EP0695291A1 - Bismuth dithiocarbamate und deren verwendung als additive fuer schmiermitteln - Google Patents
Bismuth dithiocarbamate und deren verwendung als additive fuer schmiermittelnInfo
- Publication number
- EP0695291A1 EP0695291A1 EP94913165A EP94913165A EP0695291A1 EP 0695291 A1 EP0695291 A1 EP 0695291A1 EP 94913165 A EP94913165 A EP 94913165A EP 94913165 A EP94913165 A EP 94913165A EP 0695291 A1 EP0695291 A1 EP 0695291A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- optionally substituted
- bismuth
- compound
- oil
- 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- Withdrawn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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/10—Groups 5 or 15
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
Definitions
- This invention relates to organic bismuth compounds and their use as extreme pressure lubricant additives in oils and greases.
- EP additives for lubricant oils and greases.
- US 3139405 discloses the use of antimony salts of dialkyldithiocarbamic acids as EP additives, especially antimony dipentyl- and dihexyl- dithiocarbamates. This patent states that these two compounds impart "incredibly high load- bearing capacity" to lubricants and this is stated to be surprising and unexpected since various other metallic salts of dialkyldithio ⁇ carbamic acids tested alongside the antimony compounds impart only moderate or low load bearing capacities to lubricants or are ineffective e.g. by being insoluble.
- antimony compounds described in US 3139405 have been successfully used as EP additives for many years and are commercially available e.g. under the trade name Vanlube 73.
- Vanlube 73 none of the antimony dialkyldithio- carbamates is ideal; some exhibit low solubility and/or poor stability in typical lubricant systems and, furthermore, antimony salts are toxic and can cause health and environmental problems.
- the present invention provides a compound of the formula (I) :
- each R 1 and R 2 is, independently, C ⁇ _i2 alkyl, C 7 _i2 aralkyl optionally substituted by C*L_I2 alkyl, cyclohexyl optionally substituted by C]__i2 alkyl; or
- R* 1 - and R 2 together with the nitrogen atom to which they are attached form a heterocyclic ring optionally substituted by C ⁇ _-j_2 alkyl, with the proviso that R 1 and R 2 are not both ethyl, n-butyl or ti-pentyl.
- R 1 is C * j__i2 alkyl, C 7 _i2 aralkyl optionally substituted by C ⁇ _i2 alkyl or cyclohexyl optionally substituted by C ⁇ _-j_2 alkyl; and R 2 is C6_i2 alkyl, 07.12 aralkyl optionally substituted by C1.12 alkyl, cyclohexyl optionally substituted by C-j__i2 alkyl, isopropyl, isobutyl, tertiary butyl or branched pentyl.
- R 1 or R 2 represents or includes alkyl
- the alkyl group may be linear or branched.
- alkyl are methyl, ethyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, 1-methyl- pentyl, 2-ethylbutyl, 2-ethylhexyl and 1-methylhexyl.
- Rl or R 2 is aralkyl it is preferably benzyl or phenylethyl, optionally substituted in the phenyl ring by C-*__i2 alkyl.
- the phenyl ring may contain more than one alkyl group, but preferably carries one alkyl group which is preferably present in the 4-position.
- An example of an alkyl substituted aralkyl group is 4-methylbenzyl.
- R 1 or R 2 is alkyl substituted cyclohexyl
- the cyclohexyl ring may contain more than one alkyl substituent.
- it is preferably a singly alkyl substituent, which is preferably in the 4-position.
- substituted cyclohexyl groups are 4-methylcyclohexyl, 4-propylcyclohexyl, 4-butyl- cyclohexyl, 4-isopropylcyclohexyl, 4-tertiary butylcyclohexyl and 4-nonylcyclohexyl.
- the ring When R 1 and R 2 together with the nitrogen atom to which they are attached form a heterocyclic ring, the ring preferably contains 6 atoms as in morpholino, piperazino or piperidino. Where the ring is piperazino, both nitrogen atoms may carry a dithiocarbamyl radical whereby there is the possibility that the resulting bismuth salt is polymeric. However, it is preferred that one of the nitrogen atoms of the piperazino ring is substituted by C ⁇ _**_2 alkyl, especially C ⁇ _ ⁇ alkyl and more especially 0- ⁇ . alkyl.
