WO2020151607A1 - Composite microsphere having radial fibrous mesoporous shell layer/hollow core layer structure and preparation method therefor - Google Patents

Composite microsphere having radial fibrous mesoporous shell layer/hollow core layer structure and preparation method therefor Download PDF

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WO2020151607A1
WO2020151607A1 PCT/CN2020/072911 CN2020072911W WO2020151607A1 WO 2020151607 A1 WO2020151607 A1 WO 2020151607A1 CN 2020072911 W CN2020072911 W CN 2020072911W WO 2020151607 A1 WO2020151607 A1 WO 2020151607A1
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substituted
hollow core
microspheres
mesoporous shell
core layer
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French (fr)
Chinese (zh)
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卓胜池
王宏宇
江蒙
陈凤
花玉芳
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长兴特殊材料（珠海）有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—Styrene

Definitions

  • the invention belongs to the field of organic polymer compounds, and specifically relates to a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure and a preparation method thereof.
  • the mesoporous silicon material has a series of advantages such as large specific surface area, uniform and continuously adjustable pore size in nanometer size, and functionalization of surface groups.
  • Hollow microspheres with particle sizes ranging from nanometers to micrometers have the advantages of large specific surface area, low density, good stability and surface permeability.
  • Hollow structure mesoporous silicon material integrates the characteristics of mesoporous structure and hollow structure, effectively utilizes the advantages of the two and can derive new synergistic properties, and has extensive scientific research and application prospects.
  • Chinese invention patent CN2012104725129 which describes a method for preparing monodisperse spheres with hollow silica core/mesoporous silica shell structure, wherein the main component of the hollow mesoporous silica material is silica, specifically Using polystyrene microspheres as a template, an inorganic silicon source was added in two steps and the polystyrene template was removed by calcination to obtain monodisperse spheres with both double-layer shells of silica.
  • the hollow microspheres composed of pure silica are easy to agglomerate and are difficult to disperse in the substrate.
  • the monodisperse spheres prepared by this patent are not ideal in terms of light transmittance, haze, and diffusibility.
  • the current preparation of hollow microspheres generally involves first preparing core-shell composite microspheres, and then removing the core particles through solvent dissolution or high-temperature treatment. These method steps are cumbersome, the synthesis conditions are harsh, the calcination and removal of organic templates (such as PS balls, etc.) will generate a large amount of harmful gases and the resulting hollow microspheres have serious agglomeration, which greatly limits the hollow microspheres with mesoporous shells. application.
  • the technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a composite microsphere with a radial fibrous mesoporous shell/hollow core layer structure, which has a good spherical shape and a narrow particle size distribution. , The performance is diverse and the performance can be adjusted. When the composite microspheres are miscible with the substrate, their performance loss is kept to a minimum.
  • the inventor of the present invention has conducted intensive research to solve the above problems and found that composite silicone microspheres having both a radial fibrous mesoporous shell layer and a hollow structure solve the above problems. Therefore, the inventors completed the present invention.
  • the present invention provides a composite microsphere having a radial fibrous mesoporous shell layer/hollow core layer structure, the composite microspheres each comprising a cavity, a hollow core layer and a radial fibrous layer.
  • the composite microspheres have an average particle diameter in the range of 65 nm to 10 ⁇ m.
  • the diameter of the cavity of the composite microsphere is preferably 40 nm to 10 ⁇ m
  • the thickness of the hollow core layer is preferably 5 nm to 2 ⁇ m
  • the thickness of the radial fibrous mesoporous shell layer is preferably 20 nm to 200 nm.
  • the material composing the radial fibrous mesoporous shell layer is selected from compounds represented by the general formula R 1 Si(OR 4 ) 3 , compounds represented by the general formula R 2 R 3 Si(OR 4 ) 2 and general formula formula Si (oR 4) one of the compounds shown in 4 or more thereof, compound of formula Si (oR 4) 4 composed of the hollow core material layer;
  • R 4 is a C 1 -6 alkyl
  • R 1 , R 2 , R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted Or an unsubstituted C 2-6 alkynyl group, a substituted or unsubstituted C 6-12 aryl group, wherein the substituted refers to an amino group substituted with a C 1-6 aminoalkyl group, C 1-6 alkoxy, an oxygen-substituted C 1-6 alkoxy or C 1-6 acyl
  • the material constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or a compound represented by the general formula R 2 R 3 Si(OR 4 ) 2 .
  • the first material is a compound represented by the general formula Si(OR 4 ) 4
  • the second material is selected from the compound represented by the general formula R 1 Si(OR 4 ) 3 , the general formula R 2 R 3 Si( OR 4 ) A combination of one or more of the compound represented by OR 4 ) 2 and the compound represented by the general formula Si(OR 4 ) 4 ; wherein R 4 is a C 1-6 alkyl group; R 1 , R 2 , R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, A substituted or unsubstituted C 6-12 aryl group, wherein the substituted refers to an amino group substituted with a C 1-6 aminoalkyl group, a C 1-6 alkoxy group, a substituted with oxygen C 1-6 alkoxy or C 1-6 hydrocarbyl acyloxy group is substitute
  • the composite microsphere has a cavity, a hollow core layer and a radial fibrous mesoporous shell layer, the diameter of the cavity is preferably 40 nm-10 ⁇ m, and the thickness of the hollow core layer is preferably The thickness of the radial fibrous mesoporous shell layer is preferably 20 nm to 200 nm, and the average particle diameter of the composite microspheres is preferably 65 nm to 10 ⁇ m.
  • the material constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or the general formula R 2 R 3 Si(OR 4 ) The compound shown in 2 .
  • the mass ratio of the polystyrene microspheres, the first material, the first emulsifier, and the water is 1:(0.5-2) :(0.5 ⁇ 2):(20 ⁇ 50).
  • the volume ratio of the water, the alcohol dispersant and the alkaline regulator is 1:(0.2-1):(0.025-0.2).
  • the feed mass ratio of the polystyrene microspheres in step (2), the second material in step (3) and the second emulsifier in step (3) is It is 1:(0.5 ⁇ 5):(0.5 ⁇ 2).
  • the hollow microspheres that can contribute to the complete hollow will not produce residual polystyrene microspheres, and the prepared composite microsphere shell with a radial fibrous mesoporous shell/hollow core layer structure can meet demand.
  • the volume ratio of the water in step (2) to the organic solvent in step (3) is 1:(0.1-10). More preferably, the feed volume ratio of the water in step (2) to the organic solvent in step (3) is 1:(1-2).
  • the organic solvent is selected from hydrocarbon solvents, benzene solvents, alcohol solvents or ketone solvents, wherein the hydrocarbon solvents are selected from cyclohexane A combination of one or more of alkane, n-hexane, gasoline and pentane, the benzene solvent is a combination of one or more selected from benzene, toluene and xylene, and the alcohol solvent is selected From one or a combination of methanol, ethanol and propanol; the ketone solvent is acetone and methyl ethyl ketone.
  • the alkalinity regulator is a combination of one or more selected from the group consisting of aqueous alkali metal hydroxides, urea, ammonia and triethanolamine.
  • the first emulsifier is preferably a cationic emulsifier.
  • the second emulsifier is preferably a cationic emulsifier.
  • the first emulsifier and the second emulsifier may be the same or different.
  • the cationic emulsifier is selected from cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and cetyl trimethyl p-toluene One or more combinations of ammonium sulfonate.
  • the first emulsifier is selected from cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium bromide.
  • step (2) the temperature of the first polymerization reaction is 25-70°C, and the reaction time is 4-24 h.
  • step (3) the temperature of the second polymerization reaction is 35-80°C, and the reaction time is 0.5-8h.
  • a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure which has the advantages of good spherical shape, narrow particle size distribution, diverse performance and adjustable performance. Compared with the existing microspheres, the performance of the microspheres of the present invention is significantly improved.
  • the light diffusion plate can be applied to the light diffusion plate to meet the requirements of high light transmittance, high haze and good diffusivity of the light diffusion agent such as the thinning of the lighting device, the reduction of the absorbance and the thinning of the diffusion layer; for example, the application in cosmetics, It can be used as a functional powder with high oil absorption, soft focus and other effects; for example, it can be used as a lightweight filler in plastics, resins and other substrates to prepare lightweight composite materials; for example, it can also be used in thermal insulation materials and catalytic products , Porous carriers, sustained-release drug carriers, etc.
  • a method for preparing composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure is provided.
  • the preparation of the composite microspheres is based on a polystyrene microsphere modified with siloxane as a template.
  • siloxane as a template.
  • the formation of the radial fibrous mesoporous shell and the polystyrene are completed in one step. Removal of microspheres.
  • the synthesis process of the invention is simple and easy to implement, easy to industrialized production, and has broad application prospects.
  • Figure 1 is an SEM photo of the PS microspheres of Example 1, and the inset in Figure (b) is the corresponding TEM photo;
  • Figure 2 is a TEM photograph of the composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure of Example 1 ( Figures a and b are different magnifications);
  • Example 3 is the nitrogen absorption-desorption curve of the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure of Example 1, and the inset is the corresponding BJH pore size distribution diagram;
  • Figure 4 is a TEM photograph of PS@SiO2 microspheres in Comparative Example 1 before (a) solid PS@SiO 2 composite microspheres and after (b) ordinary hollow mesoporous silica microspheres;
  • Figure 5 is the nitrogen absorption-desorption curve of ordinary hollow mesoporous silica microspheres of Comparative Example 1, and the inset is the corresponding BJH pore size distribution diagram;
  • Figure 6 is a TEM photograph of the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure of Example 2 ( Figures a and b are different magnifications);
  • Fig. 7 is an enlarged TEM photograph of the composite microsphere with a radial fibrous mesoporous shell/hollow core layer structure in Fig. 6-b.
  • the inventor proposed a siloxane-modified polystyrene microsphere as a template.
  • a hollow microsphere with a radial fibrous mesoporous shell was synthesized in one step. Ball method.
  • the composite microsphere prepared by this method has a radial fibrous mesoporous shell layer and a hollow core layer structure.
  • the obtained product has a variety of excellent properties, so it has good application prospects in light diffusion plates, cosmetics and the like.
  • the inventor completed the present invention.
  • C 1-6 hydrocarbon group refers to an alkyl group, alkenyl group, or alkynyl group, etc., having 1 to 6 carbon atoms.
  • C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl and the like are examples of alkyl groups.
  • C 1-6 alkyl refers to a straight or branched chain alkyl group having 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl , Sec-butyl, tert-butyl, or similar groups.
  • C 2-6 alkenyl refers to a linear or branched alkenyl group having 2-6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1- Butenyl, 2-butenyl, or similar groups.
  • C 2-6 alkynyl refers to a linear or branched alkynyl group having 2-6 carbon atoms, such as ethynyl, propynyl, and the like.
  • C 6-12 aryl refers to a monocyclic or bicyclic aromatic hydrocarbon group, such as phenyl, naphthyl, or the like.
  • C 1-6 alkoxy refers to a linear or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isobutoxy, sec-butoxy, tert-butoxy, or similar groups.
  • C 1-6 aminoalkyl refers to a C 1-6 alkyl substituted with an amino group, that is, it means that any position of the alkyl group is substituted with an amino group.
  • siloxane monomers mentioned in the first material and the second material respectively
  • the present invention is used to prepare composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure
  • the first material is a compound represented by the general formula Si(OR 4 ) 4
  • the second material It is one selected from a compound represented by the general formula R 1 Si(OR 4 ) 3 , a compound represented by the general formula R 2 R 3 Si(OR 4 ) 2 and a compound represented by the general formula Si(OR 4 ) 4 A combination of one or more; wherein R 4 is C 1-6 alkyl; R 1 , R 2 , and R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted Or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, substituted or unsubstituted C 6-12 aryl; wherein, the substituted refers to the selected since amino, amino C 1-6 alkyl substituted amino, C 1-6 alkoxy,
  • the present invention provides a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure.
