CN1171981A - 含有二膦配位体的铑配合物催化剂体系及其在制备醛方面的应用 - Google Patents
含有二膦配位体的铑配合物催化剂体系及其在制备醛方面的应用 Download PDFInfo
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- CN1171981A CN1171981A CN97111175A CN97111175A CN1171981A CN 1171981 A CN1171981 A CN 1171981A CN 97111175 A CN97111175 A CN 97111175A CN 97111175 A CN97111175 A CN 97111175A CN 1171981 A CN1171981 A CN 1171981A
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- rhodium
- carbon atom
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000003446 ligand Substances 0.000 title claims abstract description 43
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 title claims description 68
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000001299 aldehydes Chemical class 0.000 title description 5
- 150000003283 rhodium Chemical class 0.000 title description 2
- 239000010948 rhodium Substances 0.000 claims abstract description 61
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 45
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 ammonium cations Chemical class 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 53
- 229910052799 carbon Inorganic materials 0.000 claims description 27
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- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 claims description 9
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
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- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
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- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
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- 150000003839 salts Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 150000003284 rhodium compounds Chemical class 0.000 description 7
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- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 5
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- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 5
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- 230000008859 change Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- YJLPJNLZCOKVAM-UHFFFAOYSA-N 2-ethylhexanoic acid;rhodium Chemical compound [Rh].CCCCC(CC)C(O)=O YJLPJNLZCOKVAM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
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- 238000007598 dipping method Methods 0.000 description 2
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- 229910052736 halogen Inorganic materials 0.000 description 2
