CN107674236B - Super-amphiphilic polyurethane foam material and preparation method thereof - Google Patents
Super-amphiphilic polyurethane foam material and preparation method thereof Download PDFInfo
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- CN107674236B CN107674236B CN201711081325.7A CN201711081325A CN107674236B CN 107674236 B CN107674236 B CN 107674236B CN 201711081325 A CN201711081325 A CN 201711081325A CN 107674236 B CN107674236 B CN 107674236B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/365—Coating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
The invention discloses a super-amphiphilic polyurethane foam material and a preparation method thereof, belonging to the technical field of functional composite materials. The dispersion liquid of the nano-cellulose and graphene powder is respectively coated on the surface of the polyurethane sponge by a dip-coating method according to the sequence, so that the super-amphiphilic surface with the synergistic effect of the nano-cellulose and the graphene is obtained, and water and oil can be rapidly adsorbed. The contact angles of the super-amphiphilic polyurethane foam material prepared by the method of the invention to water and oil are zero. The discovery of the super-amphiphilic surface provides a foundation for developing a new material with a special surface wettability and application thereof.
Description
Technical Field
The invention relates to the technical field of functional composite materials, in particular to a preparation method for preparing a super-amphiphilic polyurethane foam material by the synergistic effect of nano-cellulose and graphene.
Background
Graphene has excellent mechanical, electrical, magnetic, thermal, and optical properties, making it the most promising carbon nanomaterial. The graphene has hydrophobic property due to the structural characteristics, and the super-hydrophobic property can be easily obtained through shape control. The thickness of the graphene is only one or a few carbon atom layers, and the specific surface area of the graphene is 2630m2The solid adsorbent has good chemical stability, so that the solid adsorbent attracts more attention in the aspect of oil and organic reagent adsorption. Graphene foam has higher adsorption capacity due to its low density and large surface area, soThe graphene network structure is of great interest in catalysis and energy storage material research.
At present, foam nickel is used as a substrate, graphene is deposited on the substrate by using a chemical vapor deposition/electrochemical deposition method, and then the foam nickel substrate is corroded, so that a three-dimensional porous graphene structure can be obtained. The chemical vapor deposition equipment involved in the method is expensive, the process is complicated, a large amount of chemical reagents are used in the corrosion and electrochemical processes, and the method is not suitable for industrial mass production. The porous three-dimensional graphene foam can be directly obtained by freeze drying the aqueous graphene oxide solution, and has hydrophobic property and good oil absorption property. The graphene oxide is obtained by oxidizing graphite with a strong oxidant and then reducing the oxidized graphite, the preparation process is complex, and meanwhile, the three-dimensional structure obtained by adopting a freeze drying method is poor in uniformity and is not suitable for practical application. In view of the hydrophobicity of graphene, the obtained graphene three-dimensional structure is basically a hydrophobic material, the oil absorption effect is good, and the graphene three-dimensional structure has potential application in the field of oil-water separation.
Recently, the task group of Chenxi professor of Xiamen university firstly takes graphene oxide as an initial material, selects polyhydroxy phytic acid as a gel, a doping agent and a surface modifier, obtains a novel super-hydrophilic and super-oleophilic three-dimensional graphene foam (PAGF) by a hydrothermal synthesis method, and the obtained super-amphiphilic PAGF is loose and porous in the interior, has zero contact angle to water and oil, has the amphiphilic characteristic of super-infiltration to water/oil, and initiates the research on super-amphiphilic graphene-based materials. The method is also a first time to synthesize a three-dimensional graphene material with super-amphiphilic performance (Angew. chem. int. Ed. (DOI:10.1002/ange.201511064), but the hydrothermal method adopted by the method is complex in operation process, and the size of a sample is not easy to control.
