技术领域technical field
本发明涉及一种碱性膜及其制备方法，特别涉及一种含二茂钴阳离子-苯并咪唑类聚合物的碱性膜及其制备方法，属于燃料电池碱性阴离子交换膜制备技术领域。The invention relates to an alkaline membrane and a preparation method thereof, in particular to an alkaline membrane containing a cobaltocene-benzimidazole polymer and a preparation method thereof, and belongs to the technical field of preparation of alkaline anion exchange membranes for fuel cells.
背景技术Background technique
近年来，燃料电池(Fuel cells)基于其高效，清洁，环境友好等特点受到了广泛的关注。相比于常规动力技术，燃料电池具有能量转换效率高(50％～70％)、燃料多样化、噪音低、环境友好、即可分散供电也可几种供电等突出的优越性。特别是，质子交换膜燃料电池(proton exchange membrane fuel cells(PEMFCs))已经得到了广泛的商业化应用探索。In recent years, fuel cells (Fuel cells) have received extensive attention based on their high efficiency, cleanliness, and environmental friendliness. Compared with conventional power technologies, fuel cells have outstanding advantages such as high energy conversion efficiency (50% to 70%), diversified fuels, low noise, environmental friendliness, decentralized power supply and several kinds of power supply. In particular, proton exchange membrane fuel cells (PEMFCs) have been extensively explored for commercial applications.
然而，质子交换膜燃料电池的关键材料：铂催化剂和全氟磺酸膜的成本和寿命问题成为了制约其实现商业化的重要阻碍因素。因此，碱性阴离子交换膜燃料电池(anionexchange membrane fuel cells(AEMFCs))由于其可以在碱性条件下使用非贵金属催化剂、在阴极具有更快的氧化还原反应动力学而受到了越来越多的关注。碱性膜是碱性膜燃料电池的核心部件。理想的碱性膜应当在较高的PH和温度下具有高的离子传导率，和好的碱稳定性以及尺寸稳定性。然而，碱性膜中有机阳离子和骨架的化学稳定性成为了制约其发展的重要因素。However, the key materials of proton exchange membrane fuel cells: the cost and life of platinum catalyst and perfluorosulfonic acid membrane have become an important obstacle restricting its commercialization. Therefore, alkaline anion exchange membrane fuel cells (AEMFCs) have received increasing attention due to their ability to use non-precious metal catalysts under alkaline conditions and faster redox reaction kinetics at the cathode. focus on. Alkaline membrane is the core component of alkaline membrane fuel cell. An ideal alkaline membrane should have high ion conductivity at higher pH and temperature, and good alkali stability and dimensional stability. However, the chemical stability of organic cations and frameworks in alkaline membranes has become an important factor restricting its development.
目前主要的阳离子有：季铵阳离子，咪唑阳离子，胍盐阳离子，季磷阳离子，叔硫阳离子，以及有机金属阳离子。然而，在碱性条件下这些有机阳离子容易发生霍夫曼降解(E2)、亲核取代(SN2)、磷叶丽德、环开环等降解[Hugar.M.K,Kostalik.H.A,IV,Coates.G.W.J.Am.Chem.Soc.2015,137,8730-8737]。At present, the main cations are: quaternary ammonium cation, imidazolium cation, guanidinium cation, quaternary phosphorus cation, tertiary sulfur cation, and organometallic cation. However, these organic cations are prone to Hoffmann degradation (E2), nucleophilic substitution (SN2), phosphorus ylide, ring opening and other degradations under alkaline conditions [Hugar.M.K, Kostalik.H.A, IV, Coates.G.W.J.Am .Chem.Soc.2015,137,8730-8737].
为了避免这些降解的发生，有科学家提出将有机金属阳离子作为碱性膜的阳离子官能团来提高碱性阳离子的化学稳定性。比如使用：多配位金属铑阳离子、冠醚阳离子等。但是，多配位的金属铑阳离子的稳定性受制于其本身的配位稳定性。其容易发生脱配位反应。将Na+、K+络合到冠醚中用于作为碱性阳离子是一个非常好的思路。但是这种冠醚的碱性膜在水环境条件下工作时，冠醚络合的金属阳离子容易从冠醚中流失，使得碱性膜的离子传导率降低[Zha,Y；el at.J.Am.Chem.Soc.2012,134,4493-4496]。In order to avoid these degradations, some scientists proposed to use organometallic cations as cationic functional groups of alkaline membranes to improve the chemical stability of alkaline cations. For example, use: multi-coordinate metal rhodium cations, crown ether cations, etc. However, the stability of multicoordinated metal rhodium cations is limited by their own coordination stability. It readily undergoes decoordination reactions. It is a very good idea to complex Na+ and K+ into crown ethers as basic cations. However, when the alkaline membrane of the crown ether works in the water environment, the metal cations complexed by the crown ether are easily lost from the crown ether, which reduces the ion conductivity of the alkaline membrane [Zha, Y; el at. J. Am. Chem. Soc. 2012, 134, 4493-4496].
