CN109678838A - The method and its catalyst of carbon dioxide and epoxide synthesis of cyclic carbonic acid styrene esters - Google Patents
The method and its catalyst of carbon dioxide and epoxide synthesis of cyclic carbonic acid styrene esters Download PDFInfo
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- CN109678838A CN109678838A CN201811522130.6A CN201811522130A CN109678838A CN 109678838 A CN109678838 A CN 109678838A CN 201811522130 A CN201811522130 A CN 201811522130A CN 109678838 A CN109678838 A CN 109678838A
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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Abstract
It is a kind of for be catalyzed carbon dioxide and Styryl oxide reaction generate cyclic carbonate styrene esters catalyst system include the first catalytic active component and the second catalytic active component.First catalytic active component is ammonium halide, wherein second catalytic active component is selected from aluminum oxide and hydroxy compounds.
Description
Technical field
The present invention relates to catalysis carbon dioxide and epoxide, especially phenyl ring oxidative ethane, synthesis of cyclic carbonic acid benzene second
The catalyst of enester.The present invention is further directed to catalysis carbon dioxide and phenyl ring oxidative ethane synthesis of cyclic carbonic acid styrene esters
Method.
Background technique
Carbon dioxide is the final product of carbon and carbon compound oxidation, and leads to the most important gas of greenhouse effects
Body.It is big with reserves, at low cost, be easy to get and obtain however, simultaneously, carbon dioxide is also the most abundant carbon source on the earth
The advantages that mode of obtaining is safe and harmless.For decades, people be always can effectively and economic utilization carbon dioxide and ongoing effort.
Many using in carbon dioxide process, using carbon dioxide and benzene reacting ethylene oxide synthesis of cyclic carbonic acid styrene esters, it is
Most promising carbon dioxide is currently known using one of method.Cyclic carbonate styrene esters are widely used in weaving, print
Dye is used for many organic matters as intermediate, such as the synthesis of polycarbonate, thermosetting resin, electrochemistry and metal extraction are all
It is multi-field.Under field conditions (factors), carbon dioxide and phenyl ring oxidative ethane will be difficult to happen reaction, or both reaction and generate cyclic annular carbon
The efficiency of sour styrene esters is extremely low.Similar with other chemical reactions, suitable catalyst can effectively improve carbon dioxide and phenyl ring
Oxidative ethane reaction generates the efficiency of cyclic carbonate styrene esters.
The catalyst for being currently used for catalysis carbon dioxide and benzene reacting ethylene oxide generation cyclic carbonate styrene esters is main
There are metal complex catalysts, such as 4- methyl porphyrin chromium, ionic-liquid catalyst, such as quaternary ammonium salt, metal oxide catalyst, such as
Magnesia and alumina mixture catalyst and loaded ionic liquid body catalyst.However, it is existing these catalysis carbon dioxide and
When phenyl ring oxidative ethane synthesis of cyclic carbonic acid styrene esters, harsh reaction condition, such as high pressure, high temperature are needed mostly.Existing
In carbon dioxide and the reaction of phenyl ring oxidative ethane synthesis of cyclic carbonic acid styrene esters, higher reaction condition, which greatly reduces, utilizes dioxy
Change the economy of the technique of carbon and phenyl ring oxidative ethane synthesis of cyclic carbonic acid styrene esters.Especially, it is currently used for catalysis titanium dioxide
The catalyst that carbon and benzene reacting ethylene oxide generate cyclic carbonate styrene esters needs to develop new complicated preparation process system mostly
It is standby, it is with high costs and be unfavorable for large-scale industrial production.
Summary of the invention
Main advantage of the invention is that it provides a kind of new energy efficient catalytic carbon dioxide and benzene ethylene oxide synthesis
The catalyst of cyclic carbonate styrene esters.
Another advantage of the present invention is that it provides a kind of catalyst, and wherein the catalyst, which contains, has catalysis carbon dioxide
With the active hydroxy compounds of phenyl ring oxidative ethane synthesis of cyclic carbonic acid styrene esters, what wherein the catalyst contained there is catalysis to live
Property hydroxy compounds under mild reaction conditions still have higher catalytic activity.
It is a kind of for being catalyzed carbon dioxide and phenyl ring oxidative ethane synthesis of cyclic carbon that another advantage of the present invention is that it is provided
The catalyst of sour styrene esters, wherein the catalyst is existing goods reagent, and the synthesis technology without developing or developing new goes to give birth to
Produce, be easily obtained with it is cheap.In other words, the present invention is for being catalyzed carbon dioxide and phenyl ring oxidative ethane synthesis of cyclic carbon
The catalyst of sour styrene esters may be regarded as a kind of new opplication of existing compound (or composition).Correspondingly, catalyst of the present invention
Production will be without developing new equipment or technique.
It is a kind of for being catalyzed carbon dioxide and phenyl ring oxidative ethane synthesis of cyclic carbon that another advantage of the present invention is that it is provided
The catalyst of sour styrene esters, wherein the catalyst is in catalysis carbon dioxide and phenyl ring oxidative ethane synthesis of cyclic carbonic acid styrene esters
After, it easily can mutually be separated with reactant carbon dioxide, phenyl ring oxidative ethane and final product cyclic carbonate styrene esters,
So as to significantly reduce the cost of synthetic reaction.
Other advantage and characteristics of the invention are able to fully demonstrate and can be by appended rights by following detailed descriptions
The combination of the means and device specially pointed out in it is required that is achieved.
According to the present invention, the catalyst of the present invention that can be realized foregoing purpose and other purposes and advantage includes having catalysis two
Carbonoxide and the active hydroxy compounds of phenyl ring oxidative ethane synthesis of cyclic carbonic acid styrene esters, with following structural formula:
According to present pre-ferred embodiments, catalyst of the present invention further comprises tetraethylammonium bromide.
