Development of Condensative Chain Polymerization in Biphase

Synthesis of polymers and materials of controlled architectures is of current interest in both industrial and academic research.In polycondensation，however，polymers of having a defined molecular weight and a narrow molecular weight distribution have not been synthesized，because polycondensation proceeds in a step-growth reaction manner.We have proposed that one of approaches to controlled polycondensation with the formation of that fulfill all of the above-mentioned requirements to make polycondensation proceed in a chain-growth reaction manner from an initiator like living polymerizations.We call this type polycondensation“Condensative Chain Polymerization”according to the recent IUPAC recommendations.An important thing for successful condensative chain polymerizations is to prevent the reaction of monomer with each other leading to ordinary step polycondensations。It occurred to us that the phase transfer catalyst(PTC)would be an attractive route to condensative chain poly…More merizations。Thus，monomer in water or as solid does not react with each other and the monomer transferred to organic solvent with PTC would react with an initiator and/or the polymer and group in organic solvent.In the polycondensation of potassium4-bromomethyl-2-n-octyloxybenzoate1 in water dichloromethane，the molecular weights were controlled by the feed ratios of 1/initiator，but the molecular weight disibutions.In the polycondensation1 with18-crown-6or tetrabutylammonium iodide in acetone，polyesters with a defined molecular weight and a narrow molecular weight distribution(M I D2wⅡD2/MⅡD2&lt；1.3)were obtained。The molecular weights increased in proportion to conversion，and the M I D2w I D2/M I D2n ii D2 ratios were less than 1.3 over the whole conversion range.The ratios of end group to initiator agreed with the features of living polymerizations of vinyl monomers and cyclic monomers.Consequently，the polycondensation of 1 proceeds not in a step polymerization manner but in a chain polymerization manner。Less：Less

Synthesis of polymers and materials of controlled architectures is of current interest in both industrial and academic research. In polycondensation, however, polymers of having a defined molecular weight and a narrow molecular weight distribution have not been synthesized, because polycondensation proceeds in a step-growth reaction manner. We have proposed that one of approaches to controlled polycondensation with the formation of that fulfill all of the above-mentioned requirements to make polycondensation proceed in a chain-growth reaction manner from an initiator like living polymerizations. We call this type polycondensation "Condensative Chain Polymerization" according to the recent IUPAC recommendations. An important thing for successful condensative chain polymerizations is to prevent the reaction of monomer with each other leading to ordinary step polycondensations. It occurred to us that the phase transfer catalyst (PTC) would be an attractive route to condensative chain poly … More merizations. Thus, monomer in water or as solid does not react with each other and the monomer transferred to organic solvent with PTC would react with an initiator and/or the polymer and group in organic solvent.In the polycondensation of potassium 4-bromomethyl-2-n-octyloxybenzoate 1 in water dichloromethane, the molecular weights were controlled by the feed ratios of 1/initiator, but the molecular weight distributions were broad. In the polycondensation 1 with 18-crown-6 or tetrabutylammonium iodide in acetone, polyesters with a defined molecular weight and a narrow molecular weight distribution(MィイD2wィエD2/MィイD2nィエD2 < 1.3) were obtained. The molecular weights increased in proportion to conversion, and the MィイD2wィエD2/MィイD2nィエD2 ratios were less than 1.3 over the whole conversion range. The ratios of end group to initiator agreed with the features of living polymerizations of vinyl monomers and cyclic monomers. Consequently, the polycondensation of 1 proceeds not in a step polymerization manner but in a chain polymerization manner. Less