CN102140250A - Hollow organosilane microsphere with rough surface structure and preparation method thereof - Google Patents
Hollow organosilane microsphere with rough surface structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a hollow organosilane microsphere with a rough surface structure and a preparation method thereof. The hollow organosilane microsphere with the rough surface structure is characterized by being prepared by the following steps of: providing an alkaline solution with the pH value of between 10 and 13; mixing at least two types of organosilane to obtain an organosilane mixture; adding the organosilane mixture into the alkaline solution; undergoing a hydrolytic polycondensation reaction; and standing and ageing. Organosilane microsphere particles are provided with folds on the surface and are hollow inside, and the particle sizes of the particles have high uniformity. The method provided by the invention is simple and feasible. By adopting the method, the problems of non-uniform particle size and breakage of a large number of sphere bodies caused by the conventional hollow microsphere preparation method can be solved.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of organosilane microballoon and preparation method thereof with hollow rough surface structure.
Background technology
Organosilane is the hybrid inorganic-organic structure that a class has molecular level, and wherein Siliciumatom constitutes inorganic silica " skeleton ", and Siliciumatom can be introduced multiple organo-functional group by side group and constitute organic structure division.This structure makes it have the excellent properties of inorganic materials and organic materials concurrently, nuclear energy suppressed the chain movement of polymer molecule and gives the hybrid material good heat-resistant in it was inorganic, and organic substituent and macromolecular chain are given good toughness of hybrid material and workability.Organosilane also has good optical property, thermotolerance, weathering resistance, hydrophobicity and electrical insulating property and dielectric properties, is widely used in Electronic Packaging in recent years, fields such as optics conduction.The resistates of organosilane material after decomposes is mainly uninflammability SiO
2, and SiO
2Massfraction can be up to 87%.Therefore, compare with common flame retarded polymeric material, the polymkeric substance that contains organosilane can prolong ignition time and reduce burning heat release degree greatly, and flame retardant properties is very good.So organosilane not only can be used as matrix material and directly uses, use after also can adding traditional filler such as glass fibre.
Hollow organosilane particle is because its low density, stable heat, light, electricity, magnetic property so can be widely used in microreactor, pharmaceutical carrier, also can be used as the usefulness of the properties-correcting agent of dye dispersant, absorbing material, organic resin.The template auxiliary law is a kind of typical method of synthetic hollow organosilane micro-capsule, and as timbering material, the shape and the cavity size of final gained hollow microsphere can be controlled by template with template.Usually the material as template mainly contains polyalcohol emulsion particle, inorganic metal nanoparticle, block copolymer micelle, tensio-active agent ordered aggregation or the like.Prepare earlier after these mould materials, silane precursor obtains the coating layer of organosilane at the template surface hydrolytic polymerization, and this nucleocapsid structure mixture etches away template through calcining or organic solvent again, obtains hollow microsphere.Template is not only loaded down with trivial details, and the hollow microsphere pattern irregularity of preparation, a large amount of breakages can occur incessantly, and the reunion behavior of template itself also makes hollow microsphere become very difficult in the inhomogeneity control of size.
Summary of the invention
In view of this, the present application people finds through broad research with after testing repeatedly, a kind of surface has the organosilane microballoon that gauffer, inside have hollow, particle diameter uniformity coefficient height, and synthetic method is simple, can solve the problem of the uneven and a large amount of spheroid breakages of particle diameter that traditional hollow microsphere preparation method caused.
Main purpose of the present invention is to provide a kind of rough surface structure hollow organosilane microballoon that has, it is characterized in that providing the pH value is 10～13 basic solution, mix at least two kinds of organosilanes and obtain the organosilane mixture, described organosilane mixture is joined in the described basic solution, be hydrolyzed after the polycondensation, still aging and get.
Another purpose of the present invention the steps include: for a kind of preparation method with rough surface structure hollow organosilane microballoon is provided
It is 10～13 basic solution that the pH value is provided;
Mix at least two kinds of organosilanes and obtain the organosilane mixture;
Described organosilane mixture is joined in the described basic solution, stirred 10 minutes～10 hours down at 0 ℃～70 ℃, polycondensation is hydrolyzed; And
Still aging 1 hour～20 hours, centrifugal, washing, lyophilize.
