EP0815077A1 - Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam - Google Patents
Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactamInfo
- Publication number
- EP0815077A1 EP0815077A1 EP96919687A EP96919687A EP0815077A1 EP 0815077 A1 EP0815077 A1 EP 0815077A1 EP 96919687 A EP96919687 A EP 96919687A EP 96919687 A EP96919687 A EP 96919687A EP 0815077 A1 EP0815077 A1 EP 0815077A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium dioxide
- caprolactam
- liquid phase
- water
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- -1 6-amino caproic acid nitrile Chemical class 0.000 title claims abstract description 13
- 239000007791 liquid phase Substances 0.000 title claims abstract description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title description 22
- 229960002684 aminocaproic acid Drugs 0.000 title description 3
- 239000010936 titanium Substances 0.000 title description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title 1
- 229910052719 titanium Inorganic materials 0.000 title 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- GWCFTYITFDWLAY-UHFFFAOYSA-N 1-ethylazepan-2-one Chemical compound CCN1CCCCCC1=O GWCFTYITFDWLAY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/08—Preparation of lactams from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles
Definitions
- the present invention relates to a new process for the preparation of cyclic lactams by reacting aminocarbonitriles with water in the presence of catalysts.
- US Pat. No. 2,301,964 relates to the uncatalyzed conversion of 6-aminocapronitrile to caprolactam in aqueous solution at 285 ° C. The yields are below 80%.
- FR-A 2 029 540 describes a process for the cyclization of 6-aminocapronitrile to caprolactam by means of homogeneous metal catalysts from the zinc and copper group in aqueous solution, with caprolactam being obtained in yields of up to 83%.
- caprolactam being obtained in yields of up to 83%.
- the complete separation of the catalyst from the valuable product caprolactam poses problems since this forms complexes with the metals used.
- the object of the present invention was therefore to provide a process for the preparation of cyclic lactams by reacting aminocarbonitriles with water which does not have the disadvantages described above.
- the starting materials in the process according to the invention are aminocarbonitriles, preferably those of the general formula I.
- n and m can each have the values 0, 1, 2, 3, 4, 5, 6, 7, 8 and 9 and the sum of n + m is at least 3, preferably at least 4.
- R 1 and R 2 can in principle be substituents of any kind, it should only be ensured that the desired cyclization reaction is not influenced by the substituents.
- R 1 and R 2 are independently Ci-C ⁇ -alkyl or C 5 -C 7 cycloalkyl groups or C 6 -Ci 2 ⁇ aryl groups.
- Particularly preferred starting compounds are aminocarboxylic acid nitriles of the general formula
- m has a value of 3, 4, 5 or 6, in particular 5.
- the starting compound is 6-aminocaproic acid nitrile.
- the reaction is carried out in the liquid phase at temperatures of generally 140 to 320 ° C, preferably 160 to 280 ° C; the pressure is generally in the range from 1 to 250 bar, preferably from 5 to 150 bar, care being taken that the reaction mixture under the conditions used is predominantly, i.e. without the catalyst present in the solid phase, is liquid.
- the residence times are generally in the range from 1 to 120, preferably 1 to 90 and in particular 1 to 60 minutes. In some cases, dwell times of 1 to 10 minutes have proven to be completely sufficient.
- At least 0.01 mol, preferably 0.1 to 20 and in particular 1 to 5 mol, of water are used per mol of aminocarbonitrile.
- the aminocarbonitrile is advantageously in the form of a 1 to 50% by weight, in particular 5 to 50% by weight, particularly preferably 5 to 30% by weight solution in water (in which case the solvent is also the reactant) or used in water / solvent mixtures.
- solvents are alkanols such as methanol, ethanol, n- and i-propanol, n-, i- and t-butanol and polyols such as diethylene glycol and tetraethylene glycol, hydrocarbons such as petroleum ether, benzene, toluene, xylene, lactams such as pyrrolidone or caprolactam or alkyl-substituted lactams such as N-methylpyrrolidone, N-methylcaprolactam or N-ethylcaprolactam and carboxylic acid esters, preferably called carboxylic acids having 1 to 8 carbon atoms.
- Ammonia can also be present in the reaction.
- Mixtures of organic solvents can of course also be used.
- Mixtures of water and alkanols in a water / alkanol weight ratio of 1 to 75 to 25 to 99, preferably 1 to 50 50 to 99 have proven to be particularly advantageous in some cases.
- the process according to the invention is carried out in the presence of titanium dioxide catalysts which have a rutile content in the range from 0.1 to 95, preferably from 1 to 90% by weight and an anatase content in the range from 99.9 to 5, preferably from 99 to 10 wt .-%, each based on the total content of titanium dioxide.