- R 1 or R 2 is alkyl substituted aralkyl or cyclohexyl or R 1 and R 2 together with the nitrogen atom to which they are attached form an N-alkyl piperazino ring
- the alkyl group is preferably C- ⁇ . ⁇ alkyl, and especially C . alkyl and may be linear or branched.
- R 1 and R 2 are both linear or branched C ⁇ _i2 alkyl, and it is especially preferred that at least one of R 1 and R 2 is, or contains, branched alkyl since such compounds are easier to formulate and dissolve in oils and greases than when R 1 and R 2 are both linear alkyl.
- R 1 or R 2 and desirably R 1 and R 2 are not both linear short chain (C*L_5) alkyl groups and this forms a particular aspect of the invention.
- R 1 and R 2 can be mixed groups, particularly of groups of the same carbon chain length e.g. mixed pentyl groups.
- R 1 and R 2 may be different, they are preferably the same because of the greater availability of symmetrical secondary amines from which the dialkyldithiocarbamic acids are conveniently derivable.
- 'symmetrical secondary amines' include amines made with mixed alkyl groups, especially of the same chain length as in secondary (mixed pentyl) amine.
- the bismuth salts may be made from the single dialkyldithio ⁇ carbamic acid or may be made from a mixture of such acids.
- the bismuth salt is made from a mixture of dialkyldithiocarbamic acids the three dialkyldithiocarbamic acid radicals in formula (I) are not the same.
- compatibility of the EP additive in a lubricant system such as an oil or grease can be increased.
- dialkyldithiocarbamic acids can be made by methods known in the art. However, since some dialkyldithiocarbamic acids are unstable, they are generally made as a salt which exhibits greater stability.
- the salt may be formed with an amine or an alkali metal. In one preferred method, the salt is formed with an amine and is typically made by reacting an excess of a secondary amine of the formula R-*-R 2 NH with carbon disulphide in an appropriate organic solvent.
- the amount of amine used is preferably, 10 moles, more preferably 5 moles and especially 2 moles per mole of carbon disulphide. Such a method is described for example in M ⁇ m. services Chim 6tat, (Paris), 34., 411-12 (1948).
- Preferred solvents are inert to the reactants and include ketones such as acetone.
- the reaction is facile and is generally carried out at temperatures below 60°C, preferably below 20°C and especially below 10°C.
- stoichiometric amounts of the amine and carbon disulphide are reacted together, and the dialkyldithiocarbamic acid then converted to a salt, e.g. an alkali metal salt, by addition of a base, e.g. an alkali metal hydroxide.
- the bismuth salts of this invention are preferably made by reacting the appropriate dialkyldithiocarbamic acid with a suitable bismuth halide such as bismuth trichloride in the presence of a suitable organic reaction medium.
- a suitable bismuth halide such as bismuth trichloride
- 1 mole of bismuth halide is used with about three moles of the dithiocarbamic acid.
- the organic reaction medium is desirably chosen to be a solvent for the dialkyldithiocarbamic acid and a non-solvent (or a poor solvent) for the bismuth salt to ease separation of the bismuth salt from the reaction mixture.
- Suitable solvents for the reaction of the bismuth trihalide with the dialkyldithiocarbamic acid are aliphatic hydrocarbons and chloro- hydrocarbons and, especially, ketones such as acetone.
- the reaction is typically carried out at temperatures below 120°C, preferably below 100°C and especially below 60°C. Where appropriate, the reaction may be carried out in a solvent at reflux.
- the bismuth salts of this invention are typically pale yellow solids melting below 100°C if derived from dialkyldithiocarbamic acids ⁇ containing linear alkyl groups, but they can be oily liquids if derived from a dialkyldithiocarbamic acid containing branched alkyl groups.
- the bismuth salts of this invention exhibit useful properties as EP additives in lubricating oils and greases. Some also exhibit useful antioxidant properties and superior stability to the antimony analogues, especially against light.
- the invention provides a composition comprising a bismuth salt of the formula I and a lubricant.
