Summary of the invention
It is good to the objective of the invention is to propose a kind of heat endurance and chemical stability, preparation simply, multiple layer polymer hollow microcapsule and preparation method thereof efficiently.
The multiple layer polymer hollow microcapsule that the present invention proposes is to adopt dispersion copolymerization method to prepare melamine resin (MF) Nano microsphere earlier; Utilizing coupling agent that the MF microsphere surface is carried out chemical modification handles; Be template with the MF microballoon again, the method by micro-emulsion polymerization coats one layer of polymeric P1 at above-mentioned MF nano-particle surface; Method by electrochemically oxidative polymerization coats another strata compound of one deck P2 at the MF/P1 particle surface again, and preparing with the MF nanoparticle like this is nuclear, and P1 and P2 are the MF/P1/P2 multiple layer polymer nano core-shell structure microcapsules that the chemical bond of shell is connected; Remove template core MF with the method for acid etch at last, prepare stable multiple layer polymer hollow capsule of nano, this hollow microsphere is of a size of micron to nanoscale.This method is applicable to the multiple layer polymer hollow microcapsule of preparation more than three layers and three layers too.Wherein,
The said polymer P1 is polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinylcarbazole, polyvinyl imidazole, polyvinylpyrrolidone, polyvinyl pyridine, polyacrylonitrile, polyvinyl alcohol or polyvinyl acetate; Polymer P 2 is polyaniline, substituted polyaniline, polypyrrole, replacement polypyrrole, polyacetylene, gathers right-penylene, polythiophene, poly quinoline, gathers right-penylene acetylene, polyphenyl bithiophene or gather two alkynes.
The preparation method of above-mentioned multiple layer polymer hollow microcapsule is as follows:
(1) in the there-necked flask that reflux condensate device and agitator are housed, adds 5~50g melamine and 5~50mL formalin, melamine and formaldehyde mole ratio are 1: 1~6,30-60 ℃ stirred in water bath 0.5~3 hour, obtain the prepolymer melamine methylol.And then add 25~150g deionized water, 0.5~5.0g polyvinyl alcohol, pH value with acetate conditioned reaction solution is 4~6, after in 30-60 ℃ water-bath, reacting 10~45 minutes, frozen water cooling fast, cessation reaction, products therefrom centrifugal sedimentation under 3500 rev/mins condition, remove and add deionized water again behind the supernatant liquor and disperse again, centrifugal sedimentation again repeats this process 2~4 times, obtain the MF powder, be lower than under the room temperature and preserve;
(2) be that Dropwise 5~50mL concentration is the ethanolic solution of the coupling agent of 0.025g/mL in the alcoholic solution of MF nanoparticle of 0.025g/mL in 5~10mL concentration.Reaction is 30-40 hour in 30-60 ℃ of water-bath, and 25~45 ℃ of vacuum drying promptly obtained the MF nanoparticle of coupling agent treatment more than 12 hours;
(3) in the there-necked flask of reflux condensate device is housed, be scattered in 10~50mL absolute ethyl alcohol the MF nanoparticle of the above-mentioned coupling agent treatment of 0.5~5g is ultrasonic, add 0.1~1.0g buffer simultaneously, 0.05~0.5g emulsifying agent and 50~250mL deionized water, after ultrasonic being uniformly dispersed, add 5~25mL polymer monomer P1,45-55 ℃ after pre-emulsification 1-2 hour, temperature is elevated to 75-85 ℃, Dropwise 5~50mL concentration is the initiator solution of 0.012g/mL, drip the back and continue reaction 6~24 hours, stop reaction and obtain white emulsion, after this emulsion centrifugal filtration and the purification process, use solvent wash again, remove homopolymers, 60~100 ℃ of vacuum drying promptly obtained MF/P1 polymer nanocomposite core-shell particle more than 12 hours;
(4) in the electrochemically oxidative polymerization device, the deionized water that adds 100~1000mL in advance, the concentrated sulfuric acid that slowly adds 1~15mL then, add 0.5-0.8gMF/P1 polymer nanocomposite core-shell particle and 5mL polymer monomer P2 more successively, add deionized water at last to 1800-2000mL, constantly stir, be uniformly dispersed until the MF/PVI powder.Open the voltage-stabilized power supply switch, react about 4~12h at ambient temperature.The positive electrode that reaction will deposit a large amount of products after finishing takes out, and product is scraped in the culture dish, then product is passed through suction filtration, ammonia is washed and step such as deionized water washing, is neutrality until filtrate.Solid product after at last washing being filtered places 30-40 ℃ vacuum drying oven dry, promptly obtains the MF/P1/P2 multiple layer polymer micronucleus shell particulate of purifying.Here the PVI powder is meant the polymer nanocomposite core-shell particle.
