CN105254805B - A kind of preparation method of polymethyl methacrylate glycol ester microballoon - Google Patents
A kind of preparation method of polymethyl methacrylate glycol ester microballoon Download PDFInfo
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- CN105254805B CN105254805B CN201510672638.4A CN201510672638A CN105254805B CN 105254805 B CN105254805 B CN 105254805B CN 201510672638 A CN201510672638 A CN 201510672638A CN 105254805 B CN105254805 B CN 105254805B
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Abstract
The present invention provides a kind of preparation methods of polymethyl methacrylate glycol ester microballoon, include the following steps:A) ethylene glycol dimethacrylate, 4 vinylpyridines, alcohol and water are mixed, obtain mixed solution, the alcohol is methanol and/or ethyl alcohol;B the mixed solution is irradiated using gamma-rays), obtains polymethyl methacrylate glycol ester microballoon.Preparation method in the present invention causes the polymerization of ethylene glycol dimethacrylate monomer with gamma Rays, can be to avoid the impurity for having initiator residue to introduce it is not necessary that initiator is added, also, it is reaction dissolvent that the application, which uses alcohol solution, without post-processing, and small toxicity, it is environmentally friendly.Not only there is good monodispersity, also higher yield and preferable thermal stability using the polymethyl methacrylate glycol ester microballoon that this method obtains.
Description
Technical field
The invention belongs to synthesis of polymer material field more particularly to a kind of polymethyl methacrylate glycol ester microballoons
Preparation method.
Background technology
Monodisperse cross-linked polymer microspheres refer to grain size in tens nanometer to hundreds of microns range scale, particle diameter distribution it is equal
Even and shape is spherical or other solids cross-linked polymer particles.Monodisperse cross-linked degree polymer microballoon is because of its high-ratio surface
Product and mechanical strength, excellent thermal stability and solvent resistance and the advantages that conveniently recycle and reuse, biosensor,
Many fields such as drug and catalyst carrier, liquid-phase chromatographic column stationary phase and liquid crystal display are widely used.Such as by
The polymethyl methacrylate glycol ester of the high-crosslinking-degree of bifunctional monomer's ethylene glycol dimethacrylate (EGDMA) synthesis
(PEGDMA) microballoon is a kind of to be widely used general molecular engram carrier material.
The main preparation method of polymethyl methacrylate glycol ester microballoon of high-crosslinking-degree is precipitation polymerization at present, including
Classical precipitation polymerization, distillation precipitation polymerization and living radical precipitate poly- (G.L.Li, H.
D.G.Shchukinab.Chemical Society Review.2013,42,3628-3646.).These preparation methods technique ratio
It is more ripe, and the grain size of prepared microballoon can be regulated and controled between hundreds of nanometers to several microns.
But the above-mentioned reaction being related to is usually using highly toxic organic solvent as reaction medium, such as acetonitrile, and it is anti-
It answers and also needs to that initiator or chain-transferring agent is added in system, not only increased the cost of synthesis, but also by initiator or chain tra nsfer
The impurity such as the residue of agent introduce in microballoon, to limit application of the these preparation methods in biological field.
Invention content
The present invention provides a kind of preparation method of polymethyl methacrylate glycol ester microballoon, preparations provided by the invention
Method small toxicity, it is environmentally friendly and at low cost, impurity is few.
The present invention provides a kind of preparation method of polymethyl methacrylate glycol ester microballoon, includes the following steps:
A) ethylene glycol dimethacrylate, 4-vinylpridine, alcohol and water are mixed, obtain mixed solution, the alcohol
For methanol and/or ethyl alcohol;
B the mixed solution is irradiated using gamma-rays), obtains polymethyl methacrylate glycol ester microballoon.
Preferably, the ethylene glycol dimethacrylate and the volume ratio of 4-vinylpridine are (6~10):1.
Preferably, the volume ratio of the alcohol and water is (1~5):1.
Preferably, the step A) volume fraction of ethylene glycol dimethacrylate is 0.1~5% in mixed solution.
Preferably, the step B) in irradiate absorbed dose of radiation be 80~100Gy/min.
Preferably, the step B) in irradiate time be 1~4 hour.
Preferably, the step B) in irradiate temperature be 20~35 DEG C.
