聚3,4-乙烯二氧噻吩/聚苯胺复合材料的制备与性能

以过硫酸铵(APS)和FeCl3为复合氧化剂,采用原位化学氧化聚合法合成了导电聚3,4-乙烯二氧噻吩/聚苯胺(PEDOT/PANI)复合材料,研究了苯胺浓度及加入时间、复合氧化剂配比和复合乳化剂配比对复合材料性能的影响,并对复合材料进行了分析. 结果表明,PEDOT/PANI复合材料合成的较佳工艺条件为：3,4-乙烯二氧噻(EDOT) 0.6 mol/L、复合氧化剂 0.6 mol/L(FeCl3:APS=1:2, mol)、复合乳化剂 0.4 mol/L(SDBS:CTAB=2:3, mol)、复合掺杂剂1.2 mol/L(H2SO4:SSA=4:1, mol)及苯胺0.8 mol/L, EDOT聚合2 h后加入苯胺溶液继续反应8 h. 复合材料的导电性、结晶性和热稳定性比纯导电聚合物好.     

以低分子量聚乙烯基苯磺酸钠为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能

通过RAFT聚合,制备了低分子量的聚乙烯基苯磺酸钠(PSS);其次以低分子量的聚乙烯基苯磺酸钠为模板制备了聚3,4-二氧乙烯噻吩(PEDOT):聚乙烯基苯磺酸钠(PSS)水分散体,研究了作为模板的聚乙烯基苯磺酸钠的不同分子量对PEDOT:PSS水分散体结构和性能的影响。结果显示:通过核磁氢谱(1H NMR)表征,证明成功制备了分子量为3900,4900,9600和18300的聚乙烯基苯磺酸钠。用荧光探针法发现低分子量PSS在水中能形成胶束,临界胶束浓度在10~(-6) g·ml~(-1)左右。用四探针表面电阻测试发现,低分子量PSS为模板可明显提高PEDOT薄膜的导电性,最大提高了近3倍。用紫外可见分光光度计(UV)研究发现,以低分子量PSS为模板使PEDOT的透明性有一定的下降,这主要是由于RAFT试剂部分和PEDOT:PSS的相分离造成的。热稳定性的测试表明,低分子量PSS为模板对PEDOT的热稳定性没有明显的影响。     

以核壳型聚乙烯基苯磺酸钠/聚丙烯酸丁酯为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能

通过无皂乳液聚合,制备了以聚丙烯酸丁酯(PBA)为核,聚乙烯基苯磺酸钠(PSSNa)为壳的核壳型聚乙烯基苯磺酸钠/聚丙烯酸丁酯(PSSNa/PBA),并以此为模板制备了核壳型聚3,4-二氧乙烯噻吩(PEDOT)水分散体,研究了核壳型模板对PEDOT水分散体结构和性能的影响。结果显示:通过透射电镜(TEM)表征,证明成功制备了核壳型模板PSSNa/PBA和具有核壳结构的聚3,4-二氧乙烯噻吩:聚乙烯基苯磺酸钠/聚丙烯酸丁酯(PEDOT:PSSNa/PBA)水分散体。聚合动力学研究表明,以核壳型PSSNa/PBA为模板时,EDOT的聚合速率加快。表面方块电阻测试表明,较PEDOT:PSSNa薄膜,PEDOT:PSSNa/PBA薄膜的方块电阻降低近16倍,说明核壳结构的模板可改善PEDOT薄膜的导电性。     

导电聚合物单体3，4-乙烯二氧噻吩的合成

以硫代二甘酸为起始原料,经过五步反应得到产物3,4-乙烯二氧噻吩（EDOT）,过程如下：首先在浓硫酸催化条件下,硫代二甘酸与甲醇酯化生成硫代二甘酸二甲酯,产率为93．2％;产物进而与草酸二乙酯反应后得到3,4-二羟基噻吩-2,5-二甲酸二甲酯,产率为92．0％;然后经O-烷基化反应,反应中加入四丁基溴化铵作为相转移催化剂,得到3,4-乙烯二氧噻吩-2,5-二羧酸二甲酯,再经水解得到3,4-乙烯二氧噻吩-2,5-二甲酸;在DMSO为溶剂、氮气保护条件下,3,4-乙烯二氧噻吩-2,5-二甲酸在碱式碳酸铜催化作用下脱去两分子C02得到终产物EDOT。本方法中间产物及终产物的结构经由IR证实,并经过GC含量分析,总收率为34．6％。     