(5) above-mentioned MF/P1/P2 multiple layer polymer micronucleus shell particulate is added in the hydrochloric acid solution of 5~50mL 10%, ultrasonic dispersion after 1~8 hour again room temperature placed 2~6 days, suction filtration and be washed to neutrality, 45~100 ℃ of vacuum drying promptly obtained multiple layer polymer hollow capsule of nano more than 12 hours.
Among the present invention, polymer P 1 can be polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinylcarbazole, polyvinyl imidazole, polyvinylpyrrolidone, polyvinyl pyridine, polyacrylonitrile, polyvinyl alcohol or polyvinyl acetate.Polymer P 2 can be polyaniline, substituted polyaniline, polypyrrole, replacement polypyrrole, polyacetylene, gathers right-penylene, polythiophene, poly quinoline, gather right-penylene acetylene, polyphenyl bithiophene and poly-two alkynes etc.
Among the present invention, coupling agent can be KH-570, fertile blue (methacrylate-chromic chloride complex) or titanate coupling agent 5S, and its chemical structural formula is shown below respectively:
Among the present invention, buffer can be sodium acid carbonate, sodium carbonate, potash, potassium phosphate, calcium monohydrogen phosphate, calcium citrate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate or sodium hydrogen phosphate.
Among the present invention, emulsifying agent can be neopelex, lauryl sodium sulfate, hexadecyltrimethylammonium chloride, OTAC, OP series (OP-10, OP-15, OP-20), tween (Tween) series (as Tween-20, Tween-40, Tween-60, Tween-80) or class of department (Span) series (as Span-20, Span-40, Span-60 or Span-80).
Among the present invention, initator can be ammonium persulfate and potassium peroxydisulfate.
Advantage of the present invention is: adopt methods such as coupling agent treatment, micro-emulsion polymerization, electrochemically oxidative polymerization and acid etch to prepare a kind of multiple layer polymer hollow microcapsule of brand new, not only simple to operate, efficient is high, the polymer microcapsule size is even, and its size can be regulated by reaction condition.The thermal stability and the chemical stability of this sandwich construction hollow microcapsule are higher, its polymeric material can be selected polyvinylcarbazole, polyvinyl imidazole, the polyethylene benzimidazole, the p-phenylene vinylene, polyaniline, polythiophene, photoelectric functional macromolecular materials such as polypyrrole, have unique physicochemical properties and the superior photoelectric properties of Optoelectronic polymers material, and the multiple layer polymer hollow microcapsule that this method obtains demonstrates particular structure and changeable performance, in material science, life science, Electronics Science and Technology, biomedical engineering, catalytic science and technology etc. all have broad application prospects and use value in many fields.
The specific embodiment
Above-mentioned multiple layer polymer hollow microcapsule, its preparation method is at first to add 5~50g melamine and 5~50mL formalin (melamine and formaldehyde mole ratio are 1: 1~6) in the there-necked flask that reflux condensate device and agitator are housed, 30-60 ℃ stirred in water bath 0.5~3 hour, obtain the prepolymer melamine methylol.And then add 25~150g deionized water, 0.5~5.0g polyvinyl alcohol, after being 4~6 with the pH value of acetate conditioned reaction solution, after 30-60 ℃ stirred in water bath is reacted 10~45 minutes, frozen water cooling fast, cessation reaction, products therefrom centrifugal sedimentation under 3500 rev/mins condition, remove and add deionized water again behind the supernatant liquor and disperse again, repeat this process 2~4 times, sample low temperature is preserved, and promptly obtains the MF powder.
Be that Dropwise 5~50mL concentration is the ethanolic solution of the coupling agent of 0.025g/mL in the alcoholic solution of MF nanoparticle of 0.025g/mL in 5~10mL concentration then.Reaction is 30-40 hour in 30-60 ℃ of water-bath, and 25~45 ℃ of vacuum drying promptly obtained the MF nanoparticle of coupling agent treatment more than 12 hours.
Then in the there-necked flask of reflux condensate device is housed, the MF nanoparticle that the above-mentioned coupling agent treatment of 0.5~5g is good is ultrasonic to be scattered in 10~50mL absolute ethyl alcohol, add 0.1~1.0g buffer simultaneously, 0.05~0.5g emulsifying agent and 50~250mL deionized water, after ultrasonic being uniformly dispersed, add 5~25mL monomer 1,45-55 ℃ after pre-emulsification 1-2 hour, temperature is elevated to 75-85 ℃, Dropwise 5~50mL concentration is the initiator solution of 0.012g/mL, drip the back and continue reaction 6~24 hours, stop reaction and obtain white emulsion, after this emulsion centrifugal filtration and the purification process, use solvent wash again, remove homopolymers, 60~100 ℃ of vacuum drying promptly obtained MF/ polymer nanocomposite core-shell particle more than 12 hours.
