CN102838982B - Polymer microsphere with broad spectrum and persistent autofluorescence and its preparation method - Google Patents
Polymer microsphere with broad spectrum and persistent autofluorescence and its preparation method Download PDFInfo
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Abstract
The invention provides a polymer microsphere product with a broad spectrum and persistent autofluorescence and its preparation method. The polymer microsphere is characterized in that: the observation range of the autofluorescence of the microsphere can cover three channels of 330-380nm, 450-490nm and 510-560nm; the fluorescence duration time is more than 30 days; the particle size of the microsphere is controllable in the range of 5-100 micrometers; the particle size is uniform, the distribution coefficient is less than 15%; and the specific surface area is in the range of 20-1500m<2>/g. The preparation method consists of: dispersing an oil phase containing a monomer, a pore-forming agent and the like into a water phase through a membrane emulsification technology so as to form a homogeneous oil-in-water emulsion, then raising the temperature and conducting suspension polymerization to form an initial microsphere, which is subjected to a reaction under the action of a metal catalyst so as to derive the microsphere product with autofluorescence.
Description
Technical field
The present invention relates to and a kind ofly have polymer microballoon of wide spectrum and lasting autofluorescence and preparation method thereof, belong to polymeric material field, this polymer microballoon is suitable for as spike and calibration materials etc. for fluorometric analysis detection technique field.
Background technology
Fluorescent polymer microballoon, as the standard substance in the modern instruments such as fluoroimmunoassay, biosensor, micro-fluidic chip and critical material, is widely used in the various fields such as medical diagnosis on disease, drug invention, high throughput analysis, metabolic process analysis.Along with the continuous expansion of each Application Areas in recent years, the involved diversity of testing molecule in structure, physico-chemical property, biological activity etc. constantly increases, fluorescent microsphere is proposed to the requirement of more performances, as: (1) fluorescence intensity will be stablized lastingly, not easily cancellation; (2) fluorescence emission spectral limit is wide, to meet the detection of multiple wave band; (3) microspherulite diameter is homogeneous as far as possible, to ensure test repeatability and to reduce system deviation; (4) porous high-specific surface area structure is possessed, to provide the loading capacity load function material of abundance as medicine etc.; (5) preparation cost is lower etc., reduces testing cost.By these performances integrated, to obtaining quicker, efficient, cheap detection analytical results.
At present, the main path that microballoon is introduced fluorophor has following a few class: (1) surface modification, namely at microsphere surface grafting luminophore, this method stable luminescence, but it is complicated operation, high to requirement of experiment, and technology of preparing is many is abroad monopolized, price is very expensive, causes testing cost to remain high; (2) method of loading, i.e. embedding or absorption fluorescent substance in microballoon, this method is simple, but fluorescence dye combines unstable, easily reveals, causes the problems such as cancellation enhancing, and the fluorescein toxicity revealed also reduces the biological safety of such microballoon; (3) monomer copolymerization approach, by specificity fluorescent monomer and microballoon backbone monomer copolymerization balling-up, this method fluorescence molecule is in conjunction with highly stable, but optional fluorescent monomer is limited and preparation is very difficult.Based on the restriction that existing approach exists, how on fluorescent microsphere, to realize the integrated of multiple performance and to seek the up-to-date challenge that simple preparation technology is current fluorescent microsphere Materials.
Summary of the invention
The object of the present invention is to provide a kind of polymer microballoon with wide spectrum and lasting autofluorescence.This product feature is, microballoon had both had the autofluorescence of wide spectrum and lasting stability, can have comparatively homogeneous particle diameter and high-specific surface area again.Wherein, the range of observation of autofluorescence covers 330 ~ 380nm, 450 ~ 490nm and 510 ~ 560nm tri-passages (see accompanying drawing 1).Especially, have stronger absorption (see accompanying drawing 2,3) under 405nm and 488nm excitation wavelength, the weather resistance of autofluorescence feature, more than 30 days, especially, can reach more than 720 days (accompanying drawings 4).Microspherulite diameter is controlled within the scope of 5 ~ 100 μm, and particle diameter can be homogeneous, and size distribution coefficient can <15%, and size distribution coefficient CV is calculated as follows:
Wherein d
ibe the mean diameter of i-th microballoon, d is the mean diameter of drop, and n is the total ball number calculated, n>200.The specific surface area of microballoon is at 20 ~ 1500m
2within the scope of/g, aperture is within the scope of 0-50nm.