According to some embodiments of the present invention, the structural formula of the hydroxy compounds are as follows:
Wherein R is an electron donating group, and wherein X is halogen.
According to some embodiments of the present invention, X=Cl.
According to some embodiments of the present invention, the hydroxy compounds is selected from 1- chloro-2-methyl-2-propanol, benzoglycols
And trimethylene chlorohydrin.
According to some embodiments of the present invention, second catalytic active component is neutral aluminum oxide.
According to another aspect of the present invention, the present invention includes a cyclic carbonate styrene esters synthetic method comprising following
Step:
A) it is catalyzed carbon dioxide and Styryl oxide reaction generates the cyclic carbonate styrene esters, wherein for being catalyzed two
The catalyst that carbonoxide and Styryl oxide reaction generate the cyclic carbonate styrene esters includes one first catalytic active component
With one second catalytic active component, urged wherein first catalytic active component and second catalytic active component cooperate with to play
Change effect, wherein first catalytic active component is ammonium halide, wherein second catalytic active component is selected from three oxidations two
Aluminium and hydroxy compounds.
According to some embodiments of the present invention, the structural formula of the hydroxy compounds are as follows:
Wherein R is an electron donating group, and wherein X is halogen.
According to some embodiments of the present invention, carbon dioxide and Styryl oxide reaction generate the cyclic carbonate styrene
The reaction condition of ester includes: that reaction environment is 1.0MPa pressure carbon dioxide.
According to some embodiments of the present invention, carbon dioxide and Styryl oxide reaction generate the cyclic carbonate styrene
The reaction condition of ester includes: that reaction temperature is 100 DEG C~110 DEG C.
According to some embodiments of the present invention, carbon dioxide and Styryl oxide reaction generate the cyclic carbonate styrene
The reaction time of ester is 4~8 hours.
According to some embodiments of the present invention, carbon dioxide and Styryl oxide reaction generate the cyclic carbonate styrene
The reaction condition of ester includes: that reaction temperature is 100 DEG C, and wherein carbon dioxide and Styryl oxide reaction generate the cyclic carbonate
The reaction time of styrene esters is 4 hours.
According to some embodiments of the present invention, first catalytic active component is tetraethylammonium bromide, wherein the hydroxyl
Based compound is selected from 1- chloro-2-methyl-2-propanol, benzoglycols and trimethylene chlorohydrin.
According to some embodiments of the present invention, the cyclic carbonate styrene esters synthetic method further comprises following step
It is rapid:
B) reaction product is separated, to obtain the cyclic carbonate styrene esters, wherein the separating step includes following step
It is rapid:
B11 organic phase) is extracted；
B12 extractant) is removed；With
B13) chromatographic isolation, to obtain the cyclic carbonate styrene esters.
According to some embodiments of the present invention, it is chloroform that step b11, which is used to extract the extractant of organic phase, wherein
Step b13 obtains the cyclic carbonate styrene esters by way of pillar layer separation.
According to some embodiments of the present invention,
According to some embodiments of the present invention, second catalytic active component is aluminum oxide, wherein the ring-type
Carbonic acid styrene esters synthetic method further includes steps of
B) reaction product is separated, to obtain the cyclic carbonate styrene esters, wherein the separating step includes following step
It is rapid:
B21 organic phase) is extracted；
B22 it is centrifugated organic phase) to obtain liquid phase organic phase；
B23 the extractant in the liquid phase organic phase) is removed；With
B24) chromatographic isolation, to obtain the cyclic carbonate styrene esters；
Wherein first catalytic active component is tetraethylammonium bromide.
According to some embodiments of the present invention, it is chloroform that step b21, which is used to extract the extractant of organic phase, wherein
Step b24 obtains the cyclic carbonate styrene esters by way of pillar layer separation.
According to some embodiments of the present invention, the cyclic carbonate styrene esters synthetic method further comprises following step
It is rapid:
C) second catalytic active component is recycled, so that second catalytic active component is recycled.
According to some embodiments of the present invention, first catalytic active component is tetraethylammonium bromide.Described first urges
The dosage for changing active constituent is 0.01 times of mole of the Styryl oxide dosage.
According to some embodiments of the present invention, first catalytic active component is tetraethylammonium bromide.Described second urges
The dosage for changing active constituent is 0.01 times of mole of the Styryl oxide dosage.
By the understanding to subsequent description and attached drawing, further aim of the present invention and advantage will be fully demonstrated.
These and other objects of the invention, feature and advantage, by following detailed descriptions, drawings and claims are obtained
To fully demonstrate.
Detailed description of the invention
Fig. 1 illustrates a cyclic carbonate styrene esters synthetic method according to some embodiments of the present invention.
Fig. 2 illustrates a cyclic carbonate styrene esters synthetic method of first preferred embodiment according to the present invention.
Fig. 3 illustrates a cyclic carbonate styrene esters synthetic method of second preferred embodiment according to the present invention.
Fig. 4 illustrates a cyclic carbonate styrene esters synthetic method of third preferred embodiment according to the present invention.
Fig. 5 illustrates a cyclic carbonate styrene esters synthetic method of the 4th preferred embodiment according to the present invention.
Fig. 6 illustrates a cyclic carbonate styrene esters synthetic method of the 5th preferred embodiment according to the present invention.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.It defines in the following description
Basic principle of the invention can be applied to other embodiments, deformation scheme, improvement project, equivalent program and do not carry on the back
Other technologies scheme from the spirit and scope of the present invention.
