阅读说明：本技术 一种石墨烯负离子再生纤维素复合纤维及其制备方法 (Graphene anion regenerated cellulose composite fiber and preparation method thereof ) 是由 沙嫣 沙晓林 马立国 于 2021-09-18 设计创作，主要内容包括：本发明公开了一种石墨烯负离子再生纤维素复合纤维及其制备方法,该方法包含：步骤1,按比例称取各原料；原料中包含纤维素、石墨烯材料、改性剂、负离子粉；步骤2,使用球磨机对负离子粉进行研磨,然后干燥；步骤3,将纤维素、石墨烯、改性剂分散于溶剂中,通过搅拌使纤维素充分溶解,配制纺丝液；步骤4,将步骤3所得的包含完全溶解的纤维素的纺丝液,使用干喷湿法纺丝工艺进行纺丝。本发明还提供了该方法制备的石墨烯负离子再生纤维素复合纤维。本发明提供的石墨烯负离子再生纤维素复合纤维及其制备方法,制备的复合纤维具备抗菌、释放负离子等功能,能够扩展纤维素纤维应用范围。(The invention discloses a graphene anion regenerated cellulose composite fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder; step 2, grinding the negative ion powder by using a ball mill, and then drying; step 3, dispersing cellulose, graphene and a modifier in a solvent, fully dissolving the cellulose by stirring, and preparing a spinning solution; and 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process. The invention also provides the graphene anion regenerated cellulose composite fiber prepared by the method. According to the graphene anion regenerated cellulose composite fiber and the preparation method thereof, the prepared composite fiber has the functions of resisting bacteria, releasing anions and the like, and the application range of the cellulose fiber can be expanded.)

1. A preparation method of graphene anion regenerated cellulose composite fibers is characterized by comprising the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder;

step 2, grinding the negative ion powder by using a ball mill, and then drying;

step 3, dispersing cellulose, graphene and a modifier in a solvent, fully dissolving the cellulose by stirring, and preparing a spinning solution;

and 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

2. The method for preparing the graphene negative ion regenerated cellulose composite fiber according to claim 1, wherein the raw material comprises, by mass, 89-99% of cellulose, 0.1-10% of graphene material, 0.1-5% of modifier, and 0.1-5% of negative ion powder.

3. The preparation method of the graphene negative ion regenerated cellulose composite fiber according to claim 2, wherein the modifier is a surfactant, and polyethylene glycol, polyvinylpyrrolidone and hydroxymethyl cellulose are adopted according to a mass ratio of 1: (1-2): (2-3) mixing.

4. The method for preparing the graphene negative ion regenerated cellulose composite fiber according to claim 2, wherein the graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method and a redox method.

5. The method for preparing the graphene negative ion regenerated cellulose composite fiber according to claim 2, wherein the negative ion powder is tourmaline and/or rare earth element powder.

6. The method for preparing graphene negative ion regenerated cellulose composite fibers according to claim 1, wherein in the step 2, the negative ion powder is ground to a particle size of less than 1 μm by using a ball mill and then dried.

7. The method for preparing the graphene negative ion regenerated cellulose composite fiber according to claim 1, wherein in the step 3, the cellulose, the graphene and the modifier are dispersed in the NMMO aqueous solution, and the mixture is sufficiently stirred for 50-100min by a stirrer to completely dissolve the cellulose, thereby preparing the spinning solution.

8. The method for preparing the graphene negative ion regenerated cellulose composite fiber according to claim 7, wherein the concentration of the cellulose in the spinning solution is 5 to 15% by mass, and the viscosity of the spinning solution is 2500 to 4000 Pa-S.

9. The preparation method of the graphene negative ion regenerated cellulose composite fiber according to claim 1, wherein in the step 4, the spinning temperature of the dry-jet wet spinning process is 90-95 ℃, the blowing speed of the fiber after exiting a spinneret plate and before entering a coagulation bath is 35-40m/s, the coagulation bath is an NMMO aqueous solution, the mass concentration is 10-20%, and the spinning speed is 1-5 m/s.

