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Active Chain End (active + chain_end)
Selected AbstractsPhotoinitiated curing of mono- and bifunctional epoxides by combination of active chain end and activated monomer cationic polymerization methodsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2007Marco Sangermano Abstract Photoinitiated cationic polymerization of mono- and bifunctional epoxy monomers, namely cyclohexeneoxide (CHO), 4-epoxycyclohexylmethyl-3,,4,-epoxycyclohexanecarboxylate (EEC), respectively by using sulphonium salts in the presence of hydroxylbutyl vinyl ether (HBVE) was studied. The real-time FTIR spectroscopic, gel content determination, and thermal characterization studies revealed that both hydroxyl and vinyl ether functionalities of HBVE take part in the polymerization. During the polymerization, HBVE has the ability to react via both active chain end (ACE) and activated monomer mechanisms through its hydroxyl and vinyl ether functionalities, respectively. Thus, more efficient curing was observed with the addition of HBVE into EEC-containing formulations. It was also demonstrated that HBVE is effective in facilitating the photoinduced crosslinking of monofunctional epoxy monomer, CHO in the absence of a conventional crosslinker. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4914,4920, 2007 [source] Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry study on copolymers obtained by the alternating copolymerization of bis(,-lactone) and epoxide with potassium tert -butoxideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2005Chenxi Zhang Abstract Oligomer samples obtained by the anionic copolymerization of a bis(,-lactone), 2,8-dioxa-1-methylbicyclo[3.3.0]octane-3,7-dione (1), and glycidyl phenyl ether with potassium tert -butoxide have been analyzed by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. The MALDI-TOF mass spectra of these cooligomers show well-resolved signals that can be reliably assigned to linear, alternating cooligomers that have carboxylate chain ends or alkoxide chain ends and cyclic ones. The formation of these three series of cooligomers suggests that the polymerization process involves concomitant intermolecular transesterification and intramolecular back-biting. The intramolecular back-biting reaction causes the formation of cyclic cooligomers, whereas the intermolecular transesterification causes the reduction of the molecular weight and the transformation of the alkoxide active chain end into a carboxylate chain end. The MALDI-TOF mass spectrometry study has shown that an excess of monomer 1 enhances the selectivity of propagation by increasing the probability of the attack of the alkoxide chain end to 1. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2643,2649, 2005 [source] Synthesis of Organosilica Films Through Consecutive Sol/Gel Process and Cationic PhotopolymerizationMACROMOLECULAR MATERIALS & ENGINEERING, Issue 4 2010Davy-Louis Versace Abstract The cationic photopolymerization of epoxy polysilsesquioxane resins synthesized through a acid-catalyzed sol/gel process is studied. To elucidate the effect of the organic substituent on sol/gel reaction kinetics, two organotrimethoxysilanes with different organic groups were employed. Effects of UV irradiation on the microstructure of the epoxy-functional polysilsesquioxanes were also studied. 29Si solid-state MAS NMR proved that UV-generated Brönsted acids favored a work-up of the silicate network by promoting new sol/gel condensation reactions. There was a significant slowdown of epoxy conversion rates with increasing sol aging, which may be due to a competition between an active chain end and an activated monomer mechanism for the epoxy cationic polymerization. [source] Living radical polymerization of vinyl chloride initiated with iodoform and catalyzed by nascent Cu0/tris(2-aminoethyl)amine or polyethyleneimine in water at 25 °C proceeds by a new competing pathways mechanismJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2003Virgil Percec Abstract The first example of living radical polymerization of vinyl chloride carried out in water at 25 °C is reported. This polymerization was initiated by iodoform and catalyzed by nascent Cu0 produced by the disproportionation of CuI in the presence of strongly CuII binding ligands such as tris(2-aminoethyl)amine or polyethyleneimine. The resulting poly(vinyl chloride) was free of structural defects, had controlled molecular weight and narrow molecular weight distribution, contained two ,CHClI active chain ends, and had a higher syndiotacticity (62%) than the one obtained by conventional free-radical polymerization at the same temperature (56%). This novel polymerization proceeds, most probably, by a combination of competitive pathways that involves activation by single electron transfer mediated by nascent Cu0 and degenerative chain transfer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3283,3299, 2003 [source] | ||||||||||