韩语翻译高分子考试.docx

摘要具有导电性的聚偏二氟乙烯-聚苯胺混合物含有不同成分。这个混合物是由苯胺在聚偏二氟乙烯和二甲基甲酰胺的混合物中通过化学聚合产生的。可以通过电导率测量方法，紫外-可见-近红外和红外光谱仪对其研究。 引导；把拿给看，把领（送）到showed to suitable alternative方案用于获取共混聚合物的路线给出了一个方案，用于获得PVDF/ PANI- TSA的高导电性混合物。路线用来获取聚合物共混物可以提供替代性的主要表现为以获得PANI-TSA混合PVDF /高导电性。简介导电聚合物已在过去几十年中受了极大的关注，特别是作为防腐蚀涂料，变色元件生物传感器，以及作为电池电极的潜在应用方面。由于；因为；为了的缘故on account of在导电聚合物中，由于其特殊的电学和光学性质，聚苯胺是迄今为止被研究最多的聚合物之一。Among the conducting polymers, polyaniline (PANI) is by far the most investigated one, due to its particular electrical and optical properties.One disadvantage of chemically obtained PANI is its low solubility in most of the organic solvents and low fusibility, thus making it difficult to prepare cast films and so on. 化学方法获得的聚苯胺的缺点之一是其溶解度低，在大多数的有机溶剂和低熔性，从而难以准备挤塑薄膜等。It is easilysynthesized chemically as well as electrochemically,easily doped by protonic acids and alsobecause it is chemically stable at room temperatureconditions. 这是很容易化学合成以及作为电化学，容易被质子酸掺杂，还因为它是在室温下化学性质稳定条件。Several methods have been developed for preparation of blends and composites of PANI-isolating polymers as by solution 7,8, fusion 9,10, emulsion 1115, and inverse emulsion 1619. 已经开发了几种方法来制备共混物和绝缘的聚苯胺聚合物复合材料，如通过溶解，融合，乳化，反相乳化聚合。As by 如通过在目前的工作中，我们已经开发了一种可替代的方法来获取聚偏二氟乙烯/聚苯胺共混物，其中通过苯胺的在PVDF和N，N 二甲基甲酰胺在再溶解状态下并使用对甲苯磺酸-TSA作为掺杂酸时发生氧化聚合。In the present work we have developed an alternative method to obtain PVDF/PANI blends in which the oxidative polymerization of aniline is performed in solution of PVDF and N,N-dimethylformamide DMF using the p-toluene sulfonic acidTSA as dopant. in solution再溶解状态下Prior to being used, Aniline (Aldrich, 99.5%) was purified under vacuum distillation. PVDF SOLEF 1008/1001 (Solvay fluoropolymers), ammonium persulfate (NH4)2S2O8, Merck, N,N-dimethylformamide DMF (Merck), p-toluenesulfonic acidTSA (Aldrich), chloroform (Merck) and 1-methyl-2-pyrrolidone NMP (Merck), were used as received材料正在使用之前，苯胺（Aldrich公司，99.5）是在真空条件下被蒸馏纯化。 工程塑料1008/1001（含氟化合物），过硫酸铵（NH4）2S2O8，默克，N，N -二甲基甲酰胺（默克公司），对甲苯磺酸- TSA（Aldrich公司），氯仿（默克）和1 - 甲基- 2 -吡咯烷酮，NMP（默克公司），这些材料作为给定的被使用。共混物获得通过化学合成的聚苯胺在PVDF和DMF的解决方案。交融中取得了一定的聚苯胺在聚偏二氟乙烯和二甲基甲酰胺溶液中的化学合成。2、合成The blends were obtained through the chemical synthesis of PANI in a solution of PVDF and DMF. 2合成共混物通过聚苯胺在聚偏二氟乙烯和二甲基甲酰胺溶液中的化学合成获得。In a typical experiment, 1.0 g of PVDF was dissolved in 10ml of DMF heated at 70 C. Afterwards, the solution was cooled at room temperature and 0.5 g of aniline was added under stirring. 在一个典型的实验中，1.0 g的PVDF的溶解到10毫升被加热到70 C的DMF. 之后，该溶液在室温下冷却，并且搅拌着加入0.5 g的苯胺。Then, a 20ml DMF solution of 1.22 g ammonium persulfate and 4.28 g p-toluenesulfonic acid was slowly added. Subsequently, 44.5ml of chloroform was added into the solution. 然后，缓慢加入一个溶有1.22克过硫酸铵和4.28克p-TSA的20毫升的DMF溶液。随后，再加入44.5毫氯仿升。The polymerization reaction was allowed to proceed at room temperature for 2 h with continuous stirring. At the end of polymerization, distilled water was introduced into the system to precipitate the blend.