CN116285475A - Hydrophobic silicon dioxide and preparation method thereof - Google Patents
Hydrophobic silicon dioxide and preparation method thereof Download PDFInfo
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- CN116285475A CN116285475A CN202310106172.6A CN202310106172A CN116285475A CN 116285475 A CN116285475 A CN 116285475A CN 202310106172 A CN202310106172 A CN 202310106172A CN 116285475 A CN116285475 A CN 116285475A
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- polydimethylsiloxane
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 65
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 73
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 73
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 66
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910021485 fumed silica Inorganic materials 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000443 aerosol Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003999 initiator Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000002562 thickening agent Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 62
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001816 cooling Methods 0.000 description 11
- 238000011049 filling Methods 0.000 description 10
- 238000000746 purification Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010504 bond cleavage reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 125000005375 organosiloxane group Chemical group 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VXSIXFKKSNGRRO-MXOVTSAMSA-N [(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate;[(1s)-2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-3-[(e)-3-methoxy-2-methyl-3-oxoprop-1-enyl Chemical class CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1.CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VXSIXFKKSNGRRO-MXOVTSAMSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- 229960002695 phenobarbital Drugs 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- 229940070846 pyrethrins Drugs 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
Abstract
The invention provides hydrophobic silicon dioxide and a preparation method thereof, and the specific steps are as follows: and heating the fumed silica nano particles under the anaerobic condition, adding ethylene carbonate, and adding polydimethylsiloxane to react after the ethylene carbonate is adsorbed on the fumed silica nano particles to obtain the hydrophobic silica. In the invention, in the presence of ethylene carbonate as a siloxane bond rupture initiator, polydimethylsiloxane with different polymer chain lengths can be used for carrying out surface hydrophobic modification on the silicon dioxide nano particles, the method does not need toxic catalyst catalysis, and can be completed at a relatively low temperature at the same time, and the prepared hydrophobic silicon dioxide has good waterproof effect and is widely added into various complex resin liquids as a thickening agent to achieve the characteristic of a hydrophobic coating.
Description
Technical Field
The invention relates to the technical field of super-hydrophobic coatings, in particular to hydrophobic silicon dioxide and a preparation method thereof.
Background
At present, a plurality of hydrophobic coatings are available on the market, but the waterproof effect of the coating is limited mainly through organic polymers or resins, and the prepared silica nano material passes through toxic catalysts so that a plurality of products cannot meet the requirement of environmental protection.
Ethylene Carbonate (DEC) is mainly used as an intermediate for organic synthesis and pharmaceutical synthesis, and also as a solvent for resins, oils, nitrocellulose, cellulose ethers, and the like. As solvents for nitrocellulose, natural and synthetic resins. Are also important intermediates for organic synthesis, for the synthesis of phenobarbital and pyrethrins, and for the coating of cathodes in electron tubes.
Poly (dimethylsiloxane) (PDMS) is a hydrophobic silicone material, but is generally considered inert because of the absence of readily hydrolyzable groups, and is not suitable for surface hydrophobic modification of silica (SiO 2) nanoparticles.
Aiming at the problems and defects that the poly (dimethylsiloxane) is not suitable for carrying out surface hydrophobic modification on the silicon dioxide (SiO 2) nano-particles in the prior art, the process for carrying out surface hydrophobic modification on the silicon dioxide (SiO 2) nano-particles by the poly (dimethylsiloxane) needs further improvement and development.
Disclosure of Invention
The invention provides hydrophobic silicon dioxide and a preparation method thereof, and the specific technical scheme is as follows:
a preparation method of hydrophobic silicon dioxide comprises the following specific steps: heating the fumed silica nano-particles under the anaerobic condition, adding ethylene carbonate, and adding polydimethylsiloxane to react after the ethylene carbonate is adsorbed on the fumed silica nano-particles to obtain hydrophobic silica;
further, the volume ratio of the added ethylene carbonate to the polydimethylsiloxane is 1-3:1;
further, the volume ratio of the added ethylene carbonate to the polydimethylsiloxane is 1:1;
further, the amount of polydimethylsiloxane, in weight fraction, is 15% to 20% of the weight of silica;
further, the amount of polydimethylsiloxane, in weight fraction, was 17% of the weight of silica;
further, ethylene carbonate and polydimethylsiloxane are added through a nozzle in the form of an aerosol, respectively;
further, the heating temperature is 200-240 ℃;
further, stopping heating after the reaction is finished, cooling to room temperature, and purifying, cleaning and drying;
further, purifying with n-hexane as solvent at 60-70deg.C for 1 hr;
the invention also provides hydrophobic silica.
