结构用自修复型高分子材料的制备

自修复型高分子材料属于智能材料的一类,仿照生物体损伤自愈合的功能,通过材料内部的自诊断和自响应机制,及时修复材料在成型加工或使用过程产生的微小裂纹,避免其进一步扩展.近年来本课题组针对结构用自修复型高分子材料的强度恢复问题,综合利用高分子化学、高分子物理、材料力学等学科的理论和方法,设计、合成了一系列外植型和本征型自修复高分子材料,提出的自修复策略适用于典型热固性和热塑性高分子材料.此外,深入研究了相关的合成路线、配方优化、制备工艺、材料结构与性能、自修复的微观机制、使用稳定性等,为此类材料的实际应用提供依据.     

生物基类玻璃高分子材料的研究进展

高分子材料在人类生活中应用广泛,它给人类带来便利的同时也存在2个急需解决的问题.其一,使用后产生的塑料垃圾正在破坏人类赖以生存的环境,尤其是热固性塑料,受到交联网络的限制,材料一旦成型就难以被再次加工.通过引入"类玻璃(vitrimer)"高分子概念,能够使损坏的热固性塑料得到修复,延长其使用寿命并减少塑料垃圾.其二,高分子材料的制备往往需要消耗不可再生的化石资源.面对化石资源的减少及其造成的污染问题,使用可再生的生物质资源制备高分子材料成为有效的解决办法.本文以交联高分子材料为主线,综述了近年来关于使用可再生生物质资源制备类玻璃高分子材料的研究进展,其内容主要包括两方面.第一个方面综述了类玻璃高分子材料的发展史和特点,着重强调了动态共价键往往同时具有重排和分解2种机理;第二个方面综述了生物基类玻璃高分子材料的研究进展,其中涉及的动态共价键种类包括羟基-酯、席夫碱、二硫键和羟基-氨酯,涉及的生物质原料主要包括植物油、木质素、纤维素、天然橡胶、松香及香草醛等.本综述旨在推动解决塑料污染治理及绿色材料的研究和应用.     

氢键交联超分子聚合物材料：从结构性能到功能应用

高分子材料的大量消耗与持续积累已经在全球范围内造成了严重的环境污染与资源浪费.发展可修复、可循环、可降解和可回收的新一代高分子材料是解决上述挑战的根本途径.基于动态可逆的非共价键将聚合物链段进行交联可以有效地构建这些材料.本专论系统总结了我们课题组在氢键交联超分子聚合物材料方面的系列研究进展.基于多重氢键的协同性与动态性、氢键与动态共价键的协同,以及材料微相结构的调控,发展了系列兼具高强度与高韧性的超分子聚合物材料,实现了材料的修复、循环、降解与回收;不仅突破了非共价交联高分子材料力学性能弱的瓶颈,而且化解了高分子材料强度与韧性的矛盾.相关研究为发展传统高分子材料的可持续替代品提供了新的思路.同时,发展了系列基于氢键交联的功能超分子聚合物材料,展示了其在柔性电子、固态锂电池及水下黏合剂等方面的应用.     

导电自修复材料的研究进展

导电高分子材料因具备良好的导电性、质轻和易加工特性而被广泛应用于航空、生物医学设备、化学生物传感器和能源等领域。然而,导电高分子材料在使用过程中不可避免地会产生微裂纹,从而破坏导电通路并使整个电子设备瘫痪。受生物体启发,设计和构筑具备自修复功能的导电高分子材料是研究的热点。本文介绍了导电自修复材料的最新研究动态,综述了自修复机理和材料的制备方法及应用前景,最后简要分析导电自修复材料目前存在的主要问题并展望其发展方向。     

离聚物型自修复高分子材料的研究进展

自修复是指材料在受到损伤后可自行修复,并在一定程度上恢复其力学性能的特性,对提高材料的使用寿命及安全性具有重要意义。离聚物中的离子基团在一定条件下由于静电相互作用及与主链的不相容性而相互聚集,形成动态可逆的物理交联点,从而赋予了离聚物材料在无外加修复剂的条件下即可实现自修复的特性。本文系统评述了离聚物型高分子材料的自修复过程与机理、常用的离聚物体系、激发离聚物自修复行为的方式及影响离聚物自修复特性的因素。     