Then in the electrochemically oxidative polymerization device, the deionized water that adds 100~1000mL in advance, the concentrated sulfuric acid that slowly adds 1~15mL then, add 0.6g MF/ polymer nanocomposite core-shell particle and 5mL monomer 2 more successively, add deionized water at last to 1800mL, constantly stir, be uniformly dispersed until the MF/PVI powder.Open the voltage-stabilized power supply switch, react about 4~12h at ambient temperature.The positive electrode that reaction will deposit a large amount of products after finishing carefully takes out, and product is scraped in the culture dish, uses the deionized water rinsing electrode, then product is passed through suction filtration, ammonia is washed and step such as deionized water washing, is neutrality until filtrate.Solid product after at last washing being filtered places 35 ℃ vacuum drying oven dry, promptly obtains MF/ (polymer 1)/(polymer 2) multiple layer polymer micronucleus shell particulate of purifying.
At last above-mentioned MF/ (polymer 1)/(polymer 2) multiple layer polymer micronucleus shell particulate is added in the hydrochloric acid solution of 5~50mL 10%, ultrasonic dispersion after 1~8 hour again room temperature placed 2~6 days, suction filtration and be washed to neutrality, 45~100 ℃ of vacuum drying promptly obtained multiple layer polymer hollow capsule of nano more than 12 hours.
Polymer 1 can be polystyrene, polyvinyl chloride, polymethyl methacrylate, polyvinylcarbazole, polyvinyl imidazole, polyvinylpyrrolidone, polyvinyl pyridine, polyacrylonitrile, polyvinyl alcohol or polyvinyl acetate.Polymer 2 can be polyaniline, substituted polyaniline, polypyrrole, replacement polypyrrole, polyacetylene, gathers right-penylene, polythiophene, poly quinoline, gather right-penylene acetylene, polyphenyl bithiophene and poly-two alkynes etc.Coupling agent is KH-570, fertile blue (methacrylate-chromic chloride complex) and titanate coupling agent 5S, preferred KH-570.Buffer is sodium acid carbonate, sodium carbonate, potash, potassium phosphate, calcium monohydrogen phosphate, calcium citrate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate or sodium hydrogen phosphate, preferred sodium acid carbonate, potash or potassium dihydrogen phosphate.Emulsifying agent is neopelex, lauryl sodium sulfate, hexadecyltrimethylammonium chloride, OTAC, OP-10, OP-15, OP-20, Tween-20, Tween-40, Tween-60, Tween-80, Span-20, Span-40, Span-60 or Span-80, preferred neopelex, lauryl sodium sulfate, OP-20, Tween-80 and Span-60.Initator is ammonium persulfate or potassium peroxydisulfate.
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.
Embodiment 1
Add 14g melamine and 11g formalin (both mol ratios are 1: 3.3) in the there-necked flask that reflux condensate device and agitator are housed, the magnetic stirrer reaction is 20 minutes in 60 ℃ of water-baths, obtains the prepolymer melamine methylol.Then in the 250mL there-necked flask, add the 110g deionized water, after 0.6g polyvinyl alcohol, reaction solution are regulated pH value to 4.6 with acetic acid solution in advance, under 60 ℃ of water bath condition, above-mentioned pre-polymerization liquid is slowly added, stirring reaction stops reaction after 15 minutes again, and frozen water cooling fast.With the centrifugal sedimentation under 3500 rev/mins condition of products therefrom dispersion, remove and add deionized water again behind the supernatant liquor and disperse again, repeat 4 times this process, sample low temperature is preserved, and promptly obtains the MF nanoparticle.
