CN101591407A - A kind of preparation method of polystyrene nanoparticle - Google Patents
A kind of preparation method of polystyrene nanoparticle Download PDFInfo
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- CN101591407A CN101591407A CNA200810113781XA CN200810113781A CN101591407A CN 101591407 A CN101591407 A CN 101591407A CN A200810113781X A CNA200810113781X A CN A200810113781XA CN 200810113781 A CN200810113781 A CN 200810113781A CN 101591407 A CN101591407 A CN 101591407A
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Abstract
A kind of preparation method of polystyrene nanoparticle belongs to field of nano material preparation.There are shortcomings such as dosage of surfactant is big, equipment is complicated, temperature of reaction height in the preparation method of existing polystyrene nanoparticle.The present invention places under the ultraviolet radiation by with after vinylbenzene, water, alkyl brometo de amonio cationoid tensio-active agent and the crack type photoinitiator stirring and emulsifying, and initiated polymerization afterwards after filtration or centrifugal, obtains polystyrene nanoparticle; When adding linking agent in the polymerization reaction system, then obtain polystyrene nanometer gel particle.The inventive method adopts water as reaction medium, at room temperature be polymerizable, and monomer concentration is higher in the reaction system, and dosage of surfactant is low, and speed of reaction is fast, the monomer conversion height, and the equipment simple economy is easy to large-scale industrial production.
Description
Technical field
The invention belongs to field of nano material preparation, be specifically related to a kind of preparation method of polystyrene nanoparticle.
Background technology
In recent years, because nanotechnology develops rapidly, the preparation of polymer nano-particle becomes the focus of studying in the nanotechnology gradually.Polymer nano-particle has the stable morphology structure, can design, synthesize and the preparation polymer nano-particle from molecular level by selective polymerization mode and polymerization single polymerization monomer, and its size easy to control and size-grade distribution, make it to have small-size effect, in the time of surface effects and quantum tunneling effect, also has other specific function, as responsivenesss such as temperature, pH, electric field and magnetic fields.Polystyrene nanoparticle has potential application foreground widely as a kind of common polymer nano-particle in stealth material, information material, high-performance soil layer material, tackiness agent, biomedicine and fields such as the space flight and the energy.Micro-emulsion polymerization and letex polymerization are two kinds of methods commonly used of preparation polymer particle.Micro-emulsion polymerization can obtain polymer nano-particle at an easy rate, and experimental installation is simple, easy handling, but need a large amount of tensio-active agents, and monomer concentration is little.The use of exhibiting high surface promoting agent is bigger to the product property influence, and its application is restricted.And the required dosage of surfactant of letex polymerization is much smaller than micro-emulsion polymerization, but use letex polymerization to be difficult to obtain the less polystyrene nanoparticle of particle diameter, as at document MACROMOLECULAR 2001,34, adopt the RAFT compositions and methods that in emulsion system, adds low chain transfer constant to obtain polystyrene nanoparticle among the 4416-4423.But, increased production cost, and owing to adopt thermal initiation, required temperature of reaction is higher owing to used complex structure, special chain-transfer agent.And for example, adopt microwave radiation to cause letex polymerization among the 6388-6390 and obtained polystyrene nanoparticle at document MACROMOLECULAR 1997,30.Yet the size of particles that obtains is still bigger, and required equipment is comparatively complicated.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and a kind of preparation method of simple and easy to do polystyrene nanoparticle is provided.The inventive method dosage of surfactant is low, temperature of reaction is low and avoided complex apparatus such as use microwave radiation source, and monomer concentration height in the reaction system can make particle diameter and be the polystyrene nanoparticle about 20 nanometers at normal temperatures.When adding linking agent in the reaction system, also can obtain the polystyrene nanometer gel particle of same size.
Key of the present invention is to use UV-light as the initiation means, and cooperates specific light trigger, its principle as shown in Figure 1: 1) under ultraviolet radiation, light trigger decompose to produce a large amount of free radicals, and initiated polymerization forms a large amount of latex particles; 2) after polymerization was finished, latex particle was polystyrene nanoparticle; 3) when adding linking agent in system, polymerization is finished then can obtain polystyrene nanometer gel particle.
