阅读说明：本技术 一种石墨烯复合醋酸超过滤吸附纤维及其制备方法 (Graphene composite acetic acid ultrafiltration adsorption fiber and preparation method thereof ) 是由 沙嫣 沙晓林 马立国 于 2021-08-09 设计创作，主要内容包括：本发明公开了一种石墨烯复合醋酸超过滤吸附纤维及其制备方法,该方法包含：步骤1,按比例选取各原料；步骤2,将二氯甲烷加入丙酮中,搅拌均匀,得到二氯甲烷丙酮溶液；步骤3,将醋酸纤维素、碳酸钙、石墨烯粉体,加入二氯甲烷丙酮溶液中,充分搅拌；步骤4,将N-N-二甲基甲酰胺加入步骤3所得的溶液中,继续搅拌,得到醋酸纤维纺丝液；步骤5,采用步骤4所得的醋酸纤维纺丝液进行纺丝,然后使碳酸钙溶出,得到石墨烯复合醋酸超过滤纤维。本发明还提供了通过该方法制备的石墨烯复合醋酸超过滤吸附纤维。本发明通过将石墨烯加入到醋酸纤维中,能够改进醋酸纤维的吸附性能,提高过滤吸附效率。(The invention discloses a graphene composite acetic acid ultrafiltration adsorption fiber and a preparation method thereof, wherein the method comprises the following steps: step 1, selecting raw materials according to a proportion; step 2, adding dichloromethane into acetone, and uniformly stirring to obtain a dichloromethane acetone solution; step 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and fully stirring; step 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring to obtain an acetate fiber spinning solution; and 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber. The invention also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method. According to the invention, the graphene is added into the acetate fibers, so that the adsorption performance of the acetate fibers can be improved, and the filtration adsorption efficiency is improved.)

1. A preparation method of graphene composite acetic acid ultrafiltration adsorption fibers is characterized by comprising the following steps:

step 1, selecting raw materials according to a proportion; the raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate, N-N-dimethylformamide;

step 2, adding dichloromethane into acetone, and uniformly stirring to obtain a dichloromethane acetone solution;

step 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and fully stirring;

step 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring to obtain an acetate fiber spinning solution;

and 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber.

2. The preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber according to claim 1, wherein in the step 1, the raw materials comprise, by mass: 60-70% of cellulose acetate, 2-5% of graphene, 2-5% of dichloromethane, 5-10% of acetone, 5-10% of calcium carbonate and 8-10% of N-N-dimethylformamide.

3. The preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber according to claim 1, wherein in the step 2, acetone is added into dichloromethane, and the mixture is stirred at a rotating speed of 150-200 r/min for 15-20 min at normal temperature.

4. The preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber according to claim 1, wherein in the step 3, a dichloromethane acetone solution is added into cellulose acetate, calcium carbonate and graphene powder, and the mixture is stirred at a rotating speed of 300-400 r/min for 6-8 h at normal temperature.

5. The method for preparing graphene composite acetic acid ultrafiltration adsorption fiber according to claim 1, wherein in the step 4, N-N-dimethylformamide is added into the obtained solution, and the mixture is continuously stirred at normal temperature at the rotation speed of 200-300r/min for 2-4 h.

6. The method for preparing the graphene composite acetic acid ultrafiltration adsorption fiber according to claim 1, wherein in the step 5, the acetic acid fiber spinning solution is placed in a reaction kettle, a high-pressure pump is connected, the pressure and the temperature are set, the spinning solution is continuously and stably sprayed out from a spray head, a spinning roller is used for drawing the spinning solution into a filament, and then the filament is immersed in a continuous phase to dissolve calcium carbonate, so that the graphene composite acetic acid ultrafiltration fiber is obtained.

7. The method for preparing the graphene composite acetic acid ultrafiltration adsorption fiber according to claim 6, wherein the pressure range is 0.02Mpa to 1.5 Mpa.

