Tyzor® TPT

The standard manufacturing method for tetraalkyl titanates, such as TYZOR TPT, or tetra- -butyi titanate, TYZOR TBT [5593-70 ] involves the addition of TiCl to an alcohol. In a series of reversible displacement reactions, the alkoxy substitution products and hydrochloric acid form as follows ... 

TYZOR TPT and the tetraethyl titanate, TYZOR ET [3087-36-3], have also been prepared by direct electrochemical synthesis. The reaction involves anode dissolution of titanium in the presence of the appropriate alcohol and a conductive admixture (3). 

Fluoroall l-SubstitutedTitanates. Tetraliexafluoroisopropyl titanate [21416-30-8] can be prepared by the reaction of TiCl and hexafluoroisopropyl alcohol [920-66-17, in a process similar to that used for TYZOR TPT (7). Alternatively, it can be prepared by the reaction of sodium hexafluoroisopropoxide and TiCl ia excess hexafluoroisopropyl alcohol (8). The fluoroalkyl material is much more volatile than its hydrocarbon counterpart, TYZOR TPT, and is used to deposit titanium on surfaces by chemical vapor-phase deposition (CVD). 

Titanium Complexes of Unsaturated Alcohols. TetraaHyl titanate can be prepared by reaction of TYZOR TPT with aHyl alcohol, followed by removal of the by-product isopropyl alcohol. EbuUioscopic molecular weight determinations support its being the dimeric product, octaaHoxydititanium. A vinyloxy titanate derivative can be formed by reaction of TYZOR TPT with vinyl alcohol formed by enolization of acetaldehyde (11) ... 

Thermolysis is used in the coating of glass and other surfaces with a film of titanium dioxide. When a lower alkoxide, eg, TYZOR TPT, vaporizes in a stream of dry air and is blown onto hot glass botdes above ca 500°C, a thin, transparent protective coating of Ti02 is deposited. 

Chelated titanates are made simply by mixing the chelating agent with TYZOR TPT or another alkoxide. The Hberated alcohol is usually left in the product to maintain the products fluidity. It may, however, be removed by distillation if desirable. Organic titanates are normally shipped in 208-L dmms, totes, cylinders, or tank tmcks. Most titanates are moisture-sensitive and must be handled with care, preferably under dry nitrogen. 

Reaction of 2,4-diorgano-l,3-diols, such as 2-ethylhexane-l,3-diol, with TYZOR TPT in a 2 1 molar ratio gives the solvent soluble titanate complex, TYZOR OGT [5575-43-9] (4) (73). If the reaction is conducted in an inert solvent, such as hexane, and the resultant slurry is treated with an excess of water, an oligomeric hydrolysis product, also solvent-soluble, is obtained (74). 

The reaction products of TYZOR TPT with 2—4 moles of 1,3-diols having two to three alkyl substituents, such as 2,2,4-trimethyl-l,3-pentanediol, gives complexes that could be used as cross-linking agents for hydroxy group containing powdered lacquer resins (76). 

TYZOR LA [65104-06-5] (5), an aqueous solution of the ammonium salt of the titanium bis-lactate complex, is prepared from two equivalents of lactic acid to one of TYZOR TPT. The by-product isopropyl alcohol is removed by distillation and the resultant solution is neutralized with ammonium hydroxide. 

P-Diketone Chelates. P-Diketones, reacting as enols, readily form chelates with titanium alkoxides, Hberating in the process one mole of an alcohol. TYZOR AA [17927-72-9] (6) is the product mixture from TYZOR TPT and two moles of acetylacetone (acac) reacting in the enol form. The isopropyl alcohol is left in the product (87). The dotted bonds of stmcture (6) indicate electron... 

P-Ketoester Chelates. p-Ketoesters react in a fashion similar to the p-diketones. TYZOR DC [27858-32-8] is the hght-yeUow Hquid from TYZOR TPT and two moles of ethyl acetoacetate (eaa) after removal of the isopropyl alcohol. TYZOR BEAT, the bis-ethylacetoacetate [20753-28-0] derived from the tetra- -butyl titanate, and TYZOR IBAY [83877-91-2] the isobutoxy analogue, perform similarly to TYZOR DC. Both, however, have better cold-storage stabiHty. 

