CN111530511A - 一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜及其制备方法 - Google Patents
一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜及其制备方法 Download PDFInfo
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Abstract
本发明属于离子交换膜材料领域,具体涉及一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜及其制备方法。本发明先通过叔胺化双酚芴、双酚芴和十氟联苯的缩聚反应合成含氟聚芳醚化合物,再加入十溴丙基柱[5]芳烃作为交联剂,浇铸成膜。接着,将所得膜浸泡在碘甲烷水溶液中进行季胺化,即得柱[5]芳烃交联含氟聚芳醚阴离子交换膜。通过改变交联剂十溴丙基柱[5]芳烃的投料量,可得不同交联程度和微观结构的阴离子交换膜。本发明所涉及的合成工艺简单,制得的阴离子交换膜交联度高,且具有较高的阴离子传导率、良好的尺寸稳定性、机械性能和热稳定性。
Description
技术领域
本发明涉及一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜及其制备方法,属于离子交换膜材料领域。
背景技术
阴离子交换膜是一种功能性的高分子电解质膜,它由聚合物骨架、连接在聚合物骨架上的阳离子基团和可移动的阴离子三部分组成。聚合物骨架决定阴离子交换膜的机械性能、热稳定性和尺寸稳定性;阳离子基团决定阴离子交换膜的离子交换和传导功能;阴离子可被交换和传导。
理想的阴离子交换膜应该具有优异的机械稳定性、热稳定性、尺寸稳定性和高离子传导率等特点;为了提高阴离子交换膜的阴离子传导率,最为直接的方法就是通过提高膜的离子交换容量来实现。但随之而来的问题是,离子交换容量过大会造成阴离子交换膜的溶胀率和吸水率的增大,破坏膜的内部结构,进而导致膜的机械性能下降。因此,阴离子传导率和机械性能的平衡是阴离子交换膜在实际应用中需要解决的问题。
在阴离子交换膜中构筑交联结构是平衡机械性能和阴离子传导率最直接有效的方法。交联可使聚合物内部形成网状结构从而抑制膜的溶胀率和吸水率,提高膜的化学稳定性和机械性能。因此,提出交联改性的方法提升膜的性能,对于高性能阴离子交换膜的开发具有重要意义。但是,目前交联方法仍存在如下的问题:1.交联剂具有刺激性、毒性、诱变性能。2.交联工艺复杂,反应速度慢。需要受催化剂、高温和光化学等特定条件的引发才能发生交联,交联过程发生副反应或产生有毒有害物质。3.交联结构在高温下不稳定。4.交联结构严重降低了阴离子传导率。
针对以上问题,本发明选用高机械强度和化学稳定性的聚芳醚化合物作为主链,选用具有密集多官能团的十溴丙基柱[5]芳烃作为交联剂,采用卤烷烃基与胺基聚合物前驱体发生亲核取代反应而交联;此交联方法操作简便,且能明显提升膜材料的力学性能,是阴离子交换膜领域最常采用的交联策略;整个制备过程不需要设计特殊的官能团来交联,反应简单易行,用时短,无副反应,在室温下便可交联,操作简单,是一种不需要通过卤甲基化步骤制备高性能阴离子交换膜的绿色路线,可以卤甲基化试剂毒性较大的问题;由十溴丙基柱[5]芳烃作为交联剂,在极低投料比的条件下,其有效地限制了聚合物链的活动性,有效抑制的吸水率、保持良好的尺寸稳定性、机械性能和化学稳定性等,制备了综合性能优异的阴离子交换膜。
发明内容
本发明的目的是为了克服现有技术的不足,提供一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜。该阴离子交换膜具有制备工艺简单、离子传导率高、机械性能好和化学稳定性好等优点,在阴离子交换膜材料领域拥有巨大的发展前景。
为实现上述目的,本发明采用如下技术方案是:
