CN106563398A - Preparation method of organic/inorganic composite microspheres with raspberry-like structures and application thereof - Google Patents
Preparation method of organic/inorganic composite microspheres with raspberry-like structures and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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Abstract
The invention discloses a preparation method of organic/inorganic composite microspheres with raspberry-like structures and application thereof. The preparation method of the organic/inorganic composite microsphere comprises the following steps: firstly adding a stabilizer which is polyvinylpyrrolidone (PVP), monomers and an oil-soluble initiator into an ethanol/water mixed solution to prepare monodisperse polymer microspheres, dispersing the prepared monodisperse polymer microspheres into the ethanol/water mixed solution, adding ammonia water and uniformly stirring and mixing; and then adding tetraethoxysilane to obtain the raspberry-like organic/inorganic composite microspheres. The preparation method of the organic/inorganic composite microspheres with the raspberry-like structures has the beneficial effects that the preparation method is simple, the reaction conditions are mild, toxic organic solvents are not needed, expensive chemical materials or complex large-sized instruments are not needed, the large-scale production can be achieved, the surface shape of the prepared microspheres can be accurately adjusted and controlled by adjusting the molecular weight of PVP and the addition amount of ammonia water, extremely strong Van der Waals force exists between polymer kernels and silicon dioxide particles, the microspheres are not easily influenced by external environment, and the microspheres are excellent in stability.
Description
Technical field
The present invention relates to a kind of technical field of polymer preparation, especially a kind of organic/inorganic of raspberry shape structure are compound
The preparation method and applications of microballoon.
Background technology
Raspberry shape particle is referred to large specific surface area, high surfaces roughness and light scattering characteristic, on apparent
The particulate of similar raspberry.Raspberry shape particle has special configuration of surface and surface is easily designed because of it, in particles self assemble, super
Hydrophobic and super-hydrophilic coating preparation aspect is widely used.At present, raspberry shape compound particle is broadly divided into from material composition
Organic/organic, organic/inorganic and inorganic/inorganic compounding particle three types.Wherein, organic/inorganic compound particle it is inorganic/have
Machine raspberry shape compound particle causes the concern of numerous researchers due to having the performance of inorganic matter and organic matter concurrently.Prepare it is organic/
The method of inorganic raspberry shape particle mainly has physical method and chemical method.Physical method mainly includes electrostatic interaction, and hydrogen bond is made
With π-π effects and interparticle chemical bonding etc..Chemical method includes emulsion polymerization, thin breast according to the difference of polymerization system
Liquid polymerization, dispersion copolymerization method, surfactant- free emulsion polymerization and Pickering emulsion polymerizations etc..But, prepared by physical method
The efficiency of compound particle is low, and the compound particle pattern for being obtained is changed greatly in the presence of system influence factor, it is difficult to essence
Really regulate and control compound particle case shell structure.Chemical method generally requires the reactions steps of complexity, expensive reaction kit equipment
And material, percent grafting is low.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of preparation of the organic/inorganic complex microsphere of raspberry shape structure
Method and its application, the method is simple, efficiently, overcomes that raspberry shape particle combined coefficient in prior art is low, and apparent form is difficult
With accuracy controlling, the problem that the further functionalized application of organic/inorganic raspberry shape microballoon is limited to a certain extent.
