CN110358014A - A kind of preparation method of polymer beads - Google Patents
A kind of preparation method of polymer beads Download PDFInfo
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- CN110358014A CN110358014A CN201910450068.2A CN201910450068A CN110358014A CN 110358014 A CN110358014 A CN 110358014A CN 201910450068 A CN201910450068 A CN 201910450068A CN 110358014 A CN110358014 A CN 110358014A
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- polymer beads
- seed
- oily phase
- phase fluid
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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
- C08F2/00—Processes of polymerisation
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
Abstract
The invention discloses a kind of preparation methods of polymer beads, and the preparation method comprises the following steps: polymer seeds being added in the aqueous solution containing stabilizer, are stirred evenly, seed suspension liquid is formed；Monomer and initiator are uniformly mixed, oily phase fluid is formed；The oily phase fluid is formed into uniform oil droplet with eruption mode, and forms oil/water type suspension with the seed suspension liquid；One-step polymerization reaction, obtains polymer beads.The method of the present invention is easier to obtain the partial size of required size, and size tunable is higher, and uniform particle diameter further gets a promotion.Moreover, the preparation method high production efficiency of the embodiment of the present invention, is suitable for large-scale production.
Description
Technical field
The present invention relates to polymer material field, in particular to a kind of preparation method of polymer beads.
Background technique
In recent years, polymer beads separation analysis, Solid-phase organic synthesis chemistry, drug controlled release, immunoassays and
The fields such as food safety detection are widely used.But the polymer beads of uniform particle diameter, structure-controllable how are synthesized,
It is the hot and difficult issue of presently relevant area research.
The conventional method of prior art synthetic polymer particle mainly has suspension polymerization, dispersion copolymerization method and seed multistep
Swollen-state polymerization method.Suspension polymerization is mixed using mechanical stirring paddle, each section liquid discontinuity in reaction kettle, so as to cause
Polymer beads partial size is larger, size substep is wide.
Dispersion copolymerization method is usually the monomer that organic solvent or water are dissolved in using one or more, is generated by polymerization insoluble
In the polymer of the solvent, and form the polymerization methods of the dispersion of Colloidal stability.The colloidal stability of system is from poly-
The stabilizer or dispersing agent that are present in continuous phase of polymer particle adsorption, effect is in the nature stereoscopic stable effect.
Seed multi-step swelling polymerization is to be swollen polymer seeds in organic solvent and monomer, by being swollen and inhaling
Enter monomer to repeat to further increase the particle size of particle.
CN102603929 discloses a kind of method for being used to prepare monodisperse polymer particles, by preparing seed respectively
Then monomer suspension and initiator hanging drop are added to seed respectively and hanged by suspension, monomer suspension, initiator suspension
Supernatant liquid compares above-mentioned conventional method, improves the controllability of polymer beads, reduces the polymer particle sizes dispersion of distribution,
However in this method, polymer seeds growth course uncontrollable factor is still more, and monomer cannot be made completely by neutron absorption
Polymer beads in the phenomenon that having many little particle impurity, and reaction time is long, and production efficiency is lower, is unfavorable for advising greatly
Mould production, production stability are to be improved.
Summary of the invention
In order to solve the above technical problems, the embodiment of the invention provides a kind of preparation methods of polymer beads.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
The embodiment of the invention provides a kind of preparation methods of polymer beads, and the preparation method comprises the following steps:
S10, polymer seeds are added in the aqueous solution containing stabilizer, are stirred evenly, form seed suspension liquid；
S20, monomer and initiator are uniformly mixed, form oily phase fluid；
S30, the oily phase fluid is formed into uniform oil droplet with eruption mode, and is formed uniformly with the seed suspension liquid
Oil/water suspension；
S40, one-step polymerization reaction, obtain the polymer beads.
Further, the polymer seeds are as follows: by the poly- of emulsion polymerization, dispersion copolymerization method or suspension polymerization preparation
Styrene seed or styrene-divinylbenzene seed.
Further, the monomer is hydrophobicity vinyl monomer, and the initiator is oiliness initiator.
Further, the monomer is selected from least one of following vinyl monomer: styrene, divinylbenzene, 2,4- bis-
Chlorostyrene, acrylic acid, methyl methacrylate, methyl acrylate, ethyl acrylate, vinylacetate, methacrylic acid contracting
Water glyceride or derivatives thereof.
