CN104403041A - PH-responsive type magnetic composite microsphere with Janus structure, and preparation method thereof - Google Patents
PH-responsive type magnetic composite microsphere with Janus structure, and preparation method thereof Download PDFInfo
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- CN104403041A CN104403041A CN201410736747.3A CN201410736747A CN104403041A CN 104403041 A CN104403041 A CN 104403041A CN 201410736747 A CN201410736747 A CN 201410736747A CN 104403041 A CN104403041 A CN 104403041A
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Abstract
The invention relates to a pH-responsive type magnetic composite microsphere with a Janus structure, and a preparation method thereof, and belongs to the fields of composite materials and nanotechnologies. The pH-responsive type magnetic composite microsphere is of a core-shell structure, an inner core is made of polystyrene wrapped with Fe3O4, and a shell layer is made of poly(tert-butylmethacrylate). The preparation method comprises the following steps: preparing magnetic Fe3O4 nano-particles, then adding oleic acid, washing to neutral to obtain oleic modified Fe3O4 nano-particles, then dissolving in normal octane, adding a styrene monomer and a tert-butyl methacrylate monomer after ultrasound to obtain a magnetofluid, and adding in a bottle equipped with a reflux condensing tube and a thermometer, adding deionized water, lauryl sodium sulfate and NaHCO3 in sequence, heating in a water bath, then introducing N2, adding ammonium persulfate, preparing a magnetic composite microsphere solution with the Janus structure after emulsion polymerization, then centrifuging, separating a lower sediment, washing to neutral, putting in the container after drying, and adding deionized water and trifluoroacetic acid with different pH values to obtain a product.
Description
Technical field
The invention belongs to matrix material and field of nanometer technology, relate to a kind of pH response type magnetic composite microsphere with Janus structure and preparation method thereof, is Specifically a kind ofly have magnetic nanometer composite material of unsymmetric structure and Modulatory character and preparation method thereof.
Background technology
Janus nano particle has for describing a class the asymmetric microballoon of anisotropy that center is asymmetric, two hemisphere surface have different chemical composition, because it has special form or chemical constitution, so this type of microballoon has unique physicochemical property, and then in New-type emulsifier, molecular recognition and biological intelligence material etc., there are huge potentiality, as can be seen here, to the preparation of Janus microballoon and morphology Control mechanism and self-assembly research thereof, in fundamental research or all significant in practical application.
But, the preparation of Janus microballoon is also in the initial development stage, and difficulty is larger for isotropic polymer microballoon, because for a microballoon, because of the requirement of thermodynamic stability, its surface free energy is always tending towards minimum, and then causes final microballoon to trend towards having the regular spherical of homogeneous surface and minimum energy, so adopt traditional synthesis technique, be difficult to obtain Janus microballoon.Such as, (the method utilizing liquid/liquid interface to react a step to prepare amphiphilic Janus golden nanometer particle such as Luo Kun, Chinese patent CN 103611945 A) utilize triphenyl phosphorus chlorine gold to react in toluene/water interface with Tetrakis hydroxymethyl phosphonium chloride, form amphiphilic Janus golden nanometer particle self-assembled film.This method stability is relatively better, and be convenient to the application of amphiphilic Janus golden nanometer particle in each association area, but the method actually operating technical process control difficulty is higher, yield rate is lower.So far, also mostly rest in the exploration of preparation method and the sign of correlated performance in the world to the research of two-sided refreshing particle, particularly the parents of Janus particle modify and functionalization.So, a kind of simple Janus nanoparticle preparation method just seems and is even more important.
In addition, along with people's deepening continuously to various Janus particle studies such as inorganic, inorganic/organic mixing of different-shape and polymer-types, the Janus matrix material that functional motif is contained on numerous surface is developed, wherein, the super-paramagnetism nano complex microsphere with Janus structure demonstrates good application prospect at numerous areas such as biomedical environment.Such as, in inorganic type Janus particles fields, Sun etc. utilize Au@Fe
3o
4the anisotropic surface characteristic of composite structure and multi-functional unit, devise the novel magnetic multifunctional carrier having targeted drug delivery and molecular imaging function concurrently, and platiniferous compound medicine is connected to gold grain in composite structure and Fe with the form of covalent linkage
3o
4particle surface, by the design to attachment chemistry, can also realize discharging at the low ph containing platinic compound, thus the selective killing of cancer cells can be realized to a certain extent, and because having biocompatibility, be widely used the optics in biological medicine and mr detection, but Janus particle two component prepared by this method is inorganic particulate, if further modify and functionalization, its complex steps, has certain limitation.In inorganic/organic mixed Janus particles fields, Chang Zhenqi etc. (magnetic opposite sex Janus microballoon that a kind of particle diameter and pattern are all controlled and preparation method thereof and microfluidic control device used, Chinese patent CN 103846067 A) utilize microfluidic control device to prepare the magnetic opposite sex Janus microballoon of particle diameter and morphology controllable.This Janus particle is that controllability is very strong on microspherulite diameter and pattern, but does not possess environmental response performance.
