容易从顺式聚丁二烯橡胶获得羧基封端的聚丁二烯和聚乙烯,Journal of Applied Polymer Science

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容易从顺式聚丁二烯橡胶获得羧基封端的聚丁二烯和聚乙烯
Journal of Applied Polymer Science ( IF 2.7 ) Pub Date : 2018-07-19 , DOI: 10.1002/app.46934
Lu Dai ₁ , Xixi Wang ₁ , Zhiyang Bu ₁ , Bo-Geng Li ₁ , Suyun Jie ₁

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羧基封端的聚丁二烯（CTPB）是一种广泛使用的远螯液态橡胶，主要通过1,3-丁二烯的阴离子或自由基聚合制备。众所周知，液态聚丁二烯橡胶的微观结构会极大地影响其加工性能和机械性能。然而，在自由基或阴离子聚合中难以控制其微观结构。在这项研究中，通过顺式聚丁二烯橡胶（BR）的氧化和选择性氧化，首次制备了一系列具有高顺式-1,4含量的CTPB 。他们CC双键的加氢p甲苯磺酰肼/三ñ丙胺（TSH / TPA）试剂可提供羧基封端的聚乙烯（CTPE）。为了进行比较，还对通过1,3-丁二烯的自由基聚合反应制得的商用CTPB（FCTPB）进行了氢化处理，使FCTPE带有更多的乙基支链。线性CTPE（L-CTPE）是在马来酸存在下通过1,5-环辛二烯的开环易位聚合和随后的氢化反应合成的。聚合物的微观结构通过FT-IR，¹ H NMR，¹³ C NMR和GPC确定，其热性质通过DSC和TGA确定。©2018 Wiley Periodicals，Inc.J.应用 Polym。科学 2019，136，46934。

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Facile access to carboxyl‐terminated polybutadiene and polyethylene from cis‐polybutadiene rubber

Carboxyl‐terminated polybutadiene (CTPB) is a widely used telechelic liquid rubber, which is mainly prepared by anionic or free‐radical polymerization of 1,3‐butadiene. It is known that the microstructure of liquid polybutadiene rubber largely affects its processability and mechanical properties. However, it is hard to control its microstructure in the free radical or anionic polymerization. In this study, a series of CTPB with high cis‐1,4 content has been prepared for the first time via the oxidolysis and selective oxidation of cis‐polybutadiene rubber (BR). Hydrogenation of their CC double bonds with p‐toluenesulfonyl hydrazide/tri‐n‐propylamine (TSH/TPA) reagents afforded carboxyl‐terminated polyethylenes (CTPE). For comparison, commercial CTPB (FCTPB), prepared by free‐radical polymerization of 1,3‐butadiene, was also hydrogenated and gave FCTPE with more ethyl branches. Linear CTPE (L‐CTPE) was synthesized by ring‐opening metathesis polymerization of 1,5‐cyclooctadiene in the presence of maleic acid and subsequent hydrogenation. The microstructure of the polymers was established by FT‐IR, ¹H NMR, ¹³C NMR, and GPC and their thermal properties were determined by DSC and TGA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 46934.

更新日期：2018-07-19

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