CN106084228A - Monodispersity porous polysilsesquioxane microsphere and preparation method - Google Patents
Monodispersity porous polysilsesquioxane microsphere and preparation method Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
The invention discloses monodispersity porous polysilsesquioxane microsphere and preparation method, the mean diameter of monodispersity porous polysilsesquioxane microsphere is in 0.5 10 μm, and pore volume is at 0.3 1.2mL/g, and specific surface area is at 272.413 823.698m2/ g, aperture is at 1.7 30nm.The monodispersity porous polysilsesquioxane microsphere porosity of the present invention is high, and specific surface area is big, good hydrothermal stability, and its preparation method process is simple, and condition is easily-controllable, and product yield is high.Can be as chromatograph packing material.
Description
Technical field
The present invention relates to monodispersity porous polysilsesquioxane microsphere and preparation method, belong to porous organic glue microsphere
Technology of preparing.
Background technology
Hybrid material is the forth generation material after single component material, composite and function-graded material.It is one
Plant uniform heterogeneous composite material, be combined on nanometer level by chemical bond or intermolecular interaction so that be separated chi
Very little less than nanometer scale.Compared with the conventional composite materials with bigger microfacies size, it has in structure and performance
Significantly difference.Wherein, hybrid inorganic-organic materials, as the new material of excellent performance, is led at optics, electronics and biology etc.
Territory has broad application prospects.Organic and the inorganic component of composition hybrid material is compound on nanoscale or molecular level, interior
Portion's even structure.In most of the cases, inorganic part provides mechanical strength and be distributed in whole object, organic moiety then and
Inorganic building block connects.Being combined by material function, it is achieved the complementation of performance and optimization.Therefore, hybrid material shows many
Unique performance.Such as, inorganic molecule group or the nano-particle with special optics, electronics or magnetic can merge at organic high score
In submatrix.The machine-shaping of hybrid material can be realized under medium and low temperature.Chemical stability and the machinery of hybrid material are strong
Degree is above the inorganic and organic materials of correspondence.
Polysilsesquioxane is the hybrid inorganic-organic materials that a class is novel, both contains " organic group in its construction unit
Group " contain again " inorganic structure ", therefore have Organic Polymer Chemistry good stability and high excellent of inorganic polymer mechanical strength concurrently
Opposite sex energy.According to the characteristic of organo-functional group, polysilsesquioxane can be divided into single organo-functional group and bridged polysilsesquioxane
Two big classes.Generally with the silane reagent such as trialkoxy silane reagent of trifunctional as precursor molecule, in the presence of a catalyst, warp
Cross the reactions such as hydrolysis-condensation, form general molecular formula for (RSiO1.5)nThe polysilsesquioxane of (R in formula is organic group).
Polyphenylsilsesquioxane and the poly methyl silsesquioxane with excellent electric characteristic are well known mainstream product.
Additionally, the most poly-benzyl silsesquioxane, poly-amyl group silsesquioxane, polyvinyl silsesquioxane.When being connected with on silicon atom
After vinyl, can have the polysilsesquioxane of reactivity, the correlated response of ethylene, similar group can be further participated in
Also have methacryloxy, amino, epoxy radicals, chloropropyl, mercapto propyl group etc..These active groups can be with inorganic material surface
Living radical polymerization, forms firm chemical bond.
Bridged polysilsesquioxane is a kind of hybrid inorganic-organic materials with special construction.At aforementioned monosubstituted base
In polysilsesquioxane, organic group is to be suspended in siloxane backbone with the form of side arm.And at bridged polysilsesquioxane
In, organic group is uniformly embedded in siloxane network structure, thus realizes the most organic and inorganic component
Hydridization.The presoma of bridged polysilsesquioxane be general molecular formula be (R ' O)3Si-R-Si(OR’)3(in formula, R ' is alkyl, and R is
Organofunctional group) six functional groups silane reagent, in sol-gel process than corresponding trifunctional silane reagent more
It is easily formed gel.Additionally, due to organic component is the inherent ingredient of hybrid material, as long as by the group changing organic group
Divide the overall performance (such as texture, heat stability, refractive index, dielectric constant etc.) that just can change material.Furthermore it is possible to by choosing
Select different sol-gel technologies and carry out the bridged polysilsesquioxane that processability is different.
