CN103920438A - Method for preparing monodisperse microspheres with uniform sizes - Google Patents
Method for preparing monodisperse microspheres with uniform sizes Download PDFInfo
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- CN103920438A CN103920438A CN201410169661.7A CN201410169661A CN103920438A CN 103920438 A CN103920438 A CN 103920438A CN 201410169661 A CN201410169661 A CN 201410169661A CN 103920438 A CN103920438 A CN 103920438A
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Abstract
The invention relates to a method for preparing monodisperse microspheres with uniform sizes, and aims to solve the problem that conventional phenolic resin microspheres are non-uniform in size and have adhesive properties. The method comprises the following steps: 1, preparing a uniform mixed solution by utilizing resorcinol, deionized water, tetraethoxysilane and benzaldehyde; 2, heating the uniform mixed solution under a sealed condition, cooling, and standing at room temperature, so as to obtain a reacted solution; and 3, washing the reaction solution for a couple of times by adopting the deionized water and ethanol, ultrasonically dispersing, centrifugally separating, and finally drying to obtain the phenolic resin microspheres. The method has the advantages that the phenolic resin microspheres have the uniform sizes and the high dispersibility. The method is mainly used for preparing the phenolic resin microspheres.
Description
Technical field
The present invention relates to a kind of preparation method of mono-dispersion microballoon of size homogeneous.
Background technology
Spherical activated carbon material, due to its special geometry and porous, has obtained application study in many aspects.In report, generally all take phenolic resins, Lauxite is raw material in the past, adopts suspension polymerisation or emulsion polymerisation to prepare phenolic resin microspheres.Yet all processing technology is complicated, the reaction time is long for these methods, have the shortcomings such as accessory substance generation.And there is big or small heterogeneity, have the problem of adhesive in existing phenolic resin microspheres.
Summary of the invention
The present invention seeks to solve existing phenolic resin microspheres size heterogeneity, there is the problem of adhesive, and a kind of preparation method of mono-dispersion microballoon of size homogeneous is provided.
A kind of preparation method of mono-dispersion microballoon of size homogeneous, specifically according to following steps, carry out: one, first resorcinol is dissolved in deionized water, after mixing, adding ethyl orthosilicate and benzaldehyde, is to stir 10min～30min under the water bath condition of 50 ℃ in temperature, and liquid is uniformly mixed; Two, first the liquid that is uniformly mixed in step 1 is transferred in polytetrafluoroethyllining lining reactor, after sealing, be placed in Muffle furnace, heating rate with 1～3 ℃/min rises to 160～200 ℃ from room temperature, and be to react 4h～8h at 160～200 ℃ in temperature, the cooling room temperature of putting, obtains reacting rear solution; Three, by obtaining reacting rear solution in step 2, adopt deionized water washing 2～3 times, adopt again ethanol washing 2～3 times, then ultrasonic being dispersed to evenly, centrifugation under 7000r/min～10000r/min condition again, it is dry 4h～8h in 60～90 ℃ of baking ovens that the solid that separation obtains is placed on temperature, obtains phenolic resin microspheres;
The quality of the resorcinol described in step 1 and the volume ratio of deionized water are (1～6) g:200mL;
The quality of the resorcinol described in step 1 and the volume ratio of ethyl orthosilicate are (2～21) g:14mL;
The quality of the resorcinol described in step 1 and the volume ratio of benzaldehyde are (2～15) g:10mL.
Advantage of the present invention: the present invention, on the basis of one kettle way, has introduced phenyl ring, added tetraethyl orthosilicate, makes original phenolic resin ball have the size of homogeneous more, dispersed better.Just because of these good characteristics, make that its catalytic activity when making catalyst is high, long catalytic life, large availability; Stability as carrier is high.The processing technology of phenolic resin ball is in the past compared, and method of the present invention is more easy, and the product obtaining is more excellent, and performance is more outstanding.
Accompanying drawing explanation
Fig. 1 is SEM (SEM) figure of the phenolic resin microspheres of test one preparation;
Fig. 2 is the X-ray diffractogram (XRD) of the phenolic resin microspheres of test one preparation;
Fig. 3 is Fourier transform infrared spectroscopy (FTIR) figure of the phenolic resin microspheres of test one preparation.
