Stannous(II) trifluoromethane sulfonate: a versatile catalyst for the controlled ring‐opening polymerization of lactides: Formation of stereoregular surfaces from polylactide “brushes”

Stannous(II) trifluoromethane sulfonate: a versatile catalyst for the controlled ring‐opening polymerization of lactides: Formation of stereoregular surfaces from polylactide “brushes”
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三氟甲磺酸亚锡(II):一种用于丙交酯受控开环聚合的多功能催化剂:由聚丙交酯“刷”形成立构规整表面

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发表时间:
2001
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通讯作者:
N. Abbott
N. Abbott
中科院分区:
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文献类型:
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作者:
M. Möller;Fredric Nederberg;Lisa S. Lim;Rikard Kånge;C. Hawker;J. Hedrick;Yuedong Gu;R. Shah;N. Abbott

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介绍了在溶液和固体载体中可控合成聚丙交酯的一般方法。对三氟甲烷磺酸亚锡[Sn(OTf)2]和三氟甲烷磺酸钪[Sc(OTf)3]作为L-, D-和L,D-丙交酯开环聚合(ROP)催化剂的评价,描述了在温和和高选择性条件下制备聚丙交酯的途径。这些三酸盐催化剂必须与亲核化合物(如醇)结合使用,醇是通过活性金属醇氧化合物产生的实际引发物。与这一过程相一致的是,1H NMR分析表明α-链端带有起始醇的酯,活性金属醇链端水解后,明显检测到ω-羟基链端。根据可控的聚合过程,以高收率获得了可预测分子量和窄多分散性的聚合物。碱作为溶剂或添加剂的加入显著地提高了聚合速率,而对聚合控制的损失最小。由引发剂HO(CH2CH2O)3(CH2)11SH产生的丙交酯异构体的ROP在生活条件下使用Sn(OTf)2产生的聚丙交酯刷在金表面上自组装,并提供了通过聚合对映体纯单体制备立体规则或手性表面的机会。©2001 John Wiley & Sons, Inc[J] .化学工程学报,2009,31 (3):559 - 559
A general method for the controlled synthesis of polylactide in solution and from solid supports is presented. The evaluation of stannous(II) trifluoromethane sulfonate [Sn(OTf)2] and scandium(III) trifluoromethane sulfonate [Sc(OTf)3] as catalysts for the ring-opening polymerization (ROP) of L-, D-, and L,D-lactide is described as a route to polylactide using mild and highly selective conditions. These triflate catalysts must be used in conjunction with a nucleophilic compound such as an alcohol that is the actual initiating species via the active metal alkoxide species. Consistent with this process, 1H NMR analysis revealed that the α-chain-end bears the ester from the initiating alcohol, and upon hydrolysis of the active metal alkoxide chain end, a ω-hydroxyl chain end was clearly detected. Polymers of predictable molecular weights and narrow polydispersities were obtained in high yields in accordance with a controlled polymerization process. The addition of base either as a solvent or additive significantly enhanced the polymerization rate with minimal loss to the polymerization control. The ROP of lactide isomers from an initiator, HO(CH2CH2O)3(CH2)11SH, self-assembled onto a gold surface using Sn(OTf)2 produced polylactide brushes under living conditions and provides the opportunity to prepare stereoregular or chiral surfaces by polymerization of enantiomerically pure monomers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3529–3538, 2001