CN104828803A - A preparing method of a monodisperse phenolic resin carbon microbead - Google Patents
A preparing method of a monodisperse phenolic resin carbon microbead Download PDFInfo
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Abstract
A preparing method of a monodisperse phenolic resin carbon microbead is provided. The method includes following steps of: forming water-in-oil phenolic resin liquid drops in a micro-channel reactor by a microfluidic liquid drop technique; preparing the phenolic resin liquid drops into phenolic resin microbeads by thermocuring; washing and separating the phenolic resin microbeads to obtain a monodisperse phenolic resin microbead; and subjecting the monodisperse phenolic resin microbead to high-temperature carbonization in an inert atmosphere to form the monodisperse phenolic resin carbon microbead. The method overcomes the defects in the prior art, namely complex processes, difficulty in accurate control of product particle sizes, irregular morphology, and the like, and has advantages of simple and rapid preparation process, controllable microbead particle size, uniform particle size, good degrees of sphericity, and the like.
Description
Technical field
The present invention relates to a kind of preparation method of single dispersing resol carbon microspheres, particularly relate to a kind of Microfluidic droplet technology that utilizes and the method for controlled quick preparation is carried out to single dispersing resol carbon microspheres, belong to carbon microspheres technical field.
Background technology
Carbon microspheres not only has higher thermostability, chemical stability, modifiability and biocompatibility, also has the Some features being better than particle charcoal, such as good fluidity, packing density is high, physical strength is high.Therefore, carbon microspheres is widely used in the fields such as electrode materials, sorbent material, support of the catalyst and pharmaceutical carrier.
Prepare thermoset microballoon with phenol resin oligomer and have the features such as foreign matter content is low, structure-controllable, abundant raw material, preparing carbon microspheres with it for raw material has become people's study hotspot.
Preparing the operational path that alkyd resin based microballoon adopts in CN1255457C is: after lacquer resin mixes with certain proportion with solidifying agent hexamethylenetetramine by (1), be dissolved in ethanol or/and form resol alcoholic solution in methyl alcohol; (2) tensio-active agent and water are made into the aqueous solution containing tensio-active agent with certain proportion; (3) resol alcoholic solution is joined in the aqueous solution containing tensio-active agent, under at the uniform velocity agitation condition, be heating and curing, obtain alkyd resin based microballoon.The microspherulite diameter that this method obtains is difficult to accurate control, size-grade distribution heterogeneity.
Preparing the operational path that phenolic resin activated carbon microballon adopts in CN101774577A is: resole solutions adopts the method for spraying dry or fluidised bed drying to be prepared into phenolic resin microspheres by (1); (2) phenolic resin microspheres drying obtained heats up and carries out thermofixation; (3) by solidification after phenolic resin microspheres in nitrogen atmosphere, high temperature cabonization.The drying temperature that this method obtains and solidification value is high, microballoon sphericity is bad, particle diameter is uncontrollable, size-grade distribution heterogeneity.
Visible, still there is complex process in prior art, product granularity is difficult to the shortcoming such as accurate control, pattern irregularity; Therefore, improve preparation technology further, the preparation method researching and developing novel phenolic resin microspheres and carbon microspheres is significant.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of single dispersing resol carbon microspheres.This preparation method adopts Microfluidic droplet technology to prepare single dispersing phenolic resin microspheres, and then prepares its carbon microspheres, has the advantages such as preparation technology is simple, quick, microspherulite diameter is controlled.
For achieving the above object, the invention provides a kind of preparation method of single dispersing resol carbon microspheres, it comprises the following steps:
(1) in micro passage reaction, water in oil resol drop is formed by Microfluidic droplet technology;
(2) described resol drop is then made to form phenolic resin microspheres by thermofixation;
(3) wash, be separated described phenolic resin microspheres, obtain single dispersing phenolic resin microspheres;
(4) make described single dispersing phenolic resin microspheres carry out high temperature carbonization again under inert atmosphere protection, form single dispersing resol carbon microspheres.
