CN104851546A - Magnetic porous-polymer functional nanoparticle and preparation method thereof - Google Patents
Magnetic porous-polymer functional nanoparticle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic porous-polymer functional nanoparticle and a preparation method thereof. The magnetic porous-polymer functional nanoparticle is provided with a rough porous structure on the surface, polystyrene is used as a spherical base, phenolic resin is used as a support frame, hydroxide radical on the phenolic resin and ferroferric oxide magnetic nanoparticles constitute coordination, and the ferroferric oxide magnetic nanoparticles wrap the ball. The magnetic porous-polymer functional nanoparticle comprises, by weight, 0.02-0.20 g of hexahydrate perchloride iron, 0.1-0.4 g of base catalysis phenolic resin prepolymer, 3-13 mL of glycol, 0.01-0.05 g of polyvinyl pyrrolidone, 0.1-0.3 g of sodium acetate trihydrate and 0.5-2.0 mL of styrene. The preparation method of the magnetic porous-polymer functional nanoparticle provides a convenient and feasible one-step solvothermal method and can prepare the magnetic porous-polymer functional nanoparticle with magnetic response, surface porous structure and functional radical group, and the magnetic porous-polymer functional nanoparticle is uniform and stable and 400 nm in particle diameter and has the unique adsorption advantages.
Description
Technical field
The invention belongs to function nano field of material technology, be specifically related to a kind of magnetic porous polymers function Nano microsphere and preparation method thereof.
Background technology
The controlled dispersed nano level polymers function microballoon of size is widely used in chemistry, chemical industry, material, biological and medical field, is the important function nano material of a class.Wherein, magnetic porous polymers function Nano microsphere integrates magnetic response, small particle diameter, loose structure, bigger serface and can the many merits such as functionalization because of it, receive extensive concern in recent years, especially in fields such as NMR (Nuclear Magnetic Resonance) imaging, biologic medical, chromatogram absorption, separating-purifying, medicine controlled releasing and synthesis catalytics, there is great potential application foreground.
At present, the method for the polymer microballoon of synthesizing magnetic and porous mainly contains emulsion polymerization, suspension polymerization and solvent-thermal method.(the He X D such as He, Ge X W, Liu H R, et al.Chemistry of materials, 2005,17 (24): 5891-5892.) utilize Polystyrene latex spheres as seed, and the mixing of another kind of monomer, obtain the hollow porous nucleocapsid structure microballoon of a kind of caged by emulsion polymerisation.But its preparation process is comparatively loaded down with trivial details, and gained porous polymer microsphere particle diameter is about 20 μm, limits its application in multiple field.(the Konishi N such as Konishi, Fujibayashi T, Tanaka T, et al.Polymer journal, 2010,42 (1): 66-71.) difference of two kinds of monomer hydrophilic and hydrophobics is utilized, " golf the is spherical " microballoon in a kind of " many holes, surface " has been prepared with the method for emulsion polymerisation and solvent evaporation, particle diameter is 1 μm, but surface is without specific functional groups, nonmagnetic response.(the Liu J such as Liu, Qiao S Z, Liu H, et al.Angewandte Chemie International Edition, 2011,50 (26): 5947-5951.) with resorcinol and formaldehyde for raw material, utilize the classical way Stober method preparing silicon dioxide, prepare the single dispersing phenolic resin microspheres that a kind of particle diameter is about 500nm under hydrothermal conditions, but also nonmagnetic response, surface is also without loose structure.
Summary of the invention
The object of the present invention is to provide a kind of magnetic porous polymers function Nano microsphere.
Another object of the present invention is to the preparation method that above-mentioned magnetic porous polymers function Nano microsphere is provided.
Technical scheme of the present invention is as follows:
A kind of magnetic porous polymers function Nano microsphere, it is apparent has rough porous structure, polystyrene is as pellet base, phenolic resins is as support frame, hydroxyl on phenolic resins and ferroferric oxide magnetic nano-particles form coordination, be loaded on ball by magnetic ferroferric oxide nano-particles bag, its raw material components comprises the material of following ratio:
The preparation method of above-mentioned base catalysis phenolic resins prepolymer is as follows: prepare certain density sodium hydroxide solution, get this sodium hydroxide solution a certain amount of and phenol adds in reaction vessel respectively, mechanical agitation 20 ~ 30min at 45 ~ 50 DEG C, it is made fully to dissolve, then dropwise add a certain amount of formalin in proportion, be warming up to 58 ~ 65 DEG C of stable rear reaction 1.5 ~ 2h, add the sodium hydroxide solution of remainder again, after insulation reaction 10 ~ 15min, add appropriate formalin again, be warming up to 68 ~ 73 DEG C, insulation reaction 30 ~ 40min, be warming up to 90 ~ 95 DEG C again, insulation reaction 1 ~ 1.3h, free phenol finally at 50 ~ 55 DEG C in rotary evaporation removing system and other accessory substances, obtain described base catalysis phenolic resins prepolymer.
