Peroxide-Mediated Alkyl–Alkyl Coupling of Dialkylzinc: A Useful Tool for Synthesis of ABA-Type Olefin Triblock Copolymers,Macromolecules

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Peroxide-Mediated Alkyl–Alkyl Coupling of Dialkylzinc: A Useful Tool for Synthesis of ABA-Type Olefin Triblock Copolymers
Macromolecules ( IF 5.1 ) Pub Date : 2018-06-25 00:00:00 , DOI: 10.1021/acs.macromol.8b00907
Sung Dong Kim ₁ , Tae Jin Kim ₁ , Su Jin Kwon ₁ , Tae Hee Kim ₁ , Jun Won Baek ₁ , Hee Soo Park ₁ , Hyun Ju Lee ₁ , Bun Yeoul Lee ₁

Affiliation

A practical and simple method for the preparation of ABA-type olefin triblock copolymers, e.g., PE-b-poly(ethylene-co-propylene)-b-PE, has been described. The performance of the so-called “coordinative chain transfer polymerization” (CCTP) by sequential feed of ethylene and ethylene/propylene mixed gas generated a Zn-bound diblock copolymer (i.e., (PE-b-poly(ethylene-co-propylene)yl)₂Zn). Treatment of the Zn-bound diblock copolymer with lauroyl peroxide (CH₃(CH₂)₁₀C(O)O-OC(O)(CH₂)₁₀CH₃) led to a C(sp³)–C(sp³) coupling reaction between the two diblock chains bound on the zinc site and an ABA-type olefin triblock copolymer, PE-b-poly(ethylene-co-propylene)-b-PE, was formed. Upon the treatment with lauroyl peroxide, the number-average molecular weight increased by 1.5–1.7 times. The occurrence of the coupling reaction was verified using a model compound, (Oct)₂Zn. The ABA-type triblock copolymer exhibited thermoplastic elastomeric properties and dramatically improved mechanical properties (twice the tensile strength and 10-fold increase in the elongation at break) as compared to the diblock congener.

中文翻译：

过氧化物介导的二烷基锌的烷基-烷基偶联：合成ABA型烯烃三嵌段共聚物的有用工具

用于制备ABA型的烯烃三嵌段共聚物，例如，PE-一种实用而简单的方法b -聚（乙烯-共-丙烯） - b -PE，进行了说明。通过依次进料乙烯和乙烯/丙烯混合气体进行的所谓“配位链转移聚合”（CCTP）的性能生成了锌键合的二嵌段共聚物（即，（PE- b-聚（乙烯-共-丙烯） yl）₂ Zn）。用月桂酰过氧化物（CH ₃（CH ₂）₁₀ C（O）O-OC（O）（CH ₂）₁₀ CH ₃）处理与Zn结合的二嵌段共聚物会导致C（sp ³）–C（sp ³）结合在锌位点上的两个双嵌段链与ABA型烯烃三嵌段共聚物PE- b-聚（乙烯-共-丙烯）b- PE形成偶联反应。用过氧化月桂酰处理后，数均分子量增加了1.5-1.7倍。使用模型化合物（Oct）₂ Zn验证了偶联反应的发生。与二嵌段同类物相比，ABA型三嵌段共聚物具有热塑性弹性体性能和显着改善的机械性能（拉伸强度和断裂伸长率提高了两倍）。

更新日期：2018-06-25

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