CN104707652B - A kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof - Google Patents
A kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof, the catalyst of preparation is to make in ionic liquid structure while contain active end carboxyl functional group and polyethers macromolecular chain by way of chemical bonding, the synergic catalytic effect, base position blanketing effect and infinite dilution effect of catalyst are realized well, effectively reduce accessory substance generation, have high activity, high selectivity, active component are stable, dosage it is few, easily separated, easy reclaim, can be recycled, long lifespan, the good characteristic such as environment-friendly；Propene carbonate process is prepared for carbon dioxide and expoxy propane addition, the propene carbonate new product of high yield, high-purity can be obtained under lower temperature and pressure.
Description
Technical field
The present invention relates to a kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof, specifically one kind passes through
The reactive hydroxyl end group of Hydrin is converted into end carboxyl intermediate, then is reacted with tertiary ammoniac compounds, is formed with end carboxylic
Polyoxyalkylene nonionic liquid catalyst of base functional group and preparation method thereof.
Background technology
Cyclic carbonate is the good solvent for producing the high polymers such as polyamide, polyacrylonitrile, polyvinyl chloride, also acts as spinning
Reel off raw silk from cocoons liquid and other auxiliary chemicals knitted, also can be as the solvent of removing commercial acid gas and the additive of concrete.
Medical aspect can be used as the component and organic synthesis intermediate of pharmacy, also act as the stabilization of plastics blowing agent and synthetic lubricant fluid
Agent.Industrial in capacitor batteries, the mixed solution of ethylene carbonate and propene carbonate has higher dielectric constant, can conduct
The electrolyte of lithium battery, as the increasingly popularization of mobile phone and computer, market demand and development potentiality are huge.
At present, it is main in propene carbonate industrialized production use quaternary ammonium salt catalyst, the activity of such catalyst with
Selectivity is high, and production cost is low, but temperature height, pressure are big in catalytic process, and catalyst activity component is easy to run off, short life, use
Amount is big, and yield is not high enough.Therefore, it is that research expoxy propane and carbon dioxide are direct to seek environment-friendly efficient catalyst
Addition reaction prepares the power of propene carbonate, has now been found that many catalyst have catalytic effect to this reaction, such as transition gold
The catalyst system and catalyzing such as metal complex, major element complex, quaternary ammonium salt, phosphonium salt and alkali metal salt, ionic liquid.
Patent 1817877 and 1817878 individually discloses the synthetic method and high activated catalyst of a kind of cyclic carbonate
The method of catalytic preparation of cyclic carbonic ester, using transition metal salt respectively with two tooth ionic liquids and halogenation quaternary phosphonium salt ionic liquid
The binary catalyst of body composition.Patent 101037431 discloses carbon dioxide and epoxide cycloaddition reaction synthesis of cyclic
The method of carbonic ester, catalyst, reaction pressure 0.5-10MPa, reaction are formed using metal salt, ionic liquid and quaternary ammonium salt
30-200 DEG C of temperature.Patent 1631886 discloses the synthetic method of cyclic carbonate, using zinc salt and imidazoles halogeno salt, pyridine
Halo class ionic liquid, one kind in quaternary ammonium salt is as catalyst, reaction pressure 0.5-5MPa, 50-200 DEG C of reaction temperature,
Cyclic carbonate is prepared by being catalyzed carbon dioxide and epoxides.These ionic-liquid catalysts are required for adding auxiliary catalysis
Agent, and comparatively ideal catalytic activity is just can guarantee that at higher temperature or elevated pressures, and it is difficult to continuous industry metaplasia
Production.
Patent 102049303A discloses a kind of catalyst of synthesizing acrylic ester and preparation method thereof, catalyst be by
Zinc salt, halogen and organic amine are active component, and inexpensive, efficient catalytic process is realized by carrier of silica, reaction
150-170 DEG C of temperature, pressure 3-4MPa, reaction time 8h.The catalytic process reaction time is longer, and catalytic activity is easy to run off.