The character of hybrid material and application are not only determined by its chemical composition, the also close phase with the structure and morphology of material
Close.In recent years, spherical polysilsesquioxane material potentiality in scientific research and commercial Application attract wide attention.Poly-first
Typical case's application of base silsesquioxane microsphere includes the coating material of optics and electronic device, and cosmetics, plastics and light diffusion are thin
Powder additive in film, the flow control additive of electroscopic powder.The superhydrophobic characteristic of poly methyl silsesquioxane microsphere
Become excellent cotton fabric coating material, there is for preparation the textile of self-cleaning ability.Having surface can function
The organic silica gel microsphere changing group cannot be only used for the combinatorial compound carrier of nucleic acid and polypeptide, it is possible to as label for biology
The high throughput testing of molecule.
Polysilsesquioxane microsphere can be prepared by different methods.Typical method includes emulsion polymerization, is spray-dried
Method, surfactants' templating and sol-gel process.In emulsion polymerization, polysilsesquioxane presoma is dispersed in and contains
Having in the aqueous solution of surfactant, form emulsion, under acid or base catalyst effect, the presoma in drop hydrolyzes
Condensation reaction, generates silsesquioxane polymer microsphere.The size of microsphere is determined by droplet size, generally at submicron water
Flat.Spray drying method is that precursor solution is separated into fine particle by the jet-action utilizing high velocity air, waves in thermal current
Send out and remove solvent, obtain the microsphere that size is uneven.In template, with bridging siloxanes as presoma, surfactant is knot
Structure directed agents, under acidity or base catalysis effect, has high-sequential, the homogeneous duct of size through hydrolysis-condensation reaction generation
Mesoporous material.Organic bridge linkage group is embedded in hole wall skeleton, is the organic component of mesoporous material structure.This kind of material
Feature be that specific surface area is big, aperture is adjustable, and good hydrothermal stability and mechanical strength are high.Sol-gel process can be according to catalysis bar
Part is different and is divided into one-step method and two-step method.In one-step method, presoma mixes with suitable polar solvent and water, is formed all
Phase, under acid or base catalysis, presoma experience hydrolysis-condensation reaction, generate polymer, separate out from aqueous phase with microspheres form.?
In two step method, hydrolysis and condensation reaction use different catalyst or different catalytic conditions, therefore, hydrolyzes and be condensed anti-
Should carry out step by step, the generation to microsphere has the most handling.Except template, the microsphere prepared by all these methods
It is medicine ball.Although template can prepare mesoporous microsphere, but this method is only applicable to bridging siloxanyl monomers.And quantity is huge
Big and the miscellaneous monosubstituted trialkoxy silane of commodity is due to can not be at surfactant micellar as bridging siloxanes
Surface-assembled, it is impossible to prepare porous microsphere by template.
Porous microsphere is big due to specific surface area and pore volume, can serve as adsorbent, catalyst carrier, drug release
Carrier and chromatograph packing material, have broad application prospects in the industrial circles such as chemistry, pharmacy, biology.Therefore, development is based on poly-times
The porous microsphere of half siloxanes and preparation method have important economic results in society.
Summary of the invention
It is an object of the invention to provide a kind of monodispersity porous polysilsesquioxane microsphere.
The second object of the present invention is to provide the preparation method of a kind of monodispersity porous polysilsesquioxane microsphere.
Technical scheme is summarized as follows:
Monodispersity porous polysilsesquioxane microsphere, the average particle of described monodispersity porous polysilsesquioxane microsphere
Footpath is at 0.5-10m, and pore volume is at 0.3-1.2mL/g, and specific surface area is at 272.413-823.698m2/ g, aperture is at 1.7-30nm.