因此开发一种具有很好热和化学稳定性的新型阳离子，用于制备满足碱性燃料电池工作的膜材料，将具有很广阔的研究和应用前景。Therefore, the development of a new type of cation with good thermal and chemical stability for the preparation of membrane materials for alkaline fuel cells will have broad research and application prospects.
二茂钴类阳离子的同系物具有很好的热和化学稳定性，以及很好的抗氧化性，并且在碱性条件下具有较高的解离常数[Gu.S,Wang.J.H,Robert B.K,Fang.Q.R,Zhang B.Z,Coughlin.E.B,Yan.Y.S.Scientific Reports.2015,5,11668.]。因此，二茂钴类的阳离子具有非常广阔的碱性膜应用前景。然而，二茂钴类阳离子的碱稳定性与其结构之间的关系还尚未被系统的研究，而且目前尚没有有效的方法将二茂钴类的阳离子通过C-C键，稳定的负载到聚合物上。Homologues of dicene cobalt cations have good thermal and chemical stability, good oxidation resistance, and high dissociation constants under alkaline conditions [Gu.S, Wang.J.H, Robert B.K , Fang.Q.R, Zhang B.Z, Coughlin.E.B, Yan.Y.S. Scientific Reports.2015, 5, 11668.]. Therefore, the cations of cobaltocenes have very broad application prospects in alkaline membranes. However, the relationship between the alkali stability of cobaltocene cations and their structures has not been systematically studied, and there is no effective method to stably load cobaltocene cations on polymers through C-C bonds.
为了更好的研究二茂钴阳离子的碱稳定性与其结构之间的关系，本发明人对三种不同的二茂钴阳离子：Cp2Co+、(Cp-CH3)2Co+、(Cp-COOH)2Co+进行了碱稳定性研究。测试发现，(Cp-CH3)2Co+具有最好的碱稳定性，而(Cp-COOH)2Co+的稳定性最差。因此，本发明人得出结论：茂环上给电子取代基有利于提高二茂钴阳离子的碱稳定性，吸电子取代基则不利于碱稳定性。In order to better study the relationship between the alkali stability of cobaltocene cations and their structures, the inventors studied three different cobaltocene cations: Cp2 Co+ , (Cp-CH3 )2 Co+ , (Cp -COOH)2 Co+ was studied for alkali stability. The test found that (Cp-CH3 )2 Co+ has the best alkali stability, while (Cp-COOH)2 Co+ has the worst stability. Therefore, the inventors concluded that the electron-donating substituents on the cyclocene ring are beneficial to improve the alkali stability of the cobaltocene cation, while the electron-withdrawing substituents are not conducive to the alkali stability.
在这个研究的基础上，本发明人提出了一种新的聚合物结构：含二茂钴阳离子-苯并咪唑类聚合物，通过二酸与联苯四胺(DAB)，以多聚磷酸(PPA)为溶剂在微波条件下合成含二茂钴类的苯并咪唑聚合物。经烷基化、流延成膜、碱化制备相应的碱性膜。On the basis of this study, the inventors have proposed a new polymer structure: cobalt-containing cation-benzimidazole polymer, through diacid and biphenyltetramine (DAB), with polyphosphoric acid ( PPA) is used as a solvent to synthesize benzimidazole polymers containing cobaltocenes under microwave conditions. The corresponding alkaline film is prepared by alkylation, film casting and alkalization.
发明内容Contents of the invention
本发明的目的之一是提供一种具有优良的热和化学稳定性，较高的离子传导率，以及在高湿度下，具有较低的溶胀，制膜工艺简单，变形性小，机械强度高等特点的碱性膜。One of the objects of the present invention is to provide a film with excellent thermal and chemical stability, high ion conductivity, and low swelling under high humidity, simple film making process, small deformability, high mechanical strength, etc. characteristic alkaline membrane.
本发明的上述发明目的是通过以下技术方案达到的：The above-mentioned purpose of the invention of the present invention is achieved by the following technical solutions:
一种含二茂钴阳离子-苯并咪唑类聚合物的碱性膜，其特征在于，所述的碱性膜主链上同时含有苯并咪唑类聚合物与二茂钴阳离子。An alkaline membrane containing cobaltocene cation-benzimidazole polymer is characterized in that the main chain of the alkaline membrane contains both benzimidazole polymer and cobaltocene cation.
优选地，所述二茂钴阳离子-苯并咪唑类聚合物为1,1’-二茂钴阳离子-5,5’-二苯并咪唑(Cp2Co+-PBI)，1,1’-二茂钴阳离子-1,1’-丁基-5,5’-二苯并咪唑(Cp2Co+-Butyl-PBI)或1,1’-二茂钴阳离子-对苯基-5,5’-二苯并咪唑(Cp2Co+-PP-PBI)。Preferably, the cobaltocene-benzimidazole polymer is 1,1'-cobaltocene-5,5'-dibenzimidazole (Cp2 Co+ -PBI), 1,1'- Cobaltocene-1,1'-butyl-5,5'-dibenzimidazole (Cp2 Co+ -Butyl-PBI) or 1,1'-cobaltocene-p-phenyl-5,5 '-Bibenzimidazole (Cp2 Co+ -PP-PBI).
