CN104628924A - Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by water-soluble initiator - Google Patents
Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by water-soluble initiator Download PDFInfo
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Abstract
The invention discloses a method for preparing an aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by a water-soluble initiator. The method comprises the steps of dissolving an aggregation-induced emission type fluorescent monomer and a co-stabilizer into a monomeric compound to obtain an oil-phase solution; dissolving a water-soluble emulsifying agent into water to obtain a water solution of the emulsifying agent; and adding the oil-phase solution into the water solution of the emulsifying agent, stirring and pre-emulsifying to obtain a rough emulsion, carrying out ultrasonic dispersion on the rough emulsion in a 0-DEG C ice water bath to prepare a monomeric mini-emulsion, adding a water-soluble initiator, then, introducing nitrogen, removing oxygen, and reacting at the temperature of 40-90 DEG C for 0.5 hour to 2 days under the protection of nitrogen gas to prepare an emulsion of the aggregation-induced emission type polymer fluorescent nanoparticle. The method disclosed by the invention has the advantages that the nanoparticle size, size distribution and fluorescent brightness are conveniently regulated, the stability of a system is good, the preparation process is simple, the process flow is short, and no organic solvents are consumed in preparation and after-treatment processes.
Description
(1) technical field
The present invention relates to a kind of preparation method of aggregation-induced emission polymer fluorescent nano particle, be specifically related to the method that the free-radical polymerized preparation of a kind of miniemulsion utilizing water soluble starter to cause has the polymer fluorescent nano particle of aggregation-induced emission characteristic.
(2) background technology
Fluorescent nano particles is widely used in fields such as chemical sensitisation, optical material, coating, biological monitoring and cell images.Traditional luminescent organic molecule has good photoluminescent property in dilute solution, and state of aggregation or solid-state time, fluorescence significantly weakens, even luminous.This character constrains the application of luminescent organic molecule in solid luminescent material to a certain extent.Aggregation-induced emission phenomenon refers to that some molecule is not luminous under solution state, but in the phenomenon of state of aggregation or solid luminescent.The luminescent behavior of aggregation-induced emission molecule uniqueness, has attracted the concern of numerous scientist, has become the study hotspot in photoelectric functional material field in recent years.Aggregation-induced emission type polymer fluorescent nano particle, because of its good biocompatibility and high fluorescence intensity, also has very large using value in bio-imaging field.
At present, the method preparing aggregation-induced emission type fluorescent nano particles mainly contains entrapping method, covalent bonding method and sol-gel method etc.
(1) people such as Qin prepares the bovine serum albumin particle of load fluorescence molecule I by entrapping method.Molecule I is first dissolved in tetrahydrofuran (THF) by them, then dye solution is added in the aqueous solution of bovine serum albumin, through ultrasonic, crosslinked, desolventizing process, the self-assembly in water of bovine serum albumin molecule obtains the bovine serum albumin nanoparticle (Adv Funct Mater 2012,22 (4): 771-779) of coated fluorescence molecule.
(2) crosslinkable aggregation-induced emission fluorescent monomer and soluble macromonomer methacrylic acid macrogol ester are obtained multipolymer by Invertible ideal by the people such as Zhang, then by multipolymer redispersion in water, fluorescent nano particles (Polym.Chem. is formed by self-assembly, 2013,4 (19): 5060-5064.).
(3) people such as Faisal has prepared the Nano particles of silicon dioxide of load aggregation-induced emission fluorescence dye by secondary sol-gel method.They are first by 1,2-bis-[4-brooethyl-phenyl]-stilbene fluorescence molecule and aminopropyl triethoxysilane addition, then form aggregation-induced emission fluorescent core by first time sol-gel process; Then the ethanolic soln of tetraethoxy is dropwise added, by secondary sol-gel process, silica deposit is surperficial to fluorescent core, form " nucleocapsid " type fluorescent nano particles (Chem Eur J 2010,16 (14): 4266-4272.).
Although above method can obtain aggregation-induced emission type fluorescent nano particles, there is certain limitation.For method (1), the nanoparticle adopting entrapping method to prepare, inevitably there will be fluorescence dye leakage problem in storage process, cause fluorescence intensity unstable, and preparation process needs organic solvent, easily pollutes.For method (2), first need pass through active free radical polymerization synthetic copolymer, redispersion is in water, fluorescent nano particles is formed by the self-assembly effect of self, step is relatively many, and there is particle size relatively large (>100nm), the problem that size distribution is wider.For method (3), need carry out twice sol-gel process, be removing unreacted precursor, need first to obtain product by centrifugation, when being applied to cell imaging, also need fluorescent nano particles being scattered in water, process is loaded down with trivial details, and subsequent disposal is complicated.
