CN1882640B - 用电子束交联的聚合物电解质 - Google Patents
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Abstract
本发明提供一种制备交联聚合物的方法及由其制备的聚合物,该方法包括以下步骤:提供一种高度氟化的含氟聚合物,通常是全氟化的含氟聚合物,其包含有侧基,所述侧基包括依照通式-SO2X的基团,其中X为F、Cl、Br、OH或O-M+,其中M+为一价阳离子,将所述含氟聚合物暴露于电子束辐射下,以形成交联。通常,依照本发明的方法还包括如下步骤:将所述含氟聚合物形成膜,膜的厚度通常为90微米或以下,更通常为60微米或以下,最通常为30微米或以下。
Description
技术领域
本发明涉及一种制备交联聚合物的方法及由其制备的聚合物,该方法包括以下步骤:提供一种高度氟化的含氟聚合物,通常是全氟化的含氟聚合物,其包含有侧基,所述侧基包括依照通式-SO2X的基团,其中X为F、Cl、Br、OH或-O-M+,其中M+为一价阳离子,将该含氟聚合物暴露于电子束辐射下,以形成交联。
背景技术
美国专利4,230,549公开了由辐射接枝技术制备的用于电化学电池中的聚合物膜。
美国专利6,225,368和6,387,964公开了由辐射交联和接枝方法制备的单体接枝的交联聚合物。在一些实施方式中,单体接枝的交联聚合物可以是含氟聚合物。在一些实施方式中,单体接枝的交联聚合物可以随后被磺化,并用作电化学电池中的离子交换膜。
美国专利6,255,370公开了一种固体聚合电解质燃料电池,其包括固态聚合电解质膜,该固态聚合电解质膜中的水含量更加接近于负极。在一方面,据称通过控制膜中的交联程度来控制水含量。该参考文献中指出,“当在主链共聚物膜上引入侧链时,侧链物质或交联物质只接触该膜的一个表面,因此在膜上形成的侧链的浓度或者膜中交联的程度可以按照预期方式加以控制。”(‘370,第5栏第57-61行)。在此处理之后有硫化处理。(‘370,第6栏第31-48行)。
美国专利5,260,351公开了在没有固化剂情况下照射固化的全氟弹性体。该参考文献涉及固化完全氟化的聚合物,如从四氟乙烯、全氟烷基全氟乙烯基醚制备的那些聚合物,并且在生成的三聚物中固化位置或交联单元提供至少一个腈、全氟苯基、溴或碘。
发明概述
简要地,本发明提供一种制备交联聚合物的方法,包括以下步骤:提供一种高度氟化的含氟聚合物,通常是全氟化的含氟聚合物,其包含有侧基,所述侧基包括依照通式-SO2X的基团,其中X为F、Cl、Br、OH或-O-M+,其中M+为一价阳离子,将该含氟聚合物暴露于电子束辐射下,以形成交联。该侧基通常依照通式-R1-SO2X,其中R1是包含1-15个碳原子和0-4个氧原子的支链或非支链的全氟烷基或全氟醚基,最通常为-O-(CF2)4-SO2X。通常,依照本发明的方法还包括如下步骤:将所述含氟聚合物形成膜,该膜的厚度通常为90微米或以下,更通常为60微米或以下,最通常为30微米或以下。通常,该电子束的辐射剂量为4兆拉德(Mrad)或以上,更通常为5兆拉德或以上,最通常为6兆拉德或以上。通常,电子束辐射的剂量低于14兆拉德,更通常低于10兆拉德。
另一方面,本发明提供依照本发明的任一方法制备的交联聚合物。
本领域中没有描述过,也是本发明所提供的一种利用电子束辐射对包含侧基的聚合物进行交联的方法,所述侧基包括依照通式-SO2X的基团,其中X为F、Cl、Br、OH或-O-M+,通常是一种用作聚合物电解质的膜。
在本申请中:
聚合物的“当量重量”(EW)意为将中和一当量碱的聚合物重量。
聚合物的“水合积”(HP)指按膜中存在的每当量磺酸基团计,膜吸附的水的当量(摩尔)乘以聚合物的当量重的数值;和
“高度氟化”意为含氟量为40wt.%或以上,通常为50wt.%或以上,更通常为60wt.%或以上。
附图简要说明
图1显示了两种对比聚合物(A和B)和一种本发明聚合物(C)产生的动态力学分析(DMA)。
图2显示了两种对比聚合物(0兆拉德和2兆拉德)和一种本发明聚合物(6兆拉德)的Tg。