Patent 102294264A discloses a kind of oxirane and carbon dioxide of being used for and prepares the hud typed of ethylene carbonate
Catalyst and preparation method thereof, the catalyst system and catalyzing are using silicon dioxide microsphere as nuclear phase, with the metal salt of polyethyleneimine complexing
For shell phase, the catalyst activity is high and active component not easily runs off, but catalyst amount is big, hardly possible recovery, and preparation technology is more multiple
Miscellaneous, catalyst stability is poor, therefore industrialization has little significance.
Patent 102728402 discloses a kind of catalyst for synthesizing propene carbonate and preparation method and application, the catalysis
Agent system is using ionic liquid as active component, using mesopore silicon oxide foamed material as carrier, need not add cocatalyst
Or under solvent condition, make catalytic process compared with showing high activity and selectivity under temperate condition.The disclosure of patent 102513158
A kind of continual multi-phase agent prepares the method and catalyst of ethylene carbonate, and the catalyst system and catalyzing is with functionalized ion liquid
High polymer absorption realizes fixed bed continuous catalysis process on inorganic carrier, reaction pressure 1-6MPa, 80-150 DEG C of temperature, when
Between 1-6h, catalytic process is simple, and activity is high, less energy consumption, and without separating rectifying, conversion ratio is up to 97%, and selectivity is up to 98%.
Document Wei-Li Dai etc. (Catal Lett, 2010,137:74-80) report a kind of imidazole ion liquid containing functional groups
It is grafted onto on high polymer and inorganic carrier silica and catalyst is made, carbon dioxide and epoxidation is catalyzed under autoclave
Thing cycloaddition prepares cyclic carbonate, and reaction pressure 2MPa, 120-140 DEG C of reaction temperature, reaction time 2-4h, catalytic activity is very
High and catalyst is not lost in.
Patent 101225163A provides a kind of method that polyethers macromolecular ionic liquid is prepared by epoxychloropropane, for this
The standby end carboxyl polyoxyalkylene nonionic liquid catalyst of patent system provides certain theoretical foundation, but unlike this patent by its end
Based structures carry out chemical constitution improvement, excellent catalytic performance are made it have, particularly suitable for expoxy propane and titanium dioxide
Carbon catalyzes and synthesizes propene carbonate research.
Although ionic-liquid catalyst and traditional catalyst, such as transient metal complex, major element complex, quaternary ammonium
Salt, phosphonium salt are compared with catalyst system and catalyzings such as alkali metal salts, show excellent catalytic performance, but conventional ion liquid is used alone and urges
The product yield and purity that agent obtains be not high.The cocatalysts such as lewis acid or lewis alkali are added, can significantly improve and urge
Activity, the selectivity of agent, increase product yield, but by a definite limitation in separation and recovery of catalyst and recycling.
Particularly immobilized ionic liquid, homogeneous catalysis system is converted into heterogeneous catalytic system can solve conventional ion liquid well
The problems such as separation of catalyst is difficult and adds co-catalyst.But the immobilized ionic liquid using SBA-15, silica gel as representative is urged
Change system still suffers from problems, as duct is smaller, it is necessary to the deficiencies of solvent and poor catalyst stability.
The content of the invention
Goal of the invention：
The invention provides a kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof, improve ionic liquid and urge
The chemical constitution of agent, make to contain polyethers macromolecular chain and end carboxyl active group in ionic liquid structure, improve catalyst
Activity and selectivity, extend the service life cycle of catalyst；Its purpose is to overcome catalyst effect in the prior art
The shortcomings of rate and not high enough, side reaction is big, service life cycle is short, severe reaction conditions selectivity.