In above-mentioned preparation method, preferably, step (1) specifically comprises: be 5-1000mps using viscosity, solid content is that the water soluble phenol resin of 30-60% is as disperse phase solution; Mixed by the oil that tensio-active agent and difficulty are volatilized, being mixed with containing surfactant qualities percentage concentration is that the organic solution of 1%-10% is as continuous phase solution; Described disperse phase solution and continuous phase solution circulation are entered in micro passage reaction, and to control disperse phase solution flow rate be 0.1-3mL/h, continuous phase solution flow velocity is 1-20mL/h, through the shearing of external phase, forms water in oil resol drop.
In above-mentioned preparation method, the described water soluble phenol resin in step (1) can adopt commercially available prod or adopt ordinary method to be prepared.
In above-mentioned preparation method, preferably, in step (1), described tensio-active agent is oil-soluble, and it comprises the combination of one or more in the composition etc. of Span80, DC0749, EM90, Span80 and Tween20; The oil of described difficulty volatilization comprises the combination of one or more in the difficult alkane, liquid paraffin, mineral oil and the plant wet goods that volatilize, and more preferably, the alkane of described difficulty volatilization comprises dodecane and/or n-Hexadecane etc.
In above-mentioned preparation method, preferably, in step (1), also comprise thermoplastic material in described disperse phase solution as pore-forming material, for the preparation of porous carbon microspheres, described thermoplastic material comprises the combination of one or more in polyoxyethylene glycol, polyvinyl alcohol and water soluble starch etc.
In the preparation process in accordance with the present invention, by adjusting flow velocity and the concentration of disperse phase solution and continuous phase solution, and/or by adjusting the channel size of micro passage reaction, the particle diameter of phenolic resin microspheres is controlled, to prepare the phenolic resin microspheres of different-grain diameter.Preferred technical scheme is: in step (1), and described disperse phase solution comprises that viscosity is 10-300mps, solid content is the water soluble phenol resin of 40-60%; It is the organic solution (such as: paraffin solution, mineral oil solution etc.) of the EM90 of 1-5% that described continuous phase solution comprises containing mass percent concentration; The flow velocity of described disperse phase solution is 0.1-1mL/h, and the flow velocity of described continuous phase solution is 1-15mL/h.
In above-mentioned preparation method, preferably, in step (1), can arrange collection tube in micro passage reaction, disperse phase solution and continuous phase solution are met at collection tube mouth of pipe place, to form resol drop, as illustrated in figs. ia and ib.
In above-mentioned preparation method, preferably, in step (1), the disperse phase solution in described micro passage reaction identical with the circulating direction of continuous phase solution (as shown in Figure 1a) and/or reverse (as shown in Figure 1 b).When to adopt disperse phase solution and the scheme that the circulating direction of continuous phase solution is identical and reverse simultaneously, can merge as shown in figures i a andb flow to scheme, even if disperse phase solution flows into micro passage reaction from a direction, make continuous phase solution flow into micro passage reaction from both direction simultaneously.
In above-mentioned preparation method, preferably, in step (1), described disperse phase solution and the continuous phase solution circulation method entered in micro passage reaction is made to be: described disperse phase solution and continuous phase solution to be respectively charged in syringe that (syringe arranges two or three according to the scheme that flows to adopted, adopt two phase flow to arranging two syringes time identical or contrary, adopt two phase flow to arranging three syringes time identical and contrary) simultaneously, described syringe is positioned over respectively (a corresponding micro-injection pump of syringe) on micro-injection pump, and make described syringe connect micro passage reaction, then in micro passage reaction, described disperse phase solution and continuous phase solution is injected respectively by described micro-injection pump.
In above-mentioned preparation method, in step (1), multiple micro passage reaction parallel connection can be used, the reactor used in parallel can adopt the mode that disperse phase solution is as shown in Figure 1a identical with continuous phase solution circulating direction, also the mode that disperse phase solution is as shown in Figure 1 b contrary with continuous phase solution circulating direction can be adopted, two kinds of modes can also be combined, namely a part of reactor adopts the mode that circulating direction is identical, another part adopts the mode that circulating direction is contrary, or adopts the mode that circulating direction is identical and contrary simultaneously.