Preferably: the mean diameter of microsphere is at 3.2-10m.
The preparation method of monodispersity porous polysilsesquioxane microsphere, comprises the steps:
(1) 10-150, by deionized water and monosubstituted trialkoxy silane mix homogeneously, is stirred at room temperature in molar ratio
Reaction 0.25-10h, obtains polysilsesquioxane prepolymer dispersions system；
(2) strong aqua ammonia is joined the polysilsesquioxane prepolymer that step (1) obtains by 0.00001-0.05 by volume
In dispersion, after stirring, standing and reacting 0.5-12h, filters, collects microsphere, with absolute ethanol washing, obtain poly-sesquialter
Silicone gel microsphere, and calculate polysilsesquioxane gel micro-ball solid content；
(3) polysilsesquioxane gel micro-ball is added in deionized water by 0.01-0.1 in mass ratio, mixing；
(4) strong aqua ammonia is joined the polysilsesquioxane gel micro-ball that step (3) obtains and mixes by 0.05-0.5 by volume
In fit system, at 70 DEG C-240 DEG C, stirring reaction 4-24h；It is filtered to remove solvent, microsphere absolute ethanol washing, is dried, obtains
Monodispersity porous polysilsesquioxane microsphere.
Monosubstituted trialkoxy silane is preferably MTMS, vinyltrimethoxy silane, mercapto propyl group three
In methoxy silane and r-chloropropyl trimethoxyl silane at least one.
The monodispersity porous polysilsesquioxane microsphere porosity of the present invention is high, and specific surface area is big, good hydrothermal stability,
Its preparation method process is simple, and condition is easily-controllable, and product yield is high.
Accompanying drawing explanation
Fig. 1 is the electromicroscopic photograph that embodiment 3 prepares monodispersity porous polymethyl silsesquioxane microsphere；
Fig. 2 is monodispersity porous polymethyl silsesquioxane (PMSQ) microsphere of embodiment 8 preparation, prepared by embodiment 9
Monodispersity porous polyethylene base/methyl hydridization silsesquioxane (V-PMSQ) microsphere, embodiment 11 preparation monodispersity
Porous polychlorostyrene propyl group/methyl hydridization silsesquioxane (C-PMSQ) microsphere and the poly-mercapto of monodispersity porous third of embodiment 10 preparation
Nitrogen adsorption curve (Fig. 2 a) of base/methyl hydridization silsesquioxane (M-PMSQ) microsphere and pore size distribution curve (Fig. 2 b).
Fig. 3 tests monodispersity porous polymethyl silsesquioxane (PMSQ) microsphere, the list that compound is prepared in embodiment 8
Dispersibility porous polyethylene base/methyl hydridization silsesquioxane (V-PMSQ) microsphere, monodispersity porous polychlorostyrene propyl group/methyl are miscellaneous
Change silsesquioxane (C-PMSQ) microsphere and monodispersity porous poly-mercapto propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere
Separation on chromatographic stationary phases.
Chromatographic condition: chromatographic column, 250x 4.6mm；Flowing phase, methanol-20mM potassium phosphate solution, pH 7.0 (80:20, v/
v)；Flow velocity, 1mL/min；Column temperature, 30 DEG C；Detection wavelength, 254nm.Test compound: 1. uracil, 2. toluene, 3. ethylbenzene, 4.
Anthraquinone, 5. amitriptyline
Detailed description of the invention
Below by specific embodiment, the present invention is further illustrated.The following examples are in order to make this area
Technical staff better understood when the present invention, but does not impose any restrictions the present invention.
