CN103560259A

Movatterモバイル変換

Info

Publication number: CN103560259A
Application number: CN201310543122.0A
Authority: CN
Inventors: 潘海燕; 张媛媛; 浦鸿汀; 常志宏
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2013-11-06
Filing date: 2013-11-06
Publication date: 2014-02-05

Abstract

The invention belongs to the technical field of functional high molecular materials and electrochemistry, and specifically relates to a POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as a preparation method thereof. The preparation method comprises the following steps: firstly, synthesizing a sulfonated polyimide polymer with a crosslinkable group imidazole group on a main chain, wherein the degree of sulfonation is controlled within 10-190%; and preparing a membrane forming liquid, adding a functional POSS crosslinking agent, carrying out reaction with the imidazole group, crosslinking the sulfonated polyimide polymer in a membrane forming process to form the crosslinking type sulfonated polyimide proton exchange membrane. The crosslinking membrane is endowed with good mechanical property and has higher hydrolytic stability and anti-oxidation stability. The method disclosed by the invention is good in controllability of the preparation process. Compared with conventional sulfonated polyimide membranes, the crosslinking type sulfonated polyimide proton exchange membrane is high in mechanical strength, strong in hydrolytic resistance and oxidation resistance, and good in dimensional stability, and has a broad application prospect in polymer electrolyte membrane fuel cells.

Description

Translated fromChinese

一种 POSS 交联型磺化聚酰亚胺质子交换膜及其制备方法 A sort of POSS Cross-linked sulfonated polyimide proton exchange membrane and preparation method thereof

技术领域technical field

本发明属于功能高分子材料和电化学技术领域，具体涉及一种POSS交联型磺化聚酰亚胺质子交换膜及其制备方法。The invention belongs to the technical field of functional polymer materials and electrochemistry, and in particular relates to a POSS cross-linked sulfonated polyimide proton exchange membrane and a preparation method thereof.

背景技术Background technique

质子交换膜燃料电池（PEMFCs）是目前世界上最成熟的一种能将氢气与空气中的氧气化合成洁净水并释放出电能的技术，具有能量效率高，排放低，环境友好的优点。质子交换膜是PEMFC的核心组件，决定了整个电池的性能和使用寿命。目前PEMFC中应用的主要是全氟磺酸膜（如Nafion^®），但价格昂贵、机械强度不高、尺寸稳定性差和渗透率高等缺点限制了它的广泛应用。Proton exchange membrane fuel cells (PEMFCs) are currently the most mature technology in the world that can convert hydrogen and oxygen in the air into clean water and release electricity. It has the advantages of high energy efficiency, low emissions and environmental friendliness. The proton exchange membrane is the core component of PEMFC, which determines the performance and service life of the entire battery. At present, perfluorosulfonic acid membrane (such as Nafion^® ) is mainly used in PEMFC, but its disadvantages such as high price, low mechanical strength, poor dimensional stability and high permeability limit its wide application.

磺化聚酰亚胺质子膜具有几个比较突出特点：（1）对外部温度变化不敏感（其玻璃化温度高）；（2）每个离子团的水分子数目不依赖于EW；（3）质子传导率与膜中水含量相关性弱；（4）单体所含离子相的内部结构不是水滴而是聚合物链的离子部分；（5）膜的微结构可能是层状，而不是像Nafion^®的椭球状。因此，磺化聚酰亚胺被认为是很有希望获得应用的一类膜材料。然而，与Nafion^®相比，磺化碳氢聚合物膜的抗自由基氧化稳定性都比较差，从而影响燃料电池的使用寿命。The sulfonated polyimide proton membrane has several outstanding features: (1) It is not sensitive to external temperature changes (its glass transition temperature is high); (2) The number of water molecules per ion cluster does not depend on EW; (3 ) the proton conductivity is weakly correlated with the water content in the membrane; (4) the internal structure of the ionic phase contained in the monomer is not water droplets but the ionic part of the polymer chain; (5) the microstructure of the membrane may be lamellar rather than Ellipsoid like Nafion^® . Therefore, sulfonated polyimide is considered to be a class of membrane materials with great promise for application. However, compared with Nafion^® , the sulfonated hydrocarbon polymer membranes are less stable against free radical oxidation, which affects the service life of fuel cells.

