CN100443157C - Application of continuous microwave reactor - Google Patents
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- CN100443157C CN100443157C CNB2006101316384A CN200610131638A CN100443157C CN 100443157 C CN100443157 C CN 100443157C CN B2006101316384 A CNB2006101316384 A CN B2006101316384A CN 200610131638 A CN200610131638 A CN 200610131638A CN 100443157 C CN100443157 C CN 100443157C
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Abstract
The present invention is the application of continuous microwave reactor in preparing ionic liquid. The continuous microwave reactor developed based on household microwave oven is applied in preparing ionic liquid in the general expression of A+B-, where, A+ is organic cation, B- is inorganic anion. The ionic liquid has smelting point at 1 atm (101.325kPa) lower than 100 deg.c. The continuous microwave reactor has high reaction rate of preparing ionic liquid, 10-1000 times higher than conventional process, and the continuous process results in effectively lowered cost.
Description
Technical field
The present invention relates to a kind of continuous microwave reactor and be used to prepare ionic liquid.
Technical background
Technical background
Chemical reaction often needs heating or high temperature, high pressure to carry out, heating means in the past mostly adopt the mode of heat conduction and thermal convection current, these heating means are to conduct heat by the external world to inside reactor, firing rate is slow, and the reaction system external temperature is higher than internal temperature, it is inhomogeneous to be heated, and causes reaction yield and selectivity also unsatisfactory, is difficult to satisfy the requirement of some chemical reaction.Microwave then can the direct irradiation reactant mixture in each molecule, comprise solvent, reaction mass and catalyst, reaction vessel is materials such as the borosilicate that do not absorb microwave, quartz, polytetrafluoroethylene (PTFE).Can farthest utilize the energy like this, and be heated evenly, can accelerate chemical reaction rate, increase reaction yield, simplify course of reaction, improve research and production efficient.
1986, Canada professor Gedye has delivered the paper (TetrahedronLett. of first piece of microwave catalysis chemical synthesis, 1986,27,4945-4958), he with the means of microwave electromagnetic field as the acceleration chemical reaction, finds that the microwave radiation can improve organic reaction speed greatly, increases productive rate in the family expenses micro-wave oven.From then on, the microwave assistant chemical has caused people's extensive concern.Because the microwave assistant chemical has the flexibility and the control ability that can't obtain in the conventional method, the transmission of microwave continuous or with molecule or ion coupling, brought continuous heating.This mode of heating makes reaction rate improve 10-1000 doubly than traditional mode of heating, and it is undoubtedly the fastest current, the method for effective accelerated reaction.Association areas such as Synthetic Organic Chemistry, molecular biology, analytical chemistry, inorganic chemistry, mineral chemistry, material science, pharmaceutical chemistry and biologic pharmacological science now have been widely used in.
Usually the temperature of reaction system can be risen progressively along with the increase of energy input, must control the energy input of course of reaction in order to prevent destruction that high temperature causes reactant, i.e. just be interrupted reaction after microwave radiation a period of time, continues reaction after the reactant cooling again.As the auxiliary intermittent reaction of the microwave of CN2284100Y report, reaction vessel is placed household microwave oven, be used for the organic or pharmaceutical chemical multiple reaction of catalysis, it not only can be finished low boiling or the solution reaction of penetrating odor is arranged, can also organic solid phase reaction of catalysis and the reaction of higher boiling polar liquid phase.But microwave irradiation is inhomogeneous in this microwave reactor, can not carry out magnetic agitation, therefore for avoiding hot-spot, need often to be interrupted microwave irradiation in the course of reaction, the taking-up reactant stirs and makes it to be heated evenly, and need be cooled to lower temperature, discharge and continue reaction behind the unnecessary heat again; Reaction also needs constantly to change microwave power, makes that like this microwave irradiation is inhomogeneous, and temperature control is inaccurate,
Microwave reactor commonly used also has the auxiliary flow reactor of microwave except the auxiliary batch reactor of microwave.Nineteen ninety, people (S.Chen, S.Chiou, J.Chem Soc.Chem.Commun., 1990,807) such as the Chen of Taiwan Univ. have reported the microwave continuous reaction technology, and reactant enters in the microwave reactor through pump housing pressurization, flows out after the microwave radiation and enters receiver.This device can high yield the acid hydrolytic reaction that carries out sucrose, 1, the cyclization of 4-butanediol etc., Racemization of Amino Acids reaction etc.Yet the temperature of this reaction system can't effectively be controlled equally, in addition, does not have decompressor in the exit of sample, has brought huge trouble to reception.1994, Australia CSIRO (the T.Cablewski of company, A.F.Faux, Journal of Organic Chemistry., 1994., 9,3408) and reported a kind of continuous microwave reactor, this reactor is to place micro-wave oven to form in one group of transverse type coil pipe, and material can react by reactor continuously.As a kind of connecting technique, it can process the raw material of a great deal of, more is applicable to optimize reaction; But heat exchanger is in the reactor outside, can not the better controlled reaction temperature, and when needs reaction in the time of the long period, can cause in the reactor material local temperature too high, influence reaction yield, some low-temp reactions also can't carry out in this microwave reactor.