By adopting the technical scheme, the invention has the beneficial technical effects that:
1. the invention provides an environment-friendly preparation method of hydrophobic silicon dioxide, which does not need toxic catalyst catalysis and can be completed at a relatively low temperature;
2. according to the invention, the surface of the silicon dioxide nano particles is subjected to hydrophobic modification by using ethylene carbonate and polydimethylsiloxane which is not suitable for surface modification, and the prepared hydrophobic silicon dioxide has good waterproof effect and is widely added into various complex resin liquids as a thickening agent so as to achieve the characteristic of a hydrophobic coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A preparation method of hydrophobic silicon dioxide comprises the following specific steps: and heating the fumed silica nano particles under the anaerobic condition, adding ethylene carbonate, and adding polydimethylsiloxane to react after the ethylene carbonate is adsorbed on the fumed silica nano particles to obtain the hydrophobic silica. In this embodiment ethylene carbonate is used as the siloxane bond cleavage initiator and the siloxane oligomer is reacted with free silanol groups on the silica surface in the presence of ethylene carbonate to form a stable hydrophobic coating having a carbon content greater thanThe high carbon content gives the hydrophobic layer good thermal and chemical stability, 8 wt%. The experimental results show that the carbon content of the hydrophobic silica is higher than that of the hydrophobic silica modified with pure polydimethylsiloxane in the case of ethylene carbonate as initiator. SiO with polydimethylsiloxane in the absence of ethylene carbonate 2 The surface modification results in the formation of small patches of adsorbed organic layers that are readily desorbed in a polar medium.
The volume ratio of the added ethylene carbonate to the polydimethylsiloxane is 1-3:1, and the added volume ratio of the ethylene carbonate to the polydimethylsiloxane is in the range of 1-3:1, so that the modification reaction is facilitated, and when the ethylene carbonate is added, the ethylene carbonate reacts with silanol groups on the surface of silicon dioxide to form grafted ethoxy groups, which can serve as an additional reaction center for the chemical adsorption of the organosiloxane. When polydimethylsiloxane is added, siloxane oligomer formed by interaction of ethylene carbonate and polydimethylsiloxane reacts with surface silanol. When more ethylene carbonate is added, the grafted ethoxy groups cannot be chemically bonded with sufficient polydimethylsiloxane, so that a stable hydrophobic effect cannot be achieved; when a small proportion of ethylene carbonate is added, the ethylene carbonate cannot sufficiently depolymerize polydimethylsiloxane to form an oligomer, and a good reaction effect cannot be achieved. It is further preferred that the added volume ratio of ethylene carbonate to polydimethylsiloxane is 1:1, and when the added volume ratio of ethylene carbonate to polydimethylsiloxane is 1:1, the ethylene carbonate adsorbs onto the silica surface to react with silanol groups on the silica surface to form grafted ethoxy groups, which can serve as additional reaction centers for organosiloxane chemisorption and promote adequate reaction of siloxane bonds with the equivalent amount of polydimethylsiloxane.
The amount of polydimethylsiloxane, in weight fraction, is 15% to 20% of the weight of silica. When the amount of the polydimethylsiloxane is 15% -20% of the weight of the silicon dioxide, a film layer formed on the surface of the coating is relatively compact, the coating achieves the optimal balance between the superhydrophobic performance and the coating-substrate binding force, when the amount of the polydimethylsiloxane is less than 15%, the polydimethylsiloxane cannot wrap all the silicon dioxide, and the silicon dioxide which is not wrapped by the polydimethylsiloxane forms a stack on the surface of the coating, so that the adhesion between the coating and a substrate is reduced, and the mechanical stability of the coating is affected. It is further preferred that the amount of polydimethylsiloxane is 17% by weight of silica and that the reaction is sufficient at the other levels relative to the amount of polydimethylsiloxane being 17% by weight of silica to provide silica nanoparticles having a uniform particle size distribution and a relatively dense film layer formed on the surface of the coating to achieve optimal hydrophobic effect.
The ethylene carbonate and the polydimethylsiloxane are respectively added through the nozzle in the form of aerosol, and the form of aerosol is more beneficial to the full contact of the modifier and the fumed silica so as to achieve better reaction effect.
Stopping heating after the reaction is finished, cooling to room temperature, and purifying, cleaning and drying. Purifying with n-hexane as solvent at 60-70deg.C for 1 hr. After the reaction, impurities such as water and carbon dioxide gas are also present, and in order to further improve the purity of the hydrophobic silica, purification is performed at 60 to 70 ℃ for 1 hour using n-hexane as a solvent.