Preferably, the grain size of the polymethyl methacrylate glycol ester microballoon is 0.2~1.0 μm.
Preferably, the step B) in irradiation carried out under the closed environment of anaerobic.
Preferably, further include after the irradiation:
Mixed solution after the irradiation is centrifuged and is dried successively, the poly dimethyl propylene post-processed
Sour glycol ester microballoon.
The present invention provides a kind of preparation methods of polymethyl methacrylate glycol ester microballoon, include the following steps:A)
Ethylene glycol dimethacrylate, 4-vinylpridine, alcohol and water are mixed, obtain mixed solution, the alcohol be methanol and/or
Ethyl alcohol;B the mixed solution is irradiated using gamma-rays), obtains polymethyl methacrylate glycol ester microballoon.The present invention
In preparation method with gamma Rays cause ethylene glycol dimethacrylate monomer polymerization can it is not necessary that initiator is added
To avoid the impurity for having initiator residue to introduce, also, it is reaction dissolvent that the application, which uses alcohol-water solution, without post-processing,
And small toxicity, it is environmentally friendly.The polymethyl methacrylate glycol ester microballoon obtained using this method not only has good
Monodispersity, also higher yield and preferable thermal stability.The experimental results showed that being prepared into using the method in the present invention
The polymethyl methacrylate glycol ester microballoon polydispersity coefficient arrived is between 1.01~1.13, and yield is up to 95.1%, microballoon
Initial pyrolyzation temperature be up to 266 DEG C, 300 DEG C of heat loss are less than 25%.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the infrared spectrogram for the product that the embodiment of the present invention 1 obtains;
Fig. 2 is the SEM figures for the PEGDMA microballoons that the embodiment of the present invention 1 obtains;
Fig. 3 is the thermal multigraph for the PEGDMA microballoons that the embodiment of the present invention 1 obtains;
Fig. 4 is the SEM figures for the PEGDMA microballoons that the embodiment of the present invention 2 obtains;
Fig. 5 is the thermal multigraph for the PEGDMA microballoons that the embodiment of the present invention 2 obtains;
Fig. 6 is the SEM figures for the PEGDMA microballoons that the embodiment of the present invention 3 obtains;
Fig. 7 is the thermal multigraph for the PEGDMA microballoons that the embodiment of the present invention 3 obtains.
Specific implementation mode
The present invention provides a kind of preparation methods of polymethyl methacrylate glycol ester microballoon, include the following steps:
A) ethylene glycol dimethacrylate, 4-vinylpridine, alcohol and water are mixed, obtain mixed solution, the alcohol
For methanol and/or ethyl alcohol;
B the mixed solution is irradiated using gamma-rays), obtains polymethyl methacrylate glycol ester microballoon.
Preparation method small toxicity provided by the invention, it is environmentally friendly and at low cost, impurity is few.
The present invention mixes ethylene glycol dimethacrylate (EGDMA), 4-vinylpridine (4-vp), alcohol and water, obtains
To mixed solution, the present invention preferably first mixes the alcohol and water, obtains alcohol water mixed solution, then again by the dimethyl propylene
Olefin(e) acid glycol ester and comonomer 4-vinylpridine are added in the alcohol water mixed solution, obtain mixed solution.In this hair
In bright, the volume ratio of the ethylene glycol dimethacrylate and 4-vinylpridine is preferably (6~10):1, more preferably (7
~9):1, most preferably (8~8.5):1;The alcohol is methanol and/or ethyl alcohol, the volume ratio of the alcohol and water be preferably (1~
5):1, more preferably (1.5~4.5):1, most preferably (2.5~3):1.Preferably, when using methanol-water solution as solvent,
The volume ratio of the methanol and water is preferably (3~5):1, more preferably (3.5~4.5):1, most preferably 4:1;With ethyl alcohol-
When aqueous solution is solvent, the volume ratio of the ethyl alcohol and water is preferably (1~2.5):1, more preferably (1.5~2):1.In this hair
In bright, the volume fraction of ethylene glycol dimethacrylate is preferably 0.1~5% in the mixed solution, more preferably 0.2~
3%, most preferably 0.3~2%, the most preferably 0.5~1.8%.The present invention carries out the mixing preferably in round-bottomed flask.
