Facile Synthesis of Hydroxyl-Ended, Highly Stereoregular, Star-Shaped Poly(lactide) from Immortal ROP of rac-Lactide and Kinetics Study
作者：Wei Zhao, Dongmei Cui, Xinli Liu, and Xuesi Chen
关键字：metathesis reaction; ring-opening polymerization; polylactides; heterotactic
论文来源：期刊
具体来源：http://pubs.acs.org/doi/pdf/10.1021/ma101202g
发表时间：2010年
Triethanolamine
(TEA) reacted with 3 equiv of yttrium alkyl complex 1 bearing
O,N,N,Otetradentate Salan ligand to give a trinuclear yttrium alkoxide
counterpart 2 via metathesis reaction. Complex 2 initiated the ring-opening
polymerization of rac-lactide in a livingness mode under mild conditions. Remarkably,
2 was so tolerant of the protic TEA that under various TEA-to-yttrium molar
ratios ranging from 1:3 up to 81:1, the polymerization performed smoothly,
suggesting an immortal characteristic. The resultant polylactides had variable
molecular weights (Mn = 1.36 104 to
32.54 104 ) but narrow molecular weight
distributions (PDI = 1.02-1.09), and, especially, pure heterotactic (Pr =
0.99), hydroxyl-functionalized and star-shaped architecture, which were fully
characterized by NMR spectroscopy and MALDI-TOF mass spectrum analyses and
confirmed further by calculating the contraction factor value g0 (g0 = 0.96)
via Mark-Houwink equations. Detailed investigation of the “immortal”
polymerization gave a unique kinetics law of -d[LA]/dt = kp[LA][TEA]-0.352.
