Baulu Nicolas, Langlais Marvin, Dugas Pierre-Yves, Thuilliez Julien, Jean-Baptiste-Dit-Dominique François, Lansalot Muriel, Boisson Christophe, D'Agosto Franck
Université Lyon 1, CPE Lyon, CNRS UMR 5128, Laboratoire CP2M, Équipe PCM, 43 Bd du 11 Nov. 1918, 69616, Villeurbanne, CEDEX, France.
Manufacture des pneumatiques Michelin, 23 Place des Carmes Dechaux, 63040, Clermont-Ferrand, France.
Chemistry. 2022 Oct 26;28(60):e202202089. doi: 10.1002/chem.202202089. Epub 2022 Aug 26.
Block copolymers based on ethylene (E) and butadiene (B) were prepared using the ansa-bis(fluorenyl) complex {Me Si(C H ) Nd(BH ) Li(THF)} in combination with (n-Bu)(n-Oct)Mg (BOMAG) as a chain-transfer agent. The diblock copolymers incorporating a soft poly(ethylene-co-butadiene) segment, called ethylene butadiene rubber (EBR), and a hard polyethylene (PE) one were obtained by simply adjusting the different feeds of monomers during the polymerization. The soluble EBR block was formed first by feeding the catalytic system dissolved in toluene at 70 °C with a mixture of ethylene and butadiene (E/B molar ratio 80 : 20). Then the feeding was stopped leading to the consumption of a large part of the residual monomers. The reactor was finally fed with ethylene to form the PE block. By varying the molar mass of the latter, it is shown that the resulting soft-b-hard block copolymers can self-assemble simultaneously to the growth of the PE block in agreement with a polymerization-induced self-assembly (PISA) mechanism. The self-assembly is discussed considering the reaction conditions, the crystallization of the PE block, and the polymerization mechanism involved.
基于乙烯（E）和丁二烯（B）的嵌段共聚物采用ansa - 双（芴基）配合物{MeSi(C₅H₄)Nd(BH₄)Li(THF)}与(n - Bu)(n - Oct)Mg（BOMAG）作为链转移剂制备。通过在聚合过程中简单调整不同单体进料，获得了包含软质聚（乙烯 - 共 - 丁二烯）链段（称为乙烯 - 丁二烯橡胶（EBR））和硬质聚乙烯（PE）链段的二嵌段共聚物。首先，将溶解在甲苯中的催化体系在70°C下与乙烯和丁二烯的混合物（E/B摩尔比80∶20）进料，形成可溶的EBR链段。然后停止进料，导致大部分残留单体被消耗。最后向反应器中加入乙烯以形成PE链段。通过改变后者的摩尔质量表明，所得的软 - 硬 - 嵌段共聚物能够与聚合诱导自组装（PISA）机制一致地在PE链段生长的同时进行自组装。考虑到反应条件、PE链段的结晶以及所涉及的聚合机制对自组装进行了讨论。
