CN108395504A - The method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons - Google Patents
The method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons Download PDFInfo
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- CN108395504A CN108395504A CN201810349247.2A CN201810349247A CN108395504A CN 108395504 A CN108395504 A CN 108395504A CN 201810349247 A CN201810349247 A CN 201810349247A CN 108395504 A CN108395504 A CN 108395504A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
The invention discloses a kind of methods that surfactant- free emulsion polymerization prepares pH and ionic strength double responsiveness polymer Janus microballoons, this method is using general vinyl compound and acrylic compounds as monomer, using one pot of two step Emulsifier-free Emulsion Polymerization Technology, by accurately controlling monomer ratio, double responsiveness circle mushroom shaped polymer Janus microballoons are successfully synthesized.The synthetic method have many advantages, such as it is simple for process, of low cost, rapidly and efficiently, safety clean.The polymer Janus microballoons of synthesis not only have the special microcosmic structure of anisotropy, and with to pH and the double response characteristics of ionic strength.The polymer Janus microballoons of this structure and performance are with a wide range of applications in fields such as solid surfactant, micro- reaction vessel, interfacial catalysis agent, environment-responsive materials.
Description
Technical field
The present invention provides a kind of preparation methods of Janus microballoons more particularly to a kind of preparation of emulsifier-free emulsion polymerization to have
The method of pH and ionic strength double responsiveness polymer Janus microballoons, belong to function and intelligent macromolecule material technical field.
Background technology
Stimulating responsive polymer refers to that the structure of itself can be with external environmental condition with performance（Such as：PH value, ion are dense
Degree, temperature, light, magnetic etc.）Change and the high molecular material accordingly changed occurs.It is suitable that this kind of polymer usually possesses good environment
Ying Xing, unique functional character are a kind of important intellectual materials.These unique performances make stimulating responsive polymer exist
Water-oil separating, catalysis oxidation, biosensor, chemical imaging, chemistry storage and transport and gene and drug conveying etc. are many
Field is with a wide range of applications.
PH responses and ionic strength responsive polymer are two kinds of relatively common stimulating responsive polymers.PH is responded
Property polymer polymer chain or side group on possess unique susceptible functionality, when environment pH value change when, ionize and go
Ionization, protonation can occur with phenomena such as deprotonation in these functional groups, cause the pattern variation of polymer, parent/dredge
Aqueous to change correspondingly, other performances also change therewith.Equally, ionic strength responsive polymer be also in this way, its also according to
It holds in the palm in the susceptible functionality on polymer chain or side group, when the salinity in environment changes, the pattern of polymer, parent/
Hydrophobicity also changes therewith.
Stimulating responsive polymer Janus microballoons are a kind of special stimulating responsive polymers.Its own pattern with
While environmental change and change, also there is the asymmetry of Space expanding, this makes it show double properties,
This double properties assign their fascinating characteristics.It is flexible that CN104910338A discloses a kind of temperature/pH double responsiveness
The preparation method of polymer Janus hollow balls is 2- bromine isobutyl acylbromides to be anchored in silicon ball surface, using SNP as hard template to obtain
SNP-Br be initiator, then using Me6TREN as ligand, CuBr is catalyst, causes NIPAM atom transfer radical polymerization and obtains
To SNP-g-PNIPAM-Br；Then SNP-g-PNIPAM-Br is initiator, and PMDETA is ligand, and CuBr is catalyst, EGDMA
For crosslinking agent, causes DEAEMA monomer polymerizations and obtain SNP-g-PNIPAM-b-cPDEAEMA；Finally at room temperature by SNP-g-
Target product is obtained after PNIPAM-b-cPDEAEMA hf etchings.This flexible polymer being made of PNIPAM/cPDEAEMA
The hollow ball materials of object Janus are assigned since the inside and outside one polymer of composition hollow ball is respectively provided with temperature and pH responses
Hollow ball dual responsiveness.When temperature reaches LCST values (37 DEG C) or more, the polymer of hollow ball internal layer is rolled up, and is shown
Hydrophobicity；And when below LCST values, the polymer of hollow ball internal layer, which is unfolded, shows hydrophily.When pH pKa value (7.2) with
When lower, the polymer of outer layer, which is unfolded, shows hydrophily, and when pH value reaches pKa value or more, outer layer copolymer, which is rolled up, to be shown
Hydrophobicity.Therefore when one polymer is all more unfolded inside and outside hollow ball, drug can be loaded into inside spherical cavity by osmosis,
Reach the different releasing effects to drug by controlling the conditions such as temperature, pH, therefore in the controlled release and target administration of drug
Etc. have potential application value.However, this method complex process, synthesis cost is high, is not easy to industrialized production.
