CN1943847A - Aromatic polymer sulfonate micro capsule, its preparking method and its use - Google Patents
Aromatic polymer sulfonate micro capsule, its preparking method and its use Download PDFInfo
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Abstract
The present invention belongs to the field of functional polymer material technology, and is especially aromatic polymer sulfonate microcapsule and its preparation process and composite hollow microsphere of aromatic polymer sulfonate prepared with the microcapsule as template. The polymer sulfonate microcapsule is prepared through the first dispersive polymerization or emulsion polymerization of aromatic monomer to obtain aromatic polymer microcapsule, the subsequent sulfonation treatment to convert into polymer gel microcapsule and final counter ion solution treatment. Functional precursor is combined to the wall of the polymer sulfonate microcapsule via adsorption and deposition to form the composite hollow microsphere of aromatic polymer sulfonate. The present invention has simple operation, short preparation period, high efficiency, effective control of the size and structure of the microcapsule and the microsphere and industrial application value.
Description
Technical field
The invention belongs to the functional high molecule material technical field, be specifically related to a kind of new aromatic polymer sulfonate microcapsules, its preparation method and application thereof.
Background technology
Microcapsules are to utilize film forming matter that the space in the capsule and the capsule external space are kept apart to form the material of particular geometric configuration, and its inside can be filled, and also can be hollow.Tradition microcapsules size usually at micron to the millimeter level, wall thickness in sub-micron to the hundreds of micron.It is little because of its granularity that size is equal to or less than micron-sized capsule, and the surface-active height is suspended in and forms stable colloidal solutions in the solvent, has more unique character; Can be widely used in a plurality of fields such as medicine, food, agricultural chemicals, cosmetics, coating, printing ink.
The technology of preparing that at present relevant size is equal to or less than micron-sized polymer capsule has: interfacial polymerization [Al Khouri Fallouh N., Roblot-Treupel L., Fessi H., Devissaguet J.P., Puisieux F., Development of a New Process for the Manufacture of Poly-(isobutylcyanoacrylate) Nanocapsules, Int.J.Pharm., 1986,28 (2-3): 125-132], micro emulsion polymerization [Watnasirichaikul S., Rades T., Tucker I., Davies N., Effects of Formulation Variables on Characteristics of Poly (ethyl-cyanoacrylate) Nanocapsules Prepared from W/O Microemulsions, Int.J.Pharm., 2002,235:237-246], interface sedimentation [Fessi H., Puisieux F., DevissaguetP., Ammoury N., Benita S., Nanocapsules Formation by InterfacialDeposition following Solvent Displacement, Int.J.Pharm., 1989,55:R1-R4], complex phase emulsion solvent volatility process [Lu Z., Bei J.Z., Wang S.G., A Method forthe Preparation of Polymeric Nanocapsules without Stabilizer, J.Control.Release, 1999,61:107-112], copolymer self-assembly method [Dou H.J., Jiang M., PengH.S., Chen D.Y., Hong Y., pH-Dependent Self-Assembly:Micellization andMicelle-Hollow-Sphere Transition of Cellulose-Based Copolymers, Angew.Chem.Int.Ed., 2003,42:1516-1519] and the colloid template on polyelectrolyte sedimentation [Caruso F. progressively, Yang W.J., Trau D., Renneberg R., Microencapsulation ofUncharged Low Molecular Weight Organic Materials by PolyeletrolyteMultilayer Self-Assembly, Langmuir, 2000,16 (23): 8932-8936].But self-assembly method and template require harsh to system, need to carry out under extremely low polymer concentration, and wherein template also need be handled through stoning, waste raw material and fragile capsule shell, thereby their practical application is restricted.In addition,, exist solvent or dispersion liquid need big respectively, shortcoming such as the Size Distribution of microcapsules is wide, shell thickness is difficult to control, heat endurance and chemical stability are lower through post processing removal, emulsifying agent consumption though other several methods are simple, efficient.
Summary of the invention
In view of the foregoing, the present inventor furthers investigate the technology of preparing of microcapsules, in the hope of developing the part defective that a kind of novel microcapsule preparation method remedies prior art, found that by sulfonation and counter ion processing to prepare aromatic polymer sulfonate microcapsules to the aromatic polymer microballoon.The present invention is based on above-mentioned discovery is accomplished.
