CN109705288A - The preparation method of super-hydrophobic superoleophobic magnetic composite microsphere - Google Patents
The preparation method of super-hydrophobic superoleophobic magnetic composite microsphere Download PDFInfo
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- CN109705288A CN109705288A CN201910021560.8A CN201910021560A CN109705288A CN 109705288 A CN109705288 A CN 109705288A CN 201910021560 A CN201910021560 A CN 201910021560A CN 109705288 A CN109705288 A CN 109705288A
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Abstract
The present invention provides a kind of preparation method of super-hydrophobic superoleophobic magnetic composite microsphere, and super-amphiphobic complex microsphere is added crosslinking agent and initiator, the monodisperse Fe of modifier modification is added dropwise using vinyl and acrylic monomer as polymer monomer3O4Nanoparticle occurs miscellaneous phase polymerization, forms the magnetic polymer microsphere with surface secondary structure, obtains super-hydrophobic superoleophobic magnetic polymer microsphere using fluorine containing silane modification.
Description
Technical field
The invention belongs to Emulsifier-free Emulsion Polymerization Technology fields, are related to a kind of system of super-hydrophobic superoleophobic magnetic composite microsphere
Preparation Method.
Background technique
Due to superoleophobic higher to material surface structural requirement, it is necessary to have coarse second level and the above structure that could be formed
Indispensable air layer between material and liquid, is just able to achieve superoleophobic effect, therefore, super thin in research achievement at home and abroad at present
The superoleophobic magnetic composite microsphere of water is rarely reported.
Summary of the invention
In view of this, providing a kind of super-hydrophobic superoleophobic magnetism the purpose of the present invention is making up the blank of domestic and international technology
The preparation method of complex microsphere.
The present invention solves technical solution used by above-mentioned the deficiencies in the prior art: a kind of super-hydrophobic superoleophobic magnetic multiple
Close the preparation method of microballoon, which is characterized in that this method comprises: (1), with vinyl monomer, acrylic compounds are monomer, are added and hand over
Join agent, add initiator and be warming up to 60-85 DEG C, the monodispersed of vinyl silanes modifier modification is added dropwise through Dropping feeder
Fe3O4Nanoparticle causes miscellaneous phase polymerization, forms the magnetic polymer microsphere with surface secondary structure；It (2) will be in step (1)
The magnetic polymer microsphere of two obtained structures obtains super-hydrophobic superoleophobic magnetic poly- by the modification of the modified magnetic bead of fluorine containing silane
Close object microballoon.
Preferably, the vinyl monomer and acrylic monomer are styrene, methyl styrene, aromatic styrene
Compound, acrylic acid, unsaturated carboxylic acid class acrylic acid, acrylic acid, methylbenzene olefin(e) acid ethyl ester, butyl methacrylate, halogen second
Vinyl compound combination of two or more therein.
Preferably, the crosslinking agent includes divinylbenzene, Diacetone Acrylamide, N, N- methylene bisacrylamide acyl
Amine, bisphenol-A dual-allyl ether be one such or multiple combinations.
Preferably, the modifying agent is one of vinyltriethoxysilane, vinyltrimethoxysilane.
Preferably, the initiator is that ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate are one such.
Preferably, the Dropping feeder is peristaltic pump.
Preferably, the modification magnetic bead is metal ion, compound or simple substance.
Preferably, the ellipse that the modification magnetic bead is 0.001-10 μm, round, triangle, cube.
Preferably, the fluorine containing silane be heptadecafluorodecyl triethoxysilane, 17 fluorine ruthenium trimethoxysilanes,
Perfluorooctylethyl group acrylate, perfluoro capryl methacrylate are one such or two kinds are combined.
Compared to the prior art, the preparation method of super-hydrophobic superoleophobic magnetic composite microsphere of the invention, magnetic obtained
Property polymer microballoon can effectively control the circulation and barrier of waterborne liquid and oil-based liquid by the manipulation of external Contactless magnetic
Function, thus realize that microfluid shunts, the function of interflow and the contactless mixing of microfluid, since magnetic polymer is micro-
Ball has super-hydrophobic superoleophobic function, thus will not liquid in pollution channels, guarantee that liquid is effectively equal by pollution-free free of losses
Even mixing has broad application prospects, furthermore magnetic bead in Microfluidic droplet super-amphiphobic control switch and contactless mixing field
Will not by fluid soak pollute, so can magnetic force recycle and be used repeatedly, effectively reduce cost.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.It defines in the following description
Basic principle of the invention can be applied to other embodiments, deformation scheme, improvement project, equivalent program and do not carry on the back
Other technologies scheme from the spirit and scope of the present invention.
