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Development of New Type Polymerization Using Crystalline Media

使用结晶介质的新型聚合的开发

基本信息

批准号：
14550832
负责人：
MASAHITO Suzuki
金额：
$ 2.37万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

1) The oxidative coupling polymerization of 2,6-dihydroxynaphthalene to poly(2,6-dihydroxy-1,5-naphthylene) took place by grinding with FeCl_3/6H_2O without any solvent. Using the cocrystals with amines, especially bezylamine, promoted the polymerization giving the higher molecular weight (Mn=〜10000) polymer.2) Arene dimethanol derivatives underwent solid-state polycondensation forming polyether. Typically, grinding and heating (100℃ under a N_2 flow) the crystals of dl-1,3-bis(hydroxyphenylmethyl)benzene with powder of camphorsulfonic acid (5 mol%) produced the polymer (Mn:〜40000). Interestingly, the reaction mixture was white powdery throughout the polymerization without any change in appearance. The diastereomeric isomers showed different polymerizability in the solid-state but the same in the solution.3) Solid-state polycondensations of natural mono-and di-saccharides took place in the presence of H_3PO_4 (5 mol%) by heating at 110℃ under a N_2 flow, giving a highly branched polysa … More ccharide (Conv. 11〜84%, Mw=1400〜19,000, Mn=1200〜3700); the reaction mixture was powdery throughout the polymerization. Interestingly, α- and β-anomers showed different polymerization behavior ; the former was polymerized more slowly, however, they gave comparable molecular weight polymers. Sugar fluorides underwent powder-to-powder polycondensation without any catalyst at 110-160℃ under vacuum, giving highly branched polysaccharides (Conv.=40〜95%, Mw=1400〜20000). The cross-polarized optical microscopic images at 110℃ indicated that the crystal shape of α-glucosyl fluoride was unchanged before and after the polymerization in spite of producing the amorphous polymer. 4) Various silanediols and disiloxanediols produced cyclic oligosiloxanes or linear polysiloxane by the treatment with acid or base catalyst without any solvent. Interestingly, the copolymerization of the silanediols that afforded the cyclic oligosilane produced high molecular weight polysiloxanes (10^4〜10^5), which was also obtained from the disiloxanediols. Less

1)在无溶剂条件下，用FeCl_3/6H_2O研磨2，6-二羟基萘制备聚2，6-二羟基-1，5-萘。2）芳烃二甲醇衍生物固相缩聚生成聚醚。典型地，将dl-1，3-双（羟苯甲基）苯晶体与5mol%的邻苯二磺酸粉末一起研磨并加热（在N_2气流下100℃），得到聚合物（Mn：40000）。有趣的是，反应混合物在整个聚合过程中为白色粉末状，外观没有任何变化。3）天然单、双嵌段共聚物在H_3PO_4（5mol%）存在下，于110℃、N_2流下进行固相缩聚反应，得到高度支化的多嵌段共聚物 ...更多信息 charide（Conv. 11 - 84%，Mw=1400 - 19，000，Mn=1200 - 3700）;反应混合物在整个聚合过程中为粉末状。有趣的是，α-和β-端基异构体显示出不同的聚合行为;前者聚合得更慢，然而，它们得到相当的分子量聚合物。氟化糖在110-160℃真空条件下进行粉末-粉末缩聚反应，得到高度支化的多糖（Conv.= 40 - 95%，Mw=1400 - 20000）。在110℃下的正交偏光显微镜图像表明，尽管生成了无定形聚合物，但聚合前后α-葡萄糖基氟的晶体形状没有变化。4)在无溶剂条件下，用酸或碱催化剂处理各种硅二醇和二甘醇，生成环状低聚硅氧烷或线性聚硅氧烷。有趣的是，得到环状低聚硅烷的硅烷二醇的共聚产生了高分子量聚硅氧烷（10^4 × 10^5），其也是从二甘醇中获得的。少