磺化聚苯并咪唑具有极好的抗自由基氧化性能，但由于碱性咪唑基与酸性磺酸基之间强烈的相互作用，质子传导受到阻碍，使得磺化聚苯并咪唑膜的质子导电率很低。如果采用合适的方法，将苯并咪唑结构引入到聚酰亚胺中，两者便可取长补短。本发明结合聚酰亚胺和聚苯并咪唑的特点与性能，在磺化聚酰亚胺主链中引入苯并咪唑基，并在成膜过程中利用咪唑基上的活泼N-H结构，加入功能化的多面体低聚倍半硅氧烷（POSS）交联剂使其形成交联型的质子交换膜材料，可望在提高膜的抗自由基氧化性能的同时，大幅度提高膜的抗水解稳定性能，延长膜的使用寿命。Sulfonated polybenzimidazole has excellent resistance to free radical oxidation, but due to the strong interaction between the basic imidazole group and the acidic sulfonic acid group, the proton conduction is hindered, making the proton conduction of the sulfonated polybenzimidazole membrane The rate is very low. If a suitable method is adopted to introduce the benzimidazole structure into polyimide, the two can learn from each other. The present invention combines the characteristics and properties of polyimide and polybenzimidazole, introduces benzimidazole group into the main chain of sulfonated polyimide, and utilizes the active N-H structure on the imidazole group in the film forming process to add functional Polyhedral oligomeric silsesquioxane (POSS) cross-linking agent is used to form a cross-linked proton exchange membrane material, which is expected to greatly improve the anti-hydrolysis stability of the membrane while improving the anti-free radical oxidation performance of the membrane. performance and prolong the service life of the membrane.

发明内容Contents of the invention

本发明的目的是提供一种POSS交联型磺化聚酰亚胺质子交换膜及其制备方法。The purpose of the present invention is to provide a POSS cross-linked sulfonated polyimide proton exchange membrane and a preparation method thereof.

本发明提出的POSS交联型磺化聚酰亚胺质子交换膜，是在磺化聚酰亚胺类聚合物主链上引入苯并咪唑基，并在成膜过程中利用咪唑基上的活泼N-H结构与多面体低聚倍半硅氧烷(POSS)交联剂发生反应，使其交联而得到的，其原料组成包括：The POSS cross-linked sulfonated polyimide proton exchange membrane proposed by the present invention introduces benzimidazole groups into the main chain of sulfonated polyimide polymers, and utilizes the active properties of imidazole groups in the film-forming process. The N-H structure is obtained by reacting with polyhedral oligomeric silsesquioxane (POSS) cross-linking agent to make it cross-linked. Its raw material composition includes:

磺化聚酰亚胺 1份(摩尔数)1 part of sulfonated polyimide (number of moles)

POSS交联剂 0.025-0.5份(占磺化聚酰亚胺的质量比)POSS crosslinking agent 0.025-0.5 parts (accounting for the mass ratio of sulfonated polyimide)

有机溶剂 160-500份(摩尔数)；160-500 parts (moles) of organic solvent;

其中，所述磺化聚酰亚胺为主链含苯并咪唑基。 Wherein, the main chain of the sulfonated polyimide contains benzimidazole groups.

本发明中，所述磺化聚酰亚胺磺化度（磺化二胺单体的摩尔数乘以二除以二酐单体的摩尔数）由合成过程中的加料比来控制。其中磺化度为 10%-190%中的任意一个值。 In the present invention, the degree of sulfonation of the sulfonated polyimide (the number of moles of sulfonated diamine monomer multiplied by two divided by the number of moles of dianhydride monomer) is controlled by the feed ratio in the synthesis process. The degree of sulfonation is any one of 10%-190%.

本发明中，所述POSS交联剂为含多面体低聚倍半硅氧烷（POSS）结构的可与磺化聚酰亚胺中的苯并咪唑基发生反应的化合物，如Hybrid Plastics公司的八环氧基取代的多面体低聚倍半硅氧烷、三环氧基取代的多面体低聚倍半硅氧烷等，但不仅限于此。 In the present invention, the POSS crosslinking agent is a compound containing a polyhedral oligomeric silsesquioxane (POSS) structure that can react with the benzimidazole group in the sulfonated polyimide, such as Hybrid Plastics' eight Epoxy-substituted polyhedral oligomeric silsesquioxane, triepoxy-substituted polyhedral oligomeric silsesquioxane, etc., but not limited thereto.

