CA1325642C - Process for the preparation of cycloalkadienes - Google Patents
Process for the preparation of cycloalkadienesInfo
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- CA1325642C CA1325642C CA000599576A CA599576A CA1325642C CA 1325642 C CA1325642 C CA 1325642C CA 000599576 A CA000599576 A CA 000599576A CA 599576 A CA599576 A CA 599576A CA 1325642 C CA1325642 C CA 1325642C
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- catalyst
- cyclopolyoctenylene
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- 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
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- 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
PROCESS FOR THE PREPARATION OF CYCLOALKADIENES ABSTRACT OF THE DISCLOSURE A process for the preparation of cycloalkadienes in a liquid phase, by a metathesis reaction, is disclosed. The reaction takes place in the presence of a supported catalyst based on R?2O1/Al2O3, which includes bringing a cyclopolyoctenylene, or a cycloalkamonoene/cyclopolyoctenylene mixture cyclopolyoctenylene having a polymerization degree of at least three, in the form of a 0.005 - 0.2 molar solution at a residence time of 10 - 600 seconds, into contact with the supported catalyst.
Description
~2~1~42 BACKGI'IOUN~ OF TI IE INVENTION
This present invenlion relates to a process for the preparalion of cycloalkadienes in liquid pilase by a metathesis reaceion in the presence of a carrier cataiyst based on l~e;207 /AI203.
It is known from U.S. Palent No. 4,~68,836 how to prepare cycloalkadienes by metathesis of cycloalkamanoen~s in the presence of a carrier catalyst based on Re207/~ -Al203 /Sr;i~4.
~:
In all metalhetical dimerizations of cycloalkenes to cyeloall<adienes, despite optimum conditions higher cyclo-all<apolyenes having a polymeriza~ion degree of greater than or equal to three are formed. In the dimerization o~ cyclooctene to cyclo hexadecadiene, these amount to, for example, between 50 and 70%
by weight (relalive to the amount of cyclooctene used) of higher cyclopolyoctenylenes. A useful applicalion of these cyclopolyoc-tenylene mixtures is so ~ar not known.
"
Accordingly, it is an obJect o~ the present invention to 20 provide a novel process for the preparation of cycloalkadienes in liquid phase by a metathesis reaction in the presence of a carrier cataiyst based on Re20l /AI203.
SUMMARY OF T3-lE INVENTION
~.
The loregoing and related ob~ects are readily attained according to the present invenlion in a process lor the preparation of cycloalkadianes In liquid phass by a metathesis reaction in the presence of a carriejr catalyst based on Re20, /AI203, which comprises ~ -J 30 bringing a cyclopolyoctenylene having a polymerization degree of ,/ : , .' ~, ,.
1325~42 grealer than or equal to lllree In lho form of ~.005 to 0.2 molar solulions at r~sicience lilnes of 1~ lo ~)0 seconds inlo conlact wltl lhe carrier ca~alyst.
By rneans of lhe process according to th~ invenllon, cyclopoly octenylenes, wllic11 are ~ormecl in ~h~ melatllasis r~aclion o~ cyclooctene to cyclohexadecaciien~ can b~ raacled to giva cyclo alkacllenes also In a metathesis reactlon. Surprisingly, tlle ylelds with r~specl to the cycloalkaciienes obtainable in this reaction are sig-nilicanlly higller lllan could be expecled Irom Ihe posilion o~ e thermodynamie equilibrium. Thus, yields of up to 40% can b~
achfevecl in the degradalion o~ cyclopolyoclenylenes.
~he yields are lllere~ore approximately equal to lhose , ~ whicll can be achieved In llle metatllesis oF cyclooctene, although lhe metalllesls of cyclopolyoctenylene Is a degradatlon reaction, while the metalllesis of cyclooclene is a buil~-up reaclion By means o~ the process according to ~he invenlion, 2U the cyclopolyoclenylenes, whicl-l are lormed In the melalhesis o~
f cyclooctene, can be utllized to give much more use~ul cyclo-all~aclienes.
Moreover, since it has been found that almost identical reactlon behavior is pr~s~nt ciuring synll~esis and d~gradation, it is also possible lo use cycloalkarnonoen~/cyclopolyoclenylene mixlures for the preparalion of cycloall<aclienes.