CN104403041A discloses a kind of pH response type magnetic composite microspheres with Janus structures, has very significant Janus
Structure and pH sensibility, the magnetic composite microsphere after trifluoroacetic acid hydrolysis occur under different pH environment swelling with disappear it is molten
It is swollen, and pH sensibility can control by adjusting the dosage of trifluoroacetic acid, method is simple, and feasibility is high.However, the complex microsphere needs
It to be synthesized in the environment of starvation, synthesis condition is harsh, and synthesis cost is relatively high.
Emulsifier-free Emulsion Polymerization Technology is a kind of method for producing polymer of environment-protecting clean, and this method is not required to during the reaction
Emulsifier is added, compared with conventional emulsion polymerization, there is of low cost, environmental-friendly, product relative molecular mass height, synthesis
Simple operation and other advantages.Therefore, it explores and prepares Janus microballoons with potential application prospect using Emulsifier-free Emulsion Polymerization Technology.
Invention content
The object of the present invention is to provide a kind of simple and effective double responsiveness circle mushroom shaped polymer Janus microballoons synthesis sides
Method, the polymer microballoon have the double responsiveness of pH and salinity, can be applied to micro- reaction vessel, phase stabiliser, intelligence breast
The fields such as agent.
One, the preparation of double responsiveness polymer Janus microballoons
The present invention is close by regulating and controlling with one pot of two step surfactant- free emulsion polymerization using acrylate and its derivative as polymerized monomer
The ratio of water/hydrophobic monomer successfully prepares double responsiveness circle mushroom shaped polymer Janus microballoons.Its specific preparation method is as follows：
（1）The preparation of polymethacrylate emulsion：Methacrylate is added in initiator solution and mixes monomer, ultrasound
Emulsification obtains methacrylate mix monomer/initiator emulsion；Again under stiring by methacrylate mix monomer/draw
Hair agent emulsion is added in the distilled water that temperature is 55 DEG C ~ 85 DEG C, and constant temperature is kept to be stirred to react 1.0 ~ 3.0h, is obtained
Polymethacrylate emulsion.
It is methyl methacrylate, ethyl methacrylate, butyl methacrylate, first that methacrylate, which mixes monomer,
The mixture of two or three of monomer in base glycidyl acrylate；When two kinds of monomer mixing, mixed proportion 1:1.5~1:
3.5；When three kinds of monomer mixing, mixed proportion 1:1.5:2.5~1:3.5:3.5.
The initiator is potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate；Initiator amount mixes for methacrylate
The 0.5% ~ 3% of monomer mass.
（2）The preparation of mix monomer/initiator emulsion：Vinyl monomer and acrylic monomer are added to initiator
In aqueous solution and ultrasonic emulsification, mix monomer/initiator emulsion is obtained.
Vinyl monomer is styrene, methyl styrene or ethyl styrene；Acrylic monomer is acrylic acid or methyl
Acrylic acid；The mass ratio of vinyl monomer and acrylic monomer is 4:1~7:1.
The initiator is potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate；Initiator amount is vinyl monomer and propylene
The 1% ~ 3.5% of acrylic monomer gross mass.
（3）The preparation of polymer Janus microballoons：By step（2）The mix monomer of preparation/initiator emulsion is added to step
Suddenly（1）In the polyacrylate dispersion of preparation, 15 ~ 25 DEG C of control system temperature is stirred to react 10 ~ 60 min；Again by reactant
System is warming up to 55 DEG C ~ 85 DEG C, continues to be stirred to react 1.0 ~ 3.0 h；It is cooled to room temperature after reaction, obtains double responsiveness polymerization
Object Janus microballoon lotions；The white powder product that the lotion is centrifuged, 3 are washed respectively with water and absolute ethyl alcohol ~
5 times to get to the polymer Janus microsphere solids of white powder.
