Development of Condensative Chain Polymerization in Biphase

双相缩合链聚合的进展

• 批准号: 10650873
• 负责人: YOKOZAWA Tsutomu
• 金额: $ 2.18万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650873/
• 关键词: Condensative Chain Polymerization; Phase Transfer Catalyst; Polycondensation; Polyster; Control over Molecular weight; Molecular Weight Distribution; Crown Ether; Ammonium Salt; リビング重合; 相分離

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

聚合物的合成和受控体系结构的材料在工业和学术研究中均具有目前的关注。然而，在多浓度中，尚未合成具有定义的分子量和狭窄的分子量分布的聚合物，因为多浓度以阶级增长反应方式进行。我们提出，一种控制的多浓度的方法是满足所有上述要求，以使多浓度以链生长反应的方式从启动器（如生活聚合）中进行。根据最近的IUPAC建议，我们称这种类型的多浓度为“凝结链聚合”。成功的凝结链聚合物的重要一件事是防止单体彼此的反应导致普通的阶跃多态度。在我们看来，相位转移催化剂（PTC）将是凝结链poly…更多序列的有吸引力的途径。那个月份或固体的月份不会彼此反应，并且用PTC转移到有机溶液中的月份会与有机溶液中的聚合物和/或聚合物和组反应。在4-溴甲基-2-N-辛基氯辛基钾的多趋化度中，在水二氯乙烷中，二氯甲烷的权重均在diChale interection中，但分布均由二甲烷的权重，但分布率，但均一量分发率，但供应率，但广泛。在丙酮中具有18-Crown-6或碘化碘化物的多敏1中，获得了分子量定义的聚酯和狭窄的分子量分布（MII D2WIE D2/MII D2NIE D2NIE D2 <1.3）。分子量与转化成比例增加，MII D2WIE D2/MII D2NIE D2比率在整个转换范围内小于1.3。最终组与引发剂的比率同意乙烯基单体和环状单体的生存聚合的特征。因此，1的多浓度不是以阶级聚合方式而是以链聚合方式进行。较少的

项目成果

Tsutomu Yokozawa: "Tandem Dimerization and Double Annulation of 3,3,4,4-Tetracyanobutanal Acetal. Synthesis of a Bicyclic 2-Aminopyridine Derivative"Tetrahedron Lett.. 40・25. 4707-4710 (1999)

横泽努：“3,3,4,4-四氰基丁醛缩醛的串联二聚和双环化。双环2-氨基吡啶衍生物的合成”Tetrahedron Lett.. 40・25 (1999)

Mary S.Gin: "Helical Bias in Solvophobically Folded Oligo(phenylene ethyneynels" J.Am.Chem.Soc.(印刷中). (1999)

Mary S.Gin：“疏溶剂折叠寡核苷酸（苯乙炔）中的螺旋偏向”，J.Am.Chem.Soc（出版中）。

Mary S. Gin: "Helical Bias in Solvophobically Folded Oligo(phenylene ethynylene)s"J. Am. Chem. Soc.. 121・11. 2643-2644 (1999)

Mary S. Gin：“疏溶剂折叠寡聚物（亚苯基乙炔基）中的螺旋偏向”J. Am. Soc. 121・11（1999）。

Tsutomu Yokozawa: "Condensative Chain Polymerization in Solid-Liquid Phase. Synthesis of Polyesters with a Difined Molecular Weight and a Narrow Molecular Weight Distribution by Polycondensation"J. Am. Chem. Soc.. 121・49. 11573-11574 (1999)

Tsutomu Yokozawa：“固-液相缩聚链聚合。通过缩聚合成具有细化分子量和窄分子量分布的聚酯”J. Am Chem. 121・49。

T.YOKOZAWA: "Condensative Chain Polymerization in Solid-Liquid Phase. Synthesis of with a Defined Molecular Weight and a Narrow Molecular Weight Distribution by Polycondensation."J. AM. Chem. Soc.. 121. 11573-11574 (1999)

T.YOKOZAWA：“固-液相缩合链聚合。通过缩聚合成具有确定分子量和窄分子量分布的聚合物。”J。