优选地，所述的二茂钴阳离子-苯并咪唑类聚合物的分子量在4.5-40万范围。Preferably, the molecular weight of the cobaltocene-benzimidazole polymer is in the range of 45,000-400,000.
本发明的另一目的是提供一种上述含二茂钴阳离子-苯并咪唑类聚合物的碱性膜的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned alkaline membrane containing cobaltocene-benzimidazole polymer.
本发明的上述目的是通过以下技术方案达到的：Above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种含二茂钴阳离子-聚苯并咪唑的碱性膜的制备方法，其具体步骤如下：A kind of preparation method of the alkaline film containing dicyclocene cobalt cation-polybenzimidazole, its concrete steps are as follows:
(1)1,1’-二羧基二茂钴六氟磷酸盐((Cp-COOH)2Co+PF6-)的制备(1) Preparation of 1,1'-dicarboxycobaltocene hexafluorophosphate ((Cp-COOH)2 Co+ PF6- )
取一定量的1,1’-二甲基二茂钴六氟磷酸盐溶于去离子水中，加入过量的高锰酸钾，中性条件下氧化，80℃下搅拌一定时间，抽滤浓缩，调节PH，然后加入六氟磷酸钾水溶液进行沉淀，收集沉淀，烘干；Dissolve a certain amount of 1,1'-dimethyldicenecobalt hexafluorophosphate in deionized water, add excess potassium permanganate, oxidize under neutral conditions, stir at 80°C for a certain period of time, and concentrate by suction filtration. Adjust the pH, then add an aqueous solution of potassium hexafluorophosphate for precipitation, collect the precipitate, and dry it;
(2)二茂钴阳离子-二苯并咪唑聚合物的制备(2) Preparation of cobaltocene-dibenzimidazole polymer
取等量的步骤(1)所得的(Cp-COOH)2Co+PF6-，与联苯二胺(DAB)加入到微波反应瓶中，加入足量的多聚磷酸(PPA)作为溶剂，氮气保护下进行聚合反应，然后在水和NaHCO3中洗涤多次，抽滤，烘干，得到聚合物沉淀；Take an equal amount of (Cp-COOH)2 Co+ PF6- obtained in step (1), add benzphenyldiamine (DAB) into a microwave reaction flask, add a sufficient amount of polyphosphoric acid (PPA) as a solvent, Carry out the polymerization reaction under the protection of nitrogen, then wash in water andNaHCO for several times, filter with suction, and dry to obtain a polymer precipitate;
(3)碱性膜的制备(3) Preparation of alkaline membrane
将步骤(2)所得聚合物溶解在二甲基亚砜或N,N-二甲基乙酰胺中，加入一定浓度的KOH/H2O,反应一定时间之后加入甲基化试剂，待反应完全之后，在去离子水中沉淀，抽滤，用水和丙酮洗涤多次，收集沉淀，烘干，得到甲基化后的聚合物，然后将其重新溶解在二甲基亚砜或N,N-二甲基乙酰胺中制成铸膜液，流延成膜，最后在碱液中浸泡，得到相应的碱性膜。Dissolve the polymer obtained in step (2) in dimethyl sulfoxide or N,N-dimethylacetamide, add a certain concentration of KOH/H2 O, add a methylating reagent after a certain period of time, and wait until the reaction is complete After that, precipitate in deionized water, filter with suction, wash with water and acetone several times, collect the precipitate, and dry to obtain the methylated polymer, which is then re-dissolved in dimethyl sulfoxide or N,N-di Methylacetamide is used to make a casting solution, cast to form a film, and finally soaked in alkali solution to obtain the corresponding alkaline film.
优选地，所述步骤(2)中，同时加入有机二酸HOOC-X-COOH,X为：(CH2)n,或n＝3-8。Preferably, in the step (2), organic diacid HOOC-X-COOH is added at the same time, X is: (CH2 )n , or n=3-8.
优选地，所述有机二酸为1,6-己二酸或对苯二甲酸。Preferably, the organic diacid is 1,6-adipic acid or terephthalic acid.
优选地，所述步骤(2)如下：Preferably, the step (2) is as follows:
(2)取等当量的步骤(1)所得(Cp-COOH)2Co+PF6-与1,6-己二酸，2倍当量的联苯四胺(DAB)，加入到微波反应器中，加入足量的多聚磷酸(PPA)作为溶剂，氮气保护下进行聚合反应，然后在水和NaHCO3中洗涤多次，抽滤，烘干，得到聚合物沉淀。(2) Take an equivalent amount of (Cp-COOH)2 Co+ PF6- and 1,6-adipic acid obtained in step (1), and add 2 times the equivalent of diphenyltetramine (DAB) into the microwave reactor , adding a sufficient amount of polyphosphoric acid (PPA) as a solvent, carrying out polymerization reaction under nitrogen protection, then washing in water and NaHCO3 times, suction filtration, and drying to obtain a polymer precipitate.
