Macromonomer synthesis. New functionalization methods
Macromonomer synthesis. New functionalization methods
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大分子单体合成。
DOI：
10.1002/macp.1987.021880909
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发表时间：
1987
影响因子：
2.5
通讯作者：
P. Rempp
中科院分区：
文献类型：
--
作者：
Y. Gnanou;P. Rempp
到目前为止，用不饱和亲电试剂对“活的”阴离子聚合物进行端盖合成大单体的研究并不总是定量的。现在，我们发现用肽合成的方法可以顺利地从ω-羟基聚环氧乙烷（PEO）制备端基不饱和的高分子单体，并定量地得到产率。以定量收率制备了端基为羧基、对甲苯磺酸基或氯羰基的中间体PEO。它们分别在二环己基碳二亚胺和1-羟基苯并三唑或三乙胺存在下，与2-（4-乙烯基苯基）乙醇或4-乙烯基苯胺反应，以定量收率转化为4-乙烯基苯基取代的PEO大单体。以ω-羟基PEO和2-异氰酸酯甲基丙烯酸乙酯为原料制备了端基为甲基丙烯酰的PEO。通过双键含量测定和核磁共振氢谱对合成的高分子单体进行了表征。
So far, the syntheses of macromonomers by end-capping of “living” anionic polymers with unsaturated electrophiles, were not always quantitative. Now, we found that macromonomers with unsaturated end groups can be smoothly prepared with quantitative yields from ω-hydroxy-poly(ethyleneoxide)s (PEO) applying methods of peptide synthesis. The intermediate PEO with carboxylic, p-toluenesulfonate or chlorocarbonyl end groups were prepared with quantitative yields. They were transformed into the 4-vinylphenyl substituted PEO macromonomers by reaction with 2-(4-vinylphenyl)ethanol or 4-vinyl-aniline, in quantitative yields, in the presence of dicyclohexylcarbodiimide and 1-hydroxybenzotriazole or triethylamine, respectively. PEO with methacryloyl end groups were prepared from ω-hydroxy-PEO and 2-isocyanato ethyl methacrylate. The resulting macromonomers were characterized by determination of the double bond content and by 1H NMR spectroscopy.