EP0113581B1 - Compositions distillées intermédiaires avec propriété d'écoulement à basse température améloirée - Google Patents
Compositions distillées intermédiaires avec propriété d'écoulement à basse température améloirée Download PDFInfo
- Publication number
- EP0113581B1 EP0113581B1 EP83307869A EP83307869A EP0113581B1 EP 0113581 B1 EP0113581 B1 EP 0113581B1 EP 83307869 A EP83307869 A EP 83307869A EP 83307869 A EP83307869 A EP 83307869A EP 0113581 B1 EP0113581 B1 EP 0113581B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- vinyl ester
- wax
- copolymer
- molecular weight
- ethylene
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
Definitions
- Mineral oils containing paraffin wax have the characteristic of becoming less fluid as the temperature of the oil decreases. This loss of fluidity is due to the crystallization of the wax into plate-like crystals which eventually form a spongy mass entrapping the oil therein.
- compositions act as wax crystal modifiers when blended with waxy mineral oils. These compositions modify the size and shape of wax crystals and reduce the adhesive forces between the wax and oil in such a manner as to permit the oil to remain fluid at a lower temperature.
- United Kingdom Patent 1263152 suggests that the size of the wax crystals may be controlled by using a copolymer having a lower degree of side chain branching.
- Fuels are frequently characterised by their Initial Boiling Point, Final Boiling Point and the interim temperatures at which certain volume percentages of the initial fuel have distilled. Fuels whose 20% to 90% distillation point differ within the range from 70 to 100°C (ASTM D86) and 90% boiling temperature is generally from 10 to 30 ° C especially 10 to 25 ° C of the final boiling point have been found particularly difficult to treat sometimes being virtually unaffected by additives or otherwise requiring very high levels of additive. All distillations referred to herein are according to ASTM D86.
- Typical sharply fractionated fuels have a 90% to final boiling point of 10 to 20 ° C usually with a 20 to 90% boiling range of 90 to 110°C. Both types of fuel have final boiling points above 350 ° C generally a final boiling point in the range 350 ° C to 375 ° C especially 350 ° C to 370 ° C.
- copolymers of ethylene and vinyl acetate which have found widespread use for improving the flow of the previously widely available distillate fuels generally contained up to 30 wt % vinyl acetate where the additive was used to control the size of wax crystals forming in the fuel or they contained around 36 wt % or more vinyl acetate where their prime function was to lower the pour point of the distillate fuel. We have not found either of these types of additive to be effective in the treatment of the narrow boiling and/or sharply fractionated fuels described above.
- EP-A-61 894 describes inter alia, the improvement of the flow properties of a distillate fuel whose 20% and 90% distillation points differ by 106°C and whose 90% boiling point temperature is 31 ° C below its final boiling temperature of 375 ° C, said fuel being described as "Fuel 3" on page 14 thereof.
- the document describes providing the improvement by adding "Polymer 15" to the fuel, which polymer being a mixture of about 75 wt % of a wax growth arrestor consisting of a copolymer of ethylene and about 38 wt % of vinyl acetate and having a number average molecular weight of about 1800 and about 25 wt % of a wax crystal nucleator consisting of a copolymer of ethylene and about 16 wt % of vinyl acetate and having a number average molecular weight of about 3000.
- a wax growth arrestor consisting of a copolymer of ethylene and about 38 wt % of vinyl acetate and having a number average molecular weight of about 1800 and about 25 wt % of a wax crystal nucleator consisting of a copolymer of ethylene and about 16 wt % of vinyl acetate and having a number average molecular weight of about 3000.
- Polymer 15 is described in the above-mentioned US-A-3 961 916, the arrestor being referred to as Copolymer B and the nucleator as Copolymer H, and is considered to be one of the most preferred additives disclosed in that document.
- the present invention therefore provides the use as an additive for improving the flow properties of a distillate petroleum fuel oil whose 20% and 90% distillation points differ within the range of from 70 to 100°C and whose 90% boiling-temperature is from 10 to 30 ° C of the final boiling point, and whose final boiling point is above 350 ° C of an additive comprising
- the present invention further provides a distillate fuel whose 20% and 90% distillation points differ by 70 ° C to 100°C, whose 90% boiling-temperature is from 10 to 30 ° C of the final boiling point, and whose final boiling point is above 350 ° C containing from 50 to 500 ppm of
- the additive is a mixture of two copolymers such as those generally described in the above-mentioned United States Patent 3,961,916, it may or may not contain the same vinyl ester. Such an additive mixture is particularly useful for treating the above type of fuel since it allows added flexibility.
