CN111663330A - Plant tannin mediated super-hydrophobic cellulose material and preparation method and application thereof - Google Patents
Plant tannin mediated super-hydrophobic cellulose material and preparation method and application thereof Download PDFInfo
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- CN111663330A CN111663330A CN202010567132.8A CN202010567132A CN111663330A CN 111663330 A CN111663330 A CN 111663330A CN 202010567132 A CN202010567132 A CN 202010567132A CN 111663330 A CN111663330 A CN 111663330A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/238—Tannins, e.g. gallotannic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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Abstract
A super-hydrophobic cellulose material mediated by plant tannin and a preparation method and application thereof are disclosed, wherein a plant tannin aqueous solution is prepared, an alkaline solution is used for adjusting the pH value of the tannin aqueous solution, then the cellulose material is immersed in the tannin aqueous solution, soaked at room temperature, taken out, cleaned by deionized water, and placed in an oven for drying, so as to obtain the plant tannin modified cellulose material; soaking the plant tannin modified cellulose material into a tetrahydrofuran solution of functionalized POSS, soaking at room temperature, taking out, and drying in an oven to obtain the plant tannin mediated super-hydrophobic cellulose material. The super-hydrophobic cellulose material prepared by the method provided by the invention also shows super-oleophylic performance, and can be applied to the field of oil-water separation. The preparation method disclosed by the invention is simple in preparation process, the reaction can be carried out at room temperature, the source of the plant tannin is wide, the price is low, the requirements on the type and the shape of the base material are not high, the application range is wide, and the large-scale production and application are easy to realize.
Description
Technical Field
The invention belongs to the field of chemical surface engineering, and particularly relates to a plant tannin mediated super-hydrophobic cellulose material, and a preparation method and application thereof.
Background
With the decreasing petrochemical resources and the increasing environmental pollution, the development and use of new sustainable materials are becoming urgent. Cellulose is a natural polymer material with the most abundant natural resources, has the properties of low cost, no toxicity, good chemical stability, reproducibility, biodegradability, low density, strong mechanical property and the like, and has important application in the fields of fabrics, paper, green packaging materials, electronic device substrates and the like. But the surface of the cellulose material is rich in hydrophilic groups and has strong hydrophilicity. Therefore, in a humid environment, hydrogen bonds of the cellulose material are easily damaged by water molecules adsorbed on the surface, so that the mechanical property and the isolation property of the cellulose material are greatly reduced, and the application of the cellulose material in practice is severely restricted. At present, surface modification of cellulose materials to improve the hydrophobicity thereof becomes the most effective method.
The super-hydrophobic surface is a surface with a water contact angle of more than 150 degrees and a sliding angle of less than 10 degrees, and has great application value in the fields of self-cleaning and oil-water separation due to high hydrophobic property. The combination of low surface energy materials and rough structures is a basic method for realizing a super-hydrophobic surface, and researchers have succeeded in constructing a super-hydrophobic surface on a cellulose material by various methods. However, the used low surface energy materials are mostly non-renewable petrochemical resources or contain fluorine elements harmful to human bodies, and the preparation method has the defects of complex process, expensive equipment and the like, so that the application of the super-hydrophobic surface in actual life is greatly limited.
In recent years, a mussel biomimetic-based surface modification technology has become a very important method for preparing a special wettability surface. Dopamine and L-dopa in mussels have similar structures, are easily oxidized into polydopamine under the weak alkali condition, and can be tightly attached to the surface of a base material in the forms of covalent bonds, non-covalent bonds, hydrophobic bonds, pi-pi stacking and the like. Free catechol groups in the polydopamine can perform Schiff base or Michael addition reaction with compounds containing amino or sulfhydryl groups, so that the purpose of surface modification is achieved. But the high cost limits the widespread use of dopamine. Plant tannin is a secondary metabolite with a polyphenol structure widely existing in plants. Because the structure contains abundant catechol structure, the structure has similar properties with dopamine. In recent years, the dopamine-producing substance has been widely studied as a substitute for dopamine due to its wide source and low cost. However, no report has been found on the research of constructing a superhydrophobic surface on the surface of a cellulose material by using plant tannin as a binder and functionalized cage-type polysilsesquioxane (functionalized POSS) as a hydrophobic agent.
