CN110528269B - Preparation method of grape polyphenol modified hydrophobic cotton fabric - Google Patents
Preparation method of grape polyphenol modified hydrophobic cotton fabric Download PDFInfo
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
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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
- D06M13/152—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 having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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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
- D06M13/322—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 nitrogen
- D06M13/325—Amines
- D06M13/328—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom
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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
- D06M13/322—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 nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/415—Amides of aromatic carboxylic acids; Acylated aromatic amines
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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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- Engineering & Computer Science (AREA)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a preparation method of a grape polyphenol modified hydrophobic cotton fabric, which comprises the steps of taking grape polyphenol extracted from waste grape skin as a main reagent, taking folic acid self-assembled nano columnar particles as a template, grafting the nano columnar particles onto the cotton fabric through oxidative polymerization to form a specific nano structure, and grafting a low surface energy substance octadecylamine onto the nano particles through Michael addition to endow the cotton fabric with super-hydrophobic performance. The invention has the advantages of environment-friendly raw materials, quick and simple process and mild conditions. The super-hydrophobic fabric has high hydrophobic property, and the contact angle to water is as follows: 150-160 degrees, has good washing durability and can be used in the fields of oil-water separation and the like.
Description
Technical Field
The invention relates to the technical field of textile dyeing and finishing processing, in particular to a preparation method of grape polyphenol modified hydrophobic cotton fabric.
Background
The recycling rate of waste textiles such as leftover materials, old clothes, home textiles and the like in the existing textile processing is low, and huge resource waste is caused. Meanwhile, the bionic super-hydrophobic surface has wide prospects in the field of textiles. The super-hydrophobic/super-oleophilic material has selective adsorption performance on oil and water, can efficiently self-clean, adsorb and separate oil and water mixtures so as to solve the problems of offshore oil leakage, resource waste caused by improper treatment of waste textiles and the like, and has become one of the focuses of people and research. The micro-nano structure and the low surface energy are the keys for preparing the bionic super-hydrophobic surface.
The polyphenol compounds are the most important plant secondary metabolites in fruits and vegetables. The polyphenol has various varieties and complex structures, but all contain benzene ring structures with one or more hydroxyl groups, and play an important role in performing super-hydrophobic modification on fabrics. However, the micro-nano structure is simply modified by polyphenol, and extra nano particles are required to be doped to realize the construction of the micro-nano structure.
Recently, the method inspired by mussels in the bionic technology is highly valued by people and obtains good practical application effect. However, the method for preparing the super-hydrophobic fabric by utilizing the characteristic of the bionic modification of the dopamine has high functionalization cost, long polymerization time consumption and limited dopamine analogs, so the application of the dopamine analogs is limited. Chinese patent No. CN106087404A discloses a method for preparing a super-hydrophobic fabric modified by phenol, which comprises the steps of sequentially immersing a fabric in a solution of ferric chloride and a polyphenol compound to obtain a fabric modified by a surface metal-polyphenol film layer, and then immersing the fabric modified by the surface metal-polyphenol film layer in a mixed solution of ethanol and water containing low-surface-energy substances. Folic acid is also called vitamin M, is a compound containing a pteroylglutamic acid structure, is prepared by combining 2-amino-4-hydroxypteridine with p-aminobenzoic acid through a methylene bridge to form pteroic acid, and then combining the pteroic acid with glutamic acid, and can improve the micro-nano structure in the dopamine polymerization process. The cloth is put into a mixed solution pretreated by dopamine hydrochloride and folic acid to obtain the cloth with a micro-nano structure, and then the cloth is put into an ethanol solution of octadecylamine to obtain the super-hydrophobic oil-water separation cloth. However, the super-hydrophobic fabrics prepared by the method have limited varieties and low durability, or the green environmental protection process is still to be improved.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of grape polyphenol modified hydrophobic cotton fabric.