Microwave reactor can be divided into two kinds: the reactor that professional microwave synthesis system and household microwave oven are transformed.The microwave synthesis system of specialty has the reaction under high pressure of going for, and can measure temperature accurately, and stability is high, and reaction condition such as can monitor at advantage, but cost is than higher.The MARS5 type microwave multimode of CEM company is quickened the organic synthesis system needs hundreds thousand of units, some common microwave reactors also need units up to ten thousand, and reactor cannot further transform in experimental requirement, and treating capacity is also smaller, usually only several milliliters, also can be very high even amplify synthetic cost.Therefore, this type of professional microwave synthesis system is only applicable to few products synthetic of high added value.
Household microwave oven is low, the simple structure of cost then, can transform under the condition of safety as required, and treating capacity is also bigger, is applicable to the large-scale production of general chemistry product.Especially domestic microwave successive reaction equipment not only can overcome deficiencies such as aforesaid complex operation, treating capacity be little, the more important thing is can be continuous heating using microwave, this just makes large-scale continuous production become possibility.In sum, need a kind of flow reactor of on the basis of family expenses micro-wave oven, reequiping of design, it can not only be within the specific limits, the temperature of reasonable control reaction, reactant can be heated evenly, reduce accessory substance, the stopping reaction productive rate, and can be as required, control is reflected under the lower temperature to be carried out; Simultaneously can also be large-scale industrialization production, provide that a kind of technical process is simple, workable, equipment stable, reliable, cheap, the continuous microwave consersion unit that can popularize and promote.
Ionic liquid at room temperature, be meant near the molten salt system that constitutes by ion that is in a liquid state under the temperature room temperature or the room temperature, since ionic liquid at room temperature have liquid wide ranges, to inorganic and organic matter fine solubility, low-steam pressure, strong polarity are arranged, to most stable reagents be easy to peculiar properties such as recycling, application study at aspects such as separation process, chemical reaction and electrochemistry has obtained many gratifying results, therefore, be considered to have in the synthetic and cleaner production of a kind of green the novel environmental close friend's of wide application prospect green solvent.
Ion liquid conventional preparation method is described in WO96/18459 and WO95/21871.The method that WO96/18459 adopts leaded anion and halogen-containing cationoid reaction to generate the precipitation lead halide prepares ionic liquid, it is wider that the method prepares kind, yet reaction needed is carried out in methanol solution, and leaded anionic price is more expensive, dissolubility in solution is bad, and lead halide also is difficult to precipitation fully.WO95/21871 places sealed vacuum Corius pipe with reactant, and 100 ℃ are reacted a week down, can prepare most of ionic liquids.But the reaction time is longer, severe reaction conditions.Preparation cost is higher equally, is difficult to satisfy its continuous and requirement of large-scale production.Therefore, need improving one's methods in ion liquid preparation field.
Because micro ware auxiliary catalysis can shorten the reaction time greatly, save cost, improve productive rate, therefore, the application of microwave technology in ion liquid synthesizing caused the attention of Many researchers.Introduced the auxiliary synthetic ion liquid method of microwave among the patent CN1361716A: will promptly finish reaction with 5 fens kinds of microwave irradiation down at 170 ℃ after methylimidazole and chlorobutane and the amount of ethyl acetate mixing.The freezing sedimentation of product gets final product, and need not purifying.Yet there are two aspect problems in this patent: 1, methylimidazole decomposes easily 170 ℃ of instabilities.2, the purpose of dividing ethyl acetate to be difficult to play purifying on a small quantity, the solubility of methylimidazole in product is still very big, and degree of purity of production is difficult to guarantee.R.S.Varma, and V.V.Namboodiri. (ChemComm, 2001,643-644) use household microwave oven and prepare ionic liquid, do not need with an organic solvent in the course of reaction, really realized the essence of ion liquid green solvent; Reaction is fast, the time short, from several hrs and even shortened to a few minutes in several days; The productive rate height, good product purity.But reactive mode is an intermittent reaction, in order to prevent hot-spot, needs intermittently heating and cooling, complex operation, and treating capacity is also little.M.Deetlefs, K.R.Seddon. (Green Chemistry, 2003,5,181-186.) quicken synthetic ionic liquid in the organic synthesis system, the temperature automatically controlled pressure control of computer in the MARS5 of CEM company type microwave multimode, the reaction treatment amount can be amplified to 2mol, and productive rate can reach 99%.This system also needs to control stablely by stopping microwave irradiation, belongs to intermittent reaction; And expensive price, can't the large-scale industrial production ionic liquid.
At present, ion liquid synthesizing utilized microwave technology, mainly adopts the microwave batch reactor, and treating capacity is all very little, complex operation, and the microwave continuous reactor can overcome above deficiency, but about utilizing the synthetic ion liquid document of continuous microwave reactor to yet there are no report both at home and abroad.
Summary of the invention:
The purpose of this invention is to provide a kind of continuous microwave reactor and be used to prepare ionic liquid.
