CN106349421A - Polymer microsphere and preparation method thereof - Google Patents
Polymer microsphere and preparation method thereof Download PDFInfo
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- CN106349421A CN106349421A CN201610737139.3A CN201610737139A CN106349421A CN 106349421 A CN106349421 A CN 106349421A CN 201610737139 A CN201610737139 A CN 201610737139A CN 106349421 A CN106349421 A CN 106349421A
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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
- C08F220/10—Esters
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- 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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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- C—CHEMISTRY; METALLURGY
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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Abstract
The invention discloses a preparation method of a polymer microsphere. The preparation method specially includes that suspension polymerization is performed on single phase by taking water phase as continuous phase under existence of an initiator and a suspension stabilizer and reaction and separation are performed to obtain the polymer microsphere; the single phase is composed of, by weight, 30-94wt% of a hydrophobic polymerizable radical monomer with double bond, 5-20wt% of a functional monomer and 1-50wt% of a cross-linked monomer; the functional monomer is at least one of formulas below: CH2=CR<1>C(O)OR<4>OH, R<1> refers to hydrogen or methyl, and R<4> refers to C2-C6 alkyl; the suspension stabilizer is composed of, by weight, 55-95wt% of a non-polymerizable suspension stabilizer and 5-45wt% of a polymerizable suspension stabilizer; weight ratio of deionized water to the monomer is 2-10:1; the suspension stabilizer is 0.1-10wt% of that of the deionized water. The invention further provides the polymer microsphere and the preparation method thereof, residual monomer of the polymer microsphere is within 100ppm in content and between 100nm to 1000mum in particle, and the polymer microsphere is easy to disperse in water.
Description
Technical field
The present invention relates to polymeric material field, more particularly, to a kind of residual monomer content is low, can rapid dispersion in water
Polymer microsphere and preparation method thereof.
Background technology
Polymer microsphere refers to diameter in nanometer to micron order, is shaped as spherical macromolecular material or macromolecule is combined
Material, its pattern can be solid, hollow, porous, dumbbell shape and Bulbus Allii Cepae type etc..Polymer microsphere have specific surface area big,
The strong feature of adsorptivity, has obtained the wide concern sent out in recent years, has all been widely used in every field.From coating, paper table
The versatile materials such as finishing coat, cosmetics all have application to high value added products such as medicament slow release controlled release, Separation of Proteins.
At present, the synthetic method of polymer microsphere mainly has emulsion polymerization, emulsifier-free emulsion polymerization, precipitation polymerization, dispersion poly-
Conjunction, seed swelling polymerization and suspension polymerisation etc..The particle diameter of the polymer microballoon of emulsion polymerization preparation is typically small, is nanoscale
To submicron order, but emulsion polymerization needs to use substantial amounts of emulsifying agent, and the microspheres product of therefore emulsion polymerization preparation is general all
It is directly directly to use in the form of an emulsion.The microspherulite diameter that emulsifier-free emulsion polymerization is obtained is typically slightly larger than emulsion polymerization, generally
In hundreds of nanometer to several microns.Emulsifier content used by soap-free emulsion is extremely low to be consolidated it is adaptable to prepare not even using emulsifying agent
Body product.Microspherulite diameter wider range that precipitation polymerization can be prepared, can be between 0.1-100 μm.The solvent that precipitation polymerization adopts
Typically polymerized monomer can only be dissolved and the polymer of generation can not be dissolved, therefore generate after polyreaction reaches to a certain degree
Polymer just obtains polymer microballoon after separating out from system.Dispersin polymerization is a kind of special precipitation polymerization, poly- using dispersion
Need to add a large amount of dispersants during the polymer microballoon closing preparation, such as Polyvinylpyrrolidone, polyvinyl alcohol, Polyethylene Glycol etc.,
Obtained polyalcohol microspherulite diameter is typically between 1-15 μm.Seed swelling polymerization is first with emulsifier-free emulsion polymerization or to divide
Dissipate the methods such as polymerization and make seed microsphere, then with monomer, cross-linking agent and inert molecule, swelling post polymerization is carried out to seed, thus making
Obtain the polymer microballoon of big particle diameter.Polymer microballoon between 1-100 μm for the particle diameter can be prepared using seed swelling polymerization method, and
Monodispersity is fine.Suspension polymerization is by the monomer dissolved with initiator in the presence of dispersant, is made by strong stirring
Monomer droplet suspends in water the method being polymerized, and preparation process is convenient, and prepared microspherulite diameter can be in submicron to milli
Meter level.
