Polymerization of alkyl diazoacetates initiated by the amidinate/Pd system: efficient synthesis of high molecular weight poly(alkoxycarbonylmethylene)s with moderate stereoregularity
Polymerization of alkyl diazoacetates initiated by the amidinate/Pd system: efficient synthesis of high molecular weight poly(alkoxycarbonylmethylene)s with moderate stereoregularity
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DOI：
10.1039/c7py00816c
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发表时间：
2017-07
影响因子：
4.6
通讯作者：
Hiroaki Shimomoto;Junya Kawamata;Hirokazu Murakami;K. Yamashita;T. Itoh;E. Ihara
中科院分区：
文献类型：
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作者：
Hiroaki Shimomoto;Junya Kawamata;Hirokazu Murakami;K. Yamashita;T. Itoh;E. Ihara
研究了脒基/钯引发重氮乙酸酯聚合的新体系。该体系有效地从重氮基乙酸乙酯（EDA，例如，Mn = 45 × 100，44%产率）和重氮基乙酸甲酯（MDA，例如，Mn = 26 200，产率56%）。重氮乙酸正己酯（nHDA）和重氮乙酸苄酯（BDA）通过脒基/Pd体系聚合得到高Mn聚合物（Mn =约100 000），尽管产率低于10%。该体系在EDA与nHDA、BDA和环己基重氮乙酸酯（cHDA）的共聚中也是有效的，以中等产率提供高Mn共聚物。与该系统得到的产物的NMR光谱表明，聚合进行显着更高的立构规整性相比，与以前报道的Pd基引发系统。
The initiating ability of a new system, amidinate/Pd, for the polymerization of diazoacetates is described. The system is effective in affording relatively high number-average molecular weight (Mn) polymers from ethyl diazoacetate (EDA, e.g., Mn = 45 100, 44% yield) and methyl diazoacetate (MDA, e.g., Mn = 26 200, 56% yield) in moderate yield. The polymerization of n-hexyl diazoacetate (nHDA) and benzyl diazoacetate (BDA) by the amidinate/Pd system yields high Mn polymers (Mn = ca.100 000), although the yield was below 10%. The system is also effective in the copolymerization of EDA with nHDA, BDA, and cyclohexyldiazoacetate (cHDA), affording high Mn copolymers in moderate yield. NMR spectra of the products obtained with the system suggest that the polymerization proceeds with significantly higher stereoregularity compared to that with previously reported Pd-based initiating systems.