CN108948557A - A kind of preparation method of fluorescent magnetic microspheres - Google Patents
A kind of preparation method of fluorescent magnetic microspheres Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of fluorescent magnetic microspheres, it include: that fluorescent molecule and hydrophobing agent are added in dispersing agent or solvent mixed solution, it stirs evenly, forms fluorescent monomer suspension, fluorescent monomer weight accounts for 60% or less fluorescent monomer suspension weight；The synthesis of magnetic particle: soluble trivalent iron salt and enuatrol are reacted in the system of n-hexane and ethyl alcohol, obtain dry iron oleate；Iron oleate and fluorescent monomer are added in stabilizer/solvent mixed solution, stirred evenly, iron oleate fluorescent monomer suspension is formed；Polymer seeds are added in the aqueous solution containing dispersing agent, is sufficiently stirred, forms evenly dispersed seed suspension liquid；At the polymerization temperature, iron oleate fluorescent monomer suspension and initiator are added in seed suspension liquid makes seed growth, after reaching preset microspherulite diameter stops that iron oleate fluorescent monomer suspension and initiator is added, heat up to obtain fluorescent magnetic microspheres.
Description
Technical field
The present invention relates to a kind of preparation methods of polymer microsphere, and in particular to a kind of preparation side of fluorescent magnetic microspheres
Method.
Background technique
Fluorescent magnetic microspheres refer generally to microsphere surface indicate structure in fluorescent material and magnetisable material or microsphere contain it is glimmering
The microballoon of light and magnetisable material (as embedded or polymerizeing), can be excited fluorescence by outside energy stimulation and magnetism is presented.It is one
Kind is loaded with the composite functional microballoon of fluorescent molecule and magnetic molecule, and shape is mostly spherical shape.
Fluorescent magnetic microspheres have a wide range of applications in bio-separation engineering and biomedical engineering, especially mention in nucleic acid
Take, cell separation, immobilised enzymes, immune detection, targeted drug, protein and enzyme isolate and purify etc. have in fields it is tempting
Application prospect.
About fluorescent magnetic microspheres preparation method there are many, be generally divided into physisorphtion, self-assembly method, embedding hair,
Chemical bonding, copolymerization method etc., wherein fluorescent material is exposed to microballoon appearance in physisorphtion, be easy by external environment and
The influence of medium, stability and reproducibility are all bad, and microballoon properties made from copolymerization method are greatly improved, be most by
One of method of welcome.Often particle diameter distribution is wider for the fluorescent magnetic microspheres of prior art preparation, and stability is also to be improved.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defects of the prior art, provide a kind of fluorescent magnetic microspheres preparation side
Method, the fluorescent microsphere size tunable obtained by the preparation method and uniform particle diameter, fluorescent magnetic microspheres stability are high.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
The embodiment of the invention provides a kind of preparation methods of fluorescent magnetic microspheres, comprising steps of
(1) synthesis of fluorescent monomer:
Fluorescent molecule one of is selected from the group or a variety of: naphthalimide dyestuff, fluoresceins dyestuff, two pyrrole of boron fluoride
Cough up class dyestuff, naphthalenes dyestuff, fluorenes-diazosulfide copolymer fluorescent dye, nitrobenzoxadiazole, calcein；Two (three
Chloromethanes) carbonic ester；
Hydrophobing agent is selected from the group: hexadecane, n-octyl alcohol；
Above-mentioned reactant is added in solvent, is stirred evenly, fluorescent monomer suspension is formed, fluorescent monomer weight accounts for fluorescence
60% or less monomer suspension weight；
(2) synthesis of magnetic particle:
At 70-90 DEG C, soluble trivalent iron salt and enuatrol are reacted in the system of n-hexane and ethyl alcohol, vacuum
It is dry, obtain dry iron oleate；
(3) magnetic fluorescence monomer suspension is prepared:
Iron oleate and fluorescent monomer are added in stabilizer and solvent mixed solution, stirred evenly, iron oleate fluorescence is formed
Monomer suspension；
(4) polymer seeds suspension is prepared:
Polymer seeds are added in the aqueous solution containing dispersing agent, is sufficiently stirred, forms evenly dispersed seed suspension
Liquid, polymer seeds account for 60% or less seed suspension liquid weight；
(5) cause polymerization:
At the polymerization temperature, iron oleate fluorescent monomer suspension and initiator are added in seed suspension liquid keeps seed raw
It is long, after reaching preset microspherulite diameter stop that iron oleate fluorescent monomer suspension and initiator is added, heating polymerization for the first time is anti-
It answers, fluorescence iron oleate polymer composite microsphere can be obtained；Second of heating, makes iron oleate pyrolysis synthesizing magnetic nanometer
Fluorescent magnetic microspheres can be obtained in particle.