Disclosure of Invention
The invention aims to provide a super-amphiphilic polyurethane foam material and a preparation method thereof. Meanwhile, the sample size is not limited, and the method has industrial application prospect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a super-amphiphilic polyurethane foam material comprises the steps of sequentially coating nano-cellulose and graphene on polyurethane sponge, and drying to obtain the super-amphiphilic polyurethane foam material. The method specifically comprises the following steps:
(1) preparing a nano-cellulose aqueous dispersion liquid:
dispersing nano-cellulose into water, and performing ultrasonic treatment for 10-60min to obtain nano-cellulose aqueous dispersion liquid, wherein the content of the nano-cellulose is 0.25-1.0 wt%;
(2) pre-coating of nanocellulose: soaking the polyurethane sponge in the nano-cellulose aqueous dispersion for 10-60min, taking out and drying to obtain the nano-cellulose coated polyurethane sponge;
(3) preparing a super-amphiphilic polyurethane foam material:
and (3) soaking the polyurethane sponge coated with the nano-cellulose in the graphene dispersion liquid for 10-60min, taking out and drying to obtain the super-amphiphilic polyurethane foam material.
The nano-cellulose is prepared by chemically hydrolyzing plant fibers, and the preparation process comprises the following steps: putting the plant fiber into 5 wt% NaOH solution, carrying out oil bath at 95 ℃ for 2h, then washing with water until the pH value of the washing solution is neutral, and drying; weighing 4g of the treated fiber, placing the fiber in 200mL of 50-60 wt% sulfuric acid solution, carrying out oil bath for 4h at 55 ℃ under the stirring condition, centrifuging to obtain a nano-cellulose solution, and drying to obtain the nano-cellulose;
the polyurethane sponge is cleaned before use, and the treatment process comprises the following steps: cutting the polyurethane sponge into blocks with required sizes, then sequentially cleaning the blocks by using ethanol and distilled water, and drying the blocks for later use.
In the step (3), the preparation process of the graphene dispersion liquid is as follows: according to the graphene: water ═ 1 g: (200-.
The super-amphiphilic polyurethane foam material prepared by the method has the super-amphiphilic performance because the nano-cellulose/graphene composite layers are uniformly distributed on the surface of the continuous network framework of the polyurethane sponge; can adsorb water and oil simultaneously.
The polyurethane foam has zero contact angles with water and oil.
The invention has the following advantages and beneficial effects:
1. the invention provides a polyurethane foam material with Super-amphiphilic property on the surface, which is characterized in that flexible porous polyurethane sponge is used as a continuous network, dispersion liquid of nano-cellulose and commercialized graphene powder is respectively coated on the surface of the polyurethane sponge by a dip-coating method according to the sequence, a Super-amphiphilic (Super-amphiphilic) surface with synergistic effect of the nano-cellulose and the graphene is obtained, and water and oil can be rapidly adsorbed. The contact angles of the super-amphiphilic polyurethane foam material prepared by the method of the invention to water and oil are zero. The discovery of the super-amphiphilic surface (nano interface material) provides a foundation for developing a new material with a special wettability on the surface and the application thereof, has great value for the deep research of material surface science, and has great significance for the development and application of the new material.
2. Compared with the super-amphiphilic graphene foam obtained by a hydrothermal method of Xiamen university, the method has the advantages of easy operation process, excellent mechanical property stability of the obtained sample, good elasticity, reusability and long service life. Meanwhile, the sample size is not limited, and the method has industrial application prospect.
3. The polyurethane sponge has the advantages of rich pore structures, good elasticity and the like. The raw materials for producing the nano-cellulose have wide sources and are renewable resources.
4. The raw material of the graphene used in the invention is commercial graphene powder in the market, a new idea is provided for the direct utilization of the graphene, the application and development of related products of the graphene are promoted, and the problem of excessive graphene productivity is solved.
Description of the drawings:
FIG. 1 is a scanning electron micrograph of the polyurethane material prepared in comparative example 1.
FIG. 2 is a scanning electron micrograph of a raw polyurethane sponge, comparative examples 2 to 3, example 1 and example 4, and polyurethane foams prepared therefrom; wherein: (a) raw polyurethane sponge; (b) comparative example 2; (c) comparative example 3; (d) example 1; (e) example 4.