Described at least two kinds of organosilanes comprise be hydrolyzed after polycondensation possess hydrophilic property and at least a organosilane of at least a organosilane and are hydrolyzed in basic solution and have hydrophobicity after the polycondensation in basic solution, and the mass ratio that has hydrophobic organosilicon alkane behind the hydrolysis condensation reaction behind the organosilane of possess hydrophilic property and the hydrolysis condensation reaction is 1: 1～1: 10.
The invention has the beneficial effects as follows: a kind of preparation method's prepared organic silane microballoon that the present invention discloses with rough surface structure hollow organosilane microballoon, obtain the high organosilane microballoon of particle diameter uniformity coefficient by quite simple method and gentle reaction conditions, solve loaded down with trivial details fabrication steps in prior art-template.In addition, solved also that the reunion behavior because of template itself causes hollow microsphere in the uppity problem of size homogeneity in the prior art.
Description of drawings
Fig. 1 is embodiment 3 resulting stereoscan photographs with rough surface structure hollow organosilane microballoon;
Fig. 2 is the hollow organosilane microballoon section stereoscan photograph of embodiment 3;
Fig. 3 is the size distribution measurement figure of the hollow organosilane microballoon of embodiment 3;
Fig. 4 is the hollow organosilane microballoon transmission electron microscope photo of embodiment 7;
Embodiment
To have a rough surface structure hollow organosilane microballoon hollow organosilane microspherulite diameter all once high according to provided by the present invention, particle size distribution range is narrow, the polydisperse system numerical value that calculates according to the ratio (Dv/Dn) of the equal particle diameter of body and number average bead diameter is less than 1.05, Dv is a volume average particle size in the formula, Dn is the number average median size, preferably, the ratio of volume average particle size and number average median size is 1.0～1.05.Using under the different organosilane collocation, the median size of organosilane microballoon provided by the present invention can be 50 nanometers～5 micron.
Disclosed organosilane among the present invention can be monomer or oligomer, and the present invention places the basic solution system with at least two kinds organosilane, is 10 weight parts in basic solution, and the content of described organosilane is 0.6～5 weight part.Above-mentioned at least two kinds of organosilanes comprise be hydrolyzed after polycondensation possess hydrophilic property and at least a organosilane of at least a organosilane and are hydrolyzed in basic solution and have hydrophobicity after the polycondensation in basic solution, and the mass ratio that has hydrophobic organosilicon alkane behind all hydrolysis condensation reactions behind the organosilane of possess hydrophilic property and all hydrolysis condensation reactions is 1: 1～1: 10.Generally speaking, in alkaline polar aprotic solvent, the speed of response of the organosilane of possess hydrophilic property is very fast behind the hydrolysis condensation reaction, the speed of response that has hydrophobic organosilicon alkane behind the hydrolysis condensation reaction is slower, so the first polymerization of hydrophilic organic silicon alkane meeting forms the organosilane microballoon, then, hydrophobic organosilicon alkane polymerization and be coated on the surface of organosilane microballoon.Owing to exist the difference of hydrophilic and hydrophobic inside and outside the whole microballoon, being positioned at inner hydrophilic polymer from inside outwards expands, and hydrophobic polymer from outside inward the migration, and then overturn inside and outside making polymkeric substance silane microballoon, therefore the special construction that the organosilane microballoon that makes has uneven surface and hollow, and the microspherulite diameter that forms is very even.
Because organosilane microballoon outside surface has folded structure, has the characteristic of oil suction, can be used as the treatment agent of paper, coating surface; Add effects such as to increase product delustring, wear-resisting, insulation, sound insulation in the organic resin; Simultaneously, hollow structure can also also can be used as the usefulness of drug microcapsule, dye dispersant, microwave absorbing material as carrier, the microreactor of filling catalyzer.