10. The graphene negative ion regenerated cellulose composite fiber prepared by the method of any one of 1-9.

Technical Field

The invention relates to a graphene composite fiber and a preparation method thereof, and particularly relates to a graphene negative ion regenerated cellulose composite fiber and a preparation method thereof.

Background

Graphene is a single-layer carbon atom material stripped from graphite, and a single-layer two-dimensional honeycomb lattice structure is formed by tightly packing carbon atoms, and is known to be the material with the thinnest thickness, the hardest texture and the best conductivity. Graphene has excellent mechanical, optical and electrical properties and a very stable structure, researchers have not found that graphene has a missing carbon atom, the linkage between carbon atoms is very flexible, and is harder than diamond, the strength is 100 times higher than that of the world's best steel, if graphene is used for making a packaging bag, the graphene can bear about two tons of articles, the graphene is almost completely transparent, but is very compact, waterproof and airtight, helium gas with the minimum atomic size cannot pass through the graphene, the graphene has good conductivity, the movement speed of electrons in graphene reaches 1/300 of the light speed, the conductivity exceeds that of any traditional conductive material, the chemical properties are similar to the surface of graphite, various atoms and molecules can be adsorbed and desorbed, and the graphene also has the capability of resisting strong acid and strong alkali.

According to the graphene antibacterial principle, graphene is densely distributed in the fiber and on the surface, part of graphene is embedded into the fiber, and part of graphene is exposed out of the surface of the fiber, so that a graphene nanometer knife which is more beneficial to killing bacteria is formed, the bacteria are killed, and the antibacterial purpose is achieved.

The negative ion function is that nano tourmaline powder with negative ion releasing function is added in the production process of the fiber, the tourmaline powder is embedded on the surface of the fiber, and the electrons emitted by the tourmaline hit oxygen molecules around the fiber to form charged negative oxygen ions.

According to the literature, the negative oxygen ion known as 'air vitamin' is beneficial to the physical and mental health of human body. It mainly influences the physiological activities of human body through the nervous system and blood circulation of human body. The negative oxygen ions can strengthen the inhibition process of the cerebral cortex of a human and regulate the function of the cerebral cortex, thereby playing the roles of calming, hypnotizing and reducing blood pressure; after the negative oxygen ions enter the respiratory tract of the human body, the smooth muscle of the bronchus is relaxed, and the spasm of the smooth muscle is relieved; the negative oxygen ions enter the blood of human body, so that the sedimentation rate of erythrocyte is slowed, the coagulation time is prolonged, the content of erythrocyte and blood calcium is increased, the content of leucocyte, blood calcium and blood sugar is reduced, and the content of lactic acid in fatigue muscle is reduced. The negative oxygen ions can enhance the oxidation process of human tissues such as kidney, liver, brain, etc., wherein the brain tissue is most sensitive to the negative oxygen ions.

Cellulose fibers themselves have good mechanical properties and hygroscopicity, but are not functional. The traditional functional cellulose fiber is mainly realized by carrying out post-treatment on the surface of the fiber, and the functional fiber prepared by the method has the defects of poor water washing resistance and serious pollution caused by post-treatment, so that the application of the cellulose fiber is limited to a certain extent.

Disclosure of Invention

The invention aims to provide graphene composite fibers and a preparation method thereof, and the prepared graphene negative ion regenerated cellulose composite fibers have the functions of resisting bacteria, releasing negative ions and the like and can expand the application range of cellulose fibers.

In order to achieve the above object, the present invention provides a method for preparing graphene anion regenerated cellulose composite fibers, wherein the method comprises: step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder; step 2, grinding the negative ion powder by using a ball mill, and then drying; step 3, dispersing cellulose, graphene and a modifier in a solvent, fully dissolving the cellulose by stirring, and preparing a spinning solution; and 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

The preparation method of the graphene anion regenerated cellulose composite fiber comprises the following raw materials, by mass, 89-99% of cellulose, 0.1-10% of graphene material, 0.1-5% of modifier and 0.1-5% of anion powder.