Cn101787138a adopts emulsion dispersion solvent evaporation method, under high velocity agitation, polymethyl methacrylate is molten
Liquid is added in polyvinyl alcohol water solution by certain flow velocity, forms uniform, stable emulsion, volatilize through ultrasonic disperse, solvent,
After the steps such as sucking filtration, washing, prepare a kind of monodisperse micron-level poly (methyl methacrylate) micro-sphere, its particle diameter is in 10-100
Between μm.
Cn1362973a discloses a kind of method preparing monodisperse polymer particles.With Polyvinylpyrrolidone or fibre
The plain ether of dimension is stabilizer, in the presence of resist in place, by by polymer seeds using multi-step swelling after the method be polymerized again
Obtain monodisperse polymer particles.The method complex steps, time-consuming, and need to use a large amount of organic solvents.
Cn 103554376a discloses a kind of preparation method of monodisperse cross-linked poly (methyl methacrylate) micro-sphere.First
By methyl methacrylate and initiator for reaction obtained solution a, then methyl methacrylate is reacted obtained solution with cross-linking agent
B, the monodisperse cross-linked microsphere that will just can collect after a and two kinds of solution hybrid reactions of b in product.
Cn 102786635 discloses a kind of preparation method of monodispersed large grain-size crosslinked polymethylmethacrylaparticles microsphere.
It is that polymethyl methacrylate bulb is obtained by dispersin polymerization first, poly- heating up by seeds swelling and after reaching required particle diameter
Close and be obtained.
Although crosslinked or noncrosslinking polymer microsphere can be prepared using above method, adopt hydrophobic monomer system
Standby polymer microsphere, because property compatible with water is bad, is therefore placed in water and can swim in for a long time on the water surface it is difficult to quick divide
Dissipate.
Content of the invention
The present invention provides the preparation method of a kind of polymer microsphere and this polymer microsphere.It is prepared by the method for the present invention
The polymer microsphere residual monomer content obtaining is within 100ppm, particle diameter is between 100nm to 1000 μm, and is easy in water
Middle dispersion.
The technical scheme is that a kind of preparation method of polymer microsphere, described method is particularly as follows: single phase exists
In the presence of initiator, suspension stabilizer, with aqueous phase as continuous phase, carry out suspension polymerisation, after reacting and separating, obtain macromolecule
Microsphere；
Described single phase is by the function of the hydrophobic polymerizable free radical monomer with double bond for the 30-94wt%, 5-20wt%
Monomer, the cross-linking monomer composition of 1-50wt%；
Described function monomer is at least one with formula: ch2=cr1c(o)or4Oh, wherein r1For hydrogen or
Methyl, r4For c2-c6Alkyl；
Described suspension stabilizer is polymerisable by the non-polymerisable suspension stabilizer of 55-95wt% and 5-45wt%'s
Suspension stabilizer forms；
The weight of described deionized water and single phase is than for 2～10:1；Described suspension stabilizer is equivalent to deionization
The 0.1-10wt% of water.
In the preparation method of above-mentioned polymer microsphere, comprise the following steps:
Step 1: single phase and initiator mixture mixed dissolution obtain oil-phase solution a；
Step 2: suspension stabilizer is dissolved in deionized water, forms aqueous phase solution b；
Step 3: adopt homogenizer homogenizing after liquid b compatible with water for oil-phase solution a is mixed, homogenizer rotating speed is 500-
20000rpm, forms suspension c after homogenizing；
Step 4: suspension c is transferred in polyplant, after logical nitrogen, is first polymerized 1-10 hour at 55-75 DEG C, then
70-90 DEG C of polymerization 2-10 hour, prepared polymer microsphere suspension；
Step 5: prepared polymer microsphere suspension is separated, washs and be dried to obtain polymer microsphere powder.