- the reaction is carried out in a fixed bed, the catalysts being used in the form of strands or tablets, the tablets and strands preferably having a diameter between 1 and 10 mm.
- titanium dioxide powder which already has the desired content of anatase and rutile or which is obtained by pyrolysis either starting from a pure anatase modification or a mixed form is used
- Anatase and rutile phases or a mixture of pure anatase and rutile modifications are obtained by using the appropriate temperature and residence time (both are known to the person skilled in the art, for example from Catalysis Today 14, (1992) 225-242). pyrolyzed until the desired anatase to rutile ratio is reached.
- Corresponding powders are available on the market, for example the titanium dioxide powders P25® (20 to 30% by weight of rutile and 80 to 70% by weight of anatase) from Degussa as well as S150® and S140® (each 100% by weight). % Anatas) by Finti-Kemira.
- the titanium dioxide can be used as such or as a supported catalyst, whereby it can usually be applied to a mechanically and chemically stable support, usually with a high surface area.
- the titanium dioxide can have been produced by precipitation from aqueous solutions, e.g. after the sulfate process or by other methods such as the pyrogenic production of fine titanium dioxide powders, which are commercially available.
- the rutile / anatase-containing titanium dioxide can be mixed with other oxides such as aluminum oxide, zirconium oxide or cerium oxide.
- oxides or their precursor compounds which can be converted into the oxides by calcining, can be prepared from solution, for example, by co-precipitation. In general, a very good distribution of the two oxides used is obtained.
- the oxide or Precursor mixtures can also be precipitated by precipitation of one oxide or precursor in the presence of the second oxide or precursor, which is present as a suspension of finely divided particles.
- Another method consists in mechanical mixing of the oxide or precursor powder, this mixture being able to be used as a starting material for the production of strands or tablets.
- a ceramic support can be coated with titanium dioxide in a thin layer by hydrolysis of titanium isopropylate or other Ti alkoxides.
- Another suitable compound is TiCl.
- Suitable carriers are powders, extrudates or tablets of titanium dioxide itself or other stable oxides such as silicon dioxide. The carriers used can be designed to be macroporous in order to improve the mass transport. It is important that care is taken in the pyrolysis of the titanium dioxide that both rutile and anatase phases occur in the above-mentioned areas.
- the process according to the invention gives cyclic lactams, in particular caprolactam, in high yield with good selectivities and good constancy of the catalyst activity.
- a solution of 6-aminocapronitrile (ACN) in water and ethanol was introduced into the in a heated tubular reactor of 25 ml (diameter 6 mm; length 800 mm) filled with titanium dioxide in the form of tablets or strands at 100 bar weight ratios given in the table.
- the product stream leaving the reactor was analyzed by gas chromatography. The results are also shown in the table. table
- Example catalyst form sulfate content rutile anatase BET A U S [%] [%] [m / g]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Polyamides (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19517821 | 1995-05-18 | ||
| DE19517821A DE19517821A1 (de) | 1995-05-18 | 1995-05-18 | Verfahren zur Herstellung von Caprolactam |
| PCT/EP1996/001891 WO1996036600A1 (de) | 1995-05-18 | 1996-05-07 | Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0815077A1 true EP0815077A1 (de) | 1998-01-07 |
Family
ID=7761968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96919687A Withdrawn EP0815077A1 (de) | 1995-05-18 | 1996-05-07 | Titandioxidkatalysierte cyclisierung in flüssiger phase von 6-aminocapronsäurenitril zu caprolactam |
Country Status (20)
| Country | Link |
|---|---|
| EP (1) | EP0815077A1 (cs) |
