CN109183393B - Graphene modified conductive protein fiber and preparation method and application thereof - Google Patents
Graphene modified conductive protein fiber and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a method for preparing graphene modified conductive protein fibers, which comprises the steps of combining graphene oxide with protein fibers in a graphene oxide solution in a surface modification mode to obtain graphene oxide modified protein fibers; and reducing the graphene oxide-modified protein fiber in an aqueous solution of a sulfinic acid compound at a temperature of 50 ℃ to 100 ℃ to obtain a graphene-modified conductive protein fiber. The resistance of the obtained graphene modified conductive protein fiber is 1 multiplied by 101Omega to 1X 105Omega, an absolute value of a rate of change in resistance after the washing resistance test is 5% to 70%, and thus has excellent washing resistance and conductivity. The invention also provides the graphene modified conductive protein fiber obtained by the method. In addition, the invention also provides application of the graphene modified conductive protein fiber in intelligent sensors, electromagnetic shielding, electric heating medical supplies, conductive textiles or antistatic textiles.
Description
Technical Field
The invention relates to a modified conductive fiber, a preparation method and application thereof, in particular to a graphene modified conductive protein fiber, a preparation method and application thereof.
Background
Graphene is a two-dimensional monoatomic layer sheet-like crystalline material formed by closely arranging sp 2-hybridized carbon atoms in a honeycomb hexagonal structure. The special nano structure enables the material to have the characteristics of excellent strength, electric conduction, heat conduction and the like, so that the material has great application potential in the fields of composite materials, intelligent materials, electronic devices, energy storage, drug carriers and the like. Meanwhile, as graphene has an ultrathin flexible structure and excellent performance characteristics, the graphene is increasingly widely applied to the field of textile fiber materials, such as pure graphene fibers, graphene composite fibers, graphene coating fibers, textiles and the like.
At present, the following two methods are mainly used for applying graphene to conductive fibers: one is that the surface of the conventional fiber is coated with a graphene conductive material; and the other is to blend and spin graphene and fiber raw materials to prepare the conductive fiber. The fiber prepared by the coating method has excellent conductivity, but the water washing resistance and the durability are not ideal enough, and the blending spinning method has the problems of agglomeration, unsmooth spinning and the like in the spinning process.
In recent years, the preparation of conductive fibers by reducing graphene oxide-modified fibers has also gained increasing attention. The reduction method of graphene oxide mainly comprises a chemical reduction method, a thermal reduction method and an electrochemical reduction method, wherein the chemical reduction method is low in cost, high in yield and popular with researchers. Currently, the effective reducing agents are hydrazines and NaBH4HI and the like, and the C/O of reduced graphene oxide (rGO) prepared by utilizing the reducing agents can reach about 10, even more than 12. However, these agents tend to be strongerToxic or corrosive, presenting a serious threat to the health of the workers and to the surrounding environment. For this reason, an attempt has been made to reduce graphene oxide with ascorbic acid or chitosan as a reducing agent, but it has been found that it is difficult to obtain a good reduction effect even with a long reaction time.
Therefore, a nontoxic, efficient and energy-saving reduction method is urgently needed in the field so as to obtain the graphene modified conductive fiber with good washing resistance and conductivity.
Disclosure of Invention
The invention aims to provide a method for preparing nontoxic, efficient and energy-saving graphene modified conductive protein fibers so as to obtain the graphene modified conductive protein fibers with high conductivity and good washing resistance, thereby overcoming the defects in the prior art.
According to an aspect of the present invention, there is provided a method of preparing a graphene-modified conductive protein fiber, the method comprising: combining graphene oxide with protein fibers in a graphene oxide solution in a surface modification manner to obtain graphene oxide modified protein fibers; and reducing the graphene oxide-modified protein fiber in an aqueous solution of a sulfinic acid compound at a temperature of 50 ℃ to 100 ℃ to obtain a graphene-modified conductive protein fiber.
