CN106536583A - 阴离子交换膜和用于该阴离子交换膜的聚合物 - Google Patents
阴离子交换膜和用于该阴离子交换膜的聚合物 Download PDFInfo
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Abstract
本发明的实施方式一般涉及阴离子交换膜,更具体地,涉及包含苯乙烯嵌段共聚物的阴离子交换膜及其制造方法。在一个实施方案中,本发明提供了式IV的聚合物,其中x和y为mol%,QA或R1和R2各自独立地为直链烷基链或环状烷基链,并且Z选自由直链烷基链、环状烷基链和亚烷基醚链组成的组。其中x和y是mol%,QA是
Description
相关申请的交叉引用
本申请要求2014年7月22日提交的共同未决的美国临时专利申请62/027,497号的权益,其在此并入本文如同完整阐述。
关于联邦政府资助的研究或开发的声明
本发明是在国家科学基金会授予的资助号0747667的政府支持下完成的。政府享有本发明的部分权利。
发明背景
碱性交换膜或阴离子交换膜(AEM)允许在电化学反应中将阴离子(例如OH-、Cl-、Br-)从阴极输送到阳极。AEM是AEM燃料电池的关键组件,其中氢和氧用于发电,水作为副产物。AEM也用于水电解,其中水利用电分裂成氢和氧。在AEM燃料电池和水电解中,氢氧根离子(OH-)连同水分子一起输送通过AEM。AEM也可以用于例如电池、传感器,以及用作致动器。
已知的AEM通常不适合用于AEM燃料电池或水电解。许多商购的AEM基于聚苯乙烯,其通常被认为是AEM燃料电池或水电解的不良选择。其它AEM材料在中段链中含有亚芳基醚键(-O-),而在侧链中含有苄基三甲基铵基。然而,已经发现这种组合是化学不稳定的,并且在高度碱性的条件下容易降解。
发明内容
在一个实施方式中,本发明提供了一种式IX的聚合物
其中x和y是mol%,n是1~10。
在另一个实施方式中,本发明提供了一种XII的聚合物
其中x和y是mol%,n是1~10。
在又另一个实施方式中,本发明提供了一种IV的聚合物
其中x和y是mol%,QA是R1和R2各自独立地为直链烷基链或环状烷基链,并且Z选自由直链烷基链、环状烷基链和亚烷基醚链组成的组。
在又另一个实施方式中,本发明提供了一种阴离子交换膜,其包含选自下组的至少一种聚合物:
式IV的聚合物
其中x和y是mol%,QA是R1和R2各自独立地为直链烷基链或环状烷基链,并且Z选自由直链烷基链、环状烷基链和亚烷基醚链组成的组;
式IX的聚合物
其中x和y是mol%,n是1~10;以及
式XII的聚合物
其中x和y是mol%,n是1~10。
附图说明
通过结合描绘本发明的各种实施方式的附图对本发明的各个方面的以下详细描述,将更容易理解本发明的这些和其它特征,其中:
图1显示了制备根据本发明的实施方式聚合物的说明性方法中包括的化学反应;
图2显示了可以引入本发明的各种实施方式的聚合物中的各种胺基团的实例;
图3显示了制备根据本发明的另一个实施方式聚合物的方法中包括的化学反应;和
图4显示了制备根据本发明的又另一个实施方式聚合物的方法中包括的化学反应。
注意,本发明的附图不是按比例的。附图旨在仅描绘本发明的典型方面,因此不应被认为限制本发明的范围。
具体实施方式
本发明的实施方式包括由苯乙烯-丁二烯嵌段共聚物(SEBS)制备的一类新的含季铵化氢氧化铵的聚合物。这类新的聚合物可以用于碱性交换膜(AEM),在聚合物主链中缺少亚芳基醚键,并且可以在聚合物侧链中具有多种季铵基团中的任何一种的情况下制备。
图1显示了由SEBS形成含季铵化氢氧化铵的聚合物的方法中涉及的化学反应。采用SEBS(化合物I),其中x和y是各重复单元的mol%,并且2x+y=100。例如,在本发明的一些实施方式中,x是15,y是70。当然,如本领域技术人员将意识到,其它值是可能的。然后使用双(频哪醇合)二硼(B2Pin2)进行铱催化的硼烷化,以将硼酸酯基团引入SEBS的芳环,产生化合物II。
然后用含芳基溴化物的胺进行钯催化的Suzuki偶联反应以产生化合物III。根据所采用的含芳基溴化物的胺,可以以各种胺基取代化合物II中的硼酸酯基。例如,含芳基溴化物的胺的R基团可具有下式V或式VI,其中R1和R2各自独立地为直链烷基链或环状烷基链,并且Z选自由直链烷基(例如,-(CH2)n-)链、环状烷基链和亚烷基醚链(例如,-(CH2CH2O)n-CH2CH2-)组成的组。
然后将所得聚合物浇注成膜,然后进行聚合物中胺基的甲基化和离子交换反应以形成化合物IV——本发明一个实施方式的含季铵基的苯乙烯嵌段共聚物(SEBS-QA)。申请人已经发现本发明的SEBS-QA即使在高度碱性的环境中也是化学稳定的并且适合用于AEM。
