CN106632224B - A kind of preparation method of mesomethylene carbon vinyl acetate - Google Patents
A kind of preparation method of mesomethylene carbon vinyl acetate Download PDFInfo
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- CN106632224B CN106632224B CN201610977168.7A CN201610977168A CN106632224B CN 106632224 B CN106632224 B CN 106632224B CN 201610977168 A CN201610977168 A CN 201610977168A CN 106632224 B CN106632224 B CN 106632224B
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- 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
- C07D317/38—Ethylene carbonate
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
To overcome the problems, such as that the loss of mesomethylene carbon vinyl acetate product method of purification is serious, time-consuming, purity is low in the prior art, the present invention provides a kind of methods of purification of mesomethylene carbon vinyl acetate, include the following steps: S1, provide mesomethylene carbon vinyl acetate crude product；S2, purification processes, the purification processing method are carried out to above-mentioned mesomethylene carbon vinyl acetate crude product are as follows: decrease temperature crystalline is carried out to the mesomethylene carbon vinyl acetate crude product, crystal and raffinate is obtained, isolates crystal；Then crystal is heated, and isolates solid matter, obtain mesomethylene carbon vinyl acetate finished product.Meanwhile the invention also discloses the methods for preparing mesomethylene carbon vinyl acetate based on the above method.Mesomethylene carbon vinyl acetate product method of purification provided by the invention loses less, is time-consuming short, with high purity, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of mesomethylene carbon vinyl acetate.
Background technique
Mesomethylene carbon vinyl acetate is a kind of novel lithium-ion battery electrolytes additive.Its energy is reported according to existing literature
Stable SEI film is formed in anode, effectively improves battery life and high-temperature behavior to be formed, and there is similar be even better than
The function of vinylene carbonate (VC).
Synthesizing the method for mesomethylene carbon vinyl acetate in the prior art includes: by propilolic alcohol and CO2In catalyst and high pressure
Under the conditions of reacted, so that mesomethylene carbon vinyl acetate be prepared.But this method carries out under high pressure, to production equipment
It is more demanding, and its reaction process is more difficult to control, and product yield is low, and production cost is too high.
Meanwhile in the prior art there is also first preparing propargyl tert-butyl carbonate, then cyclization under the action of catalyst
The method for forming mesomethylene carbon vinyl acetate.But this method need to be largely using mercurous sulfonate or containing golden sulfonate etc., a side
Looking unfamiliar, it is very expensive to produce cost of material, brings high production cost, and safety and environmental protection side is given in a large amount of offal treatments of another aspect process
Bring major hidden danger in face.
Also, in the preparation method of various mesomethylene carbon vinyl acetates in the prior art, to the purification process master of product
It concentrates on column chromatography and distills two kinds repeatedly, but above two scheme has that product loss is serious, time-consuming and product is pure
Spend low problem.
Summary of the invention
The technical problem to be solved by the present invention is to for mesomethylene carbon vinyl acetate product method of purification in the prior art
The problem that loss is serious, time-consuming, purity is low, provides a kind of preparation method of propargyl tert-butyl carbonate.
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
The present invention also provides a kind of preparation methods of mesomethylene carbon vinyl acetate, include the following steps:
Step 1: propargyl tert-butyl carbonate is provided；
The propargyl tert-butyl carbonate is prepared via a method which to obtain: under dry atmosphere, by propargyl alcohol, two uncles
Butyl dicarbonate and basic catalyst mixing, are reacted under agitation, obtain the propargyl tert-butyl carbonate；
The basic catalyst is selected from one of diethylamine, triethylamine or a variety of；
Step 2: the propargyl tert-butyl carbonate being mixed with containing mercury catalyst, is reacted under agitation,
Then Na is added into reaction solution2S·5H2O is simultaneously stirred, and by filtering and rectifying, it is thick to obtain mesomethylene carbon vinyl acetate
Product；The propargyl tert-butyl carbonate and Na2S·5H2The ratio between additive amount of O is 1:0.001-0.05；
Step 3: purification processes, the purification processing method are as follows: to institute are carried out to above-mentioned mesomethylene carbon vinyl acetate crude product
It states mesomethylene carbon vinyl acetate crude product and carries out decrease temperature crystalline, obtain crystal and raffinate, isolate crystal；Then crystal is added
Heat, and solid matter is isolated, obtain mesomethylene carbon vinyl acetate finished product；
Wherein, cool down since 18-30 DEG C to the mesomethylene carbon vinyl acetate crude product, the rate of temperature fall when cooling
For 0.5-2 DEG C/h；
The heating rate when heating is 0.5-2 DEG C/h.
