复合磺酸体系原位聚合聚苯胺性能研究

采用不同比例的十二烷基苯磺酸(DBSA)与对甲基苯磺酸(TSA)复合磺酸体系替代盐酸体系,合成了具有一定溶解率的聚苯胺(PANI),研究了不同DBSA/TSA比例对掺杂态PANI的产率、掺杂程度、溶解率和电导率的影响.结果表明,DBSA/TSA摩尔比为7/3时所得PANI同时具有较好的电导率和溶解性.采用该体系合成的掺杂态PANI的电导率为1.1S/cm,在N-甲基吡咯烷酮(NMP)、丙酮、四氯化碳和二甲苯中的溶解率(质量分数)分别为70%,40%,26%和19%.     

乳液聚合DBSA/TSA掺杂聚苯胺的XPS表征

以乳液聚合法制备DBSA/TSA复合磺酸掺杂态聚苯胺,主要采用XPS手段对其性能进行了表征.结果表明:当DBSA/TSA的摩尔比为3/2时,合成的掺杂态PANI具有较高导电率,可达6.32×10-2S/cm;乳化剂以两种方式存在:提高PANI导电率的掺杂剂和独立存在的稳定剂.     

掺杂态聚苯胺的XPS研究

对经不同质子酸盐酸 (HCl)、对甲基苯磺酸 (TSA)及磺基水杨酸 (SSA)掺杂的聚苯胺 (PAn)进行 3h空气浴的热处理 ,并用电导率和 XPS对其进行了表征。结果表明 ,PAn·HCl在 16 0℃时其电导率下降了六个数量级 ,其表面掺杂率随温度的升高而降低 ,并且具有不同结合能 Cl的相对组成也随之发生了变化 ;PAn·TSA及 PAn·SSA在 2 0 0℃的电导率分别下降了两个和一个数量级 ,但其表面掺杂率未发生明显的变化。随着温度的升高 ,掺杂态 PAn膜的脆性和表面氧化的程度增加     

二次掺杂聚苯胺的合成及其导电性能的研究

掺杂态的聚苯胺(PANI)合成是采用快速直接法合成盐酸/PANI,用氨水水解掺杂态,得到本征态PANI,再用对甲苯磺酸对PANI进行二次掺杂。在不同反应摩尔比、不同反应时间、不同反应温度下合成的对甲苯磺酸/PANI,用于测量电导率,得出优化条件。采用透射电镜(TEM)观察其形貌,并利用红外光谱和紫外光谱对其结构进行了表征。     

4,4''''-双(2-磺基苯乙烯基)联苯二酸掺杂聚苯胺的研究

采用4,4'-双(2-磺基苯乙烯基)联苯二磺酸(BSBD)掺杂本征态的聚苯胺,得到BSBD掺杂的聚苯胺(PANI/BSBD),探讨了掺杂温度、掺杂酸用量对PANI/BSBD电导率和溶解性的影响.结果表明,提高掺杂温度有利于提高PANI的掺杂程度和电导率,但过高的温度会引起PANI/BSBD的部分脱掺杂,电导率下降.增加BSBD的用量也可提高PANI的掺杂程度,提高PANI/BSBD电导率;但过量的游离BSBD会以固体杂质形式析出,使PANI/BSBD电导率下降.在90℃下,PANI链中亚胺氮(-N＝)原子与掺杂酸中H+之比为1时,电导率达到最大值1.0×10-2S/cm.紫外可见光光谱(UV-Vis)分析表明,随BSBD用量的增大和掺杂温度的提高,表征醌式结构的吸收峰强度逐渐下降,同时有一定红移,表明PANI/BSBD掺杂率的升高.傅立叶变换红外光谱(FTIR)表明,随着BSBD用量的增加,掺杂态聚苯胺的特征峰位置向低频移动,掺杂主要发生在-N＝原子上.     