In the preparation method of above-mentioned polymer microsphere, the described hydrophobic polymerizable free radical monomer with double bond is tool
There is ch2=cr1r2The compound of structure, wherein r1For hydrogen or methyl, r2For phenyl, aminomethyl phenyl, ethylphenyl or-c (o) or3,
Wherein r3For c1-c18Alkyl.
In the preparation method of above-mentioned polymer microsphere, the described hydrophobic polymerizable free radical monomer with double bond is
(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) octadecyl ester, benzene second
One or more of alkene, methyl styrene, ethyl styrene.
In the preparation method of above-mentioned polymer microsphere, described function monomer is Hydroxypropyl acrylate, acrylic acid hydroxyl
One of ethyl ester, hy-droxybutyl, hydroxyethyl methylacrylate or Hydroxypropyl methacrylate.
In the preparation method of above-mentioned polymer microsphere, described cross-linking monomer is divinylbenzene, ethylene glycol bisthioglycolate (first
Base) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, dipropylene glycol two (first
Base) acrylate, tripropylene glycol two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, polypropylene glycol two (first
Base) acrylate, 1,4- butanediol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, (methyl) propylene
Allyl propionate, trimethylolpropane tris (methyl) acrylate, ethoxyquin trimethylolpropane tris (methyl) acrylate, season penta
One or more of tetrol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate combine.
In the preparation method of above-mentioned polymer microsphere, the weight of initiator is the 0.1-10wt% of single phase weight,
Initiator mixture is made up of than the low temperature initiators for 1:9-9:1 and high-temperature initiator weight；Low temperature initiators are drawn with high temperature
Send out agent 10 hours half life temperatures differ 8 DEG C and more than.
In the preparation method of above-mentioned polymer microsphere, described initiator is peroxy dicarbonate two (3- methoxyl group
Butyl ester) and tert-Butyl peroxypivalate combination, the combination of peroxide-butyl carbonate and decanoyl peroxide, peroxidating
New heptanoic acid tert-butyl ester and the combination of benzoyl peroxide, the combination of lauroyl peroxide and benzoyl peroxide, azo two different heptan
Nitrile and the combination of AMBN, or the combination of azodiisobutyronitrile and benzoyl peroxide.
In the preparation method of above-mentioned polymer microsphere, non-polymerisable suspension stabilizer be specially polyvinyl alcohol, poly- third
One of olefin(e) acid, vinylpyrrolidone/vinyl acetate copolymer, hydroxypropyl cellulose, silica sol；Polymerisable
Suspension stabilizer is specially methoxypolyethylene glycol (2000) acrylate, methoxypolyethylene glycol (950) methacrylate, poly- second
One of glycol methyl ether (480) acrylate.
Meanwhile, the invention also discloses a kind of polymer microsphere, according to the preparation method preparation of above-mentioned polymer microsphere
Obtain, described polymer microsphere residual monomer content is within 100ppm, particle diameter between 100nm to 1000 μm, and
In water, jitter time is not more than 25min.
Beneficial effects of the present invention are as follows:
The present invention provide polymer microsphere residual monomer content within 100ppm, particle diameter 100nm to 1000 μm it
Between, function monomer, suspension stabilizer combination, can make the microsphere of preparation rapid dispersion in water simultaneously.Solve tradition by outstanding
The problem of the polymer microballoon dispersive property difference that floating polymerization obtains.
Specific embodiment
With reference to specific embodiment, technical scheme is described in further detail, but do not constitute right
Any restriction of the present invention.
Embodiment 1
Weigh 23.7g methyl methacrylate, 6g 2-(Acryloyloxy)ethanol, 0.3g ethylene glycol dimethacrylate, mixing
It is uniformly mixing to obtain mix monomer.Weigh 0.003g peroxy dicarbonate two (3- methoxybutyl) and 0.027g peroxidating is new
Pentanoate is added in above-mentioned mix monomer, is uniformly mixed and obtains oil-phase solution a.
