CN1024800C - 芳烃钒的生产方法 - Google Patents
芳烃钒的生产方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 18
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 150000004292 cyclic ethers Chemical class 0.000 claims description 5
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 7
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000004711 α-olefin Substances 0.000 abstract description 3
- 150000004996 alkyl benzenes Chemical class 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 229910052720 vanadium Inorganic materials 0.000 description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 239000000725 suspension Substances 0.000 description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 238000002425 crystallisation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- UOJLVZGSZRGVSK-UHFFFAOYSA-I [V+5].[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O Chemical compound [V+5].[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O.[O-][I](=O)=O UOJLVZGSZRGVSK-UHFFFAOYSA-I 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910016467 AlCl 4 Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910001511 metal iodide Inorganic materials 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- HNJCODZEFXEUHM-UHFFFAOYSA-M [V]I Chemical compound [V]I HNJCODZEFXEUHM-UHFFFAOYSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000000925 erythroid effect Effects 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Bridges Or Land Bridges (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polymerisation Methods In General (AREA)
- Steroid Compounds (AREA)
Abstract
通过用金属形式的锌、锰或铁、或二环戊二烯钴还原碘化芳烃钒以高产率制备芳烃钒[V(arene)2](芳烃Arene=苯或单、双或多烷基取代苯)。
芳烃钒可用于制备对乙烯聚合反应或乙烯与α-烯烃共聚反应有活性的催化剂组分。
Description
本发明涉及一种高反应收率的生产芳烃钒的方法。1989年9月9日本申请人申请的申请号为89107055.9的中国专利申请公开了一种经芳烃钒与四氯化钛的反应而得到的固体催化剂组分。这一催化剂组分,与三烷基铝一起,无论是在低压、低温的悬浮法中,还是在高压、高温进行的管状反应器或高压釜(容器)中,或是在高温条件的溶液法中,对乙烯的聚合反应或乙烯与C3-C10α-烯烃的共聚反应都显示出高的活性。
至于芳烃钒的制备,上述专利申请参考了E.O.Fischer和H.S.Kogler在chem.Ber.90.250(1957),F.Calderazzo在Inorg.Chem3,810(1964)中描述的方法。不幸的是,用这些方法只能得到非常低收率的有用反应产物(总收率在15%一级),因此,从工业生产的角度来看没有吸引力。
本发明人发现,通过使用特殊的还原剂还原相应的碘化芳烃钒,可以得到极好收率的芳烃钒,而碘化芳烃钒可通过在芳烃中让氯化钒与金属铝和三氯化铝反应以制得[V(Arene)2].AlCl4配合物,然后用碱金属碘化物处理这种配合物而获得,这与先有技术是一致的。
按照上述,本发明涉及用还原碘化芳烃钒[V(Arene)2I]来制备芳烃钒[V(Arene)2]的方法,此外的“芳烃”表示苯或单、双或多烷基取代苯,其特征在于,作为还原剂的试剂选自金属形式的锌、锰、或铁或二环戊二烯钴。
尤其是,还原反应的反应式可为:
其中M表示锌、锰或铁。
在用二环戊二烯钴作还原剂的情况下,反应可用下式表达:
反应有利于在惰性液体介质中进行。作为惰性液体介质使用的有脂族烃,如庚烷,或环醚,如四氢呋喃。使用环醚可以获得较高的反应速率。使用由脂烃和环醚组成的混合溶剂操作。也可获得好的结果。
反应物通常使用当量用量,或使用比化学计量稍多的还原试剂。
反应温度通常包括在20℃-60℃范围内,反应时间包括在15分钟到20小时范围内。
芳烃钒可通过传统的方法从反应混合物中分离出来。在使用环醚时,根据优选的实施方案,分离是通过在减压和室温下从混合物中除去溶剂来完成的。将蒸馏残渣溶于烃(较好为庚烷)中,并从如此而得的溶液,经初步过滤后,冷却结晶出芳烃钒。
经在上述条件下操作,相对于作为起始产物的碘化芳烃钒,可获得摩尔收率高达75%的芳烃钒。
如上所述,碘化芳烃钒可用先有技术已知的方法获得,如上述F.Calderazzo的方法,根据该法,氯化钒、铝和氯化铝在芳烃中反应以制得[V(arene)2].AlCl4配合物,然后与碱金属碘化物,特别是碘化锂反应,以制得碘化芳烃钒。第一个反应发生在高温,如100-120℃阶次;而第二个反应发生在低温(如,约0℃)和四氢呋喃等溶剂中,反应产物从中析出。这些反应使之有可能得到收率在70%级别的碘化芳烃钒。
如上所述,采用根据本发明的方法获得的芳烃钒是乙烯均聚和共聚反应催化剂的有用组分。特别是,将芳烃钒与四氯化钛反应以产生一种固定催化剂组分,这一固体组分,与三烷基铝结合,无论在高压、低温的悬浮法中,还是高压、高温技术的管状反应器或高压釜中,以及在高温的溶液法中,以乙烯的聚合反应或乙烯与α-烯烃的共聚反应过程都呈现高的活性。
为了更好地说明本发明,提供下列实施例。
实施例1
将0.68g(10.4mmol)锌粉,100ml无水四氢呋喃及7.27g碘化
钒[V(mes)2I](后者根据F.Calderazzo在Inorganic chemistry3,810页(1964)中描述的方法获得),在惰性保护气氛下按上述次序加入到一个装有侧面接管部件的250ml容量试管中。
如此而得的亮棕色悬浮液在25℃维持搅拌15小时,在这段时间的最后,得到一种由红色溶液中的灰色固体构成的悬浮液。四氢呋喃在室温(20-25℃)减压下除去,残余的固体重新悬浮于50ml无水正庚烷中。过滤红综色悬浮液,滤器上的固体每次用10ml无水正庚烷共洗涤五次。将得到的红色、透明庚烷溶液浓缩到约40ml体积。如此而得的红色结晶在低温下,通过倾出母液快速地分离出来,并于室温下在真空中干燥。
实施例2
将2.24gCo(C5H5)2(119mmol),50ml无水四氢呋喃及5.03g碘化
钒(后者根据F.Calderazzo在Inorganic Chemistry,3,810页(1964)中描述的方法获得),在惰性保护气氛下按上述次序加入到一个装有侧面接管部件的100ml容量的试管中。
在室温下搅拌1小时后,得到一种由红色溶液中的黄色固体构成的悬浮液。四氢呋喃在室温(20-25℃)减压下除去,并将残余固体重新悬浮于50ml无水正庚烷中。过滤悬浮液,并将滤器上的剩余固体每次用10ml无水正庚烷共洗涤三次。得到的红色、澄清正庚烷溶液被浓缩到约30ml体积,并冷却至-78℃,然后,在此温度下放置过夜。如此而得的红色结晶在低温下通过倾出母液快速地分离出来,并于室温下真空干燥。
实施例3
根据反应2V(mes)2I+Fe-2V(mes)2+FeI2制备
钒:
将4.29g碘代
钒(10.2mmol)(根据F.Cacderazzo在Inorganic Chemistry,3,810页(1964)中描述的方法获得),50ml无水四氢呋喃和0.282铁粉(5.05mmol)在惰性保护气氛下按上述次序加入到一个容量为250ml的试管中。
如此而得的亮棕色悬浮液在室温下维持搅拌15小时。在这段时间的最后,得到一种微红色的悬浮液,在室温(20-25℃)减压下将其浓缩至干,并将残余的固体重新悬浮于50ml无水正庚烷中。悬浮液于70-80℃过滤,过滤器上的固体每次用10ml无水正庚烷共洗涤三次。所得的红色、透明庚烷溶液冷至约-78℃,并在这一温度下放置过夜。如此而得的红色结晶在低温下从母液中快速分离出来并于室温下真空干燥。
实施例4
将0.228g锰粉(4.15mmol),50ml无水四氢呋喃和3.45g碘化
钒(后者根据F.Calderazzo在Inorganic Chemistry,3,810页(1964)中描述的方法制备),在惰性保护气氛下按上述次序加入到一个容量为250ml的事先干燥过的试管中。
如此而得的悬浮液在室温下(20-25℃)保持搅拌15小时。产生的在红色溶液中含有灰棕色固体的悬浮液于室温减压下浓缩至干。残余的固体重新悬浮于50ml无水正庚烷中。悬浮液在70-80℃加热30分钟,并用高温过滤分离固体。滤器上的残余固体每次用5ml无水正庚烷共洗涤三次。得到的红色、透明庚烷溶液冷却至约-78℃,并在此温度下放置5小时。如此而得的红色结晶在低温下从母液中快速分离出来,并于室温下(20-25℃)真空干燥。
实施例5
按反应2V(mes)2I+Zn→2V(mes)2+ZnI2,制备
钒:
将0.07g锌粉(1.07mmol),20ml无水正庚烷和0.805g碘化
钒(后者根据F.Calderazzo在Inorganic Chemistry,3,810页(1964)中描述的方法而得),在惰性保护气氛下按上述次序加入到一个装
有侧面接管部件的50ml)容量的试管中。