It will be understood by those skilled in the art that in exposure of the invention, term " longitudinal direction ", " transverse direction ", "upper",
The orientation of the instructions such as "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom" "inner", "outside" or position are closed
System is to be based on the orientation or positional relationship shown in the drawings, and is merely for convenience of description of the present invention and simplification of the description, without referring to
Show or imply that signified device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore above-mentioned art
Language is not considered as limiting the invention.
It is understood that term " one " is interpreted as " at least one " or " one or more ", i.e., in one embodiment,
The quantity of one element can be one, and in a further embodiment, the quantity of the element can be it is multiple, term " one " is no
It can be interpreted as the limitation to quantity.
For a better understanding of the present invention, the present invention is further elaborated herein in conjunction with following embodiments.Therefore, under
It illustrates the present invention with stating being given for example only property of embodiment, but should not be understood as any limitation of the invention.
According to a particular embodiment of the invention, catalyst and Styryl oxide are added in a reaction vessel, it will
Carbon dioxide is passed through in the reaction vessel.Under default reaction condition, the effect of Styryl oxide and carbon dioxide in catalyst
Under react, generate cyclic carbonate styrene esters.Preferably, catalyst is catalyzed epoxy benzene second under the conditions of pressure carbon dioxide
Alkane and carbon dioxide react.According to a particular embodiment of the invention, it is generated for being catalyzed Styryl oxide and carbon dioxide
One catalyst system of cyclic carbonate styrene esters includes an ammonium halide and monohydroxy compound, to be catalyzed carbon dioxide and epoxy benzene
Ethane reaction generates cyclic carbonate styrene esters.Specifically, ring-type is generated for being catalyzed carbon dioxide and Styryl oxide reaction
The catalyst of carbonic acid styrene esters includes the first catalytic active component and the second catalytic active component, wherein first catalysis is lived
Property ingredient is ammonium halide, wherein second catalytic active component be used to stablize reaction intermediate.First catalytic activity
Ingredient is preferably tetraethylammonium bromide.Tetraethylammonium bromide generates cyclic carbonate benzene second in catalysis Styryl oxide and carbon dioxide
Br anion is provided in the reaction of enester.
With reference to Fig. 1, a cyclic carbonate styrene esters synthetic method according to some embodiments of the present invention includes following step
It is rapid:
A) hybrid epoxidized vinylbenzene, ammonium halide and hydroxy compounds, to obtain a raw mixture；
B a carbon dioxide environment) is provided to the raw mixture, thus mix carbon dioxide with the raw mixture,
To obtain a reaction mixture, wherein the reaction mixture is in carbon dioxide environment；
C the reaction mixture) is stirred；With
D heat) is provided to the reaction mixture, the reaction mixture is placed in a preset temperature condition.
According to some embodiments of the present invention, step D and step D are persistently carried out, to obtain under the conditions of the preset temperature
One product mixtures wherein contain cyclic carbonate styrene esters in the product mixtures.
According to some embodiments of the present invention, which further includes steps of
E reaction product is separated) to obtain cyclic carbonate styrene esters.
According to some embodiments of the present invention, the carbon dioxide in step B serves not only as the raw material chemically reacted, and
And a reaction environment is provided, to prevent other gases, such as air from having an impact to chemical reaction.In addition, carbon dioxide also mentions
For a reaction pressure environment.
According to some embodiments of the present invention, carbon dioxide environment described in step B refers to that pressure carbon dioxide is 1Mpa.
Specifically, step B the following steps are included:
B1 the air in the raw mixture local environment) is driven；
B2 a pressurized carbon dioxide force environment) is generated in the raw mixture.
According to some embodiments of the present invention, step D is embodied are as follows:
The reaction mixture is heated, to provide one 100 DEG C~110 DEG C of temperature environment to the reaction mixture.Step D is held
It is continuous to carry out preset time.While step D, step C is persistently carried out, and to prevent hot-spot and keeps reaction mixture mixing equal
It is even.Preferably, first starting stirring, restarts heating, produces to prevent hot-spot or other unexpected situations to default chemical reaction
It is raw to influence.
First preferred embodiment according to the present invention prepares target product cyclic carbonate styrene esters, and right
Its structure is identified.
First preferred embodiment according to the present invention, using 1,3-diamino-2-propanol and tetrabutylammonium bromide as
Catalyst.The two collaboration plays catalytic action, is catalyzed Styryl oxide and carbon dioxide reaction generates cyclic carbonate styrene esters.
Solvent is also used in the one cyclic carbonate styrene esters synthetic method of first preferred embodiment according to the present invention.According to
First preferred embodiment of the invention, the solvent are n,N-Dimethylformamide.
Specifically, a cyclic carbonate styrene esters synthetic method of first preferred embodiment according to the present invention include with
Lower step:
A ') hybrid epoxidized vinylbenzene, 1,3-diamino-2-propanol, tetrabutylammonium bromide and n,N-Dimethylformamide, with
Obtain a raw mixture；
B ') carbon dioxide environment is provided to the raw mixture, thus mix carbon dioxide with the raw mixture,
To obtain a reaction mixture, wherein the reaction mixture is in carbon dioxide environment；
C ') stir the reaction mixture；With
D ') to reaction mixture offer heat, the reaction mixture is placed in 110 DEG C of temperature conditions.
First preferred embodiment according to the present invention, step D ' and step C ' are persistently carried out, in the preset temperature item
A product mixtures are obtained under part, and cyclic carbonate styrene esters are wherein contained in the product mixtures.
First preferred embodiment according to the present invention, which further comprises following
Step:
E ') separation reaction product, to obtain cyclic carbonate styrene esters.