In the prior art, the mere use of polydimethylsiloxane with high molecular weight for chemical modification of silica surface requires high energy consumption, and the reaction temperature is generally above 400 ℃, while the heating temperature of the application is 200-240 ℃, because ethylene carbonate without adding any toxic reagent is an effective reagent for the siloxane bond cleavage reaction on the surface sites of the polydimethylsiloxane, thus facilitating the chemical adsorption of the polydimethylsiloxane on the silica surface at relatively low temperature.
Example 1
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 220 ℃;
(3) Stop ofCharging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, after the ethylene carbonate is adsorbed on the fumed silica nano particles, adding polydimethylsiloxane aerosol into the glass reactor by using the nozzle (the code of polydimethylsiloxane is PDMS-50, the linear and the viscosity is 45-55 mm) 2 S, molecular weight-3500 Da, polymerization degree 23-28), volume ratio of ethylene carbonate to polydimethylsiloxane 1:1, and polydimethylsiloxane amount being 17% of fumed silica weight;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 68 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Example 2
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 200 ℃;
(3) Stopping charging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, adsorbing the ethylene carbonate on the fumed silica nanoparticles, and adding polydimethylsiloxane aerosol (PDMS-50, linear, and viscosity of 45-55 mm) into the glass reactor by using the nozzle 2 S, molecular weight-3500 Da, polymerization degree 23-28), volume ratio of ethylene carbonate to polydimethylsiloxane is 2:1, and the amount of polydimethylsiloxane is 15% of the weight of fumed silica;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 60 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Example 3
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 240 ℃;
(3) Stopping charging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, adsorbing the ethylene carbonate on the fumed silica nanoparticles, and adding polydimethylsiloxane aerosol (PDMS-50, linear, and viscosity of 45-55 mm) into the glass reactor by using the nozzle 2 S, molecular weight-3500 Da, polymerization degree 23-28), volume ratio of ethylene carbonate and polydimethylsiloxane is 3:1, and the amount of polydimethylsiloxane is 20% of the weight of fumed silica;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 70 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Example 4
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 220 ℃;
(3) Stopping charging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, adsorbing the ethylene carbonate on the fumed silica nanoparticles, and adding polydimethylsiloxane aerosol (PDMS-20, linear and viscosity 18-22 mm) into the glass reactor by using the nozzle 2 S, molecular weight-2000 Da, polymerization degree 13-15), ethylene carbonateAnd the volume ratio of polydimethylsiloxane was 1:1, the amount of polydimethylsiloxane being 17% by weight of fumed silica;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 68 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Example 5
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 220 ℃;
(3) Stopping charging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, adsorbing the ethylene carbonate on the fumed silica nanoparticles, and adding polydimethylsiloxane aerosol (PDMS-100, linear, viscosity 95-105 mm) into the glass reactor by using the nozzle 2 S, molecular weight-6000 Da, degree of polymerization 35-65), volume ratio of ethylene carbonate to polydimethylsiloxane is 1:1, and the amount of polydimethylsiloxane is 17% of the weight of fumed silica;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 68 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Comparative example 1
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 220 ℃;
(3) The nitrogen filling into the reactor was stopped and a polydimethylsiloxane aerosol (PDMS-50, linear, viscosity 45-55 mm) was added to the glass reactor using a nozzle 2 S, molecular weight of 3500Da, polymerization degree of 23-28), the amount of polydimethylsiloxane being 17% by weight of fumed silica;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 68 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Comparative example 2
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 220 ℃;
(3) Stopping charging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, adsorbing the ethylene carbonate on the fumed silica nanoparticles, and adding polydimethylsiloxane aerosol (PDMS-50, linear, and viscosity of 45-55 mm) into the glass reactor by using the nozzle 2 S, molecular weight-3500 Da, polymerization degree 23-28), volume ratio of ethylene carbonate and polydimethylsiloxane is 1:3, and the quantity of polydimethylsiloxane is 17% of fumed silica weight;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 68 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Comparative example 3
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 220 ℃;
(3) Stopping charging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, adsorbing the ethylene carbonate on the fumed silica nanoparticles, and adding polydimethylsiloxane aerosol (PDMS-50, linear, and viscosity of 45-55 mm) into the glass reactor by using the nozzle 2 S, molecular weight-3500 Da, polymerization degree 23-28), volume ratio of ethylene carbonate to polydimethylsiloxane 1:1, and polydimethylsiloxane 10% by weight of fumed silica;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 68 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
Comparative example 4
The preparation method of the hydrophobic silica comprises the following specific steps:
(1) After loading 1L of fumed silica in a glass reactor, filling nitrogen in the reactor, wherein the glass reactor is provided with a glass stirrer, and the rotating speed of the glass reactor is 200rpm;
(2) Heating the glass reactor to 220 ℃;
(3) Stopping charging nitrogen into the reactor, adding ethylene carbonate aerosol into the glass reactor by using a nozzle, adsorbing the ethylene carbonate on the fumed silica nanoparticles, and adding polydimethylsiloxane aerosol (PDMS-50, linear, and viscosity of 45-55 mm) into the glass reactor by using the nozzle 2 S, molecular weight-3500 Da, polymerization degree 23-28), volume ratio of ethylene carbonate to polydimethylsiloxane 1:1, and polydimethylsiloxane amount 25% of fumed silica weight;
(4) Stopping heating after the reaction is finished, cooling the obtained mixture to room temperature, and purifying in a Soxhlet device for 1 hour at 68 ℃ by taking normal hexane as a solvent;
(5) After purification, the mixture was washed and dried in a muffle furnace at 80℃for 2 hours.
