CN105585413A - Synthetic method of vinyl norbornene - Google Patents
Synthetic method of vinyl norbornene Download PDFInfo
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- CN105585413A CN105585413A CN201410557300.XA CN201410557300A CN105585413A CN 105585413 A CN105585413 A CN 105585413A CN 201410557300 A CN201410557300 A CN 201410557300A CN 105585413 A CN105585413 A CN 105585413A
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Abstract
The invention discloses a synthetic method of vinyl norbornene. Dicyclopentadiene containing high concentration of cyclopentadiene and 1,3-butadiene are used as raw materials to react by the adoption of a multi-lateral-lines feed type tubular reactor. The multi-lateral-lines feed type tubular reactor is divided into multiple reaction sections. The front end of each reaction section is provided with a feed inlet. The feed inlet at the front end of a first reaction section is a main-line feed inlet, and the rest is lateral-line feed inlets. According to the invention, dicyclopentadiene containing high concentration of cyclopentadiene is poured into a reaction channel of the reaction section through the main-line feed inlet while 1,3-butadiene is poured respectively through the main-line feed inlet and any one or more multi-lateral-lines feed inlets into a reaction channel of a corresponding reaction section so as to synthesize vinyl norbornene. The invention has beneficial effects as follows: the method of the invention is continuously operated under conditions of high temperature and high pressure; and the method has strong controllability, high safety and high yield of vinyl norbornene.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of synthetic method of vinyl norbornene.
Background technology
Vinyl norbornene is a kind of Organic Ingredients, and it can synthesize ethylidene norborneol by isomerization reaction easilyAlkene. At present, ENB is mainly used to synthesis of ternary EP rubbers (EPDM).
Under high-temperature and high-pressure conditions, 1,3-butadiene and cyclopentadiene carry out Diels-Alder reaction synthesis of vinyl and fall iceSheet alkene. Reaction equation is as follows:
1,3-butadiene is strong exothermal reaction with reacting of cyclopentadiene, Δ H °298=-22kcal/mol. React high at high temperatureDepress reaction, therefore there is potential safety hazard under traditional synthesis.
In addition, because cyclopentadiene and 1,3-butadiene are all conjugated diolefins, and diene body and parent are two each other acrossAlkene body. Therefore, have other dimer, tripolymer, the generation of polymer accessory substance.
Dimer accessory substance be in building-up process, produce maximum. Wherein, VCH (VCH) and ring pungent twoAlkene (COD) is generated by 1,3-butadiene dimerization. Tetrahydroindene (THI) is by cyclopentadiene (CPD) and butadiene(BD) directly generate or vinyl norbornene (VNB) be heated isomery generate. Reaction equation is as follows.
All kinds of dimers in system (VCH, VNB, THI, DCPD) still have activated double bonds, can be used as parent twoAlkene body again reacts and forms trimer by-products through Diels-Alder with diene body (BD, CPD) under higher temperature.In addition at high temperature autohemagglutination very easily also of 1,3-butadiene.
Chinese patent CN1580015 (2005) is taking the alpha-Naphthol of 50-3000ppm as polymerization inhibitor, toluene or justHexane is solvent, and (dicyclopentadiene in cyclopentadiene contains reaction mass cyclopentadiene liquid quality fraction 70-80%Amount is less than 5-8wt%), molar ratio 1,3-butadiene: cyclopentadiene=1/1-2/1, temperature 130-160 DEG C, pressurePower 1-8MPa once feeds intake and carries out in autoclave batch reactor, and the reaction time is 0.25-4h; And think and to the greatest extent canCompletely under liquid status, operation will be favourable to this reaction, so also propose to adopt singly to enter singly to go out TFR, stopTime is 0.25-1h. Vinyl norbornene be only selectively 25.91-36.28%, side reaction is on the high side, particularlyNot yet mention polymer class accessory substance.
