阅读说明：本技术 一种氧化石墨烯和再生丝素蛋白共混纺丝工艺 (Graphene oxide and regenerated silk fibroin blending spinning process ) 是由 陈茹鸣 于 2021-06-17 设计创作，主要内容包括：本发明涉及纺丝技术领域,特别涉及一种氧化石墨烯和再生丝素蛋白共混纺丝工艺,包括丝素蛋白溶液、氧化石墨烯溶液、导电涂层和防脱剂,导电涂层属于掺合型导电涂层,是由细铜颗粒、细银颗粒、无机黏结剂以及稀释剂混合而成的涂层,防脱剂又称硅烷偶联剂,丝素蛋白溶液的制备方法有以下几个步骤：步骤一：将比例配制为10：1的水与氯化钙混合溶液放入反应器中,随后将脱胶后的蚕丝放入反应器内部,并对反应器加热至混合溶液沸腾,加热的同时不断对其搅拌,通过导电涂层提供的静态导电性能能够有效提高氧化石墨烯和再生丝素蛋白共混纺丝的导电性能,使氧化石墨烯和再生丝素蛋白共混纺丝的导电性能得以保障提高。(The invention relates to the technical field of spinning, in particular to a graphene oxide and regenerated silk fibroin blending spinning process, which comprises a silk fibroin solution, a graphene oxide solution, a conductive coating and an anti-shedding agent, wherein the conductive coating belongs to a blending conductive coating and is a coating formed by mixing fine copper particles, fine silver particles, an inorganic adhesive and a diluent, the anti-shedding agent is also called as a silane coupling agent, and the preparation method of the silk fibroin solution comprises the following steps: the method comprises the following steps: preparing the raw materials in a ratio of 10: 1, placing the mixed solution of water and calcium chloride into a reactor, then placing degummed silk into the reactor, heating the reactor until the mixed solution boils, continuously stirring the mixed solution while heating, and effectively improving the conductivity of the graphene oxide and regenerated silk fibroin blended spinning through the static conductivity provided by the conductive coating, so that the conductivity of the graphene oxide and regenerated silk fibroin blended spinning is ensured to be improved.)

1. A blending spinning process of graphene oxide and regenerated silk fibroin comprises a silk fibroin solution, a graphene oxide solution, a conductive coating and an anti-shedding agent, and is characterized in that: the conductive coating belongs to a blending conductive coating and is a coating formed by mixing fine copper particles, fine silver particles, an inorganic adhesive and a diluent, and the anti-falling agent is also called a silane coupling agent.

2. The blending spinning process of graphene oxide and regenerated silk fibroin according to claim 1, which is characterized in that: the preparation method of the silk fibroin solution comprises the following steps:

the method comprises the following steps: preparing the raw materials in a ratio of 10: 1, putting the mixed solution of water and calcium chloride into a reactor, then putting the degummed silk into the reactor, heating the reactor until the mixed solution is boiled, and continuously stirring the mixed solution while heating until the silk is fully dissolved in the mixed solution;

step two: pouring out and filtering the mixed solution for dissolving the silk, adding an ammonium sulfate solution into the filtered solution, continuously stirring the solution in the adding process, standing for natural layering of the solution, wherein the white precipitate below the layered solution is the silk fibroin solution.

3. The blending spinning process of graphene oxide and regenerated silk fibroin according to claim 1, which is characterized in that: the preparation method of the graphene oxide solution comprises the following steps:

the method comprises the following steps: firstly, putting a substrate metal foil into a clean and dry furnace, and then introducing hydrogen and argon to play a certain protection role;

step two: heating a furnace containing the substrate metal foil to 900-1000 ℃, keeping the temperature stable for 15-20 minutes, stopping introducing hydrogen and argon into the furnace, introducing carbon source (such as methane) gas into the furnace, and completing the reaction within about 25 minutes;

step three: after about 25 minutes, closing the carbon source gas introduced into the furnace, introducing the protective gas again so as to discharge the carbon source gas in the furnace, and taking out the metal foil under the environment of the protective gas until the temperature in the furnace is cooled to normal room temperature, so that the graphene on the metal foil can be obtained;

step four: oxidizing the obtained graphene with strong acid to prepare graphene oxide, washing the graphene oxide, drying the powder, and preparing the graphene oxide powder into a graphene oxide solution by using ultrasonic treatment.