The preparation method of the graphene anion regenerated cellulose composite fiber comprises the following steps of (1): (1-2): (2-3) mixing.

In the preparation method of the graphene anion regenerated cellulose composite fiber, the graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method and an oxidation-reduction method.

The preparation method of the graphene anion regenerated cellulose composite fiber comprises the step of preparing the graphene anion regenerated cellulose composite fiber, wherein the anion powder is tourmaline and/or rare earth element powder.

In the preparation method of the graphene anion regenerated cellulose composite fiber, in the step 2, the anion powder is ground by using a ball mill until the particle size is less than 1 μm, and then the anion powder is dried.

In the step 3, the cellulose, the graphene and the modifier are dispersed in the aqueous solution of NMMO, and the mixture is fully stirred for 50-100min by a stirrer to completely dissolve the cellulose, so as to prepare the spinning solution.

According to the preparation method of the graphene anion regenerated cellulose composite fiber, the concentration of cellulose in the spinning solution is 5-15% by mass percent, and the viscosity of the spinning solution is 2500-4000 Pa.S.

In the step 4, the spinning temperature of the dry-jet wet spinning process is 90-95 ℃, the blowing speed of the fiber after exiting the spinneret plate and before entering the coagulating bath is 35-40m/s, the coagulating bath is an NMMO aqueous solution, the mass concentration is 10-20%, and the spinning speed is 1-5 m/s.

The invention also provides the graphene anion regenerated cellulose composite fiber prepared by the method.

The graphene anion regenerated cellulose composite fiber and the preparation method thereof provided by the invention have the following advantages:

the invention is prepared by adopting an environment-friendly cellulose production process, the solvent can be recovered by more than 99 percent and can be reused, the production process does not generate traditional alkaline wastewater, and the method is safe and environment-friendly. The graphene anion fiber has the outstanding characteristics that the composite fiber has the performances of antibiosis, anion and the like, has the functional water washing resistance, does not need a separate post-treatment process, is safe and environment-friendly, and better meets the requirements of current people on functional, comfortable and healthy textiles.

The composite fiber prepared by the invention has excellent antibacterial performance, wherein escherichia coli and golden grapeThe bacteriostasis rate of the coccus and the Candida albicans reaches 99 percent, and the anion number reaches 5000/cm³As described above, the functionality is excellent.

The graphene anion composite fiber prepared by the method has the advantages of simple and easy operation process, low cost and high economic benefit, and is suitable for large-scale industrial production.

Detailed Description

The following further describes embodiments of the present invention.

The invention provides a preparation method of graphene anion regenerated cellulose composite fiber, which comprises the following steps: step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder; step 2, grinding the negative ion powder by using a ball mill, and then drying; step 3, dispersing cellulose, graphene and a modifier in a solvent, fully dissolving the cellulose by stirring, and preparing a spinning solution; and 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

Preferably, the raw material comprises, by mass, 89-99% of cellulose, 0.1-10% of graphene material, 0.1-5% of modifier and 0.1-5% of anion powder.

The modifier is a surfactant, and polyethylene glycol, polyvinylpyrrolidone (PVP) and hydroxymethyl cellulose are adopted according to the mass ratio of 1: (1-2): (2-3) mixing.

The graphene material is graphene or graphene oxide prepared by any one of a mechanical stripping method, a chemical vapor deposition method, a redox method and the like.

The anion powder is tourmaline and/or rare earth element powder.

In the step 2, the negative ion powder is ground by a ball mill until the particle size is less than 1 μm, and then dried.

In the step 3, cellulose, graphene and a modifier are dispersed in an NMMO (N-methylmorpholine-N-oxide) aqueous solution with the mass concentration of 10-20%, and the mixture is fully stirred for 50-100min by a stirrer to completely dissolve the cellulose, so that a spinning solution is prepared.

The concentration of cellulose in the spinning solution is 5-15% by mass percent, and the viscosity of the spinning solution is 2500-4000 Pa.S.

