Patent GB-786388-A (GB)
Title: Titanium and zirconium organic compounds
IPC: C07F7/00
Filed: 1955-11-02
Abstract: The invention comprises esters of orthotitanic or orthozirconic acid and an aminoalcohol of the general formula <FORM:0786388/IV (b)/1> wherein R represents an ethylene or alkyl-substituted ethylene radical, and when R11 represents a divalent alkylene radical containing from 1 to 3 carbon atoms the R1 radicals are hydrogen or b -hydroxyalkyl or b -aminoalkyl radicals and R111 is a b -hydroxyalkyl or b -aminoalkyl radical, and when R11 represents a divalent alkylene amine radical of the formula -CH2CH2NXCH2CH2-, R1, R111 and X are hydrogen or b -hydroxyalkyl radicals, and the preparation thereof by reacting an alkyl orthotitanate, orthotitanic acid, an alkyl orthozirconate or orthozirconic acid with an alcohol of the above general formula.  The preferred esters contain more than one aminoalcoholic hydroxyl radical for each titanium or zirconium atom, and for each five carbon atoms at least one hydroxy or amino radical, the hydroxy or amino radical being present as a substituent in an R1 or R11 radical in the above formula.  At least one of the R1 or R11 radicals may be a b -hydroxyethyl or b -aminoethyl radical.  The aminoalcohol of the above general formula may be N,N,N1,N1 - tetrakis - (2 - hydroxypropyl) ethylene diamine, N,N1,N11 - tri - (b  - hydroxy - ethyl) diethylene triamine, N,N1 - di - (b  - hydroxyethyl) diethylene triamine or N-(b -hydroxyethyl) diethylene triamine. The alkyl titanate or zirconate used in the above process may be a condensed alkyl titanate containing a Ti-O-Ti linkage or a condensed alkyl zirconate containing a Zr-O-Zr linkage, e.g. as obtained by the partial hydrolysis of monomeric alkyl orthotitanates and orthozirconates.  The above process involving an ester exchange between the aminoalcohol and an alkyl orthotitanate or orthozirconate may be carried out with an ortho ester of orthotitanic or orthozirconic acid derived from a low boiling alcohol, e.g. butyl alcohol, preferably by mixing the reactants together.  The reaction appears to involve the substitution of titanium or zirconium for hydrogen in the above formula and, in some cases a similar substitution of titanium or zirconium for hydrogen atoms in other free hydroxyl radicals contained in the X, R1, R11 and R111 radicals. The composition of the ester products using alkyl orthotitanates or zirconates as reactants may be varied by the quantities of reactants used.  Normal orthotitanates and zirconates are obtained if the quantity of aminoalcohol used is sufficient to provide four alcoholic hydroxyl radicals for each molecule of alkyl orthotitanate or zirconate used.  If less than this quantity is used the products will be mixed alkyl aminoalkyl orthotitanates or orthozirconates.  The orthotitanic or orthozirconic acid used in the above process may be prepared, for example, by the hydrolysis at room temperature of titanium or zirconium salt solutions.  The resulting orthotitanic or orthozirconic acid pulp is then mixed with an aminoalcohol of the above formula and heated until dissolved.  The esters produced by this method normally have slightly condensed structures containing Ti-O-Ti or Zr-O-Zr linkages.  Esters containing condensed structures may also be obtained by reacting alkyl orthotitanates or zirconates with aminoalcohols of the above formula in the presence of water.  In the examples, esters are prepared by reacting: (1) N,N,N1,N1 - tetrakis - (2 - hydroxypropyl) ethylene diamine with tetraisopropyl orthotitanate in a mol. ratio of 1 : 2, 1 : 1 and 2 : 1; (2) N,N,N1,N1 - tetrakis - (2 - hydroxypropyl) ethylene diamine with an orthozirconic acid produced by hydrolysing zirconium tetrachloride; (3) N-(b -hydroxyethyl) diethylene triamine, N,N1,N11-tri-(b -hydroxyethyl) di-ethylene triamine or a mixture of isomeric di-(b -hydroxyethyl) diethylene triamines with tetraisopropyl orthotitanate.  Starting compounds.  N - (b  - hydroxyethyl) diethylenetriamine is prepared by the reaction of one mol. of ethylene dioxide with one mol. of diethylene triamine; and a mixture of isomeric di-(b -hydroxyethyl) diethylene triamines is prepared by the reaction of two mols. of ethylene dioxide with one mol. of diethylene triamine.ALSO:Animal fibres, e.g. wool, are treated with solutions of esters of orthotitanic or orthozirconic acid derived from aminoalcohols of the general formula: <FORM:0786388/IV (b)/1> wherein R represents an ethylene or alkylsubstituted ethylene radical, and when R11 represents a divalent alkylene radical containing from 1 to 3 carbon atoms, the R1 radicals are b -hydroxyalkyl or b -aminoalkyl radicals or hydrogen and the R111 radical is a b -hydroxyalkyl or b -aminoalkyl radical, and when R11 represents a divalent alkylene amine radical of the formula: -CH2-CH2-NX-CH2-CH2-R1, R111 and X are b -hydroxyalkyl radicals or hydrogen.  