  • the composite microsphere has a cavity, a hollow core layer and a radial fibrous mesoporous shell layer.
  • the average particle diameter of the composite microspheres can be freely designed according to their applications, and therefore is not particularly limited.
  • the average particle size is usually in the range of 65 nm to 10 ⁇ m.
  • the diameter of the cavity of the composite microsphere is preferably 40 nm to 10 ⁇ m; more preferably 500 nm to 1.5 ⁇ m.
  • composite microspheres with adjustable diameters can be obtained by adjusting the particle size of the microspheres.
  • the template microspheres used to generate the cavity are preferably polystyrene microspheres.
  • the thickness of the hollow core layer of the composite microspheres is preferably 5 nm to 2 ⁇ m; more preferably 10 to 500 nm.
  • the hollow core layer of the composite microsphere is preferably obtained by polymerizing siloxane monomers.
  • the siloxane monomer constituting the hollow core layer is selected from the general formula Si(OR 4 ) 4 ; wherein R 4 is a C 1-6 alkyl group ; Its examples are preferably tetraethoxysilane, tetramethoxysilane.
  • the hollow core layer of the present invention needs to have certain solvent resistance, outer emulsifier adsorbability, and through-hole structure stability, so that the hollow structure of the composite microsphere can withstand the swelling of organic solvents and can be effectively removed by the through-hole
  • the template microspheres do not damage the hollow structure and can accept the adsorption of emulsifiers to effectively form a mesoporous shell.
  • the thickness of the mesoporous shell layer of the composite microsphere is preferably 20 nm to 200 nm; more preferably 150 to 200 nm.
  • the radial fibrous mesoporous shell layer of the composite microsphere is preferably obtained by polymerizing siloxane monomers, wherein the siloxane monomer constituting the radial fibrous mesoporous shell layer is selected from the general formula R 1 Si(OR 4 ) 3 A combination of one or more of the compound shown, the compound represented by the general formula R 2 R 3 Si(OR 4 ) 2 and the compound represented by the general formula Si(OR 4 ) 4 ; wherein R 4 is C 1-6 alkyl; R 1 , R 2 , and R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted Or unsubstituted C 2-6 alkynyl, substituted or unsubstituted C 6-12 aryl, wherein the substituted refers to an amino group selected from the group consisting of amino and substituted by C 1-6 aminoalkyl , C 1-6 alk
  • the siloxane monomer constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or the general formula R 2 R 3 Si(OR 4 ) 2
  • the siloxane monomer constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or the general formula R 2 R 3 Si(OR 4 )
  • the compound shown in 2 also optionally contains a compound shown in the general formula Si(OR 4 ) 4 , an example of which is preferably tetraethoxysilane (TEOS) and selected from C 6 H 5 Si(OCH 3 ) 3 ( Phenyltrimethoxysilane), CH 3 Si(OCH 3 ) 3 (methyltrimethoxysilane), methylphenyldimethoxysilane, diphenyldimethoxysilane, methacryloxypropyl Trimethoxysilane, glycidoxypropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, methylphenyldiethoxysilane
  • the siloxane monomer constituting the radial fibrous mesoporous shell layer is a combination selected from the group consisting of TEOS and glycidoxypropyltrimethoxysilane, TEOS and phenyltrimethoxysilane, TEOS and aminopropyltrimethoxysilane or TEOS and diphenyldimethoxysilane.
  • the siloxane monomer constituting the radial fibrous mesoporous shell layer is more preferably phenyltrimethoxysilane and selected from CH 3 Si(OCH 3 ) 3 (methyltrimethoxysilane), methylphenyl two Methoxysilane, diphenyldimethoxysilane, methacryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ - Aminopropyltrimethoxysilane, methylphenyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, ⁇ -(2,3-ring Oxypropoxy) propyl trimethoxy silane, ⁇ -(methacryloxy) propyl trimethoxy silane, aminopropyl trimethoxy silane, tetraethoxy silane (TEOS),
  • the siloxane monomer constituting the radial fibrous mesoporous shell layer is a combination selected from: phenyltrimethoxysilane and MTEOS, phenyltrimethoxysilane and vinyltriethoxysilane , Phenyltrimethoxysilane and dimethyldimethoxysilane, phenyltrimethoxysilane and ⁇ -(2,3-glycidoxy)propyltrimethoxysilane, phenyltrimethoxysilane and ⁇ -(Methacryloxy)propyltrimethoxysilane, phenyltrimethoxysilane and aminopropyltrimethoxysilane or radical trimethoxysilane, MTEOS and phenylmethyldimethoxysilane.
  • the composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure of the present invention are preferably prepared according to the following method:
  • the polystyrene microspheres prepared in step 1), the first emulsifier, water, and alcohol dispersant are mixed and dispersed uniformly in a certain proportion, and the alkaline regulator is added to adjust the solution
  • the alkaline regulator is added to adjust the solution
  • the first material ie, siloxane monomer, such as a siloxane monomer or a mixture of siloxane monomers
  • the polymerization reaction for a period of time (such as 4-24h) to obtain A first reaction mixture of polystyrene microspheres coated with a silicon layer on the surface. Therefore, the hollow core layer of the composite microsphere is obtained by polymerizing the siloxane monomer in step 2).
  • step 2 the second emulsifier and organic solvent are added to the first reaction mixture and mixed uniformly, and finally the second material (ie, siloxane monomer, such as a siloxane) is added.
  • the second material ie, siloxane monomer, such as a siloxane
  • the template polystyrene microspheres
  • a mesoporous shell containing radial fibers is formed Layer/hollow core layer structure of the second reaction mixture of composite microspheres.
  • the radial fibrous shell layer of the composite microsphere is obtained by polymerizing the siloxane monomer in step 3), and the above-mentioned polymerization reaction is preferably carried out under heating conditions, which is beneficial to the formation of the shell layer.
  • the weight ratio of the hollow core layer and the radial fibrous mesoporous shell layer is approximately equal to the siloxane added in step 2) and step 3) The weight ratio of monomers.
  • the hollow core layer in the composite microsphere and the radial fibrous mesoporous shell can meet the needs.
  • the siloxane monomer can be selected from one or more of the aforementioned siloxane monomers of the present invention.
  • the implementation of the above-mentioned preparation method of the present invention can break through the limitation of the current calcination method to prepare hollow composite microspheres in the shape of the radial fibrous mesoporous shell.
  • the composite microspheres with radial fibrous mesoporous shell layer/hollow core layer structure of the present invention have the characteristics of high specific surface area. It also has more levels of pores, which make it have good permeability, large pore volume, and improve the load capacity of guest molecules.
  • the multi-layered pores can make the substrate more penetrate into the gap, forming a transition layer with a refractive index gradient function and beneficial to light diffusion. In mechanics, multi-level pores are conducive to a closer combination of the substrate and the microspheres and better mechanical strength.
  • the composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure of the present invention has the advantages of good spherical shape, narrow particle size distribution, diverse performance, adjustable performance and the like. Compared with the existing microspheres, the performance of the microspheres of the present invention is significantly improved. Therefore, it has a wide range of application prospects. For example, it can be applied to the light diffusion plate, which can cope with the thinning of the lighting device, the reduction of the absorbance and the thinning of the diffusion layer. Requirements; for example, in cosmetics, it can be used as a functional powder with high oil absorption, soft focus and other effects; for example, in plastics, resins and other substrates to prepare lightweight thermal insulation composite materials, which can be used as fillers.
  • CAB cetyltrimethylammonium bromide
  • the temperature of the reaction system was increased to 50°C, 300mg of cetyltrimethylammonium bromide (CTAB) and 20mL of cyclohexane were added to the system, and after magnetic stirring for 10 minutes, 3.5g of TEOS and 0.3g of methyl were added. Acryloyloxypropyl trimethoxysilane. The reaction was carried out for 1 hour under 800 rpm magnetic stirring.
  • CAB cetyltrimethylammonium bromide
  • the reaction solution was centrifuged (5000r/min) with an HC-2518ZONKIA centrifuge to obtain a solid product, washed with industrial ethanol for 3 times, and then placed in an electric blast drying oven at 50°C for drying.
  • the TEM picture of the product morphology is shown in Figure 2. It is a composite microsphere with a radial fibrous mesoporous shell/hollow core layer structure. The cavity size is similar to that of polystyrene template microspheres. The radial fibrous mesoporous shell The thickness is about 40nm.
  • the nitrogen absorption-desorption curve test of the product and the corresponding BJH pore size distribution (before the test, the sample is placed in a vacuum condition of 60 °C for degassing for 2 hours) as shown in Figure 3.
  • the absorption and desorption isotherm curve belongs to type IV curve, and The existence of H3 type hysteresis ring indicates that the microsphere wall has a mesoporous structure.
  • the BET specific surface area of the composite microspheres calculated from Figure 3 is 704.4m 2 /g, and the corresponding BJH pore size distribution diagram shows that the mesopore size distribution is mainly concentrated around 10nm.
  • a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure was prepared in the same manner as in Example 1, except that the first polymerization reaction time for preparing the hollow core layer was 12 hours.
  • the TEM photograph of the composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure is shown in FIG. 6, and FIG. 7 is an enlarged view of the composite microspheres in FIG. 6-b, and the average particle size of the corresponding composite microspheres is 1 ⁇ m.
  • the composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure were prepared in the same manner as in Example 1, except that the organic solvent was replaced by n-hexane.
  • a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure was prepared in the same manner as in Example 1, except that the second polymerization reaction for preparing the fibrous mesoporous shell layer was carried out at room temperature. .
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g TEOS and 0.3g glycidoxypropyltrimethoxysilane were replaced, and the thickness of the fibrous mesoporous shell was about 20nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g TEOS and 0.5g phenyltrimethoxysilane were replaced, and the thickness of the fibrous mesoporous shell layer was about 50nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of TEOS and 0.3g aminopropyltrimethoxysilane, the thickness of the fibrous mesoporous shell is about 55-60nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of TEOS and 0.3g of diphenyldimethoxysilane, the thickness of the fibrous mesoporous shell is about 42nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g MTEOS, the thickness of the fibrous mesoporous shell is about 40nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g vinyltriethoxysilane, the thickness of the fibrous mesoporous shell is about 40nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g dimethyldimethoxysilane, the thickness of the fibrous mesoporous shell layer is about 20nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g ⁇ -(2,3-glycidoxy)propyltrimethoxysilane, the thickness of the fibrous mesoporous shell is about 50nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g gamma-(methacryloxy)propyltrimethoxysilane, the thickness of the fibrous mesoporous shell layer is about 55nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g aminopropyltrimethoxysilane, the thickness of the fibrous mesoporous shell is about 55-60nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane, 0.15g MTEOS and 0.15g phenylmethyldimethoxysilane, the thickness of the fibrous mesoporous shell is about 45nm.
  • the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the average particle diameter of the polystyrene microspheres used to prepare the cavity template was 40 nm , The average particle size of the corresponding composite microspheres is 90nm.
  • the nitrogen absorption-desorption curve test of ordinary hollow mesoporous silica microspheres and the corresponding BJH pore size distribution (the sample is placed under vacuum at 60°C for 2h before the test) is shown in Figure 5.
  • the adsorption and desorption isotherm curve of ordinary hollow mesoporous silica microspheres belongs to the IV type curve, and there is an H3 type hysteresis loop, which indicates that the sphere wall has a mesoporous structure.
  • the calculated BET specific surface area is 186.2 m 2 /g, which is much lower than the BET specific surface area of the hollow fiber-like mesoporous silica microspheres.
