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United States Patent (19) 11) 4,425,278 Wirth et al. 45 Jan. 10, 1984

54) COMPLEX COMPOUNDS, PROCESS FOR 3,972,868 8/1976 Avela ...... 260/439 RX THEIR PREPARATION, AND THEIR USE Primary Examiner-Helen M. S. Sneed (75) Inventors: Hermann O. Wirth, Bensheim; Attorney, Agent, or Firm-Luther A. R. Hall Hans-Helmut Friedrich, Lautertal, both of Fed. Rep. of Germany 57 ABSTRACT A complex compound of a salt or salt 73 Assignee: Ciba-Geigy Corporation, Ardsley, and an ansolvo- or -acid, of the general for N.Y. mula I 21 Appl. No.: 278,763 22) Filed: Jun. 29, 1981 . Related U.S. Application Data in which M is a m-valent cation of a metal or metalloid, a metal-oxy or metal-dioxy cation or a atom, 62 Division of Ser. No. 938,172, Aug. 30, 1978, Pat. No. X is a n-valent anion of a n-basic inorganic proton-acid 4,336,148. or of a n-basic selected from the of 51 Int. Cl...... C07F 11/00; CO7F 15/04 the aliphatic and cycloaliphatic carboxylic with 52 U.S. C...... 260/429 R; 260/429.5; up to 8 C atoms, which can be substituted by 260/429.9; 260/438.1; 260/448 R; 556/482; and/or hydroxyl groups, the aromatic monocarboxylic, 568/6; 568/852 dicarboxylic and tricarboxylic acids, which may be (58) Field of Search ...... 260/429 R, 439 R, 448 AD, substituted by hydroxyl, halogen and/or nitro groups, 260/448 R, 429.5; 568/852; 556/482 the organic oxyacids of and sulphur, the organic thioacids of phosphorus, and the mercaptans, (56) References Cited the inorganic or organic acid having a pKa value of at U.S. PATENT DOCUMENTS most 15.8 or, if M is a proton, of at most 11, Y is 2,150,349 3/1939 van Peski et al...... 260/439 RX or a neutral organic molecule which can be bound 2,466,445 4/1949 Landau ...... 260/439 R coodinatively by the cation or the anion, Z is a com 3,219,635 li/1965 Emrick ...... 568/852 X plex-forming vicinal diol with at least 6 C atoms, p is 0 3,420,932 1/1969 Jones et al. . 260/448 AD X or a value between 0 and 2, q is a value from 1 to 32, m 3,507,896 4/1970 Jones et al...... 260/448 AD 3,511,864 5/1970 Ugelow ...... 260/448 AD is an integer from 1 to 6 and, if M is a hydrogen atom, 3,629,229 12/1971 Schmank ...... 260/448 RX is 1 and n is an integer from 1 to 4, and mixtures of such 3,686,249 8/1972 Hartmann ...... 260/448 AD compounds. 3,901,931 8/1975 Rasberger et al...... 260/439 R 3,944,625 3/1976 Neal ...... 260/439 RX 8 Claims, No Drawings

4,425,278 1. 2 scribed is their low heat stability, which results from the COMPLEX COMPOUNDS, PROCESS FOR THEIR low complexing capacity of the proposed . PREPARATION, AND THEIR USE German Offenlegungsschrift No. 2,330,906 describes nickel complexes of nickel salts of hydroxy-substituted This is a divisional of application Ser. No. 938,172, and alkyl-substituted phenylcarboxylic acids with alco filed on Aug. 30, 1978, now U.S. Pat. No. 4,336,148, hols or polyols, which complexes have good heat stabil issued on June 22, 1982. ity and are used as light stabilisers in polymers. This The present invention relates to complex compounds publication again does not tackle the problem of con of preferably inorganic salts and proton-acids or ansol verting salts, by means of one particular complexing voacids with vicinal diols, a process for their prepara 10 reagent, into products which are soluble in, for exam tion, and their use as antistatic additives in natural and ple, hydrocarbons. synthetic hydrocarbon-based polymers, lubricants and For completeness, it should be mentioned that the fuels, category of metal salts complexed with crown ethers It is known to react various inorganic salt-like com can also comprise compounds which are soluble in pounds with monofunctional or polyfunctional alco 15 non-polar, aprotic solvents. A disadvantage of these hols, the resulting compounds being described as alco complexes is that the crown ethers have a specific com hol complexes. plexing capacity for certain cations only, and that the For example, U.S. Pat. No. 3,420,932 describes reac synthesis of the crown ethers themselves is expensive tion products of basic aluminium salts with organic and uneconomical. polyhydroxy compounds; in addition to various diols, 20 It is an object of the present invention to provide a glycerol is mentioned. These products, obtained by complexed heat-stable compound of a metal salt or direct reaction of the basic aluminium salts with the metalloid salt, and of a proton-acid or ansolvo-acid, polyhydroxy compounds, have the disadvantage that which is soluble even in non-polar aprotic solvents and they are only soluble in polar protic solvents, for exam which is an effective antistatic additive in this solvent, ple alcohols, but not in non-polar aprotic solvents, for 25 in lubricants or in polymers. A further object of the example aliphatic or aromatic hydrocarbons. This be present invention is to provide a general process for the haviour may be explained, for example, by the fact that preparation of this complex compound. in the reaction described complex polymers are pro The present invention relates to complex compounds duced via the formation of an alcoholate, as is stated to of a metal salt of metalloid salt and an ansolvo-acid or be the case for a similar process in German Patent Spec proton-acid, which have the composition I ification No. 1,468,537, column 4, lines 10-21. The products described in the latter patent are also sparingly M".Xmp Y.qZ (I) soluble in alcohols but only dispersible in a polar or ganic solvent, for example a halogenated hydrocarbon. in which M is a m-valent cation of a metal or metalloid, Anal. Chemie 41 (II), 1456-58 (1969) discloses that 35 a metal-oxy or metal-dioxy cation or a hydrogen atom, barium forms alcoholates with diglycerol X is a n-valent anion of a n-basic inorganic proton-acid and that residual free hydroxyl groups of the diglycerol or of a n-basic organic acid selected from the group of can form chelate bonds with the barium cation. As a the aliphatic and cycloaliphatic carboxylic acids with result of the strongly polar character of the ligand, these up to 8 C atoms, which can be substituted by halogen chelated alcohols are also virtually insoluble in hydro 40 and/or hydroxyl groups, the aromatic monocarboxylic, . dicarboxylic and tricarboxylic acids, which may be Kim. Tekknol. Topal. Masel, 11, 25-28 (1974), de substituted by hydroxyl, halogen and/or nitro groups, scribes the reaction of molybdenum pentachloride with the organic oxyacids of phosphorus and sulphur, the C12-C14-1,2-diols, alcoholates being formed as the reac organic thioacids of phosphorus, and the mercaptans, tion products, with elimination of hydrogen halide. 45 the inorganic or organic acid having a pKa value of at Alcoholates from diols and molybdenum halides are most 15.8 or, if M is a proton, of at most 11, Y is water also described in German Patent Specification No. or a neutral organic molecule which can be bound coor 954,448. These alcoholates are soluble in mineral oils. A dinatively by the cation or the anion, Z is a complex disadvantage of these compounds is that active constitu forming vicinal diol with at least 6 C atoms, p is 0 or a ents of the compound, in the present case the halogen 50 value between 0 and 2, q is a value from 1 to 32, m is an atoms, are replaced as a result of the formation of the integer from 1 to 6 and, if M is a hydrogenatom, is 1 and alcoholate. n is an integer from 1 to 4, and mixtures of such com J. inorg. nucl. Chem., 34,357-59 (1972) discloses that pounds. lanthanum in aqueous can form The composition I only comprises monomeric salts; complexes with polyols, for example glycerol. These 55 hence, in the part MnXn of the formula, the subscript complexes again are insoluble in non-polar aprotic sol indices n and m are always 1 if the superscript indices m Vents. and n are identical. However, in the monomeric salts X Reaction products of, for example, lead , fatty can be a polymeric anion. acids or higher carboxylic acids and alkoxy-alcohols, The m-valent cation is preferably derived from a for example 2-ethoxyethanol, or polyols, for example metal of group la to 8a and 1b to 5b of the periodic table sorbitol, are described, in French Patent Specification of the elements, the lanthanides, uranium, plutonium or No. 2,264,082, as oil-soluble metal complexes. The solu the , , germanium and . bility of these products results from the -rich acid In the present application, valency is to be understood portion and from the alkoxyalkanol or polyol. Accord as the number m of electrons which a metal can release, ingly, this patent does not tackle the problem of con 65 with formation of a metal carrying an m-fold verting salts, by means of only one complexing reagent, charge, and is familiar to those skilled in the art. into products which are then soluble in non-polar Preferred cations are those of the Li, Na, K, aprotic solvents. A disadvantage of the products de Be, Mg, Ca, Sr, Ba, Al, Sc, La, Ce, Eu, Ti, Zr, Hf, Th,

