CN1580015A - Method for synthesizing 5-vinyl-2-norbornaene - Google Patents
Method for synthesizing 5-vinyl-2-norbornaene Download PDFInfo
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Abstract
The invention refers to the synthesizing method of 5-ethylene-2-norborene. The mol ratio of the butadiene and cyclopentadiene is 1-2:1. The invention chooses toluene or normal hexane as the solvent and the weight ratio of the reactants added to the solvent is between 20% and 30%. It chooses alpha-naphthol as the inhibitor and its dosage is between 50ppm and 3000ppm of the reactants. We put the material into the reaction kettle, increase the temperature when or after whisking and make them reacting for between 0.25 hour and 4 hours at the temperature of between 130deg.C and 160deg.C and at the pressure of between 1MPa and 8MPa. Or after being mixed we put the material into the reaction kettle or the tubular reactor and stay for between 0.25 hour and 1.0 hour at the temperature of between 130deg.C and 160deg.C and at the pressure of 1.8MPa. The weight ration of the dicyclopentadiene in the material of cyclopentadiene is less than between 5% and 8%. The invention obviously increases the yield of the turnoff by over 5mol%.
Description
Technical field
The present invention introduces the key intermediate synthetic method of ethylene-propylene rubber(EPR) the 3rd monomer 5-ethylidene-2-norbornylene, relates to the synthetic method of 5-vinyl-2-norbornylene specifically.
Background technology
Ethylene-propylene rubber(EPR) (EPM) is the elastomerics with good characteristic.But EPM is a kind of saturated rubber, thereby can not carry out usually said sulfuration, its mechanical property is crisp, has limited its application, has developed the carried out sulfurized ethylene-propylene-non-conjugated diene hydrocarbon terpolymer rubber (EPDM) with unsaturated double-bond afterwards.As the also useful dicyclopentadiene of non-conjugated diene hydrocarbon and 1,4-hexadiene etc.But its vulcanization rate is too slow, and the most frequently used non-conjugated diene hydrocarbon is ethylidene norbornene (ENB).ENB has at first applied for first piece of patent by U.S. associating carbide company in 1967.The said firm's throughput reaches scale more than 30000 tons/year at present.After this Britain BP.Chemical company and Japanese three oil companies are respectively at setting up industrialized unit in 1979.SUMITOMO CHEMICAL chemical company had set up the ENB production equipment in 1986.Its industrial scale reaches more than 20000 tons/year at present.The present throughput of EXXON company reaches more than 10000 tons/year.
As the key intermediate VNB that produces ENB, generally prepare through diene synthesis reaction (being also referred to as the Diels-Alder reaction) through divinyl (BD) and cyclopentadiene (CPD) or dicyclopentadiene (DCPD).
U.S. Pat 3728406 has been introduced in the 1L autoclave, at 170 ℃, under 40 normal atmosphere (atm), with BD: CPD=1.1: the 1mol ratio, with toluene is solvent, adding 2, the 6-di-tert-butyl hydroquinone reacts for the intermittent type D.A. that has carried out under the situation of stopper 45 minutes, and the CPD transformation efficiency reaches 20mol%.The VNB selectivity reaches 66mol%, and the VNB yield reaches 13.2mol%.In the still formula successive reaction,, under the 40atm, be 1 hour successive reaction than having carried out the residence time with BD: CPD=0.97: 1mol at 170 ℃.Its as a result the CPD transformation efficiency reach 37mol%, the VNB selectivity reaches 63mol%, the VNB yield reaches 23.3mol%.CPD transformation efficiency and VNB yield are all not high.
US4777309 has introduced in the 20ml autoclave, at 130 ℃, and 35Kg/cm
2Under the pressure, with BD: CPD=1.3: the 1mol ratio, with N, the N-diethyl hydroxylamine is a stopper, has carried out 50 minutes still formula continuous processing D.A reaction.Its as a result the BD transformation efficiency reach 21.0mol%, the VNB selectivity reaches 70.1mol%, the VNB yield reaches 14.91mol%, this method is not used solvent.
VNB carries out diene synthesis (D.A) reaction by BD and CPD to come synthetic under certain pressure.Because used BD and CPD be conjugated diene, therefore in diene synthesis, can be across mutually as diene body and dienophile, so its reaction product more complicated.Its principal reaction product and by product are as follows:
Tripolymer:
Polymkeric substance:
Primary product in this process and by product have vinyl norbornene (VNB) as mentioned above, vinyl cyclohexene (VCH), and tetrahydroindene (THI), 1,5-cyclooctadiene (COD), dicyclopentadiene (DCPD) also has a spot of tripolymer and polymkeric substance.Therefore cause the selectivity of principal product and yield not high.