The invention aims to disclose a preparation method of a grape polyphenol modified hydrophobic cotton fabric, which comprises the following steps:
(1) activation of cotton fabric: immersing the cotton fabric into a hydrogen peroxide solution according to a bath ratio of 1:30, wherein the concentration of hydrogen peroxide is 1-5 mL/L, then adjusting the pH value to 8-9, and treating for 5-15 minutes at the temperature of 80-90 ℃;
(2) oxidative polymerization of grape polyphenols on cotton fabric: adding the activated cotton fabric into the reaction solution in a bath ratio of 1: 20-1: 50, and reacting at 50-80 ℃ and under the condition that the pH value is 8-9; the reaction liquid comprises grape polyphenol and folic acid, the concentration of the grape polyphenol is 0.5-2.0 mg/mL, and the concentration of the folic acid is 0.1-1.0 mg/mL;
(3) low surface energy grafting treatment: immersing the oxidative-polymerized cotton fabric into an octadecylamine solution for treatment at the temperature of 25-40 ℃ for 10-22 hours in a bath ratio of 1: 20-1: 50; and drying the treated cotton fabric to obtain the grape polyphenol modified hydrophobic cotton fabric.
Further, in step (1), hydrochloric acid and a tris buffer solution are used to adjust the pH.
Further, in the step (2), the reaction time is 1-3 h.
Further, in the step (2), the pH of the reaction solution is 8 to 9.
Further, in the step (3), the concentration of the octadecylamine solution is 1-9 mmol/L.
Further, in the step (3), the solvent of the octadecylamine solution is ethanol and water, and the volume ratio of the ethanol to the water is 7: 3.
Further, in the step (3), a step of washing the treated cotton fabric is further included before drying.
Further, in the step (3), the drying temperature of the cotton fabric is 40-60 ℃.
Further, in the step (2), the grape polyphenols are derived from the discard or waste grape skin after the grape juice is extracted.
According to the invention, a benzene ring structure with one or more hydroxyl groups in polyphenol and nanoparticles generated by polymerization of the benzene ring structure and a mixed solution of folic acid are deposited on the surface of the fabric to construct a rough structure required by a super-hydrophobic surface, and the fabric is endowed with super-hydrophobicity after being treated by a low-surface-energy substance.
Grape polyphenols are a mixture of polyphenols derived from the waste of squeezed grape juice and the grape skin from spitting grapes. In order to utilize the natural polyphenols, the invention prepares the plant grape polyphenols super-hydrophobic fabric by utilizing the nanoparticles on the surfaces of the fibers formed by oxidative polymerization of the natural polyphenols. However, the purity of the folic acid is not high, the amount of impurities is large, and the folic acid is difficult to polymerize into the required nano particles, so that the folic acid which is also of plant origin is added to promote the folic acid to polymerize into the corresponding nano structure. Since hydroxypteridine can form a 4-mer through 4 hydrogen bonds, the 4-mer can form a nano-columnar structure through pi-pi interaction. The invention takes the structure-directing agent as a structure-directing agent, and leads the grape polyphenol to polymerize through pi-pi interaction to form a nano columnar structure, thereby forming a super-hydrophobic nano structure. After the cotton fabric is subjected to oxidation activation, more active groups are formed, and stronger combination can be formed between the cotton fabric and grape polyphenol so as to improve the washing fastness of the cotton fabric.
By the scheme, the invention at least has the following advantages:
the method takes grape polyphenol extracted from waste grape skins as a main reagent, takes nano columnar particles self-assembled by folic acid as a template, grafts the nano columnar particles on cotton fabric through oxidative polymerization to form a specific nano structure, and grafts a low surface energy substance octadecylamine onto the nano particles through Michael addition to endow the cotton fabric with super-hydrophobic performance. The method is based on the green environment-friendly process, the waste grape polyphenol and the folic acid are utilized to jointly prepare the super-hydrophobic fabric with the micro-nano structure, the raw materials are environment-friendly, the method is rapid and simple, the conditions are mild, the process is simple, and the scale production can be realized.
