CN100374400C - Method of preparing exo-dicyclopentadiene from endo-dicyclopentadiene or cyclopentadiene - Google Patents
Method of preparing exo-dicyclopentadiene from endo-dicyclopentadiene or cyclopentadiene Download PDFInfo
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- CN100374400C CN100374400C CNB2006100153411A CN200610015341A CN100374400C CN 100374400 C CN100374400 C CN 100374400C CN B2006100153411 A CNB2006100153411 A CN B2006100153411A CN 200610015341 A CN200610015341 A CN 200610015341A CN 100374400 C CN100374400 C CN 100374400C
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Abstract
The invention discloses a preparation method for exo-dicyclopentadiene from bridge-type dicyclopentadiene or cyclopentadiene, belonging to the exo-dicyclopentadiene preparation technology. The method includes preparing a solution composed of bridge-type dicyclopentadiene or cyclopentadiene, and benzene, or toluene, or benzyl alcohol, or decalin, or cyclohexane, or heptane, or hexane at a certain quality ratio, adding p-tert-butylcatechol, or 2, 5-di-tert-butylhydroquinone, or 2,6-di-tertbutyl-4-methylphenol, or hydroquinone, or 2-methyl-1,4-dihydroxybenzene, or o-hydroquinone inhibitor and carrying out reaction at a certain temperature and pressure, distilling and separating to obtain the exo-dicyclopentadiene. The invention has the advantages of one-step synthesis without catalyst, mild reaction conditions and high yield, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind ofly prepare the method for hanging dicyclopentadiene, belong to the hanging dicyclopentadiene technology of preparing by bridge dicyclopentadiene or cyclopentadiene.
Background technology
Dicyclopentadiene (DCPD) is important chemical intermediate, and is general by the C in the petrochemical complex
5Product-cyclopentadiene (CPD) dimerization at normal temperatures forms.DCPD is the raw material or the intermediate of synthetic a series of high-performance chemical product, comprise high molecular polymers such as petroleum resin, unsaturated polyester, ethylene-propylene rubber(EPR), reaction injection moulding, coating resin, the high energy density fuel that guided missile, aircraft, racing car etc. are used, and synthetic perfume, medicine intermediate etc.DCPD mainly contains two kinds of configurations, and the bridge-type configuration accounts for 95.5%, and hanging configuration is about 4.5%.The Molecular Geometries of DCPD has a significant impact for follow-up synthesis technique and product performance.Document [ROMP reactivity of endo-and exo-dicyclopentadiene, Macromolecules 2002,35:7878-7882] report, in the DCPD polymerization process, the polymerizable raw material time of hanging configuration is shorter, technology is simpler; U.S. Pat 6294706B1 report, the macromolecular material mechanical property that hanging polymerizable raw material obtains is more excellent; Document [synthetic high Density Hydrocarbon Fuels progress, chemical progress 2005,17:359-367] report, the hydrogenation products freezing point of hanging dicyclopentadiene is than low 50 ℃ of bridge-type raw material hydrogenation products, having extraordinary low-temperature performance, is the high-density propellant of excellent performance.As seen, hanging dicyclopentadiene is the good raw material or the intermediate of synthesized high-performance chemical.Document [An improved procedure for the preparation of exo-dicyclopentadiene.Synthesis 1975,105-106] be raw material with the bridge dicyclopentadiene, deviate from two-step approach by HBr addition, HBr and make hanging DCPD, but this procedure complexity.Document [The endo to exo isomerisation of dicyclopentadiene.Acta ChemicaScandinavica 1990,44:860-861] to adopt the silicoaluminate of carried noble metal platinum be catalyzer, the bridge-type DCPD gas of lower concentration is tautomerized to hanging dicyclopentadiene, but yield and output are lower.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing hanging dicyclopentadiene by bridge dicyclopentadiene or cyclopentadiene.This procedure is simple, is easy to large-scale production.