Technical scheme：
The present invention is achieved through the following technical solutions：
A kind of end carboxyl polyoxyalkylene nonionic liquid catalyst, it is characterised in that：Traditional tertiary ammoniac compounds are passed through into chemistry
Bonding method is connected on the polyethers macromolecular chain with end carboxyl functional group, forms this functionalised polyethers ionic liquid；
The general structure of the end carboxyl polyoxyalkylene nonionic liquid catalyst is：
Wherein, tertiary ammoniac compounds NR3It is N- alkyl imidazoles and its derivative, alkyl pyridine and derivative, N- alkyl piperidines
Pyridine and derivative, thiazole and its derivative, pyrroles and its derivative, quinoline and its derivates, pyrazine and its derivative or three hydrocarbon
The tertiary ammonia of base；Its anion X—For Cl—、Br—、Al2Cl7 —、BF4 —、PF6 —、CH3COO—、SbF6 —、AsF6 —、ZnCl3 —、SnCl3 —、N
(C2F5SO2)2 —、N(FSO2)2 —、C(CF3SO2)2 —、CF3CO2 —、CF3SO3 —Or CH3SO3 —。
The polyethers macromolecular chain of connection is Hydrin.
A kind of preparation method of end carboxyl polyoxyalkylene nonionic liquid catalyst as described above, it is characterised in that：Step is as follows：
1), by Based On Hydroxy-terminated Polyepichlorohydrin and monoxone in molar ratio 1:2.2 ratio is added to equipped with condenser pipe
In three-necked flask, using acetonitrile as solvent, temperature is stirring reaction 1h under the conditions of 80 DEG C；
2), by Na2CO3Powder is added gradually in reaction system, until system can not be redissolved, continues 7~8h of reaction；
3), hydrochloric acid is added drop-wise in reaction system using dropwise addition mode, regulation pH value is acidity, system point during dropwise addition
Layer, upper strata is liquid phase, and lower floor is granular white solid；
4) it is, 70 DEG C in temperature by upper phase, rotary evaporation under 0.09MPa vacuums, removes acetonitrile solvent；Again will production
Thing is washed with deionized 5 times, removes some small molecules and excessive monoxone, then with 70 DEG C, rotated under conditions of 0.09Mpa
Evaporation, removes a small amount of water, obtains end carboxyl Hydrin intermediate；
5), by the end carboxyl Hydrin intermediate synthesized above and tertiary ammoniac compounds NR3In molar ratio 1:1.2
It is added in three-necked flask, is stirred in the case where temperature is 60 DEG C of water bath with thermostatic control, react 8h, stop reaction；
6), product is washed 3 times with ethyl acetate, 12h is dried at 70 DEG C, obtains brown color viscous liquid, is
The functionalized ion liquid catalyst of load aggregation thing type.
Building-up process operation is carried out under nitrogen protection.
Tertiary ammoniac compounds NR3It is N- alkyl imidazoles and its derivative, alkyl pyridine and derivative, N- Alkylpiperidines and spreads out
Biology, thiazole and its derivative, pyrroles and its derivative, quinoline and its derivates, pyrazine and its derivative or the tertiary ammonia of trialkyl.
Advantage and effect：
The present invention provides a kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof, has advantages below：
(1) make traditional tertiary ammoniac compounds be connected to the polyethers with function perssad carboxylate by chemical bonding to divide greatly
In subchain, new functionalization polyethers ionic liquid is formed, the activated carboxylic acid groups in its structure and halide anion etc. have
Preferable cooperative effect, improve catalytic activity；Its polyethers macromolecular chain connected, catalyst can be made to produce base position blanketing effect
With infinite dilution effect, by-product is few, and purity is high, yield is big；
(2) catalyst amount is few, high conversion rate, and post processing is simple, easily separated purification；
(3) catalyst life grow, ensure high conversion and it is selective while, increase catalyst recycle number, drop
Low production cost.
(4) catalytic process is carried out under the conditions of relatively mild, and reaction safety is high, and easy to control, corrosivity is small, technique letter
It is single, industrialized beneficial to realizing.