In above-mentioned preparation method, preferably, the thermosetting in step (2) turns to online thermofixation or off-line thermofixation.More preferably, described online thermofixation comprises: the one end oozing material at the liquid phenolic resin of micro passage reaction connects a collection container, directly carries out temperature programming to the resol drop in described collection container, forms phenolic resin microspheres; Described off-line thermofixation comprises: collect the resol drop that step (1) generates, and be placed in baking oven, then carry out temperature programming, forms phenolic resin microspheres.
In above-mentioned preparation method, preferably, in the process of above-mentioned online solidification, described collection container is coil pipe, the material of described coil pipe is the combination of one or more in copper, aluminium, glass, quartz and high molecule plastic etc., described high molecule plastic comprises the combination of one or more in polypropylene, polyethylene and tetrafluoroethylene etc., and the length of described coil pipe is 50-500cm.
In above-mentioned preparation method, preferably, the heating schedule of the thermofixation in step (2) is: at 50-80 DEG C of insulation 0.5-5h, then at 80-95 DEG C of insulation 0.5-5h, again at 95-105 DEG C of insulation 0.5-2h, finally selectively at 110-150 DEG C of insulation 0.5-3h.
In the preparation process in accordance with the present invention, at thermo-curing stage, no matter adopt online or off-line thermofixation mode, solidification process all needs temperature programming, low temperature Procuring, and then hot setting, solidification value and the degree of crosslinking of phenolic resin microspheres can be affected set time, and finally affect macroscopic view and the microtexture of carbon microspheres, namely affect the particle diameter of microballoon, sphericity, specific surface area etc.In addition, if direct hot setting (>=100 DEG C), in water-in-oil (W/O) liquid droplet system, drop internal vapour pressure is greater than water saturation vapour pressure, demulsifying phenomenon can occur, occur coacervation.Can avoid occurring the problems referred to above by adopting thermofixation heating schedule provided by the present invention, the thermofixation heating schedule that the present invention adopts is: at 50-80 DEG C of insulation 0.5-5h, then at 80-95 DEG C of insulation 0.5-5h, again at 95-105 DEG C of insulation 0.5-2h, finally selectively at 110-150 DEG C of insulation 0.5-3h.If only perform front 3 temperature program(me)s, hollow carbon microspheres can be obtained; And if complete execution 4 temperature program(me)s, then can obtain solid carbon microspheres.Therefore, by regulating thermofixation heating schedule simply, the carbon microspheres of different structure can be prepared.
In above-mentioned preparation method, preferably, in step (2), the collection liquid (online and off-line thermofixation all needs to collect liquid) collecting resol drop is close with the density of resol drop, is more preferably equal, in order to avoid under gravity, drop will float or sink, demixing phenomenon occurs, and drop dense arrangement can be flocculated together, coalescent, final breakdown of emulsion.Described collection liquid can comprise the mixed solution of one or more in liquid paraffin, chloroform, tetracol phenixin, methylene dichloride, methyl-sulphoxide and oil of mirbane etc.
In above-mentioned preparation method, preferably, the washing in step (3) is organic solvent washing and/or ultrasonic washing, is separated into centrifugation.Wherein, the number of times adopting organic solvent washing can be 3-5 time, described organic solvent comprises the combination of one or more in the alkane of low carbon chain, acetone, butanols and ethanol etc., can rinse with water after organic solvent washing, then carry out centrifugation, finally can at 50-90 DEG C dry 1-2h (such as adopting baking oven).Ultrasonic washing is the method adopting ultrasonic emulsion breaking, and concrete steps, for phenolic resin microspheres is put into ultrasonator, are also named in ultrasonic cleaning instrument, ultrasonic 2-10min, then can carry out centrifugation, and can clean 3-10 time with water, optionally can also carry out drying.
