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Hyperbranched homo and thermoresponsive graft copolymers by using ATRP-macromonomer initiators

Allı, Sema | Allı, Abdulkadir | Hazer, Baki

Article | 2012 | Journal of Applied Polymer Science124 ( 1 ) , pp.536 - 548

Macromonomer initiators behave as macro cross-linkers, macro initiators, and macromonomers to obtain branched and cross-linked block/graft copolymers. A series of new macromonomer initiators for atom transfer radical polymerization (MIM-ATRP) based on polyethylene glycol (M n = 495D, 2203D, and 4203D) (PEG) were synthesized by the reaction of the hydroxyl end of mono-methacryloyl polyethylene glycol with 2-bromo propanoyl chloride, leading to methacryloyl polyethylene glycol 2-bromo propanoyl ester. Poly (ethylene glycol) functionalized with methacrylate at one end was reacted with 2-bromopropionyl chloride to form a macromonomeric . . .initiator for ATRP. ATRP was found to be a more controllable polymerization method than conventional free radical polymerization in view of fewer cross-linked polymers and highly branched polymers produced from macromonomer initiators as well. In another scenario, ATRP of N-isopropylacrylamide (NIPAM) was initiated by MIM-ATRP to obtain PEG-b-PNIPAM branched block/graft copolymers. Thermal analysis, FTIR, 1H NMR, TEM, and SEM techniques were used in the characterization of the products. They had a thermo-responsive character and exhibited volume phase transition at â 36°C. A plasticizer effect of PEG in graft copolymers was also observed, indicating a lower glass transition temperature than that of pure PNIPAM. Homo and copolymerization kinetics were also evaluated. © 2011 Wiley Periodicals, Inc Daha fazlası Daha az

Effect of the composition of methanol-water mixtures on tacticity of poly(N-ethylacrylamide) gel

Biswas, Chandra Sekhar | Sulu, Elvan | Hazer, Baki

Article | 2015 | Journal of Applied Polymer Science132 ( 12 ) , pp.536 - 548

Two series of macroporous poly(N-ethylacrylamide) (PNEAM) gels are synthesized in different composition of methanol-water mixtures (xm=0, 0.06, 0.13, 0.21, 0.31, and 0.43; where xm=mole fraction of methanol) in presence as well as in the absence of 0.1M Y(OTf)3 Lewis acid as additive. The gels synthesized in the absence of Lewis acid are atactic and in the presence of the same are isotactic. Synthesis of the corresponding linear PNEAM homopolymers shows that, the isotacticity (meso dyad, %) of the resulted polymers increases for the gels prepared in the presence of Lewis acid (LA) and remains constant for the gel prepared in the abs . . .ence of LA, respectively, with the increase in the concentration of the synthesis solvent methanol. SEM micrographs reveal that, the hydrogels synthesized in the presence of LA are more porous than the gels prepared in the absence of LA. Swelling ratio of all the hydrogels decreases with the increase in the temperature and LA gels show higher swelling ratio values than non LA gels (NLA). Deswelling rate of the hydrogels prepared in methanol-water mixture in presence of LA is faster than the hydrogels prepared in absence of LA. Moreover, reswelling rate increases with increase in the isotacticity of the PNEAM segment in the gel. All these results have been explained on the basis of the formation of highly porous hydrogels with higher isotactic PNEAM chain segment in the presence of LA in methanol-water mixtures. © 2014 Wiley Periodicals, Inc Daha fazlası Daha az

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