CN108187682A - A kind of solid base catalyst for synthesizing 4- hydroxy butyl vinyl ethers and its preparation method and application - Google Patents
A kind of solid base catalyst for synthesizing 4- hydroxy butyl vinyl ethers and its preparation method and application Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
- C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
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Abstract
The invention discloses a kind of solid base catalysts for synthesizing 4 hydroxy butyl vinyl ethers and its preparation method and application.Catalyst of the present invention is with zirconium dioxide(ZrO2)For carrier, Cu, K bi-component are activated centre, and the mass percent of each component is:Active component cuprous oxide(Cu2O)It is 1% ~ 15%, potassium oxide(K2O)It is 10 ~ 35%, carrier ZrO2It is 50% ~ 89%.Preparation method is:Mantoquita, sylvite are mixed with zirconates, after being fully ground, add in deionized water stir evenly, then through drying, roasting and liquid-phase reduction and etc. be made catalyst.This method is simple for process, strong operability, is easy to industrialized production, and of low cost.Prepared catalyst synthesizes 4 hydroxy butyl vinyl ethers for acetylene method, and target product yield solves the problems, such as that existing solid base catalyst catalytic activity is low, poor selectivity up to 67.39%.
Description
Technical field
The present invention relates to a kind of solid base catalysts for synthesizing 4- hydroxy butyl vinyl ethers and its preparation method and application, belong to
In catalyst preparation technical field.
Background technology
Vinyl ethers is a kind of important polymer monomer and organic synthesis intermediate, and homopolymer and copolymer are due to tool
The features such as having hypotoxicity, tasteless, lower shrinkage, high intensity, high adhesion, solubility, excellent flexibility and being readily synthesized, it can make
Be reactive diluent for the systems such as epoxy resin, acrylic resin and unsaturated polyester (UP), be also used for making adhesive, coating,
Oils viscosity modifier, plasticizer, lubricant, hair spray, elastomer, foamed material, insecticide and surface protecting material etc..Make
For organic synthesis intermediate, vinyl ethers can be used for synthesis tetramethoxy propane, γ-picoline, 2- aminopyrimidines and property
Fungicide glutaraldehyde that can be excellent etc..In addition, vinyl ethers is also widely used for the necks such as fragrance, flavoring agent and drug products
Domain.
4- hydroxy butyl vinyl ethers are one kind important in vinyl ethers compound.In the presence of potassium hydroxide, 1,
4- butanediols and acetylene reaction can generate 4- hydroxy butyl vinyl ethers (HBVE).Reaction equation is as follows:
1,4-butanediol contains there are two hydroxyl, after a hydroxyl and molecule acetylene reaction generation HBVE, theoretically also
Can continue with another molecule acetylene reaction generation 1,4-butanediol divinyl ether (DBVE), but due to two hydroxyl distances compared with
Closely, steric hindrance causes another hydroxyl to be not easy to react with acetylene molecule, thus divinyl ether yield is relatively low.Reaction equation is such as
Under:
Meanwhile using KOH as the homogeneous reaction of catalyst during, inevitably generate many side reactions, specific mistake
Journey is as follows:
Intramolecular ring closure dehydration occurs for 1,4-butanediol, generates tetrahydrofuran,
Acetylene cyclotrimerization generates benzene,
Self-condensation, generation cyclic acetal by-product -2- methyl-1s, 3- dioxepins occur for hydroxy butyl vinyl ether
(MDOP),
Numerous by-products that homogeneous catalytic reaction process generates do not only result in target product selectivity reduction, and can make
Ingredient is from difficulty.
Deutsche Bundespatent (GB773331) is described using KOH as catalyst, and acetylene method prepares dihydric alcohol mono vinyl ether
Method.The patent by filling ceramic packing in reaction column, increase acetylene and dihydric alcohol (ethylene glycol, propylene glycol, butanediol,
Hexylene glycol etc.) contact time, to reduce the generation of cyclic acetal by-product, but can still contain 5~20% ring in reaction product
Shape acetal by-product.