Mini-emulsion polymerization system is a kind of heterogeneous reaction system being disperse phase with the monomer droplet of 50 ~ 500 nanometers, and it is by ultrasonic or high pressure homogenization preparation.Each drop in mini-emulsion polymerization system can regard as independently reactor, forms polymer particle by monomer fluid nucleation mode.Mini-emulsion polymerization is very suitable for preparing various polymer nano-particle.In reaction process, without the need to transmitting monomer between drop, therefore mini-emulsion polymerization system is also highly suitable for the copolymerization carrying out super-hydrophobic monomer or the participation of facile hydrolysis monomer.
(3) summary of the invention
The object of the invention is to provide a kind of method preparing aggregation-induced emission (AIE) fluorescent nano particles based on miniemulsion copolymerization process, and the method is simple and easy to do, and system stability is good.The present invention, in mini-emulsion polymerization system, forms aggregation-induced emission type polymer nano-particle in the mode of nano single drop nucleated directly, and the size of particle can regulate easily in 50-500 nanometer range.The fluorescence intensity of aggregation-induced emission type polymer nano-particle regulates and controls by the amount of fluorescent monomer, and glow color is by the type adjustment of fluorescent monomer.The nucleation mode of monomer droplet make some facile hydrolysis or super-hydrophobic aggregation-induced emission fluorescent monomer also by miniemulsion copolymerization to prepare aggregation-induced emission type polymer fluorescent nano particle.Aggregation-induced emission polymer fluorescent nano particle prepared by the present invention has good biocompatibility, chemical stability and higher fluorescent brightness, has broad application prospects in bio-imaging field.
The technical solution used in the present invention is:
The mini-emulsion polymerization that water soluble starter causes prepares a method for aggregation-induced emission type polymer fluorescent nano particle emulsion, said method comprising the steps of:
(1) aggregation-induced emission fluorescent monomer and co-stabilizer are dissolved in monomeric compound, obtain oil-phase solution;
Described aggregation-induced emission fluorescent monomer is one or more mixing of following compounds:
In formula (II), R
1for the fatty straight or branched alkylidene group of C1 ~ C8;
One or more the mixing that described monomeric compound is following compounds: vinylbenzene, the acrylic ester compound shown in formula (VI);
In formula (VI), R
2for H or CH
3; R
3for the fatty straight or branched alkyl of C1 ~ C10, hydroxyethyl, dimethylaminoethyl or trifluoroethyl;
Described co-stabilizer is selected from one or more mixing below: the fatty straight or branched alkane of C14 ~ C22, the fatty alcohol of C14 ~ C22;
(2) by soluble in water for water miscible emulsifying agent, obtain the aqueous solution of emulsifying agent, described water miscible emulsifying agent be selected from following one or more: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, the compound shown in formula (VII), OP 10 emulsifying agent, fatty alcohol and ethylene oxide condensate (MOA);
In formula (VII), R
4for the fatty straight or branched alkyl of C12 ~ C18, X is Cl or Br.
(3) oil-phase solution in step (1) is added in the aqueous solution of the emulsifying agent in step (2); through stirring pre-emulsification; obtain thick emulsion; the container that thick emulsion is housed is placed in the ice-water bath of 0 DEG C; ultrasonic disperse obtains monomer miniemulsion; water soluble starter is added in obtained monomer miniemulsion; then letting nitrogen in and deoxidizing; under nitrogen protection; react 0.5 hour ~ 2 days at 40 ~ 90 DEG C of temperature, obtained aggregation-induced emission type polymer fluorescent nano particle emulsion.
The emulsion of the aggregation-induced emission type polymer fluorescent nano particle that the present invention obtains, by centrifugation, drying, can obtain aggregation-induced emission type polymer fluorescent nano particle further.
Described water soluble starter be selected from following one or more: persulphate, 2, the redox system that 2 '-azo diisobutyl amidine dihydrochloride, oxygenant and reductive agent are formed, in described redox system, described reductive agent is sodium bisulfite, Sulfothiorine, S-WAT, tertiary amine alcohol or primary amine, and described oxygenant is persulphate or hydrogen peroxide.Described persulphate is generally ammonium persulphate or Potassium Persulphate.
