IPN结构的SIS-PAn导电复合物

合成了互穿网络（ＩＰＮ）结构的ＳＩＳ（苯乙烯－异戊二烯－苯乙烯嵌段共聚物）－ＰＡｎ（聚苯胺）导电复合物。Ａｎ／ＳＩＳ的投料比为０．２ｇ／１．０ｇ时，制得复合物膜电导率即可达７Ｓ·ｍ－１。复合物的电导率随基体ＳＩＳ交联程度的增大而降低。研究了溶剂、反应时间和分散剂用量对复合物膜性能的影响。     

聚苯胺的化学合成及其电化学表征

本文用化学聚合法合成了在Ｎ－甲基吡咯烷酮（ＮＭＰ）中可溶的聚苯胺（ＰＡＮＩ）。通过溶液法定量（浓度与体积）制膜，对ＰＡＮＩ膜修饰电极的循环伏安（ＣＶ）性质进行了研究，证实了ＰＡＮＩ膜在１０．０ｍｏｌ／Ｌ ＨＣｌ的介质中，－０．１５￣０．６５Ｖ（ｖｓ．ＳＣＥ）的电位范围内氧化还原单元为八隅体单元。比较了恒电流聚合与化学聚合所得的聚苯胺的ＣＶ性质，发现两者有很好的一致性。     

阳离子型微乳液对显色剂1—（2—吡啶偶氮）—2—萘酚的增溶作用

以光度法研究了阳离子型微乳液对显色剂１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）的增溶作用，通过测定ＰＡＮ在阳离子型ＣＴＭＡＢ／ｎ－Ｃ５Ｈ１１ＯＨ／ｎ－Ｃ９Ｈ２０微乳液中的“胶束位”ｎ和结合常数Ｋ，并与相同表面活性剂胶束体系比较，探讨了微乳液对显色剂ＰＡＮ的增溶作用。     

吸水性淀粉－丙烯腈接枝共聚物的一步合成

以硝酸铈铵为引发剂，在几种水－有机溶剂体系中一步合成了吸水性淀粉－丙烯腈接枝共聚物。其中所含的ＰＡＮ均聚物比水作溶剂时的多。在水－正丁醇溶液（Ｖ／Ｖ＝１∶３）中，ＰＡＮ的接枝效率为８３％，淀粉的接枝效率为７２％，产品的吸水倍数为８２０ｇ／ｇ。     

聚环氧氯丙烷聚氨酯／聚（甲基丙烯酸甲酯－苯乙烯）IPN的研究

改变聚（甲基丙烯酸甲酯－苯乙烯）（Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）中甲基丙烯酸甲酯的含量（Ｗ_（ＭＭＡ）），通过一步法合成出聚环氧氯丙烷聚氨酯（ＰＵ（ＰＥＣＨ）／Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）ＩＰＮ．ＤＳＣ、ＴＥＭ和动态粘弹谱研究结果表明：当Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）中Ｗ_（ＭＭＡ）大于０．６时，ＩＰＮ仅有一个Ｔｇ；当Ｗ_（ＭＭＡ）小于０．４时，ＩＰＮ有２个Ｔ_ｇ，ＴＥＭ上出现相区，Ｐ（ＭＭＡ－ｃｏ－Ｓｔ）溶度参数（δ）及δ的氢键作用分量（δｈ）与相态、力学性能有密切关系。     

Electrochemical Behavior of Chemically Prepared Ring-Substituted Polyanilines

聚邻甲苯胺（ＰＯＴ）、聚２，５二甲氧苯胺（ＰＤＭＡｎ）和聚间氯代苯胺（ＰＣｌＡｎ）由化学法合成而得，用它们的二甲基甲酰胺溶液在铂上成膜以制得聚合物修饰电极．循环伏安实验表明：在１ｍｏｌ／ＬＨ２ＳＯ４中，ＰＯＴ的氧化还原分两步进行，呈现两对氧化还原峰，ＰＤＭＡｎ只在较负的电位区呈现两对氧化还原峰，而ＰＣｌＡｎ不呈氧化还原活性．不同电位下的交流阻抗特征与循环伏安图相对应．三种聚合物膜电极在０．５ｍｏｌ／ＬＫ３［Ｆｅ（ＣＮ）６］溶液中的伏安图也证明铁氰离子的还原速度依ＰＯＴ＞ＰＤＭＡｎ＞ＰＣｌＡｎ的顺序而下降．环取代基的影响用电子效应和几何效应进行解释．可溶性聚苯胺便于制作大面积器件，环取代基对调节聚苯胺的电化学性能具有重要作用，值得进一步研究．     