- the additive comprises from 10 to 15 parts by weight of a synthetic polymeric material having the property of a wax growth arrestor in said fuel for each part of a synthetic polymeric material having the properties of a wax growth stimulator, said wax growth arrestor and growth stimulator being copolymers of ethylene and vinyl esters of carboxylic acids containing from 1 to 4 carbon atoms the average ester content of said copolymers being in the range 32 to 35 wt, % and the number average molecular weight thereof being in the range 1000 to 6000.
- the fuel contains from 50 to 500 ppm (parts per million) of the additive mixture of the above-mentioned preferred embodiment.
- the fuels used in the present invention may have final boiling points between 350 ° C and 375 ° C more usually between 350 ° C and 370 ° C.
- the wax growth stimulator or nucleator is a synthetic polymeric material which is soluble in the distillate at temperatures substantially above the saturation temperature but on cooling of the distillate progressively separates out in the form of small particles as the temperature of the distillate approaches the saturation point, e.g. is cooled from a point slightly above (e.g. 10°C above; preferably about 5°C above) said saturation temperature.
- saturation temperature is defined as the lowest temperature at which solute, e.g. wax, cannot be crystallized out of the solution even if known crystallization inducement methods are used. Whilst not known certainly it is believed that as cooling continues, additional nucleator particles separate out in a more or less continuous manner.
- additional particles act as nucleators for continued wax crystallization, which in effect, would prevent substantial supercooling of the distillate.
- the advantages of having fresh nucleator particles formed continuously is that the supersaturation of the distillate with n-paraffins is kept at the lowest possible level thus facilitating a molecule of growth arrestor to build itself into the growth center of growing crystals and by so doing to stop the further growth.
- the inhibitory effect of a growth arrester is believed to result from the presence of bulky groups in its molecule. Additional nucleator should separate out to replace the deactivated growth centers.
- the wax growth arrester is more soluble in said distillate than said nucleator and it acts as a growth arrester as the wax crystal forms.
- the nucleator should not be insoluble in the distillate at elevated temperatures nor should it start to separate out at a temperature substantially above that at which wax crystallization can occur. If nucleators separate out at a temperature substantially above the temperature at which crystallization can occur, then they tend to settle at the bottom of the vessel holding the distillate, instead of remaining dispersed within the distillate. This factor is especially important when the distillate is subjected to repeated warming and cooling as during the warm and cool parts of a day since it does not result in adequate redispersion of the nucleant particles in the distillate.
- the synthetic polymeric materials used as wax growth stimulators and wax growth arresters may contain the same or different vinyl esters.
- wax crystal growth stimulators for the purpose of this invention, wax nucleators and nucleants for wax are all considered equivalent terms and are used interchangeably.
- Wax growth arresters (hereinafter sometimes referred to as wax arresters), generally include in their molecular structure wax-like polymethylene segments which are capable of building themselves into the lattice of the wax crystals at the point of lattice dislocation, and also contain bulky groups which prevent incorporation of further molecules of n-paraffins at the point of lattice dislocation and by so doing stop further growth of crystal.
- a good synthetic polymeric wax nucleator can be chosen by visually comparing a transparent container containing a 0.1 to 3.0 wt.% solution of the potential nucleator in a distillate to an identical container with the same distillate having no additive, as the temperature of the two materials is lowered.
- the onset of the wax crystallization from the distillate containing a polymeric material which has nucleator characteristics will occur at a higher temperature than that at which the crystallization will start in the absence of said nucleator.
- a wax arrester usually is characterized by the ability to delay onset of crystallization.
- the synthetic polymers used as nucleating agents and as wax growth arresters are copolymers of ethylene and vinyl ester and may contain the same or different ester monomer.
- the vinyl ester content and molecular weight are the average over the mixture.
- the additive may however also be single polymer by which is meant material produced in a single polymerisation. In this instance the materials may be obtained by the well known high pressure or solution polymerisation techniques that have previously been suggested for the production of ethylene vinyl ester, especially vinyl acetate copolymers for fuel additives.
- Typical vinyl esters for both mixtures and single polymers include vinyl acetate, vinyl propionate, and vinyl butyrate.
- the molecular weight is the average of the two polymers and in general, the preferred number average molecular weight (VPO) for the nucleator will be within the range of 500-6000, more preferably 1200-6000.
- VPO number average molecular weight
- a relatively low molecular weight ethylenevinyl ester copolymer with a relatively high vinyl ester content has been found to act as a wax growth arrester.
- a relatively high molecular weight copolymer of ethylene with a vinyl ester which copolymer has a relatively low content of vinyl ester acts as a nucleating agent.