The catalyst that the present invention is prepared using still reaction evaluating apparatus is used for carbon dioxide and expoxy propane adds
Quantitative end carboxyl polyoxyalkylene nonionic liquid catalyst (is accounted for into expoxy propane quality first into preparing propene carbonate, during experiment
1-5%) add in reactor, because Catalyst Viscosity is larger, it is necessary to which the solvent of the quality such as addition is catalyzed again after being diluted, so
After seal reactor, using nitrogen to whole reaction system carry out air replace 3-5 times, use carbon dioxide after being replaced
Bypass to reactor and be pressurized to 0.5MPa, add expoxy propane 130mL (107.9g) into reactor by measuring pump, setting is anti-
Kettle temperature programming is answered, starts stirring, sets revolution.Regulation of carbon dioxide pressure-reducing valve opens carbon dioxide mass flow to 1MPa
Meter, proceeds by reaction.Observing response kettle temperature degree and pressure, because of exothermic heat of reaction, and the beginning stage of reaction is violent, temperature and pressure
It is whard to control, therefore closing presure valve, and forbidden by cooling water control temperature in the kettle more than 120 DEG C.As reaction is carried out,
Pressure can decline in kettle, now open pressure valve, be continually fed into carbon dioxide.After reacting certain time, work as carbon dioxide flow
It is zero to count flow, continues to react 10min, then opens cooling water, reactor is cooled, and after temperature is down to room temperature, is closed
Cooling water is closed, product is pressed into distillation tower reactor and is evaporated under reduced pressure, the colorless liquid product steamed is propene carbonate, bottom
Thing is the ionic-liquid catalyst reclaimed, can direct reuse.
The method catalytic process reaction pressure of the present invention is 1~1.5MPa, reactor temperature be typically maintained in 60 DEG C~
100 DEG C, the reaction time is 80~150min, is 200~250r/min according to temperature adjustment agitation revolution, epoxypropane conversion rate
98.0~100%, propene carbonate selectivity is up to 95.0~99.5%.Catalyst prepared by the method for the present invention is passing through
Learning the mode of bonding makes in ionic liquid structure while contains active end carboxyl functional group and polyethers macromolecular chain, real well
The synergic catalytic effect, base position blanketing effect and infinite dilution effect of catalyst are showed, have effectively reduced accessory substance generation, there is height
Activity, high selectivity, active component are stable, the good characteristic such as long lifespan, environment-friendly can be recycled, for carbon dioxide and
Expoxy propane addition prepares propene carbonate process, gentle with reaction condition, the spies such as catalytic activity is high, easily separated, by-product is few
Point.
Brief description of the drawings
Fig. 1 end carboxyl polyoxyalkylene nonionic liquid catalysts prepare schematic diagram；
Fig. 2 end carboxyl polyethers imidazole ion liquid is catalyzed expoxy propane and CO2Process schematic；
Fig. 3 is that the FTIR of the catalyst of embodiment 1 schemes, i.e. end carboxyl polyethers methylimidazole ionic liquid infrared spectrogram；
Fig. 4 is that the HNMR of the catalyst of embodiment 1 schemes, i.e. end carboxyl polyethers methylimidazole ionic liquid hydrogen nuclear magnetic spectrogram.
Embodiment
A kind of end carboxyl polyoxyalkylene nonionic liquid catalyst, it is characterised in that：Traditional tertiary ammoniac compounds are passed through into chemistry
Bonding method is connected on the polyethers macromolecular chain with end carboxyl functional group, forms this functionalised polyethers ionic liquid, tool
There are good base position blanketing effect, synergic catalytic effect and infinite dilution effect, improve catalytic activity and selectivity.
The general structure of the end carboxyl polyoxyalkylene nonionic liquid catalyst is：
Wherein, tertiary ammoniac compounds NR3Can be N- alkyl imidazoles and its derivative, alkyl pyridine and derivative, N- alkane
Phenylpiperidines and derivative, thiazole and its derivative, pyrroles and its derivative, quinoline and its derivates, pyrazine and its derivative or
Tertiary ammonia of trialkyl etc.；Its anion X—For Cl—、Br—、Al2Cl7 —、BF4 —、PF6 —、CH3COO—、SbF6 —、AsF6 —、ZnCl3 —、
SnCl3 —、N(C2F5SO2)2 —、N(FSO2)2 —、C(CF3SO2)2 —、CF3CO2 —、CF3SO3 —Or CH3SO3 —。
The polyethers macromolecular chain of connection is Hydrin.