聚N－烷基丙烯酰胺类凝胶及其温敏特性

 研制成功５种聚Ｎ－烷基丙烯酰胺类温敏凝胶：聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡ），聚Ｎ－异丙基丙烯酰胺＋甲基丙烯酰胺（ＰＮＩＰＡ／ＭＡＡ），聚Ｎ，Ｎ－二乙基丙烯酰胺（ＰＮＤＥＡ），聚Ｎ－正丙基丙烯酰胺（ＰＮＮＰＡ），聚Ｎ，Ｎ－二乙基丙烯酰胺＋Ｎ－叔丁基丙烯酰胺（ＰＮＤＥＡ／ＮＴＢＡ），并系统研究了这些凝胶的温敏相交特性．以聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡ）凝胶相交特性为基础的凝胶萃取过程对牛血清白蛋白和兰葡聚糖溶液的浓缩实验表明，凝胶萃取对于浓缩和制备贵重生化制品是很有效的．     

聚N－烷基丙烯酰胺类凝胶及其温敏特性

研制成功５种聚Ｎ－烷基丙烯酰胺类温敏凝胶：聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡ），聚Ｎ－异丙基丙烯酰胺＋甲基丙烯酰胺（ＰＮＩＰＡ／ＭＡＡ），聚Ｎ，Ｎ－二乙基丙烯酰胺（ＰＮＤＥＡ），聚Ｎ－正丙基丙烯酰胺（ＰＮＮＰＡ），聚Ｎ，Ｎ－二乙基丙烯酰胺＋Ｎ－叔丁基丙烯酰胺（ＰＮＤＥＡ／ＮＴＢＡ），并系统研究了这些凝胶的温敏相交特性．以聚Ｎ－异丙基丙烯酰胺（ＰＮＩＰＡ）凝胶相交特性为基础的凝胶萃取过程对牛血清白蛋白和兰葡聚糖溶液的浓缩实验表明，凝胶萃取对于浓缩和制备贵重生化制品是很有效的．     

影响水滑石晶体结构的因素

制备了Ｍｇ１－ｘＡｌｘ（ＯＨ）２（Ａ＾ｎ－）ｘ／ｎ．ｍＨ２Ｏ型水滑石，讨论了配料组成，滴料方式，陈化过程等制备条件对水滑石晶体组成和晶体结构的影响。在配料Ｍｇ／Ａｌ比相同的条件下，得到的Ｍｇ１－ｘＡｌｘ９ＯＨ）２（ＣＯ３）０．５ｘ．ｍＨ２Ｏ晶体中Ｍｇ／Ａｌ比并不一定相同。     

导电高聚物聚2，5－二甲基苯胺的化学合成与特性

报道了聚２，５－二甲基苯胺（ＰＤＭｅＡｎ）的化学合成，并用标准四探针方法测定其电导率，以ＦＴＩＲ、ＵＶ－Ｖｉｓ吸收光谱、元素分析和ＣＶ法对其性质进行了研究，ＰＤＭｅＡｎ的结构与聚苯胺和聚２，５－二甲氧基苯胺的结构类似，是由其单元通过氮原子（Ｎ）在对位上键合而成，本征态的ＰＤＭｅＡｎ能溶于多种有机溶剂，如ＣＨ２Ｃｌ２、ＣＨＣｌ３、ＤＭＳＯ、ＤＭＦ等。     

THE RHEOLOGICAL PROPERTIES OF POLYANILINE SOLUTION

This paper presents our work on the rheological properties of the solution of polyaniline(PAn) in N-methyl-2-pyrrolidone (NMP). The result s indicate that the solution's non-Newtonian property becomes more prominent with the increase in solution-oncentration,exhibiting the behavior of pseudo-plastic fluid. Besides, there is a critical concentration C.(around 0.06 g/ml), beyond which the viscosity of the PAn/NMP solution takes a suddenincrease. With temperature rising, both the viscosity and the thixotropy of the solutiondecrease, implying that there exist physical cross-linking interactions between the molecularchains in the solution.     

