聚苯胺的制备及导电性能研究

文章通过采用控制不同的反应时间、不同的质子酸浓度和不同的反应温度,运用化学氧化法制备了掺杂态的导电聚苯胺。并用四探针法和红外光谱对其电阻率和结构进行了表征。实验表明:在反应温度0℃,盐酸浓度为1 mol/L,过硫酸铵与苯胺摩尔比为1,反应时间为4 h时的聚苯胺导电性能最好。     

导电聚苯胺的合成及性能研究

采用直接化学氧化聚合法,用一步掺杂的方法合成了导电聚苯胺,在聚苯胺链上引入磺酸基团。讨论了氧化剂的用量、反应介质酸的用量、反应温度和反应时间对导电聚苯胺性能的影响。获得了最佳参数为：反应温度为10℃;c（盐酸）=0.3 mol/L;n（过硫酸铵）∶n（苯胺）=0.4∶1;反应时间为4h。其在二甲基亚砜（DMSO）中溶解度超过85%,产率超过80%,电导率大于8 S/cm。     

乳液聚合法制备聚苯胺及其导电性能

以十二烷基苯磺酸(DBSA)为乳化剂,十六醇(CA)为助乳化剂,盐酸和十二烷基苯磺酸（DBSA）为掺杂剂, 过硫酸铵为引发剂,采用乳液聚合法合成了导电聚苯胺（PAn）.研究了反应温度、反应时间及苯胺、十二烷基磺酸、十六醇、盐酸和过硫酸铵配比对聚苯胺电导率的影响.研究结果表明,较佳的工艺条件为：反应温度为7 ℃,反应时间为6 h,较佳的原料物质的量的比为苯胺∶十二烷基苯磺酸∶十六醇∶盐酸∶ 过硫酸铵=0.05∶0.028∶0.04∶0.01∶0.05;以十六醇为助乳化剂,采用十二烷基苯磺酸和盐酸为掺杂剂,提高了聚苯胺的导电性.同时对聚苯胺导电机理进行了分析.     

聚苯胺-碳纤维导电纸的制备

采用改良的分步液相原位聚合法使得聚苯胺均匀生长在碳纤维纸基体上.考察了碳纤维质量分数、引发剂过硫酸铵(APS)与苯胺用量,以及浸渍时间和反应时间对聚苯胺-碳纤维导电纸导电性能的影响.采用SEM观察导电纸的微观形貌,利用FTIR与EDS分别表征其表面结构与元素变化.结果表明,当碳纤维质量分数为20％,引发剂APS浓度为0.375 mol/L,n(苯胺):n(盐酸,1 mol/L)=2:1,反应时间为12 h,浸渍时间为1 min时,制备的导电纸(PANI-CP)的导电性能最佳.相对于碳纤维原纸(CP),制备的PANI-CP电导率为5.435 S/cm,导电性能提高250.0％,抗张指数为27.665 N·m/g,抗张指数提高37.3％.相对于液相原位聚合法制备的导电纸(L-PANI-CP),PANI-CP导电性能提高85.9％,总色差值(DE)下降66.0％.     

含导电聚苯胺类锂离子电池复合材料的现状及发展趋势

导电聚苯胺(PANI)是近十年来研究最多的导电聚合物,具有比容量高、氧化还原可逆性好、电导率高、合成方法简单、成本低等特点,在化学电源和超级电容器中的应用最为广泛。导电聚苯胺复合材料的合成方法主要分为:原位复合法、共混法、自组装和电化学复合法等。导电聚苯胺复合材料可作为高能物质用于研发电极材料,但目前利用导电聚苯胺对锂离子电池三元正极材料进行修饰改性的研究较少。综述了导电聚苯胺及其复合材料的热电化学性能,重点对导电聚苯胺/锂离子电池复合正极材料的性能进行了阐述。最后对导电聚苯胺复合材料的应用和研究方向进行了总结,并简述了导电聚苯胺包覆改性LiNi_(1-x-y)Co_xMn_yO_2复合材料的应用和展望。     

