CN114395082A - Preparation method of sulfonated polystyrene nano-microspheres - Google Patents
Preparation method of sulfonated polystyrene nano-microspheres Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 88
- 229920001467 poly(styrenesulfonates) Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000004793 Polystyrene Substances 0.000 claims abstract description 54
- 229920002223 polystyrene Polymers 0.000 claims abstract description 54
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 27
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 27
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 27
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 57
- 239000002077 nanosphere Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 abstract description 20
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000012876 carrier material Substances 0.000 abstract 1
- 239000002612 dispersion medium Substances 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 239000003381 stabilizer Substances 0.000 abstract 1
- 238000006557 surface reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000003756 stirring Methods 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000001000 micrograph Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
- C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of sulfonated polystyrene nano microspheres, belonging to the technical field of high polymer materials. Adding styrene serving as a reaction monomer, polyvinylpyrrolidone serving as a stabilizer and azodiisobutyronitrile serving as an initiator into a three-necked flask together by using ethanol and water as dispersion media, and heating to react to obtain polystyrene nano microspheres; and slowly adding concentrated sulfuric acid into the polystyrene nano-microspheres for reaction to obtain the sulfonated polystyrene nano-microspheres. The sulfonated polystyrene nano-microsphere prepared by the invention has excellent properties of good surface reaction capability, uniform particle size, large specific surface area and the like, can be used as a good carrier material due to the properties, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of sulfonated polystyrene nano microspheres.
Background
The monodisperse Polystyrene (PST) nano-microsphere prepared by dispersion polymerization is easy to prepare, has large specific surface area, high reaction activity and good adsorbability, and also has the advantages of good mechanical property, chemical stability and the like. The polystyrene nano-microsphere can endow the microsphere with functions of light, electricity, magnetism, catalysis and the like, and has better application prospect in the fields of catalysis, biomedicine, materials and the like. However, the surface of the PST microsphere is not provided with functional groups, so that the PST microsphere is difficult to be directly combined with other substances, and the application of the PST microsphere is greatly limited. Therefore, modification of PST microspheres is an important step. After the surface of the polystyrene microsphere is modified, the polystyrene microsphere is combined with other substances with excellent performance, so that the composite material coated on the surface of the polystyrene microsphere is prepared, and the performance of the material is researched, so that the polystyrene microsphere has wide application prospect.
Sulfonated polystyrene (PST-SO)3) The nano-microsphere is prepared by adding concentrated sulfuric acid to modify the surface of polystyrene nano-microsphere. Firstly, preparing a monodisperse PST microsphere by a dispersion polymerization method, and then reacting the PST microsphere with concentrated sulfuric acid, thereby grafting a sulfonic group onto the polystyrene nano microsphere. The sulfonated polystyrene has similar catalytic properties to concentrated sulfuric acid due to the introduction of sulfonic acid groups on the molecular structure, for example, the sulfonated polystyrene can catalyze the esterification reaction between alcohol and carboxylic acid and can catalyze the hydrolysis reaction of ester. And because the catalyst exists in the form of powder and belongs to a different phase from the reactants and the reaction products, the catalyst is convenient to separate from the rest reactants and products, has high recycling rate and is a green catalyst with great potential.
Disclosure of Invention
The invention aims to provide a preparation method of a sulfonated polystyrene nano microsphere which is monodisperse and has uniform particle size and sulfonic group on the surface.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of sulfonated polystyrene nano microspheres, which comprises the following steps:
1) adding azodiisobutyronitrile into styrene to obtain a mixed solution;
2) adding the mixed solution into a preheated ethanol water solution of polyvinylpyrrolidone for reaction to obtain a polystyrene nano microsphere solution;
3) adding concentrated sulfuric acid into the polystyrene nano microsphere solution to react to obtain a product, and centrifuging and washing the product to be neutral to obtain the sulfonated polystyrene nano microsphere.
Further, the mass ratio of the azodiisobutyronitrile to the styrene is 0.5-1.5: 20 to 30.
Further, the preheating temperature in the step 2) is 60-80 ℃.
Further, the mass ratio of ethanol to water in the ethanol aqueous solution of polyvinylpyrrolidone is 7: 3-9: 1, the mass concentration of the ethanol water solution of the polyvinylpyrrolidone is 5-20%.
Further, the reaction temperature in the step 2) is 60-80 ℃, and the reaction time is 6-10 hours.