The specific embodiment
The specific embodiment one: present embodiment is a kind of preparation method of mono-dispersion microballoon of size homogeneous, specifically according to following steps, carry out: one, first resorcinol is dissolved in deionized water, after mixing, add ethyl orthosilicate and benzaldehyde, in temperature, be to stir 10min～30min under the water bath condition of 50 ℃, liquid is uniformly mixed; Two, first the liquid that is uniformly mixed in step 1 is transferred in polytetrafluoroethyllining lining reactor, after sealing, be placed in Muffle furnace, heating rate with 1～3 ℃/min rises to 160～200 ℃ from room temperature, and be to react 4～8h at 160～200 ℃ in temperature, the cooling room temperature of putting, obtains reacting rear solution; Three, by obtaining reacting rear solution in step 2, adopt deionized water washing 2～3 times, adopt again ethanol washing 2～3 times, then ultrasonic being dispersed to evenly, centrifugation under 7000r/min～10000r/min condition again, it is dry 4h～8h in 60～90 ℃ of baking ovens that the solid that separation obtains is placed on temperature, obtains phenolic resin microspheres.
The quality of the resorcinol described in present embodiment step 1 and the volume ratio of deionized water are (1～6) g:200mL.
The quality of the resorcinol described in present embodiment step 1 and the volume ratio of ethyl orthosilicate are (2～21) g:14mL.
The quality of the resorcinol described in present embodiment step 1 and the volume ratio of benzaldehyde are (2～15) g:10mL.
Ethyl orthosilicate described in present embodiment step 1 is the ethyl orthosilicate that distillation purifying is crossed.
The volume of polytetrafluoroethyllining lining reactor described in present embodiment step 2 is 4:5 with the volume ratio of even mixed liquor.
Present embodiment solves these problems, and adopts hydro-thermal method successfully to synthesize single phenolic resin microspheres that disperses of size homogeneous.Hydro-thermal method be utilize the aqueous solution of HTHP make those under atmospheric conditions insoluble or indissoluble substance dissolves, or reaction generates the lysate of this material, by controlling the temperature difference of solution in autoclave, make to produce convection current and separate out the method for grown crystal to form hypersaturated state.Hydro-thermal method produce have that the particle of being purity is high, good dispersion, good crystalline and can control, the feature such as production cost is low.
Microballoon prepared by present embodiment can be for the structure of catalysis, pharmaceutical carrier, structure complexity, nanometer casting and electrochemistry.This microballoon is high as the catalytic activity of catalyst, large availability, long catalytic life.Stability as carrier is high.Yet microballoon homogeneity is in the past bad, bad dispersibility, this has just limited its application in medicine carrying, water treatment, catalysis etc. greatly.In order to apply in practice better carbon ball, preparation one class is uniform, and the microballoon of good dispersion is necessary.