Present invention also offers a kind of preparation method with the polymer microballoon of wide spectrum and lasting autofluorescence, comprise the steps:
(1) oil phase containing monomer, pore-creating agent, initiator, cosurfactant is mixed;
(2) aqueous phase containing stablizer, tensio-active agent, inorganic salt, stopper is mixed;
(3) the oil phase high-speed stirring mixed is formed emulsion or utilize film emulsifying technology to enter aqueous phase by porous-film under pressure and form homogeneous emulsion;
(5) emulsion is moved to reactor, intensification suspension polymerization forms the initial microballoon of porous polymer;
(6) add swelling agent by after initial microballoon washing drying, then react under catalyst action, washing and drying forms the controlled high-specific surface polymer microsphere of the uniform particle diameter with autofluorescence.
In oil phase of the present invention, monomer is oil-soluble vinyl, methacrylic, acrylic acid or the like, methyl acrylic ester, esters of acrylic acid, methacryloyl amine, acrylic amide, bi-vinyl class, Vinylstyrene class, triethylene base class, styrenic etc., also can be its mixture etc.The mass content of monomer in oil phase is 1% ~ 100%, more applicable in 20% ~ 100% scope.Addible pore-creating agent is inert compound being dissolved in monomer and composition thereof, can be that liquid alkane is as octane, heptane, hexane etc., also can be benzene class as dimethylbenzene, toluene, chlorobenzene etc., also can be linear polymer, the massfraction in oil phase be 0% ~ 80%.The present invention's polymerization starter used can be peroxide type initiators, as benzoyl peroxide; Also can be azo-initiator, as Diisopropyl azodicarboxylate.The consumption of initiator is 0.01% ~ 10% of all polymerisable monomer quality, but is preferably limited to 2% ~ 7% better.Cosurfactant is used for the stable of drop, and can be the alcohols or the linear polymer that are dissolved in monomer, as lauryl alcohol, hexadecanol or polystyrene etc., consumption be 0.01% ~ 30% of selected polymerisable monomer quality, but preferably better 5% ~ 20%.
In aqueous phase of the present invention, stablizer for ensureing the stability of drop, can be water-soluble polymers as gelatin, polyvinyl alcohol (PVA), Mierocrystalline cellulose, polyvinylpyrrolidone etc., content is 0.1 ~ 10% of aqueous phase quality.Tensio-active agent is used for preventing drop Bing from gathering or helping drop to depart from from fenestra in film emulsion process, and can be sodium lauryl sulphate (SDS), sodium laurylsulfonate (SLS) etc., content controls within 2% of aqueous phase quality.Inorganic salt prevent drop Bing from gathering for the charge distribution balanced in emulsion, can be the sodium potassium class inorganic salt such as sodium sulfate.Stopper is used for preventing secondary short grained generation in suspension polymerization, can be the water-soluble cpdss such as Resorcinol.
Film emulsifying technology of the present invention, described film emulsifying technology can select the microporous membrane of the multiple material such as ceramic membrane, glassy membrane, and preferred SPG film, can prepare the homogeneous microballoon of size between 5 ~ 100 μm according to the selection of membrane pore size (1 ~ 10 μm) herein.