Therefore one of purpose of the present invention provides a kind of method for preparing aromatic polymer sulfonate microcapsules.This method is not only different with existing microcapsule method on principle, and operate simple and easy, efficient is high, can be applied to large-scale industrialization production, and the preparation of the aromatic polymer sulfonate microcapsules of various ingredients and structure is all had good universality.This method constituted with interfacial polymerization, micro emulsion polymerization, interface sedimentation, complex phase emulsion solvent volatility process, copolymer self-assembly method and colloid template on polyelectrolyte these existing methods of sedimentation one class new method of having complementary advantages progressively.
Two of purpose of the present invention provides a kind of aromatic polymer sulfonate microcapsules.This microcapsule structure is stable, and resistance to acids and bases is good, and environmental stimulus has response characteristic (as solvent polarity is changed, the variation of counter ion kind and concentration thereof all can produce corresponding pattern proterties and change) to external world; The thickness and the permeability of its chemical constituent and functional group content, size and distribution, cyst wall can both be effectively controlled.These microcapsules can be used as control releasable material, sorbing material, catalyst carrier, and the template that further prepares functional materials such as conductive material, magnetic material, optical material.
Three of purpose of the present invention provides uses the compound hollow microsphere of aromatic polymer sulfonate that these aromatic polymer sulfonate microcapsules are the template preparation.After these microcapsules and function precursor substance [reaching wherein one or more mixture as the salt of conductive high polymer monomer, magnetic Nano metal particle, molysite or molysite and other transition metals, the nanometer noble metal microparticles with catalysis, inorganic gel presoma, Nano semiconductor particulate, (fluorescence) dyestuff, large biological molecule] were assembled, the compound hollow microsphere of preparing had more rich functions; All has potential significant application value in many fields such as material science, life science, Electronics Science and Technology, biomedical engineering, catalytic science and technology.
Other purposes of the present invention, feature and advantage will become cheer and bright after reading this specification in conjunction with the accompanying drawings.
The accompanying drawing summary
Fig. 1 is the transmission electron microscope photo of the kayexalate microcapsules of embodiment 6 preparations.
Fig. 2 is the transmission electron microscope photo of the kayexalate/polypyrrole composite conducting hollow microsphere of embodiment 10 preparations.
Detailed Description Of The Invention
Aromatic polymer sulfonate microcapsules of the present invention are to obtain single aromatic polymer microballoon that disperses by dispersin polymerization or emulsion polymerisation first, then process by sulfonation and change the aromatic polymer gel micro-ball into, obtain with the counter ion solution-treated again.
In aromatic polymer sulfonate microcapsules of the present invention, contained aromatic rings is selected from phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring, etc. Described single aromatic polymer microballoon that disperses is selected from aromatic series homopolymers microballoon, aromatic copolymer microballoon, cross-linking type aromatic polymer microballoon, etc.; Preferred polystyrene, crosslinked polystyrene or styrene based copolymer microballoon.
In aromatic polymer sulfonate microcapsules of the present invention, described single particle diameter that disperses the aromatic polymer microballoon is between 50 nanometers to 10 micron, preferably between 100 nanometers to 5 micron.
Aromatic polymer sulfonate microcapsules of the present invention are preferably dimensioned to be 50 nanometers-10 micron, and wall thickness is preferably the 10-300 nanometer.
In the styrene based copolymer microballoon, used styrenic monomers is styrene or substituted phenylethylene, and such as AMS etc., and used comonomer is selected from vinyl monomer, especially (methyl) acrylic monomer.
The concrete preparation method of aromatic polymer sulfonate microcapsules of the present invention may further comprise the steps:
1) adopts dispersin polymerization or the emulsion polymerization prepared particle size range single aromatic polymer microballoon that disperses in 50 nanometers to 10 micron, and handle as centrifugation and freeze drying obtain the aromatic polymer microballoon powder of drying by conventional method;
2) will be scattered in an amount of sulfonated reagent from the aromatic polymer microballoon powder of step 1) as in 98% concentrated sulfuric acid or sulfuric acid and the acid anhydride mixture etc., isothermal reaction certain hour under uniform temperature, stirring or the effect of batch (-type) sonic oscillation;
3) will come from step 2) sulfonating reaction liquid add solvent dilution, centrifugation, the product after centrifugal disperses again with solvent again, becomes uniform aromatic polymer gel micro-ball dispersion liquid;
4) will mix vibration with finite concentration counter ion solution from the aromatic polymer gel micro-ball dispersion liquid of step 3), leave standstill, centrifugation; With
5) will fully disperse with solvent or counter ion solution from the product after the centrifugation of step 4), promptly obtain the monodispersed aromatic polymer sulfonate of the present invention microcapsules.
