Characteristics of PPG-based thermoplastic polyurethane doped with lithium perchlorate

Segmented thermoplastic polyurethane (TPU) was synthesized from methylene bis(cyclohexyl isocyanate) (H₁₂MDI), ethylenediamine (EDA), and poly(propylene glycol) (PPG) with a molecular weight of 1000. The ratio of hard segment to soft segment (NCO/OH) is changed to test the chemical and physical properties. Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance spectroscopy (IS) were utilized to monitor the phase change of these TPU samples with various lithium perchlorate (LiClO₄) concentrations. Significant changes occur in the FTIR spectrum of the TPU with LiClO₄ concentration above 0.5 mmol/g TPU, indicating that an interaction existed between the lithium cation and the hard segment or soft phase. The soft-segment T_g increased with increasing LiClO₄ concentration through the examination of DSC. IS results indicate an increase in bulk conductivity as the salt concentration is increased. Electrochemical stability of the TPU sample was studied by cyclic votammetry (CV). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 389–399, 2001     

聚苯胺/PE复合材料的制备探究

采用原位化学氧化聚合法制备苯胺/PE导电复合材料,使苯胺在基体高分子PE的水溶液中进行聚合,研究反应体系中聚苯胺的含量、反应时间、温度对复合材料电导率的影响,确定了较佳的聚合反应条件,并且通过红外对光谱复合材料的结构、光电性能和稳定性进行了表征和分析。     

Synthesis of conducting polyaniline/TiO2 composite nanofibres by one‐step in situ polymerization method

Conducting polyaniline (PANI)/titanium dioxide (TiO₂) composite nanofibres with an average diameter of 80–100 nm were prepared by one‐step in situ polymerization method in the presence of anatase nano‐TiO₂ particles, and were characterized via Fourier‐transform infrared spectra, UV/vis spectra, wide‐angle X‐ray diffraction, thermogravimetric analysis, and transmission electron microscopy, as well as conductivity and cyclic voltammetry. The formation mechanism of PANI/TiO₂ composite nanofibres was also discussed. This composite contained ～ 65% conducting PANI by mass, with a conductivity of 1.42 S cm^?1 at 25°C, and the conductivity of control PANI was 2.4 S cm^?1 at 25°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis by in situ chemical oxidative polymerization and characterization of polyaniline/iron oxide nanoparticle composite

Polyaniline (PANI) is a well‐studied material and is the pre‐eminent electrically conducting organic polymer with the potential for a variety of applications such as in batteries, microelectronics displays, antistatic coatings, electromagnetic shielding materials, sensors and actuators. Its good environmental as well as thermal stability and electrical conductivity tunable by appropriate doping make PANI an ideal active material for several applications. In this paper, we report the synthesis of water‐dispersible colloidal PANI/iron oxide composite nanoparticles using an in situ chemical oxidation polymerization method in a micellar medium of sodium dodecylsulfate, where the cores (iron oxide) are embedded in a PANI matrix layer. Transmission electron micrographs showed evidence of the formation of an iron oxide core/PANI shell composite with a thin layer of PANI over the iron oxide cores. The results of thermogravimetric, Fourier transform infrared and UV‐visible analysis indicated that the iron oxide nanoparticles could improve the composite thermal stability possibly due to the interaction between iron oxide particles and PANI backbone. We believe that the synthetic route described can also be adapted for the assembly of hierarchical structures of other metal oxides or hydroxides onto various cores. Copyright © 2010 Society of Chemical Industry     

稀溶液粘度法测定TPU/PSF和TPU/PMMA相容性

以N,N-二甲基甲酰胺(DMF)为溶剂,采用DSV研究了聚氨酯/聚砜(TPU/PSF)和聚氨酯/聚甲基丙烯酸甲酯(TPU/PMMA)两种共混体系的相容性。运用μ和α判据分别对TPU/PSF和TPU/PMMA两共混体系的相容性进行了判断,结论完全一致,TPU/PSF体系相容,而TPU/PMMA体系不相容。     

TPU／EPDM共混体系相态与力学性能的研究

从亚微相态和拉伸性能出发，对比了TPU／EPDM和TPU／EPDM／POE－g-MAH多相共混体系。结果发现：当EPDM添加量控制在较为适宜的范围时，由于形成了网状结构，TPU／EPDM体系拉伸强度明显提高。在EPDM添加量为10％时，共混体系的拉伸强度达到最大。还讨论了EPDM的加入对TPU流变性能的影响。     