The production technology of SUMITOMO CHEMICAL chemical company (SumitomoChemical, 1990 (2): 4-11) is first with inertiaAromatic hydrocarbons is solvent, and the liquid phase that adds polymerization inhibitor to carry out dicyclopentadiene is decomposed, and rectifying obtains highly purified cyclopentadiene.1,3-butadiene and high-purity cyclopentadiene are squeezed in 200mL voltage-resistant reactor and are carried out with the mol ratio of 1.2:1Diels-Alder addition reaction, 140 DEG C of temperature, pressure 4MPa, the time of staying is 35min. This reactor is not depositedIn gas phase part, generate in order to suppress polymer, US Patent No. 4777309 (1988) is in reaction systemAlso add the N of a small amount of (2500ppm), N-diethyl hydroxylamine or 4-oxygen-2,2,6,6-tetramethyl piperidine-1-oxygen radicalAs polymerization inhibitor. Under the full liquid status of reactor maintenance, successive reaction is after 1000 hours, and in reactor, inwall is totally seen notThe polymer that goes out to separate out, in reactant liquor, polymer concentration only has 0.04wt%, and chromatography result butadiene conversion is21-22%, product vinyl norbornene be selectively 67.8%.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of simple, efficient vinyl norbornene. It is high to containThe dicyclopentadiene of concentration cyclopentadiene is raw material, under high-temperature and high-pressure conditions, by many side entry feed tubular reactorSynthesis of vinyl ENB, conversion ratio is high, also selectively good.
The concrete technical scheme that the present invention takes is described below.
A synthetic method for vinyl norbornene, it adopts many side entry feed tubular reactor to synthesize; WhereinDescribed many side entry feed tubular reactor is divided into multiple conversion zones, and the front end of each conversion zone arranges charging aperture, whereinThe charging aperture of the first conversion zone front end charging aperture of serving as theme, all the other are side entry feed mouth, each charging aperture and pump coupling are establishedPut; Between each conversion zone and charging aperture, static mixer is set; Each side line injection port front end arranges check-valves,The middle rear end of a rear conversion zone arranges counterbalance valve, and end arranges discharging opening; Concrete steps are as follows:
The reaction channel of the first conversion zone will be put into from main line charging aperture containing the dicyclopentadiene of high concentration cyclopentadieneIn, 1,3-butadiene is put into conversion zone from described main line charging aperture and more than one side entry feed mouth respectively simultaneouslyIn reaction channel, the reaction temperature of reaction in channel is that 120 DEG C-220 DEG C, pressure are 2-15MPa, and the time of staying is24-120min, obtains vinyl norbornene; Wherein said contains in the dicyclopentadiene of high concentration cyclopentadiene,Cyclopentadiene accounts for 50wt%-100wt%, and the dicyclopentadiene containing high concentration cyclopentadiene is converted into cyclopentadieneMeter, the mol ratio of the dicyclopentadiene of described 1,3-butadiene and described high concentration cyclopentadiene is (0.1-2): 1.
Further, above-mentioned 1,3-butadiene with the mol ratio of the dicyclopentadiene containing high concentration cyclopentadiene is(0.2-1)∶1。
Further, above-mentioned reaction temperature is 140 DEG C-180 DEG C.
Further, above-mentioned reaction pressure is 4-10MPa.
Further, above-mentioned side entry feed mouth is 1-4.
Further, above-mentioned side entry feed mouth is 1-2.
Further, in the present invention, the above-mentioned dicyclopentadiene containing high concentration cyclopentadiene is directly fed intake, orAfter being formulated as solution containing the dicyclopentadiene of high concentration cyclopentadiene, feed intake again, wherein containing high concentration cyclopentadieneThe mass fraction of dicyclopentadiene be 10%-100%; Its solvent is selected from straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon or aromatic hydrocarbonsIn one several. Preferably, described solvent is one or more in octane, cyclohexane or toluene.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) tubular reactor is applied to the two of 1,3-butadiene and high concentration cyclopentadiene under HTHP by the present inventionCyclopentadiene reacts the production process of preparing vinyl norbornene by Diels-Alder, due to this tubular reactorAdopt the many side entry feed of 1,3-butadiene, thereby make 1,3-butadiene in system remain at a lower level,Reduce the generation of 1,3 butadiene autohemagglutination and other side reaction, therefore greatly improved vinyl norbornene production processSecurity and combined coefficient.
(2) the present invention does not use polymerization inhibitor, has alleviated the difficulty that subsequent products separates.
