CN112512668A - 用于阴离子交换膜的芳香族聚合物的交联 - Google Patents
用于阴离子交换膜的芳香族聚合物的交联 Download PDFInfo
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Abstract
一种离子交换膜材料由交联的聚合物网络组成,所述交联的聚合物网络包括第一聚(苯乙烯‑b‑乙烯‑r‑丁烯‑b‑苯乙烯)三嵌段共聚物(SEBS)、第二SEBS和交联所述第一SEBS和所述SEBS的连接剂。所述第一SEBS和所述第二SEBS的至少一个苯基被烷基官能化,并且在这些烷基的苄基位置的碳被至少两个另外的烷基饱和。所述连接剂是结合到所述烷基官能团的二胺。所述离子交换膜材料通过基本上同时的季铵化和二胺连接剂与被烷基卤基团官能化的SEBS间的交联反应来制备。增加交联剂的浓度将产生具有降低的水吸收的膜,导致在水合条件下提高的稳定性和更大的耐久性的预期。有利地,这种水吸收的减少几乎没有改变离子交换能力。
Description
相关申请的交叉引用
本申请要求2018年4月24日提交的美国临时申请号62/661,705的利益,该申请通过引用并入本文,如同其全部内容在本文中公开。
关于联邦资助研发的声明
本发明是在政府支持下完成的,能源部授予合同号DE-AR0000769。政府拥有本发明的某些权利。
背景技术
也称为阴离子交换膜的碱性交换膜(AEM)允许在电化学反应中阴离子如OH-、Cl-、Br-等从阴极传输到阳极。AEM是在其中氢气和氧气被用于产生电和水副产物的AEM燃料电池的组成部分。AEM还被用于水电解中,在此过程中水借助电力分解为氢气和氧气,这是最清洁、最理想的制氢过程。在AEM燃料电池和水电解中,氢氧离子(OH-)在水分子的帮助下通过膜传输。AEM使用的其他领域包括电池、传感器和致动器(由于离子的迁移,塑料膜可逆地摆动)。
在近几年中,几个研究小组开发了新的AEM材料。然而,这些材料往往不利地在高碱性下容易降解。目前,大多数阴离子AEM是由沿侧链含有季铵基团的聚合物制备的。不幸的是,这些离子性侧基与水强烈地相互作用,这起到增塑剂的作用并在水合时引起聚合物的软化和溶胀。
发明概述
本公开的一些实施方案涉及由交联的聚合物网络组成的离子交换膜材料,所述交联的聚合物网络包括第一聚(苯乙烯-b-乙烯-r-丁烯-b-苯乙烯)三嵌段共聚物(SEBS),其中所述第一SEBS的至少一个苯基被第一烷基官能化,并且在所述第一烷基的苄基位置的碳被至少两个另外的烷基饱和;第二聚(苯乙烯-b-乙烯-r-丁烯-b-苯乙烯)三嵌段共聚物(SEBS),其中所述第二SEBS的至少一个苯基被第二烷基官能化,并且在所述第二烷基的苄基位置的碳被至少两个另外的烷基饱和;和结合到所述第一烷基和所述第二烷基的二胺连接剂。在一些实施方案中,所述第一SEBS的至少一个苯基被未交联的烷基官能化,在该未交联的烷基的苄基位置的碳被至少两个另外的烷基饱和,并且该未交联的烷基包括季铵基团。在一些实施方案中,所述第二SEBS的至少一个苯基被未交联的烷基官能化,在该未交联的烷基的苄基位置的碳被至少两个另外的烷基饱和,并且该未交联的烷基包括季铵基团。在一些实施方案中,在所述交联的聚合物网络中二胺连接剂的浓度大于约5mol%。在一些实施方案中,在所述交联的聚合物网络中二胺连接剂的浓度大于约30mol%。在一些实施方案中,在所述交联的聚合物网络中二胺连接剂的浓度为约50mol%。在一些实施方案中,所述二胺连接剂是N,N,N,N′-四甲基-1,6-己二胺。
本公开的一些实施方案涉及制备离子交换膜的方法,该方法包括:用一种或多种烷基卤基团官能化芳族嵌段共聚物,在所述一种或多种烷基卤基团的苄基位置的碳被至少两个另外的烷基饱和;将所述官能化的芳族嵌段共聚物与二胺混合,以用季铵基团替代一个或多个卤素基团;和通过所述二胺将所述官能化的芳族嵌段共聚物与另一官能化的芳族嵌段共聚物交联,以产生交联的聚合物。在一些实施方案中,所述连接剂是二胺连接剂,多元醇,多芳族化合物,烯烃二聚体,二硫醇或它们的组合。在一些实施方案中,所述二胺具有两个叔胺基团。在一些实施方案中,所述方法包括将三烷基胺添加到所述交联的聚合物中,以将未反应的烷基卤基团转化为季铵基团。在一些实施方案中,所述芳族嵌段共聚物是联苯聚合物。
附图的简要说明
附图显示了为了说明本发明的目的的、所公开的主题的实施方案。但是,应该理解,本申请不限于附图中所显示的精确布置和手段,其中:
图1是根据本公开的一些实施方案的用于制造离子交换膜的离子交换材料的示意图;
图2是根据本公开的一些实施方案的用于制造离子交换膜的方法的图表;
图3是显示根据本公开的一些实施方案的离子交换材料中吸水率随着交联剂的增加而减少的表;