发明详述
本发明提供了一种制备交联聚合物的方法,待交联的聚合物包含侧基,该侧基包括依照通式-SO2X的基团,其中X为F、Cl、Br、OH或-O-M+,其中M+为一价阳离子,通常是碱金属阳离子,例如Na+,但最通常为OH。这种聚合物可被用于制备聚合物电解质膜(PEM’s),例如用于电解电池,如燃料电池。
由依照本发明的交联聚合物制备的PEM’s可用来制备用于燃料电池的膜电极组件(MEA’s)。MEA是质子交换膜燃料电池(如氢燃料电池)的中心元件。燃料电池是通过将例如氢的燃料和例如氧的氧化剂催化化合产生可用电能的电化学电池。通常的MEA’s包括聚合物电解质膜(PEM)(也称为离子导电膜(ICM)),其功能是作为固体电解质。PEM的一侧与阳极电极层接触,相对侧和阴极电极层接触。每个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)促使气体在阳极和阴极电极材料之间传输,并传导电流。GDL还可被称为流体传输层(FTL)或扩散器/电流收集器(DCC)。阳极和阴极电极层可以催化剂油墨的形式用于GDL’s,形成的涂覆GDL’s插入PEM,形成五层MEA。可选择地,阳极和阴极电极层可以催化剂油墨形式用于PEM的两个相对侧,形成的涂覆有催化剂的膜(CCM)插到两层GDL’s间,形成五层MEA。该五层MEA的五层按顺序分别是:阳极GDL、阳极电极层、PEM、阴极电极层和阴极GDL。在通常的PEM燃料电池中,在阳极由氢的氧化产生质子,通过PEM传输到阴极和氧发生反应,在与电极相连的外部电路中产生电流。PEM在反应气体间形成稳定、非多孔、不导电的机械阻挡层,而H+容易通过。
待交联的聚合物包括主链,其可以是支链或非支链的,但通常是非支链的。该主链是高度氟化的,更通常为全氟的。该主链可以包括衍生自四氟乙烯(TFE)的单元和衍生自共聚单体的单元,其通常包括至少一个依照通式CF2=CY-R的单元,其中Y通常为F,但也可以是CF3,其中R为侧基,该侧基包括依照通式-SO2X的基团,其中X为F、Cl、Br、OH或-O-M+,其中M+为一价阳离子,通常是碱金属阳离子,例如Na+。X最通常为OH。在一个可选的实施例中,侧基R可以通过接枝加到主链中。通常,侧基R是高度氟化的,更通常为全氟的。R可以是芳香族或非芳香族。通常,R是-R1-SO2X,其中R1是包含1-15个碳原子和0-4个氧原子的支链或非支链的全氟烷基或全氟醚基,R1通常为-O-R2-,其中R2是包含1-15个碳原子和0-4个氧原子的支链或非支链的全氟烷基或全氟醚基。R1更通常为-O-R3-,其中R3是包含1-15个碳原子的全氟烷基。R1的实例包括:
-(CF2)n-,其中n为1、2、3、4、5、6、7、8、9、10、11、12、13、14或15;
(-CF2CF(CF3)-)n,其中n为1、2、3、4或5;
(-CF(CF3)CF2-)n,其中n为1、2、3、4或5;
(-CF2CF(CF3)-)nCF2-,其中n为1、2、3或4;
(-O-CF2CF2-)n,其中n为1、2、3、4、5、6或7;
(-O-CF2CF2CF2-)n,其中n为1、2、3、4或5;
(-O-CF2CF2CF2CF2-)n,其中n为1、2或3;
(-O-CF2CF(CF3)-)n,其中n为1、2、3、4或5;
(-O-CF2CF(CF2CF3)-)n,其中n为1、2或3;
(-O-CF(CF3)CF2-)n,其中n为1、2、3、4或5;
(-O-CF(CF2CF3)CF2-)n,其中n为1、2或3;
(-O-CF2CF(CF3)-)n-O-CF2CF2-,其中n为1、2、3或4;
(-O-CF2CF(CF2CF3)-)n-O-CF2CF2-,其中n为1、2或3;
(-O-CF(CF3)CF2-)n-O-CF2CF2-,其中n为1、2、3或4;
(-O-CF(CF2CF3)CF2-)n-O-CF2CF2-,其中n为1、2或3;
-O-(CF2)n-,其中n为1、2、3、4、5、6、7、8、9、10、11、12、13或14;