8. The method for preparing the graphene composite acetic acid ultrafiltration adsorption fiber according to claim 6, wherein the temperature range is 120-280 ℃.

9. The method for preparing the graphene composite acetic acid ultrafiltration adsorption fiber according to claim 6, wherein the continuous phase is water and the temperature is 30-60 ℃.

10. The graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method of any one of claims 1 to 9.

Technical Field

The invention relates to a graphene composite fiber material and a preparation method thereof, and particularly relates to a graphene composite acetic acid ultrafiltration adsorption fiber and a preparation method thereof.

Background

The acetate fiber is also called cellulose acetate, and is artificial fiber prepared by esterification reaction of acetic acid and cellulose. Three major functions of cigarette filters include direct interception, inertial compaction and diffusion precipitation. With the development of technology, the variety of the filter itself has also changed greatly. Filters made of cellulose acetate have become a widely used one.

The acetate fibers are classified into two types, i.e., type II acetate fibers and type III acetate fibers. The acetate fiber is usually referred to as type II acetate fiber. It is one kind of artificial fiber, which is made up by using refined cotton seed velvet as raw material to prepare cellulose triacetate, dissolving it in dichloromethane to form silk-like solution, and then using dry spinning method to make it into the invented product. It can also be made into strong acetate fiber.

Cellulose acetate is a thermoplastic resin obtained by esterification of acetic acid as a solvent and acetic anhydride as an acetylating agent in the presence of a catalyst. Is the cellulose organic acid ester which is produced commercially at the earliest time in cellulose derivatives and is continuously developed. The cellulose acetate is used as a porous membrane material, and has the characteristics of high selectivity, large water permeability, simple processing and the like.

Cellulose acetate can be used for preparing enteric coating of medicines, and also can be used for preparing cellulose acetate plastics, cellulose acetate filtering membranes and the like.

Currently, there are only 20 manufacturers producing cellulose acetate globally, including Eastman, Celanese, s. amereic, novacea in italy, mitsubishi acetate in japan, imperial, coulter in the united kingdom, etc., accounting for about 90% of the total world production.

After washing with acetic acid, the fabric is not wrinkled and hard, and the cellulose acetate has low expansibility to water, so that the fabric has good dimensional stability and attractive appearance when being made into a fabric, and is not easy to wrinkle due to stable fiber form.

Meanwhile, as a new high-quality material which is developed rapidly in recent years, graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. 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.

Disclosure of Invention

The invention aims to provide a graphene composite fiber material and a preparation method thereof.

In order to achieve the purpose, the invention provides a preparation method of graphene composite acetic acid ultrafiltration adsorption fibers, wherein the method comprises the following steps: step 1, selecting raw materials according to a proportion; the raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate, N-N-dimethylformamide; step 2, adding dichloromethane into acetone, and uniformly stirring to obtain a dichloromethane acetone solution; step 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and fully stirring; step 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring to obtain an acetate fiber spinning solution; and 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber.

The preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber comprises the following raw materials in percentage by mass in the step 1: 60-70% of cellulose acetate, 2-5% of graphene, 2-5% of dichloromethane, 5-10% of acetone, 5-10% of calcium carbonate and 8-10% of N-N-dimethylformamide.

In the preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber, in the step 2, dichloromethane is added into acetone, and the mixture is stirred at the rotating speed of 150-200 r/min for 15-20 min at normal temperature.

In the step 3, the cellulose acetate, the calcium carbonate and the graphene powder are added into a dichloromethane acetone solution, and the mixture is stirred at a rotating speed of 300-400 r/min for 6-8 hours at normal temperature.

In the step 4, the N-N-dimethylformamide is added into the obtained solution, and the mixture is continuously stirred at the normal temperature at the rotating speed of 200-300r/min for 2-4 h.

