光响应性有机-无机杂化分子印迹聚合物的制备及表征

以4-硝基苯酚、 2,4-二氯苯氧乙酸和3-氯丙基三乙氧基硅烷为原料, 经氧化偶合、 酰化、 酯化反应合成了共价结合模板分子2,4-二氯苯氧乙酸(2,4-D)的光响应性含有机硅的偶氮苯功能单体, 通过溶胶-凝胶法制备了光响应性的有机-无机杂化分子印迹聚合物(OIHMIP). 研究了该分子印迹聚合物光响应性能、 对2,4-D的吸附性能和选择识别及光控释放与吸收能力, 用原子力显微镜对其形貌进行了表征. 结果表明, 制得的OIHMIP具有规则的球形, 粒径介于150～200 nm之间. OIHMIP对2,4-D具有良好的吸附和选择识别能力, 在365和440 nm的紫外-可见光交替照射下, 可控制2,4-D的释放与吸收.     

超支化偶氮大分子重氮盐静电层-层自组装膜的制备及光响应性研究

利用超支化偶氮大分子重氮盐作为聚阳离子,与聚阴离子PSSA进行静电层-层自组装,通过紫外光谱、椭偏仪和原子力显微镜等对体系自组装过程及自组装膜的表面形貌进行了表征.在线偏振488nmAr+激光的作用下,自组装多层膜可产生明显的光致二向色性,其取向有序度约为0.02.在干涉的Ar+激光作用下,多层膜表面可形成规则的表面起伏光栅结构.     

含氟偶氮苯光响应性聚合物的合成及性能

以1,2,3,4,5-五氟苯胺为原料, FeSO-4?7H2O负载的KMnO4为氧化剂, 制得全氟代偶氮苯, 在KOH作用下醇解, 进行丙烯酰化反应, 得到光响应性的功能单体4-甲基丙烯酰氧基九氟偶氮苯, 用GC-MS, 元素分析及NMR等方法对功能单体进行表征, 并研究了其光异构化性能. 以4-甲基丙烯酰氧基九氟偶氮苯(MANFAB)为功能单体, 与十字交联剂三羟甲基丙烷三甲基丙烯酸酯(TRIM)在自由基引发下合成了光响应性的三维交联聚合物, 并研究了其光响应性质.     

含胆酸高分子化合物的制备和特性*

胆酸是哺乳动物体内合成的一种天然化合物,具有特殊的分子结构和优良的生物适应性。由胆酸合成的高分子化合物保持了胆酸的部分性质,如双亲性、手性、侧基反应活性和自组装性能等。在化学和药学领域,含胆酸高分子材料具有重要的应用价值。本文从自由基聚合形成的含胆酸高分子化合物、胆酸修饰的高分子化合物和胆酸聚合物等几个方面综述了含胆酸高分子化合物的制备和特性,并对胆酸在高分子材料方面的新用途作了展望。     

含偶氮苯的咔唑类双功能光折变聚合物的合成及表征

通过后重氮偶合方法制备了一系列不同生色团含量的咔唑类双功能光折变聚合物，并用IR、^1H-NMR、UV-vis、DSC以及GPC等对聚合物进行了分析和表征。IR和UV-vis谱图显示偶氮苯基团已接到咔唑环上。UV-vis结果表明：反应时间对该反应的影响非常大，当反应时间从6h增加到60h时，聚合物中生色团的含量从13.5%升高到66.7%。GPC结果显示后重氮偶合法比常规方法得到的该类聚合物的分子量明显提高。DSC结果显示聚合物的玻璃化转变温度随偶氮苯含量的增加而升高。     

Preparation and Characterization of Trans‐Resveratrol Imprinted Polymers

Abstract

In order to selectively extract trans‐resveratrol from Chinese herbs, molecularly imprinted polymers (MIPs) were prepared with trans‐resveratrol as the template molecule. The influences of porogenic solvents and functional monomers on the recognition properties of the polymer were studied. The MIP, which was prepared in acetone using 4‐vinylpyridine as functional monomer, displayed good affinity and recognition property for the template molecule. This indicates that the 4‐vinylpyridine can form hydrogen‐bonding or ionic interaction with trans‐resveratrol. Experimental result also indicated that the MIP column can separate trans‐resveratrol from matrix components in the Polygonum cuspidatum extract.     

Photoresponsive Amphiphilic Macrocycles Containing Main‐Chain Azobenzene Polymers

Herein, the first example of photosensitive cyclic amphiphilic homopolymers consisting of multiple biphenyl azobenzene chromophores in the cyclic main chain tethered with hydrophilic tetraethylene glycol monomethyl ether units is presented. The synthetic approach involves sequentially performed thermal catalyzed “click” step‐growth polymerization in bulk, and Cu(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) intramolecular cyclization from α‐alkyne/ω‐azide linear precursors. It is observed that such amphiphilic macrocycles exhibit increased glass transition temperatures (T_g), slightly faster trans–cis–trans photoisomerization, and enhanced fluorescence emission intensity compared with the corresponding linear polymers. In addition, the cyclic amphiphilic homopolymers self‐assemble into spherical nanoparticles with smaller sizes which possess slower photoresponsive behaviors in a tetrahydrofuran/water mixture compared with those of the linear ones. All these interesting observations suggest that the cyclic topology has a great influence on the physical properties and self‐assembly behavior of these photoresponsive amphiphilic macrocycles in general.