Further, the preferred Potassium Persulphate of described water soluble starter, 2, the one in the redox initiation system that the redox initiation system that 2 '-azo diisobutyl amidine dihydrochloride, sodium bisulfite and ammonium persulphate are formed, trolamine and hydrogen peroxide are formed.
Described water soluble starter be oxygenant and reductive agent form redox initiation system time, general first in monomer miniemulsion, add reductive agent, letting nitrogen in and deoxidizing, be heated to temperature of reaction under nitrogen protection after, then add oxygenant, initiated polymerization.This is that art technology people is known.
The quality consumption of described aggregation-induced emission fluorescent monomer is 0.5% ~ 50% of monomeric compound total mass.
The quality of described co-stabilizer is 0.01 ~ 0.13:1, preferably 0.03 ~ 0.1:1 with the ratio of monomeric compound total mass.
In described step (1), the total mass of monomeric compound and the mass ratio of the middle water of step (2) are 0.01 ~ 0.3:1, preferably 0.04 ~ 0.2:1.
The quality consumption of described water miscible emulsifying agent is 0.1% ~ 10% of the quality consumption of water.
The quality consumption of described water soluble starter is 0.1% ~ 12% of monomeric compound total mass, preferably 0.6 ~ 10%.
In described step (3), ultrasonic power is 100 ~ 950W, and ultrasonic time is 0.5 minute ~ 60 minutes.
Described monomeric compound is preferably vinylbenzene or methyl methacrylate.
Consider the cost that aggregation-induced emission fluorescent monomer is higher, under the prerequisite ensureing enough fluorescence intensity, the consumption of fluorescent monomer is preferably 0.5% ~ 35% of monomeric compound total mass, and more preferably 5 ~ 33%.
Consider system stability, one in described water miscible emulsifying agent preferably sodium dodecyl sulfate, Sodium dodecylbenzene sulfonate, the compound shown in formula (VII), or sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, a kind of and a kind of composite emulsifying system be mixed to get in OP-10 or MOA in the compound shown in formula (VII).Preferred, described water miscible emulsifying agent is the one in the composite emulsifying system of composite emulsifying system, octadecyl trimethyl ammonium chloride and the MOA-9 mixing that sodium lauryl sulphate, cetyl trimethylammonium bromide, Sodium dodecylbenzene sulfonate and OP-10 mix.
The quality consumption of water miscible emulsifying agent is preferably 0.3% ~ 5% of the quality consumption of water, and more preferably 0.5% ~ 3.2%.
Described fatty alcohol and ethylene oxide condensate (MOA) are a conventional class emulsifying agent, and can direct market purchase obtain, can be MOA-3, MOA-4, MOA-5, MOA-7, MOA-9 etc.
Consider the stability of drop, the fatty straight or branched alkane of preferred C16 ~ C22 is co-stabilizer, and more preferably co-stabilizer is n-Hexadecane or NSC 62789.
Consider the structural stability of aggregation-induced emission fluorescent monomer, polymeric reaction temperature is preferably 40 ~ 80 DEG C, more preferably 40 ~ 70 DEG C; Preferably 1 hour ~ 24 hours reaction times, more preferably 3 ~ 24 hours.
In described step (3), the ice-water bath thick emulsion being positioned over 0 DEG C carries out ultrasonic, is to prevent it from crossing thermal initiation thermopolymerization.Ultrasonic power is 125 ~ 750W preferably, ultrasonic time preferably 2 ~ 50 minutes.
Contriver finds through further investigation, and the aggregation-induced emission fluorescent monomer that the present invention relates to can be dissolved in conventional hydrophobic monomer, forms homogeneous hydrophobic sol together with co-stabilizer.After this monomer solution mixes with emulsifier aqueous solution, by homogenizing process, stable monomer miniemulsion can be obtained.The size of monomer droplet with the increase of ultrasound intensity, the increase of emulsifier, the decline of monomer solution and water ratio and reducing.Emulsifier type is also very large on the impact of drop size, compared with nonionic emulsifier, adopts the strong ionic emulsifying agent of emulsifying capacity can obtain the less monomer droplet of size.
