1957-10-16

Abstract of GB784852 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

0

1957-10-16

C01G25/00 ; C07F7/00 ; C22B3/26 ; C22B3/32 ; C22B3/34 ; C01G25/00 ; C07F7/00 ; C22B3/00

C01G25/00B ; C07F7/00B2 ; C22B3/00D2B2A ; C22B3/00D2B2G2 ; C22B3/00D2B2K

GB19530028009 19531012

DEX784852 19521011

1	Organic compounds of zirconium and their preparation
	Inventor:	Applicant: HOECHST AG
	EC:C01G25/00B; C07F7/00B2; (+3)	IPC: C01G25/00; C07F7/00; C22B3/26(+5)
	Publication info: GB784852 A - 1957-10-16

1	Monolithic gel and powder of transition element oxides, process for the manufacture of the gel and process for the preparation of thin layers of these oxides
	Inventor: HENRY MARC; VIOUX ANDRE; (+1)	Applicant: CENTRE NAT RECH SCIENT (FR)
	EC:B01J13/00D6; C01B13/32; (+6)	IPC: B01J13/00; C01B13/32; C01F7/36(+16)
	Publication info: FR2585973 - 1987-02-13

What we claim is: -

1 A process for the manufacture of zirconium compounds containing acid radicals of carboxylic or sulphinic acids, wherein a zirconium alcoholate as hereinbefore defined is reacted with a carboxylic or sulphinic acid, if desired in the presence of an inert solvent or diluent and, if desired, the reaction product is heated at an elevated temperature.

2 A process as claimed in Claim 1, wherein the reaction is carried out in such a manner that one of the components is first reacted with a part of the other component and the remainder of the latter is added when the reaction product is heated at an elevated temperature.

3 A process as claimed in Claim 1 or 2, wherein 1 mol of a zirconium tetra-alcoholate is reacted with less than 4 mols of the carboxylic or sulphinic acid 60 4 A process as claimed in Claims 1 or 2, wherein a zirconium alcoholate is used containing, per equivalent of zirconium, less than 1 equivalent of organic radical bound to zirconium through oxygen in the manner of an 65 alcoholate.

A process as claimed in any one of Claims 1, 2 or 4, wherein a zirconium alcoholate containing, per equivalent of zirconium, 0 5-0 9 equivalent of organic radical bound through 70 oxygen in the manner of an alcoholate to zirconium is reacted with 0 1-0 3 equivalent of monocarboxylic acid per equivalent of zirconium.

6 A process for the manufacture of zir 75 conium compounds of carboxylic or sulphinie acids substantially as described in any one of the examples herein.

7 A process as claimed in any one of Claims 1-6, wherein the reaction is conducted in 80 the presence of a volatile organic compound containing a carbonyl group which compound is capable of forming a chelate compound with zirconium alcoholate.

8 A process as claimed in any one of Claims 85 3-6, wherein the reaction product contains an alcoholate group bound to the zirconium and is subjected to the addition of, or further reacted with a volatile organic compound containing a carbonyl group which compound is 90 capable of forming a chelate compound with zirconium alcoholate.

9 A process as claimed in Claim 7 or 8, wherein the organic compound containing a carbonyl group which is capable of forming a 95 chelate compound with zirconium alcoholate is acetyl acetone or acetoacetic ester.

Zironium compounds of carboxylic or sulphinic acids of the formula Zr (S) (OR),- 100 wherein S represents an acyloxy radical of a carboxylic or sulphinic acid radical, R an alkyl radical, and N stands for an integer greater than zero and smaller than 4.

11 Zirconiurn compounds of carboxylic or 105 sulphinic acids obtained by the process as claimed in Claim 5.

12 Any one of the zirconium compounds of carboxylic or sulphinic acids described in Examples 2-6 and 8-11 herein 110 ABEL & IMRAY, Agents for the Applicants, Quality House, Quality Court, Chancery Lane, London, W C 2.

Leamington Spa: Printed for Her Majesty's Stationery Office, by the Courier Press, 1957.

Published at the Patent Office, 25, Southampton Buildings, London, W C 2, from which copies may be obtained.

