CN101898939A - Method for preparing compound 4-hydroxy butyl vinyl ether - Google Patents
Method for preparing compound 4-hydroxy butyl vinyl ether Download PDFInfo
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Abstract
The invention belongs to a method for preparing a vinyl ether compound, in particular to the method for preparing 4-hydroxy butyl vinyl ether. In the reaction of 1,4-butanediol and acetylene, dimethyl sulfoxide is added so that beneficial effects are achieved for the reaction, wherein the content of a 4-hydroxy butyl vinyl ether crude product is improved to 81 percent from 72 percent before adding; and a cyclic acetal byproduct is reduced to about 4 percent from 6 percent before adding. The content of the crude product can be further improved by 1 to 2 percent by adding a cationic surface active agent, namely octadecyl trimethyl ammonium chloride.
Description
Technical field
The invention belongs to the preparation method of vinyl ether compound, particularly a kind of preparation method of 4-hydroxy butyl vinyl ether.
Background technology
Vinyl ethers compound is a unsaturated ethers; be a kind of very important organic synthesis intermediate and the monomer of superpolymer; its homopolymer and multipolymer are widely used in tackiness agent, coating, lubricant, softening agent, sterilant, and many fields such as surface protecting material.In recent years, developing very fast is vinyl ethers reactive thinner as radiation curable coating, or with vinyl ether epoxy resin modification is become to contain the oligopolymer of vinyl ether function, and is applied in the ultraviolet-curing paint.For this reason, the vinyl ethers compound application prospect is extremely wide.
The 4-hydroxy butyl vinyl ether is important a kind of in the vinyl ethers compound.
4-hydroxy butyl vinyl ether suitability for industrialized production mainly is an acetylene method: in the presence of potassium hydroxide, and 1,4-butyleneglycol and acetylene reaction, obtain the 4-hydroxy butyl vinyl ether.
Reaction formula is as follows:
German Patent GB773331 has introduced dihydroxy alcohol mono vinyl ether preparation method's improvement, compares with other acetylene methods, and the advantage of this patent is: fed nitrogen in the reaction 1..2. reaction column is filled ceramic packing.Obtain the higher vinyl ether of content.
Specifically describe as follows:
The relevant dihydroxy alcohol mono vinyl ether of GB773331 preparation method's improvement
Example one
To a high 100cm, in the iron reaction column of diameter 7cm (volume 3.8L), adding 2000g contains the ethylene glycol of 7% potassium hydroxide, slowly be heated to 200 ℃, take the moisture that reaction produces out of with the exsiccant nitrogen gas stream, then, acetylene air-flow with drying and preheating, speed with 80-180L/hr is passed through this reaction column, fills ceramic packing, bed stuffing height 80cm in the post, reaction mixture continuous still battery discharging, the content of glycol monomethyl vinyl ether, the acetylene gas flow velocity according to different changes between 50-70%, in addition, also form the cyclic acetal by product of 5-20%, and unreacted ethylene glycol, no ethylene glycol bis vinyl ether generates.
Can strengthen distillation rate with faint vacuum.
With this process and the continuous exsiccant ethylene glycol that adds, to keep the liquid level in the reaction column, reaction is continuously carried out, per hour obtain the distillate that 60g contains the glycol monomethyl vinyl ether.
Use contains the ethylene glycol of 6.8% potassium hydroxide, 202 ℃ of temperature of reaction, and acetylene gas flow velocity 130L/hr per hour obtains the 80g distillate, wherein contains 66% glycol monomethyl vinyl ether, 18%2-methyl isophthalic acid, 3-dioxolane and 16% unreacted raw material.
Use contains the ethylene glycol of 4.9% potassium hydroxide, 201 ℃ of temperature of reaction, and acetylene gas flow velocity 125L/hr per hour obtains the 93g distillate, wherein contains 66% glycol monomethyl vinyl ether, 11%2-methyl isophthalic acid, the 3-dioxolane.
Use contains the ethylene glycol of 0.9% potassium hydroxide, 196 ℃ of temperature of reaction, and acetylene gas flow velocity 110L/hr per hour obtains the 52g distillate, wherein contains 21% glycol monomethyl vinyl ether, 2%2-methyl isophthalic acid, the 3-dioxolane.
Example four
Adopt the method identical with example one, the reaction column that use is thinner than example one, with the Diethylene Glycol that contains 1% potassium hydroxide, be heated to 200 ℃, feed the acetylene gas and the nitrogen gas stream (200L/hr) of equivalent, can obtain to contain the vapor of mixture liquid of 75% Diethylene Glycol mono vinyl ether continuously, wherein also contain diethylene glycol bis-vinyl ether and the unreacted Diethylene Glycol of 3-5%.