In one embodiment, the particle size of the graphene oxide is any one selected from the group consisting of: 0.1 μm to 7.0 μm, 0.2 μm to 6.5 μm, 0.3 μm to 6.0 μm, 0.4 μm to 5.5 μm, 0.5 μm to 5.0 μm, 0.6 μm to 4.5 μm, 0.8 μm to 4.0 μm, 1.0 μm to 3.5 μm, 1.2 μm to 3.0 μm, 1.5 μm to 2.5 μm, 1.8 μm to 2.0 μm.
In one embodiment, the protein fiber is one or more selected from the group consisting of: animal protein fibers, for example, wool, rabbit hair, silk, casein protein fibers, silkworm pupa protein fibers, pearl protein fibers or milk protein fibers; vegetable protein fibers, for example, peanut protein fibers, corn protein fibers, soy protein fibers, or hemp seed kernel protein fibers, or combinations thereof.
In one embodiment, the sulfinic acid compound is one or more selected from the group consisting of: alkylsulfinic acids, such as hydroxymethylsulfinic acid, 3-methylsulfinic acid, 2-hydroxy-2-sulfinatoacetic acid, trifluoromethylsulfinic acid, 1-hydroxyethylsulfinic acid, 1-hydroxypropylsulfinic acid, 1-hydroxybutylsulfinic acid, 1-hydroxy-1-methylethylsulfinic acid, 1-hydroxy-1-ethylpropylsulfinic acid, 1-hydroxy-1-methylpropylsulfinic acid or 1-hydroxy-1-methylpentylsulfinic acid, or salts thereof; arylsulfinic acids, for example, 3-nitrobenzenesulfinic acid, 4-chlorobenzenesulfinic acid, 4-cyanobenzenesulfinic acid, 4-ethoxycarbonylbenzenesulfinic acid, 4-trifluoromethylbenzenesulfinic acid, 3-trifluoromethylbenzenesulfinic acid, 1-anthraquinonesulfinic acid, 1-naphthalenesulfinic acid, 2-naphthalenesulfinic acid, phenylsulfinic acid, p-methoxyphenylsulfinic acid, p-methylphenylsulfinic acid, p-chlorophenylsulfinic acid, p-bromophenylsulfinic acid, p-iodophenylsulfinic acid, p-nitrophenylsulfinic acid, o-chlorophenylsulfinic acid, o-nitrophenylsulfinic acid or naphthylsulfinic acid, or salts thereof; or a combination thereof, wherein the sulfinic acid compound is preferably hydroxymethylsulfinic acid, 3-methylsulfinic acid or a salt thereof, more preferably sodium hydroxymethylsulfinate or ammonium 3-methylsulfinate.
In one embodiment, the weight ratio of the graphene oxide to the protein fiber in the graphene oxide solution is 1.0:10 to 3.0:10, 1.5:10 to 2.5:10, or 1.8:10 to 2.0: 10.
In one embodiment, the weight ratio of the sulfinic acid compound to the graphene oxide-modified protein fiber in the aqueous sulfinic acid compound solution is 1.0:10 to 3.0:10, 1.5:10 to 2.5:10, or 1.8:10 to 2.0: 10.
According to another aspect of the present invention, there is provided the graphene-modified conductive protein fiber prepared by the method as described above, wherein the graphene-modified conductive protein fiber has an absolute value of a rate of change in resistance of 5% to 70% after a water washing resistance test.
In one embodiment, the graphene-modified conductive protein fiber has an absolute value of a rate of change in resistance of 10% to 65%, 15% to 60%, 20% to 55%, 25% to 50%, 30% to 45%, or 35% to 40% after a water washing resistance test.
