3,4-乙撑二氧噻吩的原位化学氧化受限聚合动力学研究

利用紫外-可见光谱,分别研究了3,4-乙撑二氧噻吩在45、65和85℃条件下的原位化学氧化受限聚合动力学规律。结果表明,温度的升高可以非常显著地加快单体的聚合速度,反应体系在45、65和85℃下完成聚合反应的时间分别为600、240和8min。温度对聚合反应的进程也有较显著的影响,在相对较低温度下（45和65℃）,反应进程基本相同,都有比较明显的3个阶段（反应开始、稳定反应和反应终了阶段）,而在相对较高温度下（85℃）,反应进程则更简单,只有快速反应阶段和反应终了阶段。这些动力学数据可以为3,4-乙撑二氧噻吩在某些应用领域如固体电容器制备工艺中确定聚合温度和时间等工艺条件提供参考依据。     

单体溶剂对液相沉降聚合聚3,4-乙撑二氧噻吩分子结构及性能的影响

将吸附有FeCl_3的聚酰亚胺(PI)膜悬于不同溶剂的3,4-乙撑二氧噻吩(EDOT)溶液中,在PI膜表面原位合成了导电聚3,4-乙撑二氧噻吩(PEDOT)涂层。以UV-vis分析溶剂的溶剂化效应,以红外光谱和X射线光电子能谱分析PEDOT的分子结构和氧化态,研究溶剂对液相沉降聚合PEDOT的共轭链长度和掺杂度及导电性的影响。在研究的正庚烷、环己烷、甲苯和氯仿中,溶剂的溶剂化作用依次增强,在其EDOT溶液中沉降聚合产物PEDOT的共轭链长度和掺杂度也依次增大,PEDOT涂层的电导率分别为33.7 S/cm,43.8 S/cm,163.2 S/cm和77.2 S/cm,对PI膜的附着力由0级上升到5B级。溶剂的溶解能力和溶剂化效应增强,液相沉降聚合PEDOT分子的共轭链长度和掺杂度上升,涂层的电导率和附着力增加;溶剂化效应的影响尤为突出。     

木质素磺酸钠掺杂聚(3,4-乙撑二氧噻吩)水分散性复合材料的制备和表征

在水性介质中,以可再生资源木质素磺酸钠作为新型掺杂剂和软模板,采用化学氧化聚合法制备了在水中稳定分散的聚(3,4-乙撑二氧噻吩)—木质素磺酸复合材料。采用红外光谱、紫外-可见吸收光谱、TGA、SEM以及电导率仪对其性能进行了相关测试和表征。结果表明:所制备的材料呈现管状或纤维状的微观构型,当木质素磺酸钠与3,4-乙撑二氧噻吩单体的质量比为1.5∶1时,所制备的复合材料室温电导率可达1.15·10-3 S/cm,并具有热稳定性和分散稳定性好等优点,该材料在抗静电涂层和生物医用导电高分子领域具有潜在的应用前景。     

对苯醌二亚胺与3,4-乙撑二氧噻吩共聚物的合成及表征

以N,N′-二氯对苯醌二亚胺、2,5-二甲基-N,N′-二氯对苯醌二亚胺与2,5-二溴-3,4-乙撑二氧噻吩为单体,1,3-二(二苯基膦)丙烷二氯化镍(Ⅱ)为催化剂,采用金属配合物催化法合成了聚(N,N′-对苯醌二亚胺-3,4-乙撑二氧噻吩)和聚(2,5-二甲基-N,N′-对苯醌二亚胺-3,4-乙撑二氧噻吩)两种共聚物。通过红外光谱(FT-IR)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)、X射线衍射(XRD)、紫外分光光度计(UV-Vis)和循环伏安(CV)等测试对其进行了结构表征及性能测试。结果表明,两种共聚物在CF3COOH(TFA)溶液中的UV-Vis最大吸收波长分别在500 nm和511 nm处;氧化还原峰出现在-0.2 V-0.8 V之间;通过碘掺杂后共聚物的电化学窗口拓宽,电化学活性提高。     

聚3,4-乙二氧噻吩包覆碳纳米管的原位化学氧化合成

报道了不同溶剂体系中原位化学氧化合成PEDOT/CNTs纳米复合物的实验,用红外光谱( IR)、拉曼光谱、透射电子显微镜(TEM) 以及四探针电导率仪对合成的纳米复合物进行了表征,可以看出:采用乙腈作为反应介质环境,可以获得反应充分完全的具有理想形态的聚乙二氧噻吩包覆碳纳米管的纳米复合纤维;通过对合成纳米复合纤维进行导电性方面的表征,证明通过一维纳米形态的碳纳米管和导电聚乙二氧噻吩的复合,可以获得具有更高导电性的纳米复合纤维.     

