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。     

PEDOT:PSS导电自支撑薄膜的合成与制备

以3,4-乙烯二氧噻吩（EDOT）为原料，聚对苯乙烯磺酸钠（PSS-Na）为分散剂和掺杂剂，通过化学氧化合成法在水体系中聚合制备了聚(3,4-乙烯二氧噻吩):聚苯乙烯磺酸（PEDOT:PSS）悬浮液，通过真空抽滤的方法制备了PEDOT:PSS自支撑柔性导电薄膜。通过FTIR、UV-Vis对聚合产物结构进行了表征与确认，通过四探针电导率测试、SEM、拉伸断裂强度测试对PEDOT:PSS薄膜的导电性、微观形貌与力学性能进行了表征。结果表明，成功制备了PEDOT:PSS目标产物，在氧化剂与单体物质的量之比为0.875时达到最佳电导率（19.19 S/cm）。自支撑薄膜厚度约18 μm，在25 ℃，40%~60%相对湿度范围内拉伸断裂强度达到45~60 MPa，具有良好的导电性与机械性能。     

PEDOT/PSS质量分数对纺丝液流变性能及导电纤维可纺性的影响

将质量分数为10％的聚乙烯醇(PVA)水溶液与聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸(PEDOT/PSS)水分散液共混,经过恒温高速搅拌,制备出均匀的PVA/PEDOT/PSS共混纺丝液,随后通过湿法纺丝制备出PVA/PEDOT/PSS纤维.借助旋转式流变仪探究不同PEDOT/PSS质量分数的纺丝液在纺丝温度的差异下,纺...     

NIPAM改性PEDOT:PSS导电聚合物的制备及在电致变色器件中的应用

以柔性疏水小分子N-异丙基丙烯酰胺（NIPAM）对聚苯乙烯磺酸盐（PSS）进行共聚改性，制备了一系列聚[(苯乙烯磺酸盐)-共-异丙基丙烯酰胺][P(SS-co-NIPAM)]，并以其为模板采用氧化聚合法与3,4-乙烯二氧噻吩（EDOT）制备了导电聚合物PEDOT:P(SS-co-NIPAM)。与PEDOT:PSS薄膜相比，NIPAM摩尔分数（以对苯乙烯磺酸钠物质的量为基准，下同）为15%时，PEDOT:P(SS-co-NIPAM)薄膜平均透光率保持在80%左右，水接触角从18.5°增至39.0°，疏水性提高，并且弯曲1000次后方阻变化量为5.71 kΩ/sq，远小于PEDOT:PSS薄膜（10.60 kΩ/sq）。以NIPAM摩尔分数为15%的PEDOT:P(SS-co-NIPAM)薄膜作为离子储存层的电致变色器件的光学对比度（ΔT）为9.83%，循环800次后ΔT仍达到9.55%，衰减量为0.28%，衰减量与PEDOT:PSS器件相当，说明NIPAM共聚改性能改善PEDOT:PSS导电聚合物的柔韧性和疏水性，以其作为离子储存层的器件可维持优异的电致变色性能。     

基于PEDOT:PSS导电聚合物的透明电极制备及其光电性能研究

通过掺杂改性,在玻璃和柔性塑料衬底上采用旋涂法制备了高导电性和高透明性的PEDOT:PSS薄膜。然后以此为基础,研究了PEDOT:PSS为阳极的绿光OLED标准器件和黄光电致磷光器件性能。以CBP掺杂磷光材料(MPPZ)₂Ir(acac)为发光层制备了柔性和平面OLED器件,考察了以ITO、PEDOT:PSS/玻璃、PEDOT:PSS/PET三种不同阳极器件的性能。实验结果表明,以PEDOT:PSS/玻璃阳极的器件启动电压为3.83 V,最大亮度可达18 632 cd/m²,最大电流效率可达21.61 cd/A,显示了PEDOT:PSS透明导电薄膜作为OLED阳极材料具有很大的发展潜力。     

CPDB为链转移试剂的脱氢枞酸基单体的RAFT聚合研究

以脱氢枞酸（β-甲基丙烯酰氧基丙基）酯（DAHPMA）为单体,偶氮二异丁腈（AIBN）为引发剂,2-氰基-2-丙基苯并二硫（CPDB）为链转移试剂,在四氢呋喃溶液中进行可逆加成-断裂转移自由基聚合反应（RAFT）制备得到脱氢枞酸基酯均聚物。动力学研究表明了脱氢枞酸基单体可以在RAFT聚合下具有活性可控的特征,同时探讨了CPDB的浓度对松香基单体的RAFT聚合的影响,发现CPDB的浓度对聚合过程的速率和可控性以及相对分子量和相对分子质量分布都有一定的影响。通过核磁证实了该松香基均聚物的成功合成,接触角测试表明该聚合物具有高疏水性。     