First preferred embodiment according to the present invention, what the carbon dioxide in step B ' served not only as chemically reacting
Raw material, and a reaction environment is provided, to prevent other gases, such as air from having an impact to chemical reaction.
First preferred embodiment according to the present invention, carbon dioxide environment described in step B ' refer to carbon dioxide just
Pressure.
Specifically, step B ' the following steps are included:
B1 ') drive air in the raw mixture local environment；
B2 ') a pressurized carbon dioxide force environment is generated in the raw mixture.
First preferred embodiment according to the present invention, step D ' specific implementation are as follows:
The reaction mixture is heated, to provide one 110 DEG C of temperature environment to the reaction mixture.Step D ' is persistently carried out
8 hours.While step D ', step C ' is persistently carried out, and to prevent hot-spot and is uniformly mixed reaction mixture.
More specifically, Styryl oxide 2.0ml, 1,3-diamino-2-propanol (CAS:616-29-5) 0.2ml, the tetrabutyl
Ammonium bromide 0.60g, n,N-Dimethylformamide 15ml are added in 100ml round-bottomed flask, with carbon dioxide gas displacement flask
Interior air three times, then under carbon dioxide positive pressure protection, react 8 hours, reaction solution be transferred to 250ml by 110 DEG C of oil bath heatings
In beaker, 100ml ice water is added, filters, obtains white crystal 0.27g.Nuclear magnetic data is analyzed as follows: 1H NMR (600MHz,
CDCl3): δ 7.44-7.37 (m, 5H), δ 5.68 (t, J=8.1Hz, 1H), δ 4.81 (t, J=8.7Hz, 1H), δ 4.35 (t, J=
8.1Hz, 1H), it is consistent with the data of cyclic carbonate styrene esters of reported in literature.
That is, the cyclic carbonate styrene esters synthetic method of first preferred embodiment according to the present invention
Step E ' the following steps are included:
E1 ') low temperature environment is provided, so that target product cyclic carbonate styrene esters are precipitated from liquid environment；With
E2 ') it is separated by solid-liquid separation, to obtain target product cyclic carbonate styrene esters.
Second preferred embodiment according to the present invention, using neutral aluminum oxide and tetraethylammonium bromide as catalysis
Agent.The two collaboration plays catalytic action, is catalyzed Styryl oxide and carbon dioxide reaction generates cyclic carbonate styrene esters.
Specifically, neutral aluminum oxide, tetraethylammonium bromide, Styryl oxide are added in a reaction vessel, then
Carbon dioxide is passed through into the reaction vessel, makes carbon dioxide and Styryl oxide in neutral aluminum oxide and tetraethyl bromination
It is reacted under default reaction condition under the catalytic action of ammonium.After reaction, reactant is separated, to obtain product
Cyclic carbonate styrene esters.
More specifically, a cyclic carbonate styrene esters synthetic method of second preferred embodiment according to the present invention includes
Following steps:
A ") hybrid epoxidized vinylbenzene, neutral aluminum oxide and tetrabutylammonium bromide, to obtain a raw mixture；
B ") carbon dioxide environment is provided to the raw mixture, thus mix carbon dioxide with the raw mixture,
To obtain a reaction mixture, wherein the reaction mixture is in carbon dioxide environment；
C ") stir the reaction mixture；With
D ") to reaction mixture offer heat, the reaction mixture is placed in 100 DEG C of temperature conditions.
Second preferred embodiment according to the present invention, step D " and step C " are persistently carried out, in the preset temperature item
A product mixtures are obtained under part, and cyclic carbonate styrene esters are wherein contained in the product mixtures.
Second preferred embodiment according to the present invention, which further comprises following
Step:
E ") separation reaction product, to obtain cyclic carbonate styrene esters.
Second preferred embodiment according to the present invention, what the carbon dioxide in step B " served not only as chemically reacting
Raw material, and a reaction environment is provided, to prevent other gases, such as air from having an impact to chemical reaction, and pass through two
Carbonoxide provides a pressure environment to the environment, to promote the progress of default chemical reaction.
Second preferred embodiment according to the present invention, carbon dioxide environment described in step B " refer to pressure carbon dioxide
For 1.0MPa.
Specifically, step B " the following steps are included:
B1 ") drive air in the raw mixture local environment；
B2 ") a pressurized carbon dioxide force environment is generated in the raw mixture.
Second preferred embodiment according to the present invention, step D " specific implementation are as follows:
The reaction mixture is heated, to provide 100 DEG C of temperature environment to the reaction mixture.Step D " persistently carries out 4
Hour.While step D ", step C " is persistently carried out, and to prevent hot-spot and is uniformly mixed reaction mixture.
The step E " of the cyclic carbonate styrene esters synthetic method of second preferred embodiment according to the present invention is wrapped
Include following steps:
E1 ") extraction organic phase；
E2 ") it is separated by solid-liquid separation；
E3 ") removal extractant, to obtain a mixing organic phase；With
E4 ") the mixing organic phase is separated, to obtain target product cyclic carbonate styrene esters.
Second preferred embodiment according to the present invention, step E1 " use chloroform for extractant；Step E2 "
It is separated by solid-liquid separation by way of centrifuge separation, to obtain liquid phase organic phase.Step E3 " is separated by way of rotary evaporation
Chloroform in the liquid phase organic phase；Step E4 " separates the mixing organic phase by way of pillar layer separation, with
To product circular ethylene carbonate.