4,425,278 3 4. V, Nb, Ta, Cr, Mo, W, U, Mn, Fe, Co, Ni, Rh, Pd, Os, thioarsenite, thioantimonite, trithionophosphate, tetra Jr, Pt, Cu, Ag, Au, Zn, Cd, Hg, Sn, Pb and Bi and of the thiophosphate and trithiophosphite. metalloids B, Si, Ge and Sb. Examples of anions of oxy-acids of the amphoteric In particular, cations of the metals Li, Na, K, Mg, Ca, elements and of the metalloids are: , metaborate, Sr, Ba, Al, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, , metasilicate, germanate, antimonite, antimon Ag, Au, Zn, Cd, Sn, Pb and Bi and of the metalloids B, ate, aluminate, titanate, zirconate, vanadate, chromate, Si and Sb deserve mention. dichromate, molybdate, tungstate, , perman Some metals can also form metal-oxo cations, which ganate, stannite and stannate. These anions also include contain one or two atoms. Amongst these tita polymeric anions. nyl, vanadyl, zirconyl and uranyl are preferred. The O Anions of inorganic complex acids are to be under tetravalent cation tungstenyl and the monovalent cati stood as anions composed of a central metal atom or ons antimonyl and bismuthyl should also be mentioned. metalloid atom and complex-forming acido-ligands. The inorganic acid and the organic acids defined Examples of suitable metals and metalloids are B, Si, above, from which the anion is derived, preferably have Ge, As, Sb, Al, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Zn, a pKa value of at most 10, especially at most 4; in the 15 Cd, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Sn, case of the strongest acids, this value ranges down to Pb and Bi. Examples of suitable acido-ligands are the about - 10. halides, especially fluoride and chloride, the pseudoha It has been found that those of the complex com lides, especially cyanide and thiocyanate, the CO group pounds according to the invention, of the formula I, and oxalate. These complex anions in the main belong to which are derived from strong acids are particularly 20 the type MX4, DMX5 and MX6), in which M is the stable. The upper limit of the pKa value of 15.8 still metal ion or metalloid ion, X is the acido-ligand and n is includes water as a weak acid. the basicity (negative charge) resulting from the va X is the anion of a n-basic inorganic or organic pro lency of the metal or metalloid and the charge of the ton-acid, as defined above. This definition also em acido-ligand. It should also be mentioned that the nu braces proton-acids which do not exist in the free form 25 merous complex anions include polynuclear anions. but only in the form of their salts, for example of the Examples are: tetrafluoroborate, hexafluorosilicate, ammonium salts. The basicity n indicates the number of hexafluoroarsenate, hexafluoroantimonate, penta negative charges formed in the anion as a result of the fluoroantimonate (III), hexafluorophosphate, tetra elimination of n . In addition to the anions of fluoroaluminate, hexafluoroaluminate, hexafluorotita monobasic acids, for example , anions 30 nate, hexafluoromolybdate, hexafluorotungstate, hexa of tetrabasic acids, for example silicate or titanate, are fluorochromate (III), hexafluoroferrate, hexafluoroco also known and n therefore denotes an integer from 1 to baltate, hexafluoroplatinate, tetrafluorozincate, hexa 4. X also includes polymeric anions, for example those fluorostannate, hexafluoroplumbate, hexafluoromanga of the , titanates, , , zircon nate, hexafluororhodanate, hexachloroiridate, hexa ates, vanadates, , molybdates, tungstates and 35 fluorotantaliate, hexafluoroniobate, tetrachloroalumi antimonates. nate, hexachlorotitanate, hexachlorovanadate, tetra The anion X is preferably derived from inorganic chlorovanadate, hexachlorochromate, hexachloroman proton-acids from the group of the hydrogen halides ganate, hexachloromolybdate, hexachlorotungstate, and hydrogen pseudohalides and hydrogen selenide, the hexachloroferrate, tetrachloronickelate, hexachlorohe inorganic oxy-acids or thioacids, and the inorganic nate, hexachlororuthenate, hexachloroosmate, hexa complex acids. chlorostannate, hexachloroplumbate, hexachloroanti Examples of the hydrogen halides and hydrogen monate, hexachlorobismuthate, tetrabromocadmiu peudohalides are HF, HCl, HBr, HI, HCN, HCNO, mate, tetracyanozincate, tetrachloromercurate, tetra HCNS and HN3. bromomercurate, tetraiodomercurate, tetracyanomer The inorganic oxy-acids are preferably derived from 45 curate, tetrathiocyanatomercurate, hexacyanovanadate, the elements C, N, P, As, S, Se, Cl, Br and and trioxalatovanadate, hexacyanochromate, trioxalato from the amphoteric elements and the metalloids. Ex chromate, pentacyanonitrosochromate, hexacyanoman amples of amphoteric elements are B, Al, Zn, Ti, Si, Zr ganate, hexathiocyanatomanganate, trioxalatomanga and Sn. nate, hexacyanoferrate, tetracyanocobaltate, tet The inorganic thioacid is preferably H2S or is derived 50 racyanonickeiate, tetracyanocuprate, tetraoxalatozir from the elements C, V, Mo, W, Sn, P, As, Sb and S. conate, hexarhodanomolybdate, octacyanomolybdate, Examples of anions of the oxy-acids of the above octacyanotungstate, octacyanorhenate, hexacyanoplati elements are: , bicarbonate, , , nate, hexacyanoosmate, tetracyanopalladate, pentacar hypophosphite, phosphite, orthophosphate, polyphos bonylmanganate, tetracarbonylferrate and tetracar phates, for example diphosphates, metaphosphates, for 55 bonylcobaltate. example metaphosphate, trimetaphosphate or tet Some of the complex acids are known in the free form rametaphosphate, fluorophosphate, arsenite, , whilst others are only known in the form of their salts, sulphite, sulphate, peroxomonosulphate, peroxodisul for example the ammonium salts. phate, thiosulphate, , , pyrosulphite, X can also be the anion of a n-basic aliphatic or cy pyrosulphite, polythionate, fluorosulphate, selenite, 60 cloalphatic with at most 8 C atoms, selenate, tellurite, , , , chlo preferably 1 to 4 C atoms, which can be substituted by rate, , bromite, , iodate and perio halogen or hydroxyl. Preferably, the carboxylic acid is date. substituted in the a-position, especially by fluorine, Examples of thioacids, in addition to sulphide, are or , and preferably the carboxylic acid polysulphides, for example disulphide, thiocarbonate, 65 is monobasic or dibasic. Examples are formate, acetate, thionocarbonate, thiothionocarbonate, dithionocarbon propionate, butyrate, oxalate, malonate, succinate, fu ate, trithiocarbonate, thiovanadate, thiomolybdate, thi marate, maleate, dithiodipropionate, hydroxyacetate, otungstate, thiostannate, thioantiomonate, thioarsenate, mono-, di- and tri-fluoroacetate, mono-, di- and tri 4,425,278 5 6 chloroacetate, mono-, di- and tri-bromoacetate, ot of the formula I, in which X is an anion as defined chloropropionate, a-chloromalonate, ot-bronomalon above, and one or more compounds of the formula I, in ate, 1,2-dichlorosuccinate and 1,2-dibromosuccinate. which X is an alcoholate anion. The alcoholate anion X can also be the anion of an aromatic carboxylic acid can be derived from alkanols or with, prefera with, preferably, at most 12 C atoms, which is prefera bly, 1 to 8C atoms, in which case X can at the same time bly selected from the group comprising the monobasic, also be an alcoholate anion derived from a vicinal diol dibasic and tribasic phenylcarboxylic and naphthylcar of the formula Z. Preferably, X only is the last-men boxylic acids, and which can be substituted by halogen, tioned alcoholate anion. These mixtures are obtained by in particular fluorine, chlorine or bromine, or by nitro reacting a metal alcoholate or metalloid alcoholate, groups. Examples are benzoate, isophthalate, tere 10 obtained from the abovementioned alcohols and an at phthalate, 2-naphthenate, 2,6-dinaphthenate, chloroben least divalent metal or metalloid, with a less than stoi zoate and nitrobenzoate. chiometric amount of an anhydrous compound of the X can also be the anion of an organic oxy-acid of formula HX or an ammonium salt of the formula phosphorus and sulphur, and of an organic thioacid of AX. In this reaction, statistical mixtures are obtained, phosphorus. Preferably, such acids are the phosphonic, 15 the composition of which is essentially determined by phosphinic, thiophosphonic, thiophosphinic, sulphonic the degree of shortfall from the stoichiometric amount. and sulphinic acids. The acids of phosphorus can be This mixture may or may not contain unconverted start represented by the following general formula: ing material. If X is to be an alkanolate or phenolate anion, a reaction product of a metal or metalloid al coholate or phenolate with a less than stoichiometric amount of a vicinal diol of the formula Z is employed. Some preferred anions are hydroxyl, fluoride, chlo X ride, bromide, iodide, cyanide, , thiocyanate, azide, perchlorate, bromate, iodate, , perman in which R is a hydrocarbon radical of aliphatic or 25 aromatic character, with preferably up to 18, especially ganate, sulphide, bisulphide, hydrogen-difluoride, ni up to 8, C atoms, which can be substituted by halogen, trite, nitrate, sulphite, sulphate, thiosulphate, bisulphate, especially fluorine and chlorine, X can independently fluorosulphate, bisulphite, , hydrogen-phos be oxygen or sulphur and R is the group-X"H or a phate, phosphite, hypophosphite, metaphosphate, poly hydrogen atom or independently is defined like R. 30 phosphate, monofluorophosphate, carbonate, bicarbon The oxy-acids of sulphur can be represented by the ate, thiocarbonate, thionocarbonate, dithiocarbonate, thionothiocarbonate, trithionocarbonate, carbamate, following formula xanthate, trithionophosphate, tetrathiophosphate, trithi O ophosphate, silicate, metasilicate, titanate, borate, me 35 taborate, molybdate, vanadate, aluminate, chromate, dichromate, selenate, tungstate, arsenite, arsenate, anti rt-i-oh monate, stannate, thioarsenite, thioarsenate, thioanti (Oy monate, thiostannate, thiomolybdate, thiotungstate, in