Elucidation of high ring‐opening polymerizability of methylated 1,6‐anhydro glucose
Elucidation of high ring‐opening polymerizability of methylated 1,6‐anhydro glucose
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甲基化1,6-脱水葡萄糖的高开环聚合性的阐明
DOI：
10.1002/pola.23178
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
Takashi Yoshida
中科院分区：
文献类型：
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作者：
Dai Yoshida;Takashi Yoshida
1,6-脱水葡萄糖是从木焦油中提取的，木焦油是木炭制造的副产品。 1,6-脱水葡萄糖甲基化后，得到起始单体1,6-脱水-2,3,4-三-O-甲基-β-D-吡喃葡萄糖(LGTME)。我们发现LGTME具有较高的开环聚合能力并且在温和的条件下聚合。在常压、N2气氛和0℃下，使用BF3OEt2催化剂，LGTME以高产率得到具有1,6-α立构规整性的高分子量聚合物，尽管在相同的聚合条件下，苄基化1,6-脱水葡萄糖单体(LGTBE)没有得到聚合物。 GPC 曲线显示两个吸收对应于 = 272 × 103 和 = 390 × 104，比例为 4.5:1。此外，在0℃的高真空条件下，LGTME生成了相应的聚合物，并且较低的分子量增加至= 364×103。为了揭示LGTME的高聚合性，进行了两步聚合。在0℃常压下第一阶段聚合6小时后，将第二LGTME单体添加到聚合混合物中，然后继续聚合。发现所得聚合物的较低分子量增加至=394×103，产率为78%。这些结果表明，第一阶段聚合后的聚(LGTME)具有稳定的增长末端，具有开环聚合的重新启动能力。 © 2009 Wiley periodicals, Inc. J Polym Sci Part A：Polym Chem 47：1013–1022，2009
1,6-Anhydro glucose was extracted from a wood tar that is a by-product of charcoal manufacture. After methylation of the 1,6-anhydro glucose, the starting monomer, 1,6-anhydro-2,3,4-tri-O-methyl-β-D-glucopyranose (LGTME), was obtained. We found that LGTME had high ring-opening polymerizability and polymerized under mild conditions. With BF3OEt2 catalyst under ordinary pressure and N2 atmosphere at 0 °C, LGTME gave high molecular weight of polymer with 1,6-α stereoregularity in a high yield, even though benzylated 1,6-anhydro glucose monomer (LGTBE) gave no polymers by the same polymerization conditions. The GPC profile showed two absorptions corresponding to = 272 × 103 and = 390 × 104 in the proportion of 4.5:1. Furthermore, under high vacuum condition at 0 °C, LGTME gave the corresponding polymer and the lower molecular weight increased to = 364 × 103. To reveal the high polymerizability of LGTME, two-step polymerization was performed. After the first stage of polymerization under ordinary pressure for 6 h at 0 °C, the second LGTME monomer was added to the polymerization mixture and then the polymerization was continued. It was found that the lower molecular weight of the resulting polymer increased to = 394 × 103 and the yield was 78%. These results suggest that poly(LGTME) after the first-stage polymerization has stable propagating end which has a restarting ability for the ring-opening polymerization. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1013–1022, 2009