A kind of continuous microwave reactor of the present invention, as shown in Figure 1.Described a kind of continuous microwave reactor is constructed as follows: it has the wave microwave oven 19 of commentaries on classics and microwave cavity cavity 4, also has:
Reactant blender 1, magnetic stirring apparatus 2, constant flow pump 3, reactor 5, cooling device 6, product separator 7, product gathering-device 8, feed pipe 9, discharge nozzle 10, side pipe 11, push pipe 12, condensate liquid flow into pipe 13, condensate liquid flows out pipe 14, reactor carriage 15, microwave rf generator 16, glass container 17, iron stand 18, stirrer 20, loading hopper 21, side opening 22, apical pore 23, condensate stream incoming interface 24, condensate stream outgoing interface 25, charging interface 26, discharging interface 27, plug I28, pump head 29, plug II30 and baiting valve 31;
Microwave cavity cavity 4 is microwave cavity cavitys of micro-wave oven 19; Microwave rf generator 16 is welded in the bottom of microwave cavity cavity 4; place the glass container that fills water 17 that a protection microwave rf generator promptly is used for load on the microwave rf generator 16; sidepiece and top at microwave cavity cavity 4 are drilled with side opening 22 and apical pore 23 respectively; weld side pipe 11 and push pipe 12 respectively on this side opening 22 and this apical pore 23; side pipe 11 and the diameter of push pipe 12 and frequency of oscillation and the wavelength that length depends on micro-wave oven; its length be greater than micro-wave oven wavelength 1/2; its internal diameter be less than micro-wave oven wavelength 1/4, microwave just can not leak into the external world.
Reactor 5 is the hard glass bend pipe, and it is positioned in the cooling device 6, and the two ends of reactor 5 are respectively charging interface 26 and discharging interface 27; The two ends of cooling device 6 are respectively condensate stream incoming interface 24 and condensate stream outgoing interface 25, condensate stream incoming interface 24 flows into pipe 13 with condensate stream outgoing interface 25 and condensate liquid and condensate liquid outflow pipe 14 is tightly connected, cooling device 6 places on the reactor carriage 15, reactor carriage 15 contains four foot supports of groove for glass tube curves, the diameter of groove radian and cooling device 6 is complementary, and reactor carriage 15 is positioned on the microwave rf generator 16;
One end of feed pipe 9 and the charging interface 26 of reactor 5 are tightly connected, and feed pipe 9 passes from side pipe 11 again, are fixed in then in the pump head 29 of constant flow pump 3, and the other end of feed pipe 9 is closely holed and passed plug I28, communicates with reactant blender 1;
One end of discharge nozzle 10 and the discharging interface 27 of reactor 5 are tightly connected, and closely, discharge nozzle 10 passes from side pipe 12 again, and closely plug II 30 is passed in boring, and the other end of discharge nozzle 10 communicates with product separator 7;
Reactant blender 1 is positioned on the magnetic stirring apparatus 2, places stirrer 20 in the reactant blender 1, and 21 another holes from the plug I28 of the bottleneck of reactant blender 1 of loading hopper are closely passed;
Magnetic stirring apparatus 2 is positioned on the constant flow pump 3;
Product separator 7 has baiting valve 31, and product gathering-device 8 places on the iron stand 18 under product separator 7;
Described reactor 5, reactor carriage 15, glass container 17, cooling device 6 and feed pipe 9 and discharge nozzle 10, condensate liquid flow into pipe 13 and condensate liquid flows out pipe 14, is that insulating materials is made, because insulator can permeate microwave, microwave is partly reflected, but major part then sees through, and has only very little part microwave to be absorbed.Therefore in microwave system, use the insulating materials of glass, pottery, polytetrafluoroethylene (PTFE), polypropylene plastics and so on according to different situations.
Material flows in reactor 5, and reactor 5 outsides are connected with condensed water and carry out countercurrent heat exchange, and temperature is controlled.Reaction system is heated evenly, and system temperature is stable.
Reactant blender 1 is a glass apparatus, the high polymer that can also adopt materials such as plastics, polytetrafluoroethylene (PTFE), polyethylene, polypropylene or polystyrene to make.
The high polymer that product separator 7 and product gathering-device 8 can be made for materials such as glass apparatus, plastics, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polystyrene.
Feed pipe 9 used among the present invention is the constant flow pump dedicated pipe, and discharge nozzle 10 is a silicone tube, and condensate liquid flows into pipe 13 and condensate liquid outflow pipe 14 is an emulsion tube.Because constant flow pump requires to use the flexible pipe of 1.6mm wall thickness, so the feed pipe 9 from plug I 28 to charging interface 26 all is the flexible pipe of 1.6mm wall thickness.Discharge nozzle 10, promptly from discharging interface 27 to plug II30, all be the cheap silicone tube of price comparison.Constant flow pump dedicated pipe both feed pipe 9 and discharge nozzle 10 used silicone tubes all is can be high temperature resistant, etch-proof flexible pipe.Condensing agent among the present invention is a water, so condensate liquid flows into pipe 13 and condensate liquid outflow pipe 14 is that common emulsion tube gets final product.
Used condensate liquid is a water among the present invention.Make condensing agent with water following advantage is arranged: 1, microwave is stronger to its penetration capacity, can penetrate water layer smoothly and shine on the reaction mass.2, condensation effect is better.3, water is also less expensive, can save synthetic cost greatly.The penetration depth of microwave is relevant with the temperature of material, and microwave frequency of the present invention is the microwave frequency 2.45GHz of household microwave oven.When water temperature was 15 ℃, the penetration capacity of microwave was 0.9cm, and in the time of 25 ℃, the penetration capacity of microwave is 1.3cm, and in the time of 75 ℃, the penetration capacity of microwave is 3.2cm.Can select the reactor of different size according to the needs of experimental temperature.Reactor diameter is 3cm among the present invention, and microwave can penetrate fully.The outer wall of the cooling device 6 of selected reflux condensing tube and the outer wall of reactor 5 be spaced apart 3mm, microwave can see through fully, meets requirement of experiment fully.4, after the simple cooling of water process, reusable edible, energy savings reduces synthetic cost.