图4是根据本公开的一些实施方案的用于制造离子交换膜的方法的图表;
图5是根据本公开的一些实施方案的用于制造离子交换膜的方法的图表;
图6是根据本公开的一些实施方案的用于制造离子交换膜的方法的图表;
图7是根据本公开的一些实施方案的用于制造离子交换膜的方法的图表;
图8是根据本公开的一些实施方案的用于制造离子交换膜的方法的图表;
图9是根据本公开的一些实施方案的用于制造离子交换膜的方法的图表。
详细说明
现在参考图1,所公开的主题的一些方面包括离子交换材料100。在一些实施方案中,所述离子交换材料适合用作用于例如燃料电池、水水解系统、电化学氢压缩机、电池、传感器、致动器等的离子交换膜。在一些实施方案中,所述离子交换膜是阴离子交换膜。
在一些实施方案中,离子交换材料100包括交联的聚合物网络102。在一些实施方案中,交联的网络102包括一个或多个聚合物链104和连接所述一个或多个聚合物链104的一个或多个连接剂106。在一些实施方案中,聚合物链104是聚芳族聚合物、共聚物、嵌段共聚物或它们的组合。在一些实施方案中,聚合物链104被一个或多个官能团官能化。
在一些实施方案中,聚合物链104中的一个或多个是聚(苯乙烯-b-乙烯-r-丁烯-b-苯乙烯)三嵌段共聚物(SEBS)。在一些实施方案中,聚合物链104如SEBS的至少一个苯基被至少一个烷基官能化。在一些实施方案中,在所述至少一个烷基的苄基位置的碳被至少两个另外的碳、烷基等饱和。在一些实施方案中,所述至少一个烷基在经由一个或多个连接剂106交联到另一聚合物链104上之前是卤代烷基,这将在下面更详细地讨论。在一些实施方案中,连接剂106通过聚合物链上的烷基官能团之间的结合使聚合物链104交联。在一些实施方案中,连接剂106是二胺。在一些实施方案中,所述二胺包括至少两个叔胺基团,在它们之间具有烷基。在一些实施方案中,所述连接剂是N,N,N′,N′-四甲基-1,6-己二胺。在一些实施方案中,交联的网络102的至少一个苯基被未交联的烷基官能化,在所述未交联的烷基的苄基位置的碳被至少两个另外的烷基饱和,该未交联的烷基包括季铵基团。
在一些实施方案中,所述交联的聚合物网络中连接剂的浓度大于烷基官能团的约5mol%。在一些实施方案中,所述交联的聚合物网络中连接剂的浓度大于烷基官能团的约30mol%。在一些实施方案中,所述交联的聚合物网络中连接剂的浓度为烷基官能团的约50mol%。在一些实施方案中,在交联的聚合物网络中连接剂的浓度大于烷基官能团的约50mol%。
举例来说,并且仍然参考图1,交联的聚合物网络102包括第一SEBS链104,其中所述第一SEBS的至少一个苯基被第一烷基官能化,并且在所述第一烷基的苄基位置的碳被至少两个另外的烷基饱和。第一SEBS链104与第二SEBS链104'交联,其中所述第二SEBS的至少一个苯基被第二烷基官能化,并且在所述第二烷基的苄基位置的碳被至少两个另外的烷基饱和。二胺连接剂106与第一烷基和第二烷基键合,得到式I的结构:
其中R1包括H或CH3并且R2包括CH3。
现在参考图2,本公开的一些实施方案涉及用于制造离子交换膜的方法,例如反应路径。在202,用一种或多种烷基卤基团官能化芳族嵌段共聚物如SEBS。在一些实施方案中,在所述一种或多种烷基卤基团的苄基位置的碳被至少两个另外的烷基饱和。在204,将所述官能化的芳族嵌段共聚物与连接剂混合以用季铵基团替代一个或多个卤素基团,并通过所述连接剂将所述官能化的芳族嵌段共聚物与另一官能化的芳族嵌段共聚物交联以形成交联的聚合物网络。在206,通过添加三烷基胺将未反应的烷基卤基团转化为季铵基团。参考图3,连接剂的浓度(mol%)越高,网络以及膜的吸水率越低。
再次参考图1,在一些实施方案中,一个或多个聚合物链104是联苯嵌段聚合物。在一些实施方案中,所述联苯嵌段聚合物被一个或多个烷基官能化。在一些实施方案中,连接剂106通过链上烷基官能团间的结合使所述联苯嵌段聚合物交联。在一些实施方案中,所述连接剂是二胺连接剂,多元醇,多芳族化合物,烯烃二聚体,二硫醇或它们的组合,如将在下面更详细地讨论的。在一些实施方案中,连接剂在所述交联的联苯嵌段聚合物网络中的浓度大于烷基官能团的约5mol%。在一些实施方案中,连接剂在所述交联的联苯嵌段聚合物网络中的浓度大于烷基官能团的约30mol%。在一些实施方案中,连接剂在所述交联的联苯嵌段聚合物网络中的浓度为烷基官能团的约50mol%。在一些实施方案中,连接剂在所述交联的联苯嵌段聚合物网络中的浓度大于烷基官能团的约50mol%。在一些实施方案中,至少一个烷基官能团是未交联的并且包括季铵基团。
现在参考图4,在一些实施方案中,一种或多种联苯嵌段聚合物被烷基卤基团官能化。在一些实施方案中,将所述一种或多种联苯嵌段聚合物与连接剂例如二胺混合如浇铸,进行基本上同时的季铵化和交联反应并交联至其他联苯嵌段聚合物。在一些实施方案中,通过添加三烷基胺将未反应的烷基卤基团转化为季铵基团。
