CN1882642A - 通过腈三聚合交联的聚合物电解质膜 - Google Patents
通过腈三聚合交联的聚合物电解质膜 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
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- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明提供一种制备通常为膜形式的交联聚合物电解质的方法,该膜在电解电池(例如燃料电池)中用作聚合物电解质膜,该方法包括三聚合从该聚合物悬挂的腈基团。生成的聚合物电解质膜包括高度氟化的聚合物,该聚合物包括全氟化的主链、包括磺酸基团的第一侧基和包括下式(I)的三价基团的交联键,所述第一侧基通常如下式所示:-R1-SO3H,其中R1是包括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团,更通常是-O-CF2-CF2-CF2-CF2-SO3H或-O-CF2-CF(CF3)-O-CF2-CF2-SO3H。
Description
发明领域
本发明涉及一种制造通常为膜形式的交联聚合物电解质的方法,该膜在电解电池如燃料电池中用作聚合物电解质膜,所述方法通过三聚合从该聚合物悬挂的腈基团。
发明背景
国际专利申请公开号WO 02/50142A1公开了氟磺化的腈可交联的弹性体,其以偏二氟乙烯为基础,并具有低Tg。
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。
美国专利5,527,861公开了含腈全氟弹性体,其由过氧化物、活性助剂和使用腈基团形成交联键的催化剂的组合来进行固化。
美国专利4,334,082,4,414,159,4,440,917和4,454,247公开了一种用在氯-碱电解电池中的离子交换膜,该膜由下式的乙烯基醚单体的共聚物形成:
Y2CFO(CF(CF3)CF2O)nCF=CF2
其中Y选自CF2CN,CF2CO2R,CF2CO2H,CF2CO2M,CF2CONH2和CF2CONR;选自四氟乙烯、六氟丙烯和全氟烷基乙烯基醚的全氟化共聚单体;和
CF2=CF(OCF2CF(CF3))nOCF2CF2SO2F
其中n是1或2。(4,454,247的权利要求1)。这些参考文献公开了通过三聚腈形成三嗪环来固化氟弹性体的方法。(4,454,247的第10栏,第60-68行)。
发明概述
简言之,本发明提供一种聚合物电解质膜,其包括高度氟化的聚合物,该聚合物包括全氟化的主链、包括磺酸基团的第一侧基和包括下式的三价基团的交联键:
所述第一侧基通常如下式所示:-R1-SO3H,其中R1是包括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团,更通常是-O-CF2-CF2-CF2-CF2-SO3H或-O-CF2-CF(CF3)-O-CF2-CF2-SO3H。
在另一个方面中,本发明提供一种制造聚合物电解质膜的方法,该方法包括如下步骤:a)提供高度氟化的聚合物,其包括全氟化的主链、包括磺酰卤基团的第一侧基和包括腈基团的第二侧基;b)使氟聚合物形成膜;c)通过三聚合腈基团形成交联键;和d)使磺酰卤基团转化成磺酸基团。所述第二侧基通常如下式所示:-C≡N或-R11-C≡N,其中R11是包括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团。所述第一侧基通常如下式所示:-R1-SO2X,其中X是卤素,及其中R1是包括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团,最通常是-O-CF2-CF2-CF2-CF2-SO2X或-O-CF2-CF(CF3)-O-CF2-CF2-SO2X。
在另一个方面中,本发明提供由本发明任一种方法制得的交联聚合物。
在本申请中:
聚合物的″当量重″(EW)指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″指含氟量为40wt%或更大,通常50wt%或更大,更通常60wt%或更大。
详细说明
本发明提供一种交联的聚合物电解质膜。该膜衍生于一种聚合物,该聚合物包括高度氟化的主链、包括如式-SO2X所示的第一侧基和包括腈基团(-C≡N)的第二侧基,其中X是卤素,所述腈基团可被三聚合形成包括下式的三价基团的交联键:
这种交联的聚合物电解质膜(PEM′s)可用在电解电池(如燃料电池)中。
从本发明的交联聚合物制得的PEM′s可用于制造燃料电池中所用的膜电极组件(MEA′s)。MEA是质子交换膜燃料电池的中心元件,如氢燃料电池。燃料电池是电化学电池,其通过燃料如氢和氧化剂如氧的催化化合产生有用的电流。普通MEA′s包括聚合物电解质膜(PEM)(也称作离子导电膜(ICM)),其作为固体电解质。PEM的一侧与阳极电极层接触,其相对侧与阴极电极层接触。每个电极层包括电化学催化剂,通常包括铂金属。气体扩散层(GDL′s)促进气体在阳极和阴极电极材料间的传输,并传导电流。GDL也可被称作流体传输层(FTL)或扩散器/电流收集器(DCC)。阳极和阴极电极层可以催化剂涂料的形式应用到GDL′s上,得到的涂覆的GDL′s间插入PEM形成五层MEA。可选择地,阳极和阴极电极层可以催化剂涂料的形式应用到PEM的两个相对侧,得到的催化剂涂覆的膜(CCM)夹在两层GDL′s之间形成五层MEA。该五层MEA的五层顺序是: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,在阳极通过氢氧化形成质子,并穿过PEM传输到阴极与氧反应,从而使电流在与电极连接的外部电路中流动。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+离子容易通过。
