Patent GB-825878-A (GB)
Title: Improvements relating to polymeric reaction products of aluminium alkoxides
Inventor: HARSON SAMUEL EDWARD
IPC: C08G79/10
Filed: 1956-07-06
Abstract: Polymeric organic aluminium compounds suitable for use in lubricating oils and greases are prepared by heating aluminium alkoxides with water and, if desired, with monocarboxylic acids, alcohols and/or phenols, the reaction being continued until two mols. of alkoxide alcohol have been removed per mol. of water added.  The reaction may be effected with the reactants specified in any order or simultaneously.  The mono-carboxylic acids may be aliphatic, particularly short branched chain acids, cycloaliphatic, aromatic or substituted aromatic.  Up to 20% of the mono-carboxylic acid may be replaced by di- or poly-carboxylic acids or other acidic materials such as halogenated acids, sulphur-treated fatty acids, phosphatidic acids, silicic acids, medium ot high molecular weight phosphonic acids, sulphonic acids, dimerized fatty acids having 11 or more carbon atoms, still bottom residues, or polyester resins.  Convenient forms of aluminium alkoxide for use as starting material are aluminium isopropoxide and butoxides, but alkoxides derived from halogenated or substituted alcohols or alcohols having 11 or more carbon atoms may be used.  The reaction may be carried out in an inert diluent, e.g. a medium boiling solvent such as benzene or toluene, a lubricating oil, or an aromatic solvent of minimum boiling point 200 DEG  C. depending on the use to be made of the reaction products.  The aluminium alkoxide starting material may be prepared in situ.  The products may be cyclic, possibly of formula <FORM:0825878/III/1> or linear, of possible formula <FORM:0825878/III/2> where each X is acyl, alkoxy or phenoxy.  The primary polymeric products may be reacted with further acid, alcohol or phenol, which may be different from those used in the first step. Thus reaction of a cyclic structure with further acid HY could give successively <FORM:0825878/III/3> and then <FORM:0825878/III/4> Hydrolysis with water of the primary products will produce soaps AlX2OH and AlX(OH)2 (when HX is an acid).  Many examples are given of the production of polymers starting from aluminium isopropoxide and sec.-butoxide in spindle oil, an aromatic petroleum fraction, a naphthenic blended base oil, or toluene, by reaction with water, other reactants or modifiers being one or two materials selected from stearic, lauric, myristic, behenic, oleic, isooctanoic acids; tall oil, coconut oil, hydrogenated fish oil, hydrogenated castor oil and montan wax acids; sebacic, adipic and azelaic acid dimerized fatty acid, terephthalic acid, dimerized rosin, run Congo resin, non-drying alkyd resin; 2-ethyl-hexanol, cetyl alcohol; o- and m-cresol and o-phenylphenol; p-toluenesulphonic acid; and precipitated silica. The products, when prepared or dissolved in lubricating oils, serve as oils and greases.  Known additives such as anti-wear and anti-corrosion additives may be added.ALSO:Polymeric organic aluminium compounds are prepared by heating aluminium alkoxides with water and, if desired, with monocarboxylic acids, alcohols and/or phenols, the reaction being continued until two mols. of alkoxide alcohol have been removed per mol. of water added.  The reaction may be effected with the reactants specified in any order or simultaneously.  The mono-carboxylic acids may be aliphatic, particularly short branched chain acids, cycloaliphatic, aromatic or substituted aromatic.  Up to 20% of the mono-carboxylic acid may be replaced by di- or poly-carboxylic acids or other acidic materials such as halogenated acids, sulphur treated fatty acids, phosphatidic acids, silicic acids, medium to high molecular weight phosphonic acids, sulphonic acids, dimerized fatty acids having 11 or more carbon atoms, still bottom residues, or polyester resins. Convenient forms of aluminium alkoxide for use as starting material are aluminium isopropoxide and butoxides, but alkoxides derived from halogenated or substituted alcohols or alcohols having 11 or more carbon atoms may be used.  The reaction may be carried out in an inert diluent, e.g. a medium boiling solvent such as benzene or toluene, a lubricating oil, or an aromatic solvent of minimum boiling point 200 DEG  C., depending on the use to be made of the reaction products.  The aluminium alkoxide starting material may be prepared in situ.  The products may be cyclic, possibly of formula <FORM:0825878/IV (b)/1> or linear, of possible formula <FORM:0825878/IV (b)/2> where each X is acyl, alkoxy or phenoxy.  