More specifically, by neutral aluminum oxide (100~200 mesh) 0.5mmol, tetraethylammonium bromide 0.5mmol, epoxy
Vinylbenzene 50mmol is added in the 100ml stainless steel autoclave with magnetic agitation and temperature control heating device, uses dioxy
Change air in carbon gas displacement kettle three times, then to keep pressure carbon dioxide 1.0MPa, 100 DEG C, react 4 hours.After cooling, delay
Slowly it is deflated to normal pressure, with 20ml chloroform extraction organic phase.Organic phase is washed three times with distillation.Organic phase centrifugation.Supernatant
Chloroform is separated by rotary evaporation, remaining organic phase obtains product circular carbonic acid styrene esters, yield through pillar layer separation
72%.
Aluminum oxide has the advantages that be easy to get, quality is stable, and is easy to after catalytic action occurs and reaction solution carries out
Separation, is easy to be recovered.The aluminum oxide being recovered can still play catalytic action, so as to be recycled, from
And give full play to its effectiveness.Aluminum oxide is industrialization product cheap and easy to get, and catalytic performance is good, to have good
Industrial applications prospect.
In above-mentioned second preferred embodiment according to the present invention, extracts after resulting water phase is oven-dried and be recycled for
The reaction of carbon dioxide and Styryl oxide synthesis of cyclic carbonic acid styrene esters.Specifically, it is recycled after water phase is oven-dried
In the synthetic reaction of cyclic carbonate styrene esters.Quilt after used aluminum oxide is washed after being recovered with methanol in reaction
Drying, is then recycled in the synthetic reaction of cyclic carbonate styrene esters.More specifically, recycling aluminum oxide with
It dries, is recycled after the washing of 10ml methanol.So circulation 3 times, the separation yield of each cyclic carbonate styrene esters is shown in Table
1。
Table 1: cyclic carbonate styrene esters yield
| Catalyst circulation number | Cyclic carbonate styrene esters separation yield |
| It is fresh | 72% |
| Circulation 1 time | 71% |
| Circulation 2 times | 69% |
| Circulation 3 times | 67% |
Therefore, the cyclic carbonate styrene esters synthetic method of second preferred embodiment according to the present invention is further
Include the steps that recycling second catalytic active component.
Other than above-mentioned aluminum oxide, hydroxy compounds is also good stable cyclic carbonate styrene esters synthetic reaction
The substance of intermediate.
Third preferred embodiment according to the present invention is using trimethylene chlorohydrin and tetraethylammonium bromide as catalyst.3-
Trimethylewne chlorohydrin 3- and tetraethylammonium bromide collaboration play catalytic action, are catalyzed carbon dioxide and Styryl oxide reaction generation is cyclic annular
Carbonic acid styrene esters, the wherein structural formula of trimethylene chlorohydrin are as follows:
Specifically, a cyclic carbonate styrene esters synthetic method of third preferred embodiment according to the present invention include with
Lower step:
A " ') hybrid epoxidized vinylbenzene, trimethylene chlorohydrin and tetrabutylammonium bromide, to obtain a raw mixture；
B " ') carbon dioxide environment is provided to the raw mixture, to keep carbon dioxide and the raw mixture mixed
It closes, to obtain a reaction mixture, wherein the reaction mixture is in carbon dioxide environment；
C " ') stir the reaction mixture；With
D " ') to reaction mixture offer heat, the reaction mixture is placed in 100 DEG C of temperature conditions.
Third preferred embodiment according to the present invention, step D " ' and step C " ' are persistently carried out, in the preset temperature
Under the conditions of obtain a product mixtures, wherein in the product mixtures contain cyclic carbonate styrene esters.
Third preferred embodiment according to the present invention, which further comprises following
Step:
E " ') separation reaction product, to obtain cyclic carbonate styrene esters.
Third preferred embodiment according to the present invention, the carbon dioxide in step B " ' serve not only as chemically reacting
Raw material, and provide a reaction environment, to prevent other gases, such as air from having an impact to chemical reaction, and pass through
Carbon dioxide provides a pressure environment to the environment, to promote the progress of default chemical reaction.
Third preferred embodiment according to the present invention, carbon dioxide environment described in step B " ' refer to pressurized carbon dioxide
Power is 1.0MPa.
Specifically, step B " ' the following steps are included:
B1 " ') drive air in the raw mixture local environment；
B2 " ') a pressurized carbon dioxide force environment is generated in the raw mixture.
The third preferred embodiment according to the present invention, step D " ' specific implementation are as follows:
The reaction mixture is heated, to provide 100 DEG C of temperature environment to the reaction mixture.Step D " ' persistently carries out 4
Hour.While step D " ', step C " ' is persistently carried out, and to prevent hot-spot and is uniformly mixed reaction mixture.
The step E " ' of the cyclic carbonate styrene esters synthetic method of the third preferred embodiment according to the present invention is wrapped
Include following steps:
E1 " ') extraction organic phase；
E2 " ') it is separated by solid-liquid separation；
E3 " ') removal extractant, to obtain a mixing organic phase；With
E4 " ') the mixing organic phase is separated, to obtain target product cyclic carbonate styrene esters.
The third preferred embodiment according to the present invention, step E1 " ' use chloroform for extractant；Step
E2 " ' is separated by solid-liquid separation by way of centrifuge separation, to obtain liquid phase organic phase.The side that step E3 " ' passes through rotary evaporation
Formula separates the chloroform in the liquid phase organic phase；It is organic that step E4 " ' separates the mixing by way of pillar layer separation
Phase, to obtain product circular ethylene carbonate.
More specifically, being added to trimethylene chlorohydrin, tetraethylammonium bromide and Styryl oxide with magnetic agitation and temperature
In the stainless steel autoclave for controlling heating device；Three times with air in carbon dioxide gas displacement kettle；Keep default titanium dioxide
Carbon pressure power；Control a reaction temperature condition；Catalysis reaction preset time；It is cooling；It is deflated to normal pressure；Extract organic phase；Organic phase
Centrifugation；Remove chloroform；Pillar layer separation obtains product circular carbonic acid styrene esters.