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- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 2
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- CHOLPKIHPFNIPE-UHFFFAOYSA-N phosphanylphosphane rhodium Chemical compound [Rh].PP CHOLPKIHPFNIPE-UHFFFAOYSA-N 0.000 description 2
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- XBGUIVFBMBVUEG-UHFFFAOYSA-N 1-methyl-4-(1,5-dimethyl-4-hexenylidene)-1-cyclohexene Chemical compound CC(C)=CCCC(C)=C1CCC(C)=CC1 XBGUIVFBMBVUEG-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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Abstract
本发明涉及新的基于含有二膦配位体的水不溶性铑配合物的催化剂体系。二膦配位体为含有单电荷或多电荷二膦阴离子和相应数量铵阳离子作为抗衡离子的羧酸铵,磺酸铵或膦酸铵形式。本发明进一步涉及新催化剂体系在烯属不饱和化合物与一氧化碳和氢气均相反应制备醛方面的应用。
Description
本发明涉及新的含有二膦配位体的铑配合物的催化剂体系以及它们在烯属不饱和化合物与氢气和一氧化碳均相反应制备醛方面的应用。
膦被广泛地用于各种生产过程中。其中特别重要的是它们用作金属配合物催化剂的配位体,这些金属配合物催化剂优选含有元素周期表中VIII族金属作为中心原子,如果必要,除膦配位体之外,还存在其它能形成配合物的基团。
现今,工业上广泛进行的烯烃的醛化越来越多的是在含叔膦或亚磷酸根作为配位体的铑配合物催化剂体系存在下进行。由于这些配位体一般过量存在,因此催化剂体系是由配合物和附加的纯净配位体组成。由于这些催化剂体系在有机介质中是可溶的,因此加氢甲酰化是在均相中进行的。为分离反应产物和回收均匀溶在反应产物中的催化剂,一般是将反应产物从反应混合物中蒸出。然而,由于所形成的醛的对热敏感性,这种蒸馏法仅适用于分子中含有至多约8个碳原子的低级烯烃的加氢甲酰化后的产物处理。长链烯烃或具有官能团的烯烃化合物的加氢甲酰化导致形成高沸点产物,通过蒸馏,已不能令人满意地将这些产物与催化剂分离开:由于粘稠油品的形成,被蒸馏物质的热应力导致所要产物有相当多的损失,并且由于配合物的分解,也导致催化剂损失。这样也就从经济上明显减少了这些方法的吸引力。
从EP-A-0374615中已知,利用选择性半透性聚芳酰胺分离膜,可以无损失地,即不降低金属化合物的催化活性地从有机溶剂中分离和回收含有磷(III)化合物作为配位体的有机金属配合物。分离过程的推动力在这里可以是压差(加压过滤)或浓度差(渗析)。此方法特别适于从有机溶液中分离出在前被用作均相催化剂的含有磷(III)化合物作为配位体的有机金属配合物和/或羰基金属。EP-A-0374615中提及的铑配合物为HRhCO[P(C6H5)3]3,RhCl[P(C6H5)3]3以及含有下式磺化或羧化三芳基膦的烷基铵盐或芳基铵盐作为配位体的化合物:其中x为磺酸根(SO3 -)或羧酸根(COO-),x1,x2,和x3为0或1,R1和R2各自相同或不同并为C4-C12烷基,C6-C12芳基或C6-C12环烷基,并且R1也可以为氢。
这类含有磺化或羧化三芳基膦的烷基铵盐或芳基铵盐作为配位体的铑配合物被用于烯属不饱和化合物的均相加氢甲酰化,但它们需要大大过量的游离未配位配位体加以稳定。
这种大大过量配位体本身导致加氢甲酰化混合物中的盐浓度过高,而这种过高盐浓度可能对烯烃与一氧化碳和氢气的反应产生不利影响,因为它们能降低反应物在反应混合物中的溶解度,另外还加速起泡。在加氢甲酰化后通过膜过滤使催化剂体系与反应产物分离的情况下,大大过量的配位体,亦即过高盐浓度也具有不利作用;一方面,它们降低了膜过滤的经膜通量,这只能通过采用更大膜面积弥补,另一方面,它们降低滞留物可被浓缩的最大程度。在再循环含催化剂的滞留物进行加氢甲酰化反应情况下,这种情况导致其它反应物可利用的反应器体积减少,象需要较大膜面积一样,结果导致工艺成本增加,因此,从经济角度上降低了此方法的吸引力。
蒸馏处理加氢甲酰化混合物时,过高盐浓度也干扰此处理过程,这是因为它们会引起含盐的粘稠油的比例增加。
因此,本发明的目的是提供新的含有有机磷配位体的铑配合物催化剂体系,该催化剂体系可用于烯属不饱和化合物的均相加氢甲酰化,它们在这种方法中具有高活性或高选择性并能通过简单方式从加氢甲酰化的反应混合物中分离出。
此目的利用含有二膦作为配位体的铑配合物催化剂体系达到,其中所用二膦为下述式I化合物:其中R1为羧酸根(COO-),磺酸根(SO3 -),膦酸根(PO3 2-)或2-氨基乙烷二膦酸根基团[-NH-CH2-CH(PO3 2-)2],R2为含有1-8个碳原子的直链亚烷基,含有2-6个碳原子的含氧亚烷基,含有3-10个碳原子的亚环烷基或式II,III,IV或V基:a,b,c,d,e,f,g,h,k和l相同或不同并为0或1,其中参数a,b,c,d,e,f,g,h,k和l中至少一个必须等于1,x相同或不同并为0或1,R3和R4相同或不同并为C4-C26烷基,取代或未取代C6-C10芳基或C6-C10环烷基或苄基,并且R3也可以为氢。
