Aluminum polymer backbones

Transfer to polymer (Sect. 5.3) has been described by Aleksiuk a.o. in polymerization of 3-chloromethyl-3-methyloxetane initiated with aluminum allQ ls. High molecular weight polymers (M = 6 to 8 10 ) with narrow molecular weight distribution (Mw/M = 1.29) were formed from very beginning of reaction and were independent of conversion. These data suggest slow initiation, fast propaption and unimolecular decomposition process. Authors propose the termination on the own polymer backbone and formation of nonreactive branched oxonium ion. Similar mechanism described earlier for 3,3-bis(chloromethyl)oxetane is discussed in Sect. 3.2.11. 

The use of the binaphthyl-based chiral polymers in catalysis has been explored. We have demonstrated that incorporation of aluminum metal centers into the rigid binaphthyl polymer backbones leads to greatly enhanced catalytic activity over the monomeric aluminum complex. The catalytic activity of the polymeric aluminum and titanium complexes in the Mukaiyam aldol reaction has been studied. These polymeric metal complexes represent a new generation of polymer-based catalysts... 

Attempts to perform the cationic polymerization of vinylcyclohexane have been reported. While coordination-type polymerization of vinylcyclohexane monomer gives isotactic PCHE, polymerization under conditions that lead to the formation of carbocationic intermediates leads to polymers with a differentiated backbone structure. Instead of propagating via the vinyl carbons, the cationic polymerization proceeds via hydride shift to a tertiary carbocation, which then propagates to provide the polymer shown in Scheme 23.3 [32]. Conditions for these polymerizations typically involved the use of aluminum halide catalysts in halogenated hydrocarbon solvents at low temperatures [32,38]. For the most part, molecular weights are relatively low. 

Besides the continuous fibers, application of metallorganic polymers to heat-resistant coatings, dense ceramic moldings, porous bodies, and SiC matrix sources in advanced ceramics via polymer infiltration pyrolysis (PIP) have been developed. Novel precursor polymers have been synthesized and investigated for ceramics in addition to PCS (Table 19.1). For SiC ceramics, various Si-C backbone polymers have been synthesized. Their polymer nature (e.g., viscosity, stability, cross-linking mechanism, and ceramic yield) are, however, fairly different from PCS. On the other hand, polysilazane, perhydropolysilazane, polyb-orazine, aluminum nitride polymers, and their copolymers have been investigated... 

A large variety of aluminum and silicon polymers with metal oxygen backbones have been made besides the poly(siloxanes). Poly(aluminosiloxanes) contain an Si-O-Al-0 backbone. A typical example results from the reaction of sodium salts of dimethylsiloxane oligomers with aluminum chloride. Polymers with Si/Al ratios of 0.8 to 23 have been made. Low Si/Al ratios are brittle and insoluble having a 3-dimensional structure while those with Si/Al ratios of 7 to 23 are soluble. 

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