形状记忆聚合物及其应用

形状记忆材料可对热、化学、机械、光、磁或电等外加刺激的触发作出响应,从而改变自身的技术参数。形状记忆聚合物作为一类重要的形状记忆材料,在航空航天、生物医学、电力电子、包装、智能控制系统等领域具有广泛的应用。分析了形状记忆聚合物的形状记忆机理,并介绍了几类常见的形状记忆聚合物及其在各领域中的应用,最后提出了形状记忆材料研究中的一些不足及解决措施。     

聚合物形状记忆材料的研究进展

聚合物形状记忆材料作为一种重要的刺激响应材料,近10年内得到了快速的发展,出现了新的分类方向,机理解释、转变结构和应用。在航空航天、传感制动和生物医药等领域展现了优越的性能,研究成果受到了学术和工业上的极大重视,成为当今最富有活力的研究领域之一。本文全面总结了近期国内外学者对聚合物形状记忆材料的研究进展,阐述了聚合物形状记忆材料的记忆机理及分类和功能应用,并探讨了未来的研究前景和方向,以期为聚合物形状记忆材料的研究提供参考。     

双向形状记忆结晶聚合物及其复合材料的研究进展

形状记忆聚合物是一种典型的智能材料,具有质轻、形变量大、可对多种刺激进行响应等优点.根据形状记忆过程的可逆性进行分类,形状记忆效应可以分为2种:单向与双向形状记忆效应.与不可逆的单向形状记忆过程相比,双向形状记忆过程是可逆的,样品不需要使用者进行再次变形,就可以在原始形状与临时形状之间进行可逆转换,因此其具有极高的实用价值与广阔的应用前景,受到各国研究人员的广泛关注,成为当前的研究热点之一.本文总结了近年来所研究的双向形状记忆结晶聚合物及其复合材料,包括恒外力条件下(外力≠0)的准双向形状记忆结晶聚合物,无外力条件下的双向形状记忆结晶聚合物及其复合材料.具体来说,前者包括在恒外力作用下的化学或物理交联的结晶聚合物.后者包括双层或核-壳聚合物复合材料、由分步交联得到的双网络交联结晶聚合物、化学交联的双组分结晶聚合物、具有较宽熔融转变的化学交联结晶聚合物与物理交联的结晶聚合物.重点关注了这些材料的制备方法、影响因素及相应的双向形状记忆机理,并对其研究前景进行了展望.     

结晶行为对无定型/结晶聚合物共混体系形状记忆性能影响的研究进展

形状记忆聚合物因其具有质轻、低耗、形变量大、回复率高、形状可调、刺激方式多样等众多优点而受到广泛关注。相较于其它类型的形状记忆聚合物而言,共混型形状记忆聚合物的制备则更为简单方便。目前最常见的共混型形状记忆材料是无定型/结晶聚合物体系,其中结晶聚合物的结晶行为是影响整个体系形状记忆性能的关键。本文结合了该领域的研究现状,就结晶度、晶体尺寸以及晶体取向对共混体系形状记忆性能影响的研究进展进行了综述。     

电致变形聚合物材料及其应用

电致变形聚合物材料(EISCP)是一类对电刺激有变形响应的材料,即在某一电场或电流的间歇或持续刺激下,该材料的形状会做出特定的变形响应,当电场或电流消失后,形状又会趋于恢复。EISCP在智能器件、人工肌肉、仿生机器人以及药物载体等领域有广泛的应用前景。本文提出将EISCP的变形机理分为电场响应型与电流响应型两大类,并进一步将两种机理细致划分。另外,从材料出发,综述了基于介电弹性体、铁电聚合物、电致液晶弹性体、电致伸缩接枝弹性体、碳纳米管复合材料、离子聚合物-金属复合材料、电致变形水凝胶、电致形状记忆聚合物及导电聚合物九种EISCP的研究进展及应用。最后,基于目前EISCP存在的一些问题(如响应速度慢、变形量小以及变形响应高度依赖"开-关"刺激等),对其发展做出了展望。     

