Patent GB-734113-A (GB)
Title: Stable complex titanic acid esters and their production
IPC: C07F7/00
Filed: 1951-07-19
Abstract: Stable complex titanic acid esters are obtained by reacting aliphatic hydroxy ketones, aliphatic hydroxy aldehydes, or aliphatic keto compounds which react readily in their enolic form, e.g. a ketonic acid or its ester or a diketone, with a tetra-alkyl or tetrachloroalkyl ester of ortho-titanic acid (see Group IV (b)).  The titanic acid ester may be reacted with for example diacetone alcohol, beta-hydroxy butyraldehyde, acetoacetic ester, diacetyl, acetyl acetone or polymeric vinyl methyl ketone.  The products are stated to have utility in the chemistry of high molecular weight organic compounds since they do not react p  instantaneously by cross-linking when incorporated in solutions in volatile solvents of high molecular weight compounds containing hydroxyl groups, e.g. nitrocellulose, or high molecular weight condensation products derived from polyhydroxy alcohols and poly-basic acids, but cross-linking may be effected later, e.g. by slightly heating the product and evaporating the solvent.ALSO:Stable complex titanic acid esters are obtained by reacting aliphatic hydroxy ketones, aliphatic hydroxy aldehydes or aliphatic keto compounds which react readily in their enolic form, e.g. a ketonic acid or its ester or a diketone, with a tetra-alkyl or tetra-chloroalkyl ester of orthotitanic acid.  The titanic acid ester may be reacted with, for example, diacetone alcohol, beta-hydroxy-butyraldehyde, acetoacetic ester, diacetyl, acetyl acetone or polymeric vinyl methyl ketone.  The complex esters are preferably obtained by the interchange of ester radicals of titanic acid esters containing up to 8 carbon atoms in the aliphatic residue, e.g. from titanic acid tetraethyl ester and diacetone alcohol, or they can be obtained by reacting a titanic acid tetra-alkyl ester and a diketone such as one having the formula: CH3.CO.R1.CO.CH3 in which R1 is an alkylene radical such as -CH2- or -CH4- In examples: (1) titanic acid tetrabutyl ester is heated under reflux with diacetone alcohol to yield a viscous yellow-orange coloured product which is only gradually affected by water and does not react with solutions of nitrocellulose with instantaneous cross-linking; (2) acetoacetic acid ethyl ester is added to titanic acid tetrabutyl ester and the ester product is isolated by distilling off the ethanol formed as by-product or the solution of the ester in the ethanol may be used as such.  On mixing with acetyl cellulose solutions cross-linking only occurs after hours or days or on evaporating the solvent; (3) titanic acid tetrabetachloroethyl ester is mixed with acetyl acetone to yield a liquid, complex, orange-yellow derivative which is comparatively stable to hydrolysis and has properties similar to the products of (1) and (2).  The ester products of the invention do not react instantaneously by cross-linking when incorporated in solutions in volatile solvents of high molecular weight compounds containing hydroxyl groups, e.g. nitrocellulose or high molecular weight condensation products derived from polyhydroxy alcohols and polybasic acids, but cross-linking may be effected later, e.g. by slightly heating the product and evaporating the solvent.