tbd催化阴离子开环聚合六甲基环三硅氧烷：一种可控合成PDMS的新途径

IF 3.9 2区化学 Q2 POLYMER SCIENCE

Polymer Chemistry Pub Date : 2024-12-18 DOI:10.1039/d4py01254b

Alice Corfa , Sylvain Caillol , Julien Pinaud , Vincent Ladmiral

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引用次数: 0

摘要

采用多种引发剂对六甲基环三硅氧烷（D3）的可控阴离子开环聚合进行了优化，得到了易于使用的商业化有机催化剂1,5,7-三氮杂环[4.4.0]十二-5-烯（TBD）。比较了醇类和硅烷醇类合成单官能团和远旋团PDMS的方法。采用1H NMR谱、MALDI-TOF质谱和SEC对聚合过程进行了监测，比较了引发剂结构和催化剂浓度对聚合过程的影响。当使用硅烷醇作为引发剂时，TBD可以控制D3的AROP，从而提供定义明确的PDMS结构。当使用醇作为引发剂时，由于引发速度较慢，聚合过程的控制水平较低。这些起始速率的差异可能源于硅烷醇和醇之间pKa的差异。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

TBD-catalyzed anionic ring-opening polymerization of hexamethylcyclotrisiloxane: a new route for the controlled synthesis of PDMS†

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TBD-catalyzed anionic ring-opening polymerization of hexamethylcyclotrisiloxane: a new route for the controlled synthesis of PDMS†

The controlled anionic ring-opening polymerization of hexamethylcyclotrisiloxane (D₃) was optimized for a commercial and easy-to-use organic catalyst, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), employing various types of initiators. Alcohols and silanols were compared for the synthesis of monofunctional and telechelic PDMS. Polymerizations were monitored by ¹H NMR spectroscopy, MALDI-TOF mass spectroscopy and SEC to compare the effects of the initiator structure and catalyst concentration. TBD was shown to control the AROP of D₃ when using silanols as the initiator, thus affording well-defined PDMS structures. When alcohols were used as initiators, the polymerization proceeded with a lower level of control due to slower initiation. These differences in initiation rates likely originated from the differences in pK_a between silanols and alcohols.

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来源期刊

Polymer Chemistry POLYMER SCIENCE-

CiteScore

8.60

自引率

8.70%

发文量

535

审稿时长

1.7 months

期刊介绍： Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.