Patent GB-755728-A (GB)
Title: Improvements in or relating to organic titanium and zirconium compounds
IPC: C07F7/00
Filed: 1953-06-04
Abstract: The invention comprises esters including polymeric esters (useful as modifiers for resin films and alkyd varnishes) of orthotitanic or orthozirconic acid and an aminoalcohol of the general formula <FORM:0755728/IV(a)/1> wherein R represents an ethylene or alkyl substituted ethylene radical, R1 represents a b -hydroxyalkyl or b -aminoalkyl radical, and R11 represents hydrogen, an alkyl hydrocarbon carbon radical containing from 1 to 3 carbon atoms or a b -hydroxyalkyl or b -aminoalkyl radical, and the preparation thereof by reacting an alkyl orthotitanate or zirconate or orthotitanic or orthozirconic acid and an aminoalcohol of the above general formula. The preferred esters are those in which there are at least three aminoalcoholic radicals for each titanium atom, and for each 3 carbon atoms at least one hydroxyl or amino radical, the hydroxyl or amino radical being present as a substituent in an R1 or R11 radical of the above formula.  In addition, it is preferable for each of the R, R1 and R11 radicals to contain about 3 carbon atoms, and in the case of a mixed alkyl-aminoalkyl titanate in which the aminoalkyl radical is derived from the above aminoalcohol, the free alkyl radical preferably contains not more than about three carbon atoms.  The radical R1 may be a b -hydroxyethyl or b -aminoethyl radical, and R11 may be hydrogen or an alkyl hydrocarbon group containing from 1 to 3 carbon atoms or a b -hydroxyethyl or b -aminoethyl radical.  The aminoalcohol may be diethanolamine, triethanolamine, methyl-diethanolamine or b -aminoethyl-ethanolamine.  The alkyl titanate or zirconate used in the above process can be a condensed titanate or zirconate containing Ti-O-Ti or Zr-O-Zr linkages, e.g. as obtained by the partial hydrolysis of monomeric alkyl orthotitanates or zirconates.  The reaction with the alkyl orthotitanate or zirconate is preferably carried out by mixing with the aminoalcohol and involves substitution of titanium or zirconium for hydrogen in the above general formula.  In some cases, a substitution of titanium or zirconium for hydrogen in the terminal hydroxy groups of the radicals R1 and R11 takes place. Thus in the case of an aminoalcohol containing more than one hydroxyl group, polymeric products are obtainable in which different titanium or zirconium atoms are linked to the hydroxy groups in one molecule of aminoalcohol.  The orthotitanic or orthozirconic acid used in the above process may be prepared, for example, by the hydrolysis of titanium or zirconium salts, and after reaction with the aminoalcohol form esters having the condensed structures referred to above.  Esters having condensed structures are also obtainable by reacting an alkyl orthotitanate or zirconate with the amonoalcohol in the presence of water.  In the example (1) a methyl diethanolamine orthotitanate soluble in water, methanol, butanol or toluene is prepared by reacting methyldiethanolamine and tetrabutyl orthotitanate to replace 94 per cent of the butoxy groups of the orthotitanate; (2) a similar orthotitanate soluble in water or benzene is prepared in which 2 of the butoxy groups of the tetraburyl orthotitanate are reacted; (3) a titanate soluble in water, ethanol, butanol or benzene is obtained by reacting an orthotitanic acid and tri-isopropanolamine; (4) a titanate soluble in water, benzene, ethanol, butanol or acetone is obtained by reacting b -aminoethylethanolamine and tetrabutyl orthotitanate as in (1); (5) a zirconate soluble in water, ethanol, butanol or benzene is obtained by reacing an orthozirconic acid and triethanolamine.ALSO:The invention comprises esters of orthotitanic or orthozirconic acid and an aminoalcohol of the general formula <FORM:0755728/IV(a)/1> wherein R represents an ethylene or alkyl substituted ethylene radical, R1 represents a b -hydroxyalkyl or b -aminoalkyl radical, and R11 represents hydrogen, an alkyl hydrocarbon radical containing from 1 to 3 carbon atoms or a b -hydroxyalkyl or b -aminoalkyl radical, and the preparation thereof by reacting an alkyl orthotitanate, orthotitanic acid, an alkyl orthozirconate or orthozirconic acid and an aminoalcohol of the above general formula.  The preferred esters are those in which there are at least three aminoalcoholic radicals for each titanium atom, and for each 3 carbon atoms at least one hydroxyl or amino radical, the hydroxyl or amino radical being present as a substituent in an R1 or R11 radical of the above formula.  