NO174745B - Procedure for the preparation of cycloalkadienes - Google Patents
Procedure for the preparation of cycloalkadienes Download PDFInfo
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- NO174745B NO174745B NO891941A NO891941A NO174745B NO 174745 B NO174745 B NO 174745B NO 891941 A NO891941 A NO 891941A NO 891941 A NO891941 A NO 891941A NO 174745 B NO174745 B NO 174745B
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- cyclopolyoctenylene
- catalyst
- mixture
- weight
- cycloalkadienes
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- -1 halogen radical Chemical class 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910018516 Al—O Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 13
- 239000004913 cyclooctene Substances 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 4
- 150000001925 cycloalkenes Chemical class 0.000 description 4
- QIOLVKNDAOPVBC-UHFFFAOYSA-N cyclohexadeca-1,3-diene Chemical compound C1CCCCCCC=CC=CCCCCC1 QIOLVKNDAOPVBC-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical group C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000402754 Erythranthe moschata Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UCIYGNATMHQYCT-OWOJBTEDSA-N cyclodecene Chemical compound C1CCCC\C=C\CCC1 UCIYGNATMHQYCT-OWOJBTEDSA-N 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- KDQHJGWPOQNCMI-UHFFFAOYSA-N tetrabutylplumbane Chemical group CCCC[Pb](CCCC)(CCCC)CCCC KDQHJGWPOQNCMI-UHFFFAOYSA-N 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical group CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical group CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical group CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical group C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
- C07C6/06—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond at a cyclic carbon-to-carbon double bond
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Fremgangsmåte for fremstilling av cycloalfcadiener i flytende fase ved metatesereaksjon i nærvær av en bærerkatalysator på basis av Re.Et cyclopolyoctenylen med en polymerisasjonsgrad som er høyere eller lik tre, bringes i form av 0,005-0,2 molare oppløsninger i kontakt med bærerkatalysatoren ved oppholdstider av 10-600 s.Process for the preparation of cycloalfcadienes in the liquid phase by metathesis reaction in the presence of a support catalyst based on Re. 10-600 s.
Description
Oppfinnelsen angår en fremgangsmåte for fremstilling av cycloalkadiener i flytende fase ved en metatesereaksjon i nærvær av en bærerkatalysator på basis av Re207/Al203. The invention relates to a method for producing cycloalkadienes in the liquid phase by a metathesis reaction in the presence of a carrier catalyst based on Re 2 O 7 /Al 2 O 3 .
Fra US patent nr. 4668836 er det kjent å fremstille cycloalkadiener ved metatese av cycloalkamonoener i nærvær av en bærerkatalysator på basis av 7-A^O^/SnR^ . From US patent no. 4668836 it is known to prepare cycloalkadienes by metathesis of cycloalkamonoenes in the presence of a carrier catalyst based on 7-A^O^/SnR^ .
Ved alle metatetiske dimeriseringer av cycloalkener til cycloalkadiener dannes samtidig høyere cycloalkapolyener med en polymerisasjonsgrad som er større eller lik tre, til tross for optimale betingelser. Ved dimeriseringen av cycloocten til cyclohexadecadien er dette for eksempel mellom 50 og 70 vekt% (basert på tilført mengde cycloocten) høyere cyclopolyoctenylener. En fornuftig anvendelse av disse cyclo-polyoctenylenblandinger har hittil ikke vært kjent. In all metathetic dimerizations of cycloalkenes to cycloalkadienes, higher cycloalkapolyenes with a degree of polymerization greater than or equal to three are simultaneously formed, despite optimal conditions. In the dimerization of cyclooctene to cyclohexadecadiene, this is, for example, between 50 and 70% by weight (based on the added amount of cyclooctene) higher cyclopolyoctenylenes. A sensible application of these cyclo-polyoctenylene mixtures has not been known to date.
Oppfinnelsen angår en fremgangsmåte for fremstilling The invention relates to a method for production
av cycloalkadiener i flytende fase ved metatesereaksjon i nærvær av en bærerkatalysator på basis av Re^O^/A^O^ og som er særpreget ved at et cyclopolyoctenylen med en polymerisasjonsgrad som er større eller lik tre, i form av 0,005-0,2 molare oppløsninger bringes i kontakt med bærerkatalysatoren under of cycloalkadienes in the liquid phase by metathesis reaction in the presence of a support catalyst based on Re^O^/A^O^ and which is characterized by the fact that a cyclopolyoctenylene with a degree of polymerization greater than or equal to three, in the form of 0.005-0.2 molar solutions are brought into contact with the supported catalyst below
■anvendelse av oppholdstider på fra 10 til 600 sekunder. ■use of residence times from 10 to 600 seconds.