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,更通常是全氟化的。该主链可以包括衍生于四氟乙烯(TFE)的单元,即通常是-CF2-CF2-单元,和衍生于共聚单体的单元,通常包括通式CF2=CY-R中的至少一种,其中Y通常是F,但也可以是CF3,其中R是包括式-SO2X的基团的第一侧基,其是磺酰卤基团。X最通常是F。在可选择的实施方案中,第一侧基R可通过接枝加到主链上。通常,第一侧基团R是高度氟化的,更通常是全氟化的。R可以是芳香或非芳香的。通常,R是-R1-SO2X,其中R1是包括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团。R1通常是-O-R2-,其中R2是包括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团。R1更通常是-O-R3-,其中R3是包括1-15个碳原子的全氟烷基。R1的例子包括:
-(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通常是-O-CF2CF2CF2CF2-SO2X或-O-CF2-CF(CF3)-O-CF2-CF2-SO2-X,最通常是-O-CF2CF2CF2CF2-SO2X。在聚合过程中,-SO2X最通常是-SO2F,即X为F。-SO2X基团通常在使用氟聚合物作为聚合物电解质之前的某点转化成-SO3H。
提供第一侧基R的氟单体可通过任何适合的方法来合成,包括美国专利6,624,328中所述的方法。
此外,含氟聚合物包括含有C≡N基团的第二侧基Q。第二侧基可以衍生于式CF2=CY-Q的共聚单体,其中Y通常是F,但也可以是CF3,其中Q是含有式-C≡N的基团的第二侧基。在可选择的实施方案中,第二侧基Q可通过接枝加到主链上。通常,第二侧基Q是高度氟化的,更通常是全氟化的,除了在溴位置。通常,Q是-R11-C≡N,其中R11可以是上述任何-R1,但与R1独立地选择。
最通常地,氟聚合物是TFE、上述CF2=CY-R和上述CF2=CY-Q的三聚合物。
聚合物可通过任何适合的方法制备,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。在一种通用聚合中,CF2=CF-O-CF2CF2CF2CF2-SO2F(MV4S)在高剪切下(24,000rpm)用乳化剂(全氟辛酸铵,C7H15COONH4)在水中预乳化。无氧聚合釜安装有叶片搅拌系统,向其中充入去离子水,并加热到50℃,然后将预乳液加到聚合釜中。向釜中充入腈-官能单体,如CF2=CF-O-C5F10-C≡N,通常在预乳液中。还向釜中加入气态四氟乙烯(TFE)至绝对反应压力为6-8bar。在50℃和240rpm搅拌速度下,通过加入亚硫酸氢钠和过氧化硫酸氢铵引发聚合。在反应过程中,反应温度保持在50℃。通过将另外的TFE加到气相中,使反应压力绝对值保持在6-8bar。在反应过程中,第二部分MV4S预乳液可以连续加到液相中。在反应过程中,另外的腈-官能单体也可以连续加到反应器中。加入足量TFE后,中断单体给料,进行连续聚合降低单体气相的压力。然后排空反应器,充入氮气。
通常,聚合物在交联之前形成膜。可以使用任何形成膜的适当方法。聚合物通常从悬浮液中浇铸。可以使用任何适当的浇铸方法,包括棒涂法、喷涂法、狭缝涂覆法、刷涂法等。可选择地,该膜可在熔融过程中从纯聚合物形成,例如挤出法。形成后,可以使膜退火。通常膜的厚度为90微米或更小,更通常60微米或更小,最通常30微米或更小。较薄的膜对离子通过的抵抗性较低。在燃料电池使用中,这样会导致较冷的操作和较大的有用能量输出。较薄的膜必须由在使用时可保持其结构完整性的材料制成。在一种常用方法中,通过用刮刀将含有20%固体的水悬浮液涂覆在玻璃板上,并在80℃下干燥10分钟形成厚度约30微米的薄膜,从而浇铸成膜。
交联步骤(腈三聚合)可以通过任何适当的方法完成。通常,在适当引发剂或催化剂存在下,交联通过加热来完成,通常加热到160℃或更高。适合的引发剂或催化剂可以包括氨水、铵化合物,包括铵盐和季铵化合物的盐,包括环状化合物,如1,8-二氮杂双环[5.4.0]十一-7-烯(DBU)的盐,包括氟化羧酸、Lewis酸的盐等。交联聚合物的步骤可以在膜退火过程中完成或部分地进行,或可以在与任何退火步骤不同的步骤中进行。在交联步骤中,腈基团三聚形成包括三嗪基团的键,即下式的三价基团:
交联后,第一侧基的含硫官能团可以通过任何适当的方法转化成磺酸形式。磺酰卤基团可以通过水解转化。在一种通常方法中,聚合物浸渍在强碱的水溶液中,然后酸化。在一种常用实施方案中,聚合物膜浸渍在15%KOH水溶液中,在80℃下保持1小时,然后用20%的硝酸在80℃洗涤两次,然后在去离子水中煮沸两次。
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。
酸官能侧基通常以足量存在,从而使当量重(EW)小于1200,更通常小于,更通常小于1000,更通常小于900。
在另一个实施方案中,在交联之前,聚合物可以吸入到多孔支撑基质中,基质通常是薄膜形式,厚度为90微米或更小,更通常60微米或更小,最通常30微米或更小。可使用任何适当的方法将聚合物吸入到支撑基质的孔中,包括过压法、真空法、芯吸法、浸渍法等。交联后,共混物嵌在基质中。可以使用任何适当的支撑基质。通常,支撑基质是不导电的。通常,支撑基质由氟聚合物构成,更通常是全氟化的。常见基质包括多孔聚四氟乙烯(PTFE),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、在侧基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。