(3) tubular reactor of the present invention is provided with static mixer in charging place, can realize rapid mixing even, passesMatter efficiency is high, can reduce the side reaction causing because mass transfer is bad, improves the selective of reaction, with conventional tank reactorCompare, without moving equipment such as agitators, be not only conducive to reduce energy consumption, reduce production costs, and be conducive to reactionThe sealing of device, improves the security of producing;
(4) tubular reactor heat transfer efficiency of the present invention is high, heat can be moved into or shift out system fast, makes anti-Should under the condition close to isothermal, carry out, avoid reacting the generation of focus, thereby effectively suppress side reaction.
(5) tubular reactor heat-resistant pressure-resistant grade of the present invention is high, is particularly suitable for synthesis of vinyl ENB thisOperating condition harshness, inflammable and explosive reaction;
(6) the vinyl norbornene yield that the present invention obtains and purity is all higher than popular response device, 1,3 butadieneSelective (generate the amount of 1,3 butadiene and 1,3 butadiene total amount of consumption that vinyl norbornene consumesRatio, lower with) can be up to 86.1%, the conversion ratio of 1,3-butadiene (1, the 3 butadiene amount that reaction consumes with addThe ratio of 1, the 3 butadiene total amount entering, lower same) be 33.6%.
Brief description of the drawings
Fig. 1 is many side entry feed of the present invention tubular reactor schematic diagram.
Detailed description of the invention
In embodiment, the dicyclopentadiene of high concentration cyclopentadiene be by thick DCPD (purity is 80-85wt%, onSea petrochemical industry C 5 fraction) refine and obtain smart DCPD at rectifying column, smart DCPD continues depolymerization at rectifying column, and tower top is receivedIntegrate cyclopentadiene (purity is as 50wt%-100wt%), and store at low temperatures. The many side lines that adopt in embodimentAs shown in Figure 1, its diameter is Dn20 to charging tubular type structure of reactor, is always about 50 meters, is divided into 5 sections, section startStatic mixer is installed, is promoted gas-liquid mixed. Each intersegmental with 180 ° of elbows connections, to reduce floor space. ReactionSection entrance has 1 main line charging aperture and 4 side entry feed mouths, and first is for pumping dicyclopentadiene solution and 1,3-Butadiene liquid, other 4 is 1,3-butadiene liquid sidedraw charging aperture. In addition, equal before each side entry feed mouthBe provided with check-valves.
Below in conjunction with specific embodiment, the present invention will be further described, but embodiments of the present invention are not limited to this.
Embodiment 1
The dicyclopentadiene toluene solution containing cyclopentadiene that preparation mass fraction is 60wt%, wherein in dicyclopentadieneCyclopentadiene accounts for 100wt%. Under normal temperature condition, the dicyclopentadiene toluene solution of high concentration cyclopentadiene is from main lineCharging aperture is directly delivered in pipe reaction device, and 1,3-butadiene is from main line charging aperture, the first side entry feed mouth andTwo side entry feed mouths divide three bursts of equivalent to be delivered in pipe reaction device, and total 1,3-butadiene mass flow is20.5g/min, the dicyclopentadiene toluene solution mass flow of high concentration cyclopentadiene is 210.0g/min, 1,3-fourth twoThe mol ratio of the dicyclopentadiene of alkene and high concentration cyclopentadiene (taking be converted into cyclopentadiene mole as, lower with)Be 0.2. Two strands of materials of 1,3-butadiene and dicyclopentadiene enter conversion zone after static mixer mixes, anti-in tubular typeAnswer in device and react. Reaction temperature is 140 DEG C, and reaction pressure is 7MPa, and the time of staying is 48 minutes. Through gasAnalysis of hplc, in corresponding outlet material, 1,3-butadiene be selectively 86.1%, corresponding 1,3-butadieneConversion ratio be 33.6%.
Embodiment 2
The dicyclopentadiene toluene solution containing cyclopentadiene that preparation mass fraction is 60wt%, wherein in dicyclopentadieneCyclopentadiene accounts for 80wt%. Under normal temperature condition, the dicyclopentadiene toluene solution of high concentration cyclopentadiene enters from main lineMaterial mouthful is directly delivered in pipe reaction device, and 1,3-butadiene is from main line charging aperture, the first side entry feed mouth and secondThree bursts of equivalent of side entry feed mouth are delivered in pipe reaction device, and total 1,3-butadiene mass flow is 35.7g/min,The dicyclopentadiene toluene solution mass flow of high concentration cyclopentadiene is 182.0g/min, 1,3-butadiene and high concentrationThe mol ratio of the dicyclopentadiene of cyclopentadiene is 0.4. Two strands of materials of 1,3-butadiene and dicyclopentadiene are through state blenderAfter mixing, enter conversion zone, in tubular reactor, react. Reaction temperature is 160 DEG C, and reaction pressure is 10MPa,The time of staying is 72 minutes. Through gas chromatographic analysis, in corresponding outlet material, 1,3-butadiene be selectively65.4%, the conversion ratio of corresponding 1,3-butadiene is 53.9%.