聚苯胺／含联苯结构聚芳砜导电复合膜的研究

采用溶液共混法得到了聚苯胺／含联苯结构聚芳砜导电复合膜。该复合膜有良好的力学性能和导电性能，对其导电规律进行了探讨。热分析结果表明复合膜有良好的热稳定性，用扫描电镜观察了复合膜的微观形貌，表明ＰＡｎ与ＬＰＥＳ的共混相容性较好。     

煤的缔合结构研究Ⅱ溶液黏度变化

采用Pal-Rhodes方程描述了一种煤可溶组分PI-1溶液黏度随时间的变化关系,并计算得到了缔合物的缔合维数。25 ℃下PI-1在NMP和CS2/NMP混合溶剂中缔合物的缔合维数分别为2.08和2.19,表明其在低温下缔合属于反应控制机理。随着温度的提高,缔合维数趋于减小,表明在较高温度下,PI-1具有较快的缔合动力学过程,在50 ℃时PI-1在NMP中的缔合维数大于在CS2/NMP混合溶剂中的缔合维数,表明PI-1在NMP的缔合速率相对低于CS2/NMP混合溶剂。     

煤的缔合结构研究 Ⅰ 溶液缔合动力学

研究了煤可溶组分——吡啶不溶物（PI）在溶液中的缔合动力学，该PI系二硫化碳/N-甲基-2-吡咯烷酮（CS2/NMP）混合溶剂可溶组分。结果表明PI在NMP溶液中的缔合属于反应控制机理，并提出了二步动力学反应过程，即基本缔合单元的生成和缔合单元之间的缔合。通过实验获得了有关缔合的动力学参数，PI在NMP溶液中二步缔合的活化能分别为73.3 kJ/mol和21.6 kJ/mol。温度对缔合速率的影响显著，随着温度的升高，缔合速率增加。由于PI分子在CS2/NMP混合溶剂中相对NMP具有较高的扩散性，因而其在CS2/NMP混合溶剂中缔合速率较NMP快。此外，还讨论了PI在溶液中的缔合机理。     

间甲酚溶液中掺杂聚苯胺的氧化-还原行为研究

在有、无外加恒定磁场(0.4T)条件下,采用乳液聚合法合成了十二烷基苯磺酸掺杂聚苯胺(PAn),通过傅立叶红外光谱(FT-IR)、在有/无外电场作用下产物/m-cresol溶液的电导率、pH及其颜色随温度变化的分析表征,系统研究了温度对PAn/m-cresol溶液中PAn氧化-还原(掺杂-脱掺杂)行为的影响.溶液电导率和pH的测试结果显示,溶液电导率与溶液中游离掺杂酸的浓度成正比,PAn的掺杂度随温度的升高而降低,随温度的降低而增大,且在相同温度下,有、无外电场作用时PAn/m-cresol溶液的电导率存在突跃.与无磁场条件下合成的PAn所制备的m-cresol溶液相比,磁场条件下合成的PAn所制备的m-cresol溶液电导率的突跃更加显著.经脱掺杂处理后的PAn/m-cresol溶液的电导率均较低,对温度变化的响应极其微弱,且在有、无外电场作用时不发生突跃.分析认为,这是由于外电场作用下m-cresol溶液中掺杂态的PAn分子发生了取向重排,而脱掺杂的PAn则无此变化.PAn在外电场作用下的取向重排及氧化-还原性均与其掺杂程度相关,掺杂程度越高,氧化-还原及取向重排越显著.     

Light scattering and membrane formation studies on polysulfone solutions in NMP and in mixed solvents of NMP and ethyl acetate

The relationship between the characteristics of the polymer dope solution and the skin formation mechanism as well as the performance of the asymmetric membrane has been investigated. The solution characteristics have been studied on the polysulfone (PSf) dope solution as a function of the concentrations of both polymer and the cosolvent, ethyl acetate (EA), by dynamic light scattering. An anomalous light scattering was observed at small angles in both PSf/NMP and PSf/NMP:EA (6:4 by weight) solutions, indicating the inhomogeneity of the dope solutions. In the case of the PSf/NMP:EA (6:4) solution, an integrally skinned asymmetric membrane without defects having high gas selectivity was obtained while the membrane from the PSf/NMP solution had a defective skin. The scattered light intensity of the dope solution of PSf/NMP:EA (6:4) increased with the aging time while no notable change was observed in the PSf/NMP solution. The characteristics of the solution affect the final morphology of the membrane, particularly when phase separation occurred significantly before the immersion into the gelation medium.     

