CN102639540A - 基于2,5-呋喃二甲酸或2,5-噻吩二甲酸的金属-有机骨架材料 - Google Patents
基于2,5-呋喃二甲酸或2,5-噻吩二甲酸的金属-有机骨架材料 Download PDFInfo
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- CN102639540A CN102639540A CN2010800540781A CN201080054078A CN102639540A CN 102639540 A CN102639540 A CN 102639540A CN 2010800540781 A CN2010800540781 A CN 2010800540781A CN 201080054078 A CN201080054078 A CN 201080054078A CN 102639540 A CN102639540 A CN 102639540A
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- dioctyl phthalate
- metal
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Classifications
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种多孔金属骨架材料,其包含至少一种至少双齿的有机化合物,所述有机化合物与至少一种金属离子配位,其中所述至少一种至少双齿的有机化合物衍生自2,5-呋喃二甲酸或2,5-噻吩二甲酸。本发明进一步涉及包含所述骨架材料的成型体、其制备方法及其用途,尤其是用于储存气体和分离气体。
Description
本发明涉及一种多孔金属-有机骨架材料,包含该骨架材料的成型体、其制备方法及其用途。
多孔金属-有机骨架材料是现有技术所已知的。特别地,其特征在于其孔隙率且通常可用于与所谓的无机沸石相当的应用场合。
金属-有机骨架材料通常包含至少双齿的有机化合物,其与金属离子配位且与至少两种金属离子以桥接形式连接,并因此与所述金属离子一起形成所述金属-有机骨架材料的骨架。
适当选择金属和/或有机化合物可优化骨架材料对于所需应用领域的性能。此时,例如,有机化合物的选择可影响孔的分布。此外,所述金属可对吸附过程作出贡献。
因此,一直需要特定的金属-有机骨架材料,其尤其具有可归因于所述金属和有机化合物的选择的优异性能。
因此,本发明的目的是提供这类材料、其制备方法及其用途。
所述目的通过一种多孔金属-有机骨架材料实现,其包含至少一种至少双齿的有机化合物,所述有机化合物与至少一种金属离子配位,其中所述至少一种至少双齿的有机化合物衍生自2,5-呋喃二甲酸或2,5-噻吩二甲酸。
业已发现本发明的金属-有机骨架材料可特别适用于分离CO2/CO、CH4/H2O和/或储氢。
本发明的多孔金属-有机骨架材料具有金属-有机骨架材料的上述典型性能。此处,本发明的多孔金属-有机骨架材料包含2,5-呋喃二甲酸或2,5-噻吩二甲酸作为至少双齿的有机化合物或衍生自这些。
就本发明而言,术语“衍生”意指2,5-呋喃二甲酸或2,5-噻吩二甲酸可以以部分脱质子形式或完全脱质子形式存在于所述骨架中。此外,2,5-呋喃二甲酸或2,5-噻吩二甲酸可包含取代基或大量独立的取代基。这类取代基的实例为OH、NH2、OCH3、CH3、NH(CH3)、N(CH3)2、CN和卤素。然而,所述至少双齿的有机化合物优选衍生自未取代的2,5-呋喃二甲酸或2,5-噻吩二甲酸。此外,就本发明而言,术语“衍生”还意指一个或多个羧基官能团可以以相应的硫类似物形式存在。硫类似物为官能团C(=O)SH及其互变异构体C(=S)SH,其可用于代替一个或两个羧基。然而,优选不使用硫类似物。
