CN106432594B - A kind of photo-thermal magnetic multiple response microgel and preparation method thereof - Google Patents
A kind of photo-thermal magnetic multiple response microgel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of photo-thermal magnetic multiple response microgels and preparation method thereof, the microgel, have core nuclear membrane nucleocapsid three-decker, magnetic ferroferric oxide（Fe3O4）For core, the poly-dopamine with light thermal property（PDA）For nuclear membrane, thermosensitive hydrogel polyisopropyl acrylamide（PNIPAm）For nuclear shell.The microgel is with a wide range of applications in biomedical sector; such as NMR imaging, photo-thermal and photoacoustic imaging, photo-thermal therapy; in addition carrying medicament can also be used to target controllable drug release on nucleocapsid or in protective layer, and can be used for GAP-associated protein GAP separation etc. in surface modification specific function group.
Description
Technical field
The present invention relates to a kind of photo-thermal magnetic multiple response microgel extremely preparation methods, belong to material and biologic applications field.
Background technology
Currently, environmental sensitivity（Such as temperature sensor, light, electric field, magnetic field, stress, p H value variations）Polymer gel
Have become the hot spot studied now as new function material.Microgel is generally referred to as scale in 10 nm to several microns models
Interior crosslinked polymer gel is enclosed, can be swollen in a solvent, and structure can be maintained not dissolve.With bulk hydrogel phase
Not only there is good biocompatibility than, microgel and since its size is smaller, more to the response speed of extraneous environmental factor
Soon.Different microgels have the response signal of environmental stimulus different application values, further according to monosomy confrontation gel
It modifies and compound, forms the important research direction that the multi-functional microgel gel of multiple response has become this field.
Preparation in relation to composite microgel in recent years, performance and in catalysis, medicine controlled releasing, sensor, immobilised enzymes, cell
The research report of culture, temperature-sensitive switch film etc. is swift and violent to be increased.By other functional components and microgel be attached to one it is compound
In system, it can make the new material prepared that multiple performance be presented, give full play to the synergistic effect between different materials.For example, Mei
By Au and Ag nanometer particle loads on Temperature-Sensitive Microgel PNIPAm, nano-particle is evenly distributed on Y et al. with independent individual
In microgel network, composite microgel is formed.The composite microgel can adjust it by changing the swellbility of gel shell
To the catalytic activity of p-nitrophenol, and nano-particle is difficult to be removed from polymer network, it is easy to recycling.For another example
There is research by different sizes, the vanadium dioxide of pattern（VO2）Nano-particles filled imparts in PNIPAm network structures
Temperature-Sensitive Microgel light sensitive characteristic, and the composite microgel is further explored in efficient Thermochromic smart window field.
Multiple response microgel is also confined to Lazer's property at present, such as Thermo-sensitive-pH sensibility, Thermo-sensitive-light sensitivity, temperature sensitive
Property-magnetic responsiveness.
By retrieval, there is presently no the multiple response that optical and thermal-magnetic susceptibility is formed by simple synthetic method is multi-functional micro-
Gel.
Invention content
The purpose of the invention is to overcome shortcoming and defect of the existing technology, and provide a kind of photo-thermal magnetic multiple response
Microgel has light, thermal and magnetic multiple response performance simultaneously.
Another object of the present invention is to provide a kind of preparation method of photo-thermal magnetic multiple response microgel, this method is simple
It is easy to operate, it is convenient for industrial applications.
First purpose to realize the present invention, the technical scheme is that with Fe3O4For magnetic core and introduce have
The poly-dopamine of photothermy is nuclear membrane, constitutes Fe3O4@PDA particles, introducing the polyisopropyl acrylamide with Thermo-sensitive is
Nucleocapsid forms Fe3O4Fe of the@PDA particles dispersed encapsulateds in polyisopropyl acrylamide network structure3O4@PDA@PNIPAm are micro-
Gel, the Fe3O4@PDA@PNIPAm microgels have optical and thermal-magnetic multiple response characteristic.
Further setting is the Fe3O4Grain size be the nm of 10 nm ~ 30.
Further setting is Fe3O4The whole grain size of@PDA particles is in the nm of 10 nm ~ 50.