Further, the initiator is oil soluble peroxides and oil-soluble azo-compound and their mixing
Object.
Further, the oil soluble peroxides are benzoyl peroxide, lauroyl peroxide and peroxidating formic acid uncle
Butyl ester
Further, the oil-soluble azo-compound is 2,2 '-azos bis- (2- methylbutyronitriles) and 2, and 2 '-azos are double
At least one of (2,4- methyl pentane nitrile).
Further, the stabilizer is one or more kinds of surfactant.
Further, the surfactant is polyvinyl alcohol, polyvinylpyrrolidone, cellulose, hydroxypropyl cellulose
Or mixtures thereof.
Further, step S30 is further comprising the steps of:
S31, the oily phase fluid is added in jet flow suspension polymerization device；
S32, the oily phase fluid is formed described in entrance by the nozzle jet of the jet flow suspension polymerization device
Oil droplet in seed suspension liquid.
Further, the average grain diameter of the polymer beads is 100nm~1000 μm.
The embodiment of the invention provides a kind of preparation method of polymer beads, using eruption mode by oily phase fluid jet flow
Uniform oil droplet is formed, and forms uniform oil/water type suspension in seed suspension liquid, seed rapidly absorbs oil droplet and life
Long, one-step polymerization obtains the polymer beads of uniform particle diameter.Because monomer oil droplet size of the invention is uniform, it is easier to by seed
It fully absorbs, whole preparation process is completed in 2 hours, and the time greatly shortens.In addition, uniform monomer oil droplet is easier to be planted
Son fully absorbs, and little particle impurity is free of in the polymer beads of preparation.Therefore, the partial size of polymer beads prepared by the present invention
Controllability is higher, and uniform particle diameter further gets a promotion.Moreover, the preparation method high production efficiency of the embodiment of the present invention, is fitted
In large-scale production.
Detailed description of the invention
Fig. 1 is the electron microscope of polymer beads in the embodiment of the present invention one；
Fig. 2 is the grading curve of polymer beads in the embodiment of the present invention one.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
Attached drawing, the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair
Bright a part of the embodiment, rather than whole embodiments.Based on described the embodiment of the present invention, those skilled in the art institute
The every other embodiment obtained, belongs to the scope of the present invention.
The embodiment of the invention provides a kind of preparation method of polymer beads, preparation method the following steps are included:
S10, polymer seeds are added in the aqueous solution containing stabilizer, are stirred evenly, form seed suspension liquid；
S20, monomer and initiator are uniformly mixed, form oily phase fluid；
S30, oily phase fluid is formed into oil droplet with eruption mode, and forms the uniform oil/water type that obtains with seed suspension liquid and suspends
Liquid；
S40, one-step polymerization reaction, obtain polymer beads.
The preparation method of the embodiment of the present invention prepares polymer beads using the continuous growth of seed, and reaction condition is easier
Control, not only preparation process is simple, further improves size tunable and uniform particle diameter, stable product quality is more
It is good.Specifically, it can be realized by the size and dosage, monomer dosage and oil droplet size that control polymer seeds to partial size
Control.In oil/water type suspension, monomer and initiator make polymer seeds grow up, the monomer and initiator being present in oil droplet
The adsorption efficiency that can be improved polymer seeds avoids the generation of little particle impurity.
In some embodiments of the invention, step S30 is further comprising the steps of:
S31, oily phase fluid is added in jet flow suspension polymerization device；
S32, oily phase fluid is sprayed to be formed into seed suspension liquid by the nozzle of jet flow suspension polymerization device
Oil droplet.
Jet flow suspension polymerization device can be manufactured according to the record of Chinese patent CN200320129701.2.Wherein, it sprays
The aperture of mouth can be adjusted as needed, such as in some embodiments of the invention, and the aperture of nozzle can be the μ of 50nm~5000
M, it is preferable that the aperture of nozzle is 10 μm~200 μm.
In some embodiments of the invention, the average grain diameter of polymer beads is 100nm~1000 μm.The present invention is implemented
The method of example can not only make nanoscale polymerized composition granule, can also make micron-sized polymer beads.
