In situ synthesis of novel trans-1, 4-polyisoprene/isotactic polybutene reactor blends with multi-component structure

Huafeng Shao, Pengcheng Xia, Shulei Wang, Aihua He
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Abstract

In this paper, a series of novel trans-1, 4-polyisoprene/isotactic polybutene (TPI/iPB) in-reactor blends were synthesized by isoprene and butene sequential two-stage polymerization technology with spherical TiCl4/MgCl2 type Ziegler-Natta catalyst. The components, structures, and properties of the as-obtained TPI/iPB reactor blends were characterized by gel permeation chromatography, Fourier transform Infrared spectroscopy, and differential scanning calorimetry. The active trans-1, 4-polyisoprene (TPI) particles obtained in the initial isoprene polymerization by the Z-N catalyst can be acted as microreactors to initiate butene polymerization subsequently. The TPI/iPB reactor blends with varied components were in situ synthesized within the reactor. The preparative-temperature rising elution fractionation (p-TREF) technique was used to fractionate the TPI/iPB reactor blends based on the elution temperature ranged from −40°C to 90°C. The weight distribution and microstructure of each fraction were investigated. The reactor blends are composed of crystallizable high trans-1, 4-uint polyisoprene obtained from the first-stage isoprene polymerization, high isotactic polybutene obtained from the second-stage butene polymerization and TPI-b-iPB block copolymer with different sequence structure obtained from the initial time of the second stage. This work is expected to propose the possible polymerizations of a-olefins and conjugated dienes by using heterogeneous Ziegler-Natta catalyst and provide a kind of novel rubber/plastic reactor blend materials.

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原位合成具有多组分结构的新型反式-1, 4-聚异戊二烯/异actic 聚丁烯反应器共混物
本文采用球形 TiCl4/MgCl2 型 Ziegler-Natta 催化剂,通过异戊二烯和丁烯顺序两级聚合技术合成了一系列新型反式-1,4-聚异戊二烯/异构聚丁烯(TPI/iPB)反应器内共混物。凝胶渗透色谱法、傅立叶变换红外光谱法和差示扫描量热法对得到的 TPI/iPB 反应器共混物的组分、结构和性质进行了表征。Z-N 催化剂在异戊二烯初始聚合过程中获得的活性反式-1, 4-聚异戊二烯(TPI)颗粒可用作微反应器,随后启动丁烯聚合。不同成分的 TPI/iPB 反应器混合物是在反应器内原位合成的。采用预处理-升温洗脱分馏(p-TREF)技术,根据-40°C 至 90°C 的洗脱温度对 TPI/iPB 反应器混合物进行分馏。对每种馏分的重量分布和微观结构进行了研究。反应器混合物由第一阶段异戊二烯聚合得到的可结晶高反式-1,4-uint 聚异戊二烯、第二阶段丁烯聚合得到的高异方性聚丁烯和第二阶段初期得到的具有不同序列结构的 TPI-b-iPB 嵌段共聚物组成。这项工作有望提出利用异相齐格勒-纳塔催化剂聚合 a- 烯烃和共轭二烯的可能性,并提供一种新型橡胶/塑料反应器共混材料。
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Long-term durability of thermoplastic elastomer containing antiviral additives for mobility applications In situ synthesis of novel trans-1, 4-polyisoprene/isotactic polybutene reactor blends with multi-component structure
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