Further, the mass ratio of the mixed solution to the ethanol aqueous solution of polyvinylpyrrolidone is 20-30: 100 to 120.
Further, the mass ratio of the concentrated sulfuric acid to the polystyrene nano microsphere solution is 30-50: 5 to 10.
Further, the reaction temperature in the step 3) is 40-70 ℃, and the reaction time is 4-6 h.
Further, the rotating speed of the centrifugation is 6000-9000 r/min, and the time of the centrifugation is 10-30 min.
The invention has the beneficial effects that:
the preparation method has simple process and low cost, the polystyrene microspheres and the sulfonated polystyrene microspheres synthesized by the method have controllable sizes and uniform particle sizes, the synthesized sizes are between nano-scale and micron-scale, the requirements of various occasions and sizes can be met, and the possibility is provided for realizing industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of the apparent morphology of sulfonated polystyrene nanospheres prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the apparent morphology of sulfonated polystyrene nanospheres prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of the apparent morphology of sulfonated polystyrene nanospheres prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of the apparent morphology of sulfonated polystyrene nanospheres prepared in example 4 of the present invention;
FIG. 5 is an infrared curve diagram of sulfonated polystyrene nanospheres prepared in examples 1-4 of the present invention.
Detailed Description
The invention provides a preparation method of sulfonated polystyrene nano microspheres, which comprises the following steps:
1) adding azodiisobutyronitrile into styrene to obtain a mixed solution;
2) adding the mixed solution into a preheated ethanol water solution of polyvinylpyrrolidone for reaction to obtain a polystyrene nano microsphere solution;
3) adding concentrated sulfuric acid into the polystyrene nano microsphere solution to react to obtain a product, and centrifuging and washing the product to be neutral to obtain the sulfonated polystyrene nano microsphere.
In the invention, the mass ratio of the azodiisobutyronitrile to the styrene is 0.5-1.5: 20 to 30, preferably 0.8 to 1.2: 22 to 28, and more preferably 1.0: 25.
in the invention, before mixing the styrene and the azobisisobutyronitrile, refining treatment is required, wherein the refining treatment comprises washing away a polymerization inhibitor in the styrene by using a NaOH solution with the mass concentration of 2-10%, and then washing away the residual NaOH by using water, preferably a NaOH solution with the mass concentration of 5%.
In the invention, the temperature of the preheated ethanol aqueous solution of polyvinylpyrrolidone in the step 2) is 60-80 ℃, preferably 65-75 ℃, and more preferably 70 ℃.
In the invention, the mass ratio of ethanol to water in the ethanol aqueous solution of polyvinylpyrrolidone is 7: 3-9: 1, preferably 8: 2; the mass concentration of the ethanol aqueous solution of the polyvinylpyrrolidone is 5-20%, preferably 9-15%, and more preferably 12%.
In the present invention, the polyvinylpyrrolidone is preferably K30.
In the invention, the reaction temperature in the step 2) is 60-80 ℃, and the reaction time is 6-10 h; preferably, the reaction temperature is 65-75 ℃, and the reaction time is 7-9 h; more preferably, the reaction temperature is 70 ℃ and the reaction time is 8 h.
In the invention, the mass ratio of the mixed solution to the ethanol water solution of polyvinylpyrrolidone is 20-30: 100-120, preferably 22-28: 105 to 115, more preferably 25: 110.
in the invention, the particle size of the polystyrene nano-microsphere is 300-800 nm, and the obtained microsphere has uniform particle size.
In the invention, the mass ratio of the concentrated sulfuric acid to the polystyrene nano microsphere solution is 30-50: 5-10, preferably 35-45: 6-9, and more preferably 40: 8; the concentration of the concentrated sulfuric acid is 80-98%, and the preferred concentration is 98%.
In the invention, the reaction temperature in the step 3) is 40-70 ℃, and the reaction time is 4-6 h; preferably, the reaction temperature is 50-60 ℃, and the reaction time is 5-6 h; more preferably, the reaction temperature is 55 ℃ and the reaction time is 5 h.
In the invention, the rotating speed of the centrifugation is 6000-9000 r/min, and the time of the centrifugation is 10-30 min; preferably, the rotating speed of centrifugation is 7000-8000 r/min, and the time of centrifugation is 15-25 min; further preferably, the rotation speed of the centrifugation is 8000r/min, and the time of the centrifugation is 20 min.
