CN106631800A - A method of preparing propargyl tert-butyl carbonate and a method of preparing methylene ethylene carbonate - Google Patents
A method of preparing propargyl tert-butyl carbonate and a method of preparing methylene ethylene carbonate Download PDFInfo
- Publication number
- CN106631800A CN106631800A CN201610976313.XA CN201610976313A CN106631800A CN 106631800 A CN106631800 A CN 106631800A CN 201610976313 A CN201610976313 A CN 201610976313A CN 106631800 A CN106631800 A CN 106631800A
- Authority
- CN
- China
- Prior art keywords
- tert
- propargyl
- butyl
- preparation
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
To overcome a problem that propargyl tert-butyl carbonate preparing costs in the prior art are high, a method of preparing propargyl tert-butyl carbonate is provided. The method includes mixing propargyl alcohol, di-tert-butyl dicarbonate and a catalyst in a dry atmosphere, and reacting the mixture under stirring to obtain the propargyl tert-butyl carbonate. The catalyst is one or more selected from diethylamine, triethylamine and pyridine. In addition, the invention also discloses a method of preparing methylene ethylene carbonate based on the above-mentioned method. The cost of the propargyl tert-butyl carbonate is low and the method of preparing the propargyl tert-butyl carbonate is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of propargyl tert-butyl carbonate, and the preparation of mesomethylene carbon vinyl acetate
Method.
Background technology
Mesomethylene carbon vinyl acetate is a kind of new lithium-ion battery electrolytes additive.Its energy is reported according to existing document
Stable SEI films are formed in anode, so as to be formed battery life and high-temperature behavior are effectively improved, be even better than with similar
The function of vinylene carbonate (VC).
Synthesizing the method for mesomethylene carbon vinyl acetate in prior art includes：By propilolic alcohol and CO2In catalyst and high pressure
Under the conditions of reacted, so as to prepare mesomethylene carbon vinyl acetate.But the method is carried out under high pressure, to production equipment
Requirement it is higher, and the more difficult control of its reaction process, product yield is low, and production cost is too high.
Meanwhile, there is also in prior art and first prepare propargyl tert-butyl carbonate, then the cyclization under catalyst action
The method for forming mesomethylene carbon vinyl acetate.But catalysis needed for the method for propargyl tert-butyl carbonate is prepared in prior art
The usage amount of agent is big, and cost of material and cost for purification are high.
The content of the invention
The technical problem to be solved is the cost for preparing propargyl tert-butyl carbonate in prior art
A kind of high problem, there is provided preparation method of propargyl tert-butyl carbonate.
The technical scheme that present invention solution above-mentioned technical problem is adopted is as follows：
A kind of preparation method of propargyl tert-butyl carbonate is provided, including：In the case where atmosphere is dried, by propargyl alcohol, two uncles
Butyl dicarbonate and catalyst mix, and are reacted under agitation, and the tertiary fourth of the propargyl is obtained Jing after vacuum distillation
Base carbonic ester；The catalyst is selected from one or more in diethylamine, triethylamine, pyridine.
Meanwhile, present invention also offers a kind of preparation method of mesomethylene carbon vinyl acetate, comprises the steps：
S1, propargyl tert-butyl carbonate is prepared using method as above；
S2, by the propargyl tert-butyl carbonate with mix containing mercury catalyst, reacted under agitation and essence
Evaporate.
In the preparation method of the propargyl tert-butyl carbonate that the present invention is provided, using special catalyst (diethylamine, three
Ethamine, pyridine), improve catalytic efficiency, and the usage amount of required catalyst is little, so as to reduce cost of material and after
Continuous waste disposal cost.
Specific embodiment
In order that technical problem solved by the invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
The preparation method of the propargyl tert-butyl carbonate that the present invention is provided includes：In the case where atmosphere is dried, by propargyl alcohol, two
Di-tert-butyidicarbonate and catalyst mix, and are reacted under agitation, and the propargyl uncle is obtained Jing after vacuum distillation
Butylcarbonate.
The catalyst adopted in the present invention is selected from one or more in diethylamine, triethylamine, pyridine.Especially preferably three
Ethamine is used as catalyst.