After obtaining mixed solution, the mixed solution is positioned in gamma-rays environment by the present invention, is irradiated, and is gathered
Ethylene glycol dimethacrylate microballoon.The present invention leads to nitrogen preferably in the mixed solution, to remove in reaction environment
Oxygen leads to nitrogen about after ten minutes, the round-bottomed flask is sealed, is put into gamma-rays environment, is irradiated, obtains poly- diformazan
Base acrylic acid glycol ester microballoon.In the present invention, the gamma-ray radiation absorber amount is preferably 80~100Gy/min,
More preferably 83.5~95Gy/min;The time of the irradiation is preferably 1~4 hour, more preferably 2~3 hours;The irradiation
Temperature be preferably 20~35 DEG C, more preferably 25~30 DEG C.The present invention is not special to the type of the gamma-rays radioactive source
Limitation, it is common using those skilled in the art, specifically, in an embodiment of the present invention, can be used60Co is radiated
Source.The present invention preferably carries out above-mentioned irradiation under conditions of magnetic agitation.The present invention causes dimethyl propylene using the method for radiation
Initiator is added without additional in the polymerization of olefin(e) acid glycol ester monomer, and without high temperature and pressure, at normal temperatures and pressures energy
Polymerization, can both reduce the danger of reaction, can also be greatly lowered by heating tape Lai cost.
After completed irradiation, the present invention preferably post-processes the mixed solution obtained after irradiation, is post-processed
Polymethyl methacrylate glycol ester microballoon, the present invention preferably the mixed solution obtained after irradiation is centrifuged successively and
It is dry, the polymethyl methacrylate glycol ester microballoon post-processed.Specifically, the present invention is molten by the mixing after the irradiation
Liquid centrifuges 5~10min under the rotating speed of 8000~8500rpm, collects lower sediment, is dispersed in absolute ethyl alcohol, then
It is centrifuged again, obtains the product centrifuged for the first time, the process that above-mentioned first time centrifuges is repeated twice,
The solid of last mobile phone is dried to constant weight, the polymethyl methacrylate glycol ester microballoon post-processed, the drying
Temperature is preferably 50~60 DEG C.Present invention preferably employs electric drying oven with forced convections to carry out the drying, specifically, the present invention's
In embodiment, the electric heating air-blowing drier of model GXZ-9070MBE can be used.
Precipitation polymerization process is to dissolve monomer and initiator in a solvent in general, raw after polymerisation starts
At polymer solubility in a solvent it is extremely low, such polymer can be precipitated out from homogeneous reaction system.Because of precipitation
Lack some components (such as emulsifier or dispersant) for reducing surface energy, thus the polymer meeting being precipitated out in polymerization system
Because higher surface energy agglomerates into rapidly block materials.Therefore the usual monomer concentration of precipitation polymerization is all very low (5vol%),
Yield is not also high, and needs matched dicyandiamide solution.The precipitation polymerization of polyfunctional monomer is due to being crosslinked, solvent selection
Range smaller, the overwhelming majority reported at present is acetonitrile, and this kind of organic solvent of ethyl acetate is more toxic, also not to environment
It is friendly.
The method of some precipitation polymerizations such as solvent heat precipitation polymerization process, reacts under high-temperature and high-pressure conditions, generates
Polymer core dissolubility and Brownian movement rate it is all higher than under normal temperature and pressure, reduce the probability of core coalescence so that core
Stability increases, thus can obtain dispersed preferable polymethyl methacrylate glycol ester microballoon (PEGDMA microballoons).But
Solvent thermal reaction system is because carried out under closed environment, and pressure can increase system during the reaction, therefore is filled to experiment
It sets and experiment safety has very high requirement.Such as think to synthesize PEGDMA microballoons at normal temperatures and pressures, causes system and solvent
System these two aspects wants matched just right, just can guarantee that the coalescence probability of the polymer core of generation is sufficiently low, such ability
Obtain polymer microballoon material.High-energy ray radiation-initiated polymerization is used in the present invention, and dicyandiamide solution is using specific proportioning
Alcohol-aqueous solvent, the problem of not only solving room temperature initiation reaction, and keep the dissolubility of polymer core in a solvent best, make
The probability of collision coalescence between them reduces, and further improves its yield and dispersibility.