In sum, Janus magnetic nano-particle is worth because unique appearance structure makes it have important research and apply, therefore, in order to meet the different demand in each field, to seek a kind of preparation technology simple and can modify Janus magnetic nano-particle and just seem particularly important.
Summary of the invention
The object of the present invention is to provide a kind of pH response type magnetic composite microsphere with Janus structure and preparation method thereof.
The chemical general formula of the pH response type magnetic composite microsphere of the described Janus of having structure is Fe
3o
4@P (St-co-tBMA), in nucleocapsid structure, kernel is polystyrene and wraps up Fe
3o
4, shell is polymethyl tert-butyl acrylate, and the particle diameter with the pH response type magnetic composite microsphere of Janus structure is 300 ~ 500nm.
The pH response type magnetic composite microsphere of the described Janus of having structure is by oleic acid MODIFIED Fe
3o
4nano particle, styrene monomer, Tert-butyl Methacrylate monomer obtain through the initiated polymerization that once feeds intake.Described oleic acid MODIFIED Fe
3o
4nano particle is segregated in has Janus structure magnetic complex microsphere stratum nucleare, and content is controlled.The pH susceptibility of the pH response type magnetic composite microsphere of the described Janus of having structure utilizes trifluoroacetic acid hydrolysis Fe
3o
4@P (St-co-tBMA) forms polymethyl acrylic acid gained afterwards.
The described preparation method with the pH response type magnetic composite microsphere of Janus structure, comprises the following steps:
1) chemical coprecipitation is utilized to prepare magnetic Fe
3o
4nano particle, then add oleic acid, washing, to neutral, obtains oleic acid MODIFIED Fe
3o
4nano particle;
2) by oleic acid MODIFIED Fe
3o
4nano particle is dissolved in octane, adds styrene monomer and Tert-butyl Methacrylate monomer, obtain magnetic fluid after ultrasonic;
3) magnetic fluid is added in the four-hole bottle that reflux condensing tube and thermometer are housed, add deionized water, anionic emulsifier sodium lauryl sulphate (SDS), buffer reagent NaHCO successively
3, stir and heating in water bath, then pass into N
2gas, then adds initiator ammonium persulfate (APS), and after emulsion polymerization, obtained have Janus structure magnetic complex microsphere solution, more centrifugal, isolates lower sediment, and washing is extremely neutral, dry for standby;
4) take and there is Janus structure magnetic complex microsphere in container, add the trifluoroacetic acid (TFA) of deionized water and different pH value, stir, namely obtain the pH response type magnetic composite microsphere with Janus structure.
In step 1) in, described Fe
3o
4be 2 with the mass ratio of oleic acid: (0.5 ~ 1.5); Described washing can respectively with the ethanol of 5 ~ 15mL and deionized water wash 2 ~ 4 times to neutral; Gained oleic acid MODIFIED Fe
3o
4the particle diameter of nano particle can be 2 ~ 10nm.
In step 2) in, described oleic acid MODIFIED Fe
3o
4the proportioning of nano particle, octane, styrene monomer, Tert-butyl Methacrylate monomer can be (0.1 ~ 1.0) g: (0.5 ~ 1.5) mL: (0.5 ~ 4.0) mL: (0.2 ~ 1.0) mL, wherein, oleic acid MODIFIED Fe
3o
4nano particle is calculated in mass, and octane, styrene monomer, Tert-butyl Methacrylate monomer are calculated by volume; The described ultrasonic time can be 5 ~ 15min.
In step 3) in, the add-on of described deionized water can be 50 ~ 100mL, and the add-on of anionic emulsifier sodium lauryl sulphate (SDS) can be 0.02 ~ 0.1g, buffer reagent NaHCO
3add-on can be 0.5 ~ 1mL, buffer reagent NaHCO
3volumetric molar concentration can be 0.1mol/L; The temperature of described heating in water bath can be 70 ~ 85 DEG C; Describedly pass into N
2the time of gas can be 30 ~ 50min; The time of described emulsion polymerization can be 20 ~ 30h; Described centrifugal condition can under 4000 ~ 8000rpm rotating speed centrifugal 30 ~ 60min; Described washing can respectively wash 2 ~ 4 times to neutral with 10mL ethanol and deionized water respectively.