优选地，所述步骤(2)如下：Preferably, the step (2) is as follows:
(2)取等当量的步骤(1)所得(Cp-COOH)2Co+PF6-与对苯二甲酸，2倍当量的联苯二胺(DAB)，加入到微波反应器中，加入足量的多聚磷酸(PPA)作为溶剂，氮气保护下进行聚合反应，然后在水和NaHCO3中洗涤多次，抽滤，烘干，得到聚合物沉淀。(2) Take an equivalent amount of (Cp-COOH)2 Co+ PF6- obtained in step (1) and terephthalic acid, 2 times the equivalent of diphenylenediamine (DAB), add it to the microwave reactor, and add enough A certain amount of polyphosphoric acid (PPA) was used as a solvent, and the polymerization was carried out under the protection of nitrogen, and then washed several times in water and NaHCO3 , suction filtered, and dried to obtain a polymer precipitate.
本发明所述的含二茂钴阳离子-聚苯并咪唑(MCp2Co+OH--PBI)聚合物具有很好的热稳定性，骨架的降解温度>480℃。The cobaltocene-containing cation-polybenzimidazole (MCp2 Co+ OH- -PBI) polymer of the present invention has good thermal stability, and the degradation temperature of the skeleton is >480°C.
本发明提供的含二茂钴阳离子-苯并咪唑类聚合物的碱性膜具有优良的热和化学稳定性，较高的离子传导率，以及在高湿度下，具有较低的溶胀，制膜工艺简单，变形性小，机械强度高等特点。The alkaline membrane containing dicyclocene cobalt cation-benzimidazole polymer provided by the present invention has excellent thermal and chemical stability, higher ion conductivity, and lower swelling under high humidity, and is easy to form into a membrane The process is simple, the deformability is small, and the mechanical strength is high.
本发明含二茂钴阳离子-苯并咪唑类聚合物碱性膜的制备方法，通过(Cp-COOH)2Co+PF6-、DAB以PPA为溶剂在微波条件下缩合制备。其中三元二茂钴阳离子缩聚物是通过(Cp-COOH)2Co+PF6-与不同的二酸和DAB，以PPA为溶剂在微波条件下缩聚制备。然后经烷基化试剂进行烷基化，溶于有机溶剂后制成铸膜液，流延成膜。最后浸泡在1M的KOH/H2O中得到相应的碱性膜。The preparation method of the present invention contains cobaltocene-cobalt cation-benzimidazole polymer alkaline film, which is prepared by condensing (Cp-COOH)2 Co+ PF6- , DAB with PPA as a solvent under microwave conditions. The ternary cobaltocene polycondensate is prepared by polycondensation of (Cp-COOH)2 Co+ PF6- with different diacids and DAB, using PPA as a solvent under microwave conditions. Then it is alkylated with an alkylating agent, dissolved in an organic solvent to make a casting solution, and cast to form a film. Finally, soak in 1M KOH/H2 O to obtain the corresponding alkaline film.
本发明与背景技术相比，具有以下增益效果：Compared with the background technology, the present invention has the following gain effects:
(1)将二茂钴阳离子作为碱性膜新的阳离子官能团；(1) Using dicyclocene cobalt cations as new cationic functional groups of alkaline membranes;
(2)首次通过C-C键将二茂钴阳离子接枝到碱性膜的聚合物上；(2) For the first time, cobaltocene cations are grafted to the polymer of the basic membrane through the C-C bond;
(3)所制备的碱性膜具有突出的热和化学稳定性；(3) The prepared alkaline membrane has outstanding thermal and chemical stability;
(4)所制备的碱性膜具有较高的离子传导率，以及较低的溶胀，符合现阶段燃料电池碱性膜的要求。(4) The prepared alkaline membrane has high ion conductivity and low swelling, which meets the requirements of the alkaline membrane of the fuel cell at the present stage.
下面通过附图和具体实施方式对本发明进行详细说明。应该理解的是，所述的实施例仅涉及本发明的优选实施方案，在不脱离本发明的精神和范围情况下，各种成分及含量的变化和改进都是可能的。The present invention will be described in detail below with reference to the drawings and specific embodiments. It should be understood that the examples described only refer to the preferred embodiments of the present invention, and various changes and improvements are possible without departing from the spirit and scope of the present invention.
附图说明Description of drawings
图1为本发明实施例1、2、3中微波合成的三种聚合物核磁氢谱(1HNMR)，溶剂选用氘代二甲基亚砜(DMSO)：1,1’-二茂钴阳离子-5,5’-二苯并咪唑(Cp2Co+-PBI)，1,1’-二茂钴阳离子-1,1’-丁基-5,5’-二苯并咪唑(Cp2Co+-Butyl-PBI)或1,1’-二茂钴阳离子-对苯基-5,5’-二苯并咪唑(Cp2Co+-PP-PBI)。Fig. 1 is the hydrogen nuclear magnetic spectrum (1 HNMR) of three polymers synthesized by microwave in Examples 1, 2, and 3 of the present invention, and the solvent is deuterated dimethyl sulfoxide (DMSO): 1,1'-cobaltocene cation -5,5'-dibenzimidazole (Cp2 Co+ -PBI), 1,1'-dibenzimidazole cation-1,1'-butyl-5,5'-dibenzimidazole (Cp2 Co+ -Butyl-PBI) or 1,1'-cobaltocene-p-phenyl-5,5'-bibenzimidazole (Cp2 Co+ -PP-PBI).
