CA1215399A - Manufacture of norbornene - Google Patents
Manufacture of norborneneInfo
- Publication number
- CA1215399A CA1215399A CA000432420A CA432420A CA1215399A CA 1215399 A CA1215399 A CA 1215399A CA 000432420 A CA000432420 A CA 000432420A CA 432420 A CA432420 A CA 432420A CA 1215399 A CA1215399 A CA 1215399A
- Authority
- CA
- Canada
- Prior art keywords
- reactor
- ethylene
- norbornene
- diene
- mpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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
- C07C2/50—Diels-Alder conversion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the manufacture of norbornene is disclosed. The process comprises the steps of (a) feeding ethylene, cyclopentadiene and/or dicyclopentadiene, and inert aliphatic hydrocarbon solvent into a reactor, (b) maintaining the ratio of ethylene:diene at at least 3:1 (molar basis), the reactor temperature at at least 200°C, the reactor pressure at at least 5 MPa and a residence time in the reactor of at least 5 minutes, and (c) separating the norbornene so formed. The inert solvent is preferably pentane, hexane, heptane and/or cyclohexane. The norbornene may be copolymerized with ethylene to form high molecular weight polymers for the packaging or other plastics industries.
A process for the manufacture of norbornene is disclosed. The process comprises the steps of (a) feeding ethylene, cyclopentadiene and/or dicyclopentadiene, and inert aliphatic hydrocarbon solvent into a reactor, (b) maintaining the ratio of ethylene:diene at at least 3:1 (molar basis), the reactor temperature at at least 200°C, the reactor pressure at at least 5 MPa and a residence time in the reactor of at least 5 minutes, and (c) separating the norbornene so formed. The inert solvent is preferably pentane, hexane, heptane and/or cyclohexane. The norbornene may be copolymerized with ethylene to form high molecular weight polymers for the packaging or other plastics industries.
Description
i3~
Manufacture of Norbornene The present invention relates to the manufacture of norbornene i.e. bicyclo(2,2,1)-2-heptene, by the reaction of ethylene with c~clopentadiene and/or dicyclopentadiene in an inert hydrocarbon solvent.
Norbornene may be polymerized to give tough trans~
parent materials. In addition norbornene i5 capable of being copolymerized with ethylene to give polymers that have potential in a variety of appli~ations including moul~ed ancl extruded articles and film. The polyethylene and elastomer businesses, to which such copolymers relate, is very compet-itive and it is therefore important that the methods used to obtain any comonomers be efficient and economic.
Processes for the manufacture of norbornene are known. A vapour phase process in which dicyclopentadiene is reacted with ethylene at elevated ternperature and pressure is disclosed in U.S. Patent 3 007 977 of A.B. Hill et al, which issued 1961 November 07. The use of excess olefin in 2C a vapour phase process is disclosed in U.S. Patent 3 763 253 of M.S. Wing et al, which issued 1973 October 02. The manu-facture of norbornene from ethylene and cyclopentadiene or dicyclopentadiene in the presence of an inert solvent is disclosed in U.S. Patent 3 766 283 of N.~. Lorette, which issued 1973 October 16. The solvents used are high boiling inert solvents having a boiling point greater than about 100C, examples of which are stated to be commercial aromatic hydrocarbons such as xylene, diisopropylbenzenes, toluene, ethyl methyl benzenes, trimethyl benzenes, naphtha and the like. Such processes are capable of improvement, especially with respect to the conversion obtained and the selectivity of the reaction in producing norbornene.
~n improved process for the manufacture of norbor-nene from ethylene and cyclopentadiene and/or dicyclopenta-diene has now been found.
~s3c~
Accordingly the present invention provides a proc-ess for the manufacture of norbornene comprising the steps of:
(a~ feeding ethylene, a diene selected from the group consisting of cyclopentadiene and dicyclopentadiene, and mixtures thereof, and inert aliphatic hydrocarbon sol-vent into a reactor;
(b) maintaining the ratio of ethylene:diene at least 3:1 on a molar basis, a reactor temperature of at least 200~C, a reactor pressure of at least 5 MPa and a residence time in the reactor of at least 5 minutes; and (c) separating the norbornene so formed from inert solvent and unreacted diene.