The technical scheme is that：A kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, its feature
It is to comprise the following steps：
1) mixed solution of ethanol/water, is added in single-necked flask, then gathers monomer, oil-soluble initiator, stabilizer
Dissolve in the mixed solution of vinylpyrrolidone (PVP) addition ethanol/water；The matter of the mixed solution of the monomer and ethanol/water
Measuring number ratio is：1：10～20, the mass fraction ratio of monomer and oil-soluble initiator is：1：0.01～0.03, the list
Body and stabilizer polyvinylpyrrolidone (PVP) mass fraction ratio are：1：0.05～0.4；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, single-necked flask is placed in into temperature for 60～75
DEG C oil bath pan in react 1-24h；
3) after, reaction terminates in oil bath pan, cleaned 3 times with the mixed solution dispersion of ethanol/water, be then in rotating speed
2-10min is centrifuged under 6000～12000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere for preparing is scattered in the mixed solution of ethanol/water, ammoniacal liquor is added, and
It is uniformly mixed, is subsequently adding tetraethyl orthosilicate, room temperature reaction 24h, the monodisperse polymer micro-sphere is mixed with ethanol/water
The mass ratio for closing solution is 0.1～1：100, the monodisperse polymer micro-sphere is 1 with the mass ratio of ammoniacal liquor：5～30, it is single
Dispersed polymeres microballoon is (1 with the mass ratio of tetraethyl orthosilicate：1～3)；
5) it is then 6000～12000 turns/min in rotating speed after being cleaned with the mixed solution of ethanol/water after, reaction terminates
Lower centrifugation 2-10min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, raspberry shape structure
Organic/inorganic complex microsphere surface topography can be adjusted by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone
Control.
In above-mentioned technical proposal, step 1) in, monomer is styrene, methyl methacrylate, EMA, first
Base isobornyl acrylate, butyl methacrylate, lauryl methacrylate, Isobutyl methacrylate, methacrylic acid
Isodecyl ester, EHMA, methyl acrylate, ethyl acrylate, isobornyl acrylate, butyl acrylate, propylene
Any one or a few mixing in sour lauryl, isobutyl acrylate, isodecyl acrylate or Isooctyl acrylate monomer.
In above-mentioned technical proposal, step 1) in, the oil-soluble initiator is azodiisobutyronitrile (AIBN), azo two is different
Any one or a few mixing of heptonitrile, benzoyl peroxide, TBHP, peroxidized t-butyl perbenzoate etc..
In above-mentioned technical proposal, step 1) in, the stabilizer polyvinylpyrrolidone (PVP) is for relative molecular mass
Any one or a few mixing in 8kg/mol, 10kg/mol, 40kg/mol, 58kg/mol, 130kg/mol.
In above-mentioned technical proposal, step 1 and 3) in, in the mixed solution of ethanol/water the mass ratio of ethanol/water be 100/0
～80/20.
A kind of application of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
S1 Long carbon chain silane coupler), is added in absolute ethyl alcohol, after stirring prehydrolysis 2h, having for raspberry shape is added
Machine/inorganic composite microsphere, stirs at ambient temperature 2h, organic/inorganic complex microsphere and the absolute ethyl alcohol of the raspberry shape
Mass ratio is 0.06～0.12：1, the organic/inorganic complex microsphere of the raspberry shape and the quality of Long carbon chain silane coupler
Ratio is 2～12:1；
S2), under the conditions of rotating speed is 6000-12000 turn/min after centrifugation 2-10min, by the material for obtaining dispersion
In absolute ethyl alcohol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 100～120 DEG C of baking oven dry；
S4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, substrate surface is coated in, is done under the conditions of temperature is for 45 DEG C
Dry film forming, obtains a kind of material of super-hydrophobic/oleophobic, as super-double-hydrophobic surface.
Above-mentioned technical proposal, step S1) in, the Long carbon chain silane coupler be carbon number more than ten (including ten)
Long carbon chain silane coupler in the mixing of one or more.
The present invention is stabilizer by using polyvinylpyrrolidone, and using dispersin polymerization monodispersed polyphenyl is prepared
Ethene microballoon, then with this microballoon as template absorption tetraethyl orthosilicate in situ, hydrolyzes silica, prepares PS/SiO2Organic/nothing
Machine raspberry shape structure microspheres.
Beneficial effects of the present invention are：
The organic/inorganic complex microsphere preparation method of raspberry shape structure the 1st, proposed by the invention is simple, reaction condition temperature
With without the need for any toxic organic solvents, without the need for the large-scale instrument of expensive chemical material or complexity, be produced on a large scale.
2nd, the organic/inorganic complex microsphere surface topography of the raspberry shape structure for preparing can be by adjusting polyvinylpyrrolidone
Molecular weight and ammoniacal liquor addition accuracy controlling.
