Patent GB-755558-A (GB)
Title: Polymeric zirconium compounds and methods of preparing same
Inventor: BALTHIS JOSEPH HENDRICKSON
IPC: C07F7/00
Filed: 1954-04-13
Abstract: Polymeric organic zirconium compounds are obtained by reacting an organic zirconium ester having the formula Zr(OR)4, in which R is an alkyl, alkoxyalkyl, cycloalkyl, aryl or aralkyl radical, in the presence or absence of an organic solvent with an anhydrous aliphatic carboxylic acid in the proportion of 0.5 to 4 molar equivalent of acid per mol. of ester, and continuing the reaction until a polymeric zirconium ester or a polymeric zirconium ester carboxylate is formed. Examples describe the reaction of (1) tetraethyl zirconate and stearic acid (in molar ratio 1 : 3); (2) tetraethyl zirconate and linseed oil acids (1 : 3); (3) acetic acid and tetraethyl zirconate. The products are useful as dispersing and milling agents for pigments, as additives with flake aluminium to paints, rust inhibitors, and ingredients of paints, enamels, lacquers and alkyd resins, as lead scavengers in gasoline and as lubricating oil additives and pour-point depressants, and in waterproofing textiles. For the last purpose it may be baked on the fibre, together with paraffin wax.ALSO:A method of preparing an organic, polymeric zirconium compound comprises reacting an organic zirconium ester having the formula Zr(OR)4, in which R is an alkyl, alkoxyalkyl, cycloalkyl, aryl or aralkyl radical, in the presence or absence of an organic solvent, with an anhydrous aliphatic carboxylic acid in the proportion of at least 0.5 molar equivalent of acid per mol. of ester, and continuing the reaction until a polymeric zirconium ester or polymeric zirconium ester carboxylate is formed. Suitably 0.5 to 4 mols. of a straight chain, saturated, aliphatic monocarboxylic acid per mol. of orthozirconate is employed.  When tetraethyl zirconate is heated at 50 DEG  to 112 DEG  C. with, for example, stearic acid, advantageously with azeotropic distillation of ethanol formed, the dimer hexaethyl dizirconate of the formula (C2H5O)3Zr-O-Zr(OC2H5)3 is formed when 0.5 equivalent of acid is used.  With 1 mol. a polymeric ester is formed.  With two or more mols. of acid a polymeric zirconium ester containing carboxylate groups is obtained.  The products can be purified by distillation or extraction, e.g. with acetonitrile.  The ester starting materials are obtainable by addition of anyhydrous ammonia to a mixture of zirconium tetrachloride and the alcohol in a liquid such as anhydrous heptane. The group R in the zirconate employed may represent methyl, ethyl, isopropyl, amyl, octyl, dodecyl, 2-ethyl-hexyl, benzyl, cyclohexyl, phenyl, ethoxyethyl and b -naphthyl radicals.  Specific examples of suitable acids are acetic, propionic, butyric, valeric, caprylic, heptylic, capric, lauric, myristic, palmitic, dodecanoic, oleic, ricinoleic, linoleic, stearic, b -eleostearic, arachidic and acids derived from drying and semi-drying oils.  Reaction temperatures of 0 DEG  to 225 DEG  C., suitably 50 DEG  to 112 DEG  C., are mentioned. Examples describe the reaction of (1) tetraethyl zirconate and stearic acid (in molar ratio 1:3) to give products which may have the formulae <FORM:0755558/IV(a)/1> or <FORM:0755558/IV(a)/2> (2) tetramethyl zirconate and linseed oil acids (1 : 3); (3) acetic acid and tetraethyl zirconate (1 : 1).  Further general formulae of the possible structure of the products are given.  The products are useful in waterproofing textiles, as oil and gasoline additives and dry-cleaning soaps in coating compositions, cosmetics, catalysts for ester-interchange reactions and synthetic resinous compositions, e.g. alkyd resins (see Groups III, IV (a) and VIII).ALSO:Polymeric zirconium esters or polymeric zirconium ester carboxylates, obtained by reacting an organic zirconium ester having the formula Zr(OR)4, in which R is an alkyl, alkoxyalkyl, cycloalkyl, aryl, or aralkyl radical, in the presence or absence of an organic solvent with an anhydrous aliphatic carboxylic acid in the proportion of at least 0.5 molar equivalent of acid per mole of ester are useful as dispersing and milling agents for pigments such as chlorinated or chlorine - free copper phthalocyanines, additives with flake aluminium to paints resistant to high temperatures, rust inhibitors for steel and for increasing the hardness and reducing the drying time of coating compositions such as paints, enamels, lacquers and alkyd resins. They are also useful as lead scavengers in gasoline, lubricating oil additives and pour-point depressants for lubricating oils. There is described the application to steel panels of ethoxy zirconyl stearate, which acts as a rust inhibiting material.  Also a xylene solution of an ethoxy zirconium linseed oil arylate forms a tack-free coating when poured on to glass.  The preparation of the esters is described in detail (see Group IV(b)).