In a preferred embodiment of the process of the present invention, the ethylene and diene are each fed to the reactor in inert solvent.
In the process of the present invention, ethylene, diene and inert solvent are each fed to a reactor. The diene may be cyclopentadiene or dicyclopentadiene~ or mixtures thereof. DicyclopentaAiene is preferred because of its stability, relative to cyclopentadiene, and to facili-tate separation of the products of the reaction. Both the ethylene and the diene are preferably admixed with solvent prior to being fed to the reactor, with additiona] solvent optionally being fed to the reactor.
Reactors suitable for carrying out a process of the type described herein are known in the art and include tubular reactors and stirred reactors. The latter are preferred.
The solvent used in the process of the present invention is an inert aliphatic hydrocarbon solvent. As used herein, aliphatic hydrocarbon solvent means linear, branched and cyclic aliphatic hydrocarbon solven-ts, examples of which are pentane, hexane, heptane and cyclo-hexane. Mixtures of such solvents may be used. The prefer-~lS3~
red solvent is heptane.
The reaction i5 carried out at a temperature of at least 200C and preferably 200-300C. In preferred embodi-ments the temperature is 240 to 300C, and especially 2S0 to 290C. The reaction pressure should be maintained at at least 5 MPa, especially 5-60 MPa and preferably in the range 15 to 25 MPa. The residence or hold-up time in the reactor should be maintained at at least 5 minutes, especially in the range of 5 to 30 minutes and preferably in the range of 6 to 18 minutes. It will, however, be understood by those skilled in the art that relatively high reaction temperatur-es, high reaction pressures and long hold-up times many not be desirable on ecomonic grounds and the increased possibil-ity of the formation of by-products.
The ethylene and diene are fed to the reactor such that the ratio of ethylene to diene, on a molar basis, is at least 3:1. Preferred ratios of ethylene to diene are in the r~nge 4:1 to 30:1, especially 8:1 to 20:1.
The norbornene produced in the reactor may be separated from inert solvent and any unreacted ethylene and/or diene by techniques known in the art. In particular the norbornene may be separated hy distillation. Unreacted ethylene and diene, and the inert solvent are preferably recycled to the reactor, although a small portion of the recycled material may be bled off or otherwise separated so as to control impurity levels in the reactor, as in known in the art.
Norbornene may be copolymerized with ethylene to form high molecular weight polymers that may be used in the packaging and other plastics industries.
The invention is illustra-ted by the following examples.
Example I
A solution of n-hep-tane containing 26-27%, by weight, of ethylene was pumped at a rate of 14.4 mL/min.
1~2~3~9~
into a stirred autoclave. The autoclave was a~proximately cylindrical with a diameter of 8.9 cm and a length of 7.0 cm, the volume being 475 cm3. The reactor was stirred at 700-900 rpm. A solution of dicyclopentadiene in n-heptane S (1:1 by volume) was admixed at a rate of 2.6 mL/min. with the ethylene solution just prior to the reactor. An addi tional 3.6 mL/min. of n-hep~ane was fed directly to the reactor. The molar ratio of ethylene:dicyclopentadiene was, therefore, 9.66:1. The residence time in the reactor was 16.7 minutes.
The reactor was maintained at a temperature of 200C and under a pressure of 12.5 MPa.
The effluent from the reactor was mc~nitored using an on-line gas chromatograph. It was found that the conver-sion to products was 52.0~ and t~at the yield to norbornene in the product was 99%; yield to norbornene is defined as product less detected by-products.
Example II
The procedure of Example I was repeated using different reaction conditions. Further experimental details and the results obtained are given in Table I, together with the results for Example I (Run 1).
Example III
The procedure of Example I was repeated using a reactor with an inside diameter of 6.2 cm and a length of 4.9 cm, the volume being 150 cm3. Further experimental details and the results obtained are given in Table II as Runs 16-22.
Example IV
The procedure of Example III was repeated using cyclohexane as solvent instead of n-heptane. Further experimental details and the results obtained are given in Table II as Runs 23-24.
