Titanium addition initiated

The mechanism of initiation in cationic polymerization using Friedel-Crafts acids appeared to be clarified by the discovery that most Friedel-Crafts acids, particularly haUdes of boron, titanium, and tin, require an additional cation source to initiate polymerization. Evidence has been accumulating, however, that in many systems Friedel-Crafts acids alone are able to initiate cationic polymerization. The polymerization of isobutylene for instance can be initiated, reportedly even in the absence of an added initiator, by AlBr or AlCl (19), TiCl ( )- Three fundamentally different... 

Precipitation of a hydrated titanium oxide by mixing aqueous solutions of titanium chloride with alkaU forms the precipitation seeds, which are used to initiate precipitation in the Mecklenburg (50) variant of the sulfate process for the production of pigmentary titanium dioxide. Hydrolysis of aqueous solutions of titanium chloride is also used for the preparation of high purity (>99.999%) titanium dioxide for electroceramic appHcations (see Ceramics). In addition, hydrated titanium dioxide is used as a pure starting material for the manufacture of other titanium compounds. 

The initial uses of colorants in plastics were as extenders and additives. Carbon black and titanium dioxide were and are stiU used as fillers (qv) because of their low cost. Almost from plastics inception the limitation of black and white did not offer sufficient color choices for end users looking to differentiate their products. The increase in aesthetic requirements along with different performance requirements and resin compatibiUties led to a great expansion in the number of different chemical classes of colorants and forms in which these colorants are available in today s market. 

It is recommended that the concentration of sulfuric acid in the initial solution be kept at 2-4 mol per liter for the extraction of tantalum, whereas for the extraction of niobium, the concentration of sulfuric acid must be increased to a minimum of 6 mol per liter [458,481]. In some cases, the presence, in the initial solution, of titanium in the form of fluorotitanic acid ensures the successful and selective extraction and purification of tantalum and niobium with no addition of any other mineral acid [482]. 

Cultivation of strictly anaerobic organisms requires not only that the medium be oxygen-free, but also that the redox potential of the medium be compatible with that required by the organisms. This may be accomplished by addition of reducing agents such as sulfide, dithionite, titanium(III) citrate, or titanium(IIl) nitrilotriacetate. Any of these may, however, be toxic so that only low concentrations should be employed. Attention has been drawn to the fact that titanium(III) citrate-reduced medium may be inhibitory to bacteria during initial isolation (Wachenheim and Hespell 1984). 

Nitroalkenes are also reactive Michael acceptors under Lewis acid-catalyzed conditions. Titanium tetrachloride or stannic tetrachloride can induce addition of silyl enol ethers. The initial adduct is trapped in a cyclic form by trimethylsilylation.316 Hydrolysis of this intermediate regenerates the carbonyl group and also converts the ad-nitro group to a carbonyl.317... 

The latter mechanism is supported by evidence obtained from the initiation and termination steps in the syndiospecific polymerization of styrene [190]. The 13C-enriched titanium catalyst afforded polystyrene with a CH(Ph)CH213CH3 end group, which indicates that the initiation step proceeded by secondary insertion (2,1-insertion) of styrene into the Ti-13C bond of the active species (Eq. 10). In contrast to this mechanism, termination by the addition of 13C-enriched methanol or tert-butyl alcohol afforded polymers without 13CH30 or tertbutoxy end groups. 

Note added in proof. Marek and Chmelir [40b, c] found that the polymerization of isobutene in heptane by aluminium bromide is greatly accelerated by addition of titanium tetrachloride. They suggested that the polymerization by aluminium bromide only is initiated by a cation such as AlBr2+ which adds to the isobutene and which is formed by self-dissociation of the catalyst. The enhancement of the rate by titanium tetrachloride they attribute to an increase in the concentration of ions by the reaction... 

In the latest paper from Marek s group [29] they once again introduce the self-ionisation of titanium tetrachloride in order to explain their photo-initiation results. Unfortunately, their reaction scheme is very obscure, but evidently it does not involve addition of a metal-containing cation to the monomer. 

The titanium-mediated photocatalytic oxidation of a pyridine solution was conducted by Low et al. (1991). They proposed that the reaction of OH radicals with pyridine was initiated by the addition of a OH radical forming the 3-hydro-3-hydroxypyridine radical followed by rapid addition of oxygen forming 2,3-dihydro-2-peroxy-3-hydroxypyridine radical. This was followed by the opening of the ring to give At-(formylimino)-2-butenal which decomposes to a dialdehyde and formamide. The dialdehyde is oxidized by OH radicals yielding carbon dioxide and water. Formamide is unstable in water and decomposes to ammonia and formic acid. Final products also included ammonium, carbonate, and nitrate ions. 

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