CN116285379A - Super-hydrophobic modified nano material and preparation method and application thereof - Google Patents

Super-hydrophobic modified nano material and preparation method and application thereof Download PDF

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CN116285379A
CN116285379A CN202211613108.9A CN202211613108A CN116285379A CN 116285379 A CN116285379 A CN 116285379A CN 202211613108 A CN202211613108 A CN 202211613108A CN 116285379 A CN116285379 A CN 116285379A
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cardanol
acrylic
nano material
castor oil
super
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张猛
赵宝正
宋飞
周永红
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Institute of Chemical Industry of Forest Products of CAF
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
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    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/168After-treatment
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20Controlling water pollution; Waste water treatment
    • Y02A20/204Keeping clear the surface of open water from oil spills

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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a super-hydrophobic modified nano material, a preparation method and application thereof, and belongs to the field of super-hydrophobic materials. According to the invention, the amino-containing nano material and the acrylic castor oil, the acrylic cardanol or the cardanol glycidyl ether are mixed and reacted in a solvent, the reaction temperature is 0-50 ℃, and the reaction time is 6-36 hours, so that the bio-based super-hydrophobic nano material is obtained. According to the invention, natural renewable, environment-friendly and low-cost castor oil or cardanol is used as a raw material, acrylic castor oil, acrylic cardanol and cardanol glycidyl ether are obtained through reaction, then the amino-containing nano material is subjected to hydrophobic modification, the modified nano material has good hydrophobic performance, the stable contact angle is up to 160 ℃ or more, the oil-water separation efficiency is up to about 99%, and the modified nano material has good application prospects in the fields of oil-water separation, self-cleaning, medicine, ice coating prevention and the like.