Further setting is Fe3O4@PDA are 5 with the molar ratio range of reacting of NIPAm:1~10:1, gained Fe3O4@PDA@
The grain size of PNIPAm microgels is in the nm of 500 nm ~ 1500.
Further setting is Fe3O4The saturation magnetization of@PDA@PNIPAm microgels is 20.54 ~ 45.348（emu/g）、
Photothermal conversion efficiency is that 8.5% ~ 13.1%, swelling ratio is 12 ~ 25.5.
Realize second goal of the invention of the present invention, technical solution is a kind of preparation side of photo-thermal magnetic multiple response microgel
Method includes the following steps：
（1）Fe is prepared using coprecipitation3O4, by controlling Fe3+ / Fe2+Molar ratio 1:1~2:1, it obtains grain size and exists
The Fe of the nm of 10 nm ~ 303O4；
（2）It is aggregated in Fe by solution oxide3O4One strata dopamine of surface aggregate constitutes Fe3O4@PDA particles gather more
Bar amine is 2 nm ~ 15 nm, Fe as the thickness of core mould3O4The whole grain size of@PDA particles is in the nm of 10 nm ~ 50；
（3）Using N-isopropylacrylamide as monomer, N, N- methylene-bisacrylamides are crosslinking agent, by Fe3O4@PDA particles
It is mixed with, and using ammonium persulfate as initiator, may be polymerized reaction, the molar ratio of monomer and crosslinking agent is 10:1~5:1,
Fe3O4@PDA are 5 with the molar ratio range of reacting of NIPAm:1~10:1, obtain Fe3O4The grain size of@PDA@PNIPAm microgels is 500
nm~1500 nm。
Further setting is the step（1）It is mixed under ultrasound with ferrous sulfate solution for liquor ferri trichloridi
Even, the molar ratio of ferric trichloride and ferrous sulfate is 1:1~2:1, above-mentioned mixed solution is slowly dropped to 2 mol/L
NaOH solution in, 60 min of mechanical agitation at 80 DEG C, stop heating after continue stir 60 min, with pH be 6.4 phosphate
It is 6.4 that buffer solution is washed till pH by Magnetic Isolation, obtains Fe3O4Magnetic nano-particle.
Use dynamic light scattering（DLS）To obtained Fe3O4The grain size and monodispersity of magnetic nano-particle are characterized
Detection.Use transmission electron microscope（TEM）To Fe3O4The pattern of magnetic nano-particle further characterizes.Using vibrating example magnetic
Strong meter（VSM）Magnetic measurement, synthesized Fe are carried out to sample at room temperature3O4@PDA can be retained in microgel again with good
Good magnetism.
Further setting is the step（2）Take above-mentioned Fe3O4Magnetic nano-particle is configured to 100 mL, 0.03 mol/L
Poly-dopamine is added in solution, 15 min of ultrasound, and concentration ratio ranging from 1 ~ 3 mg/L of poly-dopamine, mixed solution is in ice water
Quick mechanical stirs the h of 1 h ~ 5 in bath, by Magnetic Isolation and is washed till solution into neutrality, obtains Fe3O4@PDA particles, ultra-pure water
Disperse spare.
Using transmission electron microscope to Fe3O4The pattern of@PDA magnetic nano-particles further characterizes.Using vibrating example
Magnetometer（VSM）Magnetic measurement is carried out to sample at room temperature.Use uv-visible absorption spectra（UV-Vis）Detection is in near-infrared
The spectral absorption situation in area.Its light thermal property is detected using 808 nm near infrared lasers and digital temperature monitor, is obtained
Fe3O4@PDA particles, which have both, to be magnetic and light thermal property.
Further setting is the step（3）Fe3O4The preparation of@PDA@PNIPAm microgels：Take 50 mL above-mentioned
Fe3O4@PDA nano-particle solutions, addition N-isopropylacrylamide monomer, N, N- methylene-bisacrylamide cross-linking agent aqueous solutions,
Fe3O4@PDA particles are 5 with the molar ratio range of reacting of NIPAM:1~10:1, the molar ratio of monomer and crosslinking agent is 10:1~5:1,
It is passed through nitrogen stirring at low speed and removes oxygen, be heated to 70 DEG C and constant temperature keeps 30 min, it is molten that 0.45 mmol/L ammonium persulfates are added
Liquid initiated polymerization, 70 DEG C of reaction constant temperature keep leading to 6 h of nitrogen, and cooled to room temperature is washed till neutrality by Magnetic Isolation.