In a preferred embodiment of the invention, its raw material components comprises the material of following ratio:
Preferred further, the preparation method of described base catalysis phenolic resins prepolymer is as follows: prepare certain density sodium hydroxide solution, get this sodium hydroxide solution a certain amount of and phenol adds in reaction vessel respectively, mechanical agitation 20min at 45 DEG C, it is made fully to dissolve, then dropwise add a certain amount of formalin in proportion, be warming up to 60 DEG C stable after react 1.5h, add the sodium hydroxide solution of remainder again, after insulation reaction 10min, add appropriate formalin again, be warming up to 70 DEG C, insulation reaction 30min, be warming up to 95 DEG C again, insulation reaction 1h, free phenol finally at 50 DEG C in rotary evaporation removing system and other accessory substances, obtain described base catalysis phenolic resins prepolymer.
A preparation method for above-mentioned magnetic porous polymers function Nano microsphere, comprises the steps:
(1) base catalysis phenolic resins prepolymer is prepared;
(2) each raw material components is taken in proportion;
(3) by after six chloride hydrate high ferros, described base catalysis phenolic resins prepolymer, ethylene glycol mixing, ultrasonic disperse 15 ~ 20min, obtains dispersion liquid;
(4) in the obtained dispersion liquid of step (3), add styrene while stirring, add rear continuation stirring 0.5 ~ 1h;
(5) be dissolved in deionized water by PVP and three Heshui sodium acetates, ultrasonic process adds in the material of step (4) gained after making it fully dissolve, and stirs 1 ~ 1.5h;
(6) step (5) gained material is placed in high pressure water heating kettle, naturally cool after isothermal reaction 8 ~ 12h at 180 ~ 200 DEG C, add ethanol and carry out centrifuge washing, add deionized water again and carry out centrifuge washing, finally precipitate and be again scattered in ethanol, obtain described magnetic porous polymers function Nano microsphere.
In a preferred embodiment of the invention, described step (3) is: after six chloride hydrate high ferros, described base catalysis phenolic resins prepolymer, ethylene glycol mixing, ultrasonic disperse 15min, obtains dispersion liquid.
In a preferred embodiment of the invention, described step (4) is: in the obtained dispersion liquid of step (3), add styrene while stirring, add rear continuations stirring 0.5h.
In a preferred embodiment of the invention, described step (5) is: be dissolved in deionized water by PVP and three Heshui sodium acetates, ultrasonic process adds in the material of step (4) gained after making it fully dissolve, stir 1h.
In a preferred embodiment of the invention, described step (6) is: step (5) gained material is placed in high pressure water heating kettle, naturally cool after isothermal reaction 12h at 180 DEG C, add ethanol and carry out centrifuge washing, add deionized water again and carry out centrifuge washing, finally precipitate and be again scattered in ethanol, obtain described magnetic porous polymers function Nano microsphere.
The invention has the beneficial effects as follows:
1, an a kind of simple and feasible step solvent-thermal method of proposition of the present invention, prepare a kind ofly having magnetic response, surface porosity and with functional groups concurrently, particle diameter is at homogeneous, the stable magnetic porous polymers function Nano microsphere of about 400nm.With six chloride hydrate high ferros for source of iron, jointly react with ethylene glycol, sodium acetate trihydrate, at high temperature obtain ferriferrous oxide nano-particle, in system, pass through high-temperature cross-linking phenolic resins prepolymer and thermal-initiated polymerization styrene simultaneously, form pellet base.Wherein, the hydroxyl of phenolic resins can form coordination with iron ion, makes magnetic nano-particle embedding or load on ball, gives microballoon magnetic, the rough porous pattern on surface, have unique absorption advantage, more expanded its range of application.