磺基水杨酸掺杂聚苯胺/石墨复合粉体的研究

研究了磺基水杨酸(SSA)对PANi/EP的机械力化学掺杂作用,通过电导率测定、SEM观察和FT-IR研究了体系的导电性能和掺杂机理.结果表明,SSA与PANi/EP粉体按照一定比例共碾磨,在复合粉体与SSA质量比为2.5时,共碾磨90 min电导率达到最高值0.438 S/cm,105 ℃退火2 h,测试其电导率为2.762 S/cm,提高了约5倍,但仍低于盐酸掺杂样品.可见高熔点有机酸对聚苯胺的固相机械力化学掺杂,避免了溶剂体系对环境的污染,是一种低成本绿色工艺.SEM表明,SSA掺杂PANi/EP复合粉体具有疏松多孔不规则形貌特征,粒径大小在0.5 μm～1 μm;FT-IR比较发现,SSA的特征峰3113 cm-1消失,1667 cm-1减弱并发生左移,1068 cm-1和1582 cm-1合并成一个1582 cm-1峰.表明SSA与PANi/EP发生了化学反应,即SSA与PANi/EP发生了掺杂.     

4,4′-双(2-磺基苯乙烯基)联苯二酸掺杂聚苯胺的研究

采用4,4′ 双(2 磺基苯乙烯基)联苯二磺酸(BSBD)掺杂本征态的聚苯胺,得到BSBD掺杂的聚苯胺(PANI/BSBD),探讨了掺杂温度、掺杂酸用量对PANI/BSBD电导率和溶解性的影响。结果表明,提高掺杂温度有利于提高PANI的掺杂程度和电导率,但过高的温度会引起PANI/BSBD的部分脱掺杂,电导率下降。增加BSBD的用量也可提高PANI的掺杂程度,提高PANI/BSBD电导率;但过量的游离BSBD会以固体杂质形式析出,使PANI/BSBD电导率下降。在90℃下,PANI链中亚胺氮(-N=)原子与掺杂酸中H+之比为1时,电导率达到最大值1.0×10-2S/cm。紫外可见光光谱(UV Vis)分析表明,随BSBD用量的增大和掺杂温度的提高,表征醌式结构的吸收峰强度逐渐下降,同时有一定红移,表明PANI/BSBD掺杂率的升高。傅立叶变换红外光谱(FTIR)表明,随着BSBD用量的增加,掺杂态聚苯胺的特征峰位置向低频移动,掺杂主要发生在-N=原子上。     

可溶性DBSA掺杂PANI接枝MWNTs复合材料的结构与性能

多壁碳纳米管(MWNTs)经对苯二胺功能化后,苯胺基团以3.7%的含量通过酰胺键连接到MWNTs表面(p-MWNTs),以十二烷基苯磺酸(DBSA)为掺杂剂和乳化剂,通过原位聚合,制备了在四氢呋喃(THF)中稳定溶解的DBSA掺杂聚苯胺(PANI)接枝MWNTs(PANI-g-MWNTs)导电复合材料.采用Raman光谱、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、紫外-可见光谱(UV-vis)、透射电子显微镜(TEM)、X射线衍射仪(XRD)和四电极电导率仪研究复合材料的结构与性能.实验结果表明,p-MWNTs表面的苯胺基团参与原位聚合反应,使PANI与p-MWNTs通过酰胺键连接起来,形成以p-MWNTs为核、DBSA掺杂PANI为壳的纳米结构.包覆层中DBSA掺杂PANI受限生长在p-MWNTs表面,其结构规整度较纯DBSA掺杂PANI提高.DBSA掺杂PANI-g-MWNTs复合材料溶解在THF中获得31.55 mg/mL的溶解度和至少1个月的稳定性,该复合材料的室温电导率为6.23×10-1 S/cm,较纯DBSA掺杂PANI提高1个数量级.     