R通常为-O-CF2CF2CF2CF2-SO2X或
-O-CF2-CF(CF3)-O-CF2-CF2-SO2X,最通常为-O-CF2CF2CF2CF2-SO2X,其中X为F、Cl、Br、OH或-O-M+,但最通常为OH。
依照通式I的含氟单体可以用任何适当的方法合成,包括如美国专利6,624,328中所公开的方法。
待交联的聚合物可以用任何适当的方法制备,包括乳液聚合、挤出聚合、超临界二氧化碳中聚合、溶液或悬浮液聚合等,其可以是间歇的或连续的。
酸官能侧基通常以足量存在,从而使水合积(HP)大于15,000,更通常大于18,000,更通常大于22,000,最通常大于25,000。通常,较高HP与较高离子电导相关。
酸官能悬挂基团通常以足量存在,从而使当量重(EW)小于1200,更通常小于1100,更通常小于1000,更通常小于900。
通常,聚合物在交联之前先形成膜。可使用成膜的任何适当方法。聚合物通常从悬浮液浇铸。可使用任何适当的浇铸方法,例如棒涂法、喷涂法、狭缝涂覆法、刷涂法等。可选择地,该膜可以由纯态聚合物用熔融方法形成,例如挤出法。膜在形成后进行退火,温度通常为120℃以上,更通常为130℃以上,最通常为150℃以上。通常,膜的厚度为90微米以下,更通常为60微米以下,最通常为30微米以下。较薄的膜对离子通过的抵抗性较低。在用于燃料电池时,这样会导致较冷的操作和较大的有用能量输出。较薄的膜必须由在应用中可维持其结构整体性的材料组成。
交联步骤包括以下步骤:将含氟聚合物暴露于电子束辐射中,以形成交联。通常,该电子束辐射的剂量为4兆拉德或以上,更通常为5兆拉德或以上,最通常为6兆拉德或以上。通常,电子束辐射的剂量少于14兆拉德,更通常少于10兆拉德。可使用任何适当的装置。连续的暴露处理可以用来处理成卷的优良膜。
任选地,可以添加交联剂。交联剂可以任何适当的方法添加,包括在成膜之前与聚合物混合,和将交联剂应用于膜,例如通过在交联剂溶液中浸渍。通常的试剂可包括多官能化合物,例如多官能烯烃、多官能丙烯酸酯、多官能乙烯基醚等,其可以是非氟化的或低度氟化的,但更通常为高度氟化的,更通常为全氟化的。
在另一个实施方式中,该聚合物在交联之前被吸入多孔支撑基质中,通常以薄膜形式,所述膜厚度为90微米以下,更通常为60微米以下,最通常为30微米以下。可使用任何适当的将聚合物吸入支撑基质孔中的方法,包括过压法、真空法、芯吸法、浸渍法等。经过交联,混合物嵌到基质中。可使用任何适当的支撑基质。通常,支撑基质是非导电性的。通常,支撑基质由含氟聚合物构成,更通常其为全氟化的。通常的基质包括多孔聚四氟乙烯(PTFE),例如双轴拉伸的PTFE料片。
可以理解,用本发明方法制得的聚合物和膜,其化学结构、交联结构、交联位置、酸官能团位置、在悬挂基团上存在或不存在交联键或在交联键上存在或不存在酸官能团等方面不同于用其他方法得到的那些。
本发明可用于制备用在电解电池(例如燃料电池)中的增强聚合物电解质膜。
本发明的目的和优点可以通过下面的实施例做进一步说明,但这些实施例中的特定材料和用量,以及其它条件和细节,都不应当被解释为对本发明不适当的限制。
实施例
除非特别指出,所有试剂都来自或可获自Aldrich Chemical Co.,Milwaukee,WI,或者可由已知方法合成得到。
聚合物
用于本实施例的聚合物电解质由四氟乙烯(TFE)和用美国专利6,624,328中所述方法合成的CF2=CF-O-(CF2)4-SO2F(MV4S)乳化共聚制备而成。
使用T25型分散器S25KV-25F(IKA-WerkeGmbH & Co.KG,Staufen,Germany),在水中将MV4S和APFO乳化剂(全氟辛酸铵,C7F15COONH4)高剪切(24000转/分)预乳化2分钟。在带有叶片搅拌器的聚合釜中装入去离子水。将该釜加热到50℃,然后将预制乳状液装到无氧的聚合釜中。在50℃下,向釜中进一步加入气态四氟乙烯(TFE)至6bar的绝对反应压力。在50℃和240转每分钟的搅拌速度下,加入亚硫酸氢钠和过氧化硫酸氢铵开始聚合。在反应过程中,反应温度保持在50℃。通过在气相中加入另外的TFE使反应压力保持在6bar绝对压力。如上所述制备第二份MV4S-预乳化液。在反应过程中将第二份预乳化液连续加到液相中。