式I化合物为含有单电荷或多电荷二膦阴离子和相应数量铵阳离子作为抗衡离子的羧酸铵,磺酸铵或膦酸铵形式。它们在水中一般是不溶的或仅仅是微溶的。相反,它们在有机溶剂中则具有良好乃至非常优良的溶解性,因此特别适于在有机相中使用。
由于结合两个三价磷原子,因此式I化合物非常适于在本发明的催化剂体系中用作螯合配位体。
式I中,R1为羧酸根,磺酸根,膦酸根或2-氨基乙烷二膦酸根基团,其中优选磺酸根。
R2为含有1-8个,优选1-5个,特别是1-3个碳原子的直链亚烷基。R2还可以为含有2-6个,优选2-4个碳原子的含氧亚烷基,特别是含4个碳原子的,如式-(CH2)2-O-(CH2)2-所示的含氧亚烷基。R2也可以为含有3-10个,优选6-10个碳原子的亚环烷基或为式II,III,IV或V所示基团,优选式II所示基团。
在式I,II,III,IV和V中,a,b,c,d,e,f,g,h,k和l相同或不同并为0或1,其中参数a,b,c,d,e,f,g,h,k和l中至少一个必须等于1。对于其中R2为式II基的式I化合物,表示R1基数量的a,b,c,d,e和f的总和优选为1-3;倘如R2为式III基,则a,b,c,d,g和h的总和优选为1或2。如果R2为式IV和V基,则a,b,c,d和k的总和或a,b,c,d和l的总和优选为1-3。如果R2为含有1-8个碳原子的直链亚烷基,含有2-6个碳原子的含氧亚烷基或为含有3-10个碳原子的亚环烷基时,则a,b,c和d的总和优选为2-4。
式I中,R3和R4相同或不同并为C4-C26-,优选C18-C22-烷基,取代或未取代C6-C10芳基,优选苯基,C6-C10环烷基,优选环己基,或苄基。R3也可以为氢。因此,铵阳离子[H-NR3R4R4]+衍生自仲-或叔胺NR3R4R4,其中取代基R3和R4中包含总数为8-78个,优选12-72个,特别优选21-60个,特别是36-54个碳原子。铵阳离子优选衍生自二-2-乙基己胺,三-正辛胺,三异辛胺,三异壬胺,三异癸胺,二硬脂基胺,甲基二硬脂基胺,三鲸蜡基胺或三-二十烷基胺。
式I中,可提及的特别合适的二膦阴离子为磺化二膦阴离子,如:双(二磺酸根合苯基膦基)甲烷1,2-双(二磺酸根合苯基膦基)乙烷1,3-双(二磺酸根合苯基膦基)丙烷1,4-双(二磺酸根合苯基膦基)丁烷1,5-双(二磺酸根合苯基膦基)戊烷双(二苯基膦基甲基)醚双(二苯基膦基乙基)醚。
X-R2-X VII其中R2的定义同上,X为卤素,优选为氯或溴,产生式VIII二膦氧化物:并在有或无溶剂存在下,于80-160℃下用式HSiClmR5 n硅烷还原上述二膦氧化物,其中式HSiClmR5 n中的m为2或3,n为0或1,m+n等于3,且R5为甲基或苯基,产生式IX二膦:并在0至50℃下利用发烟硫酸磺化式IX二膦,用水稀释磺化混合物并加入溶在水不溶的有机溶剂中的水不溶性胺NR3R4R4,式I中的铵阳离子[H-NR3R4R4]+由此胺衍生得到。
有关此合成方法的详细描述见与本申请同天递交的德国专利申请。
本发明进一步提供了在上述含有式I二膦配位体的铑配合物的催化剂体系存在下,通过烯属不饱和化合物与一氧化碳和氢气反应制备醛的方法。
由铑或铑化合物与式I二膦化合物形成本发明催化剂体系或是在加氢甲酰化上游的步骤中进行(称作预形成),或者并特别是在连续法中,在加氢甲酰化反应期间就地进行。
加氢甲酰化上游的预形成优选在于其后其中还进行加氢甲酰化的相同反应器中进行,但也可以在单独的反应容器中进行。
如果通过预形成方式制备催化剂体系时,则是在加氢甲酰化反应器或在单独装置中,将铑组分(铑或铑化合物)与式I二膦化合物化合。这里,不仅铑或铑化合物,而且还包括式I二膦化合物都是以溶于有机溶剂中的形式使用,或者在元素铑情况下,是以悬浮在有机溶剂中的悬浮液形式使用。适当溶剂为在后续加氢甲酰化条件下呈惰性的有机溶剂,例如甲苯,邻-二甲苯,间-二甲苯,对-二甲苯,异构二甲苯混合物,2-乙基己醇,乙基苯,1,3,5-三甲基苯,这些化合物的混合物或脂族烃。优选使用2-乙基己醇。
其后,将铑/二膦混合物用一氧化碳和氢气处理,并在15-25MPa一氧化碳/氢气压力下,于80-150℃反应至少1小时,以形成铑配合物,它们含有二膦作为配位体并且在水中是不溶的,但溶于有机介质。与溶于有机溶剂内的过量二膦一起,它们形成本发明的催化剂体系。如果制备是在单独装置中进行的,然后可以将催化剂体系溶液转移到加氢甲酰化反应器内并与欲加氢甲酰化的烯烃混合。
如果催化剂的制备是在加氢甲酰化反应期间现场进行的,则可以将上述各组分,铑或铑化合物和二膦,与烯烃同时加料到加氢甲酰化反应器内。
在形成催化剂体系时,现已发现,不使用化学计量比铑和式I二膦(即对应于所形成的铑配合物的化学成分),而使用过量二膦是有用的。铑与二膦的比率可以在较宽范围内变化,每摩尔铑可以使用约1至l00mol二膦。铑与二膦的比率优选为1∶(1-45)。特别优选使用的比率为1∶(1-25),尤其是1∶(1-10)。
所使用的铑或为金属形式或为化合物形式。就金属形式而言,是使用小颗粒或在载体如活性炭,碳酸钙,硅酸铝或钒土上沉积成薄层形式的金属。可能的铑化合物为在有机溶剂中是可溶的或可悬浮的,或在反应条件下变成在有机溶剂中为可溶的或可悬浮的物质。合适的化合物包括各种铑氧化物,无机氢酸或含氧酸的盐,还包括一元脂族羧酸或多元脂族羧酸的盐。铑盐的实例有硝酸铑,硫酸铑,乙酸铑,2-乙基己酸铑,丙二酸铑。反之,由于所产生的配合物的低活性和卤离子的腐蚀性质,卤化铑化合物不是特别适当。除外,也有可能使用羰基铑化合物如Rh3(CO)12或Rh6(CO)16或铑的配合物盐,如环辛二烯基铑化合物。优选氧化铑,特别优选乙酸铑和2-乙基己酸铑。