Method of purification loss of material provided by the invention is few, product purity is high after time-consuming short, purification, up to 99.9% with
On.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, 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 used to explain
The present invention is not intended to limit the present invention.
The method of purification of mesomethylene carbon vinyl acetate provided by the invention includes the following steps:
S1, mesomethylene carbon vinyl acetate crude product is provided；
S2, purification processes, the purification processing method are as follows: to the Asia are carried out to above-mentioned mesomethylene carbon vinyl acetate crude product
Methyl carbonic acid vinyl acetate crude product carries out decrease temperature crystalline, obtains crystal and raffinate, isolates crystal；
Then crystal is heated, and isolates solid matter, obtain mesomethylene carbon vinyl acetate finished product.
Above-mentioned mesomethylene carbon vinyl acetate crude product can obtain for various approach, such as can voluntarily prepare, buy or pass through
Raffinate is recycled to obtain.
For the progress handled convenient for subsequent purification, the efficiency of product purification is improved, under preferable case, the methylene carbonic acid
In vinyl acetate crude product, the content of mesomethylene carbon vinyl acetate is 85.0% or more, more preferably 85.0%-99.0%.
When being purified to above-mentioned mesomethylene carbon vinyl acetate crude product, first the mesomethylene carbon vinyl acetate crude product is carried out
Decrease temperature crystalline obtains crystal and raffinate, isolates crystal；Then crystal is heated, and isolates solid matter, obtain Asia
Methyl carbonic acid vinyl acetate finished product.
By cooling, target product mesomethylene carbon vinyl acetate preferential crystallization forms mesomethylene carbon vinyl acetate content more
High crystal and the higher raffinate of magazine content, separates crystal and raffinate.Then crystal is heated again, makes to cool down
It is preferentially melted out and is separated by the magazine ingredient of methylene ethylene carbonate crystallization package in crystallization process, to further increase methylene
Base ethylene carbonate purity.
According to the present invention, it should be noted that initial temperature when carrying out decrease temperature crystalline is affected to refining effect, if
Temperature is too low, easily makes material tied, purification effect is not achieved, if temperature is excessively high, will lead to cooling and takes long time, and reduces efficiency.
Under preferable case, in the step S2, after rectifying, fraction is cooled down since 18-30 DEG C.
During above-mentioned decrease temperature crystalline, rate of temperature fall also has larger impact, and cooling is too fast also to make material crystallization too fast,
It is unfavorable for methylene ethylene carbonate to separate with other components, under preferable case, the rate of temperature fall when cooling is 0.5-2 DEG C/
h.Similar, heating rate when heating is also unsuitable too fast, if heating rate is too fast, be unfavorable for other components orderly melt out and
Separation.Under preferable case, the heating rate when heating is 0.5-2 DEG C/h.
It according to the present invention, further include to the raffinate in the step S2 under preferable case to further increase yield
Rectifying is carried out, the purification processes are then carried out to fraction using proposition processing method above-mentioned.
When being proposed by above-mentioned method of purification to mesomethylene carbon vinyl acetate crude product, loss of material is few, time-consuming is short, mentions
Product purity is high after pure, up to 99.9% or more.