Above-mentioned steps（1）Middle methacrylate mixes the total amount and step of monomer（2）Medium vinyl monomer and acrylic acid
The ratio of class monomer total amount is 1:1.5~1:3.5.The emulsification ultrasound is ultrasound 1 min ~ 5 min in ultrasonic case.
Two, the structure of double responsiveness Janus microballoons
1, microscopic appearance
Fig. 1 is the scanning electron microscope of polymer Janus microballoons prepared by the above method（SEM）Figure., it is apparent that polymer
There is Janus microballoons the circle mushroom shape of the microcosmic structure of anisotropy, the microballoon monomer good dispersion to belong to typical Janus microballoons；
Microspherulite diameter is uniform, and average grain diameter is in 200 ~ 250 nm.
2, infrared spectrum analysis
Fig. 2 is the infrared absorption spectrum that double responsiveness justifies mushroom shaped polymer Janus microballoons.In figure, 3447 cm-1Neighbouring broad peak
Belong to the characteristic absorption peak of carboxylic-OH stretching vibrations；3026 cm-1Neighbouring peak should belong to the flexible absorption of shaking of C-H in phenyl ring
Dynamic peak；2926 cm-1The peak at place should belong on alkyl chain the stretching vibration absworption peak for being saturated C-H；1733 cm-1It answers at the peak at place
Belong to carbonyl（C=O）Stretching vibration absworption peak；756cm-1With 695cm-1The peak of fingerprint region also demonstrates depositing for phenyl ring at two
.From infrared spectrum as can be seen that existing hydrophilic radical in the polymer microballoon（-COOH）, also there is hydrophobic group（Phenyl ring
With alkyl chain）.
Three, the response test of double responsiveness polymer Janus microballoons
It is 0.25% to prepare solid content（w/v）Polymer Janus microballoon lotions, toluene as oil phase, with water-soluble dye and
Oil-soluble dyes are respectively marked water phase and oil phase, observe emulsification shape of the circle mushroom shaped polymer microballoon in oil water mixture
Looks and pH, ionic strength response.
1, pH responses
In order to evaluate the relationship of round mushroom shaped polymer Janus microballoons and environmental pH, oil-soluble dyes are used（Red Ⅲ）As
Water phase label tests the emulsifiability of circle mushroom shaped polymer microballoon in different pH environment.The results are shown in Figure 3, it can be seen that
Justify increase of the mushroom shaped polymer microballoon with pH, emulsifiability changes from W/O to O/W.Illustrate that it, with pH responses, passes through tune
Environment pH is saved, the microstructure of the circle mushroom shaped polymer Janus microballoons can change with hydrophilic/hydrophobic, this causes this
The emulsifiability of Janus microballoons also changes correspondingly.
2, ionic strength response
In order to evaluate the ionic strength response of polymer microballoon, water-soluble dye is used（Rhodamine B）As water phase label, compare
Circle mushroom shaped polymer microballoon lotion is salt-free（Distilled water）, low concentration salt solution（0.03 mol/L NaCl）, higher concentration salt it is molten
Liquid（0.27 mol/L NaCl）Emulsibility under environment.The results are shown in Figure 4, it can be seen that circle mushroom shaped polymer microballoon lotion
What is formed in the case where distilling water environment is water-in-oil type（W/O）, formed under low concentration salt solution environment is water-in-oil type（W/O）Breast
What is formed under change liquid, higher concentration salting liquid environment is oil-in-water type（O/W）Emulsion.Illustrate round mushroom shaped polymer microballoon to salt
Solution concentration has very strong salt response, and with the increase of salinity, the emulsifiability of Janus microballoons changes from W/O to O/W.
In conclusion the present invention is using general vinyl compound and acrylic compounds as monomer, using one pot of two step
It is micro- to successfully synthesize double responsiveness circle mushroom shaped polymer Janus by accurately controlling monomer ratio for Emulsifier-free Emulsion Polymerization Technology
Ball.The synthetic method have many advantages, such as it is simple for process, of low cost, rapidly and efficiently, safety clean.The polymer Janus of synthesis
Microballoon not only has the special microcosmic structure of anisotropy, and with double response characteristics to pH and ionic strength.With this
The polymer Janus microballoons of structure and performance are in solid surfactant, micro- reaction vessel, interfacial catalysis agent, environment-responsive
The fields such as material are with a wide range of applications.
