CN100543001C - 2, the preparation method of 5-norbornadiene - Google Patents
2, the preparation method of 5-norbornadiene Download PDFInfo
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- CN100543001C CN100543001C CNB2006101174843A CN200610117484A CN100543001C CN 100543001 C CN100543001 C CN 100543001C CN B2006101174843 A CNB2006101174843 A CN B2006101174843A CN 200610117484 A CN200610117484 A CN 200610117484A CN 100543001 C CN100543001 C CN 100543001C
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- norbornadiene
- dicyclopentadiene
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- preparation
- acetylene
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 17
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000010924 continuous production Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 7
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical group CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of 2, the preparation method of 5-norbornadiene, be included in the tank reactor dicyclopentadiene that adds metering, be equivalent to the solvent acetone of 1.5～3.0 times of dicyclopentadiene weight and be equivalent to the stopper 2 of dicyclopentadiene weight 0.03%, the 6-di-tert-butyl-4-methy phenol, under constantly stirring, feed acetylene, make the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 4.0～6.0: 1, be mixed with reaction mass; Reaction mass is imported reaction generation 2 in the tubular reactor, 5-norbornadiene; Obtain 2 by rectification under vacuum again, 5-norbornadiene product.Preparation method of the present invention has suppressed 2, the series connection side reaction of 5-norbornadiene, thus significantly improved reaction yield, guaranteed the stability of quality product, reduced production cost, solved the problem that exists in the prior art production technique effectively.
Description
Technical field
The present invention relates to a kind of preparation method of organic compound, particularly a kind of 2, the preparation method of 5-norbornadiene.
Background technology
2, (2,5-norbornadiene NBD) is a kind of inflammable liquid to the 5-norbornadiene, can be dissolved in sherwood oil, and is water insoluble, relative density 0.909 (20 ℃), 89 ℃ of boiling points.2, containing massfraction in the commodity of 5-norbornadiene is 500 * 10
-62,6 ditertiary butyl p cresol as stablizer.NBD is because ethene suppressing is to the effect of plants such as fresh flower, fruits and vegetables effectively, and the freshness date of prolongation plant can be mixed with preservation agent with the ethene biosynthesis inhibitor.Another important use of NBD is that luminous energy stores, and by the isomerization reaction between it and its isomer, can absorb or discharge the luminous energy of 69KJ/mol.In addition, NBD also is applied to behind the ligand of various olefinic polymerization three-dimensional arrangement adjusting control agents, homogeneous phase noble metal catalyst and the full hydrogenation high energy fuels as racing car, guided missile and rocket.
The preparation method of prior art NBD all adopts the Diels-Alder reaction scheme of cyclopentadiene and acetylene.United States Patent (USP) 2875256 discloses the synthetic method of a kind of NBD.Adopt this method, when temperature is that the mol ratio of 150-400 ℃, acetylene and cyclopentadiene is 1～10:1, pressure is normal pressure～1.76MPa, when the reaction zone residence time is 1～15 minute, and the yield of reaction is 3.7～25.0%.The feature of this method is to be reflected under high temperature, the low pressure to carry out, but that the main drawback of this reaction is a reaction yield is lower, makes production cost higher.Therefore, it is necessary seeking a kind of technology that can improve reaction yield, reduce production costs.
Chinese patent CN03142244.6 discloses the synthetic method of a kind of NBD.This method is by introducing the yield that acetone solvent has improved NBD effectively.In tank reactor, when the mol ratio of acetylene and dicyclopentadiene is 1.0～3.0:1, the weight ratio of solvent acetone and dicyclopentadiene is 1～2.5:1, being warming up to 170～230 ℃ after reinforced reacts, afterreaction finished in 5 hours, this moment reaction conversion ratio (in dicyclopentadiene) 〉=80%, 2, the selectivity of 5-norbornadiene 〉=40%.The principal character of this method has been to use the solvent of acetone as reaction.But, reaction yield is reduced because of NBD series connection side reaction, and can be unfavorable for reducing production costs, and increase the complicacy of operation because reactor adopts tank reactor.
Summary of the invention
Purpose of the present invention provides a kind of new 2, the preparation method of 5-norbornadiene exactly in order to overcome the problems referred to above that prior art exists.
