Impact of Cross-Link Density on Polybutadiene Permanent and Vitrimer Networks.

IF 5.1 Q1 POLYMER SCIENCE
Dana Ezzeddine, Daniel C Barzycki, Ralm G Ricarte
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引用次数: 0

Abstract

Vitrimers are polymer networks that undergo structural rearrangement through dynamic associative bond exchange without compromising the overall topological connectivity. In this study, we investigate the impact of cross-link density on the structural, viscoelastic, and glass transition properties of both vitrimer and permanent networks. We synthesized polybutadiene (PB) networks using a photoinitiated thiol-ene click reaction to incorporate either dynamic dioxaborolane or permanent 1,4-benzenedimethanethiol cross-links, with the number of cross-links per chain ranging from 2 to 15. To quantify the actual cross-link density, we developed a network disassembly procedure in which an excess of 1,2-octanediol de-cross-links the PB vitrimer, after which the resulting fragments are analyzed using 1H nuclear magnetic resonance spectroscopy. Although both networks exhibit identical gel fractions, small-amplitude oscillatory shear measurements combined with phantom network theory analysis reveal that vitrimers have a higher effective cross-link density than do their permanent counterparts. Vapor swelling experiments further indicated that PB vitrimers have fewer defects than permanently cross-linked networks. Differential scanning calorimetry demonstrated that vitrimers and permanent networks exhibit distinct relationships between the glass transition temperature and cross-link density. Overall, our findings underscore the significant influence of dynamic associative cross-links on the behavior and performance of elastomeric materials.

交联密度对聚丁二烯永久网络和玻璃体网络的影响。
玻璃体是通过动态结合键交换进行结构重排而不影响整体拓扑连通性的聚合物网络。在这项研究中,我们研究了交联密度对玻璃体和永久网络的结构、粘弹性和玻璃化转变性能的影响。我们利用光引发的硫醇-烯点击反应合成了聚丁二烯(PB)网络,并加入了动态二恶硼烷或永久1,4-苯二甲硫醇交联,每个链的交联数从2到15不等。为了量化实际交联密度,我们开发了一种网络拆卸程序,其中过量的1,2-辛二醇使PB vitrimer脱交联,之后使用1H核磁共振波谱分析产生的片段。尽管这两种网络都表现出相同的凝胶组分,但小振幅振荡剪切测量结合幻影网络理论分析表明,与永久性网络相比,vitrimers具有更高的有效交联密度。气胀实验进一步表明,与永久交联网络相比,PB聚合物具有更少的缺陷。差示扫描量热法表明,玻璃化转变温度与交联密度之间存在明显的关系。总的来说,我们的研究结果强调了动态缔合交联对弹性体材料的行为和性能的重要影响。
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
CiteScore
10.40
自引率
3.40%
发文量
209
审稿时长
1 months
期刊介绍: ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.
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