基于3,4-乙撑二氧噻吩-亚乙烯基的杂化型电致变色聚合物的合成与表征

合成了2个基于EDOT-vinylene(3,4-乙撑二氧噻吩-亚乙烯基)的杂化型新单体BEDOT-V-F[双(3,4-乙撑二氧噻吩亚乙烯基)呋喃]和BEDOT-V-T[双(3,4-乙撑二氧噻吩亚乙烯基)噻吩]。分别对这2种材料进行电化学、光谱电化学、动力学和表面形貌的表征,考查了它们的电致变色性质。结果表明PBEDOT-V-F和PBEDOT-V-T具有非常低的初始氧化电位、良好的电化学稳定性和较低的带隙值,它们在近红外区的光对比度分别为31.5%(950nm)和36.7%(980nm),且都具有在蓝色和透过态之间可逆变化的电致变色能力,因此在近红外光学器件领域具有潜在的应用价值。     

纤维表面原位化学氧化聚合制备复合导电可纺纤维

采用原位化学氧化聚合方法在纤维(聚丙烯腈、蚕丝蛋白)表面生长导电聚合物(聚苯胺、聚吡咯和聚3,4-乙撑二氧噻吩),制备得到纤维表面均匀覆盖导电聚合物的复合导电可纺纤维,其电导率随不同的纤维、不同的导电聚合物而处于10-1～10-3S/cm.纤维表面与导电聚合物的相互作用改善了原纤维的耐热性能,但对其力学性能没有造成伤害.     

聚3,4-乙撑二氧噻吩的合成及性能

介绍了聚3,4-乙撑二氧噻吩(PEDT)的合成过程、性能及测试方法.通过聚苯乙烯磺酸(PSS)掺杂,解决了PEDT的加工问题,研究了氧化剂及掺杂剂的用量、反应体系的浓度、反应温度、反应时间、PSS的磺化度和加料方式对PEDT性能的影响.     

聚噻吩/碳纳米管复合物的元件制作及其气敏响应性的应用测试

本文通过化学氧化法以3,4-乙撑二氧噻吩聚合聚3,4-乙撑二氧噻吩(PEDOT),得到固体粉末样品,用液体胶水作为联体,在其掺杂功能化碳纳米管(f-CNTS)与聚噻吩,制备了复合纳米材料,并制作系列工作电极,利用自制气敏装置,应用于含甲醛的饱和汽体测试研究。测试数据表明,掺杂不同含量的碳纳米管与聚噻吩,对不同浓度的甲醛气敏响应性测试,由其电极材料的微型结构的变化,电阻规律性变化表现出不同的气敏响应性。同时,与单一种物质作用相比,复合材料膜有更好的电子传递行为,表现灵敏的响应性。     

碳纳米管／导电聚合物纳米复合物的合成与表征

为实现制备出导电性能优良的有机透明导电涂层,需要把具有导电性的碳纳米管在树脂中组装成一体化导电结构网络.运用可以在树脂中自组装的导电聚乙撑二氧噻吩和聚苯胺来实现碳纳米管自组装的方法,分别合成出了导电聚乙撑二氧噻吩和聚苯胺薄膜均匀覆盖的碳纳米管/聚乙撑二氧噻吩复合物与碳纳米管/聚苯胺纳米复合物,并运用透射电镜(TEM)、傅立叶红外光谱(FTIR)和四探针法对其进行了分析与表征,结果发现这种复合物的导电性较碳纳米管和聚乙撑二氧噻吩以及聚苯胺自身导电性都有一定程度的提高.     

Synthesis, characterization, and electrical properties of regioregular alkyl-substituted PEDOTt

The regioregular hexyl-substituted poly(3,4-ethylenedioxy-2-thiophenylthiophene) (PEDOTt), structurally alternating copolymer of EDOT and thiophene, was synthesized via the Grignard Metathesis (GRIM) using catalytic amounts of Ni(dppp)Cl2. The products were characterized by 1H NMR spectroscopy, UV-vis spectroscopy and XRD. The alkyl-substituted conjugated polymer showed an enhancement of solubility in common organic solvents. Based on XRD data, the regioregular hexyl-substituted poly(3,4-ethylenedioxy-2-thiophenylthiophene) (PEDOTt) shows better crystallinity than the regiorandom hexyl-substituted PEDOTt owing to self-ordering. In addition, regioregular hexyl-PEDOTt has a conductivity of 0.788 S/cm by iodine doping.     