The object of the present invention is achieved like this: a kind of 2, the preparation method of 5-norbornadiene may further comprise the steps:
A, in tank reactor, add metering dicyclopentadiene, be equivalent to the solvent acetone of 1.5～3.0 times of dicyclopentadiene weight and be equivalent to the stopper 2 of dicyclopentadiene weight 0.03%, the 6-di-tert-butyl-4-methy phenol, under constantly stirring, feed acetylene, make the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 4.0～6.0:1, be mixed with reaction mass;
B, step a gained reaction mass is imported in the tubular reactor, generate 2, the 5-norbornadiene in 180～200 ℃ of reactions;
C, step b gained reaction product is moved into rectifying tower carry out rectification under vacuum, obtain 2,5-norbornadiene product.
Preferred 4.5～the 5.5:1 of the mol ratio of acetylene described in the step a and dicyclopentadiene, the add-on of described solvent acetone is preferably 1.6～2.4 times of dicyclopentadiene weight.
Temperature of reaction described in the step b is 180～200 ℃, preferred 185～195 ℃; The residence time of material in tubular reactor is 10～30 minutes, preferred 15～25 minutes.
Tubular reactor described in the step b is the continuous production tubular reactor, can continuous production 2, and the 5-norbornadiene wherein is provided with the chuck that is used to feed heating medium, and heating medium is generally selected thermal oil.
The purity of the dicyclopentadiene described in the step a 〉=78%.
By experiment the reaction mechanism of acetylene and cyclopentadiene is studied, found that, this reaction is cascade reaction, at first be that the reaction of acetylene and cyclopentadiene generates target product 2, the 5-norbornadiene, 2, the 5-norbornadiene continues then to generate by product with the cyclopentadiene reaction, and with the generation of cyclopentadiene trimerization and polymer.From the kinetics angle, adopt the plug flow tubular reactor the most favourable to this type reaction process, can overcome the defective of the full back-mixing of tank reactor material, can effectively reduce the generating rate of side reaction, improve the purpose product selectivity.The consumption of increase acetylene and the shortening residence time of material under comparatively high temps be generating rate and the raising 2 to reducing side reaction all, and the yield of 5-norbornadiene is favourable.
Method of the present invention makes to be reflected in the tubular reactor carries out, and is solvent with acetone, makes dicyclopentadiene be cracked into cyclopentadiene under High Temperature High Pressure, and cyclopentadiene and acetylene the Diels-Alder reaction take place changes into 2, the 5-norbornadiene.The use of tubular reactor has reduced the speed of reaction of side reaction significantly, has improved the yield of target product.Compared with prior art, adopt tubular reactor not only to suppress NBD series connection side reaction comparatively serious in tank reactor, and improved throughput and quality product stability, reduced production cost, simplified operation, thereby solved the problem that exists in the prior art production technique effectively.
Embodiment
Embodiment 1
15 kilograms in 10 kilograms of dicyclopentadiene, the acetone and 2 that in tank reactor, add purity 〉=78%, 6-di-tert-butyl-4-methy phenol 3 grams, under constantly stirring, feed acetylene, making the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 4.0:1, be mixed with reaction mass; With the speed set squeeze in the stainless steel tubular type reactor of the Φ 25mm * 1000mm that have chuck with pump this reaction mass then, it is 180 ℃ that the thermal oil that the interior feeding of chuck is heated to certain temperature makes temperature of charge, material residence time in reactor is 10 minutes, and reaction pressure is regulated by the pressure controller of reactor exit.The exit reactant is cooled to room temperature, reclaims unreacted acetylene, reuse as raw material after compression.It is in 15 the rectifying tower, under reduced pressure to distill that material moves into a theoretical plate number, and with 2, the 5-norbornadiene steams, and collects and obtains 2, and 5-norbornadiene content is 99.6% product.The transformation efficiency of dicyclopentadiene is 91%, 2 in the present embodiment, and the selectivity of 5-norbornadiene is 52.6%.
Embodiment 2
18 kilograms in 10 kilograms of dicyclopentadiene, the acetone and 2 that in tank reactor, add purity 〉=78%, 6-di-tert-butyl-4-methy phenol 3 grams, under constantly stirring, feed acetylene, making the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 4.5:1, be mixed with reaction mass; Squeeze into this reaction mass in the stainless steel tubular type reactor of a Φ 25mm * 1000mm who has a chuck with pump then, feed the thermal oil that is heated to certain temperature in the chuck material was reacted 15 minutes under 185 ℃ of hot environments, reaction pressure is regulated by the pressure controller of reactor exit.The exit reactant is cooled to room temperature, reclaims unreacted acetylene, reuse as raw material after compression.It is in 15 the rectifying tower, under reduced pressure to distill that material moves into a theoretical plate number, and with 2, the 5-norbornadiene steams, and collects and obtains 2, and 5-norbornadiene content is 99.6% product.The transformation efficiency of dicyclopentadiene is 92.6%, 2 in the present embodiment, and the selectivity of 5-norbornadiene is 54.8%.