本发明骨架材料中的金属组分优选选自Ia、IIa、IIIa、IVa至VIIIa族和Ib至VIb族。特别优选Mg、Ca、Sr、Ba、Sc、Y、Ln、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ro、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Si、Ge、Sn、Pb、As、Sb和Bi,其中Ln表示镧系元素。
镧系元素为La、Ce、Pr、Nd、Pm、Sm、En、Gd、Tb、Dy、Ho、Er、Tm、Yb。
就这些元素的离子而言,特别优选可提及Mg2+、Ca2+、Sr2+、Ba2+、Sc3+、Y3+、Ln3+、Ti4+、Zr4+、Hf4+、V4+、V3+、V2+、Nb3+、Ta3+、Cr3+、Mo3+、W3+、Mn3+、Mn2+、Re3+、Re2+、Fe3+、Fe2+、Ru3+、Ru2+、Os3+、Os2+、Co3+、Co2+、Rh2+、Rh+、Ir2+、Ir+、Ni2+、Ni+、Pd2+、Pd+、Pt2+、Pt+、Cu2+、Cu+、Ag+、Au+、Zn2+、Cd2+、Hg2+、Al3+、Ga3+、In3+、Tl3+、Si4+、Si2+、Ge4+、Ge2+、Sn4+、Sn2+、Pb4+、Pb2+、As5+、As3+、As+、Sb5+、Sb3+、Sb+、Bi5+、Bi3+和Bi+。
还特别优选Mg、Al、Y、Sc、Zr、Ti、V、Cr、Mo、Fe、Co、Cu、Ni、Zn、Ln。更优选Al、Mg、Fe、Cu和Zn。非常特别优选Al。
制备本发明骨架材料的本发明方法包括:作为步骤(a),使包含对应于所述至少一种金属离子的金属盐、2,5-呋喃二甲酸或2,5-噻吩二甲酸以及溶剂的反应溶液在100-150°C的温度下反应至少3小时;和(b)分离沉淀的固体。
所述反应优选在搅拌至少一部分时间,尤其是在反应开始时搅拌下进行。
将金属盐用作起始化合物。该金属盐在反应混合物中的初始浓度优选为0.05-0.8mol/l。初始浓度更优选为0.1-0.5mol/l。特别地,初始浓度为0.15-0.3mol/l。
将所述金属盐以使得反应溶液中的金属离子浓度在步骤(b)中由于固体沉淀而降低的量引入反应溶液中。
此外,优选所用2,5-呋喃二甲酸或2,5-噻吩二甲酸的初始摩尔量与所用金属盐的初始摩尔量之比基于所述金属为0.5:1-2:1。该比值更优选为1:1-1.8:1,更优选为1:1-1.7:1。
用于制备本发明骨架材料的本发明方法步骤(a)的反应混合物进一步包含溶剂。
所述溶剂必须适于将所用原料至少部分溶解。此外,所述溶剂必须以使得能够满足所需温度范围的方式选择。
因此,用于制备本发明材料的本发明方法中的反应在溶剂存在下进行。此时,此时可使用溶剂热条件。就本发明而言,术语“热”是指如下制备方法,其中反应在加压容器中进行且在反应过程中所述容器密闭,施加升高的温度以使得加压釜中的反应介质中的压力由于所存在的溶剂的蒸气压而累积。适当的话,可以以此方式获得所需的反应温度。
所述反应优选不在含水介质中进行,同样也不在溶剂热条件下进行。
因此,本发明方法中的反应优选在非含水溶剂存在下进行。
所述反应优选在不大于2巴(绝对压力)的压力下进行。然而,压力优选不大于1230毫巴(绝对压力)。所述反应尤其优选在大气压下进行。然而,此时由于装置的原因也可为稍微超过一大气压或低于一大气压。因此,就本发明而言,术语“大气压”是指由实际主导大气压±150毫巴的压力范围。
所述反应在100-150°C的温度范围内进行。温度优选为115-140°C。温度更优选为120-130°C。
反应溶液可进一步包含碱。当使用酸时,这尤其用于使所述酸易于溶解。使用有机溶剂时,通常不必使用这类碱。然而,可对本发明方法的溶剂进行选择,以使得其具有碱性反应,但这并非实施本发明方法所必需的。
同样可使用碱。然而,优选不添加任何额外的碱。