As can be seen from the above description, German Patent GB773331 also has weak point: the content of reaction back vinyl ether is still not high, the cyclic acetal by product is higher, this be because, the acetylene method reaction is the gas-liquid phase reaction, GB773331 to increase the time (with not filling ceramic packing relatively) that acetylene gas contacts with glycols, is far from being enough but only depend on this method by filling ceramic packing in the reaction column post.Increasing acetylene gas and contact with glycols, it is fully reacted, with the content of further raising product, reduce the cyclic acetal by product and produce, is the problem that we are badly in need of solving.
Summary of the invention
The reaction that traditional employing acetylene method obtains vinyl ether is the gas-liquid phase reaction, and Here it is runs into inhomogeneous reaction through regular meeting in organic synthesis, and the shortcoming of inhomogeneous reaction is that productive rate is low.
In order to address this problem, we find to have method that acetylene gas and glycols are fully reacted, and improve productive rate.
We find: under the catalysis of potassium hydroxide, 1,4-butyleneglycol and acetylene reaction, in the preparation 4-hydroxy butyl vinyl ether, add dimethyl sulfoxide (DMSO) in the reaction, this reaction is produced useful effect, the content in crude product of 4-hydroxy butyl vinyl ether brings up to 81% by 72% before adding, and the cyclic acetal by product is by being reduced to about 4% 6% before adding.
The reason that forms above-mentioned beneficial effect is: dimethyl sulfoxide (DMSO) is easily molten to acetylene, every liter of dimethyl sulfoxide (DMSO) can be dissolved 33 liters of acetylene, behind the dmso solution acetylene, acetylene is entered in the liquid, prolong with 1,4-butyleneglycol duration of contact, reaction is fully carried out.
We find: dimethyl sulfoxide (DMSO) to 1,4-butyleneglycol and acetylene reaction do not have adverse influence, do not produce new by product, and in rectifying, can separate well and reclaim.
We find: among the preparation method of above-mentioned 4-hydroxy butyl vinyl ether, the consumption of dimethyl sulfoxide (DMSO) is: 1,4-butyleneglycol: dimethyl sulfoxide (DMSO)=1: 0.1-0.2, w/w.
We find: in the presence of potassium hydroxide, 1,4-butyleneglycol and acetylene prepare in the reaction process of 4-hydroxy butyl vinyl ether, add a small amount of octadecyl trimethyl ammonium chloride, can promote 1, the raising of 4-butyleneglycol transformation efficiency, can make the content of 4-hydroxy butyl vinyl ether improve 1-2%.
Acetylene/1,4-butyleneglycol/potassium hydroxide/dimethyl sulfoxide (DMSO) are reaction raw materials, and the 4-hydroxy butyl vinyl ether is a reaction product, their solvability difference, and this reaction belongs to phase-transfer-catalyzed reactions.
Phase-transfer-catalyzed reactions belongs to the two phase reaction in the inhomogeneous reaction, one is salt mutually, acid, the aqueous solution of alkali or solid, another is the organic medium solution that is dissolved with reactive material mutually. common this two phase reaction is because immiscible, negatively charged ion and the speed of response between the reactant in the organic phase in the water (or solid phase) are very low, even do not react. and utilize phase-transfer catalyst, can with reactant from a phase transition to another mutually, increase along with probability of collision, reaction is quickened, thereby makes ionic compound and water-fast organic substance that reaction successfully take place in low polar solvent.
We find: among the preparation method of above-mentioned 4-hydroxy butyl vinyl ether, add cats product and can make reaction quicken.
Contain nitrogen-atoms in the hydrophilic group ion of cats product, be divided into amine salt, quaternary ammonium salt and heterocyclic type three classes according to the position difference of nitrogen-atoms in molecule.
Especially add: cats product is the quaternary ammonium type tensio-active agent.
Especially add: the quaternary ammonium type tensio-active agent is Tetrabutyl amonium bromide, trimethyl benzyl ammonia chloride, tri-n-octyl methyl ammonium chloride, cetyl trimethylammonium bromide, triethyl benzyl ammonia chloride, TBuA hydrosulfate or trialkyl methyl ammonium chloride, octadecyl trimethyl ammonium chloride.