Embodiment 3
The dicyclopentadiene containing cyclopentadiene taking mass fraction as 100wt% is raw material, wherein in dicyclopentadiene, encirclesPentadiene accounts for 50wt%. Under normal temperature condition, the dicyclopentadiene of high concentration cyclopentadiene is directly defeated from main line charging apertureDeliver in pipe reaction device, 1,3-butadiene is from main line charging aperture, the first side entry feed mouth and the second side entry feed mouthThree bursts of equivalent are delivered in pipe reaction device, and total 1,3-butadiene mass flow is 30.3g/min, high concentration ringThe dicyclopentadiene toluene solution mass flow of pentadiene is 37.0g/min, 1,3-butadiene and high concentration cyclopentadieneThe mol ratio of dicyclopentadiene is 1.0. Two strands of materials of 1,3-butadiene and dicyclopentadiene mix laggard through static mixerEnter conversion zone, in tubular reactor, react. Reaction temperature is 200 DEG C, and reaction pressure is 4MPa, when stopBetween be 120 minutes. Through gas chromatographic analysis, in corresponding outlet material, 1,3-butadiene be selectively 44.7%,The conversion ratio of corresponding 1,3-butadiene is 62.4%.
Embodiment 4
The dicyclopentadiene toluene solution containing cyclopentadiene that preparation mass fraction is 30wt%, wherein in dicyclopentadieneCyclopentadiene accounts for 100wt%. Under normal temperature condition, the dicyclopentadiene toluene solution of high concentration cyclopentadiene is from main lineCharging aperture is directly delivered in pipe reaction device, and 1,3-butadiene is from main line charging aperture, the first side entry feed mouth andTwo three bursts, side entry feed mouth equivalent are delivered in pipe reaction device, and total 1,3-butadiene mass flow is 9.8g/min,The dicyclopentadiene toluene solution mass flow of high concentration cyclopentadiene is 400.0g/min, 1,3-butadiene and high concentrationThe mol ratio of the dicyclopentadiene of cyclopentadiene is 0.1. Two strands of materials of 1,3-butadiene and dicyclopentadiene are through static mixingDevice enters conversion zone after mixing, and in tubular reactor, reacts. Reaction temperature is 220 DEG C, and reaction pressure is15MPa, the time of staying is 24 minutes. Through gas chromatographic analysis, in corresponding outlet material, the choosing of 1,3-butadieneSelecting property is 66.8%, and the conversion ratio of corresponding 1,3-butadiene is 46.8%.
Embodiment 5
The dicyclopentadiene toluene solution containing cyclopentadiene that preparation mass fraction is 10wt%, wherein in dicyclopentadieneCyclopentadiene accounts for 50wt%. Under normal temperature condition, the dicyclopentadiene toluene solution of high concentration cyclopentadiene enters from main lineMaterial mouthful is directly delivered in pipe reaction device, and 1,3-butadiene is from main line charging aperture, the first side entry feed mouth and secondThree bursts of equivalent of side entry feed mouth are delivered in pipe reaction device, and total 1,3-butadiene mass flow is 11.3g/min,The dicyclopentadiene toluene solution mass flow of high concentration cyclopentadiene is 69.0g/min, 1,3-butadiene and high concentration ringThe mol ratio of the dicyclopentadiene of pentadiene is 2.0. Two strands of materials of 1,3-butadiene and dicyclopentadiene are through static mixerAfter mixing, enter conversion zone, in tubular reactor, react. Reaction temperature is 180 DEG C, and reaction pressure is 2MPa,The time of staying is 120 minutes. Through gas chromatographic analysis, in corresponding outlet material, 1,3-butadiene be selectively35.7%, the conversion ratio of corresponding 1,3-butadiene is 71.4%.