乙二胺后扩链TDI型聚氨酯水分散体的过程

以甲苯二异氰酸酯（TDI）、聚氧化丙烯二醇和二羟甲基丙酸等为主要原料制备了聚氨酯水分散体,研究了水、扩链温度、原料的-NCO/-OH摩尔比及扩链比对乙二胺（EDA）后扩链TDI型聚氨酯水分散体过程的影响。FT-IR测试表明,分散体中的H₂O可通过与聚氨酯中残留异氰酸酯基团（-NCO）的竞争反应影响EDA的后扩链过程。分子量及粒径与zeta电位测试表明,H₂O扩链导致分散体失稳;低扩链比时,H₂O对EDA的后扩链过程影响明显,但高扩链比时,后扩链聚氨酯的分子量降低;扩链温度升高,经EDA后扩链聚氨酯的分子量降低,而分散体粒径增大。当原料的-NCO/-OH摩尔比为1.20、扩链温度为30℃、扩链比为60%时,可有效降低H₂O对EDA后扩链聚氨酯过程的影响。     

系列磺酸钠型Gemini表面活性剂的合成及表征

通过两步反应,合成了三种磺酸钠型Gemini表面活性剂6, 6’-（丙基-1, 3-二基双氧）双（3-壬基苯磺酸钠）（9B-3-9B）、6, 6’-（正丁基-1, 4-二基双氧）双（3-壬基苯磺酸钠）（9B-4-9B）和6, 6’-（正戊基-1, 5-二基双氧）双（3-壬基苯磺酸钠）（9B-5-9B）,并讨论了反应温度和反应时间对产物产率的影响,优化了反应条件。利用傅里叶变换红外光谱仪（FTIR）、核磁共振仪（¹H NMR）和元素分析仪表征产物结构,并通过DCTA21表面界面张力仪测定其在水溶液中的表面张力。结果表明：与传统表面活性剂十二烷基苯磺酸钠（SDBS）相比,Gemini表面活性剂9B-m-9B（m=3, 4, 5）具有更高的表面活性,其临界胶束浓度（CMC）分别为0.14、0.11、0.12 mmol·L^-1,对应的表面张力g_CMC分别为29.43、29.26、28.22 mN·m^-1。     

基于二甲氧基乙醇处理聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐做透明电极在有机太阳能电池中的应用

聚3,4-乙烯二氧噻吩/聚苯乙烯磺酸盐（PEDOT:PSS）具有优异的光电性能,目前研究者尝试用PEDOT:PSS材料来取代常用透明电极氧化铟锡（ITO）,由于未经处理过的PEDOT:PSS电导率极低,目前急需寻找到新的方法来提高PEDOT:PSS的电导率。本文使用了热（130℃）二甲氧基乙醇多次处理PEDOT:PSS薄膜,结果表明随着处理次数的增加,PEDOT:PSS薄膜电阻逐渐减小。采用了原子力扫描电镜（AFM）和X射线衍射（XRD）等表征手段,发现热二甲氧基乙醇溶剂处理能有效的去除PSS,从而提升了薄膜的电导率。经过热二甲氧基乙醇溶剂处理六次后的品质因素（FoM）高达51.61,并将热二甲氧基乙醇处理六次后的PEDOT:PSS薄膜作为无ITO有机太阳能电池的透明电极,光电转化效率为2.05%,达到了ITO电极的83.67%。     

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     

Preparation and performance of a transparent poly(3,4‐ethylene dioxythiophene)–poly(p‐styrene sulfonate‐co‐acrylic acid sodium) film with a high stability and water resistance

Poly(p‐styrene sulfonate‐co‐acrylic acid sodium) (PSA) from the copolymerization of acrylic acid sodium and p‐styrene sulfonate monomers were used to dope poly(3,4‐ethylene dioxythiophene) (PEDOT) to generate PEDOT–PSA antistatic dispersions. Compared to those of the PEDOT–poly(p‐styrene sulfonate sodium) (PSS), the physical and electrical properties of the PEDOT–PSA conductive liquids were much better. The PEDOT–PSA films possessed a better water resistance without a decrease in the conductivity. The sheet resistance of the PEDOT–PSA–poly(ethylene terephthalate) (PET) films was about 1.5 × 10⁴ Ω/sq with a 100 nm thickness, the same as the PEDOT–PSS–PET films. The transmittance of the PEDOT–PSA–PET films exceeded 88%. Furthermore, the environmental dispersity of the PEDOT–PSA antistatic dispersion was apparently improved by the dopant PSA so that the stability was extraordinarily promoted. Meanwhile, the water resistances of the PEDOT–PSA–PET and PEDOT–PSA films were also enhanced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45163.     

