CN101898939B - 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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- CN101898939B CN101898939B CN2010102472723A CN201010247272A CN101898939B CN 101898939 B CN101898939 B CN 101898939B CN 2010102472723 A CN2010102472723 A CN 2010102472723A CN 201010247272 A CN201010247272 A CN 201010247272A CN 101898939 B CN101898939 B CN 101898939B
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- butyl vinyl
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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 the 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 Pottasium Hydroxide, and 1,4-butyleneglycol and acetylene reaction, obtain the 4-hydroxy butyl vinyl ether.
Reaction formula is following:
German Patent GB773331 has introduced dihydroxy alcohol mono vinyl ether preparing 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 preparing method's improvement
Instance one
To a high 100cm, in the iron reaction column of diameter 7cm (volume 3.8L), add the terepthaloyl moietie that 2000g contains 7% Pottasium Hydroxide, slowly be heated to 200 ℃; Take the moisture that reaction produces out of with the exsiccant nitrogen gas stream, then,, pass through this reaction column with the speed of 80-180L/hr with the acetylene air-flow of drying and preheating; Fill ceramic packing, bed stuffing height 80cm, reaction mixture continuous still battery discharging, the content of glycol monomethyl vinyl ether in the post; 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 terepthaloyl moietie, no ethylene glycol bis vinyl ether generates.
Can strengthen distillation rate with faint vacuum.
With this process and the continuous exsiccant terepthaloyl moietie 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 terepthaloyl moietie of 6.8% Pottasium 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 terepthaloyl moietie of 4.9% Pottasium 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 terepthaloyl moietie of 0.9% Pottasium 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.
Instance four
Adopt the method identical with instance one; The reaction column that use is thinner than instance one; Diethylene Glycol with containing 1% Pottasium Hydroxide is heated to 200 ℃, feeds 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%.
Can find out from above description; German Patent GB773331 also has weak point: the content of reaction back vinyl ether is still not high, and 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 through 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 the Traditional use 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 Pottasium Hydroxide; 1,4-butyleneglycol and acetylene reaction; In the preparation 4-hydroxy butyl vinyl ether, add DMSO 99.8MIN. 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: DMSO 99.8MIN. is prone to dissolve to acetylene; Every liter of DMSO 99.8MIN. can dissolve 33 liters of acetylene, behind the dmso solution acetylene, acetylene is got in the liquid; Prolong with 1,4-butyleneglycol duration of contact, make reaction be able to fully carry out.
We find: DMSO 99.8MIN. 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 DMSO 99.8MIN. is: 1,4-butyleneglycol: DMSO 99.8MIN.=1: 0.1-0.2, w/w.
We find: in the presence of Pottasium Hydroxide; 1,4-butyleneglycol and acetylene prepare in the reaction process of 4-hydroxy butyl vinyl ether; Add a small amount of OTAC, 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/Pottasium Hydroxide/DMSO 99.8MIN. are reaction raw materials, and the 4-hydroxy butyl vinyl ether is a reaction product, and their solvability is different, 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 the aqueous solution or the solid of salt, acid, alkali mutually; Another is the organic medium solution that is dissolved with RM mutually. common this two phase reaction is because immiscible, and 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; Along with the increase of 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 three types of amine salt, quaternary ammonium salt and heterocyclic types 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, OTAC.
We find: among the preparation method of above-mentioned 4-hydroxy butyl vinyl ether, the OTAC consumption is: 1,4-butyleneglycol: OTAC=1: 0.003-0.005, w/w.
We find: acetylene gas and nitrogen are mixed into reactor drum; 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 Pottasium Hydroxide/DMSO 99.8MIN./cats product is catalyzer, synthesizes to obtain the 4-hydroxy butyl vinyl ether, and DMSO 99.8MIN. 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 system
4: the acetylene gas valve
5: the nitrogen valve
6: addition funnel
7: condensing surface
8: susceptor
9: thermal oil
Embodiment
Embodiment 1
With 2000g1,4-butyleneglycol, 180g Pottasium Hydroxide joins in the 3000ml there-necked flask, starts to stir; Oil bath is heated to 140 ℃, under the 0.05MPa vacuum, distills, and slips out about 200g colourless transparent liquid; Obtain 1980g left and right sides brown viscous liquid, add the 400g DMSO 99.8MIN., it is subsequent use to stir.
As shown in Figure 1: as to 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 system 3, with thermal oil 9 oil bath heat supplies; After reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, through under meter; Acetylene gas: the proportioning of nitrogen=60: 40 (V/V) feeds in the tower, and mixed gas flow is 15-20L/H, opens addition funnel 6 simultaneously and adds reaction raw materials; Make quantity of distillate and additional amount balance, slip out liquid, get into susceptor 8 collections through condensing surface 7 and slip out liquid from cat head; Obtain 4-hydroxy butyl vinyl ether bullion, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 81.3%, cyclic acetal 3.8%.
With 2000g1,4-butyleneglycol, 180g Pottasium Hydroxide joins in the 3000ml there-necked flask, starts to 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 DMSO 99.8MIN. and 10g OTAC, it is subsequent use to stir.