In some embodiments of the invention, polymer seeds be styrene homopolymer or copolymer, such as: styrene
Homopolymer or styrene diethylene benzene copoly mer.Preferably, polymer seeds are as follows: by emulsion polymerization, dispersion copolymerization method or
The polystyrene seed or styrene-divinylbenzene seed of suspension polymerization preparation.
Polymer seeds are generally up to 60% weight of water slurry, preferential 10-55% weight, and stabilizer is usually
0.2-20% based on polymer seeds, preferential 1-15% weight.Monomer is generally up to 80% weight of water slurry, preferentially
10-60% weight, and stabilizer is typically based on the 0.1-30% weight of monomer, preferential 0.5-20% weight.Initiator is usual
Up to 20% weight of water slurry, preferential 0.2-10% weight, and stabilizer is typically based on the 0.05-10% of initiator
Weight, preferential 0.1-5% weight.
Polymerization temperature is preferably 70~90 DEG C, and more preferably 85 DEG C.In some embodiments of the invention, monomer is hydrophobic
Property vinyl monomer, initiator be oiliness initiator.
In some embodiments of the invention, monomer is selected from least one of following vinyl monomer: styrene, divinyl
Benzene, 2,4 dichloro benzene ethylene, acrylic acid, methyl methacrylate, methyl acrylate, ethyl acrylate, vinylacetate, methyl
Glycidyl acrylate or derivatives thereof.
In some embodiments of the invention, initiator be oil soluble peroxides and oil-soluble azo-compound and it
Mixture.
In some embodiments of the invention, oil soluble peroxides are benzoyl peroxide, lauroyl peroxide and mistake
Aoxidize t-butyl formate
In some embodiments of the invention, oil-soluble azo-compound be 2,2 '-azos bis- (2- methylbutyronitriles) and 2,
At least one of 2 '-azos bis- (2,4- methyl pentane nitriles).
In some embodiments of the invention, stabilizer is one or more kinds of surfactant.Further, table
Face activating agent is or mixtures thereof polyvinyl alcohol, polyvinylpyrrolidone, cellulose, hydroxypropyl cellulose.
Preparation method of the invention is described further combined with specific embodiments below, it is to be understood that the present invention
It is not limited to following embodiment:
Embodiment one
In the reaction kettle of 5L, 60g monodisperse polystyrene seed (its granularity is 4.6 microns, CV=3%) is added and is contained
Have in the 1000g deionized water of 1g polyvinylpyrrolidone, stirred evenly under 120 revs/min of mixing speed seed is outstanding
Supernatant liquid.It is uniformly mixed by 200g styrene and by 5g benzoyl peroxide, forms oily phase fluid.It is filled in jet flow suspension polymerization
Set the oily phase fluid of middle addition；Oily phase fluid is sprayed to be formed into seed suspension by the nozzle of jet flow suspension polymerization device
Oil droplet in liquid.Oil droplet average grain diameter is 50 microns.Under 80 DEG C of steady temperatures, 25min is reacted, is then cooled down, through centrifugation point
From, washing, drying etc. processes, polymer beads can be obtained.Using Beckman Coulter Counter measure its partial size and
Particle diameter distribution, partial size are 10 microns, CV (Coefficient of Variation)=2.8%.
Illustrate: above-mentioned material amounts being expanded into 2 times, 10 times, 50 times, 100 times, 500 times of productions respectively in proportion, per secondary
Cheng Jun is repeated 3 times, and having obtained partial size is 10 microns, and CV (Coefficient of Variation)=2.8% obtains polymer
Particle, no little particle generates, and particle size is uniform, and as depicted in figs. 1 and 2, the quality of production is stablized.
Embodiment two
In the reaction kettle of 5L, 50g monodisperse polystyrene seed (its granularity is 100nm, CV=2.8%) is added and is contained
Have in the 1000g deionized water of 1g polyvinyl alcohol, stirs evenly to obtain seed suspension liquid in 120 revs/min of mixing speeds；It will
500g styrene and 5g benzoyl peroxide are uniformly mixed, and form oily phase fluid.It is added in jet flow suspension polymerization device
Oily phase fluid；Oily phase fluid is sprayed into the oil to be formed into seed suspension liquid by the nozzle of jet flow suspension polymerization device
Drop.Oil droplet average grain diameter is 5 microns.The polymerization reaction under 85 DEG C of steady temperatures is reacted 30min, is then cooled down, through centrifugation point
From, washing, drying etc. processes, polymer beads can be obtained.Using Beckman Coulter Counter measure its partial size and
Particle diameter distribution, partial size 800nm, CV (Coefficient of Variation)=2.8%.