Ved hjelp av den foreliggende fremgangsmåte kan ved metatesereaksjonen fra cycloocten til cyclohexadecadien cyclopolyoctenylen som dannes, likeledes omsettes til cycloalkadiener ved en metatesereaksjon. Det er overraskende at de oppnåelige utbytter hva gjelder cycloalkadienene da ligger betydelig høyere enn hva som var å forvente ut fra stillingen for den termodynamiske likevekt. Således kan utbytter på inntil 40% oppnås ved nedbygningen av cyclopolyoctenylener. By means of the present method, in the metathesis reaction from cyclooctene to cyclohexadecadiene, the cyclopolyoctenylene that is formed can also be converted to cycloalkadienes by a metathesis reaction. It is surprising that the achievable yields with regard to the cycloalkadienes are then significantly higher than what was to be expected based on the position of the thermodynamic equilibrium. Thus, yields of up to 40% can be obtained by the degradation of cyclopolyoctenylenes.
Utbyttene ligger derved tilnærmet likt med de utbytter som kan erholdes ved cyclooctenmetatesen selv om det ved cyclopolyoctenylenmetatesen dreier seg om en nedbygnings-reaksjon, mens det ved cyclooctenmetatesen dreier seg om en oppbygningsreaksjon. The yields are thus approximately the same as the yields that can be obtained in the cyclooctene metathesis, even though the cyclopolyoctenylene metathesis involves a degradation reaction, while the cyclooctene metathesis involves a build-up reaction.
Ved hjelp av den foreliggende fremgangsmåte kan de cyclopolyoctenylener som dannes ved cyclooctenmetatesen, foredles til vesentlig mer verdifulle cycloalkadiener. With the help of the present method, the cyclopolyoctenylenes that are formed by the cyclooctene metathesis can be refined into substantially more valuable cycloalkadienes.
I tillegg kommer at da det har vist seg at et nesten likeartet reaksjonsforhold foreligger ved oppbygning og ned-bygning, kan også cycloalkamonoen/cyclopolyoctenylen-blandinger anvendes for fremstilling av cycloalkadiener. In addition, as it has been shown that an almost similar reaction ratio exists for building up and down building, cycloalkamonoene/cyclopolyoctenylene mixtures can also be used for the production of cycloalkadienes.
Oppfinnelsen angår således også en fremgangsmåte for fremstilling av cycloalkadiener i flytende fase ved metatesereaksjon i nærvær av en bærerkatalysator på basis av Re207/Al202 og som er særpreget ved at en cycloalkamonoen/cyclopolyoctenylenblanding, idet cyclopolyoctenylenet oppviser en polymerisasjonsgrad på større eller like tre, i form av 0,005-0,2 molare oppløsninger bringes i kontakt med bærerkatalysatoren under anvendelse av oppholdstider på fra 10 til 600 sekunder. The invention thus also relates to a process for the production of cycloalkadienes in the liquid phase by metathesis reaction in the presence of a carrier catalyst based on Re207/Al202 and which is characterized by the fact that a cycloalkamonoene/cyclopolyoctenylene mixture, the cyclopolyoctenylene having a polymerization degree of greater than or equal to three, in the form of 0.005-0.2 molar solutions are contacted with the supported catalyst using residence times of from 10 to 600 seconds.
Molangivelsen for konsentrasjonene av oppløsningene gjelder i henhold til oppfinnelsen beregnede cyclooctenen-heter som fås når cyclopolyoctenylen deles i raonomerene, såvel som anvendelsen av cycloalkamonoen/cyclopolyoctenylen-blandinger med de tilsatte cycloalkamonoenenheter addert. The molar expression for the concentrations of the solutions applies according to the invention calculated cyclooctene units which are obtained when the cyclopolyoctenylene is divided into the raonomers, as well as the use of cycloalkamonoene/cyclopolyoctenylene mixtures with the added cycloalkamonoene units added.
Ved fremgangsmåten ifølge oppfinnelsen foretrekkes 0,01-0,05 molare oppløsninger. Foretrukne oppholdstider er 10-200 sekunder. In the method according to the invention, 0.01-0.05 molar solutions are preferred. Preferred residence times are 10-200 seconds.
