CN100468852C - 通过芳香砜交联的聚合物电解质 - Google Patents
通过芳香砜交联的聚合物电解质 Download PDFInfo
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- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- XQYMIMUDVJCMLU-UHFFFAOYSA-N phenoxyperoxybenzene Chemical class C=1C=CC=CC=1OOOC1=CC=CC=C1 XQYMIMUDVJCMLU-UHFFFAOYSA-N 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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- B01D71/32—Polyalkenyl halides containing fluorine atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F214/18—Monomers containing fluorine
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Abstract
本发明提供一种制备具有侧磺酸基团的交联聚合物的方法,该方法通过交联磺酸基团或其前体与芳香交联剂或芳香侧交联基团以形成芳香砜。所述交联聚合物可用来制备用于电解电池如燃料电池的聚合物电解质膜(PEM’s)。
Description
发明领域
本发明涉及一种制备具有磺酸侧基的交联聚合物的方法,该方法通过交联磺酸基团或其前体与芳香交联剂或芳香侧交联基团,形成芳香砜。所述交联聚合物可用于制备用在电解电池如燃料电池中的聚合物电解质膜(PEM’s)。
发明背景
四氟乙烯(TFE)与依照式
FSO2-CF2-CF2-O-CF(CF3)-CF2-O-CF=CF2的共聚单体的共聚物是公知的,并以磺酸形式(即,FSO2-端基水解成HSO3-)由DuPontChemical Company,Wilmington,Delaware以商品名出售。通常用于制备用在燃料电池中的聚合物电解质膜。
四氟乙烯(TFE)与依照式FSO2-CF2-CF2-O-CF=CF2的共聚单体的共聚物是公知的,并在制备用于燃料电池的聚合物电解质膜中以磺酸形式使用,即,FSO2-端基水解成HSO3-。
于2002年12月19日申请的美国专利申请No.10/325,278公开了
一种厚度为90μm或更少且包括聚合物的聚合物电解质膜,所述聚合物包括高度氟化的主链和依照式YOSO2-CF2-CF2-CF2-CF2-O-[聚合物主链]的重复侧基,其中Y是H+或一价阳离子,例如碱金属阳离子。通常,所述膜为浇铸膜。通常,聚合物的水合值大于22000。通常.聚合物的当量重为800-1200。
国际专利申请公开号WO 01/27167公开了具有憎水性官能团的交联碳氟聚合组合物,其通过氟化交联基团交联。
美国专利申请No.2003/0032739公开了由一种或多种聚合物组成的共价交联的聚合物或聚合物膜,其可带有阳离子交换基团的前体,所述聚合物通过聚合物上的亚磺酸酯基团-SO2Me与可包括卤代芳香烃的交联剂反应而交联,形成可包括聚合物-SO2-亚芳基-SO2-聚合物的交联桥。
美国专利No.6,090,895公开了一种制备用作离子导电膜的交联酸性聚合物的方法,例如交联的磺酸化的聚醚酮类、磺酸化的聚砜类、磺酸化的聚苯乙烯类和其他的酸性聚合物,所述方法通过与产生酸官能团的物类交联。交联剂优选通过将酸基团转化成酰亚胺官能团而结合到酸官能团上,由于N-H键的酸度,该结合弥补了酸基团被占据而导致的酸度损失,因而保留了膜的导电性,同时有利于膜的强度和耐膨胀性。
美国专利申请No.2003/0092940公开了一种制备芳香酰亚胺和芳香-次甲基三磺酰基物类的方法,其通过芳香物类与依照式(X-SO2-)m-QH-(-SO2-R1)n的反应物反应,其中Q为C或N;其中X各自独立地选自卤素,通常为F或Cl;其中R1各自独立地选自脂肪族和芳香族基团,其可任选地为直链、支链、环状、杂芳香、聚合、卤代、氟化或取代的基团;其中m大于0;当Q为N时,m+n=2;当Q为C时,m+n=3。Ar可衍生自芳香聚合化合物。另外,所述文献公开了依照式(Ar-SO2-)m-QH-(-SO2-R1)n的化合物,其中R1包括高酸性基团,选自磺酸、羧酸和膦酸,且Ar衍生自芳香化合物。
发明概述
本发明提供交联聚合物和通过如下步骤制备交联聚合物的方法:
a)提供一种包含有侧基的高度氟化的聚合物,所述侧基包括依照式-SO2X的基团,其中X各自独立地选自F、Cl、Br、I、OH或-O-SO2R2,其中R2是包含1-18个碳原子的可被取代的脂肪族基团;