Summary of the invention
The objective of the invention is to overcome the existing in prior technology deficiency, a kind of synthetic method that improves principal product 5-vinyl-2-norbornylene yield is provided.
The objective of the invention is to be achieved by following technical solution.
The synthetic method of a kind of 5-vinyl-2-norbornylene is a raw material with BD and CPD, and the mol ratio that it is characterized in that BD and CPD is 1-2: 1; With toluene and normal hexane is solvent, and the weight percent that this solvent adds reaction mass is 20-30%; With the hindered phenol naphthyl alcohol is stopper, and its consumption is the 50-3000PPm of reaction mass amount, and reaction mass is added in the reactor, stirs or stops to stir down, progressively heats up and in 130-160 ℃ 1.0-8.0Mpa reaction 0.25-4 hour down; Or with in reaction mass mixing back feeding still formula or the tubular reactor, in 130-160 ℃, 1.0-8.0Mpa is reaction down, and the residence time is 0.25-1.0 hour.
Above-mentioned synthetic method, the weight content of DCPD≤5～8wt% among the CPD.
Above-mentioned synthetic method, the mol ratio of its BD and CPD are 1.10-1.70mol.
Above-mentioned synthetic method, its temperature of reaction are 140-155 ℃, and reaction pressure is 2.0-3.0Mpa.
Above-described synthetic method, its reaction times is 0.25-1.0 hour.
Above-mentioned synthetic method, its described solvent recuperation utilization.
Reaction of the present invention can be undertaken by still formula rhythmic reaction or still formula continuous processing or tubular type continuous reaction method.The material proportion that uses in the reaction generally adopts BD: CPD=1.10～1.7: 1; Reaction pressure 2.0～3.0Mpa.Temperature of reaction can adopt 130～160 ℃; The solvent that uses in the reaction can be aliphatic saturated hydrocarbon or aromatic hydrocarbons, and as toluene or normal hexane etc., its usage quantity can be 20～40wt% of reaction mass amount.The stopper that uses in reaction can be a hindered phenol, and as naphthyl alcohol, its consumption can be 50～2500ppm of reaction mass.Under the situation of still reaction, the reaction times can be 0.25～3.0 hour.If adopt the continuous reaction process, then its residence time can be 0.25～1.0 hour.
For reducing the polymerization of divinyl, in reaction, make as much as possible to be in full liquid status in the reactor, avoid occurring the gas space as far as possible.For preventing from reaction process to decompose reaction pressure is jumped, should guarantee that the DCPD content in the used CPD raw material controls to below 5～8wt% because of dicyclopentadiene.Preferably use the existing resulting CPD of decomposing D CPD.And before decomposing D CPD, preferably remove light constituent earlier.If prepared CPD can not use immediately, preferably CPD is kept at below-20 °, with delay CPD again dimerization become the speed of DCPD.The reversible reaction each other as follows of the depolymerization reaction of DCPD and CPD dimerization reaction:
K in the following formula
1=36 * 10
5, k
-1=1570 * 10
5k
-1Compare k
1Big 43.6 times.Therefore at normal temperatures, the new CPD that decomposes also can very fast dimerization again become DCPD.
The present invention compared with prior art has following unusual effect:
(1) technical scheme provided by the invention when adopting still formula rhythmic reaction, stirs or stops stirring, and under controlled temperature and the pressure, reacts 0.25-4 hour; And during with still formula or tubular reactor, the residence time only needs 0.25-1.0 hour, so flexible operation, elasticity is big, adaptability is strong.
(2) the CPD transformation efficiency exceeds more than the 30mol% than prior art;
(3) be stopper with naphthyl alcohol, make the purpose product yield obviously improve more than the 5mol%;
(4) reaction times is 0.25 hour, and the purpose product yield reaches 22.47-29.93%.
(5) help realizing pipe reaction.
(6) temperature of reaction and pressure are lower, and Controllable Temperature is made as 130-160 ℃, and pressure is 2-3Mpa.
