CN1303140C - Hollow polymer microsphere and method for preparing same - Google Patents
Hollow polymer microsphere and method for preparing same Download PDFInfo
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- CN1303140C CN1303140C CNB2004100890391A CN200410089039A CN1303140C CN 1303140 C CN1303140 C CN 1303140C CN B2004100890391 A CNB2004100890391 A CN B2004100890391A CN 200410089039 A CN200410089039 A CN 200410089039A CN 1303140 C CN1303140 C CN 1303140C
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Abstract
The present invention relates to a hollow polymer microsphere and a preparation method thereof, which belongs to the technical field of functional macromolecular materials. A polymer layer is chemically bonded on the surface of an inorganic material nanometer microsphere by a microemulsion polymerization method, a microsphere in a polymer/ inorganic material nanometer compound core shell structure is formed, and the inorganic materials are removed by a strong acid etching method to prepare the hollow polymer microsphere, and furthermore, the dimension of the hollow polymer microsphere is in the micrometer to nanometer stage. The method has the advantages of simple operation and high efficiency, the dimensions of the microspheres are uniform, and the prepared hollow polymer microsphere has the advantages of good thermal stability and chemical stability and broad application prospects.
Description
Technical field
The invention belongs to the functional high molecule material technical field, be specifically related to a kind of polymer hollow particles and preparation method thereof.
Background technology
The hollow structure polymer microballoon is a kind of functional materials with special construction, and its hollow space can be that gas, liquid or other have the activeconstituents of specific function, and outer shell for the polymkeric substance composition.Size of particles has had small size, hollow and feature that spheroid capsule three be integrated in one to the polymkeric substance hollow Nano microsphere between micron because of it in nanometer, be with a wide range of applications in fields such as biology, catalysis, electronics, optics and magnetics, become hot research in recent years gradually.The method for preparing polymeric hollow microsphere mainly contains 3 kinds of self-assembly method, template and emulsion methods etc.These two kinds of methods of self-assembly method and template require tighter to system, and need carry out under extremely low polymer concentration, thereby their practical application is subjected to very big restriction.And though emulsion polymerization is simple, efficient and reappears, its thermostability and chemical stability are still waiting improvement.
Summary of the invention
It is good to the objective of the invention is to propose a kind of thermostability and chemical stability, preparation simply, polymer hollow particles and preparation method thereof efficiently.
The polymer hollow particles that the present invention proposes, be earlier by the surface chemistry keyed jointing one layer of polymeric layer of microemulsion polymerization method at the inorganic materials Nano microsphere, forming the inorganic materials Nano microsphere is the polymer/inorganic nanometer compound nucleus shell structure microballoon that the chemical bond of shell connects for nuclear, polymkeric substance; Then etch away the built-in nuclear of inorganic materials Nano microsphere with strong acid and obtain, this hollow microsphere is of a size of micron to nano level.
The preparation method of above-mentioned polymer hollow particles is as follows:
(1) in the there-necked flask that reflux condensate device and agitator are housed, adds the ammoniacal liquor of 5～50ml inorganic materials Nano microsphere, 50～500ml dehydrated alcohol and 5～15ml, 20-30 ℃ stirred in water bath 6～36 hours, part ethanol is removed in evaporation then, can obtain the alcoholic solution of inorganic materials nanoparticle;
(2) be that Dropwise 5～50ml concentration is the ethanolic soln of the coupling agent of 0.025g/ml in the alcoholic solution of inorganic materials nanoparticle of 0.025g/ml in 5～10ml concentration.Reaction is 30-40 hour in 30-40 ℃ of water-bath, and 25～45 ℃ of vacuum-dryings promptly obtained the inorganic materials Nano microsphere of coupling agent treatment more than 12 hours;
(3) in the there-necked flask of reflux condensate device is housed, the inorganic materials Nano microsphere ultra-sonic dispersion that the above-mentioned coupling agent treatment of 0.5～5g is good is in 10～50ml dehydrated alcohol, add 0.1～1.0g buffer reagent simultaneously, 0.05～0.5g emulsifying agent and 50～250ml deionized water, after ultra-sonic dispersion is even, add 5～25ml polymer monomer, 45-55 ℃ after pre-emulsification 1-2 hour, temperature is elevated to 75-85 ℃, Dropwise 5～50ml concentration is the aqueous solution of the persulphate of 0.012g/ml, drip the back and continue reaction 6～24 hours, stopped reaction obtains white emulsion, after this emulsion centrifuging and the purification process, use toluene wash again, remove homopolymer; 60～100 ℃ of vacuum-dryings promptly obtained inorganic materials/polymer nanocomposite core-shell particles more than 12 hours;
(4) above-mentioned inorganic materials/polymer nanocomposite core-shell particles is added in the hydrofluoric acid solution and 5～50ml deionized water of 5～25ml 40%, ultra-sonic dispersion after 1～8 hour room temperature placed 2～6 days; Suction filtration and be washed to neutrality, 45～100 ℃ of vacuum-dryings promptly obtained polymkeric substance hollow Nano microsphere more than 12 hours.
