阅读说明：本技术 石墨烯改性纤维/织物及其制备方法 (Graphene modified fiber/fabric and preparation method thereof ) 是由 李春 蹇木强 张冕 于 2020-06-30 设计创作，主要内容包括：本发明提供一种石墨烯改性纤维/织物及其制备方法,该方法包括：将纤维/织物置于具有活性基团的染料中进行浸染；浸染后的纤维/织物浸渍于功能化石墨烯溶液中进行反应；反应后的产物进行固色处理；及固色处理后的产物经还原处理得到石墨烯改性纤维/织物。本发明通过利用染料分子的活性基团与功能化石墨烯进行反应形成共价连接,从而提高了功能化石墨烯在纤维/织物表面的附着力,使所得的石墨烯改性纤维/织物在具有高导电、抗菌、抗紫外等功能的同时,还具有良好的耐水洗性,提高了材料使用寿命。本发明的方法工艺简单、成本低,易于规模化生产、能耗低、废水易处理,具有良好的应用前景。(The invention provides a graphene modified fiber/fabric and a preparation method thereof, wherein the method comprises the following steps: putting the fiber/fabric into a dye with active groups for dip dyeing; soaking the dyed fiber/fabric in a functionalized graphene solution for reaction; carrying out color fixing treatment on the product after reaction; and reducing the product after color fixing treatment to obtain the graphene modified fiber/fabric. According to the invention, the covalent connection is formed by reacting the active group of the dye molecule with the functionalized graphene, so that the adhesion of the functionalized graphene on the surface of the fiber/fabric is improved, the obtained graphene modified fiber/fabric has high conductivity, antibacterial property, ultraviolet resistance and other functions, and simultaneously has good water washing resistance, and the service life of the material is prolonged. The method has the advantages of simple process, low cost, easy large-scale production, low energy consumption, easy treatment of wastewater and good application prospect.)

1. A preparation method of graphene modified fiber/fabric is characterized by comprising the following steps:

putting the fiber/fabric into a dye with active groups for dip dyeing;

soaking the dyed fiber/fabric in a functionalized graphene solution for reaction;

fixing the color of the product after the reaction; and

and reducing the product after the color fixing treatment to obtain the graphene modified fiber/fabric.

2. The method of claim 1, wherein the fiber/fabric is a fiber and/or fabric selected from one or more of a protein fiber/fabric, a cellulose fiber/fabric, and a synthetic fiber/fabric; the protein fiber/fabric is selected from one or more of wool/wool fabric, silk/silk fabric and soybean protein fiber/soybean protein fiber fabric; the cellulose fiber/fabric is selected from one or more of cotton fiber/cotton fiber fabric, hemp fiber/hemp fiber fabric, viscose fiber/viscose fiber fabric, bamboo fiber/bamboo fiber fabric, modal fiber/modal fiber fabric, lyocell fiber/lyocell fiber fabric, acetate fiber/acetate fiber fabric and cuprammonium fiber/cuprammonium fiber fabric.

3. The preparation method according to claim 1, wherein the active group is an amino group, and the functionalized graphene is one or more selected from graphene oxide, carboxylated graphene, hydroxylated graphene and acylchlorinated graphene.

4. The method of claim 1, wherein the dye having a reactive group is selected from one or more of direct yellow brown 3G, direct lake blue 5B, reactive blue KNR, reactive brilliant blue K-GR, and reactive yellow S3R.

5. The preparation method according to claim 1, wherein the mass concentration of the functionalized graphene in the functionalized graphene solution is 0.1-100 g/L, and the sheet diameter of the functionalized graphene is 1 nm-100 μm; the solvent in the functionalized graphene solution is selected from one or more of deionized water, ethanol, ethyl acetate, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and toluene.

6. The preparation method according to claim 1, wherein the functionalized graphene solution further contains a surfactant, the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinylpyrrolidone, polyvinyl alcohol, chitosan and cellulose derivatives, and the mass ratio of the surfactant to the functionalized graphene is 1: 0.1-1.

7. The preparation method according to claim 1, wherein the mass ratio of the dye with the active group to the functionalized graphene is 1: 0.01-1: 100.

8. The preparation method according to claim 1, wherein the time for soaking the dip-dyed fiber/fabric in the functionalized graphene solution is 1-60 min, and the reaction temperature is 20-100 ℃.

9. The preparation method according to claim 1, characterized in that the fixing agent used in the fixing treatment is selected from one or more of chitosan acetic acid solution, chitosan acetic acid solution and chitosan hydrochloric acid solution; the reducing agent adopted in the reduction treatment is one or more selected from sodium hydrosulfite, thiourea dioxide lye and hydrazine hydrate.