Chinese patent (CN101898939) prepares 4- hydroxyl butyl vinyls equally using KOH as catalyst, using acetylene method
Ether.The patent specifically adds solvent of the dimethyl sulfoxide (DMSO) as acetylene in the reaction system, by extending acetylene and Isosorbide-5-Nitrae-fourth
The time of contact of glycol improves the content of 4- hydroxy butyl vinyl ethers, reduces the content of cyclic acetal by-product;Further
By adding in surfactant octadecyltrimethylammonium chloride, the raising of 1,4-butanediol conversion ratio is also promoted.
United States Patent (USP) (US20060205984) is reported using potassium alcoholate as catalyst, is continuously made with acetylene reaction by methanol
The method of standby methyl vinyl ether.Compared with KOH is as catalyst, second alkyne conversion is promoted as catalyst using potassium alcoholate.
It is above-mentioned using KOH or potassium alcoholate as the homogeneous catalytic reaction system of catalyst, by filling ceramic packing, it is molten to change reaction
Agent is additionally added surfactant or is changed replacing the measures such as KOH by potassium alcoholate, reduces cyclic acetal by-product to a certain extent
The generation of object improves the content of 4- hydroxy butyl vinyl ethers, but there are still by-product is more, catalyst separation is difficult, can not weigh
The problems such as multiple use, equipment corrosion and environmental pollution.
Peng Chunrui [synthesising process research [D] the Nanjing Forestry University of the farsighted hydroxy butyl vinyl ethers of Peng Chun, 2011.] is used
Equi-volume impregnating is prepared for KOH/Al2O3, K2CO3/Al2O3With the solid base catalysts such as KOH/AC, and it is catalyzed for acetylene method
Synthesize 4- hydroxy butyl vinyl ethers.Wherein, with K2CO3/Al2O3It is compared with KOH/AC etc., KOH/Al2O3Catalytic activity it is best,
But it is catalyzed the content of target product 4- hydroxy butyl vinyl ethers in the product of reaction and is also only 10.8%.
It is well known that the environmental pollution getting worse that chemical industry is brought, Search green chemistry and environmental friendly catalysis work
Skill is very urgent.Solid base catalyst played an important role in environmental-friendly novel catalyzing technology, especially become more meticulous
Product receive the favor of researcher in catalyzing and synthesizing.However, for acetylene method synthesizes hydroxy butyl vinyl ether, existing solid
Base catalyst is primarily present that catalytic activity is low, the problems such as can not recycling.Therefore, rationally setting for structure is formed by catalyst
The optimization innovation of meter, preparation method improves the catalytic activity of solid base catalyst, recycles performance, is current urgently to be resolved hurrily
The problem of.
Invention content
The present invention is intended to provide a kind of solid base catalyst for synthesizing 4- hydroxy butyl vinyl ethers and preparation method thereof, this hair
The bright application for additionally providing the catalyst in 4- hydroxy butyl vinyl ethers are synthesized.
The present invention provides a kind of solid base catalyst for synthesizing 4- hydroxy butyl vinyl ethers, which is Cu2O-K2O/
ZrO2, with zirconium dioxide (ZrO2) it is carrier, with cuprous oxide (Cu2O), potassium oxide (K2O it is) active component, the matter of each component
Measuring percentage is:
Active component Cu2The mass percentage of O is 1%~15%, K2The mass percentage of O is 10~35%, carrier
ZrO2Mass percentage be 50%~89%.
Preferably, in the catalyst, the mass percent of each component is:
Active component Cu2O:5%~10%,
Active component K2O:15%~30%,
Carrier ZrO2:60%~80%.