3rd, the raspberry shape structure microspheres prepared by the present invention, exist extremely strong between polymer core and silicon dioxide granule
Van der Waals force, it is not easy to affected by external environment, excellent in stability.
4th, the present invention adopts the raspberry shape microballoon of synthesis Jing after low-surface energy substance modification, with preferably super-hydrophobic/super
Oil-wet behavior, can be used for the fields such as automatically cleaning, water-oil separating.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of the monodisperse polymer micro-sphere of embodiment 1 and the Static Contact of raspberry shape microballoon
Angle；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon prepared by embodiment 2；
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon prepared by embodiment 3；
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon prepared by embodiment 4；
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon prepared by embodiment 5；
Fig. 6 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon prepared by embodiment 6.
Specific embodiment
The specific embodiment of the present invention is described further below in conjunction with the accompanying drawings：
Embodiment 1
A kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
1) mixed solution of 18g ethanol/waters (14.4/3.6), is added in single-necked flask, then by 1.8g monomer polyphenyl
Ethene (St), 0.04g oil-soluble initiator azodiisobutyronitriles (AIBN), 0.3g stabilizer polyvinylpyrrolidone (PVP) (phases
To molecular mass be 40kg/mol) add ethanol/water mixed solution in dissolve；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, it is 70 DEG C that single-necked flask is placed in into temperature
8h is reacted in oil bath pan；
3) after, reaction terminates in oil bath pan, cleaned 3 times with the mixed solution dispersion of ethanol/water, be then in rotating speed
2-10min is centrifuged under 6000～12000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere of 0.1g is scattered in the mixed solution of 120mL ethanol/waters (100/20), plus
Enter 2.0mL ammoniacal liquor, and be uniformly mixed, be subsequently adding 0.5mL tetraethyl orthosilicates, room temperature reaction 24h.
5) after, reaction terminates, after being cleaned with the mixed solution of ethanol/water, then it is centrifuged in the case where rotating speed is 10000 turns/min
5min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, the organic/inorganic of raspberry shape structure
Complex microsphere surface topography can be regulated and controled by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone.
A kind of application of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
S1 1mL Long carbon chain silane coupler hexadecyl trimethoxy silanes, stirring), are added in 100mL absolute ethyl alcohols
After prehydrolysis 2h, the organic/inorganic complex microsphere of 6g raspberry shapes is added, 2h is stirred at ambient temperature；
S2), under the conditions of rotating speed is 6000-12000 turn/min after centrifugation 2-10min, by the material for obtaining dispersion
In absolute ethyl alcohol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 120 DEG C of baking oven dry；
S4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, substrate surface is coated in, is done under the conditions of temperature is for 45 DEG C
Dry film forming, obtains a kind of material of super-hydrophobic/oleophylic, as super hydrophobic surface.
Fig. 1 is the Monodisperse Polystyrene Microspheres and raspberry shape PS@SiO for preparing2The SEM figures of microballoon, it can be seen that synthesizing in figure
The Monodisperse Polystyrene Microspheres of two kinds of particle diameter distributions and microsphere surface success coated silica particle, illustrate depositing in stabilizer PVP
Under, tetraethyl orthosilicate is successfully adsorbed onto Surfaces of Polystyrene Microparticles, and in-situ hydrolysis obtain nanosized silica particles, shape
Into raspberry shape PS/SiO2Particle.
Embodiment 2
A kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
1) mixed solution of 18g ethanol/waters (14.4/3.6), is added in single-necked flask, then by 1.0g monomer polyphenyl
Ethene (St), 0.03g oil-soluble initiator azodiisobutyronitriles (AIBN), 0.40g stabilizer polyvinylpyrrolidones (PVP)
Dissolve in the mixed solution of (relative molecular weight is 10kg/mol) addition ethanol/water；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, it is 70 DEG C that single-necked flask is placed in into temperature
8h is reacted in oil bath pan；
3) after, reaction terminates in oil bath pan, cleaned 3 times with the mixed solution dispersion of ethanol/water, be then in rotating speed
2-10min is centrifuged under 10000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere of 0.15g is scattered in the mixed solution of 120mL ethanol/waters (100/20), plus
Enter 2.0mL ammoniacal liquor, and be uniformly mixed, be subsequently adding 0.5mL tetraethyl orthosilicates, room temperature reaction 24h.