含酞菁功能基聚苯胺的合成及性能研究Ⅰ.酞菁铜磺酸掺杂聚苯胺的合成与表征

以耐晒翠蓝为原料合成了酞菁铜磺酸(CuPcS),用其对本征态聚苯胺分别在水相和油相中进行掺杂,获得了具有酞菁功能基聚苯胺的分子结构.该聚合物具有优良的溶解性能和成膜能力,电导率达到10S/m,红外谱图证实了所合成产物的结构,紫外吸收分析表明,用酞菁铜磺酸掺杂聚苯胺后在可见光区、近红外区具有较强的吸收,可大幅度提高其光电导性能.     

高电导率聚苯胺的合成

采用樟脑磺酸(CSA)做掺杂剂,对聚苯胺(PANI)进行了掺杂研究,考查了掺杂时间、温度、掺杂剂用量及间甲酚(m-c)与三氯甲烷(ch)的混合溶剂比例对其导电性的影响,并用红外光谱对掺杂产物进行了表征。结果表明,掺杂温度对聚苯胺的电导率影响较大,通过控制温度,可以制备出电导率达400S.cm-1的磺化聚苯胺薄膜,且具有良好的环境稳定性,在空气中放置6个月,其电导率基本不变。     

Preparation and characterization of soluble and DBSA doped polyaniline grafted multi-walled carbon nanotubes nano-composite

Soluble and highly doped polyaniline (PANI) grafted multi-walled carbon nanotubes (MWNTs) nano-composite was synthesized by in situ oxidation polymerization, de-doping with ammonium hydroxide and doping the PANI-Emeraldine base (PANI-EB) grafted MWNTs nano-composite in N-methyl-2-pyrrolidinone (NMP) with Dodecyl benzene sulfonic acid (DBSA). Transmission electron microscope (TEM), Raman spectra, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and standard four-probe methods were employed to characterize morphology, chemical structure and electronic conductivity of the nano-composite. The results show that oxidized phenylamine groups of phenylamine groups contained MWNTs (p-MWNTs) initiate PANI polymerization on the surface of p-MWNTs. PANI coatings graft on the surface of p-MWNTs via amide bond forming homogeneous core (p-MWNTs)–shell (PANI) nano-structures. After doping PANI-EB grafted MWNTs nano-composite with DBSA, the attachment of soluble DBSA doped PANI chains on the surface of p-MWNTs via covalent bonding renders p-MWNTs compatible with polymer matrix and lead to DBSA doped PANI grafted MWNTs nano-composite soluble and stable in NMP. Owing to incorporation of p-MWNTs and chemical bridges between p-MWNTs and PANI chains, conductivity of DBSA doped PANI grafted MWNTs nano-composite at room temperature is increased by about two orders of magnitude over neat DBSA doped PANI.     

Comparative studies of solid-state synthesized polyaniline doped with inorganic acids

Polyaniline (PANI) salts doped with inorganic acids (HCl, H₂SO₄ and H₃PO₄) were directly synthesized by using solid-state polymerization method. The FTIR spectra, UV–vis absorption spectra and X-ray diffraction patterns were used to characterize the molecular structures of the PANI salts. Voltammetric study was done to investigate the electrochemical behaviors of all these PANI salts. The PANI salts were affected by varying the protonation media (HCl, H₂SO₄ and H₃PO₄). The FTIR and UV–vis absorption spectra revealed that all PANI salts contained the conducting emeraldine salt phase at different oxidation state. The crystallinity of PANI doped with HCl was better than those doped with H₂SO₄ and H₃PO₄. The conductivity of the PANI doped with HCl is the highest among the inorganic acid doped PANI.     