10. A graphene modified fiber/fabric prepared by the method of any one of claims 1-9.

Technical Field

The invention relates to the technical field of composite materials, and particularly relates to a graphene modified fiber/fabric and a preparation method thereof.

Background

Graphene is a honeycomb two-dimensional nano carbon material formed by tightly packing single-layer carbon atoms, and is found in 2004 by the geom professor research group of manchester university in england. Graphene, the thinnest two-dimensional material in the world, has extremely excellent properties such as high tensile strength (130GPa), high Young's modulus (1000GPa), and excellent electricity (electron mobility up to 200000cm at room temperature)²V · s), thermal properties (thermal conductivity 5000W/(m · K)), and the like. In recent years, related technology research and development centers of graphene are established in many times in China, European Union, America, UK and the like, a special research and development plan for graphene is set, a wider application field of graphene is searched, and the commercialization process of graphene is promoted.

At present, the preparation method of the graphene modified fiber/fabric mainly comprises the following three methods: the first method is to blend and spin graphene and fiber spinning solution or spinning master batch into graphene fiber, which is generally called as a blend spinning method. The second method is to blend graphene and fiber material monomer to synthesize polymer fiber material, and prepare graphene fiber through spinning, which is generally called as in-situ spinning method. And thirdly, preparing the graphene fiber by coating the surface of the conventional fiber/fabric with graphene, which is generally called a post-treatment method. The fibers prepared by the first two methods have high mechanical properties, but the added graphene has extremely limited content due to the problems of easy occurrence of agglomeration, unsmooth spinning and the like, so that the fibers have poor performances of conductivity, antibiosis and the like. The fiber/fabric prepared by the third method has excellent performances of conductivity, antibiosis and the like, but the water washing resistance and the durability are not ideal enough. The application of the fiber in the fields of textile, medical treatment and the like is limited.

Therefore, a new graphene modified fiber/fabric and a preparation method thereof are needed to solve the problems in the prior art.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The invention aims to overcome at least one of the defects of the prior art and provides a graphene modified fiber/fabric and a preparation method thereof, so as to solve the problems that the graphene modified fiber/fabric prepared by the existing method has poor performances of conductivity, antibiosis and the like, and is not ideal in water washing resistance and durability.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a preparation method of graphene modified fiber/fabric, which comprises the following steps: putting the fiber/fabric into a dye with active groups for dip dyeing; soaking the dyed fiber/fabric in a functionalized graphene solution for reaction; carrying out color fixing treatment on the product after reaction; and reducing the product after color fixing treatment to obtain the graphene modified fiber/fabric.

According to one embodiment of the invention, the fiber/fabric is a fiber and/or fabric selected from one or more of a protein fiber/fabric, a cellulose fiber/fabric and a synthetic fiber/fabric; the protein fiber/fabric is selected from one or more of wool/wool fabric, silk/silk fabric, and soybean protein fiber/soybean protein fiber fabric; the cellulose fiber/fabric is selected from one or more of cotton fiber/cotton fiber fabric, hemp fiber/hemp fiber fabric, viscose fiber/viscose fiber fabric, bamboo fiber/bamboo fiber fabric, modal fiber/modal fiber fabric, lyocell fiber/lyocell fiber fabric, acetate fiber/acetate fiber fabric and cuprammonium fiber/cuprammonium fiber fabric.

According to one embodiment of the present invention, the active group is an amino group, and the functionalized graphene is selected from one or more of graphene oxide, carboxylated graphene, hydroxylated graphene and chlorinated graphene.

According to one embodiment of the invention, the dye having a reactive group is selected from one or more of direct yellow brown 3G, direct lake blue 5B, reactive blue KNR, reactive brilliant blue K-GR and reactive yellow S3R.

According to one embodiment of the invention, in the functionalized graphene solution, the mass concentration of the functionalized graphene is 0.1 g/L-100 g/L, and the sheet diameter of the functionalized graphene is 1 nm-100 μm; the solvent in the functionalized graphene solution is selected from one or more of deionized water, ethanol, ethyl acetate, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and toluene.

According to one embodiment of the invention, the functionalized graphene solution further contains a surfactant, the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, polyvinylpyrrolidone, polyvinyl alcohol, chitosan and cellulose derivatives, and the mass ratio of the surfactant to the functionalized graphene is 1: 0.1-1: 1.

According to one embodiment of the invention, the mass ratio of the dye with the active group to the functionalized graphene is 1: 0.01-1: 100.

According to one embodiment of the invention, the time for soaking the dip-dyed fiber/fabric in the functionalized graphene solution is 1-60 min, and the reaction temperature is 20-100 ℃.