The present invention provides a kind of preparation method for the solid base catalyst for synthesizing 4- hydroxy butyl vinyl ethers, including following
Step:
(1) weigh mantoquita, sylvite is mixed with zirconates, after being fully ground, add in deionized water stir evenly, wherein zirconates is dense
It spends for 0.541mol/L~2.705mol/L, the mantoquita, sylvite and zirconates mass ratio are 0.001~0.139:0.009~
0.689:1;
(2) by above-mentioned solution in 80~150 DEG C of dry 3~15h, then in air atmosphere 300~700 DEG C of roastings 1~
12h obtains CuO-K2O/ZrO2;
(3) compound concentration is the reducing agent aqueous solution of 0.01~0.45mol/L, and 5~15% ammonium hydroxide are instilled under magnetic agitation,
It is 8~11 to adjust pH value of solution, by the CuO-K obtained by step (2)2O/ZrO2It is added in above-mentioned solution, at 70~100 DEG C, stirs
Mix 0.5~1h of reflux;
The reducing agent and CuO-K2O/ZrO2Mass ratio be 0.001~0.154:1;
(4) through filtering after reacting, by filter cake at 60~80 DEG C dry 6~10h to get to Cu2O-K2O/ZrO2Solid base
Catalyst.
In above-mentioned preparation method, the mantoquita is one or more in copper chloride, copper sulphate, copper nitrate, copper acetate.
In above-mentioned preparation method, the sylvite is potassium nitrate, potassium carbonate, potassium hydroxide, potassium chloride, saleratus, sulfuric acid
It is one or more in potassium.
In above-mentioned preparation method, the zirconates is one or more in zirconium nitrate, zirconyl nitrate, zirconium oxychloride.
In above-mentioned preparation method, in step (2), the solution dry 5~8h at 100~130 DEG C, in air atmosphere
3~8h is roasted at 400~600 DEG C.
In above-mentioned preparation method, the reducing agent is ascorbic acid, formaldehyde, acetaldehyde, sodium borohydride, glucose, unsaturation
It is one or more in alcohol, sodium citrate, hydrazine hydrate.
The present invention provides application of the above-mentioned solid base catalyst in acetylene method synthesizes 4- hydroxy butyl vinyl ethers.Specifically
Ground, by catalyst obtained by the present invention in acetylene method synthesis 4- hydroxy butyl vinyl ethers:By 1,4- butanediols and Cu2O-K2O/
ZrO2Catalyst is added in the three-necked flask of 100ml, Cu2O-K2O/ZrO2Mass ratio with 1,4- butanediols is 10~30:
100, acetylene is passed through, and acetylene flow is controlled to start stirring, oil bath heating is to 140~160 DEG C, instead for 0.03~0.07L/min
Answer 5~12h.After reaction, filtering reacting liquid recycling catalyst, dries after ethyl alcohol washs, for recycling.
Cu prepared by the present invention2O-K2O/ZrO2Catalyst synthesizes 4- hydroxy butyl vinyl ethers, target production for acetylene method
Object yield can reach 67.39%.
Beneficial effects of the present invention:
(1) catalyst prepared by the present invention is solid base, is avoided using general in the homogeneous catalysis systems such as KOH or potassium alcoholate
All over existing by-product is more, catalyst separation is difficult, it is not reproducible use, equipment is corroded and the drawbacks such as environmental pollution.
(2) compared with existing solid base catalyst, which has catalytic activity height, target product yield high and can
The advantages that recycling.
(3) catalyst preparation process is simple, and raw material sources are extensive, cheap, to human body and environmentally friendly, is easy to real
Existing industrialized production, has a good application prospect.
Specific embodiment
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Embodiment 1:
Weigh 0.84g Cu (NO3)2·3H2O, 0.89g KOH and 15.69g ZrOCl2·8H2O is mixed, after being fully ground,
It adds in a certain amount of deionized water to stir evenly, dry 6h, 4h is roasted in air atmosphere at 500 DEG C at 120 DEG C, is prepared
10% ammonium hydroxide is added dropwise under magnetic agitation for the glucose solution of 40mL 0.18mol/L, and it is 10 to adjust pH value of solution, will at 90 DEG C
CuO-K2O/ZrO2Be added in above-mentioned solution, be stirred at reflux 1h, through filtering after reaction, by filter cake at 60 DEG C dry 6h to get
To Cu2O-K2O/ZrO2Solid base catalyst.