Under initiator effect, monomer miniemulsion forms fluorescent polymer particles by droplet nucleation mode, and the size of monomer droplet determines the size of fluorescent polymer particles.The fluorescence intensity of polymer nano-particle can be regulated by the content of fluorescent monomer, in general, improves fluorescent monomer content and is conducive to improving its fluorescent brightness.For the aggregation-induced emission monomer molecule of structural stability difference, extend the reaction times or improve temperature of reaction, aggregation-induced emission structural damage can be caused and fluorescence intensity is declined.
The emission wavelength of fluorescent polymer particles regulates and controls by the type of aggregation-induced emission fluorescent monomer.For different sorts aggregation-induced emission fluorescent monomer, after monomeric compound copolymerization, the polymer fluorescent nano particle of gained can present the color developing effect of this fluorescent monomer substantially.But the kind of monomeric compound also can affect the luminescent properties of fluorescent nano particles to a certain extent, the molecular structure of this and monomeric compound, as conjugated degree, sterically hindered have much relations.
The present invention proposes to utilize miniemulsion copolymerization to prepare the polymer fluorescent nano particle having aggregation-induced emission characteristic first.First pass through ultrasonic fine crankshaft by containing the aggregation-induced emission monomer of vinyl and the mixing solutions of monomeric compound, be scattered in emulsifier aqueous solution, obtain monomer miniemulsion; Under certain temperature and nitrogen protection, obtain aggregation-induced emission polymer fluorescent nano particle by miniemulsion radical copolymerization.
The advantage of the inventive method is: the fine emulsion polymerization technique that (1) the present invention relates to is simple, a step aggregation-induced emission fluorescent monomer and conventional monomeric can be connected to form polymer nano-particle by covalent linkage.As conventional water base heterogeneous polymerization system, miniemulsion reaction system easily amplifies production.(2) the aggregation-induced emission monomer that miniemulsion system can introduce super-hydrophobic or facile hydrolysis participates in copolymerization and prepares aggregation-induced emission type polymer nano-particle.(3) by the ratio of comonomer, the composition of polymkeric substance can be regulated and controled, and then regulate the fluorescence intensity of aggregation-induced emission fluorescent nano particles within the specific limits; The size of aggregation-induced emission fluorescent nano particles can be regulated and controled easily by conditions such as emulsifier and type, water-oil ratio, ultrasound intensity and times.(4) the present invention's made aggregation-induced emission type polymer fluorescent nano particle emulsion is the aqueous dispersions of good stability, through simple except after emulsifying agent process, and can directly as imaging biological cells agent.(5) reaction of the present invention and last handling process are all without the need to organic solvent, environmental friendliness.
Beneficial effect of the present invention is mainly reflected in: the present invention proposes a kind of method being prepared aggregation-induced emission polymer fluorescent nano particle by miniemulsion copolymerization technology newly, the advantage of the method is: the regulation and control of the size of nanoparticle, distribution of sizes and fluorescent brightness are convenient, system stability is good, preparation process is simple, technical process is short, preparation and last handling process be without the need to organic solvent.By introducing functional response monomer, functionalized modification can also be carried out to polymer nano-particle, being convenient to biological coupling modifier.The polymer fluorescent nano particle of aggregation-induced emission characteristic that what the present invention obtained have, can be used as fluorescent probe has large potential using value in biological detection and cell imaging field.
(4) accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of embodiment 1 gained aggregation-induced emission type polymer fluorescent nano particle.
Fig. 2 is the fluorescence emission spectrogram of embodiment 1 gained aggregation-induced emission type polymer fluorescent nano particle emulsion.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
Sodium lauryl sulphate selected by emulsifying agent, takes 4 grams, is dissolved in 125 grams of distilled water, obtains emulsifier aqueous solution.
1.0 grams of 1-allyl group-1-methyl-2,3,4,5-tetraphenyl thiophenes are coughed up and are dissolved in 9.0 grams of methyl methacrylates with 0.6 gram of n-Hexadecane, obtain oil-phase solution.Gained oil-phase solution joins in emulsifier aqueous solution, and gained mixed dispersion liquid obtains thick emulsion through stirring after pre-emulsification, the container filling thick emulsion is placed in the ice-water bath of 0 DEG C, is the ultrasonic echography 10 minutes of 400W, obtains stable monomer miniemulsion with power.
In above-mentioned monomer miniemulsion, add 0.5 gram of water soluble starter Potassium Persulphate, letting nitrogen in and deoxidizing, temperature rises to 70 DEG C, reacts 3 hours under nitrogen protection, obtains aggregation-induced emission type polymer fluorescent nano particle emulsion.