一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜,该膜是以基于叔胺化双酚芴、双酚芴和十氟联苯缩聚反应合成的含氟聚芳醚化合物为前驱体,以十溴丙基柱[5]芳烃为交联剂,将含氟聚芳醚化合物上的部分胺基与十溴丙基柱[5]芳烃上的溴丙基进行反应而交联并同时生成季铵盐阳离子基团,将含氟聚芳醚化合物上的剩余胺基与碘甲烷反应引入季铵盐阳离子基团,制得柱[5]芳烃交联含氟聚芳醚阴离子交换膜。
本发明的另一目的在于提供一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜的制备方法,具体包括以下步骤:
(1)将叔胺化双酚芴、双酚芴、十氟联苯溶于极性非质子溶剂中,制得1520wt%的溶液,加入氟化铯作为催化剂、加入氢化钙作为除水剂;在惰性气体的保护下,室温进行聚合反应12~36h;反应结束后将产物缓慢倒入去离子水中析出沉淀,过滤收集沉淀并在60℃的真空烘箱中干燥12-36h;将所得固体溶解于二氯甲烷中制成1 10wt.%的溶液,再缓慢倒入甲醇中析出沉淀,其中甲醇的体积为二氯甲烷体积的5-50倍;过滤收集沉淀,在60-80℃的真空烘箱中干燥12-36h,得到含氟聚芳醚化合物;
上述叔胺化双酚芴参考文献(Journal of Polymer Science Part A PolymerChemistry,2016,54(7):935-944)合成,其化学结构式如下所示:
上述聚合过程的反应式如下所示:
式中m为1~400,n为10~400。
(2)在室温下,将十溴丙基柱[5]芳烃溶于极性非质子溶剂中,充分搅拌使十溴丙基柱[5]芳烃完全溶解,制得1~10wt%十溴丙基柱[5]芳烃溶液;所用十溴丙基柱[5]芳烃的摩尔量为步骤(1)中得到的含氟聚芳醚化合物中所含胺基摩尔量的0.005~0.05倍。
上述十溴丙基柱[5]芳烃参考文献(Journal of the American ChemicalSociety,2016,138(3):754-757)合成,其化学结构式如下所示:
(3)在室温下,将步骤(1)得到的含氟聚芳醚化合物溶于极性非质子溶剂中,制得1~10wt%的含氟聚芳醚溶液,然后加入步骤(2)中制备的十溴丙基柱[5]芳烃溶液,在室温下搅拌1h,使含氟聚芳醚化合物与十溴丙基柱[5]芳烃发生交联反应,得到铸膜液。接着,将铸膜液浇铸在水平放置的玻璃板上,于60~100℃的普通烘箱中干燥12~36h,即在玻璃板表面得到一层致密膜,膜厚度为30-300微米;待玻璃板冷却至室温,将膜从玻璃板表面揭下。
(4)在室温下,将步骤(3)得到的致密膜浸泡于0.05~0.5M的碘甲烷水溶液中,避光密封并搅拌3~7d,进行季铵化反应,然后将膜取出,浸在去离子水A中在60℃下浸泡12~36h,洗去多余碘甲烷;最后,将膜浸泡于1MNaCl水溶液中,在60℃下浸泡12~36h,进行离子交换反应,再用去离子水B浸泡,洗去多余NaCl,得到柱[5]芳烃交联含氟聚芳醚阴离子交换膜。上述去离子水A的体积与膜的质量之比为100-1000:1(mL/g);所述去离子水B的体积与膜的质量之比为100-1000:1(mL/g);1M NaCl水溶液的体积与膜的质量之比为100-1000:1(mL/g)。
上述柱[5]芳烃交联含氟聚芳醚阴离子交换膜的结构示意图如下:
步骤(1)所述叔胺化双酚芴、双酚芴、十氟联苯、氟化铯、氢化钙的摩尔比为x:1-x:1:3~6:0.01~1,其中0<x<1;所述极性非质子溶剂与十氟联苯的质量之比为5~50:1;所述去离子水与极性非质子溶剂的体积比为100~1000:1。
以上所述步骤中的极性非质子溶剂为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲基亚砜中的任意一种。
步骤(4)中所述碘甲烷的摩尔量是含氟聚芳醚化合物中胺基摩尔量的1~10倍。
本发明的柱[5]芳烃交联含氟聚芳醚阴离子交换膜,以十溴丙基柱[5]芳烃为交联剂,直接与含氟聚芳醚化合物上的胺基进行亲核取代反应而交联,并同时季铵化。成膜后剩余胺基与卤烷基通过甲基化反应实现季胺化,制得柱[5]芳烃交联含氟聚芳醚阴离子交换膜,该膜材料表现出优良的稳定性。
本发明与现有技术相比,具有如下有益效果:
(1)采用十溴丙基柱[5]芳烃作为交联剂,在低投料比的条件下,即可有效地限制了聚合物链的活动性,交联效率高。
(2)采用十溴丙基柱[5]芳烃作为交联剂,交联点高度集中,非交联链段较长,所得交联产物的结构与传统的交联剂所得的结构不同。这种特殊结构有利于优化交联度与膜性能之间的关系。
(3)利用卤烷基与胺基聚合物前驱体反应而交联,不需要设计特殊的官能团进行交联,反应简单易行,用时短,无副反应,在室温下便可交联,操作简单。
(4)通过改变交联剂投料比可以控制交联程度,所制备的交联膜具有阴离子传导率高、尺寸稳定性高、机械性能和热稳定性高等优点,综合性能优异。
附图说明
图1是实施例1中含氟聚芳醚化合物FPAE60的核磁共振氢谱;
图2是实施例2中含氟聚芳醚化合物FPAE80的核磁共振氢谱;
图3是实施例6中柱[5]芳烃交联含氟聚芳醚阴离子交换膜的红外光谱图;
图4是柱[5]芳烃交联含氟聚芳醚阴离子交换膜的热重分析图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1含氟聚芳醚化合物FPAE60的制备
将1.3500g(4mmol)十氟联苯、0.5607g(1.6mmol)双酚芴和1.1151g(2.4mmol)叔胺化双酚芴单体以及14mLN-甲基吡咯烷酮加入到三口烧瓶中,完全溶解后,再加入0.05g氢化钙、3.00g氟化铯,在氩气的保护下于室温反应20h,将产物倒入1L去离子水中析出沉淀;过滤收集沉淀并在60℃的真空烘箱中干燥12-36h;溶解于30ml二氯甲烷中,再在500ml甲醇中析出沉淀,反复洗涤三次,在60℃真空烘箱干燥24h,即得到含氟聚芳醚化合物FPAE60,产率为86%。
实施例2含氟聚芳醚化合物FPAE80的制备
将实施例1中双酚芴的投料量改为0.2803g(0.8mmol),叔胺化双酚芴单体投料量改为1.4868g(3.2mmol),其余操作按实施例1,即得到含氟聚芳醚化合物FPAE80,产率为88%。
实施例3柱[5]芳烃交联含氟聚芳醚阴离子交换膜QAFPAE60-P5Br-5%的制备
准确称取0.5g实施例1中所得的含氟聚芳醚化合物FPAE60于10mL的N,N-二甲基乙酰胺中,在室温下搅拌至完全溶解,得到澄清透明溶液。同时准确称取0.07646g十溴丙基柱[5]芳烃(P5Br)于1ml N,N-二甲基乙酰胺中搅拌至完全溶解,得到澄清透明溶液。含氟聚芳醚化合物(FPAE60)所含胺基和十溴丙基柱[5]芳烃(P5Br)的摩尔比为20:1。将上述两种溶液于室温下均匀混合并搅拌1h,使其发生交联反应并同时季铵化,然后过滤并浇铸到干净的玻璃平板上,置于80℃烘箱中干燥20h,待玻璃板冷却至室温后,浸泡在去离子水中至膜从玻璃板上脱落。在室温下,将致密膜浸泡于0.5M的碘甲烷水溶液中,避光密封并搅拌3d,再浸泡于去离子水中24h,随后在60℃下浸泡于1mol/L的NaCl溶液中24h,然后用去离子水反复清洗、浸泡24h至中性,即得到柱[5]芳烃交联含氟聚芳醚阴离子交换膜,记为QAFPAE60-P5Br-5%膜。
实施例4柱[5]芳烃交联含氟聚芳醚阴离子交换膜QAFPAE60-P5Br-2.5%的制备
与实施例3中QAFPAE60-P5Br-5%的制备方法相似,不同之处在于制膜过程中所称取的十溴丙基柱[5]芳烃(P5Br)的质量为0.0382g,含氟聚芳醚化合物(FPAE60)所含胺基和十溴丙基柱[5]芳烃(P5Br)的摩尔比为40:1,记为QAFPAE60-P5Br-2.5%膜。
实施例5柱[5]芳烃交联含氟聚芳醚阴离子交换膜QAFPAE80-P5Br-5%的制备
与实施例3中QAFPAE60-P5Br-5%的制备方法相似,不同之处在于制膜过程中称取的含氟聚芳醚化合物为实施例2中所得的含氟聚芳醚化合物FPAE80,所称取的十溴丙基柱[5]芳烃(P5Br)的质量为0.0990g,含氟聚芳醚化合物(FPAE80)所含胺基和十溴丙基柱[5]芳烃(P5Br)的摩尔比为20:1,记为QAFPAE80-P5Br-5%膜。
实施例6柱[5]芳烃交联含氟聚芳醚阴离子交换膜QAFPAE80-P5Br-2.5%的制备