Embodiment
Now, the present invention is further described as follows in conjunction with embodiment:
Embodiment 1:
With 325gBD (purity: 98.636wt%), CPD 310.0g (contains 93.26%CPD, 6.276%DCPD), (BD: CPD=1.27: 1mol is than=1.039: the 1wt ratio), 225g toluene and 0.5g (about 600ppm) naphthyl alcohol joins in the 1L autoclave, stir and be warmed up to gradually 154～155 ℃ with 460 rev/mins of speed, carry out reaction in 3 hours under the 2.1Mpa.Reaction finishes the logical water coolant in back cools off, and obtains reaction solution 825g.The reactor courage is put into refrigerator-freezer be cooled to-20 ℃.Stratographic analysis is carried out in sampling, and its result is as follows:
Product consists of: BD:5.511wt%=44.64g; CPD:6.178wt%=50.05g; VCH:9.32wt%=75.49g; VNB:17.669wt%=143.12g; Toluene: 24.083wt%=195.07g; COD:0.466wt%=3.775g; THI:5.751wt%=46.58g; DCPD:30.085wt%=243.69g.
CPD transformation efficiency=93.7wt%=93.31mol%
VNB selectivity=60.19wt%=33.10mol%
VNB yield=50.40wt%=30.89mol%
Embodiment 2:
With 300gBD (purity: 98.636wt%), CPD 315.0g (contains 90.2%CPD, 8.0%DCPD), (BD: CPD=1.081: 1mol is than=0.956: the 1wt ratio), 225g toluene and 0.5g (about 600ppm) naphthyl alcohol joins in the 1L autoclave, stirs 5 minutes before the reaction, stop then stirring, being warmed up to 154～155 ℃, under 2.1Mpa, carrying out reaction in 3 hours. reaction finishes the logical water coolant in back cools off, and obtains reaction solution 825g.The reactor courage to be put into refrigerator-freezer be cooled to-20 ℃. stratographic analysis is carried out in sampling, and its result is as follows:
Product consists of: BD:5.511%=44.64g; CPD:6.178wt%=50.04g; VCH:9.32wt%=75.49g; VNB:17.669wt%=143.12g; Toluene: 24.083wt%=195.07g; COD:0.466wt%=3.775g; THI:5.751wt%=46.58g; DCPD:35.085wt%=243.69g.
CPD transformation efficiency=82.84wt%=82.80mol%
VNB selectivity=59.22wt%=32.23mol%
VNB yield=49.03wt%=26.90mol%
Embodiment 3:
With 300gBD (purity: 98.636wt%), CPD 315.0g (contains 92.6%CPD, 4.6%DCPD), (BD: CPD=1.27: 1mol is than=1.039: the 1wt ratio), 225g toluene and 0.5g (about 600ppm) naphthyl alcohol joins in the 1L autoclave, stirs 5 minutes before the reaction, stops then stirring, be warmed up to 154～155 ℃ gradually, under 2.1Mpa, carry out reaction in 1 hour.Reaction finishes the logical water coolant in back cools off, and obtains reaction solution 825g.The reactor courage is put into refrigerator-freezer be cooled to-20 ℃.Stratographic analysis is carried out in sampling, and its result is as follows:
Product consists of: BD:9.429%=12.75g; CPD:6.406wt%=34.3g; VCH:5.845wt%=43.39g; VNB:14.984wt%=126.6g; Toluene: 24.083wt%=195.07g; COD:0.466wt%=3.775g; THI:2.688wt%=22.71g; DCPD:35.063wt%=296.28g.
CPD transformation efficiency=87.92wt%=87.90mol%
VNB selectivity=50.7wt%=27.91mol%
VNB yield=44.57wt%=mol%=24.53mol%
Embodiment 4: the reaction of tubular type continuous processing
With 295gBD (purity: 98.636wt%), 315.0g CPD (contains 91.84%CPD, DCPD:6.22%) (BD: CPD=1.19: 1mol is than=0.942: the 1wt ratio), after 225g toluene and 0.5g (about 600ppm) naphthyl alcohol mixes in material-compound tank, be passed in the tubular reactor (Φ 33mm * 220mm coil pipe type reactor) that is heated to 155 ℃ in advance with the 17ml/ component velocity, under 2.8MPa, react.The residence time is 1 hour.In the cooling storage tank of reactor outlet, in 1 hour, collect the 840g reaction solution altogether.
Reaction product consists of: BD:9.429wt%=12.75g; CPD:6.406wt%=34.3g; VCH:5.845wt%=43.39g; VNB:14.984wt%=126.6g; Toluene: 24.845wt%=206.94g; COD=0.221wt%=1.8564g; THI:2.688wt%=22.71g; DCPD:35.06wt%=296.28g.