, according to the invention it is preferred to first mix propargyl alcohol and catalyst, then di-t-butyl is added by the way of being added dropwise
Two carbonic esters.By first mixing propargyl alcohol and catalyst, and stir, make catalyst dispersed in propargyl alcohol.So
Afterwards di-tert-butyl dicarbonic acid ester is added by the way of being added dropwise, the di-tert-butyl dicarbonic acid ester for now adding is relative to propargyl alcohol
On a small quantity, in instantaneously relatively excessive propargyl alcohol, di-tert-butyl dicarbonic acid ester can be made to be fully contacted reaction with propargyl alcohol, makes reaction
More completely, conversion rate of products is improved.Simultaneously as the reaction is exothermic reaction, under agitation, by the way of being added dropwise
Add di-tert-butyl dicarbonic acid ester to control effectively to course of reaction, it is to avoid in reaction system local reaction excessively acutely and
Cause to be heated uneven, so as to avoid the problem that caused side reaction product increases because being heated inequality.
For above-mentioned dropwise addition process, under preferable case, at 0-60 DEG C, time for adding is 0.5-2h to temperature control.
According to the present invention, under catalyst action, di-tert-butyl dicarbonic acid ester and propargyl alcohol haptoreaction work as di-t-butyl
After the addition of two carbonic esters is finished, to make reaction more abundant, stirring reaction is preferably continued to.It is described under preferable case in the present invention
Reaction temperature is 0-80 DEG C, and the reaction time is 1-6h.
In the preparation method of the propargyl tert-butyl carbonate that the present invention is provided, using in diethylamine, triethylamine, pyridine
One or more as catalyst, the amount of the catalyst needed for reaction is fewer than existing catalyst.Under preferable case, the alkynes third
Alcohol, di-tert-butyl dicarbonic acid ester, the mol ratio of catalyst are 1：1-2：0.01-5.
For preferably to reaction be monitored, make reaction more complete, preferably during the course of the reaction adopt gas-chromatography pair
Reaction process is monitored.When being shown without propargyl alcohol and/or during di-tert-butyl dicarbonic acid ester raw material by gas-chromatography, that is, show
Reaction terminates.
After above-mentioned reaction terminates, rectification under vacuum is carried out to reactant liquor, you can obtain required propargyl tert-butyl carbonate.
For above-mentioned reaction, need to carry out in the case where atmosphere is dried, it is preferred to use inert gas is protected to course of reaction.Institute
State inert gas and be preferably nitrogen.
Invention also provides a kind of preparation method of mesomethylene carbon vinyl acetate, comprises the steps：
S1, propargyl tert-butyl carbonate is prepared using method as above；
S2, by the propargyl tert-butyl carbonate with mix containing mercury catalyst, reacted under agitation and essence
Evaporate.
Such as step S2, prepared after propargyl tert-butyl carbonate using preceding method, conventional method can be adopted, by institute
State propargyl tert-butyl carbonate and mix containing mercury catalyst, reacted under agitation, you can reaction generates methylene
Ethylene carbonate, then carries out rectifying to product.
In above-mentioned reaction, what is adopted can adopt for conventional, such as TFMS mercury containing mercury catalyst.Mercurous catalysis
The consumption of agent is also conventional, without particular/special requirement in the present invention, be will not be described here.
In the presence of containing mercury catalyst, exothermic heat of reaction is obvious.(such as magnetic agitation or mechanical agitation) is stirred, can
Avoid because be heated in reaction vessel it is uneven cause side reaction product to increase problem.
The feed postition of catalyst preferably divides 2-10 addition using adding or being slowly added dropwise by several times, preferably.
, according to the invention it is preferred to first mix propargyl tert-butyl carbonate with solvent, after stirring, add mercurous
Catalyst.In the present invention, the solvent that can be adopted selected from dichloromethane, ethyl acetate, methyl tertiary butyl ether(MTBE), dimethyl carbonate,
One or more in toluene.Under conditions of above-mentioned solvent is present, reaction can be control effectively.In the present invention, solvent
Addition can in interior variation in a big way, under preferable case, the addition of the propargyl tert-butyl carbonate and solvent it
Mol ratio is 1：0-10, more preferably 1:1-8.
Due to the catalytic action containing mercury catalyst, the ring-closure reaction of propargyl tert-butyl carbonate is more violent, to avoid
Reaction excessively acutely, in the present invention, is preferably added to 1,1,3,3- tetramethylurea.Under preferable case, the propargyl tert-butyl group carbon
The mol ratio of the addition of acid esters and 1,1,3,3- tetramethylureas is 1：0-0.1, more preferably 1:0.01-0.1.
In above-mentioned steps S2, reaction temperature is preferably -10～60 DEG C, and the reaction time is 1-8h.