Technical scheme of the present invention is: a kind ofly prepare the method for hanging dicyclopentadiene by bridge dicyclopentadiene or cyclopentadiene, its feature comprises following process:
1. be 1/10～5/1 by mass ratio, with bridge dicyclopentadiene or cyclopentadiene and benzene, or toluene, or phenylcarbinol, or perhydronaphthalene, or hexanaphthene, or heptane, or normal hexane wiring solution-forming, and the adding mass content is the p-ten.-butylcatechol of 0～50000ppm in this solution, or 2, the 5-di-tert-butyl hydroquinone, or 2, the 6-ditertbutylparacresol, or Resorcinol, or adjacent methyl hydroquinone, or pyrocatechol stopper, in temperature is 90 ℃～190 ℃, pressure is to react under the condition of 0.1MPa～6.0MPa, reaction times is 1min～30min, obtains containing the hanging dicyclopentadiene product.
2. the product with step 1 adopts air distillation, and distillation temperature is 175 ℃～185 ℃, obtains hanging dicyclopentadiene.
The invention has the advantages that: compare with existing method, the one-step synthesis hanging dicyclopentadiene does not need catalyzer, the liquid-phase reaction condition gentleness, and yield is higher, is suitable for industrial production.
Embodiment
The following examples have embodied the process that the present invention describes, but the present invention is not limited to these examples.
Embodiment 1
The 100g bridge dicyclopentadiene is joined in the 200g perhydronaphthalene, and the adding mass content is the p-ten.-butylcatechol of 50ppm in this solution, be that 150 ℃, pressure are that the condition of 4.0MPa is reacted 2min, 5min, 10min and 30min respectively with temperature in fixed-bed reactor, the transformation efficiency of bridge dicyclopentadiene, the selectivity of hanging dicyclopentadiene and yield see the following form:
| Reaction times min | Bridge dicyclopentadiene transformation efficiency % | Hanging dicyclopentadiene selectivity % | Hanging dicyclopentadiene yield % |
| 2 | 21.3 | 89.4 | 19.0 |
| 5 | 42.6 | 82.9 | 30.2 |
| 10 | 73.4 | 53.7 | 39.4 |
| 30 | 85.0 | 42.1 | 35.7 |
Embodiment 2
The 200g bridge dicyclopentadiene is joined in the 200g benzene, and the adding mass content is 2 of 300ppm in this solution, the 5-di-tert-butyl hydroquinone, in temperature is that 100 ℃, pressure are reaction 3 minutes under the condition of 2.0MPa, the transformation efficiency of bridge dicyclopentadiene is 15.2%, the selectivity of hanging dicyclopentadiene is 76.4%, and yield is 11.6%, obtains hanging dicyclopentadiene 23.2g after 180 ℃ of fractionation by distillation of normal pressure.
Embodiment 3
The 100g cyclopentadiene is joined in the 1000g toluene, is that 190 ℃, pressure are reaction 7 minutes under the condition of 6.0MPa in temperature, and the transformation efficiency of cyclopentadiene is 95.1%, and the selectivity of hanging dicyclopentadiene is 91.6%, and yield is 87.2%.
Embodiment 4
The 1000g bridge dicyclopentadiene is joined in the 5000g phenylcarbinol, and the adding mass content is 2 of 20ppm in this solution, the 6-ditertbutylparacresol, in temperature is that 150 ℃, pressure are reaction 30 minutes under the condition of 0.9MPa, the transformation efficiency of bridge dicyclopentadiene is 72.3%, the selectivity of hanging dicyclopentadiene is 75.9%, and yield is 54.8%, obtains hanging dicyclopentadiene 548g after 175 ℃ of fractionation by distillation of normal pressure.
Embodiment 5
The 3000g cyclopentadiene is joined in the 1000g hexanaphthene, and the adding mass content is the Resorcinol of 5000ppm in this solution, in temperature is that 120 ℃, pressure are reaction 20 minutes under the condition of 0.1MPa, the transformation efficiency of cyclopentadiene is 67.7%, the selectivity of hanging dicyclopentadiene is 63.4%, yield is 42.9%, obtains hanging dicyclopentadiene 1287g after 185 ℃ of fractionation by distillation of normal pressure.
Embodiment 6
The 400g cyclopentadiene is joined in the 100g heptane, and the adding mass content is the adjacent methyl hydroquinone of 10000ppm in this solution, in temperature is that 130 ℃, pressure are reaction 15 minutes under the condition of 3.0MPa, the transformation efficiency of cyclopentadiene is 43.7%, hanging cyclopentadiene selectivity is 42.5%, and yield is 18.5%.