A kind of preparation method of end carboxyl polyoxyalkylene nonionic liquid catalyst as described above, is carried out according to the following steps：
1), by Based On Hydroxy-terminated Polyepichlorohydrin and monoxone in molar ratio 1:2.2 ratio is added to equipped with condenser pipe
In three-necked flask, using acetonitrile as solvent, temperature is stirring reaction 1h under the conditions of 80 DEG C.
2), by Na2CO3Powder is added gradually in reaction system, until system can not be redissolved, continues 7~8h of reaction.
3), hydrochloric acid is added drop-wise in reaction system using dropwise addition mode, regulation pH value is acidity, system point during dropwise addition
Layer, upper strata is liquid phase, and lower floor is granular white solid.
4) it is, 70 DEG C in temperature by upper phase, rotary evaporation under 0.09MPa vacuums, removes acetonitrile solvent.Again will production
Thing is washed with deionized 5 times, removes some small molecules and excessive monoxone, then with 70 DEG C, rotated under conditions of 0.09Mpa
Evaporation, removes a small amount of water, obtains end carboxyl Hydrin intermediate.
5), by the end carboxyl Hydrin intermediate synthesized above and tertiary ammoniac compounds in molar ratio 1:1.2 plus
Enter into three-necked flask, stirred in the case where temperature is 60 DEG C of water bath with thermostatic control, react 8h, stop reaction.
6), product is washed 3 times with ethyl acetate, 12h is dried at 70 DEG C, obtains brown color viscous liquid, is
End carboxyl
Polyoxyalkylene nonionic liquid catalyst.
Above-mentioned steps 1) in the synthesis of Based On Hydroxy-terminated Polyepichlorohydrin need to carry out under nitrogen protection, be with boron trifluoride
Ether is catalyst, and carrying out cation open loop in dichloromethane solvent by the way of epoxychloropropane monomer is slowly added dropwise gathers
Close.
Described catalyst is used for tank polymerization technique, available for the propene carbonate product for preparing high-purity, high yield.
Traditional tertiary ammoniac compounds of small molecule are connected to pendant carboxylic group by the present invention in catalyst preparation process
On the polyethers macromolecular chain of group, form the polyoxyalkylene nonionic liquid that differs greatly of zwitterion radius, this new polyethers from
Sub- liquid catalyst is provided with synergic catalytic effect, base position blanketing effect and infinite dilution effect simultaneously, further increases production
The purity and yield of thing, improve the activity and selectivity of catalyst.Tertiary ammoniac compounds by taking alkyl imidazole as an example, urge by the type
Agent preparation process is as shown in Figure 1.Fig. 1 is that end carboxyl polyoxyalkylene nonionic liquid catalyst prepares process schematic.
This polyoxyalkylene nonionic liquid with end carboxyl active group has stronger compared with other ionic-liquid catalysts
Bronsted acid and hydrogen bond donor, end carboxyl and polyether chain therein be more beneficial for the activation and open loop of expoxy propane, suppress
Accessory substance generates, and it is catalyzed expoxy propane and the process of carbon dioxide is as shown in Figure 2.Fig. 2 is end carboxyl polyethers imidazol ion liquid
Body is catalyzed expoxy propane and CO2Process schematic.
The present invention is described in detail with reference to embodiments, but the scope of the present invention is not limited to following embodiments.
Embodiment 1
First by Based On Hydroxy-terminated Polyepichlorohydrin and monoxone in molar ratio 1:2.2 ratio is added to equipped with condenser pipe
In three-necked flask, acetonitrile is solvent, opens stirring, temperature is 80 DEG C, after reacting 1h, by a small amount of Na2CO3Powder is added to three mouthfuls
In flask, after all dissolving, addition is repeated, until system can not be redissolved.About 7-8h is reacted again, the liquid that will be obtained
Hydrochloric acid regulation pH value is added dropwise in body as acidity, system layering during dropwise addition, upper strata is liquid phase, and lower floor is granular white solid.