Embodiment 6
The dicyclopentadiene raw material containing cyclopentadiene taking mass fraction as 100wt%, wherein encircles penta in dicyclopentadieneDiene accounts for 100wt%. Under normal temperature condition, be directly delivered to from main line charging aperture containing the dicyclopentadiene of cyclopentadieneIn pipe reaction device, 1,3-butadiene from main line charging aperture, that two bursts of equivalent of the second side entry feed mouth are delivered to tubular type is anti-In should installing, total 1,3-butadiene mass flow is 54.0g/min, the dicyclopentadiene first of high concentration cyclopentadieneBenzole soln mass flow is 160.0g/min, the mol ratio of the dicyclopentadiene of 1,3-butadiene and high concentration cyclopentadieneBe 0.4. Two strands of materials of 1,3-butadiene and cyclopentadiene enter conversion zone after static mixer mixes, at pipe reactionIn device, react. Reaction temperature is 160 DEG C, and reaction pressure is 15MPa, and the time of staying is 48 minutes. Through gas phaseChromatography, in corresponding outlet material, 1,3-butadiene be selectively 65.76%, corresponding 1,3-butadieneConversion ratio is 51.9%.
Embodiment 7
The dicyclopentadiene toluene solution containing cyclopentadiene that preparation mass fraction is 10wt%, wherein in dicyclopentadieneCyclopentadiene accounts for 80wt%. Under normal temperature condition, dicyclopentadiene toluene solution is directly delivered to pipe from main line charging apertureIn formula reaction unit, 1,3-butadiene enters from main line, the first side entry feed mouth, the second side entry feed mouth, the 3rd side lineMaterial mouth and five bursts of equivalent of the 4th side entry feed mouth are delivered in pipe reaction device, and total 1,3-butadiene mass flow is26.2g/min, the dicyclopentadiene toluene solution mass flow of high concentration cyclopentadiene is 160.0g/min, 1,3-fourth twoThe mol ratio of the dicyclopentadiene of alkene and high concentration cyclopentadiene is 2.0. Two strands of material warps of 1,3-butadiene and cyclopentadieneStatic mixer enters conversion zone after mixing, and in tubular reactor, reacts. Reaction temperature is 120 DEG C, reactionPressure is 7MPa, and the time of staying is 48 minutes. Through gas chromatographic analysis, in corresponding outlet material, 1,3-fourth twoAlkene be selectively 42.9%, the conversion ratio of corresponding 1,3-butadiene is 49.1%.
Comparative example 1
Compare with embodiment 1, the dicyclopentadiene toluene containing cyclopentadiene that preparation mass fraction is 60wt% is moltenLiquid, wherein in dicyclopentadiene, cyclopentadiene accounts for 100wt%. Under normal temperature condition, 1,3-butadiene and dicyclo penta 2Alkene toluene solution is directly delivered to pipe reaction device from main line charging aperture, and 1,3-butadiene mass flow is20.5g/min, dicyclopentadiene toluene solution mass flow is 210.0g/min, the mol ratio of butadiene and cyclopentadieneBe 0.2. Two strands of materials of 1,3-butadiene and dicyclopentadiene enter conversion zone after static mixer mixes, anti-in tubular typeAnswer in device and react, reaction temperature is 140 DEG C, and reaction pressure is 7MPa, and the time of staying is 48 minutes. Through gasAnalysis of hplc, in corresponding outlet material, 1,3-butadiene be selectively 69.8%, corresponding 1,3-butadieneConversion ratio be 40.3%.
Comparative example 2
Compare with embodiment 2, the dicyclopentadiene toluene containing cyclopentadiene that preparation mass fraction is 60wt% is moltenLiquid, wherein in dicyclopentadiene, cyclopentadiene accounts for, 80wt%. Under normal temperature condition, 1,3-butadiene and dicyclo penta 2Alkene toluene solution is directly delivered to pipe reaction device from main line charging aperture, and 1,3-butadiene mass flow is35.7g/min, dicyclopentadiene toluene solution mass flow is 182.0g/min, the mol ratio of butadiene and cyclopentadieneBe 0.4. Two strands of materials of 1,3-butadiene and dicyclopentadiene enter conversion zone after static mixer mixes, anti-in tubular typeAnswer in device and react, reaction temperature is 160 DEG C, and reaction pressure is 10MPa, and the time of staying is 72 minutes. WarpGas chromatographic analysis, in corresponding outlet material, 1,3-butadiene selective 53.8%, corresponding 1,3-butadieneConversion ratio be 58.4%.