We find: among the preparation method of above-mentioned 4-hydroxy butyl vinyl ether, the octadecyl trimethyl ammonium chloride consumption is: 1,4-butyleneglycol: octadecyl trimethyl ammonium chloride=1: 0.003-0.005, w/w.
We find: acetylene gas and nitrogen are mixed into reactor, nitrogen accounts for the 40-45% (V/V) of gas mixture, 50% (V/V) comparison with the nitrogen of common employing accounts for gas mixture can guarantee that still 4-hydroxyl butylethylene is not oxidized, improves yield in unit time 5-10% simultaneously.
In sum, by acetylene/1,4-butyleneglycol is raw material, with potassium hydroxide/dimethyl sulfoxide (DMSO)/cats product is catalyzer, the synthetic 4-hydroxy butyl vinyl ether that obtains, dimethyl sulfoxide (DMSO) can make acetylene/1,4-butyleneglycol be converted into liquid phase reaction by the gas-liquid phase reaction, cats product can make the 4-hydroxy butyl vinyl ether that is produced during alkaline solution one mutually better form organic phase, improves the productive rate of organic phase.
Description of drawings
The synthetic schemes of Figure 14-hydroxy butyl vinyl ether.
1: the filler reaction tower
2: ceramic ring
3: the heat supply Controlling System
4: the acetylene gas valve
5: the nitrogen valve
6: addition funnel
7: condenser
8: susceptor
9: thermal oil
Embodiment
Embodiment 1
With 2000g1,4-butyleneglycol, 180g potassium hydroxide joins in the 3000ml there-necked flask, starts to stir, oil bath is heated to 140 ℃, distills under the 0.05MPa vacuum, slips out about 200g colourless transparent liquid, obtain 1980g left and right sides brown viscous liquid, add the 400g dimethyl sulfoxide (DMSO), it is standby to stir.
As shown in Figure 1: take by weighing the about 400g of above-mentioned raw materials, join in the filler reaction tower 1, filler reaction tower height 70cm, diameter 5cm (volume 0.9L, actual useful volume is 0.6L behind the filling ceramic ring), filler is a ceramic ring 2, opens heat supply Controlling System 3, with thermal oil 9 oil bath heat supplies, after reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, by under meter, acetylene gas: the proportioning of nitrogen=60: 40 (V/V) feeds in the tower, mixed gas flow is 15-20L/H, open addition funnel 6 simultaneously and add reaction raw materials, make quantity of distillate and additional amount balance, slip out liquid from cat head, enter susceptor 8 collections by condenser 7 and slip out liquid, obtain 4-hydroxy butyl vinyl ether crude product, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 81.3%, cyclic acetal 3.8%.
With 2000g1,4-butyleneglycol, 180g potassium hydroxide joins in the 3000ml there-necked flask, start and stir, oil bath is heated to 140 ℃, under the 0.05MPa vacuum, distill, slip out about 200g colourless transparent liquid, obtain 1980g left and right sides brown viscous liquid, add 400g dimethyl sulfoxide (DMSO) and 10g octadecyl trimethyl ammonium chloride, it is standby to stir.
As shown in Figure 1: take by weighing the about 400g of above-mentioned raw materials, join in the filler reaction tower 1, filler reaction tower height 70cm, diameter 5cm (volume 0.9L, actual useful volume is 0.6L behind the filling ceramic ring), filler is a ceramic ring 2, opens heat supply Controlling System 3, with thermal oil 9 oil bath heat supplies, after reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, by under meter, acetylene gas: the proportioning of nitrogen=60: 40 (V/V) feeds in the tower, mixed gas flow is 15-20L/H, open addition funnel 6 simultaneously and add reaction raw materials, make quantity of distillate and additional amount balance, slip out liquid from cat head, enter susceptor 8 collections by condenser 7 and slip out liquid, obtain 4-hydroxy butyl vinyl ether crude product, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 83.4%, cyclic acetal 2.9%.
With 2000g1,4-butyleneglycol, 180g potassium hydroxide joins in the 3000ml there-necked flask, start and stir, oil bath is heated to 140 ℃, under the 0.05MPa vacuum, distill, slip out about 200g colourless transparent liquid, obtain 1980g left and right sides brown viscous liquid, add 300g dimethyl sulfoxide (DMSO) and 8g octadecyl trimethyl ammonium chloride, it is standby to stir.