In above-mentioned preparation method, preferably, step (4) specifically comprises: make described single dispersing phenolic resin microspheres at N
2be warming up to 600-1000 DEG C with the speed of 2-10 DEG C/min in atmosphere, insulation 1-5h carbonizes, and after cooling, obtains single dispersing resol carbon microspheres.
In the preparation process in accordance with the present invention, the macroscopic view such as particle diameter, sphericity, specific surface area of the single dispersing resol carbon microspheres prepared and the structural parameter of microcosmic, mainly controlled by the addition of the high temperature carbonization heating schedule in the thermofixation heating schedule in step (2) and step (4) and pore-forming material.Preferably, the particle diameter of described single dispersing phenolic resin microspheres is 70-1000 μm, and the particle diameter of described single dispersing resol carbon microspheres is 50-500 μm.
The Preparation Method of single dispersing resol carbon microspheres provided by the invention mainly has following beneficial effect:
(1) size tunable, good sphericity, the homogeneous grain diameter of single dispersing phenolic resin microspheres and carbon microspheres thereof, carbon microspheres particle size range is 50-500 μm, simply controlled;
(2) reaction unit and technological process simple possible, micro passage reaction yardstick is adjustable controlled, prepared Microsphere Size can conveniently regulating and controlling;
(3) reaction is carried out in micro passage reaction, and strengthen the mass-and heat-transfer process of reaction, make solidification value can be lower, the solidification value time be shorter, thus provides necessary precondition for preparing single dispersing phenolic resin microspheres;
(4) separation of phenolic resin microspheres can adopt the technique of ultrasonic emulsion breaking, centrifugation, can reduce the use of chemical reagent, and operational path is simple, and greatly reduce production cost, product does not introduce other detrimental impurity, reduces environmental pollution;
(5) be different from traditional reaction unit, less energy-consumption, continuous operation can be realized in micro passage reaction, if by simple for multiple micro passage reaction parallel connection, can increase yield fast, enhance productivity, without any scale effect.
In sum, the preparation method of single dispersing resol carbon microspheres provided by the invention overcomes complex process that prior art exists, product granularity is difficult to the shortcoming such as accurate control, pattern irregularity, have preparation technology simple, quick, microspherulite diameter is controlled, the advantage of homogeneous grain diameter, good sphericity etc.
Accompanying drawing explanation
Fig. 1 a be in micro passage reaction disperse phase solution identical with continuous phase solution circulating direction flow to schematic diagram;
Fig. 1 b be in micro passage reaction disperse phase solution contrary with continuous phase solution circulating direction flow to schematic diagram;
Fig. 2 is the optical microscopy map of the single dispersing resol carbon microspheres in embodiment 1, and scale is 100 μm;
Fig. 3 is the optical microscopy map of the single dispersing resol carbon microspheres in embodiment 3, and scale is 100 μm;
Fig. 4 is the optical microscopy map of the phenolic resin microspheres in embodiment 4, and scale is 500 μm;
Fig. 5 is the optical microscopy map of the single dispersing phenolic resin microspheres in embodiment 6, and scale is 500 μm;
Fig. 6 is the optical microscopy map of drop breakdown of emulsion process in the solidification process in comparative example 1, and scale is 500um;
Fig. 7 is the optical microscopy map of the phenolic aldehyde phenolic resin microspheres in comparative example 2, and scale is 100 μm.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
The preparation method of single dispersing resol carbon microspheres provided by the invention can comprise the following steps:
(1) be 5-1000mps using viscosity, solid content is that the water soluble phenol resin of 30-60% is as disperse phase solution, mixed by the oil that tensio-active agent and difficulty are volatilized, being mixed with containing surfactant qualities percentage concentration is that the organic solution of 1%-10% is as continuous phase solution, described disperse phase solution and continuous phase solution are respectively charged in syringe, described syringe is positioned on micro-injection pump respectively, and make described syringe connect micro passage reaction, then in micro passage reaction, described disperse phase solution and continuous phase solution is injected respectively by described micro-injection pump, described disperse phase solution and continuous phase solution circulation is made to enter in micro passage reaction, the circulating direction of disperse phase solution and continuous phase solution can identical (as shown in Figure 1a) and/or oppositely (as shown in Figure 1 b), and to control disperse phase solution flow rate be 0.1-3mL/h, continuous phase solution flow velocity is 1-20mL/h, in micro passage reaction, collection tube is set, disperse phase solution and continuous phase solution are met at collection tube mouth of pipe place, through the shearing of external phase, form water in oil resol drop, and flow out micro passage reaction through collection tube,