More specifically, by trimethylene chlorohydrin (CAS:627-30-5) 0.5mmol, tetraethylammonium bromide 0.5mmol and epoxy
Vinylbenzene 50mmol is added in the 100ml stainless steel autoclave with magnetic agitation and temperature control heating device；Use dioxy
Change air in carbon gas displacement kettle and three times, then keeps pressure carbon dioxide 1.0MPa.Reaction 4 is small under the conditions of 100 DEG C of temperature
When.It is cooling, then slowly it is deflated to normal pressure.With 20ml chloroform extraction organic phase.Organic phase is washed three times with distillation.It is organic
It is mutually centrifuged, supernatant separates chloroform by rotary evaporation.Remaining organic phase obtains product circular carbonic acid through pillar layer separation
Styrene esters, yield 91%, conversion ratio 96%.
4th preferred embodiment according to the present invention is using benzoglycols and tetraethylammonium bromide as catalyst.Benzene second two
Alcohol (CAS:93-56-1) and tetraethylammonium bromide collaboration play catalytic action, are catalyzed carbon dioxide and Styryl oxide reaction life
Circlewise carbonic acid styrene esters, the wherein structural formula of benzoglycols are as follows:
Specifically, a cyclic carbonate styrene esters synthetic method of the 4th preferred embodiment according to the present invention include with
Lower step:
A " ") hybrid epoxidized vinylbenzene, benzoglycols and tetrabutylammonium bromide, to obtain a raw mixture；
B " ") carbon dioxide environment is provided to the raw mixture, to keep carbon dioxide and the raw mixture mixed
It closes, to obtain a reaction mixture, wherein the reaction mixture is in carbon dioxide environment；
C " ") stir the reaction mixture；With
D " ") to reaction mixture offer heat, the reaction mixture is placed in 100 DEG C of temperature conditions.
4th preferred embodiment according to the present invention, step D " " and step C " " persistently carry out, in the preset temperature
Under the conditions of obtain a product mixtures, wherein in the product mixtures contain cyclic carbonate styrene esters.
4th preferred embodiment according to the present invention, which further comprises following
Step:
E " ") separation reaction product, to obtain cyclic carbonate styrene esters.
Carbon dioxide in 4th preferred embodiment according to the present invention, step B " " serves not only as chemically reacting
Raw material, and provide a reaction environment, to prevent other gases, such as air from having an impact to chemical reaction, and pass through
Carbon dioxide provides a pressure environment to the environment, to promote the progress of default chemical reaction.
Carbon dioxide environment described in 4th preferred embodiment according to the present invention, step B " " refers to pressurized carbon dioxide
Power is 1.0MPa.
Specifically, step B " " the following steps are included:
B1 " ") drive air in the raw mixture local environment；
B2 " ") a pressurized carbon dioxide force environment is generated in the raw mixture.
4th preferred embodiment according to the present invention, step D " " specific implementation are as follows:
The reaction mixture is heated, to provide 100 DEG C of temperature environment to the reaction mixture.Step D " " persistently carries out 4
Hour.In step D " " while carry out, step C " " it is lasting carry out, to prevent hot-spot and be uniformly mixed reaction mixture.
The step E " of the cyclic carbonate styrene esters synthetic method of the 4th preferred embodiment according to the present invention " packet
Include following steps:
E1 " ") extraction organic phase；
E2 " ") it is separated by solid-liquid separation；
E3 " ") removal extractant, to obtain a mixing organic phase；With
E4 " ") the mixing organic phase is separated, to obtain target product cyclic carbonate styrene esters.
4th preferred embodiment according to the present invention, step E1 " " uses chloroform for extractant；Step
E2 " " is separated by solid-liquid separation by way of centrifugation；Step E3 " ") chloroform is separated by way of rotary evaporation；Step
E4 " " separates the mixing organic phase by way of pillar layer separation, to obtain product circular ethylene carbonate.
More specifically, by benzoglycols 0.5mmol, tetraethylammonium bromide 0.5mmol, Styryl oxide 50mmol are added
Into the 100ml stainless steel autoclave with magnetic agitation and temperature control heating device, in carbon dioxide gas displacement kettle
Air three times, then keeps pressure carbon dioxide 1.0MPa, 100 DEG C, reacts 4 hours, after cooling, be slowly deflated to normal pressure, use
20ml chloroform extraction organic phase, three times with distillation washing, organic phase centrifugation, supernatant is separated organic phase by rotary evaporation
Chloroform, remaining organic phase obtain product circular carbonic acid styrene esters, yield 95%, conversion ratio 98% through pillar layer separation.
It is further preferable that second catalytic active component selects the hydroxy compounds for the formula that has following structure:
Wherein R is electron donating group, and X is halogen, wherein having the advantages that as X=Cl at low cost.
5th preferred embodiment according to the present invention is using 1- chloro-2-methyl-2-propanol and tetraethylammonium bromide as urging
Agent.1- chloro-2-methyl-2-propanol (CAS:558-42-9) and tetraethylammonium bromide collaboration play catalytic action, are catalyzed dioxy
Change carbon and Styryl oxide reaction generate cyclic carbonate styrene esters, wherein the structural formula of 1- chloro-2-methyl-2-propanol are as follows:
There are two electron donating group, the dissociation constants and synthesis of cyclic of hydroxyl in the carbochain of 1- chloro-2-methyl-2-propanol
The molecular forms of the reaction intermediate of carbonic acid styrene esters are close, so as to more preferably play the role of stable intermediate, thus
It is cooperateed with tetraethylammonium bromide and plays good catalytic action.