The preparation method of polystyrene nanoparticle provided by the present invention may further comprise the steps:
1) monomer styrene, alkyl brometo de amonio cationoid tensio-active agent, crack type photoinitiator and deionized water are mixed, stirring and emulsifying, wherein, the quality percentage composition of monomer styrene is 1-10% in the reaction system, the quality percentage composition of tensio-active agent is 0.3-0.6%, and the volumetric molar concentration of light trigger is every liter of a 1-20 mmole;
2) with the reaction system after the emulsification in the step 1) under 20-25 ℃ and ultraviolet radiation condition, stirred polyreaction 2.5 hours, wherein the ultraviolet light intensity is every square centimeter of a 1300-8000 microwatt, carry out centrifugation after polyreaction finishes or adopt sand core funnel to filter, obtain polystyrene nanoparticle.
Wherein, the alkyl brometo de amonio cationoid tensio-active agent described in the step 1) is octadecyl trimethylammonium bromide, cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide or Trimethyllaurylammonium bromide; Preferred cetyl trimethylammonium bromide.
Crack type photoinitiator described in the step 1) is 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone (trade(brand)name I rgacure 2959) or 2-hydroxy-2-methyl-1-phenyl-1-acetone (trade(brand)name Irgcure 1173); Preferred 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
Adding the linking agent Vinylstyrene in the reaction system in the step 1) mixes with monomer styrene, alkyl brometo de amonio cationoid tensio-active agent, crack type photoinitiator and deionized water, stirring and emulsifying, wherein, the quality percentage composition of linking agent and monomer sum is 1-10% in the reaction system, linking agent accounts for the 25-100% of monomer and linking agent total mass, the quality percentage composition of tensio-active agent is 0.3-0.6%, and the volumetric molar concentration of light trigger is every liter of a 1-20 mmole; Again with the reaction system after the emulsification in step 2) in carry out polyreaction and carry out centrifugation or adopt sand core funnel to filter, obtain polystyrene nanometer gel particle.
Compared with prior art, the present invention has following beneficial effect:
1) provided by the present invention method is simple, do not need special reaction unit and equipment, also do not need the violent reaction conditions of high temperature, therefore can carry out scale operation through simple improvement.
2) the inventive method dosage of surfactant is low, and aftertreatment is easy and cost is lower, produces for its large-scale industrialization and haves laid a good foundation.
3) monomer concentration is higher in the reaction system of the present invention, helps effective utilization of tensio-active agent etc.
4) the present invention can obtain polystyrene nanometer gel particle or not crosslinked polystyrene nanoparticle by adding or do not add linking agent.
Description of drawings
Fig. 1: polystyrene nanoparticle preparation process reaction mechanism synoptic diagram.
The laser particle analyzer analytical results of the polystyrene nanoparticle that obtains among Fig. 2: the embodiment 1.
Cinnamic polymerization conversion curve among Fig. 3: the embodiment 1.
The laser particle analyzer analytical results of the polystyrene nanoparticle that obtains among Fig. 4: the embodiment 2.
Cinnamic polymerization conversion curve among Fig. 5: the embodiment 2.
The laser particle analyzer analytical results of the polystyrene nanometer gel particle that obtains among Fig. 6: the embodiment 3.
Cinnamic polymerization conversion curve among Fig. 7: the embodiment 3.
The laser particle analyzer analytical results of the polystyrene nanoparticle that obtains among Fig. 8: the embodiment 4.
The laser particle analyzer analytical results of the polystyrene nanoparticle that obtains among Fig. 9: the embodiment 6.
Embodiment
Embodiment 1
1) with vinylbenzene 5g, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.2g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and filters with the G4 funnel, and filtrate is the product polystyrene nanoparticle.
As seen from Figure 2, the particle diameter of polystyrene nanoparticle is about 25 nanometers; Cinnamic as seen from Figure 3 transformation efficiency can reach more than 95%.
