DE1086226B - Process for the preparation of cyclododecatriene (1, 5, 9) - Google Patents
Process for the preparation of cyclododecatriene (1, 5, 9)Info
- Publication number
- DE1086226B DE1086226B DEF27911A DEF0027911A DE1086226B DE 1086226 B DE1086226 B DE 1086226B DE F27911 A DEF27911 A DE F27911A DE F0027911 A DEF0027911 A DE F0027911A DE 1086226 B DE1086226 B DE 1086226B
- Authority
- DE
- Germany
- Prior art keywords
- cyclododecatriene
- butadiene
- mixture
- catalyst
- high polymers
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 7
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 title description 24
- 238000002360 preparation method Methods 0.000 title description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 21
- -1 aluminum alkyl halide Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HTMQZWFSTJVJEQ-UHFFFAOYSA-N benzylsulfinylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)CC1=CC=CC=C1 HTMQZWFSTJVJEQ-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- LFMTUFVYMCDPGY-UHFFFAOYSA-N n,n-diethylethanamine oxide Chemical compound CC[N+]([O-])(CC)CC LFMTUFVYMCDPGY-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- LKQUDAOAMBKKQW-UHFFFAOYSA-N N,N-dimethylaniline N-oxide Chemical compound CN(C)(=O)C1=CC=CC=C1 LKQUDAOAMBKKQW-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FNIKAGQFQKBVLX-UHFFFAOYSA-N n-cyclohexylbutan-1-imine oxide Chemical compound CCCC=[N+]([O-])C1CCCCC1 FNIKAGQFQKBVLX-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000020075 ouzo Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/44—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of conjugated dienes only
- C07C2/46—Catalytic processes
- C07C2/465—Catalytic processes with hydrides or organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Description
Verfahren zur Herstellung von Cyclododecatrien- (1, 5, 9) Es ist bekannt, Cyclododecatrien- (1, 5, 9) und verwandte cyclische Kohlenwasserstoffe mit mindestens 8 C-Atomen durch Einwirkung von Katalysatoren auf Diolefine, wie Butadien, Isopren, PiperyIen und Dimethylbutadien, herzustellen. Process for the preparation of cyclododecatriene- (1, 5, 9) It is known, cyclododecatriene (1, 5, 9) and related cyclic hydrocarbons with at least 8 carbon atoms by the action of catalysts on diolefins, such as Butadiene, isoprene, piperyIen and dimethylbutadiene.
Als Katalysatoren finden bei diesem Verfahren Kombinationen von Aluminiumalkylhalogeniden mit Titanhalogeniden Verwendung. Als Lösungsmittel werden dabei vorzugsweise aliphatische, aromatische oder halogenierte Kohlenwasserstoffe benutzt. Bei der Cyclisierung des Butadiens werden Ausbeuten von 50 bis 810/0 Cyclododecatrien erhalten. Als Nebenprodukte entstehen geringe Mengen von Vinyleyclohexen- (3) und Cyclooctadien-(1, 5), höhere Ringhomologe des Cyclododecatriens und vor allem kettenförmige, lineare Hochpolymere des Butadiens. Die Entstehung dieser Hochpolymeren ist besonders unerwünscht, da sie hartnäckig Cyclododecatrien eingeschlossen enthalten und im allgemeinen nur durch Ausfällen mit größeren Mengen Aceton oder Methanol entfernt werden können. Abgesehen davon bewirken die in der Reaktionsmischung zunächst gelösten Hochpolymere eine erhebliche Viskositätssteigerung der Lösung, so daß die Butadienaufnahme nach einer gewissen Zeit infolge mangelnder Durchmischung der viskosen Lösung nachläßt. Catalysts used in this process are combinations of aluminum alkyl halides with titanium halides use. Aliphatic, aromatic or halogenated hydrocarbons are used. In the cyclization of the Butadiene yields of 50 to 810/0 cyclododecatriene are obtained. As by-products small amounts of vinyl cyclohexene (3) and cyclooctadiene (1, 5), higher Ring homologues of cyclododecatriene and especially chain-like, linear high polymers of butadiene. The formation of these high polymers is particularly undesirable because they persistently contain cyclododecatriene included and in general only can be removed by precipitation with larger amounts of acetone or methanol. Apart from this, the high polymers initially dissolved in the reaction mixture have the effect a considerable increase in the viscosity of the solution, so that the butadiene uptake after decreases after a certain time due to insufficient mixing of the viscous solution.
