Polymeric metal complexes homopolymers

A viable process for manufacturing polyolefin-clay nanocomposifes by in situ polymerization requires adequate catalytic activity, desirable polymer microstructure, and physical properties including processibility, a high level of clay exfoliation fhaf remains stable under processing conditions and, preferably, inexpensive catalysf components. The work described in the previous two sections focused on achieving in situ polymerization with clay-supported transition metal complexes, and there was less emphasis on optimization of polymer properties and/or clay dispersion. Since 2000, many more comprehensive studies have been undertaken that attempt to characterize and optimize the entire system, from the supported catalyst to the nanocomposite material. The remainder of this chapter covers work published in the past decade on clay-polyolefin nanocomposites of ethylene and propylene homopolymers, as well as their copolymers, made by in situ polymerization. The emphasis is on the catalyst compositions and catalyst-clay interactions that determine the success of one-step methods to synthesize polyolefins with enhanced physical properties. 

Titanium alkoxides are also effective and sought-after initiators for the ROP of lactides due to a low toxicity, which minimizes the problems linked to the presence of catalyst residues in commercial PLA products [18, 19]. Despite impressive advancements in the use of Lewis acidic metal initiators in the preparation of PLAs, surprisingly little attention has been paid to the group 4 metal (Ti, Zr, Hf) initiators, probably due to the highly oxophilic nature of M(1V) which has a natural tendency to form aUcoxy-bridged multinuclear complexes. Verkade and coworkers previously demonstrated a series of titanium aUcoxide complexes 118-122 (Fig. 17) that function as moderately efficient initiators in bulk homopolymeization of L-lactide and rac-lactide, some of these initiators displaying a well-controlled polymerization behavior [119]. 

Week [203] developed a monomer salen complex linked to a norbomene via a stable phenylene-acetylene linker and its subsequent polymerization by means of the controlled ROMP method using 3 generation Grubb s catalyst (Scheme 137). This polymerization methodology led to fully functionalized immobilized metal-salen catalyst. By this way, the supported catalyst showed catalytic activities and stereoselectivities similar to the nonsupported Jacobsen catalyst. Moreover, activities and selectivities seemed to depend on the density of the catalytic moieties homopolymer 324 were less selective than their copolymer analogs 325. For example, AE of 1,2-dihydronaphtalene led in both cases to total conversion and 76% ee for the homopolymer 324 vs 81% ee for copolymer 325a. Recycle was possible and after 3 recyles a drastic decrease in ee was observed. AE of dihydronaphtalene led to 81% ee for the first cycle vs 6% ee for the third one. 

TG-DTA-MS has obvious synthetic polymer applications. TA-MS has been appHed to study the thermal behavior of homopolymers, copolymers, polymeric blends, composites, residual monomers, solvents, additives, and toxic degradation products. In the latter context, FICl evolution from heated polyfvinyl chloride) materials is readily quantified by TA-MS and such data are of major significance in the design of fire-resistant polymeric materials. Pyrotechnic materials have been studied by TA-MS. A complex sequence of thermal events relates to the decomposition of these materials involving interactions between the nitrocellulose, perchlorate, and metal components with periodic release of carbon dioxide and oxygen. Only by EGA is it possible to rationalize the thermal behavior of such materials. TA-FTIR has also been applied extensively to study the thermal characteristics of synthetic polymers... 

An important improvement was the development of another initiation strategy, dubbed simultaneous reverse and normally initiated (SR NI) ATRP In this technique, a low concentration of active catalyst can be used and block copolymers, although not absolutely free of homopolymer impurities, can be synthesized. The reaction mixture contains an alkyl halide (which may be polymeric or functionalized), a smaller amount of radical source and the oxidatively stable higher oxidation state metal halide complex (deactivator). The reaction starts with the decomposition of the conventional radical source. The formed radicals initiate some chains and reduce the higher oxidation state metal halide complex to afford an ATRP activator, which can then activate the alkyl halide and concurrently mediate normal ATRP. The amount of catalyst used in this technique is determined not by the number of chains but only by its activity. SR NI ATRP has been... 

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