Anvendte cyclopolyoctenylener svarer til den generelle formel Cyclopolyoctenylenes used correspond to the general formula
og oppviser en polymerisasjonsgrad n av minst 3, fortrinnsvis 3-50, spesielt 3-20. and exhibits a polymerization degree n of at least 3, preferably 3-50, especially 3-20.
Dersom cyclopolyoctenylen/cycloalkamonoenblandinger anvendes, foretrekkes en andel av cycloalkamonoener av 1-90 vekt% (basert på den samlede vekt av blandingen), spesielt 1-50 vekt%. If cyclopolyoctenylene/cycloalkamonoene mixtures are used, a proportion of cycloalkamonoenes of 1-90% by weight (based on the total weight of the mixture), especially 1-50% by weight, is preferred.
Foretrukne anvendte cycloalkamonoener er cyclo-penten, cyclohepten, cycloocten, cyclodecen og cyclododecen. Spesielt anvendes cycloocten eller cyclohepten. Preferred cycloalkamonoenes used are cyclopentene, cycloheptene, cyclooctene, cyclodecene and cyclododecene. In particular, cyclooctene or cycloheptene are used.
Spesielt anvendes slike bærerkatalysatorer som oppviser Y-A1-0-. som bærermateriale. Bærermaterialets spesifikke overflate utgjør fortrinnsvis 100-300 m 2/g i henhold til BET. In particular, such support catalysts are used which exhibit Y-A1-0-. as carrier material. The carrier material's specific surface is preferably 100-300 m 2 /g according to BET.
Bærermaterialet blir spesielt anvendt i form av hulstrenger, kuler, sylindre, terninger, kjegler eller lig-nende formstykker. The carrier material is particularly used in the form of hollow strings, spheres, cylinders, cubes, cones or similar shaped pieces.
Vektandelen av Re20^ til den samlede vekt av katalysatoren utgjør fortrinnsvis 3-20 vekt%., spesielt 3-7 vekt%. The weight proportion of Re 2 O 3 to the total weight of the catalyst is preferably 3-20% by weight, especially 3-7% by weight.
I henhold til oppfinnelsen er det foretrukket å anvende slike bærerkatalysatorer på basis av ~A^2°3 som i tillegg inneholder kokatalysatorer. Mengden av kokatalysator avpasses slik at det molare forhold mellom Re og kokatalysator utgjør fra 50:1 til 1:2, fortrinnsvis fra 5:1 til 1:2. According to the invention, it is preferred to use such carrier catalysts on the basis of ~A^2°3 which additionally contain cocatalysts. The amount of cocatalyst is adjusted so that the molar ratio between Re and cocatalyst is from 50:1 to 1:2, preferably from 5:1 to 1:2.
Foretrukne kokatalysatorer er forbindelser med formelen MRR'm, Preferred cocatalysts are compounds of the formula MRR'm,
hvor R betyr en alkyl- eller arylgruppe og where R means an alkyl or aryl group and
R' halogenradikal eller en alkyl- eller arylgru<p>pe,og M betyr aluminium når m er lik 2, og tinn eller bly når m er lik 3. R' halogen radical or an alkyl or aryl group, and M means aluminum when m is equal to 2, and tin or lead when m is equal to 3.
Eksempler på grupper R og R<1> er methyl-, ethyl-, n-butyl- og fenylgruppen. Et eksempel på et halogenradikal er klorradikalet. Examples of groups R and R<1> are the methyl, ethyl, n-butyl and phenyl groups. An example of a halogen radical is the chlorine radical.
Spesielt anvendte kokatalysatorer er bly- eller tinn-forbindelser med den ovenfor angitte formel. Eksempler på disse er tinntetramethyl, tinntetraethyl, tinntetra-n-butyl, blytetramethyl, blytetraethyl og blytetra-n-butyl. Particularly used cocatalysts are lead or tin compounds with the above formula. Examples of these are tin tetramethyl, tin tetraethyl, tin tetra-n-butyl, lead tetramethyl, lead tetraethyl and lead tetra-n-butyl.
Fremstillingen av bærerkatalysatorene som skal anvendes er i og for seg kjent, og den utføres for eksempel ved impregnering av bærermaterialet med en vandig oppløs-ning av ammoniumperrhenat med påfølgende varmebehandling av godset, hvorved rheniumforbindelsen blir overført til oxydet. The production of the carrier catalysts to be used is known per se, and it is carried out, for example, by impregnating the carrier material with an aqueous solution of ammonium perrhenate followed by heat treatment of the material, whereby the rhenium compound is transferred to the oxide.