- the nucleant is an ethylene/vinyl acetate copolymer its number average molecular weight is preferably at least 500, preferably 1000, higher and/or the ester content at least 5% lower than the corresponding property of the wax growth arrester.
- nucleator can comprise an ethylene-vinyl acetate copolymer of a higher molecular weight if the vinyl acetate content of both polymeric materials is about equal. Where two synthetic polymers are used they may be made separately or they can be made consecutively in one batch by varying the reaction conditions.
- reaction conditions can be selected so that the initial polymerization reaction produces a polymer having primarily nucleator characteristics and the reaction conditions can be changed to produce a polymer having primarily wax growth arresting properties or vice versa. In this manner, a mixture of polymers can be produced having both types of functions.
- the relationships between the concentration of vinyl acetate in the copolymer and molecular weight of the copolymers are important since they are factors which determines the role of the particular copolymer in the fuel. That is, they determine, given the other polymer properties are similar whether or not the copolymer as a whole will be performing within the composition as a wax arrester or as a wax nucleating agent.
- the nucleating agents should have relatively long polymethylene segments, and so as these synthetic polymers approach low molecular weight ranges, the proportion of vinyl acetate should also decrease.
- the specific wax nucleating agents will comprise a copolymer of ethylene and a relatively low proportion of vinyl acetate with a relatively high molecular weight.
- the wax arrester on the other hand will, in general, be a relatively low molecular weight copolymer of a relatively high vinyl acetate content since the function of wax arresting depends more on the presence of bulky groups, such as ester groups, attached to the backbone of the molecule of the copolymer.
- both the preferred relatively lower molecular weight high vinyl acetate (second) copolymer and the preferred first , the relatively high molecular weight low vinyl acetate copolymer may be dissolved in a kerosene or heavy aromatic naphtha.
- Preferred concentrates will contain 5-60%, preferably 10-50% total copolymer with the balance being a hydrocarbon oil solvent.
- the arrester copolymers may be prepared by known procedures employing free-radical initiators, preferably organic peroxide compounds. Suitable procedures are high temperature and high pressure processes or the solution processes described in U.S. specifications, such as U.S. Pat. Nos. 3,048,479 or 3,093,623, and in United Kingdom Patent Specification 1263152.
- the fuels to which the present invention relates are difficult to treat with conventional additives because of the relatively narrow boiling range of the 20% to 90% degree fraction of the fuel, the 90% fraction boiling from 70 to 100° C above that of the 20% fraction and because of the relatively small gap between the 90% boiling point and the final boiling point of from 10 to 30 C, such as to 25 ° C and even, in some instances to 20 C.
- the polymeric materials may be used in ratios of 10 to 15 parts by weight of growth arrester, per part of the nucleator.
- an additive of the present invention was an oil solution containing 63 wt.% of a combination of polymers comprising 13 parts by weight of a wax crystal growth arrestor comprising an ethylene vinyl acetate copolymer of number average molecular weight 2500 and vinyl acetate content of 36 wt.% and 1 part by weight of wax crystal simulator of number average molecular weight 3500 and a vinyl acetate content of about 13 wt.%
- Additive B was an oil solution containing 45 wt.% of an additive combination of 3 parts by weight of the abovemen- tioned wax crystal growth arrestor and 1 part of the wax crystal simulator according to United States Patent 3961916.
- Additive C is 50 wt.% solution in oil of an ethylene acetate copolymer of number average molecular weight 2000 and vinyl acetate content 30 wt.%.
- the fuels used in the Examples were as follows:
- the Wax Crystal Size at Fast Cooling Rates is measured by the Cold Filter Plugging Point test (CFPP).
- CFPP Cold Filter Plugging Point test
- This test is carried out by the procedure described in "Journal of the Institute of Petroleum", Volume 52, No. 510, June 1966, pp. 173-185.
- the CFPP test is carried out with a 45 ml sample of the oil to be tested.
- the oil placed in the ASTM cloud point jar is cooled in a bath maintained at about -30 ° F. Every two degrees drop in temperature, starting from 4 ° F.
- the oil is forced at a suction of 8 inches of water through a filter element provided with a 350 mesh screen into a pipette to a mark indicating a volume of 20 ml., at which time the oil is allowed to return by gravity flow to the cooling chamber.
- the test is repeated with each 2 ° C drop in oil temperature until the oil fails to fill the pipette in a period of 60 seconds to the aforesaid mark.
- the results of the test are reported as the Cold Filter Plugging Point which is the highest temperature at which the oil fails to fill the pipette.