The inventive method the 1st) in the step, single aromatic polymer microballoon that disperses can adopt conventional dispersin polymerization or emulsion polymerisation process preparation [referring to Cao Tongyu, Liu Qingpu, Hutchinson, Paul C., polymer emulsion composition principle, performance and application, Beijing: Chemical Industry Press, 1997].
The inventive method the 2nd) step in, adopt general method of sulfonating to prepare aromatic polymer gel micro-ball (referring to Chinese patent ZL 01100391.X).The time of sulfonating reaction is 0.5-20 hour.The mass ratio of aromatic polymer microballoon powder and sulfonated reagent is 1: 0.5-1: 100.Sulfonation temperature is 20-100 ℃, preferred 30-80 ℃.
The inventive method the 3rd), 4) and 5) in the step, the solvent in used solvent and the counter ion solution is selected from water, alcohol compound, ketone compounds, ether compound, nitrile compounds, halogenated compound, amides compound, pyrrolidones and one or more mixture wherein; Be preferably water, ethanol, acetone, acetonitrile, carrene, N, dinethylformamide, N-methyl pyrrolidone; Most preferably be water, ethanol, acetone, N, dinethylformamide.The concentration of aromatic polymer gel micro-ball dispersion liquid is 0.01-100g/L.
The inventive method the 4th) in the step, use counter ion solution that the aromatic polymer gel micro-ball dispersion liquid from step 3) is handled.The counter ion that counter ion solution is adopted derives from inorganic salts, as halide, hydroxide, sulfate, disulfate, phosphate, hydrophosphate, dihydric phosphate, nitrate, carbonate and bicarbonate, wherein the counter ion kind is selected from hydrogen ion, alkali metal ion, alkaline-earth metal ions, transition metal ions, ammonium ion etc.; Preferred hydrogen ion, sodium ion, potassium ion, iron ion, copper ion and ammonium ion.The counter ion solution concentration is 30-0.03mol/L, preferred 10-1mol/L.
Aromatic polymer sulfonate microcapsules of the present invention are characterised in that Stability Analysis of Structures, and resistance to acids and bases is good, and environmental stimulus has response to external world; And the thickness and the permeability of its chemical constituent and functional group content, size and distribution, cyst wall can both be effectively controlled within the specific limits.Its preparation method is simple, only by sulfonation and different counter ion solution-treated, can realize by the aromatic polymer microballoon to the aromatic polymer gel micro-ball, again to the transformation of aromatic polymer sulfonate microcapsules.The parietal layer of these microcapsules and function precursor substance are [as conductive high polymer monomer, the magnetic Nano metal particle, the salt of molysite or molysite and other transition metals, nanometer noble metal microparticles with catalysis, the inorganic gel presoma, the Nano semiconductor particulate, (fluorescence) dyestuff, large biological molecule and wherein one or more mixture absorption, in conjunction with, different function precursor employings is reacted accordingly (as oxidative coupling polymerization, sol-gel reaction etc.), has the function of enriching (as electrical property just can form, magnetic property and catalytic performance etc.) the compound hollow microsphere of aromatic polymer sulfonate.The inventive method is applicable to the aromatic polymer sulfonate microcapsules of various ingredients and structure and the preparation of compound hollow microsphere.Have industrial value and market application foreground.Existing preparation hollow microsphere preparation method's list of references has: [Caruso F., Susha A.S., Giersig M., Mohwald H., Magnetic Core-ShellParticles:Preparation of Magnetite Multilayers on Polymer LatexMicrospheres, Adv.Mater., 1999,11 (11): 950-953].
Embodiment
The present invention is described in detail by following reference example and embodiment, is understood that these embodiment do not limit the scope of the invention.
Reference example 1
The universal method for preparing monodisperse polystyrene system (PSt) microballoon by dispersin polymerization
In the four-hole bottle that thermometer, mechanical agitator, spherical condensation tube and wireway are housed, add the certain amount of dispersant aqueous solution; under nitrogen protection, be warming up to 70 ℃; stir and add styrene and crosslinking agent after 30 minutes; continue to stir 30 minutes; the aqueous solution of initiator potassium persulfate is added in the reaction system; keep reaction 10 hours, stop reaction, promptly obtain the polystyrene dispersoid.With dispersion with the ethanol centrifugation, add 2-10 that water is diluted to original volume doubly, obtain required polystyrene microballoon powder after the freeze drying.Representative formula is as shown in table 1.