Description

Super-hydrophobic modified nano material and preparation method and application thereof
Technical Field
The invention belongs to the field of super-hydrophobic materials, and particularly relates to a super-hydrophobic modified nano material, and a preparation method and application thereof.
Background
In recent years, nano materials such as metal organic frameworks, carbon nanotubes, graphene, silicon dioxide, titanium dioxide and the like are widely applied to the fields of nano electronic devices, medical health, aerospace, biotechnology and the like. In order to improve the chemical reactivity, dispersibility and other properties of the nanomaterial, chemical modification is required. For example, the specific surface area and the surface energy of the carbon nanotubes are large, the carbon nanotubes are agglomerated and bent and entangled together by stronger van der Waals force, the reinforcing effect of the carbon nanotubes on the composite material is reduced, and the carbon nanotubes can be subjected to amination chemical modification in order to uniformly disperse the carbon nanotubes in a polymer matrix and form stronger interface bonding strength with the polymer; for another example, in order to ensure the interface combination of graphene and a matrix material, or to utilize the functional groups on the surface of graphene to perform a composite reaction with other materials, amino groups, carboxyl groups and other groups can be introduced on the surface of graphene through chemical modification. In general, modification of the nanomaterial may better perform the nanomaterial itself.
However, these chemically modified nanomaterials have poor stability in harsh environments such as strong acids, strong bases or high salts, and are greatly limited in application in some special fields, because the hydrophobic properties of the materials are poor (the contact angle is generally lower than 90 °), so that the pore channels are in contact with water in a large amount, and the surfaces of the materials are soaked by the water to reduce the properties.
Therefore, improvements are needed.
Disclosure of Invention
The present invention aims at providing one kind of nanometer material modifying super hydrophobic method with castor oil or cardanol as material and with the material being natural, environment friendly and low in cost.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the super-hydrophobic modified nano material comprises the steps of mixing and reacting the amino-containing nano material with acrylic castor oil, acrylic cardanol or cardanol glycidyl ether in a solvent at the reaction temperature of 0-50 ℃ for 6-36 h to obtain the bio-based super-hydrophobic nano material.
Preferably, the reaction temperature is 25 ℃, and the reaction time is 12-24 hours.
Preferably, the mass ratio of the amino group-containing nano material to the acrylic castor oil, the acrylic cardanol or the cardanol glycidyl ether is 1:5-1:10.
Preferably, the solvent is ethanol.
Preferably, the preparation method of the acrylic castor oil and the acrylic cardanol comprises the steps of carrying out esterification reaction on castor oil or cardanol and acrylic acid, and separating and purifying to obtain the acrylic castor oil or the acrylic cardanol.
Preferably, the preparation method of the cardanol glycidyl ether comprises the steps of carrying out substitution reaction on cardanol and epichlorohydrin, and separating and purifying to obtain the cardanol glycidyl ether.
Preferably, the nano material containing amino is UiO-66-NH 2 One or more of aminated carbon nanotubes, aminated graphene, aminated silicon dioxide and aminated titanium dioxide.
The super-hydrophobic modified nano material prepared by the method.
The super-hydrophobic modified nano material prepared by the preparation method is applied to oil-water separation, self-cleaning, medical science or ice coating prevention.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, natural renewable, environment-friendly and low-cost castor oil or cardanol is used as a raw material, acrylic castor oil, acrylic cardanol and cardanol glycidyl ether are obtained through reaction, then the amino-containing nano material is subjected to hydrophobic modification, the modified nano material has good hydrophobic performance, the stable contact angle is up to 160 ℃ or more, the oil-water separation efficiency is up to about 99%, and the modified nano material has good application prospects in the fields of oil-water separation, self-cleaning, medicine, ice coating prevention and the like.
(2) The preparation method provided by the invention has extremely strong universality, is suitable for the superhydrophobic modification of nano materials such as metal organic frameworks, carbon nanotubes, graphene, silicon dioxide, titanium dioxide and the like, and has important theoretical and practical significance for the preparation of the superhydrophobic nano materials.
(3) The preparation method has the advantages of simple process, low cost, strong operability and easy implementation.
Drawings
FIG. 1 is a schematic reaction diagram of an acrylic castor oil of the present invention;
FIG. 2 is a schematic illustration of the reaction of cardanol acrylate of the present invention;
FIG. 3 is a schematic illustration of the reaction of cardanol glycidyl ether of the present invention;
FIG. 4 is a superhydrophobic UiO-66-NH of example 1 of the invention 2 Contact angle test patterns of (2);
FIG. 5 is a superhydrophobic UiO-66-NH of example 2 of the invention 2 Contact angle test patterns of (2);
FIG. 6 is a superhydrophobic UiO-66-NH of example 3 of the invention 2 Contact angle test patterns of (2);
FIG. 7 is a graph showing the contact angle test of the super-hydrophobic aminated carbon nanotube according to example 4 of the present invention;
FIG. 8 is a graph of contact angle measurements for the superhydrophobic aminated silica of example 5 of the invention;
FIG. 9 is a graph of contact angle measurements for superhydrophobic aminated titanium dioxide of example 6 of the invention;
FIG. 10 is a graph of the contact angle test of the superhydrophobic aminated graphene of example 7 of the present invention;
fig. 11 is a graph showing the dichloromethane separation efficiency test of the superhydrophobic nanomaterial obtained in examples 1-7 of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments.
The raw materials used in each example were derived as follows:
castor oil: shanghai Ling Peak chemical reagent Co., CAS number 8001-79-4;
cardanol: jiangsu Leen environmental protection technologies Co., ltd., industrial purity, CAS number 501-24-6;
UiO-66-NH 2 : jiangsu Xianfeng nano materials science and technology Co., ltd., CAS number 1072413-89-8, number XFF32-2;
aminated carbon nanotubes: jiangsu Xianfeng nanomaterial technologies Co., ltd., CAS number 1333-86-4, number XFM62;
aminated graphene: jiangsu Xianfeng nano materials science and technology Co., ltd., CAS number 7440-44-0, cargo number 100017;
aminated silica: jiangsu Xianfeng nanomaterials science and technology Co., ltd., size: 150nm, cat: 103747;