CPD transformation efficiency=87.92wt%=87.90mol%
VNB selectivity=50.70wt%=27.91mol%
VNB yield=44.57wt%.=24.53mol%
Embodiment 5:
With 295gBD (purity: 98.636wt%), 230g CPD (contains 93.34%CPD, 5.74%DCPD) (BD: CPD=1.56: 1mol is than=1.28: the 1wt ratio), 175g normal hexane and 0.5g (about 600ppm) naphthyl alcohol stopper joins in the 1L autoclave, before reaction, stirred 5 minutes, stop then stirring, progressively be warmed up to 170 ℃, reaction is 1 hour under 5.0MPa.Cool off rapidly with frozen water reaction back, cools to below 98 ℃ in 5 minutes, obtains reaction solution 740g.The reactor courage is put into refrigerator-freezer be cooled to-20 ℃.Stratographic analysis (with the area normalization standard measure) is carried out in sampling, and its result is as follows:
Reaction product consists of: BD:10.484wt%=79.92g; CPD:6.183wt%=50.54g; VCH:8.80wt%=65.11g; Normal hexane: 17.14%=126.84g; VNB:20.26%=149.9g; COD:0.420wt%=3.108g; THI:5.662wt%=41.90g; DCPD:27.033wt%=200.04g.
CPD transformation efficiency=82.53wt%=82.53mol%
VNB selectivity=62.77%=28.49mol%
VNB yield=51.80wt%.=23.51mol%
Embodiment 6: reclaim the toluene utilization
(purity: 98.636wt%), (contain 76.34%CPD, 22.22%DCPD) (BD: CPD=1: 1.0mol is than=1.0: the 1.0wt ratio), 225g reclaims toluene and (contains BD:0.261% 310g CPD with 295gBD; CPD:6.186%; VCH:1.755%; Toluene: 88.198%) and 0.5g (about 600ppm) naphthyl alcohol stopper join in the 1L autoclave, before reaction, stirred 5 minutes.Stop then stirring, progressively be warmed up to 154-155 ℃, reaction is 1 hour under 2.5MPa.Cool off rapidly with frozen water reaction back, cools to below 98 ℃ in 5 minutes, obtains reaction solution 810g.The reactor courage is put into refrigerator-freezer be cooled to-20 ℃.Stratographic analysis (with the area normalization standard measure) is carried out in sampling, and its result is as follows:
Reaction product consists of: BD:4.97wt%=40.257g; CPD:3.880wt%=31.49g; VCH:8.341wt%=67.56g; Toluene: 23.913%=193.70g, VNB:17.845%=144.50g; COD:0.318wt%=2.58g; THI:3.74wt%=30.29g; DCPD:35.931wt%=291.0g.
CPD transformation efficiency=90.28wt%=90.24mol%
VNB selectivity=49.5%=27.24mol%
VNB yield=44.69wt%.=24.54mol
Embodiment 7: be the experiment of solvent with the industrial toluene
With 300gBD (purity: 96.689wt%), 310g CPD (contains 80.72%CPD, 17.55%DCPD) (BD: CPD=1.013: 1mol is than=0.95: the 1wt ratio), 220g industrial toluene (99.078%) and 0.5g (about 600ppm) naphthyl alcohol stopper joins in the 1L autoclave, stirs before reaction 5 minutes.Stop then stirring, progressively be warmed up to 153-155 ℃, reaction is 1 hour under 5.0MPa.Cool off rapidly with frozen water reaction back, cools to below 98 ℃ in 5 minutes, obtains reaction solution 830g.The reactor courage is put into refrigerator-freezer be cooled to-20 ℃.Stratographic analysis (with the area normalization standard measure) is carried out in sampling, and its result is as follows:
Reaction product consists of: BD:7.163wt%=58.74g; CPD:3.668wt%=30.08g; VCH:8.68wt%=71.17g; Toluene: 22.712%=186.24g, VNB:18.00%=147.6g; COD:0.314wt%=2.68g; THI:4.56wt%=37.69g; DCPD:33.790wt%=277.1g.