As it was previously stated, similar, preferably reaction process is monitored by gas-chromatography, when gas-chromatography is shown without alkynes
During propyl group tert-butyl carbonate, that is, show that reaction terminates.
Reaction generates mesomethylene carbon vinyl acetate after terminating.
, according to the invention it is preferred to add Na in reactant liquor2S·5H2O, and being stirred, with mercurous in reactant liquor
Catalyst is processed.Under preferable case, the propargyl tert-butyl carbonate and Na2S·5H2The ratio of the addition of O is 1：
0.001-0.05, preferably 1：0.001-0.01.
Subsequently carry out rectification under vacuum process.
For ease of the carrying out of subsequent purification process, the efficiency of product purification is improved, under preferable case, by the rectifying
Afterwards, the content for making cut methylene ethylene carbonate reaches more than 85.0%, more preferably 85.0%-99.0%.
, according to the invention it is preferred in the case of, in step S2, after rectifying, purification processes are carried out to cut；The purification
Processing method is：Decrease temperature crystalline is carried out to cut, crystal and raffinate is obtained, crystal is isolated；Then crystal is heated, then
Solid matter is isolated, the mesomethylene carbon vinyl acetate is obtained.
By cooling, target product mesomethylene carbon vinyl acetate preferential crystallization, mesomethylene carbon vinyl acetate content is formed more
The higher raffinate of high crystal and magazine content, separates to crystal and raffinate.Then crystal heated again, makes cooling
Preferentially melted out and separated by the magazine composition that methylene ethylene carbonate crystallizes parcel in crystallization process, so as to further improve methylene
Base ethylene carbonate purity.
According to the present invention, it should be noted that initial temperature when carrying out decrease temperature crystalline affects larger to refining effect, if
Temperature is too low, easily makes material tied, does not reach purification effect, if temperature is too high, cooling will be caused time-consuming long, reduces efficiency.
Under preferable case, in step S2, after rectifying, cut is started into cooling from 18-30 DEG C.
During above-mentioned decrease temperature crystalline, rate of temperature fall also has considerable influence, and cooling is too fast also to make boring crystallization too fast,
Be unfavorable for that methylene ethylene carbonate is separated with other components, under preferable case, the rate of temperature fall during cooling be 0.5-2 DEG C/
h.Similar, heating rate during heating is also unsuitable too fast, if heating rate is too fast, be unfavorable for other components melt out in order and
Separate.Under preferable case, the heating rate during heating is 0.5-2 DEG C/h.
It is further to improve yield according to the present invention, under preferable case, in step S2, also includes to the raffinate
Rectifying is carried out, secondary cut is obtained；Then the purification processes are carried out to secondary cut using aforesaid proposition processing method.
As it was previously stated, when preparing mesomethylene carbon vinyl acetate by propargyl tert-butyl carbonate reaction, atmosphere need to be dried
Under carry out, it is preferred to use inert gas is protected to course of reaction.The inert gas is preferably nitrogen.
Mesomethylene carbon vinyl acetate of the purity more than 99.9% can be prepared by said method.
The present invention compared with prior art, with advantages below：
1st, more excellent synthetically prepared route is adopted, it is raw materials used except major part is inexpensive, it is easy to get；
2nd, present invention process is simple, course of reaction normal temperature and pressure, is adapted to industrialized production；
3rd, by changing charging technology, the consumption of partial material is optimized；
4th, product purity is high after purification processes, up to more than 99.9%.
The present invention is further detailed by the following examples.
Embodiment 1
The present embodiment is used to illustrate the preparation method of mesomethylene carbon vinyl acetate crude product disclosed by the invention.
Under room temperature condition, propilolic alcohol 350g (6.24mol), triethylamine 325g are sequentially added in 2L there-necked flasks
(3.20mol), after magnetic agitation 5min, di-tert-butyl dicarbonic acid ester 1360g (6.24mol) is slowly dropped into, is controlled after dripping off anti-
Oil bath temperature is answered at 25 DEG C or so, after dripping off, gas-chromatography monitoring reaction process reacts altogether 5h, and reaction is complete.Plus short vertical thorn
Still is protected, and is removed reaction under reduced pressure and is generated light component and triethylamine, collects propargyl tert-butyl carbonate crude product 878g, gas
The main content 92.3% of phase chromatogram detection product, yield 83.3%.