Disclosure of Invention
The technical problem to be solved is as follows: the invention overcomes the defects in the prior preparation technology and provides a plant tannin mediated super-hydrophobic cellulose material, a preparation method and application thereof.
The technical scheme is as follows: a method for preparing super-hydrophobic cellulose material mediated by plant tannin comprises the following steps: preparing a plant tannin aqueous solution, adjusting the pH value of the tannin aqueous solution to 7-10 by using an alkaline solution, then soaking the cellulose material into the tannin aqueous solution, soaking at room temperature for 2-12 h, taking out, cleaning with deionized water, and drying in an oven at 40-60 ℃ to obtain the plant tannin modified cellulose material; soaking the plant tannin modified cellulose material into a tetrahydrofuran solution of functionalized POSS (polyhedral oligomeric silsesquioxane), soaking for 2-12 h at room temperature, taking out, and drying in an oven at 60-120 ℃ for 6-12 h to obtain the plant tannin mediated super-hydrophobic cellulose material.
Preferably, the cellulose material is one of cotton fabric, ramie fabric, absorbent cotton, kapok fiber, filter paper, A4 paper and wood.
Preferably, the concentration of the plant tannin aqueous solution is 1-20 mg/mL.
Preferably, the functionalized POSS is one of aminopropylisobutyl-POSS, aminoethylaminopropylisobutyl-POSS, octaaminophenyl-POSS or mercaptopropylisobutyl-POSS, and the concentration of the functionalized POSS in tetrahydrofuran is 1-50 mg/mL.
Preferably, the alkaline solution is a NaOH solution.
The plant tannin mediated super-hydrophobic cellulose material prepared by the preparation method.
The super-hydrophobic cellulose material is applied to oil-water separation.
The super-hydrophobic cellulose material is applied to preparing oil-water separation products.
Has the advantages that: the method of the invention adopts plant tannin with wide sources and low price as the binder, makes up the defects of the existing method of using dopamine as the binder, can greatly reduce the production cost, and is beneficial to the practical application of the super-hydrophobic material. The method of the invention depends on the characteristics of rapid polymerization, strong adhesion and secondary reaction activity of the plant tannin, realizes the adhesion and deposition of the plant tannin on the surface of the cellulose by simple soaking at room temperature, simultaneously, free catechol groups in the plant tannin are easy to be oxidized into o-diquinone groups under the alkaline condition, and the o-diquinone groups can be chemically reacted with hydrophobic compounds with mercaptan or amido at room temperature, thereby fixing hydrophobic substances on the surface of the material and obtaining the super-hydrophobic cellulose material mediated by the plant tannin. In addition, the hydrophobic compound adopted in the method is functionalized POSS, the POSS has a core/shell cage-shaped structure and can be assembled on the surface of the base material to form a nano rough structure, so that the functionalized POSS super-hydrophobic material simultaneously plays a role in reducing the surface energy and improving the roughness in the preparation process. The method has no limit on the types and the appearances of the cellulose materials, does not damage the self structures of the materials, has simple preparation process, does not cause pollution to the environment, and is favorable for large-scale popularization and application of the super-hydrophobic materials.
Detailed Description
Example 1
Preparing 50mL of tannin aqueous solution with the concentration of 1 mg/mL, adjusting the pH value of the tannin aqueous solution to 8.5 by using 0.01mol/L NaOH solution, then soaking the cotton fabric into the tannin aqueous solution at room temperature for 6 hours, taking out the cotton fabric, cleaning the cotton fabric by using deionized water, and drying the cotton fabric in a 45 ℃ drying oven to obtain tannin modified cotton fabric; dissolving aminopropyl isobutyl-POSS in tetrahydrofuran to prepare 30mL of POSS solution of 5 mg/mL, soaking the cotton cloth modified by the tannin in the POSS solution at room temperature for 6h, taking out the cotton cloth, washing the cotton cloth with ethanol, and drying the cotton cloth in an oven at 80 ℃ for 6h to obtain the POSS modified cotton cloth. The water contact angle of the obtained hydrophobic cotton fabric is 105.3 degrees, the oil contact angle is 0 degree, and the oil-water separation efficiency is 75.50 percent.