用聚3,4-乙撑二氧噻吩对聚丙烯腈进行导电改性的研究

采用原位化学氧化聚合方法在聚丙烯腈纤维表面生成聚3,4-乙撑二氧噻吩,制备得到纤维表面均匀覆盖聚3,4-乙撑二氧噻吩的改性导电纤维,其电导率约为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,并对其力学性能没有造成伤害。     

聚3,4-乙烯二氧噻吩聚苯乙烯磺酸复合LB膜对有机电致发光器件性能的优化

采用Langmuir-Blodgett(LB)膜诱导沉积法制备聚3,4-乙烯二氧噻吩高度有序导电聚合物复合薄膜,研究了薄膜的导电性能并进一步研究薄膜在改善器件性能方面的作用。将其应用于有机电致发光二极的空穴缓冲层,将聚3,4-乙烯二氧噻吩聚苯乙烯磺酸复合LB膜沉积于铟锡氧化物(ITO)电极上,制备了以复合LB膜为空穴缓冲层的有机电致发光二极。发现复合LB膜改善了器件性能(启动电压降低、最大亮度增加),但进一步的研究表明,LB膜器件在一定时间后出现性能劣化,X射线反射率(XRR)分析表明薄膜的结构发生一定程度的改变,是导致器件性能变差的可能原因。     

辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠的合成及表面活性

以正辛酸、苯酚、多缩乙二醇和溴代烷烃为原料,经酰化、酯化、Fries重排、催化加氢、威廉逊醚化及磺化等反应,合成了8种辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠表面活性剂。经红外、核磁和电喷雾质谱对产物进行了结构鉴定。用W ilhelmy法测定了该系列表面活性剂的表面张力。结果表明,合成的辛基-[ω-烷氧基-聚(氧乙烯)]基-苯磺酸钠结构明确,具有良好的表面活性,水溶液中CMC达到10-5mol/L数量级,γCMC最低达25.79mN/m;固定烷基碳数,随着EO数的增加,CMC和γCMC先降低后升高,当EO数为4时,增加烷基碳数,CMC显著降低,γCMC减小。     

聚(3,4-乙撑二氧噻吩)/木质素磺酸核壳粒子的制备工艺优化

以过硫酸钠为氧化剂,在木质素磺酸(LS)水溶液中通过化学氧化法聚合3,4-乙撑二氧噻吩(PEDOT),制备聚(3,4-乙撑二氧噻吩)/木质素磺酸(PEDOT/LS)水分散液。研究了木质素磺酸用量、氧化剂添加量、p H值、固含量和反应温度对产物PEDOT/LS的粒径及导电性的影响。实验得出较佳的反应条件是:木质素磺酸与EDOT单体质量比为2.0~2.5:1,氧化剂与EDOT摩尔比为1.3:1,反应体系p H值约1.5,固含量在1.8%~2.5%,反应温度10~20℃。用PEDOT/LS配制得到的涂层,表面电阻小于108??sq?1,光滑透明且附着力达到二级,满足抗静电剂的要求。     

聚(3,4-乙烯二氧噻吩)/碳纸复合材料的制备及其在作为超级电容器电极材料的应用

利用气相沉积法在碳纸表面生长聚(3,4-乙烯二氧噻吩)(PEDOT)纳米颗粒,通过控制单体用量,制备了一系列PEDOT/碳纸复合材料,通过场发射扫描电镜、傅里叶红外光谱、X射线衍射、拉曼光谱、X射线光电子能谱分析了不同复合材料的形貌与结构,同时利用循环伏安、恒流充放电、交流阻抗方法对所制备的复合材料进行了电化学性能的测试。结果表明,PEDOT呈纳米短棒状均匀生长于碳纸上,且当单体用量为20μL时,所得PEDOT/碳纸复合材料显示了较好的电化学性能,在0.1mA/cm2充放电电流下,面积比电容达到138.75mF/cm2,经过4 000次循环测试后其面积比电容仍可保留原来的72.6%,以碳纸为基材大大缩短了离子传输和电荷转移路径,从而使得复合材料呈现良好的电化学性能。     

Interaction of sodium dodecyl sulfate with polyelectrolyte complex from diazoresin and poly(sodium styrene sulfonate) in aqueous solution

Polyelectrolyte complex diazoresin–poly(sodium styrene sulfonate) (DR–PSS) from diazoresin (DR) as cationic polyelctrolyte and poly(sodium styrene sulfonate) (PSS) as anionic polyelectrolyte does not dissolve in water or organic solvent because of its electrostatic crosslinking structure. It was found that the complex dissolves considerably aqueous solution of sodium dodecyl sulfate (SDS) and confirmed that the DR–PSS—SDS system possesses extraordinary thermostability as well as high photosensitivity and can be used directly to produce a photoimaging coating. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1817–1821, 1998     