b)使所述聚合物与依照式ArnR1的交联剂反应,形成包括依照式(-SO2Ar)nR1的单元的交联键,其中Ar各自独立地选自含6-24个碳或氮原子的芳香基团,各个Ar可被取代,其中R1可为直接键或芳香族或脂肪族连接基团,其中R1可为直链、支链、环状、杂芳族、聚合、卤代、氟代或取代的,其中n至少为2。在一个实施方式中,聚合物包括包含有-SO2F的侧基,-SO2F基团的至少一部分转化成用于反应的-SO2Cl或-SO2-O-SO2R2。在一个实施方式中,在交联前使聚合物形成膜,其厚度通常为90μm或更少。通常,剩余-SO2X基团在交联后转化成磺酸基团。
在另一个方面,本发明提供高度氟化的交联聚合物,其包括:主链、包括磺酸基团的侧基和依照式(-SO2Ar)nR1的交联键,其中Ar各自独立地选自包含6-24个碳或氮原子的芳香基团,其中每个Ar可被取代,其中R1可为直接键或芳香族或脂肪族连接基团,其中R1可为直链、支链、环状、杂芳族、聚合、卤代、氟代或取代的,其中n至少为2。在一个实施方式中,聚合物是聚合物电解质膜,其厚度通常为90μm或更少。侧基通常包括依照式-O-(CF2)4-SO3H的基团和依照式-O-CF2-CF(CF3)-O-CF2-CF2-SO3H的基团。
在另一个方面,本发明提供一种制备交联聚合物的方法,其包括如下步骤:
a)提供一种高度氟化的聚合物,其包含有第一侧基,该侧基包括依照式-SO2X的基团,其中X各自独立地选自F、Cl、Br、I、OH或-O-SO2R2,其中R2是包含1-18个碳原子可被取代的脂肪族基团;和包括基团-Ar的第二侧基,其中Ar各自独立地选自包含6-24个碳或氮原子的芳香基团,且各个Ar可被取代;
b)使所述聚合物反应,以在第一和第二侧基间形成包括依照式-SO2Ar-的单元的交联键。在一个实施方式中,聚合物包括包含有-SO2F的第一侧基,-SO2F基团的至少一部分然后转化成用于反应的-SO2Cl或-SO2-O-SO2R2。在一个实施方式中,所述聚合物在交联前形成膜,其厚度通常为90μm或更少。通常,剩余的-SO2X基团在交联后转化成磺酸基团。
在另一个方面,本发明提供一种高度氟化的交联聚合物,其包括:主链、包括磺酸基团的侧基和包括依照式-SO2Ar-的单元的交联键,其中Ar各自独立地选自包含6-24个碳或氮原子的芳香基团,其中各个Ar可被取代。在一个实施方式中,聚合物是聚合物电解质膜,其厚度通常为90μm或更少。侧基通常包括依照式-O-(CF2)4-SO3H的基团和依照式-O-CF2-CF(CF3)-O-CF2-CF2-SO3H的基团。
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。
“取代的”指对于化学物类,被常规取代基取代,这些取代基不会干扰所需要的产物或方法,例如,取代基可为烷基、烷氧基、芳基、苯基、卤素(F、Cl、Br、I)、氰基、硝基等。
详细说明
简单地讲,本发明提供一种制备具有磺酸侧基的交联聚合物的方法,该方法通过交联磺酸基团或其前体与芳香交联剂或芳香侧交联基团以形成芳香砜。这类交联聚合物可用于制备用在电解电池如燃料电池中的聚合物电解质膜(PEM’s)。
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。该主链是氟化的,通常是高度氟化的,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,通常包括依照式CF2=CY-R10中的至少一种,其中Y通常是F,但也可以是CF3,其中R10是包括依照式-SO2X的基团的第一侧基,其中X选自F、Cl、Br、I、-OH或-O-SO2-R2,其中R2是包含1-18个碳原子的可被取代的脂肪族基团。其中-SO2X是磺酰卤,X最通常是F。在可选择的实施方案中,第一侧基R10可通过接枝加到主链上。通常,第一侧基团R10是高度氟化的,更通常是个氟化的。R可以是芳香或非芳香的。通常,R10是-R11-SO2X,其中R11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个氟醚基团。R11通常是-O-R12-,其中R12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团。R11更通常是-O-R13-,其中R13是包含1-15个碳原子的全氟烷基。R11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;
R10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R10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。
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。包括于2003年10月30日提交的美国专利申请No.10/697,768[代理案卷号:58585US002]中公开的以及其中引用的方法。
