Polydisperse high-molecular-weight polymeric

Most of the LFRP research ia the 1990s is focused on the use of nitroxides as the stable free radical. The main problems associated with nitroxide-mediated styrene polymerizations are slow polymerization rate and the iaability to make high molecular weight narrow-polydispersity PS. This iaability is likely to be the result of side reactions of the living end lea ding to termination rather than propagation (183). The polymerization rate can be accelerated by the addition of acids to the process (184). The mechanism of the accelerative effect of the acid is not certain. 

A micro-mixed, seeded reactor will produce a broad polymer distribution with a high molecular weight tail and polydispersity index that approaches 2 at large degrees of polymerization. 

Characteristic initiation behavior of rare earth metals was also found in the polymerization of polar and nonpolar monomers. In spite of the accelarated development of living isotactic [15] and syndiotactic [16] polymerizations of methyl methacrylate (MMA), the lowest polydispersity indices obtained remain in the region of Mw/Mn = 1.08 for an Mn of only 21 200. Thus, the synthesis of high molecular weight polymers (Mn > 100 x 103) with Mw/Mn < 1.05 is still an important target in both polar and nonpolar polymer chemistry. Undoubtedly, the availability of compositionally pure materials is a must for the accurate physical and chemical characterization of polymeric materials. 

However, the ROP of lactide and glycolide remains by far the most extensively practiced method in industry and academia for the preparation of polyesters. This method allows a better control of polymerization in terms of high molecular weight, narrow polydispersity, monomer-to-initiator ratio and sequence, well-defined... 

Similarly, a turn-over frequency (TON) of 227 of the polymerization process was distinctly low for 77d with [M]/[I] = 350, at 110 °C for 6 h, using in the melt polymerization conditions. Biocompatible calcium complex 77a used as catalyst at 110 °C produced in 30 min PLAs with high molecular weight (65,000-110,600) and narrow polydispersities (1.02-1.05) using [M]/[I] = 350-700. It is worthy of note that complex 77a displayed a notable heteroselectivity (probability of racemic linkages between monomers, = 0.73, see Sect. 4.2) in polymerization of rac-lactide in THF at 33 °C. Data on the aforementioned calcium initiators and their lactide polymerization are listed in Table 4. 

The quasi living polymerization of ethene and norbornene has been reviewed, among other topics in living polymerization of alkenes (19). Specifically, arylimido-aryloxo-vanadium(V) complexes with methylaluminoxane or Et2AlCl as co-catalyst have been used as catalyst systems. The polymers exhibit a low polydispersity and a high molecular weight (20). 

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