Specifically, a cyclic carbonate styrene esters synthetic method of the 5th preferred embodiment according to the present invention include with
Lower step:
A " " ') hybrid epoxidized vinylbenzene, benzoglycols and tetrabutylammonium bromide, to obtain a raw mixture；
B " " ') carbon dioxide environment is provided to the raw mixture, to keep carbon dioxide and the raw mixture mixed
It closes, to obtain a reaction mixture, wherein the reaction mixture is in carbon dioxide environment；
C " " ') stir the reaction mixture；With
D " " ') to reaction mixture offer heat, the reaction mixture is placed in 100 DEG C of temperature conditions.
5th preferred embodiment according to the present invention, step D " " ' and step C " " ' persistently carry out, in the default temperature
A product mixtures are obtained under the conditions of degree, and cyclic carbonate styrene esters are wherein contained in the product mixtures.
5th preferred embodiment according to the present invention, which further comprises following
Step:
E " " ') separation reaction product, to obtain cyclic carbonate styrene esters.
Carbon dioxide in 5th preferred embodiment according to the present invention, step B " " ' serves not only as chemically reacting
Raw material, and provide a reaction environment, to prevent other gases, such as air from having an impact to chemical reaction, and pass through
Carbon dioxide provides a pressure environment to the environment, to promote the progress of default chemical reaction.
Carbon dioxide environment described in 5th preferred embodiment according to the present invention, step B " " ' refers to pressurized carbon dioxide
Power is 1.0MPa.
Specifically, step B " " ' the following steps are included:
B1 " " ') drive air in the raw mixture local environment；
B2 " " ') a pressurized carbon dioxide force environment is generated in the raw mixture.
5th preferred embodiment according to the present invention, step D " " ' specific implementation are as follows:
The reaction mixture is heated, to provide 100 DEG C of temperature environment to the reaction mixture.Step D " " ' is persistently carried out
4 hours.In step D " " ' carry out while, step C " " ' is lasting carries out, and to prevent hot-spot and keep reaction mixture mixing equal
It is even.
The step E " of the cyclic carbonate styrene esters synthetic method of the 5th preferred embodiment according to the present invention " '
The following steps are included:
E1 " " ') extraction organic phase；
E2 " " ') it is separated by solid-liquid separation；
E3 " " ') removal extractant, to obtain a mixing organic phase；With
E4 " " ') the mixing organic phase is separated, to obtain target product cyclic carbonate styrene esters.
5th preferred embodiment according to the present invention, step E1 " " ' uses chloroform for extractant；Step
E2 " " ' is separated by solid-liquid separation by way of centrifuge separation；E3 " " ' separates chloroform by way of rotary evaporation；Step
E4 " " ' separates the mixing organic phase by way of pillar layer separation, to obtain product circular ethylene carbonate.
More specifically, by 1- chloro-2-methyl-2-propanol 0.5mmol, tetraethylammonium bromide 0.5mmol, Styryl oxide
50mmol is added in the 100ml stainless steel autoclave with magnetic agitation and temperature control heating device, uses carbon dioxide gas
Air three times, then keeps pressure carbon dioxide 1.0MPa, 100 DEG C, reacts 4 hours, after cooling, slowly deflate in body displacement kettle
To normal pressure, with 20ml chloroform extraction organic phase, three times with distillation washing, organic phase centrifugation, supernatant passes through rotation to organic phase
Turning evaporation separation chloroform, remaining organic phase obtains product circular carbonic acid styrene esters through pillar layer separation, yield 96%,
Conversion ratio 98%.
It should be understood by those skilled in the art that foregoing description and the embodiment of the present invention shown in the drawings are only used as illustrating
And it is not intended to limit the present invention.
The purpose of the present invention has been fully and effectively achieved.Function and structural principle of the invention is opened up in embodiment
Show and illustrate, under without departing from the principle, embodiments of the present invention can have any deformation or modification.
Claims (19)
1. a cyclic carbonate styrene esters synthetic method, which comprises the following steps:
A) it is catalyzed carbon dioxide and Styryl oxide reaction generates the cyclic carbonate styrene esters, wherein for being catalyzed titanium dioxide
The catalyst that carbon and Styryl oxide reaction generate the cyclic carbonate styrene esters includes one first catalytic active component and one
Second catalytic active component, wherein first catalytic active component and second catalytic active component collaboration play catalysis and make
With, wherein first catalytic active component is ammonium halide, wherein second catalytic active component be selected from aluminum oxide and
Hydroxy compounds.
2. cyclic carbonate styrene esters synthetic method according to claim 1, wherein carbon dioxide and Styryl oxide are anti-
It is 1.0MPa pressure carbon dioxide that the reaction condition that the cyclic carbonate styrene esters should be generated, which includes: reaction environment,.
3. cyclic carbonate styrene esters synthetic method according to claim 1, wherein carbon dioxide and Styryl oxide are anti-
It is 100 DEG C~110 DEG C that the reaction condition that the cyclic carbonate styrene esters should be generated, which includes: reaction temperature,.
4. cyclic carbonate styrene esters synthetic method according to claim 1, wherein carbon dioxide and Styryl oxide are anti-
The reaction time that the cyclic carbonate styrene esters should be generated is 4~8 hours.
5. cyclic carbonate styrene esters synthetic method according to claim 1, wherein carbon dioxide and Styryl oxide are anti-
It is 100 DEG C that the reaction condition that the cyclic carbonate styrene esters should be generated, which includes: reaction temperature, wherein carbon dioxide and epoxy benzene
The reaction time that ethane reaction generates the cyclic carbonate styrene esters is 4 hours.