反应混合物在60℃保持搅拌6小时,在这段时间的最后,得到一种由在红色溶液中的灰棕色固体构成的悬浮液。过滤悬浮液,滤器上残余的固体每次用10ml无水正庚烷共洗涤三次。庚烷溶液被浓缩到约10ml体积,冷却至约-78℃并在此温度下保持4小时。如此而得的红色结晶在低温下快速分离出来并于室温下真空干燥。
如此而得的_钒相对于用作起始产物的碘化_钒的摩尔收率为50%。
实施例6
按反应2V(mes)2I+Zn→2V(mes)2+ZnI2制备钒:
将1.3g锌粉(19.88mmol),200ml无水正庚烷,2ml无水四氢呋喃和14g碘化 钒(33.4mmol)((后者根据F.Calderazzo在Inorganic Chemistry,3,810页(1964)中描述的方法获得),在惰性保护气氛下按上述次序加入到一个装有侧面接管部件的500ml容量的试管中。
反应混合物在60℃保持搅拌6小时,并在这段时间的最后得到一种由红色溶液中的灰色固体构成的悬浮液。过滤悬浮液并将滤器上残余固体每次用30ml无水正庚烷共洗涤四次。庚烷溶液浓缩至约50ml体积,冷却至约-78℃,并在此温下放置4小时。如此而得的红色结晶在低温下快速分离出来并在真空干燥。
得到6.03g_钒,相对于用作为起始产物的碘化_钒,摩尔收率为62%。
Claims (3)
1、通过用还原剂还原碘化芳烃钒[V(芳烃2)Ⅰ]制备芳烃[V(芳烃)2]的方法,其中芳烃是莱,其特征在于所说的还原剂选自金属形式的锌、锰或铁,或二环戊二烯钴,并且反应是在液体环醚中进行的。
2、根据权利要求1的方法,其特征在于使用化学计算量的反应物,或稍过量的还原剂。
3、根据权利要求1的方法,其特征在于该方法在20℃-60℃下进行15分钟-20小时。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT8920522A IT1229737B (it) | 1989-05-16 | 1989-05-16 | Procedimento per la produzione di vanadio areni. |
IT20522A/89 | 1989-05-16 |
Publications (2)
Publication Number | Publication Date |
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CN1047304A CN1047304A (zh) | 1990-11-28 |
CN1024800C true CN1024800C (zh) | 1994-06-01 |
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Application Number | Title | Priority Date | Filing Date |
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CN90103521A Expired - Lifetime CN1024800C (zh) | 1989-05-16 | 1990-05-15 | 芳烃钒的生产方法 |
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US (1) | US4980491A (zh) |
EP (1) | EP0398402B1 (zh) |
JP (1) | JP2873718B2 (zh) |
KR (1) | KR930005258B1 (zh) |
CN (1) | CN1024800C (zh) |
AT (1) | ATE113954T1 (zh) |
BR (1) | BR9002122A (zh) |
CA (1) | CA2015997C (zh) |
CZ (1) | CZ280389B6 (zh) |
DD (1) | DD300106A5 (zh) |
DE (1) | DE69013977T2 (zh) |
DK (1) | DK0398402T3 (zh) |
ES (1) | ES2063898T3 (zh) |
FI (1) | FI97620C (zh) |
HU (1) | HU208698B (zh) |
IT (1) | IT1229737B (zh) |
NO (1) | NO174671C (zh) |
PL (1) | PL163355B1 (zh) |
RU (1) | RU1838319C (zh) |
SK (1) | SK230890A3 (zh) |
ZA (1) | ZA903154B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1238071B (it) * | 1990-01-19 | 1993-07-03 | Enichem Anic Srl | Procedimento perfezionato per la produzione di vanadio areni |
AU647296B2 (en) * | 1991-07-12 | 1994-03-17 | Ecp Enichem Polimeri S.R.L. | Procedure for the producing of vanadium bis-arenes from vanadium oxychloride |
IT1269805B (it) * | 1994-05-20 | 1997-04-15 | Enichem Spa | Catalizzatore per la (co)polimerizzazione dell'etilene e procedimento per il suo ottenimento |