In 1L there-necked flasks, under the conditions of ice-water bath, propargyl tert-butyl carbonate 432g (2.76mol, gas phase color are initially charged
The main content of spectrum detection is 92.3%) dimethyl carbonate 300ml and 1,1,3,3- tetramethylurea 0.65g (5.6mmol), and magnetic force is stirred
After mixing 10min, fraction time adds TFMS mercury to amount to 2.5g (5.0mmol), every 1h, gas chromatographic detection reactant liquor,
Until when total amount accumulation is to 2.5g mercury salts, solution colour change is obvious in reactor, rapidly goes to dark brown solution, gas-chromatography
Detection, without intermediate, reaction is complete, and now target compound gas-chromatography content is 31%, adds the Na of 2.0g2S·5H2O
After stir about 1h, filter, collect filtrate decompression and distill to obtain mesomethylene carbon vinyl acetate crude product 208g, gas chromatographic detection product
Main content 92.0%, yield 69.2%.
Embodiment 2
The present embodiment is used to illustrate the preparation method of mesomethylene carbon vinyl acetate crude product disclosed by the invention.
Under room temperature condition, propilolic alcohol 100g (1.78mol), triethylamine 338g are sequentially added in 1L there-necked flasks
(3.56mol), after magnetic agitation 5min, di-tert-butyl dicarbonic acid ester 400g (1.83mol) is slowly dropped into, control reaction after dripping off
At 45 DEG C or so, after dripping off, gas-chromatography monitoring reaction process reacts altogether 4h to oil bath temperature, and reaction is complete.Plus short vertical thorn point
Fractional distillation column is protected, and is removed reaction under reduced pressure and is generated light component and triethylamine, collects propargyl tert-butyl carbonate crude product 220g, gas phase
The main content 94.3% of chromatogram detection product, yield 74.6%.
In 1L there-necked flasks, under the conditions of ice-water bath, propargyl tert-butyl carbonate 202g (1.29mol, gas phase color are initially charged
The main content of spectrum detection is 94.3%) 1,1,3,3- tetramethylurea 0.30g (2.6mmol), and after magnetic agitation 10min, fraction time adds
Enter TFMS mercury and amount to 0.95g (1.9mmol), every time plus fashionable, reaction very exothermic, gas chromatographic detection reactant liquor,
Until when total amount accumulation is to 0.95g mercury salts, solution colour change is obvious in reactor, rapidly goes to dark brown solution, gas phase color
Spectrum detection, without intermediate, reaction is complete, and now target compound gas-chromatography content is 71%, adds the Na of 1.0g2S·
5H2After O stir about 1h, filter, collect filtrate decompression and distill to obtain mesomethylene carbon vinyl acetate crude product 80g, gas chromatographic detection
The main content 89.0% of product, yield 55.2%.
Embodiment 3
The present embodiment is used to illustrate the preparation method of mesomethylene carbon vinyl acetate crude product disclosed by the invention.
Under room temperature condition, propilolic alcohol 200g (3.56mol), pyridine 540g (6.82mol) are sequentially added in 2L there-necked flasks,
After magnetic agitation 5min, di-tert-butyl dicarbonic acid ester 800g (3.66mol) is slowly dropped into, control reaction oil bath temperature exists after dripping off
80 DEG C or so, after dripping off, gas-chromatography monitoring reaction process reacts altogether 6h, and reaction is complete.Plus short vertical thorn still protection,
Remove reaction under reduced pressure and generate light component and triethylamine, collect propargyl tert-butyl carbonate crude product 508g, gas chromatographic detection
The main content 95.0% of product, yield 86.9%.
In 1L there-necked flasks, under the conditions of ice-water bath, propargyl tert-butyl carbonate 200g (1.28mol, gas phase color are initially charged
The main content of spectrum detection is 95.0%) dichloromethane 200ml, and after magnetic agitation 10min, fraction time adds TFMS mercury to be total to
Meter 1.0g (2.0mmol), every 1h, gas chromatographic detection reactant liquor, until total amount is accumulated when arriving 1.0g mercury salts, it is molten in reactor
Substantially, gas chromatographic detection, without intermediate, reacts complete to liquid color change, and now target compound gas-chromatography content is
28.6%, add the Na of 2.0g2S·5H2After O stir about 1h, filter, collect filtrate decompression distillation, obtain mesomethylene carbon vinyl acetate
Crude product 76g, the main content 90.4% of gas chromatographic detection product, yield 54.0%.
Embodiment 4
The present embodiment is used to illustrate the preparation method of mesomethylene carbon vinyl acetate crude product disclosed by the invention.