which R is as defined above and y is 0 or 1. R can tetrafluoroborate, hexafluorosilicate, hexafluorotita be linear or branched alkyl, cycloalkyl, aryl or aralkyl, nate, hexafluoroaluminate, hexachlorostannate, hexa which can be substituted, in particular by fluorine or chloroferrate, hexacyanoferrate, octacyanomolybdate, chlorine and by alkyl with 1 to 6 C atoms. Cycloalkyl is hexafluoroantimonate, hexacyanochromate, tet preferably cyclohexyl and aryl and aralkyl are prefera racyanonickelate, trioxalatomanganate, methylphos bly derived from phenyl and naphthyl. phonate, methylphosphinate, phenylphosphonate, tosy Examples are: methyl, ethyl, propyl, butyl, isobutyl, late, phenylsulphonate, methylsulphinate, formate, ace octyl, octadecyl, phenyl, naphthyl, p-methylphenyl, tate, propionate, benzoate, terephthalate, trifluoroace butylphenyl, dibutylphenyl, hexylphenyl, chloro tate, trichloroacetate, chlorobenzoate, trifluoromethyl methyl, chloroethyl, chlorophenyl, fluoromethyl and sulphonate, oxalate, malonate, maleate, fumarate, hy trifluoromethyl. droxyacetate, naphthylsulphonate, dithiodipropionate, X can also be the anion of a mercaptain which prefera 50 methylmercaptide, phenylmercaptide, octoxycarbonyl bly contains up to 18, especially up to 12, C atoms. methylmercaptide and 9-hydroxyethylmercaptide. Preferably, the mercaptain corresponds to the formula In the compounds according to the invention, of the formula I, particularly preferred anions are those which R6 -SH . are derived from inorganic acids which in particular 55 have a pKa value of at most 7.5, and those derived from in which R6 is linear or branched, optionally oxygen organic acids which have a pKa value of at most 4. If M interrupted, alkyl, hydroxyalkyl or alkoxycarbonylal is a hydrogen atom, the pKa value is preferably at most kyl, or phenyl which is unsubstituted or substituted by 9.5, and more particularly at most 4. C1-C12-alkyl. Examples are: methyl, ethyl, propyl, M.X can also be an ansolvo-acid. Examples are hexyl, octyl, decyl, dodecyl, octadecyl, S-hydrox BF3, BCl3, AlF3, AlCl3, SiCl4, TiCl4, SnCl2, SnCl4, yethyl, 6-hydroxypropyl, alkoxycarbonylmethyl and SbF5, boron trialcoholates and alkyl-tin . Further As-alkoxycarbonylethyl, for example i-octoxycarbonyl examples are familiar to those skilled in the art. methyl or -ethyl, thiophenyl and nonylthiophenyl. M in formula I can also be a hydrogen atom. In that The anion X can also be derived from dibasic, tribasic case, the formula is to be understood to represent the and tetrabasic oxy-acids which are partially esterified, 65 inorganic and organic oxygen-containing and oxygen preferably with C1-C12-alkanols or phenols. free proton-acids of which the anions have been defined The present invention also encompasses mixtures earlier. The oxygen-containing proton-acids are pre which contain a compound according to the invention, ferred.

4,425,278 7 8 Where Y is water, it can, in the compounds of the exhibits the desired solubility properties and is em formula I, be coordinatively bonded to the cation or braced by the present invention. Of course it is also also to the anion, or be present as water of crystallisa possible to employ mixtures of vicinal diols Z in prepar tion. In some cases the water may not be entirely re ing the compounds, whereby the solubility can be influ movable. Preferably, the compounds contain little or no enced. Water. If M is a proton, q is preferably from 1 to 6, especially Y in formula I can also be an organic molecule which from 1 to 3. In that case, it is particularly preferred if can be bonded coordinatively, preferably , di one vicinal diol of the formula Z is present per proton in ethyl ether, tetrahydrofuran, dimethylformamide, di compound . methylsulphone or tetramethylenesulphone. These 10 Compounds according to the invention, of the for compounds can, in small amounts, remain in the com mula I, can be prepared in accordance with processes plex compounds of the formula I when the compounds identical with, or analogous to, those described in Ger have been prepared in the corresponding solvents. man Offenlegungsschrift No. 2,330,906. It has been In general, however, water and the organic mole found that those compounds according to the invention, cules mentioned, of the formula Y, can be removed 15 of the formula I, which are derived from water-soluble virtually completely, so that p preferably has a value or organo-soluble inorganic metal salts or metalloid from 0 to 1 and is in particularly 0. salts, ansolvo-acids or proton-acids can be prepared by The vicinal diol Z can contain 6 to 30 C atoms. Pref the above process. The solubility of inorganic salts in erably, it contains at least 8 C atoms and especially 8 to organic solvents is described in, for example, J. Jander 22 C atoms. It may be linear, branched or cyclic. Prefer and Ch. Lafrenz "Wasserähnliche Lösungsmittel', Ver ably, it has the formula II lag Chemie (1968). Accordingly, the present invention further relates to Ri R2 (II) a process for the preparation of complex compounds of metal salts, metalloid salts, ansolvo-acids or proton R---R 25 acids, of the formula I, which are derived from water OHOH soluble or organo-soluble metal salts or metalloid salts, in which R, R1,R2 and R3 independently of one another ansolvo-acids or proton-acids, wherein the soluble are a hydrogen atom or linear or branched alkyl with, metal salts or their hydrates (aquo-complexes), ansolvo preferably, up to 22 C atoms, or phenyl, or R1 and R2 30 acids or proton-acids are reacted directly, in aqueous together are alkylene with 3 to 6 C atoms. R2 and R3 solution or in solution in an organic solvent, with q mols preferably are alkyl with 1 to 12 C atoms and especially of a vicinal diol of the formula Z per mol of metal salt hydrogen atoms and R is preferably alkyl with 1 to 20 C or acid, after which the water or solvent may or may atoms. In a preferred sub-group, R and R2 are hydro not be removed from the reaction mixture. gen atoms and R and R3 independently of one another 35 The process, which exists in a plurality of embodi are alkyl with 1 to 18 C atoms. ments, is preferably carried out attemperatures of up to Preferably, the diols Z have a terminal vicinal diol 150° C., especially from 30° C. to 120° C. group and in particular have the formula R In one embodiment, the anhydrous metal salts or CHOH-CH2OH, in which R is linear or branched metalloid salts, ansolvo-acids or proton-acids are re alkyl with at least 4 C atoms, preferably 4 to 30, espe acted directly with the vicinal diols of the formula Z. cially 4 to 20 and more particularly 6 to 18 C atoms. The reaction is accelerated by warming. In the case of The vicinal diols Z are known compounds or can be crystalline diols of the formula Z it is advantageous to prepared in a known manner by hydroxylation of epox select a reaction temperature above the melting point of ides, the epoxides being obtainable from olefins and the diol. The reaction is complete after the salt em per-compounds, for example H2O2 or organic per-acids. 45 ployed has dissolved. Thereafter, any insoluble constit The value q indicates the number of complex-forming uents can be filtered off. Examples of anhydrous salts compounds Z in formula I; q is preferably from 1 to 20, are MgCl2, CaCl2, ZnCl2, SnCl2, Snbr2, MnOl2 and especially from 1 to 16, more especially from 1 to 10 and CuCl2. Gaseous acids, for example HCl or HBr, can be very particularly from 1 to 6. In some compounds ac passed into the vicinal diols of the formula Z. When cording to the invention, the desired solubility reaches a carrying out a reaction with ansolvo-acids it is advanta very good level even if only one molecule of the com geous not to use excessively high temperatures, in order plexing compound of the formula Z is present, so that to repress the replacement of the anions by alcoholate the lower limit of q is 1. bonds. It has also been found that in compounds of the for In another embodiment, the metal salts, metalloid mula I, which contain a relatively low-molecular com salts or acids which contain water of crystallisation are pound of the formula Z, the solubility can be improved employed and reacted with the vicinal diols Z. by increasing the number q of vicinal diol molecules Z. In this case, the water of crystallisation can be re Conversely, with higher-molecular compounds of the moved by warming, if appropriate in vacuo, or by azeo formula Z, a relatively low number q suffices to achieve tropic distillation with an organic solvent, for instance a good solubility. 60 hydrocarbon, for example hexane, heptane, petroleum If the compounds according to the invention, of the ethers, benzene, toluene or xylene, or chloroform. formula I, contain high proportions of vicinal diol of the In general, the salt dissolves at the rate at which the formula Z, i.e. if q in formula I is greater than about 16, water of crystallisation is displaced. After the reaction, there is the possibility that in fact only a part is bonded the mixture can be freed from insoluble constituents by directly to the salt, preferably to the cation. 65 filtration and the compound according to the invention In that case, the product would consist of a very can be isolated by distilling off the solvent. Examples of concentrated solution of the compound according to salts containing water of crystallisation are the hydrates the invention in the vicinal diol Z, which solution also of NiCl2, Ni(CH3COO)2, Fe(Cl2, AIC3, CuCl2, CoCl2,

