CN103933903A - Method for preparing nanometer organic silicon microsphere with hollow structure - Google Patents
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- CN103933903A CN103933903A CN201410127819.4A CN201410127819A CN103933903A CN 103933903 A CN103933903 A CN 103933903A CN 201410127819 A CN201410127819 A CN 201410127819A CN 103933903 A CN103933903 A CN 103933903A
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Abstract
The invention discloses a method for preparing a nanometer organic silicon microsphere with a hollow structure. The method comprises the following steps: (1) mixing a silane coupling agent with water to obtain silane coupling agent dispersion liquid; (2) adding ammonia water into the silane coupling agent dispersion liquid obtained in step (1) to obtain a monodisperse organic silicon solid sphere; (3) carrying out hydrothermal treatment on the organic silicon solid sphere obtained in step (2) to obtain the nanometer organic silicon sphere with the hollow structure. According to the method for preparing the nanometer organic silicon microsphere with the hollow structure, disclosed by the embodiment of the invention, the surface appearance of the nanometer organic silicon microsphere with the hollow structure can be kept complete.
Description
Technical field
The invention belongs to Material Field, particularly, the present invention relates to a kind of method of preparing hollow-core construction nano-organosilicon microballoon.
Background technology
In recent years, hollow ball-type nano structural material has been subject to people's extensive concern because of its special structure and pattern, and the research of this tiny balloon has been had to significant achievement at aspects such as different size, pattern, structure and surface naturies.Hollow ball has the characteristic of low-density, high-specific surface area, the low coefficient of expansion, and therefore they have very large application potential at aspects such as catalyst, refractive surface coating, rechargeable battery, lithium battery and medicament transport and slowly-releasings.The micella for example prepared by functional polymer, vesica, hydrogel etc., and SiO
2, Fe
3o
4, the inorganic nano-particle such as Au.Mesoporous silicon dioxide nano particle is due to good biocompatibility, good monodispersity, and large specific area, surface hydroxyl modifiability and natural controlled drug release become the study hotspot of medicine intelligence carrier in recent years.The silicon nano of hollow has the higher medicine amount of carrying, and therefore has larger advantage.As need the large molecule such as load DNA, RNA to need silicon particle surface to there is larger duct, therefore, the silicon ball of development hollow and large aperture high capacity rate is extremely important.
The main preparation methods of hollow silicon ball has hard template method, soft template method, spray-on process, without methods such as template.Hard template method is mainly passed through the whole bag of tricks, control presoma and form shell at the surface deposition of the cores such as monodispersed polystyrene and carbon ball or reaction, and then remove kernel by the method for calcining or dissolve, and obtaining hollow-core construction, its size is determined by the size of template.As the coating technology layer by layer based on hard template method, utilization be the electrostatic interaction between different materials, the colloidal particle obtaining is coated layer by layer, can be controlled shell thickness by coated number of times.Current this method is widely used.The people such as chen carry out modification by the method for atom transferred free radical to template, introduce functional group, and functional group and monomer form shell material in interface polymerization, have synthesized SiO
2tiny balloon.Soft template method is widely used, can use micro emulsion drop as template, the growth of carrying out shell material by the surface at drop forms the structure of microcapsules, then first use the corresponding organic solvent of method utilization dissolving to dissolve the drop in shell, the means that re-use high temperature sintering are removed unnecessary surfactant and organic solvent, can obtain corresponding tiny balloon.Simultaneously owing to adopting the method for dissolving to remove capsule-core, to have caused spherical shell surface to produce mesoporous.The people such as Barbe have synthesized SiO in emulsion
2tiny balloon, microreactor used is exactly drop.Make template with CTAB, by regulator solution concentration and pH value, in slightly soluble liquid, just can use TEOS to prepare nano level SiO
2tiny balloon.Bubble also can be used as soft template.First, bubble forms, and nano particle is attached on the gas/liquid interface of bubble, and then gathers around bubble, forms closely knit shell.What the synthetic hollow-core construction of phonochemistry was the most frequently used is exactly bubble soft template, and bubble, from the collision of sound wave whirlpool, by ultrasonic facility, can synthesize SiO in the aqueous solution that contains ethyl orthosilicate and surfactant
2hollow ball, submicron order, and on shell, have mesoporous.
