CN1882643A - 通过电子束交联的溴、氯或碘官能聚合物电解质 - Google Patents

通过电子束交联的溴、氯或碘官能聚合物电解质 Download PDF

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CN1882643A
CN1882643A CNA2004800336318A CN200480033631A CN1882643A CN 1882643 A CN1882643 A CN 1882643A CN A2004800336318 A CNA2004800336318 A CN A2004800336318A CN 200480033631 A CN200480033631 A CN 200480033631A CN 1882643 A CN1882643 A CN 1882643A
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麦克尔·A·扬德拉希茨
史蒂文·J·汉姆洛克
克劳斯·辛策
阿尔内·塔勒
福士达夫
景乃勇
卡伊·H·洛哈斯
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Abstract

本发明提供一种交联聚合物电解质的制备方法以及由此制备的聚合物，该电解质通常为膜的形式以聚合物电解质膜用于电解电池例如燃料电池，该方法包括对高度氟化的含氟聚合物施加电子束辐射，所述高度氟化的含氟聚合物含有：部分得自四氟乙烯单体的主链；包括式－SO2X的基团的第一侧基，其中X是F、Cl、Br、OH或－O－M+，其中M+是一价阳离子；和包括Br、Cl或I的第二侧基。典型地，该膜具有90微米或更小，更典型地60微米或更小，最典型地30微米或更小的厚度。

Description

通过电子束交联的溴、氯或碘官能聚合物电解质
发明领域
本发明涉及一种通过对高度氟化的含氟聚合物施加电子束辐射制备交联聚合物电解质的方法，该电解质通常为膜的形式以聚合物电解质膜用于电解电池例如燃料电池，所述高度氟化的含氟聚合物含有：部分得自四氟乙烯单体的主链；包括式-SO2X的基团的第一侧基，其中X是F、Cl、Br、OH或-O-M+，其中M+是一价阳离子；和包括Br、Cl或I的第二侧基。
发明背景
美国专利4,470,889据称公开了一种电解电池，它通过氟化聚合物膜分成阳极室和阴极室；其中该膜包括：(a)至少60mol％[CFX-CF2]，其中X＝F或Cl；(b)至少600的离子交换当量；(c)磺酰基离子交换侧基；和(d)没有离子交换官能度的基本上氟化的碳侧基。这些没有离子交换官能度的基本上氟化的碳侧基可以包括Br。
美国专利公开号US 2003/0181615 Al据称公开了某些氟磺化的氟单体、某些溴化的氟单体、和非(no)四氟乙烯(TFE)单体的聚合物。(′615的第234段和第64-68段)。该文献据称公开了特定交联方法。
美国专利5,260,351据称公开了在没有固化剂的情况下通过辐射固化的全氟弹性体。该文献据称涉及全氟化聚合物的固化以及固化位置或交联单元，所述全氟聚合物为例如由四氟乙烯、全氟烷基全氟乙烯基醚获得的那些聚合物，所述固化位置或交联单元在所得三聚物中提供腈、全氟苯基、溴或碘中的至少一种。
发明内容
简言之，本发明提供了一种交联聚合物的制备方法，它包括步骤：a)提供一种高度氟化的含氟聚合物，该聚合物含有：部分得自四氟乙烯单体的主链；包括式-SO2X的基团的第一侧基，其中X是F、Cl、Br、OH或-O-M+，其中M+是一价阳离子；以及包括Br、Cl或I，典型地包括Br的第二侧基；和b)将所述含氟聚合物暴露于电子束辐射下以致形成交联。在所述步骤b)之前，该方法还可以包括步骤：c)使该含氟聚合物形成膜。典型地，该膜具有90微米或更小，更典型地60或更小，最典型地30微米或更小的厚度。典型地，该高度氟化的含氟聚合物被全氟化。典型地第一侧基是式-O-(CF2)4-SO2X的基团，并且典型地X是OH。典型地将该含氟聚合物暴露于大于1Mrad的电子束辐射，更典型地大于3Mrad的电子束辐射下。