4.425,278 9 10 CaCl2, MgCl2, MinCl2, ZnCl2, CdCl2, CrCl3, in a second stage of the reaction. This general process Mg(CH3COO)2, Cu(CH3COO)2 and Co(HCOO)2. can also be used to convert metal salts or metalloid salts When using salts which in particular are strong Lewis or proton-oxyacids, which are insoluble in water and in acid (ansolvo-acids), discolourations of the reaction organic solvents, into the soluble compounds according product are frequently observed in the above method of 5 to the invention. The reaction is simple, takes place with preparation. It has been found that these discolourations virtually quantitative yields and has the advantage that can be avoided by starting from an anhydrous solution virtually all metal salts of acids can be prepared in the of the Lewis acid in an ether or , warming the form according to the invention. mixture, after addition of the vicinal diols Z to the reac The present invention further relates to a process for tion, and then removing the ether or alcohol by distilla 10 the preparation of a complex compound of a metal salt tion, if appropriate in vacuo. When using a solution in or metalloid salt or proton-oxyacid, which compound an ether, it is also possible to remove the ether, before corresponds to the general formula I, or the preparation adding the vicinal diol Z, to the point that the ether of a mixture of such compounds, wherein first a basic or adduct of the Lewis acid remains, and to use the adduct non-basic metal alcoholate or metal-oxy alcoholate, or a as the starting material. Suitable ethers and alcohols are 15 non-basic metalloid alcoholate, or an ester of an acid in particular low-molecular compounds which are eas with q mols of a vicinal diol Z, or a compound of the ily removable by distillation, for example diethyl ether, formula I, in which X is hydroxyl, is prepared, and tetrahydrofuran, methanol and ethanol. Examples of (a) this basic or non-basic alcoholate or compound of Lewis acids are AlCl3, FeCl3, SnCl4, MoCl5, SbCl5, the formula I, in which X is hydroxyl, is then reacted in SbF5, BF3 and SbF3. In a further embodiment of the process, the com the stoichiometric amount with an anhydrous com pounds according to the invention are obtained by dis pound of the formula HX, in which n and X are as solving the anhydrous salts or acids, or the salts or acids defined earlier, which in aqueous solution forms an acid containing water of crystallisation, in a suitable organic having a pKa value of at most 15.8 or, if M is a hydrogen solvent and then adding a vicinal diol Z and carrying 25 atom, having a pKa value of at most 11, or with an out the reaction. After removing the solvent, the de ammonium salt AX, in which A is an ammonium sired product is obtained. In this process, the water of cation and n and X are as defined earlier, with removal crystallisation is in general removed together with the of water, or amine, or solvent. Preferred solvents are those which are also (b) the basic alcoholate or a compound of the formula capable of dissolving vicinal diols Z. Examples are I, in which X is hydroxyl, is then reacted with a stoi - ethers, for instance diethyl ether and tetrahydrofuran, chiometric amount of an , an acid halide alcohols, for instance methanol and ethanol, and chloro or an acid ester of the acids defined for the compounds form, dimethylformamide, dimethylsulphoxide and ace of the formula I, with removal of the alcohol when tonitrile, whilst examples of salts are KI, NaBr, AgNO3, using the acid ester, or CuSO4.5H2O, Na2S2O3.5H2O and CdCCH3COO)2.2- 35 (c) to prepare the compounds, in which M is a hydro H2O. gen atom, the ester of a proton-oxyacid with a complex In a particular embodiment of the process, complex forming compound of the formula Z, or an ester with an compounds of the formula I, in which X is hydroxyl, aliphatic alcohol, in the presence of q mols of a vicinal are prepared by reacting a metal hydroxide or oxide or diol Z, is reacted with the stoichiometric amount of a hydrate thereof with q mols of a vicinal diol Z per mol 40 water, accompanied by removal of the alcohol formed of hydroxide or oxide, and thereafter sufficient water is in the case where an aliphatic ester of the acid is used. expelled to leave a number of hydroxyl groups corre In the compounds HX and AX, n is preferably an sponding to the valency of the metal cation. When using integer from 1 to 3 and the pKa value of the acid is at the metal oxides, it is assumed that alcoholates are first most 7, in particular at most 4. By way of explanation, formed, with elimination of water, and that these ai 45 it should be mentioned that the pKa value of 15.8 just coholates are again hydrolysed by the water of reaction. includes water as the weakest acid. Metal oxides and preferred in this case are The reaction can be carried out in the presence or those which in aqueous solution have pK values of at absence of a solvent. Suitable solvents are, in particular, most 9, preferably at most 4.5, with negative values volatile ethers, for example diethyl ether, but preferably indicating very strong bases. Examples are the oxides hydrocarbons, for example pentane, hexane, benzene, and hydroxides of the alkali metals and alkaline earth toluene and xylene, which can easily be removed again metals, of monovalent thallium and of silver. from the reaction mixture by distillation, if appropriate The processes with the proton acids are in principle in vacuo, in order to prepare the pure complex com no different. Thus, the proton-acids to be complexed pounds according to the invention. Any insoluble con can be introduced directly into the vicinal diol Z, in the 55 stituents can be filtered off before the distillation. presence or absence of a solvent, for example a hydro The process is in general carried out at room temper carbon. Advantageously the mixture is cooled both ature (for example 2.0 C) up to temperatures of 150 C., during this addition, and during the post-reaction re preferably 50° C. On adding the reactants (anhydrous quired to obtain a clear solution, so as not to exceed a proton-acid, acid anhydride, acid ester and acid halide) temperature of 50° C. When using a dilute aqueous 60 a strong exothermic effect is in general observed. In proton-acid, the water is advantageously removed in some cases it may therefore be advantageous to cool the the presence of a vicinal diol Zby azeotropic distilla reaction mixture. To remove the solvent used, warming tion, it also being possible to use solvents. may or may not be necessary. The complex compounds according to the invention, The metal alcoholates, metalloid alcoholates and of the formula I, can, surprisingly, also be prepared by 65 metal oxide-alcoholates of the complex-forming com a novel two-stage process which starts from basic or pounds of the formula Z, which are used as starting nonbasic metal alcoholates or metalloid alcoholates or materials for the process according to the invention, are esters of oxy-acids and in which the anion is introduced prepared in accordance with various known processes:

4,425,278 1. 12 (a) In the simplest case, a metal oxide or hydroxide, talline anhydrous proton-acids, for example phosphoric or a hydrate thereof, is reacted with the vicinal diol Z. acid, are preferably added as solids, whilst liquid pro and, to prepare the pure alcoholate, the water of reac ton-acids, for example concentrated sulphuric acid, are tion formed is removed, for example by azeotropic also added undiluted, advantageously to a cooled solu distillation. To form the basic alcoholates, only a part of tion of the alcoholates in petroleum ether. After com the water of reaction is removed. pletion of the addition, the mixture is in general allowed This process is in particular suitable for strong metal to react further. Thereafter, any insoluble constituents bases, for example bases of the alkali metals and alkaline can be filtered off and the compound according to the earth metals, for instance NaOH, KOH, LiOH, RbCH, invention can be isolated in accordance with the cus Sr(OH)2, Ca(OH)2, SrO, CaO, BaO and Ba(OH)2.8- 10 tomary methods. H2O. If the basic alcoholates, and the compounds of the ... (b) The reaction of alkali metal alcoholates or alkaline formula I, in which X is hydroxyl, are prepared in situ, earth metal alcoholates, especially the Li, Na and K either the water is added in the presence of an anhy alcoholates, of the vicinal diods Z with metal halides, drous compound HX, an ammonium salt or an acid metalloid halides and metal oxyhalides also gives the 15 anhydride, acid halide or acid ester, or the abovemen corresponding alcoholates, with formation of an alkali tioned starting materials are first prepared and only then metal halide or alkaline earth metal halide. is the reagent for introducing the anion X added, with (c) The reaction of metal halides, for example the out isolating the starting materials which have been chlorides or bromides, with the vicinal diols Z, in the formed. presence or absence of catalytic amounts of an alkali 20 The compounds of the formula I, in which X is hy metal such as Li or Na, also gives the alcoholates, with droxyl, are obtained by the process according to the elimination of hydrogen halide. This reaction is in gen invention by reacting the metal alcoholates, metal-oxy eral carried out at temperatures of up to 200° C. or alcoholates