Titanates preparation

The overall yield is essentially 100 by any of the preparation methods, but the physical characteristics of the ion exchangers are dependent on preparation conditions. For example, sodium titanate prepared by Eqs. la and lb with hydrolysis in one liter of water per mole of Ti(OC3H7)4 has a bulk density of 0.U5 g/cm3 and a specific surface area of lO-UO m /g. The same material prepared by Eqs. la and lb and hydrolyzed in a solution of 100 ml of water in 1000 ml of acetone for each mole of Ti(OC2H7)4 has a bulk density of 0.35 g/cm3 and a specific surface area of 200-UOO m /g. In all cases, the materials consist of agglomerates of 50-100 A particles with the degree of aggregation of the particles determining both the bulk density and surface area. 

Electroceramics. Titanates like barium, strontium, calcium and lead titanate prepared from finely divided, high-purity TiOz hydrolysates are used in capacitors, PTC-resistors and piezoelectric materials. The specifications of the Ti02 starting materials with respect to purity, reactivity, and sintering properties are expected to become more stringent. The market is estimated to be several thousand of tonnes a year as TiOz. A strong annual growth is expected. 

An interesting way of aluminium titanate preparing was proposed in [61,62]. A mixture of metallic aluminium with Ti02-H20 hydrogel was... 

Table 5.10 Properties of nanocrystalline powders of barium titanate prepared in modes with different heating rates...

Photoluminescence studies on rare earth titanates prepared by self-propagating high temperature synthesis method. Spectrochim. Acta. A. Mol Biomol Spectrosc., 71 (4), 1281-1285. 

Altitough aldehydes are in general more reactive than ketones or a-keto acids, the co-TA-catalyzed amination of aldehydes has been less frequently explored most of the examples about aldehydes concern the kinetic characterization of new enzymes rather titan preparative synthetic applications. The transformation of 2-phenyl propanal derivatives to the corresponding p-chiral amines has been recently investigated using co-TAs (Scheme 2.10) [61]. 

Dialkylaminoethyl acryhc esters are readily prepared by transesterification of the corresponding dialkylaminoethanol (102,103). Catalysts include strong acids and tetraalkyl titanates for higher alkyl esters and titanates, sodium phenoxides, magnesium alkoxides, and dialkyitin oxides, as well as titanium and zirconium chelates, for the preparation of functional esters. Because of loss of catalyst activity during the reaction, incremental or continuous additions may be required to maintain an adequate reaction rate. 

The most significant commercial product is barium titanate, BaTiO, used to produce the ceramic capacitors found in almost all electronic products. As electronic circuitry has been rniniaturized, demand has increased for capacitors that can store a high amount of charge in a relatively small volume. This demand led to the development of highly efficient multilayer ceramic capacitors. In these devices, several layers of ceramic, from 25—50 ]lni in thickness, are separated by even thinner layers of electrode metal. Each layer must be dense, free of pin-holes and flaws, and ideally consist of several uniform grains of fired ceramic. Manufacturers are trying to reduce the layer thickness to 10—12 ]lni. Conventionally prepared ceramic powders cannot meet the rigorous demands of these appHcations, therefore an emphasis has been placed on production of advanced powders by hydrothermal synthesis and other methods. 

Another important class of titanates that can be produced by hydrothermal synthesis processes are those in the lead zirconate—lead titanate (PZT) family. These piezoelectric materials are widely used in manufacture of ultrasonic transducers, sensors, and minia ture actuators. The electrical properties of these materials are derived from the formation of a homogeneous soHd solution of the oxide end members. The process consists of preparing a coprecipitated titanium—zirconium hydroxide gel. The gel reacts with lead oxide in water to form crystalline PZT particles having an average size of about 1 ]lni (Eig. 3b). A process has been developed at BatteUe (Columbus, Ohio) to the pilot-scale level (5-kg/h). 

Twelve-membered rings have been obtained using coordination catalysts. The transJmns,ds-cyc. ododec2Lti ien.e has been prepared with a tetrabutyl titanate—diethylalurninum chloride catalyst (48,49) and with a chromium-based system (50). The trans,trans,trans-isom.e-i. has been prepared with a nickel system. 

