CN108579633B - Preparation method of rare earth nano particle/polystyrene composite microsphere - Google Patents
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Abstract
The invention discloses a preparation method of rare earth nano particle/polystyrene composite microspheres. The method adopts a layer-by-layer self-assembly strategy to improve the carboxyl content and the roughness of the surface of the polystyrene microsphere, and enables rare earth ions to be connected with a large amount of carboxyl on the surface through coordination bonds, so that the coating rate of rare earth nanoparticles is improved, the coating rate of the rare earth nanoparticles is 85-95%, and the rare earth nanoparticle/polystyrene composite microsphere with high coating rate is successfully prepared.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic/high-molecular composite materials, and particularly relates to a preparation method of a rare earth nanoparticle/polystyrene composite microsphere material.
Background
The rare earth nano particle/polystyrene composite microsphere material is an important functional material, and due to the special optical property, the rare earth nano particle/polystyrene composite microsphere material finds wide application in many fields in recent years, such as: material science, medical imaging, disease diagnosis, biomolecule detection, and the like. At present, the common preparation method is to synthesize rare earth nanoparticles and polystyrene microspheres respectively, then perform functional modification on the surfaces of the rare earth nanoparticles and the polystyrene microspheres, and then compound the particles and the polystyrene microspheres by strategies such as layer-by-layer self-assembly, click chemistry and the like.
However, in the existing preparation method, the rare earth nanoparticles are easy to agglomerate in the complex modification and compounding process, so that the coating rate of the nanoparticles is low, and the fluorescence intensity is attenuated, so that the requirements of certain industries cannot be met.
Disclosure of Invention
Aiming at the defects of the prior art, the inventor explores through long-term technology and practice, and improves the carboxyl content and the roughness of the surface of the polystyrene microsphere by adopting a layer-by-layer self-assembly strategy, so that rare earth ions are connected with a large amount of carboxyl on the surface through coordination bonds, the coating rate of rare earth nanoparticles is improved, and the rare earth nanoparticle/polystyrene composite microsphere with high coating rate is successfully prepared.
One of the purposes of the invention is to provide a preparation method of rare earth nano-particle/polystyrene composite microspheres.
The second purpose of the invention is to provide the rare earth nano particle/polystyrene composite microsphere obtained by the preparation method.
The invention also aims to provide the application of the rare earth nano particle/polystyrene composite microsphere.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method for preparing rare earth nanoparticle/polystyrene composite microspheres, the method comprising:
s1, synthesizing polystyrene microspheres: dissolving polyvinylpyrrolidone in a mixed solution of styrene and ethanol I, adding a surfactant and azodiisobutyronitrile, heating and reacting for a period of time under an inert gas atmosphere, adding a mixed solution of methacrylic acid and ethanol II, and continuously heating and reacting to obtain a milky solution;
s2, modification of the surface of the polystyrene microsphere: s1, purifying the milky white solution to obtain a polystyrene solid, dispersing the polystyrene solid in ethanol, adding polyethyleneimine into the ethanol, stirring, purifying, dispersing the solid in water, adding a polycarboxyl organic acid into the water, and stirring and purifying to obtain polystyrene solid microspheres with surface modified carboxyl groups;
s3, synthesis of rare earth nano particles/polystyrene composite microspheres: and (3) slowly adding a rare earth salt aqueous solution into the aqueous solution of the polystyrene solid microsphere with the surface modified carboxyl group prepared in the step S2, heating, stirring and purifying, then re-dispersing the obtained solid in water, slowly adding an alkali metal salt aqueous solution into the solution, continuously heating and stirring for a period of time, and then purifying to obtain the rare earth nano particle/polystyrene composite microsphere.
Further, in the step S1,
the ethanol I and the ethanol II are both absolute ethyl alcohol;
the surfactant is triton; more preferably triton X-305;
the mass ratio of the styrene to the absolute ethyl alcohol I to the polyvinylpyrrolidone to the absolute ethyl alcohol II is 6: 34: 1: 0.2-0.3: 0.12-0.24: 16; preferably, the mass ratio is 6: 34: 1: 0.25: 0.12-0.24: 16; wherein, the molecular weight of the polyvinylpyrrolidone is preferably 55000;
before adding methacrylic acid and ethanol II, heating to react at 70 ℃ for 2-4h, and after adding methacrylic acid and ethanol II, heating to react at 70 ℃ for 20-22 h;
further, in the step S2. the step,
the mass ratio of the polystyrene solid to the polyethyleneimine is 5-10: 1;
the molar ratio of the polycarboxyl organic acid to the polyethyleneimine is 5-10: 1;
wherein the molecular weight of the polyethyleneimine is 600 or 1800;
the polycarboxyl organic acid is citric acid, D-malic acid, L-malic acid or DL-malic acid;
the stirring time is 4-6 h;
further, in the step s3. in the step,
the mol ratio of the rare earth salt to the carboxyl in the polycarboxy organic acid in the step S2. is 1: 1;
the molar ratio of rare earth salt to alkali metal salt is 1: 1-3.5;
wherein the rare earth salt is terbium chloride, europium chloride, terbium nitrate or europium nitrate;
the alkali metal salt is sodium fluoride, potassium fluoride, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate;
heating and stirring at 40-60 deg.C for 4-6 h; continuously heating and stirring at 40-60 deg.C for 1-2 h;
the purification in the invention refers to a process of taking a solid product out of a solvent, and comprises the steps of washing, centrifuging and the like;
the second aspect of the invention discloses the rare earth nano particle/polystyrene composite microsphere prepared by the preparation method, wherein the coating rate of the rare earth nano particle is 85-95%;
the third aspect of the invention discloses the application of the rare earth nano particle/polystyrene composite microsphere in material science, medical imaging, disease diagnosis or biomolecule detection.
The invention has the beneficial effects that:
(1) in the preparation of the polystyrene microspheres, methacrylic acid with low toxicity and strong hydrophobicity is taken as a comonomer, and a surfactant of triton X-305 is added into a reaction system, so that the dispersity of the whole reaction system is enhanced, the reaction temperature is reduced, and the production cost is saved;
(2) according to the method, the carboxyl group combined with the rare earth comes from the polycarboxy organic acid introduced after layer-by-layer self-assembly, the polycarboxy organic acid is introduced by adopting a layer-by-layer self-assembly strategy, the using amount of the acid is increased, and the selected organic acid can contain a plurality of carboxyl groups, so that the carboxyl content on the surface of the final microsphere is greatly increased, and the coating rate of the nano particles is improved.
Drawings
FIG. 1 is a schematic diagram of the preparation of rare earth nanoparticle/polystyrene composite microspheres of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As mentioned above, in the prior art, rare earth nanoparticles are easy to agglomerate in the complicated modification and compounding process, so that the coating rate of the nanoparticles is low, and the fluorescence intensity is attenuated, which cannot meet the requirements of some industries.
In view of the above, the present invention provides a method for preparing rare earth nanoparticles/polystyrene composite microspheres, which comprises:
s1, synthesizing polystyrene microspheres: dissolving polyvinylpyrrolidone in a mixed solution of styrene and ethanol I, adding a surfactant and azodiisobutyronitrile, heating and reacting for a period of time under an inert gas atmosphere, adding a mixed solution of methacrylic acid and ethanol II, and continuously heating and reacting to obtain a milky solution;
s2, modification of the surface of the polystyrene microsphere: s1, purifying the milky white solution to obtain a polystyrene solid, dispersing the polystyrene solid in ethanol, adding polyethyleneimine into the ethanol, stirring, purifying, dispersing the solid in water, adding a polycarboxyl organic acid into the water, and stirring and purifying to obtain polystyrene solid microspheres with surface modified carboxyl groups;
s3, synthesis of rare earth nano particles/polystyrene composite microspheres: and (3) slowly adding a rare earth salt aqueous solution into the aqueous solution of the polystyrene solid microsphere with the surface modified carboxyl group prepared in the step S2, heating, stirring and purifying, then re-dispersing the obtained solid in water, slowly adding an alkali metal salt aqueous solution into the solution, continuously heating and stirring for a period of time, and then purifying to obtain the rare earth nano particle/polystyrene composite microsphere.
In still another embodiment of the present invention, the step s1,
the ethanol I and the ethanol II are both absolute ethyl alcohol;
the surfactant is triton; more preferably triton X-305;
the mass ratio of the styrene to the absolute ethyl alcohol I to the polyvinylpyrrolidone to the absolute ethyl alcohol II is 6: 34: 1: 0.2-0.3: 0.12-0.24: 16; preferably, the mass ratio is 6: 34: 1: 0.25: 0.12-0.24: 16; wherein, the molecular weight of the polyvinylpyrrolidone is preferably 55000;
before adding methacrylic acid and ethanol II, heating to react at 70 ℃ for 2-4h, and after adding methacrylic acid and ethanol II, heating to react at 70 ℃ for 20-22 h;
in another embodiment of the present invention, in step s2,
the mass ratio of the polystyrene solid to the polyethyleneimine is 5-10: 1;
the molar ratio of the polycarboxyl organic acid to the polyethyleneimine is 5-10: 1;
wherein the molecular weight of the polyethyleneimine is 600 or 1800;
the polycarboxyl organic acid is citric acid, D-malic acid, L-malic acid or DL-malic acid;
the stirring time is 4-6 h;
in another embodiment of the present invention, in step s3. the step of,
the mol ratio of the rare earth salt to the carboxyl in the polycarboxy organic acid in the step S2. is 1: 1;
the molar ratio of rare earth salt to alkali metal salt is 1: 1-3.5;
wherein the rare earth salt is terbium chloride, europium chloride, terbium nitrate or europium nitrate;
the alkali metal salt is sodium fluoride, potassium fluoride, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate;
heating and stirring at 40-60 deg.C for 4-6 h; continuously heating and stirring at 40-60 deg.C for 1-2 h;
the purification in the invention refers to a process of taking a solid product out of a solvent, and comprises washing and centrifuging;
in another specific embodiment of the present invention, the rare earth nanoparticle/polystyrene composite microsphere prepared by the above preparation method is provided, wherein the coating rate of the rare earth nanoparticle is 85-95%;
in another embodiment of the present invention, there is provided an application of the above rare earth nanoparticle/polystyrene composite microsphere in material science, medical imaging, disease diagnosis or biomolecule detection.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example one
1. Synthesis of polystyrene microspheres
(1) Placing 6g of styrene in a 250mL three-necked round bottom flask;
(2) adding 34g of absolute ethyl alcohol, and uniformly mixing;
(3) adding 1g of polyvinylpyrrolidone with the molecular weight of 55000, and stirring until the solid is dissolved;
(4) 0.35g of triton X-305 is dripped in and mixed evenly;
(5) adding 0.25g of azobisisobutyronitrile into the mixed solution, and uniformly stirring;
(6) after the addition, nitrogen is introduced below the liquid level for 1 hour;
(7) heating to 70 ℃, and continuously stirring for 2 hours under the protection of nitrogen atmosphere;
(8) adding a mixed solution of 0.24g of methacrylic acid and 16g of absolute ethyl alcohol;
(9) continuously heating and stirring for 20 hours;
(10) after the reaction is stopped, alternately washing and centrifuging for 5 times by using ethanol and water, and removing unreacted reactants to obtain the polystyrene microsphere with the surface carboxyl content of 4%;
2. modification of surface of polystyrene composite microsphere
(1) Dispersing the solid (1g) centrifuged in the step 1 in 10mL of absolute ethanol;
(2) adding polyethyleneimine (0.2g,0.33mmol) with molecular weight of 600, stirring at room temperature for 4 hours, alternately washing with water and anhydrous ethanol, centrifuging, and dispersing the obtained solid in 10mL of water;
(3) citric acid (0.32g, 1.67mmol) was added, stirred at room temperature for 4 hours, washed with water and centrifuged 5 times;
3. synthesis of rare earth nano particle/polystyrene composite microsphere
(1) Dispersing the microspheres obtained in the step 2 into 10mL of water;
(2) slowly dripping 5mL of 1mol/L europium chloride aqueous solution, heating to 50 ℃, stirring for 4 hours, washing with water and centrifuging for several times;
(3) slowly dripping 5.2mL of 1mol/L sodium dihydrogen phosphate solution, and continuously heating and stirring for 2 hours;
(4) after the reaction, the mixture was washed with water and centrifuged 5 times, and the coating rate was 90%.
Example two
1. Synthesis of polystyrene microspheres
(1) Placing 6g of styrene in a 250mL three-necked round bottom flask;
(2) adding 34g of absolute ethyl alcohol, and uniformly mixing;
(3) adding 1g of polyvinylpyrrolidone with the molecular weight of 55000, and stirring until the solid is dissolved;
(4) 0.35g of triton X-305 is dripped in and mixed evenly;
(5) adding 0.25g of azobisisobutyronitrile into the mixed solution, and uniformly stirring;
(6) after the addition, nitrogen is introduced below the liquid level for 1 hour;
(7) heating to 70 ℃, and continuously stirring for 2 hours under the protection of nitrogen atmosphere;
(8) adding a mixed solution of 0.24g of methacrylic acid and 16g of absolute ethyl alcohol;
(9) continuously heating and stirring for 22 hours;
(10) after the reaction is stopped, alternately washing and centrifuging for 5 times by using ethanol and water, and removing unreacted reactants to obtain the polystyrene microsphere with the surface carboxyl content of 4%;
2. modification of surface of polystyrene composite microsphere
(1) Dispersing the solid (1g) centrifuged in the step 1 in 10mL of absolute ethanol;
(2) adding polyethyleneimine (0.2g,0.33mmol) with molecular weight of 600, stirring at room temperature for 4 hours, alternately washing with water and anhydrous ethanol, centrifuging, and dispersing the obtained solid in 10mL of water;
(3) adding DL-malic acid (0.22g, 1.67mmol), stirring at room temperature for 4 hr, washing with water, and centrifuging for 5 times;
3. synthesis of rare earth nano particle/polystyrene composite microsphere
(1) Dispersing the microspheres obtained in the step 2 into 10mL of water;
(2) slowly dripping 3.4mL of 1mol/L europium chloride aqueous solution, heating to 50 ℃, stirring for 4 hours, washing with water and centrifuging for a plurality of times;
(3) slowly dripping 3.6mL of 1mol/L sodium dihydrogen phosphate solution, and continuously heating and stirring for 2 hours;
(4) after the reaction, the mixture was washed with water and centrifuged 5 times, and the coating rate was 85%.
EXAMPLE III
1. Synthesis of polystyrene microspheres
(1) Placing 6g of styrene in a 250mL three-necked round bottom flask;
(2) adding 34g of absolute ethyl alcohol, and uniformly mixing;
(3) adding 1g of polyvinylpyrrolidone with the molecular weight of 55000, and stirring until the solid is dissolved;
(4) 0.35g of triton X-305 is dripped in and mixed evenly;
(5) adding 0.25g of azobisisobutyronitrile into the mixed solution, and uniformly stirring;
(6) after the addition, nitrogen is introduced below the liquid level for 1 hour;
(7) heating to 70 ℃, and continuously stirring for 2 hours under the protection of nitrogen atmosphere;
(8) adding a mixed solution of 0.24g of methacrylic acid and 16g of absolute ethyl alcohol;
(9) continuously heating and stirring for 20 hours;
(10) after the reaction is stopped, alternately washing and centrifuging for 5 times by using ethanol and water, and removing unreacted reactants to obtain the polystyrene microsphere with the surface carboxyl content of 4%;
2. modification of surface of polystyrene composite microsphere
(1) Dispersing the solid (1g) centrifuged in the step 1 in 10mL of absolute ethanol;
(2) adding polyethyleneimine (0.2g, 0.11mmol) with molecular weight of 1800, stirring at room temperature for 4 hours, alternately washing with water and anhydrous ethanol, centrifuging, and dispersing the obtained solid in 10mL of water;
(3) citric acid (0.17g,0.88mmol) was added, stirred at room temperature for 4 hours, washed with water and centrifuged 5 times;
3. synthesis of rare earth nano particle/polystyrene composite microsphere
(1) Dispersing the microspheres obtained in the step 2 into 10mL of water;
(2) slowly dripping 2.6mL of 1mol/L europium chloride aqueous solution, heating to 50 ℃, stirring for 4 hours, washing with water and centrifuging for a plurality of times;
(3) slowly dripping 2.8mL of 1mol/L sodium dihydrogen phosphate solution, and continuously heating and stirring for 2 hours;
(4) after the reaction, the mixture was washed with water and centrifuged 5 times, and the coating rate was 95%.
Example four
1. Synthesis of polystyrene microspheres
(1) Placing 6g of styrene in a 250mL three-necked round bottom flask;
(2) adding 34g of absolute ethyl alcohol, and uniformly mixing;
(3) adding 1g of polyvinylpyrrolidone with the molecular weight of 55000, and stirring until the solid is dissolved;
(4) 0.35g of triton X-305 is dripped in and mixed evenly;
(5) adding 0.25g of azobisisobutyronitrile into the mixed solution, and uniformly stirring;
(6) after the addition, nitrogen is introduced below the liquid level for 1 hour;
(7) heating to 70 ℃, and continuously stirring for 2 hours under the protection of nitrogen atmosphere;
(8) adding a mixed solution of 0.24g of methacrylic acid and 16g of absolute ethyl alcohol;
(9) continuously heating and stirring for 20 hours;
(10) after the reaction is stopped, alternately washing and centrifuging for 5 times by using ethanol and water, and removing unreacted reactants to obtain the polystyrene microsphere with the surface carboxyl content of 4%;
2. modification of surface of polystyrene composite microsphere
(1) Dispersing the solid (1g) centrifuged in the step 1 in 10mL of absolute ethanol;
(2) adding polyethyleneimine (0.2g, 0.11mmol) with molecular weight of 1800, stirring at room temperature for 4 hours, alternately washing with water and anhydrous ethanol, centrifuging, and dispersing the obtained solid in 10mL of water;
(3) adding DL-malic acid (0.14g,1mmol), stirring at room temperature for 4 hr, washing with water, and centrifuging for 5 times;
3. synthesis of rare earth nano particle/polystyrene composite microsphere
(1) Dispersing the microspheres obtained in the step 2 into 10mL of water;
(2) slowly dripping 2mL of 1mol/L europium chloride aqueous solution, heating to 50 ℃, stirring for 4 hours, washing with water and centrifuging for several times;
(3) slowly dripping 6.5mL of 1mol/L sodium fluoride solution, and continuously heating and stirring for 1 hour;
(4) after the reaction, the mixture was washed with water and centrifuged 5 times, and the coating rate was 90%.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (11)
1. A preparation method of rare earth nano particle/polystyrene composite microspheres is characterized by comprising the following steps:
s1, synthesizing polystyrene microspheres: dissolving polyvinylpyrrolidone in a mixed solution of styrene and ethanol I, adding a surfactant and azodiisobutyronitrile, heating and reacting for a period of time under an inert gas atmosphere, adding a mixed solution of methacrylic acid and ethanol II, and continuously heating and reacting to obtain a milky solution;
the surfactant is triton;
s2, modification of the surface of the polystyrene microsphere: s1, purifying the milky white solution to obtain a polystyrene solid, dispersing the polystyrene solid in ethanol, adding polyethyleneimine into the ethanol, stirring, purifying, dispersing the solid in water, adding a polycarboxyl organic acid into the water, and stirring and purifying to obtain polystyrene solid microspheres with surface modified carboxyl groups;
s3, synthesis of rare earth nano particles/polystyrene composite microspheres: and (3) slowly adding a rare earth salt aqueous solution into the aqueous solution of the polystyrene solid microsphere with the surface modified carboxyl group prepared in the step S2, heating, stirring and purifying, then re-dispersing the obtained solid in water, slowly adding an alkali metal salt aqueous solution into the solution, continuously heating and stirring for a period of time, and then purifying to obtain the rare earth nano particle/polystyrene composite microsphere.
2. The preparation process according to claim 1, wherein, in step S1,
the ethanol I and the ethanol II are both absolute ethyl alcohol;
the triton is triton X-305.
3. The preparation process according to claim 1, wherein, in step S1,
the mass ratio of the styrene to the ethanol I to the polyvinylpyrrolidone to the azodiisobutyronitrile to the methacrylic acid to the ethanol II is 6: 34: 1: 0.2-0.3: 0.12-0.24: 16.
4. the method according to claim 3, wherein the mass ratio of styrene to ethanol I to polyvinylpyrrolidone to azobisisobutyronitrile to methacrylic acid to ethanol II is 6: 34: 1: 0.25: 0.12-0.24: 16; wherein, the molecular weight of the polyvinylpyrrolidone is 55000.
5. The preparation process according to claim 1, wherein, in step S1,
heating to react at 70 ℃ for 2-4h before adding the methacrylic acid and the ethanol II, and heating to react at 70 ℃ for 20-22h after adding the methacrylic acid and the ethanol II.
6. The preparation process according to claim 1, wherein, in step S2,
the mass ratio of the polystyrene solid to the polyethyleneimine is 5-10: 1;
the molar ratio of the polycarboxyl organic acid to the polyethyleneimine is 5-10: 1;
wherein the molecular weight of the polyethyleneimine is 600 or 1800;
the polycarboxyl organic acid is citric acid, D-malic acid, L-malic acid or DL-malic acid.
7. The preparation process according to claim 1, wherein, in step S2,
the stirring time is 4-6 h.
8. The preparation process according to claim 1, wherein, in step S3,
the mol ratio of the rare earth salt to the carboxyl in the polycarboxy organic acid in the step S2. is 1: 1;
the molar ratio of rare earth salt to alkali metal salt is 1: 1-3.5;
wherein the rare earth salt is terbium chloride, europium chloride, terbium nitrate or europium nitrate;
the alkali metal salt is sodium fluoride, potassium fluoride, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.
9. The preparation process according to claim 1, wherein, in step S3,
heating and stirring at 40-60 deg.C for 4-6 h; continuously heating and stirring at 40-60 deg.C for 1-2 h.
10. The rare earth nano particle/polystyrene composite microsphere prepared by the preparation method of any one of claims 1 to 9, wherein the coating rate of the rare earth nano particle is 85-95%.
11. The use of the rare earth nanoparticle/polystyrene composite microspheres of claim 10 in material science, medical imaging, disease diagnosis or biomolecule detection.
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