(2) described resol drop is then made to form phenolic resin microspheres by thermofixation, the heating schedule of this thermofixation is: at 50-80 DEG C of insulation 0.5-5h, then at 80-95 DEG C of insulation 0.5-5h, again at 95-105 DEG C of insulation 0.5-2h, last selectively at 110-150 DEG C of insulation 0.5-3h, this thermofixation can be online thermofixation or off-line thermofixation, wherein online thermofixation comprises: the one end oozing material at the liquid phenolic resin of micro passage reaction connects a collection container, the collection liquid close with resol drop density is contained with in this collection container, directly temperature programming is carried out to the resol drop in described collection container, form phenolic resin microspheres, this collection container can be coil pipe, the material of described coil pipe is copper, aluminium, glass, the combination of one or more in quartz and high molecule plastic etc., described high molecule plastic comprises polypropylene, the combination of one or more in polyethylene and tetrafluoroethylene etc., the length of described coil pipe is 50-500cm, off-line thermofixation comprises: utilize the resol drop that the container collection being contained with the collection liquid close with resol drop density flows out from the collection tube of micro passage reaction, and be placed in baking oven, then carry out temperature programming, form phenolic resin microspheres,
(3) wash, be separated described phenolic resin microspheres, obtain single dispersing phenolic resin microspheres; Washing wherein can be organic solvent washing and/or ultrasonic washing, and separation can be centrifugation; Adopt the number of times of organic solvent washing can be 3-5 time, can rinse with water after organic solvent washing, then carry out centrifugation, finally can at 50-90 DEG C dry 1-2h (such as adopting baking oven); Ultrasonic washing is the method adopting ultrasonic emulsion breaking, and concrete steps, for phenolic resin microspheres is put into ultrasonator, are also named in ultrasonic cleaning instrument, ultrasonic 2-10min, then can carry out centrifugation, and can clean 3-10 time with water, optionally can also carry out drying;
(4) make described single dispersing phenolic resin microspheres at N
2be warming up to 600-1000 DEG C with the speed of 2-10 DEG C/min in atmosphere, insulation 1-5h carbonizes, and after cooling, obtains single dispersing resol carbon microspheres.
Technical scheme of the present invention is further illustrated below with some specific embodiments.
Embodiment 1
Take 2.0g EM90 to add in the beaker being contained with 100mL mineral oil, magneton slowly stirs, and filters, and obtains continuous phase solution; By commercially available water soluble phenol resin, viscosity is 60mps, and solid content is 47%, filters, and obtains disperse phase solution.Two kinds of solution are respectively charged in the syringe of 20mL, be placed on micro-injection pump, and be connected with micro passage reaction, the internal diameter of this micro passage reaction is 0.9mm, and external diameter is 1.1mm, makes the circulating direction of disperse phase solution and continuous phase solution oppositely (as shown in Figure 1 b), and arranging disperse phase solution flow rate is 0.5mL/h, continuous phase solution flow velocity is 5mL/h, and the collection tube mouth of pipe place of two-phase in micro passage reaction is met, and constantly generates the resol drop of size uniformity.Collect with the collector that liquid paraffin is housed the drop generated, put into baking oven and carry out temperature programming solidification, at 70 DEG C of insulation 1.5h, 90 DEG C of insulation 0.5h, 100 DEG C of insulation 1h, then at 110 DEG C of insulation 1h, obtain phenolic resin microspheres.After repeatedly washing this phenolic resin microspheres with normal heptane, acetone, rinse with water, and centrifugation, obtain single dispersing phenolic resin microspheres, particle diameter is about 130 μm.The tube furnace that this single dispersing phenolic resin microspheres puts into nitrogen protection is carried out high temperature carbonization; carbonization process rises to 650 DEG C with the speed of 5 DEG C/min; insulation 1h; under nitrogen protection after naturally cooling; obtain single dispersing resol carbon microspheres; particle diameter is about 100 μm, and its optical microscopy map is shown in Fig. 2, as seen its homogeneous grain diameter, good sphericity.