Embodiment 1: the preparation method of monodispersity porous polymethyl silsesquioxane microsphere, comprises the steps:
(1) in 250mL there-necked flask, different mol ratio 10,38,150 is pressed respectively by deionized water and methyl trimethoxy epoxide silicon
Alkane mix homogeneously, is stirred at room temperature reaction 0.5h, obtains poly methyl silsesquioxane prepolymer dispersions system；
(2) it is the 0.00001 poly methyl silsesquioxane prepolymer that strong aqua ammonia is joined, and step (1) obtains by volume
In dispersion, after stirring, standing and reacting 5h, filters, collects microsphere, with absolute ethanol washing three times, obtain poly-methyl
Silsesquioxane gel micro-ball, and calculate polysilsesquioxane gel micro-ball solid content；
(3) polysilsesquioxane gel micro-ball is added in deionized water by mass ratio 0.01, mixing；
(4) 0.2 strong aqua ammonia (14.7mol/L) is joined the polysilsesquioxane gel that step (3) obtains by volume
In microsphere mixed system, at 70 DEG C, stirring reaction 10h；It is filtered to remove solvent, microsphere absolute ethanol washing three times, after drying
Both three kinds of monodispersity porous polymethyl silsesquioxane microspheres had been obtained.
The sign data of monodispersity porous polymethyl silsesquioxane microsphere are mean diameter, particle diameter distribution (d90/
d10), specific surface area, pore volume, aperture is shown in Table 1.
Table 1 different mol ratio monodispersity methyl silsesquioxane (PMSQ) particle diameter is distributed
Embodiment 2: the preparation method of monodispersity poly methyl silsesquioxane microsphere, comprises the steps:
(1) in three 250mL there-necked flasks in molar ratio 38, it is separately added into deionized water (100mL) and methyl trimethoxy oxygen
Base silane (20g), mix homogeneously, under room temperature magnetic agitation respectively 0.25,3,10h, obtain poly methyl silsesquioxane prepolymer
Dispersion；
(2) 0.00001 strong aqua ammonia joined the poly methyl silsesquioxane prepolymer that step (1) obtains divide by volume
In prose style free from parallelism system, after stirring, standing and reacting 5h, filters, collects microsphere, with dehydrated alcohol cyclic washing three times；Obtain poly-first
Base silsesquioxane gel micro-ball: and calculate polysilsesquioxane gel micro-ball solid content；
Step (3)-(4), with embodiment 1 (3)-(4), obtain monodispersity porous polymethyl silsesquioxane microsphere.
The sign data of monodispersity porous polymethyl silsesquioxane microsphere include mean diameter, particle diameter distribution (d90/
d10), specific surface area, pore volume, aperture is shown in Table 2.
Table 2 stirs monodispersity methyl silsesquioxane (PMSQ) microsphere pore structure parameter under different time
Embodiment 3: the preparation method of monodispersity porous polymethyl silsesquioxane microsphere, comprises the steps:
(1) in three 250mL there-necked flasks, 38 it is separately added into deionized water (100mL) and methyl trimethoxy epoxide in molar ratio
Silane (20g), mix homogeneously, magnetic agitation 0.5h under room temperature, obtain poly methyl silsesquioxane prepolymer dispersions system；
(2) the most by volume 0.00001,0.001,0.05, strong aqua ammonia is joined the poly-methyl times that step (1) obtains
In half siloxane prepolymer dispersion, after stirring, standing and reacting 5h, filters, collects microsphere, repeatedly wash with dehydrated alcohol
Wash three times；Obtain poly methyl silsesquioxane gel micro-ball: and calculate polysilsesquioxane gel micro-ball solid content；
Step (3)-(4), with embodiment 1 (3)-(4), obtain monodispersity porous polymethyl silsesquioxane microsphere.
Monodispersity porous polymethyl silsesquioxane microsphere be characterized as environmental scanning electron microscope photo and transmission
Electromicroscopic photograph, is shown in Fig. 1.
Wherein:
Fig. 1 a is strong aqua ammonia and environmental scanning during the volume ratio 0.00001 of poly methyl silsesquioxane prepolymer dispersions system
Electron micrograph；
Fig. 1 b is strong aqua ammonia and environmental scanning electricity during the volume ratio 0.001 of poly methyl silsesquioxane prepolymer dispersions system
Sub-microphotograph；
Fig. 1 c is strong aqua ammonia and transmission electron microscope during the volume ratio 0.05 of poly methyl silsesquioxane prepolymer dispersions system shines
Sheet.
Embodiment 4: the preparation method of monodisperse porous poly methyl silsesquioxane (PMSQ) microsphere, comprises the steps:
(1) in molar ratio 38 by deionized water and MTMS mix homogeneously in three 250mL there-necked flasks,
It is stirred at room temperature reaction 0.5h, obtains poly methyl silsesquioxane prepolymer dispersions system；
(2) 0.00001 strong aqua ammonia joined the poly methyl silsesquioxane prepolymer that step (1) obtains divide by volume
In prose style free from parallelism system, after stirring, respectively standing and reacting 0.5,5,12h, filter, collect microsphere, with absolute ethanol washing three times,
To poly methyl silsesquioxane gel micro-ball: and calculate polysilsesquioxane gel micro-ball solid content；
Step (3)-(4), with embodiment 1 (3)-(4), obtain monodispersity porous polymethyl silsesquioxane microsphere.
The sign data of monodispersity porous polymethyl silsesquioxane microsphere include ratio mean diameter, particle diameter distribution (d90/
d10), specific surface area, pore volume, aperture is shown in Table 3.
Table 3 stands differential responses time monodispersity methyl silsesquioxane (PMSQ) microsphere pore structure parameter
Embodiment 5: the preparation method of monodispersity porous polymethyl silsesquioxane (PMSQ) microsphere, including walking as follows
Rapid:
(1) with embodiment 3 step (1)；
(2) 0.00001 strong aqua ammonia joined the poly methyl silsesquioxane prepolymer that step (1) obtains divide by volume
In prose style free from parallelism system, after stirring, standing and reacting 5h, filters, collects microsphere, with absolute ethanol washing three times, obtain poly-methyl times
Half silicone gel microsphere: and calculate polysilsesquioxane gel micro-ball solid content；
(3) polysilsesquioxane gel micro-ball is added in deionized water by mass ratio 0.01, mixing；
(4) 0.05,0.1,0.5 respectively strong aqua ammonia (14.7mol/L) is joined what step (3) obtained by volume respectively
In polysilsesquioxane gel micro-ball mixed system, at 70 DEG C, stirring reaction 10h；It is filtered to remove solvent, microsphere dehydrated alcohol
Wash three times, the most both obtained monodispersity porous polymethyl silsesquioxane microsphere.
The sign data of monodispersity porous polymethyl silsesquioxane microsphere include mean diameter, particle diameter distribution (d90/
d10), specific surface area, pore volume, aperture is shown in Table 4.
Monodispersity methyl silsesquioxane (PMSQ) microsphere pore structure parameter under the different ammonia volume ratio of table 4
Embodiment 6: the preparation method of monodispersity porous polymethyl silsesquioxane (PMSQ) microsphere, including walking as follows
Rapid:
(1)-(3) are with embodiment 4 (1)-(3)；
(4) 0.2 strong aqua ammonia (14.7mol/L) is joined the polysilsesquioxane gel that step (3) obtains by volume
In microsphere mixed system, at 70,140,240 DEG C, react 10h；It is filtered to remove solvent, microsphere absolute ethanol washing three
Secondary, the most both obtained monodispersity porous polymethyl silsesquioxane microsphere.
The sign data of monodispersity porous polymethyl silsesquioxane microsphere include mean diameter, particle diameter distribution (d90/
d10), specific surface area, pore volume, aperture is in table 5.
Table 5 differential responses temperature monodispersity methyl silsesquioxane (PMSQ) microsphere pore structure parameter
Embodiment 7: the preparation method of monodispersity porous polymethyl silsesquioxane (PMSQ) microsphere, including walking as follows
Rapid:
(1)-(3) are with embodiment 4 (1)-(3)；
(4) 0.2 strong aqua ammonia (14.7mol/L) is joined the polysilsesquioxane gel that step (3) obtains by volume
In microsphere mixed system, at 70 DEG C, react 4 respectively, 10,24h；It is filtered to remove solvent, microsphere absolute ethanol washing three times,
The most both monodispersity porous polymethyl silsesquioxane microsphere had been obtained.