The method of more than introducing, no matter by soft template or hard template, all needs to carry out the preparation of template, then by calcination method and dissolution method, template is removed.Process prepared by template inevitably can be wasted some materials, and hollow-core construction is always had to destruction while removing template.This has just hindered the further application of hollow ball to a certain extent.And the preparation method of some template also must be through extremely loaded down with trivial details step.Just because of this, the preparation method without template is being explored in scientific research circle always.Without the basis of template, be exactly the mechanism of " Ostwald ripening ", the process of mechanism is completely spontaneous, and namely, due to the accumulation of energy, granule is accumulated as bulky grain.The people such as Lou have realized a step and have exempted from template, have successfully synthesized the SnO of polycrystalline
2hollow-core construction, when reaction, in the mixed solution of alcohol-water, adds potassium stannate (K
2snO
33H
2o) make presoma.In the initial stage of reaction, potassium stannate is hydrolyzed, form unformed solid particle, along with the carrying out of reaction, with the first crystallization of top layer nano particle that around solution phase contacts, therefore, in the inside of solid particle, form a kind of trend to surface crystallization bulky grain diffusion dissolution, " Ostwald ripening " from inside to outside, spontaneous driving force is also just provided.Dissolving is originated near solids surface or center, utilizes the character of the progressive maturation of nano particle, has produced hollow microballoon or nucleocapsid structure particle.
Although without the also imperfection of theory support of template, there is this method of a lot of researchers to synthesize miscellaneous hollow oxide microsphere.
In sum, in the research of preparing at hollow silicon ball, in certain template surface growth, then remove the material of capsule-core by dissolving, sintering etc. method, thereby obtain tiny balloon often.And for two-layer above multilayer hollow microballoon, often needing more complicated method, etching or constantly volume contraction produce.In this process, not only complicated process of preparation, the meeting that is difficult to avoid causes destruction in various degree to shell material.
Therefore the method for, preparing hollow-core construction nano-organosilicon microballoon need further research.
Summary of the invention
The present invention is intended to one of solve the problems of the technologies described above at least to a certain extent.For this reason, one object of the present invention is to propose a kind of method of preparing hollow-core construction nano-organosilicon microballoon, and the method can keep the complete of hollow-core construction nano-organosilicon microsphere surface pattern.
In one aspect of the invention, the present invention proposes a kind of method of preparing hollow-core construction nano-organosilicon microballoon, the method comprises:
(1) silane coupler is mixed with water, to obtain silane coupled agent dispersing liquid;
(2) in the described silane coupled agent dispersing liquid obtaining to step (1), add ammoniacal liquor, to obtain single organosilicon medicine ball that disperses; And
(3) described organosilicon medicine ball step (2) being obtained carries out hydrothermal treatment consists, to obtain described hollow-core construction nano-organosilicon microballoon.
According to the method for preparing hollow-core construction nano-organosilicon microballoon of the embodiment of the present invention taking silane coupler as raw material, in preparation process, pass through to use hydro-thermal method, template can be do not added and multilayer tiny balloon can be once formed, thereby waste of material and the loaded down with trivial details technique of corrosion template are avoided, in system, can add emulsifying agent simultaneously, therefore avoided the residue problem of emulsifying agent subsequent treatment, the structure of silicon microballoon can regulate and control by regulation experiment condition in addition, and the hollow-core construction nano-organosilicon microballoon obtaining can meet multi-purpose needs.
In addition, the method for preparing hollow-core construction nano-organosilicon microballoon according to the above embodiment of the present invention can also have following additional technical characterictic:
In some embodiments of the invention, in step (1), described silane coupler is at least one being selected from ethyl orthosilicate, silane coupling A 151, Silane coupling agent KH550, silane coupler KH580, silane coupler KH792 and silane coupler KH602.Thus, can effectively prepare hollow-core construction nano-organosilicon microballoon.
In some embodiments of the invention, in step (1), based on the gross weight of described silane coupled agent dispersing liquid, the content of described silane coupler is 1～65 quality %.Thus, can further effectively prepare hollow-core construction nano-organosilicon microballoon.
In some embodiments of the invention, in step (1), along with stirring, described silane coupler is mixed with water, wherein, the speed of described stirring is 200～8000 revs/min.Thus, silane coupler is dispersed in water.
In some embodiments of the invention, in step (1), before silane coupler is mixed with water, in advance emulsifying agent is dispersed in water.
In some embodiments of the invention, described emulsifying agent is at least one being selected from polyvinylpyrrolidone, block polyether, polyvinyl alcohol, lauryl sodium sulfate, neopelex, sorbester p18 and polysorbate60.
In some embodiments of the invention, based on the gross weight of described silane coupled agent dispersing liquid, the content of described emulsifying agent is below 4 quality %.