新型聚苯胺系防腐蚀导电涂料的制备与研究

用化学氧化聚合方法（辅以超声分散技术）合成了具有纳米尺寸的聚苯胺,以其为导电填料,以丙烯酸酯为成膜物,制备出一种电导率在18～10^4S／m范围内的新型防腐导电涂料。讨论了聚苯胺含量对涂膜的电导率、外观、硬度、冲击力、附着力以及耐化学试剂性的影响,同时采用交流阻抗、电化学极化曲线研究了涂有该涂料的电极的电化学行为。结果表明,当聚苯胺质量分数在15％～30％范围时,涂膜具有良好的导电性、光泽以及耐化学试剂性,抗冲击强度为50kg／cm^2,附着力为1～2级,硬度为3日～1HB,Tafel曲线及EIS研究进一步表明该导电涂料有良好的抗腐蚀性。     

A novel approach to the preparation of thermoplastic polyurethane elastomer and polyamide 6 blends by in situ anionic ring‐opening polymerization of ε‐caprolactam

Blends of thermoplastic polyether‐based urethane elastomer (TPEU) and monomer casting polyamide 6 (MCPA6) were prepared using ε‐caprolactam as reactive solvent, with caprolactam sodium as a catalyst in the presence of TPEU, with TPEU content varying from 2.5% to 10% by weight. In situ anionic ring‐opening polymerization and in situ compatibilization to prepare TPEU/MCPA6 blends were carried out in one step. The TPEU chains, which underwent thermal dissociation in amine solvents to bear isocyanate groups, acted as macroactivator to initiate MCPA6 chain growth from the TPEU chains and form graft copolymers of TPEU‐co‐MCPA6 to improve compatibility between TPEU and MCPA6. The structure and thermal properties were characterized by means of Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, differential scanning calorimetry and scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

X‐ray photoelectron spectroscopy and electrical conductivity of polyaniline doped with dodecylbenzenesulfonic acid as a function of the synthetic method

X‐ray photoelectron spectroscopy (XPS) has been employed to investigate the protonation degree of polyaniline doped with dodecylbenzenesulfonic acid (Pani. DBSA) obtained by different synthetic methods. The protonation degree has been compared to electrical conductivity. Pani.DBSA prepared through the redoping process in an agate mortar displays conductivity values within the range of 1 S/cm. A protonation level of 48% with almost all imine groups being protonated. Pani.DBSA was also synthesized by oxidative polymerization of aniline in the presence of DBSA, which acts simultaneously as a surfactant and as protonating agent. This in situ doping polymerization was carried out in aqueous or toluene media. In both cases, protonation degrees higher than 50% have been achieved, indicating that a substantial portion of amine units have also been protonated. Higher doping degree has been achieved by aqueous dispersion polymerization of aniline. The C/N and S/N molar ratios obtained by XPS analysis indicate that the polyaniline chains obtained by in situ polymerization are protonated by both sulfonate and hydrogen sulfate anions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 556–565, 2001     

A novel electrospun TPU/PVdF porous fibrous polymer electrolyte for lithium ion batteries

Novel blend-based gel polymer electrolyte (GPE) films of thermoplastic polyurethane (TPU) and poly(vinylidene fluoride) (PVdF) (denoted as TPU/PVdF) have been prepared by electrospinning. The electrospun thermoplastic polyurethane-co-poly (vinylidene fluoride) membranes were activated with a 1M solution of LiClO₄ in EC/PC and showed a high ionic conductivity about 1.6 mS cm⁻¹ at room temperature. The electrochemical stability is at 5.0 V versus Li⁺/Li, making them suitable for practical applications in lithium cells. Cycling tests of Li/GPE/LiFePO4 cells showed the suitability of the electrospun membranes made of TPU/PVdF (80/20, w/w) for applications in lithium rechargeable batteries. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

HGB/TPU复合泡沫材料的制备及泡孔结构研究

采用空心玻璃微珠（HGB）填充热塑性聚氨酯（TPU）,制备了HGB/TPU复合泡沫材料。研究了硅烷偶联剂KH550对HGB的表面处理,并借助SEM探讨了不同发泡方式、发泡剂含量、HGB含量对复合泡沫材料微观形态结构的影响。结果表明：经KH550处理的HGB与TPU基体界面结合良好;通过注塑发泡得到的泡沫材料发泡效果较好;当发泡剂含量为1%、HGB含量为2%时复合泡沫材料的泡孔分布均匀,尺寸较为均一。     

Polyaniline/carbon black composite as Pt electrocatalyst supports for methanol oxidation: Synthesis and characterization