The present invention provides a kind of preparation to have the method for rough surface structure hollow organosilane microballoon in addition, it is characterized in that, comprises the steps:
It is 10～13 basic solution that the pH value is provided;
Mix at least two kinds of organosilanes and obtain the organosilane mixture;
Described organosilane mixture is joined in the described basic solution, stirred 10 minutes～10 hours down at 0 ℃～70 ℃, polycondensation is hydrolyzed; And
Still aging 1 hour～20 hours, centrifugal, washing, lyophilize
Described organosilane can be organosilane monomer or organosilane oligomer.
Described at least two kinds of organosilanes comprise be hydrolyzed after polycondensation possess hydrophilic property and at least a organosilane of at least a organosilane and are hydrolyzed in basic solution and have hydrophobicity after the polycondensation in basic solution.
As is behind hydrolysis condensation reaction, the described organosilane of Let exists the difference of hydrophilic and hydrophobic, implement aspect according to of the present invention one, described organosilane Hui has different organic substituents, described organic substituent can be simple alkyl, also can be polar structure or functional group, more excellent organic substituent comprises straight chained alkyl, thiazolinyl, aryl radical, alkoxyl group, amido.
The organosilane of possess hydrophilic property can be the siloxanes of tetraethoxy, band hydrogen atom or the siloxanes of band chlorine atom, preferably tetraethoxy behind the described hydrolysis condensation reaction.
The mixture that has hydrophobic organosilicon alkane behind the described hydrolysis condensation reaction and can be vinyltrimethoxy silane, phenyltrimethoxysila,e, dimethyldimethoxysil,ne, methyltrimethoxy silane, aminopropyl triethoxysilane or form by these several organosilanes.
The mass ratio that has hydrophobic organosilicon alkane behind described all hydrolysis condensation reactions behind the organosilane of possess hydrophilic property and described all hydrolysis condensation reactions is 1: 1～1: 10.
Described organosilane is 10 weight parts in basic solution, and its content is 0.6～5 weight part.
Described basic solution comprises alkaline matter, and employed alkaline matter can be mineral alkali or organic bases, preferably uses mineral alkali.
Described mineral alkali can be ammoniacal liquor, sodium hydroxide or potassium hydroxide.
Described organic bases can be quadrol or triethylamine.
Described basic solution comprises solvent, and described solvent can be selected water or alcohol, for example is ethanol.
The present invention uses at least two kinds of organosilanes, and with it uniform mixing, form organic silane mixture, when existing hydrophilic and hydrophobic difference behind the hydrolytie polycondensation between formed polymkeric substance, be positioned at inner hydrophilic polymer and from inside outwards expand, and hydrophobic polymer from outside migration inward, and then make the inside and outside upset of polymkeric substance silane microballoon, therefore the special construction that the organosilane microballoon that makes has uneven surface and hollow, and the microspherulite diameter that forms is very even.
Implement aspect according to of the present invention one, the organosilane mixture joined in the described basic solution under 0 ℃～70 ℃, preferably stir 1.5 hours～9 hours after, polycondensation is hydrolyzed; Preferred still aging 12 hours～18 hours, after reaction is finished, separate organosilane microballoon and basic solution in the centrifugal mode, after using pure water repetitive scrubbing organosilane microballoon again, lyophilize, carry out the drying of organosilane microballoon, and with unreacted organosilane in the basic solution, recycling.
Implement aspect according to of the present invention one, adopt weak base less as the resulting hollow organosilane of hydrolyst grain diameter, in addition, adopt higher temperature, also can obtain the less hollow organosilane microballoon of particle diameter, therefore, can use the change of reaction conditions to control the grain size size of the hollow organosilane microballoon that will obtain.
A kind of preparation method with rough surface structure hollow organosilane microballoon that the present invention disclosed made the organosilane microballoon, obtain by quite simple method and gentle reaction conditions that the high organosilane of particle diameter uniformity coefficient is little to solve fabrication steps loaded down with trivial details in prior art-template, and, need not calcining or organic solvent and etch away template, the hollow microsphere pattern of preparation is regular, breakage can not occur.In addition, solved also that the reunion behavior because of template itself causes hollow microsphere in the uppity problem of size homogeneity in the prior art.