or metal-dioxy alcoholates of the vicinal O. diois Z and the metals with a stoichiometric amount of (d) It is also possible to start from the metal alcoho 25 water. This reaction is advantageously carried out in a lates, metalloid alcoholates and metal-oxy alcoholates hydrocarbon solvent, for example n-heptane, and at with lower, volatile alcohols, for example methanol or temperatures of up to 50 C., preferably at room tem ethanol, and react these with a vicinal diol Z, the alco perature. Further particularly suitable solvents are hy hol formed being removed by distillation. For example, drocarbons, for example pentane, hexane, petroleum the alcoholates of the metals Mg, Al, Sb, Ca, Ti and Sn ether, octane, benzene and toluene. or of the zirconyl cation are obtained in this way. In the reaction with anhydrous proton-acids, the (e) It is also possible to react metal complexes, for non-basic alcoholates are preferred as starting materials, example the acetylacetonates, with vicinal diois Z, with since in that case the desired compounds according to displacement of the ligand, for example acetylacetone, the invention are obtained directly when the solvent to give the corresponding metal alcoholates, for exam 35 used is removed. However, it is also possible to employ ple in the case of complexes of Ni, Cu, Zn and Sn(II). the basic alcoholates or the compounds of the formula I, (f) The action of vicinal diols Z on metal acetates, for in which X is hydroxyl, without this causing difficulties. example of lead or bismuth, in many cases also gives the It is merely necessary to remove the water of reaction corresponding alcoholates, with removal of acetic acid. formed, preferably by azeotropic distillation. This reac (g) The complex compounds according to the inven 40 tion is therefore advantageously carried out with hy tion, of the formula I, in which X is hydroxyl, can also drocarbons as solvents, with which the water can at the be used as starting materials for the process according same time be azeotropically removed. to the invention and can furthermore themselves be A large number of proton-acids of the formula HX prepared in accordance with this process of the inven which can be prepared in the anhydrous form is known. tion. 45 Crystalline proton-acids may contain water of crystalli (h) The basic metal alcoholates and metal-oxy al sation but this does not interfere with the process ac coholates and the compounds according to the inven cording to the invention and can be removed after the tion, of the formula I, in which X is hydroxyl, can, reaction. In addition to the proton-acids already men when used as starting materials, also be prepared in situ. tioned, H2Fe(CN)6), H2PtF6 and HMn(CO)5 may be For this purpose, the metal alcoholates, metalloid al 50 mentioned as examples of inorganic complex acids. coholates or metal-oxy alcoholates of q mols of a vicinal Some of the proton-acids are unstable in the free form diol Z and the metal are reacted with a stoichiometric or do not exist in this form, and it is to be regarded as an amount of water or with less than this quantity, down to important advantage of the process according to the half the stoichiometric amount. invention that the anions of unstable acids can be intro The process according to the invention may be car 55 duced into the starting materials used according to the ried out in various forms. In the case of the reaction of invention via their stable ammonium salts. However, the virtually anhydrous proton-acids HX with the this embodiment of the process according to the inven abovementioned starting materials, the procedure fol tion is not restricted to these ammonium salts but can be lowed is in general to add the anhydrous proton-acid, carried out generally for all ammonium salts. It should preferably in portions, to the starting materials. Virtu 60 also be mentioned that instead of the proton-acids ally anhydrous means, in the present context, that only HX the complex acids according to the invention, of traces of moisture, which do not adversely affect the the formula HX.qZ, can generally be used as starting process according to the invention, are present. Gase material, and this is very advantageous in the case of, ous proton-acids, for example the hydrogen halides and for example, and the hypo hydrogen pseudohalides, are, in this reaction, intro 65 phosphites. duced continuously, preferably into the solution of the Specifically, the procedure followed in this embodi starting materials in hydrocarbons; exact metering (to ment is to warm the starting materials and the ammo give the stoichiometric amount) is advantageous. Crys nium salts of the formula AX together, whereby the 4,425,278 13 14 resulting ammonia, the amine and the water of reaction, derived from volatile aliphatic alcohols with 1 to 4 C which is formed when using the basic alcoholates of atoms. In particular, the methyl esters and ethyl esters formula I according to the invention, in which X is are used. The possible methods of preparation of esters hydroxyl, are expelled. The water, is advantageously are known from the literature. In the reaction of the removed by azeotropic distillation. Preferably, the non 5 esters of the amphoteric elements, it is preferred to start basic alcoholates are used as starting materials. from the compounds according to the invention, of the Amongst the ammonium salts, those which form formula I, in which X is hydroxyl. Examples of esters volatile amines during the reaction are particularly suit are dimethyl carbonate, diethyl carbonate, methyl or able. A in the formula AX is preferably NH469 or thocarbonate, dimethyl phosphite, dimethyl phosphate, alkylammonium with C1-C4-alkyl groups, especially O dimethyl phosphonite, dimethyl , diethyl with C1-C2-alkyl groups. Particularly preferred groups sulphite, dimethyl sulphate, methyl esters and ethyl are NH46b and monoalkylammonium, with methyl and esters of the sulphonic and sulphinic acids, trimethyl ethyl as alkyl. The reaction temperature is up to 150 C., arsenite, trimethyl arsenate, trimethyl antimonite, tri preferably up to 110° C. The compounds according to methyl antimonate, tetraethyl silicate, tetramethyl sili the invention are isolated by conventional methods. 15 cate, tetramethyl germanate, tetramethyl stannate, tri In a further embodiment, the basic alcoholates and methyl borate, trimethyl aluminate, tetraethyl zircon the compounds according to the invention, of the for ate, tetramethyl titanate, dimethyl molybdate, dimethyl mula I, can be used as starting materials and reacted tungstate, diethyl chromate and trimethyl vanadate. with acid anhydrides, acid halides and acid esters. This To carry out the reaction, the esters are added to the reaction can be carried out with or without solvent and 20 starting materials. Thereafter the mixture is preferably in general takes place exothermically so that additional warmed and the alcohol formed distilled off continu warming of the reaction mixture is not necessary. In ously; this can be accelerated by applying a vacuum. general, the acid ester, acid halide or acid anhydride is The reaction can be carried out with or without solvent, added to the alcoholate either all at once or in portions and depending thereon, the product obtained after com or, in the case of gases, continuously. The desired prod pletion of the reaction consists of the complex com ucts are isolated in accordance with the customary pounds according to the invention or their , methods. The reaction is best carried out at room tem which are purified in accordance with the customary perature, if necessary with cooling. methods. Suitable acid anhydrides are in particular the anhy In this way it is also possible to obtain complex com drides of the organic acids, and the acid-forming oxides pounds of those oxyacids which are derived from cer of the elements C, N, P, S, Se, Cl, Brand I. Examples tain non-metals and from the amphoteric elements and are CO2, N2O5, P2O3, P2O5, SO2, SO3, SeO3, Cl2O7, which tend to form condensed anions. Examples of BrO3, I2O5, N2O3 or I2O7, as well as acetic anhydride, these are P, As, Sb, Si, Ge, Sn, B, Al, Cr, Mo, W, V, Ti, trifluoroacetic anhydride and benzoic anhydride. When and Zr. These elements are known to give, for example, using mixed organic anhydrides, such as the mixed an 35 dimeric, trimeric, tetrameric and polymeric anions of hydride of benzoic acid and acetic acid, mixtures of various structures. Depending on the process of prepa compounds of the formula I, in which X is, for example, ration, these compositions obtained according to the benzoate and acetate, are obtained. invention still contain acid ester bonds in the anions, for Particularly suitable acid halides are the chlorides example if the oxo-acid ester used is hydrolysed with an and bromides. The acid component is preferably de 40 excess of H2O. On complete hydrolysis of the oxo-acid rived from inorganic and organic acids and from or ester used, the corresponding ortho-anions are first ganic oxy-acids of phosphorus and sulphur. Examples formed, from which polyaniors are formed by conden are SC12, S2Cl2, SeCl2, SOC2, SO2Cl2, POCl3, COCl2, sation with removal of the water of reaction, preferably SO2Br2, POBr3, CH3COCl, C6HsCOCl, methylsulpho by means of azeotropic distillation. It is also possible for nyl bromide and phenylphosphonyl chloride. When 45 such condensation reactions already to take place