Behandlingen av Re207/Al203-kontakten med kokatalysator utføres hensiktsmessig ved behandling av katalysator-materialet med oppløsninger av den tilsvarende forbindelse i alifatiske eller aromatiske hydrocarboner. Eksempler på slike oppløsningsmidler er metateseinerte oppløsnings-midler som også anvendes for å fortynne utgangsmaterialene, som alkaner, for eksempel pentan, hexan, heptan, cyclopentan eller cyclohexan, petrolethere med et kokeområde fra 30 til 60°C, klorerte hydrocarboner, for eksempel methylenklorid, kloroform eller tetraklorkullstoff, eller aromater,for eksempel klorbenzen eller m-diklorbenzen. The treatment of the Re 2 O 7 /Al 2 O 3 contact with co-catalyst is conveniently carried out by treating the catalyst material with solutions of the corresponding compound in aliphatic or aromatic hydrocarbons. Examples of such solvents are metathesized solvents which are also used to dilute the starting materials, such as alkanes, for example pentane, hexane, heptane, cyclopentane or cyclohexane, petroleum ethers with a boiling range from 30 to 60°C, chlorinated hydrocarbons, for example methylene chloride, chloroform or carbon tetrachloride, or aromatics, for example chlorobenzene or m-dichlorobenzene.
Det arbeides fortrinnsvis i en fast-sjiktanordning, hvorved oppløst cyclopolyoctenylen eventuelt i blanding med cycloalkamonoen i form av flytende fase strømmer gjennom katalysatorsjiktet. Strømningshastigheten blir ifølge oppfinnelsen regulert slik at oppholdstider på 10-600 s, fortrinnsvis 10-200 s, blir opprettholdt. Work is preferably carried out in a fixed-bed device, whereby the dissolved cyclopolyoctenylene, optionally mixed with the cycloalkamonoene in the form of a liquid phase, flows through the catalyst layer. According to the invention, the flow rate is regulated so that residence times of 10-600 s, preferably 10-200 s, are maintained.
Reaksjonstemperaturene ligger fortrinnsvis innen om-rådet 0-100°C. Reaksjonen blir fortrinnsvis utført ved trykk av 0,1-100 bar, spesielt 1-10 bar. Når det arbeides under forhøyet trykk, kan reaksjonstemperaturen uten videre forhøyes. The reaction temperatures are preferably within the range 0-100°C. The reaction is preferably carried out at a pressure of 0.1-100 bar, especially 1-10 bar. When working under elevated pressure, the reaction temperature can easily be increased.
For eksempel blir ved gjennomføring av fremgangsmåten en rørreaktor som er vertikalt anordnet og fylt med katalysator, gjennomstrømmet av en oppløsning av cyclopolyoctenylener og eventuelt cycloalkamonoener. Reaksjonsblandingen som forlater reaktoren blir tilført til en destillasjonsanordning og separert i dens komponenter. Målproduktet dannes som en forholdsvis høytkokende fraksjon. I praksis blir som oftest kontinuerlig drift opprettholdt, hvorved oppløsningsmidlet som dannes som lettkokende, såvel som eventuelt ikke omsatt cycloalkamonoen resirkuleres og efter beskikning med nytt utgangsprodukt ledes tilbake til reaktoren. For example, when carrying out the method, a tube reactor which is vertically arranged and filled with catalyst is flowed through with a solution of cyclopolyoctenylenes and possibly cycloalkamonoenes. The reaction mixture leaving the reactor is fed to a distillation device and separated into its components. The target product is formed as a relatively high-boiling fraction. In practice, continuous operation is usually maintained, whereby the solvent which is formed as low-boiling, as well as any unreacted cycloalkamonoe, is recycled and, after coating with new starting product, is led back to the reactor.