By upper phase temperature be 70 DEG C, rotary evaporation under 0.09Mpa, remove acetonitrile solvent.Product is washed with deionized 5 again
It is secondary, some small molecules and excessive monoxone are removed, then with 70 DEG C, rotary evaporation under conditions of 0.09Mpa, remove a small amount of
Water, obtain end carboxyl Hydrin.
Again by the end carboxyl Hydrin of above-mentioned synthesis and N- methylimidazoles in molar ratio 1:1.2 are added to three mouthfuls of burnings
In bottle, stirring is opened, 8h is reacted in the case where temperature is 60 DEG C of water bath with thermostatic control, stops reaction；Product is washed 3 times with ethyl acetate,
Product is dried into 12h at 70 DEG C, it is the end carboxyl polyethers methyl that anion is chlorion to obtain brown color viscous liquid
Imidazole ion liquid catalyst, yield are about 74%.
By the catalyst that the present invention obtains by still reaction device, carbon dioxide and expoxy propane addition reaction system are carried out
Standby propene carbonate, reactor volume is 300mL, and loaded catalyst is 3.24g (account for expoxy propane quality 3%), specifically
Additive process condition：100 DEG C, 1~1.5Mpa of reaction pressure, speed of agitator 250r/min of reaction temperature, reaction time 100min
Afterwards it was observed that carbon dioxide mass flow count value is unchanged, measuring propene carbonate product purity after completion of the reaction is
99.4%, calculate epoxypropane conversion rate be 100.0%, selectivity be 98.5%.
Embodiment 2
In the same equipment with being used in embodiment 1, under the same terms, catalyst amount is simply changed to 5.40g and (accounted for
Expoxy propane quality 5%), the nearly 90min of its catalytic reaction observes that carbon dioxide mass flow count value is unchanged, has reacted
Propene carbonate product purity is measured after finishing as 99.6%, calculate epoxypropane conversion rate is 100.0%, be selectively
99.2%.
Embodiment 3
In the same equipment with being used in embodiment 1, under the same terms, catalyst amount is simply changed to 1.08g and (accounted for
Expoxy propane quality 1%), reaction 2.5h observe that carbon dioxide mass flow count value is unchanged, measure after completion of the reaction
Propene carbonate product purity is 99.1%, calculate oxirane conversion ratio is 99.8%, ethylene carbonate is selectively
98.2%.
Embodiment 4
In the same equipment with being used in embodiment 1, under the same terms, simply N- methylimidazoles are changed into N- ethyl miaows
Azoles, the nearly 130min of its catalytic reaction observe that carbon dioxide mass flow count value is unchanged, measure carbonic acid third after completion of the reaction
Alkene ester products purity be 98.6%, calculate epoxypropane conversion rate be 100.0%, selectivity be 98.3%.
Embodiment 5
In the same equipment with being used in embodiment 1, under the same terms, simply N- methylimidazoles are changed into pyridine, its
The nearly 150min of catalytic reaction observes that carbon dioxide mass flow count value is unchanged, measures propene carbonate production after completion of the reaction
Thing purity be 98.1%, calculate epoxypropane conversion rate be 99.4%, selectivity be 96.9%.
Embodiment 6
In the same equipment with being used in embodiment 1, under the same terms, simply N- methylimidazoles are changed into pyrroles, its
The nearly 150min of catalytic reaction observes that carbon dioxide mass flow count value is unchanged, measures propene carbonate production after completion of the reaction
Thing purity be 97.2%, calculate epoxypropane conversion rate be 98.2%, selectivity be 95.1%.