在加入另外的TFE之后,关闭单体阀,中断单体给料。连续聚合将单体气相压力降低到约2bar。此时,将反应器排空,用氮气冲洗。
将由此得到的聚合物分散液与2-3当量的LiOH和2当量的Li2CO3(基于磺酰氟浓度的当量)和足够的水混合,得到20%的聚合物固态混合物。将该混合物加热到250℃,保持4小时。绝大部分(>95%)的聚合物在该条件下被分散。将分散液过滤,去除LiF和未分散的聚合物,然后用Mitsubishi Diaion SKT10L离子交换树脂进行离子交换,得到酸式离子聚合物。形成的聚合物电解质是全氟化聚合物,其酸性侧链依照通式:-O-(CF2)4-SO3H。得到的混合物为含有18-19%聚合物固体的酸分散液。将此分散液与n-丙醇混合,然后真空浓缩,得到希望的在约30%水/70%n-丙醇的水/n-丙醇溶剂混合物中含20%固体分散体。此碱性分散体用于浇铸膜。
膜
将含20%固体的水/n-丙醇悬浮液(40%水/60%n-丙醇)刮涂到玻璃板上,在80℃下干燥10分钟,在200℃下退火10分钟,浇铸得到用于测试的聚合物膜样品。形成的膜厚度约为30微米。随后将膜从玻璃板上移去,切成条,放置在聚乙烯袋中,用氮气清洗。
电子束
将膜样品暴露于电子束源(Energy Sciences CB300,EnergySciences,Inc.,Wilmington,Massachusetts)。剂量控制在每次2兆拉德。总电子束剂量为0、2或6兆拉德下样品通过0、1或3次。
分析
通过对暴露于剂量为0、2或6兆拉德电子束下样品的动态力学分析(DMA)来测试Tg。在DMA中,将待测试的聚合物样品夹在施加振荡力和测试样品最终位移(resulting displacement)的测试装置中。在温度控制环境下进行该过程。倾斜升高温度进行测量。通常,该装置由此数据计算、记录和显示样品作为温度函数的弹性模量(E’)、损耗模量(E”)和阻尼因子(tanδ,tandelta)。取tanδ的最大值作为Tg。
在本实施例中,使用了频率为1赫兹(6.28拉德/秒)的RheometicsSolid Analyzer RSA II(TA Instruments,New Castle,Delaware,USA)。对约6.5mm宽×约25mm长的样品细条进行了测试。在25℃至200℃的温度范围内在张力下进行测量。
图1显示了在各剂量下的DMA结果。轨迹A表示0兆拉德(对比),轨迹B表示2兆拉德(对比),轨迹C表示6兆拉德(本发明)。图2显示了Tg,其中Tg取自图1中所示tanδ的最大值。本实施例中暴露于6兆拉德电子束辐射的样品的Tg升高,表明发生了交联。
在不脱离本发明范围和主旨的前提下,本领域的技术人员可对本发明进行各种修改和变化,应当理解为在此提出的示例性实施方式不是对本发明不适当的限制。
Claims (9)
1.一种制备交联聚合物的方法,包括以下步骤:
a)提供一种高度氟化的含氟聚合物,其包含有侧基,所述侧基包括依照通式-SO2X的基团,其中X为F、Cl、Br、OH或-O-M+,其中M+为一价阳离子;
b)将所述含氟聚合物暴露于电子束辐射下,以形成交联并且改变聚合物的玻璃化转变温度,所述玻璃化转变温度通过动态力学分析测得,
其中所述方法在所述步骤b)之前还包括以下步骤:
c)将所述含氟聚合物形成膜。
2.如权利要求1的方法,其中所述膜的厚度为90微米或以下。
3.如权利要求1的方法,其中步骤c)包括将所述含氟聚合物吸入多孔支撑基质中。
4.如权利要求3的方法,其中所述的多孔支撑基质为多孔聚四氟乙烯料片。
5.如权利要求1-4中任一项的方法,其中将所述含氟聚合物暴露于电子束辐射下的步骤包括将所述含氟聚合物暴露于大于4兆拉德的电子束辐射下。
6.如权利要求1或2的方法,其中所述高度氟化的含氟聚合物为全氟化的。