Es wurde nun gefunden, daß man die Bildung der unerwünschten Nebenprodukte bei der Herstellung von Cyclododecatrien weitgehend zurückdrängen kann, wenn man bei der Polymerisation der Diolefine einen Katalysator verwendet, der außer Aluminiumalkylhalogenid und Titanhalogenid noch eine Verbindung enthält, die eine semipolare Doppelbindung im Molekül aufweist. It has now been found that the formation of the undesired by-products can be avoided in the production of cyclododecatriene can largely push back if one in the polymerization of the diolefins a catalyst is used which, in addition to aluminum alkyl halide and titanium halide still contains a compound which has a semipolar double bond in the molecule.
I) ie semipolare Verbindung kann den einzelnen Bestandteilen der Katalysatormischung vor deren Vereinigung oder auch der fertigen Mischung der Bestandteile zugesetzt werden. I) he semipolar connection can be the individual components of the Catalyst mixture before they are combined or also the finished mixture of the constituents can be added.
Unter den semipolaren Verbindungen, die als Zusatz zu den Katalysatoren geeignet sind, seien z. B. Sulfoxyde, wie Dimethylsulfoxyd und Dibenzylsulfoxyd, Aminoxyde, wie Triäthylaminoxyd und Dimethylanilinoxyd, schließlich Nitrone, wie n-Propyl-N-cyclohexylnitron, genannt. Among the semi-polar compounds that are used as additives to the catalysts are suitable, are z. B. sulfoxides, such as dimethyl sulfoxide and dibenzyl sulfoxide, Amine oxides, such as triethylamine oxide and dimethylaniline oxide, and finally nitrones, such as n-Propyl-N-cyclohexylnitron, called.
Die Konzentration der semipolaren Verbindung in dem Katalysatorgemisch kann in weiten Grenzen schwanken. The concentration of the semipolar compound in the catalyst mixture can vary within wide limits.
Gute Ergebnisse werden z. B. mit Konzentrationen von 0, 1 bis 20 Molprozent erhalten. Die maximale Ausbeute an Cyclododecatrien, eine minimale Bildung von Nebenprodukten sowie eine maximale Zeitraumausbeute wird bei Anwendung von gleichen molaren Konzentrationen der sernipolaren Verbindung und des eingesetzten Titanhalogenids erzielt. Good results are e.g. B. with concentrations of 0.1 to 20 Mole percent obtained. The maximum yield of cyclododecatriene, a minimum formation of by-products as well as a maximum period yield is achieved when using the same molar concentrations of the sernipolar compound and the titanium halide used achieved.
Die Reaktionstemperatur ist nicht an enge Grenzen gebunden. Befriedigende Ergebnisse werden z. B. in einem Temperaturbereich von etwa 20'bis etwa 80° C und insbesondere von etwa 30° bis etwa 70°C erzieIt. Die optimale Reaktionstemperatur Regt bei etwa 50° C. The reaction temperature is not restricted to narrow limits. Satisfactory Results are e.g. B. in a temperature range of about 20 ° to about 80 ° C and in particular from about 30 ° to about 70 ° C. The optimal reaction temperature Regenerates at around 50 ° C.
Als Katalysatoren finden ebenso wie bei dem bekannten Verfahren auch hier vorzugsweise Kombinationen von Aluminiumdialkylhalogenid, namentlich AIuminiumdiäthylmonochlorid und Titantetrachlorid, Verwendung. As in the case of the known method, also find catalysts here preferably combinations of aluminum dialkyl halide, namely aluminum diethyl monochloride and titanium tetrachloride, use.
