基于离子液体和二芳基乙烯的离子凝胶的光致变色、导电、自修复及柔性传感性能

在丙烯酸聚合中原位引入4,4′-(全氟环戊烯-1,2-二基)双(5-甲基噻吩-2-甲醛)(DEA)和离子液体1-丁基-3-甲基咪唑四氟硼酸盐((BMIm)BF₄),制备了一种同时具有光致变色、导电、自黏附且具有宽温度工作区间等性能的新型离子自修复凝胶DPZI。由于(BMIm)BF₄的高热稳定性和低蒸气压,所获得的DPZI凝胶在-20～40℃较宽的温度下表现出高度稳定的机械和离子导电性能。DPZI系统中引入的Zn²⁺与—COO^- 形成动态配位键,使得凝胶具有快速的自修复能力,0.06 s即可超快恢复电阻响应;离子液体的引入同时赋予了凝胶优异的抗冻性。DPZI因光致变色单元DEA的异构化可在10 s内快速发生黄-蓝颜色可逆转变,且光致变色单元的开环/闭环异构化能够实现对凝胶导电性的调节。此外,DPZI凝胶应变/压力式传感器可迅速、精准感知人体不同部位的运动并做出相应的响应;也可对呼吸、心率、声音做出精准识别,应变灵敏度为0.2%。     

二芳基乙烯类光致变色材料的合成概述

由于具有多种潜在的应用价值, 光致变色化合物作为高级功能材料的研究在国内外广受关注. 在众多的有机光致变色化合物中, 二芳基乙烯特别是二噻吩乙烯, 由于其具有良好的热稳定性和优良的耐疲劳度而成为这类化合物的杰出代表. 近年来, 有关二芳基乙烯类光致变色化合物的各种合成及性能方面的报道已涉及到信息存储、分子开关、逻辑电路、液晶显示、磁性材料等众多领域. 主要是从有机合成的角度, 对这类材料的合成进行了较为全面的概括, 对各种合成方法分别加以介绍和分析, 对其发展趋势予以探索和展望.     

导电水凝胶基柔性电子传感系统——柔性电子创新实验设计

导电水凝胶兼具生物医用材料和导电材料特征,可应用于医疗康复、运动监测和人机交互等领域。为提高柔性电子学专业本科生的创新意识与实验技能,本实验设计了一种纳米凝胶材料交联的导电水凝胶,通过探索加聚型水凝胶聚合过程中引发剂浓度和交联机制,阐明材料结构组分对水凝胶基柔性电子器件使用耐久性能及传感性能的影响。通过创新实验设计,柔性电子学专业本科生可以学习到高分子乳液聚合、水凝胶制备以及应力应变传感性能表征等知识点,深入理解交联剂结构设计对材料功能性的影响。此外,本实验还设计了基于水凝胶柔性电子传感器的可穿戴传感系统,通过集成可控制小车移动的智能手套,以及用于控制电脑游戏的水凝胶控制器,将前沿科研与本科实验教学任务紧密结合,有利于激发柔性电子、材料、电子信息等专业本科生对于科研的兴趣和创新探索的科研精神。     

自修复聚乙烯醇/细菌纤维素水凝胶电解质制备及应用

以聚乙烯醇(PVA)、细菌纤维素(BC)和硫酸为原料,采用物理交联的冻融循环法制备了聚乙烯醇/细菌纤维素复合水凝胶电解质;经过冻融循环后,聚乙烯醇和细菌纤维素形成了大量的分子间氢键,赋予复合水凝胶良好的自修复性能和力学性能.探讨了纤维素含量对水凝胶电解质力学性能和离子电导率的影响,结果表明,BC含量为0.6％时复合水凝...     

一种新光致变色二芳基乙烯化合物的合成、光致变色反应动力学、荧光和结构研究

The photochromic diarylethene, 1,2-bis[2-methyl-5-（3-trifluoromethylphenyl）-3-thienyl]perfluorocyclopentene （BMTTP）, was synthesized and its photochromic kinetics, fluorescence and X-ray structure were investigated. This compound underwent a photochromic reaction both in solution and the single crystalline phase. Its cyclization/cycloreversion process was determined to be zeroth/first order reaction, respectively, and this is the first report on the cyclization/cycloreversion reaction order. In addition, its fluorescence property was also discussed.     