In above scheme, the initiator is azo water soluble starter.
In above scheme, the initiator is two isobutyl imidazoline hydrochloride of azo or azo diisobutyl amidine hydrochloride.
In above scheme, the polymer seeds are polystyrene seed or styrene-divinylbenzene seed, the list
Body is selected from styrene, divinylbenzene, 2,4 dichloro benzene ethylene, acrylic acid, methyl methacrylate, methyl acrylate, acrylic acid
One of ethyl ester, vinylacetate, glycidyl methacrylate or derivatives thereof are a variety of.
In above scheme, the solvent is the lower alcohol that carbon atom number is C1-C3.
In above scheme, the temperature of heating is 95-110 DEG C for the first time, and the temperature of second of heating is 300-350 DEG C.
In above scheme, the particle size of fluorescent magnetic microspheres is 0.1-5000 μm.
In above scheme, the molar ratio of the solubility trivalent iron salt and enuatrol is 1:2-1:7.
Advantageous effects of the invention:
The uniform particle diameter of the fluorescent magnetic microspheres of the method preparation of the embodiment of the present invention, microspherulite diameter is controllable, stability is strong,
Fluorescence efficiency is high, while having magnetic and fluorescence two kinds of composite performances, and by selecting suitable solvent and initiator, control
The ladder-elevating temperature temperature of reaction achievees the effect that uniform particle diameter and partial size are wide in range and controllable, and the microballoon of preparation is in label, tracer, inspection
The biological medicines such as survey are received with potential using value.
Specific embodiment
The invention will be further described combined with specific embodiments below.Following embodiment is only used for clearly illustrating
Technical solution of the present invention, and not intended to limit the protection scope of the present invention.
Embodiment 1
A kind of fluorescent magnetic microspheres preparation method, comprising steps of weighing 0.01g (0.5wt%) naphthalimide fluorescent point
Son is added in super-hydrophobic dose of hexadecane of 0.1g, and ultrasonic mixing is uniform, takes 0.002g (0.1wt%) or 0.01g (0.5wt%)
Or the Surfactant SDS (SDS) of 0.02g (1wt%) disperses in ethanol respectively, total volume 9mL, vibration
It swings and is completely dissolved；Dry iron oleate is prepared, FeCl is taken3With enuatrol be added flask in, and into flask be added dehydrated alcohol and
The mixed solution of n-hexane, after dissolution, 70 DEG C of heating stirring 4h, the iron oleate for filtering wet, then wet iron oleate is placed in 80
DEG C, drying for 24 hours, obtains dry iron oleate in vacuum oven under conditions of vacuum degree is 100Pa；By iron oleate, fluorescent monomer
It is added in ethyl alcohol, is dispersed with stirring uniformly, it is spare to form iron oleate fluorescent monomer suspension；Styrene-divinylbenzene is copolymerized
In species (0.5 μm of granularity, CV=3%) aqueous solution of the addition containing dextrin of son, it is sufficiently stirred, it is outstanding forms evenly dispersed seed
Supernatant liquid, styrene diethylene benzene copoly mer seed account for the 45% of seed suspension liquid weight；Dextrin weight is polymer seeds weight
The 8% of amount；Emulsification after benzoyl peroxide is added in the aqueous solution containing polyvinylpyrrolidone, forms initiator suspension
It is spare；At 70 DEG C, iron oleate fluorescent monomer suspension and initiator suspension are added in seed suspension liquid in 60 minutes
Make seed growth, wherein it is 6.8g/min that speed, which is added, in iron oleate fluorescent monomer suspension, and initiator suspension is added speed and is