PATENT SPECIFICATION

784,852 Date of Application and filing Complete Specification Oct 12, 1953.

&, rr P L ¦ No 28009/53.

Application made in Germany on Oct 11, 1952.

Application made in Germany on Sept 17, 1953.

Complete Specification Published Oct 16, 1957.

Index at Acceptance:-Classes 2 ( 3), C 1 E Si K( 2: 8: 9), C 2 83 (A 1: F: G 1), C 3 A 8, C 3 AO 10 A( 1: 2), C 3 AO 10 A 4 (a: IS: C: D: L), C 3 A 10 ASAI, C 3 A 13 A 1 (A 1: C), C 3 A 13 A 3 A 1 (A:

B: C), C 3 Ai 3 A 3 A( 2: 4), C 3 A 13 A 3 (B 1: C), C 3 A 13 C( 3 A: 9: 10 F), C 3 AI 4 B(I: 5), C 3 CS(A 1: C 5: E 2), C 3 C 8; and 2 ( 5), R 7 P.

International Classification: -C 07 f C 08 g.

COMPLETE SPECIFICATION

Organic Corapounds of Zirconiurn and their preparation We, FARBWERKE HOECHIST A Kl Ti ENGESELLSCHAFT vormals Meister Lucius & Bruining, a body corporate recognised under German law, of Frankfurt (Mv)-Htchst, Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performied, to be particularly described in and by the following statement: The present invention relates to zirconium compounds and a process of preparing them.

It is known that zirconium compounds of carboxylic acids can be prepared by causing carboxylic acids to act upon zirconium tetrachloride As hydrogen chloride is formed during this reaction it is necessary to protect the metal parts of the reaction vessels against the attack of this product Sulphinic acids cannot be reacted with zirconium tetrachioride as the hydrogen chloride produced during the reaction has a decomposing effect upon the former compounds.

According to the present invention zirconium compounds containing acid radicals of carboxylic or sulphinic acids can be obtained by reacting zirconium alcoholates as hereinafter defined, if desired in the presence of inert solvents or diluents, with carboxylic or sulphinic acids and, if desired, by heating the reaction product to an elevated temperature.

The reaction can also be carried out in such a manner that one of the components is first reacted with a part of the other component and the remainder of the latter is added when the reaction product is heated at an elevated temperature.

The normal reaction temperatures range from 0 C to 150 C, preferably from 20 C to 100 C The higher temperature to which the reaction product may be heated preferably ranges between 50 C and 200 C If solvents are used which boil below the reaction temperature, the operation must be carried out under pressure in a closed vessel.

When 1 mol of a zirconium tetra-alcoholate is reacted with 4 mols of carboxylic or sulphinic acid, the tetra-zirconium salt of the respective acid is obtained If less than 4 mols of acid are used, acylated zirconium alcoholates of the formula Zr (S)n (OR)4-_ are formed, wherein S represents an acyloxy radical of a carboxylic or sulphinic acid, R is the residue of the alcoholate group, especially an alkyl radical, and N stands for an integer greater than zero and smaller than 4 On heating, these acylated zirconium alcoholates condense to yield products of high molecular weight which probably have a chain-like or reticular structure The number of the alcoholate or acid groups present may vary with the chosen molar ratio of the components and with the reaction conditions The term "alcoholate" is used herein to denote " phenolates" as well as "alcoholates ".

As carboxylic acids there are suitable, for instance, aliphatic carboxylic acids such as formic acid, acetic acid or butyric acid; cycloaliphatic carboxylic acids such as cyclohexane carboxylic acid, and aromatic carboxylic acids such as benzoic acid or naphthoic acid As suiphinic acids may be mentioned aliphatic sulphinic acids such as ethane sulphinic acid, butane sulphinic acid, cyclohexane sulphinic acid, benzene sulphinic acid and naphthalene sulphinic acid.

Higher aliphatic and cycloaliphatic carboxylic and sulphinic acids are especially suitable, such as lauric acid, stearic acid, oleic acid, fatty acids obtained by oxidation of hydrocarbons and also mixtures thereof, naphthenic acids, resin acids, montanic acid, and sulphinic acids which are prepared in known manner from the sulphochlorination products of natural and synthetic diesel oils.