aminated titanium dioxide: shanghai screening quasi-biotechnology Co., ltd., size: 100nm, cat No.: ZMN-220320-10;
the rest raw materials are all conventional commercial chemicals.
Example 1
Referring to the preparation process of the acrylic castor oil shown in fig. 1: heating castor oil and hydroquinone of polymerization inhibitor to 160 ℃ under the protection of nitrogen, dropwise adding acrylic acid, heating to 230 ℃, continuing to react for 3.5 h, and cooling to obtain crude product of the acrylic castor oil, wherein the mass ratio of the castor oil to the acrylic acid to the hydroquinone is 50:12:3; pulverizing, dissolving in petroleum ether/ethyl acetate mixed solvent with volume ratio of 95:5, heating to reflux solvent of 3h, cooling to room temperature, stirring for 3h, vacuum filtering, and recrystallizing in ethyl acetate to obtain acrylic castor oil.
Acrylic castor oil, uiO-66-NH 2 Adding the mixture into a beaker filled with 20mL of absolute ethyl alcohol, reacting for 12 hours at room temperature, and obtaining the super-hydrophobic UiO-66-NH after the reaction is finished 2 Crude product, wherein the acrylic castor oil and UiO-66-NH 2 The mass ratio of (2) is 5:1; usingWashing with anhydrous ethanol for several times, and vacuum drying at 60deg.C to obtain superhydrophobic UiO-66-NH 2
Example 2
Referring to the preparation process of cardanol acrylate shown in fig. 2: heating cardanol and hydroquinone serving as a polymerization inhibitor to 160 ℃ under the protection of nitrogen, dropwise adding acrylic acid, heating to 230 ℃, continuing to react for 3.5 h, and cooling to obtain a crude product of the cardanol acrylate, wherein the mass ratio of the cardanol to the acrylic acid to the hydroquinone is 50:12:3; pulverizing, dissolving in a petroleum ether/ethyl acetate mixed solvent with a volume ratio of 95:5, heating to reflux the solvent to 3h, cooling to room temperature, continuously stirring for 3h, vacuum filtering, and recrystallizing in ethyl acetate to obtain the acrylic cardanol.
Cardanol acrylate, uiO-66-NH 2 Adding the mixture into a beaker filled with 20mL of absolute ethyl alcohol, reacting for 12 hours at room temperature, and obtaining the super-hydrophobic UiO-66-NH after the reaction is finished 2 Crude product, wherein cardanol acrylate and UiO-66-NH 2 The mass ratio of (2) is 5:1; washing with absolute ethanol for several times, and vacuum drying at 60deg.C to obtain superhydrophobic UiO-66-NH 2
Example 3
Referring to the preparation process of cardanol glycidyl ether shown in fig. 3: heating cardanol, tetrabutylammonium bromide and epoxy chloropropane to 50-55 ℃ under the protection of nitrogen, dropwise adding a sodium hydroxide solution with the concentration of 50% for 3-4 h, heating to 70-80 ℃ and reacting for 1-3 h, and sequentially performing rotary evaporation, suction filtration and water washing to obtain cardanol glycidyl ether.
Cardanol glycidyl ether and UiO-66-NH 2 Adding the mixture into a beaker filled with 20mL of absolute ethyl alcohol, reacting for 12 hours at room temperature, and obtaining the super-hydrophobic UiO-66-NH after the reaction is finished 2 Crude product, wherein cardanol glycidyl ether and UiO-66-NH 2 The mass ratio of (2) to (1); washing the crude product with absolute ethanol for several times, and vacuum drying at 60deg.C to obtain superhydrophobic UiO-66-NH 2
Example 4
The same procedure as in example 1 was used to prepare the acrylic castor oil.
Adding the acrylic castor oil and the aminated carbon nanotube into a beaker filled with 20mL of absolute ethyl alcohol, and reacting for 12 hours at room temperature to obtain a super-hydrophobic aminated carbon nanotube crude product after the reaction is finished, wherein the mass ratio of the acrylic castor oil to the aminated carbon nanotube is 2:1; and (3) washing the crude product for a plurality of times by using absolute ethyl alcohol, and vacuum drying at 60 ℃ to obtain the super-hydrophobic aminated carbon nano tube.
Example 5
The same procedure as in example 1 was used to prepare the acrylic castor oil.
Adding the acrylic castor oil and the amination silica into a beaker filled with 20mL of absolute ethyl alcohol, and reacting for 12 hours at room temperature to obtain a super-hydrophobic amination silica crude product after the reaction is finished, wherein the mass ratio of the acrylic castor oil to the amination silica is 2:1; and (3) washing the crude product for a plurality of times by using absolute ethyl alcohol, and vacuum drying at 60 ℃ to obtain the super-hydrophobic aminated silicon dioxide.
Example 6
The same procedure as in example 1 was used to prepare the acrylic castor oil.
Adding the acrylic castor oil and the aminated titanium dioxide into a beaker filled with 20mL of absolute ethyl alcohol, and reacting for 12 hours at room temperature to obtain a super-hydrophobic aminated titanium dioxide crude product after the reaction is finished, wherein the mass ratio of the acrylic castor oil to the aminated titanium dioxide is 2:1; and (3) washing the crude product for a plurality of times by using absolute ethyl alcohol, and vacuum drying at 60 ℃ to obtain the super-hydrophobic aminated titanium dioxide.
Example 7
The same procedure as in example 1 was used to prepare the acrylic castor oil.
Adding the acrylic castor oil and the aminated graphene into a beaker filled with 20mL of absolute ethyl alcohol, and reacting for 12 hours at room temperature to obtain a super-hydrophobic aminated graphene crude product after the reaction is finished, wherein the mass ratio of the acrylic castor oil to the aminated graphene is 2:1; and (3) washing the crude product for a plurality of times by using absolute ethyl alcohol, and vacuum drying at 60 ℃ to obtain the super-hydrophobic aminated graphene.
The super-hydrophobic modified nanomaterial obtained in examples 1-7 is subjected to contact angle test, and the test method comprises the following steps: the test was performed by using a ZR-SDJ-QH6 contact angle meter manufactured by Jiangsu Defeinuo electronics Inc., and the obtained results are shown in FIGS. 4 to 10.
As can be seen from FIGS. 4 to 10, the super-hydrophobic modified nanomaterial of the present invention has a contact angle of 160 ° or more, and exhibits good super-hydrophobic properties.
The super-hydrophobic modified nanomaterial obtained in examples 1-7 is subjected to oil-water separation test, and the test method comprises the following steps: filling the super-hydrophobic modified nano material on a narrow head of an injector by taking a cotton layer as a support as a separation device, injecting a dichloromethane/water mixture into the injector, and rapidly separating the layered dichloromethane/water mixture under the gravity. The oil-water separation efficiency was the ratio of the weight of collected methylene chloride to the weight of methylene chloride before separation, and the results are shown in FIG. 11.
As can be seen from fig. 11, the superhydrophobic modified nanomaterial shows a good dichloromethane/water separation capability, and the separation efficiency is about 99%.

