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Controlled Polymerization of Isoprene with Chromium‐Based Metal‐Organic Framework Catalysts: Switching from Cyclic to cis‐1,4‐Selectivity Depending on Activator
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2018-03-05 , DOI: 10.1002/marc.201800002 Fei Gao 1 , Li Zhang 1 , Chao Yu 1 , Xinwen Yan 1 , Shaowen Zhang 1 , Xiaofang Li 1
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2018-03-05 , DOI: 10.1002/marc.201800002 Fei Gao 1 , Li Zhang 1 , Chao Yu 1 , Xinwen Yan 1 , Shaowen Zhang 1 , Xiaofang Li 1
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Chromium‐based metal‐organic framework (MOF) Cr‐MIL‐100/101 activated by activator and aluminum trialkyl compound serve as unique, highly efficient heterogeneous single‐site catalysts for the controlled polymerization of isoprene, which not only exhibit quasi‐living nature in isoprene polymerization but also unprecedentedly switch from cyclic to cis‐1,4‐selectivity depending on the activator used to yield low molecular weight cyclic PIPs or extremely high molecular weight cis‐1,4‐PIPs. Such heterogeneous Cr‐MOF catalysts can be recycled approximately five times. Based on nitrogen sorption isotherm tests and powder X‐ray diffraction, a cationic mechanism is suggested, in which the polymerization takes place inside the open nanochannels of MOF catalysts and the space confinement effect of narrow open nanochannels originated from the coordination of PhNMe2 from activator [PhNHMe2][B(C6F5)4] with the multiple metal centers of MOF catalysts might give a rational explanation for such controlled adjustment on the PIP's structure and properties.
中文翻译：
铬基金属有机骨架催化剂对异戊二烯的受控聚合：取决于活化剂，从环状选择性转变为顺式1,4-选择性
由活化剂和三烷基铝化合物活化的铬基金属有机骨架（MOF）Cr-MIL-100 / 101是独特的，高效的异质单中心催化剂，可用于异戊二烯的受控聚合，不仅表现出准活泼的性质在异戊二烯聚合反应中，而且还空前地从环状切换为顺式1,4-选择性，具体取决于用于产生低分子量环状PIP或极高分子量顺式的PIP活化剂‐1,4‐PIP。此类多相Cr-MOF催化剂可循环使用约五次。基于氮吸附等温线试验和粉末X射线衍射，提出了一种阳离子机理，其中聚合发生在MOF催化剂的开放纳米通道内，狭窄的开放纳米通道的空间限制效应源自活化剂PhNMe 2的配位。MOF催化剂具有多个金属中心的[PhNHMe 2 ] [B（C 6 F 5）4 ]可能为PIP的结构和性能的这种受控调节提供合理的解释。
更新日期：2018-03-05
中文翻译：
铬基金属有机骨架催化剂对异戊二烯的受控聚合：取决于活化剂，从环状选择性转变为顺式1,4-选择性
由活化剂和三烷基铝化合物活化的铬基金属有机骨架（MOF）Cr-MIL-100 / 101是独特的，高效的异质单中心催化剂，可用于异戊二烯的受控聚合，不仅表现出准活泼的性质在异戊二烯聚合反应中，而且还空前地从环状切换为顺式1,4-选择性，具体取决于用于产生低分子量环状PIP或极高分子量顺式的PIP活化剂‐1,4‐PIP。此类多相Cr-MOF催化剂可循环使用约五次。基于氮吸附等温线试验和粉末X射线衍射，提出了一种阳离子机理，其中聚合发生在MOF催化剂的开放纳米通道内，狭窄的开放纳米通道的空间限制效应源自活化剂PhNMe 2的配位。MOF催化剂具有多个金属中心的[PhNHMe 2 ] [B（C 6 F 5）4 ]可能为PIP的结构和性能的这种受控调节提供合理的解释。
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