Designing 8-shaped polymer topology by metathesis condensation with cyclic poly(THF) precursors having allyl groups
Designing 8-shaped polymer topology by metathesis condensation with cyclic poly(THF) precursors having allyl groups
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DOI：
10.1021/ma021495a
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发表时间：
2003-01-14
期刊：
影响因子：
5.5
通讯作者：
Washizuka, M
中科院分区：
文献类型：
--
作者：
Tezuka, Y;Komiya, R;Washizuka, M
采用复分解缩合工艺合成双环8型聚(THF)。因此，首先，使具有烯丙基1的环状聚(THF)进行分子间复分解缩合。发现双分子缩合反应在格鲁布斯催化剂存在下进行，同时发生明显的并发反应。或者，制备双尾蝌蚪，即“有两个分支的环”结构，具有末端烯丙基的聚(THF)2，和在相反位置具有两个烯丙基的kyklo-遥爪聚(THF)3，用于分子内复分解缩合。即使在聚合物浓度稀释至0.2 g/L 的情况下，单分子反应也能有效进行，生成相应的8 形聚(THF)。这些产物通过 H-1 NMR、SEC 和 MALDI-TOF MASS 技术进行了明确的表征。
A metathesis condensation process was applied for the synthesis of double cyclic, 8-shaped poly(THF)s. Thus, first, a cyclic poly(THF) having an allyl group, 1, was subjected to the intermolecular metathesis condensation. The bimolecular condensation reaction was found to proceed in the presence of a Grubbs catalyst, while with noticeable concurrent reactions. Alternatively, a twin-tailed tadpole, i.e., "a ring with two branches" structure, poly(THF) having tail-end allyl groups, 2, and a kyklo-telechelic poly(THF) having two allyl groups at opposite positions, 3, were prepared for the intramolecular metathesis condensation. The unimolecular reactions proceeded effectively even under dilution of the polymer concentration at 0.2 g/L to produce the corresponding 8-shaped poly(THF)s. These products were unequivocally characterized by means of H-1 NMR, SEC, and MALDI-TOF MASS techniques.