Mit Hilfe des neuen Katalysatorgemisches können Ausbeuten bis zu 94% an Cyclododecatrien erhalten werden ; gleichzeitig kann die Bildung der als Nebenprodukte besonders unerwünschten hochmolekularen, kettenförmigen, linearen Hochpolymere des Butadiens meist bis zu einer praktisch vernachläßigbaren Menge gesenkt werden. Die Raumausbeute an Cyclododecatrien für eine gegebene Katalysatorkonzentration wird um ein Mehrfaches gesteigert. With the help of the new catalyst mixture, yields of up to 94% of cyclododecatriene are obtained; at the same time, the as By-products particularly undesirable high molecular weight, chain-like, linear High polymers of butadiene usually up to a practically negligible amount be lowered. The space yield of cyclododecatriene for a given catalyst concentration is increased several times.
Das Cyclododecatrien- (1, 5, 9) ist bekanntlich ein wertvolles Zwischenprodukt fiir die Synthese organischer Verbindungen. So führt z. B. dessen Oxydation direkt zur Bernsteinsäure. The cyclododecatriene (1, 5, 9) is known to be a valuable intermediate for the synthesis of organic compounds. So z. B. its oxidation directly to succinic acid.
In den nachfolgenden Beispielen wird das erfindungsgemäße Polymerisationsverfahren mit dem bekannten Polymerisationsverfahren verglichen. The polymerization process according to the invention is used in the following examples compared with the known polymerization process.
Beispiel 1 In einem Reaktiongefäß von 51 Inhalt werden in bekannter Weise unter Rühren in einer Stlckstoffatmosphäre 50 cm3 AIuminiumdiäthylmonochlorid, in 1, 51 absolutem Benzol gelöst, mit 10cm3 Titantetrachlorid (Molverhältnis A1 : Ti = 4, 57 : 1) vermischt. Nach dem Aufheizen auf 40° C werden im Verlauf von 6 Stunden in die braune Suspension 2, 51 kg Butadien eingeleitet. Example 1 In a reaction vessel with a capacity of 51, in known Way while stirring in a solid atmosphere 50 cm3 aluminum diethyl monochloride, dissolved in 1.51 absolute benzene, with 10cm3 titanium tetrachloride (molar ratio A1 : Ti = 4.57: 1) mixed. After heating to 40 ° C, in the course of Introduced 6 hours into the brown suspension 2.51 kg of butadiene.
Nach dem Abkühlen auf Zimmertemperatur wird Wasserdampf eingeblasen. Man erhält 2, 03 kg Cyclododecatrien- (1, 5, 9), entsprechend'einer Ausbeute von 81°/o der Theorie.After cooling to room temperature it becomes water vapor blown in. 2.03 kg of cyclododecatriene (1, 5, 9) are obtained, corresponding to a yield of 81 per cent of theory.
Der vorerwähnten Katalysatorlösung werden 7, 1 g Dimethylsulfoxyd zugesetzt. Nach dem Aufheizen auf 40°C leitet man im Vellauf von 105 Minuten unter guter Kühlung 2, 37 kg Butadien ein. Nach dem Abkühlen des dünnflüssigen Reaktionsgemisches wird Wasserdampf eingeblasen. Dabei gehen 2,3 kg Cyclododecarten über, entsprechden einer Austbeute von 90% der Theorie. 7.1 g of dimethyl sulfoxide are added to the aforementioned catalyst solution added. After heating to 40 ° C, the mixture is passed in for 105 minutes good cooling 2.37 kg of butadiene. After the liquid reaction mixture has cooled down steam is blown in. 2.3 kg of cyclododec cards pass over, correspondingly a yield of 90% of theory.
Währen sich bei der Polymerisation ohne Zusatz von Dimethylsulfoxyd nur 338 g Cyclododecatrien in der Stunde bilden, entstehen unter Mitverwendung von Dimethylsulfoxyd stündlich 1216g Cyclododecatrien, d. h. die 3, 6fache Menge. During the polymerization without the addition of dimethyl sulfoxide form only 338 g of cyclododecatriene per hour, are formed with the use of Dimethyl sulfoxide hourly 1216g cyclododecatriene, d. H. 3, 6 times the amount.
