Titanium polymer-attached catalysts

Zrrconium(IV) and hafnium(IV) complexes have also been employed as catalysts for the epoxidation of olefins. The general trend is that with TBHP as oxidant, lower yields of the epoxides are obtained compared to titanium(IV) catalyst and therefore these catalysts will not be discussed iu detail. For example, zirconium(IV) alkoxide catalyzes the epoxidation of cyclohexene with TBHP yielding less than 10% of cyclohexene oxide but 60% of (fert-butylperoxo)cyclohexene °. The zirconium and hafnium alkoxides iu combiuatiou with dicyclohexyltartramide and TBHP have been reported by Yamaguchi and coworkers to catalyze the asymmetric epoxidation of homoallylic alcohols . The most active one was the zirconium catalyst (equation 43), giving the corresponding epoxides in yields of 4-38% and enantiomeric excesses of <5-77%. This catalyst showed the same sense of asymmetric induction as titanium. Also, polymer-attached zirconocene and hafnocene chlorides (polymer-Cp2MCl2, polymer-CpMCls M = Zr, Hf) have been developed and investigated for their catalytic activity in the epoxidation of cyclohexene with TBHP as oxidant, which turned out to be lower than that of the immobilized titanocene chlorides . ... 

The termination reactions appear to be quantitative and specific for the reaction of saturated polymer molecules attached to aluminium and titanium [116], but applied to diene polymerizations the method is less satisfactory mainly because of the greater stability of allylic carbon-transition metal bonds. Polybutadiene has been labelled by terminating with tritiated methanol with the Cr(acac)3/AlEt3 catalyst [55], and similarly polyisoprene prepared with VCl3/AlEt3 [107]. Polybutadiene prepared with Til4/Al(i-Bu)3 has been labelled using C02 [115]. 

If the silica is treated with fluoride prior to titanation, which converts many of the silanol groups into Si-F surface groups, the reaction with titanium alkoxide is inhibited and the treatment is less effective. The data in Table 34 illustrate this outcome. Silica samples were treated (or not) with two fluoride compounds in aqueous solution, then they were dried at 260 °C in the normal way prior to titanation. Titanium isopropoxide was added to make the catalyst contain 5 wt% Ti. Each sample was then calcined at 815 °C in air. Chromium was applied (0.5 wt%) as bis(f-butyl) chromate) in hexane solution (two-step activation, see Section 12). After final activation in air at 315 °C, each sample was tested at 102 °C, and the polymer MI values obtained are listed in the table. The change in MI shows that the titanium did not attach well to the carrier in the presence of fluoride. As more fluoride was added, the polymer MI dropped. 

They also found that mixtures of bis-(cyclopentadienyl)-titanium dichloride and aluminum triphenyl or bis-(cyclopentadienyl)-titanium diphenyl and aluminum triethyl were active catalysts, and presumably formed similar, bridged complexes. Interestingly, the hydrocarbon substituent attached to aluminum became an end group in the polymer. 

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