The dispersibility and grain size of sample obtained under different temperatures are characterized using dynamic light scattering.Use transmission electron microscopy
Mirror further characterizes the pattern of material.Using vibrating specimen magnetometer（VSM）Magnetic measurement is carried out to sample at room temperature.It uses
808 nm laser and digital temperature monitor detect its light thermal property, confirm the Fe3O4@PDA@PNIPAm microgels have light-
Thermo-magnetic multiple response characteristic.
The microgel of the present invention is with a wide range of applications in biomedical sector, such as NMR imaging, photo-thermal and light
Acoustic imaging, photo-thermal therapy, in addition carrying medicament can also be used to target controllable drug release on nucleocapsid or in protective layer, and
It can be used for GAP-associated protein GAP separation etc. in surface modification specific function group.
The present invention is described further with specific implementation mode with reference to the accompanying drawings of the specification.
Description of the drawings
Fe in Fig. 1 embodiments 13O4The transmission electron microscope picture of@PDA@PNIPAm, top right plot is the amplification of single microgel in Fig. 1
Figure；
Fig. 2 Fe3O4The room temperature B-H loop of@PDA@PNIPAm；
Fig. 3 Fe under the action of magnet3O4@PDA@PNIPAm microgels are precipitated from solution；
Fig. 4 Fe3O4The ultraviolet-visible absorption spectroscopy of@PDA@PNIPAm；
Fig. 5 Fe3O4The photo-thermal effect figure of@PDA@PNIPAm.
Specific implementation mode
The present invention is specifically described below by embodiment, is served only for that invention is further explained, no
It can be interpreted as limiting the scope of the present invention, the technician in the field can be according to the content of foregoing invention to the present invention
Make some nonessential modifications and adaptations.
Embodiment 1：
a）Prepare Fe3O4Magnetic nano-particle solution：The ferric trichloride of 20 mL, 0.8 mol/L（FeCl3）Solution and 10
The ferrous sulfate of 0.8 mol/L of mL（FeSO4）Solution is uniformly mixed under ultrasound.Above-mentioned mixed solution is slowly dropped to 200
In the NaOH solution of 2 mol/L of mL, 60 min of mechanical agitation at 80 DEG C continues to stir 60 min after stopping heating.It is with pH
It is 6.4 that 6.4 PBS solution is washed till pH by Magnetic Isolation, and it is spare to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4100 mL of magnetic nano-particle solution surpasses
15 min of sound is added 200 mg DA Quick mechanicals in ice-water bath and stirs 3 h, removes reaction solution by centrifugation, Magnetic Isolation is simultaneously
Solution is washed till at neutral spare.
c）" pomegranate shape " Fe3O4The preparation method of@PDA@PNIPAm microgels:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticles
100 mL, 12.4 mmol/L NIPAM monomers, 1.4 mmol/L BIS cross-linking agent aqueous solutions are added in sub- solution, lead to nitrogen low speed
Stirring removes oxygen, is heated to 70 DEG C and constant temperature keeps 30 min, 0.45 mmol/L APS initiated polymerizations, reaction is added
70 DEG C of constant temperature keeps leading to 6 h of nitrogen, cooled to room temperature.It is washed till neutrality by Magnetic Isolation, freeze-drying is spare.
Pass through characterization, the Fe of embodiment synthesis3O4Grain size is between 10 ~ 15 nm, saturation magnetization intensity（Ms）For
39.245（emu/g）, coercivity shows superparamagnetism close to 0, and solution is placed after 96 h still without obvious sediment, is illustrated
Dispersion stabilization is preferable in solution.Fe3O4Although the coating layer thickness of PDA is in 10 nm or so in@PDA, composite nanoparticle is still
Show stronger magnetism, saturation magnetization（Ms）It is 28.158（emu/g）, this is because PDA is nonmagnetic.