Description of the drawings
Fig. 1 is the scanning electron microscope that double responsiveness justifies mushroom shaped polymer Janus microballoons（SEM）Figure.
Fig. 2 is the infrared spectrogram that double responsiveness justifies mushroom shaped polymer Janus microballoons.
Fig. 3 is that double responsiveness justifies mushroom shaped polymer Janus microspheres solutions at different pH（pH=2~12）Emulsion.
Fig. 4 is that double responsiveness justifies emulsion of the mushroom shaped polymer Janus microspheres solutions in various concentration NaCl solution.
Specific implementation mode
The preparation for justifying mushroom shaped polymer Janus microballoons to double responsiveness of the present invention below by specific embodiment is made further
Explanation.
Embodiment 1
（1）The preparation of polymethacrylate emulsion：10 mL sodium persulfate aqueous solutions are first added in beaker（A concentration of 3.0
g/L）, add 2.0 g methacrylates and mix monomer（0.75 g of methyl methacrylate, ethyl methacrylate 1.25
g）, and beaker is put into ultrasound 1min ~ 5min in ultrasonic case, it is made to disperse and emulsify, obtain methacrylate mix monomer/
Initiator emulsion；Then lower the methacrylate mix monomer/initiator emulsion is added to 70 mL being sufficiently stirred
In the distilled water that temperature is 65 DEG C, and constant temperature is kept to be stirred to react 1.0 h, obtains polymethacrylate emulsion；
（2）The preparation of mix monomer/initiator emulsion：3.0 g mix monomers of precise（2.6 g of styrene, acrylic acid
0.4g）, it is added to 10 mL sodium persulfate aqueous solutions（A concentration of 2.0 g/L）In, and the ultrasound min of 1 min ~ 5 in ultrasonic case are put into,
So that it is disperseed and is emulsified, obtains mix monomer/initiator emulsion；
（3）The preparation of polymer Janus microballoons：By step（2）The mix monomer of preparation/initiator emulsion is added to step
（1）In the polyacrylate dispersion of preparation, 20 DEG C of control system temperature is stirred to react 20 min；Reaction system is warming up to again
65 DEG C, continue to be stirred to react 1.5h, be cooled to room temperature after reaction, obtains polymer Janus microballoon lotions.By the lotion from
The heart detaches, and obtains white powder product；4 times are washed respectively to get to the double responsiveness of white powder with water and absolute ethyl alcohol
Polymer Janus microsphere solids.
Embodiment 2
（1）The preparation of polymethacrylate emulsion：20 mL persulfate aqueous solutions are first added in beaker（A concentration of 3.0
g/L）, add 3.5 g methacrylates and mix monomer（3.0 g of ethyl methacrylate, 0.5 g of butyl methacrylate）,
And beaker is put into the ultrasound min of 1 min ~ 5 in ultrasonic case, so that it is disperseed and is emulsified, obtain methacrylate mix monomer/
Initiator emulsion；Then lower the methacrylate mix monomer/initiator emulsion is added to 80 mL being sufficiently stirred
In the distilled water that temperature is 70 DEG C, and constant temperature is kept to be stirred to react 1.5 h, obtains polymethacrylate emulsion；
（2）The preparation of mix monomer/initiator emulsion：4.0 g mix monomers of precise（3.0 g of ethyl styrene, propylene
1.0 g of acid）, it is added to 20 mL persulfate aqueous solutions（A concentration of 4.7g/L）, and the ultrasound min of 1 min ~ 5 in ultrasonic case are put into,
So that it is disperseed and is emulsified, obtains mix monomer/initiator emulsion；
（3）The preparation of polymer Janus microballoons：By step（2）The mix monomer of preparation/initiator emulsion is added to step
（1）In the polyacrylate dispersion of preparation, 20 DEG C of control system temperature is stirred to react 40 min；Reaction system is warming up to again
70 DEG C, continue to be stirred to react 1.0h；It is cooled to room temperature after reaction, obtains double responsiveness polymer Janus microballoon lotions.It will
The lotion centrifuges, and obtains white powder product；4 times are washed respectively with water and absolute ethyl alcohol to get white powder is arrived
Double responsiveness polymer Janus microsphere solids.