6. cyclic carbonate styrene esters synthetic method as claimed in any of claims 1 to 5, wherein the hydroxylating
Close the structural formula of object are as follows:
Wherein R is an electron donating group, and wherein X is halogen.
7. cyclic carbonate styrene esters synthetic method as claimed in any of claims 1 to 5, wherein described first urges
Change active constituent be tetraethylammonium bromide, wherein the hydroxy compounds be selected from 1- chloro-2-methyl-2-propanol, benzoglycols and
Trimethylene chlorohydrin.
8. cyclic carbonate styrene esters synthetic method as claimed in any of claims 1 to 5, further comprise with
Lower step:
B) separate reaction product, to obtain the cyclic carbonate styrene esters, wherein the separating step the following steps are included:
B11 organic phase) is extracted；
B12 extractant) is removed；With
B13) chromatographic isolation, to obtain the cyclic carbonate styrene esters；
Wherein first catalytic active component is tetraethylammonium bromide.
9. cyclic carbonate styrene esters synthetic method according to claim 8, wherein step b11 is for extracting organic phase
Extractant is chloroform, and wherein step b13 obtains the cyclic carbonate styrene esters by way of pillar layer separation.
10. cyclic carbonate styrene esters synthetic method as claimed in any of claims 1 to 5, wherein described second
Catalytic active component is aluminum oxide, wherein the cyclic carbonate styrene esters synthetic method further includes steps of
B) separate reaction product, to obtain the cyclic carbonate styrene esters, wherein the separating step the following steps are included:
B21 organic phase) is extracted；
B22 it is centrifugated organic phase) to obtain liquid phase organic phase；
B23 the extractant in the liquid phase organic phase) is removed；With
B24) chromatographic isolation, to obtain cyclic carbonate styrene esters；
Wherein first catalytic active component is tetraethylammonium bromide.
11. cyclic carbonate styrene esters synthetic method according to claim 10, wherein step b21 is for extracting organic phase
Extractant be chloroform, wherein step b24 obtains the cyclic carbonate styrene esters by way of pillar layer separation.
12. cyclic carbonate styrene esters synthetic method according to claim 11, wherein the cyclic carbonate styrene esters
Synthetic method further includes steps of
C) second catalytic active component is recycled, so that second catalytic active component is recycled.
13. cyclic carbonate styrene esters synthetic method as claimed in any of claims 1 to 5, wherein described first
Catalytic active component is tetraethylammonium bromide, wherein the dosage of first catalytic active component is the Styryl oxide dosage
0.01 times of mole,.
14. cyclic carbonate styrene esters synthetic method as claimed in any of claims 1 to 5, wherein described first
Catalytic active component is tetraethylammonium bromide, wherein the dosage of second catalytic active component is the Styryl oxide dosage
0.01 times of mole.
15. generating the catalyst of cyclic carbonate styrene esters for being catalyzed carbon dioxide and Styryl oxide reaction, feature exists
In, including the first catalytic active component and the second catalytic active component, wherein first catalytic active component is ammonium halide,
Described in the second catalytic active component include aluminum oxide and/or hydroxy compounds.
16. catalyst according to claim 15, wherein first catalytic active component is tetraethylammonium bromide.
17. catalyst according to claim 15, wherein the structural formula of the hydroxy compounds are as follows:
Wherein R is electron donating group, and wherein X is halogen.
18. catalyst according to claim 15, wherein the hydroxy compounds is selected from 1- chloro-2-methyl-2-propanol, benzene
Ethylene glycol and trimethylene chlorohydrin.
19. catalyst according to claim 15, wherein second catalytic active component is neutral aluminum oxide.
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| WO2005084801A1 (en) * | 2004-03-04 | 2005-09-15 | National Institute Of Advanced Industrial Science And Technology | Catalyst for cyclic carbonate synthesis |
| CN1995032A (en) * | 2006-12-27 | 2007-07-11 | 中国科学院过程工程研究所 | Process for preparing annular carbonate |
| JP2008296066A (en) * | 2007-05-29 | 2008-12-11 | Okayama Univ | Manufacturing method of catalyst crosslinking agent used for fixed catalyst for cyclic carbonate synthesis, manufacturing method of fixed catalyst, catalyst crosslinking agent used for fixed catalyst, and fixed catalyst |
| CN105377828A (en) * | 2013-07-19 | 2016-03-02 | 国立研究开发法人产业技术综合研究所 | Method for manufacturing cyclic carbonate |
| CN105377829A (en) * | 2013-07-19 | 2016-03-02 | 丸善石油化学株式会社 | Method for continuously producing cyclic carbonate |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005084801A1 (en) * | 2004-03-04 | 2005-09-15 | National Institute Of Advanced Industrial Science And Technology | Catalyst for cyclic carbonate synthesis |
| CN1995032A (en) * | 2006-12-27 | 2007-07-11 | 中国科学院过程工程研究所 | Process for preparing annular carbonate |
| JP2008296066A (en) * | 2007-05-29 | 2008-12-11 | Okayama Univ | Manufacturing method of catalyst crosslinking agent used for fixed catalyst for cyclic carbonate synthesis, manufacturing method of fixed catalyst, catalyst crosslinking agent used for fixed catalyst, and fixed catalyst |
| CN105377828A (en) * | 2013-07-19 | 2016-03-02 | 国立研究开发法人产业技术综合研究所 | Method for manufacturing cyclic carbonate |
| CN105377829A (en) * | 2013-07-19 | 2016-03-02 | 丸善石油化学株式会社 | Method for continuously producing cyclic carbonate |
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