6.6 W cm−2500 s are irradiated under the laser of 808 nm, measure Fe3O4The photothermal conversion efficiency of@PDA is 10.1%, is higher than Fe3O4
（About 5.7%）.Fe3O4The transmission electron microscope picture of@PDA@PNIPAm is shown in that Fig. 1, upper right corner illustration are partial enlarged view, it can be seen that tiny
Fe3O4@PDA particles, as can be seen from Figure Fe3O4@PDA are uniformly wrapped in microgel, and " pomegranate is presented in entire microgel
Shape ", grain size is between the nm of 500 nm ~ 700（Desiccation）, hydration radius is in the nm of 1100 nm ~ 1200.Due to having wrapped up PDA
And microgel, compound rear saturation magnetization are reduced to 20.54（emu/g）, such as Fig. 2, but still can easily utilize external magnetic field
It is separated from solution, after withdrawing magnetic field, and is soon distributed in solution, is very beneficial for reusing, is such as schemed
3.Pass through ultraviolet-visible absorption spectroscopy（Fig. 4）, it can be clearly seen that composite microgel has absorption peak at 808 nm of near infrared region,
With Fe3O4@PDA are compared, due to the blocking of nucleocapsid, Fe3O4@PDA@PNIPAm microgel photothermal conversion efficiencies be down to 8.5%, PDA,
Fe3O4@PDA、Fe3O4Fig. 5 is shown in the comparison of@PDA@PNIPAm photothermal conversions.Due to Fe3O4@PDA are interspersed in the grid of microgel,
Fe3O4The swelling ratio of@PDA PNIPAm microgels is 12.22, is less than not compound PNIPAm, and ginseng is shown in Table 1.
1 Fe of table3O4@The swelling ratio of PDA@PNIPAM
| Project | PNIPAm | Fe3O4@PDA@PNIPAm |
| Dh 25（nm） | 907.8 | 1200.3 |
| Dh 60（nm） | 278.2 | 521.2 |
| α | 34.64 | 12.22 |
Embodiment 2：
a）Prepare Fe3O4Magnetic nano-particle solution：The ferric trichloride of 20 mL, 0.8 mol/L（FeCl3）Solution and 10
The ferrous sulfate of mL1.2 mol/L（FeSO4）Solution is uniformly mixed under ultrasound.Above-mentioned mixed solution is slowly dropped to 200
In the NaOH solution of 2 mol/L of mL, 60 min of mechanical agitation at 80 DEG C continues to stir 60 min after stopping heating.It is with pH
It is 6.4 that 6.4 PBS solution is washed till pH by Magnetic Isolation, and it is spare to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4100 mL of magnetic nano-particle solution surpasses
15 min of sound is added 200 mg DA Quick mechanicals in ice-water bath and stirs 3 h, removes reaction solution by centrifugation, Magnetic Isolation is simultaneously
Solution is washed till at neutral spare.
c）" pomegranate shape " Fe3O4The preparation method of@PDA@PNIPAM microgels:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticles
100 mL, 12.4 mmol/L NIPAM monomers, 1.4 mmol/L BIS cross-linking agent aqueous solutions are added in sub- solution, lead to nitrogen low speed
Stirring removes oxygen, is heated to 70 DEG C and constant temperature keeps 30 min, 0.45 mmol/L APS initiated polymerizations, reaction is added
70 DEG C of constant temperature keeps leading to 6 h of nitrogen, cooled to room temperature.It is washed till neutrality by Magnetic Isolation, freeze-drying is spare.
Compared with Example 1, embodiment 2 changes the molar ratio of reacted constituent, product Fe3O4Grain size increase, particle diameter distribution
In the nm of 35 nm ~ 41, saturation magnetization intensity 66.31（emu/g）, there is ferromagnetism.In the identical situation of b, c operating condition
Under, Fe3O4@PDA、Fe3O4The grain size of@PDA@PNIPAm also increased, and increase respectively to 50 ~ 60 nm, 1300 ~ 1500nm,
Saturation magnetization intensity is increased to 54.239 respectively（emu/g）With 48.954（emu/g）.Further, since Fe3O4The grain size of grain size increases
Add, specific surface area reduces, Fe3O4@The photo-thermal efficiency of PDA is slightly reduced, and Fe3O4@PDA@PNIPAm are reduced to 7.8 %, thus
It can be seen that entering the Fe of microgel network3O4@PDA amounts will have a direct impact on photo-thermal efficiency.
