Super-hydrophobic magnetic mixture and preparation method and application thereof
阅读说明：本技术 一种超疏水磁性混合物及其制备方法和应用 (Super-hydrophobic magnetic mixture and preparation method and application thereof ) 是由 黄景达 张晓春 吴强 李倩 于 2019-10-15 设计创作，主要内容包括：本发明公开了一种超疏水磁性混合物,包括相互混合的CNF水悬浮液、Fe<Sub>3</Sub>O<Sub>4</Sub>纳米粒子以及疏水改性剂,所述疏水改性剂由长链硅氧烷/氟硅烷和二乙烯三胺基丙基三甲氧基硅烷(AS)混合而成。本发明具有以下有益效果：制备出具有良好机械性能的超疏水磁性气凝胶、纸和涂层,制备过程简单环保,全程无需任何有机溶剂。(The invention discloses a super-hydrophobic magnetic mixture, which comprises CNF (carbon fiber) water suspension and Fe which are mixed with each other 3 O 4 The nano-particle and hydrophobic modifier are prepared by mixing long-chain siloxane/fluorosilane and diethylenetriaminopropyltrimethoxysilane (AS). The invention has the following beneficial effects: the super-hydrophobic magnetic aerogel, paper and coating with good mechanical properties are prepared, the preparation process is simple and environment-friendly, and no organic solvent is needed in the whole process.)
1. A superhydrophobic magnetic mixture, comprising: comprising mixing with each other an aqueous CNF suspension, Fe3O4The nano-particle and hydrophobic modifier are prepared by mixing long-chain siloxane/fluorosilane and diethylenetriaminopropyltrimethoxysilane (AS).
2. A superhydrophobic magnetic mixture, according to claim 1, wherein: the concentration of the CNF aqueous suspension is 0.1-5 wt%, and the Fe3O4The nanoparticles are added in an amount of 5-50 wt% of the aqueous CNF suspension/Fe3O4Ratio V of mixture to hydrophobic modifierCNF/Fe3O4：VHydrophobic modifier＝100：(0.5-2.5)。
3. A superhydrophobic magnetic mixture, according to claim 2, wherein: the volume ratio of the long-chain siloxane/fluorosilane to the divinyltriaminopropyltrimethoxysilane (AS) is VSiloxanes or fluorosilanes：VAS＝1：(0.5-2)。
4. A superhydrophobic magnetic mixture, according to claim 2, wherein: the CNF aqueous suspension is formed by mixing nanocellulose filaments and water, wherein the nanocellulose filaments are filamentous, the diameter of the nanocellulose filaments is 5-100nm, and the length of the nanocellulose filaments is 0.1-3 mu m.
5. The superhydrophobic magnetic mixture of claim 4, wherein: said Fe3O4The particle diameter of the nano particles is 5-100 nm.
6. The superhydrophobic magnetic mixture of claim 5, wherein: the concentration of the CNF aqueous suspension is 0.5-2 wt%, and the Fe3O4The nanoparticles are added in an amount of 10-25 wt% of the aqueous CNF suspension.
7. A superhydrophobic magnetic mixture, according to claim 3, wherein: the long-chain siloxane/fluorosilane in the hydrophobic modifier is at least one of octyl trimethoxy silane (OTMS), octyl triethoxysilane, 1H,2H,2H, -perfluorooctyl triethoxysilane (POTS), 1H,2H, 2H-perfluorodecyl triethoxysilane (PDTS), 1H,2H, 2H-perfluorooctyl trichlorosilane (PFCTS) and 1H,1H,2H, 2H-perfluorodecyl trichlorosilane (PFDTS).
8. A method of preparing a superhydrophobic magnetic mixture according to any one of claims 1-7, characterized by: the method comprises the following steps:
1) mixing aqueous CNF suspension and Fe3O4Mixing the nanoparticles, adjusting pH to 7-14, stirring for more than 5min to obtain CNF/Fe3O4Mixing;
2) then the CNF/Fe obtained in the step 1) is added3O4The mixture is mixed with a hydrophobic modifier according to a certain proportion and stirred for 3-10h to prepare CNF/Fe3O4And (3) modifying the mixture.
9. The method of claim 8, wherein the method comprises the steps of: CNF/Fe in the step 1)3O4The pH value of the mixture is 8-11, and the stirring time is 20-30 min; CNF/Fe in the step 2)3O4The stirring time of the mixture and the hydrophobic modifier is 4-8 h.