Embodiment three
In the reaction kettle of 5L, 60g monodisperse polystyrene seed (its granularity is 500 microns, CV=2.8%) is added
In 1000g deionized water containing 1g polyvinyl alcohol, seed suspension liquid is stirred evenly to obtain under 120 revs/min of mixing speed.
It is uniformly mixed by 200g styrene and by 6g benzoyl peroxide, forms oily phase fluid.In jet flow suspension polymerization device
Oily phase fluid is added；Oily phase fluid is sprayed to be formed into seed suspension liquid by the nozzle of jet flow suspension polymerization device
Oil droplet.Oil droplet average grain diameter is 25 microns.Under 80 DEG C of steady temperatures, 28min is reacted, is then cooled down, is centrifuged, washes
It the processes such as washs, dry, polymer beads can be obtained.Its partial size and partial size are measured using Beckman Coulter Counter
Distribution, partial size are 650 microns, CV (Coefficient of Variation)=2.2%.
Example IV
In the reaction kettle of 5L, 80g monodisperse polystyrene seed (its granularity is 0.55 micron, CV=3%) is added
In 1000g deionized water containing 1g polyvinyl alcohol, seed suspension liquid is stirred evenly to obtain under 120 revs/min of mixing speed.
Then 300g styrene and 5g benzoyl peroxide are uniformly mixed, form oily phase fluid.In jet flow suspension polymerization device
The oily phase fluid of middle addition；Oily phase fluid is sprayed to be formed into seed suspension liquid by the nozzle of jet flow suspension polymerization device
In oil droplet.Oil droplet average grain diameter is 5 microns.Under 85 DEG C of steady temperatures, 25min is reacted, is then cooled down, be centrifuged,
The processes such as washing, drying, can be obtained polymer beads.Its partial size and grain are measured using Beckman Coulter Counter
Diameter distribution, partial size are 1.5 microns, CV (Coefficient of Variation)=2.8%.
Embodiment five
In the reaction kettle of 5L, 100g monodisperse polystyrene seed (its granularity is 12 microns, CV=3%) is added and is contained
Have in the 1000g deionized water of 1g hydroxypropyl cellulose, seed suspension is stirred evenly to obtain under 120 revs/min of mixing speed
Liquid.200g styrene and 6g benzoyl peroxide are uniformly mixed, oily phase fluid is formed.In jet flow suspension polymerization device
Oily phase fluid is added；Oily phase fluid is sprayed to be formed into seed suspension liquid by the nozzle of jet flow suspension polymerization device
Oil droplet.Oil droplet average grain diameter is 45 microns.Under 78 DEG C of steady temperatures, 25min is reacted, is then cooled down, is centrifuged, washes
It the processes such as washs, dry, polymer beads can be obtained.Its partial size and partial size are measured using Beckman Coulter Counter
Distribution, partial size are 30 microns, CV (Coefficient of Variation)=2.9%.
Embodiment six
In the reaction kettle of 5L, 100g monodisperse polystyrene seed (its granularity is 50 microns, CV=3%) is added and is contained
Have in the 1000g deionized water of 1g hydroxypropyl cellulose, seed suspension is stirred evenly to obtain under 120 revs/min of mixing speed
Liquid.350g styrene and 5g benzoyl peroxide are uniformly mixed, oily phase fluid is formed.In jet flow suspension polymerization device
Oily phase fluid is added；Oily phase fluid is sprayed to be formed into seed suspension liquid by the nozzle of jet flow suspension polymerization device
Oil droplet.Oil droplet average grain diameter is 15 microns.Under 75 DEG C of steady temperatures, 35min is reacted, is then cooled down, is centrifuged, washes
It the processes such as washs, dry, polymer beads can be obtained.Its partial size and partial size are measured using Beckman Coulter Counter
Distribution, partial size are 95 microns, CV (Coefficient of Variation)=2.6%.