Among the present invention, polymkeric substance can be polystyrene, polyvinyl chloride, polymethylmethacrylate, polyvinyl carbazole, polyvinyl imidazole, polyvinylpyrrolidone, polyvinyl pyridine, polyacrylonitrile, polyvinyl alcohol or polyvinyl acetate (PVA).
Among the present invention, inorganic materials can be silicon dioxide nanosphere, also can be the Nano microsphere of magnesium oxide, zinc oxide, calcium oxide, ferric oxide, tungstic oxide, aluminium sesquioxide or lime carbonate, or iron powder, copper powder or lead powder etc.
Among the present invention, coupling agent can be KH-570, fertile blue (methacrylate-chromic chloride title complex) or titanate coupling agent 5S, and its chemical structural formula is shown below respectively:
Among the present invention, buffer reagent can be sodium bicarbonate, yellow soda ash, salt of wormwood, potassiumphosphate, secondary calcium phosphate, citrate of lime, potassium primary phosphate, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic.
Among the present invention, emulsifying agent can be a Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, OP series (polyoxyethylene octylphenol ether-10 (OP-10), polyoxyethylene octylphenol ether-15 (OP-15), polyoxyethylene octylphenol ether-20 (OP-20)), tween (Tween) series is (as tween 20 (Tween-20), Tween-40 (Tween-40), Tween-60 (Tween-60), tween-80 (Tween-80)), or class of department (Span) series is (as Si Ban-20 (Span-20), Si Ban-40 (Span-40), Si Ban-60 (Span-60) or span-80 (Span-80)).Among the present invention, persulphate can be ammonium persulphate and Potassium Persulphate.
Advantage of the present invention is: adopt methods such as coupling agent treatment, micro-emulsion polymerization and acid etch to prepare polymkeric substance hollow Nano microsphere, not only simple to operate, efficient is high, polymer microballoon size homogeneous, and its size can be regulated by reaction conditions.The thermal stability of microballoon is good, chemical stability is higher, its polymer materials can be selected photoelectric functional macromolecular materials such as polyvinyl carbazole, polyvinyl imidazole, polyethylene benzoglyoxaline, p-phenylene vinylene, polyaniline, Polythiophene, polypyrrole, have unique physicochemical property and the superior photoelectric properties of Optoelectronic polymers material, gather around and have broad application prospects and use value.
Description of drawings
Fig. 1 is the preparation process synoptic diagram of polymer hollow particles.
Fig. 2 is the projection Electronic Speculum figure of silicon-dioxide/polyalcohol nucleocapsid microballoon.
Fig. 3 is the polymer hollow particles of partial etching.
Fig. 4 is the polymer hollow particles of complete etching.
Fig. 5 is the size distribution figure of polymer hollow particles.
Embodiment
Above-mentioned polymkeric substance hollow Nano microsphere, its preparation method is the ammoniacal liquor that at first adds 5～50ml tetraethoxy, 50～500ml dehydrated alcohol and 5～15ml in the there-necked flask that reflux condensate device and agitator are housed, 25 ℃ stirred in water bath 6～36 hours, slowly part ethanol is removed in evaporation then, can obtain the alcoholic solution of silica nanoparticles.
