导电偶氮苯共轭聚合物的合成及性能研究

采用过硼酸钠氧化4,4′-二氨基联苯合成了主链含偶氮苯的共轭聚合物。通过傅里叶变换红外光谱、拉曼光谱、紫外-可见吸收光谱、差示扫描量热仪、四探针测试仪对偶氮苯共轭聚合物的结构和性能进行了研究。结果表明,得到的偶氮苯共轭聚合物数均相对分子质量(Mn)为4482,其玻璃化转变温度(Tg)为186℃,并在热分析测试中发现共轭聚合物主链顺式构型偶氮苯单元;盐酸掺杂的偶氮苯共轭聚合物电导率为8.7×10-5 S/cm,碘掺杂的偶氮苯共轭聚合物电导率为2.65×10-4 S/cm,钠-萘掺杂的偶氮苯共轭聚合物导电率为1.92×10-4 S/cm,偶氮苯共轭聚合物经365nm(3mW/cm2)紫外光照射后,偶氮苯共轭聚合物的电导率扩大一个数量级,换用473nm(20mW/cm2)可见光光照后,其电导率发生回复,表明偶氮苯共轭聚合物具有光调制导电特性。     

偶氮苯核心第一代不对称共轭树状聚合物的合成

以3,5-二叔丁基苯酚,三氟甲基磺酸酐和4,5-二乙炔基-2-甲氧基苯酚为原料合成4,5-双（3＇,5＇-二叔丁基苯基乙炔基）-2-甲氧基苯酚,并在其羟基上引入4,4＇-二（三甲基甲硅烷基乙炔基）偶氮苯,成功得到了以偶氮苯为核心第一代不对称共轭苯乙炔树状聚合物。该树状聚合物在波长为200～425 nm之间对紫外光有强的吸收,并在紫外光的激发下发出蓝色荧光。     

一种末端双炔类偶氮苯化合物的合成与表征

采用偶氮偶联、金属钯催化偶联法和Williamson醚合成法,合成了一种末端双炔类偶氮化合物,其结构经IR、1H NMR、DSC分析表征.     

新型含偶氮苯结构线型聚酯的合成及性能

采用熔融聚合法反应得到3种新型侧链含偶氮苯结构的线型聚酯(P1-P3),通过IR、UV-vis、1H NMR、SEC、TG-DTA和荧光等对聚酯的结构和性能进行了表征。聚酯(P1-P3)在氯仿、四氢呋喃等常用有机溶剂中有良好的溶解性,Mw分别为31 890、20 165、29 655 g/mol,5%失重温度分别为332、322、312℃。在365 nm紫外光照射下,聚酯(P1-P3)中的偶氮苯结构发生了反-顺异构化。聚酯(P1-P3)发紫色荧光。     

新型偶氮苯共轭席夫碱化合物的合成与表征

以对苯二甲醛与偶氮苯胺基化合物进行缩合反应合成系列新型具有不同取代基的含有偶氮苯共轭基团的席夫碱化合物。利用紫外光谱、红外光谱以及荧光光谱研究了目标产物的取代基效应,并用差热-热重分析方法对其热稳定性能进行测定。实验数据表明,对于分子内取代基团、共轭体系等因素的调控,可以得到性能迥异的席夫碱化合物,在功能材料等领域具有广泛的应用价值。     

对甲氧基偶氮苯星形聚合物的合成与表征

利用原子转移自由基聚合(ATRP)技术合成了对甲氧基偶氮苯星形聚合物。均苯三酚与2-溴异丁酰溴通过酯化反应得到三官能团引发剂,引发对甲氧基偶氮苯单体6-[4-(4-甲氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(MMAzo)的ATRP反应。表征了星形聚合物结构、热行为与液晶性,显示其与线性均聚物的液晶性相似,均显示近晶相和向列相,但其相转变温度有所降低。     

