Patent GB-784852-A (GB)
Title: Organic compounds of zirconium and their preparation
IPC: C22B3/34
Filed: 1953-10-12
Abstract: Zirconium compounds containing acid radicals of carboxylic or sulphinic acids are obtained by reacting a zirconium alcoholate with a carboxylic or sulphinic acid, if desired in the presence of an inert solvent or diluent, and if desired heating the reaction product at an elevated temperature.  The reaction may also be carried out by first reacting one of the components with a part of the other component and adding the remainder of the latter when the reaction product is heated at an elevated temperature.  The term "alcoholate" is used to denote phenolates as well as alcoholates.  The normal reaction temperatures range from 0 DEG C. to 150 DEG  C., preferably from 20 DEG  to 100 DEG C., and the elevated temperature to which the product may be heated is preferably between 50 DEG  C. and 200 DEG C.  If solvents are used which boil below the reaction temperature the reaction must be carried out under pressure in a closed vessel. Specified carboxylic acids are aliphatic carboxylic acids such as formic, acetic, butyric, lauric, stearic and oleic acids, fatty acids obtained by oxidation of hydrocarbons, naphthenic acids, resin acids, montanic acid, cycloaliphatic acids such as cyclohexane carboxylic acid, and aromatic acids such as benzoic acid or naphthoic acid. Specified sulphinic acids are aliphatic sulphinic acids, e.g. ethane sulphinic acid and butane sulphinic acid, cyclohexane sulphinic acid, benzene sulphinic acid and naphthalene sulphinic acid.  The zirconium alcoholates may be derived from aliphatic alcohols such as methyl, ethyl, isopropyl, butyl, amyl, hexyl and octyl alcohol but zirconium alcoholates containing per equivalent of zirconium less than 1 equivalent of organic alcoholate radicals may also be used, particularly valuable products being obtained by reacting a zirconium alcoholate containing per equivalent of zirconium 0.5 to 0.9 equivalent of organic alcoholate radical with 0.1 to 0.3 equivalent of monocarboxylic acid per equivalent of zirconium. The alcoholate radical may be aliphatic, alicyclic, aromatic, aliphaticaromatic or heterocyclic, which may be interrupted by a non-acid group, e.g. a keto group or by oxygen or sulphur atoms or by a nitrogen atom carrying a hydrogen atom or an organic radical, or which may be substituted by halogen atoms, ester groups or amino groups.  Other specific examples of alcoholate radicals include chlorethyl, dimethylaminoethyl, octadecyl, cyclohexyl, phenyl, naphthyl, benzyl, phenylethyl, furfurylmethyl, radicals of compounds capable of enolization, such as acetyl acetone and acetoacetic ester, and radicals of 2,5-hexanediol or diethylene glycol.  Any remaining valencies of the zirconium which are not bound to alcoholate radicals may be satisfied by oxygen linked in chain fashion to further zirconium atoms and/or by inorganic radicals such as halogen or hydroxyl, or by organic acid residues, e.g. the acetic acid residue. Examples of zirconium alcoholates which contain less than one equivalent of alcoholate radical per equivalent of zirconium are those alcoholates obtained by thermal and hydrolytic treatment of normal zirconium alcoholates with splitting off of part of the alkoxy groups and generally with the linking together of zirconium atoms in chain fashion through oxygen atoms, e.g. polymeric zirconium butylates, and dimeric or polymeric zirconium isopropylates.  There may also be used zirconium alcoholates containing less than four alkoxy groups which are obtained by reacting ZrOCl2-pyridine complex compounds with slightly hydrous alcohols and ammonia gas; zirconium chlortrialcoholates obtained from zirconium tetra-alcoholates and acetyl chloride and zirconium dichlordiethylates obtained from zirconium tetrachloride and ethanol.  The zirconium alcoholates may also be used in the form of compounds formed by the addition of an alkali metal alcoholate and alcohol to a zirconium alcoholate, e.g. in the form of a compound of the formula NaHZr(OC2H5)6.  The alcoholate starting materials may also be used in a form stabilized against moisture by means of a volatile organic compound which contains a carbonyl group and which is capable of forming chelate compounds with zirconium alcoholates or the reaction may be carried out in the presence of such a volatile organic compound.  The alcoholates may also be used in the form of their carbon dioxide or sulphur dioxide addition products which are stable to moisture.  When the reaction products still contain alkoxy-groups which can be split off by moisture they can be stabilized by addition of or reaction with a volatile organic compound containing a carbonyl group as defined above, e.g. acetyl acetone or acetoacetic ester.  Specified solvents which may be used in the reaction are benzine, benzene, carbon tetrachloride, trichlorethylene, ethyl acetate, amyl acetate, diethyl ether, dioxane, tetrahydrofurane and C1-C4 aliphatic alcohols.  