The sign data of monodispersity porous polymethyl silsesquioxane microsphere include mean diameter, particle diameter distribution (d90/
d10), specific surface area, pore volume, aperture is shown in Table 6.
Table 6 differential responses time monodispersity methyl silsesquioxane (PMSQ) microsphere pore structure parameter
Embodiment 8: the preparation method of monodispersity porous polymethyl silsesquioxane (PMSQ) microsphere, including walking as follows
Rapid:
(1) 38 additions deionized water (100mL) in molar ratio and MTMS mixing in 250mL there-necked flask
Uniformly, magnetic agitation 0.5h under room temperature, obtain poly methyl silsesquioxane prepolymer dispersions system；
(2) 0.00001 strong aqua ammonia joined in poly methyl silsesquioxane prepolymer dispersions system by volume, stirring
After Jun Yun, standing and reacting 5h, filters, collects microsphere, with dehydrated alcohol cyclic washing three times；Obtain poly methyl silsesquioxane to coagulate
Glue microsphere；And calculate poly methyl silsesquioxane gel micro-ball solid content；
(3) poly methyl silsesquioxane gel micro-ball is added in deionized water by mass ratio 0.1, mixing；
(4) 0.2 strong aqua ammonia (14.7mol/L) is joined the poly methyl silsesquioxane that step (3) obtains by volume
In gel micro-ball mixed system, at 70 DEG C, stirring reaction 10h；Be filtered to remove solvent, microsphere with and absolute ethanol washing three times,
50 DEG C of dry 10h, obtain monodispersity porous polymethyl hydridization silsesquioxane (PMSQ) microsphere.
The sign data of monodispersity porous polymethyl silsesquioxane (PMSQ) microsphere include mean diameter, and particle diameter is distributed
(d90/d10), specific surface area, pore volume, aperture is listed in Table 7 below.
Table 7 monodispersity porous polymethyl silsesquioxane (PMSQ) microspherulite diameter and pore structure parameter
Embodiment 9: the preparation side of monodispersity porous polyethylene base/methyl hydridization silsesquioxane (V-PMSQ) microsphere
Method, comprises the steps:
(1) in 250mL there-necked flask, 38 deionized water (100mL) and vinyl/methyl (mass ratio is added in molar ratio
20%-80%) trimethoxy silane, mix homogeneously, magnetic agitation 0.5h under room temperature, obtain polyvinyl/methyl silsesquioxane
Alkane prepolymer dispersions system；
(2) 0.00001 strong aqua ammonia joined polyvinyl/methyl silsesquioxane prepolymer dispersions system by volume
In, after stirring, standing and reacting 5h, filters, collects microsphere, with dehydrated alcohol cyclic washing three times；Obtain polyvinyl/first
Base silsesquioxane gel micro-ball；And calculate polyvinyl/methyl silsesquioxane gel micro-ball solid content；
(3) polyvinyl/methyl silsesquioxane gel micro-ball is added in deionized water by mass ratio 0.1, mixing；
(4) 0.2 strong aqua ammonia (14.7mol/L) joined polyvinyl/methyl sesquialter that step (3) obtains by volume
In silicone gel microsphere mixed system, at 70 DEG C, stirring reaction 10h；Being filtered to remove solvent, microsphere is used and absolute ethanol washing
Three times, 50 DEG C of dry 10h, obtain monodispersity porous polyethylene base/methyl hydridization silsesquioxane (V-PMSQ) microsphere.
The sign data of monodispersity porous polyethylene base/methyl hydridization silsesquioxane (V-PMSQ) microsphere include averagely
Particle diameter, particle diameter distribution (d90/d10), specific surface area, pore volume, aperture is shown in Table 8.