5) after, reaction terminates, after being cleaned with the mixed solution of ethanol/water, then it is centrifuged in the case where rotating speed is 10000 turns/min
5min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, the organic/inorganic of raspberry shape structure
Complex microsphere surface topography can be regulated and controled by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone.
A kind of application of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
S1 1mL Long carbon chain silane coupler hexadecyl trimethoxy silanes, stirring), are added in 100mL absolute ethyl alcohols
After prehydrolysis 2h, the organic/inorganic complex microsphere of 6g raspberry shapes is added, 2h is stirred at ambient temperature；
S2), under the conditions of rotating speed is 6000-12000 turn/min after centrifugation 2-10min, by the material for obtaining dispersion
In absolute ethyl alcohol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 100 DEG C of baking oven dry；
S4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, substrate surface is coated in, is done under the conditions of temperature is for 45 DEG C
Dry film forming, obtains a kind of material of super-hydrophobic/oleophylic, as super hydrophobic surface.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon manufactured in the present embodiment, and it connects in atmosphere with the static state of water
Feeler is 155 °, with preferable hydrophobic property.
Embodiment 3
A kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
1) mixed solution of 18g ethanol/waters (14.4/3.6), is added in single-necked flask, then by 1.2g monomer polyphenyl
Ethene (St), 0.036g oil-soluble initiator azodiisobutyronitriles (AIBN), 0.06g stabilizer polyvinylpyrrolidones (PVP)
Dissolve in the mixed solution of (relative molecular weight is 58kg/mol) addition ethanol/water；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, it is 70 DEG C that single-necked flask is placed in into temperature
8h is reacted in oil bath pan；
3) after, reaction terminates in oil bath pan, cleaned 3 times with the mixed solution dispersion of ethanol/water, be then in rotating speed
2-10min is centrifuged under 10000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere of 0.2g is scattered in the mixed solution of 120mL ethanol/waters (100/20), plus
Enter 2.0mL ammoniacal liquor, and be uniformly mixed, be subsequently adding 0.5mL tetraethyl orthosilicates, room temperature reaction 24h.
5) after, reaction terminates, after being cleaned with the mixed solution of ethanol/water, then it is centrifuged in the case where rotating speed is 10000 turns/min
5min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, the organic/inorganic of raspberry shape structure
Complex microsphere surface topography can be regulated and controled by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone.
A kind of application of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
S1 1mL Long carbon chain silane coupler hexadecyl trimethoxy silanes, stirring), are added in 100mL absolute ethyl alcohols
After prehydrolysis 2h, the organic/inorganic complex microsphere of 6g raspberry shapes is added, 2h is stirred at ambient temperature；
S2), under the conditions of rotating speed is 6000-12000 turn/min after centrifugation 2-10min, by the material for obtaining dispersion
In absolute ethyl alcohol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 110 DEG C of baking oven dry；
S 4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, be coated in substrate surface, temperature be 45 DEG C under the conditions of
Drying and forming-film, obtains a kind of material of super-hydrophobic/oleophylic, as super hydrophobic surface.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon manufactured in the present embodiment, and it connects in atmosphere with the static state of water
Feeler is 157 °, with preferable hydrophobic property.
