol at a temperature of 65-150 DEG  C. and at atmospheric pressure, or super-, or sub-atmospheric pressure.  The material treated may have a specific surface area of at least 1 sq. m/gm., preferably 4-400 sq. m./gm., and may be prepared by dehydrating precipitated silica to produce an aerogel or a xerogel, or by burning silicon tetrachloride or hydride or ethyl orthosilicate.  Alcohols specified are methyl, ethyl, propyl, butyl, amyl, heptyl, hexyl, octyl, nonyl, decyl, and octadecyl alcohol.  At least 0.083 mole. of butanol per 100 gms. of silica may be employed.  The hydrohalic acid is preferably added as a gas, but a concentrated aqueous solution may be used.  The acid may be absorbed on the silica before the addition of the alcohol or may be dissolved in the alcohol.  The acid may be removed during the course of the reaction or afterwards.  Excess alcohol may be removed by filtration, centrifugation, or distillation.  A high boiling having an aliphatic or cycloaliphatic hydrocarbon group containing 4-30 carbon atoms, and optionally with (iii) an aliphatic monocarboxylic acid ester of an unsaturated alcohol, the aliphatic monocarboxylic acid containing up to 30 carbon atoms and the unsaturated alcohol being an a - or b -unsaturated alcohol containing up to 20 carbon atoms, at least one of copolymers (A) and (B) being partially esterified with a polyalkylene glycol or a mono-alkyl ether thereof, in which each alkylene group contains 2-7 carbon atoms and the alkyl group contains 1-30 carbon atoms, the copolymers (A) and (B) being present in the weight ratio of 0.15-5 parts of (A) for each part of (B).  A portion of the maleic anhydride or substituted maleic anhydride of the (A) and (B) copolymers may be replaced by a derivative thereof, namely (a) the free carboxylic acid, (b) an amide, N-alkyl amide or N-cycloalkyl amide, (c) an N-alkyl or N-cycloalkyl amine salt, or (d) an alkyl or cycloalkyl ester, the alkyl or cycloalkyl group of (b), (c) or (d) containing 1-7 carbon atoms.  Furthermore, this alkyl group may have at least one hydrogen, but not more than half thereof, substituted by a polar group or atom.  Examples of such polar groups and atoms are amino, carboxyl, cyano, amido, imino, isocyano, mercapto, nitramino, nitro, nitroso, sulpho and thiocyano groups, and chlorine and bromine atoms. The lubricating oil may be mineral oil, a synthetic hydrocarbon oil (e.g. an alkylene polymer, an alkyl benzene or an oil derived from coal or shale), an alkylene oxide polymer or an ether or ester thereof, an ester of a dicarboxylic acid (e.g. di-n-hexyl fumarate polymer or dibutyl adipate), an ester of a phosphorus acid (e.g. tricresyl phosphate or diethyl ester of decane phosphonic acid), a polysiloxane or a silicate ester.  The lubricating composition may also contain oiliness agents, viscosity index improvers, pour point depressants, blooming agents and peptizing agents.  In the examples, mineral lubricating oil compositions are described containing polymeric materials obtained by reacting (A) copolymers and (B) copolymers with polyethylene glycol or its monomethyl or monolauryl ether, or polypropylene glycol or its monoethyl ether. The (A) copolymers are chosen from copolymers of maleic anhydride with allyl stearate; vinyl stearate; octadecene-1; vinyl 2-ethyl-hexyl ether; allyl stearate and vinyl 2-ethyl-hexyl ether, or maleic acid, or maleamic acid or maleimide; methallyl stearate and isobutyl maleamide or ethylene glycol monomaleate; or vinyl 2-ethyl-hexoate and octyl maleamate.  The (B) copolymers are chosen from copolymers of maleic anhydride with lauryl methacrylate (with or without allyl stearate or diisobutylene); allyl stearate and vinyl 2-ethyl-hexoate or lauryl acrylate; vinyl stearate and cetyl acrylate; methallyl stearate and lauryl acrylate; vinyl trimethyl - nonyl ether and dilauryl maleate; cetyl phenoxyethyl methacrylate; or vinyl stearyl ketone (with or without dinonyl phenoxyethyl acrylate).  Polar groups present on a portion of the maleic anhydride in some of the examples are octadecyl amido; octadecyl ammonium; hydroxyethyl amido; tetraethylene pentammonium; 2,2,2-trihydroxy methylpropanoxy (pentaerythritol ester); 2-mercapto propoxy; triethanol ammonium; 2,2-hydroxymethyl 3-oleoxy, propanoxy; N-(2-amino-ethyl) amido; 2-ethylhexyl amido; octyl thio; dihydroxyethyl ethylene diammonium; and 2-nitro ethoxy. The preparations of many copolymers are given.