在催化剂体系中使用式I二膦配位体作为单一的化合物是不必要的。例如,也有可能使用具有不同磺化度的二膦和/或带有各种铵阳离子的磺酸盐混合物。
在本发明方法中,具有2至20个碳原子和一个或多个双键的烯属不饱和化合物被反应。适当的烯属不饱和化合物为具有2至20个碳原子的取代或未取代链烯烃,具有4至10个碳原子的取代或未取代二烯,环系中具有5至12个碳原子的取代或未取代的环烯烃或二环烯烃,具有3至20个碳原子的不饱和羧酸和具有1至18个碳原子的脂族醇所形成的酯,具有2至20个碳原子的饱和羧酸和具有2至18个碳原子的不饱和醇所形成的酯,各具有3至20个碳原子的不饱和醇或醚或具有8至20个碳原子的芳脂族烯烃。
具有2至20个碳原子的取代或未取代链烯烃为端位或内部位置具有双键的直链或支链链烯烃。优选具有6至18个碳原子的直链烯烃,例如正-己-1-烯,正-庚-1-烯,正-辛-1-烯,正-壬-1-烯,正-癸-1-烯,正-十一碳-1-烯,正-十二碳-1-烯,正十八碳-1-烯和无环萜烯。同样合适的还包括支链烯烃,如二异丁烯(2,4,4-三甲基戊-1-烯),三聚丙烯,四聚丙烯和dimersol(二丁烯)。
具有4至10个碳原子的未取代二烯的优选实例为1,3-丁二烯,1,5-己二烯和1,9-癸二烯。
环系中具有5至12个碳原子的取代或未取代的环烯烃或二环烯烃的实例为环己烯,环辛烯,环辛二烯,二环戊二烯和环状萜烯,如苎烯,蒎烯,樟脑烯和红没药烯。
具有8至20个碳原子的芳脂族烯烃实例为苯乙烯。
具有3至20个碳原子的不饱和羧酸和具有1至18个碳原子的脂族醇所形成的酯中可提及的实例为醇组分中含有1-18个碳原子的丙烯酸酯和异丁烯酸酯。
具有2-20个碳原子的饱和羧酸和具有2-18个碳原子的不饱和醇所形成的酯包括羧酸组分中含有2-20个碳原子的乙烯基或烯丙基酯。
不饱和的醇或醚包括,例如,烯丙醇和乙烯基醚。
以烯属不饱和化合物的重量为基准,使用5至500ppm,优选10至100ppm,特别是15至50ppm的铑。
烯烃与一氧化碳和氢气的反应是在1.5至30.0MPa,优选2.0至27.0MPa,特别是15.0至25.0MPa压力下,于80至150℃,优选100至140℃,特别是120至130℃的温度下进行。合成气体的组成,即一氧化碳与氢气的体积比,可以在一较宽范围内延伸,并可以在例如1∶10和10∶1之间变化。一般使用其中一氧化碳与氢气的体积比为1∶1或仅偏离此数值稍许的气体混合物。
如果需要,此方法是在加氢甲酰化的条件下为惰性的有机溶剂中进行。适当的有机溶剂为芳烃如甲苯,邻-二甲苯,间-二甲苯,对-二甲苯,二甲苯异构体混合物,乙苯,1,3,5-三甲基苯,这些化合物的混合物或脂族烃。不过加氢甲酰化反应也可以在不外加有机溶剂的条件下进行;在这种情况下,起始烯烃化合物和所形成的加氢甲酰化产物充当溶剂。
存在于液相和气相中的各反应物之间的反应在常规反应器中进行,并可以以连续或分批方式进行。
加氢甲酰化作用完成之后,冷却反应产物并减压放出气体成分。其后,借助于蒸馏,提取或膜过滤方式,分离所得反应混合物。
当加氢甲酰化产物为热稳定性且不具有十分高的沸点时,优选通过(如减压)蒸馏使加氢甲酰化产物与催化剂体系分离开。
当催化剂可以很容易地转化成水溶性形式,并且然后可借助提取以水相方式被分离时,利用提取移去催化剂的方法是非常有用的。该方案能够温和地将催化剂从反应混合物中分离出。可能通过复分解,水相中的催化剂可以再转化成适于再使用的水不溶形式。
在特别适当的实施方案中,使用半透膜,优选使用聚酰胺膜,尤其是聚芳酰胺膜,通过膜过滤使加氢甲酰化产物与催化剂体系分开。在这里,优选在1至5MPa压力下,使加氢甲酰化的反应混合物通过膜,得到基本上无催化剂体系的渗透液,而包含铑配合物和二膦配位体的催化剂体系则聚集滞留物中。
合并包含催化剂体系的滞留物,并且如果需要,在进一步的预形成之后,以及如果需要,在补加了新鲜催化剂之后,它们可以再用于加氢甲酰化方法中。多次再使用是可能的,并且催化剂的活性和选择性无明显降低;预形成(用一氧化碳和氢气附加处理)和加入新鲜催化剂(铑和/或式I化合物)通常可被省去。活性态催化剂体系的处理通常必须在除去空气的条件下进行,这是因为即使有很少量氧都会损伤催化剂,即失活,这是不可逆的。这主要归因于式I化合物中的P(III)被氧化成P(V)。
使用式I二膦制备有效的催化剂体系,当其用于烯属不饱和化合物的均相加氢甲酰化时,能得到优良结果。与在前已知的均相铑-膦配合物相比,在本发明催化剂体系中,不需要大大过量的游离、未配位配位体来稳定所存在的铑-膦配合物。这可通过减小的P∶Rh比反映出。现有技术中必须使用约100∶1的P/Rh比来稳定活性铑-膦配合物,但当使用式I二膦配位体时,则可以显著减少过量配位体的量,优选减少至(2-25)∶1的P/Rh比。此外,与内含具有烷基铵或芳基铵抗衡离子的磺化三苯膦(TPPTS)单齿配位体的催化剂体系相比,对于给定条件下的均相加氢甲酰化反应,含式I二膦配位体的铑催化剂体系的活性更高。这样当使用铑-二膦催化剂体系时,有可能使用较低浓度铑。
上述优点就如下所述也十分重要,在后处理过程中,它们特别有利于膜分离铑-二膦催化剂体系与加氢甲酰化产物。由于较低的P/Rh比,加氢甲酰化混合物中盐的浓度远远低于采用现有技术铑-膦催化剂体系所得到的相应加氢甲酰化混合物中的盐浓度。这样在进行膜滤时能改善经膜流通量,为此需要非常小的膜面积。此外,浓缩滞留物到更高水平也是可能的。假如将这种含有催化剂体系的较浓滞留物返至加氢甲酰化反应器内,则可以有更大比例的反应器体积用于加料各种反应物。由于式I二膦化合物的高分子量,,不仅对于游离二膦配位体,而且对于铑-二膦配合物而言,膜过滤的滞留比都非常优良。
实施例1
采用铑/二硬脂基铵1,3-双(二-间-磺酸根合苯基膦基)丙烷催化剂体系,进行丙烯的加氢甲酰化。a) 制备1,3-双(二-间-磺酸根合苯基膦基)丙烷的二硬脂基铵盐