Of the present invention～kind of continuous microwave reactor can be used to prepare ionic liquid.
Introduce a kind of continuous microwave reactor of the present invention below and be used to prepare ion liquid method.
The ionic liquid that a kind of continuous microwave reactor of the present invention is used to prepare is the compound with following general formula:
A
+B
-
A in the formula
+Be organic cation, described organic cation A
+Be the cation that N-replaces, be preferably the N-heteroaromatic cation that N-replaces; B
-Be anion, described anion B
-Be inorganic anion; Described ionic liquid pure form of (101.325kPa) under 1 atmospheric pressure has and is lower than 100 ℃ fusing point.
Described cation A
+Has general formula [R
1R
2X]
+, its structural formula is:
X is the N-hetero-aromatic ring in the formula, R
1And R
2For containing the saturated or undersaturated alkyl of 1～20 carbon atom, be preferably the saturated or undersaturated alkyl that contains 1～8 carbon atom, R
1And R
2Can be identical also can be inequality, it links to each other with N-atom on the N-hetero-aromatic ring.
The N-heteroaromatic cation A that described N-replaces
+Be drone cation, be pyridinium, imidazoles drone, thiazole drone, oxazole drone or pyrimidine drone, wherein fragrant ring nitrogen links to each other with described alkyl;
Described imidazoles drone cation is 1-(C
1-20)-3-(C
1-20)-imidazoles drone cation; Preferred 1-(C
1-8)-3-(C
1-8)-imidazoles drone cation, more preferably 1-methyl-3-(C
1-8)-imidazoles drone cation.
Described B
-Anion is following organic and inorganic anion: F
-, Cl
-, Br
-, I
-, NO
3 -, BF
4 -, PF
6 -, FeCl
4 -, ZnCl
3 -, SnCl
5 -, AsF
6 -, SbF
6 -, AlCl
4 -, CF
3COO
-, NiCl
3 -, (CF
2SO
3 -)
2Or (CF
3)
2PF
4 -
Described B
-Be the halo group of inorganic anion, the group of preferred chlorine or bromine;
Step and condition that a kind of continuous microwave reactor of the present invention is used to prepare ion liquid method are:
Can form the cation A of positively charged
+Organic materials with can form electronegative anion: B
-Inorganic material press A
+: B
-Mol ratio is that 1.0: 1.0 proportioning is mixed, and flows in the reactant blender 1 by loading hopper 21, stirs, and passes through in feed pipe 9 inflow reactors 5 under the drive of constant flow pump 3.The flow velocity of regulating magnetic stirring apparatus 2 makes it to stir, it is 2～3 minutes that the flow velocity of adjusting constant flow pump 3 makes the flowing time of reaction mass in reactor 5, and it is 60～70 ℃ with the reaction temperatures that reach in the control reactor 5 that cooling device 6 interior feeding water carry out heat exchange.Reactant flows into product separator 7 by reactor 5 by discharge nozzle 10 under the drive of constant flow pump 3, static layering, and lower floor's material inflow places the product gathering-device 8 below the product separator 7, obtains the viscous liquid mixture.Ethyl acetate extraction with viscous liquid mixture equal volume therewith separates 2～3 times, collects lower floor's liquid phase.After removing the solvent ethyl acetate in lower floor's liquid phase under reduced pressure, 60～80 ℃ of continuous vacuum dryings obtained ionic liquid in 6～8 hours.This ionic liquid is for having general formula: A
+B
-Compound.Product is preserved under drying condition.
A kind of continuous microwave reactor of the present invention is used to prepare ionic liquid, compared with prior art has following remarkable advantage:
1) continuous microwave reactor of the present invention is to design to convert on the basis of family expenses micro-wave oven, have cheap, volume is little, simple in structure, easy amplification, advantage such as workable, applicable to the chemical reaction of various liquid materials.
2) continuous microwave reactor provided by the invention can carry out the continuous heating of reaction mass." continuously " is meant that reaction mass can constantly flow through reactor under certain dynamic action, in process of flowing, react the product outflow reactor of generation between the material.The reaction condition of each several part material is identical in the continuous microwave reactor.The flow velocity that is to say the each several part material is identical, and the time of irradiation is identical, and temperature is identical, so reaction environment is stable, and product is in stable condition, steady quality; Fan Ying treating capacity can arbitrarily be amplified simultaneously, promptly reacts the total amount that total amount depends on that reaction mass drops into, but not the volume of reactor.That is to say that the reaction total amount can be regulated by the volume that changes the reactant blender.
3) flow reactor does not need to be interrupted reaction, has saved operating procedure greatly, has simplified experimentation, can arbitrarily amplify, dwindle reaction by requirement of experiment simultaneously, and especially suitable extensive continued operation makes things convenient for industrial production.And the microwave batch reactor is to prevent that hot-spot from need need heating and cooling off and on, so the each several part material is because the different meeting of the condition of the microwave of irradiation hot-spot, need off and on heating, cooling and stirring, make it to be heated evenly and expended great amount of manpower.And the repeatability of each batch and stability also remain further check.