1.01g/min after reaching preset microspherulite diameter stops that iron oleate fluorescent monomer suspension and initiator suspension, heating is added
To 110 DEG C, the reaction was continued 30min is to get arriving fluorescence iron oleate polymer composite microsphere；It is warming up to 320 DEG C for the second time, and is protecting
It holds and keeps 2-3h at 320 DEG C, make iron oleate pyrolysis synthesizing magnetic nano particle, fluorescent magnetic microspheres can be obtained.This
Place's magnetic nanoparticle is ferroso-ferric oxide.Use that BeckmanCounter measures its partial size and particle diameter distribution obtains: partial size 1.5
μm, CV (coefficientofvariation) is 2.9%, and magnetic ferroferric oxide accounts for the 40% of entire microspheres weight, microballoon
Fluorescent emission peak position in 410nm, after fluorescent magnetic microspheres are placed 6 months, 13 months, discovery microballoon dispersibility and fluorescence
Significant change can be showed no.
Comparative example
A kind of fluorescent magnetic microspheres preparation method, comprising steps of weighing 0.01g (0.5wt%) naphthalimide fluorescent point
The Surfactant SDS of son, 0.002g (0.1wt%) or 0.01g (0.5wt%) or 0.02g (1wt%)
(SDS) disperse respectively in ethanol, total volume 9mL, oscillation is completely dissolved；Dry iron oleate is prepared, FeCl is taken3And enuatrol
It is added in flask, and the mixed solution of dehydrated alcohol and n-hexane is added into flask, after dissolution, 70 DEG C of heating stirring 4h, mistake
The iron oleate for filtering wet, then wet iron oleate is placed in 80 DEG C, drying in vacuum oven under conditions of vacuum degree is 100Pa
For 24 hours, dry iron oleate is obtained；Iron oleate, fluorescent monomer are added in ethyl alcohol, is dispersed with stirring uniformly, forms iron oleate fluorescence list
Liquid suspension is spare；By (0.5 μm of granularity, CV=3%) water of the addition containing dextrin of styrene diethylene benzene copoly mer seed
It in solution, is sufficiently stirred, forms evenly dispersed seed suspension liquid, it is outstanding that styrene diethylene benzene copoly mer seed accounts for seed
The 45% of supernatant liquid weight；Dextrin weight is the 8% of polymer seeds weight；Benzoyl peroxide addition is contained into polyvinyl pyrrole
Emulsification after in the aqueous solution of alkanone, it is spare to form initiator suspension；At 70 DEG C, by iron oleate fluorescent monomer in 60 minutes
Suspension and initiator suspension, which are added in seed suspension liquid, makes seed growth, wherein iron oleate fluorescent monomer suspension is added
Speed is 6.8g/min, and it is 1.01g/min that speed, which is added, in initiator suspension, after reaching preset microspherulite diameter stops that oil is added
Sour iron fluorescent monomer suspension and initiator suspension, are warming up to 110 DEG C, and the reaction was continued, and 30min gathers to get to fluorescence iron oleate
Close object complex microsphere；It is warming up to 320 DEG C for the second time, and keeps 2-3h in the case where being kept for 320 DEG C, synthesizes iron oleate pyrolysis
Fluorescent magnetic microspheres can be obtained in magnetic nanoparticle.Magnetic nanoparticle is ferroso-ferric oxide herein.Using
BeckmanCounter measures its partial size and particle diameter distribution obtains: partial size is 1.5 μm, and CV (coefficientofvariation) is
3.2%, magnetic ferroferric oxide accounts for the 40% of entire microspheres weight, and the fluorescent emission peak position of microballoon is in 410nm, by fluorescence magnetic
After microballoon is placed 6 months, it is found that microballoon dispersibility and fluorescence property have more apparent decline.
