Tetrachloride, titanium

Titanium tetrachloride is hydrolysed by water, to give a mixture of anions, for example [Ti(OH)Cl5]" and [TiClg] , together with some hydrated titanium dioxide (Ti02.4H2O is one possible hydrate, being equivalent to [Ti(0H)4(H20)2]). This suggests that titanium dioxide is amphoteric (see below). 

The metal was a laboratory curiosity until Kroll, in 1946, showed that titanium could be produced commercially by reducing titanium tetrachloride with magnesium. This method is largely used for producing the metal today. The metal can be purified by decomposing the iodide. 

Titanium tetrachloride is used to iridize glass. This compound fumes strongly in air and has been used to produce smoke screens. 

Conventional synthetic schemes to produce 1,6-disubstituted products, e.g. reaction of a - with d -synthons, are largely unsuccessful. An exception is the following reaction, which provides a useful alternative when Michael type additions fail, e. g., at angular or other tertiary carbon atoms. In such cases the addition of allylsilanes catalyzed by titanium tetrachloride, the Sakurai reaction, is most appropriate (A. Hosomi, 1977). Isomerization of the double bond with bis(benzonitrile-N)dichloropalladium gives the y-double bond in excellent yield. Subsequent ozonolysis provides a pathway to 1,4-dicarbonyl compounds. Thus 1,6-, 1,5- and 1,4-difunctional compounds are accessible by this reaction. 

The earliest Ziegler-Natta catalysts were combinations of titanium tetrachloride (T1CI4) and diethylalummum chloride [(CH3CH2)2A1C1] but these have given way to more effective zirconium based metallocenes the simplest of which is bis(cyclopentadi enyl)zirconmm dichlonde (Section 14 14)... 

Titanium Tetrachloride. The major use for titanium tetrachloride [7550 5-0] is in titanium dioxide production, and titanium dioxide [13463-67-7] is enjoying strong growth for use as a filler in pulp and paper manufacture and as a pigment in paint and plastic manufacture. Annual growth for this product is forecasted at between 2.5 and 3.0% through 1992. 

Titanium tetrafluoride may be prepared by the action of elemental fluorine on titanium metal at 250°C (5) or on Ti02 at 350°C. The most economical and convenient method is the action of Hquid anhydrous HF on commercially available titanium tetrachloride in Teflon or Kynar containers. Polyethylene reacts with TiCl and turns dark upon prolonged exposure. The excess of HF used is boiled off to remove residual chloride present in the intermediates. 

From the time that isoprene was isolated from the pyrolysis products of natural mbber (1), scientific researchers have been attempting to reverse the process. In 1879, Bouchardat prepared a synthetic mbbery product by treating isoprene with hydrochloric acid (2). It was not until 1954—1955 that methods were found to prepare a high i i -polyisoprene which dupHcates the stmcture of natural mbber. In one method (3,4) a Ziegler-type catalyst of tri alkyl aluminum and titanium tetrachloride was used to polymerize isoprene in an air-free, moisture-free hydrocarbon solvent to an all i7j -l,4-polyisoprene. A polyisoprene with 90% 1,4-units was synthesized with lithium catalysts as early as 1949 (5). 

Al—Ti Catalyst for cis-l,4-PoIyisoprene. Of the many catalysts that polymerize isoprene, four have attained commercial importance. One is a coordination catalyst based on an aluminum alkyl and a vanadium salt which produces /n j -l,4-polyisoprene. A second is a lithium alkyl which produces 90% i7j -l,4-polyisoprene. Very high (99%) i7j -l,4-polyisoprene is produced with coordination catalysts consisting of a combination of titanium tetrachloride, TiCl, plus a trialkyl aluminum, R Al, or a combination of TiCl with an alane (aluminum hydride derivative) (86—88). 