Embodiment 4
A kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
1) mixed solution of 18g ethanol/waters (14.4/3.6), is added in single-necked flask, then by 1.8g monomer polyphenyl
Ethene (St), 0.054g oil-soluble initiator azodiisobutyronitriles (AIBN), 0.72g stabilizer polyvinylpyrrolidones (PVP)
Dissolve in the mixed solution of (relative molecular mass is 130kg/mol) addition ethanol/water；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, it is 70 DEG C that single-necked flask is placed in into temperature
8h is reacted in oil bath pan；
3) after, reaction terminates in oil bath pan, cleaned 3 times with the mixed solution dispersion of ethanol/water, be then in rotating speed
2-10min is centrifuged under 6000～12000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere of 0.3g is scattered in the mixed solution of 120mL ethanol/waters (100/20), plus
Enter 2.0mL ammoniacal liquor, and be uniformly mixed, be subsequently adding 0.5mL tetraethyl orthosilicates, room temperature reaction 24h.
5) after, reaction terminates, after being cleaned with the mixed solution of ethanol/water, then it is centrifuged in the case where rotating speed is 10000 turns/min
5min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, the organic/inorganic of raspberry shape structure
Complex microsphere surface topography can be regulated and controled by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone.
A kind of application of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
S1 1mL Long carbon chain silane coupler hexadecyl trimethoxy silanes, stirring), are added in 100mL absolute ethyl alcohols
After prehydrolysis 2h, the organic/inorganic complex microsphere of 6g raspberry shapes is added, 2h is stirred at ambient temperature；
S2), under the conditions of rotating speed is 6000-12000 turn/min after centrifugation 2-10min, by the material for obtaining dispersion
In absolute ethyl alcohol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 120 DEG C of baking oven dry；
S4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, substrate surface is coated in, is done under the conditions of temperature is for 45 DEG C
Dry film forming, obtains a kind of material of super-hydrophobic/oleophylic, as super hydrophobic surface.
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon manufactured in the present embodiment, and it connects in atmosphere with the static state of water
Feeler is 162 °, with preferable hydrophobic property.
Embodiment 5
A kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
1) mixed solution of 18g ethanol/waters (14.4/3.6), is added in single-necked flask, then by 1.8g monomer polyphenyl
Ethene (St), 0.018g oil-soluble initiator azodiisobutyronitriles (AIBN), 0.09g stabilizer polyvinylpyrrolidones (PVP)
Dissolve in the mixed solution of (relative molecular mass is 40kg/mol) addition ethanol/water；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, it is 70 DEG C that single-necked flask is placed in into temperature
8h is reacted in oil bath pan；
3) after, reaction terminates in oil bath pan, cleaned 3 times with the mixed solution dispersion of ethanol/water, be then in rotating speed
2-10min is centrifuged under 6000～12000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere of 0.4g is scattered in the mixed solution of 120mL ethanol/waters (100/20), plus
Enter 1.0mL ammoniacal liquor, and be uniformly mixed, be subsequently adding 0.3mL tetraethyl orthosilicates, room temperature reaction 24h.
5) after, reaction terminates, after being cleaned with the mixed solution of ethanol/water, then it is centrifuged in the case where rotating speed is 10000 turns/min
5min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, the organic/inorganic of raspberry shape structure
Complex microsphere surface topography can be regulated and controled by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone.
A kind of application of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
S1 1mL Long carbon chain silane coupler hexadecyl trimethoxy silanes, stirring), are added in 100mL absolute ethyl alcohols
After prehydrolysis 2h, the organic/inorganic complex microsphere of 6g raspberry shapes is added, 2h is stirred at ambient temperature；
S2), under the conditions of rotating speed is 6000-12000 turn/min after centrifugation 2-10min, by the material for obtaining dispersion
In absolute ethyl alcohol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 120 DEG C of baking oven dry；
S4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, substrate surface is coated in, is done under the conditions of temperature is for 45 DEG C
Dry film forming, obtains a kind of material of super-hydrophobic/oleophylic, as super hydrophobic surface.
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon manufactured in the present embodiment, and it connects in atmosphere with the static state of water
Feeler is 149 °, with preferable hydrophobic property.