As zirconium alcoholates there come into consideration such alcoholates as are derived from aliphatic alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol and octyl alcohol.

784,852 Zirconium alcoholkes containing, per equivalent of zirconium, less than 1 equivalent ol organic radicals bound through oxygen in the manner of alcohoiates may also be used for the reaction.

Particularly valuable reaction products are obtained by reacting in amounts based on 1 equivalent of zirconium, about O 1-0 3 equivalent of monocarboxylic acid, if desired in successive portions, with a zirconium alcoholate containing, per equivalent of zirconium, about 0 5-0 9 equivalent of organic radicals bound to zirconium through oxygen in the manner of an alcoholate.

As organic radicals which are bound to zirconium through oxygen in the manner of an alcoholate there may be mentioned aliphatic, alicyclic, aromatic, aliphatic-aromatic and heterocyclic radicals, which may be interrupted by non-acid groups such as the keto group, or by oxygen or sulphur atoms or by nitrogen atoms carrying a hydrogen atom or an organic radical or may be substituted by halogen atoms, ester groups or amino groups.

Examples of organic radicals are methyl, ethyl, chlorethyl, dimethylaminoethyi, isopropyl, butyl, octyl, octadecyl, cyclohexyl, phenyl, naphthyl, benzyl: phenylethyl, furfurylmethyl, radicals of compounds capable of enolization such as acetyl-acetone and acetoacetic ester, radicals of aliphatic glycols of higher molecular weight than glycol, such as 2:5 hexandiol or diethylene glycol and also mixtures of these radicals Particularly valuable starting materials are such zirconium alcoholates as contain, per equivalent of zirconium, about 0 5-0 9 equivalent of organic radicals bound in the manner of an alcoholate.

The remaining valencies of the zirconium, that is to say those which are not bound through oxygen in the manner of an alcoholate to an organic radical, may be satisfied, for example, by oxygen linked in chain fashion to further zirconium atoms and/or by inorganic radicals such as halogen and hydroxyl or by organic acid residues, for instance, acetic acid residue In general, the advantage of these starting materials resides in the fact that the organic radicals bound in the manner of an alcoholate through oxygen can be split off by the action of organic acid substances Generally, they can be split off merely by the action of moisture.

For this reason, it may be of advantage in manufacture on an industrial scale to use the alcoholates in the form of their carbon dioxide and sulphur dioxide addition products, wihich are stable to moisture, or after stabilization by means of volatile organic substances which contain a carbohyl group and are capable of forming chelate compounds with the alcoholates.

As zirconium compounds containing, per equivalent of zirconium, less than one equivalent of organic radicals bound in the manner of an alcoholate through oxygen, there may be mentioned, for instance, such zirconium alcoholates as can be obtained by the thermal and hydrolytic treatment of normal zirconium tetra-aicoholates accompanied by the splitting 70 off of parl of thle alkoxy groups, and min most cases probably with the linking together of zirconium atoms in chain fashion through oxygen atoms.

Among these zirconium alconolates there 75 may be mentioned, for example, the polyineric zirconium butyiates obtained by thermal treatment by a process analogous to the process for the preparation of titanium alcoholates as described by Kraitzer (Journ Oil and 80 Colour Chemists' Assn, volume 31, ( 1948), pa,,_ 4 k 3); Lurthernore there may be cited the dimeric or polymeric zirconium isopropyiate obtained by the hydrolytic treatment of zirconium tetraisopropylate with O 5 mol or 1 85 mol of water in isopropanol solution according LO Lh process described by Winter which is likewise known for the preparation of titanium alcoholates (Canadian Paint and Varnish Mag, volume 25, pages 12-19 90 ( 1951)).

There may also be used zirconium alcoholates containing less than four alkoxy groups which are obtained by reacting Zr OC 1,pymieine complex compounds with slightly 95 hydrous alcohols and with ammonia gas, by a process analogous to that using anhydrous alcohols as described by Bradley (Journ.