As shown in Figure 1: take by weighing the about 400g of above-mentioned raw materials, join in the filler reaction tower 1, filler reaction tower height 70cm, diameter 5cm (volume 0.9L, actual useful volume is 0.6L behind the filling ceramic ring), filler is a ceramic ring 2, opens heat supply Controlling System 3, with thermal oil 9 oil bath heat supplies, after reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, by under meter, acetylene gas: the proportioning of nitrogen=55: 45 (V/V) feeds in the tower, mixed gas flow is 15-20L/H, open addition funnel 6 simultaneously and add reaction raw materials, make quantity of distillate and additional amount balance, slip out liquid from cat head, enter susceptor 8 collections by condenser 7 and slip out liquid, obtain 4-hydroxy butyl vinyl ether crude product, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 82.5%, cyclic acetal 3.0%.
With 2000g1,4-butyleneglycol, 180g potassium hydroxide joins in the 3000ml there-necked flask, start and stir, oil bath is heated to 140 ℃, under the 0.05MPa vacuum, distill, slip out about 200g colourless transparent liquid, obtain 1980g left and right sides brown viscous liquid, add 200g dimethyl sulfoxide (DMSO) and 6g octadecyl trimethyl ammonium chloride, it is standby to stir.
As shown in Figure 1: take by weighing the about 400g of above-mentioned raw materials, join in the filler reaction tower 1, filler reaction tower height 70cm, diameter 5cm (volume 0.9L, actual useful volume is 0.6L behind the filling ceramic ring), filler is a ceramic ring 2, opens heat supply Controlling System 3, with thermal oil 9 oil bath heat supplies, after reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, by under meter, acetylene gas: the proportioning of nitrogen=57: 43 (V/V) feeds in the tower, mixed gas flow is 15-20L/H, open addition funnel 6 simultaneously and add reaction raw materials, make quantity of distillate and additional amount balance, slip out liquid from cat head, enter susceptor 8 collections by condenser 7 and slip out liquid, obtain 4-hydroxy butyl vinyl ether crude product, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 82.8%, cyclic acetal 3.4%.
Rectifying: with 4-hydroxy butyl vinyl ether crude product liquid, join stuffing rectification column (tower diameter 4cm/ tower height 120cm, filling glass spring filler in the tower) in the tower still, open vacuum (0.098MPa), 120 ℃ of tower still temperature, collecting 78-82 ℃/0.098MPa cut is the 4-hydroxy butyl vinyl ether, gas phase is measured content 99.5%, after collection finishes, tower top temperature rises, and reclaiming 85-87 ℃/0.098MPa component is dimethyl sulfoxide (DMSO), reclaim 89-90 ℃/0.098MPa unreacted intact 1, the 4-butyleneglycol, remain a small amount of high debris of boiling, mainly contain by product ring-type acetal etc.
The detection of 4-hydroxy butyl vinyl ether:
Instrument: FULI-9790 type gas chromatograph
Chromatographic column: DB-FFAP type capillary column, specification Φ 0.25mm*30m
Detector: hydrogen flame ionization sensor
Testing conditions:
Gasification temperature: 220 ℃
Detected temperatures: 240 ℃
Column compartment temperature (temperature programming): 100 ℃ of initial temperature, 10 ℃/minute of temperature rise rates, temperature is 220 ℃ eventually,
Kept 30 minutes.
The carrier gas gauge pressure:
Nitrogen: 0.08MPa
Hydrogen: 0.15MPa
Air: 0.035MPa
Sample size: 0.4
Integrative approach: area normalization method
Permissible error: twice replicate(determination) result's difference is not more than 0.2%.
Claims (9)
1. the preparation method of a compound 4-hydroxy butyl vinyl ether: in the presence of potassium hydroxide, 1,4-butyleneglycol and acetylene reaction, obtain the 4-hydroxy butyl vinyl ether, it is characterized in that: added dimethyl sulfoxide (DMSO) in the reaction.
2. the preparation method of 4-hydroxy butyl vinyl ether according to claim 1 is characterized in that: also added cats product in the reaction.
3. the preparation method of 4-hydroxy butyl vinyl ether according to claim 2 is characterized in that:
1,4-butyleneglycol: dimethyl sulfoxide (DMSO)=1: 0.1-0.2, w/w.
4. the preparation method of 4-hydroxy butyl vinyl ether according to claim 3 is characterized in that: cats product is the quaternary ammonium type tensio-active agent.
5. the preparation method of 4-hydroxy butyl vinyl ether according to claim 4 is characterized in that: the quaternary ammonium type tensio-active agent is Tetrabutyl amonium bromide, trimethyl benzyl ammonia chloride, tri-n-octyl methyl ammonium chloride, cetyl trimethylammonium bromide, triethyl benzyl ammonia chloride, TBuA hydrosulfate or trialkyl methyl ammonium chloride.