另一方面，本发明提供了根据本发明的任意方法制得的交联聚合物。
本发明提供一种在现有技术中没有描述的使用电子束辐射将高度氟化的含氟聚合物交联的方法，该高度氟化的含氟聚合物含有部分得自四氟乙烯单体的主链；包括式-SO2X的基团的第一侧基，其中X是F、Cl、Br、OH或-O-M+，其中M+是一价阳离子；和包括Br、Cl或I的第二侧基；该高度氟化的含氟聚合物典型地是一种用作聚合物电解质膜的膜。
在本申请中：
聚合物的“当量”(EW)是指将中和1当量碱的聚合物的重量；
聚合物的“水合乘积(hydration product)”(HP)是指存在于膜中的单位当量的磺酸基团对应的由膜吸收的水的当量(摩尔)乘以聚合物的重量当量的数值；和
“高度氟化的”是指含有40wt％或更大，典型地50wt％或更大，更典型地60wt％或更大的量的氟。
附图简述
图1是显示一种对比聚合物(A)和两种本发明的聚合物(B、C)的动态力学分析(DMA)结果的图。
图2是显示一种对比聚合物(0Mrad)和两种本发明的聚合物(2Mrad、6Mrad)的Tg的图。
详述
本发明提供了一种交联聚合物的制备方法。待交联的聚合物含有：部分得自四氟乙烯(TFE)单体的主链；包括式-SO2X的基团的第一侧基，其中X是F、Cl、Br、OH或-O-M+，其中M+是一价阳离子；和包括Br、Cl或I的第二侧基。这种聚合物可用于制备聚合物电解质膜(PEM′s)，例如用于电解电池例如燃料电池。
由本发明的交联聚合物制得的PEM′s可用于制备用于燃料电池的膜电极装配(MEA′s)。MEA是质子交换膜燃料电池，例如氢燃料电池的中心元件。燃料电池是通过催化组合燃料例如氢和氧化剂如氧产生可用电的电化学电池。典型的MEA′s包括聚合物电解质膜(PEM)(也称之为离子导电膜(ICM))，它起固体电解质的作用。PEM的一面与阳极电极层接触，相对面与阴极电极层接触。每一电极层包括电化学催化剂，通常包括金属铂。气体扩散层(GDL′s)便于运输气体进出阳极和阴极电极材料并导电。GDL也可以称作流体运输层(FTL)或扩散器/集电器(DCC)。阳极和阴极电极层可以催化剂油墨的形式涂覆到GDL′s上，并且用一个PEM夹持所得涂布的GDL′s形成5层MEA。或者，阳极和阴极电极层可以催化剂油墨的形式涂覆到PEM的相对面，并且用两个GDL′s夹持所得催化剂涂布的膜(CCM)形成5层MEA。5层MEA的这5层依次是：阳极GDL、阳极电极层、PEM、阴极电极层和阴极GDL。在一个典型PEM燃料电池中，通过氢的氧化反应在阳极形成质子并将质子穿过PEM运输到阴极与氧反应，从而产生在连接这些电极的外部电路中流动的电流。该PEM在气体反应物之间形成一耐用的、无孔、不导电的机械屏障，但是它也能容易地使H+离子通过。
待交联的聚合物包括一主链，它可以是支化或未支化的，但是典型是未支化的。主链高度氟化，更典型地全氟化。主链包括得自四氟乙烯(TFE)的单元，即典型地-CF2-CF2-单元，以及得自共聚单体的单元，该共聚单体通常包括至少一个式CF2＝CY-R的单体，其中Y典型地是F，但是也可以是CF3，并且其中R是含有式-SO2X的基团的第一侧基，其中X是F、Cl、Br、OH或-O-M+，其中M+是一价阳离子，典型地是碱金属阳离子例如Na+。X最典型地是OH。在另一实施方案中，第一侧基R可以通过接枝加入到主链中。典型地，第一侧基R高度氟化，并且更典型地全氟化。R可以是芳香族的或非芳香族的。典型地，R是-R1-SO2X，其中R1是含有1-15个碳原子和0-4个氧原子的支化或未支化的全氟烷基或全氟醚基。R1典型地是-O-R2-，其中R2是含有1-15个碳原子和0-4个氧原子的支化或未支化的全氟烷基或全氟醚基。R1更典型地是-O-R3-，其中R3是含有1-15个碳原子的全氟烷基。R1的实例包括：
-(CF2)n-，其中n是1、2、3、4、5、6、7、8、9、10、11、12、13、14或15
(-CF2CF(CF3)-)n，其中n是1、2、3、4或5
(-CF(CF3)CF2-)n，其中n是1、2、3、4或5
(-CF2CF(CF3)-)n-CF2-，其中n是1、2、3或4
(-O-CF2CF2-)n，其中n是1、2、3、4、5、6或7