FIG. 3 is a contact angle with water of the polyurethane foams prepared in comparative examples 2 to 3, example 1 and example 4; wherein: CGPF-1 is comparative example 2, CGPF-2 is example 1, CGPF-4 is example 4, and CGPF-4 is comparative example 3.
FIG. 4 is a photograph showing the adsorption rates of soybean oil and water (dyed respectively) to the polyurethane foams prepared in examples 1 and 4; wherein: (a) and (c) and (e) are the polyurethane foams prepared in example 1; (b) and (d) and (f) the polyurethane foam prepared in example 4.
The specific implementation mode is as follows:
the present invention is described in detail below with reference to the accompanying drawings.
In the following examples or comparative examples, nanocellulose was prepared by chemical hydrolysis of plant fibers (corn stover, wood flour, flax fiber, etc.) as follows:
placing the bleached plant fiber in a 5 wt% NaOH solution, carrying out oil bath at 95 ℃ for 2h, then washing with a large amount of water until the pH value of the washing liquid is neutral, and drying; weighing 4g of the treated fiber, placing the fiber in 200mL of 50-60 wt% sulfuric acid solution, carrying out oil bath for 4h at 55 ℃ under the stirring condition, centrifuging to obtain the nano-cellulose, and drying for later use.
The polyurethane sponge is cleaned and dried before use, and the cleaning process is as follows: cutting the polyurethane sponge into blocks with certain sizes, then sequentially cleaning the blocks by using alcohol and distilled water, and drying the blocks for later use.
The preparation process of the graphene dispersion liquid comprises the following steps: according to the graphene: water ═ 1 g: (200) adding graphene into a beaker filled with water according to the proportion of 800mL, stirring vigorously for 30min, and then carrying out ultrasonic treatment for 1-36h to obtain the graphene dispersion liquid.
Example 1
The process for preparing the super-amphiphilic polyurethane foam material comprises the steps of coating nano-cellulose in advance and then dip-coating graphene, wherein the nano-cellulose is prepared by chemically hydrolyzing corn straws. The specific process is as follows:
putting the nano-cellulose into a beaker, adding tap water to a constant volume, and carrying out ultrasonic treatment for 60min under the condition of 500W of power to obtain a uniform nano-cellulose aqueous dispersion liquid, wherein the content of the nano-cellulose is 0.5 wt%.
And soaking the cleaned and dried polyurethane sponge in the nano-cellulose aqueous dispersion for 30min, taking out, fully drying in a 40 ℃ oven, and taking out to obtain the nano-cellulose coated polyurethane sponge. And then soaking the polyurethane sponge coated with the nano-cellulose in graphene dispersion liquid (1g of graphene/800 mL of water) for 40min, and drying at 20 ℃ to obtain the super-amphiphilic polyurethane foam material.
Example 2
The process for preparing the super-amphiphilic polyurethane foam material comprises the steps of coating nano-cellulose in advance and then dip-coating graphene, wherein the nano-cellulose is prepared by chemically hydrolyzing wood flour. The specific process is as follows:
putting the nano-cellulose into a beaker, adding deionized water to a constant volume, and carrying out ultrasonic treatment for 30min under the condition of 600W of power to obtain a uniform nano-cellulose aqueous dispersion liquid, wherein the nano-cellulose content is 0.6 wt%.
And soaking the cleaned and dried polyurethane sponge in the nano-cellulose aqueous dispersion for 40min, taking out, fully drying in a 50 ℃ oven, and taking out to obtain the nano-cellulose coated polyurethane sponge. And then soaking the polyurethane sponge coated with the nano-cellulose in graphene dispersion liquid (1g of graphene/300 mL of water) for 60min, and drying at 40 ℃ to obtain the super-amphiphilic polyurethane foam material.
Example 3
The process for preparing the super-amphiphilic polyurethane foam material comprises the steps of coating nano-cellulose in advance and then dip-coating graphene, wherein the nano-cellulose is prepared by chemically hydrolyzing wood flour. The specific process is as follows:
putting the nano-cellulose into a beaker, adding deionized water to a constant volume, and carrying out ultrasonic treatment for 30min under the condition of 600W of power to obtain a uniform nano-cellulose aqueous dispersion liquid, wherein the nano-cellulose content is 0.7 wt%.