Catalytic reaction process of the present invention, provide a kind of crosslinking method making microballoon produce autofluorescence, namely the residual suspended double bond of the initial microsphere surface of suspension polymerization is utilized, carry out metal catalyst activation, after forming carbonium ion, continue to react by the phenyl ring of nucleophilic attack and surrounding or contiguous double bond, form new conjugated structure, double bond disappearance in the reaction visible its at 985cm
-1the disappearance (accompanying drawing 5,6) of place's double bond infrared signature absorption peak.Its luminescent properties of reacted microballoon is caused by the bridge chain structure between phenyl ring, the conjugated structure that suspended double bond is formed after cross-linking, between adjacent phenyl rings, bridge chain is built by with the form of C-H bond, therefore the aroma system of polymer chain continues to expand, and cause the enhancing of whole system conjugacy, also make the plane configuration between phenyl ring be enhanced in addition.Because fluorescence usually occurs in the molecular structure with rigid plane and π-electron conjugated system, the structural modification of the electron conjugated degree of any π of being conducive to 2 and planeness all will improve fluorescence efficiency, therefore newly-generated after catalyzed reaction conjugated structure strengthens this class formation (see accompanying drawing 5) in microballoon inside, thus produces autofluorescence.In catalytic reaction process of the present invention, described swelling agent can be benzene, chlorobenzene, ethyl acetate, ethylene dichloride, dithiocarbonic anhydride etc., and swelling time can be 1-48 hour.Temperature of reaction can at 10 DEG C ~ 100 DEG C.Metal catalyst can be aluminum chloride, zinc chloride, boron trifluoride or iron(ic) chloride etc., and consumption is 5% ~ 40% of solvent quality.Reaction times can be 6 ~ 24 hours.
Accompanying drawing explanation
Fig. 1 is the autofluorescence picture of microballoon under three passages.Fig. 2 is the absorption spectrum of microballoon under 405nm excitation wavelength.Fig. 3 is the absorption spectrum of microballoon under 488nm excitation wavelength.Fig. 4 is that the fluorescence that microballoon was placed before and after 720 days keeps picture.Fig. 5 is the structural representation of initial microballoon catalyzed reaction.Fig. 6 is the change of the surface double-bond characteristic peak (985cm-1) of microballoon before and after catalysis.Fig. 7 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 1, and the right side is pore structure partial enlarged drawing.Fig. 8 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 2, and the right side is pore structure partial enlarged drawing.Fig. 9 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 3, and the right side is pore structure partial enlarged drawing.Figure 10 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 4, and the right side is pore structure partial enlarged drawing.Figure 11 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 5, and the right side is pore structure partial enlarged drawing.Figure 12 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 6, and the right side is pore structure partial enlarged drawing.Figure 13 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 7.Figure 14 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 8.Figure 15 is fluorescence co-focusing and the electromicroscopic photograph of fluorescent microsphere in embodiment 9.
Embodiment
Describe compound of the present invention and preparation thereof below in conjunction with embodiment, it does not limit the present invention, and scope of the present invention is defined by the claims.
Embodiment 1 vinylbenzene-toluene-aluminum chloride synthetic system
Oil phase comprises vinylbenzene 8.0g, toluene 30.0g, lauryl alcohol 1.2g, benzoyl peroxide 0.63g.Aqueous phase comprises gelatin 0.9g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The microporous membrane aperture adopted is 5.2um.Be sealed in by oil phase in storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, and makes oil phase slowly be pressed in aqueous phase under nitrogen pressure, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, is then warming up to 75 DEG C of polymerizations.Microballoon hot water after polymerization and ethanol is filtering and washing respectively, with Soxhlet extractor acetone extraction 24 hours, dries and form in the most rearmounted vacuum drying oven under normal temperature.Get above porous microsphere, with the concentration of 0.5g/10ml in 1,2-ethylene dichloride swelling 5 hours.Then its mixed solution is sealed in there-necked flask; add 20%(wt.%) catalyst aluminum chloride, catalyzed reaction 12 hours under 30 DEG C of nitrogen protections, the microballoon obtained respectively by 0.1M hydrochloric acid, acetone and water washing for several times; again through acetone extraction after 12 hours, oven dry forms.Confocal fluorescent microscope and electromicroscopic photograph are shown in accompanying drawing 7, and particle diameter is 16.2 μm; Size distribution coefficient is 13.1%; Specific surface area is 1316.3m
2/ g.
