Patent GB-733224-A (GB)
Title: Titanium organic compounds
IPC: C08F246/00
Filed: 1951-11-14
Abstract: Polymeric alkoxy titanium acylates wherein the alkoxy groups are derived from saturated aliphatic alcohols and the acylate groups from aliphatic mono- or di-carboxylic acids are prepared by the following methods.  They may be produced from the monomeric alkoxy titanium acylates, derived from aliphatic mono-carboxylic acids, by means of partial hydrolysis; when the acyl groups are unsaturated polymerizable groups, the monomers may be polymerized and, if desired, partially hydrolysed to yield polymers having properties of the thermoplastic resins as well as those of the condensation polymers.  The polymeric alkoxy titanium acylates wherein the acylate groups are derived from the dibasic acids, are prepared by reacting a tetraalkyl titanate with the dibasic acid, there being partial displacement of alkoxy groups in the form of the corresponding alcohols.  The products are useful in paint vehicles as plasticizers or bodying agents (see Group III) and in dielectrics.  In examples (1) poly(dibutoxy titanium mono-maleate) is prepared by heating tetra-butyl titanate with maleic acid and distilling off the displaced butanol; the polymer of M.W. 2230 is copolymerized with styrene using benzoyl peroxide as catalyst; (2) tributoxy titanium mono-methacrylate is copolymerized with methyl methacrylate; (3) dibutoxy titanium di-methacrylate is copolymerized with styrene or with butadiene in toluene using benzoyl peroxide as catalyst; (4) dipentoxy titanium dicrotonate is partially hydrolysed in ethereal solution by addition thereto of a small amount of water, the product being a solid mouldable resin.  The invention also includes an example wherein diundecoxy titanium dipropionate is added to a solution of cellulose acetate in ethyl lactate, the product being capable of forming clear, hard fibres.  The production of the monomers is described (see Group IV (b)).  Specification 479,470 is referred to.ALSO:The invention comprises alkoxy titanium acylates in which the alkoxy portion of the molecule is derived from a saturated aliphatic alcohol and the acylate portion from an aliphatic monocarboxylic acid.  Preferably, the alkoxy group is unsubstituted and contains 2-20 carbon atoms and the acylate group 3-36 carbon atoms; desirably, there are present 1-3 alkoxy groups and 1-3 carboxyl groups per titanium atom, the sum of both groups being substantially 4 per titanium atom.  The compounds may be prepared by reacting a tetra-alkyl titanate with a carboxylic acid, the displaced alcohol being removed by distillation under reduced pressure.  When the acid would boil at a lower temperature than the alcohol to be displaced, then the titanate of an alcohol boiling at a lower temperature than the acid is heated with the appropriate amount of the higher boiling alcohol and the displaced alcohol distilled off whereupon the resulting titanate containing mixed alkoxy groups is heated with the acid and the displaced remaining lower boiling alcohol distilled off.  The tetra-alkyl titanates may be prepared by reacting titanium tetrachloride with a monohydric alcohol, for example, as described in Specification 479,470 or in the case of higher alcohols by ester-interchange of the latter with the titanate of a lower alcohol.  The alkoxy titanium acylates may be used as plasticizers or bodying agents for paints, or used in dielectrics, and they may be polymerized or hydrolysed to titanium dioxide or titanium complexes (see Groups III and IV (a)).  In examples (1) linoleic acid is heated with tetrabutyl titanate under reduced pressure yielding, according to the proportions used, tributoxy titanium monolinoleate or monobutoxy titanium trilinoleate; (2) methacrylic acid is reacted as in (1) yielding tributoxy titanium monomethacrylate or dibutoxy titanium dimethacrylate; (3) lauric acid is reacted as in (1) yielding monobutoxy titanium trilaurate; (4) undecyl alcohol is reacted with tetrabutyl titanate to yield diundecoxy dibutoxy titanate which is reacted with propionic acid to give diundecoxy titanium dipropionate; (5) tetra-amyl titanate is reacted with crotonic acid as in (1) yielding dipentoxy titanium dicrotonate.ALSO:Monomeric and polymeric alkoxy titanium acylates wherein the acylate groups are derived from aliphatic mono-carboxylic acids and polymeric alkoxy titanium acylates wherein the acylate groups are derived from aliphatic dicarboxylic acids (see Groups IV (a) and IV (b)) may be used as plasticizers or bodying agents for paint vehicles.  The compounds may also be hydrolysed to titanium dioxide or complexes.  According to examples, hard films may be obtained from mixtures of (1) tributoxy titanium monolinoleate and a cobalt-lead drier; (2) monobutoxy titanium trilinoleate, bodied linseed oil, mineral spirits and a cobalt-lead drier; (3) monobutoxy titanium trilaurate, castor oil and mineral spirits. Specification 479,470, [Group IV], is referred to.