In the invention, the diameter of the prepared sulfonated polystyrene nano-microsphere is 600-1300 nm, preferably 700-1000 nm, and the particle size of the obtained microsphere is uniform.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing polystyrene nano microspheres: taking 70g of ethanol and 30g of water as a mixed solution, adding 10g of polyvinylpyrrolidone (K30) into the mixed solution, stirring to completely dissolve the polyvinylpyrrolidone, adding the polyvinylpyrrolidone into a three-neck flask after the polyvinylpyrrolidone is completely dissolved, heating and stirring in an oil bath kettle, wherein the reaction temperature is 65 ℃, and the stirring speed is 300 r/min. Adding NaOH solution with mass concentration of 5% into styrene (St) to wash and remove polymerization inhibitor, and then washing residual NaOH with deionized water to make the solution neutral. 25g of washed styrene (St) was taken, 0.8g of Azobisisobutyronitrile (AIBN) was added thereto and dissolved by stirring, and after complete dissolution, the mixture was put into a three-necked flask at a temperature of 70 ℃ for a reaction time of 8 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing for 4 times by using ethanol and deionized water respectively, washing away unreacted styrene monomers and micromolecular substances to obtain white polystyrene nano-microsphere precipitates, and dissolving the white polystyrene nano-microsphere precipitates in the ethanol or water to obtain a monodisperse polystyrene nano-microsphere solution with uniform particle size.
Preparation of sulfonated polystyrene nano-microspheres: 4g of polystyrene nano microsphere solution is taken, and 30g of concentrated sulfuric acid (98%) is weighed and slowly added into the polystyrene nano microsphere solution while stirring, so that the local heating temperature is prevented from being overhigh. After the addition is completed, the mixture is subjected to ultrasonic treatment for 15min to be uniformly dispersed. And adding the dispersed solution into a three-neck flask, heating and stirring, wherein the reaction temperature is 40 ℃, and the reaction time is 5 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing for 6 times by using deionized water to wash away concentrated sulfuric acid so as to enable the solution to be neutral to obtain white sulfonated polystyrene nano microsphere precipitate, and dissolving the white sulfonated polystyrene nano microsphere precipitate in ethanol or water to obtain a monodisperse sulfonated polystyrene nano microsphere solution with uniform particle size.
The scanning electron microscope image of the apparent morphology of the sulfonated polystyrene nanospheres prepared in this example is shown in fig. 1, and the particle size is 826 nm; the infrared curve of the sulfonated polystyrene nanospheres prepared in this example is shown in FIG. 5, except the characteristic peak of polystyrene, which is 1180cm-1Also has sulfonic acid group (-SO)3) The infrared characteristic peak shows that the sulfonated polystyrene nano-microsphere is successfully prepared.
Example 2
Preparing polystyrene nano microspheres: taking 75g of ethanol and 25g of water as a mixed solution, adding 15g of polyvinylpyrrolidone (K30) into the mixed solution, stirring to completely dissolve the polyvinylpyrrolidone, adding the polyvinylpyrrolidone into a three-neck flask after the polyvinylpyrrolidone is completely dissolved, heating and stirring in an oil bath kettle, wherein the reaction temperature is 65 ℃, and the stirring speed is 300 r/min. Adding NaOH solution with mass concentration of 5% into styrene (St) to wash and remove polymerization inhibitor, and then washing residual NaOH with deionized water to make the solution neutral. 25g of washed styrene (St) was taken and 0.8g of Azobisisobutyronitrile (AIBN) was added, stirred to dissolve completely and then added to a three-necked flask at a temperature of 70 ℃ for a reaction time of 8 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing for 3 times by using ethanol and deionized water respectively, washing away unreacted styrene monomers and micromolecular substances to obtain white polystyrene nano-microsphere precipitates, and dissolving the white polystyrene nano-microsphere precipitates in the ethanol or water to obtain a monodisperse polystyrene nano-microsphere solution with uniform particle size.
