CN1069310C - 在零价镍、二配位基磷化合物和路易斯酸存在下的氢氰化方法 - Google Patents
在零价镍、二配位基磷化合物和路易斯酸存在下的氢氰化方法 Download PDFInfo
- Publication number
- CN1069310C CN1069310C CN96192673A CN96192673A CN1069310C CN 1069310 C CN1069310 C CN 1069310C CN 96192673 A CN96192673 A CN 96192673A CN 96192673 A CN96192673 A CN 96192673A CN 1069310 C CN1069310 C CN 1069310C
- Authority
- CN
- China
- Prior art keywords
- compound
- pentenenitrile
- hydrocyanation
- lewis acid
- para
- 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.)
- Expired - Lifetime
Links
- 0 CC(C1=C=CC=C1)POc(cccc1)c1-c(cccc1)c1OPCC(C=CC=C1)=CC1(C)*(C)=N Chemical compound CC(C1=C=CC=C1)POc(cccc1)c1-c(cccc1)c1OPCC(C=CC=C1)=CC1(C)*(C)=N 0.000 description 8
- PHGXREMLRREHNP-UHFFFAOYSA-N CC(C1=C=CC=C1)POCc(cccc1)c1-c1c(COP)cccc1 Chemical compound CC(C1=C=CC=C1)POCc(cccc1)c1-c1c(COP)cccc1 PHGXREMLRREHNP-UHFFFAOYSA-N 0.000 description 1
- MMWILWHLUCALAE-UHFFFAOYSA-N CC(C1=C=CCC1)POCc1ccccc1COPC1=C=CC=C1 Chemical compound CC(C1=C=CCC1)POCc1ccccc1COPC1=C=CC=C1 MMWILWHLUCALAE-UHFFFAOYSA-N 0.000 description 1
- PJJKUBXIDCAIME-UHFFFAOYSA-N CC1=C=CC=C1 Chemical compound CC1=C=CC=C1 PJJKUBXIDCAIME-UHFFFAOYSA-N 0.000 description 1
- OLLMWIMVYKJKAL-UHFFFAOYSA-N CCC(C)(c1cc(F)cc(/[F]=C\CC)c1)POc1ccc(cccc2)c2c1-c(c1ccccc1cc1)c1OPC(C)C(C(C)C(F)=C1)C=C1F Chemical compound CCC(C)(c1cc(F)cc(/[F]=C\CC)c1)POc1ccc(cccc2)c2c1-c(c1ccccc1cc1)c1OPC(C)C(C(C)C(F)=C1)C=C1F OLLMWIMVYKJKAL-UHFFFAOYSA-N 0.000 description 1
- DHKUGEGNNIEQDJ-UHFFFAOYSA-N CCC(C)(c1cc(F)cc(F)c1)POc1ccccc1-c1ccccc1OPC=C Chemical compound CCC(C)(c1cc(F)cc(F)c1)POc1ccccc1-c1ccccc1OPC=C DHKUGEGNNIEQDJ-UHFFFAOYSA-N 0.000 description 1
- UOHJQGFXKCADCX-UHFFFAOYSA-N CCC(c(cc1)ccc1F)POc1ccccc1-c1ccccc1OPC(C)(C)c(cc1)ccc1F Chemical compound CCC(c(cc1)ccc1F)POc1ccccc1-c1ccccc1OPC(C)(C)c(cc1)ccc1F UOHJQGFXKCADCX-UHFFFAOYSA-N 0.000 description 1
- PFINYKRPUJCMCT-UHFFFAOYSA-N CCc1cc(F)cc(F)c1 Chemical compound CCc1cc(F)cc(F)c1 PFINYKRPUJCMCT-UHFFFAOYSA-N 0.000 description 1
- ZEWGMOQWTWMZMZ-UHFFFAOYSA-N CCc1cc(F)ccc1 Chemical compound CCc1cc(F)ccc1 ZEWGMOQWTWMZMZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/408,250 US5523453A (en) | 1995-03-22 | 1995-03-22 | Process for hydrocyanation |
| US08/408,250 | 1995-03-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1179147A CN1179147A (zh) | 1998-04-15 |
| CN1069310C true CN1069310C (zh) | 2001-08-08 |
Family
ID=23615497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96192673A Expired - Lifetime CN1069310C (zh) | 1995-03-22 | 1996-03-07 | 在零价镍、二配位基磷化合物和路易斯酸存在下的氢氰化方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5523453A (enExample) |
| EP (1) | EP0815073B1 (enExample) |
| JP (1) | JP2911608B2 (enExample) |
| KR (1) | KR100270499B1 (enExample) |
| CN (1) | CN1069310C (enExample) |
| AT (1) | ATE203233T1 (enExample) |
| BR (1) | BR9607982A (enExample) |
| CA (1) | CA2214009C (enExample) |
| DE (1) | DE69613968T2 (enExample) |
| IN (1) | IN186815B (enExample) |
| MY (1) | MY117595A (enExample) |
| TW (1) | TW343962B (enExample) |
| WO (1) | WO1996029303A1 (enExample) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293944C (zh) * | 2001-11-26 | 2007-01-10 | 因维斯塔技术有限公司 | 烯烃氢氰化用的镍/磷配体催化剂的制备方法 |
| US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
| US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