The present invention has carried out infrared spectrum detection and elemental analysis to obtained product, and the results are shown in Figure 1, and Fig. 1 is this
The infrared spectrogram for the product that inventive embodiments 1 obtain.The characteristic absorption peak of ester group is clearly seen on infrared spectrum
(1740cm-1) and pyridine ring skeletal vibration characteristic absorption peak (700~1000cm-1Between four absorption peaks).Use Element
Vario EL Cube instruments carry out elemental analysis, outturn sample gross weight 3.726mg, N element 1.56wt%, O element to product
For 31.59wt%, C element 60.46wt%, H element 7.20wt%, calculated according to elemental analysis result, carbon in sample,
Hydrogen, nitrogen, four kinds of elements of oxygen molar ratio be C:H:N:O=5:7.2:0.11:1.97, from formula as can be seen that N element can only be come
From in 4-Vp, therefore the molar ratio of 4-Vp and EGDMA should be 4-Vp in product:EGDMA=1:4.47.This feeds intake with this sample
Actual ratio 1 in formula:4.5 being consistent.The above characterization result illustrates that the product that the present invention obtains is polymethyl methacrylate second
Diol ester.
After obtaining polymethyl methacrylate glycol ester microballoon, the present invention uses the model that Jeol Ltd. provides
The polymethyl methacrylate glycol ester microballoon obtained to the present invention for the scanning electron microscope of JEM-6700F is detected.
The result shows that the polymethyl methacrylate glycol ester microballoon that the present invention obtains is spherical shape, and pattern, size are more equal
One.The present invention at least chooses 100 microballoons using Adobe Photoshop CS3 softwares from SEM photograph and measures, according to
The average grain diameter D of polymethyl methacrylate glycol ester microballoon is calculated in formula 1n, poly dimethyl propylene is calculated according to formula 2
The weight average particle diameter D of sour glycol ester microballoonw, the monodisperse of polymethyl methacrylate glycol ester microballoon is calculated according to formula 3
Coefficient (PDI).In formula 1~3, DiFor the diameter of single microballoon, niFor a diameter of DiMicroballoon number.The average grain diameter of microballoon exists
Between 0.19~0.73 μm, between polydispersity coefficient PDI is 1.01~1.13.
The present invention uses thermogravimetric analyzer (TGA, U.S. TA instrument company Q5000IR), under a nitrogen atmosphere, heating rate
The thermal stability for two ball of polymethyl methacrylate glycol ester that the present invention obtains is had detected under conditions of 10 DEG C/min, as a result table
Bright, the initial pyrolyzation temperature for the polymethyl methacrylate glycol ester microballoon that the present invention obtains may be up to 266 DEG C, 300 DEG C of heat
Loss is less than 25%.
The present invention provides a kind of preparation methods of polymethyl methacrylate glycol ester microballoon, include the following steps:A)
Ethylene glycol dimethacrylate, 4-vinylpridine, alcohol and water are mixed, obtain mixed solution, the alcohol be methanol and/or
Ethyl alcohol;B the mixed solution is irradiated using gamma-rays), obtains polymethyl methacrylate glycol ester microballoon.The present invention
In preparation method to radiate the polymerization for causing ethylene glycol dimethacrylate monomer, can be to avoid it is not necessary that initiator is added
There is the impurity that initiator residue introduces, also, it is reaction dissolvent that the application, which uses alcohol-water solution, without post-processing, and toxicity
It is small, it is environmentally friendly.Not only there is good monodisperse using the polymethyl methacrylate glycol ester microballoon that this method obtains
Property, also higher yield and preferable thermal stability.The experimental results showed that being prepared using the method in the present invention poly-
For ethylene glycol dimethacrylate microballoon polydispersity coefficient between 1.01~1.13, yield is up to 95.1%, microballoon it is initial
Heat decomposition temperature is up to 266 DEG C, and 300 DEG C of heat loss are less than 25%.
In order to further illustrate the present invention, with reference to embodiments to a kind of polymethyl methacrylate second provided by the invention
The preparation method of glycol ester microsphere is described in detail, but cannot be understood as limiting the scope of the present invention.