本发明用于制造适用于电解电池(如燃料电池)的增强聚合物电解质膜。
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 (10)
2.如权利要求1的聚合物电解质膜,其中所述第一侧基如下式所示:-R1-SO3H,其中R1是包括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团。
3.一种制造聚合物电解质膜的方法,该方法包括如下步骤:
a)提供高度氟化的聚合物,其包括全氟化的主链、包括磺酰卤基团的第一侧基和包括腈基团的第二侧基;
b)使该含氟聚合物形成膜;
c)通过三聚合所述腈基团形成交联键;和
d)使所述磺酰卤基团转化成磺酸基团。
4.如权利要求3的方法,其中所述第二侧基选自-C≡N和式-R1-C≡N的基团,其中R1是包括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团。
5.如权利要求3或4的方法,其中所述第一侧基如下式所示:-R1-SO2X,其中X是卤素,及其中R1是包括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团。
6.一种根据权利要求3-5中任一项方法制备的聚合物电解质膜。
7.一种聚合物膜,包括高度氟化的聚合物,该聚合物包括:全氟化的主链、包括式-SO2X的基团的第一侧基和包括下式的三价基团的交联键:
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7的聚合物膜,其中所述第一侧基如下式所示:-R1-SO2X,其中R1是包括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团。
10.如权利要求9的聚合物,其中所述第一侧基如下式所示:-R1-SO2X,其中R1是包括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团。
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-
2003
- 2003-11-13 US US10/712,589 patent/US7074841B2/en not_active Expired - Fee Related
-
2004
- 2004-10-13 CN CNA2004800336021A patent/CN1882642A/zh active Pending
- 2004-10-13 JP JP2006539506A patent/JP2007513219A/ja active Pending
- 2004-10-13 WO PCT/US2004/033808 patent/WO2005052040A1/en active Application Filing
- 2004-10-13 EP EP04795027A patent/EP1694751A1/en not_active Withdrawn
- 2004-10-13 CA CA002545173A patent/CA2545173A1/en not_active Abandoned
- 2004-10-13 KR KR1020067009314A patent/KR20060107779A/ko not_active Application Discontinuation
- 2004-11-12 TW TW093134824A patent/TW200524961A/zh unknown
-
2006
- 2006-05-22 US US11/419,515 patent/US7435498B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9023554B2 (en) | 2009-12-11 | 2015-05-05 | Shandong Huaxia Shenzhou New Material Co., Ltd. | Perfluorinated ion exchange resin, preparation method and use thereof |
WO2011072417A1 (zh) * | 2009-12-15 | 2011-06-23 | 山东东岳神舟新材料有限公司 | 高交换容量全氟树脂及其制备方法和用途 |
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 |
Also Published As
Publication number | Publication date |
---|---|
JP2007513219A (ja) | 2007-05-24 |
CA2545173A1 (en) | 2005-06-09 |
US7435498B2 (en) | 2008-10-14 |
US20060205829A1 (en) | 2006-09-14 |
WO2005052040A1 (en) | 2005-06-09 |
TW200524961A (en) | 2005-08-01 |
US20050107489A1 (en) | 2005-05-19 |
US7074841B2 (en) | 2006-07-11 |
EP1694751A1 (en) | 2006-08-30 |
KR20060107779A (ko) | 2006-10-16 |
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