Beispiel 2 In einem Reaktionsgefäß von 1, 251 Inhalt löst man 7, 24gAluminiumdiathylmonochlorid (60mMol) in400cm3 absoluten Benzol sowie 1, 14gTitantetrachlorid (6 mMol). Example 2 In a reaction vessel with a capacity of 1.251, 7 24g aluminum diethyl monochloride (60mMol) in 400cm3 absolute benzene and 1.14g titanium tetrachloride (6 mmol).
In die entstehende braune Suspension leitet man nach dem Aufheizen auf 50° C Butadien mit einer Geschwindigkeit von etwa 901/Stunde ein. Zur Aufrechterhaltung der Reaktionstemperatur von 50°C genügt die Kühlung mit einem schwachen Luftstrom. Nach einer Stunde unterbricht man die Butadienzufuhr, läßt die Mischung noch einige Minuten weiterreagieren und zersetzt den Katalysator mit der berechneten Menge Methanol. Durch Waschen mit der berechneten Menge 2 n-Schwefelsäure werden anorganische Katalysatorbestandteile entfernt und die hochpolymeren Anteile mit einem Methanol-Aceton-Gemisch 1 : 1 ausgefällt. Da die Hochpolymeren noch Cyclododecatrien eingeschlossen enthalten, müssen sie durch häufiges Kneten mit kleinen Mengen Aceton davon befreit werden. Auf diese Weise werden 26 g Hochpolymere erhalten. Nach dem Abdestillieren der Lösungsmittel ergibt die Vakuumdestillation des Rückstandes als Vorlauf bis 111° C/15 mm Hg : 7 g ; als Hauptfraktion 111 bis 116°C/15 mm Hg : 180 g (Schmelzpunkt -16° bis-18°C) ; Destillationsrückstand 16 g. Das Reaktionsprodukt setzt sich demnach prozentual wie folgt zusammen : Vorlauf.................... 3, 1 °l0, Cyclododecatrien............ 78, 6 °/o, Rückstand 7, 0 °/0, Hochpolymere.............. 11, 3 °/0.After heating, the resulting brown suspension is poured into it to 50 ° C butadiene at a rate of about 901 / hour. To maintain the reaction temperature of 50 ° C is sufficient cooling with a weak air stream. After an hour the butadiene feed is interrupted and the mixture is left for a few more times React further minutes and decompose the catalyst with the calculated amount of methanol. Washing with the calculated amount of 2N sulfuric acid turns inorganic catalyst components removed and the high polymer components precipitated with a methanol-acetone mixture 1: 1. Since the high polymers still contain cyclododecatriene included, they must be freed from it by frequent kneading with small amounts of acetone. To this In this way, 26 g of high polymers are obtained. After the solvents have been distilled off the vacuum distillation of the residue results as a forerun up to 111 ° C / 15 mm Hg: 7 g; as the main fraction 111 to 116 ° C / 15 mm Hg: 180 g (melting point -16 ° to -18 ° C) ; Distillation residue 16 g. The reaction product is therefore a percentage together as follows: flow .................... 3, 1 ° l0, cyclododecatriene ............ 78.6%, residue 7.0 ° / 0, high polymers .............. 11.3 ° / 0.
Nach dieser Arbeitsweise erhält man mit 8, 3 g Katalysatormischung in 400 cm3 Benzol 180 g Cyclododecatrien/Stunde. This procedure gives 8.3 g of catalyst mixture with 8.3 g in 400 cm3 benzene 180 g cyclododecatriene / hour.
