Jiao Caicai, Gao Lilong, Yu Bing, Cong Hailin, Shen Youqing
College of Materials Science and Engineering, Qingdao University Qingdao 266071 China
Institute of Biomedical Materials and Engineering, Qingdao University Qingdao 266071 China
RSC Adv. 2019 Dec 6;9(69):40455-40461. doi: 10.1039/c9ra08155k. eCollection 2019 Dec 3.
The Michael addition and alkylation reaction of active methylene compounds (AMCs) with two active hydrogens had been investigated extensively in organic chemistry, while the polymerization of AMCs had few studies. Herein, we reported active methylene-based polyaddition and polyalkylation catalyzed an organic superbase under ambient conditions. A model polymerization was first conducted between ethylene glycol diacrylate (EGDA) and methyl cyanoacetate (MCA). The molecular weight ( ) of the model polymer was up to 50 500 g mol with a high yield (99%). Eight AMCs were selected and a high-throughput parallel synthesizing instrument (HTPSI) was used to synthesize semi-library polymers of AMCs and EGDA a Michael type polyaddition. The obtained AMC-based polymers had low cell cytotoxicity. Elastomers with cyanogen groups could be prepared using trimethylolpropane triacrylate (TMPTA) as a crosslinker. Furthermore, three dihalogen compounds were explored to polymerize with MCA and malononitrile alkylation reactions. The pendent cyanogen or ester groups of the polymers could be reduced by lithium aluminum hydride. Novel polymer families were constructed based on the polyaddition and polyalkylation of AMCs.
在有机化学中，具有两个活性氢的活性亚甲基化合物（AMC）的迈克尔加成反应和烷基化反应已得到广泛研究，而AMC的聚合反应研究较少。在此，我们报道了在环境条件下由有机超强碱催化的基于活性亚甲基的聚加成和聚烷基化反应。首先在乙二醇二丙烯酸酯（EGDA）和氰基乙酸甲酯（MCA）之间进行了模型聚合反应。模型聚合物的分子量（ ）高达50500 g/mol，产率很高（99%）。选择了八种AMC，并使用高通量平行合成仪器（HTPSI）通过迈克尔型聚加成反应合成了AMC与EGDA的半文库聚合物。所得到的基于AMC的聚合物具有低细胞毒性。可以使用三羟甲基丙烷三丙烯酸酯（TMPTA）作为交联剂制备含氰基的弹性体。此外，还探索了三种二卤化合物与MCA和丙二腈发生烷基化反应进行聚合。聚合物的侧链氰基或酯基可以用氢化铝锂还原。基于AMC的聚加成和聚烷基化反应构建了新型聚合物家族。
