Effect of tetrahydrofuran on the anionic copolymerization of 4‐trimethylsilylstyrene with isoprene

IF 3.1 4区工程技术 Q2 POLYMER SCIENCE Polymers for Advanced Technologies Pub Date : 2024-06-20 DOI:10.1002/pat.6478

Dominik A. H. Fuchs, Shivani P. Wadgaonkar, Axel H. E. Müller, Holger Frey

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Abstract

The statistical anionic copolymerization of 4‐trimethylsilylstyrene (TMSS) with isoprene (I) in cyclohexane was investigated using in situ near‐infrared (NIR) spectroscopy in the presence of various amounts of the polar modifier tetrahydrofuran (THF). Polymers with narrow molecular weight distribution of 85–138 kg/mol and dispersities of 1.09–1.22 were obtained. By increasing modifier content, the reactivity ratios can be adjusted over a wide range from rTMSS < rI to rTMSS >> rI. Compared to the system styrene/isoprene (S/I) only a minute amount of modifier (0.5 eq THF relative to lithium) is sufficient to alter the reactivity ratios, resulting in an ideally random copolymerization, which validates the higher reactivity of TMSS compared to styrene. Using these reactivity ratios, molar and volume composition gradients were calculated. Additionally, the glass transition temperature and microstructure of the polyisoprene units were investigated via differential scanning calorimetry and proton nuclear magnetic resonance. The results are encouraging for the use of these materials in high‐end applications like membranes.

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四氢呋喃对 4-三甲基硅基苯乙烯与异戊二烯阴离子共聚的影响

在不同量的极性改性剂四氢呋喃（THF）存在下，使用原位近红外光谱（NIR）研究了 4-三甲基硅基苯乙烯（TMSS）与异戊二烯（I）在环己烷中的统计阴离子共聚。得到的聚合物分子量分布较窄，为 85-138 kg/mol，分散度为 1.09-1.22。通过增加改性剂的含量，可在 rTMSS < rI 到 rTMSS >> rI 的较大范围内调节反应率。与苯乙烯/异戊二烯（S/I）体系相比，只需极少量的改性剂（相对于锂而言，0.5 eq THF）就足以改变反应活性比，从而实现理想的无规共聚，这也验证了 TMSS 的反应活性高于苯乙烯。利用这些反应活性比计算出了摩尔和体积成分梯度。此外，还通过差示扫描量热法和质子核磁共振法研究了聚异戊二烯单元的玻璃化温度和微观结构。这些结果对于这些材料在膜等高端应用领域的使用是令人鼓舞的。

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来源期刊

Polymers for Advanced Technologies 工程技术-高分子科学

CiteScore

6.20

自引率

5.90%

发文量

337

审稿时长

2.1 months

期刊介绍： Polymers for Advanced Technologies is published in response to recent significant changes in the patterns of materials research and development. Worldwide attention has been focused on the critical importance of materials in the creation of new devices and systems. It is now recognized that materials are often the limiting factor in bringing a new technical concept to fruition and that polymers are often the materials of choice in these demanding applications. A significant portion of the polymer research ongoing in the world is directly or indirectly related to the solution of complex, interdisciplinary problems whose successful resolution is necessary for achievement of broad system objectives. Polymers for Advanced Technologies is focused to the interest of scientists and engineers from academia and industry who are participating in these new areas of polymer research and development. It is the intent of this journal to impact the polymer related advanced technologies to meet the challenge of the twenty-first century. Polymers for Advanced Technologies aims at encouraging innovation, invention, imagination and creativity by providing a broad interdisciplinary platform for the presentation of new research and development concepts, theories and results which reflect the changing image and pace of modern polymer science and technology. Polymers for Advanced Technologies aims at becoming the central organ of the new multi-disciplinary polymer oriented materials science of the highest scientific standards. It will publish original research papers on finished studies; communications limited to five typewritten pages plus three illustrations, containing experimental details; review articles of up to 40 pages; letters to the editor and book reviews. Review articles will normally be published by invitation. The Editor-in-Chief welcomes suggestions for reviews.