Embodiment
With reference to following description and claim, can clearer and more definite understanding be arranged to the above-mentioned characteristic of mentioning of the present invention and other characteristic, viewpoint and benefit.Also need understand, more than whole narration and the details that down will mention describe, only be demonstration example.For allow a kind of preparation method with rough surface structure hollow organosilane microballoon provided by the present invention clear more for the purpose of, in following preferred embodiment to different organosilane monomers of the utilization that the present invention disclosed and basic solution composition should be used as further introduction, and utilize the size distribution metric data of resulting organosilane microballoon among the different embodiment and sweep electron microscope figure to verify the constitutional features of organosilane microballoon provided by the present invention and the homogeneity of particle diameter.Here the median size of indication is that it is that index amount is the particle grain size distribution scope more than 95% that particle diameter mainly distributes according to the number average median size of Malvern Zeta test gained.
Embodiment 1:
0.01 restraining 25% ammoniacal liquor is distributed to 10 grams and forms homogeneous solution in the pure water, vinyltrimethoxy silane and tetraethoxy with 4: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 1.5 grams slowly is added drop-wise in the ammonia soln that is pre-mixed then, be warming up to 70 ℃, the 200rpm rotating speed is reaction 8h down, afterwards at 70 ℃ of following ageing 15h; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 0.87 μ m, and size distribution is at 0.7 μ m-1.2 μ m, and yield is 37%.
Embodiment 2:
0.5 restraining 25% ammoniacal liquor is distributed to 10 grams and forms homogeneous solution in the pure water, phenyltrimethoxysila,e and tetraethoxy with 4: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 1.6 grams slowly is added drop-wise in the ammonia soln that is pre-mixed then, be positioned in the frozen water mixed solution, the 200rpm rotating speed is reaction 8h, ageing 15h in 0 ℃ of frozen water mixed solution afterwards down; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 2.48 μ m, and particle diameter mainly is distributed in 2.2 μ m-2.6 μ m, and yield is 41%.
Embodiment 3:
0.5 restraining 25% ammoniacal liquor is distributed to 10 grams and forms homogeneous solution in the pure water, methyltrimethoxy silane and tetraethoxy with 4: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 1.2 grams slowly is added drop-wise in the ammonia soln that is pre-mixed then, be positioned in 20 ℃ the room temperature, the 200rpm rotating speed is reaction 2h down, afterwards ageing 15h at room temperature; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 1.5 μ m, and particle diameter mainly is distributed in 1.3 μ m-1.7 μ m, and yield is 46%.
Embodiment 4:
0.5 restraining 25% ammoniacal liquor is distributed to 10 grams and forms homogeneous solution in the pure water, dimethyldimethoxysil,ne, phenyltrimethoxysila,e and tetraethoxy with 2: 2: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 0.78 gram slowly is added drop-wise in the ammonia soln that is pre-mixed then, be positioned in 20 ℃ the room temperature, the 200rpm rotating speed is reaction 2h, ageing 15h under 20 ℃ room temperature afterwards down; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 1.88 μ m, and particle diameter mainly is distributed in 1.6 μ m-2.2 μ m, and yield is 40%.
Embodiment 5:
0.1 restraining 40% aqueous sodium hydroxide solution is distributed to 10 grams and forms homogeneous solution in the pure water, dimethyldimethoxysil,ne, vinyltrimethoxy silane and tetraethoxy with 2: 2: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 0.8 gram slowly is added drop-wise in the aqueous sodium hydroxide solution that is pre-mixed then, be positioned in 20 ℃ the room temperature, the 200rpm rotating speed is reaction 2h, ageing 15h under 20 ℃ room temperature afterwards down; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 1.75 μ m, and particle diameter mainly is distributed in 1.4 μ m-2.3 μ m, and yield is 51%.