In one embodiment, the graphene-modified conductive protein fiber has a resistance of 1.0 x 101Omega to 1.0 x 105Omega, or 2.0X 101Omega to 5.0 x 104Omega, or 4.0X 101Omega to 2.0 x 104Omega, or 8.0X 101Omega to 1.0 x 104Omega, or 1.0X 102Omega to 5X 103Omega, or 2X 102Omega to 2 x 103Omega, or 4.0X 102Omega to 1.0 x 103Ω。
The method has the advantages of simple operation, short process flow, easy large-scale production, low energy consumption, easy treatment of wastewater, high conductivity of the obtained graphene modified protein fiber, good washing resistance and the like. In addition, the method has the advantages of no toxicity, no irritation, low cost and the like.
According to another aspect of the present invention, there is provided a use of the graphene-modified conductive protein fiber prepared by the method in a smart sensor, an electromagnetic shielding, an electrothermal medical article, a conductive textile, or an antistatic textile.
Drawings
FIG. 1 shows (a1) an electron microscope picture of mulberry silk before modification; (a2) an electron microscope picture of graphene oxide modified mulberry silk; (b1) electron microscope pictures of graphene modified mulberry silk; and (b2) (b1) partial enlarged views of graphene-modified mulberry silk within boxes.
Fig. 2 shows (a) an electron photograph of graphene-modified conductive protein fibers; and (b) the property of the graphene modified conductive protein fiber for electrical conduction.
Detailed Description
For the purposes of the following detailed description, it is to be understood that the embodiments provided herein may assume various alternative variations and step sequences, except where expressly specified to the contrary. Furthermore, other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients used in the specification and claims are to be understood as being modified by the term "about" which refers to variables having a value of ± 10%, ± 5% or ± 3% of the respective value so modified. Accordingly, unless indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, "1 to 10" is intended to include all sub-ranges between the recited minimum value of 1 and the recited maximum value of 10 (and includes both the endpoints of 1 and 10), such as 1 to 5, 2 to 8, or 4 to 6, and the like.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. "or" means "and/or". As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a method for preparing graphene modified conductive protein fibers, which comprises the following steps: preparing graphene oxide by using an improved Hummer's method; preparing the graphene oxide into a solution, and then combining the graphene oxide with protein fibers in the graphene oxide solution by a surface modification method to obtain graphene oxide modified protein fibers; and reducing the graphene oxide-modified protein fiber in an aqueous solution of a sulfinic acid compound at a temperature of 50 ℃ to 100 ℃ to obtain a graphene-modified conductive protein fiber.
In one embodiment, the graphene-modified conductive protein fibers may further comprise additives such as abrasion resistance agents, colorants, pigments, matting agents, flame retardants, wetting agents, softeners, leveling agents, finishes, fixing agents, smoothing agents, and the like, to impart desired additional properties to the conductive protein fibers.
In one embodiment, graphene oxide may also be obtained by the brodi method and Staudenmaier method, among other methods known in the art.
In another embodiment, the particle size of the graphene oxide may be any one selected from the group consisting of: 0.1 μm to 7.0 μm, 0.2 μm to 6.5 μm, 0.3 μm to 6.0 μm, 0.4 μm to 5.5 μm, 0.5 μm to 5.0 μm, 0.6 μm to 4.5 μm, 0.8 μm to 4.0 μm, 1.0 μm to 3.5 μm, 1.2 μm to 3.0 μm, 1.5 μm to 2.5 μm, 1.8 μm to 2.0 μm. Preferably, in particular embodiments, the graphene oxide may have a particle size of 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1.0 μm. In further particular embodiments, the graphene oxide may have a particle size of 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, or 0.5 μm, so that the graphene oxide particles are uniformly dispersed in the solution.
In one embodiment, the weight ratio of graphene oxide to protein fiber in the graphene oxide solution is from 1:10 to 3: 10. In particular embodiments, the weight ratio of graphene oxide to protein fiber in the graphene oxide solution is from 1.5:10 to 2.5:10 or from 1.8:10 to 2.0: 10. In another particular embodiment, the weight ratio of graphene oxide to protein fiber in the graphene oxide solution may be 1.2:10, 1.4:10, 1.6:10, 1.8:10, 2.0:10, 2.2:10, 2.6:10, or 2.8: 10.