在室温下，有连续搅拌时聚合反应可以进行2小时。在聚合反应的最后，蒸馏水被引系统入来沉淀的共聚物。The precipitated blend was filtered and washed with distilled water and aqueous solution of TSA 0.1M and then dried under dynamic vacuum for 24 h and maintained heated at 70 C for an additional period of 24 h in order to obtain a dark-green powder color that is characteristic of PANI in the conducting form .用蒸馏水和0.1M 的TSA的溶液过滤和洗涤共聚物沉淀，然后进行动态真空干燥24 小时，另外再在70 C情况下保持加热24小时，以获得一种暗绿色粉末，具有这个颜色是导电性的PANI的特点。About 1.585 g of poly(vinylidene fluoride)/polyaniline blend (PVDF/PANI) was thus obtained. The yield of the blend was 88.2% .本实验获得了大约1.585克的聚（偏氟化物）/聚苯胺共混物（PVDF/PANI）。混合的收益率为88.2。几个组成的混合物，得到不同的PVDF/苯胺的比例。The method to obtain blends of PANI by polymerization of aniline in emulsion is very promising and has been a subject of investigation for several polymers.聚苯胺苯胺的聚合乳液共混的方法来获取是非常有前途的的，已经成为一个对几种聚合物的调查的课题。In a previous work we prepared conducting blends of poly(vinylidene fluoride) PVDF with some PANI derivatives as poly(o-methoxyaniline) POMA and poli(o-ethoxyaniline) POEA by solution and investigated some of its electrical and mechanical properties. 在以前的工作，我们制备聚偏二氟乙烯与聚苯胺衍生物的共混物，例如聚邻甲氧基苯胺和聚邻乙氧基苯胺混合溶液，并研究其电气和机械性能。However, we were not able to advance the studies of PVDF/PANI blends since, in this case, a heterogeneous material with large aggregates of PANI dispersed by the PVDF polymeric matrix was obtained. 然而，我们不能够更进一步的研究结合PVDF/聚苯胺，因为在这种情况下，可以获得含有由PVDF聚合物基质分散的大量的PANI不均匀物质。The material obtained by using this methodology is quite homogeneous and presents good mechanical stability. 通过这种方法获得的物质是相当均匀，呈现良好的机械稳定性。The synthesis was performed under several conditions of aniline/oxidant and aniline/dopant molar ratios and blend compositions.这个合成反应在苯胺/氧化剂的摩尔比和苯胺/掺杂物质摩尔比和混合组成的几个条件下进行。The blends were characterized by UVVisNIR and FTIR spectroscopy and the electrical conductivity of the films obtained were further investigated.共混物的紫外-可见-近红外和红外光谱进行了表征和薄膜的导电性得到了进一步的调查。Among the conducting polymers, polyaniline (PANI) is by far the most investigated one, due to its particular electrical and optical properties.在导电聚合物中，由于其特殊的电学和光学性质，聚苯胺是迄今为止被调查最多的一种。It is easily synthesized chemically as well as electrochemically, easily doped by protonic acids and also because it is chemically stable at room temperature conditions.化学合成很容易进行正如容易发生电化学反应，容易被质子酸掺杂，还因为在室温条件下它是化学稳定的。The chemical synthesis is more suitable when one desires a large quantity of material whereas the electrochemical syntheses is particularly suitable when one wants to obtain details on the process of charge transfer and mechanism of the reaction kinetics.当一个人希望得到大量材料时通过化学合成是特别合适的，然而，当一个人想要获得电荷转移过程和反应动力学机制中的详细资料，电化学合更适合的。On account of this, blends and composites with conventional polymers have received great attention since these new materials combine the excellent mechanical properties and high processability of the usual polymers with the electric conductivity of conducting polymers, consequently increasing the technological potential of these materials.