| US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
| US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
| US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
| US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
| US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
| US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
| US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
| US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
Families Citing this family (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2122515T3 (es) * | 1993-11-23 | 1998-12-16 | Du Pont | Procedimientos y composiciones cataliticas para hidrocianacion de monoolefinas. |
| US5693843A (en) * | 1995-12-22 | 1997-12-02 | E. I. Du Pont De Nemours And Company | Process for hydrocyanation of diolefins and isomerization of nonconjugated 2 alkyl-3-monoalkenenitriles |
| 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 |
| US5710344A (en) * | 1996-11-08 | 1998-01-20 | E. I. Du Pont De Nemours And Company | Process to prepare a linear aldehyde |
| DE19652273A1 (de) | 1996-12-16 | 1998-06-18 | Basf Ag | Monoolefinische C¶5¶-Mononitrile, Verfahren zu ihrer Herstellung und ihre Verwendung |
| US5847191A (en) * | 1997-07-29 | 1998-12-08 | E. I. Du Pont De Nemours And Company | Process for the hydrocyanation of monoolefins using bidentate phosphite ligands and zero-valent nickel |
| DE19740180A1 (de) | 1997-09-12 | 1999-03-18 | Basf Ag | Katalysator, umfassend wenigstens einen Nickel(0)Komplex auf Basis eines Phosphonitliganden und Verfahren zur Herstellung von Nitrilen |
| DE19825212A1 (de) | 1998-06-05 | 1999-12-09 | Basf Ag | Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines zweizähnigen Phosphonitliganden und Verfahren zur Herstellung von Nitrilen |
| DE19827232A1 (de) | 1998-06-18 | 1999-12-23 | Basf Ag | Katalysator, umfassend einen Komplex eines Metalls der VIII. Nebengruppe auf Basis eines Phosphinitliganden und Verfahren zur Hydroformylierung und Hydrocyanierung |
| US6048996A (en) * | 1999-08-26 | 2000-04-11 | E. I. Du Pont De Nemours And Company | Insoluble promoters for nickel-catalyzed hydrocyanation of monoolefins |
| US6365322B1 (en) | 1999-12-07 | 2002-04-02 | Clariant Finance (Bvi) Limited | Photoresist composition for deep UV radiation |
| FR2803294B1 (fr) * | 1999-12-30 | 2002-02-15 | Rhodia Polyamide Intermediates | Procede d'hydrocyanation de composes organiques insatures |
| US6362354B1 (en) | 2000-11-17 | 2002-03-26 | E. I. Du Pont De Nemours And Company | Phosphonite ligands, catalyst compositions and hydroformylation process utilizing same |
| US6437192B1 (en) | 2000-11-17 | 2002-08-20 | E. I. Du Pont De Nmeours And Company | Hydroformylation of conjugated dienes to alkenals using phosphonite ligands |
| DE10136488A1 (de) * | 2001-07-27 | 2003-02-06 | Basf Ag | Ni(O) enthaltendes Katalysatorsystem |
| FR2830530B1 (fr) * | 2001-10-08 | 2004-07-02 | Rhodia Polyamide Intermediates | Procede de transformation, d'une part, de composes a insaturation ethylenique en nitriles et, d'autre part, de nitriles branches en nitriles lineaires |
| DE10150285A1 (de) * | 2001-10-12 | 2003-04-17 | Basf Ag | Phosphonite |
| DE10150286A1 (de) * | 2001-10-12 | 2003-04-17 | Basf Ag | Phosphinite |
