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Trans‐1,4‐stereospecific copolymerization of ethylene and isoprene catalyzed by MgCl2‐supported Ziegler–Natta catalyst
Journal of Polymer Science Part A: Polymer Chemistry Pub Date : 2018-10-21 , DOI: 10.1002/pola.29255 Shaofei Song 1 , Xiaoyu Liu 1 , Hao Zhang 1 , Zhisheng Fu 1 , Junting Xu 1 , Zhiqiang Fan 1
Journal of Polymer Science Part A: Polymer Chemistry Pub Date : 2018-10-21 , DOI: 10.1002/pola.29255 Shaofei Song 1 , Xiaoyu Liu 1 , Hao Zhang 1 , Zhisheng Fu 1 , Junting Xu 1 , Zhiqiang Fan 1
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Copolymerization of ethylene and isoprene (Ip) catalyzed by TiCl4/MgCl2‐Al(i‐C4H9)3 catalyst was systematically studied. Homopolymer of ethylene and Ip were synthesized under the same conditions for making comparisons. Proton nuclear magnetic resonance was employed to characterize chain structure of the copolymer. Influences of Ip concentration, molar ratio of cocatalyst to Ti and reaction temperature on the copolymerization activity and copolymer chain structure were investigated. The copolymerization activity was evidently lowered by increasing Ip concentration, and the Ip content in copolymer was rather low under reaction conditions leading to higher activity. Insertions of Ip in polymer chain showed rather high regioselectivity for 1,4‐connections (>85%) and medium to high stereoselectivity for trans‐1,4‐isomer (>70%) under typical conditions, but the regio and stereoselectivities tended to decrease with decrease in Ip concentration and increase in Al/Ti ratio. Melting temperature of the copolymer decreased with increase of Ip content, indicating incorporation of Ip units in most of the copolymer chains. This work has proved feasibility of introducing small amount of Ip units with high trans‐1,4‐stereoselectivity into ethylene/isoprene copolymer chains by catalyzed copolymerization with MgCl2‐supported Ziegler–Natta catalysts. The copolymer is expected to be a promising candidate of easily degradable film or packaging materials. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2715–2722
中文翻译：
MgCl2负载的齐格勒-纳塔催化剂催化乙烯和异戊二烯的反式1,4-立体特异性共聚
TiCl 4 / MgCl 2 -Al（i -C 4 H 9）3催化的乙烯和异戊二烯（Ip）的共聚对催化剂进行了系统的研究。在相同条件下合成乙烯和Ip的均聚物以进行比较。利用质子核磁共振来表征共聚物的链结构。研究了Ip浓度，助催化剂与Ti的摩尔比和反应温度对共聚活性和共聚物链结构的影响。通过增加Ip浓度，共聚活性明显降低，并且在反应条件下，共聚物中的Ip含量相当低，导致较高的活性。Ip在聚合物链中的插入显示出对1,4连接的区域选择性相当高（> 85％），对反式具有中等至高的立体选择性-1,4-异构体（> 70％）在典型条件下，但是区域和立体选择性倾向于随着Ip浓度的降低和Al / Ti比的增加而降低。共聚物的熔融温度随着Ip含量的增加而降低，这表明大多数共聚物链中都掺入了Ip单元。这项工作证明了通过与MgCl 2负载的Ziegler-Natta催化剂催化共聚将少量具有高反式1,4-立体选择性的Ip单元引入乙烯/异戊二烯共聚物链的可行性。该共聚物有望成为易于降解的薄膜或包装材料的有前途的候选者。©2018 Wiley Periodicals，Inc.J.Polym。科学，A部分：Polym。化学 2018，56，2715年至2722年
更新日期：2018-10-21
中文翻译：
MgCl2负载的齐格勒-纳塔催化剂催化乙烯和异戊二烯的反式1,4-立体特异性共聚
TiCl 4 / MgCl 2 -Al（i -C 4 H 9）3催化的乙烯和异戊二烯（Ip）的共聚对催化剂进行了系统的研究。在相同条件下合成乙烯和Ip的均聚物以进行比较。利用质子核磁共振来表征共聚物的链结构。研究了Ip浓度，助催化剂与Ti的摩尔比和反应温度对共聚活性和共聚物链结构的影响。通过增加Ip浓度，共聚活性明显降低，并且在反应条件下，共聚物中的Ip含量相当低，导致较高的活性。Ip在聚合物链中的插入显示出对1,4连接的区域选择性相当高（> 85％），对反式具有中等至高的立体选择性-1,4-异构体（> 70％）在典型条件下，但是区域和立体选择性倾向于随着Ip浓度的降低和Al / Ti比的增加而降低。共聚物的熔融温度随着Ip含量的增加而降低，这表明大多数共聚物链中都掺入了Ip单元。这项工作证明了通过与MgCl 2负载的Ziegler-Natta催化剂催化共聚将少量具有高反式1,4-立体选择性的Ip单元引入乙烯/异戊二烯共聚物链的可行性。该共聚物有望成为易于降解的薄膜或包装材料的有前途的候选者。©2018 Wiley Periodicals，Inc.J.Polym。科学，A部分：Polym。化学 2018，56，2715年至2722年
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