In some embodiments of the invention, in step (2), the concentration of described ammoniacal liquor is 0.1～5 quality %.Thus, can further effectively prepare hollow-core construction nano-organosilicon microballoon.
In some embodiments of the invention, in step (2), in described silane coupled agent dispersing liquid, drip ammoniacal liquor, wherein, the rate of addition of described ammoniacal liquor is 0.5～5 ml/min, and dripping total amount is 0.5～20 milliliter.Thus, can further effectively prepare hollow-core construction nano-organosilicon microballoon.
In some embodiments of the invention, in step (3), described hydrothermal treatment consists is at the temperature of 120～200 degrees Celsius, to carry out 12～24 hours.Thus, can further effectively prepare hollow-core construction nano-organosilicon microballoon.
In some embodiments of the invention, the particle diameter of described hollow-core construction nano-organosilicon microballoon is 0.02～100 micron.Thus, can meet multi-purpose needs.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Brief description of the drawings
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination is understood becoming the description of embodiment obviously and easily, wherein:
Fig. 1 is the method flow schematic diagram of preparing according to an embodiment of the invention hollow-core construction nano-organosilicon microballoon;
Fig. 2 is the method flow schematic diagram of the preparation hollow-core construction nano-organosilicon microballoon of another embodiment according to the present invention;
Fig. 3 is the Electronic Speculum figure for preparing according to an embodiment of the invention the hollow-core construction nano-organosilicon microballoon that the method for hollow-core construction nano-organosilicon microballoon prepares;
Fig. 4 is the Electronic Speculum figure of the hollow-core construction nano-organosilicon microballoon for preparing of the method for preparing hollow-core construction nano-organosilicon microballoon of another embodiment according to the present invention;
Fig. 5 is the Electronic Speculum figure of the hollow-core construction nano-organosilicon microballoon for preparing of the method for preparing hollow-core construction nano-organosilicon microballoon of another embodiment according to the present invention;
Fig. 6 is the Electronic Speculum figure of the hollow-core construction nano-organosilicon microballoon for preparing of the method for preparing hollow-core construction nano-organosilicon microballoon of another embodiment according to the present invention;
Fig. 7 is the Electronic Speculum figure of the hollow-core construction nano-organosilicon microballoon for preparing of the method for preparing hollow-core construction nano-organosilicon microballoon of another embodiment according to the present invention.
Detailed description of the invention
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Be exemplary below by the embodiment being described with reference to the drawings, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
In one aspect of the invention, the present invention proposes a kind of method of preparing hollow-core construction nano-organosilicon microballoon.Below with reference to Fig. 1-2, the method for preparing hollow-core construction nano-organosilicon microballoon of the embodiment of the present invention is described in detail.According to embodiments of the invention, the method comprises:
S100: prepare silane coupled agent dispersing liquid
According to embodiments of the invention, silane coupler is mixed with water, thereby can prepare silane coupled agent dispersing liquid.According to embodiments of the invention, the particular type of silane coupler is also not particularly limited, according to a particular embodiment of the invention, silane coupler can be for being selected from least one in ethyl orthosilicate, silane coupling A 151, Silane coupling agent KH550, silane coupler KH580, silane coupler KH792 and silane coupler KH602.It should be explained that, silane coupling A 151 is VTES, Silane coupling agent KH550 is 3-aminopropyl triethoxysilane, silane coupler KH580 is γ-mercaptopropyl trimethoxysilane, silane coupler KH792 is N-(β mono-aminoethyl)-γ-aminopropyl front three (second) TMOS, silane coupler KH602 is N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane.According to embodiments of the invention, the consumption of silane coupler is also not particularly limited, and according to a particular embodiment of the invention, based on the gross weight of silane coupled agent dispersing liquid, the content of silane coupler can be 1～65 quality %.Inventor finds, if the too high levels of silane coupler makes whole viscosity excessive, causes particle diameter to distribute wide, thereby makes the particle diameter skewness of the hollow silicon microballoon of gained.According to embodiments of the invention, silane coupler is mixed with water be accompanied by stir and carry out, according to a particular embodiment of the invention, stir speed (S.S.) is also not particularly limited, and according to concrete example of the present invention, stir speed (S.S.) can be 200～8000 revs/min.Thus, can make silane coupler be dispersed in water.