PANI-DBSA/PAN导电薄膜的结构与性能

首先由乳液聚合制备十二烷基苯磺酸(DBSA)掺杂的可溶性聚苯胺(PANI)，然后以三氮甲烷／二甲基亚砜(DMSO)为混合溶剂，采用溶液共混的方法制备聚苯胺／聚丙烯腈(PAN)导电薄膜。对导电薄膜进行了导电性能测试、扫描电镜分析(SEM)、红外光谱(FT-IR)及广角X射线衍射分析．结果表明，PANI-DBSA／PAN共混体系的导电逾渗阈值低于4％；在较低的PANI含量时。聚苯胺在膜中央和皮层的分布形态不同。导电网络首先在皮层形成。     

The effects of composition and processing variables on the properties of thermoplastic polyaniline blends and composites

Pure polyaniline (PANI) has a high electrical conductivity and can be made soluble and thermoplastic, but it still lacks adequate mechanical properties for large-scale commercial use and therefore, it has been blended with other polymers such as poly(methyl methacrylate) (PMMA). In the work described in this paper, the scaled up synthesis of conductive polyaniline by an oxidative chemical method under controlled pH and temperature has been optimised. Re-doping of deprotonated insulating base with excess of the mono-functional organic acids such as p-toluenesulfonic (TSA) or dodecylbenzenesulfonic (DBSA) in aqueous media was successful. A wide range of techniques including TGA, GPC, EA, FTIR, XRD and SEM were employed for the characterisation of PANI powders and blends. Compositions of PANI-HCI, TSA or DBSA and thermoplastic matrix PMMA with or without a plasticiser were melt-processed by compression moulding for 3 min at 210°C to produce plaques. The effectiveness of four different phenolic plasticisers was compared and hydroquinone was found to produce the blends with the highest conductivities. A few preliminary injection-moulded plaques were made and their conductivities were compared with those of the compression-moulded samples.     

界面聚合法合成有机酸掺杂聚苯胺结构与性能研究

以苯胺为单体,过硫酸铵为氧化剂,分别以乙酸、月桂酸、硬脂酸、十二烷基苯磺酸为掺杂酸,通过界面聚合法成功制备了有机酸掺杂聚苯胺,对其导电性能、溶解性能进行评价,对其化学结构、晶型结构和微观结构进行分析。结果表明:当苯胺与掺杂酸摩尔比为1∶2时电导率普遍较好,约为(1.73～2.43)×10-4S/cm;有机酸掺杂聚苯胺在极性溶剂中溶解性较好;FT-IR分析结果证明有机酸对聚苯胺进行了成功掺杂;XRD结果说明聚苯胺在2θ=6°的衍射峰受掺杂酸尺寸影响较大,且对聚苯胺的微观形貌具有显著影响。     

聚苯胺的微波掺杂反应

研究了微波辐照下十二烷基苯磺酸(DBSA)对聚苯胺的掺杂反应,得到了可溶性的导电聚苯胺,产物的组成与性能和其他方法相比无明显差异。研究表明,微波掺杂反应受反应时间和温度的影响,高温下反应可以缩短PANI达到最大掺杂程度所需的时间,但高温下微波辐照时间过长,会引起产物的导电率降低。     

Morphology and conductivity of polyaniline sub-micron fibers prepared by electrospinning

Sub-micron fibers of pure polyaniline (PANI) doped with sulfuric acid or hydrochloric acid were prepared by electrospinning PANI with suitable molecular weight dissolved in hot sulfuric acid. A modified electrospinning setup was employed with a coagulation bath as a collector, where dilute sulfuric acid was used as coagulation bath. The factors influencing the morphology and conductivity of the synthesized PANI fibers were investigated, including the concentration of dilute H₂SO₄ solution in the coagulation bath, the doped PANI concentration in H₂SO₄ solution, the type of doping acid and the voltage applied to the solution. The morphologies of doped PANI fibers were characterized by scanning electron microscope (SEM). The structure of the resulting fibers was analyzed by Fourier transform infrared spectroscopy and UV–vis spectrometer. The conductivity of PANI fibers were characterized by I–V characteristics. Homogeneous PANI fibers with a diameter of 370 nm and a high conductivity of 52.9 S/cm were prepared. The possible mechanisms of different morphology formation and conductivity of PANI fibers were also discussed.