Embodiment 7
In the same equipment with being used in embodiment 1, under the same terms, simply N- methylimidazoles are changed into N- methyl piperazines
Piperazine, the nearly 140min of its catalytic reaction observe that carbon dioxide mass flow count value is unchanged, measure carbonic acid third after completion of the reaction
Alkene ester products purity be 97.5%, calculate epoxypropane conversion rate be 98.4%, selectivity 96.5%.
Embodiment 8
In the same equipment with being used in embodiment 1, under the same terms, simply by anion Cl-Change Br into-, it is catalyzed
React nearly 80min and observe that carbon dioxide mass flow count value is unchanged, it is pure to measure propylene carbonate ester products after completion of the reaction
Spend for 99.2%, calculate epoxypropane conversion rate is 100%, selectivity 99.5%.
Embodiment 9
In the same equipment with being used in embodiment 1, under the same terms, simply by anion Cl-Change BF into4 -, it is urged
Change the nearly 180min of reaction and observe that carbon dioxide mass flow count value is unchanged, measure propylene carbonate ester products after completion of the reaction
Purity is 97.2%, calculate epoxypropane conversion rate be 99.2%, selectivity 95.8%.
Embodiment 10
In the same equipment with being used in embodiment 1, under the same terms, simply by anion Cl-Change PF into6 -, it is urged
Change the nearly 170min of reaction and observe that carbon dioxide mass flow count value is unchanged, measure propylene carbonate ester products after completion of the reaction
Purity is 97.5%, calculate epoxypropane conversion rate be 98.3%, selectivity 96.2%.
Embodiment 11
In the same equipment with being used in embodiment 1, under the same terms, simply by anion Cl-Change CH into3COO-, its
The nearly 200min of catalytic reaction observes that carbon dioxide mass flow count value is unchanged, measures propene carbonate production after completion of the reaction
Thing purity be 94.4%, calculate epoxypropane conversion rate be 98.0%, selectivity 95.2%.
Embodiment 12
In the same equipment with being used in embodiment 1, under the same terms, temperature is simply changed to 80 DEG C, mixing speed
Observe that carbon dioxide mass flow count value is unchanged for 225r/min, reaction about 1.5h, obtaining purity after completion of the reaction is
99.1%, calculate epoxypropane conversion rate be 100.0%, propene carbonate selectively be 98.3%.
Embodiment 13
In the same equipment with being used in embodiment 1, under the same terms, temperature is simply changed to 60 DEG C, mixing speed
Observe that carbon dioxide mass flow count value is unchanged for 200r/min, reaction about 150min, obtaining purity after completion of the reaction is
96.3%, calculate epoxypropane conversion rate be 100.0%, propene carbonate selectively be 99.2%.
Embodiment 14
In the same equipment with being used in embodiment 1, under the same terms, simply the ionic-liquid catalyst of recovery is entered
The multiple reuse of row, it reuses number and epoxypropane conversion rate and selectivity, the purity of gained propene carbonate
Between relation it is as shown in table 1.
The catalyst of table 1 recycles influence of the number to product property index
Data illustrate that the type ionic-liquid catalyst can be recycled for multiple times in table 1.Catalyst recycles 10 times
When gained propene carbonate indices vary less, recycle 13 times when, gained propene carbonate indices still exist
More than 95%.This illustrates that the type catalyst activity component is relatively stable, can repeatedly use, greatly reduce and be produced into
This.
Conclusion：The present invention relates to a kind of end carboxyl polyoxyalkylene nonionic liquid catalyst and preparation method thereof, the catalyst of preparation
Extraordinary synergic catalytic effect, base position blanketing effect and infinite dilution effect are showed, effectively increases catalytic activity and choosing
Selecting property.