dur using the acid halides, mixtures of compounds of the ing the hydrolysis. Depending on the amount of the formula I, in which X is halide and another anion, of an water of reaction removed, different polyanions can inorganic or organic acid, are in principle obtained. thus be formed from one element, for example, in the Specifically, this embodiment of the process accord case of silicon, anions of the empirical formulae SiO32-, ing to the invention can be carried out by adding the 50 Si2O52- and Si3O72-, or metaphosphate, metaborate, anhydrides or acid halides all at once, or in portions, to metaaluminate, metaarsenate, metatitanate, zirconate the starting materials, and allowing the mixture to react and metaantimonate . Depending on the degree of further in order to complete the reaction. Advanta polycondensation of the anions, the products are vola geously, the process is carried out with a solvent, and at tile to oily liquids or waxy to resinous solids. The latter temperatures of up to 110° C., preferably at room tem 55 may also be used as resins, for example casting resins, perature. The isolation of the compounds according to for the production of mouldings. the invention, of the formula I, is carried out in accor Proton-oxyacids can also be complexed by this pro dance with customary methods. cess to give the compounds I according to the inven In another embodiment of the process according to tion, if the acids are in the form of an ester (variant c) of the invention, the acid esters are used as reactants for 60 the process according to the invention), by hydrolysing introducing the anion X. A great advantage of this this ester with stoichiometric amounts of water in the reaction is that in this way it is possible to introduce the presence of a vicinal diol Z. Depending on the nature of anions X of the oxo-acids, which are unstable in the free the ester, various embodiments of the process are possi form. Particularly suitable compounds used are the ble. esters of the inorganic and organic carboxylic acids, of 65 If aliphatic or aromatic esters are concerned, prefera the inorganic oxyacids of the elements N, P, S, Se and bly esters with lower alkanols which have about 1 to 6, the amphoteric elements, and of the organic oxy-acids preferably 1 to 2, C atoms, since these can easily be of sulphur and phosphorus. The esters are preferably removed by distillation after the reaction, the ester is

i 4,425,278 15 16 mixed with q mols of vicinal diol Z and the correspond -continued ing amount of H2O is added. The mixture is then stirred OH C until a homogeneous product is obtained and the alco / / hol formed has been removed (by distillation, if appro Ca .32 -- CHCOC->ba 47. priate in vacuo). OZ OCCH3 This can then be followed by a condensation reaction with removal of the water formed, as described above, (e) Compound according to the invention, of the formula I, for the preparation of the acids with oligomeric to poly in which X is hydroxyl, -- ester meric anions. The reaction can be carried out without solvents but is preferably carried out with solvents, for O 2Ba(OH)2.4Z + SiOCH3)4-G-Ba2SiO4.82 + 4CH3OH example volatile ethers and especially hydrocarbons. In general, the reaction is carried out at room temperature (f) Ester with vicinal diol -- water and preferably the temperature should not exceed 50 Si(OZ)4 + 4H2O-G>Si(OH)4.4Z C. 15 In another variant, esters of the oxyacids with q mols (g) Ester -- vicinal diol -- water of vicinal diol Z are used as the starting material and hydrolysed, in the presence or absence of solvents, with Stoichiometric amounts of water. In other respects the Ti(OCH3)4 + 3Z + 4H2O-Ge Ti(OH)4.3Z + 4CH3OH procedure described earlier can be followed. The esters (h) Hydroxide -- complex proton-acid according to the are easily obtainable by trans-esterification reactions of, invention for example, alkyl esters of the oxyacids with the vicinal diois Z. The complex compounds according to the invention, of the formula I, in which M is a proton, are for their 25 It remains to be mentioned that the compounds ac part outstandingly suitable for use as intermediates for cording to the invention, of the formula I, which con the preparation of the metal salts and metalloid salts in tain the anion of a volatile acid, can be reacted with accordance with the process of the invention. For this stronger non-volatile anhydrous acids, whereby the purpose, the complex acids of the formula HinX.pY.qZ volatile acid is displaced. In this way, compounds ac are added, in accordance with the embodiments de 30 cording to the invention can be converted into others, scribed earlier, to the basic or non-basic alcoholates and for example: the alcohol formed is removed from the reaction mix ture. Furthermore, it is possible to react metal oxides and metal hydroxides in this way, with removal of the water formed. For this purpose, the reaction tempera 35 ture can be up to 150° C., preferably up to 50-100° C. The complex salt can also be prepared by reacting a Suitable starting components for the complex acids complex with an acid which may or may not be a according to the invention are the same acids as have complex acid. This variant of the process is preferably been listed earlier in connection with the metal salts, carried out in a solvent, such as toluene or heptane. The provided they have a pKa value of at most 11. The water thereby formed can remain as the ligand Y in the inorganic acids, and the strong organic acids (pKa val system or can be removed, for example by azeotropic ues of at least 4) are particularly preferred. Preferably, dehydration. The following may be given as an example these starting acids have pKa values of at most 7, in particular at most 4. 45 To illustrate possible embodiments of the process in which q' is O or q, and q is as defined above. according to the invention, equations are given below The complex compounds according to the invention, of examples. In these, Z represents the vicinal diol of the composition I, are of a crystalline, waxy or mo which is formed by taking up a proton from the alcoho bile to viscous consistency depending on which anions, late ligand Z'O-. 50 cations and vicinal diols Z, they contain, and in what ratio. They exhibit a remarkably high heat stability, which indicates that the complexing compounds of the (a) Alcoholate -- anhydrous proton-acid formula Zare relatively firmly bonded. This conclusion is also supported by the fact that numerous examples are Ba(OZ)2.2Z + H2SO4(concentrated)-G-BaSO4.4Z 55 crystalline compounds which can be recrystallised, without change of their composition, from suitable sol (b) Alcoholate -- ammonium salt vents. The vicinal diol structural element thus evidently exhibits a surprisingly high affinity, which ensures high Mg(OZ)2.2Z -- 2NH4F-G-MgF2.4Z + 2NH3 stability and a broad range of applications. 60 The compounds according to the invention are, in (c) Basic alcoholate -- acid anhydride general, stable to air and to moisture. Thus, during the actual preparation, the compounds are not decomposed OH / by the water formed, which is introduced into the reac Ba. .3Z -- SO2-G-BaSO3.4Z tion mixture as, for example, water of crystallisation of N 65 the inorganic salts. If substantial amounts of water are OZ added, hydrolytic destruction of the compound occurs, (d) Basic alcoholiate -- acid halide especially if a solubilising additive such as tetrahydrofu ran, dioxane or methanol is also present. 4.425,278 17 8 A particularly noteworthy property is the surpris ride, for example with vinyl acetate, and mixtures of ingly good solubility of the compounds according to the these polymers with other copolymers and chlorinated invention in numerous organic solvents, even in nonpo polyolefins, with a predominating proportion of vinyl lar, aprotic solvents, for example hydrocarbons. The chloride in the total mixture. solubility can be varied through the choice, and num 6. Plasticised polyvinyl chloride, including the use of ber, of the vicinal diols Z. Thus, it has been found that butadiene-acrylonitrile copolymers, provided the pro compounds of the formula Z with branched radicals as portion of vinyl chloride in the total mixture predomi a rule give compounds according to the invention nanteS. which are of a liquid consistency and with which the Suitable plasticisers include dibutylphthalate, di-2- solubility is, in contrast to the crystalline compounds, 10 ethylhexyl phthalate, dibutyl sebacate, acetyl tributyl merely a question of miscibility. The compatibility with citrate, acetyl tri-2-ethylhexyl citrate, diphenyl 2-ethyl natural and synthetic plastics is also very good. hexyl phosphate, alkylsulphonic acid esters (C12-C20) Surprisingly, the compounds according to the inven of and of the cresols, and polymeric plasticisers, tion exhibit an excellent antistatic activity even if only for example polyesters of adipic acid with 1,3- low concentrations are added. 