Take by weighing the alcoholic solution (concentration is 0.025g/mL) of 3.5gMF nanoparticle, drip the ethanolic solution (concentration is 0.025g/mL) of 20mL silane coupler KH-570.Then reaction 36 hours in 35 ℃ of water-baths, after the centrifugation, 35 ℃ of vacuum drying are spent the night under 3200 rev/mins of conditions, promptly obtain the good MF nanoparticle of coupling agent treatment behind the purifying.In the there-necked flask of reflux condensate device is housed, the MF nanoparticle that the above-mentioned coupling agent treatment of 1.2g is good is ultrasonic to be scattered in the 10mL absolute ethyl alcohol, add 0.24g sodium bicarbonate simultaneously, 0.18g sodium lauryl sulfate and 100mL deionized water, after ultrasonic being uniformly dispersed, add 10mL ethene imidazoles monomer, 50 ℃ of pre-emulsifications are after 1 hour, temperature is elevated to 80 ℃, dripping 25mL concentration is the aqueous solution of the ammonium persulfate of 0.012g/mL, drip the back and continue reaction 12 hours, stop reaction and obtain white emulsion, after this emulsion centrifugal filtration and the purification process, again with oxolane washing 4 times, to remove the polyvinyl imidazole homopolymers.80 ℃ of vacuum drying are spent the night, and promptly obtain the PF/ nano-pipel poly vinyl imidazole core-shell particle of purifying.
In the electrochemically oxidative polymerization device, the deionized water that adds 1000mL in advance, the concentrated sulfuric acid that slowly adds 5mL98% then, add 0.6g PF/ nano-pipel poly vinyl imidazole core-shell particle and 5mL aniline more successively, add deionized water at last to 1800mL, constantly stir, even until PF/ nano-pipel poly vinyl imidazole microparticulate.Open the voltage-stabilized power supply switch, have bubble to emerge near can seeing negative electrode this moment, illustrate to react to begin.Behind the about 6h of reaction, the positive electrode that deposits a large amount of products is carefully taken out at ambient temperature, product is scraped in the culture dish, use the deionized water rinsing electrode, washing lotion is also poured culture dish into.Then product suction filtration, ammonia are washed and the deionized water washing, be neutral until filtrate.Solid product after at last washing being filtered places 35 ℃ vacuum drying oven fully dry, promptly obtains the MF/ polyvinyl imidazole/polyaniline multiple layer polymer micronucleus shell particulate of purifying.
At last above-mentioned MF/ polyvinyl imidazole/polyaniline multiple layer polymer micronucleus shell particulate is added in the hydrochloric acid solution of 25mL 10%, ultrasonic dispersion after 10 hours again room temperature placed 2 days, suction filtration and be washed to neutrality after, 60 ℃ of vacuum drying are spent the night, and promptly obtain polyvinyl imidazole/polyaniline multiple layer polymer hollow microcapsule.The preparation process schematic diagram of this multiple layer polymer hollow microcapsule as shown in Figure 1, Fig. 2 and Fig. 3 are respectively its projection electromicroscopic photograph and field emission microscope photo, Fig. 4 is the projection electromicroscopic photograph of this multiple layer polymer hollow microcapsule of partial etching.These pictures have all convincingly demonstrated end product and have had multiple layer polymer hollow microcapsule structure really.As can be seen from Figure 6, this multiple layer polymer hollow microcapsule particle diameter is distributed in 200~500nm scope, and average grain diameter is 400nm, and wherein particle diameter is that the numbers of particles of 275nm is maximum, is about 10.5% of total number.
Embodiment 2
Identical with embodiment 1, but the concentration of KH-570 becomes 0.05g/mL, and the quantitative change of ethene imidazoles and aniline monomer is 15mL and 10mL.
Embodiment 3
Identical with embodiment 1, but the concentration of KH-570 becomes 0.1g/mL, and the quantitative change of ethene imidazoles and aniline monomer is 30mL and 20mL.
Embodiment 4
Identical with embodiment 1, but the concentration of the aqueous solution of ammonium persulfate becomes 0.024g/mL.
Embodiment 5
Identical with embodiment 1, but the concentration of the aqueous solution of ammonium persulfate becomes 0.048g/mL.
Embodiment 6
Identical with embodiment 1, but 10% hydrochloric acid solution becomes 5mL, and etch period is 4 days.
Embodiment 7
Identical with embodiment 1, but 40% hydrofluoric acid solution becomes 50mL, and etch period is 1 day.
Embodiment 8
Identical with embodiment 1, but ethene imidazoles monomer changes vinyl carbazole into, and aniline changes the pyrroles into.
Embodiment 9
Identical with embodiment 1, but ethene imidazoles monomer changes vinylpyridine into, and aniline changes quinoline into.
Embodiment 10
Identical with embodiment 1, but ethene imidazoles monomer changes vinylpyrrolidone into, and aniline changes thiophene into.
Embodiment 11
Identical with embodiment 1, fertile blue but coupling agent changes into.
Embodiment 12
Identical with embodiment 1, but coupling agent changes titanate coupling agent 5S into.
The polymer hollow particles that the foregoing description 2-12 is prepared, its structure and performance and embodiment 1 come to the same thing or similar, all have good heat endurance and chemical stability, be a kind of excellent function macromolecular material.