In one embodiment, the protein fiber may be a plant protein fiber, an animal protein fiber, or a combination thereof. In one embodiment, the protein fiber may be an animal protein fiber, for example, wool, rabbit hair, silk, casein protein fiber, silkworm pupa protein fiber, pearl protein fiber, milk protein fiber, or a combination thereof. In one embodiment, the silk may be mulberry silk, pressed silk or yamamai silk. In one embodiment, the protein fiber may be a vegetable protein fiber, for example, a peanut protein fiber, a corn protein fiber, a soy protein fiber, a hemp seed protein fiber, or a combination thereof. In particular embodiments, the protein fibers may be wool, rabbit hair, mulberry silk, peanut protein fibers, corn protein fibers, soy protein fibers, or combinations thereof. In a preferred embodiment, the protein fiber may be wool, rabbit hair, peanut protein fiber, soy protein fiber, or a combination thereof.
In one embodiment, the weight ratio of the sulfinic acid compound to the graphene oxide-modified protein fiber in the aqueous sulfinic acid compound solution is from 1:10 to 3: 10. In particular embodiments, the weight ratio of the sulfinic acid compound to the graphene oxide-modified protein fiber in the aqueous sulfinic acid compound solution is from 1.5:10 to 2.5:10 or from 1.8:10 to 2.0: 10. In another particular embodiment, the weight ratio of the sulfinic acid compound to the graphene oxide-modified protein fiber in the aqueous sulfinic acid compound solution is 1.2:10, 1.4:10, 1.6:10, 1.8:10, 2.0:10, 2.2:10, 2.6:10, or 2.8: 10.
In one embodiment, the reduction time of the graphene oxide-modified protein fiber may be any one selected from the group consisting of: 0.15 to 3.0 hours, 0.2 to 2.8 hours, 0.3 to 2.5 hours, 0.4 to 2.2 hours, 0.5 to 2.0 hours, 0.6 to 1.8 hours, 0.8 to 1.5 hours, 1.0 to 1.2 hours. Preferably, in particular embodiments, the reduction time of the graphene oxide-modified protein fiber may be 0.15 hours, 0.2 hours, 0.3 hours, 0.4 hours, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, or 1.0 hour. In further particular embodiments, the reduction time of the graphene oxide-modified protein fiber may be 0.15 hours, 0.2 hours, 0.3 hours, 0.4 hours, or 0.5 hours.
In one embodiment, the graphene oxide-modified protein fiber has a reduction temperature of any one selected from the group consisting of: 50 ℃ to 100 ℃, 55 ℃ to 95 ℃, 60 ℃ to 90 ℃, 65 ℃ to 85 ℃, 70 ℃ to 80 ℃ and 75 ℃ to 78 ℃. Preferably, in particular embodiments, the graphene oxide-modified protein fiber has a reduction temperature of 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃. In further particular embodiments, the graphene oxide-modified protein fiber has a reduction temperature of 80 ℃, 90 ℃, or 100 ℃ in order to facilitate the reduction of the graphene oxide-modified protein fiber by the sulfinic acid compound.
In one embodiment, the sulfinic acid compound can be an alkyl sulfinic acid, an aryl sulfinic acid, or a salt thereof; or combinations thereof, wherein the alkyl or aryl group can be substituted or unsubstituted. In another particular embodiment, the sulfinic acid compound can be a potassium, sodium, or ammonium salt of an alkyl or aryl sulfinic acid, or the like.