Embodiment seven
In the reaction kettle of 5L, by 60g monodisperse styrene-divinylbenzene seed, (its granularity is 1.5 microns, CV=
2.8%) it is added in the 1000g deionized water containing 1g polyvinyl alcohol, is stirred evenly under 120 revs/min of mixing speed
Seed suspension liquid.100g methyl acrylate and 5g lauroyl peroxide are uniformly mixed, oily phase fluid is formed.It suspends in jet flow poly-
It closes and oily phase fluid is added in reaction unit；Oily phase fluid is sprayed to form entrance by the nozzle of jet flow suspension polymerization device
Oil droplet in seed suspension liquid.Oil droplet average grain diameter is 10 microns.Under 80 DEG C of steady temperature, 28min is reacted, is then cooled down,
It the processes such as is centrifuged, washs, drying, polymer beads can be obtained.It is measured using Beckman Coulter Counter
Its partial size and particle diameter distribution, partial size are 5.0 microns, CV (Coefficient of Variation)=2.5%.
Embodiment eight
In the reaction kettle of 5L, 100g monodisperse polystyrene seed (its granularity is 950 microns, CV=3%) is added
In 1000g deionized water containing 1g hydroxypropyl cellulose, heated under 120 revs/min of mixing speed constant at 85 DEG C.It will
200g acrylic acid and 5g benzoyl peroxide are uniformly mixed, and form oily phase fluid.It is added in jet flow suspension polymerization device
Oily phase fluid；Oily phase fluid is sprayed into the oil to be formed into seed suspension liquid by the nozzle of jet flow suspension polymerization device
Drop.Oil droplet average grain diameter is 75 microns.Under 80 DEG C of steady temperatures, 30min is reacted, is then cooled down, be centrifuged, wash,
The processes such as drying, can be obtained polymer beads.Its partial size and partial size point are measured using Beckman Coulter Counter
Cloth, partial size are 1000 microns, CV (Coefficient of Variation)=2.7%.
Embodiment nine
In the reaction kettle of 5L, 100g monodisperse polystyrene seed (its granularity is 12 microns, CV=3%) is added and is contained
Have in the 1000g deionized water of 1g hydroxypropyl cellulose, seed suspension is stirred evenly to obtain under 120 revs/min of mixing speed
Liquid.200g styrene, 100g toluene and 6g benzoyl peroxide are uniformly mixed, oily phase fluid is formed.In jet flow suspension polymerisation
Oily phase fluid is added in reaction unit；Oily phase fluid is sprayed to be formed into kind by the nozzle of jet flow suspension polymerization device
Oil droplet in sub- suspension.Oil droplet average grain diameter is 45 microns.Under 78 DEG C of steady temperatures, 25min is reacted, is then cooled down, passed through
The processes such as centrifuge separation, washing, drying, can be obtained polymer beads.It is measured using Beckman Coulter Counter
Partial size and particle diameter distribution, partial size are 32 microns, CV (Coefficient of Variation)=3.0%.
Embodiment ten
In the reaction kettle of 5L, 100g monodisperse polystyrene seed (its granularity is 10 microns, CV=3%) is added and is contained
Have in the 1000g deionized water of 1g hydroxypropyl cellulose, is heated under 120 revs/min of mixing speed constant at 85 DEG C.It will
100g styrene, 200g divinylbenzene, 200g toluene and 5g benzoyl peroxide are uniformly mixed, and form oily phase fluid.It is spraying
It flows and oily phase fluid is added in suspension polymerization device；Oily phase fluid is sprayed by the nozzle of jet flow suspension polymerization device
Form the oil droplet entered in seed suspension liquid.Oil droplet average grain diameter is 5 microns.Under 80 DEG C of steady temperatures, 30min is reacted, so
After cool down, the processes such as be centrifuged, wash, drying, polymer beads can be obtained.Using Beckman Coulter
Counter measures its partial size and particle diameter distribution, and partial size is 40 microns, CV (Coefficient of Variation)=2.7%.
The other structures of jet flow suspension polymerization device and polymer beads preparation method according to an embodiment of the present invention
All it is to be understood that and easy to accomplish to those skilled in the art with operation, therefore is not described in detail.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. a kind of preparation method of polymer beads, which is characterized in that the preparation method comprises the following steps:
S10, polymer seeds are added in the aqueous solution containing stabilizer, are stirred evenly, form seed suspension liquid；
S20, monomer and initiator are uniformly mixed, form oily phase fluid；
S30, the oily phase fluid is formed into uniform oil droplet with eruption mode, and forms oil/water type with the seed suspension liquid and hangs
Supernatant liquid；
S40, one-step polymerization reaction, obtain the polymer beads.