Synthesis and electrochemical capacitance of core-shell poly (3,4-ethylenedioxythiophene)/poly (sodium 4-styrenesulfonate)-modified multiwalled carbon nanotube nanocomposites

A noncovalent method was used to functionalize multiwalled carbon nanotubes with poly (sodium 4-styrene sulfonate). And then, the core-shell poly (3,4-ethylenedioxythiophene)/functionalized multiwalled carbon nanotubes (PEDOT/PSS-CNTs) nanocomposite was successfully realized via in situ polymerization under the hydrothermal condition. In the process, PSS served for not only solubilizing and dispersing CNTs well into an aqueous solution, but also tethering EDOT monomer onto the surface of CNTs to facilitate the formation of a uniform PEDOT coating. Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to characterize the resultant PEDOT/PSS-CNTs. In addition, the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) had a specific capacitance (SC) of 198.2 F g⁻¹ at a current density of 0.5 A g⁻¹ and a capacitance degradation of 26.9% after 2000 cycles, much better than those of pristine PEDOT and PEDOT/CNTs (50 wt.% PEDOT). The enhanced electrochemical performance of the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) should be attributed to the high uniform system of the nanocomposite, resulting in the large surface easily contacted by abundant electrolyte ions through the three-dimensional conducting matrix.     

低分子量聚丙烯酸钠的制备及其在ZrO2陶瓷料浆中的应用

以丙烯酸为单体,过硫酸铵为引发剂,水为溶剂,采用溶液聚合方法合成了低相对分子质量(550~2000)的聚丙烯酸钠(PAANa),并研究了聚丙烯酸钠在ZrO2料浆(70(wt)%)系统中的分散性能。结果表明:相对分子质量为550~2000的PAANa有很好的稀释作用,尤其分子量为550时稀释作用最好;加入聚丙烯酸钠后料浆触变性较小。     

Investigation of the interpolymer association between poly(vinyl alcohol) and poly(sodium styrene sulfonate) in aqueous solution

A viscosimetric method has been used to study the interpolymer association between poly(vinyl alcohol) (PVA) and poly(sodium styrene sulfonate) (PSSNa) in aqueous solution. At constant molecular weight of PSSNa, it was found that, the PVA and PSSNa associations were improved with the decrease of molecular weight of PVA and the decrease of its hydrolysis degree. The measurement of intrinsic viscosity [η] and the determination of Huggins associative coefficient K_H of different PVA samples were used to select the most appropriate PVA sample, which leads to homogeneous polymer–polymer mixtures (PVA with hydrolysis degree 87–89%, molecular weight 124,000–186,000 g/mol, intrinsic viscosity [η] = 1.02 dL/g, and Huggins associative coefficient K_h.ass = 0.76). The obtained results show that the interpolymer association between PVA and PSSNa, in aqueous solution, is mainly due to intermolecular hydrogen bonds between hydroxyl groups of PVA and sulfonate groups of PSSNa. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

导电聚合物PEDOT/PSS-MPEG的制备及性能

引言导电高分子既有导体材料的光电学特性,又有良好的力学性能和可加工性[1],这使得导电高分子材料具有广泛的应用前景。聚噻吩类有机导电材料[2]就是这类材料中的一种。聚噻吩的室温电导率     

Decreasing miscibility with greater heterogeneity in ternary polymer blend: poly(cyclohexyl methacrylate), poly(α‐methyl styrene) and poly(4‐methyl styrene)

A ternary blend system comprising poly(cyclohexyl methacrylate) (PCHMA), poly(α‐methyl styrene) (PαMS) and poly(4‐methyl styrene) (P4MS) was investigated by thermal analysis, optical and scanning electron microscopy. Ternary phase behaviour was compared with the behaviour for the three constituent binary pairs. This study showed that the ternary blends of PCHMA/PαMS/P4MS in most compositions were miscible, with an apparent glass transition temperature (T_g) and distinct cloud‐point transitions, which were located at lower temperatures than their binary counterparts. However, in a closed‐loop range of compositions roughly near the centre of the triangular phase diagram, some ternary blends displayed phase separation with heterogeneity domains of about 1 µm. Therefore, it is properly concluded that ternary PCHMA/PαMS/P4M is partially miscible with a small closed‐loop immisciblity range, even though all the constituent binary pairs are fully miscible. Thermodynamic backgrounds leading to decreased miscibility and greater heterogeneity in a ternary polymer system in comparison with the binary counterparts are discussed. © 2003 Society of Chemical Industry     