Embodiment 2
A kind of fluorescent magnetic microspheres preparation method, comprising steps of 0.01g fluoresceins dyestuff is added to super-hydrophobic dose of 0.1g
In hexadecane, ultrasonic mixing is uniform；The surfactant cetyl trimethylammonium bromide (CTAB) of 0.02g is taken to be dispersed in second
In alcohol, total volume 9mL, ultrasonic treatment is made it completely dissolved；Dry iron oleate is prepared, FeCl is taken3Flask is added with enuatrol
In, and into flask be added dehydrated alcohol and n-hexane mixed solution, after dissolution, 80 DEG C of heating stirring 4h filter wet
Iron oleate, then wet iron oleate is placed in 80 DEG C, drying for 24 hours, is done in vacuum oven under conditions of vacuum degree is 100Pa
Dry iron oleate；Iron oleate, fluorescent monomer are added in propyl alcohol, is dispersed with stirring uniformly, it is standby to form iron oleate fluorescent monomer suspension
With；By in (4.6 μm of granularity, CV=3%) aqueous solutions of the addition containing polyethylene glycol of styrene homopolymers seed, it is sufficiently stirred,
Evenly dispersed seed suspension liquid is formed, styrene homopolymers seed accounts for the 30% of seed suspension liquid weight；The poly- second two of dispersing agent
Alcohol weight is the 5% of styrene homopolymers seed weight；The addition of azo diisobutyl amidine hydrochloric acid salt initiators is contained into dextrin
It in aqueous solution, is sufficiently stirred, forms initiator suspension, initiator accounts for the 2% of initiator suspension weight；Dextrin weight is to draw
Send out the 1% of agent weight；At 70 DEG C, kind is added in iron oleate fluorescent monomer suspension and initiator suspension in 500 minutes
Make seed growth in sub- suspension, wherein it is 6.8g/min, initiator suspension that speed, which is added, in iron oleate fluorescent monomer suspension
Addition speed is 1.01g/min, after reaching preset microspherulite diameter stops that iron oleate fluorescent monomer suspension and initiator is added
Suspension is warming up to 95 DEG C, and the reaction was continued 30min is to get arriving fluorescence iron oleate polymer composite microsphere；It is warming up to for the second time
310 DEG C, and 2-3h is kept in the case where being kept for 310 DEG C, make iron oleate pyrolysis synthesizing magnetic nano particle, fluorescence can be obtained
Magnetic microsphere.Magnetic nanoparticle is ferroso-ferric oxide herein.Its partial size and particle diameter distribution are measured using BeckmanCounter
: partial size is 800 μm, and CV (coefficientofvariation) is 2.8%, and magnetic ferroferric oxide accounts for entire microspheres weight
55%, the fluorescent emission peak position of microballoon is in 200nm, after fluorescent magnetic microspheres are placed 6 months, 13 months, discovery microballoon point
It dissipates property and fluorescence property is showed no significant change.