Specifically, in one embodiment, the sulfinic acid compound can be an alkyl sulfinic acid, such as hydroxymethyl sulfinic acid, 3-methylsulfinic acid, 2-hydroxy-2-sulfinatoacetic acid, trifluoromethylsulfinic acid, 1-hydroxyethylsulfinic acid, 1-hydroxypropylsulfinic acid, 1-hydroxybutylsulfinic acid, 1-hydroxy-1-methylethylsulfinic acid, 1-hydroxy-1-ethylpropylsulfinic acid, 1-hydroxy-1-methylpropylsulfinic acid, or 1-hydroxy-1-methylpentylsulfinic acid, or a salt thereof. In another embodiment, the sulfinic acid compound can be an arylsulfinic acid, such as 3-nitrobenzenesulfinic acid, 4-chlorobenzenesulfinic acid, 4-cyanobenzenesulfinic acid, 4-ethoxycarbonylbenzenesulfinic acid, 4-trifluoromethylbenzenesulfinic acid, 3-trifluoromethylbenzenesulfinic acid, 1-anthraquinone sulfinic acid, 1-naphthalenesulfinic acid, 2-naphthalenesulfinic acid, phenylsulfinic acid, p-methoxyphenylsulfinic acid, p-methylphenylsulfinic acid, p-chlorophenylsulfinic acid, p-bromophenylsulfinic acid, p-iodophenylsulfinic acid, p-nitrophenylsulfinic acid, o-chlorophenylsulfinic acid, o-nitrophenylsulfinic acid, or naphthyl sulfinic acid, or a salt thereof.
Preferably, in a particular embodiment, the sulfinic acid compound can be hydroxymethylsulfinic acid, 3-methylsulfinic acid, trifluoromethylsulfinic acid, 1-hydroxyethylsulfinic acid, p-methylphenylsulfinic acid, phenylsulfinic acid, or salts thereof, or a combination thereof. More preferably, in certain embodiments, the sulfinic acid compound can be hydroxymethylsulfinic acid, 3-methylsulfinic acid, phenylsulfinic acid, or salts thereof, or a combination thereof. Most preferably, in certain embodiments, the sulfinic acid compound can be hydroxymethylsulfinic acid, sodium hydroxymethylsulfinate, ammonium 3-methylsulfonate, or a combination thereof.
The present invention also provides the graphene-modified conductive protein fiber prepared by the above method, and the absolute value of the rate of change in resistance of such graphene-modified conductive protein fiber after a water washing resistance test may be 5% to 70%.
In one embodiment, the graphene-modified conductive protein fiber may have an absolute value of a rate of change in resistance of 10% to 65%, 15% to 60%, 20% to 55%, 25% to 50%, 30% to 45%, or 35% to 40% after a water washing resistance test.
In one embodiment, the absolute value of the rate of change of resistance of the graphene-modified conductive protein fiber after the water washing resistance test may be 8%, 16%, 18%, 22%, 28%, 32%, 38%, 42%, 48%, 52%, 58%, 62%, or 68%. In certain embodiments, the graphene-modified conductive protein fiber may have an absolute value of a rate of change in resistance of 5%, 10%, 15%, 18%, 25%, or 30% after a water washing resistance test.
In one embodiment, the graphene-modified conductive protein fiber may have a resistance of 1.0 × 101Omega to 1.0 x 105Ω、2.0×101Omega to 5.0 x 104Ω、4.0×101Omega to 2.0 x 104Ω、8.0×101Omega to 1.0 x 104Ω、1.0×102Omega to 5X 103Omega, or 2X 102Omega to 2 x 103Omega, or 4.0X 102Omega to 1.0 x 103Ω。
In one embodiment, the graphene-modified conductive protein fiber may have a resistance of 1.5 × 101Ω、3.0×101Ω、6.0×101Ω、1.5×102Ω、3.0×102Ω、6.0×102Ω、1.5×103Ω、3.0×103Ω、6.0×103Ω、1.5×104Ω、3.0×104Omega or 6.0X 104Ω。
The invention also provides application of the graphene modified conductive protein fiber in intelligent sensors, electromagnetic shielding, electric heating medical supplies, conductive textiles or antistatic textiles.
