Sequence- and Microstructure-Controlled Alternating Copolymerization of 1,1-Diphenylethylene with 1-Phenyl-1,3-butadienes via Living Anionic Polymerization

IF 5.7 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2026-10-19 DOI:10.1021/acs.macromol.6c02293

Ryosuke Honda,Kotaro Koike,Naoya Yoshida,Motoyasu Kobayashi,Takashi Ishizone,Raita Goseki

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Abstract

Simultaneous control over the alternating sequence and diene microstructure remains a significant challenge in the anionic copolymerization of 1,1-diphenylethylene (DPE) with conjugated dienes. Herein, we report the synthesis of well-defined alternating copolymers of DPE and 1-phenyl-1,3-butadiene derivatives (E-1PBDs). Defect structures containing consecutive E-1PBD units were efficiently suppressed by employing a large excess of DPE ([DPE]/[E-1PBDs] > 13) combined with a bulky tert-butyldimethylsilyl (TBS) substituent on the E-1PBD framework under optimized polymerization conditions (THF, –40 °C). Consequently, highly alternating copolymers containing approximately 81% 1,4-units were obtained. Subsequent hydrogenation using p-toluenesulfonyl hydrazide proceeded quantitatively without any detectable side reactions, affording sequence-controlled alternating ternary copolymers. Hydrogenation caused only a small decrease in the glass transition temperature (from 103 to 92 °C), indicating that the thermal properties of the alternating copolymer were largely preserved after post-polymerization modification.

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序列和微观结构控制的1,1-二苯乙烯与1-苯基-1,3-丁二烯阴离子活性聚合交替共聚

在1,1-二苯乙烯（DPE）与共轭二烯的阴离子共聚过程中，同时控制交替序列和二烯的微观结构仍然是一个重大挑战。本文报道了DPE与1-苯基-1,3-丁二烯衍生物（E-1PBDs）共聚物的合成。在优化的聚合条件下（THF, -40°C），在E-1PBD框架上加入大量过量的DPE （[DPE]/[E-1PBD] bbb13）和大块的叔丁基二甲基硅基（TBS）取代基，有效抑制了含有连续E-1PBD单元的缺陷结构。因此，得到了含有约81%的1,4单元的高度交替共聚物。随后使用对甲苯磺酰肼进行定量加氢，没有任何可检测的副反应，提供顺序控制的交替三元共聚物。加氢作用仅使玻璃化转变温度（从103℃降至92℃）降低很小，说明经聚合后改性后交替共聚物的热性能得到了很大程度的保留。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.