(-O-CF2CF2CF2-)n，其中n是1、2、3、4或5
(-O-CF2CF2CF2CF2-)n，其中n是1、2或3
(-O-CF2CF(CF3)-)n，其中n是1、2、3、4或5
(-O-CF2CF(CF2CF3)-)n，其中n是1、2或3
(-O-CF(CF3)CF2-)n，其中n是1、2、3、4或5
(-O-CF(CF2CF3)CF2-)n，其中n是1、2或3
(-O-CF2CF(CF3)-)n-O-CF2CF2-，其中n是1、2、3或4
(-O-CF2CF(CF2CF3)-)n-O-CF2CF2-，其中n是1、2或3
(-O-CF(CF3)CF2-)n-O-CF2CF2-，其中n是1、2、3或4
(-O-CF(CF2CF3)CF2-)n-O-CF2CF2-，其中n是1、2或3
-O-(CF2)n-，其中n是1、2、3、4、5、6、7、8、9、10、11、12、13或14
R典型地是-O-CF2-CF2-CF2-CF2-SO2X或-O-CF2-CF(CF3)-O-CF2-CF2-SO2X，并且最典型地是-O-CF2-CF2-CF2-CF2-SO2X，其中X是F、Cl、Br、OH或-O-M+，但是最典型地是OH。
可以通过任意合适的方法，包括在美国专利6,624,328中公开的方法来合成具有第一侧基R的含氟单体。
此外，含氟聚合物包括第二侧基Q，它含有Br、Cl或I，典型地含有Br。该第二侧基可以得自式CF2＝CY-Q的共聚单体，其中Y典型地是F，但是也可以是CF3，并且Q是包括Br、Cl或I的第二侧基。在另一实施方案中，第二侧基Q可以通过接枝加入到主链中。典型地，除了溴位置之外，第二侧基Q高度氟化，并且更典型地全氟化。典型地，Q是-R1-Br，其中R1如上所述。或者，Q是Br、Cl或I，典型地是Br。
最典型地，含氟聚合物是TFE、如上所述的CF2＝CY-R和如上所述的CF2＝CY-Q的三聚物。
待交联的聚合物可以通过任意合适的方法制得，包括乳液聚合、挤出聚合、在超临界二氧化碳中聚合、溶液聚合或悬液聚合，等等，这些方法可以是间歇的或连续的。
在一个实施方案中，在聚合反应期间可以使用链转移剂提供具有Cl、Br或I端基的聚合物。在有这些端基的地方，为了本发明的目的可以将它们视作侧基。链转移剂的实例包括具有式RXn的那些链转移剂，其中R是含有1-12个碳原子的n价烷基，它可以氟化或未氟化，并且其中X′s独立地选自Cl、Br或I。在美国专利4,000,356和6,380,337中列举了其它链转移剂。此外，如EP 407 937中所述该聚合反应可以在有I-/Br-盐的情况下进行以引入Br或I端基。
酸性官能侧基的量通常足以获得大于15,000，更典型地大于18,000，更典型地大于22,000，最典型地大于25,000的水合乘积(HP)。一般说来，较高HP与较高的离子电导率有关。
酸性官能侧基的量通常足以获得小于1200，更典型地小于1100，更典型地小于1000，更典型地小于900的当量(EW)。
典型地，在交联之前将该聚合物形成膜。可以使用任意合适的成膜方法。通常将该聚合物以悬浮液浇注。可以使用任意合适的浇注方法，包括棒涂、旋涂、槽涂、刷涂，等。或者，可以由纯聚合物以熔融法例如挤出形成膜。形成之后，将膜退火，典型地在120℃或更高，更典型地在130℃或更高，最典型地在150℃或更高的温度下退火。典型地膜具有90微米或更小，更典型地60微米或更小，最典型地30微米或更小的厚度。较薄的膜可以使离子通过的阻力较低。用于燃料电池时，这样获得较冷的操作以及可用能量的较大输出。较薄的膜必须由使用时保持其结构完整性的材料制得。
交联步骤包括将含氟聚合物暴露于电子束辐射下以形成交联的步骤。典型地，电子束辐射的剂量为1Mrad或更大，更典型地3Mrad或更大，更典型地5Mrad或更大，最典型地15Mrad或更大。可以使用任意合适的设备。可以使用连续暴露方法处理卷良好的膜。
非必须地可以加入交联剂。交联剂可以通过任意合适的方法加入，包括在形成膜之前与聚合物混合以及例如通过在交联剂溶液中浸泡将该交联剂应用到膜上。典型的试剂可以包括多官能化合物例如多官能链烯、多官能丙烯酸酯类、多官能乙烯基醚类，等等，它们可以不氟化或者氟化至较低水平，但是它们更典型地高度氟化，并且更典型地全氟化。