Embodiment 3
（1）The preparation of polymethacrylate emulsion：5 mL ammonium persulfate aqueous solutions are first added in beaker（A concentration of 3.0 g/
L）, add 4.0 g methacrylates and mix monomer（3.0 g of butyl methacrylate, glycidyl methacrylate 1.0
g）, and beaker is put into the ultrasound min of 1 min ~ 5 in ultrasonic case, so that it is disperseed and is emulsified, it is single to obtain methacrylate mixing
Body/initiator emulsion；Then lower the methacrylate mix monomer/initiator emulsion is added to 65 being sufficiently stirred
In the distilled water that mL temperature is 65 DEG C, and constant temperature is kept to be stirred to react 2h, obtains polymethacrylate emulsion；
（2）The preparation of mix monomer/initiator emulsion：Precise 3.5g mix monomers（2.5 g of methyl styrene, methyl
1.0 g of acrylic acid）, it is added to 5 mL ammonium persulfate aqueous solutions（A concentration of 3.0 g/L）, and ultrasonic 1 min ~ 5 are put into ultrasonic case
Min makes it disperse and emulsify, and obtains mix monomer/initiator emulsion；
（3）The preparation of polymer Janus microballoons：By step（2）The mix monomer of preparation/initiator emulsion is added to step
（1）In the polyacrylate dispersion of preparation, 15 DEG C of control system temperature is stirred to react 30 min；Reaction system is warming up to again
65 DEG C, continue to be stirred to react 2.0h；It is cooled to room temperature after reaction, obtains double responsiveness circle mushroom shaped polymer Janus microballoons
Lotion.The lotion is centrifuged, white powder product is obtained；4 times are washed respectively to get to white with water and absolute ethyl alcohol
The double responsiveness polymer Janus microsphere solids of powder.
Embodiment 4
（1）The preparation of polymethacrylate emulsion：10 mL ammonium persulfate aqueous solutions are first added in beaker（A concentration of 1.5
g/L）, add 3.0 g methacrylates and mix monomer（0.7 g of methyl methacrylate, 1.3 g of ethyl methacrylate, first
1.0 g of base butyl acrylate）, and beaker is put into the ultrasound min of 1min ~ 5 in ultrasonic case, so that it is disperseed and is emulsified, obtains methyl
Crylic acid ester mixture monomer/initiator emulsion；Then be sufficiently stirred it is lower by the methacrylate mix monomer/initiator
Emulsion is added in the distilled water that 80 mL temperature are 60 DEG C, and constant temperature is kept to be stirred to react 2.0h, obtains poly- methyl-prop
Olefin(e) acid ester lotion；
（2）The preparation of mix monomer/initiator emulsion：Precise 2.0g mix monomers（0.6 g of ethyl styrene, methyl
1.4 g of acrylic acid）, it is added to 10mL ammonium persulfate aqueous solutions（A concentration of 2.0 g/L）, and ultrasonic 1min ~ 5 are put into ultrasonic case
Min makes it disperse and emulsify, and obtains mix monomer/initiator emulsion；
（3）The preparation of polymer Janus microballoons：By step（2）The mix monomer of preparation/initiator emulsion is added to step
（1）In the polyacrylate dispersion of preparation, 15 DEG C of control system temperature is stirred to react 50 min；Reaction system is warming up to again
75 DEG C, continue to be stirred to react 2.0h；It is cooled to room temperature after reaction, obtains double responsiveness circle mushroom shaped polymer Janus microballoons
Lotion.The lotion is centrifuged, white powder product is obtained；4 times are washed respectively to get to white with water and absolute ethyl alcohol
The double responsiveness of powder justifies mushroom shaped polymer Janus microsphere solids.