In one embodiment, the smart sensor may be a PH sweat sensor, a blood pressure pulse sensor, a respiration rate sensor, a joint flexion sensor, a human motion detection sensor, an electronic skin, or the like.
In another embodiment, the conductive textile may be a wearable device, a temperature regulating textile, an electrochromic textile, a shape memory textile, or a light emitting textile, among others.
In yet another embodiment, the electrically heated medical article may be an electrically heated medical pad, a pulse electrically heated medical tape, a surgical warming blanket, a medical warming patch, an electro-magneto-therapeutic device, or the like.
The graphene modified conductive protein fiber obtained by the method has lower resistance and good water washing resistance, so that the preparation method of the graphene modified conductive protein fiber is obviously valuable in industry.
Examples
The present invention is described in more detail below with reference to examples. However, the present invention is not limited to the following examples.
Example 1
Preparation of graphene modified conductive wool fibers
Graphene oxide was prepared using a modified Hummer's method to obtain a solution of graphene oxide having a particle size of 1 μm, and the obtained solution of graphene oxide was diluted with water to obtain a graphene oxide solution of 2 mg/ml. And then soaking the wool fibers in the graphene oxide solution at a weight ratio of graphene oxide to wool fibers of 1:10 to enable graphene oxide to carry out surface modification on the wool fibers for 2 hours, so as to obtain graphene oxide modified wool fibers.
Placing the obtained graphene oxide modified wool fiber in a hydroxymethyl sodium sulfinate aqueous solution with the weight ratio of sodium hydroxymethyl sulfinate to graphene oxide modified wool fiber being 1:10, and heating the mixture at 80 ℃ for 1.5 hours to perform a reduction reaction on the graphene oxide modified wool fiber to obtain the graphene modified conductive wool fiber.
The obtained graphene modified conductive wool fiber has the resistance of 5.0 multiplied by 104Omega, resistance of 6.0X 10 after water washing resistance test4Ω。
Example 2
Preparation of graphene modified conductive mulberry silk fiber
Graphene oxide was prepared using a modified Hummer's method to obtain a solution of graphene oxide with a particle size of 1 μm. The resulting graphene oxide solution was diluted with water to obtain a 2mg/ml graphene oxide solution. And then, soaking the mulberry silk fiber in the graphene oxide solution according to the weight ratio of 3:10 of graphene oxide to the mulberry silk fiber, so that the surface of the mulberry silk fiber is modified by the graphene oxide for 2 hours, and thus the graphene oxide modified mulberry silk fiber is obtained.
Placing the obtained graphene oxide modified mulberry silk fiber in a hydroxymethyl sulfinic acid aqueous solution with the weight ratio of 3:10 of hydroxymethyl sulfinic acid to graphene oxide modified mulberry silk fiber, and heating the mixture at 100 ℃ for 1 hour to perform a reduction reaction on the graphene oxide modified mulberry silk fiber so as to obtain the graphene modified conductive mulberry silk fiber.
The obtained graphene modified conductive mulberry silk fiber has a resistance of 8.0 × 104Omega, resistance 9.0X 10 after washing resistance test4Ω。
Example 3
Preparation of graphene modified conductive rabbit hair fiber
Graphene oxide was prepared using a modified Hummer's method to obtain a solution of graphene oxide with a particle size of 5 μm. The resulting graphene oxide solution was diluted with water to obtain a 5mg/ml graphene oxide solution. And then soaking the rabbit hair fiber in the graphene oxide solution in a weight ratio of graphene oxide to rabbit hair fiber of 2:10, so that the graphene oxide performs surface modification on the rabbit hair fiber for 2 hours to obtain the graphene oxide modified rabbit hair fiber.
Placing the obtained graphene oxide modified rabbit hair fiber in a 3-methylsulfinic acid ammonium aqueous solution at a weight ratio of 3-methylsulfinic acid ammonium to graphene oxide modified rabbit hair fiber of 2:10, and heating the mixture at 85 ℃ for 0.5 hour to perform a reduction reaction on the graphene oxide modified rabbit hair fiber to obtain the graphene modified conductive rabbit hair fiber.