4. The blending spinning process of graphene oxide and regenerated silk fibroin according to claim 1, which is characterized in that: the preparation process of the graphene oxide and regenerated silk fibroin blended spinning comprises the following steps:

the method comprises the following steps: preparing the prepared silk fibroin solution and graphene oxide solution according to the proportion of 1:8, mixing the solutions by using ultrasonic equipment, controlling the temperature to be about 25 ℃ during the use period of the ultrasonic equipment, and stirring for about 80 minutes;

step two: mixing the silk fibroin solution and the graphene oxide solution, preparing blended spinning through an electrostatic spinning technology, and then drying the obtained graphene oxide and regenerated silk fibroin blended spinning;

step three: and (3) adhering a conductive coating to the surface of the co-mixed spinning by brushing on the surface of the dried graphene oxide and regenerated silk fibroin co-mixed spinning, wherein the dosage of the conductive coating is about 30 g per square meter, and brushing the anti-shedding agent on the outer surface of the conductive coating after the conductive coating is dried.

Technical Field

The invention relates to the technical field of spinning, in particular to a blending spinning process of graphene oxide and regenerated silk fibroin.

Background

Electrostatic spinning is a special form of electrostatic atomization of high molecular fluid, at this time, the substance split by atomization is not a tiny droplet but a polymer tiny jet flow, can run for a long distance, and is finally solidified into fiber, which is a special fiber manufacturing process, a polymer solution or a melt is sprayed and spun in a strong electric field, graphene oxide is an oxide of graphene, the color of the graphene oxide is brown yellow, the graphene oxide can be regarded as a non-traditional soft material and has the characteristics of polymer, colloid, thin film and amphoteric molecules, silk fibroin is natural high molecular fiber protein extracted from silk, the content of the natural high molecular fiber protein accounts for about 70-80% of the silk, the silk fibroin contains 18 amino acids, wherein glycine (Gly), alanine (Ala) and serine (Ser) account for more than 80% of the total composition, and the silk fibroin has good mechanical property and physicochemical property, such as good flexibility, tensile strength, air permeability, moisture permeability, slow release property and the like.

At present, the graphene oxide and the silk fibroin are subjected to mixed spinning by using an electrostatic spinning technology, and the mixed spinning of the graphene oxide and the silk fibroin can be used in a plurality of fields by better combining certain excellent characteristics of the graphene oxide and the silk fibroin, but in the process of manufacturing the graphene oxide and the silk fibroin, certain excellent characteristics of the graphene oxide and the silk fibroin can be retained, and the reduction of certain characteristics can also cause the reduction of certain characteristics to be weakened, for example, the electric conduction and thermal conduction performance of the graphene can be greatly reduced, and the reduction of the characteristics can influence the use effect of the mixed spinning of the graphene oxide and the silk fibroin in certain fields, so that the production quality is reduced to a certain extent.

Disclosure of Invention

The invention aims to provide a blending spinning process of graphene oxide and regenerated silk fibroin, which aims to solve the problems that the use effect of mixed spinning of graphene oxide and silk fibroin in certain fields can be influenced and the production quality is reduced to a certain extent due to the fact that the electric and thermal conductivity of graphene is greatly reduced in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: a graphene oxide and regenerated silk fibroin blended spinning process comprises a silk fibroin solution, a graphene oxide solution, a conductive coating and an anti-dropping agent, wherein the conductive coating belongs to a blending conductive coating and is a coating formed by mixing fine copper particles, fine silver particles, an inorganic adhesive and a diluent, and the anti-dropping agent is also called a silane coupling agent.

Preferably, the preparation method of the silk fibroin solution comprises the following steps:

the method comprises the following steps: preparing the raw materials in a ratio of 10: 1, putting the mixed solution of water and calcium chloride into a reactor, then putting degummed silk into the reactor, heating the reactor until the mixed solution boils, and continuously stirring the reactor while heating until the silk is fully dissolved in the mixed solution.