Embodiment 2 styrene-ethyl benzene-zinc chloride synthetic system
Oil phase comprises vinylbenzene 8.0g, ethylbenzene 24.0g, lauryl alcohol 1.2g, benzoyl peroxide 0.63g.Aqueous phase comprises gelatin 0.9g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The SPG membrane pore size adopted is 5.2um.Be sealed in by oil phase in storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, and makes oil phase slowly be pressed in aqueous phase under nitrogen pressure, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, is then warming up to 75 DEG C of polymerizations.Microballoon hot water after polymerization and ethanol is filtering and washing respectively, with Soxhlet extractor acetone extraction 24 hours, dries and form in the most rearmounted vacuum drying oven under normal temperature.Get above porous microsphere, with the concentration of 0.5g/10ml in benzene swelling 12 hours.Then its mixed solution is sealed in there-necked flask; add 30%(wt.%) catalyzer zinc chloride, catalyzed reaction 12 hours under 40 DEG C of nitrogen protections, the microballoon obtained respectively by 0.1M hydrochloric acid, acetone and water washing for several times; again through acetone extraction after 12 hours, oven dry forms.Confocal fluorescent microscope and electromicroscopic photograph are shown in accompanying drawing 8, and particle diameter is 15.2 μm; Size distribution coefficient is 13.9%; Specific surface area is 306.3m
2/ g.
Embodiment 3 vinylbenzene-iron(ic) chloride synthetic system (without pore-creating agent, without film emulsification)
Oil phase comprises vinylbenzene 8.0g, lauryl alcohol 1.2g, benzoyl peroxide 0.63g.Aqueous phase comprises gelatin 0.9g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.Oil phase is mixed with water, stir the monomer emulsion forming oil-in-water-type under 400rpm and drip.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, is then warming up to 75 DEG C of polymerizations.Microballoon hot water after polymerization and ethanol is filtering and washing respectively, with Soxhlet extractor acetone extraction 24 hours, dries and form in the most rearmounted vacuum drying oven under normal temperature.Get above porous microsphere, with the concentration of 0.5g/10ml in dithiocarbonic anhydride swelling 3 hours.Then its mixed solution is sealed in there-necked flask; add 30%(wt.%) catalyzer iron(ic) chloride, catalyzed reaction 12 hours under 80 DEG C of nitrogen protections, the microballoon obtained respectively by 0.1M hydrochloric acid, acetone and water washing for several times; again through acetone extraction after 12 hours, oven dry forms.Electromicroscopic photograph is shown in accompanying drawing 9, and particle diameter is 43.40 μm; Size distribution coefficient is 39.1%; Specific surface area is 433.1m
2/ g.
Embodiment 4 Vinylstyrenes-normal heptane-zinc chloride synthetic system
Oil phase comprises Vinylstyrene 8.0g, normal heptane 12.0g, lauryl alcohol 1.2g, benzoyl peroxide 0.93g.Aqueous phase comprises PVA0.5g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The SPG membrane pore size adopted is 5.2um.Be sealed in by oil phase in storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, and makes oil phase slowly be pressed in aqueous phase under nitrogen pressure, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, is then warming up to 75 DEG C of polymerizations.Microballoon hot water after polymerization and ethanol is filtering and washing respectively, with Soxhlet extractor acetone extraction 24 hours, dries and form in the most rearmounted vacuum drying oven under normal temperature.Get above porous microsphere, with the concentration of 0.5g/10ml in 1,2-ethylene dichloride swelling 5 hours.Then its mixed solution is sealed in there-necked flask; add 20%(wt.%) catalyzer zinc chloride, catalyzed reaction 12 hours under 40 DEG C of nitrogen protections, the microballoon obtained respectively by 0.1M hydrochloric acid, acetone and water washing for several times; again through acetone extraction after 12 hours, oven dry forms.Electromicroscopic photograph is shown in accompanying drawing 10, and particle diameter is 28.40 μm; Size distribution coefficient is 10.1%; Specific surface area is 853.1m
2/ g.
