Synthesis of Linear High Molar Mass Glycidol-Based Polymers by Monomer-Activated Anionic Polymerization
Synthesis of Linear High Molar Mass Glycidol-Based Polymers by Monomer-Activated Anionic Polymerization
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DOI：
10.1021/ma902286a
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发表时间：
2010-02-23
期刊：
影响因子：
5.5
通讯作者：
Carlotti, Stephane
中科院分区：
文献类型：
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作者：
Gervais, Matthieu;Brocas, Anne-Laure;Carlotti, Stephane
以四辛基溴化铵为引发剂，三异丁基铝为单体活化剂，通过乙氧基乙基缩水甘油醚和叔丁基缩水甘油醚的阴离子聚合反应制备了高摩尔质量的线型聚缩水甘油。与引发剂相比，铝化合物以1.5-5倍过量使用。线性聚（乙氧基乙基缩水甘油醚）和聚（叔丁基缩水甘油醚），具有窄的链分散性和控制的高摩尔质量，高达85000克/摩尔，在0 ℃下在几个小时内制备。通过对聚合物进行酸处理来对羟基官能团进行脱保护，显示出定量且干净地进行，从而提供相应的线性聚甘油并验证这些保护基团的使用。还研究了受保护的甘油醇与环氧丙烷和环氧丁烷的共聚，目的是将这种合成方法的范围扩大到各种聚醚和共聚醚。
Linear polyglycidols of high molar masses were prepared by the monomer-activated anionic polymerization of the corresponding protected monomers, ethoxyethyl glycidyl ether and tert-butyl glycidyl ether, using a system composed of tetraoctylammonium bromide as initiator and triisobutylaluminum as monomer activator. The aluminic compound was used in 1.5-5-fold excess compared to the initiator. Linear poly(ethoxyethyl glycidyl ether) and poly(tert-butyl glycidyl ether), with narrow chain dispersity and controlled high molar masses, up to 85000 g/mol, were prepared at 0 degrees C in a few hours. Deprotection of hydroxyl functions by acidic treatment of file polymers was shown to proceed quantitatively and cleanly affording the corresponding linear polyglycerol and validating the use of these protecting groups. The copolymerization of protected glycidols with propylene oxide and butene oxide was also investigated with the goal to broaden the scope of this synthetic approach to various polyethers and copolyethers.