面向可持续发展的高分子科学教学实验设计：含席夫碱型动态共价键的可修复热固性材料的制备与表征

可自修复、可重复利用的热固性材料的设计与开发，是近年高分子材料的研究热点之一。本着为高分子教学实验探索更多可能性的初衷，本工作采用对苯二甲醛、双官能度聚醚胺和三官能度聚醚胺为原料，构建了席夫碱型的交联网络结构，成功制备了一种可自修复、可重塑的热固性材料。由于材料中含有大量的亚胺键（■），在中温（80～100℃）下发生快速且可逆的亚胺网络重排反应，材料表现出良好的自修复和重塑行为。实验条件温和且操作简便，适合作为材料类教学实验和中学生科普实验进行推广。     

基于多重可逆作用的自修复聚氨酯弹性体的制备及性能

在聚氨酯主链上引入可逆二硫键, 同时使用硼酸构建的硼酸酯键作为可逆交联点, 使聚氨酯内部形成交联网络结构, 制备了一种兼具高强度、 高韧性及高修复效率的自修复聚氨酯弹性体. 红外光谱、 动态力学分析、 力学测试、 电子显微镜及修复测试结果表明, 制备的自修复聚氨酯具有硬而韧的特性, 原样强度高达23.3 MPa, 断裂伸长率可达1177%, 并且修复条件温和, 剪断拼接的试样经60 ℃, 24 h修复后可恢复99%的原样强度, 且该修复过程可重复多次进行. 此外, 该材料还具有多通道修复特性, 通过热修复或水辅助热修复的方式均可实现材料的修复, 并且水辅助热修复速率更快.     

含双重动态共价键的松香基环氧类玻璃高分子的制备与性能

以天然松香衍生物为刚性环氧单体, 3,3’-二硫代二丙酸(DTDPA)为交联剂,通过环氧-羧基酯化反应固化,制备了含双重动态二硫键和酯键的生物松香基环氧类玻璃高分子网络.利用红外光谱和拉曼光谱对所得聚合物网络材料的结构进行了表征.结果表明,合成了含双重动态二硫键和酯键的松香基环氧高分子网络.对所有松香基环氧高分子网络进行了热机械性能、力学性能、热稳定性和应力松弛测试.结果表明,松香基环氧高分子网络具有高的热稳定性和力学性能,以及相对较快的应力松弛能力.此外,研究了交联剂添加量对所得松香基环氧高分子网络的自修复和再加工能力的影响.结果表明, DTDPA的羧基与松香环氧单体的环氧基摩尔比为100∶100的类玻璃(RE-100)网络具有最优的自修复和再加工性能.因为RE-100网络内部拥有最多的动态二硫键和酯键,在受到热刺激后,充足的动态二硫键和酯键发生可逆交换,促使网络快速重排,从而获得优异的自修复和再加工性能.     

高粘附可拉伸高分子材料与高动态稳定人体电生理监测

高动态稳定人体电生理监测在智能可穿戴健康监测、心血管疾病临床诊断、神经系统疾病治疗以及智能人机交互等领域具有广阔的应用前景.作为人与外部环境的信号交互桥梁,皮肤电极可贴合于皮肤表面,以无创的方式监测和采集各种电生理信号,成为高动态稳定电生理监测的理想平台.从材料角度出发,皮肤电极的高动态稳定性决定于基底材料的高粘附性和可拉伸性.因此,如何通过高分子结构的合理设计制备高粘附可拉伸高分子材料,构筑高度共形粘附于人体皮肤表面的电极,从而实现高动态稳定人体电生理监测,是柔性智能健康监测领域的重要研究方向.本文总结了本课题组近年来在高粘附可拉伸高分子材料制备及其在高动态稳定人体电生理监测应用方面的研究进展,并讨论了高粘附可拉伸高分子材料在下一代柔性智能健康监测领域面临的机遇和挑战.     

含有Alq3和Znq2的可交联聚合物的合成与表征

合成了溶解性优良、带有可聚合链段的8-羟基喹啉金属螯合物(Alq3和Znq2)单体,在室温下通过紫外光照射,形成热力学性能稳定、8-羟基喹啉金属螯合物含量高(50(wt)%以上)的交联聚合物.这种材料可以解决使用旋涂的方法制备器件带来的底层溶解的问题,从而实现大面积、多层电致发光器件的制备,还可以通过光刻手段实现器件涂层图案化,是器件实现全彩色、超像素方法之一.其光致发光和电致发光性质证明这种材料本身以及其加工性能在有机/高分子平面显示技术领域有一定应用价值.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.