Meanwhile the present invention also provides a kind of preparation method of mesomethylene carbon vinyl acetate, include the following steps:
Step 1: propargyl tert-butyl carbonate is provided；
Step 2: the propargyl tert-butyl carbonate is mixed with containing mercury catalyst, is reacted under agitation
And rectifying, obtain mesomethylene carbon vinyl acetate crude product；
Step 3: the mesomethylene carbon vinyl acetate crude product is purified using foregoing method, obtains methylene
Base ethylene carbonate finished product.
According to the present invention, above-mentioned propargyl tert-butyl carbonate can voluntarily be prepared.Prepare above-mentioned propargyl tert-butyl
Method in the prior art can be used in carbonic ester.But it prepares urged needed for the method for propargyl tert-butyl carbonate in the prior art
The usage amount of agent is big, and cost of material and cost for purification are high.
Under preferable case, according to the present invention, the propargyl tert-butyl carbonate is prepared via a method which to obtain: dry
Under pathogenic dryness atmosphere, propargyl alcohol, di-tert-butyl dicarbonic acid ester and basic catalyst are mixed, is reacted, is obtained under agitation
The propargyl tert-butyl carbonate.
Under preferable case, the basic catalyst is selected from one of diethylamine, triethylamine, pyridine or a variety of, more preferably
For triethylamine.In the preparation method of propargyl tert-butyl carbonate provided by the invention, using special catalyst (diethylamine,
Triethylamine, pyridine), improve catalytic efficiency, and the usage amount of required catalyst is small, thus reduce cost of material and
Subsequent waste disposal cost.
, according to the invention it is preferred to first mix propargyl alcohol and catalyst, di-t-butyl then is added by the way of being added dropwise
Two carbonic esters.It by first mixing propargyl alcohol and catalyst, and stirs evenly, keeps catalyst evenly dispersed in propargyl alcohol.So
Di-tert-butyl dicarbonic acid ester is added by the way of being added dropwise afterwards, the di-tert-butyl dicarbonic acid ester being added at this time 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 come into full contact with propargyl alcohol and reacted, make to react
More completely, conversion rate of products is improved.Simultaneously as the reaction is exothermic reaction, under agitation, by the way of dropwise addition
Di-tert-butyl dicarbonic acid ester, which is added, to control effectively to reaction process, avoid in reaction system local reaction excessively acutely and
Cause uneven heating even, so that side reaction product increases caused by avoiding the problem that because of uneven heating.
For above-mentioned dropwise addition process, under preferable case, temperature control is at 0-60 DEG C, time for adding 0.5-2h.
According to the present invention, under the action of catalyst, di-tert-butyl dicarbonic acid ester and propargyl alcohol haptoreaction, work as di-t-butyl
After two carbonic esters add, to keep reaction more abundant, preferably continue to be stirred to react.It is described under preferable case in the present invention
Reaction temperature is 0-80 DEG C, reaction time 1-6h.
In the preparation method of propargyl tert-butyl carbonate provided by the invention, using in diethylamine, triethylamine, pyridine
One or more to be used as catalyst, the amount for reacting required catalyst is fewer than existing catalyst.Under preferable case, the alkynes third
Alcohol, di-tert-butyl dicarbonic acid ester, catalyst molar ratio be 1:1-2:0.01-5.
To be preferably monitored to reaction, keeps reaction more complete, preferably use gas-chromatography pair during the reaction
Reaction process is monitored.When showing no propargyl alcohol and/or di-tert-butyl dicarbonic acid ester raw material by gas-chromatography, that is, show
Reaction terminates.
It is above-mentioned after reaction, to reaction solution carry out rectification under vacuum, required propargyl tert-butyl carbonate can be obtained.
For above-mentioned reaction, need to be carried out under dry atmosphere, it is preferred to use inert gas protects reaction process.Institute
Stating inert gas is preferably nitrogen.