9~
Table I
DCP- Residence Initial Te~p. Press. Time Conver- Yield Run (Wt.%) E/DCP* (~C) MPa (min.) sion~%) ~%) l 8.72 9.66 200 12.516.7 52.0 99.0
Manufacture of Norbornene The present invention relates to the manufacture of norbornene i.e. bicyclo(2,2,1)-2-heptene, by the reaction of ethylene with c~clopentadiene and/or dicyclopentadiene in an inert hydrocarbon solvent.
Norbornene may be polymerized to give tough trans~
parent materials. In addition norbornene i5 capable of being copolymerized with ethylene to give polymers that have potential in a variety of appli~ations including moul~ed ancl extruded articles and film. The polyethylene and elastomer businesses, to which such copolymers relate, is very compet-itive and it is therefore important that the methods used to obtain any comonomers be efficient and economic.
Processes for the manufacture of norbornene are known. A vapour phase process in which dicyclopentadiene is reacted with ethylene at elevated ternperature and pressure is disclosed in U.S. Patent 3 007 977 of A.B. Hill et al, which issued 1961 November 07. The use of excess olefin in 2C a vapour phase process is disclosed in U.S. Patent 3 763 253 of M.S. Wing et al, which issued 1973 October 02. The manu-facture of norbornene from ethylene and cyclopentadiene or dicyclopentadiene in the presence of an inert solvent is disclosed in U.S. Patent 3 766 283 of N.~. Lorette, which issued 1973 October 16. The solvents used are high boiling inert solvents having a boiling point greater than about 100C, examples of which are stated to be commercial aromatic hydrocarbons such as xylene, diisopropylbenzenes, toluene, ethyl methyl benzenes, trimethyl benzenes, naphtha and the like. Such processes are capable of improvement, especially with respect to the conversion obtained and the selectivity of the reaction in producing norbornene.
~n improved process for the manufacture of norbor-nene from ethylene and cyclopentadiene and/or dicyclopenta-diene has now been found.
~s3c~
Accordingly the present invention provides a proc-ess for the manufacture of norbornene comprising the steps of:
(a~ feeding ethylene, a diene selected from the group consisting of cyclopentadiene and dicyclopentadiene, and mixtures thereof, and inert aliphatic hydrocarbon sol-vent into a reactor;
(b) maintaining the ratio of ethylene:diene at least 3:1 on a molar basis, a reactor temperature of at least 200~C, a reactor pressure of at least 5 MPa and a residence time in the reactor of at least 5 minutes; and (c) separating the norbornene so formed from inert solvent and unreacted diene.
In a preferred embodiment of the process of the present invention, the ethylene and diene are each fed to the reactor in inert solvent.
In the process of the present invention, ethylene, diene and inert solvent are each fed to a reactor. The diene may be cyclopentadiene or dicyclopentadiene~ or mixtures thereof. DicyclopentaAiene is preferred because of its stability, relative to cyclopentadiene, and to facili-tate separation of the products of the reaction. Both the ethylene and the diene are preferably admixed with solvent prior to being fed to the reactor, with additiona] solvent optionally being fed to the reactor.
Reactors suitable for carrying out a process of the type described herein are known in the art and include tubular reactors and stirred reactors. The latter are preferred.
The solvent used in the process of the present invention is an inert aliphatic hydrocarbon solvent. As used herein, aliphatic hydrocarbon solvent means linear, branched and cyclic aliphatic hydrocarbon solven-ts, examples of which are pentane, hexane, heptane and cyclo-hexane. Mixtures of such solvents may be used. The prefer-~lS3~
red solvent is heptane.
The reaction i5 carried out at a temperature of at least 200C and preferably 200-300C. In preferred embodi-ments the temperature is 240 to 300C, and especially 2S0 to 290C. The reaction pressure should be maintained at at least 5 MPa, especially 5-60 MPa and preferably in the range 15 to 25 MPa. The residence or hold-up time in the reactor should be maintained at at least 5 minutes, especially in the range of 5 to 30 minutes and preferably in the range of 6 to 18 minutes. It will, however, be understood by those skilled in the art that relatively high reaction temperatur-es, high reaction pressures and long hold-up times many not be desirable on ecomonic grounds and the increased possibil-ity of the formation of by-products.