| JP (1) | JPH11505230A (cs) |
| KR (1) | KR19990014859A (cs) |
| CN (1) | CN1075810C (cs) |
| AU (1) | AU700098B2 (cs) |
| BG (1) | BG102027A (cs) |
| BR (1) | BR9608470A (cs) |
| CA (1) | CA2218132A1 (cs) |
| CZ (1) | CZ289460B6 (cs) |
| DE (1) | DE19517821A1 (cs) |
| EA (1) | EA199700402A1 (cs) |
| HU (1) | HU220356B (cs) |
| MX (1) | MX9708676A (cs) |
| NO (1) | NO307964B1 (cs) |
| NZ (1) | NZ308485A (cs) |
| PL (1) | PL323389A1 (cs) |
| SK (1) | SK154897A3 (cs) |
| TR (1) | TR199701385T1 (cs) |
| TW (1) | TW340840B (cs) |
| WO (1) | WO1996036600A1 (cs) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19738463C2 (de) * | 1997-09-03 | 1999-09-23 | Basf Ag | Verfahren zur Herstellung von Caprolactam |
| DE19738464A1 (de) * | 1997-09-03 | 1999-03-04 | Basf Ag | Verwendung von Formkörpern als Katalysator zur Herstellung von Caprolactam |
| CN101890370B (zh) * | 2010-08-05 | 2012-05-30 | 上海交通大学 | 基于纳米二氧化钛和聚膦腈的复合光催化剂及其制备方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2029540A (en) * | 1935-10-01 | 1936-02-04 | Porteous William | Trailer |
| US2301964A (en) * | 1941-09-12 | 1942-11-17 | Du Pont | Method of preparing lactams |
| JPS4821958B1 (cs) * | 1969-01-28 | 1973-07-02 | ||
| US4625023A (en) * | 1985-09-03 | 1986-11-25 | Allied Corporation | Selective conversion of aliphatic and aromatic aminonitriles and/or dinitriles into lactams |
| US4628085A (en) * | 1985-09-03 | 1986-12-09 | Allied Corporation | Use of silica catalyst for selective production of lactams |
| JP2969779B2 (ja) * | 1990-05-01 | 1999-11-02 | 株式会社明電舎 | 濃淡画像処理装置 |
| DE4339648A1 (de) * | 1993-11-20 | 1995-05-24 | Basf Ag | Verfahren zur Herstellung von Caprolactam |
-
1995
- 1995-05-18 DE DE19517821A patent/DE19517821A1/de not_active Withdrawn
-
1996
- 1996-05-02 TW TW085105277A patent/TW340840B/zh active
- 1996-05-07 MX MX9708676A patent/MX9708676A/es unknown
- 1996-05-07 EA EA199700402A patent/EA199700402A1/ru unknown
- 1996-05-07 JP JP8534516A patent/JPH11505230A/ja active Pending
- 1996-05-07 NZ NZ308485A patent/NZ308485A/xx unknown
- 1996-05-07 CZ CZ19973578A patent/CZ289460B6/cs not_active IP Right Cessation
- 1996-05-07 HU HU9801131A patent/HU220356B/hu not_active IP Right Cessation
- 1996-05-07 CN CN96194001A patent/CN1075810C/zh not_active Expired - Fee Related
- 1996-05-07 CA CA002218132A patent/CA2218132A1/en not_active Abandoned
- 1996-05-07 WO PCT/EP1996/001891 patent/WO1996036600A1/de not_active Application Discontinuation
- 1996-05-07 TR TR97/01385T patent/TR199701385T1/xx unknown
- 1996-05-07 BR BR9608470A patent/BR9608470A/pt unknown
- 1996-05-07 EP EP96919687A patent/EP0815077A1/de not_active Withdrawn
- 1996-05-07 KR KR1019970708204A patent/KR19990014859A/ko not_active Ceased
- 1996-05-07 PL PL96323389A patent/PL323389A1/xx unknown
- 1996-05-07 SK SK1548-97A patent/SK154897A3/sk unknown
- 1996-05-07 AU AU58147/96A patent/AU700098B2/en not_active Ceased
-
1997
- 1997-11-06 BG BG102027A patent/BG102027A/xx unknown
- 1997-11-17 NO NO975268A patent/NO307964B1/no not_active IP Right Cessation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9636600A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9801131A2 (hu) | 1998-08-28 |
| CZ289460B6 (cs) | 2002-01-16 |
| BR9608470A (pt) | 1998-12-29 |
| CN1184467A (zh) | 1998-06-10 |
| NO975268D0 (no) | 1997-11-17 |
| TR199701385T1 (xx) | 1998-04-21 |
| DE19517821A1 (de) | 1996-11-21 |
| JPH11505230A (ja) | 1999-05-18 |
| HUP9801131A3 (en) | 1999-05-28 |
| SK154897A3 (en) | 1998-07-08 |
| CZ357897A3 (cs) | 1998-04-15 |
| CN1075810C (zh) | 2001-12-05 |
| NO307964B1 (no) | 2000-06-26 |
| NO975268L (no) | 1997-11-17 |
| MX9708676A (es) | 1998-02-28 |
| PL323389A1 (en) | 1998-03-30 |
| HU220356B (hu) | 2001-12-28 |
| CA2218132A1 (en) | 1996-11-21 |
| NZ308485A (en) | 2000-01-28 |
| TW340840B (en) | 1998-09-21 |
| AU700098B2 (en) | 1998-12-24 |
| KR19990014859A (ko) | 1999-02-25 |
| WO1996036600A1 (de) | 1996-11-21 |
| AU5814796A (en) | 1996-11-29 |
| EA199700402A1 (ru) | 1999-06-24 |
| BG102027A (en) | 1998-08-31 |
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