In the step 4, the spinning temperature of the dry-jet wet spinning process is 90-95 ℃, the blowing speed of the fiber after the fiber exits from the spinneret plate and before the fiber enters the coagulating bath is 35-40m/s, the coagulating bath is an NMMO water solution, the mass concentration of NMMO in the solution is 10-20%, and the spinning speed is 1-5 m/s.

The equipment used in the present invention is known to those skilled in the art.

The invention also provides the graphene anion regenerated cellulose composite fiber prepared by the method.

The graphene anion regenerated cellulose composite fiber and the preparation method thereof provided by the invention are further described below with reference to the examples.

Example 1

A preparation method of graphene anion regenerated cellulose composite fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder.

Preferably, the raw materials comprise 99% of cellulose, 0.1% of graphene material, 0.4% of modifier and 0.5% of anion powder by mass percentage.

The modifier is a surfactant, and polyethylene glycol, polyvinylpyrrolidone and hydroxymethyl cellulose are adopted according to the mass ratio of 1: 1: 2, and mixing.

The graphene material is prepared by a mechanical stripping method.

The anion powder is tourmaline powder.

And 2, grinding the negative ion powder to a particle size of less than 1 mu m by using a ball mill, and then drying.

And 3, dispersing the cellulose, the graphene and the modifier in the NMMO aqueous solution, fully stirring for 50-100min by a stirrer to completely dissolve the cellulose, and preparing the spinning solution.

The concentration of cellulose in the spinning solution is 5-15% by mass percent, and the viscosity of the spinning solution is 2500-4000 Pa.S.

And 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

The spinning temperature is 90-95 ℃, the blowing speed of the fiber after the fiber exits from the spinneret plate and before the fiber enters the coagulating bath is 35-40m/s, the coagulating bath is an NMMO aqueous solution, the mass concentration is 10-20%, and the spinning speed is 1-5 m/s.

The embodiment also provides the graphene negative ion regenerated cellulose composite fiber prepared by the method.

Example 2

A preparation method of graphene anion regenerated cellulose composite fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder.

Preferably, the raw materials comprise, by mass, 93.9% of cellulose, 1% of graphene material, 0.1% of modifier and 5% of anion powder.

The modifier is a surfactant, and polyethylene glycol, polyvinylpyrrolidone and hydroxymethyl cellulose are adopted according to the mass ratio of 1: 2: 2, and mixing.

The graphene material is graphene oxide prepared by a mechanical stripping method.

The negative ion powder is rare earth element powder.

And 2, grinding the negative ion powder to a particle size of less than 1 mu m by using a ball mill, and then drying.

And 3, dispersing the cellulose, the graphene and the modifier in the NMMO aqueous solution, fully stirring for 50-100min by a stirrer to completely dissolve the cellulose, and preparing the spinning solution.

The concentration of cellulose in the spinning solution is 5-15% by mass percent, and the viscosity of the spinning solution is 2500-4000 Pa.S.

And 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

The spinning temperature is 90-95 ℃, the blowing speed of the fiber after the fiber exits from the spinneret plate and before the fiber enters the coagulating bath is 35-40m/s, the coagulating bath is an NMMO aqueous solution, the mass concentration is 10-20%, and the spinning speed is 1-5 m/s.

The embodiment also provides the graphene negative ion regenerated cellulose composite fiber prepared by the method.

Example 3

A preparation method of graphene anion regenerated cellulose composite fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder.

Preferably, the raw materials comprise 89% of cellulose, 5% of graphene materials, 5% of modifiers and 1% of negative ion powder in percentage by mass.

The modifier is a surfactant, and polyethylene glycol, polyvinylpyrrolidone and hydroxymethyl cellulose are adopted according to the mass ratio of 1: 2: 3, and mixing the two components.

The graphene material is prepared by a chemical vapor deposition method.

The anion powder is tourmaline and rare earth element powder.

And 2, grinding the negative ion powder to a particle size of less than 1 mu m by using a ball mill, and then drying.