此外,有利地是所述反应在搅拌下进行,在按比例放大生产时这也是有利的。
所述(不含水)有机溶剂优选为C1-6链烷醇,二甲亚砜(DMSO)、N,N-二甲基甲酰胺(DMF)、N,N-二乙基甲酰胺(DEF)、N,N-二甲基乙酰胺(DMAc)、乙腈、甲苯、二烷、苯、氯苯、甲基乙基酮(MEK)、吡啶、四氢呋喃(THF)、乙酸乙酯、卤化或未卤化的C1-200烷烃、环丁砜、乙二醇、N-甲基吡咯烷酮(NMP)、γ-丁内酯、脂环族醇如环己醇、酮如丙酮或乙酰丙酮、环状酮如环己酮、环丁烯砜或其混合物。
C1-6链烷醇为具有1-6个碳原子的醇。实例为甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、戊醇、己醇及其混合物。
卤化或未卤化的C1-200烷烃为具有1-200个碳原子且其中一个或多个直至所有氢原子可以或可能被卤素,优选被氯或氟,尤其是被氯代替的烷烃。其实例为氯仿、二氯甲烷、四氯甲烷、二氯乙烷、己烷、庚烷、辛烷及其混合物。
优选溶剂为DMF、DEF、DMAc和NMP。尤其优选DMF。
术语“不含水”优选是指最高含水量为10重量%,更优选5重量%,甚至更优选1重量%,甚至更优选0.1重量%,特别优选0.01重量%的溶剂,基于所述溶剂的总重。
反应过程中的最高含水量优选为10重量%,更优选为5重量%,甚至更优选为1重量%。
术语“溶剂”是指纯溶剂或不同溶剂的混合物。
该制备本发明骨架材料的本发明方法的步骤(a)实施至少3小时。所述反应优选实施至少6小时,更优选至少12小时,更优选至少18小时。
此外,本发明方法包括步骤(b)分离沉淀的固体。
由于本发明制备方法的步骤(a),所述骨架材料从反应混合物中以固体形式沉淀。其可通过现有技术已知的方法如过滤等分离。
本发明金属-有机骨架材料可以以粉末形式或附聚体形式存在。
本发明多孔金属-有机骨架材料可以以粉末形式原样使用或转化成成型体。
因此,本发明的另一方面为本发明多孔金属-有机骨架材料以粉末形式存在。
因此,本发明的另一方面为包含本发明多孔金属-有机骨架材料的成型体。
由金属-有机骨架材料制备成型体例如已描述于WO-A03/102000中。
制备成型体的优选方法为挤出或压片。在成型体的制备过程中,可添加其他材料如粘合剂、润滑剂或在制备工艺期间添加的其他添加剂。所述骨架材料也可包含其他组分,例如吸附剂如活性炭等。
对所述成型体的可能几何形状基本上没有任何限制。例如,可能的形状尤其为片状如盘状片、丸、球、颗粒、挤出物如棒、蜂窝、网格或中空体。
为了制备所述成型体,原则上可使用所有合适的方法。尤其优选如下方法:
-单独或与至少一种粘合剂和/或至少一种糊化剂(pasting agent)和/或至少一种模板化合物一起,捏合/盘式碾磨所述骨架材料,从而获得混合物;通过至少一种合适的方法如挤出成型所得混合物;任选洗涤和/或干燥和/或煅烧挤出物;任选进行整理处理;
-与至少一种粘合剂和/或其他助剂一起压片;
-将所述骨架材料施加至少一种任选多孔载体材料上。然后可通过上述方法对所得材料进一步加工以获得成型体;
-将所述骨架材料施加至至少一种任选多孔的基体上。
捏合/盘式碾磨和成型可通过任何合适的方法进行,例如如Ullmannsder Technischen Chemie,第4版,第2卷,第313及随后各页(1972)所述。
例如,捏合/盘式碾磨和/或成型可通过活塞挤压,在存在或不存在至少一种粘合剂下辊压,配混、粒化、压片、挤出、共挤出、发泡、纺丝、涂覆、造粒,优选喷雾造粒,喷涂、喷雾干燥或这些方法中两种或更多种的组合而进行。
非常特别优选生产粒料或片料。
捏合和/或成型可在升高的温度,例如室温至300°C,和/或在超计大气压下,例如在大气压至数百巴下,和/或在保护气体气氛下,例如在至少一种稀有气体、氮气或其中两种或更多种的混合物存在下进行。