Embodiment 5 Vinylstyrenes-normal heptane-boron trifluoride synthetic system
Oil phase comprises Vinylstyrene 8.0g, normal heptane 12.0g, lauryl alcohol 1.2g, benzoyl peroxide 0.93g.Aqueous phase comprises PVA0.5g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The SPG membrane pore size adopted is 5.2um.Be sealed in by oil phase in storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, and makes oil phase slowly be pressed in aqueous phase under nitrogen pressure, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, is then warming up to 75 DEG C of polymerizations.Microballoon hot water after polymerization and ethanol is filtering and washing respectively, with Soxhlet extractor acetone extraction 24 hours, dries and form in the most rearmounted vacuum drying oven under normal temperature.Get above porous microsphere, with the concentration of 0.5g/10ml in dithiocarbonic anhydride swelling 3 hours.Then its mixed solution is sealed in there-necked flask; add 20%(wt.%) catalyzer boron trifluoride, catalyzed reaction 12 hours under 30 DEG C of nitrogen protections, the microballoon obtained respectively by 0.1M hydrochloric acid, acetone and water washing for several times; again through acetone extraction after 12 hours, oven dry forms.Electromicroscopic photograph is shown in accompanying drawing 11, and particle diameter is 32.40 μm; Size distribution coefficient is 11.1%; Specific surface area is 863.1m
2/ g.
Embodiment 6 Vinylstyrenes-toluene-boron trifluoride synthetic system
Oil phase comprises Vinylstyrene 8.0g, toluene 16.0g, lauryl alcohol 1.2g, benzoyl peroxide 0.93g.Aqueous phase comprises PVA0.5g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The SPG membrane pore size adopted is 5.2um.Be sealed in by oil phase in storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, and makes oil phase slowly be pressed in aqueous phase under nitrogen pressure, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, is then warming up to 75 DEG C of polymerizations.Microballoon hot water after polymerization and ethanol is filtering and washing respectively, with Soxhlet extractor acetone extraction 24 hours, dries and form in the most rearmounted vacuum drying oven under normal temperature.Get above porous microsphere, with the concentration of 0.5g/10ml in dithiocarbonic anhydride swelling 3 hours.Then its mixed solution is sealed in there-necked flask; add 20%(wt.%) catalyzer boron trifluoride, catalyzed reaction 12 hours under 30 DEG C of nitrogen protections, the microballoon obtained respectively by 0.1M hydrochloric acid, acetone and water washing for several times; again through acetone extraction after 12 hours, oven dry forms.The fluorescent microscope of microballoon and electromicroscopic photograph are shown in accompanying drawing 12, and particle diameter is 15.8 μm; Size distribution coefficient is 13.3%; Specific surface area is 545.1m
2/ g.
Embodiment 7 Vinylstyrenes-ethylbenzene-linear polystyrene-zinc chloride synthetic system
Oil phase comprises Vinylstyrene 8.0g, ethylbenzene 24.0g, linear polystyrene (number-average molecular weight 5000) 0.8g, lauryl alcohol 1.2g, benzoyl peroxide 0.93g.Aqueous phase comprises PVA0.5g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The SPG membrane pore size adopted is 5.2um.Be sealed in by oil phase in storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, and makes oil phase slowly be pressed in aqueous phase under nitrogen pressure, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, is then warming up to 75 DEG C of polymerizations.Microballoon hot water after polymerization and ethanol is filtering and washing respectively, with Soxhlet extractor acetone extraction 24 hours, dries and form in the most rearmounted vacuum drying oven under normal temperature.Get above porous microsphere, with the concentration of 0.5g/10ml in 1,2-ethylene dichloride swelling 5 hours.Then its mixed solution is sealed in there-necked flask; add 30%(wt.%) catalyzer zinc chloride, catalyzed reaction 12 hours under 40 DEG C of nitrogen protections, the microballoon obtained respectively by 0.1M hydrochloric acid, acetone and water washing for several times; again through acetone extraction after 12 hours, oven dry forms.The fluorescent microscope of microballoon and electromicroscopic photograph are shown in accompanying drawing 13, and particle diameter is 30.8 μm; Size distribution coefficient is 13.3%; Specific surface area is 705.1m
2/ g.