本发明中，所述有机溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、二甲基亚砜或N－甲基吡咯烷酮、间甲酚中的任意一种或两种的混合液。 In the present invention, the organic solvent is any one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone, m-cresol or A mixture of the two.

本发明提出的POSS交联型磺化聚酰亚胺质子交换膜的制备方法，具体步骤如下：The preparation method of the POSS cross-linked sulfonated polyimide proton exchange membrane that the present invention proposes, concrete steps are as follows:

（1）将磺化聚酰亚胺浸泡在饱和NaCl溶液中，24h后取出烘干。在100℃下溶解于有机溶剂中，配成溶液。其中每50mL有机溶剂中磺化聚酰亚胺的加入量为0.5-2.5g；(1) Soak the sulfonated polyimide in a saturated NaCl solution, take it out and dry it after 24 hours. Dissolve in an organic solvent at 100°C to form a solution. Wherein the addition amount of sulfonated polyimide in every 50mL organic solvent is 0.5-2.5g;

（2）将多面体低聚倍半硅氧烷（POSS），常温溶解在有机溶剂中。其中每1mL有机溶剂中POSS的加入量为0.05-0.1g；(2) Dissolve polyhedral oligomeric silsesquioxane (POSS) in an organic solvent at room temperature. The amount of POSS per 1mL of organic solvent is 0.05-0.1g;

（3）室温下将步骤（1）和步骤（2）所得的溶液混合，搅拌后，过滤除气泡。其中：磺化聚酰亚胺与POSS交联剂的质量比为2:1～40:1；(3) Mix the solutions obtained in step (1) and step (2) at room temperature, and after stirring, filter to remove air bubbles. Among them: the mass ratio of sulfonated polyimide to POSS crosslinking agent is 2:1～40:1;

（4）将膜液浇注在10 cm×10 cm的玻璃板上，于60-90℃真空烘箱中干燥4-6 h，溶剂完全挥发。升温至150-180 ℃继续加热6-10h。得到钠盐型POSS交联型磺化聚酰亚胺质子交换膜；(4) The film solution was poured on a 10 cm×10 cm glass plate, and dried in a vacuum oven at 60-90°C for 4-6 h, and the solvent was completely evaporated. Raise the temperature to 150-180°C and continue heating for 6-10h. Obtain sodium salt type POSS cross-linked sulfonated polyimide proton exchange membrane;

5）将步骤（4）所得的质子交换膜在50-60 ℃的甲醇中浸泡6-12 h，除去质子交换膜中残留的有机溶剂。去离子水洗净后，常温下将质子交换膜浸泡在1.0 mol/L盐酸中 48 h后取出，用去离子水反复洗涤至中性，于150 ℃真空烘箱中干燥24 h，得到所需产品。5) Soak the proton exchange membrane obtained in step (4) in methanol at 50-60 °C for 6-12 h to remove the residual organic solvent in the proton exchange membrane. After washing with deionized water, soak the proton exchange membrane in 1.0 mol/L hydrochloric acid at room temperature for 48 h, take it out, wash it repeatedly with deionized water until neutral, and dry it in a vacuum oven at 150 °C for 24 h to obtain the desired product .

本发明的特点是在磺化聚酰亚胺聚合物主链上引入咪唑基团，然后使用POSS作为交联剂，使其与聚酰亚胺交联，可以显著提高磺化聚酰亚胺质子交换膜的热稳定性、抗氧化稳定性、水解稳定性及力学性能并仍具有较高的质子传导率。The feature of the present invention is to introduce imidazole groups on the main chain of sulfonated polyimide polymer, and then use POSS as a cross-linking agent to cross-link with polyimide, which can significantly increase the proton yield of sulfonated polyimide. The thermal stability, anti-oxidation stability, hydrolytic stability and mechanical properties of the exchange membrane still have high proton conductivity.

附图说明Description of drawings

图1为八环氧基取代的POSS交联型磺化聚酰亚胺质子交换膜的力学性能随磺化聚酰亚胺磺化度的变化，其中磺化聚酰亚胺的磺化度为80%，100%，120%，POSS与磺化聚酰亚胺的摩尔比为0.14:1。Fig. 1 is the change of the mechanical properties of POSS cross-linked sulfonated polyimide proton exchange membrane with the degree of sulfonation of sulfonated polyimide, wherein the degree of sulfonation of sulfonated polyimide is 80%, 100%, 120%, the molar ratio of POSS to sulfonated polyimide is 0.14:1.

