A series of 1-butene-based random copolymers were synthesized through the direct copolymerization of 1-butene with higher α-olefins, namely 1-octene (C8), 1-dodecene (C12), 1-hexadecene (C16), and 1-eicosene (C20). Four catalysts, namely rac-Et(Ind)₂ZrCl₂ (Cat.1), rac-Me₂Si(1-Ind)₂ZrCl₂ (Cat.2), Me₂C(Cp)(9-Flu)ZrCl₂ (Cat.3), and dimethyl(pyridyl-amido)hafnium (Cat.4), were adopted to promote the copolymerization upon activation with iBu₃Al/Ph₃CB(C₆F₅)₄. The post-metallocene catalyst, Cat.4, displayed superior catalytic activity (>10⁷ g_polymer mol_Hf⁻¹ h⁻¹) and α-olefin incorporation ability, yielding copolymers with ultra-high molecular weight (M_w > 10³ kDa) and isotactic selectivity (mmmm up to 90%). The copolymerizations in this study enable the synthesis of a series of rigid and tough polybutene-based thermoplastic elastomers under mild conditions, with the copolymers exhibiting impressive tensile strengths ranging from 18 to 31 MPa, elongation at breaks between 480% and 650%, and elastic recoveries ranging from 44.7% to 60.7%.

中文翻译：

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1-丁烯与高级α-烯烃共聚制备聚丁烯基热塑性弹性体

通过1-丁烯与高级α-烯烃直接共聚，合成了一系列1-丁烯基无规共聚物，即1-辛烯(C8)、1-十二碳烯(C12)、1-十六碳烯(C16)和1 -二十碳烯（C20）。四种催化剂，即rac -Et(Ind) ₂ ZrCl ₂ (Cat.1)、rac -Me ₂ Si(1-Ind) ₂ ZrCl ₂ (Cat.2)、Me ₂ C(Cp)(9-Flu)ZrCl采用iBu _{3 Al} /Ph ₃ CB(C ₆ F ₅ ) ₄活化后，采用二甲基(吡啶基氨基)铪(Cat.4)和二甲基(吡啶基氨基)铪(Cat.4)促进共聚。后茂金属催化剂Cat.4表现出优异的催化活性（>10 ⁷ g_聚合物mol _Hf ^-1 h ^-1）和α-烯烃掺入能力，产生超高分子量共聚物（M _w > 10 ³ kDa） ）和全同立构选择性（mmmm 高达 90%）。本研究中的共聚能够在温和条件下合成一系列刚性和坚韧的聚丁烯基热塑性弹性体，这些共聚物表现出令人印象深刻的拉伸强度（18至31 MPa）、断裂伸长率（480%至650%）和弹性。回收率范围为 44.7% 至 60.7%。