Under room temperature condition, propilolic alcohol 350g (6.24mol), diethylamine 65g are sequentially added in 2L there-necked flasks
(0.89mol), after magnetic agitation 5min, di-tert-butyl dicarbonic acid ester 1360g (6.24mol) is slowly dropped into, room is continued after dripping off
Temperature reaction, gas-chromatography monitoring reaction process, reacts altogether 8h, and reaction is complete.Plus short vertical thorn still protection, remove under reduced pressure anti-
Light component and triethylamine should be generated, propargyl tert-butyl carbonate crude product 918g, the main content of gas chromatographic detection product is collected
94.0%, yield 88.8%.
In 1L there-necked flasks, under the conditions of ice-water bath, propargyl tert-butyl carbonate 500g (3.20mol, gas phase color are initially charged
The spectrum main content of detection for 94.0%), methyl tertiary butyl ether(MTBE) 400ml and 1,1,3,3- tetramethylurea 0.75g (6.4mmol), magnetic force
After stirring 10min, fraction time adds TFMS mercury, every 1h, gas chromatographic detection reactant liquor, until total amount accumulation is arrived
During 3.4g (6.8mmol) mercury salt, solution colour change is obvious in reactor, rapidly goes to dark brown solution, gas chromatographic detection,
Without intermediate, reaction is complete, and now target compound gas-chromatography content is 25%, adds the Na of 4.0g2S·5H2O is stirred
After about 1h, filter, collect filtrate decompression distillation, obtain mesomethylene carbon vinyl acetate crude product 203g, gas chromatographic detection product master
Content 79.6%, yield 50.4%.
Embodiment 5
The present embodiment is used to illustrate the preparation method of mesomethylene carbon vinyl acetate crude product disclosed by the invention.
Under room temperature condition, propilolic alcohol 350g (6.24mol), triethylamine 65g are sequentially added in 2L there-necked flasks
(0.64mol), after magnetic agitation 5min, di-tert-butyl dicarbonic acid ester 1360g (6.24mol) is slowly dropped into, is controlled after dripping off anti-
Answer oil bath temperature at 55 DEG C or so, gas-chromatography monitoring reaction process reacts altogether 4h, and reaction is complete.Plus short vertical thorn still
Protection, removes reaction under reduced pressure and generates light component and triethylamine, collects propargyl tert-butyl carbonate crude product 910g, gas-chromatography
The main content 96.1% of detection product, yield 89.8%.
In 1L there-necked flasks, under the conditions of ice-water bath, propargyl tert-butyl carbonate 500g (3.20mol, gas phase color are initially charged
The spectrum main content of detection for 96.1%), ethyl acetate 400ml and 1,1,3,3- tetramethylurea 0.75g (6.4mmol), magnetic agitation
After 10min, fraction time adds TFMS mercury, every 1h, gas chromatographic detection reactant liquor, until 4.2g is arrived in total amount accumulation
(8.4mmol) during mercury salt, solution colour change is obvious in reactor, rapidly goes to dark brown solution, gas chromatographic detection, without
Intermediate, reaction is complete, and now target compound gas-chromatography content is 35%, adds Na2S·5H2O, 5.0g stir about 1h
Afterwards, filter, collect filtrate decompression distillation, obtain mesomethylene carbon vinyl acetate crude product 256g, the main content of gas chromatographic detection product
93.5%, yield 74.7%.
Embodiment 6
The present embodiment is used to illustrate the method for purification of mesomethylene carbon vinyl acetate disclosed by the invention.
Under room temperature condition, into static fusion-crystallization phases of the 20L similar to tubular heat exchanger, by N2Press-in 18.0Kg realities
Apply crude product after the mesomethylene carbon vinyl acetate rectifying that example 5 is prepared, the main content 93.5% of gas chromatographic detection product.Arrange
Initial 24 DEG C of cooling point, opens heat transferring medium cycling switch, lowers the temperature 1 DEG C every 1h, and to being cooled to 19 DEG C, tube wall starts knot occur
Crystalline substance, continues echelon and is cooled to 16 DEG C, and existing major part crystal is separated out, and crystal habit is in little block tetrahedron regular distribution, is stopped
In this temperature 2h, still there is a small amount of uncured low concentration raffinate, and color is deeper, releases, weigh 3.2Kg, and gas-chromatography shows
Raffinate methylene ethylene carbonate content is 61.0%.