可将许多季铵基团中的任何一种引入本发明的SEBS-QA中,其中一些可以具有空间位阻且是化学稳定的。图2显示了5个说明性的R基团和所得的季铵基团。说明性的季铵基团包括苄基三甲基铵基(TMA)、二甲基哌嗪鎓(DMP)、苄基二环己基甲基铵基(MCH)、苄基二异丙基甲基铵基(MiPr)、三甲基己基铵基(TMHA)和苄基二甲基己基铵基(DMHA)。如本领域技术人员将意识到的,其它季铵基团可以类似地使用,并且在本发明的范围内。其它合适的季铵基团包括例如烷基取代的咪唑鎓和烷基取代的胍鎓。
下表1示出了本发明的实施方式的SEBS-QA的比较性质。
表1.SEBS-QA代表性数据
表1中的结果表明,这些SEBS-QA具有高阴离子传导性(Cl-、HCO3 -、OH-),这允许它们用于固体电解质膜(在此情况中为AEM)和用作电化学装置内的电极中的离聚物。
由于SEBS展现出纳米级相分离形态,故本发明的SEBS-QA将类似地展现纳米级离子传输通路,允许离子的高度有效的传导。
根据本发明的其它实施方式,可以在不使用诸如铱或钯等的昂贵的过渡金属催化剂的情况下制备基于SEBS的阴离子交换膜。图3和图4显示了此种方法的实例。
图3中的插图显示了6-溴己酸的酯化及其随后甲基化为叔醇中涉及的反应,其可用于制备本发明的聚合物。在插图内的每个阶段,尽管n通常为1~10(例如5),但n也可以是任何整数值。
现在参照图3的插图。将6-溴己酸(化合物1)(0.50g,2.56mmol)、甲醇(3.8mL)和浓硫酸(0.04mL)加入到25mL圆底烧瓶中,并将混合物在55℃搅拌14小时。然后例如使用旋转式蒸发仪蒸发甲醇,将剩余产物用乙酸乙酯(15mL)稀释,用NaHCO3(3×10mL)洗涤,并在Na2SO4上干燥。然后例如通过旋转蒸发除去乙酸乙酯,并将产物真空干燥,产生6-溴己酸甲酯(化合物2)。应当注意,除甲醇之外的醇(例如乙醇、丙醇)可用于制备类似的酯化合物。
将6-溴己酸甲酯(4.8g,23.0mmol)和无水THF(20mL)在氮气下加入到100mL圆底烧瓶中并在冰浴中冷却。然后例如通过注射器向烧瓶中加入甲基溴化镁[(CH3MgBr,在乙醚中3M)23mL,69mmol]在无水THF(10mL)中的混合物。移除冰浴,将反应混合物在室温搅拌3小时。然后用饱和NH4Cl(10mL)、水(10mL)和乙醚(20mL)将反应物缓慢淬灭。然后将所得产物用乙醚(3×15mL)萃取,在MgSO4上干燥,并例如使用旋转式蒸发仪浓缩。所得叔醇(化合物3)是无色液体(4.28g,产率92%)。应当注意,除甲基溴化镁之外的格氏试剂或烷基锂化合物可用于制备类似的叔醇。
根据图3的实施方式的聚合物的制备以在例如20mL小瓶中的SEBS共聚物(化合物VII;0.50g,2.07mmol苯乙烯单元)开始,向其中加入化合物3(1.29g,6.22mmol)。然后将小瓶抽空并用氮气吹扫。
例如通过注射器加入无水二氯甲烷(5mL),并搅拌聚合物直至溶解。然后将小瓶在冰浴中冷却并且加入三氟甲磺酸(0.55mL,6.22mmol)。将反应物在冰浴中搅拌1小时,其后将反应物倒入甲醇中以使聚合物沉淀。
聚合物随后被过滤,重新溶解在氯仿中,并在甲醇中沉淀,在室温下分离和真空干燥6小时之后产生化合物VIII的SEBS-alkBr聚合物。实践中,申请人发现化合物VIII的苯乙烯单元的59.3%发生了反应(17.7mol%的烷基溴化物和12.2mol%的未官能化的苯乙烯单元)。通过GPC在30℃用THF作为洗脱剂测量的分子量为SEBS-Mn=106,315g/mol(PDI=1.04)和SEBS-alkBr-Mn=60,228g/mol(PDI=2.07)。在30℃的甲苯中测量的粘度为SEBS=0.82dL/g和SEBS-alkBR=0.68dL/g。
接下来,将0.15g化合物VIII溶解在甲苯(3mL)中,过滤,浇注到Teflon板上,并在80℃的温和空气流下干燥。然后通过浸入水中将薄SEBS-alkBr膜(约30μm~40μm厚)从板上移除并浸入三甲基胺水溶液(45重量%的水溶液)中,并且在48小时内加热至50℃。然后通过在室温下浸在1M NaOH中48小时而将膜离子交换为氢氧化物形式,产生图3的化合物IX。
图4还显示了根据本发明的另一个实施方式在不使用过渡金属催化剂的情况下制备基于SEBS的聚合物中涉及的反应。再次,该方法从SEBS共聚物(化合物VII;29.9mol%苯乙烯单元)开始。在氮气下将化合物VII(0.30g,4.64mmol苯乙烯单元)和6-溴己酰氯(化合物4;1.49g,6.96mmol,n=5)加入到100mL圆底烧瓶中。例如通过注射器加入无水二氯甲烷(15mL)。
