Highly efficient synthesis of low polydispersity core cross-linked star polymers by Ru-catalyzed living radical polymerization.
Highly efficient synthesis of low polydispersity core cross-linked star polymers by Ru-catalyzed living radical polymerization.
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DOI：
10.1002/marc.201000641
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发表时间：
2011-03
影响因子：
4.6
通讯作者：
T. Goh;S. Yamashita;K. Satoh;A. Blencowe;M. Kamigaito;G. Qiao
中科院分区：
文献类型：
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作者：
T. Goh;S. Yamashita;K. Satoh;A. Blencowe;M. Kamigaito;G. Qiao
通过可控/活性自由基聚合(LRP)和ARM-First方法有效地形成了低多分散度的核心交联星形(CCS)聚合物，发现依赖于中介催化剂体系。Ru催化剂Ru(Ind)Cl(PPh₃)₂Cat.)1和叔胺为助催化剂合成了高活性聚甲基丙烯酸甲酯(PMMA)大分子引发剂，然后与乙二醇二甲基丙烯酸酯(EGDMA)相连，形成PMMA(ARM)PEGDMA(核)CCS聚合物。对于低、中分子量大分子引发剂(M(N)=8 kDa和20 kDa)，分别观察到了CCS聚合物的定量和近定量合成。高分子量大分子引发剂(M(N)≥60 kDa)的转化率较低。总体而言，与Cat相比，可以观察到10%到20%的改善。1体系转化为传统的铜催化体系。在催化剂体系选择和CCS聚合物形成的背景下，解释了大分子引发剂到星型转化的这一重大改进。
The efficient formation of low polydispersity core cross-linked star (CCS) polymers via controlled/living radical polymerization (LRP) and the arm-first approach was found to be dependent on the mediating catalyst system. The Ru catalyst, Ru(Ind)Cl(PPh₃)₂ Cat. 1, and tertiary amine co-catalyst were used to synthesize highly living poly(methyl methacrylate) (PMMA) macroinitiators, which were then linked together with ethylene glycol dimethacrylate (EGDMA) to form PMMA(arm)PEGDMA(core) CCS polymers. The quantitative and near-quantitative synthesis of CCS polymers were observed for low to moderate molecular weight macroinitiators (M(n) = 8 and 20 kDa), respectively. Lower conversions were observed for high-molecular weight macroinitiators (M(n) ≥ 60 kDa). Overall, an improvement of between 10 and 20% was observed when comparing the Cat. 1 system to a conventional Cu-catalyzed system. This significant improvement in macroinitiator-to-star conversion is explained in the context of catalyst system selection and CCS polymer formation.