     

Miscibility of Some Polycarbonates with Polyvinyl Chloride and Chlorinated Polyvinyl Chloride

The phase behavior of several polycarbonate homopolymers and copolymers blended with PVC and chlorinated PVCs (CPVCs) has been investigated. Tetrachlorobisphenol-A polycarbonate (TCPC) is miscible in all proportions with PVC and CPVCs containing up to70.2 wt% chlorine. CPVCs having chlorine contents greater than 70.2% (by weight) are immiscible with TCPC. Tetrabromobisphenol-A polycarbonate (TBPC) exhibits phase mixing with PVC and CPVCs; however, the high T_g of this polycarbonate (260°C) prevents adequate investigation of equilibrium phase behavior. Bisphenol-A polycarbonate (BPC), tetramethylbisphenol-A polycarbonate (TMPC), and hexafluorobisphenol-A polycarbonate (HFPC) form two-phase mixtures with the vinyl polymers. Microstructural differences in the CPVCs due to chlorination method (solution chlorination vs. slurry chlorination) have no effect on the miscibility results. Miscibility was observed in several copolycarbonate/CPVC blends and was found to be dependent on copolymer composition. Using a binary interaction, mean-field theory, segmental interaction parameters were estimated for repeat unit interactions. Based on the estimated interaction parameters, miscibility in these blends is primarily the result of intramolecular repulsive effects, rather than strong intermolecular attractive forces.This revised version was published online in November 2005 with corrections to the Cover Date.     

含联芴烯单元共轭聚合物的合成及表征

以六羰基钨[W(CO)₆]为催化剂, 合成了聚吲哚芴(P1)、 聚梯型四苯(P2)、 聚梯型五苯(P3)和小分子9-联吲哚芴烯(S1).该类聚合物的重复单元含有联芴烯结构, 通过芴9位的双键连接. 光学和电化学等实验结果表明, 聚合物无荧光发射, 是一类窄带隙的共轭聚合物, 其中聚合物P1薄膜的紫外吸收值最大波长为710 nm.     

Preparation of Photoresponsive PAN-NH2@EPESP Fiber Films with Mechanical Stability for Regulating Wettability and Micro-environment Humidity

In view of the current living micro-environment and requirements of green economy, intelligent light-responsive humidification materials have become a hot spot in intelligent polymer mate-rials. In this work, reversible photoresponsive films with a mechanical stability and an excellent humidity adjustment performance are developed by modifying epoxy-ether-spiropyran(EPESP) on amino-nanofibers(PAN-NH₂), which was produced through electrospinning. Such smart films for regulating wettability and micro-environment humidity can be reversibly manipulated by the simple switch of UV and visible light irradiation because of the unique transformation between polar ring-opened status and nonpolar ring-closed status of the spiropyran units. The effects of EPESP modification amount on the morphology, wettability, tensile strength and the ability to regulate humidity were investigated in detail. The results show that with the increase of modification amount of EPESP, both the humi-dity regulation and tensile strength increased; when the modification amount exceeds 7 mg, the range of regulating humidity increases slowly.     

含联苯PPV类共轭聚合物的合成及荧光性能研究

在催化剂聚氯乙烯-四乙烯五胺负载钯配合物(PVC-TEPA-Pd)的作用下,利用Heck反应,二碘联苯与苯乙烯反应可以得到4,4′-二苯乙烯基联苯。进一步用二碘联苯和二乙烯基苯反应可以成功地将联苯基元引入聚合物主链,得到一种新型的含联苯结构的PPV类共轭聚合物,通过红外光谱对聚合物结构进行了表征,并对聚合物的荧光性能进行了研究,发现其荧光发射光谱峰位于500nm,与4,4′-二苯乙烯基联苯荧光发射光谱峰相比,发生了明显的红移。由于分子结构中存在较大共轭体系,两种物质在多种溶剂中的溶解性均较差。     

后重氮偶合法制备含硝基偶氮苯咔唑类聚合物

后重氮偶合;咔唑;生色团;后重氮偶合法制备含硝基偶氮苯咔唑类聚合物     

聚乙二醇—硝酸镧配位聚合物的表征研究

以聚乙二醇(PEG)为配位体,首次合成了三价稀土金属镧与PEG的配位聚合物。实验测定了该配位聚合物的红外光谱、示差扫描量热谱(DSC)、热失重分析(TGA)和凝胶渗透色谱(GPC),并就配位反应、热分解以及配位前后分子流体力学体积的变化进行了讨论。     