- the fuels used were: and the additives used were A, B and C as used in the previous example together with Additives D to H as follows:
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
- Detergent Compositions (AREA)
- Medicines Containing Plant Substances (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Claims (4)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB838300016A GB8300016D0 (en) | 1983-01-04 | 1983-01-04 | Middle distillate compositions |
GB8300016 | 1983-01-04 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0113581A1 EP0113581A1 (fr) | 1984-07-18 |
EP0113581B1 true EP0113581B1 (fr) | 1992-09-16 |
EP0113581B2 EP0113581B2 (fr) | 1996-08-07 |
Family
ID=10535834
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83307869A Expired - Lifetime EP0113581B2 (fr) | 1983-01-04 | 1983-12-22 | Compositions distillées intermédiaires avec propriété d'écoulement à basse température améloirée |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0113581B2 (fr) |
JP (2) | JPS59136391A (fr) |
KR (1) | KR910004942B1 (fr) |
AT (1) | ATE80651T1 (fr) |
AU (1) | AU2305183A (fr) |
CA (1) | CA1263235A (fr) |
DD (2) | DD226901A5 (fr) |
DE (1) | DE3382624T3 (fr) |
DK (1) | DK164792C (fr) |
FI (1) | FI834887A (fr) |
GB (1) | GB8300016D0 (fr) |
IN (1) | IN159929B (fr) |
NO (1) | NO172650C (fr) |
NZ (1) | NZ206666A (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8300016D0 (en) * | 1983-01-04 | 1983-02-09 | Exxon Research Engineering Co | Middle distillate compositions |
JPS6270488A (ja) * | 1985-09-24 | 1987-03-31 | Mitsubishi Petrochem Co Ltd | 燃料油添加剤および流動性の改善された燃料油 |
US5814110A (en) * | 1986-09-24 | 1998-09-29 | Exxon Chemical Patents Inc. | Chemical compositions and use as fuel additives |
GB9213909D0 (en) * | 1992-06-30 | 1992-08-12 | Exxon Chemical Patents Inc | Oil additives and compositions |
GB9213827D0 (en) * | 1992-06-30 | 1992-08-12 | Exxon Chemical Patents Inc | Oil additives and compositions |
GB9725581D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Additives and oil compositions |
GB9725579D0 (en) | 1997-12-03 | 1998-02-04 | Exxon Chemical Patents Inc | Additives and oil compositions |
DE19802690C2 (de) * | 1998-01-24 | 2003-02-20 | Clariant Gmbh | Additiv zur Verbesserung der Kaltfließeigenschaften von Brennstoffölen |
JP4796242B2 (ja) * | 2001-05-25 | 2011-10-19 | 三洋化成工業株式会社 | 流動性向上剤 |
JP4827798B2 (ja) * | 2007-06-13 | 2011-11-30 | 三菱電機株式会社 | 空調用リモートコントローラおよび空気調和機並びに空気調和システム |
WO2019145664A1 (fr) | 2018-01-25 | 2019-08-01 | Petróleo Brasileiro S.A. - Petrobras | Système et procédé auxiliaire de démarrage ou de redémarrage du flux de fluide gélifié |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3048479A (en) * | 1959-08-03 | 1962-08-07 | Exxon Research Engineering Co | Ethylene-vinyl ester pour depressant for middle distillates |
US3093623A (en) * | 1960-01-05 | 1963-06-11 | Exxon Research Engineering Co | Process for the manufacture of improved pour depressants for middle distillates |
DE1914756C3 (de) * | 1968-04-01 | 1985-05-15 | Exxon Research and Engineering Co., Linden, N.J. | Verwendung von Ethylen-Vinylacetat- Mischpolymerisaten für Erdöl-Destillate |
US3961916A (en) * | 1972-02-08 | 1976-06-08 | Exxon Research And Engineering Company | Middle distillate compositions with improved filterability and process therefor |
US3966428A (en) * | 1973-10-31 | 1976-06-29 | Exxon Research And Engineering Company | Ethylene backbone polymers in combination with ester polymers having long alkyl side chains are low viscosity distillate fuel cold flow improvers |