2. the preparation method of polymer beads according to claim 1, which is characterized in that the polymer seeds are as follows: by
The polystyrene seed or styrene-divinylbenzene seed of emulsion polymerization, dispersion copolymerization method or suspension polymerization preparation.
3. the preparation method of polymer beads according to claim 1, which is characterized in that the monomer is hydrophobicity alkenes
Monomer, the initiator are oiliness initiator.
4. the preparation method of polymer beads according to claim 1, which is characterized in that the monomer is selected from following alkenes
At least one of monomer: styrene, divinylbenzene, 2,4 dichloro benzene ethylene, acrylic acid, methyl methacrylate, acrylic acid
Methyl esters, ethyl acrylate, vinylacetate, glycidyl methacrylate or derivatives thereof.
5. the preparation method of polymer beads according to claim 3, which is characterized in that the initiator is oil-soluble mistake
Oxide and oil-soluble azo-compound and their mixture.
6. the preparation method of polymer beads according to claim 5, which is characterized in that the oil soluble peroxides are
Benzoyl peroxide, lauroyl peroxide and peroxidating t-butyl formate.The oil-soluble azo-compound is that 2,2 '-azos are double
(2- methylbutyronitrile) and 2, at least one of 2 '-azos bis- (2,4- methyl pentane nitriles).
7. the preparation method of polymer beads according to claim 1, which is characterized in that the stabilizer is one kind or one
Kind or more surfactant.
8. the preparation method of polymer beads according to claim 7, which is characterized in that the surfactant is poly- second
Or mixtures thereof enol, polyvinylpyrrolidone, cellulose, hydroxypropyl cellulose.
9. the preparation method of polymer beads according to any one of claims 1 to 8, which is characterized in that step S30 is also wrapped
Include following steps:
S31, the oily phase fluid is added in jet flow suspension polymerization device；
S32, the oily phase fluid is sprayed to be formed into the seed by the nozzle of the jet flow suspension polymerization device
Oil droplet in suspension.
10. the preparation method of polymer beads according to claim 1, which is characterized in that the polymer beads are put down
Equal partial size is 100nm~1000 μm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961149A (en) * | 2020-07-07 | 2020-11-20 | 淮阴工学院 | Microsphere for supporting liquid crystal of display screen and preparation method thereof |
| CN114014983A (en) * | 2021-12-22 | 2022-02-08 | 苏州知益微球科技有限公司 | Polymer particle and preparation method and application thereof |
| CN114230694A (en) * | 2021-12-24 | 2022-03-25 | 苏州知益微球科技有限公司 | Preparation method of polymer conductive nickel microspheres |
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| CN102344517A (en) * | 2011-07-08 | 2012-02-08 | 阳承利 | Polymer microballoons and preparation method thereof |
| CN103360529A (en) * | 2012-03-28 | 2013-10-23 | 中国石油大学(北京) | Controllable synthetic method of micro-sized mono-disperse polystyrene microsphere |
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| CN102344517A (en) * | 2011-07-08 | 2012-02-08 | 阳承利 | Polymer microballoons and preparation method thereof |
| CN103360529A (en) * | 2012-03-28 | 2013-10-23 | 中国石油大学(北京) | Controllable synthetic method of micro-sized mono-disperse polystyrene microsphere |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961149A (en) * | 2020-07-07 | 2020-11-20 | 淮阴工学院 | Microsphere for supporting liquid crystal of display screen and preparation method thereof |
| CN114014983A (en) * | 2021-12-22 | 2022-02-08 | 苏州知益微球科技有限公司 | Polymer particle and preparation method and application thereof |
| CN114230694A (en) * | 2021-12-24 | 2022-03-25 | 苏州知益微球科技有限公司 | Preparation method of polymer conductive nickel microspheres |
| CN114230694B (en) * | 2021-12-24 | 2023-08-25 | 苏州知益微球科技有限公司 | Preparation method of polymer conductive nickel microspheres |
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