现在参考图5,在一些实施方案中,一种或多种联苯嵌段聚合物被烷基卤基团官能化。在一些实施方案中,将三烷基胺和二烷基胺的混合物添加到所述联苯嵌段聚合物中,以将烷基卤基团中的卤素转化为季铵和叔胺基团的混合物。在一些实施方案中,将所述一种或多种联苯嵌段聚合物与连接剂例如二胺混合如浇铸,在所述叔胺基团上进行基本上同时的季铵化和交联反应。
现在参考图6,在一些实施方案中,一种或多种联苯嵌段聚合物被烷基卤基团官能化。在一些实施方案中,将所述一种或多种联苯嵌段聚合物与多元醇例如二醇或三醇混合如浇铸,进行醚化反应并交联至其他联苯嵌段聚合物。在一些实施方案中,通过添加三烷基胺将未反应的烷基卤基团转化为季铵基团。
现在参考图7,在一些实施方案中,一种或多种联苯嵌段聚合物被烷基卤基团官能化。在一些实施方案中,所述一种或多种联苯嵌段聚合物与碱反应以将至少一些卤素转化为乙烯基。在一些实施方案中,所述乙烯基通过酸催化的Fridel-Crafts烷基化与多芳族化合物进行交联反应,使得芳族环起到交联的聚合物网络中聚合物间的连接剂的作用。在一些实施方案中,所述多芳族化合物包括联苯化合物,联苯醚化合物,三蝶烯化合物,芴或芴衍生物化合物等,或它们的组合。在一些实施方案中,通过添加三烷基胺将未反应的烷基卤基团转化为季铵基团。
现在参考图8,在一些实施方案中,一种或多种联苯嵌段聚合物被烷基卤基团官能化。在一些实施方案中,所述一种或多种联苯嵌段聚合物与碱反应以将至少一些卤素转化为乙烯基。在一些实施方案中,然后对所述一种或多种联苯嵌段聚合物进行紫外线照射,导致乙烯基团之间的二聚成为环丁烷环,其起到交联的聚合物网络中聚合物间的连接剂的作用。在一些实施方案中,通过添加三烷基胺将未反应的烷基卤基团转化为季铵基团。
现在参考图9,在一些实施方案中,一种或多种联苯嵌段聚合物被烷基卤基团官能化。在一些实施方案中,所述一种或多种联苯嵌段聚合物与碱反应以将至少一些卤素转化为乙烯基。在一些实施方案中,所述乙烯基经由UV辐射和二硫醇的添加进行交联反应。所述硫醇-烯反应使交联的聚合物网络中的聚合物交联,其中所述二硫醇起到连接剂的作用。在一些实施方案中,所述二硫醇是烷基二硫醇,例如SH-(CH2)n)-SH。在一些实施方案中,通过添加三烷基胺将未反应的烷基卤基团转化为季铵基团。
本公开的方法作为一种从任何用烷基卤基团官能化的苯乙烯共聚物制备离子交换膜和离聚物粘结剂的通用方法是有利的。反应条件是直接的,并且由于季铵化和交联基本上同时发生,反应本身可以以相对较少的步骤进行。此外,在本文所述的反应中简单增加交联剂的浓度产生具有减少的水吸收的膜,导致在水合条件下提高的稳定性和更大的耐久性的预期。有利地,这种水吸收的减少几乎没有改变离子交换能力。按照本公开的实施方案的交联的聚合物网络可用于例如电池、阴离子交换膜燃料电池、阴离子交换膜电解、燃料电池和电解用离聚物、其他电化学能量转换装置用的膜和离聚物、水净化、气体分离(尤其是来自燃煤电厂的CO2)等的应用。
尽管已经结合其实施方案描述和举例说明了所公开的主题,但是本领域技术人员应当理解,所公开的实施方案的特征可以被组合、重新布置等,以产生在本发明的范围内的另外的实施方案,并且在不脱离本发明的精神和范围的情况下可以对其进行各种其他改变、省略和添加。
Claims (20)
1.一种离子交换膜材料,其包含交联的聚合物网络,该交联的聚合物网络包括:
第一聚(苯乙烯-b-乙烯-r-丁烯-b-苯乙烯)三嵌段共聚物(SEBS),其中所述第一SEBS的至少一个苯基被第一烷基官能化,并且在所述第一烷基的苄基位置的碳被至少两个另外的烷基饱和;
第二聚(苯乙烯-b-乙烯-r-丁烯-b-苯乙烯)三嵌段共聚物(SEBS),其中所述第二SEBS的至少一个苯基被第二烷基官能化,并且在所述第二烷基的苄基位置的碳被至少两个另外的烷基饱和;和
结合到所述第一烷基和所述第二烷基的二胺连接剂。
2.权利要求1所述的材料,其中所述第一SEBS的至少一个苯基被未交联的烷基官能化,在所述未交联的烷基的苄基位置的碳被至少两个另外的烷基饱和,所述未交联的烷基包括季铵基团。
3.权利要求1所述的材料,其中所述第二SEBS的至少一个苯基被未交联的烷基官能化,在所述未交联的烷基的苄基位置的碳被至少两个另外的烷基饱和,所述未交联的烷基包括季铵基团。
4.权利要求1所述的材料,其中二胺连接剂在所述交联的聚合物网络中的浓度大于约5mol%。
5.权利要求4所述的材料,其中二胺连接剂在所述交联的聚合物网络中的浓度大于约30mol%。
6.权利要求5所述的材料,其中二胺连接剂在所述交联的聚合物网络中的浓度为约50mol%。