According to one embodiment of the present invention, the fixing agent used in the fixing treatment is selected from one or more of a chitosan acetic acid solution, and a chitosan hydrochloric acid solution; the reducing agent used in the reduction treatment is one or more selected from sodium hydrosulfite, thiourea dioxide lye and hydrazine hydrate.

The invention also provides a graphene modified fiber/fabric prepared by the method.

According to the technical scheme, the invention has the beneficial effects that:

according to the invention, the covalent connection is formed by reacting the active group of the dye molecule with the functionalized graphene, so that the adhesion of the functionalized graphene on the surface of the fiber/fabric is improved, the obtained graphene modified fiber/fabric has the functions of high conductivity, antibiosis, ultraviolet resistance and the like, and the washing fastness of the graphene on the surface of the fiber/fabric is improved, thereby prolonging the service life of the material. The method has the advantages of simple process, low cost, easy large-scale production, low energy consumption, easy treatment of wastewater and good application prospect.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.

Fig. 1 shows a flow chart of a preparation process of graphene modified fiber/fabric according to an embodiment of the present invention.

Detailed Description

The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.

Fig. 1 shows a flow chart of a process for preparing graphene modified fiber/fabric according to an embodiment of the present invention, and as shown in fig. 1, a method for preparing graphene modified fiber/fabric according to the present invention includes: putting the fiber/fabric into a dye with active groups for dip dyeing; soaking the dyed fiber/fabric in a functionalized graphene solution for reaction; carrying out color fixing treatment on the product after reaction; and reducing the product after color fixing treatment to obtain the graphene modified fiber/fabric.

According to the invention, the existing preparation method of the graphene modified fiber/fabric mainly comprises a blending spinning method, an in-situ spinning method, a post-treatment method and the like, but the method is easy to cause the problems of agglomeration, unsmooth spinning and the like, so that the content of the added graphene is extremely limited, the conductivity, the antibacterial performance and the like of the added graphene are poor, or the water washing resistance and the durability of the obtained fiber/fabric are not ideal. The inventor of the invention finds that by selecting a dye with a specific active group capable of reacting with the functionalized graphene according to the basic properties of the fiber/fabric and the active group of the functionalized graphene, dye molecules on the surface of the fiber can chemically react with the functionalized graphene to form covalent connection, so that the adhesion of the functionalized graphene on the surface of the fiber/fabric is improved, and the method not only can endow the fiber/fabric with the functions of conductivity, antibiosis, ultraviolet resistance and the like, but also improves the adhesion fastness of the graphene on the surface of the fiber/fabric. The method has very important significance for the application of graphene in fibers/fabrics.

In some embodiments, the fiber/fabric refers to a fiber and/or a fiber fabric, that is, the graphene modified fiber is obtained by treating a fiber as a raw material and then blending the graphene modified fiber to obtain the graphene modified fiber fabric. Alternatively, the graphene modified fiber fabric can be directly obtained by directly dip-dyeing and treating the fiber fabric as a raw material, but the invention is not limited thereto.

In particular, the fibers/fabrics include, but are not limited to, one or more of protein fibers/fabrics, cellulose fibers/fabrics, and synthetic fibers/fabrics. For example, the protein fiber/fabric is selected from one or more of wool/wool fabric, silk/silk fabric, soy protein fiber/soy protein fiber fabric; the cellulose fiber/fabric is selected from one or more of cotton fiber/cotton fiber fabric, hemp fiber/hemp fiber fabric, viscose fiber/viscose fiber fabric, bamboo fiber/bamboo fiber fabric, modal fiber/modal fiber fabric, lyocell fiber/lyocell fiber fabric, acetate fiber/acetate fiber fabric and cuprammonium fiber/cuprammonium fiber fabric.

The following specifically illustrates the preparation method of the graphene modified fiber/fabric of the present invention.

First, the fiber/fabric is placed in a dye having a reactive group for exhaust dyeing. Specifically, the fiber/fabric may be placed in a solution containing a dye and the fiber/fabric dyed with dye molecules using a commonly used dyeing process. For example, the solution is heated to 70 ℃ to 95 ℃, and the fiber/fabric is taken out and dried after a period of dip dyeing.