30g 1,4-butanediol and the above-mentioned catalyst of 4.5g are added in the three-necked flask of 100ml, are passed through acetylene, and control
Acetylene flow processed is 0.04L/min, starts stirring, and oil bath heating is to 150 DEG C, after reacting 9h, is divided using gas-chromatography OV-1701
Reaction solution is analysed, 4- hydroxy butyl vinyl ethers yield is 67.39%, and by-product total recovery is less than 0.17%.
The testing conditions of gas-chromatography are as follows:
Instrument:Agilent 7890B type gas chromatographs
Column type:OV-1701
Gasification temperature:240℃
Detect temperature:280℃
Column compartment temperature (temperature programming):80 DEG C, 1~5min of constant temperature, 20 DEG C/min of heating rate of initial temperature, 160 DEG C of final temperature.
Gas gauge pressure:
Nitrogen:0.08MPa
Hydrogen:0.05MPa
Air:0.1MPa
Sample size:0.02μL.
Embodiment 2
By Cu (NO in embodiment 13)2·3H2O, KOH and ZrOCl2·8H2The quality of O be changed to respectively 0.28g, 0.4g and
13.08g, glucose solution are changed to ascorbic acid solution, and Cu is made using same method2O-K2O/ZrO2Solid base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 60.52%, secondary
Product total recovery is less than 0.41%.
Embodiment 3
By Cu (NO in embodiment 13)2·3H2O, KOH and ZrOCl2·8H2O is changed to CuSO respectively4·5H2O、K2CO3And Zr
(NO3)4·5H2O, drying temperature are changed to 110 DEG C, and Cu is made using same method2O-K2O/ZrO2Solid base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 62.18%, secondary
Product total recovery is less than 0.36%.
Embodiment 4
By Cu (NO in embodiment 13)2·3H2O, KOH and ZrOCl2·8H2O is changed to Cu (CH respectively3COO)2·H2O、KNO3
With ZrO (NO3)2·2H2O, glucose solution are changed to acetaldehyde solution, and Cu is made using same method2O-K2O/ZrO2Solid base
Catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 60.35%, secondary
Product total recovery is less than 0.42%.
Embodiment 5
By Cu (NO in embodiment 13)2·3H2O, KOH and ZrOCl2·8H2O is changed to CuCl respectively2、KHCO3And Zr
(NO3)4, glucose solution is changed to sodium borohydride solution, and calcination temperature is changed to 450 DEG C, and Cu is made using same method2O-
K2O/ZrO2Solid base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 63.47%, secondary
Product total recovery is less than 0.32%.
Embodiment 6
By Cu (NO in embodiment 13)2·3H2O, KOH and ZrOCl2·8H2The quality of O be changed to respectively 0.79g, 0.94g and
13.58g, glucose solution are changed to ascorbic acid solution, and drying temperature is changed to 100 DEG C, and Cu is made using same method2O-
K2O/ZrO2Solid base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 56.81%, secondary
Product total recovery is less than 0.47%.
Embodiment 7
By Cu (NO in embodiment 13)2·3H2O, KOH and ZrOCl2·8H2The quality of O be changed to respectively 0.79g, 0.94g and
13.58g, drying temperature are changed to 100 DEG C, and calcination temperature is changed to 400 DEG C, and Cu is made using same method2O-K2O/ZrO2Solid
Base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 60.75%, secondary
Product total recovery is less than 0.39%.
Embodiment 8
Glucose solution in embodiment 1 is changed to sodium citrate solution, ammonium hydroxide mass fraction is changed to 15%, adjusts pH value of solution
It is 9, Cu is made using same method2O-K2O/ZrO2Solid base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 65.28%, secondary
Product total recovery is less than 0.22%.
Embodiment 9
Drying temperature in embodiment 1 is changed to 130 DEG C, calcination temperature is changed to 600 DEG C, and reduction temperature is changed to 75 DEG C, uses
Cu is made in same method2O-K2O/ZrO2Solid base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 59.36%, secondary
Product total recovery is less than 0.43%.
Embodiment 10
Glucose solution in embodiment 1 is changed to sodium citrate solution, reduction temperature is changed to 85 DEG C, and return time is changed to
Cu is made using same method in 0.5h2O-K2O/ZrO2Solid base catalyst.