Det lykkes ved hjelp av den foreliggende fremgangsmåte å fremstille makrocycliske alkadiener med fortrinnsvis 15-20 carbonatomerspesielt cyclohexadecadien-1.9 og cyclopentadec.adien-1. 8 , i gode utbytter. Reaks jonsutbyttene ligger ved inntil 40%, basert på den samlede mengde av tilført cycloolefin. Det lykkes derved på økonomisk måte å fremstille forbindelser som kjemisk er vanskelig til-gjengelige. Målproduktene anvendes spesielt innen lukt-stoff sektoren, spesielt som utgangsprodukter for fremstilling av moskusluktstoffer. Using the present method, it is possible to produce macrocyclic alkadienes with preferably 15-20 carbon atoms, especially cyclohexadecadiene-1.9 and cyclopentadecadiene-1. 8 , in good yields. The reaction yields are up to 40%, based on the total amount of added cycloolefin. It is thereby possible to economically produce compounds that are difficult to access chemically. The target products are used in particular within the fragrance sector, especially as starting products for the production of musk fragrances.
Eksempel 1 Example 1
Fremstilling av cyclohexadecadien-1.9 ved metatese av en cyclopolyoctenylenblanding. Preparation of cyclohexadecadien-1.9 by metathesis of a cyclopolyoctenylene mixture.
En rørreaktor (lengde 70 cm, diameter 8 cm) anvendes vertikalt anordnet, og i denne var 1,8 kg bærerkatalysator blitt fylt. Katalysatoren inneholdt 3,5 vekt% Re207 og 1,3 vekt% tinntetramethyl. Som bærermateriale ble et T-A^O^ med en spesifikk overflate i henhold til BET av A tube reactor (length 70 cm, diameter 8 cm) is used vertically arranged, and in this 1.8 kg of carrier catalyst was filled. The catalyst contained 3.5 wt% Re 2 O 7 and 1.3 wt% tin tetramethyl. As a support material, a T-A^O^ with a specific surface according to BET of
190 m^/g og som var blitt formet til en sylinder, anvendt. 190 m^/g and which had been shaped into a cylinder, used.
En 0,0052 molar oppløsning av en cyclopolyoctenylenblanding A 0.0052 molar solution of a cyclopolyoctenylene mixture
i pentan ble ledet gjennom katalysatorsjiktet. Den anvendte cyclopolyoctenylenblandings sammensetning er gjengitt i Tabell 1. Temperaturen i katalysatorsjiktet utgjorde 20°C, og trykket var 1,03 bar. Den midlere oppholdstid for reaksjonsblandingen utgjorde 80 s. in pentane was passed through the catalyst bed. The composition of the cyclopolyoctenylene mixture used is given in Table 1. The temperature in the catalyst layer was 20°C, and the pressure was 1.03 bar. The average residence time for the reaction mixture was 80 s.
Reaksjonsblandingen som forlot reaktoren, ble til-ført til en destillasjonsanordning, hvorved n-pentan ble destillert av som efter tilførsel av fersk cyclopolyoctenylenblanding igjen ble tilbakeført til reaktoren. Reaksjonsproduktet som ble tilbake efter at n-pentanet The reaction mixture which left the reactor was supplied to a distillation device, whereby n-pentane was distilled from which, after supply of fresh cyclopolyoctenylene mixture, was again returned to the reactor. The reaction product that remained after the n-pentane
var blitt destillert av, ble analysert gasskromatografisk. had been distilled off, was analyzed gas chromatographically.
Produktblandingen hadde i henhold hertil sammen-setningen 39,5 vekt% cyclohexadecadien og 60,5 vekt% høyere cyclopolyoctenylener. According to this, the product mixture had the composition 39.5% by weight cyclohexadecadiene and 60.5% by weight higher cyclopolyoctenylenes.
Eksempel 2 Example 2
Fremstilling av cyclohexadecadien-1.9 ved metatese av en cyclopolyoctenylen/cyclooctenblanding. Preparation of cyclohexadecadien-1.9 by metathesis of a cyclopolyoctenylene/cyclooctene mixture.
En rørreaktor (lengde 155 cm, diameter 25 cm) anordnet vertikalt og fylt med 3 8 kg bærerkatalysator ble anvendt. Katalysatorens sammensetning var som beskrevet i eksempel 1. A tubular reactor (length 155 cm, diameter 25 cm) arranged vertically and filled with 38 kg of carrier catalyst was used. The composition of the catalyst was as described in example 1.