Embodiment 6
A kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
1) mixed solution of 18g ethanol/waters (14.4/3.6), is added in single-necked flask, then by 1.8g monomer polyphenyl
Ethene (St), 0.04g oil-soluble initiator azodiisobutyronitriles (AIBN), 0.3g stabilizer polyvinylpyrrolidone (PVP) (phases
To molecular mass be 40kg/mol) add ethanol/water mixed solution in dissolve；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, it is 70 DEG C that single-necked flask is placed in into temperature
8h is reacted in oil bath pan；
3) after, reaction terminates in oil bath pan, cleaned 3 times with the mixed solution dispersion of ethanol/water, be then in rotating speed
2-10min is centrifuged under 6000～12000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere of 0.5g is scattered in the mixed solution of 120mL ethanol/waters (100/20), plus
Enter 3.0mL ammoniacal liquor, and be uniformly mixed, be subsequently adding 0.3mL tetraethyl orthosilicates, room temperature reaction 24h.
5) after, reaction terminates, after being cleaned with the mixed solution of ethanol/water, then it is centrifuged in the case where rotating speed is 10000 turns/min
5min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, the organic/inorganic of raspberry shape structure
Complex microsphere surface topography can be regulated and controled by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone.
A kind of application of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
S1 1mL Long carbon chain silane coupler hexadecyl trimethoxy silanes, stirring), are added in 100mL absolute ethyl alcohols
After prehydrolysis 2h, the organic/inorganic complex microsphere of 6g raspberry shapes is added, 2h is stirred at ambient temperature；
S2), under the conditions of rotating speed is 6000-12000 turn/min after centrifugation 2-10min, by the material for obtaining dispersion
In absolute ethyl alcohol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 100 DEG C of baking oven dry；
S4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, substrate surface is coated in, is done under the conditions of temperature is for 45 DEG C
Dry film forming, obtains a kind of material of super-hydrophobic/oleophylic, as super hydrophobic surface.
Fig. 6 is the scanning electron microscope (SEM) photograph (SEM) of raspberry shape microballoon manufactured in the present embodiment, and it connects in atmosphere with the static state of water
Feeler is 156 °, with preferable hydrophobic property.
Merely illustrating the principles of the invention described in above-described embodiment and specification and most preferred embodiment, without departing from this
On the premise of spirit and scope, the present invention also has various changes and modifications, and these changes and improvements both fall within requirement and protect
In the scope of the invention of shield.
Claims (7)
1. a kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure, it is characterised in that comprise the following steps：
1) mixed solution of ethanol/water, is added in single-necked flask, then by monomer, oil-soluble initiator, stabilizer polyethylene
Dissolve in the mixed solution of pyrrolidones (PVP) addition ethanol/water；The mass parts of the mixed solution of the monomer and ethanol/water
Number ratios be：1：10～20, the mass fraction ratio of monomer and oil-soluble initiator is：1：0.01～0.03, the monomer with
Stabilizer polyvinylpyrrolidone (PVP) mass fraction ratio is：1：0.05～0.4；
2), it is passed through after nitrogen 30min in single-necked flask, stoppers rubber stopper, it is 60～75 DEG C that single-necked flask is placed in into temperature
1-24h is reacted in oil bath pan；
3) after, reaction terminates in oil bath pan, with the mixed solution of ethanol/water dispersion cleaning 3 times, then rotating speed be 6000～
2-10min is centrifuged under 12000 turns/min and obtains monodisperse polymer micro-sphere；
4), the monodisperse polymer micro-sphere for preparing is scattered in the mixed solution of ethanol/water, ammoniacal liquor is added, and is stirred
It is well mixed, is subsequently adding tetraethyl orthosilicate, room temperature reaction 24h；The monodisperse polymer micro-sphere is molten with the mixing of ethanol/water
The mass ratio of liquid is 0.1～1：100, the monodisperse polymer micro-sphere is 1 with the mass ratio of ammoniacal liquor：5～30, single dispersing
Polymer microballoon is 1 with the mass ratio of tetraethyl orthosilicate：1～3；
5) after, reaction terminates, after clean with the mixed solution of ethanol/water, then rotating speed under 6000～12000 turns/min from
Heart 2-10min, repeated washing/centrifugation 3 times, the organic/inorganic complex microsphere for obtaining raspberry shape is standby, and raspberry shape structure has
Machine/inorganic composite microsphere surface topography can be adjusted by the addition of the molecular weight and ammoniacal liquor that adjust polyvinylpyrrolidone
Control.
