Regioselective polymerization

Enantio- and regioselective polymerizations to produce functional polymers, which are very difficult to be obtained by conventional methodologies. 

M.R. Andersson, D. Seise, M. Berggren, H. Jarvinen, T. Hjertberg, O. Inganas, O. Wennerstrom, and J.-E. Osterholm, Regioselective polymerization of 3-(4-octylphenyl)thiophene with FeCl3, Macromolecules, 27 6503-6506, 1994. 

In order to keep polyamides soluble in relatively apolar solvents, the use of flexible (macro)monomers such as a, co-(diaminopropyl)polydimethylsiloxane [52] or oligoethyleneglycol-based diamines [53, 54] has been proven to be a successful approach (Fig. 10). Poly condensations of dimethyl adipate with a variety of diamines were successful in bulk and at moderate temperatures between 60 and 100 °C (reaction A in Fig. 10). The low temperatures (60-100 °C) that suffice in these polymerizations also allow the use of monomers that are thermally instable, such as diethyl fumarate [53]. Moreover, multifunctional amines could be regioselectively polymerized up to molecular weights of 9 kDa, making lipase catalysts a valuable tool for the preparation of well-defined polyamides that can be further functionalized with active groups. 

A procedure has recently been developed for the regioselective polymerization of an 3-(4-octylphenyl)thiophene with FeCl3 [253]. The slow addition of a slurry of FeCl3 in CHC13 to a solution of the monomer resulted in the formation of a polymer with 94% head-to-tail linkages. The slow addition of FeCl3 keeps the ratio of Fe3 + to Fe2 + low during the... 

Regioselective Polymerization of 1-Alkynes and Stereoselective Cyclopolymerization of a,co-Heptadiynes... 

Enzymatic regioselective polymerization of cholic acid was reported. A hydroxy group at the 3-position was regioselectively acylated by lipase CA catalyst to give the oligoester with molecular weight less than 1 x 103.226... 

Uyama, H., Fukuoka, T., Komatsu, I., Watanabe, T., and Kobayashi, S. (2002) Protease-catalyzed regioselective polymerization and copolymerization of glutamic acid diethyl ester. Biomacromolecules, 3 (2), 318-323. 

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