En 0,022 molar oppløsning (basert på cycloocten-enheter) av en cyclopolyoctenylen/cyclooctenblanding i n-pentan ble ledet gjennom katalsyatorsjiktet. Forholdet mellom cyclopolyoctenylen og cycloocten i blandingen var 3:1 (i vektdeler). Det anvendte cyclopolyoctenyl hadde den sammensetning som er gjengitt i tabell 1 i eksempel 1. Reaksjonsblandingens midlere oppholdstid utgjorde 95 s, temperaturen i katalysatorsjiktet 23°C og trykket 1,05 bar. A 0.022 molar solution (based on cyclooctene units) of a cyclopolyoctenylene/cyclooctene mixture in n-pentane was passed through the catalyst bed. The ratio of cyclopolyoctenylene to cyclooctene in the mixture was 3:1 (in parts by weight). The cyclopolyoctenyl used had the composition given in Table 1 in Example 1. The average residence time of the reaction mixture was 95 s, the temperature in the catalyst layer 23°C and the pressure 1.05 bar.
Reaksjonsblandingen som forlot reaktoren, ble til-ført til en destillasjonsanordning, hvorved oppløsnings-midlet ble destillert av og igjen tilbakeført til reaktoren efter at det til dette var blitt tilført ny cyclopolyoctenylen/ cyclooctenblanding med den ovennevnte sammensetning. The reaction mixture that left the reactor was fed to a distillation device, whereby the solvent was distilled off and returned to the reactor after a new cyclopolyoctenylene/cyclooctene mixture with the above-mentioned composition had been added to it.
På denne måte ble samlet 274,4 kg cycloolefin-blanding omsatt. En destillasjon av reaksjonsblandingen ga 6 8,6 kg cyclohexadecadien som svarte til et utbytte av 25%, basert på den anvendte samlede cycloolefinmengde. In this way, a total of 274.4 kg of cycloolefin mixture was converted. A distillation of the reaction mixture gave 68.6 kg of cyclohexadecadiene corresponding to a yield of 25%, based on the total amount of cycloolefin used.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3816453A DE3816453A1 (en) | 1988-05-13 | 1988-05-13 | PROCESS FOR THE PREPARATION OF CYCLOALCADIENES |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO891941D0 NO891941D0 (en) | 1989-05-12 |
| NO891941L NO891941L (en) | 1989-11-14 |
| NO174745B true NO174745B (en) | 1994-03-21 |
| NO174745C NO174745C (en) | 1994-06-29 |
Family
ID=6354361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO891941A NO174745C (en) | 1988-05-13 | 1989-05-12 | Process for the preparation of cycloalkadienes |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0343437B1 (en) |
| JP (1) | JPH062683B2 (en) |
| CA (1) | CA1325642C (en) |
| DE (2) | DE3816453A1 (en) |
| ES (1) | ES2039048T3 (en) |
| NO (1) | NO174745C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19835203C1 (en) | 1998-08-04 | 2000-04-27 | Miltitz Aromatics Gmbh | Continuous process and heat pump device for the enrichment of the low-concentration reaction mixtures resulting from the production of cycloalkanedienes in liquid organic reaction media |
| DE10142035A1 (en) | 2001-08-28 | 2003-03-20 | Haarmann & Reimer Gmbh | Modified supported metathesis catalysts |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3524977A1 (en) * | 1984-11-20 | 1986-05-22 | Consortium für elektrochemische Industrie GmbH, 8000 München | METHOD FOR PRODUCING CYCLOAL CADIENES |
-
1988
- 1988-05-13 DE DE3816453A patent/DE3816453A1/en not_active Withdrawn
-
1989
- 1989-05-11 EP EP89108476A patent/EP0343437B1/en not_active Expired - Lifetime
- 1989-05-11 DE DE8989108476T patent/DE58900978D1/en not_active Expired - Lifetime
- 1989-05-11 ES ES198989108476T patent/ES2039048T3/en not_active Expired - Lifetime
- 1989-05-12 NO NO891941A patent/NO174745C/en not_active IP Right Cessation
- 1989-05-12 JP JP1117613A patent/JPH062683B2/en not_active Expired - Lifetime
- 1989-05-12 CA CA000599576A patent/CA1325642C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NO174745C (en) | 1994-06-29 |
| NO891941L (en) | 1989-11-14 |
| DE58900978D1 (en) | 1992-04-23 |
| CA1325642C (en) | 1993-12-28 |
| NO891941D0 (en) | 1989-05-12 |
| JPH01319430A (en) | 1989-12-25 |
| EP0343437B1 (en) | 1992-03-18 |
| ES2039048T3 (en) | 1993-08-16 |
| JPH062683B2 (en) | 1994-01-12 |
| EP0343437A1 (en) | 1989-11-29 |
| DE3816453A1 (en) | 1989-11-23 |
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