具体实施方式Detailed ways

以下实施例是仅为更进一步具体说明本发明，在不违反本发明的主旨下，本发明应不限于以下实验例具体明示的内容。The following examples are only to further illustrate the present invention in detail, and the present invention should not be limited to the specific and express contents of the following experimental examples without violating the gist of the present invention.

所用原料如下：The raw materials used are as follows:

磺化聚酰亚胺（含苯并咪唑基和磺酸基团，SPIBI-X），按照文献所述方法实验室自制（潘海燕等，高等学校化学学报. 2007, 28(1): 173），其中X为磺化度；Sulfonated polyimide (containing benzimidazole group and sulfonic acid group, SPIBI-X), made in the laboratory according to the method described in the literature (Pan Haiyan et al., Chemical Journal of Chinese Universities. 2007, 28(1): 173) , where X is the degree of sulfonation;

八环氧基取代、三环氧基取代多面体低聚倍半硅氧烷（POSS），99.5%，Hybrid Plastics公司；Octaepoxy-substituted, triepoxy-substituted polyhedral oligomeric oligomeric silsesquioxane (POSS), 99.5%, Hybrid Plastics;

二甲亚砜（DMSO），99%，国药集团化学试剂有限公司；Dimethyl sulfoxide (DMSO), 99%, Sinopharm Chemical Reagent Co., Ltd.;

N,N-二甲基乙酰胺(DMAc)，化学纯（>98%），国药集团化学试剂有限公司；N,N-Dimethylacetamide (DMAc), chemically pure (>98%), Sinopharm Chemical Reagent Co., Ltd.;

N,N-二甲基甲酰胺(DMF)，化学纯（>98%），国药集团化学试剂有限公司；N,N-Dimethylformamide (DMF), chemically pure (>98%), Sinopharm Chemical Reagent Co., Ltd.;

N-甲基吡咯烷酮(NMP)，化学纯（>98%），国药集团化学试剂有限公司；N-Methylpyrrolidone (NMP), chemically pure (>98%), Sinopharm Chemical Reagent Co., Ltd.;

间甲酚（m-cresol），化学纯（>98%），国药集团化学试剂有限公司；m-cresol (m -cresol), chemically pure (>98%), Sinopharm Chemical Reagent Co., Ltd.;

实施例1Example 1

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-100 1份(重复单元摩尔数)1 part of SPIBI-100 (number of moles of repeating units)

八环氧基多面体低聚倍半硅氧烷（POSS） 0.025 份(占SPIBI-100的质量数)Octaepoxy polyhedral oligomeric silsesquioxane (POSS) 0.025 parts (accounting for the mass number of SPIBI-100)

二甲亚砜 160份(摩尔数)Dimethylsulfoxide 160 parts (moles)

（1）将0.6g SPIBI-100浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于13 mL二甲亚砜（DMSO）中，形成均匀溶液。(1) Add 0.6gSoak SPIBI-100 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 13 mL of dimethyl sulfoxide (DMSO) at 100 °C to form a homogeneous solution.

（2）将0.015g八环氧基取代的POSS常温溶解于1mLDMSO溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.015g octaepoxy-substituted POSS in 1mL DMSO solution at room temperature, and stir until a homogeneous solution. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

（3）将步骤（2）所得的混合液浇注在10 cm×10 cm的玻璃板上，于80 ℃真空烘箱中干燥6 h，溶剂完全挥发。升温至150 ℃继续加热10h，使交联反应进行完全。(3) The mixture obtained in step (2) was poured on a 10 cm×10 cm glass plate, and dried in a vacuum oven at 80 °C for 6 h, and the solvent was completely evaporated. Raise the temperature to 150 °C and continue heating for 10 h to complete the cross-linking reaction.

