EP1173416A1 - Verfahren zur aufreinigung von methanid-elektrolyten (ii) - Google Patents

Verfahren zur aufreinigung von methanid-elektrolyten (ii)

Info

Publication number
EP1173416A1
EP1173416A1 EP00922632A EP00922632A EP1173416A1 EP 1173416 A1 EP1173416 A1 EP 1173416A1 EP 00922632 A EP00922632 A EP 00922632A EP 00922632 A EP00922632 A EP 00922632A EP 1173416 A1 EP1173416 A1 EP 1173416A1
Authority
EP
European Patent Office
Prior art keywords
formula
methanide
product
solvent
electrolytes
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Withdrawn
Application number
EP00922632A
Other languages
German (de)
English (en)
French (fr)
Inventor
Peter Sartori
Nikolai Ignatiev
Peter Barthen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1173416A1 publication Critical patent/EP1173416A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02—Magnesium compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a method for producing organic methanide electrolytes in usable quality for use in electrochemical cells.
  • the compound class of tris (perfluoroalkanesulfonyl) methanide was first described by Turowsky et. al. in Inorgan. Chem., 1988, 27, 2135-2137 using the Ths (trifluoromethanesulfonyl) methane.
  • This C-H acidic compound reacts with bases to form the corresponding salts.
  • the anion is planar, and the negative charge can be delocalized very well by the strongly electron-withdrawing substituents.
  • the lithium salt lithium [tris (trifluoromethanesulfonyl) methanide] has been investigated for a long time because of its high conductivity and good solubility in aprotic solvents with regard to its suitability as conductive salt in secondary batteries. Further advantages of this salt are the high electrochemical and thermal stability.
  • purity levels of more than 99.5% are referred to as highly pure.
  • the object of the invention is achieved by a process for the production of highly pure methanides of the formula which are suitable as electrolytes
  • R and R 1 are independent of each other
  • the process according to the invention supplies materials with a purity content of more than 99.5%, preferably between 99.6% and 99.9%, which are therefore suitable for use as electrolytes in batteries.
  • the starting material is stabilized by the reaction with concentrated sulfuric acid and can thus be distilled without decomposition.
  • the free acid can be obtained and purified directly from its salts M 2 [R ⁇ -S ⁇ 2 - (CF 2 ) n -S ⁇ 2 -R].
  • the inventive addition of the strongly hygroscopic sulfuric acid already achieves a good drying effect, which can be increased further by adding sulfur trioxide in accordance with the water content of the raw product.
  • the reduction of the volume of the electrolyte according to the invention by distillation has the decisive advantage that the large excess of desired oxygen nucleophile present in the solution displaces undesirable nucleophiles from the coordination sphere of the lithium. This effect allows contaminants to be distilled off. A highly concentrated electrolyte is obtained, which enables low storage and transportation costs.
  • the purification essentially consists of 3 process steps, which can preferably be followed by two further steps.
  • the rectification apparatus with an isothermal column is heated under a protective gas atmosphere. The distillation bridge must be heated by heating tapes or the like. This keeps the distillation bridge at a constant temperature kept above the respective melting point. Fractional rectification is carried out in this apparatus.
  • the pure fraction from step 1 is mixed with phosphorus pentoxide in a distillation apparatus heated under a protective gas atmosphere.
  • the mixture is stirred at temperatures above and above the melting point of the acid for 15 minutes to 5 hours.
  • the reaction is preferably carried out between 30 min and 90 min.
  • the mixture is then fractionally rectified under vacuum.
  • the fractional rectification of the pure fraction from step 1 with the addition of phosphorus pentoxide leads to a pure product with a water content of preferably 10 to 30 ppm.
  • the product from step 2 is dissolved in polar organic solvents under a dry inert gas atmosphere.
  • Aprotic solvents such as DMC, DEC, EC, PC, BC, VC, cyclopentanone, sulfolane, DMS, 3-methyl-1, 3-oxazolidin-2-one, ⁇ -butyrolactone, EMC, MPC, BMC, EPC, are particularly suitable.