Embodiment 3
A kind of fluorescent magnetic microspheres preparation method, comprising steps of 0.01g fluoresceins dyestuff is added to super-hydrophobic dose of 0.1g
In hexadecane, ultrasonic mixing is uniform；The surfactant cetyl trimethylammonium bromide (CTAB) of 0.02g is taken to be dispersed in second
In alcohol, total volume 9mL, ultrasonic treatment is made it completely dissolved；Dry iron oleate is prepared, FeCl is taken3Flask is added with enuatrol
In, and into flask be added dehydrated alcohol and n-hexane mixed solution, after dissolution, 80 DEG C of heating stirring 4h filter wet
Iron oleate, then wet iron oleate is placed in 80 DEG C, drying for 24 hours, is done in vacuum oven under conditions of vacuum degree is 100Pa
Dry iron oleate；Iron oleate, fluorescent monomer are added in propyl alcohol, is dispersed with stirring uniformly, it is standby to form iron oleate fluorescent monomer suspension
With；By in (4.6 μm of granularity, CV=3%) aqueous solutions of the addition containing polyethylene glycol of styrene homopolymers seed, it is sufficiently stirred,
Evenly dispersed seed suspension liquid is formed, styrene homopolymers seed accounts for the 30% of seed suspension liquid weight；The poly- second two of dispersing agent
Alcohol weight is the 5% of styrene homopolymers seed weight；The addition of azo diisobutyl amidine hydrochloric acid salt initiators is contained into dextrin
It in aqueous solution, is sufficiently stirred, forms initiator suspension, initiator accounts for the 2% of initiator suspension weight；Dextrin weight is to draw
Send out the 1% of agent weight；At 70 DEG C, kind is added in iron oleate fluorescent monomer suspension and initiator suspension in 500 minutes
Make seed growth in sub- suspension, wherein it is 6.8g/min, initiator suspension that speed, which is added, in iron oleate fluorescent monomer suspension
Addition speed is 1.01g/min, after reaching preset microspherulite diameter stops that iron oleate fluorescent monomer suspension and initiator is added
Suspension is warming up to 95 DEG C, and the reaction was continued 30min is to get arriving fluorescence iron oleate polymer composite microsphere；It is warming up to for the second time
310 DEG C, and 2-3h is kept in the case where being kept for 310 DEG C, make iron oleate pyrolysis synthesizing magnetic nano particle, fluorescence can be obtained
Magnetic microsphere.Magnetic nanoparticle is ferroso-ferric oxide herein.Its partial size and particle diameter distribution are measured using BeckmanCounter
: partial size is 100 μm, and CV (coefficientofvariation) is 2.8%, and magnetic ferroferric oxide accounts for entire microspheres weight
55%, the fluorescent emission peak position of microballoon is in 200nm, after fluorescent magnetic microspheres are placed 6 months, 13 months, discovery microballoon point
It dissipates property and fluorescence property is showed no significant change.
Embodiment 4
A kind of fluorescent magnetic microspheres preparation method is added to comprising steps of weighing two pyroles dyestuff of 0.01g boron fluoride
In super-hydrophobic dose of hexadecane of 0.1g, ultrasonic mixing is uniform；Take the surfactant cetyl trimethylammonium bromide of 0.02g
(CTAB) in ethanol, total volume 9mL, ultrasonic treatment makes it completely dissolved for dispersion；Dry iron oleate is prepared, FeCl is taken3With
Enuatrol is added in flask, and the mixed solution of dehydrated alcohol and n-hexane, after dissolution, 80 DEG C of heating stirrings are added into flask
4h, the iron oleate for filtering wet, then wet iron oleate is placed in 80 DEG C, under conditions of vacuum degree is 100Pa in vacuum oven
Drying for 24 hours, obtains dry iron oleate；Iron oleate, fluorescent monomer are added in propyl alcohol, is dispersed with stirring uniformly, it is glimmering to form iron oleate
Light monomer suspension is spare；(5.5 μm of granularity, the CV=3%) additions of styrene homopolymers seed are contained into the water-soluble of polyethylene glycol
It in liquid, is sufficiently stirred, forms evenly dispersed seed suspension liquid, styrene homopolymers seed accounts for seed suspension liquid weight
30%；Dispersing agent polyethylene glycol weight is the 5% of styrene homopolymers seed weight；Two isobutyl imidazoline hydrochloride of azo is drawn
It sends out agent to be added in the aqueous solution containing polyethylene glycol, be sufficiently stirred, form initiator suspension, initiator accounts for initiator suspension
The 2% of weight；Dispersing agent polyethylene glycol weight is the 3% of initiator weight；It is in 240 minutes that iron oleate is glimmering at 70 DEG C
Light monomer suspension and initiator suspension, which are added in seed suspension liquid, makes seed growth, wherein iron oleate fluorescent monomer suspends
It is 6.8g/min that speed, which is added, in liquid, and it is 1.01g/min that speed, which is added, in initiator suspension, is stopped after reaching preset microspherulite diameter
Iron oleate fluorescent monomer suspension and initiator suspension is added, is warming up to 100 DEG C, the reaction was continued 30min is to get arriving fluoroleum
Sour iron polymer composite microsphere；It is warming up to 340 DEG C for the second time, and keeps 2-3h in the case where being kept for 340 DEG C, keeps iron oleate thermal decomposition anti-
Synthesizing magnetic nano particle is answered, fluorescent magnetic microspheres can be obtained.Magnetic nanoparticle is ferroso-ferric oxide herein.Using
BeckmanCounter measures its partial size and particle diameter distribution obtains: partial size is 110 μm, and CV 2.9%, magnetic ferroferric oxide accounts for whole
The 56% of a microspheres weight after placing fluorescent magnetic microspheres 6 months, 13 months, it is found that microballoon dispersibility and fluorescence property are equal
Have no significant change.