（4）将步骤（3）所得的薄膜放入60 ℃甲醇中浸泡6 h，除去膜中残留的DMSO溶剂。然后，常温将膜浸泡在1.0 mol/L盐酸中，进行48 h质子交换。将膜取出，用去离子水反复洗涤至中性，于150 ℃真空烘箱中干燥24 h，得到所需POSS交联型质子交换膜。(4) Soak the film obtained in step (3) in methanol at 60 °C for 6 h to remove the residual DMSO solvent in the film. Then, the membrane was soaked in 1.0 mol/L hydrochloric acid at room temperature for 48 h of proton exchange. The membrane was taken out, washed repeatedly with deionized water until neutral, and dried in a vacuum oven at 150 °C for 24 h to obtain the desired POSS cross-linked proton exchange membrane.

交联膜的力学性能测试：Mechanical property test of crosslinked film:

将交联型质子交换膜按照ASTM D882-02标准制成哑铃型薄膜试样，在DXLL-5000型双丝杆电子拉力机（上海德杰仪器设备有限公司）上测定交联膜的拉伸强度，拉伸速率为50mm/min。交联膜的力学性能如图1所示。The cross-linked proton exchange membrane was made into a dumbbell-shaped film sample according to the ASTM D882-02 standard, and the tensile strength of the cross-linked film was measured on a DXLL-5000 double-screw electronic tensile machine (Shanghai Dejie Instrument Equipment Co., Ltd.) , the stretching rate is 50mm/min. The mechanical properties of the crosslinked film are shown in Fig. 1.

实施例2Example 2

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-10 1份(重复单元摩尔数)1 part of SPIBI-10 (number of moles of repeating units)

八环氧基多面体低聚倍半硅氧烷（POSS） 0.15 份 (占SPIBI-10的质量数)0.15 parts of octaepoxy polyhedral oligomeric silsesquioxane (POSS) (accounting for the mass number of SPIBI-10)

二甲亚砜 400份(摩尔数)400 parts of dimethyl sulfoxide (number of moles)

（1）将0.6g SPIBI-100浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于30 mL二甲亚砜（DMSO）中，形成均匀溶液。(1) Add 0.6gSoak SPIBI-100 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 30 mL dimethyl sulfoxide (DMSO) at 100 °C to form a homogeneous solution.

（2）将0.015g八环氧基取代的POSS常温溶解于4mL DMSO溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.015g octaepoxy-substituted POSS in 4mL DMSO solution at room temperature, and stir until a homogeneous solution is obtained. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

（3）将步骤（2）所得的混合液浇注在10 cm×10 cm的玻璃板上，于80 ℃真空烘箱中干燥6 h，溶剂完全挥发。升温至150 ℃继续加热12h，使交联反应进行完全。(3) The mixture obtained in step (2) was poured on a 10 cm×10 cm glass plate, and dried in a vacuum oven at 80 °C for 6 h, and the solvent was completely evaporated. Raise the temperature to 150°C and continue heating for 12 hours to complete the crosslinking reaction.

（4）将步骤（3）所得的薄膜放入60 ℃甲醇中浸泡8 h，除去膜中残留的DMSO溶剂。然后，常温将膜浸泡在1.0 mol/L盐酸中，进行48 h质子交换。将膜取出，用去离子水反复洗涤至中性，于150 ℃真空烘箱中干燥24 h，得到所需POSS交联的质子交换膜。(4) Soak the film obtained in step (3) in methanol at 60 °C for 8 h to remove the residual DMSO solvent in the film. Then, the membrane was soaked in 1.0 mol/L hydrochloric acid at room temperature for 48 h of proton exchange. The membrane was taken out, washed repeatedly with deionized water until neutral, and dried in a vacuum oven at 150 °C for 24 h to obtain the desired POSS crosslinked proton exchange membrane.

实施例3Example 3

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-190 1份(重复单元摩尔数)1 part of SPIBI-190 (number of moles of repeating unit)

八环氧基多面体低聚倍半硅氧烷（POSS） 0.50份 (与SPIBI-190的质量比)Octaepoxy polyhedral oligomeric silsesquioxane (POSS) 0.50 parts (mass ratio to SPIBI-190)

N-甲基吡咯烷酮（NMP） 500份(摩尔数)N-Methylpyrrolidone (NMP) 500 parts (moles)

（1）将0.6g SPIBI-190浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于30 mL N-甲基吡咯烷酮（NMP）中，形成均匀溶液。(1) Add 0.6gSoak SPIBI-190 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolve in 30 mL of N-methylpyrrolidone (NMP) at 100 °C to form a homogeneous solution.