The typical dispersin polymerization prescription of table 1
| Polymer microballoon | Water (mL) | Ethanol (mL) | Lauryl sodium sulfate (g) | Styrene (mL) | Crosslinking agent (mL) | Potassium peroxydisulfate (g) |
| Single P (St-co-TPGDA) microballoon (TPGDA 1.4wt%) that disperses of the single PSt of dispersion of 470 nanometers microballoon 570 nanometers | 160 40 | 400 100 | 0.88 0.22 | 36 9 | / tripropylene glycol diacrylate (TPGDA) 0.12 | 0.80 0.21 |
Reference example 2
Prepare single styrene-methylmethacrylate copolymer [P (the St-co-MMA)] microballoon that disperses of 470 nanometers by emulsifier-free emulsion polymerization
In being housed, the 250mL four-hole bottle of thermometer, mechanical agitator, spherical condensation tube and wireway adds 100mL water; under nitrogen protection, be warming up to 70 ℃; stir and add 10mL styrene and 1.23mL methyl methacrylate after 30 minutes; continue to stir 30 minutes; the 0.05g initiator potassium persulfate is added in the reaction system; keep reaction 10 hours, stop reaction, promptly obtain P (St-co-MMA) emulsion.With emulsion with the ethanol centrifugation, add 2-10 that water is diluted to original volume doubly, obtain required P (St-co-MMA) microballoon powder after the freeze drying.
Reference example 3
Monodisperse polystyrene (PSt) microballoon for preparing 1 micron of particle diameter by dispersin polymerization
1.0g PVP (K-30), 0.5mL dodecanol, 80mL ethanol and 10mL water are added the 250mL four-hole boiling flask that thermometer, mechanical agitator, spherical condensation tube and wireway are housed, stir and make its dissolving, and be warming up to 60 ℃.Get the 0.14g azodiisobutyronitrile and be dissolved in the 10g styrene monomer, letting nitrogen in and deoxidizing adds four-hole bottle rapidly after 2 minutes, carried out polymerisation 20 hours under nitrogen protection.Promptly obtain 1 micron single styrene homopolymers microballoon dispersion of disperseing of particle diameter.With dispersion with the ethanol centrifugation, add 2-10 that water is diluted to original volume doubly, obtain required polystyrene microsphere powder after the freeze drying.
Reference example 4
Single styrene-Jia Jibingxisuanβ-Qiang Yizhi copolymer [P (St-co-HEMA)] microballoon that disperses by emulsion polymerization prepared particle diameter 100 nanometers
In being housed, the 500mL four-hole bottle of thermometer, mechanical agitator, spherical condensation tube and wireway adds 6g PVP (K-30) and 240mL water; under nitrogen protection, be warming up to 70 ℃; stir and add styrene 34mL, Jia Jibingxisuanβ-Qiang Yizhi (HEMA) 2.6mL after 30 minutes; continue to stir 30 minutes; the 16mL water that is dissolved with the 4g ammonium persulfate is added in the reaction system; keep reaction 24 hours; stop reaction, promptly obtain the single P (St-co-HEMA) of dispersion of particle diameter 100 nanometers microballoon emulsion.Emulsion is added 2-10 that water is diluted to original volume doubly, obtain required polymer microballoon powder after the freeze drying.
Reference example 5
The general method of sulfonating of polymer microballoon
The above-mentioned polymer microballoon powder of 1g is added in the round-bottomed flask, add the mixed liquor of a certain amount of 98% concentrated sulfuric acid or sulfuric acid and maleic anhydride then, magnetic agitation, sulfonating reaction a period of time under the uniform temperature.Can adopt ultrasonic processing or need not ultrasonic processing dual mode during sulfonation.Ultrasound treatment patterns was a batch (-type), every 25 minutes sonic oscillations 5 minutes.The gained reactant liquor is standby.
Embodiment 1
Is the single PSt of dispersion of 470 nanometers microballoon powder by the sulfonation 2 hours under 50 ℃ of temperature in 10mL 98% concentrated sulfuric acid of the universal method of reference example 5 with 1g from the particle diameter of reference example 1, stirs, the ultrasonic processing of batch (-type).The reactant liquor of gained fully dilutes with 80mL ethanol, and centrifugation is taken out lower floor's colloidal substance and also disperseed again with 20mL ethanol, becomes aromatic polymer gel micro-ball dispersion liquid.Add the saturated NaOH ethanolic solution of 20mL in this dispersion liquid, fully vibration mixes, and leaves standstill 2 hours, and lower floor's colloidal substance is taken out in centrifugation.Colloidal substance and the vibration of 10mL water are mixed, obtain monodispersed kayexalate micro-capsule dispersion liquid.This micro-capsule dispersion liquid outward appearance milky that is translucent has good stability, for electrolyte, place sedimentation, mechanism, freeze fusing etc. and cause that influence factor is all insensitive with fixed attention.The transmissioning electric mirror test microcapsules are of a size of 500 nanometers, and wall thickness is 30 nanometers.