2, magnetic porous polymers function Nano microsphere of the present invention can also pass through MOLECULE DESIGN, specific function finishing and other functional responses, carry out further functionalization, give it more functional, expand its purposes, such as heavy metal ion chelating, separation, molecule and functional group's specific recognition etc.In addition, described microballoon also makes porous carbon ball further by high-temperature calcination, for the field such as adsorbing.To sum up, microballoon of the present invention has potential using value widely in fields such as Magnetic Isolation, imaging, absorption, catalysis.
Accompanying drawing explanation
Large area scanning electron microscope (SEM) image of the magnetic porous polymers function Nano microsphere obtained by Fig. 1 embodiment of the present invention 1.
Partial enlargement scanning electron microscopy (SEM) image of the magnetic porous polymers function Nano microsphere of Fig. 2 obtained by the embodiment of the present invention 1.
Partial enlargement transmission electron microscope (TEM) image of the magnetic porous polymers function Nano microsphere of Fig. 3 obtained by the embodiment of the present invention 1.
Fig. 4 is the embodiment of the present invention 1, X-ray diffraction (XRD) phenogram of magnetic porous polymers function Nano microsphere, phenolic resins-Properties of Polystyrene Nano Particles and magnetic ferroferric oxide nano-particles obtained by embodiment 15, embodiment 16.
Embodiment
By reference to the accompanying drawings below by embodiment technical scheme of the present invention is further described and is described.
Embodiment 1
1) preparation of base catalysis phenolic resins prepolymer:
Precise 1.25g NaOH, ultrasonic disperse, in 5g deionized water, forms 6.25g sodium hydrate aqueous solution.Getting wherein 5g solution and 25g phenol together adds in 250mL there-necked flask, and mechanical agitation 20min at 45 DEG C, dropwise adds 33g formalin after making it fully dissolve, and rate of addition controls as about 1 drop/sec.After dropping terminates, system temperature is risen to 60 DEG C, after temperature stabilization, reaction 1.5h, adds in system by aforementioned for remaining 1.25g sodium hydroxide solution, continues reaction 10min, again with identical speed instillation 9g formalin, after dropping terminates, temperature of reaction system is risen to 70 DEG C, insulation 30min, then again temperature is risen to 95 DEG C, after 1h, reaction is taken off, rotary evaporation 5min at 50 DEG C, the free phenol in removing system and other accessory substances.Obtain described base catalysis phenolic resins prepolymer.
2) preparation of magnetic porous polymers function Nano microsphere:
Take 0.05g six chloride hydrate high ferro and 0.1g 1) described in phenolic resins prepolymer, add in serum bottle, add 7mL ethylene glycol, after ultrasonic disperse 15min, add magnetic stir bar, open magnetic agitation.In stirring, add 0.5mL styrene, continue to stir 0.5h.Take 0.03g PVP and 0.20g sodium acetate trihydrate is dissolved in 5mL deionized water, ultrasonicly make it fully dissolve, add in system, continue to stir 1h.
Above-mentioned mixed system is poured in tetrafluoro inner bag steel high-pressure water heating kettle, tighten kettle cover, put into constant temperature oven, under 180 DEG C of conditions, react 12h, take out water heating kettle, still sucking-off product is opened after naturally cooling to room temperature, add the washing of a certain amount of ethanol, carry out high speed centrifugation with the rotating speed of 10000 revs/min in centrifuges and be separated 15min, removing supernatant, three times repeatedly, then with deionized water be washing agent centrifuge washing once.Finally product is scattered in ethanol, obtains described magnetic porous polymers function Nano microsphere.
As shown in Figure 1, obtained magnetic porous polymers function Nano microsphere is uniformly dispersed, and particle diameter is comparatively homogeneous, is about 400nm ~ 500nm.According to its partial enlarged drawing as shown in Figure 2, gained magnetic porous polymers function Nano microsphere particle diameter average grain diameter is about 400nm, and surface is in coarse, loose structure, and pattern is unique and stable.Its transmission electron microscope (TEM) observes figure as shown in Figure 3, described magnetic porous polymers function Nano microsphere uniform particle diameter, spacial framework is formed after phenolic resins crosslinking curing, skeletal support effect is played in microballoon, the even balling-up of polystyrene, forms two-phase mixtures structure with phenolic resins.Hydroxyl on phenolic resins and ferriferrous oxide nano-particle form coordination, catch ferriferrous oxide nano-particle, and make it be partially embedded in ball, fractional load, on ball, is uniformly distributed.