Ths inv0nlion accordin~ly, lurther relates to a process for lhe preparation of cycloall<aclienes in liquid phase by a metathesis , ~; 2 i3256~L2 reaction in the presence of a carrier ca~alyst based on l~e207 /AI20~, which comprises bringing a cycloalkamonoene/cyclopolyoctenylene mixture, in which the cyclopolyoctenylene has a polymerization de~ree of greater than or equal to three, in the form of 0.005 to 0.2 molar solutions at residence times of 10 to 600 seconds into contact with the carrier catalyst.
J
The designation mole in the concentrations of the solutions refers in the context of the present invention to calculated 10 cyclooctene units, which are obtained by dividing the cyclopolyoc-tenylenes into the monomers, and, if cycloalkamonoene/cyclo-polyoctenylene mixtures are used, adding them to the cyclo-. alkamonoene which were added.
~, . .
In the processes according to the invention, 0.01 to ~, 0.05 molar solutions are preferred. Preferred residence or contact times are 10 to 200 seconds.
:~ :
The cyclopolyoctenylenes used con~orm to the general 20 formula i :~
r [ c~ =cH (c~l2~ : :
P, I
:' ' i3%5~;42 and have a polyrnerization degree, n, of at least 3, preferably 3 to 507 and most pre~erably, 3 to 20.
If cyclopolywtenylene/cycloalkamonoene mixtures are used, a cycloaikamonoene content of 1 to 90% by weight (relative to the total weight of the mixture), in pa~icular of 1 to 50% by weight is preferred.
The cycloalkamonoenes which are preferably used are 10 cyclopentene, cycloheptene, cyclooctene, cyclodecene and cyclo-dodecene. Cyclooctene or cycloheptene are most preferred.
In particular, those carrier catalysts are used which have ~ -Al203 as the carrier or support material. The specific surface area of the carrier material is preferably 100 to 300 m2/g according to BET.
The carrier material is used, in particular, in the forrn of hollow strands, spheres, cylinders, cubes, cones and the like.
The relative weight of Re207 in the total weight of the catalyst is preferably 3 to 20% by weight, and in particular 3 to 7% by weight.
It is preferred, Tn the context of the invention, to use those carrier catalysts based on Re207 / ~-AI203 which are additionall charged with co-catalysts. The amount of co-catalyst is such that the molar ratio, or Re to co-catalyst, is 50:1 to 1:2, preferably 5:1 to 1:2. Preferred co-catalysts are compounds of the formula 3() MRFI~, .
' ,, ~ .
. . . ..
i32~2 in which P~ stands for an alkyl or aryl radical;
R' stands for a halogen, alkyl or aryl radical; and, ~ :
M denotes aluminum, if m is 2, and tin or lead, if m is 3.
', Examples of radicals R and R ~ are the methyl, ethyl, n-butyl and phenyl radical. An example of a haiogen radical is the chlorine radical.
y 10 Co-catalysts which are in particular used are lead compounds or tin compounds of the above-mentioned formula.
Examples of these are tetramethyltin, tetraethyltin, tetra-n-butyltin, tetramethyllead, tetrae~hyllead and tetra-n-butyllsad.
Th~ preparation of the carrier catalysts to be used is known per se and is carried out, for example, by impregnation of the carrier material with an aqueous solution of ammonium perrhenate, followed by heat treatment of the material in which the rhenium compound is converted into the oxide.
, ' ~, The treatment of the Re207 /AI203 oatalyst with the co- i -~¦ catalyst is advantageously carried out by treatment of the catalyst ~ material with solutions of the corresponding compound in aliphatic or i~ aromatic hydrocarbons. Examples o~ these soivents are solvents ~ -which are inert to metathesis and can also be used for diluting the ~! ' , starting materials, such as alkanes, for example pentane, hexane, ~j heptane, cyclopentane, cyclohexane, petroleum ether of the boiling '~ range from 30 to 60C, chlorinated hydrocarbons, for example -;~ 30 methylene chloride, clhloro~orm, carbon tetrachioride or aromatics, for , . .
A ~
;
~ ., .
~ - 5 -..
,, 132~6~2 example chlorobenzene and m-dichlorobenzene.
Preferably, the reaction is carried out in a fixed bed arrangement in which the dissolved cyclopolyoctenylene, optionally, in a mixture with cycloalkamonoene, flows through the catalyst bed as the liquid phase. The flow rate is set according to the invention to a value so that residence times of iO to 600 seconds, preferably 10 to 200 seconds, are maintained.