几种酸掺杂聚苯胺-聚乙烯醇复合导电涂料的制备

采用聚乙烯醇为基质材料,以盐酸、十二烷基苯磺酸、氨基磺酸水溶液掺杂,制备了聚苯胺-聚乙烯醇(PANI-PVA)复合导电涂料。研究了PANI与PVA质量比、酸用量、氧化剂用量、反应时间以及膜干燥温度等因素对涂料膜电导率的影响。结果表明:当PVA质量分数为40%、成膜干燥温度为80℃时,PANI-PVA涂料膜的电导率最大。而且当cHCl=0.5mol/L、反应时间为6h、过硫酸铵与苯胺摩尔比为1.0时,所得HCl-PANI-PVA膜的电导率达最大,为15.0S/cm;当cDBSA=1.0mol/L、反应时间为8h、过硫酸铵与苯胺摩尔比为2.0时,所得DBSA-PANI-PVA膜的电导率达最大,为7.1S/cm;当cNH2SO3H=1.0mol/L、反应时间为6h、过硫酸铵与苯胺摩尔比为2.0时,所得NH2SO3H-PANI-PVA膜的电导率达最大,为2.0S/cm。在这几种酸掺杂的PANI-PVA复合导电涂料中,HCl-PANI-PVA膜的电导率最大。     

有机磷酸酯掺杂聚苯胺的研究

以有机磷酸酯为掺杂剂、过硫酸铵为引发剂,采用化学氧化法合成导电聚苯胺。在苯胺浓度为0．1mol/L、有机磷酸酯浓度为0．3mol／L、过硫酸铵浓度为0．12mol/L、温度10℃、聚合反应时间3．5小时的条件下,合成了电导率达0．42s/cm的聚苯胺。采用红外光谱和X－射线衍射对其结构进行了表征。     

导电聚苯胺／EAA共混物的导电性能研究

研究了实验室制备的两种导电聚苯胺材料与乙烯-丙烯酸共聚物(EAA)的共混及共混物的导电性能和微观形态。实验表明,这两种导电聚苯胺材料分别与EAA以10/90的质量比混合时,复合粒子的电导率可以达到10-7-10-6/cm,所制得的共混材料完全可以用来做抗静电材料。从扫描电镜可以看出,丙烯酸酯共聚物酸改性后的聚苯胺与EAA的相容性比十二烷基苯磺酸掺杂的聚苯胺有一定的改善,而且由于丙烯酸酯共聚物酸与EAA的二次掺杂作用,电导率也有提高。     

含导电聚苯胺类锂离子电池复合材料的现状及发展趋势

导电聚苯胺（PANI）是近十年来研究最多的导电聚合物,具有比容量高、氧化还原可逆性好、电导率高、合成方法简单、成本低等特点,在化学电源和超级电容器中的应用最为广泛。导电聚苯胺复合材料的合成方法主要分为：原位复合法、共混法、自组装和电化学复合法等。导电聚苯胺复合材料可作为高能物质用于研发电极材料,但目前利用导电聚苯胺对锂离子电池三元正极材料进行修饰改性的研究较少。综述了导电聚苯胺及其复合材料的热电化学性能,重点对导电聚苯胺/锂离子电池复合正极材料的性能进行了阐述。最后对导电聚苯胺复合材料的应用和研究方向进行了总结,并简述了导电聚苯胺包覆改性LiNi_1-x-yCo_xMn_yO₂复合材料的应用和展望。     

聚苯胺的合成及其光谱特性

:采用化学氧化聚合法 ,以苯胺为单体 ,过硫酸铵 (APS)为氧化剂 ,在酸性介质中合成聚苯胺(PAn) ,聚合物的比浓粘度 (ηSP) C=0 .1=1 d L/ g,酸掺杂后电导率 (σ)为 1 0 0 S/ cm。讨论了单体与氧化剂的比例、反应体系的温度以及聚合反应的时间对聚合产物的影响。采用傅里叶红外光谱 (FTIR)和紫外可见光光谱 (UV- Vis)对聚苯胺掺杂前后结构的变化 ,表明聚苯胺主链结构经质子酸掺杂后由于电子的离域形成了共轭结构 ,从而使聚苯胺有良好的导电性能。     

Composites based on CB/CF/Ag filled EPDM/NBR rubber blends with high conductivity

