Benzyl bispidine as an efficient replacement for (-)-sparteine in ring opening polymerisation
Benzyl bispidine as an efficient replacement for (-)-sparteine in ring opening polymerisation
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DOI：
10.1039/c2sc22053a
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发表时间：
2013-01-01
期刊：
影响因子：
8.4
通讯作者：
Dove, Andrew P.
中科院分区：
文献类型：
--
作者：
Todd, Richard;Rubio, Gabriel;Dove, Andrew P.
二苄基官能化双吡啶与 1-(3,5-双(三氟甲基)苯基)-3-环己基硫脲 (TU) 助催化剂的合成和应用已被证明是丙交酯和环状碳酸酯单体的受控开环聚合 (ROP) 的优异催化剂。值得注意的是，聚合反应进行时可忽略不计的酯交换或差向异构化，立体纯L-丙交酯的聚合提供了T-m为156℃的高度结晶聚(丙交酯)。外消旋丙交酯的ROP导致观察到适度程度的立体控制，使得全同立构链的概率P-m = 0.74。对一系列替代氢键供体助催化剂的比较表明，TU 与二苄基官能化双吡啶结合时表现出最高的聚合速率。
The synthesis and application of a dibenzyl-functionalized bispidine, in combination with 1-(3,5-bis(trifluoromethyl) phenyl)-3-cyclohexylthiourea (TU) co-catalyst, has been demonstrated to be an excellent catalyst for the controlled ring-opening polymerisation (ROP) of lactide and cyclic carbonate monomers. Notably, the polymerisation proceeds with negligible transesterification or epimerisation, with the polymerisation of stereopure L-lactide affording highly crystalline poly(lactide) with a T-m of 156 degrees C. ROP of racemic lactide results in the observation of a modest degree of stereocontrol such that the probability of isotactic enchainment, P-m = 0.74. Comparison of a range of alternative hydrogen bond donor co-catalysts revealed that TU displayed the highest polymerisation rates in combination with the dibenzyl-functionalized bispidine.