  • the solution is mixed with lithium hydride, with metallic lithium (Li), with lithium chloride, in situ by using a lithium anode or with alkyl lithium.
  • metallic sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), magnesium ( Mg), calcium (Ca), strontium (Sr) or barium (Ba) sodium, potassium, rubidium, cesium, magnesium, calcium, strontium or barium chloride, sodium, potassium, rubidium, Cesium, magnesium, calcium, strontium or barium hydride can be implemented.
  • the mixture is stirred for 10 minutes to 24 hours at temperatures between 10 ° C and 200 ° C. 25 minutes to 5 hours at temperatures between 20 ° C. and 100 ° C. is preferred implemented. Excess alkali or alkaline earth reagent is then filtered off.
  • the volume of the solution from step 3 is reduced to 2/3 to 1/4 if necessary.
  • the solvent is preferably reduced to 1/3.
  • the distillation is carried out at normal pressure at the boiling point of the corresponding solvent.
  • the distillation can also be carried out under vacuum. The boiling points shift accordingly.
  • the highly viscous electrolyte can be diluted with any solvent and solvent mixture. All solvents and mixtures that are used in electrochemical storage media are suitable. The composition of the electrolyte can thus be adapted to the special requirements.
  • the inexpensive process which can be carried out with simple means and apparatus, delivers products of a quality that are suitable for use in batteries and in good yields. No explosive or toxic by-products are formed in this process.
  • conductive salts selected from the group LiPF 6 , LiBF 4 , LiCI0 4 , LiAsF 6 , LiCF 3 S0 3 , LiN (CF 3 S0 2 ) 2 or LiC (CF 3 S0 2 ) 3 and mixtures thereof are suitable.
  • the electrolytes can also contain organic isocyanates (DE 199 44 603) to reduce the water content.
  • the electrolytes can also contain organic alkali salts (DE 199 10 968) as an additive. Alkali borates of the general formula are suitable
  • R 1 and R 2 are the same or different
  • Pyrazyl or bipyridyl which can be unsubstituted or mono- to trisubstituted by A or shark, have or each individually or together the meaning of an aromatic hydroxy acid from the group of aromatic hydroxy-carboxylic acids or aromatic hydroxy-sulfonic acids, which is unsubstituted or one to four times may be substituted by A or shark, and
  • A is alkyl with 1 to 6 carbon atoms, which can be halogenated one to three times.
  • Alkaline alcoholates of the general formula are also suitable
  • Li + OR " in which R has the meaning of an aromatic or aiphatic carbon, dicarbon or sulfonic acid residue, or has the meaning of an aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which may be unsubstituted or substituted one to four times by A or shark, or
  • heterocyclic aromatic ring from the group pyridyl, pyrazyl or bipyridyl, which may be unsubstituted or mono- to trisubstituted by A or shark, or
  • aromatic hydroxy acid from the group of aromatic hydroxy-carboxylic acids or aromatic hydroxy-sulfonic acids, which can be unsubstituted or substituted one to four times by A or shark,
  • a alkyl with 1 to 6 carbon atoms which can be halogenated one to three times.
  • R 1 and R 2 are the same or different, optionally connected directly to one another by a single or double formation, in each case individually or together, the meaning of an aromatic ring from the group phenyl, naphthyl, anthracenyl or phenanthrenyl, which is unsubstituted or one to six times Alkyl (Ci to C 6 ), alkoxy groups (C ⁇ to C 6 ) or halogen (F, Cl, Br) may have substituted, or in each case individually or jointly the meaning of an aromatic heterocyclic ring from the group pyridyl, pyrazyl or pyrimidyl which is unsubstituted or mono- to tetrasubstituted by alkyl (Ci to C 6 ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br) may have substituted,
  • R 3 -R 6 can each have the following meaning individually or in pairs, optionally directly linked to one another by a single or double bond:
  • alkyl (Ci to C 6 ), alkyloxy (d to C 6 ) or halogen (F, Cl, Br)
  • Phenyl, naphthyl, anthracenyl or phenanthrenyl which can be unsubstituted or monosubstituted to sixfold substituted by alkyl (Ci to C 6 ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br),
  • Pyridyl, pyrazyl or pyrimidyl which can be unsubstituted or mono- to tetrasubstituted by alkyl (Ci to C 6 ), alkoxy groups (Ci to C 6 ) or halogen (F, Cl, Br),