Step two: pouring out and filtering the mixed solution for dissolving the silk, adding an ammonium sulfate solution into the filtered solution, continuously stirring the solution in the adding process, standing for natural layering of the solution, wherein the white precipitate below the layered solution is the silk fibroin solution.

Preferably, the preparation method of the graphene oxide solution comprises the following steps:

the method comprises the following steps: firstly, the base metal foil is put into a clean and dry furnace, and then hydrogen and argon are introduced to play a certain protection role.

Step two: heating the furnace containing the substrate metal foil to 900-1000 ℃, keeping the temperature stable for 15-20 minutes, stopping introducing hydrogen and argon into the furnace, introducing carbon source (such as methane) gas into the furnace, and completing the reaction within about 25 minutes.

Step three: and after about 25 minutes, closing the carbon source gas introduced into the furnace, introducing the protective gas again so as to discharge the carbon source gas in the furnace, and taking out the metal foil under the environment of the protective gas until the temperature in the furnace is cooled to normal room temperature, so that the graphene on the metal foil can be obtained.

Step four: oxidizing the obtained graphene with strong acid to prepare graphene oxide, washing the graphene oxide, drying the powder, and preparing the graphene oxide powder into a graphene oxide solution by using ultrasonic treatment.

Preferably, the preparation process of the graphene oxide and regenerated silk fibroin blended spinning comprises the following steps:

the method comprises the following steps: and (3) preparing the prepared silk fibroin solution and graphene oxide solution according to the proportion of 1:8, mixing the solutions by using ultrasonic equipment, controlling the temperature to be about 25 ℃ during the use period of the ultrasonic equipment, and stirring for about 80 minutes.

Step two: and mixing the silk fibroin solution and the graphene oxide solution, preparing blended spinning by an electrostatic spinning technology, and then drying the obtained graphene oxide and regenerated silk fibroin blended spinning.

Step three: and (3) adhering a conductive coating to the surface of the co-mixed spinning by brushing on the surface of the dried graphene oxide and regenerated silk fibroin co-mixed spinning, wherein the dosage of the conductive coating is about 30 g per square meter, and brushing the anti-shedding agent on the outer surface of the conductive coating after the conductive coating is dried.

The invention has the technical effects and advantages that:

1. the static conductivity provided by the conductive coating can effectively improve the conductivity of the graphene oxide and regenerated silk fibroin blended spinning, so that the conductivity of the graphene oxide and regenerated silk fibroin blended spinning is ensured to be improved.

2. The anti-dropping agent greatly improves and enhances the bonding degree between the conductive coating and the blending spinning of the graphene oxide and the regenerated silk fibroin, effectively prevents the conductive coating from dropping, and can improve the dispersibility of the conductive coating.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a technical scheme that: a blending spinning process for graphene oxide and regenerated silk fibroin comprises a silk fibroin solution, a graphene oxide solution, a conductive coating and an anti-shedding agent, wherein the conductive coating belongs to a blending conductive coating and is a coating formed by mixing fine copper particles, fine silver particles, an inorganic adhesive and a diluent, the anti-shedding agent is also called a silane coupling agent, the silk fibroin solution is a faint yellow clarified protein aqueous solution obtained by refining silk fibers subjected to sericin shedding through a series of purification processes, the graphene oxide is an oxide of graphene, the color of the graphene oxide is brown yellow, the brown graphite flake with derived carboxylic acid groups at the edge and phenolic hydroxyl groups and epoxy groups mainly on the plane is obtained after oxidation reaction of potassium permanganate in concentrated sulfuric acid and graphite powder, the graphite flake layer can be subjected to ultrasonic or high-shear intensive stirring stripping to form graphene oxide, and the stable graphene oxide is formed in water, Light brown yellow single layer graphene oxide suspension.

The conductive coating is a film or a coating which is additionally coated on the surface of a material and has certain conductive capability, can provide excellent static conductive performance, is a protective energy absorption layer and also can provide good covering and protecting performance, the conductive coating mixed by copper particles and silver particles has excellent conductivity, and the main components of the inorganic adhesive are aluminum phosphate solution and copper monoxide powder, and has the following characteristics: 1. the inorganic adhesive can bear the temperature of about 1000 ℃ or higher; 2. the water-soluble flame-retardant polypropylene composite material is water-soluble, low in toxicity, non-combustible and free of environmental pollution; 3. the thermal expansion coefficient is small, and is only 1/10 of steel and 1/3 of ceramic; 4, oil resistance, radiation resistance, no aging and good durability; 5. can be cured at room temperature, basically does not shrink, and slightly expands.