For many applications of conductive rubbers, it is desirable to endow the conductive rubber with high conductivity at low conductive filler loading. In this work, composites based on ethylene‐propylene‐diene monomer (EPDM) rubber and nitrile‐butadiene rubber (NBR) were prepared using carbon blacks, carbon fibers, and silver powders as fillers. As the weight fraction of silver powder increased, the hardness of composites increased gradually while the tensile strength and elongation at break decreased. SEM revealed that the EPDM/NBR blends exhibited a relatively co‐continuous morphology. The differential scanning calorimetry (DSC) curves reported the EPDM/NBR rubber blends were incompatibility. The thermogravimetry (TG) studies showed that adding a small amount of silver powder could improve the thermal stability of composites. These conductive composites exhibited good electrical property. At room temperature, when the total volume fraction of fillers was 15.20%, the volume resistivity of EPDM/NBR blend was only 0.0058 Ω cm. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41357.     

乳液聚合法制备聚苯胺/聚乙烯醇电致变色材料

以十二烷基苯磺酸(DBSA)为掺杂剂,在非有机溶剂的两相体系中以聚乙烯醇(PVA)为成膜助剂,采用现场乳液聚合法合成了可直接用于制备电致变色膜的聚苯胺(PAn)/PVA乳液。研究了PVA含量、苯胺(An)与DBSA的量比、氧化剂过硫酸铵(APS)与An的量比及反应温度对膜的电致变色性、导电性的影响。实验结果表明:在w(PVA)=4 3%、n(An)∶n(DBSA)∶n(APS)=0 86∶1∶0 86、反应温度为8℃时,所制得的PAn/PVA乳液可直接制成具有良好电致变色性的自支撑膜(电致变色响应时间小于0 5s,电导率可达2 69×10-4S/m)。     

聚苯胺的制备及其导电性能

以苯胺为单体,过硫酸铵为氧化剂,盐酸为掺杂酸,采用化学氧化法制备出盐酸掺杂聚苯胺(PANI-HA),研究了过硫酸铵与苯胺单体摩尔比(n APS:n An)、HCl浓度、反应温度和反应时间对PANI-HA电导率的影响;采用正交分析法研究了各影响因素对PANI-HA电导率的主次关系。结果表明:影响PANI-HA电导率的主次关系为反应温度n APS:n An反应时间HCl浓度;制备PANI-HA的最佳工艺为nAPS:n An=1.0,HCl浓度1.0 mol/L,反应温度10℃,反应时间8 h。     

Preparation of conductive polypyrrole composites by in‐situ polymerization

Two kinds of conductive polypyrrole composites were prepared by in‐situ polymerization of pyrrole in a suspension of chlorinated polyethylene powder or in a natural rubber latex using ferric chloride as oxidizing agent. The preparation conditions were studied and the results showed that it is better to swell the chlorinated polyethylene powder with the monomer first, followed by addition of the oxidant, than to add the oxidant first, and that conversion can reach 98% for 6 h at room temperature. The conductivity percolation threshold of the composite is about 12%. The composites can be processed repeatedly, exhibiting a maximum tensile strength over 9 MPa and a maximum conductivity near 1 S cm⁻¹. The polypyrrole/natural rubber composites were prepared successfully by using a nonionic surfactant (Peregal O) as stabilizer at pH less than 3 with a molar ratio of FeCl₃/pyrrole = 2.5 below 45 °C. The latter composites show a low conductivity percolation threshold about 6%, a maximum tensile strength over 10 MPa and a maximum conductivity over 2 S cm⁻¹. The composites were characterized by FTIR and TGA. The polypyrrole/chlorinated polyethylene composites are very stable in air and almost no decrease of conductivity was observed for over 10 months examined. © 1999 Society of Chemical Industry     

PROPERTIES OF POLYPROPYLENE/NATURAL RUBBER/RECYCLE RUBBER POWDER BLENDS

Thermoplastic elastomers have been prepared by blending polypropylene (PP), natural rubber (NR), and recycle rubber powder (RRP). The blends were melt-mixed using a Brabender Plasticorder torque rheometer at 190°C and 50 rpm. A fixed 70:30 blend ratio (wt%) of PP and rubber was prepared. The effect of partial replacement of NR with RRP at a fixed rubber content (NR+RRP), 30 wt% on mechanical properties, swelling behavior, torque development, and morphological properties of PP/NR/RRP blends was studied. Results show that the tensile strength, Young's modulus, and swelling resistance increase with increasing RRP content in the PP/NR/RRP blends whereas the stabilization torque and elongation at break exhibit opposite trend.     