4) because microwave reaction speed depends primarily on the molecular assembly kinetic energy of the driving of high density microwave field density, but not the temperature of reaction system.Therefore can control reaction temperature by heat exchanger, the heat that disperse of removal system synchronously continues acquisition high density microwave.Because heat exchanger in micro-wave oven inside, can be controlled condensation temperature at optimum range at any time, make reaction system obtain required high density microwave in the novel commentaries on classics ripple continuous microwave reactor of the present invention because of what empty calory accumulation continued.Thereby guaranteed stablizing of system temperature and stablizing of goal response thing, made the reaction in constant temperature stage still keep two-forty.
The high microwave radiation of low temperature has increased synthesising reacting speed and productive rate greatly, eliminates accessory substance and produces.Prevented the reaction system hot-spot problem that batch reactor exists, and conventional flow reactor since heat exchanger in the outside of reactor, reaction system inside is heated inhomogeneous, the temperature instability causes the unsettled deficiency of productive rate.
Simultaneously, the used condensing agent of the present invention is water, and is cheap and easy to get, and inflow temperature and flow velocity that temperature controlling only needs to regulate water get final product, and be easy to operation, saved reaction cost greatly.It should be noted that because the temperature of the ability of microwave penetration condensing agent-water and water is relevant, so the distance of heat exchanger outer wall and reactor outer wall needs suitably shortening when carrying out low-temp reaction.
A kind of continuous microwave reactor of the present invention is used to prepare ionic liquid, effective fast reaction speed, reaction rate can improve 10～1000 times, very slow ion liquid synthetic the becoming of a lot of speed that conventional method is carried out realizes also finishing at a high speed easily, prepare by conventional method and to shorten in one hour in a required week, and process can carry out continuously, effectively reduced cost.
Description of drawings
Fig. 1 is a novel microwave successive reaction device structure schematic diagram.
Among the figure: reactant blender 1, magnetic stirring apparatus 2, constant flow pump 3, microwave cavity cavity 4, reactor 5, cooling device 6, product separator 7, product gathering-device 8, feed pipe 9, discharge nozzle 10, side pipe 11, push pipe 12, condensate liquid flows into pipe 13, condensate liquid flows out pipe 14, reactor carriage 15, microwave rf generator 16, glass container 17, iron stand 18, micro-wave oven 19, stirrer 20, loading hopper 21, side opening 22, apical pore 23, condensate stream incoming interface 24, condensate stream outgoing interface 25, charging interface 26, discharging interface 27, plug I 28, pump head 29, plug II 30 and baiting valve 31.
Fig. 2 is the wave-rotating furnace structural representation.
Wave-rotating furnace microwave rf generator 16 shown in the figure is placed in the bottom of micro-wave oven, is refracted to micro-wave oven 19 inner all directions through changeing the ripple device, and illuminated material 32 is heated evenly.
The specific embodiment
Embodiment 1 novel microwave successive reaction equipment
A kind of novel microwave successive reaction equipment of the present invention, as shown in Figure 1: it comprises reactant blender 1, magnetic stirring apparatus 2, constant flow pump 3, microwave cavity cavity 4, reactor 5, cooling device 6, product separator 7, product gathering-device 8, feed pipe 9, discharge nozzle 10, side pipe 11, push pipe 12, condensate liquid flows into pipe 13, condensate liquid flows out pipe 14, reactor carriage 15, microwave rf generator 16, glass container 17, iron stand 18, micro-wave oven 19, stirrer 20, loading hopper 21, side opening 22, apical pore 23, condensate stream outgoing interface 24, condensate stream incoming interface 25, charging interface 26, discharging interface 27, plug I 28, pump head 29, plug II 30 and anti-material valve 31.
Micro-wave oven 19 of the present invention is the novel wave-rotating furnace MF-2070EGZ of Haier; Microwave cavity cavity 4 is microwave cavity cavitys of micro-wave oven 19; Microwave rf generator 16 is welded in the bottom of microwave cavity cavity 4, places the glass container that fills water 17 that a protection microwave rf generator promptly is used for load on the microwave rf generator 16; Sidepiece and top at microwave cavity cavity 4 are drilled with side opening 22 and apical pore 23 respectively, weld side pipe 11, push pipe 12 respectively on this side opening 22 and this apical pore 23; Side pipe 11 and the diameter of push pipe 12 and frequency of oscillation and the wavelength that length depends on micro-wave oven, the frequency of oscillation of used micro-wave oven is 2.45GHz among the present invention, wavelength is 12.2cm.Therefore work as the length of metal tube greater than 1/2 of wavelength, i.e. 6.1cm; Its internal diameter is less than 1/4 of wavelength, and promptly during 3.05cm, microwave can not leak into the external world.Side pipe 11, push pipe 12 used among the present invention are steel pipe, and the length of steel pipe is 10cm, and greater than minimum length 6.1cm, internal diameter is 2.5cm, and less than maximum inner diameter 3.05cm, external diameter is 4.0cm, all in safe range.