15 butanediol and hexanediol, and polyesters of adipic acid By virtue of their properties, the compounds accord with 1,3-propanediol and/or 1,2-propanediol, the free ing to the invention are outstandingly suitable for the OH groups of the polyesters being acetylated or non antistatic treatment of natural and synthetic polymers, acetylated. lubricants and fuels, solutions and solvents based on 7. Polyurethanes and polyureas. hydrocarbons. The highest activity is exhibited by the 20 8. Polyacetals, for example polyoxymethylene and complex proton-acids. polyoxyethylene, as well as those polyoxymethylenes A further subject of the present invention is a mixture which contain ethylene oxide as a comonomer. of materials comprising a natural or synthetic polymer, Examples of suitable natural polymers are vegetable a natural or synthetic lubricant or a fuel, a solution or a and animal fibres which can be converted to fabrics of solvent based on hydrocarbons, and a complex com 25 pound of the formula I. all kinds. Examples include cotton, jute, hemp, sheep's Preferably, the compounds of the formula I are pres wool, camehair or silk. ent in an amount of from 0.001 to 15% by weight, pref Before, after or simultaneously with the compounds erably from 0.01 to 10, especially 0.01 to 5, and more used according to the invention, of the formula I, con particularly 0.01 to 3, 9% by weight. 30 ventional additives used for the processing, and im Examples of suitable thermoplastic polymers are the provement of properties, of these polymers may be following thermoplastics: added to the substrates, examples of such additives 1. Polymers which are derived from singly or doubly being plasticisers, heat stabilisers, antioxidants, dyes, unsaturated hydrocarbons, for example polyolefins, for fillers, especially reinforcing fillers such as sized glass instance polyethylene, which may or may not be cross 35 fibres, lubricants, light stabilisers and flameproofing linked, polypropylene, polyisobutylene, polymethylbut agents. 1-ene, polymethylpent-1-ene, polybut-1-ene, polyiso The substances to be used according to the invention prene, polybutadiene, polystyrene, polyisobutylene, can be incorporated after polymerisation, for example copolymers of the monomers on which the above ho by mixing the substances, with or without further addi mopolymers are based, for example ethylene-propylene 40 tives, into the melt, in accordance with the methods copolymers, propylene-isobutylene copolymers and customary in the art, before or during the shaping pro styrene-butadiene copolymers, as well as terpolymers of cess. The substances can also be incorporated in the ethylene and propylene with a diene, for example hexa form of a master batch, which contains the compounds diene, dicyclopentadiene or ethylidenenorbornene, and in a concentration of, for example, from 2.5 to 25% by mixtures of the abovementioned homopolymers, for 45 weight, into the polymers to be rendered antistatic. example mixtures of polypropylene and polyethylene, The compounds used according to the invention, of polypropylene and polybut-1-ene, or polypropylene the formula I, may also be used for the external antista and polyisobutylene. tic treatment of articles consisting of thermoplastic, 2. Polyamides and copolyamides which are derived thermosetting and natural polymers, especially the from diamines and dicarboxylic acids and/or from 50 treatment of fibres, by applying them, in the form of aminocarboxylic acids or the corresponding lactams, solutions, by spraying or dipping. Examples of suitable for example polyamide 6, polyamide 6/6, polyamide thermosetting plastics are epoxide resins, resins of un 6/10, polyamide 11 and polyamide 12. saturated dicarboxylic acid esters, melamine-formalde 3. Polyesters which are derived from dicarboxylic hyde resins, urea-formaldehyde resins, diallyl phthalate acids and dialcohols and/or from hydroxycarboxylic 55 resins and phenol-formaldehyde resins. Suitable sol acids or the corresponding lactones, for example poly vents for the compounds according to the invention are, ethylene terephthalate, poly-1,4-dimethylol-cyclohex in addition to hydrocarbons, ethers, alcohols, esters, ane terephthalate, polypivolactone and poly-1,4-buty sulphones and acid amides. lene terephthalate. Further substrates suitable for antistatic treatment are 4. Polyacrylonitrile and copolymers of acrylonitrile natural, for example mineral, and synthetic lubricants. with other vinyl compounds, for example acryloni The lubricants in question are familiar to those skilled in . trile/butadiene/styrene, acrylonitrile/styrene and the art and are described, for example, in the "Schmier acrylonitrile/styrene/acrylic ester copolymers. Further mittel Taschenbuch” (“Lubricant Handbook”) (Hithig vinyl compounds which may be used to form copoly Verlag, Heidelberg, 1974). mers are vinyl chloride, vinyl bromide and vinylidene 65 The lubricants may in addition contain other addi chloride. tives which are added in order to improve the proper 5. Unplasticised-including chlorinated-polyvinyl ties, for example anti-corrosion agents, antioxidants, chloride and unplasticised copolymers of vinyl chlo metal passivators, viscosity index improvers, pour point

4,425,278 19 20 depressants, dispersants, detergents and other extreme of crystallisation has been removed quantitatively. Fur pressure/anti-wear additives. ther purification can be carried out as in A. The yields Suitable fuel substrates (engine fuels) based on hydro are virtually quantitative. carbons are also familiar to those skilled in the art. They may also contain further additives, for example anti 5 Process O knock agents. A vicinal diol Z and the metal salt containing water The compounds according to the invention may also of crystallisation are mixed with toluene or n-heptane be used to render solutions or solvents based on hydro and then heated under reflux until the water of crystalli carbons antistatic, examples being pentane, hexane, sation has been removed quantitatively. The solvent is heptane, cyclohexane, petroleum ether fractions, ben 10 Zene, toluene or xylene, in order effectively to prevent then distilled off under reduced pressure. Further purifi a buildup of antistatic charge by friction during flow cation can be carried out as in A. processes, and hence to prevent the explosion hazard Process E associated therewith. The anhydrous metal salt is dissolved in dimethyl A further field of use of the compounds according to 15 the invention is for the surface treatment of glasses. In formamide and the vicinal diol Z is added. The dimeth this, direct application to the surface may suffice, or ylformamide is then distilled off in an oil pump vacuum stronger fixing, for example as a result of chemical reac at 60-70° C. The yields are virtually quantitative. Puri tions, may be effected by a heat after-treatment. Exam fication can be carried out as in A. pies of suitable compounds are titanium, tin, indium and antimony compounds of the formula I and especially Process F1 those which contain fluoride or silicate anions. A metal alcoholate of a vicinal diol Z is prepared The compounds according to the invention are also according to one of processes A to F. An anhydrous suitable for use as heat stabilisers and light stabilisers for proton-acid or water, to prepare the hydroxides, is then PVC, Compounds of the formula I particularly suitable added to the mixture at 20-30°C., with thorough stir for this purpose are those in which M is Ca, Ba, Mg, Sr, 25 ring (cooling being advantageous), and stirring is con Na, Zn, Cd, Sn or Ni and Y is a sulphite, sulphide, tinued for 30 minutes at 20-30' C. borate, phosphite, phosphate or silicate anion, and the The solvent is then distilled off under reduced pres remaining symbols are as defined above. sure. The yields are virtually quantitative. Purification The examples which follow serve to illustrate the can be carried out as in A. present invention. In these, parts are parts by weight Process F2 and percentages are percentages by weight. Sufficient water of reaction is removed from a mix EXAMPLES ture of a vicinal diol Z, a metal hydroxide and toluene as (I) Preparation Examples 1-23 35 the solvent, while stirring under reflux, that a basic The compounds listed in Table 1 have been prepared alcoholate is formed. in accordance with one of processes A-F7 below. The An acid anhydride is then added to the mixture at 25 composition of the compounds according to the inven C. (gaseous acid anhydrides are introduced until satura tion, and some properties, are also given in Table 1. tion is reached). Where other reaction temperatures or solvents have 40 The solvent is then distilled off under reduced pres been used, this is stated in the notes in Table i. Sle. The values of the refractive index or melting point Purification can be carried out as in A. can to a slight degree depend on the starting materials Process F3 used, and also on their purity. 