Embodiment 3
21 kilograms in 10 kilograms of dicyclopentadiene, the acetone and 2 that in tank reactor, add purity 〉=78%, 6-di-tert-butyl-4-methy phenol 3 grams, under constantly stirring, feed acetylene, making the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 5.0:1, be mixed with reaction mass; Squeeze into this reaction mass in the stainless steel tubular type reactor of a Φ 25mm * 1000mm who has a chuck with pump then, feed the thermal oil that is heated to certain temperature in the chuck material was reacted 20 minutes under 190 ℃ of hot environments, reaction pressure is regulated by the pressure controller of reactor exit.The exit reactant is cooled to room temperature, reclaims unreacted acetylene, reuse as raw material after compression.It is in 15 the rectifying tower, under reduced pressure to distill that material moves into a theoretical plate number, and with 2, the 5-norbornadiene steams, and collects and obtains 2, and 5-norbornadiene content is 99.6% product.The transformation efficiency of dicyclopentadiene is 96.8%, 2 in the present embodiment, and the selectivity of 5-norbornadiene is 56.9%.
Embodiment 4
24 kilograms in 10 kilograms of dicyclopentadiene, the acetone and 2 that in tank reactor, add purity 〉=78%, 6-di-tert-butyl-4-methy phenol 3 grams, under constantly stirring, feed acetylene, making the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 5.5:1, be mixed with reaction mass; Squeeze into this reaction mass in the stainless steel tubular type reactor of a Φ 25mm * 1000mm who has a chuck with pump then, feed the thermal oil that is heated to certain temperature in the chuck material was reacted 25 minutes under 195 ℃ of hot environments, reaction pressure is regulated by the pressure controller of reactor exit.The exit reactant is cooled to room temperature, reclaims unreacted acetylene, reuse as raw material after compression.It is in 15 the rectifying tower, under reduced pressure to distill that material moves into a theoretical plate number, and with 2, the 5-norbornadiene steams, and collects and obtains 2, and 5-norbornadiene content is 99.6% product.The transformation efficiency of dicyclopentadiene is 98.9%, 2 in the present embodiment, and the selectivity of 5-norbornadiene is 57.6%.
Embodiment 5
27 kilograms in 10 kilograms of dicyclopentadiene, the acetone and 2 that in tank reactor, add purity 〉=78%, 6-di-tert-butyl-4-methy phenol 3 grams, under constantly stirring, feed acetylene, making the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 6.0:1, be mixed with reaction mass; Squeeze into this reaction mass in the stainless steel tubular type reactor of a Φ 25mm * 1000mm who has a chuck with pump then, feed the thermal oil that is heated to certain temperature in the chuck material was reacted 30 minutes under 200 ℃ of hot environments, reaction pressure is regulated by the pressure controller of reactor exit.The exit reactant is cooled to room temperature, reclaims unreacted acetylene, reuse as raw material after compression.It is in 15 the rectifying tower, under reduced pressure to distill that material moves into a theoretical plate number, and with 2, the 5-norbornadiene steams, and collects and obtains 2, and 5-norbornadiene content is 99.6% product.The transformation efficiency of dicyclopentadiene is 99.5%, 2 in the present embodiment, and the selectivity of 5-norbornadiene is 58.5%.
Embodiment 6
30 kilograms in 10 kilograms of dicyclopentadiene, the acetone and 2 that in tank reactor, add purity 〉=78%, 6-di-tert-butyl-4-methy phenol 3 grams, under constantly stirring, feed acetylene, making the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 6.0:1, be mixed with reaction mass; Squeeze into this reaction mass in the stainless steel tubular type reactor of a Φ 25mm * 1000mm who has a chuck with pump then, feed the thermal oil that is heated to certain temperature in the chuck material was reacted 30 minutes under 200 ℃ of hot environments, reaction pressure is regulated by the pressure controller of reactor exit.The exit reactant is cooled to room temperature, reclaims unreacted acetylene, reuse as raw material after compression.It is in 15 the rectifying tower, under reduced pressure to distill that material moves into a theoretical plate number, and with 2, the 5-norbornadiene steams, and collects and obtains 2, and 5-norbornadiene content is 99.6% product.The transformation efficiency of dicyclopentadiene is 99.9%, 2 in the present embodiment, and the selectivity of 5-norbornadiene is 58.3%.