S200: the single organosilicon medicine ball that disperses of preparation
According to embodiments of the invention, to above-mentioned gained to silane coupled agent dispersing liquid in add ammoniacal liquor, thereby can obtain single organosilicon medicine ball that disperses.According to embodiments of the invention, add the concentration of ammoniacal liquor and be not particularly limited, according to a particular embodiment of the invention, the concentration of ammoniacal liquor can be 0.1～5 quality %.According to embodiments of the invention, the dropping mode of ammoniacal liquor is also not particularly limited, and according to a particular embodiment of the invention, the rate of addition of ammoniacal liquor can be 0.5～5 ml/min, drips total amount and can be 0.5～20 milliliter.Particularly, ammoniacal liquor can be used as the single formation that disperses organosilicon medicine ball of catalyst promotion.
S300: prepare hollow silicon microballoon
According to embodiments of the invention, obtained organosilicon medicine ball is carried out to hydrothermal treatment consists, thereby can obtain hollow-core construction nano-organosilicon microballoon.According to embodiments of the invention, the condition of hydrothermal treatment consists is not particularly limited, and according to a particular embodiment of the invention, hydrothermal treatment consists can be carried out 12～24 hours at the temperature of 120～200 degrees Celsius.According to embodiments of the invention, the particle diameter of the hollow-core construction nano-organosilicon microballoon obtaining is also not particularly limited, and according to a particular embodiment of the invention, the particle diameter of hollow-core construction nano-organosilicon microballoon can be 0.02～100 millimeter.Thus, obtain organosilicon microballoon and can meet multi-purpose needs.Concrete, hydro-thermal method is in enclosed system, taking the aqueous solution as solvent, at certain temperature (100-1000 DEG C), and under the pressure of water self generation (1-100MPa), in subcritical, critical, postcritical state, the process of synthesizing new compound by the material chemical reaction utilizing in solution.Because the course of reaction of hydro-thermal method is to be in imperfect poised state, therefore often make it have comparatively easy operability and adjustability, can make chemical reaction under relatively gentle condition, be easier to obtain the experimental result that common response cannot obtain, therefore can obtain the new product of be situated between steady structure, condensed state.For example, this principle is used to study TiO
2forming process, by the TiF of variable concentrations
4be placed in reactor, the granule in the kernel of particulate, its surface can be higher than outer field, therefore impels granule constantly to escape from inside, forms hollow-core construction.
According to the method for preparing hollow-core construction nano-organosilicon microballoon of the embodiment of the present invention taking silane coupler as raw material, in preparation process, pass through to use hydro-thermal method, template can be do not added and multilayer tiny balloon can be once formed, thereby waste of material and the loaded down with trivial details technique of corrosion template are avoided, in system, can add emulsifying agent simultaneously, therefore avoided the residue problem of emulsifying agent subsequent treatment, the structure of silicon microballoon can regulate and control by regulation experiment condition in addition, and the hollow-core construction nano-organosilicon microballoon obtaining can meet multi-purpose needs.
With reference to figure 2, further comprise according to the method for preparing hollow-core construction nano-organosilicon microballoon of the embodiment of the present invention:
S400: in advance emulsifying agent is dispersed in water
According to embodiments of the invention, before silane coupler is mixed with water, in advance emulsifying agent is dispersed in water.According to embodiments of the invention, the particular type of emulsifying agent is also not particularly limited, according to a particular embodiment of the invention, emulsifying agent can be for being selected from least one in polyvinylpyrrolidone, block polyether, polyvinyl alcohol, lauryl sodium sulfate, neopelex, sorbester p18 and polysorbate60.According to embodiments of the invention, the consumption of silane coupler is also not particularly limited, and based on the gross weight of silane coupled agent dispersing liquid, the content of emulsifying agent can be below 4 quality %.Particularly, due to the emulsification of emulsifying agent, can more uniform dispersed monomer drop, thus can obtain single dispersed silicon ball that particle diameter is less, and can regulate particle size by the amount that regulates emulsifying agent.
Below with reference to specific embodiment, present invention is described, it should be noted that, these embodiment are only descriptive, and do not limit the present invention in any way.
Embodiment 1
1) prepare silane coupled agent dispersing liquid: 5g silane coupling A 151 is mixed with 300ml deionized water, stir with refiner, setting mixing speed is 200r/min, makes silane coupling A 151 be dispersed in water and is hydrolyzed 2 hours, obtains silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.1wt%, the rate of addition of ammoniacal liquor is 0.5ml/min, dropping total amount is 0.5ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 180 DEG C of temperature, reacted after 12 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon (as Fig. 3).