Preparation of sulfonated polystyrene nano-microspheres: 6g of polystyrene nano microsphere solution is taken, and 30g of concentrated sulfuric acid (98%) is weighed and slowly added into the polystyrene nano microsphere solution while stirring, so that the local heating temperature is prevented from being overhigh. After the addition is completed, the mixture is subjected to ultrasonic treatment for 15min to be uniformly dispersed. And adding the dispersed solution into a three-neck flask, heating and stirring, wherein the reaction temperature is 50 ℃, and the reaction time is 5 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing with deionized water for 5 times to wash away concentrated sulfuric acid to make the solution neutral to obtain white sulfonated polystyrene nano-microsphere precipitate, and dissolving the white sulfonated polystyrene nano-microsphere precipitate in ethanol or water to obtain a monodisperse sulfonated polystyrene nano-microsphere solution with uniform particle size.
The scanning electron microscope image of the apparent morphology of the sulfonated polystyrene nanospheres prepared in this example is shown in fig. 2, and the particle size is 784 nm; the infrared curve of the sulfonated polystyrene nanospheres prepared in this example is shown in FIG. 5, except the characteristic peak of polystyrene, which is 1180cm-1Also has sulfonic acid group (-SO)3) The infrared characteristic peak shows that the sulfonated polystyrene nano-microsphere is successfully prepared. .
Example 3
Preparing polystyrene nano microspheres: taking 80g of ethanol and 20g of water as a mixed solution, adding 20g of polyvinylpyrrolidone (K30) into the mixed solution, stirring to completely dissolve the polyvinylpyrrolidone, adding the polyvinylpyrrolidone into a three-neck flask after the polyvinylpyrrolidone is completely dissolved, heating and stirring in an oil bath kettle, wherein the reaction temperature is 65 ℃, and the stirring speed is 300 r/min. Adding NaOH solution with mass concentration of 5% into styrene (St) to wash and remove polymerization inhibitor, and then washing residual NaOH with deionized water to make the solution neutral. 25g of washed styrene (St) was taken and 0.8g of Azobisisobutyronitrile (AIBN) was added, stirred to dissolve completely and then added to a three-necked flask at a temperature of 70 ℃ for a reaction time of 8 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing for 4 times by using ethanol and deionized water respectively, washing away unreacted styrene monomers and micromolecular substances to obtain white polystyrene nano-microsphere precipitates, and dissolving the white polystyrene nano-microsphere precipitates in the ethanol or water to obtain a monodisperse polystyrene nano-microsphere solution with uniform particle size.
Preparation of sulfonated polystyrene nano-microspheres: the polystyrene nano microsphere solution 8g is slowly added with the weighed concentrated sulfuric acid 40g (98%), and stirring is carried out while adding to prevent the local heating temperature from being overhigh. After the addition is completed, the mixture is subjected to ultrasonic treatment for 15min to be uniformly dispersed. Adding the dispersed solution into a three-neck flask, heating and stirring, wherein the reaction temperature is 60 ℃, and the reaction time is 5 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing with deionized water for 4 times to wash out concentrated sulfuric acid to make the solution neutral to obtain white sulfonated polystyrene nano-microsphere precipitate, and dissolving the white sulfonated polystyrene nano-microsphere precipitate in ethanol or water to obtain a monodisperse sulfonated polystyrene nano-microsphere solution with uniform particle size.
The scanning electron microscope image of the apparent morphology of the sulfonated polystyrene nanospheres prepared in this example is shown in fig. 3, and the particle size is 1228 nm; the infrared curve of the sulfonated polystyrene nanospheres prepared in this example is shown in FIG. 5, except the characteristic peak of polystyrene, which is 1180cm-1Also has sulfonic acid group (-SO)3) The infrared characteristic peak shows that the sulfonated polystyrene nano-microsphere is successfully prepared.
Example 4
Preparing polystyrene nano microspheres: taking 85g of ethanol and 15g of water as a mixed solution, adding 25g of polyvinylpyrrolidone (K30) into the mixed solution, stirring to completely dissolve the polyvinylpyrrolidone, adding the polyvinylpyrrolidone into a three-neck flask after the polyvinylpyrrolidone is completely dissolved, heating and stirring in an oil bath kettle, wherein the reaction temperature is 65 ℃, and the stirring speed is 300 r/min. Adding NaOH solution with mass concentration of 5% into styrene (St) to wash and remove polymerization inhibitor, and then washing residual NaOH with deionized water to make the solution neutral. 25g of washed styrene (St) was taken and 0.8g of Azobisisobutyronitrile (AIBN) was added, stirred to dissolve completely and then added to a three-necked flask at a temperature of 70 ℃ for a reaction time of 8 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing for 2 times by using ethanol and deionized water respectively, washing away unreacted styrene monomers and micromolecular substances to obtain white polystyrene nano-microsphere precipitates, and dissolving the white polystyrene nano-microsphere precipitates in the ethanol or water to obtain a monodisperse polystyrene nano-microsphere solution with uniform particle size.