The reaction temperatures are preferably in the range from 0C to 100C. Preferably, the reaclion is carried out at pres-sures of 0.1 to 100 bar, most preferably, 1 to 10 bar. If carried out under superatmospheric pressure, the reaction temperature can certainly be increased.
By way oF exarnple, the process is carried out by having a solution of cyclopolyoctenylenes, and possîbly cyclo-alkamonoenes, ~low through a vertically arranged tube reactor which is filled with the catalyst. The reaction mixture which leaves the 20 reactor is transferred to a distillation apparatus and is separated into its components. The target product is obtained as a relatively high-boiling fraction. In practice, a continuous operation is maintained in most cases, in which the solvent, which is the low-boiling compo-nent, and any unconverted cycloalkamonoenes present are circu-lated and, afler being charged with new starting material, recycled into the reactor.
' By means of the process according to the invenHon, it ~,, .
is possible to prepare macrocyciic alkadienes, which preferably have 30 l5 to 20 carbon at~ms, and in particular 1,9-cyclohexadecadiene and , ~ .
~ - 6 -.
., ~ . . .
.
~32~2 1,8-cyclopentadecadiene, in good yields. The yields of the reaction, relative to the total amount of cycloolefin used, are up to 40%. It is thus possible to prepare compounds which are, in general, dif~icult to obtain by chemical means in an economical way. The target pro-ducts are used in particular in the field of odorants, for example as starting materials for tha preparation of musk odorants.
The present invention will now be explainecl in greater detail by way of the following examples, which are intended as being 10 merely illustrative of the present invention and are not intended as defining the scope thereof.
:
Examp~e 1 The preparation of 1,9-cyclohexadecadiene by meta-thesis of a cyclopolyoctenylene mixture.
.
A vertically arranged tube or tubular reactor (length 70 cm, diarneter 8 cm), which was charged with 1.8 kg of carrier 20 catalyst, was used. ~he catalyst contained 3.5% by weight of Re207 and 1.3% by weight of tetramethyltin. The carrier material used was ~-AI20~ in the form of cylinders having a specific surface area according to BET of 190 m2/g. A 0.0052 molar solution of a cyclo-polyoctenylene mixture in pentane was passed through the catalyst bed. The composition of the cyclopolyoctenyiene mixture used is . shown in Table 1. l he temperature in the catalyst bed was 20C; the pressure 1.03 bar. The average residence time of the reaction mixture was 80 seconds.
'~
.
~32~642 Table 1 ' Gomposition of the cyclopolyoctenylene mixture in % by weight.
Polym~rization degree Percenta~by weiuht) 3 42.5 . -iO
4 23.8 13.3 , 6 . 7 and greaier 10.1 , ., The reaction mixture, which left the reactor, was trans-ferred to a distillation apparatus in which n-pentane was distilled off ~ and which, aH~r being charged with a fresh cyclopolyoctenylene mixture, was recycled into tha reactor. The reaction product remain-ing after n-pentane had been di~tilled off was analyzed by gas chromatography.
Accordingly? the product mixture was composed of 39.5% by weight of cyclohexadecadiene and 60.5% by weight of higher cyclopolyoctenylenes.
. ~
.~,, ' ' , .
.
~.
~ ' , e. 30 r~ ' ~,, ~ ' .
.
.- ;
,.
,~
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~L32~42 Example 2 Preparation of 1,9-cyclohexadecadiene by metathesis of a cyclopolyoctenylene/cyclooGtene mixture.
A vertically arranged tube reactor ~length 155 cm, diameter 25 cm), which was filled with 3~ kg of carrier catalyst, was used. The composition of the catalyst was as described in Example 1. :.
A 0.022 molar solution (based on cyclooctene uniis) of a cyclopolyoctenylene/cyclcoctene mixture in n-pentane was passed through the catalyst bed. The ratio of cyclopolyoctenylene to cyclo-J. octene was 3:1 (in parts by weigh~). The cyclopolyoctenylene used had the composition shown in Table 1 of Example 1. The average residence time of the reaction mixture was 95 seconds; the tempera-ture in the catalyst ~ed being 23C and the pressure being 1.05 bar.
~;~ The reaction mix~ure, which left the reactor, was trans-20 ferred to a distillation apparatus in which the solvent was distilled off s' and which, after bein~ char~ed with new cyclopolyoctenylene/cyclo-octene rnixture of the abovementioned composition, was recycled into the reactor.
b : .