Embodiment 2
1) prepare silane coupled agent dispersing liquid: 10g silane coupling A 151 is mixed with 300ml deionized water, and stir with refiner, setting mixing speed is 400r/min, makes silane coupling A 151 be dispersed in water and is hydrolyzed 2 hours, obtains silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.5wt%, the rate of addition of ammoniacal liquor is 0.8ml/min, dropping total amount is 1.5ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 190 DEG C of temperature, reacted after 12 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon (as Fig. 4).
Embodiment 3
1) prepare silane coupled agent dispersing liquid: 15g silane coupling A 151 is mixed with 300ml deionized water, and stir with refiner, setting mixing speed is 1000r/min, makes silane coupling A 151 be dispersed in water and is hydrolyzed 2 hours, obtains silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.15wt%, the rate of addition of ammoniacal liquor is 1.5ml/min, dropping total amount is 2.5ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 190 DEG C of temperature, reacted after 24 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon (as Fig. 5).
Embodiment 4
1) prepare silane coupled agent dispersing liquid: 20g silane coupling A 151 is mixed with 300ml deionized water, and stir with refiner, setting mixing speed is 1200r/min, makes silane coupling A 151 be dispersed in water and is hydrolyzed 2 hours, obtains silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.25wt%, the rate of addition of ammoniacal liquor is 1.75ml/min, dropping total amount is 7.0ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 200 DEG C of temperature, reacted after 15 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon (as Fig. 6).
Embodiment 5
1) prepare silane coupled agent dispersing liquid: 20g silane coupling A 151 is mixed with 300ml deionized water, and stir with refiner, setting mixing speed is 1500r/min, makes silane coupling A 151 be dispersed in water and is hydrolyzed 2 hours, obtains silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.15wt%, the rate of addition of ammoniacal liquor is 2.5ml/min, dropping total amount is 9.5ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 220 DEG C of temperature, reacted after 16 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon (as Fig. 7).
Embodiment 6
1) prepare silane coupled agent dispersing liquid: in advance the polyvinylpyrrolidine copper of 0.5wt% is dissolved in 300ml deionized water, then add the Silane coupling agent KH550 of 5g, and stir with refiner, setting mixing speed is 500r/min, make Silane coupling agent KH550 be dispersed in water and be hydrolyzed 2 hours, obtaining silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.05wt%, the rate of addition of ammoniacal liquor is 0.5ml/min, dropping total amount is 10.0ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 200 DEG C of temperature, reacted after 12 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon.
Embodiment 7
1) prepare silane coupled agent dispersing liquid: in advance the lauryl sodium sulfate of 0.5wt% is dissolved in 300ml deionized water, then add the silane coupler KH580 of 10g, and stir with refiner, setting mixing speed is 800r/min, make silane coupler KH580 be dispersed in water and be hydrolyzed 2 hours, obtaining silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.5wt%, the rate of addition of ammoniacal liquor is 1.5ml/min, dropping total amount is 12.5ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 200 DEG C of temperature, reacted after 24 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon.
Embodiment 8
1) prepare silane coupled agent dispersing liquid: in advance the lauryl sodium sulfate of 1wt% is dissolved in 300ml deionized water, then add the silane coupler KH792 of 5g, and stir with refiner, setting mixing speed is 800r/min, make silane coupler KH792 be dispersed in water and be hydrolyzed 2 hours, obtaining silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.15wt%, the rate of addition of ammoniacal liquor is 0.8ml/min, dropping total amount is 15.5ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 220 DEG C of temperature, reacted after 24 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon.
Embodiment 9
1) prepare silane coupled agent dispersing liquid: in advance the neopelex of 1.5wt% is dissolved in 300ml deionized water, then add the silane coupler KH792 of 5g, and stir with refiner, setting mixing speed is 1000r/min, make silane coupler KH792 be dispersed in water and be hydrolyzed 2 hours, obtaining silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.35wt%, the rate of addition of ammoniacal liquor is 2.5ml/min, dropping total amount is 18.5ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 220 DEG C of temperature, reacted after 24 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon.
Embodiment 10
1) prepare silane coupled agent dispersing liquid: in advance the neopelex of 2wt% is dissolved in 300ml deionized water, then add the silane coupler KH602 of 5g, and stir with refiner, setting mixing speed is 1500r/min, make silane coupler KH602 be dispersed in water and be hydrolyzed 2 hours, obtaining silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.45wt%, the rate of addition of ammoniacal liquor is 2.5ml/min, dropping total amount is 19.0ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 230 DEG C of temperature, reacted after 16 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon.