Embodiment 7
The 500g cyclopentadiene is joined in the 100g normal hexane, and the adding mass content is the pyrocatechol of 50000ppm in this solution, in temperature is that 90 ℃, pressure are reaction 8 minutes under the condition of 0.5MPa, the transformation efficiency of cyclopentadiene is 43.7%, the selectivity of hanging dicyclopentadiene is 41.5%, and yield is 18.1%.
Claims (1)
1. one kind prepares the method for hanging dicyclopentadiene by bridge dicyclopentadiene or cyclopentadiene, and its feature comprises following process:
1). by mass ratio is 1/10～5/1, with bridge dicyclopentadiene or cyclopentadiene and benzene, or toluene, or phenylcarbinol, or perhydronaphthalene, or hexanaphthene, or heptane, or normal hexane wiring solution-forming, and the adding mass content is the p-ten.-butylcatechol of 0～50000ppm in this solution, or 2, the 5-di-tert-butyl hydroquinone, or 2, the 6-ditertbutylparacresol, or Resorcinol, or adjacent methyl hydroquinone, or the stopper of pyrocatechol, in temperature is 90 ℃～190 ℃, pressure is to react under the condition of 0.1MPa～6.0MPa, reaction times is 1 minute～30 minutes, obtains containing the product of hanging dicyclopentadiene;
2). with the product air distillation that contains hanging dicyclopentadiene that step 1) obtains, distillation temperature is 175 ℃～185 ℃, obtains hanging dicyclopentadiene.
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| CN100374400C true CN100374400C (en) | 2008-03-12 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134707B (en) * | 2007-07-20 | 2010-05-19 | 西安近代化学研究所 | One-step method for preparing exo-tetrahydrodicyclopentadiene |
| CN101215218B (en) * | 2008-01-16 | 2010-06-02 | 西安近代化学研究所 | Method for preparing exo-tetrahydrocyclopentadiene |
| RU2463284C1 (en) * | 2011-05-04 | 2012-10-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Казанский национальный исследовательский технологический университет" | Method of producing dicyclopentadiene |
| DE102013204950A1 (en) | 2013-03-20 | 2014-09-25 | Evonik Industries Ag | Process and composition for inhibiting the polymerization of cyclopentadiene compounds |
| CN104130097B (en) * | 2014-06-24 | 2016-06-08 | 北京理工大学 | The technique of a kind of liquid phase continuous production hanging type tetrahydrochysene dicyclopentadiene |
| KR101661040B1 (en) | 2014-12-31 | 2016-09-28 | 한국화학연구원 | Preparation method of exo-form compound from endo-form compound using metal organic framework catalyst |
| CN106866345B (en) * | 2015-12-12 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for preparing JP-10 aviation fuel from furfuryl alcohol |
| CN107915565B (en) * | 2017-12-08 | 2020-09-25 | 西安近代化学研究所 | Method for preparing exo-dicyclopentadiene through bridge-type dicyclopentadiene isomerization |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5013370A (en) * | 1973-06-06 | 1975-02-12 | ||
| JPH0217130A (en) * | 1988-07-04 | 1990-01-22 | Maruzen Petrochem Co Ltd | Isomerization of dicyclopentadiene |
| US5648583A (en) * | 1995-04-27 | 1997-07-15 | Albemarle Corporation | Process for converting exo-isomers of alkyl substituted cyclopentadienes to endo-isomers |
| JPH10212250A (en) * | 1997-01-31 | 1998-08-11 | Maruzen Petrochem Co Ltd | Isomerization of dicyclopentadiene |
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2006
- 2006-08-17 CN CNB2006100153411A patent/CN100374400C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5013370A (en) * | 1973-06-06 | 1975-02-12 | ||
| JPH0217130A (en) * | 1988-07-04 | 1990-01-22 | Maruzen Petrochem Co Ltd | Isomerization of dicyclopentadiene |
| US5648583A (en) * | 1995-04-27 | 1997-07-15 | Albemarle Corporation | Process for converting exo-isomers of alkyl substituted cyclopentadienes to endo-isomers |
| JPH10212250A (en) * | 1997-01-31 | 1998-08-11 | Maruzen Petrochem Co Ltd | Isomerization of dicyclopentadiene |
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