Reactor 5 is the hard glass bend pipe, and body is long to be 10cm, and the pipe diameter is 3cm, and volume is 18.6ml, outer wall and inwall be spaced apart 3mm, its size can be positioned in the cooling device 6 just.The two ends of reactor 5 are respectively charging interface 26 and discharging interface 27; The two-port of reactor 5 is the diameter of charging interface 26 and discharging interface 27, is tightly connected with feed pipe 9 and discharge nozzle 10; The two ends of cooling device 6 are respectively condensate stream incoming interface 24 and condensate stream outgoing interface 25, condensate stream incoming interface 24 flows into pipe 13 with condensate stream outgoing interface 25 and condensate liquid and condensate liquid outflow pipe 14 is tightly connected, condensing agent in the cooling device 6 is to flow into pipe 13 from condensate liquid to flow into, and flows out pipe 14 from condensate liquid and flows out; Cooling device 6 places on the high reactor carriage 15 of 10cm, and reactor carriage 15 contains four foot supports of groove for glass tube curves, and the diameter of groove radian and cooling device 6 is complementary.Reactor carriage 15 is positioned on the microwave rf generator 16;
One end of feed pipe 9 and the charging interface 26 of reactor 5 are tightly connected, and feed pipe 9 passes from side pipe 11 again, are fixed in then in the pump head 29 of constant flow pump 3, and the other end of feed pipe 9 is closely holed and passed plug I28, communicates with reactant blender 1;
One end of discharge nozzle 10 and the discharging interface 27 of reactor 5 are tightly connected, and closely, discharge nozzle 10 passes from side pipe 12 again, and closely plug II30 is passed in boring, and the other end of discharge nozzle 10 communicates with product separator 7;
Reactant blender 1, promptly the 250ml three-necked bottle is positioned on the magnetic stirring apparatus 2, places stirrer 20 in the reactant blender 1, and 21 another holes from the plug I 28 of the bottleneck of reactant blender 1 of loading hopper are closely passed; These two Kong Junyu feed pipes 9 and loading hopper 21 keep sealing;
Product separator 7, promptly the 250ml separatory funnel has baiting valve 31, and product wherein flows into product gathering-device 8, i.e. 250ml beaker by baiting valve 31; Product gathering-device 8 places on the iron stand 18 under product separator 7.
Magnetic stirring apparatus 2 is a 85-1A type magnetic stirring apparatus, is positioned on the constant flow pump 3.The control rotating speed is regulated according to amount of substance in the reactant blender 1 among the present invention, it is stirred get final product.
Constant flow pump 3 is the BT01-100 type, and flow rates is between 0.5～1.0ml/min among the present invention.
Embodiment 2 usefulness continuous microwave reactor of the present invention prepares ionic liquid 1-hexyl-3-methylimidazole bromine salt
Get 79ml (1mol) 1-methylimidazole and 139ml (1mol) hexyl bromide 1 bromohexane and mix, flow in the 250ml three-necked bottle, stir by loading hopper, under the drive of constant flow pump by (microwave power is 280W) in the feed pipe inflow reactor.The flow velocity of regulating magnetic stirring apparatus makes it to stir, and regulates the flow velocity of constant flow pump and (regulates the numerical value to 1.0 of constant flow pump, flow velocity 1.86ml.s
-1), making the flowing time of reaction mass in reactor is 2.5 minutes, it is 60～65 ℃ to reach the control reaction temperature that the interior feeding of cooling device water carries out heat exchange.Flow into separatory funnel by reactor by discharge nozzle under the drive of reaction goods and materials constant flow pump, static layering, lower floor's material inflow places the beaker below the separatory funnel, obtains the viscous liquid mixture.Ethyl acetate extraction with viscous liquid mixture equal volume therewith separates 2 times, collects lower floor's liquid phase.After removing the solvent ethyl acetate in lower floor's liquid phase under reduced pressure, 80 ℃ of continuous vacuum dryings get faint yellow water soluble ion liquid [C after 7 hours
8Mim] Br, product is preserved under drying condition.This experimental technique per hour treating capacity is 111ml.h
-1, it is 92.1ml.h that product prepares speed
-1
As a comparison, adopt people's such as M.Deetlefs. synthetic method (Green Chemistry, 2003,5,181-186.) synthetic ionic liquid in the MARS5 of CEM company type microwave multimode acceleration organic synthesis system.When treating capacity is 1.5mol, get the methylimidazole of 118ml and the 1-chlorobutane of 172ml, successive reaction 5.5 hours (system regulates the irradiation time temperature control automatically) under the 1200W microwave irradiation.Product is dissolved in uses ethyl acetate extraction in the acetonitrile, take off a layer acetonitrile solvent, and 80 ℃ of vacuum drying obtained product [C in 24 hours
4Mim] Cl, productive rate 85%.
Result relatively shows at productive rate and is all under 80～90% prerequisites:
1, the synthetic ionic liquid of the microwave reactor that can adopt the much lower household microwave oven of equipment cost to transform, reaction speed has improved 100～400 times, and reaction cost is greatly reduced.
2, under the prerequisite of same treating capacity, method of the present invention not only the reaction time shorten greatly, and the power of microwave also drops to 280W from 1200W, this means " relatively mild " reaction condition.In the time of energy savings, security has also improved greatly.
3, product is only got product with Yi Suan Yi Zhi He, and has abandoned the mixed extractant of the bigger acetonitrile of ethyl acetate and toxicity, makes experimental implementation safer, and processing method is more succinct.
4, only can disposable adding reactant in the comparative example, treating capacity is 2mol to the maximum, and promptly reaction-ure mixture is 400ml to the maximum; The used continuous microwave reactor of the present invention is not limited to the 300ml treating capacity described in the embodiment, can be continuous as required in the reactant blender, add raw material, reaction is carried out continuously, operability is stronger, for large-scale industrial production provides possibility.