A total of 274.4 kg of cycloolefin mixture were reacted in this manner. Separation of the reaction mixture by distillation gave 68.6 kg of cyclohexadecadiene, which corresponds to a yield of 25%, . .
r"~ based on the total amount of cycloolefin used.
"~ l While only several examples oF the present invention ," ~ .
:`
,~
., .
g 132~2 have been shown and described, it wili be obvious to those of ordinary skill in the art that many modifications may be made to the present invention without departing from the spirit and scope thereof.
,.
~: 20 '~
~, .
.: :
. ' .
~3, . - 10-.
, ~ .
This present invenlion relates to a process for the preparalion of cycloalkadienes in liquid pilase by a metathesis reaceion in the presence of a carrier cataiyst based on l~e;207 /AI203.
It is known from U.S. Palent No. 4,~68,836 how to prepare cycloalkadienes by metathesis of cycloalkamanoen~s in the presence of a carrier catalyst based on Re207/~ -Al203 /Sr;i~4.
~:
In all metalhetical dimerizations of cycloalkenes to cyeloall<adienes, despite optimum conditions higher cyclo-all<apolyenes having a polymeriza~ion degree of greater than or equal to three are formed. In the dimerization o~ cyclooctene to cyclo hexadecadiene, these amount to, for example, between 50 and 70%
by weight (relalive to the amount of cyclooctene used) of higher cyclopolyoctenylenes. A useful applicalion of these cyclopolyoc-tenylene mixtures is so ~ar not known.
"
Accordingly, it is an obJect o~ the present invention to 20 provide a novel process for the preparation of cycloalkadienes in liquid phase by a metathesis reaction in the presence of a carrier cataiyst based on Re20l /AI203.
SUMMARY OF T3-lE INVENTION
~.
The loregoing and related ob~ects are readily attained according to the present invenlion in a process lor the preparation of cycloalkadianes In liquid phass by a metathesis reaction in the presence of a carriejr catalyst based on Re20, /AI203, which comprises ~ -J 30 bringing a cyclopolyoctenylene having a polymerization degree of ,/ : , .' ~, ,.
1325~42 grealer than or equal to lllree In lho form of ~.005 to 0.2 molar solulions at r~sicience lilnes of 1~ lo ~)0 seconds inlo conlact wltl lhe carrier ca~alyst.
By rneans of lhe process according to th~ invenllon, cyclopoly octenylenes, wllic11 are ~ormecl in ~h~ melatllasis r~aclion o~ cyclooctene to cyclohexadecaciien~ can b~ raacled to giva cyclo alkacllenes also In a metathesis reactlon. Surprisingly, tlle ylelds with r~specl to the cycloalkaciienes obtainable in this reaction are sig-nilicanlly higller lllan could be expecled Irom Ihe posilion o~ e thermodynamie equilibrium. Thus, yields of up to 40% can b~
achfevecl in the degradalion o~ cyclopolyoclenylenes.
~he yields are lllere~ore approximately equal to lhose , ~ whicll can be achieved In llle metatllesis oF cyclooctene, although lhe metalllesls of cyclopolyoctenylene Is a degradatlon reaction, while the metalllesis of cyclooclene is a buil~-up reaclion By means o~ the process according to ~he invenlion, 2U the cyclopolyoclenylenes, whicl-l are lormed In the melalhesis o~
f cyclooctene, can be utllized to give much more use~ul cyclo-all~aclienes.
Moreover, since it has been found that almost identical reactlon behavior is pr~s~nt ciuring synll~esis and d~gradation, it is also possible lo use cycloalkarnonoen~/cyclopolyoclenylene mixlures for the preparalion of cycloall<aclienes.
Ths inv0nlion accordin~ly, lurther relates to a process for lhe preparation of cycloall<aclienes in liquid phase by a metathesis , ~; 2 i3256~L2 reaction in the presence of a carrier ca~alyst based on l~e207 /AI20~, which comprises bringing a cycloalkamonoene/cyclopolyoctenylene mixture, in which the cyclopolyoctenylene has a polymerization de~ree of greater than or equal to three, in the form of 0.005 to 0.2 molar solutions at residence times of 10 to 600 seconds into contact with the carrier catalyst.