利用发烟硫酸磺化1,3-双(二苯基膦基)丙烷,并加冷水水解所生成的混合物。水解混合物中P(III)的浓度为42mmol/kg。取460.6g水解混合物置于搅拌着的烧瓶内。其后,向其中加入96.6g二硬脂基胺于386g甲苯中的溶液,并于50℃搅拌混合物60分钟。完成搅拌后,分出含硫酸的水相。45℃下,向有机相中加入5%浓度的氢氧化钠水溶液,调节pH为2.6。将混合物进一步反应20分钟。加入129g甲苯,以改进相分离。30分钟后,分离出662.9 g包含1,3-双(二-间-磺酸根合苯基膦基)丙烷的二硬脂基铵盐的有机相。b) 加氢甲酰化
用氮气冲洗51搅拌高压釜。取500g无氧甲苯放入氮气覆盖的玻璃容器内,在其中溶解103.6g上步a)所得配位体溶液和0.16mmol 2-乙基己酸盐形式的铑(15ppmRh;P/Rh比:5),并在氮气气氛下,将此溶液转移到高压釜内。然后在搅拌下,进料合成气体调节压力为27MPa。在达到125℃反应温度之后,进行预形成2小时。然后在1小时内,从压力容器中向高压釜内泵入1300g丙烯。利用鼓风机,通过冷却保持温度为125℃。丙烯进料完之后,使混合物进一步反应1小时。其后冷却高压釜至室温并在1.5小时内减压。随后借助剩余压力将高压釜内的内容物转移到配有浸入管的61三颈烧瓶内并称重。根据重量增加,可以计算出丙烯转化率为93.9%。考虑到尾气损失,实际上这相当于完全转化。取出部分产物并进行分析。测得铑浓度为7.96ppm。加氢甲酰化的结果示于表1内。c)膜过滤
将2261.5g上述反应产物通过实验室用膜过滤单元。所用膜为Hoechst AG(UF-PA5(PET 100))的聚芳酰胺膜。首先将膜在水中于100℃加热15分钟。然后借助循环泵以1501/h流量将反应产物通过膜,并设定压力为1.5MPa。有91.9%产物以渗透液形式通过膜。剩余124.8g滞留物。由于浓度增高,经膜通量从起始的92.91/m2h降至最后(平衡)阶段的59.21/m2h。
将渗透液再次膜过滤进行二级处理。其中的93.1%以渗透液形式通过膜。滞留物的量为144.2g。经膜通量在起始阶段为1191/m2h,最后(平衡)阶段为75.11/m2h。测定渗透液中催化剂各组分的含量,据此并基于所用的反应产物,可推算出铑的滞留值为96.4%。
为说明膜过滤催化剂的重复利用性,合并滞留物并如上面所述将它们再用于加氢甲酰化。结果示于下述表2内。
特别是最后(平衡)阶段的高经膜通量,高滞留值和低催化剂绝对浓度使得该催化剂体系具有工业规模使用意义。对比实施例1a和1b
采用铑/三苯膦三磺酸二硬脂基铵(DSA/TPPTS)催化剂体系,进行丙烯的加氢甲酰化。a) 制备TPPTS的二硬脂基铵盐
将253gNa-TPPTS溶液放入搅拌的烧瓶内并加热至65℃。其后加入250.3g二硬脂基胺于595g甲苯中的溶液。在60分钟内,搅拌加入90ml20%浓度硫酸,至pH达到2.6,并使混合物进一步反应2.5小时。加入170g异丙醇以改进相分离。15分钟后,分离出1037.5g含有TPPTS的二硬脂基铵盐的有机相。b) 加氢甲酰化对比实施例1a:
在与实施例1中b步所述相同的反应条件下,使用DS A/TPPTS为配位体,进行加氢甲酰化。结果列于表1内。对比实施例1b:
用氮气冲洗51搅拌高压釜。在氮气覆盖的玻璃容器内,溶解845g上步a)所得配位体溶液和1.17 mmol 2-乙基己酸盐形式的铑(80ppmRh;P/Rh比:100),并在氮气气氛下,将此溶液转移到高压釜内。然后在搅拌下,进料合成气体调节压力为27MPa。在达到125℃反应温度之后,使催化剂进行2小时预形成。然后在1.5小时内,从压力容器中向高压釜内泵入1300g丙烯。利用鼓风机,通过冷却保持温度为125℃。丙烯进料完之后,使混合物进一步反应1小时。其后冷却高压釜至室温并在1.5小时内减压。然后借助剩余压力将高压釜内的内容物转移到配有浸入管的61三颈烧瓶内并称重。根据重量增加,可以计算出丙烯转化率为85%。结果列于表1中。c)膜过滤对比实施例1a:
正如从表1中所看到的那样,加氢甲酰化仅得到不能令人满意的转化率(54.5%),因此略去了催化剂体系的膜分离步骤。对比实施例1b:将上面b)步的反应产物通过实验室用膜过滤单元。所用膜为Hoechst AG(UF-PA 5(PET 100))的聚芳酰胺膜。首先将膜在水中于100℃加热15分钟。然后借助循环泵以1501/h流量将反应产物通过膜,并设定压力为1.5MPa。有87.3%产物以渗透液形式通过膜。剩余324.2g滞留物。由于浓度增高,经膜通量从起始的1031/m2h降至最后(平衡)阶段的101/m2h。
将渗透液再次膜过滤进行二级处理。其中的90.8%以渗透液形式通过膜。滞留物的量为234.9g。经膜通量在起始阶段为1361/m2h,最后(平衡)阶段为511/m2h。基于所用的反应产物,测定渗透液中催化剂各组分的含量,据此可推算出表3中所列的滞留值。
为说明膜过滤催化剂的重复利用性,合并滞留物并如上面所述将它们再用于加氢甲酰化。结果示于下述表3内。
表2和表3表明,在第一级和第二级膜过滤中,当使用实施例1中所述的铑/DSA-螯合配位体催化剂体系时,其起始经膜通量的下降明显要比铑/DSA-TPPTS催化剂体系弱得多。表1: 丙烯的加氢甲酰化
实施例1 | 对比实施例1a | 对比实施例1b | ||
配位体 | DSA-螯合物 | DSA--TPPTS | DSA--TPPTS | |
[Rh] | ppm | 15 | 15 | 80 |
P∶Rh比 | [mol/mol] | 5 | 5 | 100 |
转化率 | % | 93.9 | 54.5 | 85 |