Weigh 0.2g polyvinyl alcohol, and 0.1g methoxypolyethylene glycol (2000) acrylate being added in 300g water,
Stirring makes polyvinyl alcohol be dissolved completely in water, obtains aqueous solution b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer homogenizing 10 minutes at 500 rpm, obtains suspension c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
It is polymerized 1 hour to 55 DEG C, be then warming up to 70 DEG C again and be polymerized 10 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
To filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, after vacuum drying, obtains final product.
Embodiment 2
Weigh 45g styrene, 9g Hydroxypropyl acrylate and 6g divinylbenzene, mixing and stirring obtains mix monomer.
Weigh 0.18g peroxide-butyl carbonate and 0.42g decanoyl peroxide is added in above-mentioned mix monomer, stirring mixing
Uniformly obtain oil-phase solution a.
Weigh 0.33g vinylpyrrolidone/vinyl acetate copolymer and 0.27g methoxypolyethylene glycol (950) methyl
Acrylate is simultaneously added in 300g water, and stirring makes vinylpyrrolidone/vinyl acetate copolymer be dissolved completely in water, obtains
To aqueous solution b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer under 1000rpm homogenizing 5 minutes, obtain suspension c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
To 65 DEG C of polyase 13 hours, then it is warming up to 80 DEG C again and is polymerized 8 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
Filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, obtains final product after vacuum drying.
Embodiment 3
Weigh 33g styrene, 30g methyl styrene, 9g Hydroxypropyl methacrylate and 18g trimethylolpropane tris third
Olefin(e) acid ester, mixing and stirring obtains mix monomer.Weigh the new heptanoic acid tert-butyl ester of 1.35g peroxidating and 1.35g benzoyl peroxide
Formyl is added in above-mentioned mix monomer, is uniformly mixed and obtains oil-phase solution a.
Weigh 3.1g hydroxypropyl cellulose and 1.4g methoxypolyethylene glycol (480) acrylate and be added to 300g water
In, stirring makes hydroxypropyl cellulose be dissolved completely in water, obtains aqueous solution b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer under 5000rpm homogenizing 5 minutes, obtain suspension c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
It is polymerized 5 hours to 65 DEG C, be then warming up to 85 DEG C again and be polymerized 6 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
Filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, obtains final product after vacuum drying.
Embodiment 4
Weigh 28g ethyl styrene, 20g methyl styrene, 30g styrene, 6g hy-droxybutyl and 36g season penta 4
Alcohol tetraacrylate, mixing and stirring obtains mix monomer.Weigh 4.5g lauroyl peroxide and 1.5g benzoyl peroxide first
Acyl is added in above-mentioned mix monomer, is uniformly mixed and obtains oil-phase solution a.
Weigh 9g silica sol and 3g methoxypolyethylene glycol (480) acrylate and be added in 300g water, stir
Mix and so that silica sol is thoroughly dispersed in water, obtain aqueous solution b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer under 10000rpm homogenizing 5 minutes, obtain suspension c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
To 70 DEG C of polymerase 17 hours, then it is warming up to 85 DEG C again and is polymerized 4 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
Filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, obtains final product after vacuum drying.
Embodiment 5
Weigh 67.5g butyl acrylate, 7.5 hydroxyethyl methylacrylates and 75g diethylene glycol diacrylate, mixing
It is uniformly mixing to obtain mix monomer.Weigh 13.5g 2,2'-Azobis(2,4-dimethylvaleronitrile) and 1.5g AMBN is added to above-mentioned mixing
In monomer, it is uniformly mixed and obtains oil-phase solution a.
Weigh 28.5g vinylpyrrolidone/vinyl acetate copolymer and 1.5g methoxypolyethylene glycol (950) acrylic acid
Ester is simultaneously added in 300g water, and stirring makes vinylpyrrolidone/vinyl acetate copolymer be thoroughly dispersed in water, obtains water-soluble
Liquid b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer under 15000rpm homogenizing 5 minutes, obtain suspension c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
It is polymerized 10 hours to 65 DEG C, be then warming up to 85 DEG C again and be polymerized 2 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
To filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, after vacuum drying, obtains final product.