Thermodynamic studies of the solvent effects in chromatography on molecularly imprinted polymers. 3. Nature of the organic mobile phase

Experimental isotherm data of the Fmoc-tryptophan (Fmoc-Trp) enantiomers were measured by frontal analysis on a Fmoc-L-Trp imprinted polymer, using different organic mobile phases, in a wide concentration range. The nonlinear regression of the data and the independent calculation of the affinity energy distributions of the two enantiomers allowed the selection of the isotherm model and the determination of the isotherm parameters. The organic solvents studied were acetonitrile (MeCN), methylene chloride, chloroform, and tetrahydrofuran (THF), all in the presence of the same concentration of acetic acid, used as an organic modifier. It was found that the highest overall affinity and enantiomeric selectivity were obtained in MeCN, which is also the solvent used in the polymerization. In the other solvents, the overall affinity decreases with increasing hydrogen-bonding ability of the solvents but not the enantiomer selectivity. In MeCN, three types of adsorption sites coexist for the two enantiomers on the MIP. The highest energy sites for Fmoc-L-Trp in MeCN are inactive in CH(2)Cl(2), CHCl(3), and THF, and only two types of sites were identified in these solvents. Increasing the acetic acid concentration from 0.2 to 0.9 M causes a large decrease in the association constant of the highest energy sites in CH(2)Cl(2), CHCl(3), and THF but not in MeCN. The overall affinity of Fmoc-L-trp in CH(2)Cl(2), CHCl(3), and THF is dominated by adsorption on the lowest energy sites, the most abundant ones. In contrast, in MeCN, the overall affinity of Fmoc-L-Trp is dominated by adsorption on the highest energy sites, the least abundant sites. In CH(2)Cl(2), CHCl(3), and THF, the number of each type of sites increases with decreasing hydrogen-bonding ability of the solvents while the association constant of the corresponding sites does not change significantly.     

1,3—二硫戊环衍生物的固载化反应

本文报导了在四种溶剂中,4-羟甲基-2-对硝基苯基-1,3-二硫戊环和4-羟甲基-2-苯基-1,3-二硫戊环与氯甲基化交联聚苯乙烯(2％DVB)的固载化反应。研究结果表明:常用的四氢呋喃(THF)不能作为本固载化反应的溶剂。二氧杂环己烷(Dioxan)、硝基苯/二甲苯(PhNO_2/xylene)和N,N-二甲基甲酰胺可用作反应溶剂,其中N,N-二甲基甲酰胺(DMF)为最佳。本文还探讨了固载化反应中的溶剂效应。     

Perfluorophenyl Ether and Related Polymers

The syntheses of perfluorophenyl ether and poly (perfluorophenylene ethers) are described. These materials were prepared by the reaction between potassium pentafluorophenoxide and hexafluorobenzene in different solvents with varying conditions of temperature and pressure. In dimethylformamide or tetrahydrofuran, potassium pentafluorophenoxide shows little tendency to react with hexafluorobenzene. In methanol, only exchange products such as pentafluoroanisole were observed. No polymers were obtained in these solvents. In water, the reactivity of pentafluorophenoxide salts was increased greatly, for reaction occurs readily with or without the presence of hexafluorobenzene. The reactions in aqueous systems are complex and give rise to a variety of products. From these reactions the following compounds were isolated and identified: perfluorophenyl ether, bis(pentafluorophenoxy)tetrafluorobenzene, 2,4,5,6-tetrafluororesorcinol, pentafluorophenoxytetrafluorophenol, and various polyperfluorophenylene ethers of varying chain lengths. Identification of the smaller molecules was made by chemical, mass spectrometer, infrared, and nuclear magnetic resonance analyses. Poly(perfluorophenylene ethers) were prepared having molecular weights of 1700, 4300, 6500, and 12,500. A crosslinked polyether of this type was also synthesized, which had rubbery characteristics above 90 °C.     