图2为本发明实施例三种聚合物制备成的三种碱性膜的离子传导率-温度变化图。Fig. 2 is a diagram of ion conductivity-temperature variation of three kinds of alkaline membranes prepared by three kinds of polymers in the embodiment of the present invention.
图3为本发明实施例三种聚合物制备成的三种碱性膜的热重分析图。Fig. 3 is a graph of thermogravimetric analysis of three kinds of alkaline films prepared by three kinds of polymers in the embodiment of the present invention.
具体实施方式Detailed ways
实施例1Example 1
1,1’-二茂钴阳离子-5,5’-(2,2’-二甲基)-二苯并咪唑(MCp2Co+OH--PBI)碱性膜的制备：Preparation of 1,1'-cobaltocene-5,5'-(2,2'-dimethyl)-bibenzimidazole (MCp2 Co+ OH- -PBI) basic membrane:
其制备过程如下所示：Its preparation process is as follows:
(1)1,1-二羧基二茂钴六氟磷酸盐((Cp-COOH)2Co+PF6-)的制备(1) Preparation of 1,1-dicarboxycobaltocene hexafluorophosphate ((Cp-COOH)2 Co+ PF6- )
取3克市售(Cp-CH3)2Co+PF6-溶于400毫升去离子水中，加入6.542克市售高锰酸钾,加热到80℃，搅拌48小时后，抽滤，得到黄色清液和褐色沉淀。去清液，旋蒸，浓缩，待冷却到室温，在冰水浴下滴加HCl(盐酸)水溶液调节PH到4，出现黄色沉淀，抽滤，用去离子水洗涤多次。收集沉淀，得到黄色凝结状沉淀。产率：52％。Dissolve 3 grams of commercially available (Cp-CH3 )2 Co+ PF6- in 400 ml of deionized water, add 6.542 grams of commercially available potassium permanganate, heat to 80°C, stir for 48 hours, and filter with suction to obtain a yellow Clear liquid and brown precipitate. Remove the supernatant, spin evaporate, concentrate, wait to cool to room temperature, add HCl (hydrochloric acid) aqueous solution dropwise in ice-water bath to adjust pH to 4, yellow precipitate appears, filter with suction, and wash with deionized water several times. The precipitate was collected to obtain a yellow coagulated precipitate. Yield: 52%.
(2)取1克步骤(1)所得(Cp-COOH)2Co+PF6-、0.5077克市售联苯二胺(DAB)加入大到微波反应器中。然后加入30克市售多聚磷酸(PPA)。充分搅拌均匀。氮气保护下进行微波聚合。通过程序升温进行温度调控。第一阶段升温至140℃进行预聚90分钟,然后升温至200℃，进行关环反应，90分钟。反应完全之后，在去离子水沉淀，滤去清液，用去离子水洗涤多次。然后用NaHCO3浸泡24小时，洗去多余的酸。抽滤收集沉淀，烘干。得到Cp2Co+HCO3--PBI(黑褐色沉淀，产率：46％)。Cp2Co+-PBI核磁氢谱(1HNMR)见图1。(2) 1 gram of (Cp-COOH)2 Co+ PF6- obtained in step (1) and 0.5077 gram of commercially available diphenyldiamine (DAB) were added into a microwave reactor. Then 30 grams of commercially available polyphosphoric acid (PPA) was added. Stir well to combine. Microwave polymerization was carried out under the protection of nitrogen. Temperature regulation is carried out by temperature programming. In the first stage, the temperature is raised to 140°C for 90 minutes of prepolymerization, and then the temperature is raised to 200°C for 90 minutes of ring closure reaction. After the reaction is complete, precipitate in deionized water, filter off the supernatant, and wash with deionized water several times. Then soak in NaHCO3 for 24 hours to wash off excess acid. The precipitate was collected by suction filtration and dried. Cp2 Co+ HCO3− -PBI was obtained (dark brown precipitate, yield: 46%). The hydrogen nuclear magnetic spectrum (1 HNMR) of Cp2 Co+ -PBI is shown in Fig. 1 .
(3)碱性膜的制备(3) Preparation of alkaline membrane
取0.5克Cp2Co+HCO3--PBI聚合物溶解在50毫升市售二甲基亚砜中，搅拌均匀，升温至70℃。加入0.72毫升3M KOH/H2O到溶液中，反应充分之后，冷却到室温加入0.2956克市售碘甲烷。反应1小时，最后，把溶液倒入400毫升去离子水中。抽滤，得到黑色沉淀。用去离子水和丙酮洗涤多次。80℃真空烘箱干燥，得到黑棕色沉淀，将沉淀重新溶解在二甲基亚砜中，制成铸膜液，流延成膜，最后将制备的膜浸泡在1M的KOH/H2O中得到MCp2Co+OH--PBI碱性膜。0.5 g of Cp2 Co+ HCO3- -PBI polymer was dissolved in 50 ml of commercially available dimethyl sulfoxide, stirred evenly, and heated to 70°C. Add 0.72 ml of 3M KOH/H2 O to the solution. After the reaction is complete, cool to room temperature and add 0.2956 g of commercially available methyl iodide. React for 1 hour, and finally, pour the solution into 400 ml of deionized water. Suction filtration to obtain a black precipitate. Wash multiple times with deionized water and acetone. Dry in a vacuum oven at 80°C to obtain a black-brown precipitate, which is redissolved in dimethyl sulfoxide to make a casting solution, cast into a film, and finally soak the prepared film in 1M KOH/H2 O to obtain MCp2 Co+ OH- -PBI alkaline membrane.