Embodiment 6
Weigh 54g octadecyl ester, 3g 2-(Acryloyloxy)ethanol and 3g tripropylene glycol diacrylate, mix and blend
Uniformly obtain mix monomer.Weigh 0.3g azodiisobutyronitrile and 0.3 benzoyl peroxide be added in above-mentioned mix monomer,
It is uniformly mixed and obtain oil-phase solution a.
Weigh 0.8g polyvinyl alcohol and and 0.1g methoxypolyethylene glycol (2000) acrylate be added in 300g water, stir
Mix and so that polyvinyl alcohol is dissolved completely in water, obtain aqueous solution b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer under 20000rpm homogenizing 5 minutes, obtain suspension c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
It is polymerized 10 hours to 75 DEG C, be then warming up to 85 DEG C again and be polymerized 10 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
To filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, after vacuum drying, obtains final product.
Comparative example 1
Weigh 27g methyl methacrylate, 1.5g 2-(Acryloyloxy)ethanol and 1.5g ethylene glycol dimethacrylate, mix
Conjunction is uniformly mixing to obtain mix monomer.Weigh 0.6g benzoyl peroxide to be added in above-mentioned mix monomer, be uniformly mixed
Obtain oil-phase solution a.
Weigh 1.5g polyvinyl alcohol and be added in 300g water, stirring makes polyvinyl alcohol be dissolved completely in water, obtains water
Solution b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer under 7000rpm emulsifying 5 minutes, suspended
Liquid c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
To 80 DEG C of polyase 13 hours, then it is warming up to 90 DEG C again and is incubated 3 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
Filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, obtains final product after vacuum drying.
Comparative example 2
Weigh 28.5g methyl methacrylate, 1.5g ethylene glycol dimethacrylate, mixing and stirring is mixed
Monomer.Weigh 0.6g benzoyl peroxide to be added in above-mentioned mix monomer, be uniformly mixed and obtain oil-phase solution a.
Weigh 1.4g polyvinyl alcohol and 0.1g methoxypolyethylene glycol (2000) acrylate and be added in 300g water, stir
Mix and so that polyvinyl alcohol is dissolved completely in water, obtain aqueous solution b.
Oil-phase solution a is mixed with aqueous solution b, using homogenizer under 7000rpm emulsifying 5 minutes, suspended
Liquid c.
Suspension c is transferred to in agitator, the round-bottomed flask of nitrogen device, thermometer and condensing tube, heats up
To 80 DEG C of polyase 13 hours, then it is warming up to 90 DEG C again and is incubated 3 hours.It is down to room temperature after the completion of polymerization, obtained using filtration under diminished pressure
Filter cake, filter cake is respectively adopted deionized water and washing with alcohol 3 times, obtains final product after vacuum drying.
Particle diameter: characterized using laser particle analyzer.
Residual monomer content: polymer microsphere residual monomer content is characterized using GC headspace injection.
Jitter time in water: weigh 1g microsphere and be added in 99g deionized water, carried out using 400 rpms of speed
Stirring, record powder is thoroughly dispersed in water and the water surface substantially floats mixing time needed for powder, when being designated as in water dispersion
Between.
Jitter time in table 1 polymer microsphere particle diameter, residual monomer content and water
| Particle diameter (μm) | Residual monomer content (ppm) | Jitter time (min) in water | |
| Embodiment 1 | 900.1 | 64 | 15 |
| Embodiment 2 | 100.3 | 48 | 12 |
| Embodiment 3 | 50.8 | 20 | 17 |
| Embodiment 4 | 5.4 | 33 | 20 |
| Embodiment 5 | 0.8 | 56 | 21 |
| Embodiment 6 | 0.2 | 15 | 23 |
| Comparative example 1 | 11.3 | 2100 | 40 |
| Comparative example 2 | 13.2 | 1950 | 37 |
The product of the present invention overcomes and is difficult scattered problem in water, and reduces its residual monomer content, passes through
Improve, so that this product all can be preferably disperseed in water, oil.
Trace it to its cause and be, present invention employs hydrophobic monomer, function monomer and composite suspension dispersant package to reach
This effect.Overcome the polymer microsphere that the hydrophobic monomer in conventional art is main component and be difficult scattered defect in water.