Preparation of sulfonated polystyrene nano-microspheres: the polystyrene nano microsphere solution 8g is slowly added with the weighed concentrated sulfuric acid 40g (98%), and stirring is carried out while adding to prevent the local heating temperature from being overhigh. After the addition is completed, the mixture is subjected to ultrasonic treatment for 15min to be uniformly dispersed. Adding the dispersed solution into a three-neck flask, heating and stirring, wherein the reaction temperature is 70 ℃, and the reaction time is 5 hours. After the reaction is finished, adding the reaction solution into a centrifugal tube, washing for 6 times by using deionized water to wash away concentrated sulfuric acid so as to enable the solution to be neutral to obtain white sulfonated polystyrene nano microsphere precipitate, and dissolving the white sulfonated polystyrene nano microsphere precipitate in ethanol or water to obtain a monodisperse sulfonated polystyrene nano microsphere solution with uniform particle size.
The scanning electron microscope image of the apparent morphology of the sulfonated polystyrene nanospheres prepared in this example is shown in fig. 4, with the particle size of 1168 nm; the infrared curve of the sulfonated polystyrene nanospheres prepared in this example is shown in FIG. 5, except the characteristic peak of polystyrene, which is 1180cm-1Also has sulfonic acid group (-SO)3) The infrared characteristic peak shows that the sulfonated polystyrene nano-microsphere is successfully prepared.
The sulfonated polystyrene microspheres prepared by the method have controllable sizes, uniform particle sizes and particle size ranges of 600-1300 nm, can meet the requirements of various occasions and sizes, and provide possibility for realizing industrial production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of sulfonated polystyrene nano-microspheres is characterized by comprising the following steps:
1) adding azodiisobutyronitrile into styrene to obtain a mixed solution;
2) adding the mixed solution into a preheated ethanol water solution of polyvinylpyrrolidone for reaction to obtain a polystyrene nano microsphere solution;
3) adding concentrated sulfuric acid into the polystyrene nano microsphere solution to react to obtain a product, and centrifuging and washing the product to be neutral to obtain the sulfonated polystyrene nano microsphere.
2. The preparation method of the sulfonated polystyrene nanosphere according to claim 1, wherein the mass ratio of azobisisobutyronitrile to styrene is 0.5-1.5: 20 to 30.
3. The method for preparing sulfonated polystyrene nanospheres according to claim 1 or 2, wherein the temperature for preheating in step 2) is 60-80 ℃.
4. The method for preparing the sulfonated polystyrene nanospheres according to claim 3, wherein the mass ratio of ethanol to water in the ethanol aqueous solution of polyvinylpyrrolidone is 7: 3-9: 1, the mass concentration of the ethanol water solution of the polyvinylpyrrolidone is 5-20%.
5. The preparation method of the sulfonated polystyrene nanospheres according to claim 1, 2 or 4, wherein the reaction temperature in step 2) is 60-80 ℃ and the reaction time is 6-10 h.
6. The preparation method of the sulfonated polystyrene nanosphere according to claim 5, wherein the mass ratio of the mixed solution to the ethanol aqueous solution of polyvinylpyrrolidone is 20-30: 100 to 120.
7. The preparation method of the sulfonated polystyrene nanospheres according to claim 4 or 6, wherein the mass ratio of the concentrated sulfuric acid to the polystyrene nanosphere solution is 30-50: 5 to 10.
8. The preparation method of the sulfonated polystyrene nanosphere according to claim 7, wherein the reaction temperature in step 3) is 40-70 ℃ and the reaction time is 4-6 h.
9. The preparation method of the sulfonated polystyrene nanospheres according to claim 6 or 8, wherein the rotation speed of the centrifugation is 6000 to 9000r/min, and the time of the centrifugation is 10 to 30 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293936A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院理化技术研究所 | Preparation method of monodisperse polystyrene microsphere with controllable particle size |
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