J
The designation mole in the concentrations of the solutions refers in the context of the present invention to calculated 10 cyclooctene units, which are obtained by dividing the cyclopolyoc-tenylenes into the monomers, and, if cycloalkamonoene/cyclo-polyoctenylene mixtures are used, adding them to the cyclo-. alkamonoene which were added.
~, . .
In the processes according to the invention, 0.01 to ~, 0.05 molar solutions are preferred. Preferred residence or contact times are 10 to 200 seconds.
:~ :
The cyclopolyoctenylenes used con~orm to the general 20 formula i :~
r [ c~ =cH (c~l2~ : :
P, I
:' ' i3%5~;42 and have a polyrnerization degree, n, of at least 3, preferably 3 to 507 and most pre~erably, 3 to 20.
If cyclopolywtenylene/cycloalkamonoene mixtures are used, a cycloaikamonoene content of 1 to 90% by weight (relative to the total weight of the mixture), in pa~icular of 1 to 50% by weight is preferred.
The cycloalkamonoenes which are preferably used are 10 cyclopentene, cycloheptene, cyclooctene, cyclodecene and cyclo-dodecene. Cyclooctene or cycloheptene are most preferred.
In particular, those carrier catalysts are used which have ~ -Al203 as the carrier or support material. The specific surface area of the carrier material is preferably 100 to 300 m2/g according to BET.
The carrier material is used, in particular, in the forrn of hollow strands, spheres, cylinders, cubes, cones and the like.
The relative weight of Re207 in the total weight of the catalyst is preferably 3 to 20% by weight, and in particular 3 to 7% by weight.
It is preferred, Tn the context of the invention, to use those carrier catalysts based on Re207 / ~-AI203 which are additionall charged with co-catalysts. The amount of co-catalyst is such that the molar ratio, or Re to co-catalyst, is 50:1 to 1:2, preferably 5:1 to 1:2. Preferred co-catalysts are compounds of the formula 3() MRFI~, .
' ,, ~ .
. . . ..
i32~2 in which P~ stands for an alkyl or aryl radical;
R' stands for a halogen, alkyl or aryl radical; and, ~ :
M denotes aluminum, if m is 2, and tin or lead, if m is 3.
', Examples of radicals R and R ~ are the methyl, ethyl, n-butyl and phenyl radical. An example of a haiogen radical is the chlorine radical.
y 10 Co-catalysts which are in particular used are lead compounds or tin compounds of the above-mentioned formula.
Examples of these are tetramethyltin, tetraethyltin, tetra-n-butyltin, tetramethyllead, tetrae~hyllead and tetra-n-butyllsad.
Th~ preparation of the carrier catalysts to be used is known per se and is carried out, for example, by impregnation of the carrier material with an aqueous solution of ammonium perrhenate, followed by heat treatment of the material in which the rhenium compound is converted into the oxide.
, ' ~, The treatment of the Re207 /AI203 oatalyst with the co- i -~¦ catalyst is advantageously carried out by treatment of the catalyst ~ material with solutions of the corresponding compound in aliphatic or i~ aromatic hydrocarbons. Examples o~ these soivents are solvents ~ -which are inert to metathesis and can also be used for diluting the ~! ' , starting materials, such as alkanes, for example pentane, hexane, ~j heptane, cyclopentane, cyclohexane, petroleum ether of the boiling '~ range from 30 to 60C, chlorinated hydrocarbons, for example -;~ 30 methylene chloride, clhloro~orm, carbon tetrachioride or aromatics, for , . .
A ~
;
~ ., .
~ - 5 -..
,, 132~6~2 example chlorobenzene and m-dichlorobenzene.
Preferably, the reaction is carried out in a fixed bed arrangement in which the dissolved cyclopolyoctenylene, optionally, in a mixture with cycloalkamonoene, flows through the catalyst bed as the liquid phase. The flow rate is set according to the invention to a value so that residence times of iO to 600 seconds, preferably 10 to 200 seconds, are maintained.
The reaction temperatures are preferably in the range from 0C to 100C. Preferably, the reaclion is carried out at pres-sures of 0.1 to 100 bar, most preferably, 1 to 10 bar. If carried out under superatmospheric pressure, the reaction temperature can certainly be increased.