Using 1 evaluation condition of embodiment, under above-mentioned evaluation condition, 4- hydroxy butyl vinyl ethers yield is 66.23%, secondary
Product total recovery is less than 0.21%.
Embodiment 11
By Cu in 1 evaluation condition of embodiment2O-K2O/ZrO210 are changed to the mass ratio of 1,4- butanediols:100, acetylene stream
Amount is changed to 0.06L/min, and oil bath temperature is changed to 145 DEG C, and other conditions are constant, Cu prepared by Example 12O-K2O/ZrO2Gu
Body base catalyst is for reacting, and 4- hydroxy butyl vinyl ether yields reach 62.73%, and by-product total recovery is less than 0.27%.
Embodiment 12
By Cu in 1 evaluation condition of embodiment2O-K2O/ZrO220 are changed to the mass ratio of 1,4- butanediols:100, acetylene stream
Amount is changed to 0.03L/min, and the reaction time is changed to 5h, and other conditions are constant, Cu prepared by Example 12O-K2O/ZrO2Solid base
Catalyst is for reacting, and 4- hydroxy butyl vinyl ethers yield is 63.27%, and by-product total recovery is less than 0.26%.
Embodiment 13
Acetylene flow in 1 evaluation condition of embodiment is changed to 0.07L/min, oil bath temperature is changed to 140 DEG C, and the reaction time changes
For 11h, other conditions are constant, Cu prepared by Example 12O-K2O/ZrO2Solid base catalyst is for reacting, 4- hydroxyl butyl second
Alkene ether yield is 63.51%, and by-product total recovery is less than 0.25%.
Embodiment 14
By Cu in 1 evaluation condition of embodiment2O-K2O/ZrO220 are changed to the mass ratio of 1,4- butanediols:100, acetylene stream
Amount is changed to 0.07L/min, and oil bath temperature is changed to 140 DEG C, and the reaction time is changed to 8h, and other conditions are constant, prepared by Example 1
Cu2O-K2O/ZrO2Solid base catalyst is for reacting, and 4- hydroxy butyl vinyl ethers yield is 64.25%, and by-product total recovery is low
In 0.24%.
The cycle performance test of catalyst:
Embodiment 15
The catalyst in embodiment 1 is recycled, labeled as Cu2O-K2O/ZrO2-1.Using 1 evaluation condition of embodiment, above-mentioned
Under evaluation condition, 4- hydroxy butyl vinyl ethers yield is 60.74%, and by-product total recovery is less than 0.39%.
Embodiment 16
The catalyst in embodiment 15 is recycled, labeled as Cu2O-K2O/ZrO2-2.Using 1 evaluation condition of embodiment, upper
Under the conditions of commentary valency, 4- hydroxy butyl vinyl ethers yield is 58.25%, and by-product total recovery is less than 0.44%.
Embodiment 17
The catalyst in embodiment 16 is recycled, labeled as Cu2O-K2O/ZrO2-3.Using 1 evaluation condition of embodiment, upper
Under the conditions of commentary valency, 4- hydroxy butyl vinyl ethers yield is 57.18%, and by-product total recovery is less than 0.45%.
Catalyst in the present invention, it is convenient to be separated and recovered after use, and embodiment 15~17 illustrates, the cyclicity of the catalyst
Can be good, it is reusable.
Claims (10)
1. a kind of solid base catalyst for synthesizing 4- hydroxy butyl vinyl ethers, it is characterised in that:The catalyst is Cu2O-K2O/
ZrO2, using zirconium dioxide as carrier, using cuprous oxide, potassium oxide as active component, the mass percent of each component is:
Active component cuprous oxide:1% ~ 15%,
Potassium oxide:10 ~ 35%,
Carrier:50%~89%.
2. the solid base catalyst of synthesis 4- hydroxy butyl vinyl ethers according to claim 1, it is characterised in that:It is described to urge
In agent, the mass percent of each component is:
Active component Cu2O:5% ~ 10%,
Active component K2O:15% ~ 30%,
Carrier ZrO2:60%~80%.