After graphene is oxidized by potassium permanganate, the conductivity of the graphene can be greatly reduced, the conductivity of the blended spinning can be effectively increased by the conductive coating, the product performance can be ensured to be improved, the anti-falling agent can be greatly improved, the physical mechanical properties such as dry-wet bending strength, compressive strength and shear strength of plastics and wet electrical properties of the plastics can be enhanced, the wettability and the dispersibility of the filler in a polymer can be improved, the anti-falling agent is an excellent adhesion promoter and is named 3-triethoxysilyl-1-propylamine, the adhesion between the conductive coating and the blended spinning can be firmer by the anti-falling agent coating, the dispersibility of the conductive coating can be improved, and the conductive coating can be effectively prevented from falling off.

As a technical optimization scheme of the invention, the preparation method of the silk fibroin solution comprises the following steps:

the method comprises the following steps: preparing the raw materials in a ratio of 10: 1, placing the degummed silk into a reactor, heating the reactor until the mixed solution boils, continuously stirring the degummed silk until the silk is fully dissolved in the mixed solution, wherein the silk fibroin content in the silk is about 70-80%, the silk has good mechanical properties and physicochemical properties, such as good flexibility, tensile strength, air permeability, moisture permeability, slow release property and the like, and different forms, such as fiber, solution, powder, membrane, gel and the like, can be obtained through different treatments.

Step two: pour out and filter the mixed solution that dissolves silk, add ammonium sulfate solution and constantly stir solution at the addition in-process in the solution after the filtration, wait for the solution natural layering of standing afterwards, the white precipitate that is in the below in the layering is silk fibroin solution promptly, can reach the filter effect with clean filtration gauze during the filtration, and what mainly filtered was the impurity in the silk.

As a technical optimization scheme of the invention, the preparation method of the graphene oxide solution comprises the following steps:

the method comprises the following steps: at present, methane is mainly used as a carbon source gas source in experiments and production, and auxiliary gases comprise hydrogen, argon, nitrogen and other gases, which can effectively reduce folds of a film, increase flatness and reduce deposition of amorphous carbon.

Step two: heating the furnace containing the substrate metal foil to 900-1000 ℃, keeping the temperature stable for 15-20 minutes, stopping introducing hydrogen and argon into the furnace, introducing carbon source (such as methane) gas into the furnace, and completing the reaction within about 25 minutes.

Step three: and after about 25 minutes, closing the carbon source gas introduced into the furnace, introducing the protective gas again so as to discharge the carbon source gas in the furnace, and taking out the metal foil under the environment of the protective gas until the temperature in the furnace is cooled to normal room temperature, so that the graphene on the metal foil can be obtained.

Step four: oxidizing the obtained graphene with strong acid to prepare graphene oxide, washing the graphene oxide, drying the powder, and preparing the graphene oxide powder into a graphene oxide solution by using ultrasonic treatment.

As a technical optimization scheme of the invention, the preparation process of the graphene oxide and regenerated silk fibroin blended spinning comprises the following steps:

the method comprises the following steps: and (3) preparing the prepared silk fibroin solution and graphene oxide solution according to the proportion of 1:8, mixing the solutions by using ultrasonic equipment, controlling the temperature to be about 25 ℃ during the use period of the ultrasonic equipment, and stirring for about 80 minutes.

Step two: and mixing the silk fibroin solution and the graphene oxide solution, preparing blended spinning by an electrostatic spinning technology, and then drying the obtained graphene oxide and regenerated silk fibroin blended spinning.

Step three: and (3) adhering a conductive coating to the surface of the co-mixed spinning by brushing on the surface of the dried graphene oxide and regenerated silk fibroin co-mixed spinning, wherein the dosage of the conductive coating is about 30 g per square meter, and brushing the anti-shedding agent on the outer surface of the conductive coating after the conductive coating is dried.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.