In the step 5, the acetate fiber spinning solution is placed in a reaction kettle, a high-pressure pump is connected, the pressure and temperature are set, the spinning solution is continuously and stably sprayed out from a spray head, a spinning roller draws the spinning solution into filaments, and the filaments are immersed in a continuous phase to dissolve out calcium carbonate, so that the graphene composite acetate ultrafiltration adsorption fiber is obtained.

The preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber is characterized in that the pressure range is 0.02MPa-1.5 MPa.

The preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber comprises the step of carrying out temperature control at 120-280 ℃.

The preparation method of the graphene composite acetic acid ultrafiltration adsorption fiber comprises the steps of preparing the graphene composite acetic acid ultrafiltration adsorption fiber, wherein the continuous phase is water, and the temperature is 30-60 ℃.

The invention also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method.

The graphene composite acetic acid ultrafiltration adsorption fiber and the preparation method thereof provided by the invention have the following advantages:

firstly, the filter effect is good, fully absorbs the poisonous and harmful gas in the flue gas.

Secondly, the preparation process is simple, environment-friendly and pollution-free.

Thirdly, the fiber is well formed, the structure is stable, and the fiber is not easy to be bonded and deformed when the temperature is raised.

Fourthly, the capacity of the fiber for adsorbing impurities is large, and the service life is long.

Detailed Description

The following further describes embodiments of the present invention.

The invention provides a preparation method of graphene composite acetic acid ultrafiltration adsorption fibers, which comprises the following steps:

step 1, selecting raw materials according to a proportion; the raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate, N-N-dimethylformamide; step 2, adding dichloromethane into acetone, and uniformly stirring to obtain a dichloromethane acetone solution; step 3, adding cellulose acetate, pore-foaming agent calcium carbonate and graphene powder into a dichloromethane acetone solution, and fully stirring; step 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring to obtain an acetate fiber spinning solution; and 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate and the like to obtain the graphene composite acetate ultrafiltration fiber.

Preferably, in step 1, each raw material comprises, by mass: 60-70% of cellulose acetate, 2-5% of graphene, 2-5% of dichloromethane, 5-10% of acetone, 5-10% of calcium carbonate and 8-10% of N-N-dimethylformamide.

In the step 2, the dichloromethane is added into acetone, and stirred for 15-20 min at the rotating speed of 150-200 r/min at normal temperature.

And 3, adding the cellulose acetate, the calcium carbonate and the graphene powder into a dichloromethane acetone solution, and stirring at the normal temperature at the rotating speed of 300-400 r/min for 6-8 h.

In the step 4, N-N-dimethylformamide is added into the obtained solution, and stirring is continued for 2-4h at the normal temperature and the rotating speed of 200-300 r/min.

And 5, placing the acetate fiber spinning solution in a reaction kettle, switching on a high-pressure pump, setting the pressure and temperature to enable the spinning solution to be continuously and stably sprayed out from a spray head, drawing the spinning solution into filaments through a spinning roller, and then immersing the filaments in a continuous phase to enable calcium carbonate to be dissolved out, so that the graphene composite acetate ultrafiltration fiber is obtained.

Wherein the pressure range is 0.02MPa-1.5 MPa. The temperature range is 120-280 ℃.

The continuous phase is water, and the temperature is 30-60 ℃.

The equipment adopted in the method is the existing process equipment in the field.

The invention also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method.

The graphene composite acetic acid ultrafiltration adsorption fiber and the preparation method thereof provided by the invention are further described below with reference to the embodiments.

Example 1

A preparation method of graphene composite acetic acid ultrafiltration adsorption fibers comprises the following steps:

step 1, selecting raw materials according to a proportion.

The raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate and N-N-dimethylformamide.

Preferably, each raw material comprises the following components in percentage by mass: 70% of cellulose acetate, 2% of graphene, 5% of dichloromethane, 5% of acetone, 10% of calcium carbonate and 8% of N-N-dimethylformamide.