因为这样，聚合物和传统复合材料得到高度重视，因为这些新材料结合优异的机械性能和高可加工性通常的聚合物与导电聚合物的导电性，从而提高这些材料的技术潜力。Investigating new methods to obtain blends of several components is important because the material can have its properties stressed or its syntheses can become cheaper, which stimulates production in a fortuitous new application.研究新的方法来获取几部分组成的混合材料是很重要的，因为它的加强它的属性及使得合成成本可以变得更加便宜，从而刺激新的应用程序有一个偶然的生产。The conductivity measuring was performed by standard four-point technique.通过标准四点技术方法测量电导率。The samples were Xexible Wlm obtained by pressing the powder at 180 C for 5min at a pressure of 15MPa.样品是在180C保持5分钟、在15MPa的压力时将粉末压制成的柔性薄膜。FTIR spectra were recorded with a NEXUS 670 spectrophotometer from Nicolet Instrument Corporation. 用来自尼高力仪器公司的Nexus670分光光度计，来记录红外光谱图。The samples for FTIR analysis were films in the case of blend and dry powder mixed with KBr for pure PANI. FTIR分析样品是在混合物和纯聚苯胺与溴化钾混合干粉的情况下的膜剂。UVVisNIR absorption spectra were recorded with a VARIAN CARY 50 spectrophotometer using the solutions of the blend in 1-Methyl-2-pyrrolidone (NMP).NMP 用瓦里安卡里50分光光度计来记录以共聚物为溶剂的甲基吡咯烷酮（NMP）溶液的紫外-可见-近红外吸收光谱图。 Elemental analysis was performed using a CE Instruments CHNS-O model EA 1110 apparatus to calculate the content of PANI. 元素分析是使用一个CE仪器CHNS- O模型的EA1110仪器来计算的聚苯胺含量。An optimum molar fraction of oxidant/aniline 1 can be observed. The conductivityof the blend increases rapidly below this optimum and decreases with further increase in oxidant concentration. As previously discussed in the literature, excess of oxidant causes shorter conjugation length which decreases the electrical conductivity.On the other hand, at low concentration of oxidant an under-oxidation of aniline takes place, which produces PANI in an oxidation state lower than the emeraldine state.氧化剂/苯胺的比率对的影响图1.l 共混体系的电导率在低于最佳比率点时增加迅速，超过该最佳比率点之后，电导率不断下降；共混体系的产量随着氧化剂/苯胺的比率增加而增大，最后到达一个高峰点。l 氧化剂过量会导致较短的共轭长度，从而降低电导率，另一方面，在氧化剂浓度低时苯胺发生氧化反应，产生氧化态聚苯胺低于苯胺绿化态聚合物。l 图一中可以观察一个最佳的氧化剂/苯胺的摩尔分数。l PVDF/PANITSA共混体系的电导率图 电动混合浓度的图2.PVDF/PANI混聚物的导电性依赖于TSA的浓度变化图。It can be noticed that the conductivity increases as the TSA:aniline molar ration increases, reaching a flat after which it decreases. The increasing observed on the left side of the curve is attributed to doping of the conducting polymer by acid, since the conductivity is related with the number of imine sites protoned.Conductivity increases as the protoneted level of the imine sites approaches 50%. On the other hand, if the maximum doping reaches the high concentration of acid it leads to polymer degradation, with consequent decreasing in the conductivity.从图中可以看出共混体系的电导率随着TSA与苯胺的比率的增大而增大，随后呈现平衡趋势。当TSA与苯胺的比率增大到一定程度之后，共混体系电导率开始下降。电导率的增加是掺杂的导电聚合物造成的。亚胺数量超过50%，电导率增加；另一方面，如果超过酸的高浓度时，它会使聚合物降解，导电率将会下降。图3.PVDF/PANI共混物的导电性依赖于聚苯胺的含量的变化图。This value is greater than the maximum value reported for blends of PVDF/poly(o-methoxyaniline) obtained by casting, corroborating the importance of using polyaniline and not its derivatives.