According to the present invention, after obtaining propargyl tert-butyl carbonate, methylene carbonic acid can be prepared by existing method
Vinyl acetate crude product, such as above-mentioned steps two mix the propargyl tert-butyl carbonate with containing mercury catalyst, in stirring condition
Under carry out reaction and rectifying, obtain mesomethylene carbon vinyl acetate crude product.
In above-mentioned reaction, use containing mercury catalyst to be conventional, such as trifluoromethanesulfonic acid mercury can be used.Mercurous catalysis
The dosage of agent be also it is conventional, the present invention in there is no particular/special requirement, details are not described herein.
In under the action of containing mercury catalyst, exothermic heat of reaction is obvious.It is stirred (such as magnetic agitation or mechanical stirring), it can
It avoids the problem that causing side reaction product to increase due to uneven heating is even in reaction vessel.
The adding manner of catalyst preferably using being added or being slowly added dropwise by several times, preferably divides 2-10 addition.
, according to the invention it is preferred to first mix propargyl tert-butyl carbonate with solvent, after mixing evenly, add mercurous
Catalyst.In the present invention, the solvent that can use be selected from methylene chloride, ethyl acetate, methyl tertiary butyl ether(MTBE), dimethyl carbonate,
One of toluene is a variety of.Under the conditions of existing for the above-mentioned solvent, it can control effectively to reaction.In the present invention, solvent
Additive amount can change in a big way, under preferable case, the additive amount of the propargyl tert-butyl carbonate and solvent it
Molar 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
It reacts excessively violent, in the present invention, is preferably added to 1,1,3,3- tetramethylurea.Under preferable case, the propargyl tert-butyl carbon
Acid esters and 1, the molar ratio of the additive amount of 1,3,3- tetramethylurea are 1:0-0.1, more preferably 1:0.01-0.1.
In above-mentioned steps S2, reaction temperature is preferably -10~60 DEG C, reaction time 1-8h.
As previously mentioned, it is similar, preferably reaction process is monitored by gas-chromatography, when gas-chromatography shows no alkynes
When propyl tert-butyl carbonate, that is, show that reaction terminates.
Mesomethylene carbon vinyl acetate is generated after reaction.
, according to the invention it is preferred to add Na into reaction solution2S·5H2O, and be stirred, to mercurous in reaction solution
Catalyst is handled.Under preferable case, the propargyl tert-butyl carbonate and Na2S·5H2The ratio between additive amount of O is 1:
0.001-0.05, preferably 1:0.001-0.01.
Then carry out rectification under vacuum processing.
For the progress handled convenient for subsequent purification, the efficiency of product purification is improved, under preferable case, pass through the decompression essence
After evaporating, the content of fraction methylene ethylene carbonate is made to reach 85.0% or more, more preferably 85.0%-99.0%.
As previously mentioned, when preparing mesomethylene carbon vinyl acetate by propargyl tert-butyl carbonate reaction, it need to be in dry atmosphere
Lower progress, it is preferred to use inert gas protects reaction process.The inert gas is preferably nitrogen.
After obtaining mesomethylene carbon vinyl acetate crude product, using method of purification provided by the invention to mesomethylene carbon vinyl acetate
Crude product, which carries out purification, can be obtained the mesomethylene carbon vinyl acetate of high-purity (purity up to 99.9% or more).
Compared with prior art, the present invention having the advantage that
1, using route is more preferably synthetically prepared, raw materials used major part of removing is inexpensive, is easy to get；
2, present invention process is simple, reaction process normal temperature and pressure, is suitble to industrialized production；
3, by changing charging technology, the dosage of partial material is optimized；
4, high by product purity after purification processes, up to 99.9% or more.
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, propilolic alcohol 350g (6.24mol), triethylamine 325g are sequentially added in 2L there-necked flask
(3.20mol) after magnetic agitation 5min, is slowly dropped into di-tert-butyl dicarbonic acid ester 1360g (6.24mol), controls after dripping off anti-
Answer oil bath temperature at 25 DEG C or so, after dripping off, gas-chromatography monitors reaction process, amounts to reaction 5h, fully reacting.Add short vertical thorn
Still protection removes reaction under reduced pressure and generates light component and triethylamine, collects propargyl tert-butyl carbonate crude product 878g, gas
Phase chromatography detects the main content 92.3% of product, yield 83.3%.