Embodiment 2
Change ethanol used among the embodiment 1 into water, saturated NaOH ethanolic solution changes saturated aqueous sodium sulfate into, and all the other prescriptions are identical with embodiment 1 with step, and the micro-capsule dispersion liquid outward appearance that the obtains milky that is translucent has good stability.
Embodiment 3
Change ethanol used among the embodiment 1 into water, saturated NaOH ethanolic solution changes the 20mL2.3mol/L aqueous sodium persulfate solution into, and the colloidal substance that centrifugation obtains at last disperseed with saturated aqueous sodium sulfate, all the other prescriptions are identical with embodiment 1 with step, the micro-capsule dispersion liquid outward appearance that the obtains milky that is translucent has good stability.
Embodiment 4
Change the ethanol among the embodiment 1 into water, saturated NaOH ethanolic solution changes saturated ferric sulfate aqueous solution into, and all the other prescriptions are identical with embodiment 1 with step, and the micro-capsule dispersion liquid outward appearance that the obtains Bluish white that is translucent has good stability.
Embodiment 5
10mL 98% concentrated sulfuric acid among the embodiment 1 is changed to 9mL 98% concentrated sulfuric acid and 2g maleic anhydride mixed liquor, and the sulfonation time is 4 hours, and all the other prescriptions are identical with embodiment 1 with step, and the micro-capsule dispersion liquid outward appearance that the obtains milky that is translucent has good stability.
Embodiment 6
Is the single P (St-co-TPGDA) of dispersion of 570 nanometers microballoon powder by the sulfonation 4 hours under 50 ℃ of temperature in 10mL 98% concentrated sulfuric acid of the universal method of reference example 5 with 1g from the particle diameter of reference example 1, does not carry out ultrasonic processing.All the other prescriptions are identical with embodiment 1 with step, and the micro-capsule dispersion liquid outward appearance that the obtains white that is translucent has good stability.Fig. 1 is the transmission electron microscope photo of these microcapsules.
Embodiment 7
Is the single P (St-co-MMA) of dispersion of 470 nanometers microballoon powder by the sulfonation 1 hour under 50 ℃ of temperature in 10mL 98% concentrated sulfuric acid of the universal method of reference example 5 with 1g from the particle diameter of reference example 2, does not carry out ultrasonic processing.All the other prescriptions are identical with embodiment 1 with step, and the micro-capsule dispersion liquid outward appearance that the obtains milky that is translucent has good stability.
Embodiment 8
The single PSt of the dispersion microballoon powder that with 1g from the particle diameter of reference example 3 is 1 micron is by the sulfonation 8 hours under 40 ℃ of temperature in 10mL 98% concentrated sulfuric acid of the universal method of reference example 5, the ultrasonic processing of batch (-type).All the other prescriptions are identical with embodiment 1 with step, and the wall thickness of the microcapsules that obtain doubles than the wall thickness of the capsule among the embodiment 1, and the dispersion liquid outward appearance is creamy white, and has good stability.
Embodiment 9
The single P (St-co-HEMA) of the dispersion microballoon powder that with 1g from the particle diameter of reference example 4 is 100 nanometers does not carry out ultrasonic processing by the sulfonation 0.5 hour under 40 ℃ of temperature in 10mL 98% concentrated sulfuric acid of the universal method of reference example 5.All the other prescriptions are identical with embodiment 1 with step, and the microcapsules wall thickness that obtains is even, dry back marshalling.The dispersion liquid outward appearance milky that is translucent has good stability.
Embodiment 10
The monodisperse polystyrene sodium sulfonate micro-capsule dispersion liquid 5mL that embodiment 1 is obtained adds in the 100mL single port flask; and add 30mL water, 1.5mg green vitriol; drip the 1mol/L dilute sulfuric acid to pH=1; 0 ℃ of ice bath and logical nitrogen protection; injection adds pyrroles 0.2mL; magnetic agitation is injected 0.4mL hydrogen peroxide initiated polymerization after 30 minutes, finish reaction after 24 hours.Need not solvent extraction removes nuclear and promptly obtains kayexalate/polypyrrole and conduct electricity compound hollow microsphere.Its wall thickness is even, has good stability, and room-temperature conductivity is 2.2 * 10
-3S/cm.Fig. 2 is the transmission electron microscope photo of kayexalate/polypyrrole composite conducting hollow microsphere.