在另一实施方案中，可以在交联前将聚合物吸收于多孔支撑基质中，该聚合物典型地以厚度为90微米或更小，更典型地60微米或更小，最典型地30微米或更小的薄膜的形式。可以使用任意合适的方法将聚合物吸收于支撑基质的孔内，包括过压、真空、芯吸(wicking)、浸入，等等。通过交联将该混合物包埋入基质内。可以使用任意合适的支撑基质。典型地该支撑基质不导电。典型地，该支撑基质由含氟聚合物构成，该聚合物更典型地全氟化。典型的基质包括多孔聚四氟乙烯(PTFE)，例如双轴拉伸的PTFE网。
应理解的是通过本发明制得的聚合物和膜与其它方法制得的聚合物和膜在化学结构、交联结构、交联位置、酸性官能团的位置、在侧基是否有交联或者在交联处是否有酸性官能团，等等方面不同。
本发明可用于制备用于电解电池例如燃料电池的增强的聚合物电解质膜。
通过下面的实施例还描述了本发明的目的和优点，但是这些实施例中引证的具体材料及其量、以及其它条件和细节，不应解释为不适当地限制本发明。
实施例
除非另有说明，可以从Aldrich Chemical Co.，Milwaukee，WI获得或者购得所有试剂，或者可以通过已知方法合成。
聚合物
用于本实施例的聚合物电解质是通过将四氟乙烯(TFE)与通过美国专利6,624,328中公开的方法合成的CF2＝CF-O-(CF2)4-SO2F(MV4S)、并与CF2＝CF-O-(CF2)2-Br(MV2Br)乳液共聚合制得的。
用15g APFO乳化剂(全氟辛酸铵，C7F15COONH4)在高剪切(24,000rpm)下，使用ULTRA-TURRAXT 25型分散器S25KV-25F(IKA-Werke GmbH&Co.KG，Staufen，Germany)将130g MV4S在水中预乳化2分钟。向一配备有叶轮搅拌器系统的4升聚合釜中倒入3.1kg去离子水。将釜加热至50℃然后将预乳化液倒入该无氧聚合釜中。在50℃下再向该釜中倒入6g MV2Br并充入178g气态四氟乙烯(TFE)至8bar绝对反应压力。在50℃和240rpm搅拌器速度下通过加入15g二亚硫酸钠和40g过氧二硫酸铵引发聚合反应。反应期间，将反应温度保持在50℃。通过向气相中加入另外的TFE使反应压力保持在6.0bar(绝对)下。使用427g MV4S，以上述相同方式和比例制备第二份MV4S-预乳化液。在反应期间将该第二份预乳化液连续加入到液相中。在反应期间还将另一26g MV2Br连续加入到反应器中。
加入800g TFE之后，将单体阀关闭并停止单体加料。该连续聚合反应使单体气相的压力降低至2.9bar。此时，使反应器通风并用氮气冲洗。
将由此获得的聚合物分散液与2-3当量的LiOH和2当量的Li2CO3(当量以磺酰氟浓度为基础)和足够水混合制得20％聚合物固体混合物。将该混合物加热至250℃持续4小时。在这些条件下大多数(＞95％)聚合物分散。将分散液过滤除去LiF和未分散的聚合物，然后在MitsubishiDiaion SKTIOL离子交换树脂上进行离子交换得到酸形式的离聚物。所得聚合物电解质是具有式：-O-(CF2)4-SO3H的酸性侧基和式-O-(CF2)2-Br的侧基的全氟化聚合物。所得混合物是聚合物固体占18-19％的酸性分散液。将该分散液与正丙醇混合然后在真空下浓缩，得到所需20％固体在约30％水/70％正丙醇的水/正丙醇溶剂混合物中的分散液。使用该基础分散液浇注膜。
膜
通过刀片将含有20％固体的水/丙醇悬浮液(40％水/60％正丙醇)刮刀涂布到玻璃板上浇注待测定的聚合物膜样品，在80℃下干燥10分钟，并在200℃下退火10分钟。所得薄膜的厚度约为30微米。然后从玻璃板上取下薄膜，切成条，放置在聚乙烯袋中并用氮冲洗。
电子束
将该膜样品暴露于电子束源中。(Energy Sciences CB300，EnergySciences，Inc.，Wilmington，Massachusetts)。将每次通过的剂量控制在2Mrad。样品经过0、1或3次通过，总电子束剂量是0、2或6Mrad。
分析