Embodiment 3 usefulness continuous microwave reactor of the present invention prepares ionic liquids ionic liquids 1-octyl group-3-methylimidazole villaumite
Get 79ml (1mol) 1-methylimidazole and 170ml (1mol) 1-chloro-octane and mix, flow in the 250ml three-necked bottle, stir by loading hopper, under the drive of constant flow pump by (microwave power is 420W) in the feed pipe inflow reactor.The flow velocity of regulating magnetic stirring apparatus makes it to stir, and regulates the flow velocity of constant flow pump and (regulates the numerical value to 0.5 of constant flow pump, flow velocity 0.67ml.s
-1), making the flowing time of reaction mass in reactor is 3 minutes, it is 65～70 ℃ to reach the control reaction temperature that the interior feeding of cooling device water carries out heat exchange.Flow into separatory funnel by reactor by discharge nozzle under the drive of reaction goods and materials constant flow pump, static layering, lower floor's material inflow places the beaker below the separatory funnel, obtains the viscous liquid mixture.Ethyl acetate extraction with viscous liquid mixture equal volume therewith separates 3 times, collects lower floor's liquid phase.After removing the solvent ethyl acetate in lower floor's liquid phase under reduced pressure, 70 ℃ of continuous vacuum dryings get faint yellow water soluble ion liquid [C after 6 hours
8Mim] Cl, product is preserved under drying condition.This experimental technique per hour treating capacity is 40ml.h
-1, it is 8.0ml.h that product prepares speed
-1
Embodiment 4 usefulness continuous microwave reactor of the present invention prepares ionic liquids ionic liquids 1-pi-allyl-3-methylimidazole villaumite
Get 79ml (1mol) N-methylimidazole and 81.5ml (1mol) allyl chloride and mix, flow in the 250ml three-necked bottle, stir by loading hopper, under the drive of constant flow pump by (microwave power is 420W) in the feed pipe inflow reactor.The flow velocity of regulating magnetic stirring apparatus makes it to stir, and regulates the flow velocity of constant flow pump and (regulates the numerical value to 0.8 of constant flow pump, flow velocity 1.48ml.s
-1), making the flowing time of reaction mass in reactor is 2 minutes, it is 60～65 ℃ to reach the control reaction temperature that the interior feeding of cooling device water carries out heat exchange.Flow into separatory funnel by reactor by discharge nozzle under the drive of reaction goods and materials constant flow pump, static layering, lower floor's material inflow places the beaker below the separatory funnel, obtains the viscous liquid mixture.Extracted with diethyl ether with viscous liquid mixture equal volume is therewith separated 2 times, collects lower floor's liquid phase.After removing the solvent ether in lower floor's liquid phase under reduced pressure, 60 ℃ of continuous vacuum dryings get faint yellow water soluble ion liquid 1-pi-allyl-3-methylimidazole villaumite after 8 hours, and product is preserved under drying condition.This experimental technique per hour treating capacity is 90ml.h
-1, it is 65ml.h that product prepares speed
-1
Claims (7)
1, a kind of application of continuous microwave reactor is characterized in that, described a kind of continuous microwave reactor is constructed as follows: it has commentaries on classics wave microwave oven (19) and microwave cavity cavity (4), also has:
Reactant blender (1), magnetic stirring apparatus (2), constant flow pump (3), reactor (5), cooling device (6), product separator (7), product gathering-device (8), feed pipe (9), discharge nozzle (10), side pipe (11), push pipe (12), condensate liquid flows into pipe (13), condensate liquid flows out pipe (14), reactor carriage (15), microwave rf generator (16), glass container (17), iron stand (18), stirrer (20), loading hopper (21), side opening (22), apical pore (23), condensate stream incoming interface (24), condensate stream outgoing interface (25), charging interface (26), discharging interface (27), plug I (28), pump head (29), plug II (30) and baiting valve (31);
Microwave cavity cavity (4) is the microwave cavity cavity that changes wave microwave oven (19); Microwave rf generator (16) is welded in the bottom of microwave cavity cavity (4), microwave rf generator (16) is gone up and is placed the glass container that fills water (17) that a protection microwave rf generator promptly is used for load, sidepiece and top at microwave cavity cavity (4) are drilled with side opening (22) and apical pore (23) respectively, weld side pipe (11) and push pipe (12) on this side opening (22) and this apical pore (23) respectively, side pipe (11) and the diameter of push pipe (12) and frequency of oscillation and the wavelength that length depends on micro-wave oven, its length be greater than micro-wave oven wavelength 1/2, its internal diameter be less than micro-wave oven wavelength 1/4;
Reactor (5) is the hard glass bend pipe, and it is positioned in the cooling device (6), and the two ends of reactor (5) are respectively charging interface (26) and discharging interface (27); The two ends of cooling device (6) are respectively condensate stream incoming interface (24) and condensate stream outgoing interface (25), condensate stream incoming interface (24) flows into pipe (13) with condensate liquid and is tightly connected, condensate stream outgoing interface (25) flows out pipe (14) with condensate liquid and is tightly connected, cooling device (6) places on the reactor carriage (15), reactor carriage (15) contains four foot supports of groove for glass tube curves, the diameter of groove radian and cooling device (6) is complementary, and reactor carriage (15) is positioned on the microwave rf generator (16);
The charging interface (26) of one end of feed pipe (9) and reactor (5) is tightly connected, feed pipe (9) passes from side pipe (11) again, be fixed in then in the pump head (29) of constant flow pump (3), the other end of feed pipe (9) is closely holed and is passed plug I (28), communicates with reactant blender (1);
The discharging interface (27) of one end of discharge nozzle (10) and reactor (5) is tightly connected, and discharge nozzle (10) passes from push pipe (12) again, and the other end of discharge nozzle (10) is closely holed and passed plug II (30), communicates with product separator (7);
Reactant blender (1) is positioned on the magnetic stirring apparatus (2), place stirrer (20) in the reactant blender (1), the lower end of loading hopper (21) is also closely passed from the plug I (28) of the bottleneck of reactant blender (1), communicates with reactant blender (1);
Magnetic stirring apparatus (2) is positioned on the constant flow pump (3);
Product separator (7) has baiting valve (31), and product gathering-device (8) places on the iron stand (18) under product separator (7);
It is characterized in that this continuous microwave reactor is used to prepare ionic liquid.