表1表明,在低铑浓度和低P∶Rh比下,本发明催化剂体系(实施例1)给出优良的转化率。在类似实验条件下,采用DSA-TPPTS配位体的催化剂体系则仅给出不能令人满意的转化率(对比实施例1a)。采用此催化剂体系,只有通过大大增加铑浓度和P∶Rh比,才有可能获得较高的转化率(参见对比实施例1b)。然而,如表3所示,这种方式对其后的膜过滤过程中的经膜通量有不利影响。
表2:实施例1的膜过滤催化剂的再用(铑/DSA-螯合配位体)
*将0.4mmol实施例1的配位体溶液加到第一级膜过滤得到的渗透液中。
再循环编号 | Rh的量mg绝对 | 转化率(%) | 基于进料量的滞留值(%)Rh | 经膜通量(1/m2/h) | |||
第1级 | 第二级 | ||||||
起始 | 平衡 | 起始 | 平衡 | ||||
01* | 18.3616,98 | 93.985,4 | 96,497,7 | 9282 | 5954 | 119112 | 7572 |
表3: 对比实验:膜过滤催化剂的再用(Rh/DSA-TPPTS)
再循环编号 | 转化率(%) | 基于进料量的滞留值(%)Rh | 经膜通量(1/m2/h) | |||
第一级 | 第二级 | |||||
起始 | 平衡 | 起始 | 平衡 | |||
0123 | 85908392 | 96.099.299.798.9 | 103979282 | 10161715 | 1361158275 | 51402924 |
Claims (21)
1.基于含有二膦配位体的铑配合物的催化剂体系,其中所存在的二膦配位体为式I化合物:其中R1为羧酸根(COO),磺酸根(SO3),膦酸根(PO3 2-)或2-氨基乙烷二膦酸根基团[-NH-CH2-CH(PO3 2-)2],R2为含有1-8个碳原子的直链亚烷基,含有2-6个碳原子的含氧亚烷基,含有3-10个碳原子的亚环烷基或为式II,III,IV或V基: a,b,c,d,e,f,g,h,k和l相同或不同并为0或1,其中参数a,,b,c,d,e,f,g,h,k和l中至少一个必须等于1,各x相同或不同并为0或1,R3和R4相同或不同并为C4-C26烷基,取代或未取代的C6-C10芳基或C6-C10环烷基或苄基,并且R3也可以为氢。
2.如权利要求1所述的催化剂体系,其中,式I中,R1为磺酸根。
3.如权利要求1或2所述的催化剂体系,其中,式I中,R2为具有1-5个,特别是1-3个碳原子的直链亚烷基,具有2-4个碳原子的含氧亚烷基,特别是具有4个碳原子如式-(CH2)2-O-(CH2)2-表示的含氧亚烷基,具有6-10个碳原子的亚环烷基或为式II基。
4.如权利要求1至3中任一项或多项所述的催化剂体系,其中R2为式II基的式I化合物中,a,b,c,d,e和f的总和为1-3。
5.如权利要求1至3中任一项或多项所述的催化剂体系,其中R2为式III基的式I化合物中,a,b,c,d,g和h的总和为1-2。
6.如权利要求1至3中任一项或多项所述的催化剂体系,其中R2为式IV或V基的式I化合物中,a,b,c,d和k或a,b,c,d和1的总和为1-3。
7.如权利要求1至3中任一项或多项所述的催化剂体系,其中R2为具有1-8个碳原子的直链亚烷基,具有2-6个碳原子的含氧亚烷基或具有3-10个碳原子的亚环烷基的式I化合物中,a,b,c,和d的总和为2-4。
8.如权利要求1至7中任一项或多项所述的催化剂体系,其中式I中的铵阳离子[H-NR3R4R4]+衍生自仲-或叔胺NR3R4R4,其中R3和R4相同或不同并各自为C18-C22烷基,取代或未取代的苯基或环己基,并且R3也可以为氢。
9.如权利要求8所述的催化剂体系,其中式I中铵阳离子[H-NR3R4R4]+的基团R3和R4中包含总数为8-78个,优选12-72个,特别优选21-60个,尤其是36-54个的碳原子。
10.如权利要求8所述的催化剂体系,其中式I中的铵阳离子[H-NR3R4R4]+衍生自二-2-乙基己胺,三-正辛胺,三异辛胺,三异壬胺,三异癸胺,二硬脂基胺,甲基二硬脂基胺,三鲸蜡基胺或三-二十烷基胺。
11.如权利要求1至10中任一项或多项所述的催化剂体系,其中它包含1至100mol,优选1-45mol,特别优选1-25mol,尤其是1-10mol的式I二膦配位体每摩尔铑。
12.如权利要求1至11中任一项或多项所述的催化剂体系,除二膦配位体外,它进一步包含能作为配位体形成配合物的基团。
13.制备醛类化合物的方法,它包括在如权利要求1至12中任一项或多项所述的催化剂体系存在下,于80至150℃以及1.5-30MPa压力下,使烯属不饱和化合物与一氧化碳和氢气反应。
14.如权利要求13所述的方法,其中催化剂体系是在方法的上游步骤中制备或者是在方法过程中就地形成。
15.如权利要求14所述的方法,其中,为在上游步骤中制备催化剂体系,将各自溶在或悬浮在有机溶剂中的铑组分和式I二膦合并,并在80-150℃下,于15-25MPa一氧化碳/氢气压力下反应至少1小时。
16.如权利要求13至15中任一项或多项所述的方法,其中所用的烯属不饱和化合物为具有2至20个碳原子的取代或未取代链烯烃,具有4至10个碳原子的取代或未取代二烯,环系中具有5至12个碳原子的取代或未取代的环烯烃或二环烯烃,具有3至20个碳原子的不饱和羧酸与具有1至18个碳原子的脂族醇所形成的酯,具有2至20个碳原子的饱和羧酸与具有2至18个碳原子的不饱和醇所形成的酯,各自具有3至20个碳原子的不饱和醇或醚或为具有8至20个碳原子的芳脂族烯烃。
17.如权利要求12-16中任一项或多项所述的方法,其中反应是以烯属不饱和化合物的重量为基准,在5-500ppm,优选10-100ppm,特别是15-50ppm铑存在下进行。
18.如权利要求13-17任一项或多项所述的方法,其中反应是在2.0至27.0MPa,特别是15.0至25.0MPa压力下,于100至140℃,特别是120至130℃温度间进行。