Embodiment 1
4mL methanol and 1mL distilled water are added in the single necked round bottom flask that capacity is 10mL.Again by 0.08mL's
The 4-Vp of EGDMA and 0.01mL is added thereto.The volume ratio that monomer accounts for overall reaction system at this time is 1.8%.Lead to nitrogen into system
Gas after ten minutes, single-necked flask ground vacuum stopper is sealed, is put into60In Co radioactive sources field, in magnetic agitation and absorbed dose of radiation
Rate be 83.5Gy/min under conditions of, irradiation 2 hours after, by gained reaction solution with HC-2518 types supercentrifuge carry out from
The heart detaches (8000rpm, 5min), collects lower sediment thing, and be dispersed in absolute ethyl alcohol, this dispersion liquid is centrifuged again and is divided
From.It repeats the above steps twice, the solid finally collected is dried extremely in GZX-9070MBE electric drying oven with forced convections at 50 DEG C
The yield of constant weight, reaction is 92.4%.
The product arrived of the present embodiment is carried out infrared test and elemental analysis by the present invention, and the results are shown in Figure 1, and Fig. 1 is
The infrared spectrogram for the product that the embodiment of the present invention 1 obtains.As seen from Figure 1, the characteristic absorption peak (1740cm of ester group-1) and
Pyridine ring skeletal vibration characteristic absorption peak (700~1000cm-1Between four absorption peaks) it is clear apparent, to product into row element point
Analysis, outturn sample gross weight 3.726mg, N element 1.56wt%, O element are 31.59wt%, C element 60.46wt%, H member
Element is 7.20wt%, carbon in sample, hydrogen, nitrogen, four kinds of elements of oxygen molar ratio be C:H:N:O=5:7.2:0.11:1.97, from
Side is as can be seen that N element can only come from 4-Vp, therefore the molar ratio of 4-Vp and EGDMA should be 4-Vp in product:EGDMA=
1:4.47.The actual ratio 1 in being formulated that feeds intake of this and this sample:4.5 being consistent.The above characterization result illustrates that the present invention obtains
Product is polymethyl methacrylate glycol ester.
The shape that gained PEGDMA microballoons are observed with scanning electron microscope (SEM, Jeol Ltd. JEM-6700F)
Looks are shown in the SEM figures that Fig. 2, Fig. 2 are the PEGDMA microballoons that the embodiment of the present invention 1 obtains.As a result show that the average grain diameter of microballoon is
0.58 μm, polydispersity coefficient (PDI) is 1.01.
Gained PEGDMA microballoons are studied its thermal stability with thermogravimetric analyzer (TGA, U.S. TA instrument company Q5000IR) and are seen
Fig. 3, Fig. 3 are the thermal multigraph for the PEGDMA microballoons that the embodiment of the present invention 1 obtains, from the figure 3, it may be seen that the initial pyrolyzation temperature of microballoon
Up to 250 DEG C, 300 DEG C of heat loss is less than 26%.
Embodiment 2
3.5mL ethyl alcohol and 1.5mL distilled water are added in the single necked round bottom flask that capacity is 10mL.Again by 0.08mL's
The 4-Vp of EGDMA and 0.01mL is added thereto.The volume ratio that monomer accounts for overall reaction system at this time is 1.8%.Lead to nitrogen into system
Gas after ten minutes, single-necked flask ground vacuum stopper is sealed, is put into60In Co radioactive sources field, in magnetic agitation and absorbed dose of radiation
Rate be 83.5Gy/min under conditions of, irradiation 2 hours after, by gained reaction solution with HC-2518 types supercentrifuge carry out from
The heart detaches (8000rpm, 5min), collects lower sediment thing, and be dispersed in absolute ethyl alcohol, this dispersion liquid is centrifuged again and is divided
From.It repeats the above steps twice, the solid finally collected is dried extremely in GZX-9070MBE electric drying oven with forced convections at 50 DEG C
Constant weight.Reaction yield is 84.3%.
The shape that gained PEGDMA microballoons are observed with scanning electron microscope (SEM, Jeol Ltd. JEM-6700F)
Looks are shown in the SEM figures that Fig. 4, Fig. 4 are the PEGDMA microballoons that the embodiment of the present invention 2 obtains.As a result show that the average grain diameter of microballoon is
0.73 μm, polydispersity coefficient (PDI) is 1.12.