含杯芳烃聚合物的合成与应用

杯芳烃在主客体化学中是继冠醚和环糊精之后被广泛关注的第三代主体分子,能够选择性地与客体分子或离子形成络合物。近年来,含杯芳烃聚合物逐渐受到人们的重视。结合聚合物稳定性好,易于加工的特性,含杯芳烃聚合物将有望被开发成为新型功能高分子材料。本文详细介绍了含杯芳烃聚合物的合成及其应用。     

基于原子转移自由基聚合技术的偶氮苯星形液晶聚合物的合成与表征

利用原子转移自由基聚合(ATRP)技术合成了含不同端基取代基的偶氮苯三臂星形侧链液晶聚合物. 均苯三酚与2-溴异丁酰溴通过酯化反应制备三官能团引发剂, 引发偶氮苯单体6-[4-(4-甲氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(MMAzo)或6-[4-(4-乙氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(EMAzo)的ATRP反应. 利用核磁共振氢谱(¹H NMR)、凝胶色谱(GPC)、差示扫描量热法(DSC)和偏光显微镜(POM)等手段对星形聚合物进行表征. 星形聚合物的液晶性与相应均聚物相似, 但偶氮苯端基取代基的不同导致星形聚合物的液晶性差别显著. 在紫外/可见光照射下星形聚合物呈现明显的异构化转变.     

Polar-Functionalized,Crosslinkable, Self-Healing,and Photoresponsive Polyolefins

The nonpolar nature of polyolefins is one of their biggest limitations. Now, an efficient route to generate polar-functionalized, crosslinkable, self-healing, photoresponsive polyolefins with thermoplastic, elastomeric, and thermosetting properties is reported. Tunable amounts of carboxylic acid and a cyclic comonomer are installed onto polyolefins by palladium-catalyzed terpolymerization reactions. The incorporated carboxylic acid unit can alter the surface properties of polyolefins. The subsequently introduced Fe³⁺/citric acid combination induces dynamic crosslinking and enables self-healing. Under UV light irradiation, citric acid reduces Fe³⁺ to Fe²⁺ and decreases the crosslinking density. The Fe²⁺ moiety can be easily oxidized back to Fe³⁺, making the process reversible at the expense of citric acid. The incorporated cyclic comonomer modulates the crystallinity of polyolefins, provides elastic properties, and installs carbon–carbon double bonds for sulfur-induced vulcanization.     

表面改性纳米SiO2复合聚合物电解质的制备及性能

通过化学方法将具有增塑效果的环状碳酸酯基团引入纳米SiO2表面,并用FTIR与TGA对改性纳米SiO2进行了表征.将改性纳米SiO2添加到以聚氧化乙烯(PEO)为基体的聚合物电解质中,制备了复合聚合物电解质.通过DSC和交流阻抗等方法对该聚合物电解质膜的热力学和电化学性能进行了研究.结果表明,掺杂改性纳米SiO2的聚合物电解质具有更高的离子电导率,室温最高离子电导率可达到1.84×10-5 S/cm;具有较高的锂离子迁移数,最高可达到0.49,且具有更好的界面稳定性.     

树枝化聚合物的合成、结构表征及其应用

本文综述了由树枝状大分子和线形聚合物结合而形成的一类新型树形聚合物--树枝化聚合物的研究进展,包括树枝化聚合物的各种合成方法、结构表征和形态分析等.同时对树枝化聚合物在催化载体、纳米材料、生化和光电功能材料等领域的应用研究进行了详尽的综述.     

活性负离子聚合法制备POSS基七臂星形聚合物及其表征

首先利用高真空活性负离子聚合方法制备聚异戊二烯锂(PI-Li)和(聚苯乙烯-b-聚异戊二烯)锂(PS-PI-Li)活性链,再与单羟基七乙烯基多面体齐聚倍半硅氧烷(VPOSS-OH)发生加成反应,一步法制备2种含羟基的七臂星形聚合物.用分级沉淀法去除低加成产物,即可得到纯的七臂星形聚合物7PI-POSS-OH和7(PS-PI)-POSS-OH,利用凝胶渗透色谱(GPC)、核磁共振波谱(1H-,13C-NMR)、红外光谱(FTIR)和基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)表征了聚合物的化学结构、分子量及分子量分布,并通过热失重分析(TGA)测试了聚合物的热分解温度.     

微胶囊填充型自修复聚合物及其复合材料

微胶囊填充型自修复聚合物及其复合材料是近年来高分子科学界的研究热点之一。本文介绍了含有微胶囊聚合物复合材料自修复的概念和机理,综述了近5年来针对不同基体材料的微胶囊自修复研究情况,包括环氧树脂、乙烯基酯树脂、纤维增强环氧树脂复合材料、弹性体以及聚甲基丙烯酸甲酯等基体材料。本文同时介绍了微胶囊的芯材和壁材、微胶囊的粒径、修复时间和压强等因素对复合材料自修复性能的影响,以及自修复效果的评价方法。最后对微胶囊填充型自修复聚合物及其复合材料的研究前景进行了展望。