Embodiment 8 glycidyl methacrylate-toluene-iron(ic) chloride synthetic system
Oil phase comprises glycidyl methacrylate 8.0g, toluene 8.0g, lauryl alcohol 1.2g, Diisopropyl azodicarboxylate 0.40g.Aqueous phase comprises PVA0.5g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The SPG membrane pore size adopted is 5.2um.Be sealed in by oil phase in tetrafluoro storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, under certain nitrogen pressure, then make oil phase slowly be pressed in aqueous phase, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, starts to be warming up to 75 DEG C of polymerizations, keeps this temperature and be polymerized 24 hours under nitrogen protection.Microballoon hot water after polymerization and industrial alcohol respectively filtering and washing, to remove PVA and organic solvent etc., with Soxhlet extractor extracting 24 hours, to remove residual monomer and pore-creating agent, are dried under normal temperature in the most rearmounted vacuum drying oven and are formed.Get above porous microsphere appropriate, with the concentration of 0.5g/10ml in 1,2-ethylene dichloride swelling 5 hours.Then its mixed solution is sealed in three mouthfuls of round-bottomed flasks; add 30%(wt.%) catalyzer iron(ic) chloride; under 80 DEG C of nitrogen protections, catalyzed reaction reacts 12 hours; at a certain temperature; carry out catalyzed reaction a few hours; the microballoon obtained is respectively by after 0.1M hydrochloric acid, acetone and water washing 4 times, then through acetone extraction after 12 hours, oven dry forms.The fluorescent microscope of microballoon and electromicroscopic photograph are shown in accompanying drawing 14, and particle diameter is 26.8 μm; Size distribution coefficient is 10.3%; Specific surface area is 1028.3m
2/ g.
Embodiment 9 glycidyl methacrylate-Vinylstyrene-normal heptane-iron(ic) chloride synthetic system
Oil phase comprises glycidyl methacrylate 8.0g, Vinylstyrene 8.0g, normal heptane 8.0g, lauryl alcohol 1.2g, benzoyl peroxide 1.86g.Aqueous phase comprises PVA0.5g, SDS0.5g, Na
2sO
40.2g, Resorcinol 0.5g, deionized water 300g.The SPG membrane pore size adopted is 5.2um.Be sealed in by oil phase in tetrafluoro storage tank, aqueous phase is placed in the beaker that magnetic agitation is housed, under certain nitrogen pressure, then make oil phase slowly be pressed in aqueous phase, forms homogeneous oil-in-water-type monomer emulsion and drips.The monomer emulsion prepared above is placed in 500ml polymeric kettle, and normal temperature is ordered the slow bubbling of nitrogen stir 1 hour, starts to be warming up to 75 DEG C of polymerizations, keeps this temperature and be polymerized 24 hours under nitrogen protection.Microballoon hot water after polymerization and industrial alcohol respectively filtering and washing, to remove PVA and organic solvent etc., with Soxhlet extractor extracting 24 hours, to remove residual monomer and pore-creating agent, are dried under normal temperature in the most rearmounted vacuum drying oven and are formed.Get above porous microsphere appropriate, with the concentration of 0.5g/10ml in 1,2-ethylene dichloride swelling 5 hours.Then its mixed solution is sealed in three mouthfuls of round-bottomed flasks; add 10%(wt.%) catalyzer iron(ic) chloride; catalyzed reaction 12 hours under 80 DEG C of nitrogen protections; at a certain temperature; carry out catalyzed reaction a few hours; the microballoon obtained is respectively by after 0.1M hydrochloric acid, acetone and water washing 4 times, then through acetone extraction after 12 hours, oven dry forms.The fluorescent microscope of microballoon and electromicroscopic photograph are shown in accompanying drawing 15, and particle diameter is 27.7 μm; Size distribution coefficient is 10.5%; Specific surface area is 618.2m
2/ g.