在另一实施方案中,捏合和/或成型在添加至少一种粘合剂下进行,其中所用粘合剂基本上可为确保待捏合和/或成型组合物的捏合和/或成型所需的粘度的任何化学化合物。因此,就本发明而言,粘合剂可为增大粘度或降低粘度的化合物。
优选的粘合剂尤其例如为例如如WO94/29408所述的氧化铝或包含氧化铝的粘合剂;例如如EP0592050A1所述的二氧化硅;例如如WO94/13584所述的二氧化硅与氧化铝的混合物;例如如JP03-037156A所述的粘土矿物质,如蒙脱石、高岭土、膨润土、多水高岭土、地开石、珍珠陶土和蠕陶土;例如如EP0102544B1所述的烷氧基硅烷,例如四烷氧基硅烷,如四甲氧基硅烷、四乙氧基硅烷、四丙氧基硅烷、四丁氧基硅烷,或者例如三烷氧基硅烷如三甲氧基硅烷、三乙氧基硅烷、三丙氧基硅烷、三丁氧基硅烷;烷氧基钛酸酯如四烷氧基钛酸酯,如四甲氧基钛酸酯、四乙氧基钛酸酯、四丙氧基钛酸酯、四丁氧基钛酸酯,或者例如三烷氧基钛酸酯,如三甲氧基钛酸酯、三乙氧基钛酸酯、三丙氧基钛酸酯、三丁氧基钛酸酯;烷氧基锆酸酯,如四烷氧基锆酸酯如四甲氧基锆酸酯、四乙氧基锆酸酯、四丙氧基锆酸酯、四丁氧基锆酸酯,或者例如三烷氧基锆酸酯如三甲氧基锆酸酯、三乙氧基锆酸酯、三丙氧基锆酸酯、三丁氧基锆酸酯;硅溶胶、两亲性物质和/或石墨。
作为增大粘度的化合物,合适的话,例如也可使用除上述化合物之外的有机化合物和/或亲水聚合物,如纤维素或纤维素衍生物如甲基纤维素,和/或聚丙烯酸酯和/或聚甲基丙烯酸酯和/或聚乙烯醇和/或聚乙烯基吡咯烷酮和/或聚异丁烯和/或聚四氢呋喃和/或聚氧化乙烯。
作为糊化剂,尤其可优选使用水或至少一种醇如具有1-4个碳原子的一元醇,如甲醇、乙醇、正丙醇、异丙醇、1-丁醇、2-丁醇、2-甲基-1-丙醇或2-甲基-2-丙醇,或水与至少一种所述醇或多元醇如乙二醇的混合物,优选水溶混性多元醇单独或与水和/或至少一种所述一元醇的混合物。
可用于捏合和/或成型的其他添加剂尤其为胺或胺衍生物如四烷基铵化合物或氨基醇,以及含碳酸根的化合物如碳酸钙。这类其他添加剂例如描述于EP0389041A1、EP0200260A1或WO95/19222。
在成型和捏合过程中,添加剂如模板化合物、粘合剂、糊化剂、增大粘度的物质的添加顺序原则上并不重要。
在另一优选实施方案中,对通过捏合和/或成型获得的成型体进行至少一个干燥步骤,所述干燥步骤通常在25-500°C,优选50-500°C,特别优选在100-350°C的温度下进行。同样可在减压下或在保护性气体气氛下干燥或通过喷雾干燥。
在特别优选的实施方案中,在该干燥工艺期间,从所述成型体中至少部分除去作为添加剂添加的至少一种化合物。
本发明金属-有机骨架材料以及本发明成型体适于储存气体。
因此,本发明的另一方面为其在储存气体中的用途。
因此,本发明的另一方面为一种储存气体的方法,其包括使所述气体与本发明骨架材料或本发明成型体接触的步骤。
氢气尤其适于该储存。
此外,本发明骨架材料或本发明成型体适于从气体混合物中分离气体。
因此,本发明的另一方面为本发明骨架材料或本发明成型体在从气体混合物中分离气体的用途。
因此,本发明的另一方面还为一种从气体混合物中分离气体的方法,其包括使本发明骨架材料或本发明成型体与所述气体混合物接触。
所述气体混合物尤其为包含CO2和CO的气体混合物。此时,优选从该气体混合物中除去CO2。
此外,所述气体混合物可为包含甲烷和水的气体混合物。优选从该气体混合物中除去气态水。所述气体混合物例如可为含水天然气。
借助附图和下文实施例对本发明进行阐述。
图1显示了本发明金属-有机骨架材料(Al-2,5-呋喃二甲酸MOF)在40°C下的吸附和解吸附。此时,以mg每克骨架材料计的吸附气体(N)的量作为以毫巴计的绝对压力p的函数显示。
从图1可以看出,由于不同的吸附等温线,可分离除去CO2。
图2显示了根据实施例1的骨架材料(Al-2,5-呋喃二甲酸)在77K下的氢气吸附,所述骨架材料在130°C下预活化4小时(77K下的P0H2=94632.4托)。图2显示了吸附的氢气量(cm3/g STP)(左侧标度)和作为相对压力p/p0的函数的氢气重量比例(重量%)(右侧标度)。
