NO147272B - PROCEDURE FOR THE PREPARATION OF DIACETOXYBUTE BY REPLACING THE 1,3-BUTADIA WITH OXYGEN AND ACETIC ACID - Google Patents
PROCEDURE FOR THE PREPARATION OF DIACETOXYBUTE BY REPLACING THE 1,3-BUTADIA WITH OXYGEN AND ACETIC ACID Download PDFInfo
- Publication number
- NO147272B NO147272B NO773326A NO773326A NO147272B NO 147272 B NO147272 B NO 147272B NO 773326 A NO773326 A NO 773326A NO 773326 A NO773326 A NO 773326A NO 147272 B NO147272 B NO 147272B
- Authority
- NO
- Norway
- Prior art keywords
- oxygen
- acetic acid
- grams
- diacetoxybute
- butadia
- Prior art date
Links
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title description 7
- 239000001301 oxygen Substances 0.000 title description 7
- 229910052760 oxygen Inorganic materials 0.000 title description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- MWWXARALRVYLAE-UHFFFAOYSA-N 2-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCC(C=C)OC(C)=O MWWXARALRVYLAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 description 5
- KUDQSWWPCLAILS-UHFFFAOYSA-N 2-acetyloxybut-1-enyl acetate Chemical compound CC(=O)OC(CC)=COC(C)=O KUDQSWWPCLAILS-UHFFFAOYSA-N 0.000 description 3
- VIRPYONDKXQHHU-UHFFFAOYSA-N 4-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCCC=COC(C)=O VIRPYONDKXQHHU-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000002334 glycols Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000238876 Acari Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 101100096319 Drosophila melanogaster Spc25 gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- -1 nitric acid anions Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av diacetoksybuten ved omsetning av butadien og molekylært oksygen og eddiksyre i nærvær av en jodholdig katalysator, og det særegne ved fremgangsmåten i henhold til oppfinnelsen er at det som jodholdig katalysator anven- The present invention relates to a method for the production of diacetoxybutene by reaction of butadiene and molecular oxygen and acetic acid in the presence of an iodine-containing catalyst, and the distinctive feature of the method according to the invention is that the iodine-containing catalyst used
des et alkalimetall- eller et jordalkalimetall-jodid. des an alkali metal or an alkaline earth metal iodide.
Det er kjent at det er mulig å omsette konjugerte diolefiner, spesielt butadien, med halogen eller halogenholdige systemer, basert på klor eller brom, til å gi halogensubstituerte pro-dukter og disse kan i sin tur underkastes videre reaksjoner, It is known that it is possible to react conjugated diolefins, especially butadiene, with halogen or halogen-containing systems, based on chlorine or bromine, to give halogen-substituted products and these can in turn be subjected to further reactions,
for eksempel med salter av karboksylsyre. De tidligere kjen- for example with salts of carboxylic acid. The previously known
te reaksjoner har imidlertid flere ulemper som har ført til at de foreløpig ikke er anvendt i industriell målestokk. However, these reactions have several disadvantages which have meant that they have not yet been used on an industrial scale.
En av de vesentlige ulemper ligger i det forhold at noen av One of the significant disadvantages lies in the fact that some of
de konvensjonelle reaksjoner foregår med et betraktelig for- the conventional reactions take place with a considerable
bruk av halogeneringsmidlet, idet dette kommer til reaksjon på en støkiometrisk måte, noe som i sterk grad kompliserer katalytiske kretsløpsprosesser. use of the halogenating agent, as this reacts in a stoichiometric manner, which greatly complicates catalytic cycle processes.