Embodiment 2
1) with embodiment 1.
2) consumption of six chloride hydrate high ferros in embodiment 1 is adjusted to 0.10g respectively, all the other consumptions and step are with embodiment 1.
Embodiment 3
1) with embodiment 1.
2) consumption of six chloride hydrate high ferros in embodiment 1 is adjusted to 0.20g respectively, all the other consumptions and step are with embodiment 1.
Embodiment 4
1) with embodiment 1.
2) consumption of ethylene glycol in embodiment 1 is adjusted to 5mL respectively, all the other consumptions and step are with embodiment 1.
Embodiment 5
1) with embodiment 1.
2) consumption of ethylene glycol in embodiment 1 is adjusted to 9mL respectively, all the other consumptions and step are with embodiment 1.
Embodiment 6
1) with embodiment 1.
2) consumption of ethylene glycol in embodiment 1 is adjusted to 11mL respectively, all the other consumptions and step are with embodiment 1.
Embodiment 7
1) with embodiment 1.
2) consumption of ethylene glycol in embodiment 1 is adjusted to 13mL respectively, all the other consumptions and step are with embodiment 1.
Embodiment 8
1) with embodiment 1.
2) consumption cinnamic in embodiment 1 is adjusted to 1.0mL respectively, all the other consumptions and step are with embodiment 1.
Embodiment 9
1) with embodiment 1.
2) consumption cinnamic in embodiment 1 is adjusted to 1.5mL respectively, all the other consumptions and step are with embodiment 1.
Embodiment 10
1) with embodiment 1.
2) consumption cinnamic in embodiment 1 is adjusted to 2.0mL respectively, all the other consumptions and step are with embodiment 1.
Embodiment 11
1) with embodiment 1.
2) consumption of phenolic resins prepolymer in embodiment 1 is adjusted to 0.15g respectively, all the other consumptions and step are with embodiment 1.
Embodiment 12
1) with embodiment 1.
2) consumption of phenolic resins prepolymer in embodiment 1 is adjusted to 0.20g respectively, all the other consumptions and step are with embodiment 1.
Embodiment 13
1) with embodiment 1.
2) consumption of phenolic resins prepolymer in embodiment 1 is adjusted to 0.25g respectively, all the other consumptions and step are with embodiment 1.
Embodiment 14
1) with embodiment 1.
2) consumption of phenolic resins prepolymer in embodiment 1 is adjusted to 0.30g respectively, all the other consumptions and step are with embodiment 1.
Embodiment 15
1) with embodiment 1.
2) only add phenolic resins, styrene, ethylene glycol, PVP and deionized water, consumption and charging sequence, operating procedure with embodiment 1, obtained phenolic resins-Properties of Polystyrene Nano Particles.
Embodiment 16
0.05g six chloride hydrate high ferro, 7mL ethylene glycol, 0.03g PVP, 0.20g sodium acetate trihydrate are carried out solvent thermal reaction by order and step in embodiment 1, obtained magnetic ferroferric oxide nano-particles.
(i) in Fig. 4, (ii) and (iii) are respectively X-ray diffraction (XRD) phenogram of the magnetic porous polymers function Nano microsphere obtained by the phenolic resins-poly styrene polymer microballoon obtained by embodiment 15, the ferriferrous oxide nano-particle obtained by embodiment 16 and embodiment 1.I Bao Feng that shown in (), figure line only has one comparatively to delay between 15 ° ~ 20 °, shows only have the polymer nano-microspheres of phenolic resins and polystyrene to be non crystallized unformed shape; (ii) be the peak type of typical ferriferrous oxide nano-particle, according to the storehouse comparison of standard x RD card data, marked the corresponding crystal face in each peak of tri-iron tetroxide, display successfully passes solvent structure magnetic ferroferric oxide nano-particles.(iii) be the figure line of aforementioned magnetic porous polymers function Nano microsphere, the slow peak too increasing phenolic resins-polystyrene microsphere outside the corresponding peak of each crystal formation remaining tri-iron tetroxide can be found out, in conjunction with the known porous polymer functional nano micro-ball successfully synthesizing embedding/load magnetic nano-particle of scanning electron microscopy (SEM) figure comprehensive characterization.