Start slow intensification to crystal, every 1h 1 DEG C of high-temperature is risen, the melting liquid collected in sweating effort is discharged, by each
Detected, when being warming up to 30 DEG C, gas-chromatography shows discharges liquid hold-up up to 99.2%, judges that container product is close to
It is qualified, temperature is improved to 45 DEG C, remaining solid is melted rapidly, obtain high-purity mesomethylene carbon vinyl acetate 10.2Kg, gas phase color
Spectrum shows that mesomethylene carbon vinyl acetate content is 99.93%, and colourity is less than 20Hazen, qualification rate 56.7%.What process collection was arrived
Uncured liquid and sweating return rectifying, then carry out crystallization purifying, move in circles.
Embodiment 7
The present embodiment is used to illustrate the method for purification of mesomethylene carbon vinyl acetate disclosed by the invention.
Each batch crystallization uncured liquid that embodiment 6 is collected and sweating merge and amount to 34Kg, in input rectifying still
The crude product 22Kg of vinyl acetate containing mesomethylene carbon, the main content 89.1% of gas chromatographic detection product are obtained after rectifying.It is placed on
In the 20L static state fusion-crystallization phases, initial 20 DEG C of cooling point is set, heat transferring medium cycling switch is opened, is lowered the temperature 1 DEG C every 1h, extremely
14 DEG C are cooled to, tube wall starts crystallization occur, continue echelon and be cooled to 10 DEG C, most of crystal is separated out, and crystal habit is in fritter
Shape tetrahedron regular distribution, stops in this temperature 2h, still there is a small amount of uncured low concentration raffinate, and color is deeper, releases, and claims
Weight 4.3Kg, gas-chromatography shows that raffinate methylene ethylene carbonate content is 71.0%.
Start slow intensification to crystal, every 1h 1 DEG C of high-temperature is risen, the melting liquid collected in sweating effort is discharged, by each
Detected, when being warming up to 27 DEG C, gas-chromatography shows discharges liquid hold-up up to 98.4%, improves temperature to 45 DEG C, rapidly
Melt remaining solid, obtain high-purity mesomethylene carbon vinyl acetate 9.1Kg, gas-chromatography shows mesomethylene carbon vinyl acetate content
For 99.91%, colourity is less than 20Hazen, qualification rate 41.4%.The uncured liquid and sweating that process collection is arrived returns rectifying,
Crystallization purifying is carried out again, is moved in circles.Embodiment 8
The present embodiment is used to illustrate the method for purification of mesomethylene carbon vinyl acetate disclosed by the invention.
Under room temperature condition, into static fusion-crystallization phases of the 20L similar to tubular heat exchanger, by N2Press-in 17Kg is implemented
Crude product after the mesomethylene carbon vinyl acetate rectifying that example 4 is prepared, the main content 79.6% of gas chromatographic detection product.Arrange just
Begin 18 DEG C of cooling point, opens heat transferring medium cycling switch, lowers the temperature 0.5 DEG C every 1h, and to being cooled to 8 DEG C, tube wall starts knot occur
Crystalline substance, continues echelon and is cooled to 6 DEG C, and existing major part crystal is separated out, and crystal habit is in little block tetrahedron regular distribution, is rested on
This temperature 2h, still there is a small amount of uncured low concentration raffinate, and color is deeper, releases, and weigh 4.5Kg, and gas-chromatography shows residual
Liquid methylene ethylene carbonate is content 67.5%.
Start slow intensification to crystal, every 1h 0.5 DEG C of high-temperature is risen, discharge the melting liquid collected in sweating effort, by
Respectively detected, when being warming up to 26 DEG C, gas-chromatography shows discharges liquid hold-up up to 98.5%, judges that container product connects
It is near qualified, temperature is improved to 45 DEG C, remaining solid is melted rapidly, obtain high-purity mesomethylene carbon vinyl acetate 6.1Kg, gas phase color
Spectrum shows that mesomethylene carbon vinyl acetate content is 99.9%, and colourity is less than 20Hazen, qualification rate 35.8%.What process collection was arrived
Uncured liquid and sweating return rectifying, then carry out crystallization purifying, move in circles.
Embodiment 9
The present embodiment is used to illustrate the method for purification of mesomethylene carbon vinyl acetate disclosed by the invention.