By size and the form of determination of transmission electron microscopy nanoparticle, see Fig. 1.Result display particle is spherical in shape, and number average bead diameter is about 58 nanometers.Measure the luminescent properties of this aggregation-induced emission polymer fluorescent nano particle emulsion by fluorescence spectrophotometer, result display emulsion is under ultraviolet excitation, and maximum emission wavelength is 482 nanometers, and as shown in Figure 2, turn blue fluorescence emission spectrum green glow.The emulsion of aggregation-induced emission type polymer fluorescent nano particle obtains polymer fluorescent nano particle by centrifugation, drying.Resulting polymers is dissolved in tetrahydrofuran (THF), obtains the tetrahydrofuran solution that polymer concentration is 0.01 grams per milliliter; Get 10 microlitre polymkeric substance tetrahydrofuran solutions, be added drop-wise in the tetrahydrofuran (THF)/water mixed solution of 2 milliliters of different water-contents, mix the luminescent properties that rear fluorescence spectrophotometer measures polymers soln.Water is the poor solvent of polymkeric substance, and experimental result shows, along with water-content in system increases, multipolymer aggregation extent increases, and the fluorescence intensity of copolymer solution increases, and illustrates that gained multipolymer has typical aggregation-induced emission feature.
Embodiment 2:
Cetyl trimethylammonium bromide selected by emulsifying agent, takes 0.6 gram, is dissolved in 40 grams of distilled water, obtains emulsifier aqueous solution.
2.5 grams of 1-vinyl-1-methyl-2,3,4,5-tetraphenyl thiophenes are coughed up and are dissolved in 7.5 grams of vinylbenzene with 1 gram of NSC 62789, obtain oil-phase solution.Gained oil-phase solution joins in emulsifier aqueous solution, gained mixed dispersion liquid, after stirring pre-emulsification, obtains thick emulsion, the container filling thick emulsion is placed in the ice-water bath of 0 DEG C, with the ultrasonic echography 50 minutes that power is 125W, obtain stable monomer miniemulsion.
In above-mentioned monomer miniemulsion, add 0.9 gram of initiator 2,2 '-azo diisobutyl amidine dihydrochloride, letting nitrogen in and deoxidizing, temperature rises to 60 DEG C, under nitrogen protection, reacts 20 hours, obtains aggregation-induced emission polymer fluorescent nano particle emulsion.
By size and the form of determination of transmission electron microscopy nanoparticle, result display particle is spherical in shape, and number average bead diameter is about 80 nanometers.Measure the luminescent properties of this aggregation-induced emission polymer fluorescent nano particle emulsion by fluorescence spectrophotometer, result display emulsion is under ultraviolet excitation, and maximum emission wavelength is 475 nanometers, blue light-emitting.Aggregation-induced emission polymer fluorescent nano particle emulsion obtains polymer fluorescent nano particle by centrifugation, drying.Resulting polymers is dissolved in tetrahydrofuran (THF), obtains the tetrahydrofuran solution that polymer concentration is 0.01 grams per milliliter; Get 10 microlitre polymkeric substance tetrahydrofuran solutions, be added drop-wise in the tetrahydrofuran (THF)/water mixed solution of 2 milliliters of different water-contents, mix the luminescent properties that rear fluorescence spectrophotometer measures polymers soln.Water is the poor solvent of polymkeric substance, and experimental result shows, along with water-content in system increases, multipolymer aggregation extent increases, and the fluorescence intensity of copolymer solution increases, and illustrates that gained multipolymer has typical aggregation-induced emission feature.
Embodiment 3:
Emulsifying agent selects Sodium dodecylbenzene sulfonate and OP-10 compound emulsion system, respectively takes 0.5 gram, is dissolved in 200 grams of distilled water, obtains emulsifier aqueous solution.
Shown in 0.5 gram of formula (IV), compound (synthetic method is see document [Polym Chem 2014,5,683-688]) and 0.3 gram of n-hexadecane are dissolved in 9.5 grams of methyl methacrylates, obtain oil-phase solution.Gained oil-phase solution joins in emulsifier aqueous solution, and gained mixed dispersion liquid, through stirring after pre-emulsification, obtains thick emulsion, the container filling thick emulsion is placed in the ice-water bath of 0 DEG C, is the ultrasonic echography 5 minutes of 600W, obtains stable monomer miniemulsion with power.