Claims (8)
1. a synthetic method for vinyl norbornene, is characterized in that, it adopts many side entry feed tubular reactor to enterRow is synthetic; Wherein said many side entry feed tubular reactor is divided into multiple conversion zones, the front end of each conversion zone arrange intoMaterial mouthful, the wherein charging aperture of the first conversion zone front end charging aperture of serving as theme, all the other are side entry feed mouth, each charging apertureArrange with pump coupling; Between each conversion zone and charging aperture, static mixer is set; Each side entry feed mouth front end arrangesCheck-valves, the middle rear end of last conversion zone arranges counterbalance valve, and end arranges discharging opening; Concrete steps are as follows:
The reaction channel of the first conversion zone will be put into from main line charging aperture containing the dicyclopentadiene of high concentration cyclopentadieneIn time, 1,3-butadiene is put into conversion zone from described main charging aperture and more than one side entry feed mouth respectivelyIn reaction channel, the reaction temperature of reaction in channel is that 120 DEG C-220 DEG C, pressure are 2-15MPa, and the time of staying is24-120min, obtains vinyl norbornene; Wherein said contains in the dicyclopentadiene of high concentration cyclopentadiene,Cyclopentadiene accounts for 50wt%-100wt%; Dicyclopentadiene containing high concentration cyclopentadiene is converted into cyclopentadieneMeter, the mol ratio of the dicyclopentadiene of described 1,3-butadiene and described high concentration cyclopentadiene is (0.1-2): 1.
2. synthetic method according to claim 1, is characterized in that: described 1,3-butadiene with containing high concentration ring pentaThe mol ratio of the dicyclopentadiene of diene is (0.2-1): 1.
3. synthetic method according to claim 1, is characterized in that: described reaction temperature is 140 DEG C-180 DEG C.
4. synthetic method according to claim 1, is characterized in that: described reaction pressure is 4-10MPa.
5. synthetic method according to claim 1, is characterized in that: described side entry feed mouth is 1-4.
6. synthetic method according to claim 1 or 5, is characterized in that: described side entry feed mouth is 1-2.
7. synthetic method according to claim 1, is characterized in that: by the described dicyclo containing high concentration cyclopentadienePentadiene directly feeds intake, or feeds intake after being formulated as solution containing the dicyclopentadiene of high concentration cyclopentadiene again;Wherein: the mass fraction that contains the dicyclopentadiene of high concentration cyclopentadiene is 10%-100%, and its solvent is selected from straight chain fatOne in fat hydrocarbon, cyclic aliphatic hydrocarbon or aromatic hydrocarbons is several.
8. synthetic method according to claim 7, is characterized in that: described solvent is octane, cyclohexane or tolueneIn one or more.
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| CN108676167A (en) * | 2018-04-03 | 2018-10-19 | 中国科学院化学研究所 | A kind of preparation facilities and method of polysilazane |
| CN114870751A (en) * | 2022-06-10 | 2022-08-09 | 山东潍坊润丰化工股份有限公司 | Continuous preparation system and method of o-methyl sodium phenoxyacetate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148412A (en) * | 2007-09-29 | 2008-03-26 | 吴兆立 | Multi-point charging EO technique for ethanolamine production |
| CN103483135A (en) * | 2013-09-02 | 2014-01-01 | 浙江恒河石油化工股份有限公司 | Preparation method of high-purity ethylidene norbornene (ENB) |
-
2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101148412A (en) * | 2007-09-29 | 2008-03-26 | 吴兆立 | Multi-point charging EO technique for ethanolamine production |
| CN103483135A (en) * | 2013-09-02 | 2014-01-01 | 浙江恒河石油化工股份有限公司 | Preparation method of high-purity ethylidene norbornene (ENB) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676167A (en) * | 2018-04-03 | 2018-10-19 | 中国科学院化学研究所 | A kind of preparation facilities and method of polysilazane |
| CN114870751A (en) * | 2022-06-10 | 2022-08-09 | 山东潍坊润丰化工股份有限公司 | Continuous preparation system and method of o-methyl sodium phenoxyacetate |
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