The esters may be monomeric esters having at least one of the ester radicals derived from an aminoalcohol of the above formula, or polymeric esters having condensed structures with Ti-O-Ti or Zr-O-Zr linkages, or polymeric esters formed by reason of the poly-functionality of both the titanium or zirconium and aminoalcohols of the above formula.  Specifications 654,450, [Group IV (b)], and 686,068 are referred to.ALSO:Paints and varnishes contain, as additives to improve the durability and hardness of the films produced therefrom, esters of orthotitanic or orthozirconic acid derived from aminoalcohols of the general formula <FORM:0786388/III/1> wherein R represents an ethylene or alkyl substituted ethylene radical, and when R11 represents a divalent alkylene radical containing from 1 to 3 carbon atoms, the R1 radicals are b -hydroxyalkyl or b -aminoalkyl radicals or hydrogen and the R111 radical is a b -hydroxyalkyl or b -aminoalkyl radical, and when R11 represents a divalent alkylene amine radical of the formula -CH2-CH2-NX-CH2-CH2-, R1, R111 and X are b -hydroxyalkyl radicals or hydrogen.  The esters may be monomeric esters having at least one of the ester radicals derived from an aminoalcohol of the above formula, polymeric esters having condensed structures with Ti-O-Ti or Zr-O-Zr linkages, or polymeric esters formed by reason of the polyfunctionality of both the titanium or zirconium and aminoalcohols of the above general formula.  The above titanium and zirconium esters and polyesters, which are soluble in water and common organic solvents, are used as dispersing agents. In an example an ester prepared from one mol. of N,N,N1,N1-tetrakis-(2-hydroxypropyl) ethylene diamine and two mols. of isopropyl orthotitanate is dissolved in water and is used as a dispersing agent for an acidic aqueous slurry of titanium dioxide.ALSO:The invention comprises esters including polymeric esters of orthotitanic or orthozirconic acid and aminoalcohols of the general formula <FORM:0786388/IV (a)/1> wherein R represents an ethylene or alkyl-substituted ethylene radical, and when R11 represents a divalent alkylene radical containing from 1 to 3 carbon atoms, the R1 radicals are hydrogen or b -hydroxyalkyl or b -aminoalkyl radicals and R111 is a b -hydroxyalkyl or b -aminoalkyl radical, and when R11 represents a divalent alkylene amine radical of the formula -CH2CH2NXCH2CH2-, R1, R111 and X are hydrogen or b -hydroxyalkyl radicals, and the preparation thereof by reacting an alkyl orthotitanate, orthotitanic acid, an alkyl orthozirconate or orthozirconic acid with an alcohol of the above general formula.  The preferred esters contain more than one aminoalcoholic hydroxy radical for each titanium or zirconium atom, and for each 5 carbon atoms at least one hydroxy or amino radical, the hydroxy or amino radical being present as a substituent in an R1 or R11 radical in the above formula.  At least one of the R1 or R11 radicals may be a b -hydroxyethyl or b -aminoethyl radical. The aminoalcohol of the above general formula may be N,N,N1,N1 - tetrakis - (2 - hydroxypropyl) ethylene diamine, N,N1,N11 - tri - (b - hydroxy - ethyl) diethylene triamine, N,N1 - di - (b  - hydroxyethyl) diethylene triamine or N-(b -hydroxyethyl) diethylene triamine. The alkyl titanate or zirconate used in the above process may be a condensed alkyl titanate containing a Ti-O-Ti linkage or a condensed alkyl zirconate containing a Zr-O-Zr linkage, e.g. as obtained by the partial hydrolysis of monomeric alkyl orthotitanates and orthozirconates.  The above process involving an ester exchange between the aminoalcohol and an alkyl orthotitanate or orthozirconate may be carried out with an ortho ester of orthotitanic or orthozirconic acid derived from a low boiling alcohol, e.g. butyl alcohol, preferably by mixing the reactants together.  The reaction appears to involve the substitution of titanium or zirconium for hydrogen in the above formula and, in some cases, a similar substitution of titanium or zirconium for hydrogen atoms in other free hydroxy radicals contained in the X, R1, R11 and R111 radicals. Thus in the case of an aminoalcohol of the above formula containing more than hydroxy radical, polymeric products are obtainable in which different titanium or zirconium atoms are linked to hydroxy radicals in one mol. of aminoalcohol.  The orthotitanic or orthozirconic acid used in the above process may be prepared, for example, by the hydrolysis at room temperature of titanium or zirconium salt solutions.  The resulting orthotitanic or orthozirconic acid pulp is then mixed with an aminoalcohol of the above formula and heated until dissolved.  The esters produced by this method normally have slightly condensed structures containing Ti-O-Ti or Zr-O-Zr linkages.  Esters containing condensed structures may also be obtained by reacting alkyl orthostitanates or zirconates with aminoalcohols of the above general formula in the presence of water.  The esters are soluble in water and in common organic solvents.  In the examples: (1) N,N, N1,N1 - tetrakis - (2 - hydro