The transformation efficiency of dicyclopentadiene is tried to achieve divided by the mole number of dicyclopentadiene in the raw material deducted the mole number of dicyclopentadiene in the product by the mole number of dicyclopentadiene in the raw material after again in the foregoing description, 2, the selectivity of 5-norbornadiene is by being converted into 2, and the mole number of the dicyclopentadiene of 5-norbornadiene is tried to achieve divided by the total mole number of the dicyclopentadiene that transforms.
Claims (6)
1, a kind of 2, the preparation method of 5-norbornadiene is characterized in that, may further comprise the steps:
A, in tank reactor, add metering dicyclopentadiene, be equivalent to the solvent acetone of 1.5～3.0 times of dicyclopentadiene weight and be equivalent to the stopper 2 of dicyclopentadiene weight 0.03%, the 6-di-tert-butyl-4-methy phenol, under constantly stirring, feed acetylene, make the acetylene that is dissolved in the solvent and the mol ratio of dicyclopentadiene reach 4.0～6.0:1, be mixed with reaction mass;
B, step a gained reaction mass is imported in the tubular reactor, generate 2, the 5-norbornadiene in 180～200 ℃ of reactions;
C, step b gained reaction product is moved into rectifying tower carry out rectification under vacuum, obtain 2,5-norbornadiene product.
2, as claimed in claim 12, the preparation method of 5-norbornadiene is characterized in that: the mol ratio of acetylene described in the step a and dicyclopentadiene is 4.5～5.5:1, and the add-on of described solvent acetone is 1.6～2.4 times of dicyclopentadiene weight.
3, as claimed in claim 12, the preparation method of 5-norbornadiene is characterized in that: the temperature of reaction described in the step b is 180～200 ℃, and the residence time of material in tubular reactor is 10～30 minutes.
4, as claimed in claim 12, the preparation method of 5-norbornadiene is characterized in that: the temperature of reaction described in the step b is 185～195 ℃, and the residence time of material in tubular reactor is 15～25 minutes.
5, as claimed in claim 12, the preparation method of 5-norbornadiene is characterized in that: the tubular reactor described in the step b is the continuous production tubular reactor, wherein is provided with the chuck that is used to feed heating medium.
6, as claimed in claim 12, the preparation method of 5-norbornadiene is characterized in that: the purity of the dicyclopentadiene described in the step a 〉=78%.
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| CNB2006101174843A CN100543001C (en) | 2006-10-24 | 2006-10-24 | 2, the preparation method of 5-norbornadiene |
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| CNB2006101174843A CN100543001C (en) | 2006-10-24 | 2006-10-24 | 2, the preparation method of 5-norbornadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249839A (en) * | 2011-05-17 | 2011-11-23 | 浙江大学 | Method for preparing norbornene in loop reactor |
| CN102757411A (en) * | 2012-06-29 | 2012-10-31 | 天津大学 | Device and method for preparing peach aldehyde |
| CN112961020B (en) * | 2021-03-03 | 2023-07-25 | 山西潞安天达新能源技术有限公司 | Method for preparing 2,5-norbornadiene by using molecular sieve as catalyst |
| CN112979407B (en) * | 2021-03-03 | 2023-07-21 | 山西潞安天达新能源技术有限公司 | Method for improving yield of 2,5-norbornadiene by using organic amine |
| CN113004116B (en) * | 2021-03-03 | 2023-07-25 | 山西潞安天达新能源技术有限公司 | Method for preparing 2,5-norbornadiene by continuous sectional reaction |
| CN112979404B (en) * | 2021-03-03 | 2023-07-25 | 山西潞安天达新能源技术有限公司 | Method for preparing 2,5-norbornadiene by using catalyst with passivated outer surface |
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2006
- 2006-10-24 CN CNB2006101174843A patent/CN100543001C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 2,5-降冰片二烯的制备. 徐泽辉等人.精细化工，第21卷第2期. 2004 |
| 2,5-降冰片二烯的制备. 徐泽辉等人.精细化工，第21卷第2期. 2004 * |
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