图3显示了在不同相对湿度(RH)下Al-2,5-噻吩二甲酸MOF对气态水的吸附。此处,量W(重量%)作为RH(%)的函数显示。
实施例
实施例1Al-2,5-呋喃二甲酸MOF
实验方法:
在2L四颈烧瓶中,将呋喃二甲酸和三氯化铝悬浮于DMF中。将具有一定比例固体的该溶液在130°C下沸腾24小时,从而形成白色悬浮液。在冷却后,滤出白色沉淀,用200ml DMF洗涤1次并用200ml甲醇洗涤4次。将滤饼在RT下真空干燥16小时。
所得重量:10.3g
颜色:白色
固体浓度:2.0%
时空产率:19.6kg/m2/d
基于Al的产率:91%
分析:
朗缪尔表面积(在130°C下预活化):1153m2/g(BET:850m2/g)
化学分析:
H2O吸附,RT,75%相对湿度:35重量%
实施例2Mg-2,5-呋喃二甲酸MOF
实验方法:
在1L四颈烧瓶中,将呋喃二甲酸和硝酸镁悬浮于DMF中。将具有一定比例固体的该溶液在130°C下沸腾24小时,从而形成白色悬浮液。在冷却后,滤出白色沉淀,用200ml DMF洗涤1次并用200ml甲醇洗涤4次。将滤饼在RT下于高真空下干燥16小时。
所得重量:15.3g
颜色:白色
固体浓度:2.9%
时空产率:29.3kg/m2/d
基于Mg的产率:79.5%
分析:
朗缪尔表面积(在130°C下预活化):10m2/g(BET:7m2/g)
化学分析:
H2O吸附,RT,75%相对湿度:41重量%
实施例3Fe-2,5-呋喃二甲酸MOF
实验方法:
在1L四颈烧瓶中,将呋喃二甲酸和硝酸铁悬浮于DMF中。在加热至130°C的过程中,所述溶液稠化以形成深褐色的粘稠凝胶。在提高搅拌器速率后,所述凝胶稍稍液化。将所述凝胶在130°C下沸腾24小时。在冷却后,滤出深褐色沉淀,用200ml DMF洗涤1次并用200ml甲醇洗涤4次。将滤饼在RT下于高真空下干燥16小时。
所得重量:17.5g
颜色:锈褐色
固体浓度:3.2%
时空产率:32.3kg/m2/d
基于Fe的产率:69.1%
分析:
朗缪尔表面积(在130°C下预活化):419m2/g(BET:303m2/g)
化学分析:
实施例4Zn-2,5-呋喃二甲酸MOF
实验方法:
在1L四颈烧瓶中,将呋喃二甲酸和硝酸锌悬浮于DMF中。将具有一定比例固体的该溶液在130°C下沸腾24小时,从而形成白色悬浮液。在冷却后,在氮气气氛下滤出白色沉淀,用200ml DMF洗涤1次并用200ml氯仿洗涤4次。将滤饼在RT下于高真空下干燥16小时。
所得重量:15.6g
颜色:白色
固体浓度:2.9%
时空产率:29.3kg/m2/d
基于Zn的产率:54.1%
分析:
朗缪尔表面积(在130°C下预活化):3m2/g(BET:2m2/g)
化学分析:
实施例5Cu-2,5-呋喃二甲酸MOF
实验方法:
在1L四颈烧瓶中,将呋喃二甲酸和氯化铜悬浮于DMF中。将具有一定比例固体的该溶液在130°C下沸腾24小时,从而形成蓝色悬浮液。在冷却后,滤出蓝色沉淀,用200ml DMF洗涤1次并用200ml甲醇洗涤4次。将滤饼在RT下于高真空下干燥16小时。
所得重量:2.5g
颜色:蓝色
固体浓度:0.5%
时空产率:7.6kg/m2/d
基于Cu的产率:9.6%
分析:
朗缪尔表面积(在130°C下预活化):307m2/g(BET:227m2/g)
化学分析:
实施例6Al-2,5-噻吩二甲酸MOF
装置:
500ml四颈烧瓶
低温冷却器
油浴
搅拌器,经PTFE涂覆
温度计
氮气保护
批料:
程序:
将146ml N,N-二甲基甲酰胺置于四颈烧瓶中,并在室温下在搅拌的同时,引入3.99g噻吩二甲酸(1)和3.33g六水氯化铝(2)。形成无色溶液。随后将该反应混合物加热至130°C(回流)。将该反应混合物在130°C下保持24小时,然后冷却至RT。