For being familiar with those skilled in the art, can carry out various adjustment and variation to the present invention not deviating under scope of the present invention and the aim.Appended claim invention required for protection should not be limited in these embodiments.To the various adjustment of the described enforcement of specification pattern of the present invention, all in claims scope.
Claims (12)
1. aromatic polymer sulfonate microcapsules is characterized in that: obtain single aromatic polymer microballoon that disperses by dispersin polymerization or emulsion polymerisation earlier; Handle through sulfonation then and change the aromatic polymer gel micro-ball into, obtain with the counter ion solution-treated, the size of wherein said microcapsules is in 50 nanometers-10 micron, and wall thickness is between the 10-300 nanometer.
2. aromatic polymer sulfonate microcapsules as claimed in claim 1 is characterized in that: contained aromatic rings is selected from phenyl ring, cyclohexyl biphenyl, terphenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring.
3. aromatic polymer sulfonate microcapsules as claimed in claim 1, wherein said single aromatic polymer microballoon that disperses is selected from aromatic series homopolymers microballoon, aromatic copolymer microballoon, cross-linking type aromatic polymer microballoon.
4. aromatic polymer sulfonate microcapsules as claimed in claim 1, wherein said mono-dispersion microballoon is selected from polystyrene, crosslinked polystyrene or styrene based copolymer microballoon.
5. aromatic polymer sulfonate microcapsules as claimed in claim 1, wherein said aromatic polymer microsphere diameter is between 50 nanometers to 10 micron.
6. method for preparing as the described aromatic polymer sulfonate of claim 1-5 microcapsules may further comprise the steps:
1) adopts dispersin polymerization or the emulsion polymerization prepared particle size range single aromatic polymer microballoon that disperses in 50 nanometers to 10 micron, and handle as centrifugation and freeze drying obtain the aromatic polymer microballoon powder of drying by conventional method;
2) will be scattered in an amount of sulfonated reagent from the aromatic polymer microballoon powder of step 1) as in 98% concentrated sulfuric acid or sulfuric acid and the acid anhydride mixture, isothermal reaction certain hour under uniform temperature, stirring or the effect of batch (-type) sonic oscillation;
3) will come from step 2) sulfonating reaction liquid add solvent dilution, centrifugation, the product after centrifugal disperses again with solvent again, becomes uniform aromatic polymer gel micro-ball dispersion liquid;
4) will mix vibration with finite concentration counter ion solution from the aromatic polymer gel micro-ball dispersion liquid of step 3), leave standstill, centrifugation;
5) will fully disperse with solvent or counter ion solution from the product after the centrifugation of step 4), promptly obtain monodispersed aromatic polymer sulfonate microcapsules.
7. method as claimed in claim 6 is characterized by in step 2) described in dry aromatic polymer microballoon powder and the mass ratio of sulfonated reagent 1: 0.5-1: between 100; Sulfonation temperature is between 20-100 ℃; The sulfonation time is between 0.5-20 hour.
8. method as claimed in claim 6 is characterized by in step 3), 4), 5) described in solvent and counter ion solution solvent for use be selected from water, alcohol compound, ketone compounds, ether compound, nitrile compounds, halogenated compound, amides compound, pyrrolidones and one or more mixture wherein.
9. method as claimed in claim 6 is characterized by in step 3), 4) described in the concentration of aromatic polymer gel micro-ball dispersion liquid be 0.01-100g/L.
10. method as claimed in claim 6 is characterized by the counter ion kind that is adopted at the counter ion solution described in the step 4) and is selected from alkali metal ion, alkaline-earth metal ions, transition metal ions, ammonium ion.
11. one kind is used according to claim 1, and aromatic polymer sulfonate microcapsules are the compound hollow microsphere of aromatic polymer sulfonate of template preparation, it is characterized in that: the parietal layer of aromatic polymer sulfonate microcapsules adsorbs mutually, combines with the function precursor, and then obtains compound hollow microsphere.
12. be selected from the salt of conductive high polymer monomer, magnetic Nano metal particle, molysite or molysite and other transition metals, nanometer noble metal microparticles, inorganic gel presoma, Nano semiconductor particulate, (fluorescence) dyestuff, large biological molecule and one or more mixture wherein with catalysis as the function precursor that claim 11 adopted.
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