Table 8 monodispersity porous polyethylene base/methyl hydridization silsesquioxane (V-PMSQ) microspherulite diameter and pore structure ginseng
Number
Embodiment 10:
The preparation method of monodispersity porous poly-mercapto propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere, including such as
Lower step:
(1) in 250mL there-necked flask, 38 deionized water (100mL) and mercapto propyl group/methyl (mass ratio is added in molar ratio
20%-80%) trimethoxy silane, mix homogeneously, magnetic agitation 0.5h under room temperature, obtain poly-mercapto propyl group/methyl silsesquioxane
Alkane prepolymer dispersions system；
(2) 0.00001 strong aqua ammonia joined poly-mercapto propyl group/methyl silsesquioxane prepolymer dispersions system by volume
In, after stirring, standing and reacting 5h, filters, collects microsphere, with dehydrated alcohol cyclic washing three times；Obtain poly-mercapto propyl group/first
Base silsesquioxane gel micro-ball: and calculate poly-mercapto propyl group/methyl silsesquioxane gel micro-ball solid content；
(3) poly-mercapto propyl group/methyl silsesquioxane gel micro-ball is added in deionized water by mass ratio 0.1, mixing；
(4) 0.2 strong aqua ammonia (14.7mol/L) joined poly-mercapto propyl group/methyl sesquialter that step (3) obtains by volume
In silicone gel microsphere mixed system, at 70 DEG C, stirring reaction 10h；Being filtered to remove solvent, microsphere is used and absolute ethanol washing
Three times, 50 DEG C of dry 10h, obtain monodispersity porous poly-mercapto propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere.
The sign data of monodispersity porous poly-mercapto propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere include averagely
Particle diameter, particle diameter distribution (d90/d10), specific surface area, pore volume, aperture is shown in Table 9.
The particle diameter of table 9 monodispersity porous poly-mercapto propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere and pore structure
Parameter
Embodiment 11: the preparation side of monodispersity porous polychlorostyrene propyl group/methyl hydridization silsesquioxane (C-PMSQ) microsphere
Method, includes the following:
(1) in 250mL there-necked flask, 38 deionized water (100mL) and chloropropyl/methyl (mass ratio is added in molar ratio
20%-80%) trimethoxy silane, mix homogeneously, magnetic agitation 0.5h under room temperature, obtain polychlorostyrene propyl group/methyl silsesquioxane
Alkane prepolymer dispersions system；
(2) 0.00001 strong aqua ammonia joined polychlorostyrene propyl group/methyl silsesquioxane prepolymer dispersions system by volume
In, after stirring, standing and reacting 5h, filters, collects microsphere, with dehydrated alcohol cyclic washing three times；Obtain polychlorostyrene propyl group/first
Base silsesquioxane gel micro-ball: and calculate polychlorostyrene propyl group/methyl silsesquioxane gel micro-ball solid content；
(3) polychlorostyrene propyl group/methyl silsesquioxane gel micro-ball is added in deionized water by mass ratio 0.1, mixing；
(4) 0.2 strong aqua ammonia (14.7mol/L) joined polychlorostyrene propyl group/methyl sesquialter that step (3) obtains by volume
In silicone gel microsphere mixed system, at 70 DEG C, stirring reaction 10h；Being filtered to remove solvent, microsphere is used and absolute ethanol washing
Three times, 50 DEG C of dry 10h, obtain monodispersity porous polychlorostyrene propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere.
The sign data of monodispersity porous polychlorostyrene propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere include averagely
Particle diameter, particle diameter distribution (d90/d10), specific surface area, pore volume, aperture is shown in Table 10.