| AR036636A1 (es) * | 2001-10-12 | 2004-09-22 | Basf Ag | Fosfonita i, su uso como ligando en complejos de metal de transicion, dichos complejos, procedimiento para la obtencion de estos ultimos, uso de complejos de metal transitorio como catalizador y procedimientos para la adicion de acido cianhidrico a un doble enlace olefinico y para la isomerizacion d |
| US6660876B2 (en) | 2001-11-26 | 2003-12-09 | E. I. Du Pont De Nemours And Company | Phosphorus-containing compositions and their use in hydrocyanation, isomerization and hydroformylation reactions |
| MY138064A (en) * | 2002-01-24 | 2009-04-30 | Basf Ag | Method for the separation of acids from chemical reaction mixtures by means of ionic fluids |
| US6906218B2 (en) | 2002-12-18 | 2005-06-14 | Invista North America S.A.R.L. | Cyclohexane derivatives and methods for their preparation |
| FR2849027B1 (fr) * | 2002-12-23 | 2005-01-21 | Rhodia Polyamide Intermediates | Procede de synthese de composes comprenant des fonctions nitriles a partir de composes a insaturations ethyleniques |
| US6936171B2 (en) * | 2003-01-08 | 2005-08-30 | Invista North America S.A.R.L. | Process for catalyst recovery from hydrocyanation product mixtures |
| US6897329B2 (en) * | 2003-01-14 | 2005-05-24 | Invista North America S.A.R.L. | Process for the preparation of nickel/phosphorous ligand catalyst for olefin hydrocyanation |
| US6844289B2 (en) * | 2003-04-08 | 2005-01-18 | Invista North America S.A.R.L. | Process for the preparation of a nickel/phosphorous ligand catalyst |
| FR2854892B1 (fr) * | 2003-05-12 | 2005-06-24 | Rhodia Polyamide Intermediates | Procede de fabrication de dinitriles |
| WO2005026106A1 (en) | 2003-09-11 | 2005-03-24 | Invista Technologies S.A R.L. | Process of hydrocyanation of unsaturated carboxylic acid derivatives |
| US7385071B2 (en) * | 2003-10-28 | 2008-06-10 | Invista North America S.A.R.L. | Hydrocyanation of pentenenitriles and/or 2-methyl-3-butenenitrile using promoters obtained from the chlorination of titanium-rich ores |
| DE10350999A1 (de) * | 2003-10-30 | 2005-06-02 | Basf Ag | Katalysator, umfassend wenigstens einen Nickel(O)Komplex stabilisiert durch einen sterisch anspruchsvollen Chelatphosphinitphosphitliganden, sowie ein Verfahren zur Herstellung von Nitrilen |
| DE10351000A1 (de) * | 2003-10-30 | 2005-06-09 | Basf Ag | Verfahren zur Herstellung von Nickel(O)-Phosphorligand-Komplexen |
| DE10351003A1 (de) * | 2003-10-30 | 2005-05-25 | Basf Ag | Verfahren zur Herstellung von Nickel-Phosphorligand-Komplexen |
| DE10351002A1 (de) * | 2003-10-30 | 2005-05-25 | Basf Ag | Einsatz von azeotrop-getrockneten Nickel(II)-halogeniden |
| US8119829B2 (en) * | 2004-09-08 | 2012-02-21 | Invista North America S.A.R.L. | Process of hydrocyanation of unsaturated carboxylic acid derivatives |
| DE102004049339A1 (de) * | 2004-10-08 | 2006-04-13 | Basf Ag | Verfahren zur Reinigung von phosphorhaltigen Chelat-Liganden |
| US7709673B2 (en) * | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
| US7709674B2 (en) * | 2006-07-14 | 2010-05-04 | Invista North America S.A R.L | Hydrocyanation process with reduced yield losses |
| US7880028B2 (en) * | 2006-07-14 | 2011-02-01 | Invista North America S.A R.L. | Process for making 3-pentenenitrile by hydrocyanation of butadiene |
| US8906334B2 (en) | 2007-05-14 | 2014-12-09 | Invista North America S.A R.L. | High efficiency reactor and process |