In above-mentioned monomer miniemulsion, add 0.1 gram of trolamine, letting nitrogen in and deoxidizing, temperature rises to 55 DEG C, under nitrogen protection, then adds 0.2 gram of hydrogen peroxide, reacts 10 hours, obtains aggregation-induced emission type polymer fluorescent nano particle emulsion.
By size and the form of determination of transmission electron microscopy nanoparticle, result display particle is spherical in shape, and number average bead diameter is about 95 nanometers.Measure the luminescent properties of this aggregation-induced emission polymer fluorescent nano particle emulsion by fluorescence spectrophotometer, result display emulsion is under ultraviolet excitation, and maximum emission wavelength is 552 nanometers, sends out light orange.Aggregation-induced emission polymer fluorescent nano particle emulsion obtains polymer fluorescent nano particle by centrifugation, drying.Resulting polymers is dissolved in a certain amount of tetrahydrofuran (THF), obtains the tetrahydrofuran solution that polymer concentration is 0.01 grams per milliliter; Get 10 microlitre polymkeric substance tetrahydrofuran solutions, be added drop-wise in the tetrahydrofuran (THF)/water mixed solution of 2 milliliters of different water-contents, mix the luminescent properties that rear fluorescence spectrophotometer measures polymers soln.Water is the poor solvent of polymkeric substance, and experimental result shows, along with water-content in system increases, multipolymer aggregation extent increases, and the fluorescence intensity of copolymer solution increases, and illustrates that gained multipolymer has typical aggregation-induced emission feature.
Embodiment 4:
Emulsifying agent selects octadecyl trimethyl ammonium chloride and MOA-9 compound emulsion system, takes 0.4 gram and 1.2 grams respectively, is dissolved in 80 grams of distilled water, obtains emulsifier aqueous solution.
Compound (synthetic method is see document [Chem.Commun2009,4974-4976]) shown in 1.5 grams of formulas (V) and 0.8 gram of n-Hexadecane are dissolved in 8.5 grams of methyl methacrylates, obtain oil-phase solution.Gained oil-phase solution joins in emulsifier aqueous solution, and gained mixed dispersion liquid, through stirring after pre-emulsification, obtains thick emulsion, the container filling thick emulsion is placed in the ice-water bath of 0 DEG C, is the ultrasonic echography 2 minutes of 750W, obtains stable monomer miniemulsion with power.
In above-mentioned monomer miniemulsion, first add 0.02 gram of sodium bisulfite, letting nitrogen in and deoxidizing, temperature rises to 40 DEG C, under nitrogen protection, then adds 0.04 gram of initiator ammonium persulfate, reacts 8 hours, obtains aggregation-induced emission type polymer fluorescent nano particle emulsion.
By size and the form of determination of transmission electron microscopy nanoparticle, result display particle is spherical preferably, and number average bead diameter is about 88 nanometers.Measure the luminescent properties of this aggregation-induced emission polymer fluorescent nano particle emulsion by fluorescence spectrophotometer, result display emulsion is under ultraviolet excitation, and maximum emission wavelength is 476 nanometers, blue light-emitting.Aggregation-induced emission polymer fluorescent nano particle emulsion obtains polymer fluorescent nano particle by centrifugation, drying.Resulting polymers is dissolved in a certain amount of tetrahydrofuran (THF), obtains the tetrahydrofuran solution that polymer concentration is 0.01 grams per milliliter; Get 10 microlitre polymkeric substance tetrahydrofuran solutions, be added drop-wise in the tetrahydrofuran (THF)/water mixed solution of 2 milliliters of different water-contents, mix the luminescent properties that rear fluorescence spectrophotometer measures polymers soln.Water is the poor solvent of polymkeric substance, and experimental result shows, along with water-content in system increases, multipolymer aggregation extent increases, and the fluorescence intensity of copolymer solution increases, and illustrates that gained multipolymer has typical aggregation-induced emission feature.
The above embodiment of the present invention can not limit the present invention to explanation of the present invention, any change in the implication suitable with claims of the present invention and scope, all should think to be included in the scope of claims.