CPD transformation efficiency=90.12wt%=90.12mol%
VNB selectivity=53.77%=29.57mol%
VNB yield=48.46wt%.=26.74mol
Embodiment 8:
With 295gBD (purity: 98.636wt%), 310.0g (BD: CPD=1.15: 1mol is than=0.941: the 1wt ratio) for CPD (containing 93.5%CPD:6.22%DCPD), 220g toluene and 0.5g (about 600ppm) naphthyl alcohol joins in the 1L autoclave, stirs before reaction 5 minutes.Stop then stirring, progressively be warmed up to 155 ℃, reaction is 0.5 hour under 1.8MPa.Reaction finishes the logical water coolant in back cools off, and obtains reaction solution 825g.The reactor courage put into refrigerator-freezer and is cooled to-20 ℃ of samplings carry out stratographic analysis (with the area normalization standard measure), its result as above:
Reaction product consists of: BD:13.58wt%=112.0g; CPD:5.26wt%=43.3g; VCH:4.959wt%=40.84g; Toluene: 25.86%=213.34g, VNB:14.29wt%=117.89g; COD:0.191wt%=1.567g; THI:2.33wt%=19.22g; DCPD:33.09wt%=272.99g.
CPD transformation efficiency=84.94wt%=84.89mol%
VNB selectivity=48.13%=26.47mol%
VNB yield=40.90wt%.=22.47mol%
Embodiment 9:
With 295gBD (purity: 98.636wt%), 315.0g CPD (containing 90.33%CPD:8.34%DCPD) (BD: CPD=1.14; 1mol is than=0.93: the 1wt ratio),, 225g toluene, 0.5g (about 600ppm) naphthyl alcohol stopper join in the 1L autoclave, stir before reaction 5 minutes.Stop then stirring, progressively be warmed up to 150～159 ℃, reaction is 0.25 hour under 2.5～7.6MPa.Cool off rapidly with frozen water reaction back, cools to below 100 ℃ in 5 minutes, obtains reaction solution 810g.The reactor courage is put into refrigerator-freezer be cooled to-20 ℃.Stratographic analysis (with the area normalization standard measure) is carried out in sampling, and its result is as follows:
Reaction product consists of: BD:8.585wt%=69.535g; CPD:4.27wt%=34.59g; VCH:3.30wt%=26.73g; Toluene: 25.399%=205.732g, VNB:14.537%=117.75g; COD:0.184wt%=1.49g; THI:2.646wt%=21.43g; DCPD:40.833wt%=330.75g.
CPD transformation efficiency=87.84wt%=87.87mol%
VNB selectivity=47.1%=25.91mol%
VNB yield=41.37wt%.=22.77mol%
Embodiment 10:
With 315gBD (purity: 98.636wt%), 240g CPD (contains 89.97%CPD, 9.21%DCPD) (BD: CPD=1.65: 1mol is than=1.305: the 1wt ratio), 225g toluene and 0.5g (about 600ppm) naphthyl alcohol stopper joins in the 1L autoclave, stirs before reaction 5 minutes.Stop then stirring, progressively be warmed up to 150～～158 ℃, reaction is 0.25 hour under 4.0MPa.Cool off rapidly with frozen water reaction back, cools to below 98 ℃ in 5 minutes.Obtain reaction solution 770g.The reactor courage is put into refrigerator-freezer be cooled to-20 ℃.Stratographic analysis (with the area normalization standard measure) is carried out in sampling, and its result is as follows:
Reaction product consists of: BD:13.16wt%=101.33g; CPD:4.87wt%=37.5g; VCH:4.45wt%=34.29g; Toluene: 25.81%=198.7g, VNB:15.23%=117.27g; COD:0.192wt%=1.48g; THI:2.43wt%=18.71g; DCPD:33.50wt%=257.95g.
CPD transformation efficiency=82.58wt%=82.50mol%
VNB selectivity=65.96%=36.28mol%
VNB yield=54.47wt%.=29.93mol%
Raw material required for the present invention, auxiliary agent etc. all can be bought from market.
Above embodiment is also non exhaustive, also can be single tube, multitube or tubulation etc. such as said tubular reactor.Solvent also can be selected from aliphatic saturated hydrocarbon or aromatic hydrocarbons again; And stopper also can be selected from Hinered phenols or hindered amines.