The preparation method of super-hydrophobic superoleophobic magnetic composite microsphere of the invention, preparation method includes the following steps:
Step (1): being polymer monomer and crosslinking agent by vinyl and acrylic monomer, be added to equipped with 100mL go from
In the three-necked flask of sub- water, leads to nitrogen 30min, then raise temperature to 60-85 DEG C, ethylene well prepared in advance is added dropwise using peristaltic pump
The monodispersed Fe of base silane modifier modification3O4Nanoparticle forms the magnetic polymer microsphere with surface secondary structure；
Step (2): the magnetic polymer microsphere of two structure obtained in step (1) obtains super thin by fluorine containing silane modification
The superoleophobic magnetic polymer microsphere of water.
Wherein, the vinyl monomer and acrylic monomer are styrene, methyl styrene, aromatic styrene
Close object, acrylic acid, unsaturated carboxylic acid class acrylic acid, acrylic acid, methylbenzene olefin(e) acid ethyl ester, butyl methacrylate, halogen ethylene
Class compound is two kinds therein, three kinds, four kinds of combinations or multiple combinations；The crosslinking agent includes divinylbenzene, diacetone
One or both of acrylamide, N,N methylene bis acrylamide, bisphenol-A dual-allyl ether or three kinds or four kinds of groups
It closes；The modifying agent is vinyltriethoxysilane, vinyltrimethoxysilane is one such；The initiator
It is one such for ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate；The Dropping feeder is peristaltic pump；The modification magnetic bead
For metal ions such as ferroso-ferric oxide, iron, manganese, cobalt, nickel, compound or simple substance；Described its shape and size of modification magnetic bead are
0.001-10 μm of ellipse, circle, triangle, cube；The fluorine containing silane be heptadecafluorodecyl triethoxysilane,
17 fluorine ruthenium trimethoxysilanes, perfluorooctylethyl group acrylate, perfluoro capryl methacrylate it is one such or
Two kinds of combinations.
The following are several embodiments of the present invention and preferred embodiments:
Embodiment 1
(1) by 50g styrene and 5g methacrylic acid 30g divinylbenzene, three mouthfuls of burnings equipped with 500mL deionized water are added to
In bottle, lead to nitrogen 30min, then raise temperature to 80 DEG C, 1g KPS initiator is added, when solution becomes translucent cream in three-necked flask
When white, the modified monodispersed Fe of vinyl silanes well prepared in advance is added dropwise with peristaltic pump3O4Nanoparticle, rate of addition
For 1s/ drop, 80 DEG C of isothermal reaction 7h, three times, alcohol is washed three times for centrifugation washing, and being dissolved in solid content in ethyl alcohol is 10%, for use.
(2) magnetic polymer microsphere 20mL obtained in step (1) is taken, the 250mL equipped with 100ml dehydrated alcohol is added to
In three-necked flask, 500 μ L heptadecafluorodecyl triethoxysilanes are added, ammonium hydroxide is added dropwise, pH to 10 is adjusted, is warming up to 50 DEG C,
50 DEG C of constant temperature 5h, taking-up centrifugation alcohol is washed dries three times.
Embodiment 2
(1) by 50g styrene and 5g acrylic acid 30g divinylbenzene, it is added to the three-necked flask equipped with 500mL deionized water
In, lead to nitrogen 30min, then raise temperature to 80 DEG C, 1g APS initiator is added, when solution becomes translucent milky white in three-necked flask
When color, the modified monodispersed Fe of vinyl silanes well prepared in advance is added dropwise with peristaltic pump3O4Nanoparticle, rate of addition are
1s/ drop, 80 DEG C of isothermal reaction 7h, three times, alcohol is washed three times for centrifugation washing, and being dissolved in solid content in ethyl alcohol is 10%, for use.
(2) magnetic polymer microsphere 20mL obtained in step (1) is taken, the 250mL equipped with 100ml dehydrated alcohol is added to
In three-necked flask, 500 μ L heptadecafluorodecyl triethoxysilanes are added, ammonium hydroxide is added dropwise, pH to 10 is adjusted, is warming up to 50 DEG C,
50 DEG C of constant temperature 5h, taking-up centrifugation alcohol is washed dries three times.
Embodiment 3
(1) by 50g styrene and 5g methacrylic acid 30g N, N- methylene-bisacrylamide, be added to equipped with 500mL go from
In the three-necked flask of sub- water, lead to nitrogen 30min, then raise temperature to 80 DEG C, 1g KPS initiator is added, when solution in three-necked flask
When becoming translucent milky, the modified monodispersed Fe of vinyl silanes well prepared in advance is added dropwise with peristaltic pump3O4Nanoparticle
Son, rate of addition are 1s/ drop, and 80 DEG C of isothermal reaction 7h, three times, alcohol is washed three times, is dissolved in solid content in ethyl alcohol and is for centrifugation washing
10%, for use.
(2) magnetic polymer microsphere 20mL obtained in step (1) is taken, the 250mL equipped with 100ml dehydrated alcohol is added to
In three-necked flask, 500 μ L heptadecafluorodecyl triethoxysilanes are added, ammonium hydroxide is added dropwise, pH to 10 is adjusted, is warming up to 50 DEG C,
50 DEG C of constant temperature 5h, taking-up centrifugation alcohol is washed dries three times.
Embodiment 4
(1) by 50g styrene and 5g methacrylic acid 30g Diacetone Acrylamide, three equipped with 500mL deionized water are added to
In mouth flask, lead to nitrogen 30min, then raise temperature to 80 DEG C, 1g APS initiator is added, when solution becomes semi-transparent in three-necked flask
When bright milky, the modified monodispersed Fe of vinyl silanes well prepared in advance is added dropwise with peristaltic pump3O4Nanoparticle is added dropwise
Speed is 1s/ drop, and 80 DEG C of isothermal reaction 7h, three times, alcohol is washed three times for centrifugation washing, and being dissolved in solid content in ethyl alcohol is 10%, for use.
(2) magnetic polymer microsphere 20mL obtained in step (1) is taken, the 250mL equipped with 100ml dehydrated alcohol is added to
In three-necked flask, 500 μ L heptadecafluorodecyl triethoxysilanes are added, ammonium hydroxide is added dropwise, pH to 10 is adjusted, is warming up to 50 DEG C,
50 DEG C of constant temperature 5h, taking-up centrifugation alcohol is washed dries three times.
Embodiment 5
(1) it by 50g styrene and 5g methacrylic acid 30g bisphenol-A dual-allyl ether, is added to equipped with 500mL deionized water
Three-necked flask in, lead to nitrogen 30min, then raise temperature to 80 DEG C, 1g KPS initiator is added, when solution becomes in three-necked flask
When translucent milky, the modified monodispersed Fe of vinyltriethoxysilane well prepared in advance is added dropwise with peristaltic pump3O4It receives
Rice corpuscles, rate of addition are 1s/ drop, and 80 DEG C of isothermal reaction 7h, three times, alcohol is washed three times, and solid content in ethyl alcohol is dissolved in for centrifugation washing
It is 10%, for use.
(2) magnetic polymer microsphere 20mL obtained in step (1) is taken, the 250mL equipped with 100ml dehydrated alcohol is added to
In three-necked flask, 500 μ L heptadecafluorodecyl triethoxysilanes are added, ammonium hydroxide is added dropwise, pH to 10 is adjusted, is warming up to 50 DEG C,
50 DEG C of constant temperature 5h, taking-up centrifugation alcohol is washed dries three times.
It should be understood by those skilled in the art that the embodiment of the present invention of foregoing description is only used as illustrating and being not intended to limit this
Invention.The purpose of the present invention has been fully and effectively achieved.Function and structural principle of the invention is shown in embodiment
And explanation, under without departing from the principle, embodiments of the present invention can have any deformation or modification.
Claims (9)
1. a kind of preparation method of super-hydrophobic superoleophobic magnetic composite microsphere, which is characterized in that this method comprises the following steps:
(1) in vinyl monomer, acrylic monomer, crosslinking agent is added, adds initiator and is warming up to 60-85 DEG C, through dripping
The monodispersed Fe of feeder apparatus dropwise addition vinyl silanes modifier modification3O4Nanoparticle causes miscellaneous phase polymerization, and being formed has table
The magnetic polymer microsphere of face secondary structure；
(2) it by the magnetic polymer microsphere of two structure obtained in step (1), is obtained by the modification of the modified magnetic bead of fluorine containing silane
Super-hydrophobic superoleophobic magnetic polymer microsphere.
2. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 1, which is characterized in that institute
The vinyl monomer and acrylic monomer stated are styrene, methyl styrene, aromatic styrene compound, acrylic acid, no
Saturated carboxylic acid class acrylic acid, acrylic acid, methylbenzene olefin(e) acid ethyl ester, butyl methacrylate, halogen ethylene compounds are therein
Combination of two or more.
3. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 1, which is characterized in that institute
The crosslinking agent stated is divinylbenzene, Diacetone Acrylamide, N, N- methylene-bisacrylamide, bisphenol-A dual-allyl ether
One such or multiple combinations.
4. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 1, which is characterized in that institute
The modifying agent stated is vinyltriethoxysilane or vinyltrimethoxysilane.
5. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 1, which is characterized in that institute
The initiator stated is one of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate.
6. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 1, which is characterized in that institute
The Dropping feeder stated is peristaltic pump.
7. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 1, which is characterized in that institute
The modification magnetic bead stated is metal ion, compound or simple substance.
8. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 7, which is characterized in that institute
The modification magnetic bead stated be 0.001-10 μm ellipse, circle, triangle, cube.
9. the preparation method of the super-hydrophobic superoleophobic magnetic composite microsphere of one kind according to claim 1, which is characterized in that institute
The fluorine containing silane stated is heptadecafluorodecyl triethoxysilane, 17 fluorine ruthenium trimethoxysilanes, perfluorooctylethyl group propylene
Acid esters, perfluoro capryl methacrylate are one such or two kinds are combined.
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Cited By (1)
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| CN112940206A (en) * | 2021-03-03 | 2021-06-11 | 广东惠和硅制品有限公司 | Modified silica sol and acrylate composite emulsion and coating |
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Application publication date: 20190503 |