In addition, it is preferable for each of the R, R1 and R11 radicals to contain about 3 carbon atoms, and in the case of a mixed alkyl-aminoalkyl titanate in which the aminoalkyl radical is derived from the above aminoalcohol, the free alkyl radical preferably contains not more than about 3 carbon atoms. The radical R1 may be a b -hydroxyethyl or b -aminoethyl radical, and R11 may be hydrogen or an alkyl hydrocarbon group containing from 1 to 3 carbon atoms or a b -hydroxyethyl or b -aminoethyl radical.  The aminoalcohol may be diethanolamine, triethanolamine, methyl-diethanolamine or b -aminoethyl-ethanolamine.  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 or zirconates. The reaction with the alkyl orthotitanate or zirconate may be carried out by mixing with the aminoalcohol and involves substitution of titanium or zirconium for hydrogen in the above general formula.  In some cases a similar substitution of titanium or zirconium for the hydrogen in the terminal hydroxy groups of the radicals R1 and R11 takes place.  The composition of the titanate or zirconate product using an alkyl titanate or zirconate reactant may be varied by the quantities of the reactants employed.  Normal orthotitanates or orthozirconates are produced when the quantity of aminoalcohol is sufficient to provide four alcoholic hydroxyl groups for each molecule of orthotitanate or orthozirconate reactant used, while alkylaminoalkyl orthotitanates or zirconates are produced if the quantity of aminoalcohol is reduced.  The orthotitanic acid or orthozirconic acid used in the above process may be prepared, for example, by the hydrolysis of titanium or zirconium salts, the resulting orthoacid is isolated, mixed with the aminoalcohol and heated until it dissolves.  The esters produced by this method normally have slightly condensed structures containing Ti-O-Ti or Zr-O-Zr linkages.  Esters containing the condensed structure may also be obtained by reacting alkyl orthotitanates or zirconates with the aminoalcohols in the presence of water.  In the examples esters are prepared by reacting methyldiethanolamine and tetrabutyl orthotitanate to replace all the butoxy radicals by aminoalkoxy radicals derived from methyldiethanolamine and to replace two of the butoxy radicals by aminoalkoxy radicals derived from methyldiethanolamine; tri-isopropanolamine and orthotitanic acid are reacted to form a polymeric ester in which the aminoalkoxy radicals are derived from tri-isopropanolamine; b  - aminoethylethanolamine and tetrabutyl orthotitanate are reacted to replace all the butoxy radicals by aminoalkoxy radicals derived from b -aminoethylethanolamine; and triethanolamine and orthozirconic acid are reacted to form an aminoalkyl zirconate in which the aminoalkoxy radicals are derived from triethanolamine. The product obtained by reacting 1 mol. of tetrabutyl titanate and 3 mols. of b -aminoethylethanolamine is also referred to.ALSO:Animal and vegetable fibres are treated with solutions of esters of orthotitanic or orthozirconic acid derived from an aminoalcohol of the formula HORN(R1)R11, wherein R represents an ethylene or alkylsubstituted ethylene radical, R1 represents a b -hydroxyalkyl or b -aminoalkyl radical, and R11 represents hydrogen or a hydrocarbon radical containing from 1 to 3 carbon atoms or a b -hydroxyalkyl or b -aminoalkyl radical.  The ester may be a monomeric ester having at least one of the ester radicals derived from an aminoalcohol of the above formula, a polymeric ester having a condensed structure with Ti-O-Ti or Zr-O-Zr linkages, or a polymeric ester in which titanium or zirconium replaces hydrogen in the hydroxy radicals which may be attached to the R1 and R11 radicals.ALSO:Drying oils are modified by the addition of an ester of orthotitanic or orthozirconic acid derived from an aminoalcohol of the formula HORN(R1)R11, wherein R represents an ethylene or alkyl-substituted ethylene radical, R1 represents a b -hydroxy-alkyl or b -aminoalkyl radical, and R11 represents hydrogen or hydrocarbon radical containing from 1 to 3 carbon atoms or a b -hydroxyalkyl or b -aminoalkyl radical.  The ester may be a monomeric ester having at least one of the ester radicals derived from an aminoalcohol of the above formula, a polymeric ester having a condensed structure with Ti-O-Ti or Zr-O-Zr linkages, or a polymeric ester in which titanium or zirconium replaces hydrogen in the hydroxy radicals which may be attached to the R1 and R11 radicals.  The esters may be used for quick-drying conjugated oils such as tung oil, oitica oil or dehydrated castor oil.  The esters are also useful for gelling vegetable oils e.g., linseed oil.