Broken Chain Self-Reconnection Strategy Enables Radiation Ultraresistance of Polyurethane

IF 5.2 1区 化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2024-11-29 DOI:10.1021/acs.macromol.4c02557
Jiading Wang, Shaoyun Guo, Xianlong Zhang
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Abstract

High-energy radiation could accelerate the deterioration of polymer properties, greatly increase the risk of equipment failure, and reduce the polymer’s service life. Inhibition of macromolecular chemical changes in polymers is the core design concept for conventional radiation resistance. Herein, we report a novel strategy that turns the radiation reaction into a repair effect for the self-reconnection of broken chains, thereby improving the radiation resistance of polyurethane (PU) concretely; the polybutadiene (PB) segments are evenly introduced into the PU with poly(propylene glycol) (PG) to prepare the PU containing PB and PG segments (PBG-PU). During irradiation, the radical addition coupling reactions of PB segments in PBG-PU allow the broken molecular chain of PBG-PU to be reconnected, thus continually repairing the radiation damage on PBG-PU. Therefore, the PBG-PU elastomers still maintain about 70% strength with minimal alterations in creep properties and recovery rates after 300 KGy radiation, while the ordinary PU elastomers have completely lost their original properties. The combination of the self-reconnection strategy and the modification method of the hard segment can even boost radiation resistance of PU to more than three times, showing excellent radiation stability. The self-reconnection strategy can also be used to increase the stability of the ultrastructure in material during high-dose gamma ray irradiation, showing great adjustability. This novel strategy demonstrates enormous potential in achieving the long-term application of polymers in nuclear industry, space mission, and radiation medicine fields.

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断链自重联策略使聚氨酯具有超强的耐辐射性能
高能辐射会加速聚合物性能的劣化,大大增加设备故障的风险,降低聚合物的使用寿命。抑制聚合物中的大分子化学变化是传统抗辐射设计的核心理念。在此,我们报道了一种新的策略,将辐射反应转化为断裂链的自重新连接的修复效应,从而具体提高聚氨酯(PU)的耐辐射性;将聚丁二烯(PB)段均匀引入聚丙二醇(PG)中,制得含PB和含PG段的PU (PBG-PU)。在辐照过程中,PBG-PU中PB片段的自由基加成偶联反应使断裂的PBG-PU分子链得以重新连接,从而不断修复PBG-PU上的辐射损伤。因此,在300 KGy辐照后,PBG-PU弹性体仍能保持70%左右的强度,蠕变性能和回复率变化很小,而普通PU弹性体完全失去了原有的性能。自重联策略与硬段改性方法相结合,甚至可以将PU的抗辐射能力提高到3倍以上,表现出优异的辐射稳定性。自重联策略还可用于提高材料在高剂量伽马射线照射下的超微结构稳定性,表现出很强的可调节性。这种新策略在实现聚合物在核工业、太空任务和辐射医学领域的长期应用方面显示出巨大的潜力。
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来源期刊
Macromolecules
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.
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