2. a kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure according to claim 1, its feature exists
In：Step 1) in, monomer is styrene, methyl methacrylate, EMA, isobornyl methacrylate, first
Base butyl acrylate, lauryl methacrylate, Isobutyl methacrylate, isodecyl methacrylate, methacrylic acid are different
Monooctyl ester, methyl acrylate, ethyl acrylate, isobornyl acrylate, butyl acrylate, lauryl acrylate, i-butyl
Any one or a few mixing in ester, isodecyl acrylate or Isooctyl acrylate monomer.
3. a kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure according to claim 1, its feature exists
In：Step 1) in, the oil-soluble initiator be azodiisobutyronitrile (AIBN), ABVN, benzoyl peroxide, uncle
Any one or a few mixing of butylhydroperoxide, peroxidized t-butyl perbenzoate etc..
4. a kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure according to claim 1, its feature exists
In：Step 1) in, the stabilizer polyvinylpyrrolidone (PVP) be relative molecular mass be 8kg/mol, 10kg/mol,
Any one or a few mixing in 40kg/mol, 58kg/mol, 130kg/mol.
5. a kind of preparation method of the organic/inorganic complex microsphere of raspberry shape structure according to claim 1, its feature exists
In：Step 1 and 3) in, in the mixed solution of ethanol/water the mass ratio of ethanol/water be 100/0～80/20.
6. the application of the organic/inorganic complex microsphere of a kind of raspberry shape structure according to any one of Claims 1 to 5,
Characterized in that, comprising the following steps：
S1 Long carbon chain silane coupler), is added in absolute ethyl alcohol, after stirring prehydrolysis 2h, the organic/nothing of raspberry shape is added
Machine complex microsphere, stirs at ambient temperature 2h, the organic/inorganic complex microsphere of the raspberry shape and the mass ratio of absolute ethyl alcohol
Example is 0.06～0.12：1, the organic/inorganic complex microsphere of the raspberry shape is 2 with the mass ratio of Long carbon chain silane coupler
～12:1；
S2), the material for obtaining is scattered in into nothing after centrifugation 2-10min under the conditions of rotating speed is 6000-12000 turn/min
In water-ethanol, super-hydrophobicity/super oleophylic complex microsphere emulsion is obtained standby；
S3), cleaning removes the dust and organic matter of substrate surface attachment, and is put in 100～120 DEG C ° of baking oven dry；
S4), by super-hydrophobicity/super oleophylic complex microsphere emulsion, substrate surface is coated in, is dried under the conditions of temperature is for 45 DEG C
Film, obtains a kind of material of super-hydrophobic/oleophobic, as super-double-hydrophobic surface.
7. the application of the organic/inorganic complex microsphere of a kind of raspberry shape structure according to claim 6, it is characterised in that：
Step S1) in, the Long carbon chain silane coupler is in Long carbon chain silane coupler of the carbon number more than ten (including ten)
The mixing of one or more.
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| CN107998997A (en) * | 2017-12-26 | 2018-05-08 | 中科院广州化学有限公司 | One species raspberry shape microballoon, super-hydrophobic coat and preparation method thereof |
| CN108101385A (en) * | 2017-12-28 | 2018-06-01 | 中科院广州化学有限公司 | A kind of transparent hydrophobic coating and its preparation method and application |
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| CN109985584A (en) * | 2019-04-23 | 2019-07-09 | 河北工业大学 | A kind of preparation method of regulatable strawberry shape silica-organic hybrid complex microsphere |
| CN112980005A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Quasi-spherical particles and preparation method and application thereof |
| CN111961206A (en) * | 2020-08-20 | 2020-11-20 | 四川大学 | Raspberry-shaped functionalized microspheres containing cage-like silsesquioxane and preparation method thereof |
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