Synthesis of Oligo(oxyethylene) Methacrylate-ended Poly( n -hexyl isocyanate) Rodlike Macromonomers and Their Radical Copolymerization Behavior with Methyl Methacrylate
Synthesis of Oligo(oxyethylene) Methacrylate-ended Poly( n -hexyl isocyanate) Rodlike Macromonomers and Their Radical Copolymerization Behavior with Methyl Methacrylate
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甲基丙烯酸低聚氧乙烯酯封端聚异氰酸正己酯棒状大分子单体的合成及其与甲基丙烯酸甲酯的自由基共聚行为
DOI：
10.1295/polymj.pj2008165
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发表时间：
2008
期刊：
影响因子：
2.8
通讯作者：
S. Kawaguchi
中科院分区：
文献类型：
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作者：
L. Liên;M. Kikuchi;A. Narumi;K. Nagai;S. Kawaguchi
合成了一系列含有α-甲基丙烯酰氧基低聚环氧乙烷和ω-乙酰基的新型棒状聚异氰酸正己酯（PHIC）大分子单体（MA-EOm-n-Ac，其中m和n分别为环氧乙烷和HIC的聚合度）。它们是通过HIC的活性配位聚合制备的，使用相应的钛（IV）醇盐络合物作为引发剂，在CH 2 Cl 2中，在室温下，随后在作为刘易斯酸的BF 3 OEt 2存在下，用乙酸酐作为终止剂终止。研究了甲基丙烯酸甲酯（MMA）与马来酸酐（MA-EOm-B-n-Ac）（M2）在苯中的自由基共聚合行为，考察了柔性间隔基（m）对共聚性能的影响。MA-EOm-n-Ac的表观反应活性（1/r1）低于MMA的表观反应活性（1/r1约为1/r1）。0.52），并随m的增加而略有下降。比较了MA-EOm-n-Ac与α-4-乙烯基苄氧基封端的PHIC大分子单体（VB-HIC-n-H）的共聚性能。甲基丙烯酸酯封端的PHIC大分子单体的可共聚性的降低最可能是由于大分子单体、共聚单体和增长聚合物链之间的不相容性，以及甲基丙烯酸酯本身比苯乙烯类单体更受聚合条件影响的事实。
A series of novel poly(n-hexyl isocyanate) (PHIC) rodlike macromonomers having an α-methacryloyloxyoligo(oxyethylene) group and an ω-acetyl group (MA-EOm-HIC-n-Ac, where m and n are the degrees of polymerization of oxyethylene (EO) and HIC, respectively) have been prepared. They were prepared by living coordination polymerization of HIC using corresponding titanium(IV) alkoxide complexes as an initiator in CH2Cl2 at room temperature, followed by termination with acetic anhydride as a terminator in the presence of BF3OEt2 as a Lewis acid. The radical copolymerization behavior of MA-EOm-HIC-n-Ac (M2) with methyl methacrylate (MMA) (M1) in benzene at 60 °C has thoroughly been investigated in order to evaluate an effect of a flexible oligo(oxyethylene) spacer (m) on the copolymerizability. The apparent reactivities (1/r1) of MA-EOm-HIC-n-Ac are lower than for MMA (1/r1 is ca. 0.52) and decrease slightly with increasing m. The copolymerizability of MA-EOm-HIC-n-Ac was compared with that of α-4-vinylbenzyoxy-ended PHIC macromonomers (VB-HIC-n-H). The decrease in the copolymerizability of the methacrylate-ended PHIC macromonomers is most likely due to the incompatibilities among the macromonomer, comonomer, and propagating polymer chain, together with the fact that methacrylate itself is much more influenced by the polymerization conditions than a styrenic monomer.
苯乙烯基封端棒状聚异氰酸正己酯大分子单体的制备及其与苯乙烯的自由基共聚行为
DOI：
--
发表时间：
2004
期刊：
Designed Monomers and Polymers 7
影响因子：
--
作者：
M.Kikuchi;S.Kawaguchi;K.Nagai
通讯作者：
K.Nagai