Metal-catalyzed simultaneous chain- and step-growth radical polymerization: marriage of vinyl polymers and polyesters.
Metal-catalyzed simultaneous chain- and step-growth radical polymerization: marriage of vinyl polymers and polyesters.
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DOI：
10.1021/ja1023892
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发表时间：
2010-05
影响因子：
15
通讯作者：
M. Mizutani;K. Satoh;M. Kamigaito
中科院分区：
文献类型：
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作者：
M. Mizutani;K. Satoh;M. Kamigaito
所有的聚合反应都被分为两大不同的家族，链增长聚合和逐步增长聚合，它们通常是不相容的。在这里，我们报告的同时链和逐步增长聚合通过金属催化自由基共聚合的共轭乙烯基单体和设计的单体具有非共轭C水平线C和活性C-Cl键。特别是在CuCl/1，1，4，7，10，10-六甲基三亚乙基四胺或RuCp*Cl（PPh（3））（2）催化下，丙烯酸甲酯（MA）进行链增长聚合，2-氯丙酸3-丁烯酯（1）进行逐步增长聚合，得到了几乎理想的含乙烯基聚合物和聚酯单元的线性无规共聚物。相反，其他过渡金属催化剂，如CuCl与三[2-（二甲氨基）乙基]胺或N，N，N ′，N ″，N ″-五甲基二亚乙基三胺和FeCl（2）/PnBu（3），通过1与MA的伴随链增长共聚产生支化结构。通过NMR和MALDI-TOF-MS分析聚合反应和模型反应，详细研究了聚合反应机理。此外，通过改变两种单体的投料比，得到了一系列由无规结构向多嵌段结构转变的共聚物。这些共聚物可以通过使用碳酸钠对主链中的酯键进行甲醇分解而容易地降解成较低分子量的低聚物或聚合物。
All polymerization reactions are categorized into two large different families, chain- and step-growth polymerizations, which are typically incompatible. Here, we report the simultaneous chain- and step-growth polymerization via the metal-catalyzed radical copolymerization of conjugated vinyl monomers and designed monomers possessing unconjugated C horizontal lineC and active C-Cl bonds. Especially, almost ideal linear random copolymers containing both vinyl polymer and polyester units in a single polymer chain were formed by the CuCl/1,1,4,7,10,10-hexamethyltriethylenetetramine- or RuCp*Cl(PPh(3))(2)-catalyzed copolymerization of methyl acrylate (MA) for the chain-growth polymerization and 3-butenyl 2-chloropropionate (1) for the step-growth polymerization. In contrast, other transition metal catalysts, such as CuCl with tris[2-(dimethylamino)ethyl]amine or N,N,N',N'',N''-pentamethyldiethylenetriamine and FeCl(2)/PnBu(3), resulted in branched structures via the concomitant chain-growth copolymerization of 1 with MA. The polymerization mechanism was studied in detail by NMR and MALDI-TOF-MS analyses of the polymerizations as well as the model reactions. Furthermore, a series of copolymers changing from random to multiblock polymer structures were obtained by varying the feed ratios of the two monomers. These copolymers can be easily degraded into lower molecular weight oligomers or polymers via methanolysis of the ester-linkages in the main chain using sodium carbonate.