（2）将0.3g八环氧基取代的POSS常温溶解于10mL NMP溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.3g of octaepoxy-substituted POSS in 10mL of NMP solution at room temperature, and stir until a homogeneous solution is obtained. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

（3）将步骤（2）所得的混合液浇注在10 cm×10 cm的玻璃板上，于80 ℃真空烘箱中干燥6 h，溶剂完全挥发。升温至150 ℃继续加热8h，使交联反应进行完全。(3) The mixture obtained in step (2) was poured on a 10 cm×10 cm glass plate, and dried in a vacuum oven at 80 °C for 6 h, and the solvent was completely evaporated. Raise the temperature to 150°C and continue heating for 8 hours to complete the crosslinking reaction.

（4）将步骤（3）所得的薄膜放入60 ℃甲醇中浸泡10 h，除去膜中残留的NMP溶剂。然后，常温将膜浸泡在1.0 mol/L盐酸中，进行48 h质子交换。将膜取出，用去离子水反复洗涤至中性，于150 ℃真空烘箱中干燥24 h，得到所需POSS交联的质子交换膜。(4) Soak the film obtained in step (3) in methanol at 60 °C for 10 h to remove the residual NMP solvent in the film. Then, the membrane was soaked in 1.0 mol/L hydrochloric acid at room temperature for 48 h of proton exchange. The membrane was taken out, washed repeatedly with deionized water until neutral, and dried in a vacuum oven at 150 °C for 24 h to obtain the desired POSS crosslinked proton exchange membrane.

实施例4Example 4

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-20 1份(重复单元摩尔数)1 part of SPIBI-20 (number of moles of repeating units)

三环氧基多面体低聚倍半硅氧烷（POSS） 0.25份 (与SPIBI-20的质量比)Triepoxy polyhedral oligomeric silsesquioxane (POSS) 0.25 parts (mass ratio to SPIBI-20)

N,N-二甲基甲酰胺（DMF） 360份(摩尔数)N,N-Dimethylformamide (DMF) 360 parts (moles)

（1）将0.6g SPIBI-20浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于25 mL N,N-二甲基甲酰胺（DMF）中，形成均匀溶液。(1) Soak 0.6g SPIBI-20 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolve in 25 mL N,N-dimethylformamide (DMF) at 100 °C to form a homogeneous solution.

（2）将0.15g三环氧基取代POSS常温溶解于5mL DMF溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.15g triepoxide-substituted POSS in 5mL DMF solution at room temperature, and stir until a uniform solution is formed. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

（4）将步骤（3）所得的薄膜放入60 ℃甲醇中浸泡6 h，除去膜中残留的DMF溶剂。然后，常温将膜浸泡在1.0 mol/L盐酸中，进行48 h质子交换。将膜取出，用去离子水反复洗涤至中性，于150 ℃真空烘箱中干燥24 h，得到所需POSS交联的质子交换膜。(4) Soak the film obtained in step (3) in methanol at 60 °C for 6 h to remove the residual DMF solvent in the film. Then, the membrane was soaked in 1.0 mol/L hydrochloric acid at room temperature for 48 h of proton exchange. The membrane was taken out, washed repeatedly with deionized water until neutral, and dried in a vacuum oven at 150 °C for 24 h to obtain the desired POSS crosslinked proton exchange membrane.

实施例5Example 5

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-120 1份(重复单元摩尔数)1 part of SPIBI-120 (number of moles of repeating units)

三环氧基取代多面体低聚倍半硅氧烷（POSS） 0.5份 (与SPIBI-120的质量比)Triepoxide-substituted polyhedral oligomeric silsesquioxane (POSS) 0.5 parts (mass ratio to SPIBI-120)

二甲亚砜 500份(摩尔数)500 parts of dimethyl sulfoxide (moles)

（1）将0.6g SPIBI-120浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于30 mL二甲亚砜（DMSO）中，形成均匀溶液。(1) Soak 0.6g SPIBI-120 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 30 mL dimethyl sulfoxide (DMSO) at 100 °C to form a homogeneous solution.