Example 2
Preparing 50mL of tannin aqueous solution with the concentration of 3 mg/mL, adjusting the pH value of the tannin aqueous solution to 8.5 by using 0.01mol/L NaOH solution, then soaking the cotton fabric into the tannin aqueous solution, soaking for 6 hours at room temperature, taking out, cleaning the cotton fabric by using deionized water, and drying the cotton fabric in a 45 ℃ drying oven to obtain tannin modified cotton fabric; dissolving aminopropyl isobutyl-POSS in tetrahydrofuran to prepare 30mL of POSS solution of 5 mg/mL, soaking the cotton cloth modified by the tannin in the POSS solution at room temperature for 6h, taking out the cotton cloth, washing the cotton cloth with ethanol, and drying the cotton cloth in an oven at 80 ℃ for 6h to obtain the POSS modified cotton cloth. The water contact angle of the obtained hydrophobic cotton fabric is 121.5 degrees, the oil contact angle is 0 degree, and the oil-water separation efficiency is 86.10 degrees.
Example 3
Preparing 50mL of tannin aqueous solution with the concentration of 5 mg/mL, adjusting the pH value of the tannin aqueous solution to 8.5 by using 0.01mol/L NaOH solution, then soaking cotton cloth into the tannin aqueous solution at room temperature for 6 hours, taking out the cotton cloth, cleaning the cotton cloth by using deionized water, and drying the cotton cloth in a 45 ℃ drying oven to obtain tannin modified cotton cloth; dissolving aminopropyl isobutyl-POSS in tetrahydrofuran to prepare 30mL of POSS solution of 5 mg/mL, soaking the cotton cloth modified by the tannin in the POSS solution at room temperature for 6h, taking out the cotton cloth, washing the cotton cloth with ethanol, and drying the cotton cloth in an oven at 80 ℃ for 6h to obtain the POSS modified cotton cloth. The water contact angle of the obtained hydrophobic cotton cloth is 145.3 degrees, the oil contact angle is 0 degree, and the oil-water separation efficiency is 91.30 percent.
Example 4
Preparing 50mL of tannin aqueous solution with the concentration of 5 mg/mL, adjusting the pH value of the tannin aqueous solution to 8.5 by using 0.01mol/L NaOH solution, then soaking cotton cloth into the tannin aqueous solution at room temperature for 6 hours, taking out the cotton cloth, cleaning the cotton cloth by using deionized water, and drying the cotton cloth in a 45 ℃ drying oven to obtain tannin modified cotton cloth; dissolving aminopropyl isobutyl-POSS in tetrahydrofuran to prepare 30mL of POSS solution of 10 mg/mL, soaking the cotton cloth modified by the tannin in the POSS solution at room temperature for 6h, taking out the cotton cloth, washing the cotton cloth with ethanol, and drying the cotton cloth in an oven at 80 ℃ for 6h to obtain the POSS modified cotton cloth. The water contact angle of the obtained hydrophobic cotton cloth is 148.7 degrees, the oil contact angle is 0 degree, and the oil-water separation efficiency is 93.90 percent.
Example 5
Preparing 50mL of tannin aqueous solution with the concentration of 5 mg/mL, adjusting the pH value of the tannin aqueous solution to 8.5 by using 0.01mol/L NaOH solution, then soaking cotton cloth into the tannin aqueous solution at room temperature for 6 hours, taking out the cotton cloth, cleaning the cotton cloth by using deionized water, and drying the cotton cloth in a 45 ℃ drying oven to obtain tannin modified cotton cloth; dissolving aminopropyl isobutyl-POSS in tetrahydrofuran to prepare 30mL of POSS solution with the concentration of 15 mg/mL, soaking the cotton cloth modified by the tannin in the POSS solution at room temperature for 6h, taking out the cotton cloth, washing the cotton cloth with ethanol, and drying the cotton cloth in an oven at the temperature of 80 ℃ for 6h to obtain the POSS modified cotton cloth. The water contact angle of the obtained hydrophobic cotton cloth is 158.3 degrees, the oil contact angle is 0 degree, and the oil-water separation efficiency is 99.99 percent.