Claims (9)
1. the method that surfactant- free emulsion polymerization prepares double responsiveness polymer Janus microballoons, comprises the following steps that：
（1）The preparation of polymethacrylate emulsion：Methacrylate is added in initiator solution and mixes monomer, ultrasound
Emulsification obtains methacrylate mix monomer/initiator emulsion；Again under stiring by methacrylate mix monomer/draw
Hair agent emulsion is added in the distilled water that temperature is 55 DEG C ~ 85 DEG C, and constant temperature is kept to be stirred to react 1.0 ~ 3.0h, is obtained
Polymethacrylate emulsion；
（2）The preparation of mix monomer/initiator emulsion：Vinyl monomer and acrylic monomer are added to initiator solution
In and ultrasonic emulsification, obtain mix monomer/initiator emulsion；
（3）The preparation of polymer Janus microballoons：By step（2）The mix monomer of preparation/initiator emulsion is added to step
（1）In the polyacrylate dispersion of preparation, 15 ~ 25 DEG C of control system temperature is stirred to react 10 ~ 60 min；Again by reaction system
55 DEG C ~ 85 DEG C are warming up to, continues to be stirred to react 1.0 ~ 3.0 h；It is cooled to room temperature after reaction, obtains double responsiveness polymer
Janus microballoon lotions；The white powder product that the lotion is centrifuged, 3 ~ 5 are washed with water and absolute ethyl alcohol respectively
It is secondary to justify mushroom shaped polymer Janus microsphere solids to get double responsiveness.
2. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：Step（1）In, it is methyl methacrylate, ethyl methacrylate, metering system that methacrylate, which mixes monomer,
The mixture of two or three of monomer in acid butyl ester, glycidyl methacrylate.
3. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：Step（1）In, the initiator is potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate；Initiator amount is metering system
Acid esters mixes the % of 0.5 % ~ 3 of monomer mass.
4. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：Step（2）In, vinyl monomer is styrene, methyl styrene or ethyl styrene.
5. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：Step（2）In, acrylic monomer is acrylic or methacrylic acid.
6. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：Step（2）In, the mass ratio of vinyl monomer and acrylic monomer is 4:1~7:1.
7. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：Step（2）In, the initiator is potassium peroxydisulfate, ammonium persulfate or sodium peroxydisulfate；Initiator amount is vinyl list
The 1% ~ 3.5% of body and acrylic monomer gross mass.
8. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：Step（1）In methacrylate mix monomer total amount and step（2）Medium vinyl monomer and acrylic compounds list
The ratio of body total amount is 1:2~1:4.
9. a kind of method that emulsifier-free emulsion polymerization prepares double responsiveness polymer Janus microballoons as described in claim 1, special
Sign is：The step（1）、（2）In, the emulsification ultrasound is ultrasound 1 min ~ 5 min in ultrasonic case.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110105506A (en) * | 2019-05-27 | 2019-08-09 | 西北师范大学 | A kind of preparation method of alms bowl shaped polymer microballoon |
| CN110172118A (en) * | 2019-05-27 | 2019-08-27 | 西北师范大学 | A kind of preparation method of the thyrsiform polymer microballoon of highly dispersible nano silver |
| CN115121194A (en) * | 2021-03-24 | 2022-09-30 | 中国科学院理化技术研究所 | Asymmetric magnetic polymer microsphere and preparation method thereof |
| CN115594786A (en) * | 2022-11-10 | 2023-01-13 | 安徽工程大学（Cn） | P (St-co-GMA) -based structural yarn dyed fabric and macro rapid preparation method thereof |
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| CN110105506A (en) * | 2019-05-27 | 2019-08-09 | 西北师范大学 | A kind of preparation method of alms bowl shaped polymer microballoon |
| CN110172118A (en) * | 2019-05-27 | 2019-08-27 | 西北师范大学 | A kind of preparation method of the thyrsiform polymer microballoon of highly dispersible nano silver |
| CN110105506B (en) * | 2019-05-27 | 2021-06-01 | 西北师范大学 | Preparation method of pot-shaped polymer microspheres |
| CN110172118B (en) * | 2019-05-27 | 2021-12-17 | 西北师范大学 | Preparation method of grape string-shaped polymer microspheres capable of highly dispersing nano silver |
| CN115121194A (en) * | 2021-03-24 | 2022-09-30 | 中国科学院理化技术研究所 | Asymmetric magnetic polymer microsphere and preparation method thereof |
| CN115121194B (en) * | 2021-03-24 | 2023-08-29 | 中国科学院理化技术研究所 | Asymmetric magnetic polymer microsphere and preparation method thereof |
| CN115594786A (en) * | 2022-11-10 | 2023-01-13 | 安徽工程大学（Cn） | P (St-co-GMA) -based structural yarn dyed fabric and macro rapid preparation method thereof |
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