2, the application of a kind of continuous microwave reactor as claimed in claim 1 is characterized in that, the described ionic liquid that is used to prepare is the compound with following general formula:
A
+B
-
A in the formula
+Be organic cation, B
-Be anion; Described organic cation A
+Cation for the N-replacement; The pure form of described ionic liquid 101.325kPa under 1 atmospheric pressure has and is lower than 100 ℃ fusing point;
Described B
-Anion is inorganic anion or organic anion, and described inorganic anion is: F
-, Cl
-, Br
-, I
-, NO
3 -, BF
4 -, PF
6 -, FeCl
4 -, ZnCl
3 -, SnCl
5 -, AsF
6 -, SbF
6 -, AlCl
4 -Or NiCl
3 -Described organic anion is: CF
3COO
-, (CF
2SO
3 -)
2Or (CF
3)
2PF
4 -
3, the application of a kind of continuous microwave reactor as claimed in claim 2 is characterized in that, described ion liquid cation A
+Has general formula [R
1R
2X]
+, its structural formula is as follows:
X is the N-hetero-aromatic ring in the formula, R
1And R
2For containing the saturated or undersaturated alkyl of 1～20 carbon atom, R
1And R
2Identical or inequality, it links to each other with N-atom on the N-hetero-aromatic ring.
4, the application of a kind of continuous microwave reactor as claimed in claim 3 is characterized in that, described ion liquid organic cation A
+In R
1And R
2Substituting group is the saturated or undersaturated alkyl that contains 1～8 carbon atom, R
1And R
2Identical or inequality, it links to each other with N-atom on the N-hetero-aromatic ring.
5, the application of a kind of continuous microwave reactor as claimed in claim 4 is characterized in that, the N-hetero-aromatic ring cation A that described ion liquid N-replaces
+Be drone cation, wherein fragrant ring nitrogen links to each other with described alkyl.
6, the application of a kind of continuous microwave reactor as claimed in claim 5 is characterized in that, the N-hetero-aromatic ring cation A that described ion liquid N-replaces
+Drone cation be imidazoles drone cation, wherein fragrant ring nitrogen links to each other with described alkyl.
7, the application of a kind of continuous microwave reactor as claimed in claim 2 is characterized in that, described B
-Anion is Cl
-Or Br
-
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| CNB2006101316384A CN100443157C (en) | 2006-11-16 | 2006-11-16 | Application of continuous microwave reactor |
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| CNB2006101316384A CN100443157C (en) | 2006-11-16 | 2006-11-16 | Application of continuous microwave reactor |
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| CN100443157C true CN100443157C (en) | 2008-12-17 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995021871A1 (en) * | 1994-02-10 | 1995-08-17 | Bp Chemicals Limited | Ionic liquids |
| WO1996018459A1 (en) * | 1994-12-13 | 1996-06-20 | Bp Chemicals Limited | Ionic liquids |
| CN2284100Y (en) * | 1997-03-19 | 1998-06-17 | 中国人民解放军国防科工委后勤部军事医学研究所 | Microwave reaction unit |
| CN2375375Y (en) * | 1999-03-10 | 2000-04-26 | 中国科学院金属研究所 | Microwave chemical reaction equipment |
| CN2386877Y (en) * | 1999-08-05 | 2000-07-12 | 北京燕山石油化工公司研究院 | Novel microwave continuous reactor |
| CN1361716A (en) * | 1999-05-26 | 2002-07-31 | 个人化学第一乌普萨拉有限公司 | Preparation and use of ionic liquids in microwave-assisted chemical transformation |
-
2006
- 2006-11-16 CN CNB2006101316384A patent/CN100443157C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995021871A1 (en) * | 1994-02-10 | 1995-08-17 | Bp Chemicals Limited | Ionic liquids |
| WO1996018459A1 (en) * | 1994-12-13 | 1996-06-20 | Bp Chemicals Limited | Ionic liquids |
| CN2284100Y (en) * | 1997-03-19 | 1998-06-17 | 中国人民解放军国防科工委后勤部军事医学研究所 | Microwave reaction unit |
| CN2375375Y (en) * | 1999-03-10 | 2000-04-26 | 中国科学院金属研究所 | Microwave chemical reaction equipment |
| CN1361716A (en) * | 1999-05-26 | 2002-07-31 | 个人化学第一乌普萨拉有限公司 | Preparation and use of ionic liquids in microwave-assisted chemical transformation |
| CN2386877Y (en) * | 1999-08-05 | 2000-07-12 | 北京燕山石油化工公司研究院 | Novel microwave continuous reactor |
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