Embodiment 3
a）Prepare Fe3O4Magnetic nano-particle solution：The ferric trichloride of 20 mL, 0.8 mol/L（FeCl3）Solution and 10
The ferrous sulfate of 0.8 mol/L of mL（FeSO4）Solution is uniformly mixed under ultrasound.Above-mentioned mixed solution is slowly dropped to 200
In the NaOH solution of 2 mol/L of mL, 60 min of mechanical agitation at 80 DEG C continues to stir 60 min after stopping heating.It is with pH
It is 6.4 that 6.4 PBS solution is washed till pH by Magnetic Isolation, and it is spare to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4100 mL of magnetic nano-particle solution surpasses
15 min of sound is added 200 mg DA Quick mechanicals in ice-water bath and stirs 5 h, removes reaction solution by centrifugation, Magnetic Isolation is simultaneously
Solution is washed till at neutral spare.
c）" pomegranate shape " Fe3O4The preparation method of@PDA@PNIPAm microgels:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticles
100 mL, 12.4 mmol/L NIPAM monomers, 1.4 mmol/L BIS cross-linking agent aqueous solutions are added in sub- solution, lead to nitrogen low speed
Stirring removes oxygen, is heated to 70 DEG C and constant temperature keeps 30 min, 0.45 mmol/L APS initiated polymerizations, reaction is added
70 DEG C of constant temperature keeps leading to 6 h of nitrogen, cooled to room temperature.It is washed till neutrality by Magnetic Isolation, freeze-drying is spare.
Compared with Example 1, the sedimentation time of PDA is changed, PDA thickness increases to 15 nm ~ 20 nm, Fe3O4@PDA
Particle size range be the nm of 30 nm ~ 40.Since the thickness of PDA increases nearly 2 times, Fe3O4The surfaces@PDA PDA coating layer thicknesses increase
Add, saturation magnetization is reduced to 15.20（emu/g）, but photothermal conversion efficiency is increased to 13.1%.It therefore, can be according to difference
Function stress demand, suitably adjust Fe3O4Grain size and PDA coating layer thicknesses take into account magnetic and photothermal conversion efficiency.
Embodiment 4
a）Prepare Fe3O4Magnetic nano-particle solution：The ferric trichloride of 20 mL, 0.8 mol/L（FeCl3）Solution and 10
The ferrous sulfate of 0.8 mol/L of mL（FeSO4）Solution is uniformly mixed under ultrasound.Above-mentioned mixed solution is slowly dropped to 200
In the NaOH solution of 2 mol/L of mL, 60 min of mechanical agitation at 80 DEG C continues to stir 60 min after stopping heating.It is with pH
It is 6.4 that 6.4 PBS solution is washed till pH by Magnetic Isolation, and it is spare to disperse to suspend.
b） Fe3O4The preparation method of@PDA：Take above-mentioned 0.03 mol/L Fe3O4100 mL of magnetic nano-particle solution surpasses
15 min of sound is added 200 mg DA Quick mechanicals in ice-water bath and stirs 3 h, removes reaction solution by centrifugation, Magnetic Isolation is simultaneously
Solution is washed till at neutral spare.
c）" pomegranate shape " Fe3O4The preparation method of@PDA@PNIPAm microgels:：Take the above-mentioned Fe of 50 mL3O4@PDA nanoparticles
Sub- solution, is added 100 mL, 12.4 mmol/L NIPAm monomers, 2 mmol/L BIS cross-linking agent aqueous solutions, and logical nitrogen low speed stirs
Removing oxygen is mixed, 70 DEG C is heated to and constant temperature keeps 30 min, 0.45 mmol/L APS initiated polymerizations are added, reaction is permanent
70 DEG C of temperature keeps leading to 6 h of nitrogen, cooled to room temperature.It is washed till neutrality by Magnetic Isolation, freeze-drying is spare.
Compared with Example 1, embodiment changes the dosage of crosslinking agent in microgel, increases the dosage of crosslinking agent and can change
Become the degree of cross linking of microgel, i.e. the aperture of microgel network structure changes.Work as Fe3O4@PDA grain sizes are smaller, in Fe3O4@
In the case of PDA and NIPAm constant rates, into microgel network Fe3O4@PDA can increase, and show the light of composite microgel
The thermal efficiency is increased to 10.7%.