  • the pore size distribution of the sample is calculated by the BJH method.
  • the mesopore size distribution of ordinary hollow mesoporous silica microspheres is about 10-100nm (the mesopore is 2-50nm), which is better than the above-mentioned fibrous hollow mesoporous silica microspheres.
  • the mesopore size distribution is wide.

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Abstract

Disclosed are a composite microsphere having a radial fibrous mesoporous shell layer/hollow core layer structure and a preparation method therefor. The composite microsphere has a cavity, a core layer and a mesoporous shell layer, wherein the mesoporous shell layer has radial fibrous mesoporous channels. The preparation method for the composite microsphere comprises: preparing styrene microspheres; mixing the styrene microspheres, a first emulsifier, water, and an alcohol dispersant and uniformly dispersing same, adding an alkaline regulator to adjust the solution to alkalinity, and adding a first material for a first polymerization reaction to obtain a first reaction mixture; adding a second emulsifier and an organic solvent, uniformly mixing same, and then adding a second material for a second polymerization reaction to obtain a second reaction mixture; and centrifuging the second reaction mixture, washing and drying same to obtain the composite microsphere.

Description

一种具有放射纤维状介孔壳层/中空核层结构的复合微球及其制备方法Composite microsphere with radial fibrous mesoporous shell layer/hollow core layer structure and preparation method thereof 技术领域Technical field
本发明属于有机高分子化合物领域，具体涉及一种具有放射纤维状介孔壳层/中空核层结构的复合微球及其制备方法。The invention belongs to the field of organic polymer compounds, and specifically relates to a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure and a preparation method thereof.
技术背景technical background
介孔硅材料具有较大的比表面积、均一的且在纳米尺寸上连续可调的孔径，表面基团可官能化等一系列优点受到了广泛关注。粒径在纳米级至微米级的中空微球具有比表面积大、密度小、稳定性好和具有表面渗透能力等优点。中空结构的介孔硅材料集介孔结构及中空结构特点于一体，有效利用二者的优点并能衍生出新的协同特性，具有广泛的科学研究和应用前景。The mesoporous silicon material has a series of advantages such as large specific surface area, uniform and continuously adjustable pore size in nanometer size, and functionalization of surface groups. Hollow microspheres with particle sizes ranging from nanometers to micrometers have the advantages of large specific surface area, low density, good stability and surface permeability. Hollow structure mesoporous silicon material integrates the characteristics of mesoporous structure and hollow structure, effectively utilizes the advantages of the two and can derive new synergistic properties, and has extensive scientific research and application prospects.
目前，如中国发明专利CN2012104725129，其述及一种中空二氧化硅核/介孔二氧化硅壳结构单分散球的制备方法，其中所述的中空介孔硅材料主要成分为二氧化硅，具体以聚苯乙烯微球为模板，分两步加入无机硅源并通过煅烧去除聚苯乙烯模板得到双层壳层均为二氧化硅的单分散球。然而单纯二氧化硅成分的中空微球易团聚，在基材中不易分散，同时此专利制备的单分散球在透光率、雾度及扩散性等方面均不甚理想。At present, for example, Chinese invention patent CN2012104725129, which describes a method for preparing monodisperse spheres with hollow silica core/mesoporous silica shell structure, wherein the main component of the hollow mesoporous silica material is silica, specifically Using polystyrene microspheres as a template, an inorganic silicon source was added in two steps and the polystyrene template was removed by calcination to obtain monodisperse spheres with both double-layer shells of silica. However, the hollow microspheres composed of pure silica are easy to agglomerate and are difficult to disperse in the substrate. At the same time, the monodisperse spheres prepared by this patent are not ideal in terms of light transmittance, haze, and diffusibility.
另外，目前中空微球的制备一般都是先制备核壳复合微球，再通过溶剂溶解或者高温处理除去核粒子。这些方法步骤繁琐、合成条件苛刻、煅烧除去有机模板(如PS球等)会产生大量的有害气体且得到的中空微球团聚现象严重，这极大地限制了具有介孔壳层的中空微球的应用。In addition, the current preparation of hollow microspheres generally involves first preparing core-shell composite microspheres, and then removing the core particles through solvent dissolution or high-temperature treatment. These method steps are cumbersome, the synthesis conditions are harsh, the calcination and removal of organic templates (such as PS balls, etc.) will generate a large amount of harmful gases and the resulting hollow microspheres have serious agglomeration, which greatly limits the hollow microspheres with mesoporous shells. application.
因此，鉴于上述中空微球存在的缺点和制备工艺的缺陷，本领域的技术人员亟待寻求一种解决上述问题的方式方法。Therefore, in view of the shortcomings of the above-mentioned hollow microspheres and the defects of the preparation process, those skilled in the art urgently need to find a way to solve the above-mentioned problems.
发明内容Summary of the invention
本发明所要解决的技术问题是为了克服现有技术中存在的不足，提供了一种具有放射纤维状介孔壳层/中空核层结构的复合微球，其具有良好的球形，粒径分布窄，性能多样且性能可调节等优点。当所述复合微球与基材混溶时，将它们的性能损耗保持到最低水平。The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a composite microsphere with a radial fibrous mesoporous shell/hollow core layer structure, which has a good spherical shape and a narrow particle size distribution. , The performance is diverse and the performance can be adjusted. When the composite microspheres are miscible with the substrate, their performance loss is kept to a minimum.
本发明同时还提供了一种用于制备上述具有放射纤维状介孔壳层/中空核层结构的复合微球的方法。The invention also provides a method for preparing the above-mentioned composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure.
本发明的发明人为了解决上述问题进行了深入细致的研究，并且发现兼具放射纤维状介孔壳层和中空结构的复合有机硅微球解决了上述问题，因而本发明人完成本发明。The inventor of the present invention has conducted intensive research to solve the above problems and found that composite silicone microspheres having both a radial fibrous mesoporous shell layer and a hollow structure solve the above problems. Therefore, the inventors completed the present invention.
在本发明的第一方面中，本发明提供了一种具有放射纤维状介孔壳层/中空核层结构的复合微 球，所述复合微球各自包含空腔、中空核层和放射纤维状介孔壳层。复合微球具有在65nm至10μm范围内的平均粒径。In the first aspect of the present invention, the present invention provides a composite microsphere having a radial fibrous mesoporous shell layer/hollow core layer structure, the composite microspheres each comprising a cavity, a hollow core layer and a radial fibrous layer. Mesoporous shell. The composite microspheres have an average particle diameter in the range of 65 nm to 10 μm.
复合微球的空腔的直径优选为40nm～10μm，中空核层的厚度优选为5nm～2μm，放射纤维状介孔壳层的厚度优选为20nm～200nm。The diameter of the cavity of the composite microsphere is preferably 40 nm to 10 μm, the thickness of the hollow core layer is preferably 5 nm to 2 μm, and the thickness of the radial fibrous mesoporous shell layer is preferably 20 nm to 200 nm.
其中，组成所述放射纤维状介孔壳层的材料为选自通式R 1Si(OR 4) 3所示的化合物、通式R 2R 3Si(OR 4) 2所示的化合物和通式Si(OR 4) 4所示的化合物中的一种或多种的组合，组成所述中空核层的材料为通式Si(OR 4) 4所示的化合物；其中，R 4为C 1-6烷基；R 1、R 2、R 3各自独立地选自氢，取代的或未被取代的C 1-6烷基，取代的或者未被取代的C 2-6烯基，取代的或者未被取代的C 2-6炔基，取代的或者未被取代的C 6-12芳基，其中所述取代的是指被选自氨基、被C 1-6氨烷基取代的氨基、C 1-6烷氧基、被氧取代的C 1-6烷氧基或C 1-6烃基酰氧基中的一个或多个取代基所取代。 Wherein, the material composing the radial fibrous mesoporous shell layer is selected from compounds represented by the general formula R 1 Si(OR 4 ) 3 , compounds represented by the general formula R 2 R 3 Si(OR 4 ) 2 and general formula formula Si (oR 4) one of the compounds shown in 4 or more thereof, compound of formula Si (oR 4) 4 composed of the hollow core material layer; wherein, R 4 is a C 1 -6 alkyl; R 1 , R 2 , R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted Or an unsubstituted C 2-6 alkynyl group, a substituted or unsubstituted C 6-12 aryl group, wherein the substituted refers to an amino group substituted with a C 1-6 aminoalkyl group, C 1-6 alkoxy, an oxygen-substituted C 1-6 alkoxy or C 1-6 acyloxy group, hydrocarbyl or more substituents.
优选地，组成所述放射纤维状介孔壳层的材料至少含有通式R 1Si(OR 4) 3所示的化合物和/或通式R 2R 3Si(OR 4) 2所示的化合物。 Preferably, the material constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or a compound represented by the general formula R 2 R 3 Si(OR 4 ) 2 .
在本发明第二方面中，提供了一种上述具有放射纤维状介孔壳层/中空核层结构的复合微球的制备方法，包括步骤：In the second aspect of the present invention, there is provided a method for preparing the above-mentioned composite microspheres having a radial fibrous mesoporous shell layer/hollow core layer structure, including the steps:
1)制备聚苯乙烯微球；1) Preparation of polystyrene microspheres;
2)将上述聚苯乙烯微球、第一乳化剂、水、醇类分散剂混合并分散均匀，加入用碱性调节剂调节溶液至碱性，加入第一材料进行第一聚合反应，得到第一反应混合物，所述第一反应混合物含有表面包覆有硅层的聚苯乙烯微球；2) Mix and disperse the above polystyrene microspheres, the first emulsifier, water, and alcohol dispersant uniformly, add the alkali regulator to adjust the solution to alkalinity, add the first material to perform the first polymerization reaction, and obtain the second A reaction mixture, the first reaction mixture contains polystyrene microspheres coated with a silicon layer;
3)将所述第一反应混合物体系温度升高，加入第二乳化剂和有机溶剂，混合均匀，再加入第二材料进行第二聚合反应，得到含有所述具有放射纤维状介孔壳层/中空核层结构的复合微球的第二反应混合物；3) Raise the temperature of the first reaction mixture system, add a second emulsifier and an organic solvent, mix uniformly, and then add a second material to perform a second polymerization reaction, to obtain a shell layer containing the radial fibrous mesoporous/ The second reaction mixture of composite microspheres with a hollow core layer structure;
4)将所述第二反应混合物进行离心、洗涤、干燥，即得具有放射纤维状介孔壳层/中空核层结构的复合微球；4) Centrifuging, washing and drying the second reaction mixture to obtain composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure;
所述第一材料为通式Si(OR 4) 4所示的化合物，所述第二材料为选自通式R 1Si(OR 4) 3所示的化合物、通式R 2R 3Si(OR 4) 2所示的化合物和通式Si(OR 4) 4所示的化合物中的一种或多种的组合；其中，R 4为C 1-6烷基；R 1、R 2、R 3各自独立地选自氢，取代的或未被取代的C 1-6烷基，取代的或者未被取代的C 2-6烯基，取代的或者未被取代的C 2-6炔基，取代的或者未被取代的C 6-12芳基，其中所述取代的是指被选自氨基、被C 1-6氨烷基取代的氨基、C 1-6烷氧基、被氧取代的C 1-6烷氧基或C 1-6烃基酰氧基中的一个或多个取代基所取代。 The first material is a compound represented by the general formula Si(OR 4 ) 4 , and the second material is selected from the compound represented by the general formula R 1 Si(OR 4 ) 3 , the general formula R 2 R 3 Si( OR 4 ) A combination of one or more of the compound represented by OR 4 ) 2 and the compound represented by the general formula Si(OR 4 ) 4 ; wherein R 4 is a C 1-6 alkyl group; R 1 , R 2 , R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, A substituted or unsubstituted C 6-12 aryl group, wherein the substituted refers to an amino group substituted with a C 1-6 aminoalkyl group, a C 1-6 alkoxy group, a substituted with oxygen C 1-6 alkoxy or C 1-6 hydrocarbyl acyloxy group is substituted by one or more substituents.
根据本发明的一些优选方面，所述复合微球具有空腔、中空核层和放射纤维状介孔壳层，所 述空腔的直径优选为40nm～10μm，所述中空核层的厚度优选为5nm～2μm，所述放射纤维状介孔壳层的厚度优选为20nm～200nm，所述复合微球的平均粒径优选为65nm～10μm。According to some preferred aspects of the present invention, the composite microsphere has a cavity, a hollow core layer and a radial fibrous mesoporous shell layer, the diameter of the cavity is preferably 40 nm-10 μm, and the thickness of the hollow core layer is preferably The thickness of the radial fibrous mesoporous shell layer is preferably 20 nm to 200 nm, and the average particle diameter of the composite microspheres is preferably 65 nm to 10 μm.
根据本发明的一些优选方面，组成所述放射纤维状介孔壳层的材料至少含有通式R 1Si(OR 4) 3所示的化合物和/或通式R 2R 3Si(OR 4) 2所示的化合物。 According to some preferred aspects of the present invention, the material constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or the general formula R 2 R 3 Si(OR 4 ) The compound shown in 2 .
根据本发明的一些优选方面，步骤(2)中，所述聚苯乙烯微球、所述第一材料、所述第一乳化剂和所述水的投料质量比为1:(0.5～2):(0.5～2):(20～50)。According to some preferred aspects of the present invention, in step (2), the mass ratio of the polystyrene microspheres, the first material, the first emulsifier, and the water is 1:(0.5-2) :(0.5～2):(20～50).
根据本发明的一些优选方面，步骤(2)中，所述水、所述醇类分散剂和所述碱性调节剂的体积比为1:(0.2～1):(0.025～0.2)。According to some preferred aspects of the present invention, in step (2), the volume ratio of the water, the alcohol dispersant and the alkaline regulator is 1:(0.2-1):(0.025-0.2).
根据本发明的一些优选方面，步骤(2)中的所述聚苯乙烯微球、步骤(3)中的所述第二材料和步骤(3)中的所述第二乳化剂的投料质量比为1:(0.5～5):(0.5～2)。在满足上述条件用量下，能够贡献完整中空的微球不会产生残留聚苯乙烯微球的现象，且制备出来的放射纤维状介孔壳层/中空核层结构的复合微球壳层能符合需求。According to some preferred aspects of the present invention, the feed mass ratio of the polystyrene microspheres in step (2), the second material in step (3) and the second emulsifier in step (3) is It is 1:(0.5～5):(0.5～2). Under the above conditions and the amount, the hollow microspheres that can contribute to the complete hollow will not produce residual polystyrene microspheres, and the prepared composite microsphere shell with a radial fibrous mesoporous shell/hollow core layer structure can meet demand.
根据本发明的一些优选方面，步骤(2)中的所述水与步骤(3)中的所述有机溶剂的投料体积比为1:(0.1～10)。更优选地，步骤(2)中的所述水与步骤(3)中的所述有机溶剂的投料体积比为1:(1～2)。According to some preferred aspects of the present invention, the volume ratio of the water in step (2) to the organic solvent in step (3) is 1:(0.1-10). More preferably, the feed volume ratio of the water in step (2) to the organic solvent in step (3) is 1:(1-2).
根据本发明的一些具体且优选的方面，步骤(3)中，所述有机溶剂选自烃类溶剂、苯类溶剂、醇类溶剂或酮类溶剂，其中所述烃类溶剂为选自环己烷、正己烷、汽油和戊烷中的一种或多种的组合，所述苯类溶剂为选自苯、甲苯和二甲苯中的一种或多种的组合，所述醇类溶剂为选自甲醇、乙醇和丙醇中的一种或多种的组合；所述酮类溶剂为丙酮和/丁酮。According to some specific and preferred aspects of the present invention, in step (3), the organic solvent is selected from hydrocarbon solvents, benzene solvents, alcohol solvents or ketone solvents, wherein the hydrocarbon solvents are selected from cyclohexane A combination of one or more of alkane, n-hexane, gasoline and pentane, the benzene solvent is a combination of one or more selected from benzene, toluene and xylene, and the alcohol solvent is selected From one or a combination of methanol, ethanol and propanol; the ketone solvent is acetone and methyl ethyl ketone.
根据本发明的一些具体且优选的方面，步骤(2)中，所述碱性调节剂为选自碱金属氢氧化物水溶液、尿素、氨水和三乙醇胺中的一种或多种的组合。According to some specific and preferred aspects of the present invention, in step (2), the alkalinity regulator is a combination of one or more selected from the group consisting of aqueous alkali metal hydroxides, urea, ammonia and triethanolamine.
根据本发明的一些优选方面，步骤(2)中，所述第一乳化剂优选为阳离子乳化剂。According to some preferred aspects of the present invention, in step (2), the first emulsifier is preferably a cationic emulsifier.
根据本发明的一些优选方面，步骤(3)中，所述第二乳化剂优选为阳离子乳化剂。According to some preferred aspects of the present invention, in step (3), the second emulsifier is preferably a cationic emulsifier.
根据本发明的一些具体且优选的方面，所述第一乳化剂和第二乳化剂可相同或不同。According to some specific and preferred aspects of the present invention, the first emulsifier and the second emulsifier may be the same or different.
根据本发明的一些具体且优选的方面，所述阳离子乳化剂为选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和十六烷基三甲基对甲苯磺酸铵中的一种或多种的组合。According to some specific and preferred aspects of the present invention, the cationic emulsifier is selected from cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and cetyl trimethyl p-toluene One or more combinations of ammonium sulfonate.
根据本发明的一些优选方面，步骤(2)中，所述第一乳化剂为选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和十六烷基三甲基对甲苯磺酸铵中的一种或多种阳离子乳化剂的组合；步骤(3)中，所述第二乳化剂为选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和十六烷基三甲基对甲苯磺酸铵中的一种或多种阳离子乳化剂的组合。According to some preferred aspects of the present invention, in step (2), the first emulsifier is selected from cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide and cetyl trimethyl ammonium bromide. A combination of one or more cationic emulsifiers in ammonium methyl p-toluenesulfonate; in step (3), the second emulsifier is selected from cetyl trimethyl ammonium chloride, cetyl A combination of one or more cationic emulsifiers in trimethylammonium bromide and cetyltrimethylammonium p-toluenesulfonate.
根据本发明的一些优选方面，步骤(2)中，所述第一聚合反应的温度为25～70℃，反应时间为4～24h。According to some preferred aspects of the present invention, in step (2), the temperature of the first polymerization reaction is 25-70°C, and the reaction time is 4-24 h.
根据本发明的一些优选方面，步骤(3)中，所述第二聚合反应的温度为35～80℃，反应时间为0.5～8h。According to some preferred aspects of the present invention, in step (3), the temperature of the second polymerization reaction is 35-80°C, and the reaction time is 0.5-8h.
相比于现有技术，本发明的主要的有益效果是：Compared with the prior art, the main beneficial effects of the present invention are:
1.提供了一种具有放射纤维状介孔壳层/中空核层结构的复合微球，其具有良好的球形，粒径分布窄，性能多样且性能可调节等优点。与现有的微球相比，本发明的微球性能均明显提高。例如应用在光扩散板上，可应对照明器件薄型化，吸光度减小以及扩散层变薄等对光扩散剂的高透光率、高雾度及良好扩散性的要求；例如应用在化妆品中，可作为具有高吸油率，柔焦等效果的功能型粉体；例如可作为轻质填料应用在塑胶、树脂等基材中，制备轻量化复合材料；例如还可应用在隔热材料、催化产品、多孔载体、缓释药物载体等方面。1. Provided is a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure, which has the advantages of good spherical shape, narrow particle size distribution, diverse performance and adjustable performance. Compared with the existing microspheres, the performance of the microspheres of the present invention is significantly improved. For example, it can be applied to the light diffusion plate to meet the requirements of high light transmittance, high haze and good diffusivity of the light diffusion agent such as the thinning of the lighting device, the reduction of the absorbance and the thinning of the diffusion layer; for example, the application in cosmetics, It can be used as a functional powder with high oil absorption, soft focus and other effects; for example, it can be used as a lightweight filler in plastics, resins and other substrates to prepare lightweight composite materials; for example, it can also be used in thermal insulation materials and catalytic products , Porous carriers, sustained-release drug carriers, etc.
2.提供了一种具有放射纤维状介孔壳层/中空核层结构的复合微球的制备方法。该复合微球的制备是以一种用硅氧烷改性的聚苯乙烯微球作为模板，在特定硅源前驱体体系中，一步法完成放射纤维状介孔壳层的形成和聚苯乙烯微球的去除。本发明合成工艺简单易行，易于工业化生产，具有广阔的应用前景。2. A method for preparing composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure is provided. The preparation of the composite microspheres is based on a polystyrene microsphere modified with siloxane as a template. In a specific silicon source precursor system, the formation of the radial fibrous mesoporous shell and the polystyrene are completed in one step. Removal of microspheres. The synthesis process of the invention is simple and easy to implement, easy to industrialized production, and has broad application prospects.
附图说明Description of the drawings
图1为实施例1的PS微球的SEM照片，图(b)内插图为相应的TEM照片；Figure 1 is an SEM photo of the PS microspheres of Example 1, and the inset in Figure (b) is the corresponding TEM photo;
图2为实施例1的具有放射纤维状介孔壳层/中空核层结构的复合微球TEM照片(图a、b为不同放大倍率)；Figure 2 is a TEM photograph of the composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure of Example 1 (Figures a and b are different magnifications);
图3为实施例1的具有放射纤维状介孔壳层/中空核层结构的复合微球的氮气吸-脱附曲线，插图为相应的BJH孔径分布图；3 is the nitrogen absorption-desorption curve of the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure of Example 1, and the inset is the corresponding BJH pore size distribution diagram;
图4为对比例1的PS@SiO2微球煅烧前(a)实心PS@SiO 2复合微球和煅烧后(b)普通中空介孔二氧化硅微球的TEM照片； Figure 4 is a TEM photograph of PS@SiO2 microspheres in Comparative Example 1 before (a) solid PS@SiO 2 composite microspheres and after (b) ordinary hollow mesoporous silica microspheres;
图5为对比例1的普通中空介孔二氧化硅微球的氮气吸-脱附曲线，插图为相应的BJH孔径分布图；Figure 5 is the nitrogen absorption-desorption curve of ordinary hollow mesoporous silica microspheres of Comparative Example 1, and the inset is the corresponding BJH pore size distribution diagram;
图6为实施例2的具有放射纤维状介孔壳层/中空核层结构的复合微球的TEM照片(图a、b为不同放大倍率)；Figure 6 is a TEM photograph of the composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure of Example 2 (Figures a and b are different magnifications);
图7为图6-b中具有放射纤维状介孔壳层/中空核层结构的复合微球的放大TEM照片。Fig. 7 is an enlarged TEM photograph of the composite microsphere with a radial fibrous mesoporous shell/hollow core layer structure in Fig. 6-b.
具体实施方式detailed description
本发明人通过长期而深入的研究，提出一种用硅氧烷改性的聚苯乙烯微球作为模板，在特定 硅源前驱体体系中，一步合成具有放射纤维状介孔壳层的中空微球的方法。该法制备的复合微球具有放射纤维状介孔壳层和中空核层结构。所得产品兼具多种优异性能，从而在光扩散板、化妆品等方面具有很好的应用前景。在此基础上，发明人完成了本发明。Through long-term and in-depth research, the inventor proposed a siloxane-modified polystyrene microsphere as a template. In a specific silicon source precursor system, a hollow microsphere with a radial fibrous mesoporous shell was synthesized in one step. Ball method. The composite microsphere prepared by this method has a radial fibrous mesoporous shell layer and a hollow core layer structure. The obtained product has a variety of excellent properties, so it has good application prospects in light diffusion plates, cosmetics and the like. On this basis, the inventor completed the present invention.
术语the term
如本文所用，术语“C 1-6烃基”是指具有1-6个碳原子的烷基、烯基或炔基等。例如C 1-6烷基、C 2-6烯基、C 2-6炔基等。 As used herein, the term "C 1-6 hydrocarbon group" refers to an alkyl group, alkenyl group, or alkynyl group, etc., having 1 to 6 carbon atoms. For example, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl and the like.
如本文所用，术语“C 1-6烷基”指具有1-6个碳原子的直链或支链烷基，例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、或类似基团。 As used herein, the term "C 1-6 alkyl" refers to a straight or branched chain alkyl group having 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl , Sec-butyl, tert-butyl, or similar groups.
如本文所用，术语“C 2-6烯基”指具有2-6个碳原子的直链或支链的烯基，例如乙烯基、烯丙基、1-丙烯基、异丙烯基、1-丁烯基、2-丁烯基、或类似基团。 As used herein, the term "C 2-6 alkenyl" refers to a linear or branched alkenyl group having 2-6 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1- Butenyl, 2-butenyl, or similar groups.
如本文所用，术语“C 2-6炔基”是指具有2-6个碳原子的直链或支链的炔基，例如乙炔基、丙炔基等。 As used herein, the term "C 2-6 alkynyl" refers to a linear or branched alkynyl group having 2-6 carbon atoms, such as ethynyl, propynyl, and the like.
如本文所用，术语“C 6-12芳基”指单环或二环的芳族烃基，例如苯基、萘基、或类似基团。 As used herein, the term "C 6-12 aryl" refers to a monocyclic or bicyclic aromatic hydrocarbon group, such as phenyl, naphthyl, or the like.
如本文所用，术语“C 1-6烷氧基”指具有1-6个碳原子的直链或支链烷氧基，例如甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、仲丁氧基、叔丁氧基、或类似基团。 As used herein, the term "C 1-6 alkoxy" refers to a linear or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, Butoxy, isobutoxy, sec-butoxy, tert-butoxy, or similar groups.
如本文所用，术语“被氧取代的C 1-6烷氧基”可指在C 1-6烷氧基的任意某个位置被氧(＝O)取代或两个位置被氧取代成环氧。 As used herein, the term "C 1-6 alkoxy substituted by oxygen" may refer to the substitution of oxygen (=O) at any position of the C 1-6 alkoxy group or the substitution of oxygen at two positions to form an epoxy .
如本文所用，术语“C 1-6氨烷基”是指氨基取代的C 1-6烷基，即是指烷基的任意位置被氨基所取代。 As used herein, the term "C 1-6 aminoalkyl" refers to a C 1-6 alkyl substituted with an amino group, that is, it means that any position of the alkyl group is substituted with an amino group.
如本文所用，术语“C 1-6烃基酰氧基”是指C 1-6烃基取代的酰氧基(C 1-6烃基-(C＝O)O-)。 As used herein, the term "C 1-6 hydrocarbyl acyloxy" refers to a C 1-6 hydrocarbyl substituted acyloxy group (C 1-6 hydrocarbyl-(C=O)O-).
第一材料和第二材料分别所述及的硅氧烷单体The siloxane monomers mentioned in the first material and the second material respectively
本发明所述的用于制备具有放射纤维状介孔壳层/中空核层结构的复合微球，所述第一材料为通式Si(OR 4) 4所示的化合物，所述第二材料为选自通式R 1Si(OR 4) 3所示的化合物、通式R 2R 3Si(OR 4) 2所示的化合物和通式Si(OR 4) 4所示的化合物中的一种或多种的组合；其中，R 4为C 1-6烷基；R 1、R 2、R 3各自独立地选自氢，取代的或未被取代的C 1-6烷基，取代的或者未被取代的C 2-6烯基，取代的或者未被取代的C 2-6炔基，取代的或者未被取代的C 6-12芳基；其中，所述取代的是指被选自氨基、被C 1-6氨烷基取代的氨基、C 1-6烷氧基、被氧取代的C 1-6烷氧基或C 1-6烃基酰氧基中的一个或多个取代基所取代。 The present invention is used to prepare composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure, the first material is a compound represented by the general formula Si(OR 4 ) 4 , and the second material It is one selected from a compound represented by the general formula R 1 Si(OR 4 ) 3 , a compound represented by the general formula R 2 R 3 Si(OR 4 ) 2 and a compound represented by the general formula Si(OR 4 ) 4 A combination of one or more; wherein R 4 is C 1-6 alkyl; R 1 , R 2 , and R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted Or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, substituted or unsubstituted C 6-12 aryl; wherein, the substituted refers to the selected since amino, amino C 1-6 alkyl substituted amino, C 1-6 alkoxy, substituted alkoxy, oxo or a C 1-6 acyloxy C 1-6 hydrocarbon group with one or more substituents Substituted.
具有放射纤维状介孔壳层/中空核层结构的复合微球Composite microsphere with radial fibrous mesoporous shell layer/hollow core layer structure
本发明提供了一种具有放射纤维状介孔壳层/中空核层结构的复合微球，所述复合微球具有空 腔、中空核层和放射纤维状介孔壳层。复合微球的平均粒径可以根据它们的应用自由设计，并且因此不受特别限制。平均粒径通常在65nm至10μm范围内。The present invention provides a composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure. The composite microsphere has a cavity, a hollow core layer and a radial fibrous mesoporous shell layer. The average particle diameter of the composite microspheres can be freely designed according to their applications, and therefore is not particularly limited. The average particle size is usually in the range of 65 nm to 10 μm.
空腔Cavity
所述复合微球的空腔的直径，优选为40nm～10μm；更优选为500nm～1.5μm。The diameter of the cavity of the composite microsphere is preferably 40 nm to 10 μm; more preferably 500 nm to 1.5 μm.
以均一单分散的微球为空腔模板微球，通过调节微球的粒径获得直径可调的复合微球，用于产生空腔的模板微球优选为聚苯乙烯微球。Using uniform monodisperse microspheres as cavity template microspheres, composite microspheres with adjustable diameters can be obtained by adjusting the particle size of the microspheres. The template microspheres used to generate the cavity are preferably polystyrene microspheres.
中空核层Hollow core layer
所述复合微球的中空核层的厚度优选为5nm～2μm；更优选为10～500nm。The thickness of the hollow core layer of the composite microspheres is preferably 5 nm to 2 μm; more preferably 10 to 500 nm.
复合微球的中空核层优选通过聚合硅氧烷单体得到，组成所述中空核层硅氧烷单体选自通式Si(OR 4) 4；其中，R 4为C 1-6烷基；其实例优选为四乙氧基硅烷、四甲氧基硅烷。本发明的中空核层需具有一定的耐溶剂性，外层乳化剂吸附性，与通孔结构稳定性，使复合微球的中空结构能够耐受有机溶剂澎润且能有效由通孔移除模板微球而不破坏中空架构且能接受乳化剂的吸附有效形成介孔壳层。 The hollow core layer of the composite microsphere is preferably obtained by polymerizing siloxane monomers. The siloxane monomer constituting the hollow core layer is selected from the general formula Si(OR 4 ) 4 ; wherein R 4 is a C 1-6 alkyl group ; Its examples are preferably tetraethoxysilane, tetramethoxysilane. The hollow core layer of the present invention needs to have certain solvent resistance, outer emulsifier adsorbability, and through-hole structure stability, so that the hollow structure of the composite microsphere can withstand the swelling of organic solvents and can be effectively removed by the through-hole The template microspheres do not damage the hollow structure and can accept the adsorption of emulsifiers to effectively form a mesoporous shell.
放射纤维状介孔壳层Radial fibrous mesoporous shell
所述复合微球的介孔壳层厚度优选为20nm～200nm；更优选为150～200nm。The thickness of the mesoporous shell layer of the composite microsphere is preferably 20 nm to 200 nm; more preferably 150 to 200 nm.
复合微球的放射纤维状介孔壳层优选通过聚合硅氧烷单体得到，其中组成所述放射纤维状介孔壳层硅氧烷单体为选自通式R 1Si(OR 4) 3所示的化合物、通式R 2R 3Si(OR 4) 2所示的化合物和通式Si(OR 4) 4所示的化合物中的一种或多种的组合；其中，R 4为C 1-6烷基；R 1、R 2、R 3各自独立地选自氢，取代的或未被取代的C 1-6烷基，取代的或者未被取代的C 2-6烯基，取代的或者未被取代的C 2-6炔基，取代的或者未被取代的C 6-12芳基，其中所述取代的是指被选自氨基、被C 1-6氨烷基取代的氨基、C 1-6烷氧基、被氧取代的C 1-6烷氧基或C 1-6烃基酰氧基中的一个或多个取代基所取代。 The radial fibrous mesoporous shell layer of the composite microsphere is preferably obtained by polymerizing siloxane monomers, wherein the siloxane monomer constituting the radial fibrous mesoporous shell layer is selected from the general formula R 1 Si(OR 4 ) 3 A combination of one or more of the compound shown, the compound represented by the general formula R 2 R 3 Si(OR 4 ) 2 and the compound represented by the general formula Si(OR 4 ) 4 ; wherein R 4 is C 1-6 alkyl; R 1 , R 2 , and R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted Or unsubstituted C 2-6 alkynyl, substituted or unsubstituted C 6-12 aryl, wherein the substituted refers to an amino group selected from the group consisting of amino and substituted by C 1-6 aminoalkyl , C 1-6 alkoxy, substituted oxo substituted with a C 1-6 alkoxy or C 1-6 acyloxy group, hydrocarbyl or more substituents.
优选地，所述组成放射纤维状介孔壳层的硅氧烷单体至少含有通式R 1Si(OR 4) 3所示的化合物和/或通式R 2R 3Si(OR 4) 2所示的化合物，其实例优选为C 6H 5Si(OCH 3) 3(苯基三甲氧基硅烷)、CH 3Si(OCH 3) 3(甲基三甲氧基硅烷)、甲基苯基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基丙烯酰氧丙基三甲氧基硅烷、缩水甘油醚氧基丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、甲基苯基二乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、二甲基二甲氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、氨丙基三甲氧基硅烷、甲基三乙氧基硅烷(MTEOS)或其组合。 Preferably, the siloxane monomer constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or the general formula R 2 R 3 Si(OR 4 ) 2 The compounds shown, examples of which are preferably C 6 H 5 Si(OCH 3 ) 3 (phenyltrimethoxysilane), CH 3 Si(OCH 3 ) 3 (methyltrimethoxysilane), methyl phenyl two Methoxysilane, diphenyldimethoxysilane, methacryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, N-(β-aminoethyl)-γ- Aminopropyltrimethoxysilane, methylphenyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, γ-(2,3-ring Oxypropoxy)propyltrimethoxysilane, γ-(methacryloxy)propyltrimethoxysilane, aminopropyltrimethoxysilane, methyltriethoxysilane (MTEOS), or a combination thereof.
更优选地，所述组成放射纤维状介孔壳层的硅氧烷单体至少含有通式R 1Si(OR 4) 3所示的化合物和/或通式R 2R 3Si(OR 4) 2所示的化合物，还选择性地含有通式Si(OR 4) 4所示的化合物，其实例优 选为四乙氧基硅烷(TEOS)与选自C 6H 5Si(OCH 3) 3(苯基三甲氧基硅烷)、CH 3Si(OCH 3) 3(甲基三甲氧基硅烷)、甲基苯基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基丙烯酰氧丙基三甲氧基硅烷、缩水甘油醚氧基丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、甲基苯基二乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、二甲基二甲氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、氨丙基三甲氧基硅烷、甲基三乙氧基硅烷(MTEOS)中至少一种的组合。 More preferably, the siloxane monomer constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or the general formula R 2 R 3 Si(OR 4 ) The compound shown in 2 also optionally contains a compound shown in the general formula Si(OR 4 ) 4 , an example of which is preferably tetraethoxysilane (TEOS) and selected from C 6 H 5 Si(OCH 3 ) 3 ( Phenyltrimethoxysilane), CH 3 Si(OCH 3 ) 3 (methyltrimethoxysilane), methylphenyldimethoxysilane, diphenyldimethoxysilane, methacryloxypropyl Trimethoxysilane, glycidoxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, methylphenyldiethoxysilane, vinyl Triethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, γ-(2,3-glycidoxy)propyltrimethoxysilane, γ-(methacryloxy) A combination of at least one of propyltrimethoxysilane, aminopropyltrimethoxysilane, and methyltriethoxysilane (MTEOS).
更优选地，所述组成放射纤维状介孔壳层的硅氧烷单体为选自以下的组合：TEOS和缩水甘油醚氧基丙基三甲氧基硅烷、TEOS和苯基三甲氧基硅烷、TEOS和氨丙基三甲氧基硅烷或TEOS和二苯基二甲氧基硅烷。More preferably, the siloxane monomer constituting the radial fibrous mesoporous shell layer is a combination selected from the group consisting of TEOS and glycidoxypropyltrimethoxysilane, TEOS and phenyltrimethoxysilane, TEOS and aminopropyltrimethoxysilane or TEOS and diphenyldimethoxysilane.
所述组成放射纤维状介孔壳层的硅氧烷单体更优选为苯基三甲氧基硅烷与选自CH 3Si(OCH 3) 3(甲基三甲氧基硅烷)、甲基苯基二甲氧基硅烷、二苯基二甲氧基硅烷、甲基丙烯酰氧丙基三甲氧基硅烷、缩水甘油醚氧基丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、甲基苯基二乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、二甲基二甲氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、氨丙基三甲氧基硅烷、四乙氧基硅烷(TEOS)、甲基三乙氧基硅烷(MTEOS)中至少一种的组合。 The siloxane monomer constituting the radial fibrous mesoporous shell layer is more preferably phenyltrimethoxysilane and selected from CH 3 Si(OCH 3 ) 3 (methyltrimethoxysilane), methylphenyl two Methoxysilane, diphenyldimethoxysilane, methacryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, N-(β-aminoethyl)-γ- Aminopropyltrimethoxysilane, methylphenyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, γ-(2,3-ring Oxypropoxy) propyl trimethoxy silane, γ-(methacryloxy) propyl trimethoxy silane, aminopropyl trimethoxy silane, tetraethoxy silane (TEOS), methyl triethoxy A combination of at least one of silane (MTEOS).
更优选地，所述组成放射纤维状介孔壳层的硅氧烷单体为选自以下的组合：苯基三甲氧基硅烷和MTEOS、苯基三甲氧基硅烷和乙烯基三乙氧基硅烷、苯基三甲氧基硅烷和二甲基二甲氧基硅烷、苯基三甲氧基硅烷和γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、苯基三甲氧基硅烷和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷、苯基三甲氧基硅烷和氨丙基三甲氧基硅烷或基三甲氧基硅烷、MTEOS与苯基甲基二甲氧基硅烷。More preferably, the siloxane monomer constituting the radial fibrous mesoporous shell layer is a combination selected from: phenyltrimethoxysilane and MTEOS, phenyltrimethoxysilane and vinyltriethoxysilane , Phenyltrimethoxysilane and dimethyldimethoxysilane, phenyltrimethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane, phenyltrimethoxysilane and γ-(Methacryloxy)propyltrimethoxysilane, phenyltrimethoxysilane and aminopropyltrimethoxysilane or radical trimethoxysilane, MTEOS and phenylmethyldimethoxysilane.
具有放射纤维状介孔壳层/中空核层结构的复合微球的制备方法Preparation method of composite microspheres with radial fibrous mesoporous shell layer/hollow core layer structure
本发明的具有放射纤维状介孔壳层/中空核层结构的复合微球优选按照如下方法制备，The composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure of the present invention are preferably prepared according to the following method:
1)制备聚苯乙烯微球作为核心模板；1) Prepare polystyrene microspheres as core templates;
2)然后，进行第一阶段的聚合反应，形成包围在步骤1)中所得聚苯乙烯微球上的壳层。2) Then, the first stage of polymerization reaction is performed to form a shell layer surrounding the polystyrene microspheres obtained in step 1).
在一定温度(如25～70℃)下，按一定比例将步骤1)制备的聚苯乙烯微球、第一乳化剂、水、醇类分散剂混合并分散均匀，加入碱性调节剂调节溶液至碱性，加入第一材料(即硅氧烷单体，如一种硅氧烷单体或多种硅氧烷单体的混合物)进行聚合反应反应一段时间(如4～24h)后，得到含有以表面包覆有硅层的聚苯乙烯微球的第一反应混合物。因此，复合微球的中空核层是由步骤2)中硅氧烷单体聚合而得。At a certain temperature (such as 25～70℃), the polystyrene microspheres prepared in step 1), the first emulsifier, water, and alcohol dispersant are mixed and dispersed uniformly in a certain proportion, and the alkaline regulator is added to adjust the solution When it is basic, add the first material (ie, siloxane monomer, such as a siloxane monomer or a mixture of siloxane monomers) and carry out the polymerization reaction for a period of time (such as 4-24h) to obtain A first reaction mixture of polystyrene microspheres coated with a silicon layer on the surface. Therefore, the hollow core layer of the composite microsphere is obtained by polymerizing the siloxane monomer in step 2).
3)接着，进行第二阶段的聚合反应以及核心模板的同步去除，得到含有所述具有放射纤维状 介孔壳层/中空核层结构的复合微球的第二反应混合物。3) Next, the second stage of polymerization reaction and simultaneous removal of the core template are performed to obtain a second reaction mixture containing the composite microspheres having the radial fibrous mesoporous shell layer/hollow core layer structure.
在一定温度(如35～80℃)下，在步骤2)第一反应混合物中加入第二乳化剂和有机溶剂混合均匀，最后加入第二材料(即硅氧烷单体，如一种硅氧烷单体或含有两种硅氧烷单体的混合物)进行第二聚合反应，同时模板(聚苯乙烯微球)溶解，一段时间(如0.5～8h)后，形成含有具有放射纤维状介孔壳层/中空核层结构的复合微球的第二反应混合物。At a certain temperature (such as 35-80°C), in step 2) the second emulsifier and organic solvent are added to the first reaction mixture and mixed uniformly, and finally the second material (ie, siloxane monomer, such as a siloxane) is added. Monomer or a mixture containing two siloxane monomers) for the second polymerization reaction, while the template (polystyrene microspheres) dissolves, after a period of time (such as 0.5-8h), a mesoporous shell containing radial fibers is formed Layer/hollow core layer structure of the second reaction mixture of composite microspheres.
4)将所述第二反应混合物进行离心、洗涤、干燥，得到具有放射纤维状介孔壳层/中空核层结构的复合微球。4) Centrifuging, washing and drying the second reaction mixture to obtain composite microspheres having a radial fibrous mesoporous shell layer/hollow core layer structure.
因此，复合微球的放射纤维状壳层是由步骤3)中硅氧烷单体聚合而得，且上述聚合反应优选于在加热的条件下进行，有利于壳层的形成。Therefore, the radial fibrous shell layer of the composite microsphere is obtained by polymerizing the siloxane monomer in step 3), and the above-mentioned polymerization reaction is preferably carried out under heating conditions, which is beneficial to the formation of the shell layer.
所述具有放射纤维状介孔壳层/中空核层结构的复合微球中，中空核层和放射纤维状介孔壳层的重量比约等于步骤2)和步骤3)中加入的硅氧烷单体的重量比。In the composite microspheres having a radial fibrous mesoporous shell layer/hollow core layer structure, the weight ratio of the hollow core layer and the radial fibrous mesoporous shell layer is approximately equal to the siloxane added in step 2) and step 3) The weight ratio of monomers.
其中，通过调整步骤2)中硅氧烷单体的种类和重量比以及步骤3)中硅氧烷单体的种类和重量比，使复合微球中的中空核层与放射纤维状介孔壳层可以满足所需。Wherein, by adjusting the type and weight ratio of siloxane monomer in step 2) and the type and weight ratio of siloxane monomer in step 3), the hollow core layer in the composite microsphere and the radial fibrous mesoporous shell The layer can meet the needs.
步骤2)或步骤3)中，硅氧烷单体可选自本发明上述所述硅氧烷单体中的一种或多种。In step 2) or step 3), the siloxane monomer can be selected from one or more of the aforementioned siloxane monomers of the present invention.
实施上述本发明制备方法能突破目前煅烧法制备中空复合微球于放射纤维状介孔壳层态样上的限制。The implementation of the above-mentioned preparation method of the present invention can break through the limitation of the current calcination method to prepare hollow composite microspheres in the shape of the radial fibrous mesoporous shell.
应用application
本发明的具有放射纤维状介孔壳层/中空核层结构的复合微球与具有传统介孔的微球相比，壳层具有放射纤维状介孔的微球除了具有高比表面积的特点，还拥有更多层次尺寸的孔道，使其具有良好的通透性、大的孔容，提升了对客体分子的负载能力。在光学上，多层次尺寸的孔道可以使基材更多渗入空隙中，形成具有折射率渐变功能以及有利于光扩散的过渡层。在力学上，多层次尺寸的孔道有利于基材和微球更紧密的结合以及更好的力学强度。Compared with the microspheres with traditional mesopores, the composite microspheres with radial fibrous mesoporous shell layer/hollow core layer structure of the present invention have the characteristics of high specific surface area. It also has more levels of pores, which make it have good permeability, large pore volume, and improve the load capacity of guest molecules. Optically, the multi-layered pores can make the substrate more penetrate into the gap, forming a transition layer with a refractive index gradient function and beneficial to light diffusion. In mechanics, multi-level pores are conducive to a closer combination of the substrate and the microspheres and better mechanical strength.
本发明的具有放射纤维状介孔壳层/中空核层结构的复合微球，其具有良好的球形，粒径分布窄，性能多样且性能可调节等优点。与现有的微球相比，本发明的微球性能均明显提高。因此其具有广泛的应用前景，例如应用在光扩散板上，可应对照明器件薄型化，吸光度减小以及扩散层变薄等对光扩散剂的高透光率、高雾度及良好扩散性的要求；例如应用在化妆品中，可作为具有高吸油率，柔焦等效果的功能型粉体；例如应用在塑胶、树脂等基材中，制备轻量化隔热复合材料，可作为填料。The composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure of the present invention has the advantages of good spherical shape, narrow particle size distribution, diverse performance, adjustable performance and the like. Compared with the existing microspheres, the performance of the microspheres of the present invention is significantly improved. Therefore, it has a wide range of application prospects. For example, it can be applied to the light diffusion plate, which can cope with the thinning of the lighting device, the reduction of the absorbance and the thinning of the diffusion layer. Requirements; for example, in cosmetics, it can be used as a functional powder with high oil absorption, soft focus and other effects; for example, in plastics, resins and other substrates to prepare lightweight thermal insulation composite materials, which can be used as fillers.
实施例Example
通过下列实施例和比较例对本发明进行具体说明，但本发明并不限定于这些实施例的范围内。 下述实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。所有的原料如无特殊说明，通常来自于商购或者通过本领域的常规方法制备而得。The present invention is specifically explained by the following examples and comparative examples, but the present invention is not limited to the scope of these examples. The experimental methods without specific conditions in the following examples usually follow the conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, all raw materials are usually purchased from commercial sources or prepared by conventional methods in the art.
实施例1Example 1
向装有100mL去离子水的三口烧瓶加入6g苯乙烯单体，在室温下机械搅拌(转速250rpm)，通氮气30min。在氮气气氛下升温至70℃时，加入60mg引发剂KPS，反应24h。将产物移至离心管，离心，乙醇洗涤、离心，并于50℃的鼓风烘箱中烘干备用。产物形貌如图1所示，平均粒径为967nm，多分散指数(PDI)为1.11。Add 6 g of styrene monomer to a three-necked flask containing 100 mL of deionized water, mechanically stir at room temperature (rotating speed 250 rpm), and bubbling with nitrogen for 30 minutes. When the temperature was raised to 70°C in a nitrogen atmosphere, 60 mg of the initiator KPS was added and reacted for 24 hours. The product is transferred to a centrifuge tube, centrifuged, washed with ethanol, centrifuged, and dried in a blast oven at 50°C for use. The morphology of the product is shown in Figure 1, with an average particle size of 967 nm and a polydispersity index (PDI) of 1.11.
称取0.4g十六烷基三甲基溴化铵(CTAB)放入100mL圆底烧瓶中，随后向烧瓶中加入20mL水、8mL无水乙醇。称取450mg制备的聚苯乙烯微球加入到烧瓶中，之后加入1mL氨水，室温搅拌30min。再往体系中滴加500μL TEOS，搅拌条件下室温反应24h。Weigh 0.4 g of cetyltrimethylammonium bromide (CTAB) into a 100 mL round bottom flask, and then add 20 mL of water and 8 mL of absolute ethanol to the flask. Weigh 450 mg of the prepared polystyrene microspheres into the flask, then add 1 mL of ammonia water, and stir for 30 min at room temperature. Then add 500 μL TEOS dropwise to the system, and react at room temperature for 24 hours under stirring.
随后，将反应体系温度升至50℃，向体系中加入300mg十六烷基三甲基溴化铵(CTAB)和20mL环己烷，磁力搅拌10min后，再加入3.5g TEOS和0.3g甲基丙烯酰氧丙基三甲氧基硅烷。800rpm磁力搅拌下反应1h。Subsequently, the temperature of the reaction system was increased to 50°C, 300mg of cetyltrimethylammonium bromide (CTAB) and 20mL of cyclohexane were added to the system, and after magnetic stirring for 10 minutes, 3.5g of TEOS and 0.3g of methyl were added. Acryloyloxypropyl trimethoxysilane. The reaction was carried out for 1 hour under 800 rpm magnetic stirring.
自然冷却至室温后，反应液用HC-2518ZONKIA离心机进行离心分离(5000r/min)出固体产物，用工业乙醇超声洗涤3次后，置于50℃的电热鼓风干燥箱中烘干。产物形貌的TEM照片如图2所示，是具有放射纤维状介孔壳层/中空核层结构的复合微球，空腔尺寸与聚苯乙烯模板微球相似，放射纤维状介孔壳层厚度约为40nm。产物的氮气吸-脱附曲线测试及相应的BJH孔径分布(测试前将样品置于60℃真空条件下脱气处理2h)如图3所示，其吸脱附等温曲线属于IV型曲线，且存在H3型回滞环，说明微球壁存在介孔结构。由图3计算出复合微球的BET比表面积为704.4m 2/g，相应的BJH孔径分布图表明介孔尺寸分布主要集中在10nm左右。 After being naturally cooled to room temperature, the reaction solution was centrifuged (5000r/min) with an HC-2518ZONKIA centrifuge to obtain a solid product, washed with industrial ethanol for 3 times, and then placed in an electric blast drying oven at 50°C for drying. The TEM picture of the product morphology is shown in Figure 2. It is a composite microsphere with a radial fibrous mesoporous shell/hollow core layer structure. The cavity size is similar to that of polystyrene template microspheres. The radial fibrous mesoporous shell The thickness is about 40nm. The nitrogen absorption-desorption curve test of the product and the corresponding BJH pore size distribution (before the test, the sample is placed in a vacuum condition of 60 ℃ for degassing for 2 hours) as shown in Figure 3. The absorption and desorption isotherm curve belongs to type IV curve, and The existence of H3 type hysteresis ring indicates that the microsphere wall has a mesoporous structure. The BET specific surface area of the composite microspheres calculated from Figure 3 is 704.4m 2 /g, and the corresponding BJH pore size distribution diagram shows that the mesopore size distribution is mainly concentrated around 10nm.
实施例2Example 2
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备中空核层的第一聚合反应时间为12小时，制备的具有放射纤维状介孔壳层/中空核层结构的复合微球的TEM照片参见图6，图7为图6-b中复合微球的放大图，相应复合微球的平均粒径为1μm。A composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure was prepared in the same manner as in Example 1, except that the first polymerization reaction time for preparing the hollow core layer was 12 hours. The TEM photograph of the composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure is shown in FIG. 6, and FIG. 7 is an enlarged view of the composite microspheres in FIG. 6-b, and the average particle size of the corresponding composite microspheres is 1 μm.
实施例3Example 3
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于有机溶剂由正己烷所代替。The composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure were prepared in the same manner as in Example 1, except that the organic solvent was replaced by n-hexane.
实施例4Example 4
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之 处在于用于制备纤维状介孔壳层的第二聚合反应在室温下进行。A composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure was prepared in the same manner as in Example 1, except that the second polymerization reaction for preparing the fibrous mesoporous shell layer was carried out at room temperature. .
实施例5Example 5
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g TEOS和0.3g缩水甘油醚氧基丙基三甲氧基硅烷所代替，纤维状介孔壳层的厚度约为20nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g TEOS and 0.3g glycidoxypropyltrimethoxysilane were replaced, and the thickness of the fibrous mesoporous shell was about 20nm.
实施例6Example 6
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g TEOS和0.5g苯基三甲氧基硅烷所代替，纤维状介孔壳层的厚度约为50nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g TEOS and 0.5g phenyltrimethoxysilane were replaced, and the thickness of the fibrous mesoporous shell layer was about 50nm.
实施例7Example 7
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g TEOS和0.3g氨丙基三甲氧基硅烷所代替，纤维状介孔壳层的厚度约为55～60nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of TEOS and 0.3g aminopropyltrimethoxysilane, the thickness of the fibrous mesoporous shell is about 55-60nm.
实施例8Example 8
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g TEOS和0.3g二苯基二甲氧基硅烷所代替，纤维状介孔壳层的厚度约为42nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of TEOS and 0.3g of diphenyldimethoxysilane, the thickness of the fibrous mesoporous shell is about 42nm.
实施例9Example 9
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g苯基三甲氧基硅烷和0.3g MTEOS所代替，纤维状介孔壳层的厚度约为40nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g MTEOS, the thickness of the fibrous mesoporous shell is about 40nm.
实施例10Example 10
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g苯基三甲氧基硅烷和0.3g乙烯基三乙氧基硅烷所代替，纤维状介孔壳层的厚度约为40nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g vinyltriethoxysilane, the thickness of the fibrous mesoporous shell is about 40nm.
实施例11Example 11
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g苯基三甲氧基硅烷和0.3g二甲基二甲氧基硅烷所代替，纤维状介孔壳层的厚度约为20nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g dimethyldimethoxysilane, the thickness of the fibrous mesoporous shell layer is about 20nm.
实施例12Example 12
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g苯基三甲氧基硅烷和0.3gγ-(2,3-环氧丙氧)丙基三甲氧基硅烷所代替，纤维状介孔壳层的厚度约为50nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3gγ-(2,3-glycidoxy)propyltrimethoxysilane, the thickness of the fibrous mesoporous shell is about 50nm.
实施例13Example 13
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g苯基三甲氧基硅烷和0.3gγ-(甲基丙烯酰氧)丙基三甲氧基硅烷所代替，纤维状介孔壳层的厚度约为55nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g gamma-(methacryloxy)propyltrimethoxysilane, the thickness of the fibrous mesoporous shell layer is about 55nm.
实施例14Example 14
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g苯基三甲氧基硅烷和0.3g氨丙基三甲氧基硅烷所代替，纤维状介孔壳层的厚度约为55-60nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane and 0.3g aminopropyltrimethoxysilane, the thickness of the fibrous mesoporous shell is about 55-60nm.
实施例15Example 15
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备纤维状介孔壳层的硅氧烷单体由3.5g苯基三甲氧基硅烷、0.15g MTEOS与0.15g苯基甲基二甲氧基硅烷所代替，纤维状介孔壳层的厚度约为45nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the siloxane monomer used to prepare the fibrous mesoporous shell was 3.5 g Instead of phenyltrimethoxysilane, 0.15g MTEOS and 0.15g phenylmethyldimethoxysilane, the thickness of the fibrous mesoporous shell is about 45nm.
实施例16Example 16
以与实施例1中相同的方式制备具有放射纤维状介孔壳层/中空核层结构的复合微球，不同之处在于用于制备空腔模板的聚苯乙烯微球的平均粒径为40nm，相应复合微球的平均粒径为90nm。The composite microspheres with a radial fibrous mesoporous shell/hollow core layer structure were prepared in the same manner as in Example 1, except that the average particle diameter of the polystyrene microspheres used to prepare the cavity template was 40 nm , The average particle size of the corresponding composite microspheres is 90nm.
对比例1 普通中空介孔SiO 2 Comparative Example 1 Ordinary hollow mesoporous SiO 2
采用同样的方法制备普通中空二氧化硅微球：取0.4g十六烷基三甲基溴化铵(CTAB)放入100mL圆底烧瓶中，随后向烧瓶中加入20mL水、8mL无水乙醇，并称取450mg聚苯乙烯微球加入到烧瓶中，之后加入1mL氨水，室温搅拌30min。再往体系中滴加750L TEOS，搅拌条件下室温反应24h。反应结束后，将反应液转移至离心管中，使用HC-2518ZONKIA离心机进行离心分离，转速为8000r/min。收集底部沉淀，用工业乙醇超声洗涤3次后，置于50℃的电热鼓风干燥箱中烘干，产物形貌如图4a所示，为实心PS@SiO 2复合微球。将产物继续置于马弗炉中于550℃下高温煅烧4h，得到如图4b所示的普通中空介孔二氧化硅微球，其壳层为普通实心SiO 2。 Use the same method to prepare ordinary hollow silica microspheres: Take 0.4g cetyltrimethylammonium bromide (CTAB) into a 100mL round bottom flask, and then add 20mL water and 8mL absolute ethanol to the flask. Weigh 450 mg of polystyrene microspheres and add them to the flask, then add 1 mL of ammonia, and stir for 30 min at room temperature. Then add 750L TEOS dropwise to the system, and react at room temperature for 24 hours under stirring. After the reaction, the reaction solution was transferred to a centrifuge tube and centrifuged using an HC-2518ZONKIA centrifuge at a speed of 8000r/min. The bottom sediment was collected, washed with industrial ethanol for 3 times, and dried in an electric blast drying oven at 50°C. The morphology of the product is shown in Figure 4a, which is solid PS@SiO 2 composite microspheres. The product was continuously placed in a muffle furnace and calcined at a high temperature at 550°C for 4 hours to obtain ordinary hollow mesoporous silica microspheres as shown in Fig. 4b, the shell layer of which was ordinary solid SiO 2 .
普通中空介孔二氧化硅微球的氮气吸-脱附曲线测试及相应的BJH孔径分布(测试前将样品置于60℃真空条件下脱气处理2h)如图5所示。普通中空介孔二氧化硅微球的吸脱附等温曲线属于IV型曲线，存在H3型回滞环，说明球壁存在介孔结构。经计算BET比表面积为186.2m 2/g， 远远低于中空纤维状介孔二氧化硅微球的BET比表面积。通过BJH法计算得到样品的孔径分布，普通中空介孔二氧化硅微球介孔尺寸分布在10～100nm左右(介孔为2-50nm)，较上述纤维状中空介孔二氧化硅微球的介孔尺寸分布宽。 The nitrogen absorption-desorption curve test of ordinary hollow mesoporous silica microspheres and the corresponding BJH pore size distribution (the sample is placed under vacuum at 60°C for 2h before the test) is shown in Figure 5. The adsorption and desorption isotherm curve of ordinary hollow mesoporous silica microspheres belongs to the IV type curve, and there is an H3 type hysteresis loop, which indicates that the sphere wall has a mesoporous structure. The calculated BET specific surface area is 186.2 m 2 /g, which is much lower than the BET specific surface area of the hollow fiber-like mesoporous silica microspheres. The pore size distribution of the sample is calculated by the BJH method. The mesopore size distribution of ordinary hollow mesoporous silica microspheres is about 10-100nm (the mesopore is 2-50nm), which is better than the above-mentioned fibrous hollow mesoporous silica microspheres. The mesopore size distribution is wide.
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。All documents mentioned in the present invention are cited as references in this application, as if each document was individually cited as a reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims (10)

  1. 一种具有放射纤维状介孔壳层/中空核层结构的复合微球，其特征在于，所述复合微球具有空腔、中空核层和放射纤维状介孔壳层，所述复合微球的平均粒径为65nm～10μm；A composite microsphere with a radial fibrous mesoporous shell layer/hollow core layer structure is characterized in that the composite microsphere has a cavity, a hollow core layer and a radial fibrous mesoporous shell layer. The composite microsphere The average particle size is 65nm～10μm;
    其中，组成所述放射纤维状介孔壳层的材料为选自通式R 1Si(OR 4) 3所示的化合物、通式R 2R 3Si(OR 4) 2所示的化合物和通式Si(OR 4) 4所示的化合物中的一种或多种的组合，组成所述中空核层的材料为通式Si(OR 4) 4所示的化合物；其中，R 4为C 1-6烷基；R 1、R 2、R 3各自独立地选自氢，取代的或未被取代的C 1-6烷基，取代的或者未被取代的C 2-6烯基，取代的或者未被取代的C 2-6炔基，取代的或者未被取代的C 6-12芳基，其中所述取代的是指被选自氨基、被C 1-6氨烷基取代的氨基、C 1-6烷氧基、被氧取代的C 1-6烷氧基或C 1-6烃基酰氧基中的一个或多个取代基所取代。 Wherein, the material composing the radial fibrous mesoporous shell layer is selected from compounds represented by the general formula R 1 Si(OR 4 ) 3 , compounds represented by the general formula R 2 R 3 Si(OR 4 ) 2 and general formula formula Si (oR 4) one of the compounds shown in 4 or more thereof, compound of formula Si (oR 4) 4 composed of the hollow core material layer; wherein, R 4 is a C 1 -6 alkyl; R 1 , R 2 , R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted Or an unsubstituted C 2-6 alkynyl group, a substituted or unsubstituted C 6-12 aryl group, wherein the substituted refers to an amino group substituted with a C 1-6 aminoalkyl group, C 1-6 alkoxy, an oxygen-substituted C 1-6 alkoxy or C 1-6 acyloxy group, hydrocarbyl or more substituents.
  2. 根据权利要求1所述的复合微球，其特征在于，组成所述放射纤维状介孔壳层的材料至少含有通式R 1Si(OR 4) 3所示的化合物和/或通式R 2R 3Si(OR 4) 2所示的化合物。 The composite microsphere of claim 1, wherein the material constituting the radial fibrous mesoporous shell layer contains at least a compound represented by the general formula R 1 Si(OR 4 ) 3 and/or the general formula R 2 A compound represented by R 3 Si(OR 4 ) 2 .
  3. 根据权利要求1所述的复合微球，其特征在于，所述空腔的直径为40nm～10μm，所述中空核层的厚度为5nm～2μm，所述放射纤维状介孔壳层的厚度为20nm～200nm。The composite microsphere according to claim 1, wherein the diameter of the cavity is 40nm-10μm, the thickness of the hollow core layer is 5nm-2μm, and the thickness of the radial fibrous mesoporous shell layer is 20nm～200nm.
  4. 一种权利要求1-3中任一项权利要求所述的具有放射纤维状介孔壳层/中空核层结构的复合微球的制备方法，其特征在于，所述制备方法包括如下步骤：A method for preparing composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure according to any one of claims 1 to 3, wherein the preparation method comprises the following steps:
    1)制备聚苯乙烯微球；1) Preparation of polystyrene microspheres;
    2)将上述聚苯乙烯微球、第一乳化剂、水、醇类分散剂混合并分散均匀，加入碱性调节剂调节溶液至碱性，加入第一材料进行第一聚合反应，得到第一反应混合物，所述第一反应混合物含有表面包覆有硅层的聚苯乙烯微球；2) Mix and disperse the above polystyrene microspheres, the first emulsifier, water, and alcohol dispersant uniformly, add an alkaline regulator to adjust the solution to alkaline, and add the first material to perform the first polymerization reaction to obtain the first A reaction mixture, the first reaction mixture containing polystyrene microspheres coated with a silicon layer on the surface;
    3)将所述第一反应混合物体系温度升高，加入第二乳化剂和有机溶剂，混合均匀，再加入第二材料进行第二聚合反应，得到含有所述具有放射纤维状介孔壳层/中空核层结构的复合微球的第二反应混合物；3) Raise the temperature of the first reaction mixture system, add a second emulsifier and an organic solvent, mix uniformly, and then add a second material to perform a second polymerization reaction, to obtain a shell layer containing the radial fibrous mesoporous/ The second reaction mixture of composite microspheres with a hollow core layer structure;
    4)将所述第二反应混合物进行离心、洗涤、干燥，即得具有放射纤维状介孔壳层/中空核层结构的复合微球；4) Centrifuging, washing and drying the second reaction mixture to obtain composite microspheres with a radial fibrous mesoporous shell layer/hollow core layer structure;
    所述第一材料为通式Si(OR 4) 4所示的化合物，所述第二材料为选自通式R 1Si(OR 4) 3所示的化合物、通式R 2R 3Si(OR 4) 2所示的化合物和通式Si(OR 4) 4所示的化合物中的一种或多种的组合；其中，R 4为C 1-6烷基；R 1、R 2、R 3各自独立地选自氢，取代的或未被取代的C 1-6烷基，取代的或者未被取代的C 2-6烯基，取代的或者未被取代的C 2-6炔基，取代的或者未被取代的C 6-12芳基，其中所述取代的是指被选自氨基、被C 1-6氨烷基取代的氨基、C 1-6烷氧基、被氧取代的C 1-6烷氧基或C 1-6烃基酰氧基中的一个或多个取代基所取代。 The first material is a compound represented by the general formula Si(OR 4 ) 4 , and the second material is selected from the compound represented by the general formula R 1 Si(OR 4 ) 3 , the general formula R 2 R 3 Si( OR 4 ) A combination of one or more of the compound represented by OR 4 ) 2 and the compound represented by the general formula Si(OR 4 ) 4 ; wherein R 4 is a C 1-6 alkyl group; R 1 , R 2 , R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-6 alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 alkynyl, A substituted or unsubstituted C 6-12 aryl group, wherein the substituted refers to an amino group substituted with a C 1-6 aminoalkyl group, a C 1-6 alkoxy group, a substituted with oxygen C 1-6 alkoxy or C 1-6 hydrocarbyl acyloxy group is substituted by one or more substituents.
  5. 根据权利要求4所述的制备方法，其特征在于，步骤(2)中，所述聚苯乙烯微球、所述第一材料、所述第一乳化剂和所述水的投料质量比为1:(0.5～2):(0.5～2):(20～50)。The preparation method according to claim 4, wherein in step (2), the mass ratio of the polystyrene microspheres, the first material, the first emulsifier, and the water is 1 :(0.5～2):(0.5～2):(20～50).
  6. 根据权利要求4所述的制备方法，其特征在于，步骤(2)中，所述水、所述醇类分散剂和所述碱性调节剂的体积比为1:(0.2～1):(0.025～0.2)。The preparation method according to claim 4, characterized in that, in step (2), the volume ratio of the water, the alcohol dispersant and the alkaline regulator is 1:(0.2~1):( 0.025～0.2).
  7. 根据权利要求4所述的制备方法，其特征在于，步骤(2)中的所述聚苯乙烯微球、步骤(3)中的所述第二材料和步骤(3)中的所述第二乳化剂的投料质量比为1:(0.5～5):(0.5～2)。The preparation method according to claim 4, wherein the polystyrene microspheres in step (2), the second material in step (3), and the second material in step (3) The feed mass ratio of the emulsifier is 1:(0.5～5):(0.5～2).
  8. 根据权利要求4所述的制备方法，其特征在于，步骤(3)中，所述有机溶剂选自烃类溶剂、苯类溶剂、醇类溶剂或酮类溶剂，其中所述烃类溶剂为选自环己烷、正己烷、汽油和戊烷中的一种或多种的组合，所述苯类溶剂为选自苯、甲苯和二甲苯中的一种或多种的组合，所述醇类溶剂为选自甲醇、乙醇和丙醇中的一种或多种的组合，所述酮类溶剂为丙酮和/丁酮。The preparation method according to claim 4, wherein, in step (3), the organic solvent is selected from hydrocarbon solvents, benzene solvents, alcohol solvents or ketone solvents, wherein the hydrocarbon solvents are selected From a combination of one or more of cyclohexane, n-hexane, gasoline and pentane, the benzene solvent is a combination of one or more selected from benzene, toluene and xylene, the alcohol The solvent is a combination of one or more selected from methanol, ethanol and propanol, and the ketone solvent is acetone and methyl ethyl ketone.
  9. 根据权利要求4所述的制备方法，其特征在于，步骤(2)中，所述碱性调节剂为选自碱金属氢氧化物水溶液、尿素、氨水和三乙醇胺中的一种或多种的组合；和/或，步骤(2)中，所述醇类分散剂为乙醇。The preparation method according to claim 4, wherein, in step (2), the alkalinity regulator is one or more selected from the group consisting of aqueous alkali metal hydroxide, urea, ammonia and triethanolamine. Combination; and/or, in step (2), the alcohol dispersant is ethanol.
  10. 根据权利要求4所述的制备方法，其特征在于，步骤(2)中，所述第一乳化剂为选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和十六烷基三甲基对甲苯磺酸铵中的一种或多种阳离子乳化剂的组合；步骤(3)中，所述第二乳化剂为选自十六烷基三甲基氯化铵、十六烷基三甲基溴化铵和十六烷基三甲基对甲苯磺酸铵中的一种或多种阳离子乳化剂的组合。The preparation method according to claim 4, characterized in that, in step (2), the first emulsifier is selected from cetyltrimethylammonium chloride, cetyltrimethylammonium bromide And one or more cationic emulsifiers in cetyltrimethylammonium p-toluenesulfonate; in step (3), the second emulsifier is selected from cetyltrimethyl chloride A combination of one or more cationic emulsifiers among ammonium, cetyltrimethylammonium bromide and cetyltrimethylammonium p-toluenesulfonate.
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