Synthesis and characterization of conductive polypyrrole with improved conductivity and processability

BACKGROUND: The solubility and conductivity of chemically synthesized polypyrrole (PPy) are dependent on the synthesis procedure and composition. Enhanced processability of PPy with high conductivity can be achieved using the anionic polyelectrolyte poly(styrene sulfonate) (PSS). RESULTS: High‐conductivity PPy with better processability was successfully synthesized by in situ chemical oxidation polymerization using various concentrations of PSS. Elemental analysis results show that the C/S and N/S molar ratios of the PPy fabricated in the presence of PSS are in good agreement with theoretical values for PPy–SO₄. The S/N ratio increases with increasing PSS content, indicating the high doping level for PPy as the PSS content increases. Scanning electron microscopy and high‐resolution transmission electron microscopy images show that the fabricated PPy has spherical structures with the average particle size for the pure PPy being about 250 nm and markedly decreasing to 20–40 nm with the addition of PSS. CONCLUSION: The conductivities of PPy synthesized with a PSS/pyrrole monomer weight ratio of 0.25 are about five times higher than that of PPy matrix. These results are perhaps due to the part played by PSS serving as a dopant to be incorporated into the PPy structure to improve the conductivity of the fabricated PPy. Copyright © 2009 Society of Chemical Industry     

Electrical conductivity of poly(3,4-ethylenedioxythiophene):p-toluene sulfonate films hybridized with reduced graphene oxide

Reduced graphene oxide-poly(3,4-ethylenedioxythiophene):p-toluene sulfonate (rGO-PEDOT:PTS) hybrid electrode films were synthesized directly on a substrate by interfacial polymerization between an oxidizing solid layer and liquid droplets of 3,4-ethylenedioxythiophene (EDOT) produced by electrospraying. The EDOT reduced the graphene oxide by donating electrons during its transformation into PEDOT:PTS, and hybrid films consisting of rGO distributed in a matrix of PEDOT:PTS were obtained. These rGO-PEDOT:PTS hybrid films showed excellent electrical conductivities as high as 1,500 S/cm and a sheet resistance of 70 Ω sq^-1. The conductivity values are up to 50% greater than those of films containing conductive PEDOT:PTS alone. These results confirm that highly conductive rGO-PEDOT:PTS hybrid films can potentially be used as organic transparent electrodes.     

Synthesis and characterisation of poly(sodium 4-styrenesulfonate) combs

A series of poly(sodium 4-styrenesulfonate) (NaPSS) combs has been synthesized. Architecturally and molecularly well-defined polystyrene combs were initially produced with the branch molecular mass fixed at 30,000 g/mol, the average number of branches being the major variable. Conditions were established whereby linear polystyrene (PS) synthesized via anionic polymerization was chloromethylated using zinc (II) chloride, side-reactions such as Friedel-Crafts alkylation being suppressed. An excess of diphenylethylene-capped polystyryllithium (PSLi) was then reacted with the functionalized backbone to yield materials having long chain branches. The polystyrene combs were then reacted with sulfuric acid to yield water-soluble poly(styrenesulfonic acid) combs and subsequently neutralized with sodium hydroxide to give the corresponding sodium 4-styrene sulfonate species. The extent of sulfonation was determined via titration and nuclear magnetic resonance spectroscopy (NMR). Aqueous triple-detector size exclusion chromatography (SEC) was used to characterize the sulfonated combs. Although the SEC traces were monomodal and the M_n values agreed well with the expected values, an increase in the polydispersity index compared to the polystyrene combs may reflect the susceptibility of the sulfonation reaction to cross-linking.     

聚4-乙烯基吡啶的合成与表征

以过氧化二苯甲酰(BPO)为引发剂,用悬浮聚合的方法制备了较高相对分子质量的聚4 乙烯基吡啶(P4VP)。通过对聚合产物相对分子质量测试结果的分析,研究了单体与水的体积比、引发剂用量、分散剂用量、反应时间、反应温度、搅拌速度等因素对4 VP聚合反应的影响。结果表明,聚合时间为1h、聚合温度为60℃、引发剂的质量分数(占单体量)为0.8%左右、分散剂的质量分数(占单体量)为0.6%、搅拌速度为300r/min时,P4VP的重均分子量就能达到6×105～9×105。另外,采用紫外吸收光谱(UV)、红外吸收光谱(IR)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)、热重 差热分析(TG DTA)等测试手段研究了P4VP的结构和性能。