Embodiment 6:
0.1 restraining 40% aqueous sodium hydroxide solution is distributed to 10 grams and forms homogeneous solution in the pure water, dimethyldimethoxysil,ne and vinyltrimethoxy silane and tetraethoxy with 2: 2: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 0.8 gram slowly is added drop-wise in the aqueous sodium hydroxide solution that is pre-mixed then, be positioned under 50 ℃, the 200rpm rotating speed is reaction 2h down, afterwards at 50 ℃ of following ageing 15h; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 1.22 μ m, and particle diameter mainly is distributed in 1.0 μ m-1.8 μ m, and yield is 53%.
Embodiment 7:
0.1 restraining 40% potassium hydroxide aqueous solution is distributed to 10 grams and forms homogeneous solution in the pure water, methyltrimethoxy silane and tetraethoxy with 4: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 1.2 grams slowly is added drop-wise in the potassium hydroxide aqueous solution that is pre-mixed then, be positioned in 20 ℃ the room temperature, react 2h in the ultrasonic reactor, afterwards ageing 15h at room temperature; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 0.87 μ m, and particle diameter mainly is distributed in 0.5 μ m-4.3 μ m, and yield is 23%.
Embodiment 8:
0.1 restraining 40% potassium hydroxide aqueous solution is distributed to 10 grams and forms homogeneous solution in the pure water, phenyltrimethoxysila,e and tetraethoxy with 4: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 1.6 grams slowly is added drop-wise in the potassium hydroxide aqueous solution that is pre-mixed then, be positioned in the frozen water mixed solution, the 200rpm rotating speed is reaction 8h, ageing 15h in 0 ℃ of frozen water mixed solution afterwards down; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 2.63 μ m, and particle diameter mainly is distributed in 2.2 μ m-3.1 μ m, and yield is 30%.
Embodiment 9:
0.01 restraining 25% ammoniacal liquor is distributed to 10 grams and forms homogeneous solution in the pure water, aminopropyl triethoxysilane and tetraethoxy with 3: 1 amount than mixing, under the 200rpm rotating speed, stir 20min, mixture with the above-mentioned organosilane of 1.2 grams slowly is added drop-wise in the ammonia soln that is pre-mixed then, be positioned in 20 ℃ the room temperature, the 600rpm rotating speed is reaction 2h down, afterwards ageing 15h at room temperature; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 0.52 μ m, and particle diameter mainly is distributed in 0.25 μ m-1.2 μ m, and yield is 23%.
Embodiment 10:
0.01 restraining 25% ammoniacal liquor is distributed to 10 grams and forms homogeneous solution in the pure water, vinyltriethoxysilane and tetraethoxy with 4: 1 amount than mixing, under the 200rpm rotating speed, stir 20min, mixture with the above-mentioned organosilane of 1.5 grams slowly is added drop-wise in the ammonia soln that is pre-mixed then, be positioned in 20 ℃ the room temperature, the 200rpm rotating speed is reaction 8h down, afterwards at 20 ℃ of following ageing 15h; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 1.57 μ m, and particle diameter mainly is distributed in 1.2 μ m-1.8 μ m, and yield is 21%.
Embodiment 11:
0.1 restraining 40% aqueous sodium hydroxide solution is distributed to 10 grams and forms homogeneous solution in the pure water, methyltrimethoxy silane and tetraethoxy with 4: 1 amount than mixing, under the 200rpm rotating speed, stir 30min, mixture with the above-mentioned organosilane of 1.2 grams slowly is added drop-wise in the aqueous sodium hydroxide solution that is pre-mixed then, be positioned in 20 ℃ the room temperature, the 200rpm rotating speed is reaction 8h down, afterwards at 20 ℃ of following ageing 15h; Centrifugal at last, use the pure water repetitive scrubbing, lyophilize, the particle median size of generation is 1.67 μ m, and particle diameter mainly is distributed in 1.5 μ m-2.0 μ m, and yield is 30%.
See also Fig. 1, Fig. 1 is embodiment 3 resulting stereoscan photographs with rough surface structure hollow organosilane microballoon.Formed as seen from Figure 1 organosilane microballoon has rough surface structure, and size suitable evenly, about about 1.5 microns.Fig. 2 is the hollow organosilane microballoon section stereoscan photograph of embodiment 3, and formed as seen from Figure 2 to have rough surface structure organosilane microballoon be hollow.