3. a kind of preparation method of the solid base catalyst of the synthesis 4- hydroxy butyl vinyl ethers described in claims 1 or 2, special
Sign is:Include the following steps:
(1)Weigh mantoquita, sylvite is mixed with zirconates, after being fully ground, add in deionized water stir evenly, wherein zirconates is a concentration of
0.541mol/L~2.705 mol/L;
(2)By above-mentioned solution in 80 ~ 150 DEG C of dry 3 ~ 15 h, then 300 ~ 700 DEG C of 1 ~ 12 h of roasting in air atmosphere,
Obtain CuO-K2O/ZrO2;
(3)Compound concentration is the reducing agent aqueous solution of 0.01 ~ 0.45 mol/L, instills 5 ~ 15% ammonium hydroxide under magnetic agitation, adjusts molten
Liquid pH is 8 ~ 11, by step(2)The CuO-K of gained2O/ZrO2It is added in above-mentioned solution, at 70 ~ 100 DEG C, is stirred at reflux
0.5~1 h;The reducing agent and CuO-K2O/ZrO2Mass ratio be 0.001 ~ 0.154:1;
(4)Through filtering after reaction, by filter cake at 60 ~ 80 DEG C dry 6 ~ 10 h to get to Cu2O-K2O/ZrO2Catalyzed by solid base
Agent.
4. the preparation method of the solid base catalyst of synthesis 4- hydroxy butyl vinyl ethers according to claim 3, feature
It is:The mantoquita is one or more in copper chloride, copper sulphate, copper nitrate, copper acetate, and mantoquita is with zirconates mass ratio
0.001~0.139:1。
5. the preparation method of the solid base catalyst of synthesis 4- hydroxy butyl vinyl ethers according to claim 3, feature
It is:The sylvite is one or more in potassium nitrate, potassium carbonate, potassium hydroxide, potassium chloride, saleratus, potassium sulfate, potassium
Salt is 0.009 ~ 0.689 with zirconates mass ratio:1.
6. the preparation method of the solid base catalyst of synthesis 4- hydroxy butyl vinyl ethers according to claim 3, feature
It is:The zirconates is one or more in zirconium nitrate, zirconyl nitrate, zirconium oxychloride.
7. the preparation method of the solid base catalyst of synthesis 4- hydroxy butyl vinyl ethers according to claim 3, feature
It is:Step(2)In, the solution dry 5 ~ 8 h at 100 ~ 130 DEG C, in air atmosphere roasting 3 at 400 ~ 600 DEG C ~
8 h。
8. the preparation method of the solid base catalyst of synthesis 4- hydroxy butyl vinyl ethers according to claim 3, feature
It is:The reducing agent is ascorbic acid, formaldehyde, acetaldehyde, sodium borohydride, glucose, unsaturated alcohol, sodium citrate, hydrazine hydrate
In it is one or more.
9. a kind of application of the solid base catalyst of the synthesis 4- hydroxy butyl vinyl ethers described in claims 1 or 2, feature exist
In:
By 1,4- butanediols and Cu2O-K2O/ZrO2Catalyst is added in flask, Cu2O-K2O/ZrO2Catalyst and 1,4- fourths two
The mass ratio of alcohol is 10 ~ 30:100, acetylene is passed through, control acetylene flow is 0.03 ~ 0.07 L/min, starts stirring, oil bath adds
Heat reacts 5 ~ 12 h to 140 ~ 160 DEG C.
10. application according to claim 9, it is characterised in that:By Cu2O-K2O/ZrO2Catalyst synthesizes for acetylene method
4- hydroxy butyl vinyl ethers, target product yield can reach 67.39%.
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CN113173837A (en) * | 2021-04-24 | 2021-07-27 | 浙江锦华新材料股份有限公司 | Preparation method of vinyl isobutyl ether |
US20220033335A1 (en) * | 2018-11-27 | 2022-02-03 | Maruzen Petrochemical Co., Ltd. | Method for producing divinyl ether compound having alkylene skeleton |
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