Then in the alcoholic solution (concentration is 0.025g/ml) of 5～10ml silica nanoparticles, the ethanolic soln of Dropwise 5～50mlKH-570 silane coupling agent (concentration is 0.025g/ml).Reaction is 36 hours in 35 ℃ of water-baths, and 25～45 ℃ of vacuum-dryings are spent the night, and promptly obtain the silicon dioxide nanosphere of coupling agent treatment.
Then in the there-necked flask of reflux condensate device is housed, the silicon dioxide nanosphere ultra-sonic dispersion that the above-mentioned coupling agent treatment of 0.5～5g is good is in 10～50ml dehydrated alcohol, add 0.1～1.0g buffer reagent simultaneously, 0.05～0.5g emulsifying agent and 50～250ml deionized water, after ultra-sonic dispersion is even, add 5～25ml polymer monomer, behind 50 ℃ of pre-emulsification 1h, temperature is elevated to 80 ℃, the aqueous solution of Dropwise 5～50ml persulphate (concentration is 0.012g/ml), drip the back and continue reaction 6～24 hours, stopped reaction obtains white emulsion, after this emulsion centrifuging and the purification process, use toluene wash 3-4 time again, remove homopolymer.60～100 ℃ of vacuum-dryings are spent the night, and promptly obtain silicon-dioxide/polymer nanocomposite core-shell particles.
At last above-mentioned silicon-dioxide/polymer nanocomposite core-shell particles is added in the hydrofluoric acid solution and 5～50ml deionized water of 5～25ml 40%, ultra-sonic dispersion after 1～8 hour room temperature placed 2～6 days.Suction filtration and be washed to neutrality, 45～100 ℃ of vacuum-dryings are spent the night, and promptly obtain polymkeric substance hollow Nano microsphere.
Polymkeric substance is polystyrene, polyvinyl chloride, polymethylmethacrylate, polyvinyl carbazole, polyvinyl imidazole, polyvinylpyrrolidone, polyvinyl pyridine, polyacrylonitrile, polyvinyl alcohol or polyvinyl acetate (PVA), preferred polystyrene, polyvinyl carbazole, polyvinyl imidazole and polyvinyl pyridine.Silicon dioxide nanosphere also can change magnesium oxide, zinc oxide, calcium oxide, ferric oxide, tungstic oxide, aluminium sesquioxide or calcium carbonate nano microballoon or iron powder, copper powder or lead powder into, preferred magnesium oxide, tungstic oxide, aluminium sesquioxide and iron powder.Coupling agent is KH-570, fertile blue (methacrylate-chromic chloride title complex) and titanate coupling agent 5S, preferred KH-570.Buffer reagent is sodium bicarbonate, yellow soda ash, salt of wormwood, potassiumphosphate, secondary calcium phosphate, citrate of lime, potassium primary phosphate, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic, preferred sodium bicarbonate, salt of wormwood or potassium primary phosphate.Emulsifying agent is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, OP-10, OP-15, OP-20, Tween-20, Tween-40, Tween-60, Tween-80, Span-20, Span-40, Span-60 or Span-80, preferred Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-20, Tween-80 and Span-60.Persulphate is ammonium persulphate or Potassium Persulphate.
The present invention will be described in detail below in conjunction with embodiment.Do not violating under the purport of the present invention, the present invention should be not limited to the content that following experimental example is specifically expressed.