The super-hydrophobic cotton fabric prepared by modifying the grape polyphenol has good washing durability and a high contact angle to water which can reach 150-160 degrees, has wide application prospect in industry and production, and can be used in the field of oil-water separation.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a scanning electron micrograph of the treated cotton fabric of example 1;
FIG. 2 is the water contact angle of the cotton fabric after treatment of example 1;
FIG. 3 is the water contact angle of the cotton fabric treated in example 1 after 50 washes;
FIG. 4 is a graph showing the effect of oil-water separation on cotton fabric treated in example 1.
Detailed Description
According to the invention, in a newly prepared mixed buffer solution of polyphenol and folic acid, the polyphenol and folic acid are polymerized and adhered to the surface of a fabric, a micro-nano coarse structure is constructed, a specific nano structure is formed by adding folic acid, the durability of a treated cotton fabric is improved, and finally, the fabric is treated by adopting a low surface energy modifier to endow the fabric with super-hydrophobicity.
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
(1) 1g of cotton fabric is cleaned and dried at the temperature of 60 ℃.
(2) Placing 50mg of weighed grape polyphenol and 25mg of weighed folic acid into 50mL of deionized water, mixing and stirring at 80 ℃ for about 1h to obtain a prepared uniform solution, and adjusting the pH of the solution to 8.5 by using a proper amount of hydrochloric acid and tris (hydroxymethyl) aminomethane to obtain a treatment solution.
(3) Immersing the cleaned and dried cotton fabric obtained in the step (1) into a hydrogen peroxide solution according to a bath ratio of 1:30, wherein the concentration of hydrogen peroxide is 2mL/L, and regulating the pH value to 9 by using hydrochloric acid and a tris (hydroxymethyl) aminomethane buffer solution, wherein the temperature is 85 ℃, and the treatment time is 10 minutes;
(4) taking out the activated cotton fabric, adding the cotton fabric into the reaction liquid prepared in the step (2) according to the bath ratio of 1:30, and reacting for 2 hours at the temperature of 70 ℃ and under the condition that the pH value is 8.5;
(5) 70mL of absolute ethyl alcohol and 30mL of deionized water are weighed and mixed in a beaker, 0.1617g of octadecylamine is weighed and placed in the mixed solution of the ethyl alcohol and the water, and the pH value of the solution is adjusted to 8.5 by using a proper amount of hydrochloric acid and tris (hydroxymethyl) aminomethane, so that an octadecylamine solution is obtained.
(6) Taking out the cotton fabric after oxidative polymerization, and immersing the cotton fabric into an octadecylamine solution for treatment at the temperature of 35 ℃ for 20 hours according to the bath ratio of 1: 30;
(7) and taking out the treated cotton fabric, washing with clear water and drying at 50 ℃ to obtain the super-hydrophobic and super-oleophylic cotton fabric.
The microstructure of the cotton fabric obtained in the step (4) of the present example is shown in fig. 1, and the result shows that the surface of the fabric has a nano-rough structure.
The water contact angle of the cotton fabric obtained in the step (7) is shown in figure 2, and the water contact angle is 155.8 degrees. The cotton fabric is washed by water for 50 times, and the contact angle after 50 times of washing is shown in figure 3, and the result shows that the water contact angle is 150 degrees. As can be seen from FIGS. 2-3, after 50 times of washing, the cotton fabric still has super-hydrophobic property.
And (3) placing the cotton fabric obtained in the step (7) serving as a filtering membrane into a filtering funnel, containing an oil-water mixture (trichloromethane-water mixed solution) in the filtering funnel, and connecting a filtering bottle below the filtering funnel. After filtering, the lower filter flask is filled with filtrate. FIG. 4 shows the oil-water separation effect of the treated cotton fabric, after filtration, chloroform enters a lower filter flask, water is left in an upper filter funnel, and the separation effect is tested, and the result shows that the separation efficiency of the treated cotton fabric on an oil-water mixture is 96 percent, and the separation speed is 0.5 mL-cm-2·s-1。
Example 2
(1) 2g of cotton fabric is cleaned and dried at 50 ℃.
(2) Placing 100mg of weighed grape polyphenol and 70mg of folic acid into 100mL of deionized water, mixing and stirring at 50 ℃, obtaining a prepared uniform solution after about 90min, and adjusting the pH of the solution to 8.5 by using a proper amount of hydrochloric acid and tris (hydroxymethyl) aminomethane to obtain a treatment solution.
(3) Immersing the cleaned and dried cotton fabric obtained in the step (1) into a hydrogen peroxide solution according to a bath ratio of 1:30, wherein the concentration of hydrogen peroxide is 3mL/L, the pH value is adjusted to 8.5 by hydrochloric acid and a trihydroxymethyl aminomethane buffer solution, the temperature is 80 ℃, and the treatment time is 13 minutes;
(4) taking out the activated cotton fabric, adding the cotton fabric into the reaction liquid prepared in the step (2) according to the bath ratio of 1:40, and reacting for 2.5 hours at the temperature of 75 ℃ and under the condition that the pH value is 9;
(5) 70mL of absolute ethyl alcohol and 30mL of deionized water are weighed and mixed in a beaker, 0.2156g of octadecylamine is weighed and placed in the mixed solution of the ethyl alcohol and the water, and the pH value of the solution is adjusted to 8.3 by using a proper amount of hydrochloric acid and tris (hydroxymethyl) aminomethane, so that an octadecylamine solution is obtained.
(6) Taking out the cotton fabric after oxidative polymerization, and immersing the cotton fabric into an octadecylamine solution for treatment at the treatment temperature of 40 ℃ for 16 hours according to the bath ratio of 1: 40;
(7) and taking out the treated cotton fabric, washing with clear water and drying at 40 ℃ to obtain the super-hydrophobic and super-oleophylic cotton fabric.
Example 3
(1) 1g of cotton fabric is cleaned and dried at 50 ℃.
(2) Placing 75mg of grape polyphenol and 40mg of folic acid into 50mL of deionized water, mixing and stirring at 50 ℃ for about 90min to obtain a prepared uniform solution, and adjusting the pH of the solution to 8.5 by using a proper amount of hydrochloric acid and tris (hydroxymethyl) aminomethane to obtain a treatment solution.
(3) Immersing the cleaned and dried cotton fabric obtained in the step (1) into a hydrogen peroxide solution according to a bath ratio of 1:30, wherein the concentration of hydrogen peroxide is 4mL/L, the pH value is adjusted to 8.2 by hydrochloric acid and a trihydroxymethyl aminomethane buffer solution, the temperature is 75 ℃, and the treatment time is 9 minutes;
(4) taking out the activated cotton fabric, adding the cotton fabric into the reaction liquid prepared in the step (2) according to the bath ratio of 1:20, and reacting for 1.8h at the temperature of 70 ℃ and under the condition that the pH value is 8.1;
(5) 70mL of absolute ethyl alcohol and 30mL of deionized water are weighed and mixed in a beaker, 0.1886g of octadecylamine is weighed and placed in the mixed solution of the ethyl alcohol and the water, and the pH value of the solution is adjusted to 8 by using a proper amount of hydrochloric acid and tris (hydroxymethyl) aminomethane, so that an octadecylamine solution is obtained.
(6) Taking out the cotton fabric after oxidative polymerization, and immersing the cotton fabric into an octadecylamine solution for treatment at the treatment temperature of 40 ℃ for 19 hours in a bath ratio of 1: 45;
(7) and taking out the treated cotton fabric, washing with clear water and drying at the drying temperature of 60 ℃ to obtain the super-hydrophobic and super-oleophylic cotton fabric.