The silica samples prepared in examples 1-5 and comparative examples 1-4 were subjected to contact angle testing, and specific data are shown in Table 1:
TABLE 1 contact angle test results for silica samples prepared in examples 1-5 and comparative examples 1-4
| Contact angle/° | |
| Example 1 | 115 |
| Example 2 | 112 |
| Example 3 | 112 |
| Example 4 | 113 |
| Example 5 | 114 |
| Comparative example 1 | 108 |
| Comparative example 2 | 111 |
| Comparative example 3 | 110 |
| Comparative example 4 | 110 |
As can be seen from the contact angle data of examples 1 and 4-5 in table 1, the silica nanoparticles can be surface hydrophobically modified with polydimethylsiloxanes (PDMS-20, PDMS-50, PDMS-100) having different polymer chain lengths in the presence of ethylene carbonate as a siloxane bond cleavage initiator, the polydimethylsiloxanes used in example 1 having a designation PDMS-50, which gives the prepared silica samples a contact angle of maximum 115 °, and the polydimethylsiloxanes used in examples 4-5 having designations PDMS-20 and PDMS-100, respectively, having contact angles of 113 ° and 114 °. In addition, in comparative example 1, the contact angle value of comparative example 1, in which ethylene carbonate was not added, was 108 ° smaller than that of example 1. Comparative examples 2-4 the contact angle data was also significantly less than that of example 1, varying the volume ratios of ethylene carbonate and polydimethylsiloxane, and the weight percent of polydimethylsiloxane relative to fumed silica, respectively. The experimental data in table 1 demonstrate that the hydrophobic effect of the silica samples obtained by the present invention is better.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. The preparation method of the hydrophobic silica is characterized by comprising the following specific steps: and heating the fumed silica nano particles under the anaerobic condition, adding ethylene carbonate, and adding polydimethylsiloxane to react after the ethylene carbonate is adsorbed on the fumed silica nano particles to obtain the hydrophobic silica.
2. The method for preparing hydrophobic silica according to claim 1, wherein the volume ratio of the added ethylene carbonate to the polydimethylsiloxane is 1-3:1.
3. A method of preparing a hydrophobic silica according to claim 2 wherein the volume ratio of ethylene carbonate to polydimethylsiloxane added is 1:1.
4. A method of preparing a hydrophobic silica according to claim 1 wherein the amount of polydimethylsiloxane, in weight fraction, is 15% to 20% of the weight of the silica.
5. A process for preparing hydrophobic silica as claimed in claim 4, wherein the amount of polydimethylsiloxane is 17% by weight of the silica.
6. A method of preparing hydrophobic silica according to claim 1 wherein ethylene carbonate and polydimethylsiloxane are added separately in aerosol form through the nozzle.
7. The method for preparing hydrophobic silica according to claim 1, wherein the heating temperature is 200-240 ℃.
8. The method for preparing hydrophobic silica according to claim 7, wherein the heating temperature is 220 ℃.
9. The method for preparing hydrophobic silica according to claim 1, wherein the heating is stopped after the reaction is completed, and the reaction mixture is cooled to room temperature and then purified, washed and dried.
10. A hydrophobic silica produced by the process for producing a hydrophobic silica according to any one of claims 1 to 9.
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