The ammoniacal liquor that adds 20ml tetraethoxy, 250ml dehydrated alcohol and 10ml in the there-necked flask that reflux condensate device and agitator are housed 25 ℃ stirred in water bath 24 hours, is removed part ethanol in slow evaporation then, can obtain SiO
2The alcoholic solution of nanoparticle.Accurately take by weighing the alcoholic solution (concentration is 0.025g/ml) of 8ml silica nanoparticles, drip the ethanolic soln (concentration is 0.025g/ml) of 20ml KH-570 silane coupling agent.Then reaction 36 hours in 35 ℃ of water-baths, 35 ℃ of vacuum-dryings are spent the night, and promptly obtain the good SiO of coupling agent treatment behind the purifying
2Nanometer powder.In the there-necked flask of reflux condensate device is housed, with the good SiO of the above-mentioned coupling agent treatment of 1.2g
2The nanometer powder ultra-sonic dispersion is in the 10ml dehydrated alcohol, add 0.24g sodium bicarbonate, 0.18g sodium lauryl sulfate and 100ml deionized water simultaneously, after ultra-sonic dispersion is even, add the 10ml styrene monomer, behind 50 ℃ of pre-emulsification 1h, temperature is elevated to 80 ℃, drip the aqueous solution (concentration is 0.012g/ml) of 25ml ammonium persulphate, drip the back and continue reaction 12 hours, stopped reaction obtains white emulsion, after this emulsion centrifuging and the purification process, use toluene wash again 4 times, to remove polystyrene homopolymer.80 ℃ of vacuum-dryings are spent the night, and promptly obtain the SiO of purifying
2/ PS nano core-shell particulate, Fig. 2 is its electron micrograph.With SiO
2/ PS nano core-shell particulate adds the tetrafluoroethylene small beaker, adds hydrofluoric acid solution and the 20ml deionized water of 5ml40%, ultra-sonic dispersion after 2 hours room temperature placed two days.Suction filtration and be washed to neutrality, 60 ℃ of vacuum-dryings are spent the night, and promptly obtain the PS hollow microsphere.Fig. 3 is the electron micrograph of the good polystyrene hollow microsphere of partial etching, and Fig. 4 is the electron micrograph of the polystyrene hollow microsphere of complete etching.
The preparation process synoptic diagram of polystyrene hollow microsphere as shown in Figure 1, as can be seen from Figure 5, its size distribution is in 300～450nm scope.
Embodiment 2
Identical with embodiment 1, but the concentration of KH-570 becomes 0.05g/ml, and the quantitative change of styrene monomer is 15ml.
Identical with embodiment 1, but the concentration of KH-570 becomes 0.1g/ml, and the quantitative change of styrene monomer is 30ml.
Embodiment 4
Identical with embodiment 1, but the concentration of the aqueous solution of ammonium persulphate becomes 0.024g/ml.
Embodiment 5
Identical with embodiment 1, but the concentration of the aqueous solution of ammonium persulphate becomes 0.048g/ml.
Embodiment 6
Identical with embodiment 1, but 40% hydrofluoric acid solution becomes 10ml, and etching time is 4 days.
Embodiment 7
Identical with embodiment 1, but 40% hydrofluoric acid solution becomes 20ml, and etching time is 6 days.
Embodiment 8
Identical with embodiment 1, but monomer changes vinyl carbazole into.
Embodiment 9
Identical with embodiment 1, but monomer changes the ethene imidazoles into.
Embodiment 10
Identical with embodiment 1, but monomer changes vinylpyridine into.
Embodiment 11
Identical with embodiment 1, but inorganic particles changes zinc oxide into.
Embodiment 12
Identical with embodiment 1, but inorganic particles changes aluminum oxide into.
Embodiment 13
Identical with embodiment 1, fertile blue but coupling agent changes into.
Embodiment 14
Identical with embodiment 1, but coupling agent changes titanate coupling agent 5S into.
The polymer hollow particles that the foregoing description 2-14 is prepared, its structure and performance and embodiment 1 come to the same thing or similar, all have good thermostability and chemical stability, be a kind of excellent function macromolecular material.
Claims (7)
1, a kind of polymer hollow particles, it is characterized in that, earlier by the surface chemistry keyed jointing one layer of polymeric layer of microemulsion polymerization method at the inorganic materials Nano microsphere, forming the inorganic materials Nano microsphere is the polymer/inorganic nanometer compound nucleus shell structure microballoon of the chemical bond connection of shell for nuclear, polymkeric substance, then etch away the built-in nuclear of inorganic materials Nano microsphere with strong acid and obtain, it is of a size of micron to nano level; Wherein, the said polymer is polystyrene, polyvinyl chloride, polymethylmethacrylate, polyvinyl carbazole, polyvinyl imidazole, polyvinylpyrrolidone, polyvinyl pyridine, polyacrylonitrile, polyvinyl alcohol or polyvinyl acetate (PVA); Said inorganic materials Nano microsphere is the Nano microsphere of silicon-dioxide, magnesium oxide, zinc oxide, calcium oxide, ferric oxide, tungstic oxide, aluminium sesquioxide or lime carbonate, or iron powder, copper powder or lead powder.