The super-hydrophobic super-oleophylic fabric is prepared by adding the grape polyphenol and the folic acid, the durability of the super-hydrophobic super-oleophylic fabric is improved, and finally the super-hydrophobic fabric is treated by adopting the low-surface-energy modifier.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of a grape polyphenol modified hydrophobic cotton fabric is characterized by comprising the following steps:
(1) activation of cotton fabric: immersing the cotton fabric into a hydrogen peroxide solution according to a bath ratio of 1:30, wherein the concentration of hydrogen peroxide is 1-5 mL/L, then adjusting the pH value to 8-9, and treating for 5-15 minutes at the temperature of 80-90 ℃;
(2) oxidative polymerization of grape polyphenols on cotton fabric: adding the activated cotton fabric into the reaction solution in a bath ratio of 1: 20-1: 50, and reacting at 50-80 ℃ and under the condition that the pH value is 8-9; the reaction liquid comprises grape polyphenol and folic acid, the concentration of the grape polyphenol is 0.5-2.0 mg/mL, and the concentration of the folic acid is 0.1-1.0 mg/mL;
(3) low surface energy grafting treatment: immersing the oxidative-polymerized cotton fabric into an octadecylamine solution for treatment at the temperature of 25-40 ℃ for 10-22 hours in a bath ratio of 1: 20-1: 50; and drying the treated cotton fabric to obtain the grape polyphenol modified hydrophobic cotton fabric.
2. The method of claim 1, wherein: in step (1), hydrochloric acid and tris buffer solution are used to adjust the pH.
3. The method of claim 1, wherein: in the step (2), the reaction time is 1-3 h.
4. The method of claim 1, wherein: in the step (2), the pH of the reaction solution is 8-9.
5. The method of claim 1, wherein: in the step (3), the concentration of the octadecylamine solution is 1-9 mmol/L.
6. The method of claim 1, wherein: in the step (3), the solvent of the octadecylamine solution is ethanol and water, and the volume ratio of the ethanol to the water is 7: 3.
7. The method of claim 1, wherein: in the step (3), a step of washing the treated cotton fabric is further included before the drying.
8. The method of claim 1, wherein: in the step (3), the drying temperature of the cotton fabric is 40-60 ℃.
9. The method of claim 1, wherein: in the step (2), the grape polyphenol is derived from the waste or discarded grape skin after grape juice is extracted.
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| CN111188183B (en) * | 2020-02-17 | 2022-06-21 | 南通纺织丝绸产业技术研究院 | Method for preparing super-hydrophobic cotton textile by utilizing thiol-ene click chemical modification |
| CN111229185A (en) * | 2020-03-09 | 2020-06-05 | 泉州师范学院 | Procyanidine-based modified shaddock peel super-hydrophobic oil-water separation material and preparation method thereof |
| CN111229190A (en) * | 2020-03-09 | 2020-06-05 | 泉州师范学院 | Preparation method of super-hydrophobic oil-water separation material based on plant polyphenol-amino silicone oil modification |
| CN112267298A (en) * | 2020-10-28 | 2021-01-26 | 苏州健雄职业技术学院 | Preparation method of hydrophobic cotton fabric and hydrophobic cotton |
| CN112323491B (en) * | 2020-11-05 | 2022-08-09 | 苏州大学 | Method for carrying out super-hydrophobic modification on waste cotton fabric by dopamine |
| CN112323490B (en) * | 2020-11-05 | 2022-08-09 | 苏州大学 | Method for carrying out super-hydrophobic modification on waste cotton fabric by polyphenol |
| CN117183041A (en) * | 2023-07-11 | 2023-12-08 | 南京林业大学 | Gelatin-lignin sulfonic acid wood composite acoustic diaphragm and preparation method and application thereof |
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| CN107938319A (en) * | 2017-11-28 | 2018-04-20 | 苏州大学 | Hydrophobic cotton fabric and its preparation method and application |
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| CN106087404A (en) * | 2016-06-03 | 2016-11-09 | 武汉纺织大学 | A kind of method that superhydrophobic fabric is prepared in polyphenol modification |
| CN107938319A (en) * | 2017-11-28 | 2018-04-20 | 苏州大学 | Hydrophobic cotton fabric and its preparation method and application |
| CN109355907A (en) * | 2018-10-26 | 2019-02-19 | 福州大学 | A kind of super-hydrophobic coat method for sorting that wearable environment protection is degradable |
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