Embodiment 2
Using containing mass percent concentration be the paraffin solution of EM90 of 2% as continuous phase solution, be 15mps using viscosity, solid content be that the water soluble phenol resin of 47% is as disperse phase solution.The inlet bore of the micro passage reaction adopted is 160 μm, and outlet bore is 200 μm.Make the circulating direction of disperse phase solution and continuous phase solution oppositely (as shown in Figure 1 b).Controlling disperse phase solution flow rate is 0.5mL/h, and continuous phase solution flow velocity is 3mL/h.Identical with embodiment 1 of other steps and parameter.Obtain the resol drop that particle diameter is about 180 μm.The particle diameter of the single dispersing phenolic resin microspheres obtained is 115 μm, and particle diameter deviation CV < 3%, size is homogeneous.
Embodiment 3
Substantially identical with the preparation method in embodiment 1, difference is: the heating schedule of thermofixation is for being incubated 1.5h at 70 DEG C, and 90 DEG C are incubated 0.5h, 100 DEG C of insulation 3h, optical microscopy map after carbon microspheres after high temperature carbonization rolls is shown in Fig. 3, and this carbon microspheres is hollow as seen.
Embodiment 4
Substantially identical with the preparation method in embodiment 1, difference is: the viscosity of water soluble phenol resin is 200mps, and solid content is 60%.Do not adopt collection liquid, the effect that the liquid phenolic resin collected drops in gravity sinks to bottom collector, put into after baking oven carries out thermofixation according to the temperature programming of embodiment 1, find that the phenolic resin microspheres slabbing after thermofixation is bonded in bottom collector, the optical microscopy map scraping sample is shown in Fig. 4.
Embodiment 5
Take 5.0g Span80 and 1.25g Tween20 (ratio with mass ratio 4:1) to add in the beaker being contained with 100mL n-Hexadecane, magneton slowly stirs, and filters, and obtains continuous phase solution; By commercially available water soluble phenol resin, viscosity is 60mps, and solid content is 47%, filters, and obtains disperse phase solution.Two kinds of solution are respectively charged in the syringe of 50mL, be placed on micro-injection pump, and be connected with micro passage reaction, the internal diameter of this micro passage reaction is 0.9mm, and external diameter is 1.1mm, makes disperse phase solution identical with the circulating direction of continuous phase solution (as shown in Figure 1a), and arranging disperse phase solution flow rate is 1.0mL/h, continuous phase solution flow velocity is 15mL/h, and the collection tube mouth of pipe place of two-phase in micro passage reaction is met, and constantly generates the resol drop of size uniformity.Collect with the collector that liquid paraffin is housed the drop generated, put into baking oven and carry out temperature programming solidification, at 70 DEG C of insulation 1h, 90 DEG C of insulation 1h, 100 DEG C of insulation 0.5h, then 110 DEG C of insulations 0.5, obtain phenolic resin microspheres.After repeatedly washing this phenolic resin microspheres with normal heptane, acetone, rinse with water, and centrifugation, obtain single dispersing phenolic resin microspheres, particle diameter is about 430 μm.The tube furnace that this single dispersing phenolic resin microspheres puts into nitrogen protection is carried out high temperature carbonization; carbonization process rises to 650 DEG C with the speed of 5 DEG C/min, and insulation 2h, under nitrogen protection after naturally cooling; obtain single dispersing resol carbon microspheres, particle diameter is about 320 μm.