高温形状记忆聚合物研究进展

形状记忆聚合物因质量轻、形变量大、性能可控、结构设计性强等优点,其相关的基础前沿研究和潜在的应用开发一直是研究者不断探索的焦点。为满足复杂环境领域（高低温、强辐射、真空等）对形状记忆聚合物的应用需求,近年来研究者开展了高温形状记忆聚合物的研究,并取得了阶段性的研究成果。本文总结了近年来高温形状记忆聚合物的最新研究进展,并对其类型、机制、调控方法及典型应用进行了阐述和分析,最后对高温形状记忆聚合物的未来发展趋势及挑战进行了总结和展望。     

刺激响应型生物医用聚合物纳米粒子研究进展

近十几年来, 纳米科学的发展极大地推动了纳米材料在生物医用领域的应用. 聚合物纳米粒子由于其独特的性能在药物传递、医学成像等医用领域备受关注. 其中, 刺激响应型聚合物纳米粒子是一类可以在外界信号刺激下(包括pH、温度、磁场、光等)发生结构、形状、性能改变的纳米粒子. 利用这种刺激响应性可调节纳米粒子的某种宏观行为, 故而刺激响应型聚合物纳米粒子也被称为智能纳米粒子. 因为其特有的“智能性”, 刺激响应型聚合物纳米粒子的研究已成为当前生物材料领域的研究热点. 本文综述了几类重要的生物医用刺激响应型聚合物纳米粒子, 侧重介绍双重及多重刺激响应型聚合物纳米粒子的制备及其生物医学应用.     

聚乙烯醇基聚合物材料在多元驱动方式下的形状记忆行为

形状记忆聚合物（SMPs）是近些年发展起来的一种环境响应型智能材料。在外界刺激驱动下分子内或分子间会发生物化变化,分子结构和形态的改变使形变后的材料在宏观上回复到起始形态。常见的SMPs有聚乙烯、聚氨酯、聚己内酯等,而聚乙烯醇（PVA）的形状记忆效应是在热致型形状记忆凝胶被发现以来才引起人们关注的。由于PVA侧链富含大量羟基,化学活性高、易与官能团进行功能化改性,因此可设计出满足不同驱动方式的分子结构。目前研究者已采用冻融循环、化学或辐射交联、接枝改性及共混复合等多种方法制备了多种刺激源（如温度,溶剂、光、电、微波及超声波等）驱动下的形状记忆聚乙烯醇（SM-PVA）、PVA衍生物及复合材料。本文综述了近年来不同刺激源驱动下SM-PVA的研究进展,阐述了不同材料的结构性能、回复机理及存在的问题,并展望了PVA在该领域的发展和应用前景。     

新型光驱动形状记忆有序多孔膜的设计及构筑

长期以来,设计和制备微纳米尺寸的有序多孔结构是材料科学领域的重要研究课题。聚合物有序多孔膜因兼具高度规则的孔结构和聚合物的多功能性,在工程技术和科学研究领域受到广泛关注。有序多孔膜的孔隙大小、形状及可重复使用等性质对其功能化和潜在应用具有重要影响。形状记忆特性是一种独特的环境响应特性。形状记忆材料能够记忆初始形状,并且在形变后能够在外界刺激下回复其初始形状。将形状记忆特性引入到有序多孔膜中,可实现多孔膜孔形状、尺寸的有效调控,并提高薄膜的可重复使用性,但由于多孔膜孔结构难以实现均匀形变,形状记忆有序多孔膜鲜有报道。华东理工大学林绍梁课题组在光驱动形状记忆多孔膜的设计和制备方面取得了一些新进展。     

纳米复合形状记忆聚合物

形状记忆聚合物(SMPs)是一种刺激响应型智能材料,在受到热、电、交变磁场、光、湿度或化学等外界刺激时,材料能够发生较大的可回复形变,在生物医用材料、航天航空、汽车、纺织等领域有广泛的应用。但SMPs强度和模量低,形状回复应力小,回复速度较慢等缺点限制了其应用,纳米复合可以克服SMPs的这些缺点。本文在介绍SMPs的基础理论基础上,从纳米改性的目的和激发方式出发,综述了不同纳米颗粒与SMPs的作用机理,并展望了纳米复合SMPs的研究和发展趋势。     

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.     

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.     

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.     

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.