Tailored sequencing of highly brominated Poly(ether ether ketone) as a means to preserve crystallizability and enhance Tg

Tailored sequencing of highly brominated Poly(ether ether ketone) as a means to preserve crystallizability and enhance Tg
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高度溴化聚醚醚酮的定制测序作为保持结晶性和提高 Tg 的手段

DOI:
10.1016/j.polymer.2022.124918
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发表时间:
2022
期刊:
影响因子:
4.6
通讯作者:
Moore, Robert B.
Moore, Robert B.
中科院分区:
化学2区
文献类型:
--
作者:
Kasprzak, Christopher R.;Anderson, Lindsey J.;Moore, Robert B.

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本文研究了聚醚醚酮(PEEK)在温和试剂N-溴代丁二酰亚胺(NBS)作用下的溴化反应。溴化进行定量的溶液状态和半结晶凝胶状态,和溴化度之间的25和175摩尔%,随机和块状BrPEEK。光谱证据显示,在相似的官能度下,块状BrPEEK的未官能化重复单元的发生率高于随机BrPEEK。此外,在类似程度的溴化,块状BrPEEK表现出增强的玻璃化转变温度,更大的结晶性,更高的熔融温度,更快的结晶动力学比随机BrPEEK,这表明在块状BrPEEK的非官能化PEEK的较长的片段。总之,这项工作表明,PEEK可以溴化到非常高的取代度,在半结晶凝胶状态,同时保持结晶性和有效地阻止了功能。
In this report, the bromination of poly(ether ether ketone) (PEEK) using the mild reagentN-bromosuccinimide (NBS) is explored to generate controlled random and blocky microstructures. Bromination proceeded quantitatively in both the solution state and semicrystalline gel-state, and degrees of bromination between 25 and 175 mol% were obtained for both random and blocky BrPEEK. Spectroscopic evidence revealed a higher prevalence of unfunctionalized repeat units for blocky BrPEEK than random BrPEEK at similar degrees of functionality. Furthermore, at similar degrees of bromination, blocky BrPEEK exhibited enhanced glass transition temperatures, greater crystallizability, higher melting temperatures, and faster crystallization kinetics than random BrPEEK, suggesting longer segments of unfunctionalized PEEK in blocky BrPEEK. Overall, this work demonstrates that PEEK can be brominated to very high degrees of substitution in the semicrystalline gel-state while preserving crystallizability and effectively blocking up the functionality.
溴化无规聚丙烯的热学研究
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