Abstract:
The chemical modification of polysulfone by the reaction of lithiated polysulfone with 1-(4-dimethylaminophenyl)-1-phenylethylene and 2,2<sup>'</sup>- vi.nylidenedipyridine, respectively, in THF at -78 °C is described. Reduced temperature was necessary during the lithiation step to prevent crosslinking. The direct lithiation of the polysulfone followed by the addition of 2,2<sup>'</sup>-vinyli- denedipyridine gave good yields of the corresponding dipyridyl functionalized polysulfone.<br><br> <sup>1</sup>H NMR and <sup>13</sup>C NMR analyses of functionalized polysulfone indicated that functionalization occurred solely on the aromatic rings ortho to the sulfone linkage. The incorporation of the dipyridyl functionality was supported by complexation reactions of the dipyridyl functionalized polymer with metal ions such as copper and nickel and by quatemization reactions in the presence of dimethyl sulfide and concentrated perchloric acid. However when 1-(4-dimethylaminophenyl)-1-phenylethylene.was added to the lithiated polysulfone, low degrees of substitution were obtained.<br><br> The syntheses of tertiary amino functionalized polystyrenes and polymethyl methacrylates by atom transfer radical polymerization (ATRP) are described. All the polymerizations were conducted under heterogeneous conditions using an initiator adduct, prepared by reacting 1~(4-dimethyl- aminophenyl)-1-phenylethylene with 1-(bromoethyl)benzene in the presence of CuBr/2,2<sup>'</sup>-bipyridyl catalyst in diphenyl ether (otxylene at 90 °C where applicable) at 130 °C. Tertiary amine functionaliziitpolymers with controlled molecular weights based on the ratio of the consumed monomer tolnitiator (M<sub>n</sub> = 2000 -10000), and narrow polydispersities (≤1.3) were obtained.<br><br> : If- The functionalized polymers were analysed by <sup>1</sup>H NMR, <sup>13</sup>C NMR, GPC and TLC. Polymerization kinetic measurements show that the polymerization follows first order rate kinetics with respect to the monomer consumption. The number average molecular weight increases linearly with conversion, resulting in polymers with narrow polydispersities (≤ 1.3).