Gained PEGDMA microballoons are studied its thermal stability with thermogravimetric analyzer (TGA, U.S. TA instrument company Q5000IR) and are seen
Fig. 5, Fig. 5 are the thermal multigraph for the PEGDMA microballoons that the embodiment of the present invention 2 obtains, as shown in Figure 5, the initial pyrolyzation temperature of microballoon
Up to 257 DEG C, 300 DEG C of heat loss is less than 25%.
Embodiment 3
2.5mL ethyl alcohol and 2.5mL distilled water are added in the single necked round bottom flask that capacity is 10mL.Again by 0.08mL's
The 4-Vp of EGDMA and 0.01mL is added thereto.The volume ratio that monomer accounts for overall reaction system at this time is 1.8%.Lead to nitrogen into system
Gas after ten minutes, single-necked flask ground vacuum stopper is sealed, is put into60In Co radioactive sources field, in magnetic agitation and absorbed dose of radiation
Rate be 83.5Gy/min under conditions of, irradiation 2 hours after, by gained reaction solution with HC-2518 types supercentrifuge carry out from
The heart detaches (8000rpm, 5min), collects lower sediment thing, and be dispersed in absolute ethyl alcohol, this dispersion liquid is centrifuged again and is divided
From.It repeats the above steps twice, the solid finally collected is dried extremely in GZX-9070MBE electric drying oven with forced convections at 50 DEG C
Constant weight.Reaction yield is 95.1%.
The shape that gained PEGDMA microballoons are observed with scanning electron microscope (SEM, Jeol Ltd. JEM-6700F)
Looks are shown in the SEM figures that Fig. 6, Fig. 6 are the PEGDMA microballoons that the embodiment of the present invention 3 obtains.As a result show that the average grain diameter of microballoon is
0.19 μm, polydispersity coefficient (PDI) is 1.13.
Gained PEGDMA microballoons are studied its thermal stability with thermogravimetric analyzer (TGA, U.S. TA instrument company Q5000IR) and are seen
Fig. 7, Fig. 7 are the thermal multigraph for the PEGDMA microballoons that the embodiment of the present invention 3 obtains, as shown in Figure 7, the initial pyrolyzation temperature of microballoon
Up to 266 DEG C, 300 DEG C of heat loss is less than 25%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of polymethyl methacrylate glycol ester microballoon, includes the following steps:
A) ethylene glycol dimethacrylate, 4-vinylpridine, alcohol and water are mixed, obtain mixed solution, the alcohol is first
Alcohol and/or ethyl alcohol;
B after the mixed solution) is led to nitrogen deoxygenation, using being irradiated under gamma-rays normal temperature and pressure, poly dimethyl third is obtained
Olefin(e) acid glycol ester microballoon.
2. preparation method according to claim 1, which is characterized in that the ethylene glycol dimethacrylate and 4- ethylene
The volume ratio of yl pyridines is (6~10):1.
3. preparation method according to claim 1, which is characterized in that the volume ratio of the alcohol and water is (1~5):1.
4. preparation method according to claim 1, which is characterized in that the step A) dimethacrylate in mixed solution
The volume fraction of glycol ester is 0.1~5%.
5. preparation method according to claim 1, which is characterized in that the step B) in irradiate absorbed dose of radiation be 80~
100Gy/min。
6. preparation method according to claim 1, which is characterized in that the step B) in time for irradiating be 1~4 small
When.
7. preparation method according to claim 1, which is characterized in that the step B) in irradiate temperature be 20~35
℃。
8. preparation method according to claim 1, which is characterized in that the polymethyl methacrylate glycol ester microballoon
Grain size is 0.2~1.0 μm.
9. preparation method according to claim 1, which is characterized in that the step B) in the irradiation ring closed in anaerobic
It is carried out under border.
10. according to preparation method as described in any one of claim 1 to 9, which is characterized in that further include after the irradiation:
Mixed solution after the irradiation is centrifuged and is dried successively, the polymethyl methacrylate second post-processed
Glycol ester microsphere.
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