The ethylene and diene are fed to the reactor such that the ratio of ethylene to diene, on a molar basis, is at least 3:1. Preferred ratios of ethylene to diene are in the r~nge 4:1 to 30:1, especially 8:1 to 20:1.
The norbornene produced in the reactor may be separated from inert solvent and any unreacted ethylene and/or diene by techniques known in the art. In particular the norbornene may be separated hy distillation. Unreacted ethylene and diene, and the inert solvent are preferably recycled to the reactor, although a small portion of the recycled material may be bled off or otherwise separated so as to control impurity levels in the reactor, as in known in the art.
Norbornene may be copolymerized with ethylene to form high molecular weight polymers that may be used in the packaging and other plastics industries.
The invention is illustra-ted by the following examples.
Example I
A solution of n-hep-tane containing 26-27%, by weight, of ethylene was pumped at a rate of 14.4 mL/min.
1~2~3~9~
into a stirred autoclave. The autoclave was a~proximately cylindrical with a diameter of 8.9 cm and a length of 7.0 cm, the volume being 475 cm3. The reactor was stirred at 700-900 rpm. A solution of dicyclopentadiene in n-heptane S (1:1 by volume) was admixed at a rate of 2.6 mL/min. with the ethylene solution just prior to the reactor. An addi tional 3.6 mL/min. of n-hep~ane was fed directly to the reactor. The molar ratio of ethylene:dicyclopentadiene was, therefore, 9.66:1. The residence time in the reactor was 16.7 minutes.
The reactor was maintained at a temperature of 200C and under a pressure of 12.5 MPa.
The effluent from the reactor was mc~nitored using an on-line gas chromatograph. It was found that the conver-sion to products was 52.0~ and t~at the yield to norbornene in the product was 99%; yield to norbornene is defined as product less detected by-products.
Example II
The procedure of Example I was repeated using different reaction conditions. Further experimental details and the results obtained are given in Table I, together with the results for Example I (Run 1).
Example III
The procedure of Example I was repeated using a reactor with an inside diameter of 6.2 cm and a length of 4.9 cm, the volume being 150 cm3. Further experimental details and the results obtained are given in Table II as Runs 16-22.
Example IV
The procedure of Example III was repeated using cyclohexane as solvent instead of n-heptane. Further experimental details and the results obtained are given in Table II as Runs 23-24.
9~
Table I
DCP- Residence Initial Te~p. Press. Time Conver- Yield Run (Wt.%) E/DCP* (~C) MPa (min.) sion~%) ~%) l 8.72 9.66 200 12.516.7 52.0 99.0
2 9.25 9.18 200 12.523.0 58.5 94.6
3 10.95 9.18 200 12.527.4 62.4 99.6
4 10.50 9.66 200 12.520.2 55.0 94.5
5 18.00 4.66 200 12.523.0 5g.4 96.9
6 13.68 6.26 200 12.623.0 56.6 g9.0
7 9.25 9.38 200 17.523.0 69.1 85.1
8 9.25 9.38 200 25.023.0 74.4 82.4
9 9.25 9.38 200 27.523.0 78.8 66.7
10 13.68 6.26 200 27.523.0 74.3 76.3
11 19.6g 4.67 200 27.523.0 73.3 61.5
12 9.25 9.38 250 25.018.3 99.0 89.3
13 9.25 9.38 300 25.018.0 99.0 73.3
14 9.25 9.38 300 25.09.0 99.0 81.4
15 9.25 9.38 300 25.06.0 99.0 85.1 Table II
DCP- ~esidence Initial Tenp. Press. Time Conver- Yield Run (Wt.~) E/DCP* (C) MPa (min.) si~n(%) (%)_
DCP- ~esidence Initial Tenp. Press. Time Conver- Yield Run (Wt.~) E/DCP* (C) MPa (min.) si~n(%) (%)_
16 6.98 16.4 250 20 8.66 98.8 99
17 6.98 16.4 250 20 5.77 97.8 99
18 6.98 16.4 275 20 8.59 99.6 99
19 6.36 20.5 280 20 7.81 99.6 99
20 9.69 10.2 300 20 4.27 99.3 99
21 6.98 16.38 300 20 5.70 99.7 99