På den annen side, selv om en katalytisk kretsløpsprosess On the other hand, although a catalytic cycle process
kunne gjennomføres, for eksempel med kobberklorider og bro- could be carried out, for example with copper chlorides and bro-
mider, ville ikke det halogenerte mellomprodukt kvantitativt inngå i den etterfølgende reaksjon med karboksylsyre, og det- mites, the halogenated intermediate would not quantitatively enter into the subsequent reaction with carboxylic acid, and it
te fører gradvis til. at katalysatoren forbrukes, da det halogenerte mellomprodukt ikke skal inngå i den uunngåelige re-sirkuleringoperasjon for tilførselsforbindelsene. Det er nå overraskende funnet at hvis reaksjonen mellom et butadien og oksygen og eddiksyre gjennomføres i nærvær av et jodid av et alkali-metall eller et jordalkali-metall, er det i et en- tea gradually leads to that the catalyst is consumed, as the halogenated intermediate is not to be included in the inevitable recycling operation for the feed compounds. It has now surprisingly been found that if the reaction between a butadiene and oxygen and acetic acid is carried out in the presence of an iodide of an alkali metal or an alkaline earth metal, it is in a
este prosesstrinn mulig å fremstille diacetoksybuten uten noe tap av det halogenerte middel, idet det siste fullstendig kan gjenvinnes etter fullført raksjon og deretter anvendes på nytt for en frisk tilførsel. På denne måte kan det gjennomføres et fullstendig katalysator-kretsløp og en kontinuerlig pros- este process step possible to produce diacetoxybutene without any loss of the halogenated agent, as the latter can be completely recovered after completion of the reaction and then used again for a fresh supply. In this way, a complete catalyst circuit can be carried out and a continuous process
ess. Reaksjonen forløper tilsynelatende i et eneste trinn. ace. The reaction apparently proceeds in a single step.
DE-AS 25 50 747 vedrører en fremgangsmåte for fremstilling DE-AS 25 50 747 relates to a method for production
av organiske monoestere av vicinale glykoler ved å reagere et olefin med oksygenholdig vann og en karboksylsyre, i væskefase, i nærvær av et katalytisk system sammensatt av: of organic monoesters of vicinal glycols by reacting an olefin with oxygenated water and a carboxylic acid, in liquid phase, in the presence of a catalytic system composed of:
1) Jod eller en jodforbindelse, 1) Iodine or an iodine compound,
2) en kobberforbindelse, 2) a copper compound,
3) et aktiverende ion. 3) an activating ion.
Den reaksjon som derved foregår er tydelig forskjellig fra den som foregår ved fremgangsmåten i henhold til oppfinnelsen. Ved den tidligere foreslåtte metode er forholdet mellom den forestrende syre og vann kritisk, og også er nærværet cerium, mangan og/eller salpetersyre-anioner kritisk, og det samme er tilfellet med forholdet mellom jod og kobber. Mange kri-tiske betingelser må således overholdes for å oppnå et slutt-resultat som i og for seg er forskjellig fra det som tilsiktes ved den foreliggende oppfinnelse, idet formålet for den tidligere foreslåtte fremgangsmåte i første rekke er å fremstille glykoler (fremstilling av glykolesterne er et sekundært for-mål) . Noen likhetspunkter med den foreliggende fremgangsmåte kan nok således sies å foreligge, men ulikhetspunkter over-veier både i antall og betydning. The reaction which thereby takes place is clearly different from that which takes place in the method according to the invention. In the previously proposed method, the ratio between the esterifying acid and water is critical, and also the presence of cerium, manganese and/or nitric acid anions is critical, and the same is the case with the ratio between iodine and copper. Many critical conditions must thus be observed in order to achieve an end result which in itself is different from what is intended by the present invention, as the purpose of the previously proposed method is primarily to produce glycols (production of the glycol esters is a secondary for goal) . Some points of similarity with the present method can thus probably be said to exist, but points of dissimilarity outweigh both in number and importance.
DE-OS 23 54 218 omhandler en nærmere beslektet teknikk, da det vedrører fremstilling av buten-diol eller homologer, men der nevnes overhodet intet om buten-diolestere. Det er her viktig å bemerke at det i den nevnte tidligere foreslåtte prosess anvendes ikke noe oksygen, og videre er det katalysatorsystem som anvendes i den tidligere foreslåtte prosess et komplekst katalysatorsystem bestående av en manganforbindelse og en halogendonor. DE-OS 23 54 218 deals with a more closely related technique, as it relates to the production of butene diol or homologues, but there is no mention whatsoever of butene diol esters. It is important to note here that no oxygen is used in the aforementioned previously proposed process, and further that the catalyst system used in the previously proposed process is a complex catalyst system consisting of a manganese compound and a halogen donor.
I motsetning hertil er det katalysatorsystem som anvendes ved fremgangsmåten i henhold til den foreliggende oppfinnelse et enkomponentsystem som er enkelt, billig, lett anvendbart og pålitelig. In contrast, the catalyst system used in the method according to the present invention is a one-component system which is simple, cheap, easy to use and reliable.