In 1L there-necked flask, under the conditions of ice-water bath, propargyl tert-butyl carbonate 432g (2.76mol, gas phase color is first added
92.3%) it is that dimethyl carbonate 300ml and 1,1,3,3- tetramethylurea 0.65g (5.6mmol), magnetic force stirs that spectrum, which detects main content,
After mixing 10min, trifluoromethanesulfonic acid mercury is added in several times and amounts to 2.5g (5.0mmol), every 1h, gas chromatographic detection reaction solution,
Until solution colour variation is obvious in reaction kettle when total amount accumulation is to 2.5g mercury salt, dark brown solution, gas-chromatography are rapidly gone to
Detection, without intermediate, fully reacting, target compound gas-chromatography content is 31% at this time, and the Na of 2.0g is added2S·5H2O
After stir about 1h, filtering collects filtrate decompression and distills 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, propilolic alcohol 100g (1.78mol), triethylamine 338g are sequentially added in 1L there-necked flask
(3.56mol) after magnetic agitation 5min, is slowly dropped into di-tert-butyl dicarbonic acid ester 400g (1.83mol), reaction is controlled after dripping off
Oil bath temperature is at 45 DEG C or so, and after dripping off, gas-chromatography monitors reaction process, amounts to reaction 4h, fully reacting.Add short vertical thorn point
Fractional distillation column protection removes reaction under reduced pressure and generates light component and triethylamine, collects propargyl tert-butyl carbonate crude product 220g, gas phase
Chromatography detects the main content 94.3% of product, yield 74.6%.
In 1L there-necked flask, under the conditions of ice-water bath, propargyl tert-butyl carbonate 202g (1.29mol, gas phase color is first added
It is 94.3%), after 1,1,3,3- tetramethylurea 0.30g (2.6mmol), magnetic agitation 10min, to add in several times that spectrum, which detects main content,
Enter trifluoromethanesulfonic acid mercury and amounts to 0.95g (1.9mmol), when being added every time, reaction very exothermic, gas chromatographic detection reaction solution,
Until solution colour variation is obvious in reaction kettle when total amount accumulation is to 0.95g mercury salt, dark brown solution, gas phase color are rapidly gone to
Spectrum detection, without intermediate, fully reacting, target compound gas-chromatography content is 71% at this time, and the Na of 1.0g is added2S·
5H2After O stir about 1h, filtering collects filtrate decompression and distills 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, it is sequentially added in 2L there-necked flask propilolic alcohol 200g (3.56mol), pyridine 540g (6.82mol),
After magnetic agitation 5min, it is slowly dropped into di-tert-butyl dicarbonic acid ester 800g (3.66mol), control reaction oil bath temperature exists after dripping off
80 DEG C or so, after dripping off, gas-chromatography monitors reaction process, amounts to reaction 6h, fully reacting.Add short vertical thorn still protection,
It removes reaction under reduced pressure and generates 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 flask, under the conditions of ice-water bath, propargyl tert-butyl carbonate 200g (1.28mol, gas phase color is first added
It is 95.0%), after methylene chloride 200ml, magnetic agitation 10min, it is total that trifluoromethanesulfonic acid mercury to be added in several times that spectrum, which detects main content,
It counts 1.0g (2.0mmol), every 1h, gas chromatographic detection reaction solution, until when total amount accumulation is to 1.0g mercury salt, it is molten in reaction kettle
Liquid color change is obvious, gas chromatographic detection, without intermediate, fully reacting, at this time target compound gas-chromatography content be
28.6%, the Na of 2.0g is added2S·5H2After O stir about 1h, filtering collects filtrate decompression distillation, obtains 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, propilolic alcohol 350g (6.24mol), diethylamine 65g are sequentially added in 2L there-necked flask
(0.89mol) after magnetic agitation 5min, is slowly dropped into di-tert-butyl dicarbonic acid ester 1360g (6.24mol), continues room after dripping off
Temperature reaction, gas-chromatography monitor reaction process, amount to reaction 8h, fully reacting.Add short vertical thorn still protection, removes 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 are collected
94.0%, yield 88.8%.