（2）将0.3g三环氧基取代POSS常温溶解于10mL DMSO溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.3g triepoxide-substituted POSS in 10mL DMSO solution at room temperature, and stir until a uniform solution is obtained. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

实施例6Example 6

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-180 1份(重复单元摩尔数)1 part of SPIBI-180 (number of moles of repeating units)

三环氧基取代多面体低聚倍半硅氧烷（POSS） 0.025份 (与SPIBI-180的质量比)Triepoxide-substituted polyhedral oligomeric silsesquioxane (POSS) 0.025 parts (mass ratio to SPIBI-180)

二甲亚砜 400份(摩尔数)400 parts of dimethyl sulfoxide (number of moles)

（1）将0.6g SPIBI-180浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于13 mL二甲亚砜（DMSO）中，形成均匀溶液。(1) Soak 0.6g SPIBI-180 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 13 mL of dimethyl sulfoxide (DMSO) at 100 °C to form a homogeneous solution.

（2）将0.015g三环氧基取代POSS常温溶解于1mL DMSO溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.015g triepoxide-substituted POSS in 1mL DMSO solution at room temperature, and stir until a uniform solution is formed. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

实施例7Example 7

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-80 1份(重复单元摩尔数)1 part of SPIBI-80 (number of moles of repeating units)

八环氧基多面体低聚倍半硅氧烷（POSS） 0.30份 (与SPIBI-80的质量比)Octaepoxy polyhedral oligomeric silsesquioxane (POSS) 0.30 parts (mass ratio to SPIBI-80)

N,N-二甲基乙酰胺(DMAc) 500份(摩尔数)N,N-Dimethylacetamide (DMAc) 500 parts (moles)

（1）将0.6g SPIBI-80浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于30 mL N,N-二甲基乙酰胺(DMAc)中，形成均匀溶液。(1) Add 0.6gSoak SPIBI-80 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 30 mL N,N-dimethylacetamide (DMAc) at 100 °C to form a homogeneous solution.

（2）将0.18g八环氧基取代的POSS常温溶解于10mL DMAc溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.18g octaepoxy-substituted POSS in 10mL DMAc solution at room temperature, and stir until a homogeneous solution. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

（4）将步骤（3）所得的薄膜放入60 ℃甲醇中浸泡6 h，除去膜中残留的DMAc溶剂。然后，常温将膜浸泡在1.0 mol/L盐酸中，进行48 h质子交换。将膜取出，用去离子水反复洗涤至中性，于150 ℃真空烘箱中干燥24 h，得到所需POSS交联的质子交换膜。(4) Soak the film obtained in step (3) in methanol at 60 °C for 6 h to remove the residual DMAc solvent in the film. Then, the membrane was soaked in 1.0 mol/L hydrochloric acid at room temperature for 48 h of proton exchange. The membrane was taken out, washed repeatedly with deionized water until neutral, and dried in a vacuum oven at 150 °C for 24 h to obtain the desired POSS crosslinked proton exchange membrane.

实施例8Example 8

所用原料的配比如下：The ratio of raw materials used is as follows:

SPIBI-60 1份(重复单元摩尔数)1 part of SPIBI-60 (number of moles of repeating units)

三环氧基多面体低聚倍半硅氧烷（POSS） 0.40份 (与SPIBI-60的质量比)Triepoxy polyhedral oligomeric silsesquioxane (POSS) 0.40 parts (mass ratio to SPIBI-60)

间甲酚（m-cresol） 360份(摩尔数)m-cresol (m -cresol) 360 parts (moles)

（1）将0.6g SPIBI-60浸泡在饱和NaCl溶液中， 24小时后取出烘干。然后在100℃下溶解于25 mL间甲酚（m-cresol）中，形成均匀溶液。(1) Soak 0.6g SPIBI-60 in saturated NaCl solution, take it out and dry it after 24 hours. Then dissolved in 25 mL m-cresol (m -cresol) at 100 °C to form a homogeneous solution.

（2）将0.24g三环氧基取代POSS常温溶解于5mLm-cresol溶液中，搅拌至均匀溶液。室温下与（1）所形成的溶液混合均匀，过滤除气泡。(2) Dissolve 0.24g triepoxide-substituted POSS in 5mLm -cresol solution at room temperature, and stir until a homogeneous solution. Mix well with the solution formed in (1) at room temperature, and filter to remove air bubbles.