Structure of polyphenylsilsesquioxane particles prepared by two-step acid-base catalyzed sol-gel process and formation of hollow particles

Spherical polyphenylsilsesquioxane (PhSiO(3/2)) particles, one of the inorganic-organic hybrid materials, were synthesized by a two-step acid-base catalyzed sol-gel process, and hollow particles were successfully prepared by washing the as-prepared particles with organic solvents. It was found that the inside and outside parts of the as-prepared particles were composed of PhSi03/2 species with relatively low and high molecular weight, respectively, i.e., the PhSiO(3/2) particles had a kind of "core-shell" structure. Because the core portion in the as-prepared particles was soluble in ethanol and tetrahydrofuran, hollow particles were obtained through washing the as-prepared PhSiO(3/2) particles with ethanol or tetrahydrofuran. Furthermore, the molecular weight of the as-prepared particles was varied by the concentration of phenyltriethoxysilane used as a starting alkoxide. As a result of the variation of the molecular weight, the hollow PhSiO(3/2) particles with different stabilities against organic solvents were formed.     

一类具有高光学透明、高可溶聚酰亚胺薄膜的合成与表征

以2,6-二甲基苯胺和苯甲醛为原料,经一步合成反应,制得了一种高纯二胺单体α,α-(3,5-二甲基-4-氨基)苯基甲烷(BADP),将其与4种商品化芳香二酐缩聚,制得了一系列主链含3,3′,5,5′-四甲基和甲苯基结构的聚酰亚胺,特性黏度在0.57～0.84dL/g之间。该聚酰亚胺表现出优异的溶解性能和光学性能:室温下不仅可以溶于高沸点的NMP、DMAc、DMF和m-Cresol等溶剂中,还能溶于低沸点的CHCl3、CH2Cl2等溶剂中,而且大部分聚合物在这类溶剂中的溶解度可达10%(质量分数)以上;所制得的聚酰亚胺薄膜颜色浅、透明性高,截断波长在341～365nm之间,500nm处的透过率均超过85%。此外,该系列聚酰亚胺还表现出良好的热学性能和力学性能:玻璃化转变温度在333℃以上,空气和氮气中10%热失重在440℃和500℃以上;其薄膜的拉伸强度、断裂伸长率和起始模量分别在62～95MPa、8.4%～15.5%和2.2～3.5GPa之间。     

乙腈对环己烷单体溶液中沉降聚合聚3,4-乙撑二氧噻吩涂层结构与光电性能的影响EI北大核心CSCD

为利用溶剂化效应来优化液相沉降聚合聚3,4-乙撑二氧噻吩(PEDOT)的结构和光电性能,将吸附Fe(OTs)3的聚对苯二甲酸乙二醇酯(PET)膜悬于含乙腈的EDOT环己烷溶液中,于60℃原位合成PEDOT涂层。以紫外-可见吸收光谱、X射线光电子能谱分析所合成PEDOT的共轭链结构和掺杂度,以四探针测量表面电阻,研究乙腈含量对合成PEDOT结构与性能的影响。当乙腈体积分数为0.05%时,添加的乙腈能抑制短共轭链的生成,提高掺杂度,在降低表面电阻的同时,改善透光率。乙腈体积分数在0.24%以内时,PEDOT的导电性随乙腈体积分数的上升而增加。当乙腈体积分数超过0.7%时,PEDOT中短共轭链数目增加,光电性能下降。当乙腈体积分数为8%时,由于吸附的Fe(OTs)_3溶解太快,无法在PET表面合成导电PEDOT膜。乙腈体积分数为0.24%时,获得的PEDOT膜的表面电阻可达174Ω,透光率80%,粘附力为5B级。     

可光交联苯并噻二唑与芴共聚物的制备及性能

采用Suzuki偶合法将苯并噻二唑结构单元引入聚芴主链,同时在芴的C-9位上引入烯丙基,合成了可交联发绿光的苯并噻二唑与芴共聚物。通过对共聚物溶液的紫外光谱和荧光光谱研究发现,引入可交联基团烯丙基以后,聚合物的光学性能并未发生明显变化。可交联的共聚物在加入光引发剂后,在紫外光作用下可以进行光交联,并且在照射9 min左右聚合物完全交联。通过对交联聚合物荧光光谱的研究发现,聚合物薄膜在交联前后的荧光光谱基本不变,表明交联对聚合物的发光性能并无影响。交联共聚物薄膜在紫外线的照射下发出明显的绿色荧光。     

导电聚合物MEH-PPV表面光电特性的研究

用接触电位差(CPD)方法研究了导电聚合物MEH-PPV薄膜的光电特性，测得MEH-PPV的能隙为2．1eV，表面功函数为4．7-4．8eV，是p型导电材料，同时研究了不同铸膜溶剂对薄膜光电特性的影响，测得由不含芳环的四氢呋喃为溶剂制得的薄膜表面功函数比由含芳环的氯苯为溶剂制得的薄膜低0．15eV。