CN111116813A - Preparation method of fluorescent microspheres based on crosslinked polymer - Google Patents
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Abstract
The invention discloses a preparation method of fluorescent microspheres based on crosslinked polymers, wherein fluorescent substances in the microspheres are organic fluorescent dyes, and the preparation method comprises the following steps: firstly, dissolving a dispersant polyvinylpyrrolidone in an alcohol-water polar medium in a certain proportion, and dispersing to obtain a clear and transparent solution; secondly, adding an initiator azobisisobutyronitrile, a rhodamine fluorescent monomer and a polymer monomer into the system; and thirdly, adding a cross-linking agent solution in which an initiator and a monomer are dissolved, stirring and dispersing uniformly, and carrying out polymerization reaction at a certain temperature under the protection of nitrogen to obtain the monodisperse cross-linked polymer fluorescent microspheres. On the basis of the traditional dispersion polymerization method, the feeding time is changed, so that the monodispersity of the fluorescent microspheres is improved; the rhodamine fluorescent dye can be directly obtained; the fluorescent microsphere prepared by using the crosslinked polymer copolymerization wrapped fluorescent dye has a stable body structure and fluorescence efficiency, and good solvent resistance and thermal stability.
Description
Technical Field
The invention relates to a preparation method of functional polymer microspheres, in particular to a preparation method of fluorescent microspheres based on crosslinked polymers.
Background
Fluorescent microspheres refer to solid particles with diameters ranging from nano-scale to micro-scale, wherein fluorescent substances are loaded on the surfaces or the inner parts of the microspheres, and the solid particles can excite fluorescence under the stimulation of external energy or visible light. The fluorescent microsphere has a stable morphological structure and high-efficiency luminous efficiency, is less influenced by external conditions such as heat, magnetism, solution and the like than an independent fluorescent substance, is widely used in the biomedical field as a novel functional polymer material, such as directional drug delivery, immunoassay, cell marking, high-flux drug screening and the like in the biomedical field, and can also be used for some experimental detections, such as flow cytometry, fluid flow field tracing display, phagocytic function detection and the like.
As a carrier of the fluorescent substance, the polymer microsphere has a stable morphological structure, and can reduce the influence of the external environment on the optical performance of the fluorescent substance. Common microsphere materials include silica, polystyrene, polymethyl methacrylate, polyacrylates, chitosan, and the like. The cross-linked polymer fluorescent microspheres are rarely reported, and the cross-linked polymer microspheres have wide application prospects as a carrier material with excellent performance, and have the advantages of good sphericity, uniform particle size, small particle size and the like compared with non-cross-linked polymer microspheres. Compared with single polymer fluorescent microspheres, the cross-linked polymer fluorescent microspheres have improved solvent resistance, thermal stability, wear resistance and the like to different degrees.
The preparation method of the fluorescent microsphere is divided into a physical method and a chemical method. The physical method obtains the fluorescent microsphere through simple adsorption, and has the defect that the dye is easy to fall off. The chemical method is to copolymerize the fluorescent monomer and the polymer monomer by suspension polymerization, emulsion polymerization, dispersion polymerization and other methods. The microsphere prepared by the dispersion polymerization method has small particle size and good monodispersity, so that the prepared fluorescent microsphere has stable performance in all aspects, and the polymerization reaction process is simple and short in time. However, it is difficult to prepare monodisperse crosslinked polymer microspheres by the conventional dispersion polymerization method, mainly because the crosslinking agent affects the nucleation stage of the reaction, so that the polymerization reaction occurs on the surface of the microspheres, and the dispersibility of the microspheres is deteriorated due to the crosslinking generated between the microspheres.
The existing patent reports a preparation method of nano fluorescent microspheres, which comprises the steps of firstly dissolving fluorescent dye in an organic solvent to obtain a fluorescent dye solution, adding a monomer, a cross-linking agent, a dispersing agent and the like, and carrying out dispersion polymerization to obtain the nano fluorescent microspheres. The fluorescent microspheres prepared by the method have poor monodispersity and poor fluorescence due to polymer agglomeration caused by adding the cross-linking agent at the beginning of the reaction.
Disclosure of Invention
The invention aims to provide a preparation method of fluorescent polymer microspheres, and particularly relates to a preparation method of crosslinked polymer fluorescent microspheres with good monodispersity, uniform particle size and high fluorescence intensity.