Embodiment 6
Substantially identical with the preparation method in embodiment 5, difference is: disperse phase solution flow rate is 0.8mL/h, continuous phase solution flow velocity is 9mL/h, and connect different lengths at micro passage reaction exit end, internal diameter is the glass coil pipe 3 of 3mm, the previous outlet of these 3 glass coil pipes is connected with a rear import, these 3 glass coil pipes are placed on 65 DEG C respectively, in the oil bath pan of 3 differing tempss of 90 DEG C and 100 DEG C (namely, make resol drop successively through 65 DEG C, the oil bath pan of 90 DEG C and 100 DEG C carries out temperature programming), find that phenolic resin curing is comparatively complete, substantially do not stick together, through washing, the particle diameter of the single dispersing phenolic resin microspheres obtained after separation is about 130 μm, its optical microscopy map is shown in Fig. 5.
Embodiment 7
Substantially identical with the preparation method in embodiment 6, difference is: adopt ultrasonic emulsion breaking, centrifugation and carry out washing, the separation of phenolic resin microspheres by washed with de-ionized water.Ultrasonic time is 2-10min, and washed with de-ionized water number of times is 3-10 time.
Embodiment 8
Substantially identical with the preparation method in embodiment 7, difference is: joined in the commercially available water soluble phenol resin of 100mL by 0.5g polyvinyl alcohol (Mw=20000), be stirred to abundant dissolving, filters, and obtains disperse phase solution.Disperse phase solution and continuous phase solution are respectively charged in the syringe of 20mL, be placed on micro-injection pump, and be connected with micro passage reaction, arranging disperse phase solution flow rate is 0.3mL/h, continuous phase solution flow velocity is 7mL/h, the internal diameter of this micro passage reaction is 0.9mm, external diameter is 1.1mm, adopt the scheme that disperse phase solution is identical and contrary with the circulating direction of continuous phase solution (even if disperse phase solution flows into micro passage reaction from a direction simultaneously, make continuous phase solution flow into micro passage reaction from both direction) simultaneously, and the collection tube mouth of pipe place of two-phase in micro passage reaction is met, the resol drop of continuous generation size uniformity.After the online thermofixation of temperature programming forms phenolic resin microspheres, with the repeatedly alternately washing of normal heptane, acetone, ethanol, rinse with water, and centrifugation, obtain single dispersing phenolic resin microspheres, particle diameter is about 240 μm.After the tube furnace that this single dispersing phenolic resin microspheres puts into nitrogen protection is carried out high temperature carbonization, the particle diameter of the single dispersing resol carbon microspheres of acquisition is about 170 μm, records its specific surface area 910m
2/ g.
Comparative example 1
Liquid phenolic resin dripping is standby with embodiment 1, and just solidification adopts single stage method solidification, namely at the curing oven 0.5h of 110 DEG C, drop breakdown of emulsion in solidification process, partial agglomeration is to together, and solidified and substantially to have existed without microballoon afterwards, the optical microscopy map of solidification process drop breakdown of emulsion is shown in Fig. 6.
Comparative example 2
Liquid phenolic resin dripping is standby with embodiment 1, and just program curing adopts 90 DEG C to be incubated 1h, and 100 DEG C of insulation 0.5h, the phenolic aldehyde phenolic resin microspheres after solidification adheres to together, and its optical microscopy map is shown in Fig. 7.
Claims (10)
1. a preparation method for single dispersing resol carbon microspheres, it comprises the following steps:
(1) in micro passage reaction, water in oil resol drop is formed by Microfluidic droplet technology;
(2) described resol drop is then made to form phenolic resin microspheres by thermofixation;
(3) wash, be separated described phenolic resin microspheres, obtain single dispersing phenolic resin microspheres;
(4) make described single dispersing phenolic resin microspheres carry out high temperature carbonization in an inert atmosphere, form single dispersing resol carbon microspheres.