纯聚苯胺的导电率的值大于聚偏二氟乙烯/聚邻甲氧基苯胺混合通过铸造获得的混聚物的导电率的值，证实使用聚苯胺而不是其衍生物的重要性。p 混合和纯聚合物的红外光谱图 图4.无任何掺杂的PVDF(a)，PVDF/PANI (b) PANI (c)混聚物的傅里叶红外光谱图。PVDF/ PANI共混体系下， 511 和 840cm-1之间存在过渡带， 另外一个过渡带在1231 和1170cm-1之间The spectrum of the PVDF/PANI blend (23wt.% PANI, Fig. 4b) shows the transition bands at 511 and 840 cm-1 characteristics of the _ phase of the pure PVDF. Other transition bands seen at 1231 and 1170cm-1 in the same spectrum are related with CF stretch of the PVDF polymeric chain.PVDF/ PANI混合物（23wt.聚苯胺，图4b）的红外光谱图显示在过渡带511和840 cm - 1处有峰值是纯PVDF阶段的特点，在1231和1170 cm - 1有1条带是PVDF聚合物链C - F键的拉伸其他过渡。The band at 1494cm-1 corresponds to the stretch of benzene rings and the peak at 1585 cm-1 corresponds to the stretch frequency of quinone ring, which confirms the presence of PANI in the blend. The band at 1680 cm-1 is attributed to DMF solvent.1494 cm- 1谱带对应于苯环的拉伸和谱带1585 cm- 1高峰对应的醌环的拉伸频率，该公司混合聚苯胺的存在。在1680 cm- 1处有谱带峰值的原因是DMF溶剂。1585 cm- 1 cm- 1图5.掺杂和不掺杂聚苯胺的甲基吡咯烷酮（NMP）溶液的的紫外-可见-近红外光谱图。UVVisNIR spectra of the PVDF/polyaniline blend (22.4 wt.% PANI) doped and undoped in NMP solution.UV- VIS - NIR光谱的图6. 掺杂和未掺杂PVDF/ PANI共混物（22.4重量聚苯胺）NMP溶液的紫外-可见-近红外光谱图。（NMP）Two absorption maxima are seen at 325 nm and 625 nm for undoped sample, assigned respectively to * transition and to an excitonic transition in the nitrogen.两吸收峰在325纳米和625纳米未掺杂样品，分别分配-*跃迁和激子过渡中的氮。l Three bands are observed in the doped PANI spectrum (Fig. 5), at 340, 430, and 790nm. 在340，430和790nm三个波段观测到掺杂聚苯胺频谱。PANI 未掺杂 TSA时的混合体系频谱中出现325nm和625nm两个吸收峰，掺杂TSA时的混合体系频谱中出现340, 430, and 790nm三个吸收峰（图5）。 The bands are assigned as follow:* transition of benzene rings in the first case and polaron bands in the last two cases. These last two bands are related to the doping process that is responsible for the polymer conductivity.最后两个波段和掺杂过程中的聚合物的导电性相关。 The spectrum of the PVDF/PANITSA blend doped and undoped is shown in Fig. 6掺杂和未掺杂的PVDF/ PANI - TSA混合物的频谱如图. 6。. The spectrum is similar to that of the doped and undoped PANI, shown in Fig. 5.频谱和图5中掺杂和未掺杂的聚苯胺的类似。 This finding is confirmed by the FTIR analysis, and enables understanding of the high electrical conductivity shown for the blend. 这一发现是由FTIR分析证实，并使得混聚物具有高导电性得以理解。PVDF/ PANI掺杂和未掺杂 TSA时的混合体系频谱与单纯PANI 未掺杂 TSA时的混合体系频谱相似。这一发现由红外光谱图分析证实，并实现混合显示的电导率高电气的理解。p PVDF/ PANI- TSA混合体系的几个温度下导电率的热稳定性 Electrical conductivity of PANITSA and the PVDF/ PANI (77.6/22.4) film as a function of time at indicated temperatures. 图7. PANI- TSA和PVDF/PANI膜（77.6/22.4）的导电率作为时间的函数在给出指示温度时的变化。The electrical conductivity of PVDF/PANI film was normalized to have the same value of PANITSA at room temperature.被标准化的PVDF-PANI膜的导电率，在室温下和PANI-TSA相同的值。It is noticed that the conductivity is basically constant for any studied temperature with slight decreasing of about one order at temperature of 100 C. The graphics show clearly that the decreasing at 100 C is lower for the neat PANI than for the PVDF/P