And soaking the cleaned and dried polyurethane sponge in the nano-cellulose aqueous dispersion for 50min, taking out, fully drying in a 60 ℃ oven, and taking out to obtain the nano-cellulose coated polyurethane sponge. And then soaking the polyurethane sponge coated with the nano-cellulose in graphene dispersion liquid (1g of graphene/600 mL of water) for 50min, and drying at 60 ℃ to obtain the super-amphiphilic polyurethane foam material.
Example 4
The process for preparing the super-amphiphilic polyurethane foam material comprises the steps of coating nano-cellulose in advance and then dip-coating graphene, wherein the nano-cellulose is prepared by chemically hydrolyzing wood flour. The specific process is as follows:
putting the nano-cellulose into a beaker, adding deionized water to a constant volume, and carrying out ultrasonic treatment for 30min under the condition of 1000W of power to obtain a uniform nano-cellulose aqueous dispersion liquid, wherein the nano-cellulose content is 0.75 wt%.
And soaking the cleaned and dried polyurethane sponge in the nano-cellulose aqueous dispersion for 60min, taking out, fully drying in a 50 ℃ oven, and taking out to obtain the nano-cellulose coated polyurethane sponge. And then soaking the polyurethane sponge coated with the nano-cellulose in graphene dispersion liquid (1g of graphene/400 mL of water) for 40min, and drying at 40 ℃ to obtain the super-amphiphilic polyurethane foam material.
Comparative example 1
The polyurethane material prepared by the comparative example is not coated with nanocellulose in advance, so that the surface of the polyurethane only contains graphene and does not contain nanocellulose. The preparation process comprises the following steps:
adding 1g of graphene into a beaker containing 400mL of water, stirring vigorously for 30min, and then carrying out ultrasonic treatment for 36h to obtain a graphene dispersion liquid. Putting the cleaned polyurethane sponge into the graphene dispersion liquid, performing ultrasonic treatment for 40min, drying at 50 ℃ and taking out a sample, wherein fig. 1 is a scanning photo of the sample, and it can be seen that the graphene in the polyurethane sponge is not uniformly dispersed, so that the surface of the polyurethane sponge is exposed.
Comparative example 2
The polyurethane material prepared by the comparative example is coated with the low-concentration nanocellulose in advance and then coated with the graphene, so that the graphene content of the polyurethane surface is low, wherein the nanocellulose is prepared by chemically hydrolyzing flax fibers. The preparation process comprises the following steps:
the preparation process of the nano-cellulose aqueous dispersion liquid comprises the following steps: putting the nano-cellulose into a beaker, adding deionized water to a constant volume, and performing ultrasonic treatment for 10min under the condition of 100W of power to obtain a uniform nano-cellulose dispersion liquid, wherein the nano-cellulose content is 0.25 wt%.
And soaking the cleaned polyurethane sponge in the nano-cellulose aqueous dispersion for 10min, taking out, and drying in an oven at 60 ℃ until the weight is not changed to obtain the nano-cellulose coated polyurethane sponge. Then, the polyurethane sponge coated with the nano-cellulose is soaked in graphene dispersion liquid (1g of graphene/200 mL of water) for 10min, and then dried at 50 ℃ until the weight is not changed, so that the hydrophobic polyurethane sponge is obtained.
Comparative example 3
The polyurethane material prepared by the comparative example is coated with the nanocellulose with higher concentration in advance and then coated with the graphene, so that the graphene content on the surface of the polyurethane is very high, and the whole nanocellulose layer is basically covered, wherein the nanocellulose is prepared by chemically hydrolyzing the xanthoceras sorbifolia shells. The preparation process comprises the following steps:
the preparation process of the nano-cellulose aqueous dispersion liquid comprises the following steps: putting the nano-cellulose into a beaker, adding tap water to a constant volume, and carrying out ultrasonic treatment for 20min under the condition of power of 800W to obtain a uniform nano-cellulose dispersion liquid, wherein the nano-cellulose content is 1.0 wt%.