2. the preparation method of single dispersing resol carbon microspheres according to claim 1, wherein, step (1) comprising: be 5-1000mps using viscosity, solid content is that the water soluble phenol resin of 30-60% is as disperse phase solution; Mixed by the oil that tensio-active agent and difficulty are volatilized, being mixed with containing surfactant qualities percentage concentration is that the organic solution of 1%-10% is as continuous phase solution; Described disperse phase solution and continuous phase solution circulation are entered in micro passage reaction, and to control disperse phase solution flow rate be 0.1-3mL/h, continuous phase solution flow velocity is 1-20mL/h, through the shearing of external phase, forms water in oil resol drop.
3. the preparation method of single dispersing resol carbon microspheres according to claim 2, wherein, described tensio-active agent comprises the combination of one or more in the composition of Span80, DC0749, EM90, Span80 and Tween20; The oil of described difficulty volatilization comprises the combination of one or more in the difficult alkane, liquid paraffin, mineral oil and the vegetables oil that volatilize, and preferably, the alkane of described difficulty volatilization comprises dodecane and/or n-Hexadecane.
4. the preparation method of single dispersing resol carbon microspheres according to claim 2, wherein, also comprise thermoplastic material in described disperse phase solution, described thermoplastic material comprises the combination of one or more in polyoxyethylene glycol, polyvinyl alcohol and water soluble starch.
5. the preparation method of single dispersing resol carbon microspheres according to claim 2, wherein, described disperse phase solution comprises that viscosity is 10-300mps, solid content is the water soluble phenol resin of 40-60%; Described continuous phase solution comprises containing mass percent concentration the organic solution of the EM90 being 1-5%; The flow velocity of described disperse phase solution is 0.1-1mL/h, and the flow velocity of described continuous phase solution is 1-15mL/h.
6. the preparation method of single dispersing resol carbon microspheres according to claim 2, wherein, the disperse phase solution in described micro passage reaction is identical with the circulating direction of continuous phase solution and/or reverse.
7. the preparation method of single dispersing resol carbon microspheres according to claim 1, wherein, the thermosetting in step (2) turns to online thermofixation or off-line thermofixation;
Preferably, described online thermofixation comprises: the one end oozing material at the liquid phenolic resin of micro passage reaction connects a collection container, directly carries out temperature programming to the resol drop in described collection container, forms phenolic resin microspheres;
Described off-line thermofixation comprises: collect the resol drop that step (1) generates, and be placed in baking oven, then carry out temperature programming, forms phenolic resin microspheres;
More preferably, collection container in described online thermofixation is coil pipe, the material of described coil pipe is the combination of one or more in copper, aluminium, glass, quartz and high molecule plastic, described high molecule plastic comprises the combination of one or more in polypropylene, polyethylene and tetrafluoroethylene, and the length of described coil pipe is 50-500cm.
8. the preparation method of the single dispersing resol carbon microspheres according to claim 1 or 7, wherein, the heating schedule of the thermofixation in step (2) is: at 50-80 DEG C of insulation 0.5-5h, then at 80-95 DEG C of insulation 0.5-5h, again at 95-105 DEG C of insulation 0.5-2h, finally selectively at 110-150 DEG C of insulation 0.5-3h.
9. the preparation method of single dispersing resol carbon microspheres according to claim 1, wherein, step (4) comprising: make described single dispersing phenolic resin microspheres at N
2be warming up to 600-1000 DEG C with the speed of 2-10 DEG C/min in atmosphere, insulation 1-5h carbonizes, and after cooling, obtains single dispersing resol carbon microspheres.
10. the preparation method of single dispersing resol carbon microspheres according to claim 1, wherein, the particle diameter of described single dispersing phenolic resin microspheres is 70-1000 μm, and the particle diameter of described single dispersing resol carbon microspheres is 50-500 μm.
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| CN105513741A (en) * | 2016-01-11 | 2016-04-20 | 中国科学院化学研究所 | Magnetic nanoparticle/macromolecular Janus microparticle and preparation method and application thereof |
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