Most catalysts for solution processes are either completely soluble or pseudo-homogeneous all their catalyst components are introduced into the reactor as Hquids but produce soHd catalysts when combined. The early Du Pont process employed a three-component catalyst consisting of titanium tetrachloride, vanadium oxytrichloride, and triisobutjlalurninum (80,81), whereas Dow used a mixture of titanium tetrachloride and triisobutylalurninum modified with ammonia (86,87). Because processes are intrinsically suitable for the use of soluble catalysts, they were the first to accommodate highly active metallocene catalysts. Other suitable catalyst systems include heterogeneous catalysts (such as chromium-based catalysts) as well as supported and unsupported Ziegler catalysts (88—90). 

The second type of solution polymerization concept uses mixtures of supercritical ethylene and molten PE as the medium for ethylene polymerization. Some reactors previously used for free-radical ethylene polymerization in supercritical ethylene at high pressure (see Olefin POLYMERS,LOW DENSITY polyethylene) were converted for the catalytic synthesis of LLDPE. Both stirred and tubular autoclaves operating at 30—200 MPa (4,500—30,000 psig) and 170—350°C can also be used for this purpose. Residence times in these reactors are short, from 1 to 5 minutes. Three types of catalysts are used in these processes. The first type includes pseudo-homogeneous Ziegler catalysts. In this case, all catalyst components are introduced into a reactor as hquids or solutions but form soHd catalysts when combined in the reactor. Examples of such catalysts include titanium tetrachloride as well as its mixtures with vanadium oxytrichloride and a trialkyl aluminum compound (53,54). The second type of catalysts are soHd Ziegler catalysts (55). Both of these catalysts produce compositionaHy nonuniform LLDPE resins. Exxon Chemical Company uses a third type of catalysts, metallocene catalysts, in a similar solution process to produce uniformly branched ethylene copolymers with 1-butene and 1-hexene called Exact resins (56). 

In this process, catalysts, such as boric acid, molybdenum oxide, zirconium, and titanium tetrachloride or ammonium molybdate, are used to accelerate the reaction. The synthesis is either carried out in a solvent (aUphatic hydrocarbon, trichlorobenzene, quinoline, pyridine, glycols, or alcohols) at approximately 200°C or without a solvent at 300°C (51,52). 

Impurities that form volatile chlorides leave as gases at the top of the furnace together with the TiCl. By cooling those gases, most impurities, with the exception of vanadium and siUcon chlorides can be separated from the titanium tetrachloride [7550-45-0]. Vanadium chlorides can be reduced to lower oxidation state chlorides that are soHds highly volatile SiCl can be removed from TiCl by fractional distillation. 

Titanium Alkoxides. Titanium alkoxides are made from titanium tetrachloride and the corresponding alcohols in the presence of ammonia. Higher titanium alkoxides are manufactured from lower alkoxides by alcoholysis. Titanium isopropoxide and -butoxide are commercially available in barrels. Annual production of titanium alkoxides is estimated at 3000—4000 metric tons at an average price of about 4/kg. 

Both the Toth and Alcoa processes provide aluminum chloride for subsequent reduction to aluminum. Pilot-plant tests of these processes have shown difficulties exist in producing aluminum chloride of the purity needed. In the Toth process for the production of aluminum chloride, kaolin [1332-58-7] clay is used as the source of alumina (5). The clay is mixed with sulfur and carbon, and the mixture is ground together, pelletized, and calcined at 700°C. The calcined mixture is chlorinated at 800°C and gaseous aluminum chloride is evolved. The clay used contains considerable amounts of silica, titania, and iron oxides, which chlorinate and must be separated. Silicon tetrachloride and titanium tetrachloride are separated by distillation. Resublimation of aluminum chloride is requited to reduce contamination from iron chloride. 

Similarly, another important esterification reaction of isopropyl alcohol iavolves the production of tetraisopropyl titanate [546-68-9], a commercial polymeri2ation catalyst, from titanium tetrachloride [7550-45-0] and isopropyl alcohol. 