Chem Soc London ( 1950), page 3450; ( 1952) page 2032) 100 As zirconium alcoholates containing halogen atoms there may be mentioned, for instance, zirconium chlortrialcoholates obtained from zirconium tetra-aicoholates and actyl chloride and zirconium dichlordiethylates obtained 105 from zirconium tetrachloride and ethanol according to the process described by Bradley (Journal of the Chemical Society, Lond, ( 1950), page 3450; ( 1952) page 4609).

There may also be used for the reaction 110 with the acids, mixtures of zirconium alcoholates having a reduced content of alkoxy groups or mixtures of these alcoholates with normal zirconium tetra-alcoholates They may also be used for the reaction with the acids in 115 ithe form of their alkoxo-acids (as hereinafter defined) and/or in a form stabilized against moisture in known manner by means of volatile organic compounds such as acetyl acetone or acetoacetic ester which contain a carbonyl 120 group which compounds are capable of forming chelate compounds with zirconium alcoholates, ( of F Schmidt, Zeitschrift fir angewandte Chemie, volume 64 ( 1952) page 538).

The reaction may also be conducted in the 125 presence of a volatile organic compound containing a carbonyl group which compound is capable of forming a chelate compound with zirconium alcoholate.

Insofar as the reaction products still con 130 784,852 tain alkoxy groups which can be split off by moisture, they can be stabilized against decomposition by moisture, particularly at room temperature, by addition of or reaction with a volatile organic compound containing a carbonyl group which compound is capable of forming a chelate compound with zirconium alcoholate, such as acetyl acetone, and acetoacetic ester.

By the use of different zirconium alcoholates the properties of the organic zirconium compounds obtained can be adapted to the intended use.

The alkoxo-acids which are mentioned above and may be used in the present process are compounds which have been formed by the addition of alkali metal alcoholate and alcohol to the zirconium alcoholates, for example, the compound of the following formula -Na Hi Zr (OC Hs)j This compound has been described for instance by Meerwin and Bersin in the Annalen der Chemie, volume 476 ( 1929) page 113.

As inert solvents or diluents for the reaction there come into consideration, for instance, hydrocarbons or chlorinated hydrocarbons such as benzine, benzene, carbon tetrachloride or trichlorethylene; low-boiling esters such as ethyl acetate or amyl acetate; dialkyl ethers such as diethyl ether; cyclic ethers such as dioxane or tetrahydrofurane, and also anhydrous, aliphatic alcohols, which contain between one and four carbon atoms.

The reaction products obtained are, according to the chosen molar ratio of the reaction components and the nature of the acid, of an oily, semi-solid, wax-like or solid consistency.

They are soluble in numerous organic solvents and are compatible with plasticisers They may be used in many industries such as the lubricant, fuel, paint and varnish industries.

The following examples illustrate the invention, the parts being by weight:EXAMPLE 1.

271 parts of zirconium tetraethylate are dissolved in 2000 parts of anhydrous ethyl alcohol, and 240 parts of glacial acetic acid are added in portions while stirring From the clear solution of the zirconium tetra-acetate thus formed, the alcohol is removed by distillation under reduced pressure 320 parts of zirconium tetra-acetate are obtained as white crystals which are easily soluble in cold ethyl alcohol or water.

Instead of zirconium tetraethylate, there may also be used 327 parts of zirconium tetraisopropylate or 383 parts of zirconium tetrabutylate.

EXAMPLE 2

271 parts of zirconium tetraethylate are dissolved in 2000 parts of anhydrous benzene mixed with 500 parts of anhydrous ethyl alcohol and, at 10 C, there are added in portions, while stirring, 274 parts of commercial stearic acid (solidification point: 52 C, molecular weight: 274) The clear solution is then stirred for another hour at 60 C and subsequently the solvent is distilled off at this temperature under reduced pressure The reaction product consists of a viscous oil which has a semi-solid consistency in the cold It is soluble in cold carbon tetrachloride, benzene, and benzine.

If, instead of stearic acid, a commercial sperm oil fatty acid (acid number= 212, saponification number= 214, iodine number= 71) is used and otherwise the same method of working is adopted as described above, a viscous oil is likewise obtained which solidifies in the cold to give a soft wax The latter is soluble in cold carbon tetrachloride, benzene, and benzine.