The resistance of the obtained graphene modified conductive rabbit hair fiber is 7.0 multiplied by 104Omega, after water washing experiment, the resistance is 8.0 multiplied by 104Ω。
Example 4
Preparation of graphene modified conductive soybean protein fiber
Graphene oxide was prepared using a modified Hummer's method to obtain a solution of graphene oxide with a particle size of 3 μm. The resulting graphene oxide solution was diluted with water to obtain a 2mg/ml graphene oxide solution. And then soaking the soybean protein fibers in the graphene oxide solution in a weight ratio of graphene oxide to soybean protein fibers of 2:10, so that the graphene oxide performs surface modification on the soybean protein fibers for 2 hours to obtain graphene oxide modified soybean protein fibers.
Placing the obtained graphene oxide modified soybean protein fiber in a 3-methylsulfinic acid ammonium aqueous solution at a weight ratio of 3-methylsulfinic acid ammonium to graphene oxide modified soybean protein fiber of 2:10, and heating the mixture at 85 ℃ for 0.5 hour to perform a reduction reaction on the graphene oxide modified soybean protein fiber to obtain the graphene modified conductive soybean protein fiber.
The obtained graphene modified conductive soybean protein fiber has a resistance of 3.0 × 104Omega, resistance 5.0X 10 after washing experiment4Ω。
Comparative example 1
Preparation of graphene modified conductive wool fibers
A comparative sample graphene-modified conductive wool fiber was prepared in the same manner as in example 1, except that hydrazine hydrate was used as a reducing agent and the heating time was 2 hours.
The obtained graphene modified conductive wool fiber has the resistance of 7.0 multiplied by 104Omega, resistance increased to 5.0X 10 after washing resistance test5Ω。
Comparative example 2
Preparation of graphene modified conductive mulberry silk fiber
A comparative sample graphene-modified conductive mulberry silk fiber was prepared in the same manner as in example 2, except that hydrazine hydrate was used as a reducing agent and the heating time was 1.5 hours.
The obtained graphene modified conductive mulberry silk fiber has a resistance of 3.0 × 105Omega m, resistance increased to 9.0X 10 after washing resistance test6Ω·m。
Comparative example 3
Preparation of graphene modified conductive rabbit hair fiber
A comparative sample graphene-modified conductive rabbit hair fiber was prepared in the same manner as in example 3, except that hydrazine hydrate was used as a reducing agent and the heating time was 1 hour.
The resistance of the obtained graphene modified conductive rabbit hair fiber is 9.0 multiplied by 104Omega, resistance increased to 6.0X 10 after wash test5Ω。
Comparative example 4
Preparation of graphene modified conductive soybean protein fiber
A comparative sample graphene-modified conductive soy protein fiber was prepared in the same manner as in example 4, except that hydrazine hydrate was used as the reducing agent and the heating time was 1 hour.
The obtained graphene modified conductive soybean protein fiber has a resistance of 3.0 × 104Omega, resistance increased to 1.0X 10 after water washing experiments5Ω。
The graphene-modified conductive protein fibers obtained in examples 1 to 4 and comparative examples 1 to 4 were subjected to a conductivity test and compared, and the results are shown in table 1. As can be seen from table 1, the conductivity and the washing resistance of the graphene-modified conductive protein fiber prepared using the sulfinic acid compound as the reducing agent are superior to those of the graphene-modified conductive protein fiber prepared using hydrazine hydrate reduction before and after washing.
TABLE 1
Test for Wash resistance
According to GB/T3921-. The prepared graphene-modified conductive protein fibers were then placed in the test solution at a weight ratio of 1:50 and stirred at 60 ℃ for 30 minutes, washed and dried. And (3) testing the resistance of the graphene modified conductive protein fiber before and after water washing, and representing the water washing resistance by using the absolute value of the change rate of the resistance of the conductive fiber.