在聚合过程中-SO2X为-SO2F的情况下,一些-SO2F基团在交联前可被转化成更加活性的基团,例如-SO2Cl、-SO2Br、-SO2I或-O-SO2R2,其中R2为包含1-18个碳原子的可被取代的脂肪族基团,更通常含有1-8个碳原子,最通常为甲基或乙基。通常,1-50%的-SO2F基团转化成了更加活性的基团。-SO2F基团可通过任何适当的方法进行转化。-SO2F基团可通过任何适当的方法转化成-SO2Cl。在一种这类方法中,通过使用适当的还原剂例如肼或硫醇(如巯基乙醇)将-SO2F基团还原成-SO2H,随后用次氯酸将其转化成-SO2Cl。在另一个这类方法中,-SO2F基团可在干燥甲苯中使用吡啶催化剂通过与草酰氯的反应转化成-SO2Cl。-SO2F基团可通过任何适当的方法转化成-O-SO2R2。在一个这类方法中,-SO2F基团可通过与R2-SO2-O-SO2-R2交换而被转化,例如CH3-SO2-O-SO2-CH3。在另一个这类方法中,-SO2F基团通过与R2-SO3H和P2O5反应被转化。
在本发明的一个实施方式中,所述聚合物还包括包含有基团-Ar的第二侧基,其中-Ar各自独立地选自包含6-24个碳或氮原子的芳香基团,其中各个Ar可被取代。Ar基团通常包括苯基、萘基、蒽基、菲基、联苯基、三联苯基、芴基、吲哚基、荧蒽基、吡啶基、puryl等。当存在取代基时,它们通常为电子供体取代基,例如烷氧基、羟基、胺、烷基等。第二侧基可通过与单体三聚引入到聚合物中,其中所述单体例如CF2=CY-R20,其中Y通常为F,但也可为CF3,其中R20为第二侧基。在可替换的实施方式中,第一侧基R20可通过接枝加到主链中。第二侧基R20可依照式-R11-Ar,其中R11如上所述。在本发明的该实施方式中,所述聚合物可通过连接第一和第二侧基而交联。如下所述,可加入另外的交联剂,但不是必需的。在所述聚合物中存在第二侧基,存在的量(摩尔)少于第一侧基的量,通常少于第一侧基的90%,更通常少于50%。
在本发明的一个实施方式中,聚合物通过与依照式ArnR1的交联剂反应而被交联,其中Ar如上所述,其中R1可为直接键或芳香族或脂肪族连接基团,其中R1可为直链、支链、环状、杂芳族、聚合、卤代、氟代或取代的,其中n至少为2。n通常为2-4,最通常为2-3,最通常为2。R1通常包含1-120个碳、氧或氮原子,但如果是聚合的可能更大。R1通常为脂肪族。R1更通常为包含1-20个碳或氧原子的直链或支链亚烷基、烷氧基或聚醚基团。R1也可为聚合物或低聚物,尤其是当n为更大数时,例如大于4时。R1通常为氟化的,更通常为高度氟化的,最通常为个氟化的。当R1为直接键时,n必须为2,且交联剂为Ar-Ar,例如,二苯基。通常,R1通过氧原子连接到各个Ar上。R1通常为-O-R3-O-,其中R3是包含1-18个碳或氧原子的脂肪族连接键,更通常包含1-8个碳或氧原子。本发明交联键的例子包括:二苯基醚、二苯氧基烷、二苯氧基醚、二苯氧基聚醚等。
交联剂和聚合物可通过任何适当的方式混合到一起,包括在溶液或悬浮液中混合、捏合、研磨等。通常选择与聚合物混合的交联剂的量,使得到的交联聚合物能够满足下述的水合积与当量重参数。
在本发明的一个实施方式中,聚合物或聚合物/交联剂混合物在交联前形成膜。可使用任何适当的成膜方法。聚合物通常从悬浮液浇铸成膜。可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。
交联反应可以通过任何适当的方法完成。通常,反应通过施加热来完成,通常温度为160℃或更高。通常,引入催化剂如路易斯酸。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,形成的芳香砜基团依照式-SO2Ar-。当使用交联剂时,得到的交联键包括依照式(-SO2Ar)nR1的单元。当第一和第二侧基结合形成交联键时,它们通常包括依照式-SO2Ar-的单元。
交联后,剩余的含硫官能团侧基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。磺酸酐基团可通过水解被转化,除去剩余的R2-SO3H。
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1100,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,聚合物或聚合物/交联剂混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,支撑基质由含氟聚合物构成,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 (6)
1.一种制备交联聚合物的方法,包括以下步骤:
a)提供一种包括侧基的高度氟化的聚合物,所述侧基包括依照式-SO2X的基团,其中X各自独立地选自F、Cl、Br、I、OH或-O-SO2R2,其中R2是包含1-18个碳原子的可被取代的脂肪族基团;