The primary polymeric products may be reacted with further acid, alcohol or phenol, which may be different from those used in the first step. Thus reaction of a cyclic structure with further acid HY could give successively <FORM:0825878/IV (b)/3> and then <FORM:0825878/IV (b)/4> and <FORM:0825878/IV (b)/5> Hydrolysis with water of the primary products will produce soaps AlX2OH and AlX(OH)2 (when HX is an acid). Many examples are given of the production of polymers starting from aluminium isopropoxide and sec.-butoxide in spindle oil, an aromatic petroleum fraction, a naphthenic blended base oil, or toluene, by reaction with water, other reactants being one or two materials selected from stearic, lauric, myristic, behenic, oleic, iso-octanoic acids; tall oil, coconut oil, hydrogenated fish oil, hydrogenated castor oil and montan wax acids; sebacic, adipic and azelaic acids; dimerized fatty acid, terephthalic acid, dimerex resin, run Congo resin, non-drying alkyd resin; 2-ethylhexanol, cetyl alcohol; o- and m-cresol and o-phenylphenol; p-toluenesulphonic acid; and precipitated silica.ALSO:Polymeric organic aluminium compounds are prepared by heating aluminium alkoxides with water and, if desired, with mono-carboxylic acids, alcohols and/or phenols, the reaction being continued until two mols. of alkoxide alcohol have been removed per mol. of water added.  The reaction may be effected with the reactants specified in any order or simultaneously.  The mono-carboxylic acids may be aliphatic, particularly short-branched chain acids, cycloaliphatic, aromatic or substituted aromatic.  Up to 20% of the mono-carboxylic acid may be replaced by di- or poly-carboxylic acids or other acidic materials such as halogenated acids, sulphur treated fatty acids, phosphatidic acids, silicic acids, medium to high molecular weight phosphonic acids, sulphonic acids, dimerized fatty acids having 11 or more carbon atoms, still bottom residues, or polyester resins.  Convenient forms of aluminium alkoxide for use as starting material are alumnium isopropoxide and butoxides, but alkoxides derived from halogenated or substituted alcohols or alcohols having 11 or more carbon atoms may be used.  The reaction may be carried out in an inert diluent, e.g. a medium boiling solvent such as benzene or toluene, a lubricating oil, or an aromatic solvent of minimum boiling point 200 DEG  C., depending on the use to be made of the reaction products.  The alcohol corresponding to the Al alkoxide may also be present as a volatile diluent.  The aluminium alkoxide starting material may be prepared in situ, using mercuric chloride as catalyst.  The products may be cyclic, possibly of formula <FORM:0825878/IV (a)/1> or linear, of possible formula <FORM:0825878/IV (a)/2> where each X is acyl, alkoxy or phenoxy.  The primary polymeric products may be reacted with further acid, alcohol or phenol, which may be different from those used in the first step.  Thus reaction of a cyclic structure with further acid HY could give successively <FORM:0825878/IV (a)/3> and then <FORM:0825878/IV (a)/4> and <FORM:0825878/IV (a)/5> Hydrolysis with water of the primary products will produce soaps AlX2OH and AlX(OH)2 (when HX is an acid).  Many examples are given of the production of polymers starting from p  aluminium isopropoxide and sec.-butoxide in spindle oil, an aromatic petroleum fraction, a naphthenic blended base oil, or toluene, by reaction with water, other reactants being one or two materials selected from benzoic, stearic, lauric, myristic, behenic, oleic, iso-octanoic acids; tall oil, coconut oil, hydrogenated fish oil, hydrogenated castor oil and montan wax acids; sebacic, adipic and azelaic acids; dimerized fatty acid, terephthalic acid, dimerex resin, run Congo resin, non-drying alkyd resin; 2 - ethyl - hexanol, cetyl alcohol; o - and m-cresol and o-phenylphenol; p-toluenesulphonic acid; and precipitated silica. Other reagents mentioned but not exemplified include phenol, alkyl phenols of C4 or more alkyl groups, higher alcohols of at least C8, and halogenated alcohols.  The resins may be compounded with: bitumens, asphalts, waxes, natural oils, fats, hydrogenated castor oil, finely-divided silica, dimerized rosin, chlorinated polyesters, the mineral oils exemplified, xylene, toluene, chlorinated diphenyl, chlorinated paraffin wax, aromatic oils, sebacate phthalate and phosphate esters of monohydric alcohols, polyglycols, polyalkylene oxide esters of monocarboxylic acids, polyalkylene oxide ethers of monohydric alcohols and the oligomeric and monomeric compounds indicated in the formul  above.  Uses.-Lubricating greases; thickeners; paints; inks; putties; lutings; linoleum.