And 3, dispersing the cellulose, the graphene and the modifier in the NMMO aqueous solution, fully stirring for 50-100min by a stirrer to completely dissolve the cellulose, and preparing the spinning solution.

The concentration of cellulose in the spinning solution is 5-15% by mass percent, and the viscosity of the spinning solution is 2500-4000 Pa.S.

And 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

The spinning temperature is 90-95 ℃, the blowing speed of the fiber after the fiber exits from the spinneret plate and before the fiber enters the coagulating bath is 35-40m/s, the coagulating bath is an NMMO aqueous solution, the mass concentration is 10-20%, and the spinning speed is 1-5 m/s.

The embodiment also provides the graphene negative ion regenerated cellulose composite fiber prepared by the method.

Example 4

A preparation method of graphene anion regenerated cellulose composite fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder.

Preferably, the raw materials comprise, by mass, 90.9% of cellulose, 8% of graphene material, 1% of modifier and 0.1% of anion powder.

The modifier is a surfactant, and polyethylene glycol, polyvinylpyrrolidone and hydroxymethyl cellulose are adopted according to the mass ratio of 1: 1: 3, and mixing the two components.

The graphene material is prepared by a redox method.

The anion powder is tourmaline or rare earth element powder.

And 2, grinding the negative ion powder to a particle size of less than 1 mu m by using a ball mill, and then drying.

And 3, dispersing the cellulose, the graphene and the modifier in the NMMO aqueous solution, fully stirring for 50-100min by a stirrer to completely dissolve the cellulose, and preparing the spinning solution.

The concentration of cellulose in the spinning solution is 5-15% by mass percent, and the viscosity of the spinning solution is 2500-4000 Pa.S.

And 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

The spinning temperature is 90-95 ℃, the blowing speed of the fiber after the fiber exits from the spinneret plate and before the fiber enters the coagulating bath is 35-40m/s, the coagulating bath is an NMMO aqueous solution, the mass concentration is 10-20%, and the spinning speed is 1-5 m/s.

The embodiment also provides the graphene negative ion regenerated cellulose composite fiber prepared by the method.

Example 5

A preparation method of graphene anion regenerated cellulose composite fiber comprises the following steps:

step 1, weighing raw materials in proportion; the raw materials comprise cellulose, a graphene material, a modifier and anion powder.

Preferably, the raw materials comprise, by mass, 89.2% of cellulose, 10% of graphene material, 0.5% of modifier and 0.3% of anion powder.

The modifier is a surfactant, and polyethylene glycol, polyvinylpyrrolidone and hydroxymethyl cellulose are adopted according to the mass ratio of 1: 1.5: 2.5 mixing to obtain the product.

The graphene material is graphene oxide prepared by a redox method.

The anion powder is tourmaline and/or rare earth element powder.

And 2, grinding the negative ion powder to a particle size of less than 1 mu m by using a ball mill, and then drying.

And 3, dispersing the cellulose, the graphene and the modifier in the NMMO aqueous solution, fully stirring for 50-100min by a stirrer to completely dissolve the cellulose, and preparing the spinning solution.

The concentration of cellulose in the spinning solution is 5-15% by mass percent, and the viscosity of the spinning solution is 2500-4000 Pa.S.

And 4, spinning the spinning solution containing the completely dissolved cellulose obtained in the step 3 by using a dry-jet wet spinning process.

The spinning temperature is 90-95 ℃, the blowing speed of the fiber after the fiber exits from the spinneret plate and before the fiber enters the coagulating bath is 35-40m/s, the coagulating bath is an NMMO aqueous solution, the mass concentration is 10-20%, and the spinning speed is 1-5 m/s.

The embodiment also provides the graphene negative ion regenerated cellulose composite fiber prepared by the method.

The fibers prepared in each example were tested and the results are shown in table 1 below.

TABLE 1 test results.

The invention provides a graphene anion regenerated cellulose composite fiber and a preparation method thereof, aiming at preparing the graphene anion regenerated cellulose composite fiber by utilizing an improved graphene dispersion technology and an improved cellulose fiber preparation process.

While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.