Embodiment 2
1) with vinylbenzene 5g, 2-hydroxy-2-methyl-1-phenyl-1-acetone 0.15g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g add in the reaction flask that has quartz cover and mix, logical nitrogen stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and with filtering with the G4 funnel, filtrate is the product polystyrene nanoparticle.
The particle diameter of polystyrene nanoparticle is about 25 nanometers as seen from Figure 4; Cinnamic as seen from Figure 5 transformation efficiency can reach 100%.
Embodiment 3
1) takes by weighing vinylbenzene 3g respectively, Vinylstyrene 2g, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.2g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and filters with the G4 funnel, and filtrate is the product polystyrene nanometer gel particle.
The particle diameter of polystyrene nanometer gel particle is about 30 nanometers as seen from Figure 6; Cinnamic transformation efficiency can reach more than 90% from Fig. 7.
Embodiment 4
1) with vinylbenzene 5g, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.01g (every liter of 1 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and filters with the G4 funnel, and filtrate is the product polystyrene nanoparticle.
As seen from Figure 8, the particle diameter of polystyrene nanoparticle is about 40 nanometers.
Embodiment 5
1) takes by weighing vinylbenzene 5g respectively, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.1g (every liter of 10 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and centrifugal with whizzer, and the upper strata stillness of night is the product polystyrene nanoparticle.
The laser particle analyzer analytical results shows that the particle diameter of polystyrene nanoparticle is about 25 nanometers.
Embodiment 6
1) with vinylbenzene 5g, 2-hydroxy-2-methyl-1-phenyl-1-acetone 0.15g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.15g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 commentaries on classics per minute kinds, reaction finishes the back discharging, and filters with the G4 funnel, and filtrate is the product polystyrene nanoparticle.
As seen from Figure 9, the particle diameter of polystyrene nanoparticle is about 45 nanometers.
Embodiment 7
1) with vinylbenzene 5g, 2-hydroxy-2-methyl-1-phenyl-1-acetone 0.15g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.3g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and filters with the G4 funnel, and filtrate is the product polystyrene nanoparticle.
The laser particle analyzer analytical results shows that the particle diameter of polystyrene nanoparticle is about 30 nanometers.
Embodiment 8
1) with vinylbenzene 5g, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.2g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 1300 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and filters with the G4 funnel, and filtrate is the product polystyrene nanoparticle.
The laser particle analyzer analytical results shows that the particle diameter of polystyrene nanoparticle is about 50 nanometers.
Embodiment 9
1) with vinylbenzene 5g, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.2g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 5000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and filters with the G4 funnel, and filtrate is the product polystyrene nanoparticle.
The laser particle analyzer analytical results shows that the particle diameter of polystyrene nanoparticle is about 30 nanometers.
1) with Vinylstyrene 5g, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.2g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g, add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and centrifugal with whizzer, and the upper strata stillness of night is the product polystyrene nanometer gel particle.
The laser particle analyzer analytical results shows that the particle diameter of polystyrene nanometer gel particle is about 20 nanometers.
Embodiment 11
1) with vinylbenzene 4g, Vinylstyrene 1g, 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone 0.2g (every liter of 20 mmole), cetyl trimethylammonium bromide 0.2g and deionized water 45g add in the reaction flask that has quartz cover and mix, logical nitrogen, stirring and emulsifying 30 minutes, 300 rpms of mixing speed;
2) reaction solution after the emulsification in the step 1) is placed under the radiation of 375W straight tube high voltage mercury lamp, adjusting incident intensity is every square centimeter of 8000 microwatt, reacted 2.5 hours, and follow stirring, rotating speed is 300 rpms, reaction finishes the back discharging, and centrifugal with whizzer, and the upper strata stillness of night is the product polystyrene nanometer gel particle.
The laser particle analyzer analytical results shows that the particle diameter of polystyrene nanometer gel particle is about 30 nanometers.