EXAMPLE 3

271 parts of zirconium tetraethylate are dissolved in 2500 parts of anhydrous benzene 85 mixed with 500 parts of anhydrous ethanol and, at 20 C, 109 parts of commercial stearic acid (solidification point: 52 C, molecular weight: 274) are added in portions while stirring The clear solution is then boiled for 90 another hour under reflux and subsequently the solvent is distilled off Finally the distillation residue is heated for one hour at about C The reaction product is a condensation product of zirconium ethylate and 95 stearic acid which, according to analysis, contains about 0 4 mol of stearic acid and 1 6 mols of ethoxyl per zirconium atom In the hot it is a viscous oil which solidifies in the cold then showing a waxy consistency At 100 room temperature it is soluble in carbon tetrachloride, xylene, and test benzine.

If, instead of commercial stearic acid, 550 parts of commercial sperm oil fatty acid (acid number= 211, saponification number= 214, 105 iodine number= 71) are used and otherwise the same method of working is adopted as described above, whilst applying a temperature of 150 C for heating the distillation residue 5 a wax-like zirconium compound is obtained 110 showing the same solubility pro Derties.

EXAMPLE 4

136 parts of zirconium tetraethylate arc dissolved in 1000 parts of anhydrous xylene and there are added dropwise at room temperature, 115 while stirring, 15 parts of glacial acetic acid.

The clear solution is boiled under reflux for another hour and subsequently the solvent and the split off ethanol are distilled off The reaction product, a condensation product of 120 zirconium ethylate and acetic acid, which, according to analysis, contains about 0 5 moi of acetic acid and 1 8 mols of ethoxyl per zirconium atom, consists of a crystalline white mass melting at 230 C The ethoxyl con 125 tent found by analysis shows that in the heating further condensation has taken place The 784,852 mass obtained is soluble in aliphatic and aromatic hydrocarbons.

EXAMPLE 5

To 327 parts of zirconium tetra-isopropylate dissolved in 1000 parts of carbon tetrachloride, are added, while stirring, 188 parts of dodecyl sulphinic acid On heating, a clear solution of a condensation product of zirconium isopropylate and dodecyl sulphinic acid is formed which is boiled under reflux for another hour Tht solvent and the split off isopropanol are then distilled off, finally under reduced pressure at a temperature of about C The reaction product is a condensation product of zirconium isopropylate and dodecyl sulphinic acid which contains about 0.8 mol of dodecyl sulphinic acid and about 2.5 mols of isopropoxyl per zirconium atom.

In the hot it is a viscous oil which solidifies slowly in the cold and finally shows a waxlike consistency It is soluble at room temperature in carbon tetrachloride, xylene, and test benzine.

If, instead of dodecyl sulphinic acid, the equivalent quantity of benzene sulphinic acid is used and the same working method is adopted as described above, a condensation product of zirconium isopropylate and benzene sulphinic acid is obtained In the hot it is a viscous oil which solidifies in the cold to show a wax-like consistency and which is soluble in xylene.

EXAMPLE 6

To 327 parts of zirconium tetraisopropylate dissolved in 1000 parts of carbon tetrachloride, are added, while stirring, 140 parts of lauric acid A condensation produdt of zirconium isopropylate and lauric acid is formed while heat is generated and isopropanol is split off The clear solution is boiled under refiux for another hour and the isopropanol is distilled off The reaction product is a condensation product of zirconium isopropylate and lauric acid which contains 0 7 mol of latric acid and 2 3 mols of isopropoxyl per zirconium atom In the hoa it is a viscous oil, i'hilst in the cold it has a wax-like consistency; it is soluble in perchlorethylene.

If, instead of lauric acid, 37 parts of benzeic acid are used and otherwise the same method of working is adopted, a condensation product of zirconium isopropylate and benzoic acid is obtaintd which contains 3 mool of benzoic acid and about 2 7 mols of isopropoxyl per zirconium atom In the hot it is a viscous oil which solidifies in the cold to show a wax-like consistency; it is soluble in xylene.

