Bohumil Masař

Multifunctional ATRP macroinitiators for the synthesis of graft copolymers

Abstract Multifunctional ATRP macroinitiators, polystyrene with 1-(2-bromopropionyloxy)ethyl or 1-(2-bromoisobutyryloxy)ethyl groups in the benzene rings and poly[4-methylstyrene- co -4-(bromomethyl)styrene], were synthesized. All the functionalized polymers were characterized by IR, 1 H and 13 C NMR spectroscopy and by size exclusion chromatography.

Stereochemical structures of some polyacrylates studied by one-dimensional and two-dimensional 13C1H n.m.r. spectroscopy

Abstract The stereochemical structures of samples of poly(ethyl acrylate) (PEA), poly(butyl acrylate) (PBuA) and poly(2-ethylhexyl acrylate) (PEHA), prepared by group transfer and anionic polymerization, were studied by 13 C and 1 H n.m.r. spectroscopy. The main-chain CH 2 spectral range was analysed by the application of the inverse 13 C 1 H HETCOR two-dimensional n.m.r. technique. A very similar HETCOR pattern was found for all polymers studied. In all cases, main-chain CH 2 lines in the 1 H and 13 C n.m.r. spectra could be assigned to configurational tetrads; for PEA and PBuA a partial assignment of carbon resonances to configurational hexads was possible. While PEHA prepared both by group transfer and anionic polymerization and PEA prepared by group transfer polymerization can be well approximated by Bernoullian statistics, for PEA and PBuA prepared by anionic polymerixation a first-order Markov model is required to fit the observed intensities at the hexad level.

Tailoring of polymers by combination of ionic and radical controlled polymerizations

Poly(methyl methacrylate)s with terminal bromine atom, prepared by bromination of anionically polymerized MMA, were used as ATRP macroinitiators giving di- and triblock copolymers with MMA, styrene and butyl acrylate blocks. Multifunctional ATRP macroinitiators were synthesized by introducing bromomethyl or 2-bromoacyloxy groups onto the main chain of polystyrene or poly(4-methyl styrene) and used for ATRP grafting of tert-butyl acrylate leading to densely grafted copolymers with more or less uniform grafts.