A preparation method of fluorescent microspheres based on cross-linked polymers is to polymerize cross-linked polymers and rhodamine dyes to obtain the fluorescent microspheres, and the fluorescent microspheres are prepared by the following method:
step one, dissolving a dispersant polyvinylpyrrolidone in an alcohol-water solution, wherein the alcohol-water solution is a polar dispersion medium, then placing the alcohol-water solution containing polyvinylpyrrolidone in a 250ml four-neck round-bottom flask equipped with a mechanical stirrer, a condenser tube and a nitrogen protection device, and obtaining a homogeneous system through mechanical stirring.
And step two, dissolving the initiator azodiisobutyronitrile and the fluorescent dye in the polymer monomer, and dispersing and mixing the polymer monomer and the fluorescent dye uniformly by ultrasonic oscillation to obtain a fluorescent monomer mixed solution.
And step three, adding the fluorescent monomer mixed solution into a reaction system, mechanically stirring at a constant speed to uniformly mix and disperse the fluorescent monomer mixed solution, keeping the polymerization reaction temperature at 60-75 ℃, then adding a cross-linking agent solution, carrying out polymerization reaction under the protection of constant-temperature water bath and nitrogen, and washing and drying after the reaction lasts for 12-24 hours to obtain the cross-linked polymer fluorescent microspheres.
In the polymerization reaction of the first step, the water polar dispersion medium is allowed to be any one of mixed solutions of isopropanol and water, ethanol and water, and methanol and water.
The isopropanol and water, the ethanol and water, and the methanol and water are mixed according to the volume ratio of 5:1 to obtain the composite material.
In the polymerization reaction of the first step, the amount of the dispersant polyvinylpyrrolidone accounts for 5-10% of the reaction system, and the reaction temperature is 60 ℃.
In the polymerization reaction of the second step, the organic fluorescent dye is allowed to be any one of rhodamine B and rhodamine 6G; the amount of the fluorescent dye is 0.2-0.5 ml/g of the reaction system.
In the polymerization reaction of the second step, the polymer monomer is allowed to be any one of styrene, methyl methacrylate and acrylamide, and the using amount of the polymer monomer accounts for 5-10% of the reaction system; and the polymer monomers styrene and acrylamide and styrene and methyl methacrylate can be mixed according to the volume ratio of 1: 1.
In the polymerization reaction of the third step, the cross-linking agent solution is allowed to be any one of a functional monomer acrylic acid solution and a divinylbenzene solution; the dosage of the cross-linking agent solution accounts for 0.05-0.1% of the reaction system.
In the polymerization reaction in the third step, the cross-linking agent solution is composed of an initiator, a monomer and a cross-linking agent, after the temperature of the cross-linking agent solution in a reaction system is raised to 70 ℃, the system begins to be turbid after 1-2 h of reaction, and the cross-linking agent solution is added.
The invention has the beneficial effects that:
(1) according to the invention, the cross-linked polymer is used as a microsphere material, so that the fluorescent dye is well wrapped in the microsphere, the fluorescent dye stably exists in the microsphere, the leakage and quenching of the fluorescent dye are reduced, the overall luminous efficiency of the microsphere is improved, and the microsphere has good solvent resistance, thermal stability and suspension property.
(2) The fluorescent dyes rhodamine B and rhodamine 6G are red or orange-red laser dyes, the maximum absorption and emission wavelengths of the laser dyes are longer, the fluorescent wavelengths cover an ultraviolet-visible light region and a near ultraviolet region and are about 600nm, and the orange-red light can provide bright contrast colors and can be well applied to fluid tracing, fluorescent labeling and the like.
(3) The invention adopts the dispersion polymerization method to prepare the cross-linked fluorescent microspheres, so that the preparation method is simple and convenient to operate, the prepared microspheres have uniform particle size and good monodispersity, and the pollution to the environment can be reduced in the preparation process.
(4) According to the invention, a two-step feeding mode is adopted, after the polymer monomer reacts for 1-2 h, the cross-linking agent solution with the initiator and the monomer is added, so that the influence of the cross-linking agent on the nucleation period of the polymer can be reduced, the initial polymer particles are taken as templates to continue polymerization, the cross-linked polymer fluorescent microspheres are finally obtained, and the monodispersity of the microspheres is improved.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example one
A preparation method of fluorescent microspheres based on crosslinked polymers comprises the following steps:
firstly, 5 wt% of dispersant polyvinylpyrrolidone and a certain proportion of methanol and aqueous solution are added into a 250ml four-neck round-bottom flask equipped with a mechanical stirrer, a condenser tube and a nitrogen conduit, and the mixture is stirred at a temperature of 60 ℃ and a mechanical stirring speed of 190r/min to form a clear and transparent dispersant solution.