7.权利要求1所述的材料,其中所述二胺连接剂是N,N,N,N′-四甲基-1,6-己二胺。
9.一种制备离子交换膜的方法,该方法包括:
用一种或多种烷基卤基团官能化芳族嵌段共聚物,在所述一种或多种烷基卤基团的苄基位置的碳被至少两个另外的烷基饱和;
将所述官能化的芳族嵌段共聚物与二胺混合,以用季铵基团替代一个或多个卤素基团;和
通过所述二胺将所述官能化的芳族嵌段共聚物与另一官能化的芳族嵌段共聚物交联,以产生交联的聚合物。
10.权利要求9所述的方法,其进一步包括将三烷基胺添加到所述交联的聚合物中,以将未反应的烷基卤基团转化为季铵基团。
11.权利要求10所述的方法,其中所述交联的聚合物中二胺连接剂的浓度大于约5mol%。
12.权利要求11所述的方法,其中所述交联的聚合物中二胺连接剂的浓度大于约50摩尔%。
13.权利要求9所述的方法,其中所述二胺连接剂包括两个叔胺基团。
14.权利要求13所述的方法,其中所述二胺连接剂是N,N,N,N’-四甲基-1,6-己二胺。
16.一种制备离子交换膜的方法,该方法包括:
用一种或多种烷基卤基团官能化芳族嵌段共聚物;
在所述一种或多种烷基卤基团处将所述官能化的芳族嵌段共聚物与另一官能化的芳族嵌段共聚物交联,以通过连接剂产生交联的聚合物;和
用三烷基胺处理所述交联的聚合物,以将未交联的烷基卤基团转化为铵基团。
17.权利要求16所述的方法,其中所述交联的聚合物中所述连接剂的浓度大于约5mol%。
18.权利要求17所述的方法,其中所述交联的聚合物中所述连接剂的浓度为约50摩尔%。
19.权利要求16所述的方法,其中所述芳族嵌段共聚物是联苯聚合物。
20.权利要求16所述的方法,其中所述连接剂是二胺连接剂、多元醇、多芳族化合物、烯烃二聚体、二硫醇或它们的组合。
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US (1) | US20210108067A1 (zh) |
EP (1) | EP3784369A4 (zh) |
JP (1) | JP7385189B2 (zh) |
KR (1) | KR20210019416A (zh) |
CN (1) | CN112512668A (zh) |
BR (1) | BR112020021926A2 (zh) |
WO (1) | WO2019209959A1 (zh) |
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KR102492841B1 (ko) | 2014-11-18 | 2023-01-26 | 렌슬러 폴리테크닉 인스티튜트 | 신규 중합체 및 이의 제조 방법 |
US11236196B2 (en) | 2014-11-18 | 2022-02-01 | Rensselaer Polytechnic Institute | Polymers and methods for their manufacture |
US11621433B2 (en) | 2016-12-20 | 2023-04-04 | Rensselaer Polytechnic Institute | Proton exchange membrane material and methods of making the same |
US20200238272A1 (en) | 2017-07-06 | 2020-07-30 | Rensselaer Polytechnic Institute | Ionic functionalization of aromatic polymers for ion exchange membranes |
EP3888172A4 (en) | 2018-11-26 | 2022-08-24 | Rensselaer Polytechnic Institute | POLYMER MEMBRANES COORDINATED WITH PHOSPHATANION-QUATERNARY AMMONIUMION PAIR |
US11969722B2 (en) | 2019-06-26 | 2024-04-30 | Ffi Ionix Ip, Inc. | Anionic membranes incorporating functional additives |
EP4065753A1 (en) | 2019-11-25 | 2022-10-05 | Twelve Benefit Corporation | Membrane electrode assembly for co x reduction |