Der vorerwähnten Katalysatorlösung wird im Verlauf von 5 Minuten eine Lösung von 6mMol Dimethylsulfoxyd = 468 mg in 20 cm3 Benzol zugesetzt. Unter geringfügiger Erwärmung färbt sich die Reaktionsmischung schwarzbraun. Nach dem Aufheizen auf 50° C leitet man Butadien mit einer Raumgeschwindigkeit von etwa 2501/Stunde ein. Die Wärmeentwicklung ist so groß, daß die Reaktionstemperatur von 50°C nur durch starkes Kiiblen mit einer Eis-Kochsalz-Mischung aufrechterhalten werden kann. Im Gegensatz zu der oben beschriebenen bleibt diese Reaktionsmischung völlig dünnflüssig. Innerhalb einer Stunde Einleitungszeit werden 585 g Butadien aufgenommen. Nach der Zersetzung des Katalysators werden durch entsprechende Aufarbeitung 5, 2 g Vorlauf, 540 g Cyclododecatrien, 27, 7 g Rückstand und 4, 1 g hochpolymere Anteile erhalten. The aforementioned catalyst solution is in the course of 5 minutes a solution of 6 mmol of dimethyl sulfoxide = 468 mg in 20 cm3 of benzene was added. Under The reaction mixture turns blackish-brown when heated slightly. After this Heating to 50 ° C., butadiene is passed at a space velocity of about 250 l / hour a. The heat development is so great that the reaction temperature of 50 ° C only can be maintained by strong kicks with a mixture of ice and table salt. In contrast to the one described above, this reaction mixture remains completely fluid. 585 g of butadiene are taken up within an hour of introduction. After Decomposition of the catalyst by appropriate work-up 5, 2 g first run, 540 g of cyclododecatriene, 27.7 g of residue and 4.1 g of high polymer fractions were obtained.
Die prozentuale Zusammensetzung der Reaktionsprodukte beträgt demnach : Vorlauf 0, 90/0, Cyclododecatrien......... 93, 6 °/o, Rückstand ..... ......... 4,8%, Hochpolymere.............. 0, 7 °/o.The percentage composition of the reaction products is accordingly : Flow 0, 90/0, cyclododecatriene ......... 93, 6 ° / o, residue ..... ......... 4.8%, high polymers .............. 0.7%.
Es haben sich je Stunde 540 g Cyclododecatrien gebildet, die 3fache Menge der bei dem Versuch ohne Zusatz von Dimethylsulfoxyd erhaltenen Menge. 540 g of cyclododecatriene formed per hour, three times as much Amount of the amount obtained in the experiment without the addition of dimethyl sulfoxide.
Beispiel 3 In ein Gemisch von 250 cm3 absolutem Benzol, 7, 24 g Aluminiumdiäthylmonochlorid und 6 mMol Dibenzylsulfoxyd tropft man 1, 14g Titantetrachlorid ein. Bei 50° C leitet man Butadien mit einer Geschwindigkeit von 2201/Stunde ein, wobei stark gekühlt werden muß. Nach 25 Minuten ist das Reaktionsgefäß bis zum Rand gefüllt. Example 3 In a mixture of 250 cm3 of absolute benzene, 7.24 g of aluminum diethyl monochloride and 6 mmol of dibenzyl sulfoxide are added dropwise 1.14 g of titanium tetrachloride. Conducts at 50 ° C one butadiene at a rate of 2201 / hour, being strongly cooled must become. After 25 minutes the reaction vessel is filled to the brim.
Die bei der Aufarbeitung des Reaktionsgemisches erhaltene Menge Cyclododecatrien beträgt das 2, 5fache der Cyclododecatrienmenge, die in einem Vergleichsversuch ohne Zusatz von Dibenzylsulfoxyd zum Katalysatorgemisch anfällt.The amount of cyclododecatriene obtained in working up the reaction mixture is 2.5 times the amount of cyclododecatriene in a comparative experiment is obtained without the addition of dibenzyl sulfoxide to the catalyst mixture.