Claims (10)
1. the mini-emulsion polymerization that water soluble starter causes prepares a method for aggregation-induced emission type polymer fluorescent nano particle emulsion, it is characterized in that said method comprising the steps of:
(1) aggregation-induced emission fluorescent monomer and co-stabilizer are dissolved in monomeric compound, obtain oil-phase solution;
Described aggregation-induced emission fluorescent monomer is one or more mixing of following compounds:
In formula (II), R
1for the fatty straight or branched alkylidene group of C1 ~ C8;
One or more the mixing that described monomeric compound is following compounds: vinylbenzene, the acrylic ester compound shown in formula (VI);
In formula (VI), R
2for H or CH
3; R
3for the fatty straight or branched alkyl of C1 ~ C10, hydroxyethyl, dimethylaminoethyl or trifluoroethyl;
Described co-stabilizer is selected from one or more mixing below: the fatty straight or branched alkane of C14 ~ C22, the fatty alcohol of C14 ~ C22;
(2) by soluble in water for water miscible emulsifying agent, obtain the aqueous solution of emulsifying agent, described water miscible emulsifying agent be selected from following one or more: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, the compound shown in formula (VII), OP 10 emulsifying agent, fatty alcohol and ethylene oxide condensate;
In formula (VII), R
4for the fatty straight or branched alkyl of C12 ~ C18, X is Cl or Br;
(3) oil-phase solution in step (1) is added in the aqueous solution of the emulsifying agent in step (2), through stirring pre-emulsification, obtain thick emulsion, the container that thick emulsion is housed is placed in the ice-water bath of 0 DEG C, ultrasonic disperse obtains monomer miniemulsion, water soluble starter is added in obtained monomer miniemulsion, then letting nitrogen in and deoxidizing, under nitrogen protection, react 0.5 hour ~ 2 days at 40 ~ 90 DEG C of temperature, obtained aggregation-induced emission type polymer fluorescent nano particle emulsion;
Described water soluble starter be selected from following one or more: persulphate, 2, the redox system that 2 '-azo diisobutyl amidine dihydrochloride, oxygenant and reductive agent are formed, in described redox system, described reductive agent is sodium bisulfite, Sulfothiorine, S-WAT, tertiary amine alcohol or primary amine, and described oxygenant is persulphate or hydrogen peroxide.
2. the method for claim 1, it is characterized in that in described step (1), the quality consumption of described aggregation-induced emission fluorescent monomer is 0.5% ~ 50% of monomeric compound total mass, and the quality of described co-stabilizer is 0.01 ~ 0.13:1 with the ratio of monomeric compound total mass; In described step (1), the total mass of monomeric compound and the mass ratio of the middle water of step (2) are 0.01 ~ 0.3:1; In described step (2), the quality consumption of described water miscible emulsifying agent is 0.1% ~ 10% of the quality consumption of water.
3. method as claimed in claim 1 or 2, it is characterized in that, in described step (3), ultrasonic power is 100 ~ 950W, ultrasonic time is 0.5 minute ~ 60 minutes.
4. method as claimed in claim 1 or 2, is characterized in that described monomeric compound is vinylbenzene or methyl methacrylate.
5. method as claimed in claim 1 or 2, is characterized in that described co-stabilizer is the fatty straight or branched alkane of C16 ~ C22.
6. the method for claim 1, it is characterized in that described water miscible emulsifying agent is sodium lauryl sulphate, one in Sodium dodecylbenzene sulfonate, the compound shown in formula (VII), or sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, a kind of and a kind of composite emulsifying system be mixed to get in OP-10 or MOA in the compound shown in formula (VII).
7. method as claimed in claim 1 or 2, is characterized in that the quality consumption of described water soluble starter is 0.1% ~ 12% of monomeric compound total mass.
8. method as claimed in claim 1 or 2, is characterized in that the temperature of described reaction is 40 ~ 80 DEG C; 1 ~ 24 hour reaction times.
9. method as claimed in claim 1 or 2, it is characterized in that described water soluble starter is Potassium Persulphate, 2, the one in the redox initiation system that the redox initiation system that 2 '-azo diisobutyl amidine dihydrochloride, sodium bisulfite and ammonium persulphate are formed, trolamine and hydrogen peroxide are formed.