- the lubricant is preferably an oil or a grease.
- the invention provides a composition comprising a grease and compound of the formula (la):
- each R 1 and R 2 is, independently, C ⁇ _i2 alkyl, C 7 _i2 aralkyl optionally substituted by alkyl, cyclohexyl optionally substituted by C* * __i2 alkyl; or
- R 1 and R 2 together with the nitrogen atom to which they are attached form a heterocyclic ring optionally substituted by C- * __i2 alkyl.
- the invention provides a composition comprising an oil and a compound of the formula (lb):
- each R 1 and R 2 is, independently, C-*__i2 alkyl, C 7 _i2 aralkyl optionally substituted by C-]__-*_2 alkyl, cyclohexyl optionally substituted by C- * __i2 alkyl; or R 1 and R 2 together with the nitrogen atom to which they are attached form a heterocyclic ring optionally substituted by C-j__i2 alkyl, with the proviso that when R 1 and R 2 are either both n-pentyl or ri-butyl the oil is not a SAE 90, high viscosity index, mineral oil having a viscosity of 87 seconds Saybolt viscosity at 210°F (equivalent to about 17 cSt at 100°C) and 1030 seconds Saybolt viscosity at 100°F (equivalent to about 190 cSt at 40°C).
- oils are gear or engines oils having a viscosity above about 200 cSt at 40°C, more preferably above 300 and especially above 400 cSt at 40°C. Such oils preferably have a viscosity below 1500 cSt at 40°C and especially below 1000 cSt at 40°C.
- oils are lighter gear or engine oils having a viscosity below 180, more preferably below 150 and especially below 100 cSt at 40°C. Such oils preferably have a viscosity above 10 and especially above 20 cSt at 40°C.
- the bismuth salt is typically used at a concentration of at least 0.01Z, preferably at least 0.1Z, more preferably at least 0.5Z, and especially at least 2Z by weight, based on the total weight of the lubricant.
- the bismuth salt may be present at a concentration up to 10Z, preferably up to 8Z, more preferably up to 6Z and especially up to 5Z by weight, based on the total weight of the lubricant.
- oils such as those described in standard texts on lubrication such as "Schmierstoff-Taschenbuch” by Schewe- Kobak, (Huethig Verlang, Heidelburg, 1974) and in “Schmierstoffe and Verwandte Kunststoff” by D Klamann, (Verlage Chemie, Weinheim, 1982) and also those described in US 3139405.
- the oil is preferably a mineral oil or a synthetic oil or a mixture of such oils.
- synthetic oils include polyalkylene glycols; poly(alpha-olefins) ; esters, especially phthalates; perfluoroalkylethers and silicones.
- Preferred lubricants are industrial oils especially gear and hydraulic oils.
- the oil may contain other additives which are generally incorporated in fluid lubricant, such as metal passivating agents, viscosity index improvers, pour point depressants, dispersing agents, • detergents, and other additives providing protection against wear, extreme pressure, corrosion, rusting and oxidation.
- additives which are generally incorporated in fluid lubricant, such as metal passivating agents, viscosity index improvers, pour point depressants, dispersing agents, • detergents, and other additives providing protection against wear, extreme pressure, corrosion, rusting and oxidation.
- the grease is preferably a mineral or synthetic oil as described above which has been thickened by the addition of a gelling agent.
- the gelling agents may be a soap, such as a lithium soap, a lithium complex soap, a non-soap gelling agent such as a clay, a carbon black, a silica or a polyurea which is preferably incorporated into the oil in finely divided form.
- the clay is preferably surface coated with an organic material to aid dispersion in the oil, such as a quaternary ammonium compound.
- the non-soap gelling agent is preferably silica, especially fused silica having an average particle diameter below one ⁇ m.
- bismuth salts which benefit from protection by the bismuth salt include iron and copper and especially alloys such as steel and brass.
- bismuth salts of the formulae (I), (la) and (lb) has been found particularly effect as an EP additive in a lubricant where the metals are in frictional contact and form part of a gear or bearing.
- the invention provides the use of a compound of one of the formula (I), (la) and (lb) as an EP additive for a lubricant, especially an oil or a grease.