US11760839B2 (en) * | 2019-11-26 | 2023-09-19 | Dow Silicones Corporation | Processes for making polysiloxazanes and using same for producing amino-functional polyorganosiloxanes |
US11465139B2 (en) | 2020-03-20 | 2022-10-11 | Rensselaer Polytechnic Institute | Thermally stable hydrocarbon-based anion exchange membrane and ionomers |
WO2024005308A1 (ko) * | 2022-06-28 | 2024-01-04 | 한화솔루션 주식회사 | 가교 공중합체, 이를 포함하는 고분자 막, 및 상기 고분자 막을 포함하는 음이온 교환막 |
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US20130292252A1 (en) * | 2010-12-12 | 2013-11-07 | Ben-Gurion University Of The Negev Research And Development Authority | Anion exchange membranes, methods of preparation and uses |
US20150017566A1 (en) * | 2012-02-29 | 2015-01-15 | Tokuyama Corporation | Catalyst Electrode Layer and Method for Producing Same |
CN106536583A (zh) * | 2014-07-22 | 2017-03-22 | 伦斯勒理工学院 | 阴离子交换膜和用于该阴离子交换膜的聚合物 |
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GB2550018B (en) * | 2016-03-03 | 2021-11-10 | Xergy Ltd | Anion exchange polymers and anion exchange membranes incorporating same |
WO2019010290A1 (en) * | 2017-07-06 | 2019-01-10 | Rensselaer Polytechnic Institute | IONIC FUNCTIONALIZATION OF AROMATIC POLYMERS FOR ION EXCHANGE MEMBRANES |
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US20130292252A1 (en) * | 2010-12-12 | 2013-11-07 | Ben-Gurion University Of The Negev Research And Development Authority | Anion exchange membranes, methods of preparation and uses |
US20150017566A1 (en) * | 2012-02-29 | 2015-01-15 | Tokuyama Corporation | Catalyst Electrode Layer and Method for Producing Same |
CN106536583A (zh) * | 2014-07-22 | 2017-03-22 | 伦斯勒理工学院 | 阴离子交换膜和用于该阴离子交换膜的聚合物 |
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EP3784369A4 (en) | 2022-04-13 |
BR112020021926A2 (pt) | 2021-01-26 |
JP7385189B2 (ja) | 2023-11-22 |
US20210108067A1 (en) | 2021-04-15 |
WO2019209959A1 (en) | 2019-10-31 |
KR20210019416A (ko) | 2021-02-22 |
EP3784369A1 (en) | 2021-03-03 |
JP2021523978A (ja) | 2021-09-09 |
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