The particle diameter of table 10 monodispersity porous polychlorostyrene propyl group/methyl hydridization silsesquioxane (M-PMSQ) microsphere and pore structure
Parameter
Embodiment 12: the preparation of porous organic glue chromatographic column and evaluation
Take microsphere prepared by each embodiment of 3g respectively, be uniformly dispersed in 30mL methanol, with methanol as displacement fluid,
Under 400bar pressure, load 250x 4.6mm rustless steel chromatographic column.Chromatographic condition: flowing phase,；Flow velocity, 1mL/min；Column temperature, 25
℃；Detection wavelength, 254nm.The test mixing thing being made up of uracil, toluene, ethylbenzene, anthraquinone and amitriptyline, for made
The chromatographic performance evaluation of standby chromatograph packing material.Uracil is used for measuring chromatographic column dead time, toluene and ethylbenzene and is used for measuring hydrophobicity
And methane selectivity, anthraquinone is used for measuring metal ion activity and amitriptyline for measuring silanol base activity.Gained chromatograph number
According to being listed in Table 11 below.
The chromatographic evaluation data of table 11 organic silica gel microsphere chromatographic column
Experiment proves, the monodispersity porous polysilsesquioxane microsphere of embodiment 1,2,4,5,6,7 preparation is as chromatograph
Filler.
Experiment proves, the mean diameter in embodiment 3 is that 0.5m (shown in Fig. 1 c) can expand as cosmetics, plastics and light
Dissipate the powder additive in thin film, the flow control additive of electroscopic powder, bio-carrier etc..
Claims (4)
1. monodispersity porous polysilsesquioxane microsphere, is characterized in that described monodispersity porous polysilsesquioxane microsphere
Mean diameter is in 0.5-10 μm, and pore volume is at 0.3-1.2mL/g, and specific surface area is at 272.413-823.698m2/ g, aperture exists
1.7-30nm。
Monodispersity porous polysilsesquioxane microsphere the most according to claim 1, is characterized in that the average of described microsphere
Particle diameter is in 3.2-10 μm.
3. the preparation method of monodispersity porous polysilsesquioxane microsphere, is characterized in that comprising the steps:
(1) 10-150, by deionized water and monosubstituted trialkoxy silane mix homogeneously, is stirred at room temperature reaction in molar ratio
0.25-10h, obtains polysilsesquioxane prepolymer dispersions system；
(2) strong aqua ammonia is joined the polysilsesquioxane prepolymer dispersion that step (1) obtains by 0.00001-0.05 by volume
In system, after stirring, standing and reacting 0.5-12h, filters, collects microsphere, with absolute ethanol washing, obtain poly-silsesquioxane
Alkane gel micro-ball, and calculate polysilsesquioxane gel micro-ball solid content；
(3) polysilsesquioxane gel micro-ball is added in deionized water by 0.01-0.1 in mass ratio, mixing；
(4) strong aqua ammonia is joined the polysilsesquioxane gel micro-ball mixture that step (3) obtains by 0.05-0.5 by volume
In system, at 70 DEG C-240 DEG C, stirring reaction 4-24h；It is filtered to remove solvent, microsphere absolute ethanol washing, is dried, obtains single point
Dissipate property porous polysilsesquioxane microsphere.
Method the most according to claim 3, is characterized in that described monosubstituted trialkoxy silane is methyl trimethoxy epoxide silicon
In alkane, vinyltrimethoxy silane, mercaptopropyl trimethoxysilane and r-chloropropyl trimethoxyl silane at least one.
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| CN108467046A (en) * | 2018-05-06 | 2018-08-31 | 天津大学 | A kind of preparation method of monodisperse porous silica gel microball |
| CN109399648A (en) * | 2018-11-10 | 2019-03-01 | 天津大学 | Micron size porous silica microballoon and preparation method thereof |
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| CN108467046A (en) * | 2018-05-06 | 2018-08-31 | 天津大学 | A kind of preparation method of monodisperse porous silica gel microball |
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| CN113881050A (en) * | 2021-10-27 | 2022-01-04 | 湖北兴瑞硅材料有限公司 | Preparation method of polymethylsilsesquioxane microspheres |
| CN113881050B (en) * | 2021-10-27 | 2022-12-02 | 湖北兴瑞硅材料有限公司 | Preparation method of polymethylsilsesquioxane microspheres |
| CN115058011A (en) * | 2022-06-21 | 2022-09-16 | 北京理工大学 | Porous polyphenyl silsesquioxane, and preparation method and application thereof |
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