- the invention provides a metal surface, particularly a gear and especially a bearing which is treated with a bismuth salt of one of the formula (I), (la) and (lb) or a lubricant composition containing a bismuth salt of one of the formula (I), (la) and (lb).
- the invention further includes a method of lubricating one or more surfaces, especially of mating metal surfaces, which comprises including in a lubricant, particularly a lubricating oil or grease, for the one or more surfaces a bismuth salt of one of the formula (I), (la) and (lb), particularly in an amount of from 0.1 to 10Z by weight of the lubricant.
- a lubricant particularly a lubricating oil or grease
- a bismuth salt of one of the formula (I), (la) and (lb) particularly in an amount of from 0.1 to 10Z by weight of the lubricant.
- BDAC (mixed) is bismuth tris-[di-(mixed pentyl isomers)dithio- carbamate] made in Synthesis Example 3.
- BDHC is bismuth tris-(dihexyldithiocarbamate) made in synthesis
- BDHC is bismuth tris-(dihexyldithiocarbamate)
- BDEHC is bismuth tris-[di-(2-ethylhexyl)dithiocarbamate]
- ADHC is antimony tris-(dihexyldithiocarbamate) made in Comparative
- ADAC is antimony tris-(dipentyldithiocarbamate) made in Comparative
- ADAC (mixed) is antimony tris-[di-(mixed pentyl isomers) dithiocarbamate] made in Comparative Synthesis Example D
- Vanlube 73 is a commercially available antimony tris-(dialkyldithio- carbamate) EP additive from Vanderbilt Company, New York USA.
- ADHC Antimony tris-(dihexyldithiocarbamate)
- Synthesis Example 1 was repeated, but substituting dipentylamine based on mixed pentyl isomers containing about 80Z branched pentyl groups (53.5 g; 0.34 mol; from Aldrich Chemicals) for the dihexylamine used in Synthesis Example 1.
- the bismuth tris-[di(mixed pentyl isomers) dithiocarbamate] was obtained as yellow solution in acetone.
- the product was recovered by distilling off the acetone and washing with methanol (4 x 200 ml) to remove excess amine.
- the methanol which formed an upper layer, was decanted and the residual oily product dissolved in methylene chloride.
- Di-n-pentyldithiocarbamic acid salt was prepared as described in Example 1(a), but substituting di-n-pentylamine (53.5 g; 0.34 mol; from Aldrich Chemicals) for the dihexylamine.
- the antimony salt was prepared by the method described in comparative Example A, but substituting di-n-pentyldithiocarbamic acid for the dihexyldithiocarbamic acid.
- the title product was obtained as a pale yellow solid. Yield : 13 . 7 g ( 67Z of theory ) ; mp 70.2 - 71.0°C .
- Example 3 was repeated, but substituting antimony trichloride for bismuth trichloride as described in Comparative Example A.
- the product was isolated as a yellow oily liquid. Yield: 12.96 g (63.3Z of theory).
- the bismuth salts BDAC, BDAC (mixed) and BDHC all exhibit superior properties as EP additives in the oil. This is contrary to the teachings of US 3139405 which demonstrates that both bismuth tris- (dipentyldithiocarbamate) and bismuth tris-(dibutyldithiocarbamate) • are significantly inferior to the antimony analogues.