  • electrolytes can be compounds of the following formula (DE 199 41 566)
  • A N, P, P (O), O, S, S (O), S0 2 , As, As (O), Sb, Sb (O)
  • A can be enclosed in different positions in R 1 , R 2 and / or R 3 ,
  • Kt may be included in a cyclic or heterocyclic ring - the groups bonded to Kt may be identical or different
  • D + selected from the group of alkali metals in a polar organic solvent with a salt of the general formula
  • Kt, A, R 1 , R 2 , R 3 , k, I, x and y have the meaning given above and
  • R 1 , R 2 , R 3 H and / or alkyl, fluoroalkyl, cycioalkyl m 0-9 and if X H, m ⁇ O
  • R 1 to R 5 are the same or different, optionally connected directly to one another by a single or double formation, each individually or jointly the meaning
  • alkyl or alkoxy radical (Ci to C 8 ) which can be partially or completely substituted by F, Cl, Br,
  • an aromatic ring optionally bonded via oxygen, from the group consisting of phenyl, naphthyl, anthracenyl or phenanthrenyl, which can be unsubstituted or substituted one to six times by alkyl (Ci to C 8 ) or F, Cl, Br
  • an aromatic heterocyclic ring optionally bonded via oxygen, from the group pyridyl, pyrazyl or pyrimidyl, which may be unsubstituted or substituted one to four times by alkyl (Ci to C 8 ) or F, Cl, Br and Z OR 6 , NR 6 R 7 , CR 6 R 7 R 8 , OS0 2 R 6 , N (S0 2 R 6 ) (S0 2 R 7 ), C (S0 2 R 6 ) (S0 2 R 7 ) (S0 2 R 8 ), OCOR 6 , where
  • R 6 to R 8 are the same or different, optionally connected directly to one another by a single or double bond, each individually or jointly the meaning
  • a hydrogen or the meaning as R 1 to R 5 prepared by reacting a corresponding boron or phosphorus-Lewis acid solvency adduct with a lithium or tetraalkylammonium imide, methanide or triflate can be used.
  • M is a metal ion or tetraalkylammonium ion
  • R 1 to R 4 are the same or different, optionally by means of a single or double bond directly bonded alkoxy or carboxy radicals (CC 8 ).
  • electrolytes can be used in electrochemical cells, with cathodes made of common lithium intercalation and insertion compounds, but also with cathode materials consisting of lithium mixed oxide particles which are coated with one or more metal oxides or polymers.
  • Lithium mixed oxide particles coated with one or more metal oxides obtained by a process (DE 199 22 522) characterized in that the particles are suspended in an organic solvent, the suspension is mixed with a solution of a hydrolyzable metal compound and a hydrolysis solution and then the coated particles are filtered off, dried and optionally calcined.
  • Lithium mixed oxide particles coated with one or more polymers obtained by a process (DE 199 46 066), characterized in that the particles in a solution containing polymers from the group polyimides, polyanilines, polypyrroles, polythiophenes, polyacetylenes, polyacrylonitriles, carbonized Polyacrylonitriles, poly-p-phenylenes, polyphenylenevinylenes, polyquinolines, polyquinoxalines, polyphtalocyaninsiloxanes, polyvinylidenfluor.de, polytetrafluoroethylenes, polyethylmetacrylates, polymethylmetacrylates, polyamides, copolymers with vinyl ethers, cellulose, polyfluorethylenes, polyvinyl alcohols and polyvinylpyridines are coated and then suspended and their derivatives are coated, and their derivatives are then coated, and their derivatives are then coated, and their derivatives are then coated, and their derivatives are then coated, and their derivatives are then coated, and their
  • step 1 A portion of the pure fraction of H 2 [(CF 3 S0 2 ) 2 C-S0 2 - (CF 2 ) 3 -S0 2 - C (CF 3 S0 2 ) 2 ] from step 1 was mixed with phosphorus pentoxide and added to that under an argon atmosphere heated distillation apparatus scheduled. The mixture was melted, stirred at 180 ° C. for one hour under normal pressure, and fractionally rectified in vacuo.
  • the volume of the electrolyte was at room temperature and a pressure of 10 "5 Pa to 100 ml reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Primary Cells (AREA)
EP00922632A 1999-04-28 2000-04-13 Verfahren zur aufreinigung von methanid-elektrolyten (ii) Withdrawn EP1173416A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19919347A DE19919347A1 (de) 1999-04-28 1999-04-28 Verfahren zur Aufreinigung von Methanid-Elektrolyten (II)
DE19919347 1999-04-28
PCT/EP2000/003320 WO2000066547A1 (de) 1999-04-28 2000-04-13 Verfahren zur aufreinigung von methanid-elektrolyten (ii)