In 1L there-necked flask, under the conditions of ice-water bath, propargyl tert-butyl carbonate 500g (3.20mol, gas phase color is first added
It is 94.0%) methyl tertiary butyl ether(MTBE) 400ml and 1,1,3,3- tetramethylurea 0.75g (6.4mmol), magnetic force that spectrum, which detects main content,
After stirring 10min, trifluoromethanesulfonic acid mercury is added in several times, every 1h, gas chromatographic detection reaction solution, until total amount accumulation is arrived
When 3.4g (6.8mmol) mercury salt, solution colour variation is obvious in reaction kettle, rapidly goes to dark brown solution, gas chromatographic detection,
Without intermediate, fully reacting, target compound gas-chromatography content is 25% at this time, and the Na of 4.0g is added2S·5H2O stirring
After about 1h, filtering collects filtrate decompression distillation, obtains 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, propilolic alcohol 350g (6.24mol), triethylamine 65g are sequentially added in 2L there-necked flask
(0.64mol) after magnetic agitation 5min, is slowly dropped into di-tert-butyl dicarbonic acid ester 1360g (6.24mol), controls after dripping off anti-
Answer oil bath temperature at 55 DEG C or so, gas-chromatography monitors reaction process, amounts to reaction 4h, fully reacting.Add 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
Detect the main content 96.1% of product, yield 89.8%.
In 1L there-necked flask, under the conditions of ice-water bath, propargyl tert-butyl carbonate 500g (3.20mol, gas phase color is first added
It is 96.1%) ethyl acetate 400ml and 1,1,3,3- tetramethylurea 0.75g (6.4mmol), magnetic agitation that spectrum, which detects main content,
After 10min, trifluoromethanesulfonic acid mercury is added in several times, every 1h, gas chromatographic detection reaction solution, until total amount is accumulated to 4.2g
When (8.4mmol) mercury salt, solution colour variation is obvious in reaction kettle, rapidly goes to dark brown solution, gas chromatographic detection, without
Intermediate, fully reacting, target compound gas-chromatography content is 35% at this time, and Na is added2S·5H2O, 5.0g stir about 1h
Afterwards, it filters, collects 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, it is similar to 20L in the static fusion-crystallization phase of tubular heat exchanger, passes through N2It is real to be pressed into 18.0Kg
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.Setting
Initial 24 DEG C of cooling point, heat transferring medium cycling switch is opened, is cooled down 1 DEG C every 1h, until being cooled to 19 DEG C, tube wall starts to tie
Crystalline substance continues echelon and is cooled to 16 DEG C, has major part crystal and is precipitated, and crystal habit is stopped in small blocky tetrahedron regular distribution
In this temperature 2h, still there is a small amount of uncured low concentration raffinate, and color is deeper, release, weigh 3.2Kg, and gas-chromatography is shown
Raffinate methylene ethylene carbonate content is 61.0%.
Crystal is started slowly to heat up, increases 1 DEG C of temperature every 1h, the melting liquid in sweating effort is collected in discharge, by each
It is detected, until gas-chromatography display discharge liquid hold-up determines that container product has been approached up to 99.2% when being warming up to 30 DEG C
Qualification improves temperature to 45 DEG C, melts remaining solid rapidly, obtain high-purity mesomethylene carbon vinyl acetate 10.2Kg, gas phase color
Spectrum display mesomethylene carbon vinyl acetate content is 99.93%, and coloration is less than 20Hazen, qualification rate 56.7%.What process collection arrived
Uncured liquid and sweating return to 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.
