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

聚合物和可控结构材料的合成是当前工业和学术研究的热点。然而，在缩聚反应中，由于缩聚反应是以阶梯生长的方式进行的，所以没有合成出分子量确定且分子量分布窄的聚合物。我们提出了一种控制缩聚的方法，其形成满足上述所有要求，使缩聚以链式生长反应的方式从引发剂如活聚合进行。根据IUPAC最近的建议，我们称这种缩聚为“缩聚链式聚合”。缩聚链聚合成功的一个重要因素是防止单体之间的反应导致普通步缩聚。相转移催化剂（PTC）是一种具有吸引力的聚合链聚合途径。因此，单体在水中或作为固体时不会相互反应，而用PTC转移到有机溶剂中的单体会与引发剂和/或有机溶剂中的聚合物和基团发生反应。4-溴甲基-2-正辛氧苯甲酸钾1在水-二氯甲烷中缩聚时，分子量受1/引发剂投料比的控制，但分子量分布较广。与18-冠-6或四丁基碘化铵在丙酮中缩聚1，得到了分子量确定且分子量分布窄（M′′φ D2w′′φ D2/M′φ D2n′φ D2 < 1.3）的聚酯。分子质量随转化率的增加而增大，在整个转化范围内，M′′φ D2w′′φ D2/M′′φ D2n′φ D2的比值均小于1.3。端基与引发剂的比例符合乙烯基单体和环状单体活性聚合的特点。因此，1的缩聚不是以步聚方式而是以链式聚合方式进行的。少

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）。

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。

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。