Lead zirconate [12060-01 -4] PbZrO, mol wt 346.41, has two colorless crystal stmctures a cubic perovskite form above 230°C (Curie point) and a pseudotetragonal or orthorhombic form below 230°C. It is insoluble in water and aqueous alkaUes, but soluble in strong mineral acids. Lead zirconate is usually prepared by heating together the oxides of lead and zirconium in the proper proportion. It readily forms soHd solutions with other compounds with the ABO stmcture, such as barium zirconate or lead titanate. Mixed lead titanate-zirconates have particularly high piezoelectric properties. They are used in high power acoustic-radiating transducers, hydrophones, and specialty instmments (146). 

Other. Insoluble alkaline-earth metal and heavy metal stannates are prepared by the metathetic reaction of a soluble salt of the metal with a soluble alkah—metal stannate. They are used as additives to ceramic dielectric bodies (32). The use of bismuth stannate [12777-45-6] Bi2(Sn02)3 5H20, with barium titanate produces a ceramic capacitor body of uniform dielectric constant over a substantial temperature range (33). Ceramic and dielectric properties of individual stannates are given in Reference 34. Other typical commercially available stannates are barium stannate [12009-18-6] BaSnO calcium stannate [12013 6-6] CaSnO magnesium stannate [12032-29-0], MgSnO and strontium stannate [12143-34-9], SrSnO. ... 

Anatase and mtile are produced commercially, whereas brookite has been produced by heating amorphous titanium dioxide, which is prepared from an alkyl titanate or sodium titanate [12034-34-3] with sodium or potassium hydroxide in. an autoclave at 200—600°C for several days. Only mtile has been synthesized from melts in the form of large single crystals. More recentiy (57), a new polymorph of titanium dioxide, Ti02(B), has been demonstrated, which is formed by hydrolysis of K Ti O to form 20, followed by subsequent calcination/dehydration at 500°C. The relatively open stmcture... 

Alkali Metal Titanates. Alkali metatitanates may be prepared by fusion of titanium oxide with the appropriate alkah metal carbonate or hydroxide. Representative alkah metal titanates ate hsted in Table 14. The alkah metal titanates tend to be more reactive and less stable than the other titanates, eg, they dissolve relatively easily in dilute acids. 

Ferrous orthotitanate [12160-20-2] Fe2Ti04, is orthorhombic and opaque. It has been prepared by heating a mixture of ferrous oxide and titanium dioxide. Ferrous dititanate [12160-10-0] FeTi20, is orthorhombic and has been prepared by reducing ilmenite with carbon at 1000°C. The metallic ion formed in the reaction is removed, leaving a composition that is essentially the dititanate. Ferric titanate [1310-39-0] (pseudobrookite), Fe2TiO, is orthorhombic and occurs to a limited state in nature. It has been prepared by heating a mixture of ferric oxide and titanium dioxide in a sealed quartz tube at 1000°C. 

Titanium Phosphates. Titanium(III) phosphate [24704-65-2] (titanous phosphate) is a purple soHd, soluble ia dilute acid, giving relatively stable solutions. It can be prepared by adding a soluble phosphate to titanous chloride or sulfate solution and raising the pH until precipitation occurs. 

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). 

Higher alkoxides, such as tetra(2-ethylhexyl) titanate, TYZOR TOT [1070-10-6], can be prepared by alcohol interchange (transestenfication) in a solvent, such as benzene or cyclohexane, to form a volatile a2eotrope with the displaced alcohol, or by a solvent-free process involving vacuum removal of the more volatile displaced alcohol. The affinity of an alcohol for titanium decreases in the order primary > secondary > tertiary, and... 

Mixed esters can be prepared from Cl Ti(OR)4 and a second alcohol in the presence of a base or by mixing a tetraalkoxide and the second alcohol in the desired proportions and flash-evaporating the mixed alcohols. Mixing of two pure tetraalkoxides of titanium also leads, via a rapid ester interchange reaction, to a mixture of ah. possible combinations of tetraalkyl titanates. 

A rarely used preparation involves the reaction of tetraamido titanates, such as tetradimethylarnino titanate [3275-24-9], with an alcohol. This reaction goes to completion because of the greater affinity of titanium for oxygen over nitrogen. 

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) ... 