Embodiment 5
A kind of fluorescent magnetic microspheres preparation method, comprising steps of weighing 0.02g fluorescent molecule is added to super-hydrophobic dose of 0.1g
In hexadecane, ultrasonic mixing is uniform, is oil mixture, and the fluorescent molecule of addition is fluoresceins, two pyroles of boron fluoride
Or naphthalenes dyestuff；The surfactant cetyl trimethylammonium bromide (CTAB) of 0.02g is taken to be dispersed in isopropanol, total volume
For 9mL, ultrasonic treatment is made it completely dissolved；Dry iron oleate is prepared, FeCl is taken3It is added in flask with enuatrol, and to flask
The middle mixed solution that dehydrated alcohol and n-hexane is added, after dissolution, 80 DEG C of heating stirring 4h, the iron oleate for filtering wet, then will
Wet iron oleate is placed in 80 DEG C, and drying for 24 hours, obtains dry iron oleate in vacuum oven under conditions of vacuum degree is 100Pa；It will
Iron oleate, fluorescent monomer are added in propyl alcohol, are dispersed with stirring uniformly, it is spare to form iron oleate fluorescent monomer suspension；By styrene
It in (152 μm of granularity, CV=3%) aqueous solutions of the addition containing polyethylene glycol of homopolymer seed, is sufficiently stirred, is formed evenly dispersed
Seed suspension liquid, styrene homopolymers seed accounts for the 50% of seed suspension liquid weight；Dispersing agent polyethylene glycol weight is benzene second
The 10% of polyamino alkenyl object seed weight；The aqueous solution containing polyethylene glycol is added in two isobutyl imidazoline hydrochloride initiator of azo
In, it is sufficiently stirred, forms initiator suspension, initiator accounts for the 8% of initiator suspension weight；Dispersing agent polyethylene glycol weight
It is the 5% of initiator weight；At 70 DEG C, iron oleate fluorescent monomer suspension and initiator suspension are added in 360 minutes
Entering in seed suspension liquid makes seed growth, wherein it is 6.8g/min that speed, which is added, in iron oleate fluorescent monomer suspension, and initiator is outstanding
It is 1.01g/min that speed, which is added, in supernatant liquid, stops that iron oleate fluorescent monomer suspension is added after reaching preset microspherulite diameter and draws
Agent suspension is sent out, is warming up to 110 DEG C, the reaction was continued 30min is to get arriving fluorescence iron oleate polymer composite microsphere；Second liter
Temperature keeps 2-3h to 350 DEG C, and in the case where being kept for 350 DEG C, makes iron oleate pyrolysis synthesizing magnetic nano particle, can be obtained
Fluorescent magnetic microspheres.Magnetic nanoparticle is ferroso-ferric oxide herein.Its partial size and partial size are measured using BeckmanCounter
Be distributed: partial size is 4500 μm, and CV 2%, magnetic ferroferric oxide accounts for the 56% of entire microspheres weight, by fluorescent magnetic microspheres
After placing 6 months, 13 months, it is found that microballoon dispersibility and fluorescence property are showed no significant change.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations
Also it should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of preparation method of fluorescent magnetic microspheres, which is characterized in that comprising steps of
(1) synthesis of fluorescent monomer:
Fluorescent molecule one of is selected from the group or a variety of: naphthalimide dyestuff, fluoresceins dyestuff, two pyroles of boron fluoride
Dyestuff, naphthalenes dyestuff, fluorenes-diazosulfide copolymer fluorescent dye, nitrobenzoxadiazole, calcein；Two (three chloromethanes
Alkane) carbonic ester；
Hydrophobing agent is selected from the group: hexadecane, n-octyl alcohol；