Claims (6)
1, the synthetic method of a kind of 5-vinyl-2-norbornylene is a raw material with divinyl and cyclopentadiene, it is characterized in that: raw material divinyl: cyclopentadiene=1-2: 1 mol ratio; With toluene or normal hexane is solvent, and the weight percent that this solvent adds reaction mass is 20-30%; With the naphthyl alcohol is stopper, and its consumption is the 50-3000ppm of reaction mass; Reaction mass is added in the reactor, stir or stop to stir down, progressively heat up, and in 130-160 ℃, 1.0-8.0Mpa reaction 0.25-4 hour down; Or with in reaction mass mixing back feeding still formula or the tubular reactor, and in 130-160 ℃, 1.0-8.0Mpa is reaction down, the residence time is 0.25-1.0 hour.
2, synthetic method according to claim 1 is characterized in that described raw material cyclopentadiene, the weight content of dicyclopentadiene wherein≤5～8wt%.
3, synthetic method according to claim 1, the mol ratio that it is characterized in that described raw material divinyl and cyclopentadiene is 1.10-1.70mol.
4, synthetic method according to claim 1 is characterized in that described temperature of reaction is 140-155 ℃, and reaction pressure is 2.0-3.0Mpa.
5, synthetic method according to claim 1 is characterized in that the described reaction times is 0.25-1.0 hour.
6, synthetic method according to claim 1 is characterized in that described solvent recuperation utilization.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980084A (en) * | 2014-06-03 | 2014-08-13 | 上海华畅环保设备发展有限公司 | Continuous isosynthesis method and continuous isosynthesis device of ethylidene norbornene |
| CN104098423A (en) * | 2014-07-25 | 2014-10-15 | 中石化上海工程有限公司 | Production method for ENB (5-ethylene-2-norbornylene) |
| CN104692994A (en) * | 2015-02-13 | 2015-06-10 | 浙江大学 | Method of synthesizing ethylidene norbornene by virtue of microchannel reactor |
| CN104744202A (en) * | 2015-02-13 | 2015-07-01 | 浙江大学 | Method for synthesizing vinyl norbornene by using one-inlet and multiple-outlet variable pressure type tubular reactor |
| CN104744201A (en) * | 2015-02-13 | 2015-07-01 | 浙江大学 | Method for synthesizing ethylidene norbornene by virtue of multi-lateral-line pressure-variable tubular reactor |
| CN105753628A (en) * | 2016-04-14 | 2016-07-13 | 大连理工大学 | Synthetic method of 5-vinyl-2-norbornene |
-
2004
- 2004-05-20 CN CN 200410010889 patent/CN1580015A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980084A (en) * | 2014-06-03 | 2014-08-13 | 上海华畅环保设备发展有限公司 | Continuous isosynthesis method and continuous isosynthesis device of ethylidene norbornene |
| CN103980084B (en) * | 2014-06-03 | 2016-03-09 | 上海华畅环保设备发展有限公司 | The continuous isoparaffin synthesis method of ethylidene norbornene and device |
| CN104098423A (en) * | 2014-07-25 | 2014-10-15 | 中石化上海工程有限公司 | Production method for ENB (5-ethylene-2-norbornylene) |
| CN104098423B (en) * | 2014-07-25 | 2016-08-17 | 中石化上海工程有限公司 | The production method of 5-ethylidene-2-norbornene ENB |
| CN104692994A (en) * | 2015-02-13 | 2015-06-10 | 浙江大学 | Method of synthesizing ethylidene norbornene by virtue of microchannel reactor |
| CN104744202A (en) * | 2015-02-13 | 2015-07-01 | 浙江大学 | Method for synthesizing vinyl norbornene by using one-inlet and multiple-outlet variable pressure type tubular reactor |
| CN104744201A (en) * | 2015-02-13 | 2015-07-01 | 浙江大学 | Method for synthesizing ethylidene norbornene by virtue of multi-lateral-line pressure-variable tubular reactor |
| CN104692994B (en) * | 2015-02-13 | 2017-01-04 | 浙江大学 | Method by micro passage reaction synthesis ethylidene norbornene |
| CN104744202B (en) * | 2015-02-13 | 2017-04-05 | 浙江大学 | One method for entering to have more variable-pressure tubular reactor synthesis of vinyl norborene |
| CN104744201B (en) * | 2015-02-13 | 2017-04-05 | 浙江大学 | The method for synthesizing ethylidene norbornene by many side line variable-pressure tubular reactors |
| CN105753628A (en) * | 2016-04-14 | 2016-07-13 | 大连理工大学 | Synthetic method of 5-vinyl-2-norbornene |
| CN105753628B (en) * | 2016-04-14 | 2018-06-08 | 大连理工大学 | A kind of synthetic method of 5- vinyl -2- norbornene |
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