See also Fig. 3, Fig. 3 is the size distribution measurement figure of the hollow organosilane microballoon of embodiment 3.As seen from Figure 3, the main microspherulite diameter of the hollow organosilane microballoon of embodiment 3 is approximately 1.5 μ m, and particle diameter mainly is distributed in 1.3 μ m-1.7 μ m.
See also Fig. 4, Fig. 4 is the hollow organosilane microballoon transmission electron microscope photo of embodiment 7.As seen from Figure 4, the organosilane microballoon by embodiment 7 gained is hollow really.So, by the electron micrograph of Fig. 1, Fig. 2 and Fig. 4 as can be known, can obtain size really by the disclosed method of the present invention and have rough surface structure hollow organosilane microballoon uniformly.
By the resulting result of the foregoing description as can be known, can obtain size incessantly by the disclosed method of the present invention and have rough surface structure hollow organosilane microballoon uniformly, more can control the size that institute's desire forms hollow organosilane microballoon by the change of reaction conditions.
By as can be known aforementioned, the present invention is with organosilane monomer or oligomer, the polymkeric substance that the polycondensation that is hydrolyzed under alkaline condition forms, embodiment 2 and embodiment 8 more as can be seen, both difference is that embodiment 2 basic solution that uses is ammonia soln, and embodiment 8 employed basic solutions are potassium hydroxide solution, therefore, by the comparative result of embodiment 2 and embodiment 8 as can be known, adopt ammonia soln to make the hollow organosilane grain diameter of Preparation of Catalyst less than adopting potassium hydroxide solution.
More also demonstrating of embodiment 3 and embodiment 11 adopts weak base less as the resulting hollow organosilane of hydrolyst grain diameter.Embodiment 3 basic solution that uses is ammonia soln, and embodiment 11 employed basic solutions are sodium hydroxide solution, therefore, by the comparative result of embodiment 3 and embodiment 11 as can be known, adopt ammonia soln to make the hollow organosilane grain diameter of Preparation of Catalyst less than adopting sodium hydroxide solution.
Temperature of reaction is another factor that influences hollow organosilane microspherulite diameter size.Compared by embodiment 1 and embodiment 10, the difference among two embodiment is that the temperature of reaction of embodiment 1 is 70 ℃, and the temperature of reaction of embodiment 10 then is 20 ℃.Resulting hollow organosilane particle median size has only that resulting hollow organosilane particle median size then is 1.57 microns among 0.87 micron embodiment 10 among the embodiment 1, and both size distribution also are respectively 0.7-1.2 micron and 1.2-1.8 micron.In view of the above, the hydrolytic polymerization that carries out organosilane monomer or oligomer under higher temperature can obtain the less hollow organosilane microballoon of particle diameter, otherwise, adopt lower hydrolytic polymerization temperature then can obtain the bigger hollow organosilane microballoon of particle diameter.
Even using the catalytic hydrolytic-polymeric reaction of highly basic, temperature of reaction also has identical influence to reaction.Embodiment 5 and embodiment 6 adopt identical beginning thing, the identical catalyzer of opening, and both difference is that the temperature of reaction of embodiment 5 is 20 ℃, and the temperature of reaction of embodiment 6 is 50 ℃.By experimental result as can be seen, embodiment 5 resulting hollow organosilane particle median sizes are 1.75 microns, and size distribution is the 1.4-2.3 micron; Embodiment 6 resulting hollow organosilane particle median sizes are 1.22 microns, and size distribution is the 1.0-1.8 micron.By the comparative result of embodiment 5 and embodiment 6 as can be known, no matter it is synthetic to use highly basic or weak base to carry out hollow organosilane particulate, temperature all is consistent to the influence of reaction.Just, adopt higher temperature can obtain the less hollow organosilane microballoon of particle diameter, adopt lower temperature then can obtain the bigger hollow organosilane microballoon of particle diameter.