22 9.72 10.24 300 20 7.50 99.6 99
23 5.63 16.73 280 20 7.73 99.7 99
24 6.18 15.75 300 20 5.63 99.6 99 DCP = dicyclcpentadiene E = ethylene DCP-Initial is the initial concentration of dicyclopentadiene *E/DCP = ratio of ethylene:dicyclcpentadiene on a mDlar basis
Claims (10)
1. A process for the manufacture of norbornene comprising the steps of:
(a) feeding ethylene, a diene selected from the group consisting of cyclopentadiene and dicyclopentadiene, and mixtures thereof, and inert aliphatic hydrocarbon solvent into a reactor;
(b) maintaining the ratio of ethylene:diene at at least 3:1 on a molar basis, a reactor temperature of at least 200°C, a reactor pressure of at least 5 MPa and a residence time in the reactor of at least 5 minutes; and (c) separating the norbornene so formed from inert solvent and unreacted diene.
(a) feeding ethylene, a diene selected from the group consisting of cyclopentadiene and dicyclopentadiene, and mixtures thereof, and inert aliphatic hydrocarbon solvent into a reactor;
(b) maintaining the ratio of ethylene:diene at at least 3:1 on a molar basis, a reactor temperature of at least 200°C, a reactor pressure of at least 5 MPa and a residence time in the reactor of at least 5 minutes; and (c) separating the norbornene so formed from inert solvent and unreacted diene.
2. The process of Claim 1 in which the reactor temperature is in the range 200-300°C.
3. The process of Claim 2 in which the reactor pressure is in the range 5-60 MPa.
4. The process of Claim 3 in which the residence time in the reactor is 5-30 minutes.
5. The process of Claim 4 in which the ethylene and diene are each admixed with inert solvent before being fed to the reactor.
6. The process of Claim 5 in which the diene is dicyclopentadiene.
7. The process of Claim 6 in which the tempera-ture is 240-300°C.
8. The process of Claim 7 in which the pressure is 15 to 25 MPa.
9. The process of Claim 7 in which the residence time is 6 to 18 minutes.
10. The process of any one of Claim 1, Claim 4 and Claim 6 in which the solvent is selected from the group consisting of pentane, hexane, heptane and cyclohexane, and mixtures thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000432420A CA1215399A (en) | 1983-07-14 | 1983-07-14 | Manufacture of norbornene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000432420A CA1215399A (en) | 1983-07-14 | 1983-07-14 | Manufacture of norbornene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1215399A true CA1215399A (en) | 1986-12-16 |
Family
ID=4125663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000432420A Expired CA1215399A (en) | 1983-07-14 | 1983-07-14 | Manufacture of norbornene |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1215399A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262074A (en) * | 2014-08-27 | 2015-01-07 | 无锡阿科力科技股份有限公司 | Production technique of norbornene |
| US9115155B1 (en) | 2014-03-20 | 2015-08-25 | Eastman Chemical Company | Low-pressure synthesis of cyclohexanedimethanol and derivatives |
| WO2024125138A1 (en) * | 2022-12-14 | 2024-06-20 | 中国石油天然气股份有限公司 | Preparation method for norbornene |
-
1983
- 1983-07-14 CA CA000432420A patent/CA1215399A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9115155B1 (en) | 2014-03-20 | 2015-08-25 | Eastman Chemical Company | Low-pressure synthesis of cyclohexanedimethanol and derivatives |
| CN104262074A (en) * | 2014-08-27 | 2015-01-07 | 无锡阿科力科技股份有限公司 | Production technique of norbornene |
| WO2024125138A1 (en) * | 2022-12-14 | 2024-06-20 | 中国石油天然气股份有限公司 | Preparation method for norbornene |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |