CN110775981A - Silica microspheres and process for producing the same - Google Patents
Silica microspheres and process for producing the same Download PDFInfo
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- CN110775981A CN110775981A CN201911169594.8A CN201911169594A CN110775981A CN 110775981 A CN110775981 A CN 110775981A CN 201911169594 A CN201911169594 A CN 201911169594A CN 110775981 A CN110775981 A CN 110775981A
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- silica microspheres
- graft copolymer
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- branched polyethyleneimine
- silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 41
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 25
- -1 alkyl orthosilicate Chemical compound 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 238000007865 diluting Methods 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims description 3
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 47
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 30
- 239000004005 microsphere Substances 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 9
- 238000009827 uniform distribution Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000004038 photonic crystal Substances 0.000 abstract description 3
- 230000005526 G1 to G0 transition Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000002077 nanosphere Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920006187 aquazol Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- RJFIXTCTBAXPDW-UHFFFAOYSA-N trihydroxy(2-methylpropoxy)silane Chemical compound CC(C)CO[Si](O)(O)O RJFIXTCTBAXPDW-UHFFFAOYSA-N 0.000 description 1
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a method for manufacturing silica microspheres with simple process and low cost, and the method can manufacture the silica microspheres with uniform distribution and average particle size in micro-nanometer level. The method comprises the following steps: preparing a graft copolymer using a branched polyethyleneimine and a polyalkylmethacrylate as reactants; diluting the graft copolymer with a solvent to a concentration of 0.5 to 5 wt%, adding alkyl orthosilicate as a silicon source to the diluted solution, and stirring at room temperature for 2 to 24 hours to obtain a suspension of silica microspheres using the graft copolymer as a template. The invention also provides the silicon dioxide microspheres prepared by the preparation method. The silica microspheres can be used as a silica photonic crystal material, and can also be used in the fields of drug slow release carriers, catalyst carriers, wear-resistant coating fillers, adsorption materials, high performance liquid chromatography stationary phase matrixes and the like.
Description
Technical Field
The present invention relates to a silica microsphere technology, and particularly to a method for producing silica microspheres using a graft copolymer of branched polyethyleneimine and polyalkylmethacrylate as a template, and silica microspheres produced by the method.
Background
Silicon dioxide (SiO)
2) Is a non-toxic, tasteless and pollution-free inorganic non-metal material, and has special performance in the aspects of sound, light, electricity, magnetism and thermodynamics, and SiO
2Micro-nanospheres have long played an extremely important role in the fields of scientific research and industrial technology. Especially, the preparation of uniform spheres is the key to the development of the silicon dioxide photonic crystal material.
At present, a plurality of methods for preparing the silicon dioxide micro/nanospheres mainly comprise a gas phase method and a liquid phase precipitation method, and other main preparation methods comprise a Stöber method, a combustion method, a sol-gel method, a carbonization method, a micelle sol method and the like, wherein in the preparation method of uniform silicon dioxide spheres, the Stöber method is a mature process, and patent document 1 discloses an ultrasonic-assisted Stöber method for preparing the silicon dioxide micro/nanospheres, and patent document 2 utilizes high-speed mechanical high-speed shearing to assist in preparing SiO by using high-speed shearing
2Nanospheres. However, the above methods all have the problems of high requirements on reaction equipment, complex process, high cost and the like.
The template method is a common method for controllably preparing micro-nano materials, and the template agent is generally an amphiphilic polymer material. Patent document 3 discloses a method for preparing hollow silica spheres by using modified polystyrene microspheres as a template. Patent document 4 discloses a method of cationic polymerization in which oxazoline monomers are polymerized and hydrolyzed to obtain Linear Polyethyleneimine (LPEI) or in which the linear polyethyleneimine is grafted to another hydrophobic polyfunctional small-molecular compound or polymer, and silica nanofibers are synthesized on the basis of the template. Therefore, there is no technology for manufacturing micro-nano silica particles by using a template.
Due to the excellent characteristics of the micro-nano spherical silica particles and the great demands on the micro-nano spherical silica particles in practical use, a method with simple process and low cost is required to obtain the silica microspheres with the average particle size in the micro-nano scale and uniform distribution.
Documents of the prior art
Patent document
Patent document 1: CN201010232223.2
Patent document 2: CN201810674615.0
Patent document 3: CN200910027828.5
Patent document 4: CN 200580017411.0.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art, and aims to provide a method for manufacturing silica microspheres with simple process and low cost to manufacture silica microspheres with uniform distribution and average particle size in micro-nanometer level.
The present inventors have made intensive studies to produce micro-nano silica microspheres by a method using a template, and as a result, have found that when a graft copolymer of branched polyethyleneimine (hereinafter, also referred to as bPEI) and polyalkylmethacrylate is used as a template, silica microspheres having a particle size of a micro-nanometer order and a uniform particle size distribution can be obtained, and that when the silica microspheres are produced, the particle size of the obtained silica microspheres can be controlled by changing the concentration of the graft copolymer, thereby completing the present invention.
The present invention includes the following technical contents.
The method for manufacturing the silica microspheres comprises the following steps:
(1) preparing a graft copolymer using a branched polyethyleneimine and a polyalkylmethacrylate as reactants;
(2) diluting the graft copolymer with a solvent to a concentration of 0.5-5 wt%, adding alkyl orthosilicate serving as a silicon source into the diluted solution, and stirring at room temperature for 2-24 hours to obtain a suspension of silica microspheres with the graft copolymer as a template.
In the method for producing silica microspheres, the branched polyethyleneimine preferably has a weight average molecular weight of 200 to 20000, and the polyalkylmethacrylate preferably has a weight average molecular weight of 10 to 100 ten thousand.
In the method for producing silica microspheres, the polyalkylmethacrylate and the branched polyethyleneimine are preferably reacted in such a manner that the molar ratio of the ester bond to the amino group is 1:1 to 1: 10.
In the method for producing silica microspheres, the polyalkylmethacrylate is preferably at least one selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate.
In the above-mentioned method for producing silica microspheres, it is preferable that the branched polyethyleneimine and the polyalkyl methacrylate are dissolved in a solvent selected from water, N-methylpyrrolidone and N, N-dimethylacetamide so that the total concentration of the reactants becomes 10 to 30 wt%, and the reaction is carried out at a temperature of 90 to 150 ℃ with stirring for 8 to 24 hours to obtain a dispersion containing the graft copolymer.
In the method for producing silica microspheres, the alkyl orthosilicate is preferably at least one selected from the group consisting of ethyl orthosilicate and methyl orthosilicate.
In the method for producing silica microspheres, the alkyl orthosilicate is preferably added in a concentration of 2 to 10 wt%.
The invention also provides a manufacturing method of the silicon dioxide microspheres, which comprises the following steps:
(1) dissolving branched polyethyleneimine and polymethyl methacrylate in a solvent selected from water, N-methylpyrrolidone or N, N-dimethylacetamide so that the total concentration is 10-30 wt%, wherein the molar ratio of ester bonds to amino groups is 1: 1-1: 10, stirring, heating to 90-150 ℃, and reacting for 8-24 hours to obtain a graft copolymer (PMMA-co-bPEI);
(2) diluting the graft copolymer (PMMA-co-bPEI) with water and ethanol to a concentration of 0.5-5 wt%, adding methyl orthosilicate or ethyl orthosilicate into the diluted solution under the condition that the concentration reaches 2-10 wt%, and stirring at room temperature for 3-10 hours to obtain a suspension of silica microspheres with the graft copolymer (PMMA-co-bPEI) as a template.
In the method for producing silica microspheres, the branched polyethyleneimine preferably has a weight average molecular weight of 200 to 20000, and the polymethyl methacrylate preferably has a weight average molecular weight of 10 to 100 ten thousand.
The invention also provides a silicon dioxide microsphere which is obtained by the preparation method of the silicon dioxide microsphere and has an average particle size of 200-800 nm.
Technical effects
According to the method for producing silica microspheres of the present invention, silica microspheres having a particle size of a micro-nanometer order and a uniform particle size distribution can be obtained by using a graft copolymer of branched polyethyleneimine and polyalkylmethacrylate as a template. Further, the particle diameter of the resultant silica microspheres can be controlled by changing the concentration of the above graft copolymer at the time of producing the silica microspheres. The preparation method of the silicon dioxide microspheres has simple process and low cost, and can obtain silicon dioxide with the average particle size of micro-nano level and uniform distribution.
Other advantageous effects of the present invention are further explained in the following disclosure.
Drawings
FIG. 1 is an infrared contrast spectrum of a polymer PMMA and a graft copolymer PMMA-co-bPEI;
FIG. 2 shows SiO prepared in example 1 of the present invention
2Scanning electron micrographs of microspheres;
FIG. 3 shows SiO prepared in example 2 of the present invention
2Scanning electron micrographs of microspheres;
FIG. 4 shows SiO prepared in example 3 of the present invention
2Scanning electron micrographs of microspheres;
FIG. 5 shows SiO prepared in example 4 of the present invention
2Scanning electron micrographs of microspheres;
FIG. 6 is SiO production in comparative example 1
2Scanning electron micrographs of microparticles;
FIG. 7 is SiO production in comparative example 2
2Scanning electron micrographs of the microparticles.
Detailed Description
The technical features of the present invention will be described below with reference to preferred embodiments and drawings, which are intended to illustrate the present invention and not to limit the present invention.
It is to be understood that the preferred embodiments of the present invention are shown in the drawings only, and are not to be considered limiting of the scope of the invention. Various obvious modifications, variations and equivalents may be made to the present invention by those skilled in the art on the basis of the examples shown in the drawings, and the technical features in the different embodiments described below may be arbitrarily combined without contradiction, and these are within the scope of protection of the present invention.
[ preparation of template agent ]
In the present invention, a graft copolymer of a branched polyethyleneimine and a polyalkylmethacrylate is used as a template for producing silica microspheres.
The branched polyethyleneimine is a branched polyethyleneimine which is a water-soluble high-molecular polymer and contains a large number of primary, secondary and tertiary amino groups in the molecule, and these amino groups can form coordinate bonds with silicon or metal ions to immobilize and form silica, reduced metal ions, or the like. In the templating agent of the present invention, the branched polyethyleneimine is present as a hydrophilic segment.
The branched polyethyleneimine to be used in the present invention is not particularly limited, but from the viewpoint of easiness of obtaining, the branched polyethyleneimine preferably has a weight average molecular weight of 200 to 20000, more preferably 400 to 10000, and still more preferably 600 to 5000. If the weight average molecular weight is less than 200, a water-soluble template is not easily formed; if the weight average molecular weight is more than 20000, the silica particles obtained tend to aggregate, and a stable silica dispersion is not easily obtained.
Specific examples of the branched polyethyleneimine include EPON series products of Japan catalyst K.K., SP-003 (molecular weight 300), SP-006 (molecular weight 600), SP-012 (molecular weight 1200), SP-018 (molecular weight 1800) and SP-200 (molecular weight 10000).
The polyalkylmethacrylate in the present invention means a polymer obtained by polymerizing an alkyl methacrylate, and is present as a hydrophobic segment in the template of the present invention. The alkyl group in the alkyl methacrylate is not particularly limited, but is preferably an alkyl group having 1-6 carbon atoms, more preferably an alkyl group having 1-4 carbon atoms. It is particularly preferable that the polyalkylmethacrylate is at least one selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, polypropylene methacrylate, and polybutyl methacrylate. The above-mentioned polyalkylmethacrylate can be synthesized in a laboratory, and a commercially available product can be used.
The polyalkylmethacrylate used as a template in the present invention is not particularly limited in weight average molecular weight, and is usually 10 to 100 ten thousand. If the molecular weight is less than 10 ten thousand, there is a possibility that the synthesized template is insufficient in hydrophobicity. If the molecular weight exceeds 100 ten thousand, synthesis is not easy, or production cost may be increased. Therefore, the weight average molecular weight of the polyalkyl methacrylate is more preferably 20 to 50 ten thousand, and still more preferably 25 to 40 ten thousand, from the viewpoint of obtaining a template having a certain hydrophobicity and cost.
The template agent of the present invention is obtained by dissolving the branched polyethyleneimine and the polyalkyl methacrylate in a solvent, stirring and heating to a temperature of 90 to 150 ℃, and reacting for 8 to 24 hours to cause an amide exchange reaction between the amino group of the branched polyethyleneimine and the polyalkyl methacrylate as shown in the following reaction formula, thereby obtaining a dispersion of a graft copolymer containing the branched polyethyleneimine and the polyalkyl methacrylate.
(in the above reaction scheme, R represents a C1-6 alkyl group.)
In the grafting reaction, the polyalkylmethacrylate and the branched polyethyleneimine are grafted under the condition that the molar ratio of the ester bond to the amino group is 1:1 to 1:10, and more preferably the molar ratio of the ester bond to the amino group is 1:2 to 1: 5. As the solvent, water, N-methylpyrrolidone or N, N-dimethylacetamide can be used, and N-methylpyrrolidone is preferably used. The concentration of the reactant (the total of the branched polyethyleneimine and the polyalkyl methacrylate) in the reaction solution is preferably 10 to 30% by weight, more preferably 10 to 25% by weight, and particularly preferably 20% by weight. The temperature of the reaction is preferably 100 to 120 ℃ and particularly preferably 110 ℃. The reaction time is more preferably 10 to 16 hours, and particularly preferably 12 hours.
The above reaction gives a dispersion containing a graft copolymer comprising a branched polyethyleneimine and a polyalkyl methacrylate, and the dispersion can be concentrated by removing a part of the solvent by distillation under reduced pressure or used as it is in the subsequent reaction.
[ production of silica microspheres ]
The dispersion of the graft copolymer containing a branched polyethyleneimine and a polyalkylmethacrylate obtained by the method for producing a templating agent of the present invention is diluted with a solvent so that the concentration of the graft copolymer is 0.5 to 5% by weight. If the concentration of the graft copolymer exceeds 5% by weight, the resulting silica fine particles tend to aggregate. The graft copolymer is more preferably diluted to a concentration of 1 to 3% by weight from the viewpoint of obtaining silica fine particles having a small and uniform particle diameter and no aggregates.
The solvent for dilution may be the same as or different from the solvent in the dispersion, and it is preferable to use a mixed solvent of water and methanol or water and ethanol in view of cost and stability of the dispersion system.
Adding alkyl orthosilicate serving as a silicon source into the diluted template agent solution, and stirring at room temperature for 2-24 hours to obtain a suspension of silicon dioxide microspheres.
Examples of the alkyl orthosilicate include methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, butyl orthosilicate, isobutyl orthosilicate, and the like, and these alkyl orthosilicates may be used alone or in combination of 2 or more. At least one of methyl orthosilicate and ethyl orthosilicate is particularly preferable from the viewpoint of reactivity.
The alkyl orthosilicate is added in a concentration of 2 to 10 wt% with respect to the concentration of the solution obtained, preferably 4 to 8 wt%. If the addition concentration of the alkyl orthosilicate is less than 2 wt%, the productivity is low; when the addition concentration exceeds 10% by weight, the produced silica fine particles are likely to aggregate and increase in particle size, and it is not easy to obtain a silica microsphere dispersion liquid stable in dispersion.
In some preferred embodiments, the silica microspheres of the present invention can be made by the following method.
Dissolving branched polyethyleneimine and polymethyl methacrylate in a solvent selected from water, N-methylpyrrolidone or N, N-dimethylacetamide to make the total concentration be 10-30 wt%, wherein the molar ratio of ester bonds to amino groups is 1: 1-1: 10, stirring, heating to 90-150 ℃, and reacting for 8-24 hours to obtain a graft copolymer PMMA-co-bPEI;
diluting the graft copolymer PMMA-co-bPEI to the concentration of 0.5-5 wt% by using a mixed solution of water and ethanol, adding methyl orthosilicate or ethyl orthosilicate into the diluted solution under the condition that the concentration reaches 2-10 wt%, and stirring at room temperature for 3-10 hours to obtain a suspension of the silica microspheres taking the graft copolymer PMMA-co-bPEI as a template.
In a more preferred embodiment, the branched polyethyleneimine has a weight average molecular weight of 200 to 20000, and the polymethyl methacrylate has a weight average molecular weight of 10 to 100 ten thousand.
[ silica microspheres ]
According to the method for manufacturing the silica microspheres, a dispersion containing the silica microspheres can be obtained, the average particle size of the silica microspheres is measured by using a scanning electron microscope, and the distribution uniformity of the particle size of the silica microspheres is observed. The result shows that the average particle size of the silicon dioxide microspheres is within the range of 200-800 nm, and the silicon dioxide microspheres are uniformly distributed.
Examples
The following examples illustrate the method for producing silica microspheres of the present invention. It should be clearly understood that the following examples 1 to 4 are only for illustrating the present invention and are not intended to limit the scope of the present invention, and in addition, the following comparative examples 1 to 2 are for highlighting the advantageous effects of the present invention.
(example 1)
Preparing a template agent:
a250 mL four-necked flask was charged with 5.0g of polymethyl methacrylate (weight-average molecular weight: 35 ten thousand) and 5.0g of branched polyethyleneimine (weight-average molecular weight: 600) in which the molar ratio of the ester bond of the polymethyl methacrylate to the amino group in the branched polyethyleneimine was 1: 2.3. Then, 42g of N-methylpyrrolidone was added so that the reactant concentration, i.e., the total solid content, became 19.2% by weight. Stirring and heating to 110 ℃, and reacting for 12 hours to obtain a reaction solution containing the graft copolymer PMMA-co-bPEI.
A part of the reaction solution was measured, and after the solvent was removed by distillation under reduced pressure, the graft copolymer PMMA-co-bPEI was confirmed by infrared spectroscopy. As shown in FIG. 1, the IR spectrum of the graft copolymer PMMA-co-bPEI showed 1730 cm adjacent to the PMMA ester carbonyl peak
-1The carbonyl peak of the newly formed amido group is 1677 cm
-1The amide exchange reaction was demonstrated to successfully graft bPEI onto the PMMA backbone.
Preparing the silicon dioxide microspheres:
the reaction solution containing the graft copolymer PMMA-co-bPEI obtained above was directly diluted with a mixed solvent of water and ethanol (volume ratio about 1: 1) without special treatment until the content of PMMA-co-bPEI became 1% by weight, the resulting solution was used as a template system, ethyl orthosilicate was added to a concentration of 4% by weight, and the mixture was stirred at room temperature for 5 hours to obtain a silica suspension having a stable system.
The SiO prepared from example 1 is shown in FIG. 2
2As can be seen from the scanning electron microscope image of the microspheres, the obtained silica particles are spherical and uniformly distributed, and the average particle size is about 370 nanometers.
(example 2)
A system-stable silica suspension was obtained in the same manner as in example 1, except that the PMMA-co-bPEI-containing solution was diluted to 2% by weight.
SiO prepared from example 2 is shown in FIG. 3
2MicrospheresThe scanning electron microscopic image of (a) shows that the obtained silica particles are spherical, uniformly distributed, and have an average particle diameter of about 560 nm.
(example 3)
A system-stable silica suspension was obtained in the same manner as in example 1, except that the PMMA-co-bPEI-containing solution was diluted to 5% by weight.
SiO prepared by example 3 is shown in FIG. 4
2In the scanning electron micrograph of the microspheres, it is found that the obtained silica particles are spherical, but are slightly aggregated, and the average particle diameter is about 700 nm.
(example 4)
A system-stable silica suspension was obtained in the same manner as in example 1, except that the concentration of added tetraethylorthosilicate was changed to 8 wt%.
SiO prepared from example 4 is shown in FIG. 5
2As can be seen from the scanning electron microscope image of the microspheres, the obtained silica particles are spherical and uniformly distributed, and the average particle size is about 820 nm.
Comparative example 1
Commercially available polyethyloxazoline (number average molecular weight 50000) 3g was dissolved in 15mL of a 5M aqueous hydrochloric acid solution. The solution was heated to 90 ℃ with an oil bath and stirred at this temperature for 10 hours. To the reaction solution, 50mL of acetone was added to completely precipitate the polymer, which was then filtered and washed with methanol 3 times to obtain a white Linear Polyethyleneimine (LPEI) powder.
A silica fine particle-containing suspension was obtained in the same manner as in example 1, except that the linear polyethyleneimine thus obtained was used in place of the branched polyethyleneimine bPEI to prepare a templating agent PMMA-co-LPEI.
SiO prepared by comparative example 1 is shown in FIG. 6
2In the scanning electron micrograph of the fine particles, it is understood that the obtained silica particles are aggregated, and substantially have a long fiber shape and are not uniformly distributed in particle size.
Comparative example 2
A silica fine particle-containing suspension was obtained in the same manner as in example 1, except that the concentration of added tetraethylorthosilicate was reduced to 2 wt%.
SiO prepared by comparative example 2 is shown in FIG. 7
2In the scanning electron micrograph of the fine particles, it is understood that the obtained silica particles are aggregated, and substantially have a long fiber shape and are not uniformly distributed in particle size.
From the results of examples 1 to 4, it is understood that when the graft copolymer PMMA-co-bPEI of the present invention, which is a specific template, is used, a silica suspension having a stable system can be obtained by adjusting the concentration of the graft copolymer PMMA-co-bPEI and the amount of tetraethoxysilane to be added within a specific range, and the obtained silica particles are spherical in a micro-nanometer order and uniformly distributed. The particle size of the obtained silicon dioxide microspheres can be controlled by properly adjusting the concentration of the graft copolymer PMMA-co-bPEI and the addition amount of the tetraethoxysilane.
Furthermore, from the results of comparative examples 1 to 2, it was found that when a graft copolymer of linear polyethyleneimine and PMMA, PMMA-co-LPEI, was used as a template, silica microspheres with a uniform distribution could not be obtained even if the amount of tetraethoxysilane added was adjusted to a low range.
Finally, it should be understood that the above description of the embodiments and examples is illustrative in all respects, not restrictive, and that various modifications may be made without departing from the spirit of the invention. The scope of the invention is indicated by the claims rather than by the foregoing description of embodiments or examples. The scope of the present invention includes all modifications within the meaning and range equivalent to the claims.
Industrial applicability of the invention
According to the preparation method of the silica microspheres, the silica microspheres with the average particle size of micro-nano-scale and uniform distribution can be prepared by the preparation method of the silica microspheres with simple process and low cost, and the silica microspheres can be used as silica photonic crystal materials and can also be used in the fields of drug slow release carriers, catalyst carriers, wear-resistant coating fillers, adsorption materials, high performance liquid chromatography stationary phase matrixes and the like.
Claims (10)
1. A method for manufacturing silica microspheres is characterized by comprising the following steps:
(1) preparing a graft copolymer using a branched polyethyleneimine and a polyalkylmethacrylate as reactants;
(2) diluting the graft copolymer with a solvent to a concentration of 0.5-5 wt%, adding alkyl orthosilicate serving as a silicon source into the diluted solution, and stirring at room temperature for 2-24 hours to obtain a suspension of silica microspheres with the graft copolymer as a template.
2. The method for producing silica microspheres according to claim 1, wherein the branched polyethyleneimine has a weight average molecular weight of 200 to 20000, and the polyalkylmethacrylate has a weight average molecular weight of 10 to 100 ten thousand.
3. The method for producing silica microspheres according to claim 1, wherein the polyalkylmethacrylate and the branched polyethyleneimine are reacted under a molar ratio of an ester bond to an amino group of 1:1 to 1: 10.
4. The method for producing silica microspheres according to any one of claims 1 to 3, wherein the polyalkylmethacrylate is at least one selected from the group consisting of polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, and polybutyl methacrylate.
5. The method for producing silica microspheres according to any one of claims 1 to 3, wherein the branched polyethyleneimine and the polyalkyl methacrylate are dissolved in a solvent selected from water, N-methylpyrrolidone, and N, N-dimethylacetamide so that the total concentration of the reactants becomes 10 to 30 wt%, and the reaction is carried out for 8 to 24 hours while stirring and raising the temperature to 90 to 150 ℃ to obtain a dispersion containing the graft copolymer.
6. The method for producing silica microspheres according to claim 1, wherein the alkyl orthosilicate is at least one selected from the group consisting of ethyl orthosilicate and methyl orthosilicate.
7. The method for producing silica microspheres according to claim 1 or 6, wherein the alkyl orthosilicate is added in a concentration of 2 to 10 wt%.
8. A method for manufacturing silica microspheres is characterized by comprising the following steps:
(1) dissolving branched polyethyleneimine and polymethyl methacrylate in a solvent selected from water, N-methylpyrrolidone or N, N-dimethylacetamide to make the total concentration be 10-30 wt%, wherein the molar ratio of ester bonds to amino groups is 1: 1-1: 10, stirring, heating to 90-150 ℃, and reacting for 8-24 hours to obtain a graft copolymer PMMA-co-bPEI;
(2) diluting the graft copolymer PMMA-co-bPEI with water and ethanol to a concentration of 0.5-5 wt%, adding methyl orthosilicate or ethyl orthosilicate into the diluted solution under the condition that the concentration reaches 2-10 wt%, and stirring at room temperature for 3-10 hours to obtain a suspension of silica microspheres with the graft copolymer PMMA-co-bPEI as a template.
9. The method for producing silica microspheres according to claim 8, wherein the branched polyethyleneimine has a weight average molecular weight of 200 to 20000, and the polymethyl methacrylate has a weight average molecular weight of 10 to 100 ten thousand.
10. Silica microspheres obtained by the method for producing silica microspheres according to any one of claims 1 to 9, having an average particle diameter of 200 to 800 nm.
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