10. The application of the super-hydrophobic magnetic mixture is characterized in that: use of the CNF/Fe of claim 8 or 93O4The modified mixture is used for respectively preparing the super-hydrophobic magnetic aerogel, the super-hydrophobic magnetic paper and the super-hydrophobic magnetic coating, and specifically comprises the following steps:
1) super-hydrophobic magnetic aerogel:
the CNF/Fe3O4Molding the modified mixture by a freeze dryer, and drying in a high-temperature oven for more than 10min at the temperature of 150-;
2) preparing super-hydrophobic magnetic paper:
subjecting the CNF/Fe3O4Filling the modified mixture into a sand core funnel, performing suction filtration molding, and then drying in a high-temperature oven for more than 5min at the temperature of 150-;
3) preparing a super-hydrophobic magnetic coating:
subjecting the CNF/Fe3O4And treating the modified mixture to the surface of a base material, and then drying the base material in a high-temperature oven for more than 5min at the temperature of 150 ℃ and 200 ℃, wherein the base material is any solid material, and the treatment to the surface of the base material can be at least one of spraying, coating and dipping.
Technical Field
The invention relates to the field of functional materials, in particular to a super-hydrophobic magnetic mixture and a preparation method and application thereof.
Background
As a natural polymer with large specific surface area, high length-diameter ratio and natural degradability, nano cellulose fiber (CNF) is a major concern in recent years for the preparation of CNF-based functional materials. The CNF-based super-hydrophobic magnetic material has huge potential application in the fields of oil-water separation, electromagnetic shielding, self-cleaning and the like. The preparation is mainly realized by dispersing inorganic magnetic particles in a CNF material and then carrying out a super-hydrophobic modification method.
However, the problems faced by the current preparation process are that the preparation process is not environment-friendly enough, organic solvents are commonly used in the super-hydrophobic modification process, and the binding force between CNF and inorganic magnetic particles is weak, so that the mechanical property is poor, and the further practical application of the CNF is hindered. Therefore, green preparation of CNF-based superhydrophobic magnetic materials with good mechanical properties is an urgent need.
Disclosure of Invention
The invention aims to provide a super-hydrophobic magnetic mixture, a preparation method and application thereof, and the super-hydrophobic magnetic aerogel, paper and a coating with good mechanical properties are prepared, the preparation process is simple and environment-friendly, and no organic solvent is needed in the whole process.
The technical purpose of the invention is realized by the following technical scheme: a super-hydrophobic magnetic mixture comprises CNF aqueous suspension and Fe3O4Nanoparticles and hydrophobic modifiersIs prepared by mixing long-chain siloxane/fluorosilane and divinyltriaminopropyltrimethoxysilane (AS).
The invention is further configured to: the concentration of the CNF aqueous suspension is 0.1-5 wt%, and the Fe3O4The nanoparticles are added in an amount of 5-50 wt% of the aqueous CNF suspension/Fe3O4Ratio V of mixture to hydrophobic modifierCNF/Fe3O4：VHydrophobic modifier＝100：(0.5-2.5)。
The invention is further configured to: the volume ratio of the long-chain siloxane/fluorosilane to the divinyltriaminopropyltrimethoxysilane (AS) is VSiloxanes or fluorosilanes：VAS＝1：(0.5-2)。
The invention is further configured to: the CNF aqueous suspension is formed by mixing nanocellulose filaments and water, wherein the nanocellulose filaments are filamentous, the diameter of the nanocellulose filaments is 5-100nm, and the length of the nanocellulose filaments is 0.1-3 mu m.
The invention is further configured to: said Fe3O4The particle diameter of the nano particles is 5-100 nm.
The invention is further configured to: the concentration of the CNF aqueous suspension is 0.5-2 wt%, and the Fe3O4The nanoparticles are added in an amount of 10-25 wt% of the aqueous CNF suspension.
The invention is further configured to: the long-chain siloxane/fluorosilane in the hydrophobic modifier is at least one of octyl trimethoxy silane (OTMS), octyl triethoxysilane, 1H,2H,2H, -perfluorooctyl triethoxysilane (POTS), 1H,2H, 2H-perfluorodecyl triethoxysilane (PDTS), 1H,2H, 2H-perfluorooctyl trichlorosilane (PFCTS) and 1H,1H,2H, 2H-perfluorodecyl trichlorosilane (PFDTS).
A preparation method of a super-hydrophobic magnetic mixture comprises the following steps:
1) mixing aqueous CNF suspension and Fe3O4Mixing the nanoparticles, adjusting pH to 7-14, stirring for more than 5min to obtain CNF/Fe3O4Mixing;
2) then the CNF/Fe obtained in the step 1) is added3O4The mixture is mixed with a hydrophobic modifier in a ratio of oneMixing at a certain ratio, stirring for 3-10h, and preparing CNF/Fe3O4And (3) modifying the mixture.
The inventor of the present application found through research that the water suspension of CNF and Fe3O4The nano particles are mixed and stirred at a certain pH value to form more uniform CNF/Fe3O4Mixing, adding hydrophobic modifier, and adding hydrophobic modifier to CNF and Fe3O4Hydrophobic modification is carried out, the adhesive force between the hydrophobic modification and the modified hydrophobic modification can be enhanced, and CNF/Fe with excellent hydrophobicity and magnetism is prepared3O4And (3) mixing.