And secondly, respectively weighing 0.1G of initiator azobisisobutyronitrile and 20mg of fluorescent dye rhodamine 6G or rhodamine B, dissolving the initiator and the rhodamine B in 5.0G of styrene monomer, and uniformly mixing and dispersing the initiator and the rhodamine B by ultrasonic oscillation to form a fluorescent monomer mixed solution.
And thirdly, adding the fluorescent monomer mixed solution in the second step into a dispersant solution, stirring and mixing uniformly, introducing nitrogen to remove oxygen for 0.5h, and sealing. Placing in a constant temperature water bath, reacting for 12h in a constant temperature water bath at 70 ℃ under the condition of stirring speed of 200r/min, adding 0.1 wt% acrylic acid solution dissolved with initiator and styrene when the system becomes emulsion, and reacting again. And finally, obtaining monodisperse fluorescent microsphere emulsion, washing with deionized water and absolute ethyl alcohol for multiple times after centrifugation to remove unreacted monomers and fluorescent dye, and drying in vacuum at 40 ℃ for 12 hours to obtain the cross-linked polymer fluorescent microsphere.
Example two
A preparation method of fluorescent microspheres based on crosslinked polymers comprises the following steps:
firstly, 5 wt% of dispersant polyvinylpyrrolidone and a certain proportion of methanol and aqueous solution are added into a 250ml four-neck round-bottom flask equipped with a mechanical stirrer, a condenser tube and a nitrogen conduit, and the mixture is stirred at a temperature of 60 ℃ and a mechanical stirring speed of 190r/min to form a clear and transparent dispersant solution.
And secondly, respectively weighing 0.1G of initiator azodiisobutyronitrile and 20mg of fluorescent dye rhodamine 6G or rhodamine B, dissolving the initiator azodiisobutyronitrile and the fluorescent dye rhodamine B in 5.0G of methyl methacrylate monomer, and uniformly mixing and dispersing the initiator azodiisobutyronitrile and the fluorescent dye rhodamine 6G or rhodamine B by ultrasonic oscillation to form a fluorescent monomer mixed solution.
And thirdly, adding the fluorescent monomer mixed solution in the second step into a dispersant solution, stirring and mixing uniformly, introducing nitrogen to remove oxygen for 0.5h, and sealing. Placing in a constant temperature water bath, reacting for 12h in a constant temperature water bath at 70 ℃ under the condition of stirring speed of 200r/min, adding 0.1 wt% acrylic acid solution dissolved with an initiator when the system becomes emulsion, and reacting again. And finally, obtaining monodisperse fluorescent microsphere emulsion, washing with deionized water and absolute ethyl alcohol for multiple times after centrifugation to remove unreacted monomers and fluorescent dye, and drying in vacuum at 40 ℃ for 12 hours to obtain the cross-linked polymer fluorescent microsphere.
EXAMPLE III
A preparation method of fluorescent microspheres based on crosslinked polymers comprises the following steps:
firstly, 5 wt% of dispersant polyvinylpyrrolidone and a certain proportion of isopropanol and aqueous solution are added into a 250ml four-neck round-bottom flask which is provided with a mechanical stirrer, a condenser tube and a nitrogen guide tube, and the mixture is stirred at the temperature of 60 ℃ and the mechanical stirring speed of 190r/min to form clear and transparent dispersant solution.
And secondly, respectively weighing 0.1G of initiator azodiisobutyronitrile and 20mg of fluorescent dye rhodamine 6G, dissolving in 5.0G of styrene monomer, and uniformly mixing and dispersing by ultrasonic oscillation to form a fluorescent monomer mixed solution.
And thirdly, adding the fluorescent monomer mixed solution in the second step into a dispersant solution, stirring and mixing uniformly, introducing nitrogen to remove oxygen for 0.5h, and sealing. Placing in a constant temperature water bath, reacting for 12h under the conditions of constant temperature water bath at 75 ℃ and stirring speed of 200r/min, adding 0.1 wt% acrylic acid solution dissolved with initiator when the system becomes emulsion, and reacting again. And finally, obtaining monodisperse fluorescent microsphere emulsion, washing with deionized water and absolute ethyl alcohol for multiple times after centrifugation to remove unreacted monomers and fluorescent dye, and drying in vacuum at 40 ℃ for 12 hours to obtain the cross-linked polymer fluorescent microsphere.