In the present invention, function monomer and polymerisable suspension stabilizer are indispensable, and function monomer consumption is less,
The hydrophilic of microsphere particle can be improved.Polymerisable suspension stabilizer can be uniformly distributed in microsphere particle, was reacting
Maintain reaction system stable in journey.Particle surface moistening can quickly be made when water-dispersible, the moisture improving granule dissipates effect
Really, prevent between granule assemble and particles float the surface of water nonwetting for a long time, do not disperse.
This achievement can enable this product be applied in different dicyandiamide solutions, greatly expands range of application.
Above-described be only presently preferred embodiments of the present invention, all made in the range of the spirit and principles in the present invention appoint
What modification, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of polymer microsphere it is characterised in that: described method is particularly as follows: single phase is in initiator, outstanding
In the presence of floating stabilizer, with aqueous phase as continuous phase, carry out suspension polymerisation, after reacting and separating, obtain polymer microsphere；
Described single phase by the hydrophobic polymerizable free radical monomer with double bond for the 30-94wt%, the function monomer of 5-20wt%,
The cross-linking monomer composition of 1-50wt%；
Described function monomer is at least one with formula: ch2=cr1c(o)or4Oh, wherein r1For hydrogen or methyl,
r4For c2-c6Alkyl；
The non-polymerisable suspension stabilizer by 55-95wt% for the described suspension stabilizer and the polymerisable suspension of 5-45wt%
Stabilizer forms；
The weight of described deionized water and single phase is than for 2～10:1；Described suspension stabilizer is equivalent to deionized water
0.1-10wt%.
2. the preparation method of polymer microsphere according to claim 1 is it is characterised in that comprise the following steps:
Step 1: single phase and initiator mixture mixed dissolution obtain oil-phase solution a；
Step 2: suspension stabilizer is dissolved in deionized water, forms aqueous phase solution b；
Step 3: adopt homogenizer homogenizing after liquid b compatible with water for oil-phase solution a is mixed, homogenizer rotating speed is 500-
20000rpm, forms suspension c after homogenizing；
Step 4: suspension c is transferred in polyplant, after logical nitrogen, is first polymerized 1-10 hour at 55-75 DEG C, then in 70-90
DEG C polymerization 2-10 hour, prepared polymer microsphere suspension；
Step 5: prepared polymer microsphere suspension is separated, washs and be dried to obtain polymer microsphere powder.
3. the preparation method of polymer microsphere according to claim 1 is it is characterised in that described can with the hydrophobic of double bond
Polymerization free radical monomer is to have ch2=cr1r2The compound of structure, wherein r1For hydrogen or methyl, r2For phenyl, aminomethyl phenyl,
Ethylphenyl or-c (o) or3, wherein r3For c1-c18Alkyl.
4. the preparation method of polymer microsphere according to claim 3 is it is characterised in that described can with the hydrophobic of double bond
Polymerization free radical monomer is (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) propylene
One or more of sour octadecane ester, styrene, methyl styrene, ethyl styrene.
5. the preparation method of polymer microsphere according to claim 1 is it is characterised in that described function monomer is propylene
In sour hydroxypropyl acrylate, 2-(Acryloyloxy)ethanol, hy-droxybutyl, hydroxyethyl methylacrylate or Hydroxypropyl methacrylate one
Kind.
6. the preparation method of polymer microsphere according to claim 1 is it is characterised in that described cross-linking monomer is diethyl
Alkenyl benzene, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid
Ester, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylic acid
Ester, polypropylene glycol two (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, 1,6-HD two (methyl) propylene
Acid esters, (methyl) allyl acrylate, trimethylolpropane tris (methyl) acrylate, ethoxyquin trimethylolpropane tris (first
Base) acrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, in dipentaerythritol acrylate one
Plant or multiple combination.
7. the preparation method of polymer microsphere according to claim 1 is it is characterised in that the weight of initiator is single phase
The 0.1-10wt% of weight, initiator mixture is made up of than the low temperature initiators for 1:9-9:1 and high-temperature initiator weight；Low
Warm initiator differ with 10 hours half life temperatures of high-temperature initiator 8 DEG C and more than.