在搅拌以溶解聚合物后,将烧瓶在冰浴中冷却,并一次性加入AlCl3粉末(0.93g,6.96mmol)。然后将混合物在冰浴中搅拌45分钟,并且在室温搅拌12小时。然后将反应混合物倒入甲醇中以使聚合物沉淀,将其过滤,再溶于氯仿中,并在甲醇中沉淀,从而产生化合物X的SEBS-acylBr聚合物。在室温真空干燥6小时后,获得0.38g化合物X的聚合物,其中100%的苯乙烯单元发生反应(即,聚合物含有29.9mol%的酰基溴化物)。
然后可以将化合物X的SEBS-acylBr的酮还原以产生化合物XI的SEBS-alkBr。为此,将化合物X的SEBS-acylBr(0.38g,0.91mmol酮)加入到100mL圆底烧瓶中,将其抽空并用氮气吹扫。加入无水二氯甲烷(19mL),并搅拌溶液直到聚合物溶解。例如通过注射器加入三乙基硅烷(Et3SiH;0.58mL,3.64mmol)和三氟乙酸(0.56mL,7.28mmol),并将混合物在45℃的油浴中搅拌。在14小时之后,将反应物倒入甲醇中以使聚合物沉淀,将其过滤,再溶解于氯仿中,并在甲醇中沉淀,从而产生化合物XI的SEBS-alkBr。在室温真空干燥6小时后,获得0.30g化合物XI的聚合物,其中100%的酮被还原。
然后可以将化合物XI的SEBS-alkBr胺化以产生化合物XII的SEBS-alkTMA。为此,将SEBS-alkBr(化合物XI;0.15g)溶解在甲苯(3mL)中,过滤,浇注到Teflon板上,并在80℃的温和空气流下干燥。通过浸入水中将薄SEBS-alkBr膜(约30μm~40μm厚)从板上移除,浸入三甲基胺水溶液(45重量%的水溶液)中并加热至50℃48小时。在48小时之后,用水冲洗膜并通过在室温浸入1M NaOH中48小时而离子交换为氢氧化物形式,产生化合物XII的SEBS-alkTMA聚合物。
如本领域技术人员是显而易见的是,本发明实施方式的聚合物可以用于任何种类的环境中,包括例如作为燃料电池碱性交换膜、燃料电池离聚物、电解碱性交换膜、作为致动器,以及用于任何种类的电池应用。
当然,本领域技术人员还将意识到,可以对上述方法进行各种改变、添加或修改,而不实质性改变所获得的化合物或其特征。因此,这样的改变、添加和修改意图在本发明的范围内。
本说明书使用实例来公开本发明(包括最佳实施方式),并且还使得本领域的任何技术人员能够实践本发明,包括制造和使用任何设备或系统以及执行任何相关或合并的方法。本发明可取得专利的范围由权利要求限定,并且可以包括本领域技术人员想到的其它实例。如果这些其它实例具有不同于权利要求的书面描述的结构元件,或者如果它们包括与权利要求的书面描述无实质差异的等同结构元件,则它们应该落在权利要求的范围内。
Claims (12)
1.一种式IX的聚合物
其中x和y是mol%,n是1~10。
2.一种制备式IX的聚合物的方法,所述方法包括:
将式VIII的聚合物浸在三甲胺水溶液中;
将混合物加热至约50℃;
用水冲洗所述聚合物;并且
将所得聚合物浸在氢氧化钠中
其中x和y是mol%,n是1~10。
3.如权利要求2所述的方法,其还包括:
通过以下步骤形成式VIII的聚合物:
将式VII的聚合物与式3的醇混合
向混合物中加入一定量的无水二氯甲烷;
冷却所述混合物;
向所述混合物中加入一定量的三氟甲磺酸;并且
使式VIII的聚合物在甲醇中沉淀,
其中x和y是mol%,n是1~10。
4.一种式XII的聚合物
其中x和y是mol%,n是1~10。
5.一种制备式XII的聚合物的方法,所述方法包括:
将式XI的聚合物浸在一定量的三甲胺中;
将混合物加热至约50℃约48小时;
用水冲洗所述聚合物;并且
将所述聚合物浸在氢氧化钠中
其中x和y是mol%,n是1~10。
6.如权利要求5所述的方法,其还包括:
通过以下步骤制备式XI的聚合物:
将式X的聚合物溶解在一定量的无水二氯甲烷中;
向混合物中加入一定量的三乙基硅烷和三氟乙酸;
使式XI的聚合物在甲醇中沉淀
其中x和y是mol%,n是1~10。
7.如权利要求6所述的方法,其还包括:
通过以下步骤制备式X的聚合物:
将式VII的聚合物与一定量的6-溴己酰氯混合;
向混合物中加入一定量的无水二氯甲烷;
冷却所述混合物;
向所述混合物中加入一定量的氯化铝
其中x和y是mol%。
8.一种式IV的聚合物
其中x和y是mol%,QA是
R1和R2各自独立地为直链烷基链或环状烷基链,并且Z选自由直链烷基链、环状烷基链和亚烷基醚链组成的组。
9.一种制备式IV的聚合物的方法,所述方法包括:
使式III的聚合物甲基化;并且