The 1-alkoxytitatranes can be synthesized by the reaction of equimolar amounts of tetraalkyl titanates and triethanolamine (105). X-ray crystallographic analysis of the soHd isolated from the reaction of one mole of triethanolamine and one mole of TYZOR TPT confirms the stmcture as a centrosymmetric dimer having a Ti isopropoxy nitrilotriethoxy ratio of 1 1 1. The titanium atoms have achieved a coordination number of six via a rather unsymmetrical titanium—oxygen bridge (106). 

Products from aminoalcohols and TYZOR TPT were obtained by a2eotropiag the isopropyl alcohol with ben2ene (121,122). From trimethylethylenediamine, dimethylethanolamine, and dimethylisopropanolamine with TYZOR TPT, the orange (11), the yellow (12), and the pale-green (13) were obtained, respectively. The lithium salt of the ligand, derived from C H Li, combiaed with (RO)2TiCl ia hexane has also been used (123). 

The ratio of yy -epoxide (shown above) to ant -eipoxide is 10—25 1 with TYZORTPT catalysis, whereas vanadjdacetylacetonate is less selective and y -chloroperoxybenzoic acid gives the reverse 1 25 ratio. It is supposed that TYZOR TPT esterifies the free hydroxyl, then coordinates with the peroxide to favor yy -epoxidation (135). This procedure is related to that for enantioselective epoxidation of other allyflc alcohols in 9—95% enantiomeric excess (135). 

Reaction of TYZOR TPT with polyperfluoroalkylene ethers containing a carbonyl group produces a complex that is an excellent surface-treating agent, imparting improved surface wettabiUty and anticorrosion properties to metal surfaces (144). These complexes can be used by themselves, or as additives to perfluoropolyethers as vacuum pump oils, lubricant oils, or mold release agents. 

Other Complexes. The reaction of TYZOR TPT with two equivalents of a semicarba2one produces complex (17), the stmcture of which has been assigned the trans-configuration (148) ... 

Addition of lithium or sodium alkoxide to TYZOR TPT gives a double alkoxide derivative, MTi2(OR), the stmcture of which has been proposed (157) as follows, where M = Na or Li. 

MetlylEsters. The addition product of two moles of TYZOR TPT and one mole of ethylene glycol, GLY—TI, can be used as a transesterification catalyst for the preparation of methyl esters. The low solubility of tetramethyl titanate has prevented the use of them as a catalyst for methyl ester preparation (488). 

Epoxy cross-linking is cataly2ed by TYZOR TPT and TYZOR TBT, alone or with piperidine, and by TYZOR TE. The soHd condensation product from 3 TPT 4 TEA (triethanolamine) has also been appHed to epoxy curing (490). Titanate curing is accelerated by selected phenoHc ethers and esters at 150°C the mixtures have along pot life at 50°C (491) (see Epoxyresins). 

Mixtures of a titanium complex of saturated diols, such as TYZOR OGT, and a titanium acylate, such as bis- -butyl-bis-caproic acid titanate, do not have a yellowing or discoloring effect on white inks used to print polyolefin surfaces (506). The complexes formed by the reaction of one or two moles of diethyl citrate with TYZOR TPT have an insignificant color on their own and do not generate color with phenol-based antioxidants (507). The complexes formed by the addition of a mixture of mono- and dialkyl phosphate esters to TYZOR TBT are also low color-generating, adhesion-promoting additives for use in printing polyolefin films (508). 

Enhanced Oil Recovery. A hydrocarbon solution of TYZOR TPT, TYZOR TBT, or TYZOR TOT can be pumped into the porous zones of an oil-bearing formation upon contact with water, an amorphous, gelatinous plug is formed, which allows water to be diverted to less porous... 

Reactions with Isocyanates, TYZOR TPT catalyzes the trimerization of isocyanates and polyisocyanates to isocyanurates and polyisocyanurates (38). Titanium alkoxides of the type Cl3TiOR initiate the living polymerization of isocyanates. Polyisocyanates possessing controlled molecular weights and narrow polydispersities can be synthesized using these catalysts (39) ... 

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