The above embodiments and examples are merely illustrative of specific embodiments of the present disclosure, but the embodiments of the present disclosure are not limited by the above. Any changes, modifications, substitutions, combinations, and simplifications which do not materially depart from the spirit and principles of the inventive concepts disclosed herein are intended to be equivalent permutations and to be included within the scope of the invention as defined by the following claims.
Claims (17)
1. A method of preparing a graphene-modified conductive protein fiber, comprising:
combining graphene oxide with protein fibers in a graphene oxide solution in a surface modification manner to obtain graphene oxide modified protein fibers; and
reducing the graphene oxide-modified protein fiber in an aqueous solution of a sulfinic acid compound at a temperature of 50 ℃ to 100 ℃ to obtain a graphene-modified conductive protein fiber,
wherein the sulfinic acid compound is selected from one or more of the following: hydroxymethanesulfinic acid, sodium hydroxymethanesulfinate or ammonium 3-methanesulfinate.
2. The method of claim 1, wherein the graphene oxide has a particle size of 0.1 μ ι η to 7.0 μ ι η.
3. The method of claim 2, wherein the graphene oxide has a particle size of 0.5 μ ι η to 5.0 μ ι η.
4. The method of claim 1, wherein the protein fiber is one or more selected from the group consisting of: animal protein fibers, plant protein fibers, or combinations thereof.
5. The method of claim 4, wherein the animal protein fiber is wool, rabbit hair, silk, casein protein fiber, silkworm pupa protein fiber, pearl protein fiber, or milk protein fiber.
6. The method of claim 4, wherein the plant protein fiber is a peanut protein fiber, a corn protein fiber, a soy protein fiber, or a hemp seed protein fiber.
7. The method of claim 1, wherein the weight ratio of the graphene oxide to the protein fiber in the graphene oxide solution is from 1.0:10 to 3.0: 10.
8. The method of claim 7, wherein the weight ratio of the graphene oxide to the protein fiber in the graphene oxide solution is from 1.8:10 to 2.0: 10.
9. The method of claim 1, wherein the weight ratio of the sulfinic acid compound to the graphene oxide-modified protein fiber in the aqueous sulfinic acid compound solution is from 1.0:10 to 3.0: 10.
10. The method of claim 9, wherein the weight ratio of the sulfinic acid compound to the graphene oxide-modified protein fiber in the aqueous sulfinic acid compound solution is from 1.8:10 to 2.0: 10.
11. The graphene-modified conductive protein fiber prepared by the method according to any one of claims 1 to 10, wherein the graphene-modified conductive protein fiber has an absolute value of a rate of change in resistance of 5% to 70% after a water washing resistance test.
12. The graphene-modified conductive protein fiber according to claim 11, wherein the graphene-modified conductive protein fiber has an absolute value of a rate of change in resistance of 10% to 65% after a water washing resistance test.
13. The graphene-modified conductive protein fiber according to claim 12, wherein the graphene-modified conductive protein fiber has an absolute value of a rate of change in resistance of 25% to 50% after a water washing resistance test.
14. The graphene-modified conductive protein fiber according to claim 11 or 12, wherein the graphene-modified conductive protein fiber has a resistance of 1.0 x 101Omega to 1.0 x 105Ω。
15. The graphene-modified conductive protein fiber according to claim 14, wherein the graphene-modified conductive protein fiber has a resistance of 4.0 x 101Omega to 2.0 x 104Ω。
16. The graphene-modified conductive protein fiber according to claim 15, wherein the graphene-modified conductive protein fiber has a resistance of 4.0 x 102Omega to 1.0 x 103Ω。
17. Use of graphene-modified conductive protein fibers obtained by the method of any one of claims 1 to 10 or the graphene-modified conductive protein fibers of any one of claims 11 to 16 in smart sensors, electromagnetic shielding, electrothermal medical supplies, conductive textiles or antistatic textiles.
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