US3884764A (en) * | 1974-03-25 | 1975-05-20 | Eastman Kodak Co | Method and composition for blood serum cholesterol analysis |
GB1593672A (en) * | 1977-10-07 | 1981-07-22 | Exxon Research Engineering Co | Polymer combinations useful in distillate hydrocarbon oils to improve cold flow properties |
EP0003489B1 (fr) * | 1977-12-20 | 1983-01-12 | Imperial Chemical Industries Plc | Huile brute ayant des propriétés améliorées d'écoulement à froid |
DE2837341C2 (de) * | 1978-08-26 | 1983-02-17 | Akzo Gmbh, 5600 Wuppertal | Verfahren zur Herstellung von organischen Mono- und Polyisocyanaten durch thermische Spaltung der Hydrochloride trisubstituierter Harnstoffe |
JPS5854703B2 (ja) * | 1979-10-04 | 1983-12-06 | 株式会社東芝 | 判定回路 |
JPS56103294A (en) * | 1980-01-23 | 1981-08-18 | Nippon Kemutetsuku Consulting Kk | Coal-containing slurry composition |
JPS6017399B2 (ja) * | 1980-04-07 | 1985-05-02 | 住友化学工業株式会社 | 石油留分燃料油の添加剤 |
EP0061894B1 (fr) * | 1981-03-31 | 1985-09-11 | Exxon Research And Engineering Company | Additif à deux composants pour améliorer l'écoulement des huiles combustibles distillats moyens |
JPS58129096A (ja) * | 1982-01-27 | 1983-08-01 | Mitsubishi Petrochem Co Ltd | 燃料油の添加剤 |
GB8300016D0 (en) * | 1983-01-04 | 1983-02-09 | Exxon Research Engineering Co | Middle distillate compositions |
JPH0247518A (ja) * | 1988-08-10 | 1990-02-16 | Mitsubishi Electric Corp | 温水装置 |
JPH0330637A (ja) * | 1989-06-27 | 1991-02-08 | Taiyo Fishery Co Ltd | 養殖マダイの体色改善法 |
-
1983
- 1983-01-04 GB GB838300016A patent/GB8300016D0/en active Pending
- 1983-12-21 NZ NZ206666A patent/NZ206666A/en unknown
- 1983-12-22 AT AT83307869T patent/ATE80651T1/de not_active IP Right Cessation
- 1983-12-22 DE DE3382624T patent/DE3382624T3/de not_active Expired - Fee Related
- 1983-12-22 CA CA000444122A patent/CA1263235A/fr not_active Expired
- 1983-12-22 EP EP83307869A patent/EP0113581B2/fr not_active Expired - Lifetime
- 1983-12-23 IN IN859/DEL/83A patent/IN159929B/en unknown
- 1983-12-30 KR KR1019830006322A patent/KR910004942B1/ko not_active IP Right Cessation
- 1983-12-30 FI FI834887A patent/FI834887A/fi not_active Application Discontinuation
- 1983-12-30 NO NO834889A patent/NO172650C/no unknown
- 1983-12-30 AU AU2305183A patent/AU2305183A/xx active Pending
-
1984
- 1984-01-03 DD DD84259173A patent/DD226901A5/de not_active IP Right Cessation
- 1984-01-03 DD DD84281022A patent/DD236940A5/de not_active IP Right Cessation
- 1984-01-04 JP JP59000192A patent/JPS59136391A/ja active Granted
- 1984-01-04 DK DK003184A patent/DK164792C/da not_active IP Right Cessation
-
1992
- 1992-07-28 JP JP4201144A patent/JP2534818B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
NZ206666A (en) | 1987-06-30 |
KR840007434A (ko) | 1984-12-07 |
FI834887A0 (fi) | 1983-12-30 |
ATE80651T1 (de) | 1992-10-15 |
DD236940A5 (de) | 1986-06-25 |
NO172650C (no) | 1993-08-18 |
DE3382624T2 (de) | 1993-01-07 |
DE3382624T3 (de) | 1997-01-02 |
EP0113581B2 (fr) | 1996-08-07 |
FI834887A (fi) | 1984-07-05 |
GB8300016D0 (en) | 1983-02-09 |
DK3184D0 (da) | 1984-01-04 |
JPS59136391A (ja) | 1984-08-04 |
DD226901A5 (de) | 1985-09-04 |
CA1263235A (fr) | 1989-11-28 |
DE3382624D1 (de) | 1992-10-22 |
DK3184A (da) | 1984-07-05 |
JPH05186782A (ja) | 1993-07-27 |
DK164792B (da) | 1992-08-17 |
AU2305183A (en) | 1984-07-05 |
NO834889L (no) | 1984-07-05 |
DK164792C (da) | 1993-01-04 |
KR910004942B1 (ko) | 1991-07-18 |
NO172650B (no) | 1993-05-10 |
EP0113581A1 (fr) | 1984-07-18 |
IN159929B (fr) | 1987-06-13 |
JPH0330637B2 (fr) | 1991-05-01 |
JP2534818B2 (ja) | 1996-09-18 |
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