The invention is further configured to: CNF/Fe in the step 1)3O4The pH value of the mixture is 8-11, and the stirring time is 20-30 min; CNF/Fe in the step 2)3O4The stirring time of the mixture and the hydrophobic modifier is 4-8 h.
The application of the super-hydrophobic magnetic mixture is characterized in that: use of the CNF/Fe of claim 8 or 93O4The modified mixture is used for respectively preparing the super-hydrophobic magnetic aerogel, the super-hydrophobic magnetic paper and the super-hydrophobic magnetic coating, and specifically comprises the following steps:
1) super-hydrophobic magnetic aerogel:
the CNF/Fe3O4Molding the modified mixture by a freeze dryer, and drying in a high-temperature oven for more than 10min at the temperature of 150-;
2) preparing super-hydrophobic magnetic paper:
subjecting the CNF/Fe3O4Filling the modified mixture into a sand core funnel, performing suction filtration molding, and then drying in a high-temperature oven for more than 5min at the temperature of 150-;
3) preparing a super-hydrophobic magnetic coating:
subjecting the CNF/Fe3O4And treating the modified mixture to the surface of a base material, and then drying the base material in a high-temperature oven for more than 5min at the temperature of 150 ℃ and 200 ℃, wherein the base material is any solid material, and the treatment to the surface of the base material can be at least one of spraying, coating and dipping.
The invention is further configured to: the time for drying in the high-temperature drying oven in the super-hydrophobic magnetic aerogel is preferably 20-30min, and the temperature is preferably 160-180 ℃.
The invention is further configured to: the time of drying in a high-temperature oven in the preparation of the super-hydrophobic magnetic paper is preferably 10-20min, and the temperature is preferably 160-180 ℃.
The invention is further configured to: the time for drying in a high-temperature oven in the preparation of the super-hydrophobic magnetic coating is preferably 10-20min, and the temperature is preferably 160-180 ℃.
The inventor of the application finds that CNF/Fe3O4The modified mixture can be used for preparing super-hydrophobic magnetic aerogel, paper and coatings by different processes, and can be CNF and Fe3O4The adhesive force between the two is enhanced, and CNF/Fe with excellent hydrophobicity and magnetism is prepared3O4A material. Specifically, the following are mentioned: the freezing and forming in the step 1) can be carried out by freezing with liquid nitrogen and pouring CNF/Fe3O4Placing the copper mold of the modified mixture in liquid nitrogen for 5-30min, preferably 10-15min, wherein the height of the liquid nitrogen is about one fourth of the height of the mold; or freezing with ultralow temperature refrigerator to pour CNF/Fe3O4The modified mixture copper mold is placed in an ultra-low temperature refrigerator at the temperature of between 40 ℃ below zero and 5 ℃ below zero for 15 to 40 hours, preferably the temperature of the low temperature refrigerator is between 30 ℃ below zero and 20 ℃ below zero, and the freezing time is 20 to 30 hours.
The invention is further configured to: drying in a freeze dryer in the step 1), wherein the parameters are set to be-70 to-55 ℃, the vacuum degree is 0-2Pa and the drying time is 60-96 h.
The invention is further configured to: the base material in the step 3) can be solid materials such as wood, aluminum alloy, paper or cloth.
In conclusion, the invention has the following beneficial effects: as the long-chain siloxane/fluorosilane and AS are not organic solvents, the process for preparing the super-hydrophobic magnetic mixture is simple and environment-friendly, and no organic solvent is needed in the whole process. Due to both CNF and Fe3O4The hydroxyl on the surface of the nanoparticle has high activity and is easily modified by a hydrophobic modifier, so that lower surface free energy is realized. In addition, Fe can be increased3O4Between the nanoparticle and CNFAdhesion, reduction or avoidance of Fe3O4The shedding of the nanoparticles occurs during use. On the other hand, the CNF has large length-diameter ratio and high specific surface area, is easy to construct a network structure, and has good magnetic Fe3O4The nano-carbon nano-particles are attached to the CNF surface, and the construction of the super-hydrophobic surface roughness is facilitated.
CNF/Fe of the invention3O4The preparation process of the materials such as the super-hydrophobic magnetic aerogel, the paper, the coating and the like is simple and convenient to operate. CNF/Fe prepared by the invention3O4The super-hydrophobic magnetic material has water contact angles of more than 150 degrees and rolling angles of less than 10 degrees; all have good magnetism and can be adsorbed by a magnet; and with unmodified CNF/Fe3O4Materials comparison, CNF and Fe3O4The binding force between the two parts is obviously improved.
Drawings
Fig. 1 is a structural microstructure of a pure CNF aerogel in the present invention;
FIG. 2 is a microstructure diagram of a CNF aerogel structure after adding a hydrophobic modifier in the present invention;
fig. 3 is a schematic diagram of the microstructure of Fe after the energy spectrum analysis of fig. 2.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
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