The specific embodiment two: present embodiment is different from the specific embodiment one: the quality of the resorcinol described in step 1 and the volume ratio of deionized water are (2～4) g:200mL.Other are identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from one of specific embodiment one to two: the quality of the resorcinol described in step 1 and the volume ratio of ethyl orthosilicate are (5～15) g:14mL.Other are identical with the specific embodiment one to two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three: the quality of the resorcinol described in step 1 and the volume ratio of benzaldehyde are (5～10) g:10mL.Other are identical with the specific embodiment one to three.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four: first the liquid that is uniformly mixed in step 1 is transferred in polytetrafluoroethyllining lining reactor in step 2, after sealing, be placed in Muffle furnace, heating rate with 1～3 ℃/min rises to 170～190 ℃ from room temperature, and be to react 5h～7h at 170～190 ℃ in temperature, the cooling room temperature of putting, obtains reacting rear solution.Other are identical with the specific embodiment one to four.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five: adopt deionized water washing 2 times by obtaining reacting rear solution in step 2 in step 3, adopt again ethanol washing 2 times, then ultrasonic being dispersed to evenly, centrifugation under 8000r/min～9000r/min condition again, it is dry 5h～7h in 70～80 ℃ of baking ovens that the solid that separation obtains is placed on temperature, obtains phenolic resin microspheres.Other are identical with the specific embodiment one to five.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of mono-dispersion microballoon of size homogeneous, specifically carries out according to following steps:
One, first 1.2g resorcinol being dissolved in 70mL deionized water, adding 4mL ethyl orthosilicate and 2.5mL benzaldehyde after mixing, is to stir 20min under the water condition of 50 ℃ in temperature, and liquid is uniformly mixed; Two, first the liquid that is uniformly mixed in step 1 is transferred in polytetrafluoroethyllining lining reactor, after sealing, be placed in Muffle furnace, with the heating rate of 2 ℃/min, from room temperature, rise to 180 ℃, and be to react 6h at 180 ℃ in temperature, the cooling room temperature of putting, obtains reacting rear solution; Three, by obtaining reacting rear solution in step 2, adopt deionized water washing 2 times, with ethanol, wash 2 times more then ultrasonic being dispersed to evenly, then centrifugation under 9000r/min condition, it is dry 6h in 80 ℃ of baking ovens that the solid that separation obtains is placed on temperature, obtains phenolic resin microspheres.
Ethyl orthosilicate described in this test procedure one is the ethyl orthosilicate that distillation purifying is crossed.
The volume of polytetrafluoroethyllining lining reactor described in this test procedure two is 50mL
Described in this test procedure two, in polytetrafluoroethyllining lining reactor, evenly the volume of mixed liquor is 100mL.
Adopt the phenolic resin microspheres of this test of sem observation preparation; As shown in Figure 1, Fig. 1 is SEM (SEM) figure of the phenolic resin microspheres of test one preparation; Phenolic resin microspheres size homogeneous, monodispersity are good as seen in Figure 1.
Adopt X-ray diffractometer to observe the alkyd resin based carbosphere of this test preparation; As shown in Figure 2, Fig. 2 is the X-ray diffractogram (XRD) of the phenolic resin microspheres of test one preparation; By Fig. 2, can find out at 25.5 ° have obvious characteristic diffraction peak.
Test two: a kind of application of monodisperse resin microballoon of size homogeneous, specifically according to following steps, carry out:
First 250mgBPO (dibenzoyl peroxide) and 3.5g divinylbenzene are added in 20g styrene, after dissolving completely, from room temperature, be warming up to 95 ℃, and be 95 ℃ of polymerization 2h in temperature, the phenolic resin microspheres that adds again 5g test one preparation, stir and continue and react, after this viscosity of system becomes large gradually, to similar to glycerine viscosity can (being that viscosity is 20Pas), naturally cool to room temperature, with twice of deionized water washing, ethanol washing once, is 80 baking oven inner dryings as for temperature, obtains phenolic resins/poly styrene composite material.
Adopt the phenolic resins/poly styrene composite material of this test of sem observation preparation; As shown in Figure 3, Fig. 3 is SEM (SEM) figure of the phenolic resins/poly styrene composite materials of test two preparations, adopts the polystyrene/phenolic resin composite materials of test two preparations to have good toughness, good electric conductivity, high temperature resistant damping and amortization good.Phenolic resin microspheres size homogeneous, the Heat stability is good with the present invention, prepared, be applicable to being mixed with composite with polystyrene.