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     

Polyethylene glycol-modified poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) counter electrodes for dye-sensitized solar cell

Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) counter electrodes, doped with polyethylene glycol (PEG) and acetylene black as binding and conductivity promoting agent, were prepared by a simple mixing method for dye-sensitized solar cell. The electrochemical properties of the electrodes were characterized by cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and Tafel polarization curves. Using PEG dopant, the electrocatalytic activity of PEDOT:PSS electrode was much improved, and further improved by adding a small amount of conducting acetylene black (0.2 wt%). The DSSC cells, using the PEDOT:PSS electrode with PEG (5 wt%) dopant and the composite electrode with PEG (5 wt%)/acetylene black, exhibited an energy conversion efficiency of 3.57 and 4.39 %, comparable with 4.50 % of the commonly used Pt electrode under the same experimental conditions. These results demonstrate that PEG-modified PEDOT:PSS counter electrode is promising to replace the expensive Pt for low cost DSSC, especially to meet the large-scale fabrication demands.     

Capacitance properties of graphite oxide/poly(3,4‐ethylene dioxythiophene) composites

Poly(3,4‐ethylene dioxythiophene) (PEDOT) and graphite oxide (GO)/PEDOT composites (GPTs) doped with poly(sodium styrene sulfate) (PSS) were synthesized by in situ polymerization in aqueous media. The electrochemical capacitance performances of GO, PEDOT–PSS, and GPTs as electrode materials were investigated. The GPTs had a higher specific capacitance of 108 F/g than either composite constituent (11 F/g for GO and 87 F/g for PEDOT–PSS); this was attributable to its high electrical conductivity and the layer‐within/on‐layer composite structure. Such an increase demonstrated that the synergistic combination of GO and PEDOT–PSS had advantages over the sum of the individual components. On the basis of cycle‐life tests, the capacitance retention of about 78% for the GPTs compared with that of 66% for PEDOT–PSS after 1200 cycles suggested a high cycle stability of the GPTs and its potential as an electrode material for supercapacitor applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

High cycling stability and well printability poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate)/multi‐walled carbon nanotube nanocomposites via in situ polymerization applied on electrochromic display

A high cycling stability material and an additive manufacturing method are reported for the fabrication of solid electrochromic devices. The poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate)/multi‐walled carbon nanotube (PEDOT:PSS/MWCNT) nanocomposites were synthesized via in situ polymerization. A carboxymethyl cellulose gel was used as the ink vehicle for screen printing. The electrochromic (EC) performance of films patterned by screen printing was also examined. The results of characterization indicate that strong interfacial interactions occurred between PEDOT:PSS and the MWCNTs and the MWCNTs formed a network in these conducting polymers film, so the composite was more conductive than pure PEDOT:PSS. Devices containing PEDOT:PSS/MWCNTs were more stable after 1000 cycles, exhibited higher rate of ion exchange and faster increases in current. The composite containing 0.3 wt % MWCNTs also had a 23% higher color contrast (ΔE*) than pure PEDOT:PSS at 2.5 V applied voltages. The EC inks with well printability not only can be used to print large area films, but also can print fine lines and pixel‐type dots in displays. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45943.     

On the mechanism of conductivity enhancement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film through solvent treatment

The conductivity of a poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film is enhanced by more than 100-folds on adding some organic compounds into PEDOT:PSS aqueous solutions or by treating the PEDOT:PSS film with organic solvents, such as ethylene glycol (EG), 2-nitroethanol, methyl sulfoxide or 1-methyl-2-pyrrolidinone. The mechanism for this conductivity enhancement was studied through various chemical and physical characterizations. The PEDOT:PSS film which is soluble in water becomes insoluble after treatment with EG. This strongly suggests an increased interchain interaction among the PEDOT chains. Raman spectroscopy indicates that this increased interchain interaction results from conformational changes of the PEDOT chains, which change from a coil to linear or expanded-coil structure. The increased interchain interaction and conformation changes are further confirmed by the temperature dependence of conductivity and the electron spin resonance (ESR). It is found that EG treatment lowers the energy barrier for charge hopping among the PEDOT chains, lowers the polaron concentration in the PEDOT:PSS film by ∼50%, and increases the electrochemical activity of the PEDOT:PSS film in NaCl aqueous solution by ∼100%. Atomic force microscopy (AFM) and contact angle measurements show that the surface morphology of the PEDOT:PSS film changes as well after the EG treatment. Conductivity enhancement was also observed when other organic compounds were used, but it was strongly dependent on the chemical structure of the organic compounds, and observed only with organic compound with two or more polar groups. These experimental results support our proposal that the conductivity enhancement is due to the conformational change of the PEDOT chains and the driving force is the interaction between the dipoles of the organic compound and dipoles or charges on the PEDOT chains.     