Claims (10)
1. there is a preparation method for the polymer microballoon of wide spectrum and lasting autofluorescence, comprise the steps:
(1) oil phase containing monomer, pore-creating agent, polymerization starter, cosurfactant is mixed;
Described monomer is the mixture of Vinylstyrene class or Vinylstyrene class and styrenes; The mass content of monomer in oil phase is 1% ~ 100%;
(2) aqueous phase containing stablizer, tensio-active agent, inorganic salt, stopper is mixed;
(3) rear stirring mixed with water for oil phase is formed emulsion, or utilize film emulsifying technology that oil phase is entered aqueous phase by the microporous membrane of different pore size under pressure to form homogeneous emulsion;
Described film emulsifying technology is for using ceramic membrane, glassy membrane, and membrane pore size is 1 ~ 10 μm;
(4) emulsion is moved to reactor, intensification suspension polymerization forms initial microballoon;
(5) by after initial microballoon washing drying, add in swelling agent swelling, then react under metal catalyst effect, washing and drying forms the polymer microballoon with autofluorescence;
In described catalytic reaction process, described swelling agent is ethylene dichloride, ethyl acetate or dithiocarbonic anhydride, and temperature of reaction is at 10 DEG C ~ 100 DEG C, and described metal catalyst is aluminum chloride, zinc chloride, boron trifluoride or iron(ic) chloride, consumption is 5% ~ 40%, and the reaction times is 6 ~ 24 hours.
2. the method for claim 1, described pore-creating agent is be dissolved at least one in the inert compound of monomer or their mixture, and the massfraction in oil phase is 0% ~ 80%.
3. method as claimed in claim 2, described pore-creating agent is heptane, hexane, dodecane, n-Hexadecane, toluene, dimethylbenzene or their mixture.
4. the method for claim 1, described polymerization starter is peroxide type initiators, or azo-initiator, the consumption of initiator is 0.01% ~ 10% of all polymerisable monomer quality, cosurfactant is the long-chain alcohols dissolving in monomer, and consumption is 0.01% ~ 30% of all polymerisable monomer quality.
5. method as claimed in claim 4, it is characterized in that, described peroxide type initiators is benzoyl peroxide.
6. method as claimed in claim 4, it is characterized in that, described azo-initiator is Diisopropyl azodicarboxylate.
7. method as claimed in claim 4, is characterized in that, described in dissolve in monomer long-chain alcohols be lauryl alcohol or hexadecanol.
8. the method for claim 1, described stablizer is polyvinyl alcohol, gelatin, Mierocrystalline cellulose or polyvinylpyrrolidone, and content is 0.1 ~ 10% of aqueous phase quality; Described tensio-active agent is sodium lauryl sulphate or sodium laurylsulfonate, and content controls within 2% of aqueous phase quality; Inorganic salt are sodium potassium class inorganic salt; Stopper is Resorcinol.
9. method as claimed in claim 8, it is characterized in that, described inorganic salt are sodium sulfate.
10. one kind has the polymer microballoon of wide spectrum and lasting autofluorescence, it is characterized in that, obtained by method described in any one of claim 1-9, described microballoon both had autofluorescence, had again the size of uniform particle diameter and had superhigh specific surface area, wherein, the range of observation of autofluorescence covers 330 ~ 380nm, 450 ~ 490nm and 510 ~ 560nm tri-passages, especially, under 405nm and 488nm excitation wavelength, have stronger absorption, the weather resistance of autofluorescence feature is more than 30 days;
Described microspherulite diameter is controlled, size uniformity, and microspherulite diameter is controlled within the scope of 5 ~ 100 μm, size distribution coefficient CV<15%, and CV is calculated as follows:
Wherein d
ibe the mean diameter of i-th microballoon, d is the mean diameter of drop, and n is the total ball number calculated, n>200.
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| DE102014004529A1 (en) * | 2014-03-27 | 2015-10-15 | Ludwig-Maximilians-Universität München | The automatic sorting of polymer materials based on the fluorescence decay time of the autofluorescence and the fluorescence of markers |
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