Synthesis of Various End-Functionalized Polyesters by Controlled/Living Ring-Opening Polymerization of Lactones using Pentafluorophenylbis(triflyl)methane as an Efficient Cationic Organocatalyst
Synthesis of Various End-Functionalized Polyesters by Controlled/Living Ring-Opening Polymerization of Lactones using Pentafluorophenylbis(triflyl)methane as an Efficient Cationic Organocatalyst
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使用五氟苯基双(三氟甲基)甲烷作为高效阳离子有机催化剂通过内酯的受控/活性开环聚合合成各种末端官能化聚酯
DOI：
10.1002/pola.24815
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
Toyoji
中科院分区：
文献类型：
--
作者：
Makiguchi;Kosuke; Satoh;Toshifumi; Kakuchi;Toyoji
以五氟苯基双（三氟）甲烷（C6F5CHTf2）为有机催化剂和醇引发剂，进行了ε‐己内酯（ε‐CL）和δ‐戊内酯（δ‐VL）的开环聚合反应。在室温条件下，以3 -苯基- 1 -丙醇（PPA）为引发剂，[ε‐CL或δ‐VL]0/[PPA]0/[C6F5CHTf2]的比例为50/1/0.1时，聚合得到了聚ε‐己内酯（PCL）和聚δ‐戊内酯（PVL），聚ε‐己内酯（PCL）具有较窄的多分散性指数。所得聚合物的分子量与[ε‐CL或δ‐VL]0/[PPA]0的初始比值和单体转化率的结果吻合较好。1h NMR、尺寸排斥色谱和基质辅助激光解吸电离飞行时间质谱测量结果表明，PCL和PVL的α -链端为3 -苯基丙氧基，ω -链端为羟基。此外，通过动力学和链延伸实验证实了C6F5CHTf2催化内酯的ROP是可控的/活的。PCL和PVL的嵌段共聚成功地得到了PCL - b - PVL和PVL - b - PCL。此外，利用6 -叠氮- 1 -己醇、2 -甲基丙烯酸羟乙酯、丙炔醇、N -（2 -羟乙基）马来酰亚胺、4 -乙烯苄基醇、5 -己烯- 1 -醇和5 -降冰片烯- 2 -甲醇等功能化引发剂，通过ε - CL和δ - VL的ROP合成了具有窄分子量分布的端功能化pcl和pvl。©2011 Wiley期刊公司高分子材料学报，2011
The ring‐opening polymerizations (ROPs) of ε‐caprolactone (ε‐CL) and δ‐valerolactone (δ‐VL) with pentafluorophenylbis(triflyl)methane (C6F5CHTf2) as the organocatalyst and alcohol initiators were carried out. For the ROP using 3‐phenyl‐1‐propanol (PPA) as the initiator in CH2Cl2at room temperature with the [ε‐CL or δ‐VL]0/[PPA]0/[C6F5CHTf2] ratio of 50/1/0.1, the polymerization homogeneously proceeded to afford poly(ε‐caprolactone) (PCL) and poly(δ‐valerolactone) (PVL) having narrow polydispersity indices. The molecular weights of the obtained polymers determined from1H NMR spectra showed good agreement with those estimated from the initial ratio of [ε‐CL or δ‐VL]0/[PPA]0and monomer conversions. The1H NMR, size exclusion chromatography, and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry measurements strongly indicated that PCL and PVL possessed the 3‐phenylpropoxy group as the α‐chain‐end and the hydroxy group as the ω‐chain‐end. In addition, the controlled/living nature for the C6F5CHTf2‐catalyzed ROP of lactones was confirmed by kinetic and chain‐extension experiments. The block copolymerization of PCL and PVL successfully proceeded to afford PCL‐b‐PVL and PVL‐b‐PCL. In addition, various end‐functionalized PCLs and PVLs with narrow molecular weight distributions were synthesized by the ROP of ε‐CL and δ‐VL using functional initiators, such as 6‐azido‐1‐hexanol, 2‐hydroxyethyl methacrylate, propargyl alcohol,N‐(2‐hydroxyethyl)maleimide, 4‐vinylbenzyl alcohol, 5‐hexen‐1‐ol, and 5‐norbornene‐2‐methanol. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011