Claims (4)
- A kind of 1. end carboxyl polyoxyalkylene nonionic liquid catalyst, it is characterised in that：Traditional tertiary amine compounds are passed through into chemical bond It is legal to be connected on the polyethers macromolecular chain with end carboxyl functional group, form this functionalised polyethers ionic liquid；The general structure of the end carboxyl polyoxyalkylene nonionic liquid catalyst is：Wherein, tertiary amine compounds NR3It is N- alkyl imidazoles and its derivative, alkyl pyridine and derivative, N- Alkylpiperidines and spreads out Biology, thiazole and its derivative, pyrroles and its derivative, quinoline and its derivates, pyrazine and its derivative or trialkyl tertiary amine； Its anion X—For Cl—、Br—、Al2Cl7 —、BF4 —、PF6 —、CH3COO—、SbF6 —、AsF6 —、ZnCl3 —、SnCl3 —、N (C2F5SO2)2 —、N(FSO2)2 —、C(CF3SO2)2 —、CF3CO2 —、CF3SO3 —Or CH3SO3 —；The preparation method of described end carboxyl polyoxyalkylene nonionic liquid catalyst, its step are as follows：1), by Based On Hydroxy-terminated Polyepichlorohydrin and monoxone in molar ratio 1:2.2 ratio is added to three mouthfuls equipped with condenser pipe In flask, using acetonitrile as solvent, temperature is stirring reaction 1h under the conditions of 80 DEG C；2), by Na2CO3Powder is added gradually in reaction system, until system can not be redissolved, continues 7~8h of reaction；3), hydrochloric acid is added drop-wise in reaction system using dropwise addition mode, regulation pH value is acidity, system layering during dropwise addition, Upper strata is liquid phase, and lower floor is granular white solid；4) it is, 70 DEG C in temperature by upper phase, rotary evaporation under 0.09MPa vacuums, removes acetonitrile solvent；Product is used again Deionized water is washed 5 times, removes some small molecules and excessive monoxone, then is rotated and steamed with 70 DEG C, under conditions of 0.09Mpa Hair, removes a small amount of water, obtains end carboxyl Hydrin intermediate；5), by the end carboxyl Hydrin intermediate synthesized above and tertiary amine compounds NR3In molar ratio 1:1.2 add Into three-necked flask, stirred in the case where temperature is 60 DEG C of water bath with thermostatic control, react 8h, stop reaction；6), product is washed 3 times with ethyl acetate, 12h is dried at 70 DEG C, brown color viscous liquid is obtained, as loads The functionalized ion liquid catalyst of polymer-type.
- 2. end carboxyl polyoxyalkylene nonionic liquid catalyst according to claim 1, it is characterised in that：The polyethers macromolecular of connection Chain is Hydrin.
- 3. end carboxyl polyoxyalkylene nonionic liquid catalyst according to claim 1, it is characterised in that：Building-up process operation exists Nitrogen protection is lower to be carried out.
- 4. end carboxyl polyoxyalkylene nonionic liquid catalyst according to claim 1, it is characterised in that：Tertiary amine compounds NR3It is N- alkyl imidazoles and its derivative, alkyl pyridine and derivative, N- Alkylpiperidines and derivative, thiazole and its derivative, pyrroles And its derivative, quinoline and its derivates, pyrazine and its derivative or the tertiary ammonia of trialkyl.
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| CN108097309B (en) * | 2016-11-24 | 2020-03-17 | 中国石油化工股份有限公司 | CO (carbon monoxide)2High-efficiency catalyst for synthesizing propylene carbonate with propylene oxide and preparation method thereof |
| CN108097331B (en) * | 2016-11-24 | 2020-03-17 | 中国石油化工股份有限公司 | CO (carbon monoxide)2Catalyst for synthesizing propylene carbonate with epoxypropane and preparation method thereof |
| CN109053633A (en) * | 2018-08-29 | 2018-12-21 | 江苏师范大学 | A kind of synthetic method of 5- amino -1,2,3- thiadiazoles |
| CN111841627B (en) * | 2020-06-12 | 2023-06-27 | 青岛科技大学 | Silica-based material supported polyether functionalized ionic liquid catalyst and preparation method thereof |
| CN115651186B (en) * | 2022-11-08 | 2024-05-14 | 浙江巨化技术中心有限公司 | Method for preparing perfluoropolyether acid |
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