Claims (6)
1. the preparation method of the mono-dispersion microballoon of a size homogeneous, the preparation method who it is characterized in that a kind of mono-dispersion microballoon of size homogeneous carries out according to following steps: one, first resorcinol is dissolved in deionized water, after mixing, add ethyl orthosilicate and benzaldehyde, in temperature, be to stir 10min～30min under the water bath condition of 50 ℃, liquid is uniformly mixed; Two, first the liquid that is uniformly mixed in step 1 is transferred in polytetrafluoroethyllining lining reactor, after sealing, be placed in Muffle furnace, heating rate with 1～3 ℃/min rises to 160～200 ℃ from room temperature, and be to react 4～8h at 160～200 ℃ in temperature, the cooling room temperature of putting, obtains reacting rear solution; Three, by obtaining reacting rear solution in step 2, adopt deionized water washing 2～3 times, adopt again ethanol washing 2～3 times, then ultrasonic being dispersed to evenly, centrifugation under 7000r/min～10000r/min condition again, it is dry 4h～8h in 60～90 ℃ of baking ovens that the solid that separation obtains is placed on temperature, obtains phenolic resin microspheres;
The quality of the resorcinol described in step 1 and the volume ratio of deionized water are (1～6) g:200mL;
The quality of the resorcinol described in step 1 and the volume ratio of ethyl orthosilicate are (2～21) g:14mL;
The quality of the resorcinol described in step 1 and the volume ratio of benzaldehyde are (2～15) g:10mL.
2. the preparation method of the mono-dispersion microballoon of a kind of size homogeneous according to claim 1, is characterized in that the quality of the resorcinol described in step 1 and the volume ratio of deionized water are for (2～4) g:200mL.
3. the preparation method of the mono-dispersion microballoon of a kind of size homogeneous according to claim 1, is characterized in that the quality of the resorcinol described in step 1 and the volume ratio of ethyl orthosilicate are for (5～15) g:14mL.
4. the preparation method of the mono-dispersion microballoon of a kind of size homogeneous according to claim 1, is characterized in that the quality of the resorcinol described in step 1 and the volume ratio of benzaldehyde are for (5～10) g:10mL.
5. the preparation method of the mono-dispersion microballoon of a kind of size homogeneous according to claim 1, it is characterized in that first the liquid that is uniformly mixed in step 1 being transferred in polytetrafluoroethyllining lining reactor in step 2, after sealing, be placed in Muffle furnace, heating rate with 1～3 ℃/min rises to 170～190 ℃ from room temperature, and be to react 5h～7h at 170～190 ℃ in temperature, the cooling room temperature of putting, obtains reacting rear solution.
6. the preparation method of the mono-dispersion microballoon of a kind of size homogeneous according to claim 1, it is characterized in that by obtaining reacting rear solution in step 2, adopting deionized water washing 2 times in step 3, adopt again ethanol washing 2 times, then ultrasonic being dispersed to evenly, centrifugation under 8000r/min～9000r/min condition again, it is dry 5h～7h in 70～80 ℃ of baking ovens that the solid that separation obtains is placed on temperature, obtains phenolic resin microspheres.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110639440A (en) * | 2019-09-24 | 2020-01-03 | 中国海洋大学 | Preparation method of carbon/silicon dioxide composite microspheres |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624437A (en) * | 2008-11-24 | 2010-01-13 | 鲁东大学 | Preparation method of phenolic resin polymer microspheres |
| KR20110048635A (en) * | 2009-11-03 | 2011-05-12 | 주식회사 폴리크롬 | Manufacture method of nano particle impregnated phytoncide |
| CN102321228A (en) * | 2011-04-01 | 2012-01-18 | 黄石理工学院 | Method for preparing organic silicon modified thermal plastic phenolic resin |
| CN102352003A (en) * | 2011-07-19 | 2012-02-15 | 黑龙江大学 | Preparation method of phenolic resin microballoons and method for preparing phenolic resin-based carbon spheres by use of preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624437A (en) * | 2008-11-24 | 2010-01-13 | 鲁东大学 | Preparation method of phenolic resin polymer microspheres |
| KR20110048635A (en) * | 2009-11-03 | 2011-05-12 | 주식회사 폴리크롬 | Manufacture method of nano particle impregnated phytoncide |
| CN102321228A (en) * | 2011-04-01 | 2012-01-18 | 黄石理工学院 | Method for preparing organic silicon modified thermal plastic phenolic resin |
| CN102352003A (en) * | 2011-07-19 | 2012-02-15 | 黑龙江大学 | Preparation method of phenolic resin microballoons and method for preparing phenolic resin-based carbon spheres by use of preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110639440A (en) * | 2019-09-24 | 2020-01-03 | 中国海洋大学 | Preparation method of carbon/silicon dioxide composite microspheres |
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