海藻酸钠-锌自修复水凝胶的制备及其对亚甲基蓝的吸附性能

废水处理中迫切需要制备多重刺激响应和具有自修复性能的吸附剂。基于此,本文选择海藻酸钠（ALG）和锌离子（Zn2+）为原料,通过一步法快速（仅2s）制备了超分子水凝胶。所制备的水凝胶显示出多重刺激（pH,金属盐等）响应性和自修复性能,这对吸附有机污染物至关重要。选择亚甲基蓝（MB）为模型染料研究了水凝胶的吸附性能。水凝胶对MB的最大吸附量为5.3 mg/g,对低浓度污染物具有良好的吸附能力（去除率超过80％）。吸附动力学均符合准二级动力学方程,Freundlich模型能很好地拟合等温吸附过程,表明ALG-Zn水凝胶对MB的吸附以多层吸附为主。制备出的ALG-Zn水凝胶适合作为吸附剂应用于废水处理。     

基于金属配位键的自修复、可重塑聚丁二烯橡胶的合成及性能

橡胶材料通常因经过硫化及补强等工艺处理而呈现出热固性,因而难以被回收处理,容易造成严重的资源浪费和环境污染.本文通过在聚丁二烯上修饰羧酸基团,再加入锌离子(Zn2+)与羧酸配位,制备了基于金属配位键交联的自修复橡胶(PB-COOH/Zn2+).该橡胶具有良好的机械性能和优秀的自修复及重塑性能,在70℃下修复3 h,其韧性可以恢复到初始强度,修复效率可达100%. PB-COOH/Zn2+较高的聚合物链段运动能力及配位键交联网络良好的动态性不仅赋予其优异的修复性能,还使得其在较温和的条件下可以进行多次重塑,在70℃及5 MPa的条件下重塑3次仍能保持原有的机械性能.此外,通过在PB-COOH/Zn2+中掺杂适量的碳纳米管,不仅增强了其机械性能,还使其具备了电致修复及传感能力,扩宽了PB-COOH/Zn2+作为环境友好型材料的应用前景.     

氢键型水凝胶自修复行为的Monte Carlo模拟

基于氢键型自修复水凝胶的结构特征构建了其横截面的格气模型, 并利用Monte Carlo模拟方法对其自修复行为进行研究. 首先根据自修复过程中的比热峰值确定了氢键的临界联结分数, 然后重点考察了氢键强度、 合作效应以及平均断面间距对其自修复行为的影响. 在此基础上, 进一步研究了氢键型凝胶的动态修复过程, 讨论了相关因素对自修复时间等动态性质的影响. 结果表明, 氢键型凝胶的自修复在本质上归属于一级热力学相变, 且氢键强度是自修复过程中的最关键因素. 同时, 初始断面间距和格子间的合作效应也可显著影响凝胶的自修复行为.     

六芳基二咪唑类化合物的合成及光致变色性能

六芳基咪唑;六芳基二咪唑类化合物的合成及光致变色性能     

Adaptive Ion-Gel: Stimuli-Responsive,and Self-Healing Ion Gels

Ion gels are an emerging class of polymer gels in which a three-dimensional polymer network swells with an ionic liquid. Ion gels have drawn considerable attention in various fields such as energy and biotechnology owing to their excellent properties including nonvolatility, nonflammability, high ionic conductivity, and high thermal and electrochemical stability. Since the first report on ion gels (published ∼30 years ago), diverse functional ion gels exhibiting impressive physicochemical properties have been reported. In this review, recent developments in functional ion gels that can modulate their physical properties in response to environmental conditions are outlined. Stimuli-responsive ion gels that can adaptively undergo phase transitions in response to thermal and light stimuli are initially discussed, followed by an evaluation of diverse self-healing ion gels that can spontaneously mend mechanical damage through judiciously designed ion-gel networks.     

Keggin结构钼磷酸/聚碳酸酯复合物的制备及光致变色性质研究

近年来，多酸－有机复合材料的研究，受到了人们的广泛关注犤１犦。杂多化合物是一类含有氧桥的多核配合物，作为高质子酸，可以提供质子与有机给体形成多酸－有机复合物，这类质子化状态的复合物具有良好的光敏性，这种特性在光化学、氧化还原催化等方面显示出重要用途。聚碳酸酯是一种综合性能优良的光学材料，研究以其为基材的杂多酸－有机复合材料的基本性能，对聚碳酸酯的改性、增进对这类复合材料的理论研究以及拓宽聚碳酸酯的应用都有重要的实际意义，迄今为止，尚未见这方面的报道。本文以Keggin结构钼磷酸（简写为PMo１２）和聚…     

Spiropyran‐Based Polymeric Vesicles: Preparation and Photochromic Properties

A direct access to photochromic polymeric vesicles was demonstrated via polymerization‐induced self‐assembly and reorganization (PISR). The resulting vesicles displayed interesting photochromic behaviors different from that of their free polymer chains in DMF, and the vesicles exhibited stronger fluorescence and excellent photostability due to confinement of conformational flexibility of the polymer chains in aggregates.