与实施例5中QAFPAE80-P5Br-2.5%的制备方法相似,不同之处在于制膜过程中所称取的十溴丙基柱[5]芳烃(P5Br)的质量为0.0495g,含氟聚芳醚化合物(FPAE80)所含胺基和十溴丙基柱[5]芳烃(P5Br)的摩尔比为40:1,记为QAFPAE80-P5Br-2.5%膜。
测定凝胶分数:凝胶分数是反映交联反应程度的典型手段。将测试膜在室温下的N,N-二甲基乙酰胺中浸泡24h。通过浸入N,N-二甲基乙酰胺之前和之后膜的重量变化来确定凝胶分数。
吸水率:通过测试膜在室温下的去离子水中浸泡24h后与干膜的重量变化进行测定。
溶胀率:通过测试膜在室温下的去离子水中浸泡24h后与干膜的长度变化进行测定。
离子传导率:在室温下测试膜在水中的阴离子传导率采用交流阻抗分析仪进行测定。
机械性能:由万能拉伸机测试拉伸强度和断裂伸长率。
表1是柱[5]芳烃交联含氟聚芳醚阴离子交换膜在室温下的凝胶分数、离子传导率、吸水率、溶胀率和机械性能
从表1可以看出,所制备的柱[5]芳烃交联含氟聚芳醚阴离子交换膜具有凝胶率高、阴离子传导率高、尺寸稳定性高、机械性能等优点。从图4可以看出,所制备的柱[5]芳烃交联含氟聚芳醚阴离子交换膜的起始热分解温度都在200摄氏度以上,具有热稳定性高的优点。以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (10)
1.一种柱[5]芳烃交联含氟聚芳醚阴离子交换膜,其特征在于,所述的阴离子交换膜以基于叔胺化双酚芴、双酚芴和十氟联苯缩聚反应合成的含氟聚芳醚化合物为前驱体,以十溴丙基柱[5]芳烃为交联剂,将含氟聚芳醚化合物上的部分胺基与十溴丙基柱[5]芳烃上的溴丙基进行反应而交联并同时生成季铵盐阳离子基团,将含氟聚芳醚化合物上的剩余胺基与碘甲烷反应引入季铵盐阳离子基团,制得柱[5]芳烃交联含氟聚芳醚阴离子交换膜。
2.一种如权利要求1所述的柱[5]芳烃交联含氟聚芳醚阴离子交换膜的制备方法,其特征在于,具体包括以下步骤:
(1)将叔胺化双酚芴、双酚芴、十氟联苯溶于极性非质子溶剂中,制成15-20 wt.%的溶液,加入氟化铯作为催化剂、加入氢化钙作为除水剂,在惰性气体的保护下,室温进行聚合反应12-36 h;反应结束后将产物缓慢倒入去离子水中析出沉淀,过滤收集沉淀并在60℃的真空烘箱中干燥12-36h;将所得固体溶解于二氯甲烷中制成1-10 wt.%的溶液,再缓慢倒入甲醇中析出沉淀,其中甲醇的体积为二氯甲烷体积的5-50倍;过滤收集沉淀,在60-80℃的真空烘箱中干燥12-36h,得到含氟聚芳醚化合物;
上述叔胺化双酚芴的化学结构如下:
上述含氟聚芳醚化合物的化学结构式如下:
式中m为1-400,n为10-400。
(2)在室温下,将十溴丙基柱[5]芳烃溶于极性非质子溶剂中,充分搅拌使十溴丙基柱[5]芳烃完全溶解,制得1-10wt.%十溴丙基柱[5]芳烃溶液;
上述十溴丙基柱[5]芳烃的化学结构式如下:
(3)在室温下,将步骤(1)得到的含氟聚芳醚化合物溶于极性非质子溶剂中,制得1-10wt.%的含氟聚芳醚溶液,然后加入步骤(2)中制备的十溴丙基柱[5]芳烃溶液,搅拌使含氟聚芳醚化合物与十溴丙基柱[5]芳烃发生交联反应,得到铸膜液;接着,将铸膜液浇铸在水平放置的玻璃板上,于60~100℃的普通烘箱中干燥12~36 h,即在玻璃板表面得到一层致密膜;待玻璃板冷却至室温,将膜从玻璃板表面揭下;
(4)在室温下,将步骤(3)得到的致密膜浸泡于0.05-0.5 M的碘甲烷水溶液中,避光密封并搅拌3~7 d,进行季铵化反应,然后将膜取出,浸在去离子水A中洗去多余碘甲烷;最后,将膜在于1M NaCl水溶液中浸泡,进行离子交换反应,再用去离子水B浸泡,洗去多余NaCl,得到柱[5]芳烃交联含氟聚芳醚阴离子交换膜。
3.根据权利要求2所述的制备方法,其特征在于,步骤(1)所述叔胺化双酚芴、双酚芴、十氟联苯、氟化铯、氢化钙的摩尔比为x : 1-x : 1 : 3~6 : 0.01~1,其中0 < x < 1;所述极性非质子溶剂与十氟联苯的质量之比为5~50 : 1;所述去离子水与极性非质子溶剂的体积比为100~1000 : 1。