The fourth embodiment is a preparation method of fluorescent microspheres based on crosslinked polymers, which comprises the following steps:
firstly, 5 wt% of dispersant polyvinylpyrrolidone and a certain proportion of isopropanol and aqueous solution are added into a 250ml four-neck round-bottom flask which is provided with a mechanical stirrer, a condenser tube and a nitrogen guide tube, and the mixture is stirred at the temperature of 60 ℃ and the mechanical stirring speed of 190r/min to form clear and transparent dispersant solution.
And secondly, respectively weighing 0.1G of initiator azodiisobutyronitrile and 20mg of fluorescent dye rhodamine 6G, dissolving the initiator azodiisobutyronitrile and the fluorescent dye rhodamine 6G in 5.0G of methyl methacrylate monomer, and uniformly mixing and dispersing the initiator azodiisobutyronitrile and the fluorescent dye rhodamine 6G by ultrasonic oscillation to form a fluorescent monomer mixed solution.
And thirdly, adding the fluorescent monomer mixed solution in the second step into a dispersant solution, stirring and mixing uniformly, introducing nitrogen to remove oxygen for 0.5h, and sealing. Placing in a constant temperature water bath, reacting for 12h under the conditions of constant temperature water bath at 75 ℃ and stirring speed of 200r/min, adding 0.1 wt% acrylic acid solution dissolved with initiator when the system becomes emulsion, and reacting again. And finally, obtaining monodisperse fluorescent microsphere emulsion, washing with deionized water and absolute ethyl alcohol for multiple times after centrifugation to remove unreacted monomers and fluorescent dye, and drying in vacuum at 40 ℃ for 12 hours to obtain the cross-linked polymer fluorescent microsphere.
EXAMPLE five
A preparation method of fluorescent microspheres based on crosslinked polymers comprises the following steps:
firstly, 5 wt% of dispersant polyvinylpyrrolidone and a certain proportion of ethanol and aqueous solution are added into a 250ml four-neck round-bottom flask which is provided with a mechanical stirrer, a condenser tube and a nitrogen guide tube, and the mixture is stirred at the temperature of 60 ℃ and the mechanical stirring speed of 190r/min to form clear and transparent dispersant solution.
And secondly, respectively weighing 0.1g of initiator azodiisobutyronitrile and 20mg of fluorescent dye rhodamine B, dissolving the initiator azodiisobutyronitrile and the fluorescent dye rhodamine B in 5.0 styrene monomer, and uniformly mixing and dispersing the initiator azodiisobutyronitrile and the fluorescent dye rhodamine B by ultrasonic oscillation to form a fluorescent monomer mixed solution.
And thirdly, adding the fluorescent monomer mixed solution in the second step into a dispersant solution, stirring and mixing uniformly, introducing nitrogen to remove oxygen for 0.5h, and sealing. Placing in a constant temperature water bath, reacting for 12h under the conditions of constant temperature water bath at 70 ℃ and stirring speed of 200r/min, adding a 0.1 wt% divinylbenzene solution dissolved with an initiator and 5.0g of acrylamide when the system becomes emulsion, and reacting again. And finally, obtaining monodisperse fluorescent microsphere emulsion, washing with deionized water and absolute ethyl alcohol for multiple times after centrifugation to remove unreacted monomers and fluorescent dye, and drying in vacuum at 40 ℃ for 12 hours to obtain the cross-linked polymer fluorescent microsphere.
The six embodiment is a cross-linked polymer-based fluorescent microsphere preparation method, which comprises the following steps:
firstly, 5 wt% of dispersant polyvinylpyrrolidone and a certain proportion of ethanol and aqueous solution are added into a 250ml four-neck round-bottom flask which is provided with a mechanical stirrer, a condenser tube and a nitrogen guide tube, and the mixture is stirred at the temperature of 60 ℃ and the mechanical stirring speed of 190r/min to form clear and transparent dispersant solution.
And secondly, respectively weighing 0.1g of initiator azodiisobutyronitrile and 20mg of fluorescent dye rhodamine B, dissolving the initiator azodiisobutyronitrile and the fluorescent dye rhodamine B in 5.0g of styrene monomer, and uniformly mixing and dispersing the initiator azodiisobutyronitrile and the fluorescent dye rhodamine B by ultrasonic oscillation to form a fluorescent monomer mixed solution.