- the base grease had a total soap content of 9.4Z by weight, lithium 0.22Z and glycerol 0.6Z, which was dispersed in a refined mineral oil derived from North West European crude having a specific gravity of 0.88, a viscosity of 576 seconds Saybolt at 100°F (about 120 cSt at 40°C) and 67 seconds Saybolt at 210°F (about 12 cSt at 100°C), a viscosity index of 95, closed flash point of 480°F (250°C) and pour point of -15°F (-26°C).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB939308091A GB9308091D0 (en) | 1993-04-20 | 1993-04-20 | Compounds and use |
GB9308091 | 1993-04-20 | ||
GB939311223A GB9311223D0 (en) | 1993-06-01 | 1993-06-01 | Compounds and use |
GB9311223 | 1993-06-01 | ||
PCT/GB1994/000830 WO1994024100A1 (en) | 1993-04-20 | 1994-04-20 | Bismuth dithiocarbamates and their use as additive for lubricants |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0695291A1 true EP0695291A1 (de) | 1996-02-07 |
Family
ID=26302776
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94913165A Withdrawn EP0695291A1 (de) | 1993-04-20 | 1994-04-20 | Bismuth dithiocarbamate und deren verwendung als additive fuer schmiermitteln |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0695291A1 (de) |
JP (1) | JPH08508993A (de) |
AU (1) | AU6541994A (de) |
CA (1) | CA2160669A1 (de) |
WO (1) | WO1994024100A1 (de) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL9400493A (nl) * | 1994-03-28 | 1995-11-01 | Skf Ind Trading & Dev | Gebruik van bismut-verbindingen in vet-smeermiddel-samenstellingen voor hoge drukken voor wentellager-toepassingen met lange levensduur. |
US6090755A (en) * | 1994-03-28 | 2000-07-18 | Skf Industrial Trading & Development Company, B.V. | Use of bismuth compounds in extreme pressure grease lubricant compositions for rolling bearing applications with extended service life |
US5576273A (en) * | 1995-11-20 | 1996-11-19 | R.T. Vanderbilt Company, Inc. | Lubricating compositions containing bismuth compounds |
GB2355466A (en) * | 1999-10-19 | 2001-04-25 | Exxon Research Engineering Co | Lubricant Composition for Diesel Engines |
JP2005042102A (ja) * | 2003-07-04 | 2005-02-17 | Koyo Seiko Co Ltd | 転がり軸受用グリース組成物および転がり軸受 |
EP2801603A1 (de) * | 2003-07-04 | 2014-11-12 | Jtekt Corporation | Schmierfettzusammensetzung für Wälzlager |
WO2014031181A1 (en) * | 2012-04-25 | 2014-02-27 | Dow Global Technologies Llc | Polyurethanes made using bismuth thiocarbamate or thiocarbonate salts as catalysts |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2716089A (en) | 1952-07-10 | 1955-08-23 | Exxon Research Engineering Co | Motor oil inhibitor |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE542726A (de) * | 1954-11-11 | |||
US3139405A (en) * | 1961-05-29 | 1964-06-30 | Vanderbilt Co R T | Extreme pressure lubricants |
US3234129A (en) * | 1962-08-01 | 1966-02-08 | Ethyl Corp | Lubricating compositions |
US3630897A (en) * | 1969-10-06 | 1971-12-28 | Phillips Petroleum Co | Color stabilization of lubricating compositions |
US3772197A (en) * | 1970-12-04 | 1973-11-13 | Cities Service Oil Co | Lubricating oil composition |
GB1284512A (en) * | 1971-03-22 | 1972-08-09 | Optimol Olwerke G M B H | Liquid lubricants |
US4524185A (en) * | 1983-03-07 | 1985-06-18 | Federal-Mogul Corporation | Halogen-containing elastomer composition, and vulcanizing process using dimercaptothiodiazole and dithiocarbamate curing system |
JPH0539495A (ja) * | 1991-08-05 | 1993-02-19 | Tonen Corp | 潤滑油組成物 |
-
1994
- 1994-04-20 EP EP94913165A patent/EP0695291A1/de not_active Withdrawn
- 1994-04-20 JP JP6522929A patent/JPH08508993A/ja active Pending
- 1994-04-20 AU AU65419/94A patent/AU6541994A/en not_active Abandoned
- 1994-04-20 CA CA002160669A patent/CA2160669A1/en not_active Abandoned
- 1994-04-20 WO PCT/GB1994/000830 patent/WO1994024100A1/en not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2716089A (en) | 1952-07-10 | 1955-08-23 | Exxon Research Engineering Co | Motor oil inhibitor |
Non-Patent Citations (1)
Title |
---|
See also references of WO9424100A1 |
Also Published As
Publication number | Publication date |
---|---|
JPH08508993A (ja) | 1996-09-24 |
CA2160669A1 (en) | 1994-10-27 |
AU6541994A (en) | 1994-11-08 |
WO1994024100A1 (en) | 1994-10-27 |
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