分子材料的彩色碎片——偶氮苯合成进展

偶氮苯作为一种特殊的结构骨架在科学领域有重要而广泛的应用。偶氮化合物主要用于化工行业,如偶氮类染料。而且由于偶氮化合物在适当的光辐射下存在有效的顺反异构现象,所以这类化合物是制备分子开关器件的首选对象。合成偶氮化合物的经典方法有偶氮偶合反应（重氮盐与活化芳香族化合物的偶合）,Mills反应（亚硝基与苯胺衍生物的反应）和Wallach反应（在酸性介质中将氧化偶氮苯转换成4-羟基取代偶氮苯衍生物）。近年来,其它的一些合成方法也有报道。本文综述了近期报道的关于偶氮苯的合成方法包括最新报道的合成方法以及它们的反应机理。     

偶氮苯二甲酰氯的合成和表征

以偶氮苯二羧酸和五氯化磷为原料,二氯乙烷为溶剂,三乙胺为酸吸收剂,合成了4种偶氮苯二甲酰氯,产率为75.3～93.6%。用红外光谱、核磁共振谱及元素分析进行了表征。     

氢化偶氮苯类化合物合成进展

氢化偶氮苯类化合物是重要的精细化工原料及有机合成中间体,在染料工业、医药工业等领域具有广阔的应用前景。本文结合近几年氢化偶氯苯类化合物的合成方法的最新发展,对其合成方法进行了总结,并对该领域的研究前景作以展望.     

对氨基偶氮苯盐酸盐合成工艺研究

讨论了对氨基偶氮苯盐酸盐的合成工艺，提出了改进措施，减少了氧化等副反应，提高了原材料利用率。     

一种新型共轭Schiff碱聚合物的合成与表征

以对苯二甲醛和水合肼为原料,无水乙醇作溶剂合成了一种共轭Schiff碱聚合物,并通过GPC、IR、1 H NMR、紫外-可见吸收光谱和荧光光谱对其分子量和组成结构进行表征。结果表明,该物质为一种分子量较大的共轭Schiff碱聚合物,具有良好的荧光性。     

Synthesis of block copolymers based on oxyethylene chains and their use as polymer electrolytes

High-molecular-weight copolymers were prepared consisting predominantly of oxyethylene and oxymethylene-oligo(oxyethylene) blocks with a small 1-phenylethylene block. Ionic conductivities of mixtures of the copolymers with CF₃SO₃Li were measured.     

Synthesis,characterization, and photophysical properties of novel poly(p‐phenylene vinylene) derivatives with conjugated thiophene as side chains

Two novel poly(p‐phenylene vinylene) (PPV) derivatives with conjugated thiophene side chains, P1 and P2, were synthesized by Wittig‐Horner reaction. The resulting polymers were characterized by ¹H‐NMR, FTIR, GPC, DSC, TGA, UV–Vis absorption spectroscopy and cyclic voltammetry (CV). The polymers exhibited good thermal stability and film‐forming ability. The absorption spectra of P1 and P2 showed broader absorption band from 300 to 580 nm compared with poly[(p‐phenylene vinylene)‐alt‐(2‐methoxy‐5‐octyloxy‐p‐phenylene vinylene)] (P3) without conjugated thiophene side chains. Cyclic voltammograms displayed that the bandgap was reduced effectively by attaching conjugated thiophene side chains. This kind of polymer appears to be interesting candidates for solar‐cell applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(N-glycidyl carbazole): A new crosslinkable conjugated polymer

A poly(N-glycidyl carbazole) was synthesized by electropolymerization of 3,6-dibromo-N-glycidyl carbazole. Characterization of both products by different chemical and electrochemical techniques is then discussed. The polymer that showed electronic conductive properties when doped was crosslinked by cis-cyclohexane 1,2 dicarboxylic anhydride. The crosslinking reaction was followed by Fourier-transform infrared spectroscopy (FT-IR). An optimization of the crosslinking conditions was first performed on the monomer and subsequently applied to the polymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1483–1492, 1999     