Under room temperature condition, into static fusion-crystallization phases of the 20L similar to tubular heat exchanger, by N2Press-in 19.4Kg realities
Apply crude product after the mesomethylene carbon vinyl acetate rectifying that example 1 is prepared, the main content 92.0% of gas chromatographic detection product.Arrange
Initial 25 DEG C of cooling point, opens heat transferring medium cycling switch, lowers the temperature 2 DEG C every 1h, and to being cooled to 18 DEG C, tube wall starts knot occur
Crystalline substance, continues echelon and is cooled to 14 DEG C, and existing major part crystal is separated out, and crystal habit is in little block tetrahedron regular distribution, is stopped
In this temperature 2h, still there is a small amount of uncured low concentration raffinate, and color is deeper, releases, weigh 3.4Kg, and gas-chromatography shows
Raffinate methylene ethylene carbonate content is 76.1%.
Start slow intensification to crystal, every 1h 2 DEG C of high-temperature is risen, the melting liquid collected in sweating effort is discharged, by each
Detected, when being warming up to 29 DEG C, gas-chromatography shows discharges liquid hold-up up to 99.2%, judges that container product is close to
It is qualified, temperature is improved to 45 DEG C, remaining solid is melted rapidly, obtain high-purity mesomethylene carbon vinyl acetate 9.8Kg, gas-chromatography
Content 99.92%, colourity is less than 20Hazen, qualification rate 50.5%.The uncured liquid and sweating that process collection is arrived returns essence
Evaporate, then carry out crystallization purifying, move in circles.
From above-described embodiment as can be seen that being catalyzed needed for the preparation method of the propargyl tert-butyl carbonate of present invention offer
Agent content is few.The purity of mesomethylene carbon vinyl acetate prepared by the preparation method of mesomethylene carbon vinyl acetate is high, especially by
After the purification processing method that the present invention is provided is purified, purity is higher.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of propargyl tert-butyl carbonate, it is characterised in that include：In the case where atmosphere is dried, by propargyl alcohol,
Di-tert-butyl dicarbonic acid ester and catalyst mix, and are reacted under agitation, and the propargyl is obtained Jing after vacuum distillation
Tert-butyl carbonate；
The catalyst is selected from one or more in diethylamine, triethylamine, pyridine.
2. preparation method according to claim 1, it is characterised in that first propargyl alcohol and catalyst are mixed, is then adopted
The mode of dropwise addition adds di-tert-butyl dicarbonic acid ester；
The temperature during dropwise addition is 0-60 DEG C, and time for adding is 0.5-2h.
3. preparation method according to claim 1, it is characterised in that the reaction temperature is 0-80 DEG C, the reaction time is
1-6h。
4. the preparation method according to any one in claim 1-3, it is characterised in that the propargyl alcohol, di-t-butyl
Two carbonic esters, the mol ratio of catalyst are 1：1-2：0.01-5.
5. a kind of preparation method of mesomethylene carbon vinyl acetate, it is characterised in that comprise the steps：
The method of S1, employing as described in any one in claim 1-4 prepares propargyl tert-butyl carbonate；
S2, by the propargyl tert-butyl carbonate with mix containing mercury catalyst, reacted under agitation and rectifying.
6. preparation method according to claim 5, it is characterised in that in step S2, first by propargyl tert-butyl group carbon
Acid esters mixes with solvent, after stirring, 1,1,3,3- tetramethyl of mercurous class catalyst and selective addition is added by several times
Urea, is reacted under agitation；
The solvent is selected from one or more in dichloromethane, ethyl acetate, methyl tertiary butyl ether(MTBE), dimethyl carbonate, toluene；
The mol ratio of the addition of the propargyl tert-butyl carbonate, solvent and 1,1,3,3- tetramethylureas is 1：0-10：0-
0.1；
The reaction temperature is -10～60 DEG C, and the reaction time is 1-8h.
7. preparation method according to claim 5, it is characterised in that in step S2, also include before the rectifying
Na is added in reactant liquor2S·5H2O, and be stirred；The propargyl tert-butyl carbonate and Na2S·5H2The addition of O
Mol ratio be 1：0.001-0.05；
After the rectifying, the content for making cut methylene ethylene carbonate reaches more than 85.0%.
8. the preparation method according to any one in claim 5-7, it is characterised in that in step S2, after rectifying,
Purification processes are carried out to cut；
The purification processing method is：Decrease temperature crystalline is carried out to cut, crystal and raffinate is obtained, crystal is isolated；
Then crystal is heated, then isolates solid matter, obtain the mesomethylene carbon vinyl acetate.
9. preparation method according to claim 8, it is characterised in that in step S2, after rectifying, by cut from 18-
30 DEG C start cooling；
The rate of temperature fall during cooling is 0.5-2 DEG C/h, and the heating rate during heating is 0.5-2 DEG C/h.