Die prozentuale Verteilung der Reaktionsprodukte nach diesem Beispiel
einerseits und einem Vergleichsversuch ohne Zusatz von Dibenzylsulfoxyd andererseits
ergibt sich aus der folgenden Zusammenstellung :
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF27911A DE1086226B (en) | 1959-03-10 | 1959-03-10 | Process for the preparation of cyclododecatriene (1, 5, 9) |
| GB8566/60A GB928812A (en) | 1959-03-10 | 1960-03-10 | Process for the production of cyclododecatri-1,5,9-enes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF27911A DE1086226B (en) | 1959-03-10 | 1959-03-10 | Process for the preparation of cyclododecatriene (1, 5, 9) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1086226B true DE1086226B (en) | 1960-08-04 |
Family
ID=7092652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF27911A Pending DE1086226B (en) | 1959-03-10 | 1959-03-10 | Process for the preparation of cyclododecatriene (1, 5, 9) |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1086226B (en) |
| GB (1) | GB928812A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1137007B (en) * | 1960-08-18 | 1962-09-27 | Basf Ag | Process for the preparation of lower, liquid oligomers from 1,3-dienes |
| DE1140569B (en) * | 1959-12-22 | 1962-12-06 | Studiengesellschaft Kohle Mbh | Process for the catalytic dimerization or trimerization of 1,3-diolefins |
| DE1283838B (en) * | 1960-06-30 | 1968-11-28 | Studiengesellschaft Kohle Mbh | Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine |
| DE1283836B (en) * | 1959-12-22 | 1968-11-28 | Studiengesellschaft Kohle Mbh | Process for the preparation of products mainly containing cyclododecatriene (1,5,9) by cyclooligomerization of 1,3-diolefins |
| DE1297600B (en) * | 1960-06-30 | 1969-06-19 | Studiengesellschaft Kohle Mbh | Process for the cyclodimerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine |
| DE1298526B (en) * | 1960-08-22 | 1969-07-03 | Columbian Carbon | Process for the preparation of hydrocarbon mixtures essentially containing cyclooctadiene (1,5) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1102833A (en) * | 1964-11-06 | 1968-02-14 | Shell Int Research | Improvements in or relating to the manufacture of cyclic oligomers |
| NL6501739A (en) * | 1965-02-12 | 1966-08-15 | ||
| US3381045A (en) * | 1965-06-29 | 1968-04-30 | Du Pont | Cyclododecatriene 1, 5, 9 process |
| DE1618246C3 (en) * | 1967-06-03 | 1980-10-23 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of ice, trans, trans-cyclododecatriene- <1,5,9) |
| DE102004054477A1 (en) * | 2004-11-11 | 2006-05-24 | Degussa Ag | Process for the preparation of trimethylcyclododecatriene |
| DE102006022014A1 (en) * | 2006-05-10 | 2007-11-15 | Degussa Gmbh | Process for the preparation of cyclododecatriene |
-
1959
- 1959-03-10 DE DEF27911A patent/DE1086226B/en active Pending
-
1960
- 1960-03-10 GB GB8566/60A patent/GB928812A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1140569B (en) * | 1959-12-22 | 1962-12-06 | Studiengesellschaft Kohle Mbh | Process for the catalytic dimerization or trimerization of 1,3-diolefins |
| DE1283836B (en) * | 1959-12-22 | 1968-11-28 | Studiengesellschaft Kohle Mbh | Process for the preparation of products mainly containing cyclododecatriene (1,5,9) by cyclooligomerization of 1,3-diolefins |
| DE1283838B (en) * | 1960-06-30 | 1968-11-28 | Studiengesellschaft Kohle Mbh | Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine |
| DE1297600B (en) * | 1960-06-30 | 1969-06-19 | Studiengesellschaft Kohle Mbh | Process for the cyclodimerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine |
| DE1137007B (en) * | 1960-08-18 | 1962-09-27 | Basf Ag | Process for the preparation of lower, liquid oligomers from 1,3-dienes |
| DE1298526B (en) * | 1960-08-22 | 1969-07-03 | Columbian Carbon | Process for the preparation of hydrocarbon mixtures essentially containing cyclooctadiene (1,5) |
Also Published As
| Publication number | Publication date |
|---|---|
| GB928812A (en) | 1963-06-19 |
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