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OALib Journal期刊
ISSN: 2333-9721
费用：99美元
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过渡金属盐催化甲基丙烯酸2-(N,N-二乙氨基)乙酯的自引发自由基聚合
DOI: 10.3724/SP.J.1105.2011.11013, PP. 1445-1453
Keywords: 甲基丙烯酸2-(N,N-二乙氨基)乙酯,自身还原性引发型单体,催化氧化聚合,氧化还原引发
Abstract:
研究了高氧化态过渡金属盐(CuX2/L、FeX3/L,X=Cl或Br;L=2,2'-联吡啶、N,N'-四甲基乙二胺、N,N,N',N″,N″-五甲基二亚乙基三胺;CuSO4)催化甲基丙烯酸2-(N,N-二乙氨基)乙酯(DEAEMA)的自引发氧化聚合,利用气相色谱跟踪单体转化率、利用凝胶渗透色谱和多角激光光散射跟踪聚合物分子量在聚合过程中的变化.结果显示,不加入任何引发剂,高氧化态过渡金属盐可在30~60℃范围内催化DEAEMA的自引发氧化聚合,且随着反应的进行,所得聚合物的分子量随转化率的增大而缓慢上升,且分子量呈现宽分布.多角激光光散射的结果则显示即使低转化率时所得PDEAEMA的绝对分子量也已呈现少见的多峰分布,并且低分子量组分的含量随聚合的进行逐渐减少.通过与CuSO4催化小分子叔胺氧化还原引发能力的比较可知,DEAEMA在高氧化态过渡金属盐的催化下起到自身还原性引发型单体的作用,高氧化态过渡金属盐通过氧化还原将DEAEMA的二乙基氨基α位C—H键氧化成Cα·自由基,引发DEAEMA的普通自由基聚合,形成线型PDEAEMA初级链.随后高氧化态过渡金属盐与PDEAEMA构成氧化还原体系,引发DEAEMA聚合,最终得到具有一定数量侧链的高分子量支化PDEAEMA.以上结果表明,自身还原性引发型单体可通过"一锅煮"式普通自由基聚合制备长链支化聚合物.
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