Patent GB-734114-A (GB)
Title: Process of producing reaction products of titanic acid esters with high molecular weight compounds containing hydroxyl groups
IPC: C07F7/00
Filed: 1951-07-25
Abstract: A stable complex titanic acid ester derived from a hydroxy ketone, hydroxy aldehyde, or keto-enolic compound and ortho-titanic acid or a halide or ester thereof, is caused to react and combine with a hydroxyl-containing compound having a molecular weight of at least 500.  The reaction results in the formation of cross-linked high molecular weight compounds which are insoluble in common organic solvents.  The hydroxyl-containing compound of molecular weight of at least 500 may be a cellulose acetate, nitrate, or other cellulose derivative; a polyester, e.g. a polymerized ester of adipic acid and trimethylol propane; a polyglucose ethyl ether or other sugar derivative; or a formaldehyde condensation product such as a polyvinyl formal.  The complex titanic acid ester may be obtained from titanic acid, or a halide or ester thereof, and diacetone alcohol, beta-ketobutanol, beta-hydroxy-butyr-aldehyde, acetoacetic ester, diacetyl, acetyl acetone or a polymeric vinyl-methyl ketone, and is probably a chelate type of compound. It may be obtained by an ester exchange process, e.g. from tetraethyl titanate and diacetone alcohol, and such process may take place at room temperature or elevated temperature.  The complex titanic acid ester may be added to a solution of the high molecular weight compound containing hydroxyl groups and the reaction may be completed after evaporation of the solvent, if necessary with heating.  The solutions or compositions may be formed into filaments, films or other articles which are rendered insoluble after the final shaping.  In an example, a stable titanium ester, obtained from tetrabutyl titanate and diacetone alcohol, is mixed with a solution of cellulose nitrate in butanol, butyl acetate and ethyl acetate.  The solution is cast in a thin layer and the solvent is evaporated, leaving a clear film which is insoluble in organic solvents.  In another example, a complex titanic acid ester, obtained from tetrapropyl titanate and acetyl acetone, is mixed with a solution in ethyl acetate of a viscous polyester, containing 10 per cent of hydroxyl groups and obtained by thermal esterification of adipic acid with trimethylol propane. The solution is sprayed into a metal sheet, and after evaporation of the solvent, if desired at elevated temperature, a hard coating which is insoluble in organic solvents is obtained.  In another example, polyvinyl formal is dissolved in a mixture of ethyl acetate and methanol.  A mixture of titanium tetrabutylate and aceto-acetic ester is added, and the solution is then formed into a film which, on drying, becomes insoluble in organic solvents. In another example, a polyglucose ethyl ether is dissolved in benzene and mixed with a reaction product of titanium tetrabutylate with acetoacetic ester.  A clear film insoluble in benzene is obtained.  Specification 734,113 is referred to.ALSO:A stable complex titanic acid ester is prepared from a hydroxy ketone, hydroxy aldehyde, or keto-enolic compound and ortho-titanic acid or a halide or ester thereof.  It may be obtained, as described in Specification 734,113, by reacting titanic acid or a halide or ester thereof, with diacetone alcohol, b -ketobutanol, b -hydroxybutyraldehyde, acetoacetic ester, diacetyl or acetyl acetone, and is probably a chelate type of compound.  It may also be obtained by ester exchange, e.g. from tetraethyl titanate and diacetone alcohol, and such reaction may take place at room temperature or elevated temperature.  In an example, a stable titanic ester is obtained by mixing tetrapropyl titanate with acetyl acetone.  After the evolution of heat has ceased, a complex orange-yellow, liquid product is obtained.  In another example, the complex ester is obtained by mixing tetrabutyl titanate and aceto-acetic ester.  The complex esters are reacted with high molecular weight hydroxy compounds to form resinous materials (see Group IV (a)).