通过电化学工作站，用交流阻抗法来测量MCp2Co+OH—PBI碱性膜的离子传导率，得到其离子传导率-温度变化图(σ-T)见图2，从图2中可以看出，膜具有较高的离子传导率。80℃时，传导率达：29.4ms/cm.。用热重分析仪(TGA)对MCp2Co+OH--PBI碱性膜进行热重分析，得到热重分析图3。从图3中可以看出：该聚合物主要有三个降解峰，50-210℃为膜内残留的水分和磷酸的蒸发峰，480-750℃为该聚合物骨架的降解峰，780-850℃为茂环的分解峰。Measure the ionic conductivity of the MCp2 Co+ OH—PBI alkaline membrane by the electrochemical workstation, and use the AC impedance method to obtain its ionic conductivity-temperature change diagram (σ-T), as shown in Figure 2. From Figure 2, it can be seen that It can be seen that the membrane has high ionic conductivity. At 80°C, the conductivity reaches: 29.4ms/cm. The thermogravimetric analysis of the MCp2 Co+ OH- -PBI alkaline film was carried out with a thermogravimetric analyzer (TGA), and the thermogravimetric analysis Figure 3 was obtained. It can be seen from Figure 3 that the polymer mainly has three degradation peaks, 50-210°C is the evaporation peak of residual water and phosphoric acid in the film, 480-750°C is the degradation peak of the polymer skeleton, and 780-850°C It is the decomposition peak of Maohuan.
实施例2Example 2
1,1’-二茂钴阳离子-1,1’-丁基-5,5’-(2,2’-二甲基)-二苯并咪唑(MCp2Co+OH--Butyl-PBI)碱性膜的制备：1,1'-Cobaltocene-1,1'-Butyl-5,5'-(2,2'-Dimethyl)-Bibenzimidazole (MCp2 Co+ OH- -Butyl-PBI) Preparation of alkaline membrane:
其制备过程如下所示：Its preparation process is as follows:
(1)1,1-二羧基二茂钴六氟磷酸盐((Cp-COOH)2Co+PF6-)的制备(1) Preparation of 1,1-dicarboxycobaltocene hexafluorophosphate ((Cp-COOH)2 Co+ PF6- )
取3克市售(Cp-CH3)2Co+PF6-溶于400毫升去离子水中，加入6.542克市售高锰酸钾,加热到80℃，搅拌48小时后，抽滤，得到黄色清液和褐色沉淀。去清液，旋蒸，浓缩，待冷却到室温，在冰水浴下滴加HCl(盐酸)水溶液调节PH到4，出现黄色沉淀，抽滤，用去离子水洗涤多次。收集沉淀，得到黄色凝结状沉淀。产率：52％。Dissolve 3 grams of commercially available (Cp-CH3 )2 Co+ PF6- in 400 ml of deionized water, add 6.542 grams of commercially available potassium permanganate, heat to 80°C, stir for 48 hours, and filter with suction to obtain a yellow Clear liquid and brown precipitate. Remove the supernatant, spin evaporate, concentrate, wait to cool to room temperature, add HCl (hydrochloric acid) aqueous solution dropwise in ice-water bath to adjust pH to 4, yellow precipitate appears, filter with suction, and wash with deionized water several times. The precipitate was collected to obtain a yellow coagulated precipitate. Yield: 52%.
(2)取0.5克步骤(1)所得(Cp-COOH)2Co+PF6-，0.1731克1,6-己二酸，0.5077克DBA加入到微波反应器中。加入30克PPA作为溶剂，氮气保护下进行聚合反应。程序升温至140℃，预聚90分钟，然后升温至200℃，进行关环反应90分钟。反应完全之后，在去离子水沉淀，滤去清液，用去离子水洗涤多次。然后用NaHCO3浸泡24小时，洗去多余的酸。抽滤，收集沉淀，烘干。得到Cp2Co+HCO3--Butyl-PBI(暗褐色沉淀，产率：48％)，Cp2Co+-Butyl-PBI核磁氢谱(1HNMR)见图1。(2) 0.5 g of (Cp—COOH)2 Co+ PF6− obtained in step (1), 0.1731 g of 1,6-adipic acid, and 0.5077 g of DBA were added to the microwave reactor. 30 g of PPA was added as a solvent, and polymerization was carried out under nitrogen protection. The temperature was programmed to rise to 140°C for 90 minutes of prepolymerization, and then the temperature was raised to 200°C for 90 minutes of ring-closing reaction. After the reaction is complete, precipitate in deionized water, filter off the supernatant, and wash with deionized water several times. Then soak in NaHCO3 for 24 hours to wash away excess acid. Filter with suction, collect the precipitate, and dry it. Cp2 Co+ HCO3− -Butyl-PBI (dark brown precipitate, yield: 48%) was obtained. The hydrogen nuclear magnetic spectrum (1 HNMR) of Cp2 Co+ -Butyl-PBI is shown in FIG. 1 .