b)使所述聚合物与依照式ArnR1的交联剂反应,形成交联键,其中Ar各自独立地选自包含6-24个碳或氮原子的芳香基团,各个Ar可被取代,其中R1为脂肪族或芳香族连接基团,和其中n至少为2。
2.如权利要求1的方法,其中所述的交联键包括依照式(-SO2Ar)nR1的单元。
3.如权利要求1或2的方法,其中所述方法还包括在所述步骤b)之前的下述步骤:
c)使所述聚合物形成膜。
4.如权利要求1或2的方法,其中所述方法在所述步骤b)之后还包括下述步骤:
d)将任何依照式-SO2X的剩余基团转变成磺酸基团。
5.如权利要求1或2的方法,其中提供高度氟化的聚合物的步骤a)包括如下步骤:
e)提供包括侧基的高度氟化的聚合物,所述侧基包括依照式-SO2F的基团;和
f)将至少一部分所述-SO2F转变成-SO2Cl。
6.一种高度氟化的交联聚合物,包括:主链、包括磺酸基团的侧基和包括依照式(-SO2Ar)nR1的单元的交联键,其中Ar各自独立地选自含有6-24个碳或氮原子的芳香基团,各个Ar可被取代,其中R1为芳香族或脂肪族连接基团,和其中n至少为2。
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2003
- 2003-11-24 US US10/720,906 patent/US7060756B2/en not_active Expired - Fee Related
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2004
- 2004-11-19 JP JP2006541568A patent/JP2007515514A/ja active Pending
- 2004-11-19 CN CNB2004800343576A patent/CN100468852C/zh not_active Expired - Fee Related
- 2004-11-19 EP EP04801095A patent/EP1690314B1/en not_active Not-in-force
- 2004-11-19 CA CA002546762A patent/CA2546762A1/en not_active Abandoned
- 2004-11-19 DE DE602004018380T patent/DE602004018380D1/de active Active
- 2004-11-19 AT AT04801095T patent/ATE417375T1/de not_active IP Right Cessation
- 2004-11-19 WO PCT/US2004/039023 patent/WO2005053076A1/en active Application Filing
- 2004-11-19 KR KR1020067009976A patent/KR20060100444A/ko not_active Application Discontinuation
- 2004-11-23 TW TW093136003A patent/TW200530273A/zh unknown
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2006
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US20060160958A1 (en) | 2006-07-20 |
CA2546762A1 (en) | 2005-06-09 |
US7060756B2 (en) | 2006-06-13 |
US20110045384A1 (en) | 2011-02-24 |
JP2007515514A (ja) | 2007-06-14 |
US8802793B2 (en) | 2014-08-12 |
ATE417375T1 (de) | 2008-12-15 |
EP1690314B1 (en) | 2008-12-10 |
US20050113528A1 (en) | 2005-05-26 |
DE602004018380D1 (de) | 2009-01-22 |
US7847035B2 (en) | 2010-12-07 |
CN1883073A (zh) | 2006-12-20 |
TW200530273A (en) | 2005-09-16 |
KR20060100444A (ko) | 2006-09-20 |
EP1690314A1 (en) | 2006-08-16 |
WO2005053076A1 (en) | 2005-06-09 |
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