Publications (1)

Publication Number Publication Date
EP1173416A1 true EP1173416A1 (de) 2002-01-23

Family

ID=7906184

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00922632A Withdrawn EP1173416A1 (de) 1999-04-28 2000-04-13 Verfahren zur aufreinigung von methanid-elektrolyten (ii)

Country Status (10)

Country Link
EP (1) EP1173416A1 (ko)
JP (1) JP2002543178A (ko)
KR (1) KR20020020697A (ko)
CN (1) CN1350518A (ko)
AU (1) AU4295400A (ko)
BR (1) BR0010024A (ko)
CA (1) CA2371613A1 (ko)
DE (1) DE19919347A1 (ko)
RU (1) RU2001130168A (ko)
WO (1) WO2000066547A1 (ko)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140039254A (ko) * 2011-06-07 2014-04-01 쓰리엠 이노베이티브 프로퍼티즈 컴파니 플루오로카본 전해질 첨가제를 포함하는 리튬-이온 전기화학 전지

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19733948A1 (de) * 1997-08-06 1999-02-11 Merck Patent Gmbh Verfahren zur Herstellung von Perfluoralkan-1-sulfonyl(perfluoralkylsulfonyl) imid-N-sulfonyl enthaltende Methanide, Imide und Sulfonate, und Perfluoralkan-1-N-(sulfonylbis(perfluoralkylsulfonyl)methaniden)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0066547A1 *

Also Published As

Publication number Publication date
WO2000066547A1 (de) 2000-11-09
RU2001130168A (ru) 2004-02-27
CA2371613A1 (en) 2000-11-09
BR0010024A (pt) 2002-01-15
DE19919347A1 (de) 2000-11-02
JP2002543178A (ja) 2002-12-17
KR20020020697A (ko) 2002-03-15
AU4295400A (en) 2000-11-17
CN1350518A (zh) 2002-05-22

Similar Documents

Publication Publication Date Title
EP1162204B1 (de) Ionische Flüssigkeiten
EP1178050B1 (de) Fluoralkylphosphate zur Anwendung in elektrochemischen Zellen
EP1162682A1 (de) Silanverbindungen als Additive in Elektrolyten für elektrochemische Zellen
DE10026565A1 (de) Ionische Flüssigkeiten
DE10008955C2 (de) Lithiumfluoralkylphosphate, Verfahren zu ihrer Herstellung und deren Verwendung als Leitsalze
WO2023001671A1 (de) Flüssige elektrolytzusammensetzung sowie eine elektrochemische zelle mit der elektrolytzusammensetzung
EP1088814A1 (de) Fluorierte Sulfonamide als schwer entflammbare Lösungsmittel zum Einsatz in elektrochemischen Zellen
DE10055811A1 (de) Tetrakisfluoroalkylborat-Salze und deren Verwendung als Leitsalze
EP1229038A1 (de) Boratsalze zur Anwendung in elektrochemischen Zellen
EP1106617A2 (de) Alkylspiroboratsalze zur Anwendung in elektrochemischen Zellen
DE10139409A1 (de) Polymerelektrolyte und deren Verwendung in galvanischen Zellen
EP1726061B1 (de) Leitsalze fur galvanische zellen, deren herstellung und verwendung
WO2012069554A1 (de) Verfahren zur herstellung organischer lithiumsalze
EP1379532B1 (de) Borchelatkomplexe
EP1236732B1 (de) Fluoralkylphosphat-Salze und Verfahren zur Herstellung dieser Substanzen
EP1187244A2 (de) Organische Amine als Additive in elektrochemischen Zellen
EP1205998A2 (de) Elektrolyte
DE10016801A1 (de) Lithiumsalze, Verfahren zu deren Herstellung, nichtwässriger Elektrolyt sowie elektrochemische Zelle
DE10119278C1 (de) Verfahren zur Herstellung von Fluoralkylphosphaten
EP1069128B1 (de) Verfahren zur Herstellung von Lithiumkomplexsalzen zur Anwendung in elektrochemischen Zellen
DE10042149A1 (de) Nichtwäßriger Elektrolyt sowie diesen enthaltende elektrochemische Zelle
EP1048648A1 (de) Verfahren zur Aufreinigung von Methanid-Elektrolyten (I)
EP1095942A2 (de) Komplexsalze zur Anwendung in elektrochemischen Zellen
EP1173416A1 (de) Verfahren zur aufreinigung von methanid-elektrolyten (ii)
EP4374446A1 (de) Flüssige elektrolytzusammensetzung sowie eine elektrochemische zelle mit der elektrolytzusammensetzung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010911

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20030124

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030604