7.如权利要求1或2的方法,其中所述的侧基为依照通式-R1-SO2X的基团,其中R1是包含1-15个碳原子和0-4个氧原子的支链或非支链的全氟烷基或全氟醚基,其中X为F、Cl、Br、OH或-O-M+,其中M+为一价阳离子。
8.如权利要求1或2的方法,其中所述的侧基为依照通式-O-(CF2)4-SO2X的基团,其中X为F、Cl、Br、OH或-O-M+,其中M+为一价阳离子。
9.一种聚合物电解质膜,其包括依照权利要求1-8中任一项的方法制备的交联聚合物。
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2003
- 2003-11-13 US US10/712,361 patent/US7179847B2/en not_active Expired - Fee Related
-
2004
- 2004-10-13 KR KR1020067009296A patent/KR20060117946A/ko not_active Application Discontinuation
- 2004-10-13 WO PCT/US2004/033807 patent/WO2005052036A1/en active Application Filing
- 2004-10-13 EP EP04795026A patent/EP1689808A1/en not_active Withdrawn
- 2004-10-13 CN CN2004800336074A patent/CN1882640B/zh not_active Expired - Fee Related
- 2004-10-13 CA CA002545172A patent/CA2545172A1/en not_active Abandoned
- 2004-10-13 JP JP2006539505A patent/JP5319067B2/ja not_active Expired - Fee Related
- 2004-11-05 TW TW093133943A patent/TW200530285A/zh unknown
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2007
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2012
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Also Published As
Publication number | Publication date |
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JP2012180529A (ja) | 2012-09-20 |
CN1882640A (zh) | 2006-12-20 |
US20050107488A1 (en) | 2005-05-19 |
US20070142563A1 (en) | 2007-06-21 |
EP1689808A1 (en) | 2006-08-16 |
JP2007514012A (ja) | 2007-05-31 |
KR20060117946A (ko) | 2006-11-17 |
US7179847B2 (en) | 2007-02-20 |
TW200530285A (en) | 2005-09-16 |
CA2545172A1 (en) | 2005-06-09 |
US7514481B2 (en) | 2009-04-07 |
JP5319067B2 (ja) | 2013-10-16 |
WO2005052036A1 (en) | 2005-06-09 |
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