19.如权利要求13-18任一项或多项所述的方法,其中催化剂体系是在反应后,通过蒸馏,提取或膜过滤方式从反应混合物中分离出。
20.如权利要求19所述的方法,其中膜过滤是在加压下经过半透膜进行。
21.如权利要求20所述的方法,其中所用半透膜为聚酰胺膜,特别是聚芳酰胺膜。
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DE19619527A DE19619527A1 (de) | 1996-05-15 | 1996-05-15 | Katalysatorsysteme auf der Basis von Rhodium-Komplexverbindungen mit Diphosphin-Liganden und ihre Verwendung bei der Herstellung von Aldehyden |
DE19619527.6 | 1996-05-15 |
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US (2) | US5922634A (zh) |
EP (1) | EP0811424A3 (zh) |
JP (1) | JP3009635B2 (zh) |
KR (1) | KR970073720A (zh) |
CN (1) | CN1171981A (zh) |
AU (1) | AU713496B2 (zh) |
BR (1) | BR9703083A (zh) |
CA (1) | CA2204675A1 (zh) |
DE (1) | DE19619527A1 (zh) |
ID (1) | ID17380A (zh) |
PL (1) | PL319896A1 (zh) |
RO (1) | RO115025B1 (zh) |
ZA (3) | ZA973986B (zh) |
Cited By (2)
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CN104475161A (zh) * | 2014-12-03 | 2015-04-01 | 中国石油大学(北京) | 铁磁性纳米颗粒固载铑络合物的氢甲酰化催化剂的制法 |
CN109364997A (zh) * | 2012-12-04 | 2019-02-22 | 陶氏技术投资有限责任公司 | 用于氢甲酰化乙烯的双齿配位体 |
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EP0810029B1 (de) * | 1996-05-15 | 2001-11-14 | Celanese Chemicals Europe GmbH | Verfahren zur Herstellung von Aldehyden |
JP3847466B2 (ja) * | 1998-09-01 | 2006-11-22 | 三菱化学株式会社 | オレフィンのヒドロホルミル化反応方法 |
CA2478256A1 (en) * | 2002-03-22 | 2003-10-02 | Kuraray Co., Ltd. | Bisphosphine, process for producing the same, and use thereof |
DE10352260B3 (de) | 2003-11-08 | 2005-04-14 | Celanese Chemicals Europe Gmbh | Verfahren zur Herstellung von TCD-Alkohol DM |
DE10352258B4 (de) | 2003-11-08 | 2013-06-13 | Oxea Gmbh | Verfahren zur Herstellung von TCD-Diamin |
DE10352261B4 (de) | 2003-11-08 | 2006-08-24 | Celanese Chemicals Europe Gmbh | Verfahren zur Herstellung von TCD-Dialdehyd |
US7631758B2 (en) * | 2005-04-13 | 2009-12-15 | Vaporlok Technology, Llc | Shipping and storage containers |
CN104209012A (zh) * | 2013-05-29 | 2014-12-17 | 成都慧成科技有限责任公司 | 一种高通量、高盐截留率反渗透膜的制备方法 |
CN109453816B (zh) * | 2018-12-12 | 2020-08-25 | 四川大学 | 一种用于烯烃氢甲酰化反应的催化剂及其制备方法和应用 |
CN113061149B (zh) * | 2021-03-29 | 2022-04-22 | 万华化学集团股份有限公司 | 一种互配型配体和氢甲酰化催化剂、及二元醇的制备方法 |
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FR2230654B1 (zh) * | 1973-05-21 | 1975-11-21 | Rhone Poulenc Ind | |
US4694109A (en) * | 1986-06-13 | 1987-09-15 | Eastman Kodak Company | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