Det er også viktig at tidligere foreslått teknikk konsekvent lærer at en jod- eller jodid-basert katalysator ikke kan anvendes alene men nødvendiggjør et "ko-ion", eller en aktiverende forbindelse, høyst sannsynlig pga. at det uten videre er forutsatt at det ville være vanskelig å overvinne aktiverings-energinivået for gjennomføring av reaksjonen uten en eller annen form for "assistanse" mens den overraskende erkjennelse som ligger til grunn for den foreliggende oppfinnelse er at slik "assistanse" ikke er nødvendig og at reaksjonen kan gjen-nomføres med jodidet alene. Reaksjonen mellom komponentene foregår ved en temperatur mellom 50 og 180° C, foretrukket mellom 120 og 16 0° C under et trykk som tilsvarer atmosfæretryk-ket eller mer. Selve eddiksyren kan utgjøre reaksjonsmediet, eller et inert fortynningsmiddel kan anvendes, valgt blant aromatiske, alifatiske og cykloalofatiske hydrokarboner. It is also important that previously proposed technology consistently teaches that an iodine or iodide-based catalyst cannot be used alone but necessitates a "co-ion", or an activating compound, most likely due to that it is readily assumed that it would be difficult to overcome the activation energy level for carrying out the reaction without some form of "assistance", while the surprising realization underlying the present invention is that such "assistance" is not necessary and that the reaction can be carried out with the iodide alone. The reaction between the components takes place at a temperature between 50 and 180° C, preferably between 120 and 160° C under a pressure which corresponds to atmospheric pressure or more. The acetic acid itself can constitute the reaction medium, or an inert diluent can be used, chosen from aromatic, aliphatic and cycloalophatic hydrocarbons.
Oppfinnelsen skal illustreres ved hjelp av følgende utførel-seseksempler. The invention shall be illustrated by means of the following design examples.
EKSEMPEL 1 EXAMPLE 1
En magnetisk omrørt laboratorie-glassautoklav tilføres 50 ml iseddik og 1,66 gram Kl, oksygen tilføres under et trykk på 3 atmosfærer og autoklaven anbringes på et termostatbad ved 13 0° C. Etter 3 0 minutter har oppløsningen antatt en rødbrun farge og gassfasen er fiolett på grunn av jod-damper. A magnetically stirred laboratory glass autoclave is filled with 50 ml of glacial acetic acid and 1.66 grams of Kl, oxygen is added under a pressure of 3 atmospheres and the autoclave is placed in a thermostatic bath at 130° C. After 30 minutes the solution has assumed a reddish-brown color and the gas phase is violet due to iodine vapors.
Autoklaven avkjøles og restoksygen slippes ut og det innføres nå 1 gram butadien. The autoclave is cooled and residual oxygen is released and 1 gram of butadiene is now introduced.
Autoklaven anbringes på nytt på badet med 13 0° C og etter 3 0 min. slippes de fiolette damper ut og den resterende oppløsning er gul. 10 cykluser som beskrevet ovenfor gjentas, ved en halvkon-tinuerlig gjennom-føring ved avvekslende tilførsel av oksygen og butadien. The autoclave is placed again in the bath with 13 0° C and after 3 0 min. the violet vapors are released and the remaining solution is yellow. 10 cycles as described above are repeated, in a semi-continuous manner with alternating supply of oxygen and butadiene.
Etter fullføring av hver av disse cykluser destilleres opp-løsningen og det oppnås 6 gram 1,4-diacetoksybuten sammen med 1,2 gram 1,2-diacetoksybuten. After completion of each of these cycles, the solution is distilled and 6 grams of 1,4-diacetoxybutene together with 1.2 grams of 1,2-diacetoxybutene are obtained.
EKSEMPLER 2- 5 EXAMPLES 2-5
Samme framgangsmåte som i eksempel 1 anvendes, men det anvendes The same procedure as in example 1 is used, but it is used
i den gitte rekkefølge 10 millomol Lii, Nal, Cal^ og Mgl^. Det oppnås henholdsvis 5,8 gram, 5,9 5 gram, 11,5 gram og 12,2 gram 1,4-diacetoksybuten og henholdsvis 1,1 gram, 1,3 gram, 2,4 gram og 2,1 gram 1,2-diacetoksybuten. in the given order 10 millimoles Lii, Nal, Cal^ and Mgl^. 5.8 grams, 5.95 grams, 11.5 grams and 12.2 grams of 1,4-diacetoxybutene and 1.1 grams, 1.3 grams, 2.4 grams and 2.1 grams respectively are obtained 1 ,2-diacetoxybutene.
