Synthesis and characterization of polymer with amphiphilic character by atom transfer radical polymerization method

The atom transfer radical polymerization (ATRP) of 2-(diethylamino)ethyl methacrylate (DEAEMA) with isobornylmethacrylate (IBMA) and styrene (St) were performed in bulk at 110 oC in bulk in the presence of ethyl 2-bromoacetate. The three-armed atom transfer radical polymerization of DEAEMA and St by using [1,3,5-tri-(2?-bromo-2?-methylpropionate)benzen](BMPB) as initiator in the presence of cuprous(I)bromide (CuBr) at 110 oC. The homo- and copolymers via ATRP of phenacyl methacrylate (PAMA) with methyl methacrylate (MMA) and t-butyl methacrylate (t-BMA) in the presence of cuprous(I)bromide (CuBr), and ethyl 2-bromoacetate was performed in bulk at 90oC in the presence of ethyl 2-bromoacetate. Also, the polymerization of PAMA was carried out at 70, 80, and 100oC. In this work, the structure of homo- and copolymers synthesized was characterized by IR, 1H and 13C-NMR techniques. The dielectric properties of poly(DEAEMA) and poly(DEAEMA-co-IBMA and St) were measured at room temperature. The average-molecular weights of polymers were determined by Gel Permeation Chromatography. The in situ addition of methylmethacrylate to a macroinitiator of poly(phenacyl methacrylate) [Mn=2800, Mw/Mn=1.16] afforded an AB-type block copolymer [Mn=13600, Mw/Mn=1.46]. For copolymerization systems, their monomer reactivity ratios were obtained by using Kelen-Tüdös method for DEAEMA-IBMA and DEAEMA-St systems, Kelen-Tüdös, Fineman-Ross and Tidwell-Mortimer methods for PAMA-MMA system. Thermal analysis measurements of homo- and copolymers prepared by ATRP method were measured by TGA-50, DSC-50 and DTA-50. The initial decomposition temperatures of the obtained copolymers increased with increasing mole fraction of IBMA moiety for poly(DEAEMA-co-IBMA). The average activation energies calculated for the first and the second decomposition stages of poly(DEAEMA) by MHRK method were 43.45 and 94.82 kj/mole, respectively. Thermal degradation of poly[2-(diethylamino)ethyl methacrylate] was investigated by programmed heating from ambient temperature to 350 oC under vacuum followed by the product collection, and using FT-IR spectra of partially degraded polymer. The cold ring fraction (CRF) of products volatile at degradation temperature but not at ambient temperature was identified by GS-MS, FT-IR. Based on degradation, the major products of CRF are triethylamine, [m/e:99(M+), 86(base peak)], diethyl 2-hydroxyethylamine [m/e:17(M+), 86(b.p)], 2-(diethylaminoethyl) methacrylate (monomer) [m/e:185(M+,very small), 113, 99, 86(b.p), 69, 58]. KEY WORDS: ATRP, 2-(diethylaminoethyl) methacrylate, isobornylmethacrylate, St, MMA, PAMA, monomer reactivity ratio, dielectric properties, DSC, DTA, TGA, GPC, thermal degradation.