And soaking the cleaned polyurethane sponge in the nano-cellulose aqueous dispersion for 30min, taking out, and drying in a 50 ℃ oven until the weight is not changed to obtain the nano-cellulose coated polyurethane sponge. Then, the polyurethane sponge coated with the nano-cellulose is soaked in graphene dispersion liquid (1g of graphene/500 mL of water) for 20min, and then dried at 60 ℃ until the weight is not changed, so that the hydrophobic polyurethane sponge is obtained.
The polyurethane foams prepared in comparative example 1, pure polyurethane sponge, comparative examples 2 to 3 and examples 1 to 4 were subjected to microstructural analysis using a scanning electron microscope, and the obtained morphologies were as shown in FIGS. 1 to 2.
The polyurethane foams prepared in comparative examples 2 to 3 and examples 1 to 4 were subjected to a contact angle with water measurement using a contact angle measuring instrument, and the photograph of the contact angle obtained is shown in FIG. 3.
The absorption speed of the soybean oil is tested by using the graphene @ polyurethane foam materials prepared in the examples 1 and 4, and as can be seen from fig. 4, the absorption speed is very high, and the absorption process can be completed within 0.2 s.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of super-amphiphilic polyurethane foam material is characterized by comprising the following steps: sequentially coating nano-cellulose and graphene on polyurethane sponge, and drying to obtain the super-amphiphilic polyurethane foam material; the method specifically comprises the following steps:
(1) preparing a nano-cellulose aqueous dispersion liquid:
dispersing nano-cellulose into water, and performing ultrasonic treatment for 10-60min to obtain nano-cellulose aqueous dispersion liquid, wherein the content of the nano-cellulose is 0.5-0.75 wt%;
(2) pre-coating of nanocellulose: soaking the polyurethane sponge in the nano-cellulose aqueous dispersion for 10-60min, taking out and drying to obtain the nano-cellulose coated polyurethane sponge;
(3) preparing a super-amphiphilic polyurethane foam material:
and (3) soaking the polyurethane sponge coated with the nano-cellulose in the graphene dispersion liquid for 10-60min, taking out and drying to obtain the super-amphiphilic polyurethane foam material.
2. The method of preparing a super-amphiphilic polyurethane foam material as claimed in claim 1, wherein: the nanocellulose is prepared by chemical hydrolysis of plant fibres.
3. The method of preparing a super-amphiphilic polyurethane foam material as claimed in claim 1, wherein: the preparation process of the nano-cellulose comprises the following steps: putting the plant fiber into 5 wt% NaOH solution, carrying out oil bath at 95 ℃ for 2h, then washing with water until the pH value of the washing solution is neutral, and drying; weighing 4g of the treated fiber, placing the fiber in 200mL of 50-60 wt% sulfuric acid solution, carrying out oil bath for 4h at 55 ℃ under the stirring condition, centrifuging to obtain a nano-cellulose solution, and drying to obtain the nano-cellulose.
4. The method of preparing a super-amphiphilic polyurethane foam material as claimed in claim 1, wherein: the polyurethane sponge is cleaned before use, and the treatment process comprises the following steps: cutting the polyurethane sponge into blocks with required sizes, then sequentially cleaning the blocks by using ethanol and distilled water, and drying the blocks for later use.
5. The method of preparing a super-amphiphilic polyurethane foam material as claimed in claim 1, wherein: in the step (3), the preparation process of the graphene dispersion liquid is as follows: according to the graphene: water ═ 1 g: (200-.
6. A super-amphiphilic polyurethane foam prepared according to the method of any one of claims 1-5.
7. The super-amphiphilic polyurethane foam material of claim 6, wherein: the polyurethane foam material is prepared by uniformly distributing nano-cellulose and graphene on the surface of a continuous network framework of polyurethane sponge, and has super-amphiphilic property; can adsorb water and oil simultaneously.
8. The super-amphiphilic polyurethane foam material of claim 6, wherein: the polyurethane foam has zero contact angles with water and oil.
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