In addition, use different initiators also influential to the hollow organosilane particulate size that is generated.Embodiment 3 is identical with the reaction conditions of embodiment 10, has only to have used methyltrimethoxy silane, vinyltrimethoxy silane and tetraethoxy with 4: 1 mixed on initiator respectively.By embodiment 3 resulting hollow organosilane particle median sizes is 1.5 microns, and size distribution is the 1.3-1.7 micron; Embodiment 10 resulting hollow organosilane particle median sizes are 1.57 microns, and size distribution is the 1.2-1.8 micron.Can obtain the bigger hollow organosilane microballoon of particle diameter after changing the methyl on the methyltrimethoxy silane into vinyl.
Yet, when the alkyl on the silane has heteroatoms to replace, played variation again for the direction that influences of hollow organosilane microspherulite diameter size.Change the methyl on the methyltrimethoxy silane of one of initiator among the embodiment 3 into aminopropyl among the embodiment 9, other conditionally complete is identical.By embodiment 3 resulting hollow organosilane particle median sizes is 1.5 microns, and size distribution is the 1.3-1.7 micron; Only promising 0.52 micron of embodiment 9 resulting hollow organosilane particle median sizes, and size distribution is the 0.25-1.2 micron.By therefore, by the comparative result of embodiment 3 and embodiment 9 as can be known, adopt organosilane with third amino can obtain the littler organosilane microballoon of organosilane particle diameter than the band methyl.
Embodiment 1-6,8-11 utilize the mode that stirs, and organosilane monomer or oligomer are placed the polymkeric substance of the polycondensation formation that is hydrolyzed under the alkaline condition, with synthetic hollow organosilane microballoon.And Chao Sheng Zhen Tang is a kind of blended mode of carrying out that stirs that is used for replacing, and following then is to inquire into the influence of Chao Sheng Zhen Tang to this hydrolysis condensation reaction.Now compare by embodiment 3, embodiment 7 and embodiment 11, embodiment 7 and embodiment 11 adopt highly basic catalysis, 3 of embodiment adopt weak base catalysis, embodiment 3 and embodiment 11 adopts the mode that slowly stirs (200rpm rotating speed) that the mixture of organosilane is distributed to mode in the basic solution, and embodiment 7 changes into adopting ultransonic mode that the mixture of organosilane is distributed in the basic solution.The result, by the median size (0.87 micron) of embodiment 7 resulting hollow organosilane microballoons median size (1.67 microns) much smaller than embodiment 11 resulting hollow organosilane microballoons, even less than the median size (1.5 microns) of the embodiment 3 resulting hollow organosilane microballoons of the catalytic polymerization that is hydrolyzed with weak base.But the size distribution (0.5-4.3 micron) of embodiment 7 resulting hollow organosilane microballoons is then come widely than resulting size distribution among other embodiment.Therefore, by the comparative result of embodiment 3 and embodiment 11 and embodiment 7 as can be known, the dispersing mode of organosilane in basic solution also can be influenced the size and the size distribution thereof of resulting hollow organosilane microballoon.
By the above result that embodiment represented as can be known, can use the change of reaction conditions to control the grain size of the hollow organosilane microballoon that will obtain.For example, adopt ammonia soln to make catalyzer and can prepare the less hollow organosilane particle of particle diameter, adopt sodium hydroxide solution or potassium hydroxide solution can prepare the bigger particle of particle diameter; Adopt higher temperature can obtain the less hollow organosilane microballoon of particle diameter, otherwise adopt lower temperature then can obtain the bigger hollow organosilane microballoon of particle diameter; The hollow organosilane microspherulite diameter that adopts the organosilane of band vinyl to obtain is bigger, and the microspherulite diameter that adopts the organosilane with third amino to obtain is less; Adopt ultransonic mode that the mixture of organosilane is distributed to and can prepare the less hollow organosilane particle of particle diameter in the basic solution, but the particle size distribution broad of ultra-sonic dispersion preparation.So, have in the present technique field and to know the knowledgeable usually when can be by exposure of the present invention, utilize change that reaction conditions and initiator make median size size and the size distribution of requiring have a rough surface structure hollow organosilane particle.