The each batch crystallization uncured liquid and sweating that embodiment 6 is collected into merge total 34Kg, put into 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 places it in
In the 20L static state fusion-crystallization phase, it is arranged initial 20 DEG C of cooling point, opens heat transferring medium cycling switch, cool down 1 DEG C every 1h, until
14 DEG C are cooled to, tube wall starts to crystallize, and continues echelon and is cooled to 10 DEG C, and most of crystal is precipitated, and crystal habit is in fritter
Shape tetrahedron regular distribution is stopped in this temperature 2h, is still had a small amount of uncured low concentration raffinate, and color is deeper, is released, claims
Weight 4.3Kg, gas-chromatography show that raffinate methylene ethylene carbonate content is 71.0%.
Crystal is started slowly to heat up, increases 1 DEG C of temperature every 1h, the melting liquid in sweating effort is collected in discharge, by each
It is detected, until gas-chromatography display discharge liquid hold-up improves temperature to 45 DEG C, rapidly up to 98.4% when being warming up to 27 DEG C
Melt remaining solid, obtain high-purity mesomethylene carbon vinyl acetate 9.1Kg, gas-chromatography shows mesomethylene carbon vinyl acetate content
It is 99.91%, coloration is less than 20Hazen, qualification rate 41.4%.The uncured liquid and sweating that process collection arrives return to 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, it is similar to 20L in the static fusion-crystallization phase of tubular heat exchanger, passes through N217Kg is pressed into implement
Crude product after the mesomethylene carbon vinyl acetate rectifying that example 4 is prepared, the main content 79.6% of gas chromatographic detection product.Setting is just
Begin 18 DEG C of cooling point, opens heat transferring medium cycling switch, cools down 0.5 DEG C every 1h, until being cooled to 8 DEG C, tube wall starts to tie
Crystalline substance continues echelon and is cooled to 6 DEG C, has major part crystal and is precipitated, and crystal habit is rested in small blocky tetrahedron regular distribution
This temperature 2h still has 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%.
Crystal is started slowly to heat up, increases 0.5 DEG C of temperature every 1h, the melting liquid in sweating effort is collected in discharge, by
It is respectively detected, until gas-chromatography display discharge liquid hold-up determines that container product has connect up to 98.5% when being warming up to 26 DEG C
It is close qualified, temperature is improved to 45 DEG C, is melted remaining solid rapidly, is obtained high-purity mesomethylene carbon vinyl acetate 6.1Kg, gas phase color
Spectrum display mesomethylene carbon vinyl acetate content is 99.9%, and coloration is less than 20Hazen, qualification rate 35.8%.What process collection arrived
Uncured liquid and sweating return to 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, it is similar to 20L in the static fusion-crystallization phase of tubular heat exchanger, passes through N2It is real to be pressed into 19.4Kg
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.Setting
Initial 25 DEG C of cooling point, heat transferring medium cycling switch is opened, is cooled down 2 DEG C every 1h, until being cooled to 18 DEG C, tube wall starts to tie
Crystalline substance continues echelon and is cooled to 14 DEG C, has major part crystal and is precipitated, and crystal habit is stopped in small blocky tetrahedron regular distribution
In this temperature 2h, still there is a small amount of uncured low concentration raffinate, and color is deeper, release, weigh 3.4Kg, and gas-chromatography is shown
Raffinate methylene ethylene carbonate content is 76.1%.
Crystal is started slowly to heat up, increases 2 DEG C of temperature every 1h, the melting liquid in sweating effort is collected in discharge, by each
It is detected, until gas-chromatography display discharge liquid hold-up determines that container product has been approached up to 99.2% when being warming up to 29 DEG C
Qualification improves temperature to 45 DEG C, melts remaining solid rapidly, obtain high-purity mesomethylene carbon vinyl acetate 9.8Kg, gas-chromatography
Content 99.92%, coloration are less than 20Hazen, qualification rate 50.5%.The uncured liquid and sweating that process collection arrives return to essence
It evaporates, then carries out crystallization purifying, move in circles.