As shown in Figure 1: as to 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 system 3, with thermal oil 9 oil bath heat supplies; After reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, through under meter; Acetylene gas: the proportioning of nitrogen=60: 40 (V/V) feeds in the tower, and mixed gas flow is 15-20L/H, opens addition funnel 6 simultaneously and adds reaction raw materials; Make quantity of distillate and additional amount balance, slip out liquid, get into susceptor 8 collections through condensing surface 7 and slip out liquid from cat head; Obtain 4-hydroxy butyl vinyl ether bullion, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 83.4%, cyclic acetal 2.9%.
With 2000g1,4-butyleneglycol, 180g Pottasium Hydroxide joins in the 3000ml there-necked flask, starts to 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 DMSO 99.8MIN. and 8g OTAC, it is subsequent use to stir.
As shown in Figure 1: as to 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 system 3, with thermal oil 9 oil bath heat supplies; After reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, through under meter; Acetylene gas: the proportioning of nitrogen=55: 45 (V/V) feeds in the tower, and mixed gas flow is 15-20L/H, opens addition funnel 6 simultaneously and adds reaction raw materials; Make quantity of distillate and additional amount balance, slip out liquid, get into susceptor 8 collections through condensing surface 7 and slip out liquid from cat head; Obtain 4-hydroxy butyl vinyl ether bullion, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 82.5%, cyclic acetal 3.0%.
With 2000g1,4-butyleneglycol, 180g Pottasium Hydroxide joins in the 3000ml there-necked flask, starts to 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 DMSO 99.8MIN. and 6g OTAC, it is subsequent use to stir.
As shown in Figure 1: as to 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 system 3, with thermal oil 9 oil bath heat supplies; After reaching 170 ℃ to temperature, open acetylene gas valve 4 and nitrogen valve 5, through under meter; Acetylene gas: the proportioning of nitrogen=57: 43 (V/V) feeds in the tower, and mixed gas flow is 15-20L/H, opens addition funnel 6 simultaneously and adds reaction raw materials; Make quantity of distillate and additional amount balance, slip out liquid, get into susceptor 8 collections through condensing surface 7 and slip out liquid from cat head; Obtain 4-hydroxy butyl vinyl ether bullion, vapor detection 4-hydroxy butyl vinyl ether content in crude product is 82.8%, cyclic acetal 3.4%.
Rectifying:, join in stuffing rectification column (filling glass spring filler in the tower diameter 4cm/ tower height 120cm, tower) the tower still with 4-hydroxy butyl vinyl ether crude product liquid; 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%, and after collection finished, tower top temperature rose; Reclaiming 85-87 ℃/0.098MPa component is DMSO 99.8MIN.; 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 (4)
1. the preparation method of a 4-hydroxy butyl vinyl ether: in the presence of Pottasium Hydroxide, 1,4-butyleneglycol and acetylene reaction, obtain the 4-hydroxy butyl vinyl ether, it is characterized in that: added DMSO 99.8MIN. and cats product in the reaction;
Wherein 1, the 4-butyleneglycol: DMSO 99.8MIN.=1: 0.1-0.2, w/w,
Wherein cats product is the quaternary ammonium type tensio-active agent,
And 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 OTAC.
2. the preparation method of 4-hydroxy butyl vinyl ether according to claim 1 is characterized in that: 1,4-butyleneglycol: OTAC=1: 0.003-0.005, w/w.
3. the preparation method of 4-hydroxy butyl vinyl ether according to claim 1 and 2 is characterized in that: acetylene gas and nitrogen are mixed into reactor drum.
4. the preparation method of 4-hydroxy butyl vinyl ether according to claim 3 is characterized in that: acetylene gas and nitrogen are mixed into reactor drum, and nitrogen accounts for the 40-45% of gas mixture, V/V.
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| 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 |
| 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 |
| CN111909368B (en) * | 2020-08-11 | 2023-09-08 | 江苏金木土新材料有限公司 | Preparation method of hydroxyl-terminated monovinyl ether |
| JPWO2022168950A1 (en) * | 2021-02-04 | 2022-08-11 | ||
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1401619A (en) * | 2002-09-17 | 2003-03-12 | 刘琳 | Method and apparatus for continuous synthesis of vinyl isobutyl ether |
| CN101555198A (en) * | 2008-07-10 | 2009-10-14 | 杭州电化集团有限公司 | Synthesis method of isobutyl vinyl ether and device thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1401619A (en) * | 2002-09-17 | 2003-03-12 | 刘琳 | Method and apparatus for continuous synthesis of vinyl isobutyl ether |
| CN101555198A (en) * | 2008-07-10 | 2009-10-14 | 杭州电化集团有限公司 | Synthesis method of isobutyl vinyl ether and device thereof |
Non-Patent Citations (1)
| Title |
|---|
| 汪伟志等.羟丁基乙烯基醚的合成.《化学世界》.2002,(第10期),第540-543，532页. * |
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