10. the mini-emulsion polymerization that water soluble starter causes prepares a method for aggregation-induced emission type polymer fluorescent nano particle, it is characterized in that said method comprising the steps of:
(1) aggregation-induced emission fluorescent monomer and co-stabilizer are dissolved in monomeric compound, obtain oil-phase solution; The quality consumption of described aggregation-induced emission fluorescent monomer is 0.5% ~ 50% of monomeric compound total mass, and the quality of described co-stabilizer is 0.01 ~ 0.13:1 with the ratio of monomeric compound total mass;
Described aggregation-induced emission fluorescent monomer is one or more mixing of following compounds:
In formula (II), R
1for the fatty straight or branched alkylidene group of C1 ~ C8;
One or more the mixing that described monomeric compound is following compounds: vinylbenzene, the acrylic ester compound shown in formula (VI);
In formula (VI), R
2for H or CH
3; R
3for the fatty straight or branched alkyl of C1 ~ C10, hydroxyethyl, dimethylaminoethyl or trifluoroethyl;
Described co-stabilizer is selected from one or more mixing below: the fatty straight or branched alkane of C14 ~ C22, the fatty alcohol of C14 ~ C22;
(2) by soluble in water for water miscible emulsifying agent, obtain the aqueous solution of emulsifying agent, described water miscible emulsifying agent be selected from following one or more: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, the compound shown in formula (VII), OP 10 emulsifying agent, fatty alcohol and ethylene oxide condensate;
In described step (1), the total mass of monomeric compound and the mass ratio of the middle water of step (2) are 0.01 ~ 0.3:1; In described step (2), the quality consumption of described water miscible emulsifying agent is 0.1% ~ 10% of the quality consumption of water
In formula (VII), R
4for the fatty straight or branched alkyl of C12 ~ C18, X is Cl or Br;
(3) oil-phase solution in step (1) is added in the aqueous solution of the emulsifying agent in step (2), through stirring pre-emulsification, obtain thick emulsion, the container that thick emulsion is housed is placed in the ice-water bath of 0 DEG C, ultrasonic disperse obtains monomer miniemulsion, water soluble starter is added in obtained monomer miniemulsion, then letting nitrogen in and deoxidizing, under nitrogen protection, react 0.5 hour ~ 2 days at 40 ~ 90 DEG C of temperature, obtained aggregation-induced emission type polymer fluorescent nano particle emulsion; Described aggregation-induced emission type polymer fluorescent nano particle emulsion, through centrifugation, drying, obtains aggregation-induced emission type polymer fluorescent nano particle;
Described water soluble starter be selected from following one or more: persulphate, 2, the redox system that 2 '-azo diisobutyl amidine dihydrochloride, oxygenant and reductive agent are formed, in described redox system, described reductive agent is sodium bisulfite, Sulfothiorine, S-WAT, tertiary amine alcohol or primary amine, and described oxygenant is persulphate or hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510018731.3A CN104628924A (en) | 2015-01-14 | 2015-01-14 | Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by water-soluble initiator |
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| CN105820813A (en) * | 2016-05-16 | 2016-08-03 | 吉林大学 | Cyanostyrene supramolecular gel film, preparation method and application thereof in detecting concentration of carbon dioxide in air |
| CN107417849A (en) * | 2017-08-23 | 2017-12-01 | 湖南科技大学 | A kind of near infrared light switch fluorescent polymer nano-particle prepares and its application |
| CN108587609A (en) * | 2018-06-28 | 2018-09-28 | 上海交通大学 | A kind of nanoparticle and preparation method and application based on gathering induced luminescence material |
| CN110092863A (en) * | 2019-05-15 | 2019-08-06 | 浙江理工大学 | A kind of preparation method of amino and peptide modified AIE polymer nano-particle |
| CN110092858A (en) * | 2019-05-15 | 2019-08-06 | 浙江理工大学 | A kind of preparation method of carboxyl and peptide modified AIE polymer nano-particle |
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| CN110156923A (en) * | 2019-05-15 | 2019-08-23 | 浙江理工大学 | A kind of preparation method of carboxyl and peptide modified AIE polymer nano-particle |
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| CN107417849A (en) * | 2017-08-23 | 2017-12-01 | 湖南科技大学 | A kind of near infrared light switch fluorescent polymer nano-particle prepares and its application |
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| CN110128583B (en) * | 2019-03-06 | 2021-05-07 | 浙江理工大学 | Preparation method of AIE polymer nanoparticles modified by amino and polypeptide |
| CN110092858A (en) * | 2019-05-15 | 2019-08-06 | 浙江理工大学 | A kind of preparation method of carboxyl and peptide modified AIE polymer nano-particle |
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| CN110092863A (en) * | 2019-05-15 | 2019-08-06 | 浙江理工大学 | A kind of preparation method of amino and peptide modified AIE polymer nano-particle |
| CN110092863B (en) * | 2019-05-15 | 2021-07-16 | 浙江理工大学 | Preparation method of AIE polymer nanoparticles modified by amino and polypeptide |
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