By way oF exarnple, the process is carried out by having a solution of cyclopolyoctenylenes, and possîbly cyclo-alkamonoenes, ~low through a vertically arranged tube reactor which is filled with the catalyst. The reaction mixture which leaves the 20 reactor is transferred to a distillation apparatus and is separated into its components. The target product is obtained as a relatively high-boiling fraction. In practice, a continuous operation is maintained in most cases, in which the solvent, which is the low-boiling compo-nent, and any unconverted cycloalkamonoenes present are circu-lated and, afler being charged with new starting material, recycled into the reactor.
' By means of the process according to the invenHon, it ~,, .
is possible to prepare macrocyciic alkadienes, which preferably have 30 l5 to 20 carbon at~ms, and in particular 1,9-cyclohexadecadiene and , ~ .
~ - 6 -.
., ~ . . .
.
~32~2 1,8-cyclopentadecadiene, in good yields. The yields of the reaction, relative to the total amount of cycloolefin used, are up to 40%. It is thus possible to prepare compounds which are, in general, dif~icult to obtain by chemical means in an economical way. The target pro-ducts are used in particular in the field of odorants, for example as starting materials for tha preparation of musk odorants.
The present invention will now be explainecl in greater detail by way of the following examples, which are intended as being 10 merely illustrative of the present invention and are not intended as defining the scope thereof.
:
Examp~e 1 The preparation of 1,9-cyclohexadecadiene by meta-thesis of a cyclopolyoctenylene mixture.
.
A vertically arranged tube or tubular reactor (length 70 cm, diarneter 8 cm), which was charged with 1.8 kg of carrier 20 catalyst, was used. ~he catalyst contained 3.5% by weight of Re207 and 1.3% by weight of tetramethyltin. The carrier material used was ~-AI20~ in the form of cylinders having a specific surface area according to BET of 190 m2/g. A 0.0052 molar solution of a cyclo-polyoctenylene mixture in pentane was passed through the catalyst bed. The composition of the cyclopolyoctenyiene mixture used is . shown in Table 1. l he temperature in the catalyst bed was 20C; the pressure 1.03 bar. The average residence time of the reaction mixture was 80 seconds.
'~
.
~32~642 Table 1 ' Gomposition of the cyclopolyoctenylene mixture in % by weight.
Polym~rization degree Percenta~by weiuht) 3 42.5 . -iO
4 23.8 13.3 , 6 . 7 and greaier 10.1 , ., The reaction mixture, which left the reactor, was trans-ferred to a distillation apparatus in which n-pentane was distilled off ~ and which, aH~r being charged with a fresh cyclopolyoctenylene mixture, was recycled into tha reactor. The reaction product remain-ing after n-pentane had been di~tilled off was analyzed by gas chromatography.
Accordingly? the product mixture was composed of 39.5% by weight of cyclohexadecadiene and 60.5% by weight of higher cyclopolyoctenylenes.
. ~
.~,, ' ' , .
.
~.
~ ' , e. 30 r~ ' ~,, ~ ' .
.
.- ;
,.
,~
::
~L32~42 Example 2 Preparation of 1,9-cyclohexadecadiene by metathesis of a cyclopolyoctenylene/cyclooGtene mixture.
A vertically arranged tube reactor ~length 155 cm, diameter 25 cm), which was filled with 3~ kg of carrier catalyst, was used. The composition of the catalyst was as described in Example 1. :.
A 0.022 molar solution (based on cyclooctene uniis) of a cyclopolyoctenylene/cyclcoctene mixture in n-pentane was passed through the catalyst bed. The ratio of cyclopolyoctenylene to cyclo-J. octene was 3:1 (in parts by weigh~). The cyclopolyoctenylene used had the composition shown in Table 1 of Example 1. The average residence time of the reaction mixture was 95 seconds; the tempera-ture in the catalyst ~ed being 23C and the pressure being 1.05 bar.
~;~ The reaction mix~ure, which left the reactor, was trans-20 ferred to a distillation apparatus in which the solvent was distilled off s' and which, after bein~ char~ed with new cyclopolyoctenylene/cyclo-octene rnixture of the abovementioned composition, was recycled into the reactor.
b : .
A total of 274.4 kg of cycloolefin mixture were reacted in this manner. Separation of the reaction mixture by distillation gave 68.6 kg of cyclohexadecadiene, which corresponds to a yield of 25%, . .
r"~ based on the total amount of cycloolefin used.
"~ l While only several examples oF the present invention ," ~ .
:`
,~
., .
g 132~2 have been shown and described, it wili be obvious to those of ordinary skill in the art that many modifications may be made to the present invention without departing from the spirit and scope thereof.