45 An alcoholate of a vicinal diol Z and an ammonium Process A salt are heated under reflux in heptane until the ammo A vicinal diol Z and a metal salt are stirred at nia gas liberated has been expelled completely. The 120°-130' C. until a clear melt is produced (up to 5 solvent is distilled off under reduced pressure. The hours). Thereafter, the material can be taken up in a yields are virtually quantitative. solvent, any turbidity can be removed by filtration, and Purification can be carried out as in A. in the case of crystalline compounds the latter can be recrystallised to purify them. The yields are virtually Process F4 quantitative. The further purification operations can To an alcoholate of a vicinal diol Z, dissolved in result in losses in yield. heptane, is added the stoichiometric amount of water 55 corresponding to the alcoholate. The mixture is stirred Process B at 20° C. until the solution is homogeneous. A vicinal diol Z and a metal salt etherate of diethyl An acid ester is then added, the mixture is heated for ether are warmed to 100-130 C., with stirring, until 30 minutes under reflux and the solvent is distilled off the ether liberated has been quantitatively removed in under reduced pressure. The yields are virtually quanti vacuo. Purification can be carried out as in A. The 60 tative. To form polymeric anions (SiO3- or Si2O52-), yields are virtually quantitative. (This process is partic the water of condensation is azeotropically removed at ularly suitable for ansolvo-acids, for example BF3, the same time. AlCl3, MoCls and SnCl2). Purification can be carried out as in A. Process C Process F5 A vicinal diol Z and a metal salt containing water of A complex metal carboxylate (metal acetate) or metal crystallisation are warmed under reduced pressure to alcoholate of a vicinal diol Z is heated under reflux with 90-100° C., using a rotary evaporator, until the water 4,425,278 21 22 an anhydrous proton-acid in heptane for some time. The pressure. In the case of dilute aqueous acids (for exam solvent together with the carboxylic acid (acetic acid) ple hypophosphorus acid), the water is removed by or alcohol is then distilled off under reduced pressure. azeotropic distillation in the presence of the complexing The last remnants of solvent and carboxylic acid (acetic agent. acid) or alcohol are removed in an oil pump vacuum at 60 C. Process F7 The yields are virtually quantitative. Purification can Complexed Si(OH)4 is prepared by hydrolysing tetra be carried out as in A. methyl silicate in the presence of the vicinal diol Z with The anhydrous proton-acid can also be employed as a a stoichiometric amount of water and distilling off complex according to the invention, of the formula I. O methanol. To prepare complexed hydrated SiO2 (silicic acid) Process F6 sufficient H2O is added to tetramethyl silicate, in the The acid to be complexed is introduced into a mixture presence of the complexing agent, that hydrated SiO2 of vicinal diol Z and solvent (heptane or toluene) at 20 must form (this would correspond to freshly precipi C. and the mixture is stirred until a clear solution is 15 tated silicic acid), and the methanol formed is distilled obtained. The solvent is then removed under reduced off. TABLE 1. Properties Composition of the compound according Prepared (melting to the invention according point, re Sator Number to pro- fractive Example acid Vicina diol Z. G CSS Notes index) BaSO4 ph ph 3 F1 57-60° C. CH3(CH2)12-15CH-CH2 2 CaCl2 ph ph 3 F1 72-77° C. CH3(CH2)12-15CH-CH2 3 MgCl2 ph pH 3 F1 80-90 C. CH3-CH2)12-15CH-CH2 4. hydrate OH OH 2 F. 60-65 C. SiO2 (sintered) CH3-CH2)12-15CH-CH2 5 MgSiO3) gh (pH 2 F4 polymer CH3(CH2)12-15CH-CH2 6 Ni(HPO3 pH (pH 2 F5 60-70 C. CH3(CH2)12-15CH-CH2 7 CaSO3) (pH (pH 2 F2 60-70 C, CH3(CH2)12-15CH-CH2 8 SiOH)4 ph pH 2 F. 60-63 C, CH3(CH2)12-15CH-cH2 9 NigTiO3) ph (pH 3 F4 polymer CH3(CH2)12-15CH-CH2 O Ni(SiO3) ph ph 3 Fs 55-57 C. CH3-(-CH2)12-15CH-CH2 11 Al(OH)3 OH OH 4 F1 Al determination 125-130 C. 6.8% (theoretical CH3-e-CH2)CH-CH2 value 6.98%) 12 Ti(OH)4 ph ph 2 F 41-43 C, CH3-CH2)CH-CH2 13 ZnH2PO32 OH OH 3 Fs smeary test substance 1. CH3--CH2)7CH-CH2 14. MgHPO3) OH OH 3 F5 45-48 C. CH3-CH2)CH-CH2

4,425,278 23 24. TABLE 1-continued Properties Composition of the compound according Prepared (melting to the invention according point, re Salt or Number to pro- fractive Example acid Vicinal diol Z. c CSS Notes index) 5 BaSiO3 pHs (pH (pH 3 F4 polymer n-C4H9-CH-CH2-CH2-CH-CH2 16 Mg(OH)2 C2H5 OH OH 3 Fi viscous solution (turbid) n-C4H9-CH-CH2-CH2-CH-CH2 7 BaBr2 OH OH 7 E wax, m.p.: 48-52 C. CH3-(CH2)12-15CH-CH2

8 NiCl2 OH OH 6 D Wax, m.p.: 65-80 C. CH3-(CH2)12-15CH-CH2 19 MnCl2 OH, OH 4 D Wax, m.p.: 65-75 C. CH3-(CH2)12-15CH-CH2

2O Cu(NO3)2 OH OH 4. C wax, m.p.: 60-65 C. CH3-(CH2)12-15CH-CH2 2. ZnCl2 OH OFH 3 A. semi-solid SS n-C8H17CH-CH2 22 BF OH OH 2. 8 semi-solid SS n-C8H17CH-CH2 23 HBO3 ph (pH 4. F6 W CH3-(CH2)12-15CH-CH2

-continued Charge Example 24 level Half-life (sec) s 40 (mV) (after after after after after (Antistatic Action) 3 days' con- 3 6 10 20 0.5% by weight of the substance according to Exam- Test substance ditioning) ddays days ddays daysd ple 23 and, by way of comparison, 0.5% by weight of OH OH 700 66 100 120 170 the vicinal diol of Example 23, are mixed into polypro CH3(CH2)12-15CH-CH2 pylene powder (Propathene HF 20 containing 0.2% of 45 phenolic antioxidant) and the mixture is extruded in a single-screw extruder at 200-260 C. Test specimens The substantially greater effect of the substance ac are cut from the extruded sheet first obtained, and are cording to the invention compared to the pure vicinal measured after an appropriate conditioning period. diol is clearly recognisable. The antistatic effect is measured by means of a Static 50 EAMPLE 25 Honestometer. This measuring instrument makes it pos sible to determine both the tendency of plastics to ac quire a charge, in terms of the charge level (mV) and OH OH the course of the charge dissipation with time, in the NiHPO3)3CH3-(-CH2-12-15CH-CH2 form of the half-life (which is an indirect measure of the 55 surface resistance). 83 g of the corresponding diol, 25g of nickel aceta Climatic conditions: 24 C., 50-55% relative atmo te.4H2O and 150 ml of heptane are heated under reflux, spheric humidity. with stirring, in an apparatus equipped with a water The results are summarised in the table which fol separator, until the water of crystallisation has been lows. 60 completely expelled. The reaction mixture is cooled to 2O C., 8.2 g of are added, the mixture is stirred for a further 30 minutes at 80°-90° C. and the Charge level Half-life (sec) solvent together with the acetic acid is then distilled off (mV) (after after after after after under reduced pressure. The last remnants of heptane 3 days' con- 3 6 O 20 5 and acetic acid are removed in an oil pump vaccum at Test substance ditioning) days days days days 6O C. according to Example 23 750 5.2 6.1 3.8 3.9 Yield: 97 g of a green wax, melting point 52-56 C.; readily soluble in n-heptane and toluene. 4.425,278 25 26 What is claimed is: and L is hydrogen, which compound in an aqueous 1. A process for the preparation of a complex com solution forms an acid having a pKa value of at most pound of a metal salt or metalloid salt and an ansolvo 15.8 or, if M is a proton, having a pKa value of at most acid or proton acid, of the formula I 11. 5 3. A process according to claim 1, wherein in the M.XmpY.qZ (I) compound of formula LX, L is an ammonium cation, with removal of ammonia or amine. in which M is a m-valent cation of a metal or metalloid, 4. A process according to claim 1, wherein n in the a metal-oxy or metal-dioxy cation or a hydrogen atom, compounds LX is an integer from 1 to 3. X is a n-valent anion of a n-basic inorganic proton-acid 10 5. A process as claimed in claim 3, wherein L in the or of a n-basic organic acid selected from the group of annonium salt of the formula LX is the ammonium the aliphatic and cycloaliphatic carboxylic acids with group NH4 or a monoalkylammonium group with 1 to up to 8 C atoms, which can be substituted by halogen 4C atoms in the alkyl group. and/or hydroxyl groups, the aromatic monocarboxylic, 6. A process according to claim 1, wherein the basic dicarboxylic and tricarboxylic acids, which may be 15 metal alcoholate or metal-oxy alcoholate, and the com substituted by hydroxyl, halogen and/or nitro groups, pound of the formula I, in which X is hydroxyl, is pre the organic oxyacids of phosphorus and sulphur, the pared in situ by reacting the metal alcoholate, metalloid organic thioacids of phosphorus, and the mercaptans, alcoholate or metal-oxy alcoholate obtained from q the inorganic or organic acid having a pKa value of at mols of a vicinal diol of the formula Z and the metal or most 15.8 or, if M is a proton, of at most 11, Y is water 20 or a neutral organic molecule which can be bound coor metalloid with water in the presence of an anhydrous dinatively by the cation or the anion, Z is a complex compound Linx, in which L is hydrogen, or of an forming vicinal diol with at least 6 C atoms, p is 0 or a ammonium salt, of formula LX, in which L is an am value between 0 and 2, q is a value from 1 to 32, m is an monium cation, or is first reacted with water and then integer from 1 to 6 and n is an integer from 1 to 4 and of 25 with an anhydrous compound LX, wherein L is hy mixtures of such compounds, wherein a basic or non drogen or with an ammonium salt of formula LX, basic metal alcoholate or non-basic metalloid alcoholate wherein L is an ammonium cation. or proton-oxyacid ester with q mols of a vicinal diol of 7. A process according to claim 6, wherein the reac the formula Z, or a compound of the formula I, in tion is carried out with a stoichiometric amount of which X is hydroxyl, is reacted in the stoichiometric 30 water or with less than this, down to half the stoichio amount with a compound of the formula LX, in metric amount. which n and X are as defined hereinabove and L is Hor 8. A process according to claim 6, wherein an anhy an ammonium cation, with removal of water, ammonia drous or aqueous proton-acid is used as the starting or amine. material for the preparation of a compound of the for 2. A process according to claim 1, wherein the com 35 mula I, in which M is a hydrogen atom. pound of the formula LX is an anhydrous compound k : k :k

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