通过动态力学分析(DMA)测定暴露于剂量为0、2或6Mrad电子束剂量下的样品的Tg。在DMA中，在施加振荡力的试验设备中将待测定的聚合物样品夹紧并测定样品的最终位移。在控温的环境下进行该过程。随着测定的进行温度上升。由该数据，设备典型地计算、记录和显示样品作为温度的函数的弹性模量(E′)、损失模量(E″)和阻尼因数(tan delta)。Tg认为是tan delta的最大值。
在本实施例中，在1赫兹(6.28rad/sec)的频率下使用RheometricsSolid Analyzer RSA II(TA Instruments，New Castle，Delaware，USA)。测定薄带样品，测得宽约6.5mm×长约25mm。在25℃-200℃的温度范围内于拉伸下进行测定。
图1是显示每一剂量下的DMA结果的图。迹线A代表0Mrad(对比)，迹线B代表2Mrad(本发明)，迹线C代表6Mrad(本发明)。图2是显示每一剂量下的Tg的图，其中Tg认为是图1代表的tan delta数据的最大值。评价暴露于2Mrad的电子束辐射下的样品的Tg，显示发生交联。还评价暴露于6Mrad的电子束辐射下的样品的Tg。
在不背离本发明的范围和原理的情况下，本发明的各种改进和改变对本领域技术人员来说都是显而易见的，并且应理解本发明不仅限于本文上面所述的描述性实施方式。

Claims (10)

1.一种交联聚合物的制备方法，包括步骤：
a)提供一种高度氟化的含氟聚合物，该聚合物含有：部分得自四氟乙烯单体的主链；包括式-SO2X的基团的第一侧基，其中X是F、Cl、Br、OH或-O-M+，其中M+是一价阳离子；和包括选自Br、Cl和I组成的组的卤素原子的第二侧基；以及
b)将所述含氟聚合物暴露于电子束辐射下以形成交联。
2.如权利要求1的方法，其中在所述步骤b)之前，所述方法还包括步骤：c)使该含氟聚合物形成膜。
3.如权利要求1或2的方法，其中步骤c)包括将所述含氟聚合物吸收到多孔支撑基质内。
4.如权利要求3的方法，其中所述多孔支撑基质是多孔聚四氟乙烯网。
5.如权利要求2、3或4中任意项的方法，其中所述膜具有90微米或更小的厚度。
6.如权利要求1-5中任意项的方法，其中将所述含氟聚合物暴露于电子束辐射下的所述步骤包括将所述含氟聚合物暴露于大于1Mrad的电子束辐射下。
7.如权利要求1-6中任意项的方法，其中所述侧基是式-R1-SO2X的基团，其中R1是含有1-15个碳原子和0-4个氧原子的支化或未支化的全氟烷基或全氟醚基，并且其中X是F、Cl、Br、OH或-O-M+，其中M+是一价阳离子。
8.如权利要求1-7中任意项的方法，其中所述侧基是式-O-(CF2)4-SO3H的基团。
9.如权利要求1-8中任意项的方法，其中包含在所述第二侧基中的所述卤素原子是Br。
10.一种聚合物电解质膜，包括根据权利要求1-9中任意项的方法制得的交联聚合物。
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US9090723B2 (en) 2009-12-15 2015-07-28 Shandong Huaxia Shenzou New Material Co., Ltd. High exchange capacity perfluorinated ion exchange resin, preparation method and use thereof

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EP1687363A1 (en) 2006-08-09
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WO2005052041A1 (en) 2005-06-09
CN100417677C (zh) 2008-09-10
JP2007515508A (ja) 2007-06-14
US7265162B2 (en) 2007-09-04
ATE440891T1 (de) 2009-09-15
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