,.
~: 20 '~
~, .
.: :
. ' .
~3, . - 10-.
, ~ .
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of cycloalkadlenes in a liquid phase by a metathesis reaction, comprising the step of:
contacting a member selected from the group consisting of a cyclopolyctenytene and a cycloalkamonoene/cyclopolyoctenylene mixture, cyclopolyctenytene having a polymerization degree of at least 3 in a form of a 0.005 - 0.2 molar solution at a residence time of approximately 10 - 600 seconds, with a carrier catalyst based on Re2O7/Al2O3.
contacting a member selected from the group consisting of a cyclopolyctenytene and a cycloalkamonoene/cyclopolyoctenylene mixture, cyclopolyctenytene having a polymerization degree of at least 3 in a form of a 0.005 - 0.2 molar solution at a residence time of approximately 10 - 600 seconds, with a carrier catalyst based on Re2O7/Al2O3.
2. The process according to Claim 1, wherein a 0.01 - 0.05 molar solution is employed in said contacting step.
3. The process according to Claim 1, wherein the residence time is 10 - 200 seconds.
4. The process according to Claim 1, wherein said member is cyclopolyoctenylene having a polymerization degree of 3 to 50.
5. The process according to Claim 1, wherein the carrier catalyst includes ?-Al2O3 as a support material.
6. The process according to Claim 5, wherein the support material has a speific surface area of 100 - 300 m2/g according to BET.
7. The process according to Claim 1, wherein the Re2O7 in the carrier catalyst, as a total weight of the carrier catalyst, has a relative weight of 3 - 20%, by weight.
8. The process according to Claim 1, wherein said contacting step occurs in the presence of a co-catalyst.
9. The process according to Claim 8, wherein the molar ratio of Re to co-catalyst is 50:1 to 1:2.
10. The process according to Claim 8, wherein the co-catalyst used is a compound of the formula MRR'm wherein, R represents a member selected from the group consisting of an alkyl radical and an aryl radical;
R' represents a member selected from the group consisting of a halogen atom, an alkyl radical and an aryl radical; and, M represents aluminum when m = 2; and, a member selected from the group consisting of tin and lead when m = 3.
R' represents a member selected from the group consisting of a halogen atom, an alkyl radical and an aryl radical; and, M represents aluminum when m = 2; and, a member selected from the group consisting of tin and lead when m = 3.
11. The process according to Claim 10, wherein R and R' are independently selected from the group consisting of a methyl radical, an ethyl radical, an n-butyl radical and a phenyl radical.
12. The process according to Claim 8, wherein said co-catalyst is a member selected from the group consisting of tetramethyltin, tetraethyltin, tetra-n-butyltin, tetramethyllead, tetraethyllead, tetra-n-butyllead and a combination thereof.
13. The process according to Claim 1, wherein said member is a cycloalkamonoene/cyclopolyoctenylene mixture having a cycloalkamonoene content of 1 - 90% by weight, relative to the total weight of said mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3816453A DE3816453A1 (en) | 1988-05-13 | 1988-05-13 | PROCESS FOR THE PREPARATION OF CYCLOALCADIENES |
| DEP3816453.1 | 1988-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1325642C true CA1325642C (en) | 1993-12-28 |
Family
ID=6354361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000599576A Expired - Lifetime CA1325642C (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 ES ES198989108476T patent/ES2039048T3/en not_active Expired - Lifetime
- 1989-05-11 DE DE8989108476T patent/DE58900978D1/en not_active Expired - Lifetime
- 1989-05-12 JP JP1117613A patent/JPH062683B2/en not_active Expired - Lifetime
- 1989-05-12 NO NO891941A patent/NO174745C/en not_active IP Right Cessation
- 1989-05-12 CA CA000599576A patent/CA1325642C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NO891941D0 (en) | 1989-05-12 |
| EP0343437A1 (en) | 1989-11-29 |
| NO174745C (en) | 1994-06-29 |
| NO891941L (en) | 1989-11-14 |
| JPH062683B2 (en) | 1994-01-12 |
| DE3816453A1 (en) | 1989-11-23 |
| ES2039048T3 (en) | 1993-08-16 |
| DE58900978D1 (en) | 1992-04-23 |
| NO174745B (en) | 1994-03-21 |
| JPH01319430A (en) | 1989-12-25 |
| EP0343437B1 (en) | 1992-03-18 |
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