(3)碱性膜的制备(3) Preparation of alkaline membrane
取0.5克步骤(2)所得Cp2Co+HCO3--Butyl-PBI聚合物溶解在50毫升二甲基亚砜中，搅拌均匀，升温至70℃。加入0.48毫升3M KOH/H2O到溶液中，反应充分之后，冷却到室温加入0.1848克碘甲烷。反应1小时，最后，把溶液倒入400毫升去离子水中。抽滤，得到暗黑色沉淀。用去离子水和丙酮洗涤多次。80℃真空烘箱干燥，得到黑棕色沉淀，将沉淀重新溶解在二甲基亚砜中，制成铸膜液，流延成膜，最后将制备的膜浸泡在1M的KOH/H2O中得到MCp2Co+OH--Butyl-PBI碱性膜。0.5 g of the Cp2 Co+ HCO3- -Butyl-PBI polymer obtained in step (2) was dissolved in 50 ml of dimethyl sulfoxide, stirred evenly, and heated to 70°C. Add 0.48 ml of 3M KOH/H2 O to the solution, after the reaction is complete, cool to room temperature and add 0.1848 g of iodomethane. React for 1 hour, and finally, pour the solution into 400 ml of deionized water. Suction filtration to obtain a dark black precipitate. Wash multiple times with deionized water and acetone. Dry in a vacuum oven at 80°C to obtain a black-brown precipitate, which is redissolved in dimethyl sulfoxide to make a casting solution, cast into a film, and finally soak the prepared film in 1M KOH/H2 O to obtain MCp2 Co+ OH- -Butyl-PBI alkaline membrane.
通过电化学工作站，用交流阻抗法来测量该聚合物膜的离子传导率，得到其离子传导率-温度变化图(σ-T)见图2，从图2中可以看出，膜的离子传导率在80℃时，传导率为：21.2ms/cm.。用热重分析仪(TGA)对MCp2Co+OH--Butyl-PBI碱性膜进行热重分析，得到热重分析图3。从图3中可以看出：该聚合物主要有三个降解峰，50-210℃为膜内残留的水分和磷酸的蒸发峰，300-720℃为该聚合物骨架的降解峰，750-850℃为茂环的分解峰。By electrochemical workstation, measure the ionic conductivity of this polymer film with AC impedance method, obtain its ionic conductivity-temperature change diagram (σ-T) see Fig. 2, as can be seen from Fig. 2, the ionic conductivity of membrane At 80°C, the conductivity is: 21.2ms/cm. Thermogravimetric analysis was performed on the MCp2 Co+ OH- -Butyl-PBI alkaline film with a thermogravimetric analyzer (TGA), and the thermogravimetric analysis Figure 3 was obtained. It can be seen from Figure 3 that the polymer mainly has three degradation peaks, 50-210°C is the evaporation peak of residual water and phosphoric acid in the film, 300-720°C is the degradation peak of the polymer skeleton, and 750-850°C It is the decomposition peak of Maohuan.
实施例3Example 3
1,1’-二茂钴阳离子-对苯基-5,5’-(2,2’-二甲基)-二苯并咪唑(MCp2Co+OH--PP-PBI)碱性膜的制备：1,1'-cobaltocene-p-phenyl-5,5'-(2,2'-dimethyl)-bibenzimidazole (MCp2 Co+ OH- -PP-PBI) basic film preparation:
其制备过程如下所示：Its preparation process is as follows:
(1)1,1-二羧基二茂钴六氟磷酸盐((Cp-COOH)2Co+PF6-)的制备(1) Preparation of 1,1-dicarboxycobaltocene hexafluorophosphate ((Cp-COOH)2 Co+ PF6- )
取3克市售(Cp-CH3)2Co+PF6-溶于400毫升去离子水中，加入6.542克市售高锰酸钾,加热到80℃，搅拌48小时后，抽滤，得到黄色清液和褐色沉淀。去清液，旋蒸，浓缩，待冷却到室温，在冰水浴下滴加HCl(盐酸)水溶液调节PH到4，出现黄色沉淀，抽滤，用去离子水洗涤多次。收集沉淀，得到黄色凝结状沉淀。产率：52％。Dissolve 3 grams of commercially available (Cp-CH3 )2 Co+ PF6- in 400 ml of deionized water, add 6.542 grams of commercially available potassium permanganate, heat to 80°C, stir for 48 hours, and filter with suction to obtain a yellow Clear liquid and brown precipitate. Remove the supernatant, spin evaporate, concentrate, wait to cool to room temperature, add HCl (hydrochloric acid) aqueous solution dropwise in ice-water bath to adjust pH to 4, yellow precipitate appears, filter with suction, and wash with deionized water several times. The precipitate was collected to obtain a yellow coagulated precipitate. Yield: 52%.