JP4906480B2 (ja) * | 2006-11-27 | 2012-03-28 | 株式会社三共 | 遊技機 |
IT1403290B1 (it) | 2010-12-27 | 2013-10-17 | Polimeri Europa Spa | Componente solido di catalizzatore, catalizzatore comprendente detto componente solido, e procedimento di (co)polimerizzazione delle alfa-olefine |
ITMI20121724A1 (it) | 2012-10-12 | 2014-04-13 | Versalis Spa | Catalizzatore a base di rutenio e suo impiego nell'idrogenazione selettiva di composti aromatici o poliinsaturi |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3123571A (en) * | 1964-03-03 | Di-akene metal catalysts | ||
BE551488A (zh) * | 1955-10-05 | |||
US4526724A (en) * | 1983-09-30 | 1985-07-02 | Standard Oil Company (Indiana) | Process for the preparation of zero valent bis-arene transition metal compounds |
-
1989
- 1989-05-16 IT IT8920522A patent/IT1229737B/it active
-
1990
- 1990-04-18 DE DE69013977T patent/DE69013977T2/de not_active Expired - Lifetime
- 1990-04-18 ES ES90200953T patent/ES2063898T3/es not_active Expired - Lifetime
- 1990-04-18 EP EP90200953A patent/EP0398402B1/en not_active Expired - Lifetime
- 1990-04-18 DK DK90200953.9T patent/DK0398402T3/da active
- 1990-04-18 AT AT90200953T patent/ATE113954T1/de not_active IP Right Cessation
- 1990-04-25 PL PL90284934A patent/PL163355B1/pl unknown
- 1990-04-25 ZA ZA903154A patent/ZA903154B/xx unknown
- 1990-04-30 US US07/516,267 patent/US4980491A/en not_active Expired - Lifetime
- 1990-05-03 CA CA002015997A patent/CA2015997C/en not_active Expired - Lifetime
- 1990-05-03 BR BR909002122A patent/BR9002122A/pt not_active IP Right Cessation
- 1990-05-10 SK SK2308-90A patent/SK230890A3/sk not_active IP Right Cessation
- 1990-05-10 CZ CS902308A patent/CZ280389B6/cs not_active IP Right Cessation
- 1990-05-10 FI FI902351A patent/FI97620C/fi active IP Right Grant
- 1990-05-10 KR KR1019900006575A patent/KR930005258B1/ko not_active IP Right Cessation
- 1990-05-11 JP JP2120127A patent/JP2873718B2/ja not_active Expired - Fee Related
- 1990-05-14 DD DD340638A patent/DD300106A5/de unknown
- 1990-05-14 NO NO902129A patent/NO174671C/no not_active IP Right Cessation
- 1990-05-15 RU SU904743897A patent/RU1838319C/ru active
- 1990-05-15 CN CN90103521A patent/CN1024800C/zh not_active Expired - Lifetime
- 1990-05-15 HU HU903046A patent/HU208698B/hu unknown
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