6. the preparation method of 4-hydroxy butyl vinyl ether according to claim 5 is characterized in that: the quaternary ammonium type tensio-active agent is an octadecyl trimethyl ammonium chloride.
7. the preparation method of 4-hydroxy butyl vinyl ether according to claim 6 is characterized in that: 1,4-butyleneglycol: octadecyl trimethyl ammonium chloride=1: 0.003-0.005, w/w.
8. according to the preparation method of the described 4-hydroxy butyl vinyl ether of claim 1-7, it is characterized in that: acetylene gas and nitrogen are mixed into reactor.
9. the preparation method of 4-hydroxy butyl vinyl ether according to claim 8 is characterized in that: acetylene gas and nitrogen are mixed into reactor, and nitrogen accounts for the 40-45% of gas mixture, V/V.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102173982A (en) * | 2011-03-21 | 2011-09-07 | 南京林业大学 | Method for synthesizing dihydric alcohol single vinyl ether and double vinyl ether |
| CN102757319A (en) * | 2011-04-27 | 2012-10-31 | 重庆市化工研究院 | Method for preparing adamantly alkyl vinyl ether |
| CN102807479A (en) * | 2011-06-03 | 2012-12-05 | 焦作新景科技有限公司 | Method for synthesizing vinyl cyclohexyl ether |
| CN102976904A (en) * | 2012-12-24 | 2013-03-20 | 厦门大学 | Preparation device of isobutyl vinyl ether and preparation method thereof |
| CN103394371A (en) * | 2013-08-19 | 2013-11-20 | 博爱新开源制药股份有限公司 | Method for producing vinyl-4-hydroxybutyl ether through acetylene method, and catalyst thereof |
| CN111909368A (en) * | 2020-08-11 | 2020-11-10 | 江苏金木土新材料有限公司 | Preparation method of hydroxyl-terminated monovinyl ether |
| CN113956137A (en) * | 2021-11-24 | 2022-01-21 | 衢州建华南杭药业有限公司 | Preparation method for alcohol head polymerization purification |
| WO2022168950A1 (en) * | 2021-02-04 | 2022-08-11 | 丸善石油化学株式会社 | Method for producing (2-methoxyethyl) vinyl ether, and method for refining (2-methoxyethyl) vinyl ether |
| CN116212846A (en) * | 2022-12-12 | 2023-06-06 | 大连理工大学 | Preparation method and application of K/Mg/Al solid base catalyst |
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| CN102173982A (en) * | 2011-03-21 | 2011-09-07 | 南京林业大学 | Method for synthesizing dihydric alcohol single vinyl ether and double vinyl ether |
| CN102173982B (en) * | 2011-03-21 | 2013-06-05 | 南京林业大学 | Method for synthesizing dihydric alcohol single vinyl ether and double vinyl ether |
| CN102757319A (en) * | 2011-04-27 | 2012-10-31 | 重庆市化工研究院 | Method for preparing adamantly alkyl vinyl ether |
| CN102807479A (en) * | 2011-06-03 | 2012-12-05 | 焦作新景科技有限公司 | Method for synthesizing vinyl cyclohexyl ether |
| CN102976904A (en) * | 2012-12-24 | 2013-03-20 | 厦门大学 | Preparation device of isobutyl vinyl ether and preparation method thereof |
| CN102976904B (en) * | 2012-12-24 | 2014-10-15 | 厦门大学 | Preparation device of isobutyl vinyl ether and preparation method thereof |
| CN103394371A (en) * | 2013-08-19 | 2013-11-20 | 博爱新开源制药股份有限公司 | Method for producing vinyl-4-hydroxybutyl ether through acetylene method, and catalyst thereof |
| CN111909368A (en) * | 2020-08-11 | 2020-11-10 | 江苏金木土新材料有限公司 | Preparation method of hydroxyl-terminated monovinyl ether |
| WO2022168950A1 (en) * | 2021-02-04 | 2022-08-11 | 丸善石油化学株式会社 | Method for producing (2-methoxyethyl) vinyl ether, and method for refining (2-methoxyethyl) vinyl ether |
| CN113956137A (en) * | 2021-11-24 | 2022-01-21 | 衢州建华南杭药业有限公司 | Preparation method for alcohol head polymerization purification |
| CN116212846A (en) * | 2022-12-12 | 2023-06-06 | 大连理工大学 | Preparation method and application of K/Mg/Al solid base catalyst |
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