Fabrication of conjugated polymer arrays by spinodal dewetting

Ordered arrays of conjugated poly(9,9‐dihexylfluorene) (PF) were prepared by the spinodal dewetting of liquid thin films on mica substrates. The size of the aggregates in the arrays was controlled by the evaporation rate of the solvent. Fast solvent evaporation resulted in smaller aggregates; slower evaporation resulted in larger aggregates. The photoluminescence of the PF arrays showed a smaller red‐shift than that of the unpatterned film when compared to PF solutions, which indicated that the aggregation of PF in the arrays is smaller than that in the unpatterned films. Copyright © 2004 Society of Chemical Industry     

一种新型两亲性聚合物的合成研究

合成了一种新型的两亲性共聚物(丙烯酰胺/醋酸乙烯酯/丙烯酸丁酯,AM/VAc/BA),探讨了在该共聚物合成过程中AM用量和VAc与BA的配比对其表面张力、离心稳定性、乳化性及发泡力的影响,并对该三元共聚物P(AM/VAc/BA)的结构进行表征。结果表明,傅立叶红外光谱(FT-IR)分析在1 680 cm-1~1 620 cm-1处无C=C伸缩振动吸收峰出现,说明体系反应较彻底;差示扫描量热(DSC)分析得共聚物的玻璃化转变温度为37.6℃。     

一种新型梳型破乳剂的合成与应用

以自制苯乙烯-马来酸酐共聚物和自制树枝状聚酰胺-胺大分子为原料,通过酰胺化反应合成一系列新型梳型破乳剂。通过凝胶色谱测定了产品的纯度,并对其结构进行了红外表征。通过瓶试法对产品进行了破乳性能评价,评价结果显示,该系列破乳剂对南堡352原油有很好的破乳效果,其中DX3在温度为70℃,加药质量浓度为90 mg/L的条件下,脱水率能够达到94.23%。     

Structure and property relationship of thermotropic liquid crystal polymer and polyester composite fibers

Poly(ethylene 2,6‐naphthalate) (PEN) and poly(ethylene terephthalate) (PET) composite fibers reinforced with a thermotropic liquid crystal polymer (TLCP) were prepared by the melt blending and spinning process to achieve high performance fibers with improved processability. Polymer composite fibers consisting of cheap polyester and small quantity of expensive TLCP are of interest from an economic point of view and from an industrial perspective. The increase in the birefringence and density of the TLCP/PEN/PET composite fibers with the spinning speed was attributable to the enhancement of the molecular orientation and effective packing between chains in the TLCP/PEN/PET composite fibers. Annealing process resulted in the formation of more ordered and perfect crystalline structure and higher crystallinity, improving the mechanical properties of the TLCP/PEN/PET composite fibers. The increase in the crystallite size and the degree of chain extension with increasing spinning speed resulted in the gradual increment of the long period for the TLCP/PEN/PET composite fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006.     

聚丙烯酸锂的合成与性能

研制了一种新型阳离子导电聚合物—聚丙烯酸锂 (PAALi) ,分子量在 2 0 ,0 0 0～4 0 0 ,0 0 0范围内 ,室温离子电导率为 10 - 8～ 10 - 9S·cm- 1;研究了聚合条件对产率的影响 ;探讨了分子量、锂离子含量、温度对其离子导电率的影响。     

新型聚三唑酯和聚三唑醚树脂的合成及性能

合成了三种含酯基和三种含醚键的炔单体,通过核磁共振氢谱(¹H NMR)、红外光谱(FT-IR)、质谱(MS)、液相色谱(LC)对其结构进行了表征。用这六种炔单体与叠氮单体反应制备了一系列新型聚三唑酯树脂(PTAE)和聚三唑醚树脂(PTAO)。利用差示扫描量热分析(DSC)、FT-IR、动态力学热分析(DMA)、力学试验机和热失重分析(TGA)表征了树脂的固化行为、固化树脂的力学性能、耐热性和热稳定性。结果表明PTAE和PTAO树脂易溶于有机溶剂,可低温(60℃)固化,固化树脂的弯曲强度超过了100 MPa,可达158 MPa,玻璃化转变温度(T _g)超过180℃,高者达251℃,热分解温度可达360℃。