US4935550A (en) * | 1988-08-12 | 1990-06-19 | Union Carbide Chemicals And Plastics Company Inc. | Catalytic metal recovery from non-polar organic solutions |
DE3842819A1 (de) * | 1988-12-20 | 1990-06-21 | Hoechst Ag | Verfahren zur abtrennung von metallorganischen verbindungen und/oder metallcarbonylen aus ihren loesungen in organischen medien |
US4960949A (en) * | 1988-12-22 | 1990-10-02 | Eastman Kodak Company | Low pressure rhodium catalyzed hydroformylation of olefins |
US5118825A (en) * | 1990-12-10 | 1992-06-02 | Ethyl Corporation | Ruthenium phosphine complex |
DE4040315A1 (de) * | 1990-12-17 | 1992-06-25 | Hoechst Ag | Verfahren zur herstellung von aldehyden |
DE4141299C2 (de) * | 1991-12-14 | 2000-09-21 | Celanese Chem Europe Gmbh | Verfahren zur Herstellung von tertiären Phosphanen |
TW225485B (zh) * | 1992-05-29 | 1994-06-21 | Hoechst Ag | |
DE4415682A1 (de) * | 1994-05-04 | 1995-11-09 | Hoechst Ag | Palladium Katalysatoren mit sulfonierten Bisphosphinen als Liganden, Verfahren zu ihrer Herstellung und ihre Verwendung für Carbonylierungsreaktionen |
DE19516968A1 (de) * | 1995-05-12 | 1996-11-14 | Basf Ag | Optisch aktive Phosphine, deren Herstellung, deren Metallkomplexe und Anwendung in der asymmetrischen Synthese |
DE19522293A1 (de) * | 1995-06-20 | 1997-01-02 | Bayer Ag | Neue Bisphospine als Katalysatoren für asymmetrische Reaktionen |
GB9517105D0 (en) * | 1995-08-21 | 1995-10-25 | Bp Chem Int Ltd | Catalyst compositions |
JP3441605B2 (ja) * | 1996-10-30 | 2003-09-02 | 高砂香料工業株式会社 | 新規光学活性ジホスフィン及び該化合物より得られる遷移金属錯体及び該錯体の存在下にて光学活性体を得る方法 |
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CN109364997A (zh) * | 2012-12-04 | 2019-02-22 | 陶氏技术投资有限责任公司 | 用于氢甲酰化乙烯的双齿配位体 |
CN104475161A (zh) * | 2014-12-03 | 2015-04-01 | 中国石油大学(北京) | 铁磁性纳米颗粒固载铑络合物的氢甲酰化催化剂的制法 |
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US5922634A (en) | 1999-07-13 |
AU2080597A (en) | 1997-11-20 |
CA2204675A1 (en) | 1997-11-15 |
JP3009635B2 (ja) | 2000-02-14 |
MX9703456A (es) | 1998-06-28 |
DE19619527A1 (de) | 1997-11-20 |
JPH1066877A (ja) | 1998-03-10 |
RO115025B1 (ro) | 1999-10-29 |
PL319896A1 (en) | 1997-11-24 |
ZA973986B (en) | 1997-12-09 |
BR9703083A (pt) | 1998-09-08 |
AU713496B2 (en) | 1999-12-02 |
KR970073720A (ko) | 1997-12-10 |
ZA973999B (en) | 1997-12-09 |
ID17380A (id) | 1997-12-24 |
ZA973982B (en) | 1997-12-09 |
EP0811424A2 (de) | 1997-12-10 |
US6020532A (en) | 2000-02-01 |
EP0811424A3 (de) | 1998-06-03 |
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