| EP2407444A3 (en) * | 2008-03-19 | 2012-12-05 | Invista Technologies S.à.r.l. | Process for the preparation of dodecanedioic acid |
| DK2658651T3 (en) | 2009-12-18 | 2019-01-14 | Invista Textiles Uk Ltd | NICKEL COMPOSITIONS FOR THE MANUFACTURE OF NICKEL METAL AND NICKEL COMPLEXS |
| US9024049B2 (en) * | 2010-09-07 | 2015-05-05 | Invista North America S.A.R.L. | Nickel compositions for preparing nickel metal and nickel complexes |
| FR2980792B1 (fr) * | 2011-09-30 | 2013-09-06 | Rhodia Operations | Procede de fabrication de composes nitriles a partir de composes a insaturation ethylenique |
| US9133223B2 (en) | 2011-12-21 | 2015-09-15 | Invista North America S.A.R.L. | Extraction solvent control for reducing stable emulsions |
| CN103547349B (zh) | 2011-12-21 | 2016-03-16 | 因温斯特北美公司 | 用于减少稳定乳液的萃取溶剂控制 |
| WO2013095852A1 (en) | 2011-12-21 | 2013-06-27 | Invista North America S.A.R.L. | Extraction solvent control for reducing stable emulsions |
| JP2015503510A (ja) | 2011-12-21 | 2015-02-02 | インヴィスタ テクノロジーズ エスアエルエル | 安定なエマルジョンを減じるための抽出溶媒制御 |
| WO2015200630A1 (en) | 2014-06-27 | 2015-12-30 | Invista North America S.A R.L. | Integrated process for nitrile manufacture with enhanced liquid-liquid extraction |
| US9914700B2 (en) | 2014-06-27 | 2018-03-13 | Invista North America S.A R.L. | Enhanced extraction of impurities from mixture comprising nitriles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5175335A (en) * | 1991-11-12 | 1992-12-29 | E. I. Du Pont De Nemours And Company | Enantioselective hydrocyanation of aromatic vinyl compounds |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3496215A (en) * | 1965-11-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins using selected nickel phosphite catalysts |
| GB1112539A (en) * | 1965-11-26 | 1968-05-08 | Du Pont | Preparation of organic nitriles |
| US3496217A (en) * | 1967-05-23 | 1970-02-17 | Du Pont | Hydrocyanation of olefins |
| US3558688A (en) * | 1967-10-26 | 1971-01-26 | Du Pont | Preparation of allylic nitriles from allylic esters and hcn in the presence of zero-valent nickel catalysts |
| NL7002580A (enExample) * | 1969-03-03 | 1970-09-07 | ||
| US3655723A (en) * | 1969-10-31 | 1972-04-11 | Du Pont | Hydrocyanation of olefins |
| US3631191A (en) * | 1970-04-08 | 1971-12-28 | Du Pont | Synthesis of zero valent nickel-tetrakis triaryl phosphite complexes |
| US3766237A (en) * | 1972-01-25 | 1973-10-16 | Du Pont | Hydrocyanation of olefins |
| US3847959A (en) * | 1972-10-25 | 1974-11-12 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
| US3846461A (en) * | 1972-10-25 | 1974-11-05 | Du Pont | Process of preparing a zerovalent nickel complex with organic phosphorus compounds |
| US3903120A (en) * | 1973-06-19 | 1975-09-02 | Du Pont | Preparation of zerovalent nickel complexes from elemental nickel |
| US4774353A (en) * | 1986-06-05 | 1988-09-27 | E. I. Du Pont De Nemours And Company | Triorganotin catalyst promoters for hydrocyanation |
| US4874884A (en) * | 1988-03-31 | 1989-10-17 | E. I. Du Pont De Nemours And Company | Promoter synergism in pentenenitrile hydrocyanation |
| US5360938A (en) * | 1991-08-21 | 1994-11-01 | Union Carbide Chemicals & Plastics Technology Corporation | Asymmetric syntheses |
-
1995
- 1995-03-22 US US08/408,250 patent/US5523453A/en not_active Expired - Lifetime
-
1996
- 1996-02-05 IN IN206CA1996 patent/IN186815B/en unknown