8. the preparation method of polymer microsphere according to claim 7 is it is characterised in that described initiator is peroxidating
Two carbonic acid two (3- methoxybutyl) and combination, peroxide-butyl carbonate and the peroxidating of tert-Butyl peroxypivalate
The combination of caprinoyl, combination, lauroyl peroxide and the benzoyl peroxide of the new heptanoic acid tert-butyl ester of peroxidating and benzoyl peroxide
Combination, the combination of 2,2'-Azobis(2,4-dimethylvaleronitrile) and AMBN, or the combination of azodiisobutyronitrile and benzoyl peroxide.
9. the preparation method according to the arbitrary described polymer microsphere of claim 1 to 8 is it is characterised in that non-polymerisable outstanding
Floating stabilizer is specially polyvinyl alcohol, polyacrylic acid, vinylpyrrolidone/vinyl acetate copolymer, hydroxypropyl cellulose, glue
One of body silicon dioxide；Polymerisable suspension stabilizer is specially methoxypolyethylene glycol (2000) acrylate, poly- second two
One of alcohol methyl ether (950) methacrylate, methoxypolyethylene glycol (480) acrylate.
10. a kind of polymer microsphere is it is characterised in that preparation side according to the arbitrary described polymer microsphere of claim 1 to 9
Method prepares, described polymer microsphere residual monomer content is within 100ppm, particle diameter between 100nm to 1000 μm,
And jitter time is not more than 25min in water.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108046832A (en) * | 2017-12-08 | 2018-05-18 | 西能化工科技(上海)有限公司 | Keep the temperature lacquer and preparation method thereof |
| CN108070060A (en) * | 2017-12-29 | 2018-05-25 | 广州瀚东新材料科技有限公司 | A kind of microballoon powder of the high cross-linked polymer of micron order and its preparation method and application |
| CN108276854A (en) * | 2017-12-08 | 2018-07-13 | 西能化工科技(上海)有限公司 | Phase-change microcapsule and its preparation method and application |
| CN110721633A (en) * | 2019-10-15 | 2020-01-24 | 江苏科技大学 | Compound dispersant, preparation method and application thereof |
| CN111690153A (en) * | 2020-05-14 | 2020-09-22 | 复旦大学 | Preparation method of polymer hydrogel microspheres |
| CN113736451A (en) * | 2021-10-08 | 2021-12-03 | 无锡瑞格生物科技有限责任公司 | Preparation method of monodisperse magnetic fluorescent microspheres |
| CN114456326A (en) * | 2022-02-17 | 2022-05-10 | 武汉纺织大学 | Carboxylated polystyrene nano-microsphere and preparation method and application thereof |
| CN116284561A (en) * | 2021-12-21 | 2023-06-23 | 中国石油化工股份有限公司 | Sustained-release tackifying polymer microsphere and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429263A (en) * | 2007-11-05 | 2009-05-13 | 日东电工株式会社 | Production method of porous resin particle having hydroxyl group |
| CN102010476A (en) * | 2010-11-02 | 2011-04-13 | 江南大学 | Method for preparing monodisperse polymer microsphere by irradiation polymerization of ultraviolet light |
-
2016
- 2016-08-26 CN CN201610737139.3A patent/CN106349421B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429263A (en) * | 2007-11-05 | 2009-05-13 | 日东电工株式会社 | Production method of porous resin particle having hydroxyl group |
| CN102010476A (en) * | 2010-11-02 | 2011-04-13 | 江南大学 | Method for preparing monodisperse polymer microsphere by irradiation polymerization of ultraviolet light |
Non-Patent Citations (1)
| Title |
|---|
| 李峰等: "一种基于高吸油树脂与聚丙烯复合吸油材料", 《河北工业大学学报》 * |
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| CN108046832B (en) * | 2017-12-08 | 2020-12-08 | 西能化工科技(上海)有限公司 | Heat-preservation stone-like paint and preparation method thereof |
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| CN108070060B (en) * | 2017-12-29 | 2020-09-08 | 广州五行材料科技有限公司 | Microsphere powder of micron-level high-crosslinked polymer and preparation method and application thereof |
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