Claims (4)
1. a kind of preparation method of photo-thermal magnetic multiple response microgel, which is characterized in that the photo-thermal magnetic multiple response microgel is with Fe3O4
It is nuclear membrane for the poly-dopamine of magnetic core and introducing with photothermy, constitutes Fe3O4@PDA particles, introducing has Thermo-sensitive
Polyisopropyl acrylamide be nucleocapsid, formed Fe3O4@PDA particles dispersed encapsulateds are in polyisopropyl acrylamide network structure
Fe3O4@PDA@PNIPAm microgels, the Fe3O4@PDA@PNIPAm microgels have optical and thermal-magnetic multiple response characteristic, Fe3O4@
The saturation magnetization of PDA@PNIPAm microgels is 20.54 ~ 45.35emu/g, photothermal conversion efficiency is 8.5% ~ 13.1%, molten
Swollen rate is 12 ~ 25.5, and preparation method includes the following steps：
(1) coprecipitation is used to prepare Fe3O4, by controlling Fe3+ / Fe2+Molar ratio 1:1~2:1, grain size is obtained in 10 nm
The Fe of ~ 30 nm3O4；
(2) Fe is aggregated in by solution oxide3O4One strata dopamine of surface aggregate constitutes Fe3O4@PDA particles, poly-dopamine are made
Thickness for core mould is 2 nm ~ 15 nm, Fe3O4The whole grain size of@PDA particles is in the nm of 10 nm ~ 50；
(3) using N-isopropylacrylamide as monomer, N, N- methylene-bisacrylamides are crosslinking agent, by Fe3O4@PDA particles are therewith
Mixing may be polymerized reaction and using ammonium persulfate as initiator, and the molar ratio of monomer and crosslinking agent is 10:1~5:1, Fe3O4@
PDA is 5 with the molar ratio range of reacting of NIPAm:1~10:1, obtain Fe3O4The grain size of@PDA@PNIPAm microgels 500 nm ~
1500 nm。
2. a kind of preparation method of photo-thermal magnetic multiple response microgel according to claim 1, it is characterised in that：The step
Suddenly（1）It is uniformly mixed under ultrasound with ferrous sulfate solution for liquor ferri trichloridi, the molar ratio of ferric trichloride and ferrous sulfate
Example ranging from 1:1~2:1, above-mentioned mixed solution is slowly dropped in the NaOH solution of 2 mol/L, mechanical agitation 60 at 80 DEG C
Min continues to stir 60 min after stopping heating, and the phosphate buffer solution for being 6.4 with pH is washed till pH by Magnetic Isolation and is
6.4, obtain Fe3O4Magnetic nano-particle.
3. a kind of preparation method of photo-thermal magnetic multiple response microgel according to claim 2, it is characterised in that：The step
（2）Take above-mentioned Fe3O4Magnetic nano-particle, is configured to 100 mL, 0.03 mol/L solution, and poly- DOPA is added in 15 min of ultrasound
Amine, concentration ratio ranging from 1 ~ 3 mg/L of poly-dopamine, mixed solution Quick mechanical in ice-water bath stir the h of 1 h ~ 5, lead to
It crosses Magnetic Isolation and is washed till solution into neutrality, obtain Fe3O4@PDA particles, it is ultrapure water-dispersed spare.
4. a kind of preparation method of photo-thermal magnetic multiple response microgel according to claim 3, it is characterised in that：The step
Suddenly（3）Fe3O4The preparation of@PDA@PNIPAm microgels：Take the above-mentioned Fe of 50 mL3O4Isopropyl is added in@PDA nano-particle solutions
Acrylamide monomer, N, N- methylene-bisacrylamide cross-linking agent aqueous solutions, Fe3O4@PDA react molar ratio range with NIPAM's
It is 5:1~10:1, the molar ratio of monomer and crosslinking agent is 10:1~5:1, it is passed through nitrogen stirring at low speed and removes oxygen, be heated to 70 DEG C
And constant temperature keeps 30 min, and 0.45 mmol/L ammonium persulfate solution initiated polymerizations are added, 70 DEG C of reaction constant temperature keeps leading to nitrogen
6 h of gas, cooled to room temperature are washed till neutrality by Magnetic Isolation.
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