废旧胶粉/聚丙烯共混物的制备及性能研究

熔融接枝法制得的马来酸酐接枝聚丙烯5076(MAH-g-5076)可改善聚丙烯与废旧胶粉的界面相容性,高熔体质量流动速率聚丙烯MF650Y可改善废旧胶粉/聚丙烯共混物的流动性能,利用双螺杆挤出机挤出制得高性能、易加工的废旧胶粉/聚丙烯共混物,研究MF650Y用量对共混物性能的影响。结果表明:随着MF650Y用量(MF650Y和MAH-g-5076用量共30份)的增大,共混物的拉伸强度先增大后减小,在MF650Y用量为5~10份范围内达到最大值,拉断伸长率呈现震荡减小趋势,熔体质量流动速率增大;随着角频率的增大,共混物的复数粘度(η*)减小,储能模量(G′)和损耗模量趋于增大,当MF650Y用量为5份时,共混物的η*和G′最大;MF650Y用量为10份时有助于保护C=C键及抑制交联反应,此时聚丙烯与废旧胶粉相容性较好,两相界面结合能力较强,共混物无明显孔洞。     

新型共混十二烷基苯磺酸掺杂的聚苯胺导电胶的合成

以摩尔比为１： １的苯胺与过硫酸铵为反应物,在 ｃ（ＨＣｌ）＝ １ｍｏｌ／Ｌ盐酸中于室温下合成的聚苯胺,经２５％（ω）氨水处理后得本征态聚苯胺,收率７２％。用５０％（ω）十二烷基苯磺酸的乙醇溶液６０ｍｌ与３ｇ本征态聚苯胺在室温下反应２４ｈ,可制得导电态的掺杂十二烷基苯磺酸的聚苯胺,电导率３．９８Ｓ／ｃｍ。然后在６０℃下将环氧树脂Ｅ－４４和上述掺杂态聚苯胺（ｍ：＝１：０,４）经良好搅拌１ｈ,得均匀的黑色导电胶。该电胶可溶解在二甲苯中,并能与体积比为１：１的邻苯二甲酸在８０℃下经４ｈ可完全固化,电导率为０．１１８Ｓ／ｃｍ。     

Quantitative analysis for reaction between epoxidized natural rubber and poly (L‐lactide) through 1H‐NMR spectroscopy

Reaction between epoxidized natural rubber and poly(L ‐lactide) (PLLA) was investigated quantitatively in terms of conversion of the epoxidized natural rubber. The epoxidized natural rubber was prepared by epoxidation of high ammonia natural rubber (HA‐NR) or deproteinized natural rubber (DPNR) with peracetic acid followed by depolymerization with ammonium persulfate. The resulting liquid HA‐NR having epoxy group (LENR) or liquid DPNR having epoxy group (LEDPNR) were subjected to heating at 473 K for 20 min, after blending with PLLA. The products were characterized through morphology observation, DSC measurement, and ¹H‐NMR spectroscopy. The conversions of the rubbers were estimated from intensity ratio of signals in ¹H‐NMR spectrum for the products after removing unreacted rubber with toluene. Difference in the estimated conversion between the LENR/PLLA and LEDPNR/PLLA blends was interpreted in relation to proteins present in the rubber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

微波法接枝改性天然胶乳的制备与表征

采用微波辐射的方法对天然浓缩胶乳进行接枝改性,单体选用甲基丙烯酸甲酯,考察了微波温度、时间、引发剂和单体用量对接枝率、接枝效率的影响,用傅里叶变换红外光谱仪、核磁共振波谱仪来表征接枝产物。结果表明,微波法接枝改性天然胶乳的方法是可行的;适宜的反应条件为:采用过硫酸钾和亚硫酸钠作为引发剂,其用量为0.4%(占橡胶质量的百分数),微波温度为80℃,反应时间为1～2h,单体与胶乳质量比为1∶1。