Example 6
Preparing 50mL of tannin aqueous solution with the concentration of 5 mg/mL, adjusting the pH value of the tannin aqueous solution to 8.5 by using 0.01mol/L NaOH solution, then soaking cotton cloth into the tannin aqueous solution at room temperature for 6 hours, taking out the cotton cloth, cleaning the cotton cloth by using deionized water, and drying the cotton cloth in a 45 ℃ drying oven to obtain tannin modified cotton cloth; dissolving aminopropyl isobutyl-POSS in tetrahydrofuran to prepare 30mL of POSS solution with the concentration of 20 mg/mL, soaking the cotton cloth modified by the tannin in the POSS solution at room temperature for 6h, taking out the cotton cloth, washing the cotton cloth with ethanol, and drying the cotton cloth in an oven at the temperature of 80 ℃ for 6h to obtain the POSS modified cotton cloth. The water contact angle of the obtained hydrophobic cotton cloth is 158.1 degrees, the oil contact angle is 0 degrees, and the oil-water separation efficiency is 99.99 percent.
Claims (8)
1. A preparation method of a plant tannin mediated super-hydrophobic cellulose material is characterized by comprising the following steps: preparing a plant tannin aqueous solution, adjusting the pH value of the tannin aqueous solution to 7-10 by using an alkaline solution, then soaking the cellulose material into the tannin aqueous solution, soaking at room temperature for 2-12 h, taking out, cleaning with deionized water, and drying in an oven at 40-60 ℃ to obtain the plant tannin modified cellulose material; soaking the plant tannin modified cellulose material into a tetrahydrofuran solution of functionalized POSS (polyhedral oligomeric silsesquioxane), soaking for 2-12 h at room temperature, taking out, and drying in an oven at 60-120 ℃ for 6-12 h to obtain the plant tannin mediated super-hydrophobic cellulose material.
2. The method of claim 1, wherein the plant tannin-mediated superhydrophobic cellulose material is selected from the group consisting of cotton fabric, ramie fabric, absorbent cotton, kapok fiber, filter paper, A4 paper, and wood.
3. The method for preparing the super-hydrophobic cellulosic material mediated by the plant tannin according to claim 1, wherein the concentration of the plant tannin aqueous solution is 1-20 mg/mL.
4. The method for preparing the super-hydrophobic cellulosic material mediated by the plant tannin as claimed in claim 1, wherein the functionalized POSS is one of aminopropyl isobutyl-POSS, aminoethylaminopropyl isobutyl-POSS, octaaminophenyl-POSS or mercaptopropyl isobutyl-POSS, and the concentration of the functionalized POSS in tetrahydrofuran is 1-50 mg/mL.
5. The method of preparing a plant tannin-mediated superhydrophobic cellulosic material of claim 1, wherein the alkaline solution is a NaOH solution.
6. A plant tannin mediated super hydrophobic cellulose material prepared by the method of claim 1-5.
7. Use of the superhydrophobic cellulosic material of claim 6 in oil-water separation.
8. Use of the superhydrophobic cellulosic material of claim 6 in the preparation of an oil-water separation product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112920440A (en) * | 2021-04-02 | 2021-06-08 | 北京理工大学 | Nano cellulose base composite membrane and preparation method and application thereof |
| CN114534527A (en) * | 2022-04-18 | 2022-05-27 | 重庆文理学院 | Membrane filtration assembly |
| TWI769089B (en) * | 2021-09-30 | 2022-06-21 | 臺北自來水事業處 | Modified cotton fabric used for oil-water separation and manufacturing method thereof |
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| CN114534527A (en) * | 2022-04-18 | 2022-05-27 | 重庆文理学院 | Membrane filtration assembly |
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