Preparation of poly(tert‐butyl acrylate)‐poly(acrylic acid) amphiphilic copolymers via radiation‐induced reversible addition–fragmentation chain transfer mediated polymerization of tert‐butyl acrylate

Poly(tert‐butyl acrylate) (PtBA) is a versatile hydrophobic macromolecule usually preferred in the development of new materials for a host of applications. PtBA homopolymers with well‐defined structure and controlled molecular weight in a wide range were successfully synthesized via radiation‐induced reversible addition–fragmentation chain transfer (RAFT) polymerization in the presence of a trithiocarbonate type RAFT agent. The polymerization of tBA was performed under ⁶⁰Co γ‐irradiation in the presence of 2‐(dodecylthiocarbonothioylthio)‐2‐methylpropionic acid (DDMAT) as the RAFT agent in toluene at room temperature with three [tBA]/[DDMAT] ratios (400, 600 and 1000) and different irradiation times. Radiation‐induced polymerization of tBA displayed controlled free radical polymerization characteristics: a narrow molecular weight distribution (M_w/M_n ~ 1.1), pseudo first order kinetics and controlled molecular weights. The system followed the RAFT polymerization mechanism even at very low amounts of RAFT agent ([tBA]/[DDMAT] = 1000), and molecular weights up to 113 900 with narrow dispersity (Ð =1.06) were obtained. PtBA was further hydrolysed into different amphiphilic PtBA‐co‐poly(acrylic acid) (PAA) copolymers by low (27.5%) and high (77.3%) degrees of hydrolysis. The pH sensitivity of the two copolymers was investigated by dynamic light scattering at pH 2 and pH 9 (above and below the pK_a value of PAA) and their hydrodynamic diameters and zeta potential values were determined. © 2020 Society of Chemical Industry     

Preparation of well‐defined block copolymer having one polystyrene segment and another poly(styrene‐alt‐maleic anhydride) segment with RAFT polymerization

Block copolymers, polystyrene‐b‐poly(styrene‐co‐maleic anhydride), have been prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization technique using three different approaches: 1‐phenylethyl phenyldithioacetate (PEPDTA) directly as RAFT agent, mediated polystyrene (PS) block as the macromolecular PS‐RAFT agent and mediated poly(styrene‐maleic anhydride) (SMA) block with alternating sequence as the macromolecular SMA‐RAFT agent. Copolymers synthesized in the one‐step method using PEPDTA as RAFT agent possess one PS block and one SMA block with gradient structure. When the macromolecular RAFT agents are employed, copolymers with one PS block and one alternating SMA block can be produced. However, block copolymers with narrow molecular weight distribution (MWD) can only be obtained using the PS‐RAFT agent. The MWD deviates considerably from the typical RAFT polymerization system when the SMA is used as the RAFT agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

可逆加成-断裂链转移聚合制备聚氯乙烯-b-聚乙二醇-b-聚氯乙烯共聚物

合成了含黄原酸酯端基的聚乙二醇（X-PEG-X）大分子链转移剂,并以其为可逆加成-断裂链转移试剂调控氯乙烯（VC）溶液和悬浮聚合,合成聚氯乙烯-b-聚乙二醇-b-聚氯乙烯（PVC-b-PEG-b-PVC）三嵌段共聚物。X-PEG-X调控VC溶液聚合得到的共聚物的分子量随聚合时间增加而增大,分子量分布指数小于1.65。X-PEG-X具有水/油两相分配和可显著降低水/油界面张力的特性,以X-PEG-X为链转移剂和分散剂,通过自稳定悬浮聚合也可合成PVC-b-PEG-b-PVC共聚物,共聚物颗粒无皮膜结构,分子量随聚合时间增加而增大;由于VC悬浮聚合具有聚合物富相和单体富相两相聚合特性,共聚物分子量分布指数略大于溶液聚合共聚物。通过乙酸乙烯酯（VAc）扩链反应进一步证实了PVC-b-PEG-b-PVC的“活性”,并合成PVAc-b-PVC-b-PEG-b-PVC-b-PVAc共聚物。水接触角测试表明PVC-b-PEG-b-PVC的亲水性优于PVC。