Embodiment 11
1) prepare silane coupled agent dispersing liquid: in advance the neopelex of 3wt% is dissolved in 300ml deionized water, then add the silane coupler KH580 of 5g, and stir with refiner, setting mixing speed is 1800r/min, make silane coupler KH580 be dispersed in water and be hydrolyzed 2 hours, obtaining silane coupled agent dispersing liquid;
2) the single organosilicon medicine ball that disperses of preparation: add ammoniacal liquor in obtained dispersion liquid, wherein, the concentration of ammoniacal liquor is 0.45wt%, the rate of addition of ammoniacal liquor is 2.5ml/min, dropping total amount is 20.0ml, then reacts after 20min, can form monodispersed organosilicon medicine ball;
3) prepare hollow silicon microballoon: obtained organosilicon medicine ball dispersion liquid is transferred in hydrothermal reaction kettle, at 220 DEG C of temperature, reacted after 16 hours, naturally cooling, obtain hollow-core construction nano-organosilicon microballoon.
In the description of this description, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And specific features, structure, material or the feature of description can be with suitable mode combination in any one or more embodiment or example.
Although illustrated and described embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention in the situation that not departing from principle of the present invention and aim, amendment, replacement and modification.
Claims (11)
1. a method of preparing hollow-core construction nano-organosilicon microballoon, is characterized in that, comprising:
(1) silane coupler is mixed with water, to obtain silane coupled agent dispersing liquid;
(2) in the described silane coupled agent dispersing liquid obtaining to step (1), add ammoniacal liquor, to obtain single organosilicon medicine ball that disperses; And
(3) described organosilicon medicine ball step (2) being obtained carries out hydrothermal treatment consists, to obtain described hollow-core construction nano-organosilicon microballoon.
2. method according to claim 1, it is characterized in that, in step (1), described silane coupler is at least one being selected from ethyl orthosilicate, silane coupling A 151, Silane coupling agent KH550, silane coupler KH580, silane coupler KH792 and silane coupler KH602.
3. method according to claim 1, is characterized in that, in step (1), based on the gross weight of described silane coupled agent dispersing liquid, the content of described silane coupler is 1～65 quality %.
4. method according to claim 1, is characterized in that, in step (1), along with stirring, described silane coupler is mixed with water, and wherein, the speed of described stirring is 200～8000 revs/min.
5. method according to claim 1, is characterized in that, in step (1), before silane coupler is mixed with water, in advance emulsifying agent is dispersed in water.
6. method according to claim 5, is characterized in that, described emulsifying agent is at least one being selected from polyvinylpyrrolidone, block polyether, polyvinyl alcohol, lauryl sodium sulfate, neopelex, sorbester p18 and polysorbate60.
7. method according to claim 5, is characterized in that, based on the gross weight of described silane coupled agent dispersing liquid, the content of described emulsifying agent is below 4 quality %.
8. method according to claim 1, is characterized in that, in step (2), the concentration of described ammoniacal liquor is 0.1～5 quality %.
9. method according to claim 1, is characterized in that, in step (2), in described silane coupled agent dispersing liquid, drips ammoniacal liquor, and wherein, the rate of addition of described ammoniacal liquor is 0.5～5 ml/min, and dripping total amount is 0.5～20 milliliter.
10. method according to claim 1, is characterized in that, in step (3), described hydrothermal treatment consists is at the temperature of 120～200 degrees Celsius, to carry out 12～24 hours.
11. methods according to claim 1, is characterized in that, the particle diameter of described hollow-core construction nano-organosilicon microballoon is 0.02～100 micron.
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| CN107946562A (en) * | 2017-11-13 | 2018-04-20 | 中航锂电（洛阳）有限公司 | A kind of graphene/silicon composite material and preparation method thereof, lithium ion battery |
| CN107946562B (en) * | 2017-11-13 | 2020-04-10 | 中航锂电（洛阳）有限公司 | Graphene/silicon composite material, preparation method thereof and lithium ion battery |
| CN111298711A (en) * | 2020-03-11 | 2020-06-19 | 湘潭大学 | Mesoporous Janus nanosheet emulsifier with pH responsiveness and preparation method and application thereof |
| CN115895139A (en) * | 2022-10-27 | 2023-04-04 | 联塑市政管道（河北）有限公司 | High-toughness high-fluidity PVC composite material and preparation method and application thereof |
| CN115895139B (en) * | 2022-10-27 | 2023-11-03 | 联塑市政管道（河北）有限公司 | High-toughness high-fluidity PVC composite material and preparation method and application thereof |
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