     

Effect of Heat Treatment and Additives on the Photochromic and Mechanical Properties of Sol-Gel Derived Photochromic Coatings Containing Spirooxazine

The experimental results on the photochromic and mechanical properties of coatings containing 1,3-dihydro-1,3,3-trimethylspiro[2H-indole-2,3′-(3H)-naphth(2,1-b)(1,4) oxazine] (SO) derived from 3-glycidyl-oxypropyltrimethoxysilane (GPTMS), bisphenolA (BPA) and 1-methylimidazole (MI) by sol-gel processing are presented. It is shown that heat treatment temperature is a conflicting factor to the photochromic intensity (ΔA ₀), photostability and abrasion resistance of the photochromic coatings. With increasing densification temperature the matrix rigidity increases leading to a decrease of ΔA ₀ and at the same time an enhancement of both abrasion resistance and photostability, the optimum heat treatment temperature is 110°C under our experimental conditions. By the use of certain additives, e.g., fluorosilanes (FAS), not only ΔA ₀ but also the photostability and the abrasion resistance of the photochromic coatings have been further improved.     

基于3D导电材料的柔性应力/应变传感器

柔性应力/应变传感器作为智能可穿戴设备的重要组成部分,在人体运动检测、健康监测、机器人和电子皮肤等方面得到了广泛应用.其中,3D导电材料(如气凝胶、海绵和泡沫等)不仅拥有3D互连微结构,还具有优异的可压缩性和导电性,在一定程度上解决了传感器同时拥有高灵敏度和宽检测限的难题.本文根据制备3D导电材料的原材料将其划分为生物...     

Self-Healing Polymer Composites: Prospects,Challenges, and Applications

Self-healing polymer composites possess the inherent ability to heal the damage event autonomically or non-autonomically with external intervention. These advanced materials can be commercialized if the challenges and limitations of different self-healing mechanisms are well known and considered. These include capsule-based healing systems, vascular healing systems, and intrinsic healing systems. To date, most of the reviews have studied and reported on different self-healing mechanisms including their response to impact, fatigue, and corrosion tests. This review focuses mostly on extrinsic and intrinsic self-healing polymer composites which have been reported during the past five years by comparing their healing efficiency, advantages, and challenges in the prospect of their future development as well as their possible applications across various industries such as aerospace, automobile, coating, electronics, energy, etc.     

One-Pot,Open-Air Synthesis of Flexible and Degradable Multifunctional Polymer Composites with Adhesion,Water Resistance,Self-Healing,Facile Drug Loading,and Sustained Release Properties

Developing proper wound management via wound dressings represents a global challenge. Ideal wound dressings shall encompass multiple integrated functionalities for variable, complex scenarios; however, this is challenging due to the complex molecular design and synthesis process. Herein, polymer composites, cross-linked poly(styrene oxide-co-hexaphenylcyclotrisiloxane)/crosslinked poly(hexaphenylcyclotrisiloxane) (cP(SO-co-HPCTS)/cPHPCTS) with multiple functionalities are prepared by a one-step, open-air method using catalytic ring-opening polymerization. The introduction of a mobile polymer cP(SO-co-HPCTS) endows the composite with good flexibility and self-healing properties at human body temperature. The hydrophobic groups in the main chain provide hydrophobicity and good water resistance, while the hydroxyl groups contained in the end groups enable good adhesion properties. Drugs can be efficiently loaded by blending and then sustainably release from the polymer composite. The material can rapidly degrade in a tetrahydrofuran solution of tetrabutylammonium fluoride due to its Si O Si bonds. The facile, one-step, open-air synthesis procedure and multiple functional properties integrated into the composites provide good prospects for their extensive application and batch production as wound dressing materials.     

N-乙基-9′-溴丁氧基螺噁嗪的合成及其化学改性PMMA的结构与光致变色性能

合成了分子结构中含活性C—Br键的N-乙基-9′-正溴丁氧基螺噁嗪(Br-SO),利用Br-SO分子结构中的化学基团C—Br与部分水解的聚甲基丙烯酸甲酯(hPMMA)反应制备含SO的PMMA高分子化合物(SO-hPMMA)。采用1 HNMR和IR对Br-SO结构进行了表征,研究了Br-SO、SO-hPMMA的光致变色性能及其影响因素。研究表明:Br-SO、SO-hPMMA均具有良好的光致变色性能,且SO-hPMMA的热稳定性明显高于Br-SO。