在所得聚合物上进行离子交换反应
其中x和y是mol%,QA是
R1和R2各自独立地为直链烷基链或环状烷基链,并且Z选自由直链烷基链、环状烷基链和亚烷基醚链组成的组。
10.如权利要求9所述的方法,其还包括:
通过以下步骤制备式III的聚合物:
使用式II的聚合物和含芳基溴化物的胺进行钯催化的Suzuki偶联反应
其中x和y是mol%。
11.如权利要求10所述的方法,其还包括:
通过以下步骤制备式II的聚合物:
使用式I的聚合物和双(频哪醇合)二硼进行铱催化的硼烷化
其中x和y是mol%。
12.一种燃料电池碱性交换膜、一种燃料电池离聚物、一种电解碱性交换膜或一种致动器,其包含选自下组的至少一种聚合物:
式IV的聚合物
其中x和y是mol%,QA是
R1和R2各自独立地为直链烷基链或环状烷基链,并且Z选自由直链烷基链、环状烷基链和亚烷基醚链组成的组;
式IX的聚合物
其中x和y是mol%,n是1~10;以及
式XII的聚合物
其中x和y是mol%,n是1~10。
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- 2015-07-22 CN CN201580039453.8A patent/CN106536583A/zh active Pending
- 2015-07-22 JP JP2017503833A patent/JP2017531700A/ja not_active Withdrawn
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US11987664B2 (en) | 2014-11-18 | 2024-05-21 | Rensselaer Polytechnic Institute | Polymers and methods for their manufacture |
US11834550B2 (en) | 2014-11-18 | 2023-12-05 | Rensselaer Polytechnic Institute | Polymers and methods for their manufacture |
US11826746B2 (en) | 2017-07-06 | 2023-11-28 | Rensselaer Polytechnic Institute | Ionic functionalization of aromatic polymers for ion exchange membranes |
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US12027731B2 (en) | 2018-11-26 | 2024-07-02 | Rensselaer Polytechnic Institute | Phosphate anion-quaternary ammonium ion pair coordinated polymer membranes |
CN111313066A (zh) * | 2018-12-11 | 2020-06-19 | 中国科学院大连化学物理研究所 | 接枝长烷基侧链的碱性聚合物电解质膜的制备方法及该膜 |
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Also Published As
Publication number | Publication date |
---|---|
WO2016014636A1 (en) | 2016-01-28 |
US10272424B2 (en) | 2019-04-30 |
US11040339B2 (en) | 2021-06-22 |
JP2017531700A (ja) | 2017-10-26 |
US20170203289A1 (en) | 2017-07-20 |
US20220143592A1 (en) | 2022-05-12 |
EP3171977A1 (en) | 2017-05-31 |
KR20170028413A (ko) | 2017-03-13 |
US10525457B2 (en) | 2020-01-07 |
EP3171977A4 (en) | 2018-06-20 |
US20190308185A1 (en) | 2019-10-10 |
US20200094241A1 (en) | 2020-03-26 |
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