The 1990s reduction process was based on work started in the early 1930s. A magnesium vacuum reduction process was developed for reduction of titanium tetrachloride to metal. Based on this process, the U.S. Bureau of Mines (BOM) initiated a program in 1940 to develop commercial production. Some years later, the BOM pubHcized its work on titanium and made samples available to the industrial community. By 1948, the BOM produced batch sizes of 104 kg. In the same year, Du Pont aimounced commercial availabiHty of titanium, thus beginning the modem titanium metals industry (1). 

The volatile chlorides ate collected and the unreactedsohds and nonvolatile chlorides ate discarded. Titanium tetrachloride is separated from the other chlorides by double distillation (12). Vanadium oxychloride, VOCl, which has a boiling point close to TiCl, is separated by complexing with mineral oil, reducing with H2S to VOCI2, or complexing with copper. The TiCl is finally oxidized at 985°C to Ti02 and the chlorine gas is recycled (8,11) (see also... 

Tetrachloride-Reduction Process. Titanium tetrachloride for metal production must be of very high purity. The requited purity of technical-grade TiCl for pigment production is compared with that for metal production in Table 4. Titanium tetrachloride for metal production is prepared by the same process as described above, except that a greater effort is made to remove impurities, especially oxygen- and carbon-containing compounds. 

Table 4. Chemical Composition of Titanium Tetrachloride Grades, Wt %...

Ti02/Na2C02/Na2AlF2/NaCl/Na2B40, at 1050°C (20). Very fine titanium diboride may be made by a gas-phase plasma process in which titanium tetrachloride and boron trichloride are reacted in a hydrogen gas heated by a d-c plasma (21). 

A number of high temperature processes for the production of titanium carbide from ores have been reported (28,29). The aim is to manufacture a titanium carbide that can subsequently be chlorinated to yield titanium tetrachloride. In one process, a titanium-bearing ore is mixed with an alkah-metal chloride and carbonaceous material and heated to 2000°C to yield, ultimately, a highly pure TiC (28). Production of titanium carbide from ores, eg, ilmenite [12168-52-4], EeTiO, and perovskite [12194-71 -7], CaTiO, has been described (30). A mixture of perovskite and carbon was heated in an arc furnace at ca 2100°C, ground, and then leached with water to decompose the calcium carbide to acetjdene. The TiC was then separated from the aqueous slurry by elutriation. Approximately 72% of the titanium was recovered as the purified product. In the case of ilmenite, it was necessary to reduce the ilmenite carbothermaHy in the presence of lime at ca 1260°C. Molten iron was separated and the remaining CaTiO was then processed as perovskite. 

Titanium carbide may also be made by the reaction at high temperature of titanium with carbon titanium tetrachloride with organic compounds such as methane, chloroform, or poly(vinyl chloride) titanium disulfide [12039-13-3] with carbon organotitanates with carbon precursor polymers (31) and titanium tetrachloride with hydrogen and carbon monoxide. Much of this work is directed toward the production of ultrafine (<1 jim) powders. The reaction of titanium tetrachloride with a hydrocarbon-hydrogen mixture at ca 1000°C is used for the chemical vapor deposition (CVD) of thin carbide films used in wear-resistant coatings. 

The reactants ate fed into the tail flame of a d-c nitrogen plasma. The reaction occurs rapidly at temperatures around 1500°C and the HCl reacts with excess ammonia to form ammonium chloride. Similar reactions have been carried out using furnaces, lasers, and r-f plasmas (34) as the source of heat. Other routes using titanium tetrachloride starting material include... 

A more recent patent describes the production of titanyl nitrate by electrolysis of titanium tetrachloride or titanyl chloride (37). Other titanium nitrogen compounds that have been described include titanous amide [15190-25-9] Ti(NH2)3, titanic amide [15792-80-0] Ti(NH)2, and various products in which amines have reacted with titanium tetrachloride (38). 

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