For different modifying or the variation that structure of the present invention is done, neither disengaging the present invention's spirit or scope.In view of the narrating content of front, all changes that the invention provides and modification be what follows claim and claim etc. adopted content contain.
Claims (12)
1. one kind has rough surface structure hollow organosilane microballoon, it is characterized in that providing the pH value is 10～13 basic solution, mix at least two kinds of organosilanes and obtain the organosilane mixture, described organosilane mixture is joined in the described basic solution, be hydrolyzed after the polycondensation, still aging and get.
2. as claimed in claim 1 have a rough surface structure hollow organosilane microballoon, it is characterized in that, described ratio As 1.0～1.05 with volume average particle size territory number average median size of rough surface structure hollow organosilane microballoon.
3. as claimed in claim 1 have a rough surface structure hollow organosilane microballoon, it is characterized in that described median size Fan Wai with rough surface structure hollow organosilane microballoon is 50 nanometers～5 micron.
4. as claimed in claim 1 have a rough surface structure hollow organosilane microballoon, described at least two kinds of organosilanes comprise be hydrolyzed after polycondensation possess hydrophilic property and at least a organosilane of at least a organosilane and are hydrolyzed in basic solution and have hydrophobicity after the polycondensation in basic solution, and the mass ratio that has hydrophobic organosilicon alkane behind the hydrolysis condensation reaction behind the organosilane of possess hydrophilic property and the hydrolysis condensation reaction is 1: 1～1: 10.
5. as claimed in claim 1 have a rough surface structure hollow organosilane microballoon, it is characterized in that described organosilane is 10 weight parts in basic solution, and its content is 0.6～5 weight part.
6. one kind prepares the method with rough surface structure hollow organosilane microballoon, it is characterized in that, comprises the steps:
It is 10～13 basic solution that the pH value is provided;
Mix at least two kinds of organosilanes and obtain the organosilane mixture;
Described organosilane mixture is joined in the described basic solution, stirred 10 minutes～10 hours down at 0 ℃～70 ℃, polycondensation is hydrolyzed; And
Still aging 1 hour～20 hours, centrifugal, washing, lyophilize;
Described at least two kinds of organosilanes comprise be hydrolyzed after polycondensation possess hydrophilic property and at least a organosilane of at least a organosilane and are hydrolyzed in basic solution and have hydrophobicity after the polycondensation in basic solution, and the mass ratio that has hydrophobic organosilicon alkane behind the hydrolysis condensation reaction behind the organosilane of possess hydrophilic property and the hydrolysis condensation reaction is 1: 1～1: 10.
7. method as claimed in claim 6 is characterized in that described organosilane is 10 weight parts in basic solution, and its content is 0.6～5 weight part.
8. method as claimed in claim 6 is characterized in that described basic solution comprises alkaline matter, and described alkaline matter is a mineral alkali, comprises ammoniacal liquor, sodium hydroxide or potassium hydroxide.
9. method as claimed in claim 6 is characterized in that described basic solution comprises alkaline matter, and described alkaline matter is an organic bases, comprises quadrol or triethylamine.
10. method as claimed in claim 6 is characterized in that described basic solution comprises solvent, and described solvent is water or ethanol.
11. method as claimed in claim 6 is characterized in that the organosilane of possess hydrophilic property is the siloxanes of tetraethoxy, band hydrogen atom or the siloxanes of band chlorine atom behind the described hydrolysis condensation reaction.
12. method as claimed in claim 6, the mixture that it is characterized in that having behind the described hydrolysis condensation reaction hydrophobic organosilicon alkane and be vinyltrimethoxy silane, phenyltrimethoxysila,e, dimethyldimethoxysil,ne, methyltrimethoxy silane, aminopropyl triethoxysilane or form by these several organosilanes.
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Also Published As
| Publication number | Publication date |
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| CN102140250B (en) | 2012-08-22 |
| TW201226451A (en) | 2012-07-01 |
| TWI558745B (en) | 2016-11-21 |
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