FT-Raman investigation of the thermal curing of PMDA/ODA polyamic acids

The effect of solvent on the curing reactions of PMDA/ODA polyamic acids has been investigated using Fourier transform (FT)-Raman spectroscopy. Films of different thicknesses were cured by: (1) doctor blading 15% solids solutions onto glass slides, (2) removing all but the bound NMP, and (3) removing all the N-methypyrrolidinone (NMP). The rate of cure and final degree of conversion of the PMDA/ODA polyamic acid to polyimide increased substantially in the presence of NMP, and this effect was attributed to the plasticizing effect of the solvent. Below a critical solvent concentration, which was estimated to be approximately 40% of the NMP concentration in the bound-solvent limit, the rate of imidization slowed down considerably. Comparison of FT-Raman data for PMDA/ODA polyamic acid: (1) in solution in NMP, (2) complexed with NMP in the solid state, and (3) in the solid state after all the NMP had been removed with water, indicated that intermolecular interactions were greatest in the latter case and weakest in solution. Spectra of PMDA/ODA in NMP solution provide strong evidence for binding of NMP to the amide carbonyl in solution. © 1993 John Wiley & Sons, Inc.     

Synthesis,doping, and processing of high molecular weight poly(o-methoxyaniline)

High molecular weight poly(o-methoxyaniline) was synthesized using a novel method in which the polymerization occurs in the presence of a neutral salt. The molecular weight of the polymer was greatly affected by the quenching procedure employed to conclude the polymerization. Conventional doping of the base form of poly(o-methoxyaniline) produced a yellow coloration of the doping solution and polymer degradation. It was found that the molecular weight of the polymer decreased significantly after washing or doping with certain aqueous acid media. The gelation conditions of N-methyl pyrrolidinone (NMP) solutions and film preparation were also investigated for polymers of various molecular weights. The gelation time in NMP decreased drastically with the increase in the polymer molecular weight (the same for solution concentration and temperature), until a critical point was reached after which its decrease was very slow. Flexible, free-standing, and stretchable films were readily obtained from the higher molecular weight polymers. Good quality doped gel films with conductivity of up to 1 S/cm were obtained under optimized doping conditions. © 1994 John Wiley & Sons, Inc.     

Morphology and mechanical properties of ultrahigh-molecular-weight polyethylene films prepared from solutions in mixtures of diphenyl and diphenylether as co-solvent

In an attempt to check solvent dependence of drawability of ultra high-molecular-weight polyethylene films, gels were prepared from diphenyl/diphenylether solution, which is well known as -solvent. The content of diphenyl in the mixed solvent was chosen to be 25 wt%. Rapid gelation occurred when the solution had been cooled down to temperature lower than 147°C. The gel shrunk drastically with the further decrease of temperature and formed a bulk specimen. The maximum draw ratio was 20 and the corresponding Young's modulus reached 27 GPa. The value of Young's modulus was higher than the maximum value of melt film stretched up to 30 times, but it was much lower than the value of film which was prepared by gelation from decalin solution and was elongated up to 300. Thus, it turned out that the drastic shrinkage in the process of rapid gelation hampers a suitable level of the entanglement mesh that effectively transmits the drawing force.     

沉淀聚合制备磺酸掺杂的聚苯胺

以二丁基萘磺酸(DBNSA)或十二烷基苯磺酸(DBSA)为有机酸,水为主要反应介质的条件下进行沉淀聚合直接制备有机酸掺杂的聚苯胺(PAn).讨论了酸度、温度和氧化剂用量等反应条件对产物的影响。2L规模扩大实验的产率约为75%～80%,所得PAn具有高电导率(3.0S·cm^-1),并易溶于普通有机溶剂。其中PAn-DBNSA在各方面较具优势。