Claims (6)
1, a kind of preparation method of polystyrene nanoparticle is characterized in that, may further comprise the steps:
1) monomer styrene, alkyl brometo de amonio cationoid tensio-active agent, crack type photoinitiator and deionized water are mixed, stirring and emulsifying, wherein, monomer styrene quality percentage composition is 1-10% in the reaction system, the quality percentage composition of tensio-active agent is 0.3-0.6%, and the volumetric molar concentration of light trigger is every liter of a 1-20 mmole;
2) with the reaction system after the emulsification in the step 1) under 20-25 ℃ and ultraviolet radiation condition, stirred polyreaction 2.5 hours, wherein the ultraviolet light intensity is every square centimeter of a 1300-8000 microwatt, carry out centrifugation after polyreaction finishes or adopt sand core funnel to filter, obtain polystyrene nanoparticle.
2, preparation method according to claim 1, it is characterized in that the alkyl brometo de amonio cationoid tensio-active agent described in the step 1) is octadecyl trimethylammonium bromide, cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide or Trimethyllaurylammonium bromide.
3, preparation method according to claim 2 is characterized in that, described alkyl brometo de amonio cationoid tensio-active agent is a cetyl trimethylammonium bromide.
4, preparation method according to claim 1, it is characterized in that, crack type photoinitiator described in the step 1) is 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone or 2,2-dimethoxy benzene benzoylformaldoxime.
5, preparation method according to claim 4 is characterized in that, described crack type photoinitiator is 1-[4-(2-hydroxy ethoxy)-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone or 2-hydroxy-2-methyl-1-phenyl-1-acetone.
6, preparation method according to claim 1, it is characterized in that, adding the linking agent Vinylstyrene in the reaction system in the step 1) mixes with monomer styrene, alkyl brometo de amonio cationoid tensio-active agent, crack type photoinitiator and deionized water, stirring and emulsifying, wherein, the quality percentage composition of linking agent and monomer sum is 1-10% in the reaction system, linking agent accounts for the 25-100% of monomer benzene and linking agent total mass, the quality percentage composition of tensio-active agent is 0.3-0.6%, and the volumetric molar concentration of light trigger is every liter of 20 mmole; Again with the reaction system after the emulsification in step 2) in carry out polyreaction and carry out centrifugation or adopt sand core funnel to filter, obtain polystyrene nanometer gel particle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665226A (en) * | 2012-09-20 | 2014-03-26 | 大连理工常熟研究院有限公司 | Method for preparing high molecular microspheres through light-initiated in-situ emulsion polymerization |
| CN107417833A (en) * | 2017-03-06 | 2017-12-01 | 山东大学 | Amido modified nano pipe/polyhenylethylene and preparation method thereof |
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| US4218371A (en) * | 1977-11-14 | 1980-08-19 | E. I. Du Pont De Nemours And Company | Process for preparing 2,2'-azobis(2,4-dimethyl-4-methoxypentanenitrile) |
| CN1583860A (en) * | 2004-06-11 | 2005-02-23 | 清华大学 | Preparing method for high cross-linked olefinic polymer/calcium carbonate composite nanometer particle |
| CN100378190C (en) * | 2005-07-26 | 2008-04-02 | 中国科学院理化技术研究所 | Nano-water soluble microgel oil displacing material and its preparation method |
| KR100814373B1 (en) * | 2006-12-28 | 2008-03-18 | 제일모직주식회사 | Styrenic polymer/clay nanocomposite and method of preparing same, and thermoplastic resin/clay nanocomposite |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665226A (en) * | 2012-09-20 | 2014-03-26 | 大连理工常熟研究院有限公司 | Method for preparing high molecular microspheres through light-initiated in-situ emulsion polymerization |
| CN103665226B (en) * | 2012-09-20 | 2015-12-02 | 大连理工常熟研究院有限公司 | A kind of light-initiated in-situ emulsion polymerization prepares the method for polymer microsphere |
| CN107417833A (en) * | 2017-03-06 | 2017-12-01 | 山东大学 | Amido modified nano pipe/polyhenylethylene and preparation method thereof |
| CN107417833B (en) * | 2017-03-06 | 2020-04-17 | 山东大学 | Amino modified nano polystyrene and preparation method thereof |
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