In step 4) in, described in there is Janus structure magnetic complex microsphere add-on can be 0.1 ~ 1.0g, the add-on of described deionized water can be 10 ~ 30mL, and the add-on of the trifluoroacetic acid (TFA) of different pH value can be 0.2 ~ 1mL; The condition of described stirring can stir 18 ~ 30h at 25 DEG C, and complete hydrolysis is become polymethyl acrylic acid by the shell polymethyl tert-butyl acrylate with Janus structure magnetic complex microsphere added; The prepared particle diameter with the pH response type magnetic composite microsphere of Janus structure can be 300 ~ 500nm.
Described have Janus structure magnetic complex microsphere (Fe
3o
4@P (St-co-tBMA)) be by oleic acid MODIFIED Fe
3o
4nano particle, styrene monomer, Tert-butyl Methacrylate monomer obtain through the initiated polymerization that once feeds intake.Fe
3o
4@P (St-co-tBMA) has nucleocapsid structure concurrently, and kernel is polystyrene and wraps up Fe
3o
4, shell is polymethyl tert-butyl acrylate.
Described oleic acid MODIFIED Fe
3o
4nano particle is segregated in has Janus structure magnetic complex microsphere stratum nucleare, and content is controlled.
The pH susceptibility of the pH response type magnetic composite microsphere of the described Janus of having structure utilizes trifluoroacetic acid hydrolysis Fe
3o
4@P (St-co-tBMA) forms polymethyl acrylic acid gained afterwards.
Described Janus structure utilizes octane in magnetic fluid to volatilize in emulsion polymerization process to cause Fe
3o
4segregation so that formation.
The present invention is by the Fe of oleic acid modification
3o
4being dissolved in octane, adding vinylbenzene and Tert-butyl Methacrylate, when reacting, utilizing the volatilization of octane to cause Fe
3o
4the segregation of magnetic nanoparticle, and the particulate prepared can form the organic/inorganic magnetic composite microsphere with pH susceptibility after trifluoroacetic acid hydrolysis, preparation method is simple.
The pH response type magnetic composite microsphere of Janus structure that prepared by the present invention have has very significant Janus structure and pH susceptibility, swelling and deswelling is there is in the magnetic composite microsphere after trifluoroacetic acid hydrolysis under different pH environment, and pH susceptibility can be controlled by the consumption adjusting trifluoroacetic acid, method is simple, and feasibility is high.Meanwhile, the Janus structure of its uniqueness, makes it have potential using value in stable emulsion, electric field break-in, field of energy conversion.
Accompanying drawing explanation
Fig. 1 is oleic acid MODIFIED Fe in embodiment 1
3o
4the XRD figure of nano particle.
Fig. 2 is the TEM figure of the pH response type magnetic composite microsphere in embodiment 1 ~ 4 with Janus structure.
Fig. 3 is the response diagram that the pH response type magnetic composite microsphere particle diameter in embodiment 5 ~ 8 with Janus structure changes with pH change.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
(1) oleic acid MODIFIED Fe
3o
4the preparation of nano particle
By 8.19g FeCl
36H
2o and 4.35g FeSO
47H
2o is dissolved in 50mL deionized water, adds the logical middle nitrogen deoxygenation 30min of the there-necked flask that reflux condensing tube is housed; 5.31gNaOH is dissolved in 10mL deionized water, then slowly add in there-necked flask, after 70 DEG C of reaction 1h, then add the 10mL oleic acid and alcohol mixed solution (oleic acid: ethanol=1:1) that prepare, be warming up to 80 DEG C of slaking 1h, obtain the magnetic Fe that size 2 ~ 10nm has superparamagnetism
3o
4nano particle.By oleic acid MODIFIED Fe
3o
4nano particle respectively washs 3 times to neutral with 10mL ethanol and deionized water respectively, dry for standby.
(2) preparation of magnetic fluid
Get 0.5g oleic acid MODIFIED Fe
3o
4nano particle is dissolved in 0.5mL octane, ultrasonic 10min, then adds 2mL styrene monomer and 0.5mL Tert-butyl Methacrylate monomer, and ultrasonic 10min obtains magnetic fluid.
