Controlled polymerisation of lactide using an organo-catalyst in supercritical carbon dioxide

Controlled polymerisation of lactide using an organo-catalyst in supercritical carbon dioxide
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DOI:
10.1039/c1gc15344g
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发表时间:
2011-01
期刊:
影响因子:
9.8
通讯作者:
I. Blakey;A. Yu;S. Howdle;A. Whittaker;K. Thurecht
I. Blakey;A. Yu;S. Howdle;A. Whittaker;K. Thurecht
中科院分区:
化学1区
文献类型:
--
作者:
I. Blakey;A. Yu;S. Howdle;A. Whittaker;K. Thurecht

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报道了在超临界二氧化碳(scCO 2)中,以苯甲醇为引发剂,1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)为有机催化剂,DL-丙交酯的可控开环聚合。尽管有报道称DBU在质子源的存在下有效地转化为碳酸盐,但发现DBU仍然是DL-丙交酯开环聚合的有效催化剂。基质辅助激光解吸电离飞行时间质谱和1H核磁共振分析表明,在所得聚合物上保持端基保真度,并且在无水条件下未观察到显著的酯交换。我们报道了一种真正的“绿色”合成聚乳酸(PLA)的方法,完全没有潜在的有毒有机溶剂和无机催化剂。此外,在scCO 2中的反应在远低于LA本体聚合所需的温度下进行。
The controlled, ring-opening polymerisation of DL-lactide in supercritical carbon dioxide (scCO2) using benzyl alcohol as an initiator and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an organo-catalyst, is reported. Despite reports of DBU being efficiently converted to a carbonate salt in the presence of a proton source, it was found that DBU was still an efficient catalyst for the ring opening polymerisation of DL-lactide. Matrix-assisted laser desorption ionisation time of flight mass spectroscopy and 1H nuclear magnetic resonance analysis demonstrated that end-group fidelity was maintained on the resulting polymer and significant transesterification was not observed under anhydrous conditions. We report a truly ‘green’ process for the synthesis of polylactic acid (PLA) with the total absence of potentially toxic organic solvents and inorganic catalysts. In addition, the reaction in scCO2 is conducted at temperatures much lower than that required for bulk polymerisation of LA.