According to the invention, the aforementioned reactive group is an amino group, i.e. the dye is a dye having an amino group. In some embodiments, the aforementioned dye having a reactive group may be selected from one or more of direct yellow brown 3G (see formula I below), direct lake blue 5B (see formula II below), reactive blue KNR (see formula III below), reactive brilliant blue K-GR (see formula IV below), and reactive yellow S3R (see formula V below), preferably direct yellow brown 3G or direct lake blue 5B dyes. The amino group of the dye and the active group on the functionalized graphene are subjected to chemical reaction to form a covalent bond, so that a strong acting force is formed between the functionalized graphene and the dye molecules, and the acting force of the chemical bond is stronger than the acting forces of hydrogen bonds, van der Waals force and the like in the conventional method, so that the adhesive force of the graphene oxide on the surface of the fiber/fabric can be effectively improved.

And then, soaking the dyed fiber/fabric in a functionalized graphene solution for reaction. Specifically, the functionalized graphene is added into a solvent, and a stably dispersed functionalized graphene solution is prepared by ultrasonic treatment and the like. Then, the fiber/fabric after the dip dyeing is dipped in the functionalized graphene solution, the dipping time is generally 1min to 60min, for example, 1min, 10min, 20min, 35min, 40min, 50min, 55min and the like, the reaction temperature is 20 ℃ to 100 ℃, for example, 20 ℃, 30 ℃, 50 ℃, 70 ℃, 80 ℃, 90 ℃ and the like, preferably 50 ℃ to 80 ℃. After the reaction is finished, washing with deionized water to remove impurities, and drying water in an oven to obtain a product for later use.

The functionalized graphene is selected from one or more of graphene oxide, carboxylated graphene, hydroxylated graphene and acyl chlorinated graphene, and is preferably graphene oxide or acyl chlorinated graphene. In some embodiments, the mass ratio of the dye to the functionalized graphene used is 1:0.01 to 1:100, preferably 1:1 to 1:10, e.g., 1:1, 1:3, 1:5, 1:6, 1:7, 1:8, 1:9, etc. In the functionalized graphene solution, the mass concentration of the functionalized graphene is 0.1g/L to 100g/L, for example, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 7g/L, 9g/L, 10g/L, and the like, and preferably 2g/L to 5 g/L. The functionalized graphene has a sheet diameter of 1nm to 100 μm, for example, 1 μm, 2 μm, 6 μm, 10 μm, 14 μm, 16 μm, 20 μm, 21 μm, and the like, and preferably 1 μm to 10 μm. The solvent in the functionalized graphene solution is selected from one or more of deionized water, ethanol, ethyl acetate, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran and toluene, and preferably is one or more of deionized water, ethanol and ethyl acetate.

In some embodiments, a surfactant, such as one or more of sodium dodecylbenzene sulfonate, sodium dodecylsulfate, polyvinylpyrrolidone, polyvinyl alcohol, chitosan, and cellulose derivatives, preferably one or more of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, and polyvinyl alcohol, may also be added to the aforementioned reaction system. The mass ratio of the surfactant to the functionalized graphene is 1: 0.1-1: 1. By adding the surfactant, the graphene and dye molecules can be combined more tightly, so that the adhesive force of the graphene is further improved.

Further, the product after the reaction is subjected to color fixing treatment. Generally, the dried product is immersed in a solution containing a fixing agent, and reacted at 25 ℃ to 50 ℃, for example, 25 ℃, 30 ℃, 32 ℃, 38 ℃, 45 ℃, 48 ℃, 50 ℃ and the like for about 30min to 60min, for example, 30min, 40min, 42min, 53min, 57min, 60min and the like, and then taken out for drying treatment. The fixing agent is chitosan acetic acid solution, chitosan hydrochloric acid solution, etc., but the present invention is not limited thereto.

And finally, placing the product after the color fixing treatment in a solution containing a reducing agent for reduction reaction. Wherein the reducing agent is one or more of sodium hydrosulfite, thiourea dioxide alkali solution and hydrazine hydrate, the reduction reaction time is 30 min-60 min, such as 30min, 33min, 42min, 50min, 52min, 55min, etc., and the temperature is 20-80 ℃, such as 20 ℃, 30 ℃, 50 ℃, 63 ℃, 72 ℃, 78 ℃, etc. After the reduction treatment, the functionalized graphene is reduced to graphene, so that the graphene modified fiber/fabric is obtained.

In conclusion, the active groups of the dye molecules are reacted with the functionalized graphene, so that the obtained graphene modified fiber/fabric has the functions of high conductivity, antibiosis, ultraviolet resistance and the like, and the washing fastness of the graphene on the surface of the fiber/fabric is improved. In addition, the method provides a reference basis for solving the problems of difficult dyeing, single color and the like of the graphene fiber/fabric. The method has the advantages of simple process, low cost, easy large-scale production, low energy consumption, easy treatment of wastewater and good application prospect.

The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, the reagents used in the present invention are commercially available.