（4）将步骤（3）所得的薄膜放入60 ℃甲醇中浸泡12 h，除去膜中残留的m-cresol溶剂。然后，常温将膜浸泡在1.0 mol/L盐酸中，进行48 h质子交换。将膜取出，用去离子水反复洗涤至中性，于150 ℃真空烘箱中干燥24 h，得到所需POSS交联的质子交换膜。(4) Soak the film obtained in step (3) in methanol at 60 °C for 12 h to remove the residualm -cresol solvent in the film. Then, the membrane was soaked in 1.0 mol/L hydrochloric acid at room temperature for 48 h of proton exchange. The membrane was taken out, washed repeatedly with deionized water until neutral, and dried in a vacuum oven at 150 °C for 24 h to obtain the desired POSS crosslinked proton exchange membrane.

上述实施例中，各组份原料和用量以及制备过程的参数，仅是为了描述发明而选取的代表。实际上大量的实验表明，在发明内容部分所限定的范围内，均能获得上述实施例相类似的POSS交联型磺化聚酰亚胺质子交换膜。In the foregoing embodiments, the raw materials and amounts of each component and the parameters of the preparation process are only selected representatives for describing the invention. In fact, a large number of experiments have shown that within the scope defined in the summary of the invention, POSS cross-linked sulfonated polyimide proton exchange membranes similar to those of the above examples can be obtained.

Claims

1. a POSS crosslinked sulfonated polyimide proton exchange membrane, it is characterized in that this cross linking membrane is to introduce benzimidazolyl on polyimide main polymer chain, and in film forming procedure, utilize active N-H structure and polyhedral oligomeric silsesquioxane POSS crosslinking agent on imidazole radicals to react and crosslinked obtaining, its raw material forms and comprises:

1 part of sulfonated polyimide (molal quantity)

Polyhedral oligomeric silsesquioxane crosslinking agent 0.025-0.5 part (accounting for the mass ratio of sulfonated polyimide)

Organic solvent 160-500 part (molal quantity);

Wherein, described sulfonated polyimide is that main chain contains benzimidazole based structures.

2. POSS crosslinked sulfonated polyimide proton exchange membrane according to claim 1, the sulfonation degree that it is characterized in that described sulfonated polyimide any one value from 10%-190%.

3. POSS crosslinked sulfonated polyimide proton exchange membrane according to claim 1, it is characterized in that POSS crosslinking agent be the polyhedral oligomeric silsesquioxane that replaces of octa-epoxy, in the polyhedral oligomeric silsesquioxane that three epoxy radicals replace any, but be not limited only to this.

4. POSS crosslinked sulfonated polyimide proton exchange membrane according to claim 1, it is characterized in that described organic solvent is N, the mixed liquor of any one or two kinds in dinethylformamide, DMA, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE.

5. a preparation method for POSS crosslinked sulfonated polyimide proton exchange membrane as claimed in claim 1, is characterized in that concrete steps are as follows:

(1) sulfonated polyimide is immersed in saturated NaCl solution, after 24h, takes out and dry; At 100 ℃, be dissolved in organic solvent wiring solution-forming; Wherein in every 50mL organic solvent, the addition of sulfonated polyimide is 0.5-2.5g;

(2) by polyhedral oligomeric silsesquioxane crosslinking agent, normal-temperature dissolution is in organic solvent; Wherein in every 1mL organic solvent, the addition of polyhedral oligomeric silsesquioxane is 0.05-0.1g;

(3) under room temperature, the solution of step (1) and step (2) gained is mixed, after stirring, filter bubble removing; Wherein: the mass ratio of sulfonated polyimide and polyhedral oligomeric silsesquioxane crosslinking agent is 2:1～40:1;

(4) film liquid step (3) being obtained is cast on the glass plate of 10 cm * 10 cm, dry 4-6 h in 60-90 ℃ of vacuum drying oven, and solvent volatilizees completely; Be warming up to 150-180 ℃ and continue heating 6-10h; Obtain sodium-salt type POSS crosslinked sulfonated polyimide proton exchange membrane;

(5) the quality proton exchange of step (4) gained is soaked to 6-12 h in the methyl alcohol of 50-60 ℃, remove organic solvent residual in proton exchange membrane; Deionized water is immersed in film in 1.0 mol/L hydrochloric acid and takes out after 48 h under normal temperature after cleaning, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain required product.