Claims (9)

1. A preparation method of a super-hydrophobic modified nano material is characterized in that the nano material containing amino is mixed and reacted with acrylic castor oil, acrylic cardanol or cardanol glycidyl ether in a solvent at the reaction temperature of 0-50 ℃ for 6-36 h, so that the super-hydrophobic modified nano material is obtained.
2. The preparation method according to claim 1, wherein the reaction temperature is 25 ℃ and the reaction time is 12-24 hours.
3. The preparation method of claim 1, wherein the mass ratio of the amino group-containing nanomaterial to the acrylic castor oil, the acrylic cardanol or the cardanol glycidyl ether is 1:1-1:5.
4. The method of claim 1, wherein the solvent is ethanol.
5. The preparation method of the acrylic castor oil and the acrylic cardanol according to claim 1, wherein the preparation method is characterized in that the castor oil or the cardanol is subjected to esterification reaction with acrylic acid, and the acrylic castor oil or the acrylic cardanol is obtained after separation and purification.
6. The preparation method of the cardanol glycidyl ether according to claim 1, wherein the cardanol glycidyl ether is obtained by substitution reaction of cardanol and epichlorohydrin and separation and purification.
7. The method according to claim 1, wherein the amino group-containing nanomaterial is UiO-66-NH 2 One or more of aminated carbon nanotubes, aminated graphene, aminated silicon dioxide and aminated titanium dioxide.
8. The superhydrophobic modified nanomaterial prepared by the method of any of claims 1-7.
9. The use of the superhydrophobic modified nanomaterial of claim 8 in oil-water separation, self-cleaning, medical science, or anti-icing.
CN202211613108.9A 2022-12-15 2022-12-15 Super-hydrophobic modified nano material and preparation method and application thereof Pending CN116285379A (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2008098069A1 (en) * 2007-02-06 2008-08-14 Nanodynamics, Inc. Directed migration of hydrophobic nanomaterials at surfaces
US20130062577A1 (en) * 2011-09-14 2013-03-14 National Taiwan University Carbon nanotube suspension and superhydrophobic film prepared therefrom
CN112552417A (en) * 2020-12-31 2021-03-26 中国林业科学研究院林产化学工业研究所 Castor oil modified nano-cellulose composite material and preparation method and application thereof
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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008098069A1 (en) * 2007-02-06 2008-08-14 Nanodynamics, Inc. Directed migration of hydrophobic nanomaterials at surfaces
US20130062577A1 (en) * 2011-09-14 2013-03-14 National Taiwan University Carbon nanotube suspension and superhydrophobic film prepared therefrom
CN112552417A (en) * 2020-12-31 2021-03-26 中国林业科学研究院林产化学工业研究所 Castor oil modified nano-cellulose composite material and preparation method and application thereof
CN113881323A (en) * 2021-11-22 2022-01-04 广东轻工职业技术学院 Preparation method and application of super-hydrophobic coating

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Title
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