10. preparation method according to claim 8, it is characterised in that in step S2, also include entering the raffinate
Row rectifying, obtains secondary cut；
The purification processes are carried out to secondary cut.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610976313.XA CN106631800A (en) | 2016-11-07 | 2016-11-07 | A method of preparing propargyl tert-butyl carbonate and a method of preparing methylene ethylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610976313.XA CN106631800A (en) | 2016-11-07 | 2016-11-07 | A method of preparing propargyl tert-butyl carbonate and a method of preparing methylene ethylene carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106631800A true CN106631800A (en) | 2017-05-10 |
Family
ID=58805187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610976313.XA Pending CN106631800A (en) | 2016-11-07 | 2016-11-07 | A method of preparing propargyl tert-butyl carbonate and a method of preparing methylene ethylene carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106631800A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845506A (en) * | 2021-10-18 | 2021-12-28 | 惠州市宙邦化工有限公司 | Dynamic crystallization purification method of ethylene carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101175743A (en) * | 2005-05-12 | 2008-05-07 | 赛拓有限责任公司 | High-purity vinylene carbonate and a method of purifying vinylene carbonate |
-
2016
- 2016-11-07 CN CN201610976313.XA patent/CN106631800A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101175743A (en) * | 2005-05-12 | 2008-05-07 | 赛拓有限责任公司 | High-purity vinylene carbonate and a method of purifying vinylene carbonate |
Non-Patent Citations (2)
| Title |
|---|
| DINESH CHALASANI ET AL.: "Methylene ethylene carbonate: Novel additive to improve the high temperature performance of lithium ion batteries", 《JOURNAL OF POWER SOURCES 》 * |
| HIROFUMI YAMAMOTO ET AL.: "Hg(OTf)2-Catalyzed cyclization of alkynyl tert-butylcarbonate leading to cyclic enol carbonate", 《TETRAHEDRON LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845506A (en) * | 2021-10-18 | 2021-12-28 | 惠州市宙邦化工有限公司 | Dynamic crystallization purification method of ethylene carbonate |
| US11958820B2 (en) | 2021-10-18 | 2024-04-16 | Shenzhen Capchem Technology Co., Ltd. | Method for purifying ethylene carbonate through dynamic crystallization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4297267B2 (en) | Method for producing high-purity fatty acid alkyl ester by single-stage continuous process | |
| CN101210005B (en) | Method for preparing fluoroethylene carbonate | |
| US4939294A (en) | Preparation of ultra high purity methyl acetate | |
| CN103570667B (en) | Method for continuously preparing epsilon-lactone | |
| JP2022554215A (en) | Gas-liquid bubbling bed reactor, reaction system, and method for synthesizing carbonate esters | |
| CN106632224B (en) | A kind of preparation method of mesomethylene carbon vinyl acetate | |
| CN104364194A (en) | Process for the production of chemical compounds from carbon dioxide | |
| CN105481826A (en) | Preparation method of ethylene sulfate | |
| CN107501096A (en) | Rectifying couples the method for preparing electron level dimethyl carbonate with crystallization | |
| CN1305452A (en) | Method for purifying acrylic acid or methacrylic acid by crystallization and distillation | |
| CN105439857A (en) | Method and apparatus for producing methyl ethyl carbonate | |
| CN102030736A (en) | Method for synthesizing chlorinated carbonate | |
| CN106146310A (en) | A kind of device producing dimethyl carbonate and technique | |
| CN113354540A (en) | Method for efficiently and continuously preparing methyl ethyl carbonate | |
| CN102093396A (en) | Method for preparing Grignard reagent | |
| CN106631800A (en) | A method of preparing propargyl tert-butyl carbonate and a method of preparing methylene ethylene carbonate | |
| CN101168505B (en) | Preparation method for sec-butyl acetate with product separating and reclaiming technique | |
| CN109776322B (en) | Method for preparing high-purity methyl ethyl carbonate by using partition wall type reaction rectifying tower | |
| CN102188832B (en) | Separation column body for reaction distillation | |
| CN108191605A (en) | The technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol | |
| CN110862323A (en) | Synthesis method of diaminodiphenylethane compound | |
| JP2002294277A (en) | Method for producing lower alkyl ester | |
| CN107673946A (en) | The method that continuity method isomerization produces durol | |
| CN110386915A (en) | The separation method of sulfuric acid vinyl ester, n-hexane and 1,2- dichloroethanes mixed liquor | |
| CN109422718A (en) | The preparation method of ethyl sulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170510 |