Above-mentioned reactant is added in solvent, is stirred evenly, fluorescent monomer suspension is formed, fluorescent monomer weight accounts for fluorescent monomer
60% or less suspension weight；
(2) synthesis of magnetic particle:
At 70-90 DEG C, soluble trivalent iron salt and enuatrol are reacted in the system of n-hexane and ethyl alcohol, vacuum is dry
It is dry, obtain dry iron oleate；
(3) magnetic fluorescence monomer suspension is prepared:
Iron oleate and fluorescent monomer are added in stabilizer and solvent mixed solution, stirred evenly, iron oleate fluorescent monomer is formed
Suspension；
(4) polymer seeds suspension is prepared:
Polymer seeds are added in the aqueous solution containing dispersing agent, is sufficiently stirred, forms evenly dispersed seed suspension liquid, are gathered
It closes species and accounts for the 60% or less of seed suspension liquid weight；
(5) cause polymerization:
At the polymerization temperature, iron oleate fluorescent monomer suspension and initiator are added in seed suspension liquid makes seed growth, reaches
Stop that iron oleate fluorescent monomer suspension and initiator is added after to preset microspherulite diameter, heat up polymerization reaction for the first time, i.e.,
Fluorescence iron oleate polymer composite microsphere can be obtained；Second of heating, makes iron oleate pyrolysis synthesizing magnetic nano particle,
Fluorescent magnetic microspheres can be obtained.
2. the preparation method of fluorescent magnetic microspheres according to claim 1, which is characterized in that the initiator is azo
Water soluble starter.
3. the preparation method of fluorescent magnetic microspheres according to claim 2, which is characterized in that the initiator is azo two
Isobutyl imidazoline hydrochloride or azo diisobutyl amidine hydrochloride.
4. the preparation method of fluorescent magnetic microspheres according to claim 1-3, which is characterized in that the polymer
Seed is polystyrene seed or styrene-divinylbenzene seed, and the monomer is selected from styrene, divinylbenzene, 2,4- bis-
Chlorostyrene, acrylic acid, methyl methacrylate, methyl acrylate, ethyl acrylate, vinylacetate, methacrylic acid contracting
One of water glyceride or derivatives thereof is a variety of.
5. the preparation method of fluorescent magnetic microspheres according to claim 1, which is characterized in that the solvent is carbon atom number
For the lower alcohol of C1-C3.
6. the preparation method of fluorescent magnetic microspheres according to claim 1 or 5, which is characterized in that the temperature of heating for the first time
Degree is 95-110 DEG C, and the temperature of second of heating is 300-350 DEG C.
7. the preparation method of fluorescent magnetic microspheres according to claim 1, which is characterized in that the fluorescent magnetic microspheres
Particle size is 0.1-5000 μm.
8. the preparation method of fluorescent magnetic microspheres according to claim 1, which is characterized in that the solubility trivalent iron salt
Molar ratio with enuatrol is 1:2-1:7.
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| CN110961071A (en) * | 2019-12-20 | 2020-04-07 | 湖北海汇化工科技有限公司 | Wastewater treatment agent, preparation method and application thereof, and wastewater treatment method |
| CN111498900A (en) * | 2020-04-28 | 2020-08-07 | 无锡迈科为生物科技有限公司 | Preparation method of zirconium dioxide microspheres |
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| CN105859973A (en) * | 2016-05-18 | 2016-08-17 | 苏州知益微球科技有限公司 | Preparation method of monodispersed fluorescent microsphere |
| CN107880877A (en) * | 2017-12-18 | 2018-04-06 | 上海艾瑞德生物科技有限公司 | A kind of preparation method and applications of monodisperse polymer fluorescent microsphere |
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