(3) there is the preparation of Janus structure magnetic complex microsphere
Get 50mL deionized water in the four-hole bottle that reflux condensing tube and thermometer are housed, add 0.05g anionic emulsifier sodium lauryl sulphate (SDS), after stirring 10min, add 1mL buffer reagent NaHCO
3(0.1mol/L) with above-mentioned magnetic fluid, lower heating in water bath to 75 DEG C is stirred, logical N
2gas 30min, add 0.02g initiator ammonium persulfate (APS) again, emulsion polymerization 18h obtains coffee-like having Janus structure magnetic complex microsphere solution, and centrifugation goes out lower sediment, 2 times are respectively washed to neutral, dry for standby respectively with 10mL ethanol and deionized water.
(4) there is the preparation of the pH response type magnetic composite microsphere of Janus structure
Get 0.1g and there is Janus structure magnetic complex microsphere in 50mL container, add 30mL deionized water and 0.5mL trifluoroacetic acid, flask is put in a water bath, back flow reaction 24h under room temperature, stir and just can obtain the pH response type magnetic composite microsphere with Janus structure.Get the magnetic composite microsphere (7 parts) after 1mL hydrolysis, its pH value is regulated with HCl (0.1mol/L) and NaOH (0.1mol/L) solution, be respectively 2,3,4,5,6,7,8, recycling DLS (dynamic light scattering) records its particle diameter.
Embodiment 2 ~ 4
With embodiment 1 technique, change Fe in (2)
3o
4feed intake and be respectively 0.1g, 0.3g, 0.7g.
Embodiment 5 ~ 8
With embodiment 1 technique, the content changing trifluoroacetic acid in (4) is respectively 0.2mL, 0.3mL, 0.4mL, 0.6mL.
The oleic acid MODIFIED Fe of gained
3o
4nano particle is characterized (shown in Fig. 1) by XRD, the structure that gained has the pH response type magnetic composite microsphere of Janus structure is characterized (shown in Fig. 2) by transmission electron microscope observation, can observe obtained microballoon and have obvious Janus structure and nucleocapsid structure, particle diameter is about 300 ~ 500nm.Wherein, stratum nucleare is polystyrene, and shell is polymethyl acrylic acid, Fe
3o
4nano particle segregation is inner in microballoon.Can be observed from Fig. 3, when changing pH value, microspherulite diameter changes, and shows pH responsiveness.
The present invention utilize emulsion polymerization once feed intake preparation a kind of magnetic composite microsphere (Fe with Janus structure
3o
4-vinylbenzene-Tert-butyl Methacrylate), by control Fe
3o
4the control to Janus particle structure and size is realized with octane concentration etc., particulate forms the organic/inorganic magnetic composite microsphere with pH susceptibility after trifluoroacetic acid hydrolysis, and pH susceptibility can be controlled by the ratio between adjustment trifluoroacetic acid and Tert-butyl Methacrylate, preparation method is simple, is a kind of a kind of novel intelligent material having application potential in drug conveying, sensing and human-body biological medicine and other fields.
The present invention is first by the Fe of oleic acid modification
3o
4be dissolved in octane, be made into a certain amount of magnetic fluid, then be tensio-active agent, vinylbenzene and Tert-butyl Methacrylate with sodium lauryl sulphate be reaction monomers, by controlling Fe in magnetic fluid
3o
4/ octane ratio, reaction monomers concentration etc. and utilize trifluoroacetic acid hydrolysis Tert-butyl Methacrylate to prepare a kind of pH response type magnetic polymer microsphere with Janus structure.Janus particle preparation method provided by the present invention is simple, pH responsiveness can be controlled by the ratio between adjustment trifluoroacetic acid and Tert-butyl Methacrylate, not only there is the feasibility of scale operation, and by carrying out satisfied different demand to magnetic microsphere surface modification and functional modification, potential application prospect can be had in fields such as stable emulsion, electric field break-in, energy transformation, drug conveying, sensings.
Claims (10)
1. there is the pH response type magnetic composite microsphere of Janus structure, it is characterized in that its chemical general formula is Fe
3o
4@P (St-co-tBMA), in nucleocapsid structure, kernel is polystyrene and wraps up Fe
3o
4, shell is polymethyl tert-butyl acrylate.
2. there is the pH response type magnetic composite microsphere of Janus structure as claimed in claim 1, it is characterized in that its particle diameter is 300 ~ 500nm.
3. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 1, it is characterized in that comprising the following steps:
1) chemical coprecipitation is utilized to prepare magnetic Fe
3o
4nano particle, then add oleic acid, washing, to neutral, obtains oleic acid MODIFIED Fe
3o
4nano particle;
2) by oleic acid MODIFIED Fe
3o
4nano particle is dissolved in octane, adds styrene monomer and Tert-butyl Methacrylate monomer, obtain magnetic fluid after ultrasonic;
3) magnetic fluid is added in the four-hole bottle that reflux condensing tube and thermometer are housed, add deionized water, anionic emulsifier sodium lauryl sulphate, buffer reagent NaHCO successively
3, stir and heating in water bath, then pass into N
2gas, then adds initiator ammonium persulfate, and after emulsion polymerization, obtained have Janus structure magnetic complex microsphere solution, more centrifugal, isolates lower sediment, and washing is extremely neutral, dry for standby;
4) take and there is Janus structure magnetic complex microsphere in container, add the trifluoroacetic acid of deionized water and different pH value, stir, namely obtain the pH response type magnetic composite microsphere with Janus structure.
4. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 3, it is characterized in that in step 1) in, described Fe
3o
4be 2 with the mass ratio of oleic acid: (0.5 ~ 1.5).
5. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 3, it is characterized in that in step 1) in, described washing uses the ethanol of 5 ~ 15mL and deionized water wash 2 ~ 4 times to neutral respectively; Gained oleic acid MODIFIED Fe
3o
4the particle diameter of nano particle can be 2 ~ 10nm.
6. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 3, it is characterized in that in step 2) in, described oleic acid MODIFIED Fe
3o
4the proportioning of nano particle, octane, styrene monomer, Tert-butyl Methacrylate monomer is (0.1 ~ 1.0) g: (0.5 ~ 1.5) mL: (0.5 ~ 4.0) mL: (0.2 ~ 1.0) mL, wherein, oleic acid MODIFIED Fe
3o
4nano particle is calculated in mass, and octane, styrene monomer, Tert-butyl Methacrylate monomer are calculated by volume.
7. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 3, it is characterized in that in step 2) in, the described ultrasonic time is 5 ~ 15min.
8. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 3, it is characterized in that in step 3) in, the add-on of described deionized water is 50 ~ 100mL, the add-on of anionic emulsifier sodium lauryl sulphate is 0.02 ~ 0.1g, buffer reagent NaHCO
3add-on be 0.5 ~ 1mL, buffer reagent NaHCO
3volumetric molar concentration be 0.1mol/L.
9. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 3, it is characterized in that in step 3) in, the temperature of described heating in water bath is 70 ~ 85 DEG C; Describedly pass into N
2the time of gas can be 30 ~ 50min; The time of described emulsion polymerization can be 20 ~ 30h; Described centrifugal condition can under 4000 ~ 8000rpm rotating speed centrifugal 30 ~ 60min; Described washing can respectively wash 2 ~ 4 times to neutral with 10mL ethanol and deionized water respectively.
10. there is the preparation method of the pH response type magnetic composite microsphere of Janus structure as claimed in claim 3, it is characterized in that in step 4) in, the add-on of the described Janus of having structure magnetic complex microsphere is 0.1 ~ 1.0g, the add-on of described deionized water is 10 ~ 30mL, and the add-on of the trifluoroacetic acid of different pH value is 0.2 ~ 1mL; The condition of described stirring can stir 18 ~ 30h at 25 DEG C, and complete hydrolysis is become polymethyl acrylic acid by the shell polymethyl tert-butyl acrylate with Janus structure magnetic complex microsphere added.
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| CN110396148A (en) * | 2019-08-05 | 2019-11-01 | 东南大学 | A kind of magnetic polystyrene microsphere and preparation method thereof |
| CN110396148B (en) * | 2019-08-05 | 2022-06-28 | 东南大学 | Magnetic polystyrene microsphere and preparation method thereof |
| CN114014370A (en) * | 2021-11-05 | 2022-02-08 | 珠海复旦创新研究院 | Multiple-responsiveness Janus ferroferric oxide nanoparticles and preparation method thereof |
| CN115286741A (en) * | 2022-09-01 | 2022-11-04 | 江苏大学 | Method for preparing magnetic mesoporous sulfonated crescent adsorbent by emulsion interfacial polymerization and application of magnetic mesoporous sulfonated crescent adsorbent to lead ion adsorption |
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Application publication date: 20150311 |