在玻璃过滤器玻璃料3号上滤出白色悬浮物/沉淀,且可以容易地过滤。
DMF洗涤:
用100ml N,N-DMF将滤饼淤浆化,保持接触达15分钟,随后吸滤滤出。重复该程序两次,每次使用100ml DMF。
甲醇洗涤:
随后用100ml AR甲醇将滤饼淤浆化,保持接触达15分钟,随后吸滤滤出。重复该程序4次,每次使用100ml AR甲醇。
干燥:
将滤饼在130°C下于真空干燥箱中在<20毫巴下干燥24小时。
颜色:无色
所得重量:3.1g
分析:
BET/LM:1021/1375m2/g
一般数据:
产率(连接剂):62.5%
产率(金属盐):105.8%
固含量(产物):2.2重量%
时空产率:21.2kg/m3/d
Claims (10)
1.一种多孔金属-有机骨架材料,其包含至少一种至少双齿的有机化合物,所述有机化合物与至少一种金属离子配位,其中所述至少一种至少双齿的有机化合物衍生自2,5-呋喃二甲酸或2,5-噻吩二甲酸。
2.如权利要求1的骨架材料,其中所述至少一种金属离子为选自如下组的金属的离子:Al、Mg、Fe、Cu和Zn。
3.一种成型体,其包含如权利要求1或2的骨架材料。
4.一种制备如权利要求1或2的骨架材料的方法,其包括如下步骤:
(a)使包含对应于所述至少一种金属离子的金属盐、2,5-呋喃二甲酸或2,5-噻吩二甲酸以及溶剂的反应混合物在100-150°C的温度下反应至少3小时;和
(b)分离沉淀的固体。
5.如权利要求4的方法,其中所述反应混合物中的金属盐初始浓度为0.05-0.8mol/l。
6.如权利要求4或5的方法,其中所用2,5-呋喃二甲酸或2,5-噻吩二甲酸的初始摩尔量与所用金属盐的初始摩尔量之比基于所述金属为0.5:1-2:1。
7.如权利要求4-6中任一项的方法,其中所述溶剂包含N,N-二甲基甲酰胺。
8.如权利要求1或2的骨架材料或如权利要求3的成型体在储存气体中的用途。
9.如权利要求8的用途,其中所述气体为氢气。
10.如权利要求1或2的骨架材料或如权利要求3的成型体在从气体混合物中分离气体中的用途。
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Also Published As
Publication number | Publication date |
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RU2561603C2 (ru) | 2015-08-27 |
BR112012012910A2 (pt) | 2017-03-01 |
CA2782054A1 (en) | 2011-06-03 |
US9688700B2 (en) | 2017-06-27 |
JP5847727B2 (ja) | 2016-01-27 |
US20120251438A1 (en) | 2012-10-04 |
KR20120105020A (ko) | 2012-09-24 |
JP2013512223A (ja) | 2013-04-11 |
ES2547729T3 (es) | 2015-10-08 |
CN102639540B (zh) | 2015-12-02 |
MX2012005885A (es) | 2012-06-19 |
KR101813732B1 (ko) | 2017-12-29 |
EP2507247B1 (de) | 2015-08-05 |
RU2012127209A (ru) | 2014-01-10 |
EP2507247A1 (de) | 2012-10-10 |
WO2011064307A1 (de) | 2011-06-03 |
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