EXAMPLE 7

327 parts of zirconium tetraisopropylate are melted, while stirring, with 800 parts of lauric acid at a temperature of about 120 C, whereby the split off isopropanol is distilled off and thus recovered The zirconium tetralaurate formed is stirred for a short time under reduced pressure at 140 C An oil is obtained which solidifies at about 140 C.

to a wax-like substance and which is soluble in carbon tetrachloride, benzene, and test benzine.

If, instead of 327 parts of zirconium isopropylate, 383 parts of zirconium tetra isobutylate are used and the same working method is adopted as described above, the same result is obtained.

EXAMPLE 8

To 327 parts of zirconium tetra isopropylate dissolved in 1000 parts of carbon tetrachloride, are added, while stirring, at about C, 270 parts of commercial stearic acid 80 (solidification point 52 C, molecular weight:

270) A clear solution of a mono-stearic acid condensation product of zirconium isopropylate is formed, while isopropanol is split off 60 parts of glacial acetic acid are then 85 added dropwise at 50 C while stirring A clear solution of a zirconium monostearatemonoacetate-diisopropylate is formed, while further isopropanol is split off The solvent is then distilled off, finally under reduced 90 pressure 510 parts of a viscous oil are obtained which solidifies in the cold to give a wax and which is soluble in benzene, carbon tetrachloride, and test benzine.

If double the amounts of commercial stearic 95 acid and glacial acetic acid are used and otherwise the same method of working is adopted as described above, a simple distearic acid and diacetic acid condensation product of zirconium isopropylate is obtained that is zir 100 conium distearate-diacetate In the hot it is a viscous oil which solidifies at 25 C to a wax-like substance It is soluble in prchlorethylene, xylene and test benzine.

EXAMPLE 9 105

552 parts of a dimeric zirconium isopropylate, prepared in the manner described by Cow and Winter for titanium alcoholates (Fette und Seifen, 1953, page 431) by the action of 1 mol of water in an isopropanol solution of 110 1 per cent strength at room temperature upon 2 mols of zirconium tetra-isopropylate dissolved in the same amount of carbon tetrachloride, and by distilling off the solvent under reduced pressure, are dissolved in 1000 parts 115 of carbon tetrachloride To the solution produced there are added while stirring and at about 400 C, 270 parts of commercial stearic acid (solidification point 52 C, molecular weight 270) and the clear mixture is then 120 heated for another hour at about 60 C.

Finally the solvent and the split off isopropanol are distilled off under reduced pressure.

The reaction product is a wax which solidifies at about 450 C and is easily soluble in 125 xylene, test benzine, and carbon tetrachioride.

784,852 EXAMPLE 10

300 parts of a polymeric zirconium isopropylate, prepared by a process analogous to that described by Bradley, which used anhydrous alcohols (Journal of the Chemical Society, Lond, ( 1952), page 2032), by reacting the Zr O C 12-pyridine complex compound with isopropanol of 98 per cent strength in benzene and ammonia gas and by subsequently filtering off the ammonium chloride with suction and distilling off the solvent, are dissolved in 1000 parts of perchiorethylene To this solution are added, at 30 C while stirring, 200 parts of lauric acid and the clear solution thus formed is boiled for another hour under reflux The solvents are then distilled off under reduced pressure A wax is obtained which has a solidification point of about 30 C and which is soluble in xylene, perchlorethyltne, and test benzine.

EXAMPLE 11

210 parts of a polymeric zirconium isopropylate prepared in the manner described in Example 9 by reacting 1 mol of water with only 1 mol of zirconium tetraisopropylate, are dissolved in the same weight of perchlorethylene and there are added, at about 50 C, while stirring, 90 parts of commercial stearic acid (molecular weight 270, solidification point 52 C) The clear mixture is boiled for one hour under reflux and the solvent and the split off isopropyl alcohol are then distilled off The reaction product is a wax which melts at about 35 C and which is easily soluble in xylene, test benzine, and carbon tetrachloride.

If, instead of stearic acid the same amount -of benzoic acid is used and otherwise the same method of working is adopted, a similar wax is obtained which solidifies at 40 C.