(2)取0.5克步骤(1)所得(Cp-COOH)2Co+PF6-，与0.1968克对苯二甲酸，0.5077克DAB加入到微波反应器中。加入30克PPA作为溶剂，氮气保护下进行聚合反应。程序升温至140℃，预聚90分钟，然后升温至200℃，进行关环反应90分钟。反应完全之后，在去离子水中沉淀，滤去清液，用去离子水洗涤多次。然后用NaHCO3浸泡24小时，洗去多余的酸。抽滤收集沉淀，烘干。得到Cp2Co+HCO3--PP-PBI(暗褐色沉淀，产率：48％)，Cp2Co+-PP-PBI的核磁氢谱(1HNMR)见图1。(2) Take 0.5 g of (Cp-COOH)2 Co+ PF6- obtained in step (1), add 0.1968 g of terephthalic acid, and 0.5077 g of DAB into a microwave reactor. 30 g of PPA was added as a solvent, and polymerization was carried out under nitrogen protection. The temperature was programmed to rise to 140°C for 90 minutes of prepolymerization, and then the temperature was raised to 200°C for 90 minutes of ring-closing reaction. After the reaction is complete, precipitate in deionized water, filter off the clear liquid, and wash with deionized water several times. Then soak in NaHCO3 for 24 hours to wash off excess acid. The precipitate was collected by suction filtration and dried. Cp2 Co+ HCO3- -PP-PBI was obtained (dark brown precipitate, yield: 48%), and the hydrogen nuclear magnetic spectrum (1 HNMR) of Cp2 Co+ -PP-PBI is shown in FIG. 1 .
(3)碱性膜的制备(3) Preparation of alkaline membrane
取0.5克步骤(2)所得Cp2Co+HCO3--PP-PBI聚合物溶解在50毫升二甲基亚砜中，搅拌均匀，升温至70℃。加入0.46毫升3M的KOH/H2O到溶液中，反应充分之后，冷却到室温加入0.18克碘甲烷。反应1小时，最后，把溶液倒入400毫升去离子水中。抽滤，得到暗黑色沉淀。用去离子水和丙酮洗涤多次。80℃，真空烘箱干燥，得到黑棕色沉淀，将沉淀重新溶解在二甲基亚砜中，制成铸膜液，流延成膜，最后将制备的膜浸泡在1M的KOH/H2O中，得到MCp2Co+OH--PP-PBI碱性膜。0.5 g of the Cp2 Co+ HCO3- -PP-PBI polymer obtained in step (2) was dissolved in 50 ml of dimethyl sulfoxide, stirred evenly, and heated to 70°C. Add 0.46 ml of 3M KOH/H2 O to the solution, after the reaction is complete, cool to room temperature and add 0.18 g of iodomethane. React for 1 hour, and finally, pour the solution into 400 ml of deionized water. Suction filtration to obtain a dark black precipitate. Wash multiple times with deionized water and acetone. Dry in a vacuum oven at 80°C to obtain a black-brown precipitate, redissolve the precipitate in dimethyl sulfoxide to make a casting solution, cast it into a film, and finally soak the prepared film in 1M KOH/H2 O , to obtain MCp2 Co+ OH- -PP-PBI basic film.
通过电化学工作站，用交流阻抗法来测量MCp2Co+OH--PP-PBI碱性膜的离子传导率，得到其离子传导率-温度变化图(σ-T)见图2，从图2中可以看出，膜的离子传导率在80℃时，传导率为：17.3ms/cm。用热重分析仪(TGA)对MCp2Co+OH--PP-PBI碱性膜进行热重分析，得到热重分析图3。从图3中可以看出：该聚合物主要有三个降解峰，50-210℃为膜内残留的水分和磷酸的蒸发峰，290-780℃为该聚合物骨架的降解峰，780-850℃为茂环的分解峰。Measure the ionic conductivity of the MCp2 Co+ OH- -PP-PBI alkaline membrane by the electrochemical workstation, and use the AC impedance method to obtain its ionic conductivity-temperature change diagram (σ-T) as shown in Figure 2, from Figure 2 It can be seen that the ion conductivity of the membrane is 17.3ms/cm at 80°C. The thermogravimetric analysis of the MCp2 Co+ OH- -PP-PBI alkaline film was carried out with a thermogravimetric analyzer (TGA), and the thermogravimetric analysis Figure 3 was obtained. It can be seen from Figure 3 that the polymer mainly has three degradation peaks, 50-210°C is the evaporation peak of moisture and phosphoric acid remaining in the film, 290-780°C is the degradation peak of the polymer skeleton, and 780-850°C It is the decomposition peak of Maohuan.
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| CN201610268691.2ACN105789659B (en) | 2016-04-27 | 2016-04-27 | Alkaline membrane of cation containing cobaltocene-benzimidazole polymer and preparation method thereof |
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| US8592539B2 (en)* | 2010-08-16 | 2013-11-26 | University Of South Carolina | Preparation of cobaltocenium-containing monomers and their polymers |
| CN104124463A (en)* | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Ionic liquid-polymer composite membrane for hydrogen chloride fuel cell and preparation and application thereof |
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