EKSEMPLER 6- 11 EXAMPLES 6-11
Med samme fremgangsmåte som i eksempel 1-5, men ved temperatur 160° C, oppnås omtrent de samme resultater. With the same procedure as in examples 1-5, but at a temperature of 160° C, approximately the same results are obtained.
EKSEMPEL 12 EXAMPLE 12
En liten glassautoklav tilføres 50 ml eddiksyre og 3 gram A small glass autoclave is filled with 50 ml of acetic acid and 3 grams
Cal2, autoklaven anbringes på et 150° C bad og en gassformet blanding av butadien og oksygen innføres kontinuerlig i volum-forholdet 2 : 1 under et trykk på 2,5 atmosfærer. Etter 8 Cal2, the autoclave is placed in a 150° C bath and a gaseous mixture of butadiene and oxygen is continuously introduced in the volume ratio 2:1 under a pressure of 2.5 atmospheres. After 8
timer avbrytes forsøket og destillasjonen gjennomføres. hours, the experiment is interrupted and the distillation is carried out.
Det oppnås 15 gram 1,4-diacetoksybuten og 3 gram 1,2-diacetoksybuten . 15 grams of 1,4-diacetoxybutene and 3 grams of 1,2-diacetoxybutene are obtained.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT27824/76A IT1068253B (en) | 1976-09-30 | 1976-09-30 | PROCESS FOR THE PREPARATION OF UNSATURATED DIHESTERS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO773326L NO773326L (en) | 1978-03-31 |
| NO147272B true NO147272B (en) | 1982-11-29 |
| NO147272C NO147272C (en) | 1983-03-09 |
Family
ID=11222403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO773326A NO147272C (en) | 1976-09-30 | 1977-09-28 | PROCEDURE FOR THE PREPARATION OF DIACETOXYBUTE BY REPLACING THE 1,3-BUTADIA WITH OXYGEN AND ACETIC ACID |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5344515A (en) |
| BE (1) | BE859270A (en) |
| CH (1) | CH626599A5 (en) |
| DE (1) | DE2743924C3 (en) |
| DK (1) | DK431577A (en) |
| FR (1) | FR2366256A1 (en) |
| GB (1) | GB1550709A (en) |
| IT (1) | IT1068253B (en) |
| LU (1) | LU78195A1 (en) |
| NO (1) | NO147272C (en) |
| SE (1) | SE7710864L (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2847068A1 (en) * | 1978-10-28 | 1980-05-08 | Basf Ag | METHOD FOR PRODUCING BUTEDIOL DIACETATES AND BUTANDIOL |
| DE3101002A1 (en) * | 1981-01-15 | 1982-08-05 | Basf Ag, 6700 Ludwigshafen | DIACYLOXYAL CADIENE AND THEIR PRODUCTION |
-
1976
- 1976-09-30 IT IT27824/76A patent/IT1068253B/en active
-
1977
- 1977-08-08 GB GB33221/77A patent/GB1550709A/en not_active Expired
- 1977-09-13 CH CH1117877A patent/CH626599A5/en not_active IP Right Cessation
- 1977-09-16 JP JP11062077A patent/JPS5344515A/en active Pending
- 1977-09-21 FR FR7728514A patent/FR2366256A1/en active Granted
- 1977-09-28 SE SE7710864A patent/SE7710864L/en not_active Application Discontinuation
- 1977-09-28 NO NO773326A patent/NO147272C/en unknown
- 1977-09-28 LU LU78195A patent/LU78195A1/xx unknown
- 1977-09-29 DE DE2743924A patent/DE2743924C3/en not_active Expired
- 1977-09-29 DK DK431577A patent/DK431577A/en not_active Application Discontinuation
- 1977-09-30 BE BE181368A patent/BE859270A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2366256A1 (en) | 1978-04-28 |
| DK431577A (en) | 1978-03-31 |
| SE7710864L (en) | 1978-03-31 |
| DE2743924A1 (en) | 1978-04-06 |
| DE2743924C3 (en) | 1980-07-24 |
| IT1068253B (en) | 1985-03-21 |
| GB1550709A (en) | 1979-08-15 |
| JPS5344515A (en) | 1978-04-21 |
| DE2743924B2 (en) | 1979-12-13 |
| CH626599A5 (en) | 1981-11-30 |
| LU78195A1 (en) | 1978-01-23 |
| NO147272C (en) | 1983-03-09 |
| BE859270A (en) | 1978-03-30 |
| FR2366256B1 (en) | 1982-10-22 |
| NO773326L (en) | 1978-03-31 |
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