The Synthesis Of Well Defined Functional Homo And Block Copolymers In Aqueous Media Via Reversible Addition Fragmentation Chain Transfer Raft Polymerization PDF Download

"Controlled radical polymerization (CRP) techniques has allowed the synthesis of numerous polymeric materials with comparable control to that of true "living" techniques without the need for stringent manipulation techniques. The control over chain length, dispersity and composition is desirable in many fields, such as stimuli-responsive (temperature or pH) drug carriers. These thermoresponsive polymers in aqueous media are often characterized by lower critical solution temperature (LCST) behavior, where the polymer becomes insoluble with temperature increases. The LCST can be tuned by the structural features of the constituent monomer, molecular weight, molecular weight distribution and copolymerization with other monomers. Narrow molecular weight distribution is the key factor determining the sharpness needed for determining the LCST, which is often exemplified by the cloud point temperature (CPT). Using CRP techniques, specifically nitroxide mediated polymerization (NMP), with an alkoxyamine unimolecular initiator, 2-([tert-butyl[1-(diethoxyphosphoryl)-2,2-dimethylpropyl]amino]oxy)-2-methylpropanoic acid (BlocBuilder) and an additional free nitroxide (SG1), the effect of controlling comonomer (9-(4-vinylbenzyl)-9H-carbazole (VBK)) on polymerization kinetics of N-(2-methacryloyloxyethyl) pyrrolidone (MAEPYR) and the effect of final copolymer composition on CPT was studied. Adding at least 5 mol% VBK, the dispersity Đ of the poly(MAEPYR-stat-VBK) copolymers was below 1.4. The CPT decreased from 59.0 °C to 49.7 °C with addition of only 1 mol% of VBK in the copolymer, and it can be further fine-tuned by changing the solution concentration and the heating rate. Another CRP technique, reversible addition fragmentation chain-transfer polymerization (RAFT), was applied to homopolymerization of N-(3-methoxypropyl) acrylamide (MPAM) to yield well-defined polymers (with (M_n)− = 14.3 - 25.2 kg mol-1 and low Đ ~ 1.17 - 1.47) needed for precise determination of CPT. Thermoresponsive behaviour of poly(MPAM) in aqueous media revealed CPTs between 73 and 92 °C, unlike other literature reports where the polymers, synthesized by conventional radical polymerization, showed conflicting results regarding their LCST" --