Core/shell composites of polyaniline (PANI) and Vulcan XC‐72 Carbon (VC), in which the carbon represents the core and PANI forms the shell, were synthesized by in situ chemical oxidation polymerization. Platinum (Pt) particles were then deposited on the PANI/VC composites by chemical reduction method. The highest conductivity is obtained when a mass ratio of PANI/VC equals to 0.28, as proved by Fourier transform infrared spectra. And it is also proved that there are some reactions happened between PANI and VC. Scanning electron microscope, transmission electron microscope, and X‐ray diffraction measurements were performed to analyze their structure and surface morphology. It has been observed that the Pt particles are smaller in size and more uniformly distributed on these composite supports than on pure VC supports, considered as a reference. Methanol oxidation performed on the electrode modified by such a composite catalyst has been measured by cyclic voltammogram focusing on the attenuation of methanol oxidation current after 200 cycles. The attenuation degree for the composite catalyst is only one‐third of the one measured for a simple Pt/VC catalyst. It is proved that the composite catalyst better resist carbon monoxide poisoning in comparison with the Pt/VC catalyst, which may be due to the synergetic effects between the composite support and the Pt catalyst. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

MnO2/Cr2O3/PANI nanocomposites prepared by in situ oxidation polymerization method: Optical and electrical behaviors

Metal oxide–polyaniline (PANI) nanocomposite with spherical morphologies were prepared in a one-pot oxidation–reduction method via various salts as reactive oxidants. Aniline monomers polymerize as a shell on the surface of one-pot prepared metal oxides, when the aqueous solutions of aniline, a free-radical oxidant, and/or a metallic salt were exposed together. The particle size and morphology of as-prepared narrowly dispersed PANI nanocomposites were revealed by field emission scanning electron microscope images. Fourier transform infrared spectra of nanocomposites indicate that the PANI exists in the emeraldine form. The ultraviolet–visible analysis not only shows PANI is in the emeraldine form, but also indicates modified optical properties of PANI in the composite form. The hypsochromic shift of the n–π* and polaron transitions of PANI reveals the incorporation of PANI by metal oxides. The direct current (dc) electrical conductivity (σ) of as-prepared nanocomposites was measured by a four-probe method in the room temperature. Compared to PANI nanoparticles, the electrical conductivity of the composites increased with the presence of metal oxides in the nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47219.     

苯酐改性聚乙二醇型聚氨酯固态电解质的制备与性能

以异佛尔酮二异氰酸酯（IPDI）、聚对苯二甲酸-3-甲基-1,5-戊二醇酯二醇（TPA-1000）、聚乙二醇（PEG-2000）、一缩二乙二醇（DEG）为主要原料合成了一系列热塑型聚氨酯弹性体,然后加入20%的锂盐（LiTFSI）制备不同的全固态电解质（SPE）。结果表明,随着TPA-1000含量的减少和PEG-2000含量的增加,SPE的耐热性增加,玻璃化转变温度减小,拉伸强度减小,断裂伸长率增加。SPE的离子电导率与温度的关系基本符合Arrhenius方程,在80℃,SPE（除纯PEG-2000的电解质外）的电化学窗口均达到4.0V以上,其中质量比TPA-1000：PEG-2000=1：2（SPE4）综合性能最佳,力学为1.87Mpa、电导率为2.15?10-4 S cm-1、窗口为4.3V。以SPE4组装的全固态电池在80℃、0.2C下放电比容量为150 mAh/g。     

Sonochemical synthesis and characterization of amine‐modified graphene/conducting polymer nanocomposites

The objective of this work is to modify graphene and study the effect of modification of graphene in thermal and electrical properties of graphene/polypyrrole and graphene/polyaniline nanocomposites. The amine functionalization of graphene was confirmed by Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. The nanocomposites were prepared by insitu oxidative polymerization method using ammonium persulfate as oxidant. Field emission scanning electron microscopy and high‐resolution transmission electron microscopy were used to study the morphology of the nanocomposites which indicates toward the better dispersion of modified graphene within the polymer matrices as compared to unmodified composites. The modification of graphene played an important role in the noticeable improvements in electrical conductivity of the prepared composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