- 1996-02-14 TW TW085101840A patent/TW343962B/zh not_active IP Right Cessation
- 1996-03-07 CA CA002214009A patent/CA2214009C/en not_active Expired - Lifetime
- 1996-03-07 AT AT96908520T patent/ATE203233T1/de not_active IP Right Cessation
- 1996-03-07 WO PCT/US1996/002551 patent/WO1996029303A1/en not_active Ceased
- 1996-03-07 KR KR1019970706561A patent/KR100270499B1/ko not_active Expired - Lifetime
- 1996-03-07 BR BR9607982A patent/BR9607982A/pt not_active Application Discontinuation
- 1996-03-07 EP EP96908520A patent/EP0815073B1/en not_active Expired - Lifetime
- 1996-03-07 JP JP8528423A patent/JP2911608B2/ja not_active Expired - Lifetime
- 1996-03-07 CN CN96192673A patent/CN1069310C/zh not_active Expired - Lifetime
- 1996-03-07 DE DE69613968T patent/DE69613968T2/de not_active Expired - Lifetime
- 1996-03-16 MY MYPI96000977A patent/MY117595A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5175335A (en) * | 1991-11-12 | 1992-12-29 | E. I. Du Pont De Nemours And Company | Enantioselective hydrocyanation of aromatic vinyl compounds |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293944C (zh) * | 2001-11-26 | 2007-01-10 | 因维斯塔技术有限公司 | 烯烃氢氰化用的镍/磷配体催化剂的制备方法 |
| US8373001B2 (en) | 2003-02-10 | 2013-02-12 | Invista North America S.A R.L. | Method of producing dinitrile compounds |
| US7897801B2 (en) | 2003-05-12 | 2011-03-01 | Invista North America S.A R.L. | Process for the preparation of dinitriles |
| US7973174B2 (en) | 2005-10-18 | 2011-07-05 | Invista North America S.A.R.L. | Process of making 3-aminopentanenitrile |
| US8178711B2 (en) | 2006-03-17 | 2012-05-15 | Invista North America S.A R.L. | Method for the purification of triorganophosphites by treatment with a basic additive |
| US7919646B2 (en) | 2006-07-14 | 2011-04-05 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
| US8394981B2 (en) | 2006-07-14 | 2013-03-12 | Invista North America S.A R.L. | Hydrocyanation of 2-pentenenitrile |
| US8101790B2 (en) | 2007-06-13 | 2012-01-24 | Invista North America S.A.R.L. | Process for improving adiponitrile quality |
| US7977502B2 (en) | 2008-01-15 | 2011-07-12 | Invista North America S.A R.L. | Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile |
| US8088943B2 (en) | 2008-01-15 | 2012-01-03 | Invista North America S.A R.L. | Hydrocyanation of pentenenitriles |
| US8247621B2 (en) | 2008-10-14 | 2012-08-21 | Invista North America S.A.R.L. | Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols |
| US8338636B2 (en) | 2009-08-07 | 2012-12-25 | Invista North America S.A R.L. | Hydrogenation and esterification to form diesters |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2214009C (en) | 2004-02-24 |
| TW343962B (en) | 1998-11-01 |
| JP2911608B2 (ja) | 1999-06-23 |
| WO1996029303A1 (en) | 1996-09-26 |
| JPH10505101A (ja) | 1998-05-19 |
| EP0815073A1 (en) | 1998-01-07 |
| CN1179147A (zh) | 1998-04-15 |
| KR19980703158A (ko) | 1998-10-15 |
| KR100270499B1 (ko) | 2000-11-01 |
| BR9607982A (pt) | 1998-06-23 |
| DE69613968D1 (de) | 2001-08-23 |
| CA2214009A1 (en) | 1996-09-26 |
| EP0815073B1 (en) | 2001-07-18 |
| ATE203233T1 (de) | 2001-08-15 |
| MY117595A (en) | 2004-07-31 |
| IN186815B (enExample) | 2001-11-17 |
| US5523453A (en) | 1996-06-04 |
| DE69613968T2 (de) | 2002-04-04 |
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