And thirdly, adding the fluorescent monomer mixed solution in the second step into a dispersant solution, stirring and mixing uniformly, introducing nitrogen to remove oxygen for 0.5h, and sealing. Placing in a constant temperature water bath, reacting for 12h under the conditions of constant temperature water bath at 70 ℃ and stirring speed of 200r/min, adding a 0.1 wt% divinylbenzene solution dissolved with an initiator and 5.0g of methyl methacrylate when the system becomes emulsion, and reacting again. And finally, obtaining monodisperse fluorescent microsphere emulsion, washing with deionized water and absolute ethyl alcohol for multiple times after centrifugation to remove unreacted monomers and fluorescent dye, and drying in vacuum at 40 ℃ for 12 hours to obtain the cross-linked polymer fluorescent microsphere. In light of the foregoing description of the preferred embodiments of the present invention, it is to be understood that various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the contents of the specification and the embodiments, and must be determined according to the scope of the claims.
Claims (8)
1. A preparation method of fluorescent microspheres based on cross-linked polymers is to polymerize cross-linked polymers and rhodamine dyes to obtain the fluorescent microspheres, and is characterized by being prepared by the following method:
dissolving a dispersant polyvinylpyrrolidone in an alcohol-water solution, wherein the alcohol-water solution is a polar dispersion medium, then placing the alcohol-water solution containing the polyvinylpyrrolidone in a 250ml four-neck round-bottom flask equipped with a mechanical stirrer, a condenser tube and a nitrogen protection device, and obtaining a homogeneous system through mechanical stirring;
dissolving initiator azobisisobutyronitrile and fluorescent dye into a polymer monomer, and dispersing and mixing the initiator and the polymer monomer uniformly by ultrasonic oscillation to obtain a fluorescent monomer mixed solution;
and step three, adding the fluorescent monomer mixed solution into a reaction system, mechanically stirring at a constant speed to uniformly mix and disperse the fluorescent monomer mixed solution, keeping the polymerization reaction temperature at 60-75 ℃, then adding a cross-linking agent solution, carrying out polymerization reaction under the protection of constant-temperature water bath and nitrogen, and washing and drying after the reaction lasts for 12-24 hours to obtain the cross-linked polymer fluorescent microspheres.
2. The method for preparing fluorescent microspheres based on crosslinked polymer according to claim 1, wherein: in the polymerization reaction of the first step, the water polar dispersion medium is allowed to be any one of mixed solutions of isopropanol and water, ethanol and water, and methanol and water.
3. The method for preparing fluorescent microspheres based on crosslinked polymer according to claim 2, wherein: the isopropanol and water, the ethanol and water, and the methanol and water are mixed according to the volume ratio of 5:1 to obtain the composite material.
4. The method for preparing fluorescent microspheres based on crosslinked polymer according to claim 1, wherein: in the polymerization reaction of the first step, the amount of the dispersant polyvinylpyrrolidone accounts for 5-10% of the reaction system, and the reaction temperature is 60 ℃.
5. The method for preparing fluorescent microspheres based on crosslinked polymer according to claim 1, wherein: in the polymerization reaction of the second step, the organic fluorescent dye is allowed to be any one of rhodamine B and rhodamine 6G; the amount of the fluorescent dye is 0.2-0.5 ml/g of the reaction system.
6. The method for preparing fluorescent microspheres based on crosslinked polymer according to claim 1, wherein: in the polymerization reaction of the second step, the polymer monomer is allowed to be any one of styrene, methyl methacrylate and acrylamide, and the using amount of the polymer monomer accounts for 5-10% of the reaction system; and the polymer monomers styrene and acrylamide and styrene and methyl methacrylate can be mixed according to the volume ratio of 1: 1.
7. The method for preparing fluorescent microspheres based on crosslinked polymer according to claim 1, wherein: in the polymerization reaction of the third step, the cross-linking agent solution is allowed to be any one of a functional monomer acrylic acid solution and a divinylbenzene solution; the dosage of the cross-linking agent solution accounts for 0.05-0.1% of the reaction system.
8. The method for preparing fluorescent microspheres based on crosslinked polymer according to claim 1, wherein: in the polymerization reaction in the third step, the cross-linking agent solution is composed of an initiator, a monomer and a cross-linking agent, after the temperature of the cross-linking agent solution in a reaction system is raised to 70 ℃, the system begins to be turbid after 1-2 h of reaction, and the cross-linking agent solution is added.
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