From above-described embodiment as can be seen that being catalyzed needed for the preparation method of propargyl tert-butyl carbonate provided by the invention
Agent content is few.The purity is high of the mesomethylene carbon vinyl acetate of the preparation method preparation of mesomethylene carbon vinyl acetate, especially by
After purification processing method provided by the invention is purified, purity is higher.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (6)
1. a kind of preparation method of mesomethylene carbon vinyl acetate, which comprises the steps of:
Step 1: propargyl tert-butyl carbonate is provided；
The propargyl tert-butyl carbonate is prepared via a method which to obtain: under dry atmosphere, by propargyl alcohol, di-t-butyl
Two carbonic esters and basic catalyst mixing, are reacted under agitation, obtain the propargyl tert-butyl carbonate；
The basic catalyst is selected from one of diethylamine, triethylamine or a variety of；
Step 2: the propargyl tert-butyl carbonate is mixed with containing mercury catalyst, is reacted under agitation, then
Na is added into reaction solution2S·5H2O is simultaneously stirred, and by filtering and rectifying, obtains mesomethylene carbon vinyl acetate crude product；Institute
State propargyl tert-butyl carbonate and Na2S·5H2The ratio between additive amount of O is 1:0.001-0.05；
Step 3: purification processes, the purification processing method are as follows: to the Asia are carried out to above-mentioned mesomethylene carbon vinyl acetate crude product
Methyl carbonic acid vinyl acetate crude product carries out decrease temperature crystalline, obtains crystal and raffinate, isolates crystal；Then crystal is heated,
And solid matter is isolated, obtain mesomethylene carbon vinyl acetate finished product；
Wherein, cool down since 18-30 DEG C to the mesomethylene carbon vinyl acetate crude product, the rate of temperature fall when cooling is
0.5-2℃/h；
The heating rate when heating is 0.5-2 DEG C/h.
2. preparation method according to claim 1, which is characterized in that first mix propargyl alcohol and basic catalyst, then
Di-tert-butyl dicarbonic acid ester is added by the way of dropwise addition；
The temperature when dropwise addition is 0-60 DEG C, time for adding 0.5-2h；
The reaction temperature is 0-80 DEG C, reaction time 1-6h.
3. preparation method described in any one of -2 according to claim 1, which is characterized in that the propargyl alcohol, di-t-butyl
Two carbonic esters, basic catalyst molar ratio be 1:1-2:0.01-5.
4. preparation method described in any one of -2 according to claim 1, which is characterized in that in the step 2, first by alkynes
Propyl tert-butyl carbonate is mixed with solvent, after mixing evenly, mercurous class catalyst is added by several times and selectively adds 1,
1,3,3- tetramethylurea, is reacted under agitation；
The solvent is selected from one of methylene chloride, ethyl acetate, methyl tertiary butyl ether(MTBE), dimethyl carbonate, toluene or a variety of；
The mercury catalyst that contains is trifluoromethanesulfonic acid mercury；
The molar ratio of the additive amount of the propargyl tert-butyl carbonate, solvent and 1,1,3,3- tetramethylurea is 1:0-10:0-
0.1；
The reaction temperature is -10~60 DEG C, reaction time 1-8h；
After the rectifying, make 85.0% or more the content of fraction methylene ethylene carbonate.
5. preparation method according to claim 1, which is characterized in that in the step 3, further include to the raffinate into
Then row rectifying carries out the purification processes to fraction.
6. method of purification according to claim 1, which is characterized in that in the mesomethylene carbon vinyl acetate crude product, methylene
The content of base ethylene carbonate is 85.0% or more.
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| CN101161647A (en) * | 2007-11-26 | 2008-04-16 | 中国海洋石油总公司 | Preparation method of vinylene carbonate for lithium ion-cell |
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