The reaction products are generally oily, semi-solid, wax-like or solid products and may be used in the lubricant, fuel, paint or vanish industries.  The Examples given include the reaction of: (1) and (2) zirconium tetraethylate and commercial stearic acid (or commercial sperm oil fatty acid) to yield viscous oils which solidify or partially solidify on cooling; (3) zirconium tetraethylate and acetic acid to yield a product containing about 0.5 mols. of acetic acid and 1.8 mols. of ethoxy per zirconium atom; (4) zirconium tetraisopropylate with dodecyl sulphinic acid to give a product containing about 0.8 mol. of dodecyl sulphinic acid and about 2.5 mols. of isopropoxyl per zirconium atom, a similar product being obtained when benzene sulphinic acid is used instead of dodecyl sulphinic acid; (5) zirconium tetraisopropylate and lauric acid (or benzoic acid) to yield a product containing some lauric acid (or benzoic acid) and some isopropoxyl radical; (6) dimeric zirconium isopropylate (prepared by the action of 1 mol. of water in isopropanol with mols. of zirconium tetra-isopropylate) with commercial stearic acid to yield a waxy product; (7) polymeric zirconium isopropylate (prepared by reacting a ZrOCl2-pyridine complex with isopropanol in benzene and ammonia gas) and lauric acid to yield a waxy product; (8) polymeric zirconium isopropylate (prepared by reacting 1 mol. of water with 1 mol. of zirconium tetraisopropylate) with commercial stearic acid (or benzoic acid) to yield a waxy product.ALSO:Zirconium compounds containing acid radicals of carboxylic or sulphinic acids are obtained by reacting a zirconium alcoholate with a carboxylic or sulphinic acid, if desired in the presence of an inert solvent or diluent, and if desired heating the reaction product at an elevated temperature.  The reaction may also be carried out by first reacting one of the components with a part of the other component and adding the remainder of the latter when the reaction product is heated at an elevated temperature.  The term "alcoholate" is used to denote phenolates as well as alcoholates.  The normal reaction temperatures range from 0 DEG  C. to 150 DEG  C. preferably from 20 DEG  to 100 DEG  C. and the elevated temperature to which the product may be heated is preferably between 50 DEG  C. and 200 DEG  C.  If solvents are used which boil below the reaction temperature, the reaction must be carried out under pressure in a closed vessel.  Specified carboxylic acids are aliphatic carboxylic acids such as formic, acetic, butyric, lauric, stearic and oleic acids, fatty acids obtained by oxidation of hydrocarbons, naphthenic acids, resin acids, montanic acid, cycloaliphatic acids such as cyclohexane carboxylic acid, and aromatic acids such as benzoic acid or naphthoic acid. Specified sulphinic acids are aliphatic sulphinic acids, e.g. ethane sulphinic acid and butane sulphinic acid, cyclohexane sulphinic acid, benzene sulphinic acid and naphthalene sulphinic acid.  The zirconium alcoholates may be derived from aliphatic alcohols such as methyl, ethyl, isopropyl, butyl, amyl, hexyl and octyl alcohol, but zirconium alcoholates containing per equivalent of zirconium less than 1 equivalent of organic alcoholate readicals may also be used, particularly valuable products being obtained by reacting a zirconium alcoholate containing per equivalent of zirconium 0.5 to 0.9 equivalent of organic alcoholate radical with 0.1 to 0.3 equivalent of monocarboxylic acid per equivalent of zirconium. The alcoholate radical may be aliphatic, alicyclic, aromatic, aliphatic-aromatic or heterocyclic, which may be interrupted by a non-acid group, e.g. a keto group or by oxygen or sulphur atoms or by a nitrogen atom carrying a hydrogen atom or an organic radical, or which may be substituted by halogen atoms, ester groups or amino groups.  Other specific examples of alcoholate radicals include chlorethyl, dimethylamino-ethyl, octadecyl, cyclohexyl, phenyl, naphthyl, benzyl, phenylethyl, furfurylmethyl, radicals of compounds capable of enolization, such as acetyl acetone and aceto-acetic ester, and radicals of 2,5-hexanediol or diethylene glycol.  Any remaining valencies of the zirconium which are not bound to alcoholate radicals may be satisfied by oxygen linked in chain fashion to further zirconium atoms and/or by inorganic radicals such as halogen or hydroxyl, or by organic acid residues, e.g. the acetic acid residue. Examples of zirconium alcoholates which contain less than one equivalent of alcoholate radical per equivalent of zirconium are those alcoholates obtained by thermal and hydrolytic treatment of normal zirconium alcoholates with splitting off of part of the alkoxy groups and generally with the linking together of zirconium atoms in chain fashion through oxygen atoms, e.g. polymeric zirconium butylates, and dimeric or polymeric zirconium isopropylates.  There may also be used zirconium alcoholates containing less than four alkoxy groups which are obtained by