4.根据权利要求2所述的制备方法,其特征在于,步骤(2)所述所用十溴丙基柱[5]芳烃的摩尔量为步骤(1)中得到的含氟聚芳醚化合物中所含胺基摩尔量的0.005~0.05倍。
5.根据权利要求2所述的制备方法,其特征在于,步骤(3)所述搅拌具体为在室温下搅拌0.5~2 h。
6.根据权利要求2所述的制备方法,其特征在于,步骤(3)所述致密膜的厚度为30-300μm。
7.根据权利要求2所述的制备方法,其特征在于,所述极性非质子溶剂为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲基亚砜中的任意一种。
8.根据权利要求2所述的制备方法,其特征在于,步骤(4)所述浸在去离子水A中洗去多余碘甲烷的条件为:在60℃下浸泡12~36 h;所述浸泡于1M NaCl水溶液中浸泡具体为在60℃下浸泡12~36h。
9.根据权利要求2所述的制备方法,其特征在于,步骤(4)中所述碘甲烷的摩尔量是含氟聚芳醚化合物中胺基摩尔量的1~10倍。
10.根据权利要求2所述的制备方法,其特征在于,步骤(4)中所述去离子水A的体积与膜的质量之比为100-1000:1(mL/g);所述去离子水B的体积与膜的质量之比为100-1000:1(mL/g);1M NaCl水溶液的体积与膜的质量之比为100-1000:1(mL/g)。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112473396A (zh) * | 2020-11-27 | 2021-03-12 | 西安建筑科技大学 | 一种扩散渗析酸回收用阴离子交换膜材料及其制备方法 |
CN114133555A (zh) * | 2021-12-09 | 2022-03-04 | 福州大学 | 一种交联型含氟聚芴醚阴离子交换膜的制备方法 |
CN114230831A (zh) * | 2022-01-13 | 2022-03-25 | 福州大学 | 一种高氧化稳定性和高离子传导率的交联型阴离子交换膜的制备方法 |
CN115322364A (zh) * | 2022-09-23 | 2022-11-11 | 福州大学 | 一种超低介电常数柱[5]芳烃型含氟聚芳醚化合物及其制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108659215A (zh) * | 2018-06-05 | 2018-10-16 | 福州大学 | 一种含有柱[5]芳烃的含氟聚芳醚化合物及其制备方法 |
CN110372902A (zh) * | 2019-07-25 | 2019-10-25 | 福州大学 | 一种侧链双季铵盐离子型含氟聚芴醚阴离子交换膜 |
-
2020
- 2020-06-18 CN CN202010562446.9A patent/CN111530511A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108659215A (zh) * | 2018-06-05 | 2018-10-16 | 福州大学 | 一种含有柱[5]芳烃的含氟聚芳醚化合物及其制备方法 |
CN110372902A (zh) * | 2019-07-25 | 2019-10-25 | 福州大学 | 一种侧链双季铵盐离子型含氟聚芴醚阴离子交换膜 |
Non-Patent Citations (2)
Title |
---|
JINWU PENG,ET AL.: "Fabrication of Cross-Linked Anion Exchange Membranes Using a Pillar[5]arene Bearing Multiple Alkyl Bromide Head Groups as Cross-Linker", 《MACROMOL. MATER. ENG.》 * |
陈栋阳等: "全钒液流电池离子交换膜的研究进展", 《高分子材料科学与工程》 * |
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