Living polymerization distributions

The statistical growth of a constant number of chains in a living polymerization leads to the narrow Poisson distribution of the mole fraction as a function of the degree of polymerization N ... 

The GPC traces in Fig. 24 reveal a broad molecular weight distribution, MJMn = 4.42, for the dual reactor blend sample. On the other hand, the diblock OBC displays an overall MJMn of 1.67. The narrowing of the distribution indicates that the polymerization has CCTP characteristics. The theoretical molecular weight distribution from an ideal living polymerization in a series of two CSTR reactors is given by the following equation, where/j and/2 are the mass fractions of polymer comprising the two blocks [11] ... 

LCB polymers can be formed by chemically linking preformed polymers (arm first or polymer first method) or by growing polymer chains from a multifunctional initiatior (core first method). In both cases living polymerization techniques are preferred because they provide better control over MW, MW distribution and the final branching architecture. However, highly selective coupling reactions e.g. with multifunctional isocyanates, or dicyclohexylcar-bodiimide (DCC) coupling, have also been successful. 

Another very important visible light-initiated reaction of alkyl aluminum porphyrins is their 1,4-addition to alkyl methacrylates to produce ester enolate species [Eq. (4)]. This enolate then acts as the active species in the subsequent polymerization of the acrylate monomer. For example, Al(TPP)Me acts as a photocatalyst to produce polymethylmethacrylate with a narrow molecular weight distribution in a living polymerization process [Eq. (4)]. Visible light is essential for both the initiation step (addition of methylmethacrylate to Al(TPP)Me) and the propagation... 

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