The above, be only preferred embodiment of the present invention, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.
Claims (8)
1. a magnetic porous polymers function Nano microsphere, is characterized in that: its raw material components comprises the material of following ratio:
The preparation method of above-mentioned base catalysis phenolic resins prepolymer is as follows: prepare certain density sodium hydroxide solution, get this sodium hydroxide solution a certain amount of and phenol adds in reaction vessel respectively, mechanical agitation 20 ~ 30min at 45 ~ 50 DEG C, it is made fully to dissolve, then dropwise add a certain amount of formalin in proportion, be warming up to 58 ~ 65 DEG C of stable rear reaction 1.5 ~ 2h, add the sodium hydroxide solution of remainder again, after insulation reaction 10 ~ 15min, add appropriate formalin again, be warming up to 68 ~ 73 DEG C, insulation reaction 30 ~ 40min, be warming up to 90 ~ 95 DEG C again, insulation reaction 1 ~ 1.3h, free phenol finally at 50 ~ 55 DEG C in rotary evaporation removing system and other accessory substances, obtain described base catalysis phenolic resins prepolymer.
2. a kind of magnetic porous polymers function Nano microsphere as claimed in claim 1, is characterized in that: its raw material components comprises the material of following ratio:
3. a kind of magnetic porous polymers function Nano microsphere as claimed in claim 1 or 2, it is characterized in that: the preparation method of described base catalysis phenolic resins prepolymer is as follows: prepare certain density sodium hydroxide solution, get this sodium hydroxide solution a certain amount of and phenol adds in reaction vessel respectively, mechanical agitation 20min at 45 DEG C, it is made fully to dissolve, then dropwise add a certain amount of formalin in proportion, be warming up to 60 DEG C stable after react 1.5h, add the sodium hydroxide solution of remainder again, after insulation reaction 10min, add appropriate formalin again, be warming up to 70 DEG C, insulation reaction 30min, be warming up to 95 DEG C again, insulation reaction 1h, free phenol finally at 50 DEG C in rotary evaporation removing system and other accessory substances, obtain described base catalysis phenolic resins prepolymer.
4. a preparation method for the magnetic porous polymers function Nano microsphere in claims 1 to 3 described in arbitrary claim, is characterized in that: comprise the steps:
(1) base catalysis phenolic resins prepolymer is prepared;
(2) each raw material components is taken in proportion;
(3) by after six chloride hydrate high ferros, described base catalysis phenolic resins prepolymer, ethylene glycol mixing, ultrasonic disperse 15 ~ 20min, obtains dispersion liquid;
(4) in the obtained dispersion liquid of step (3), add styrene while stirring, add rear continuation stirring 0.5 ~ 1h;
(5) be dissolved in deionized water by PVP and three Heshui sodium acetates, ultrasonic process adds in the material of step (4) gained after making it fully dissolve, and stirs 1 ~ 1.5h;
(6) step (5) gained material is placed in high pressure water heating kettle, naturally cool after isothermal reaction 8 ~ 12h at 180 ~ 200 DEG C, add ethanol and carry out centrifuge washing, add deionized water again and carry out centrifuge washing, finally precipitate and be again scattered in ethanol, obtain described magnetic porous polymers function Nano microsphere.
5. preparation method as claimed in claim 4, is characterized in that: described step (3) is: after six chloride hydrate high ferros, described base catalysis phenolic resins prepolymer, ethylene glycol mixing, ultrasonic disperse 15min, obtains dispersion liquid.
6. preparation method as claimed in claim 4, is characterized in that: described step (4) is: in the obtained dispersion liquid of step (3), add styrene while stirring, add rear continuations stirring 0.5h.
7. preparation method as claimed in claim 4, it is characterized in that: described step (5) is: PVP and three Heshui sodium acetates are dissolved in deionized water, ultrasonic process adds in the material of step (4) gained after making it fully dissolve, stir 1h.
8. preparation method as claimed in claim 4, it is characterized in that: described step (6) is: step (5) gained material is placed in high pressure water heating kettle, naturally cool after isothermal reaction 12h at 180 DEG C, add ethanol and carry out centrifuge washing, add deionized water again and carry out centrifuge washing, finally precipitate and be again scattered in ethanol, obtain described magnetic porous polymers function Nano microsphere.
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