And 2, adding dichloromethane into acetone, and stirring at the normal temperature at the rotating speed of 150-200 r/min for 15-20 min to obtain a dichloromethane acetone solution.

And 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and stirring at the rotating speed of 300-400 r/min for 6-8 h at normal temperature.

And 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring at the normal temperature at the rotating speed of 200-300r/min for 2-4h to obtain the cellulose acetate spinning solution.

And 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber.

Placing the acetate fiber spinning solution in a reaction kettle, switching on a high-pressure pump, and setting the pressure and temperature, wherein the pressure range is 0.02MPa-1.5MPa, and the temperature range is 120-280 ℃. And continuously and stably spraying the spinning solution from a spray head, drawing the spinning solution into filaments through a spinning roller, and then immersing the filaments into a continuous phase, wherein the continuous phase is water, the temperature is 30-60 ℃, and calcium carbonate and the like are dissolved out to obtain the graphene composite acetic acid ultrafiltration fiber.

The embodiment also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method.

Example 2

A preparation method of graphene composite acetic acid ultrafiltration adsorption fibers comprises the following steps:

step 1, selecting raw materials according to a proportion.

The raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate and N-N-dimethylformamide.

Preferably, each raw material comprises the following components in percentage by mass: 66% of cellulose acetate, 3% of graphene, 4% of dichloromethane, 9% of acetone, 9% of calcium carbonate and 9% of N-N-dimethylformamide.

And 2, adding dichloromethane into acetone, and stirring at the normal temperature at the rotating speed of 150-200 r/min for 15-20 min to obtain a dichloromethane acetone solution.

And 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and stirring at the rotating speed of 300-400 r/min for 6-8 h at normal temperature.

And 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring at the normal temperature at the rotating speed of 200-300r/min for 2-4h to obtain the cellulose acetate spinning solution.

And 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber.

Placing the acetate fiber spinning solution in a reaction kettle, switching on a high-pressure pump, and setting the pressure and temperature, wherein the pressure range is 0.02MPa-1.5MPa, and the temperature range is 120-280 ℃. And continuously and stably spraying the spinning solution from a spray head, drawing the spinning solution into filaments through a spinning roller, and then immersing the filaments into a continuous phase, wherein the continuous phase is water, the temperature is 30-60 ℃, and calcium carbonate and the like are dissolved out to obtain the graphene composite acetic acid ultrafiltration fiber.

The embodiment also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method.

Example 3

A preparation method of graphene composite acetic acid ultrafiltration adsorption fibers comprises the following steps:

step 1, selecting raw materials according to a proportion.

The raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate and N-N-dimethylformamide.

Preferably, each raw material comprises the following components in percentage by mass: 69.5% of cellulose acetate, 3.5% of graphene, 2% of dichloromethane, 10% of acetone, 5% of calcium carbonate and 10% of N-N-dimethylformamide.

And 2, adding dichloromethane into acetone, and stirring at the normal temperature at the rotating speed of 150-200 r/min for 15-20 min to obtain a dichloromethane acetone solution.

And 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and stirring at the rotating speed of 300-400 r/min for 6-8 h at normal temperature.

And 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring at the normal temperature at the rotating speed of 200-300r/min for 2-4h to obtain the cellulose acetate spinning solution.

And 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber.

Placing the acetate fiber spinning solution in a reaction kettle, switching on a high-pressure pump, and setting the pressure and temperature, wherein the pressure range is 0.02MPa-1.5MPa, and the temperature range is 120-280 ℃. And continuously and stably spraying the spinning solution from a spray head, drawing the spinning solution into filaments through a spinning roller, and then immersing the filaments into a continuous phase, wherein the continuous phase is water, the temperature is 30-60 ℃, and calcium carbonate and the like are dissolved out to obtain the graphene composite acetic acid ultrafiltration fiber.

The embodiment also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method.

Example 4

A preparation method of graphene composite acetic acid ultrafiltration adsorption fibers comprises the following steps:

step 1, selecting raw materials according to a proportion.

The raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate and N-N-dimethylformamide.

Preferably, each raw material comprises the following components in percentage by mass: 64% of cellulose acetate, 4% of graphene, 4.5% of dichloromethane, 9.5% of acetone, 8.5% of calcium carbonate and 9.5% of N-N-dimethylformamide.

And 2, adding dichloromethane into acetone, and stirring at the normal temperature at the rotating speed of 150-200 r/min for 15-20 min to obtain a dichloromethane acetone solution.

And 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and stirring at the rotating speed of 300-400 r/min for 6-8 h at normal temperature.

And 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring at the normal temperature at the rotating speed of 200-300r/min for 2-4h to obtain the cellulose acetate spinning solution.

And 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber.

Placing the acetate fiber spinning solution in a reaction kettle, switching on a high-pressure pump, and setting the pressure and temperature, wherein the pressure range is 0.02MPa-1.5MPa, and the temperature range is 120-280 ℃. And continuously and stably spraying the spinning solution from a spray head, drawing the spinning solution into filaments through a spinning roller, and then immersing the filaments into a continuous phase, wherein the continuous phase is water, the temperature is 30-60 ℃, and calcium carbonate and the like are dissolved out to obtain the graphene composite acetic acid ultrafiltration fiber.

The embodiment also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method.

Example 5

A preparation method of graphene composite acetic acid ultrafiltration adsorption fibers comprises the following steps:

step 1, selecting raw materials according to a proportion.

The raw materials comprise: cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate and N-N-dimethylformamide.

Preferably, each raw material comprises the following components in percentage by mass: 60% of cellulose acetate, 5% of graphene, 5% of dichloromethane, 10% of acetone, 10% of calcium carbonate and 10% of N-N-dimethylformamide.

And 2, adding dichloromethane into acetone, and stirring at the normal temperature at the rotating speed of 150-200 r/min for 15-20 min to obtain a dichloromethane acetone solution.

And 3, adding cellulose acetate, calcium carbonate and graphene powder into a dichloromethane acetone solution, and stirring at the rotating speed of 300-400 r/min for 6-8 h at normal temperature.

And 4, adding N-N-dimethylformamide into the solution obtained in the step 3, and continuously stirring at the normal temperature at the rotating speed of 200-300r/min for 2-4h to obtain the cellulose acetate spinning solution.

And 5, spinning by adopting the acetate fiber spinning solution obtained in the step 4, and dissolving out calcium carbonate to obtain the graphene composite acetate ultrafiltration fiber.

Placing the acetate fiber spinning solution in a reaction kettle, switching on a high-pressure pump, and setting the pressure and temperature, wherein the pressure range is 0.02MPa-1.5MPa, and the temperature range is 120-280 ℃. And continuously and stably spraying the spinning solution from a spray head, drawing the spinning solution into filaments through a spinning roller, and then immersing the filaments into a continuous phase, wherein the continuous phase is water, the temperature is 30-60 ℃, and calcium carbonate and the like are dissolved out to obtain the graphene composite acetic acid ultrafiltration fiber.

The embodiment also provides the graphene composite acetic acid ultrafiltration adsorption fiber prepared by the method.

According to the graphene composite acetic acid ultrafiltration adsorption fiber and the preparation method thereof, the material mainly comprises cellulose acetate, graphene, dichloromethane, acetone, calcium carbonate and N-N-dimethylformamide, and the graphene is added into the cellulose acetate, so that the adsorption performance of the cellulose acetate can be improved, and the filtration adsorption efficiency is improved. The prepared graphene composite acetic acid ultrafiltration adsorption fiber has a good filtering effect and can fully absorb toxic and harmful gases in smoke; the preparation process is simple, environment-friendly and pollution-free; the fiber is well formed, the structure is stable, and the fiber is not easy to be bonded and deformed when the temperature is raised; the fiber has large impurity adsorption capacity and long service life.

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.