含异氰酸酯基的低聚物和聚醚增容改性POM/TPU共混物

利用双螺杆挤出机制备了聚甲醛(POM)/热塑性聚氨酯弹性体(TPU)、POM/TPU/含异氰酸酯基的低聚物(Z)以及POM/TPU/Z/聚醚3种共混物。采用力学性能测试、差示扫描量热分析(DSC)、偏光显微镜(PLM)、傅里叶转换红外线光谱 (FTIR)、扫描电子显微镜(SEM)、动态力学性能分析(DMA)等,研究了3种共混物的力学性能、结晶行为及形态结构。结果表明：共混物的缺口冲击强度和断裂伸长率随TPU含量的增加而提高;异氰酸酯基低聚物（Z）和聚醚在促进分散相分散、增强两相间的相容性方面发挥重要作用,降低了聚甲醛的结晶度,能够有效地提高共混物的缺口冲击强度和断裂伸长率。     

过氧化钨酸-过氧化氢化学聚合法合成掺杂态聚苯胺

在过氧化钨酸-过氧化氢均相催化氧化体系中,在盐酸或对甲基苯磺酸的存在下合成出掺杂态聚苯胺(PANI/HCl和PANI/TSA)。反应终了后,加入碘化钾除去体系中剩余的过氧化氢。产物分离过程中,使用了抽滤法与甲苯-水共沸蒸馏法两种方法。与抽滤法相比,用共沸蒸馏法处理反应后的产物能得到高产率的掺杂态聚苯胺。使用傅立叶红外吸收光谱(FTIR)和紫外-可见光吸收光谱(UV-vis)研究了两种掺杂态聚苯胺的化学构造变化。使用四端子法测定了掺杂态聚苯胺的导电性能,其导电率能达到10-3S/cm数量级。     

PBT/TPU/DOPO-MA阻燃复合材料的制备及性能

通过使用9,10-二氢-9-氧杂-10-磷朵菲-10-氧化物（DOPO）和马来酸酐反应合成制备DOPO衍生物阻燃剂DOPO-MA,并且其结构使用傅里叶红外光谱分析（FTIR）和核磁共振氢谱分析（¹H NMR）技术进行表征。将阻燃剂与聚对苯二甲酸丁二醇酯（PBT）和热塑性聚氨酯（TPU）熔融共混以制备PBT/TPU/DOPO-MA阻燃复合材料。通过运用锥形量热、UL-94、极限氧指数（LOI）、热重分析（TGA）、差热分析（DSC）和力学测试,研究了阻燃剂对复合材料的性能影响。测试结果表明,PBT/TPU/DOPO-MA复合材料具有良好的阻燃性能,加入10％DOPO-MA后,LOI从23.2增加到31.6,可达到UL-94 V-1等级,热释放率峰值（PHRR）和最大成热辐射速率（MAHRE）值降低;热重分析测试结果表明,添加DOPO-MA可以使得阻燃复合材料的热稳定性有显著的提高,当加入10％DOPO-MA后,残炭量可从6.87增加到14.36。此外,随着DOPO-MA含量的增加,阻燃复合材料的结晶度可得到一定的提高。     

有机酸掺杂聚苯胺的制备及其结构分析

研究了用十二烷基苯磺酸（DBSA）、磺基水杨酸（SSA）、对氨基苯磺酸（ABSA）和柠檬酸（CA）4种有机酸作掺杂剂制备掺杂态聚苯胺DBSA-PANI、SSA-PANI、ABSA-PANI、CA-PANI的工艺,并制备了样品。经FT-IR和SEM分析表明：4种酸均具有掺杂态聚苯胺的特征吸收峰,其中DBSA-PANI和SSA-PANI的掺杂峰更明显;而ABSA和CA掺杂后的聚苯胺为微纳米粒子结构。大尺寸的有机酸离子掺杂在聚苯胺的链间,可更有效地减弱分子间的相互作用使聚苯胺溶解性提高,导电性增加。样品导电性能最好的是磺基水杨酸掺杂的聚苯胺,电导率接近1 S/cm。     

十二烷基苯磺酸掺杂聚苯胺的制备及性能

用十二烷基苯磺酸（DBSA）的水溶液对化学合成的聚苯胺（PAn)进行掺杂,获得了导电的DBSA掺杂PAn(PAn-DBSA),通过对本征态聚苯胺（PAnEB)掺杂率的计算和电导率的测定,研究了DBSA用量及其溶液浓度对掺杂效果的影响,结果表明,当DBSA／PAnEB(摩尔比）小于0．1时,溶液浓度的影响很小,当DBSA／PAnEB大于0．2时,溶液浓度的影响非常大,而且,高浓度比低浓度对提高掺杂率和电导率更有利。热重分析表明,PAnEB,PAn-DBSA在空气中的热分解温度分别为350和250℃,表现出良好的热稳定性。