Titanoxanes can also be prepared by reaction of a tetraalkyl titanate and carboxyUc acids (25). If the ratio of carboxyUc acid to tetraalkyl titanate is 1 1, a simple polymeric titanate ester is formed. If two or more moles of acid are used per mole of tetraalkyl titanate, the resulting polymeric titanate ester contains ester carboxylate groups. 

Titanoxanes can also be prepared by pyrolysis of tetraalkyl titanates at 200—250°C. Higher temperatures, however, can lead to thermal decomp o sition. 

Alternatively, titanoxanes can be prepared by reaction of tetraalkyl titanates with carboxyUc acid anhydrides (30) ... 

Organic-solvent-soluble, higher molecular weight polytitanoxanes, having a proposed mdder-shaped stmcture, can be prepared by careful addition of an alcohol solution of 1.0—1.7 moles of water per mole of tetraalkyl titanate, followed by distillation of the low boiling alcohol components. Polytitanoxanes having molecular weights up to 20,000 have been prepared by this method (31). 

Titanium-cataly2ed ester interchange can be used to prepare polyesters from diester and diols as well as from diacids and diols at considerably higher temperatures. Polymer chains bearing pendant ester and hydroxy functions can be cross-linked with titanates. 

Highly cross-linked polyol polytitanates can be prepared by reaction of a tetraaLkyl titanate with a polyol, such as pentaerythritol, followed by removal of the by-product alcohol (77). The isolated soHds are high activity catalysts suitable for use in the preparation of plasticizers by esterification and/or transesterification reactions. The insoluble nature of these complexes faciUtates their... 

Dicarboxyhc acids, eg, succinic or adipic, do not dissolve titanic acid. A phthalate has been prepared by adding acidic titanium sulfate solution to sodium phthalate solution. 

Alkoxy titanium acylate derivatives coordinated with a phosphite diester (phosphonate diester) can be prepared by reaction of a tetraalkyl titanate and an equal molar amount of a carboxyUc acid, such as methacrylic acid or isostearic acid, and a phosphite or phosphonate diester, such as dibutyl hydrogen phosphite (103). These materials reduce the viscosity of a composite system, improve... 

Alkanolamine Chelates. Alkanolamine chelates, which are prepared by reaction of tetraalkyl titanates with one or more alkanolamines, are used primarily in cross-linking water-soluble polymers (qv) (see Alkanolamines) (104). The products are used in thixotropic paint emulsion paints, in hydrauhc fracturing and drilling of oil and gas wells, and in many other fields. The stmcture of... 

Acylates. Titanium acylates are prepared either from TiCl or tetraalkyl titanates. Because it is difficult to obtain titanium tetraacylates, most compounds reported are either chloro- or alkoxyacylates. Under most conditions, TiCl and acetic acid give dichlorotitanium diacetate [4644-35-3]. The best method iavolves passiag preheated (136—170°C) TiCl and acetic acid simultaneously iato a heated chamber. The product separates as an HCl-free white powder (125) ... 

Composite Oxyalkoxides. Composite oxyalkoxides can be prepared by reaction of tetraalkyl titanates and alkaline-earth metal hydroxides. These oxyalkoxides and their derivatives can be hydroly2ed and thermally decomposed to give alkaline-earth metal titanates such as barium titanate (150). 

Titanium—Vanadium Mixed Metal Alkoxides. Titanium—vanadium mixed metal alkoxides, VO(OTi(OR)2)2, are prepared by reaction of titanates, eg, TYZOR TBT, with vanadium acetate ia a high boiling hydrocarbon solvent. The by-product butyl acetate is distilled off to yield a product useful as a catalyst for polymeri2iag olefins, dienes, styrenics, vinyl chloride, acrylate esters, and epoxides (159,160). 

Polymetallocarbosilanes. PolymetaHocarbosilanes having a number-average molecular weight of 700—100,000 can be prepared by reaction of polycarbosilane, /2 2 fx where R is H, or lower alkyl, with a tetraalkyl titanate, to give a mono-, di-, tri-, or tetrafunctional polymer... 

Complexes of titanium, such as 2,6-(RNCH2)2NC H2TiCl2, prepared by reaction of TiCl with 2,6((CH2)3Si)RNCH2)2NC H2, can react with various Grignard reagents to prepare conformationady rigid diamide mono- and dialkyl titanate complexes (218,219). 

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