2, a kind of preparation method of polymer hollow particles as claimed in claim 1 is characterized in that concrete steps are:
(1) in the there-necked flask that reflux condensate device and agitator are housed, adds the ammoniacal liquor of 5～50ml inorganic materials Nano microsphere, 50～500ml dehydrated alcohol and 5～15ml, 20-30 ℃ stirred in water bath 6～36 hours, part ethanol is removed in evaporation then, obtains the alcoholic solution of inorganic materials nanoparticle;
(2) be in the alcoholic solution of inorganic materials nanoparticle of 0.025g/ml in 5～10ml concentration, Dropwise 5～50ml concentration is the ethanolic soln of the coupling agent of 0.025g/ml, reaction is 30-40 hour in 30-40 ℃ of water-bath, 25～45 ℃ of vacuum-dryings obtained the inorganic materials Nano microsphere of coupling agent treatment more than 12 hours;
(3) in the there-necked flask of reflux condensate device is housed, the inorganic materials Nano microsphere ultra-sonic dispersion that the above-mentioned coupling agent treatment of 0.5～5g is good is in 10～50ml dehydrated alcohol, add 0.1～1.0g buffer reagent simultaneously, 0.05～0.5g emulsifying agent and 50～250ml deionized water, after ultra-sonic dispersion is even, add 5～25ml polymer monomer, 45-55 ℃ after pre-emulsification 1-2 hour, temperature is elevated to 75-85 ℃, Dropwise 5～50ml concentration is the aqueous solution of the persulphate of 0.012g/ml, drip the back and continue reaction 6～24 hours, stopped reaction obtains white emulsion, after this emulsion centrifuging and the purification process, use toluene wash again, remove homopolymer; 60～100 ℃ of vacuum-dryings obtained inorganic materials/polymer nanocomposite core-shell particles more than 12 hours;
(4) above-mentioned inorganic materials/polymer nanocomposite core-shell particles is added in the hydrofluoric acid solution and 5～50ml deionized water of 5～25ml 40%, ultra-sonic dispersion after 1～8 hour room temperature placed 2～6 days; Suction filtration and be washed to neutrality, 45～100 ℃ of vacuum-dryings promptly obtained polymkeric substance hollow Nano microsphere more than 12 hours;
Wherein, said inorganic materials Nano microsphere is silicon-dioxide, magnesium oxide, zinc oxide, calcium oxide, ferric oxide, tungstic oxide or aluminium sesquioxide microballoon, or is iron powder, copper powder or lead powder.
3, preparation method according to claim 2 is characterized in that said polymkeric substance is polystyrene, polyvinyl chloride, polymethylmethacrylate, polyvinyl carbazole, polyvinyl imidazole, polyvinylpyrrolidone, polyvinyl pyridine, polyacrylonitrile, polyvinyl alcohol or polyvinyl acetate (PVA).
4, preparation method according to claim 3 is characterized in that said coupling agent is KH-570, Wo Lan or titanate coupling agent 5S, and its chemical structural formula is shown below respectively:
5, preparation method according to claim 3 is characterized in that said buffer reagent is sodium bicarbonate, yellow soda ash, salt of wormwood, potassiumphosphate, secondary calcium phosphate, citrate of lime, potassium primary phosphate, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or Sodium phosphate dibasic.
6, preparation method according to claim 3 is characterized in that said emulsifying agent is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, polyoxyethylene octylphenol ether-10, polyoxyethylene octylphenol ether-15, polyoxyethylene octylphenol ether-20, tween 20, Tween-40, Tween-60, tween-80, Si Ban-20, Si Ban-40, Si Ban-60 or span-80.
7, preparation method according to claim 3 is characterized in that said persulphate is ammonium persulphate or Potassium Persulphate.
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