Development of New Type Polymerization Using Crystalline Media

1)用FeCl_3/6H_2O研磨，在无溶剂条件下，将2,6-二羟基萘氧化偶联聚合为聚2,6-二羟基-1,5-萘。与胺，特别是与苄胺共晶的使用促进了聚合，得到了更高分子量（Mn= ~ 10000）的聚合物。2)芳烃二甲醇衍生物经固态缩聚形成聚醚。通常，将dl-1,3-二（羟基苯基甲基）苯晶体与樟脑磺酸（5 mol%）粉末（Mn: ~ 40000）进行研磨和加热（100℃，n2流）得到聚合物。有趣的是，反应混合物在整个聚合过程中呈白色粉末状，外观没有任何变化。非对映异构体在固体中表现出不同的聚合性，但在溶液中表现出相同的聚合性。3)天然单糖和双糖在H_3PO_4 （5 mol%）存在下，在N_2流下，在110℃下加热，发生固态缩聚反应，得到高支化的多糖。反应混合物在整个聚合过程中呈粉末状。有趣的是，α-和β-分子表现出不同的聚合行为；前者的聚合速度较慢，然而，它们得到了相当分子量的聚合物。氟化糖在真空条件下，在110 ~ 160℃无催化剂条件下进行粉末-粉末缩聚，得到高支化多糖（转化率为40 ~ 95%，Mw=1400 ~ 20000）。110℃交叉极化光学显微镜图像表明，尽管制备了非晶聚合物，但聚合前后α-葡萄糖酰氟的晶体形状没有变化。4)各种硅二醇和二硅氧烷二醇在没有任何溶剂的情况下，用酸或碱催化剂处理生成环状低聚硅氧烷或线性聚硅氧烷。有趣的是，硅二醇的共聚产生了高分子量的聚硅氧烷（10^4 ~ 10^5），这也是由二硅氧烷二醇得到的。少

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