CN108411395B

CN108411395B - Conductive cellulose fiber and preparation method thereof

Info

Publication number: CN108411395B
Application number: CN201810112231.XA
Authority: CN
Inventors: 沙嫣; 沙晓林
Original assignee: Nantong Qiangsheng Graphene Technology Co ltd
Current assignee: Nantong Qiangsheng Graphene Technology Co ltd
Priority date: 2018-02-05
Filing date: 2018-02-05
Publication date: 2020-11-17
Anticipated expiration: 2038-02-05
Also published as: CN108411395A

Abstract

The invention relates to a conductive cellulose fiber and a preparation method thereof, wherein the conductive cellulose fiber comprises the following components in percentage by mass: 85-98% of cellulose pulp treating fluid, 0.5-12% of graphene solution and 1-10% of conductive polymer solution. According to the invention, on the basis of reducing the consumption of conductive polymers, the conductivity of the conductive cellulose fiber is greatly improved by adding a certain amount of graphene, and the conductivity is improved by nearly one order of magnitude after the graphene is added. The preparation method has the advantages of simple process, easy operation, low cost and high economic benefit, and is suitable for large-scale industrial production.

Description

Conductive cellulose fiber and preparation method thereof

Technical Field

The invention relates to the technical field of cellulose materials, in particular to a conductive cellulose fiber and a preparation method thereof.

Background

Cellulose fiber is a cellulose fiber with wide application, has good mechanical property and hygroscopicity, but does not have conductivity. The traditional conductive cellulose fiber is also prepared by adding conductive polymers, but the mechanical property of the cellulose fiber is influenced by adding too much conductive polymers, and the conductivity is lower by adding too little conductive polymers, so that the use is influenced.

Graphene is a two-dimensional material formed by arranging carbon atoms in a hexagon, is the most subversive new material in the century, has peculiar performance in many aspects due to a graphene monoatomic layer two-dimensional sheet structure, and can be used as a super capacitor, an efficient energy storage battery, an ultrathin and ultralight aerospace material, an ultratough and ultrastrong bulletproof vest material, a novel medical material, a nano sensor material and the like. The graphene is compounded with the common fiber, so that the fiber has certain conductivity, and can be widely applied to antistatic fabrics, anti-electromagnetic radiation clothing fabrics and the like.

The graphene structure is very stable, and researchers have not found that the graphene has a carbon atom missing condition. The connection between each carbon atom in graphene is very flexible, and when external mechanical force is applied, the surface of each carbon atom is bent and deformed, so that the carbon atoms do not need to be rearranged to adapt to external force, and the structure is kept stable.

This stable lattice structure provides carbon atoms with excellent conductivity. When electrons in the graphene move in an orbit, scattering does not occur due to lattice defects or introduction of foreign atoms. Due to the fact that the interatomic force is strong, even if the surrounding carbon atoms are extruded and collided at normal temperature, interference of electrons in the graphene is small.

The biggest characteristic of graphene is that the movement speed of electrons reaches 1/300, which is far higher than that of electrons in general conductors. This makes the properties of the electrons in graphene, or more precisely, what should be referred to as "charge carriers", very similar to the relativistic mesogens.

In the prior art, CN103046151A discloses a graphene blended regenerated cellulose fiber, which is prepared by mixing a graphene oxide solution and a regenerated cellulose solution, molding the mixture by a viscose wet spinning process, and reducing the mixture. The viscose fiber obtained by the method is slightly improved in strength, the dry breaking strength of the viscose fiber is up to 2.62cN/dtex, and the wet breaking strength of the viscose fiber is up to 1.54 cN/dtex. However, in the method, the graphene oxide regenerated cellulose fiber is prepared firstly, and then the graphene oxide regenerated cellulose fiber is prepared by a reduction method, so that the problems of insufficient reduction, generation of reduction waste liquid and the like may occur.

Patent document CN104328523A discloses a preparation method of viscose, specifically, a method for introducing non-oxidized graphene with a layer number not higher than 10 into viscose or a semi-finished viscose product, so that the obtained viscose has a greatly improved breaking strength. However, in the process of preparing graphene by the method, alkali, acid and water are adopted to wash graphene, extra waste liquid may be generated, and after dispersion in the process of preparing the graphene aqueous solution is completed, if the dispersion is insufficient, the graphene particles are too large, re-agglomeration phenomenon is generated, and the problems of difficult spinning, blockage of spinning holes and the like are caused.

Disclosure of Invention

In view of the drawbacks of the prior art, the object of the present invention is to provide an electrically conductive cellulose fiber and a method for preparing the same. The graphene solution prepared by the specific method has good conductivity, and the surfactant is screened and the proportion is adjusted, so that the graphene dispersion and the conductive polymer can be uniformly dispersed in the cellulose pulp treatment solution at the same time, and the prepared cellulose fiber has good conductivity. Polyaniline is preferred and improved in the invention, and the conductivity of the fiber is enhanced.

The purpose of the invention is realized by the following technical scheme:

the invention provides a conductive cellulose fiber which comprises the following components in percentage by mass:

85-98% of cellulose pulp treating fluid,

0.5 to 12 percent of graphene solution,

1-10% of conductive polymer solution.

Preferably, the mass ratio of the solid content of cellulose in the cellulose pulp treating solution, the solid content of graphene in the graphene solution, and the solid content of the conductive polymer solution is 100: 0.01-5: 1 to 10.

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

s1, dispersing graphene in deionized water, adding a surfactant and an alkaline reagent to adjust the solution to be neutral or weakly alkaline, and then carrying out ultrasonic treatment.

And S2, treating the solution treated in the step S1 by a microcapsule technology.

Preferably, the concentration of the graphene in the deionized water is 0.1-5 mg/mL.

Preferably, the addition amount of the surfactant and the alkaline reagent is 0.1-1% and 0.1-5% of the weight of the solution respectively;

the surfactant is one or more of polyvinyl alcohol, polyethylene glycol, sodium lignosulfonate, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, sodium dodecyl sulfonate and sodium dodecyl sulfate; the alkaline reagent is one or more of ammonia water, potassium hydroxide and sodium hydroxide.

Preferably, the conductive polymer solution is prepared by the following method:

using salicylic acid and graphene as doping agents, and synthesizing a solution containing graphene/conductive polymer material/titanium dioxide microspheres from a conductive polymer material and titanium dioxide microspheres by using a template method; the diameter of the graphene/conductive polymer material/titanium dioxide microspheres is 2-5 um; the mass ratio of the graphene to the conductive high polymer material to the titanium dioxide microspheres is 1: 0.1-5: 0.01 to 1.

Preferably, the conductive polymer material comprises at least one of polypyrrole, polythiophene and polyaniline; more preferably, the conductive polymer material is polyaniline; the content of the graphene/conductive polymer material/titanium dioxide microspheres in the conductive polymer solution is 1-20%. The solid content in the conductive polymer solution refers to the content of the graphene/conductive polymer material/titanium dioxide microspheres.

Preferably, the graphene is prepared by a mechanical exfoliation method, a liquid phase exfoliation method, or a chemical vapor deposition method.

Preferably, the cellulose pulp treatment solution is prepared by the following method:

mixing cellulose pulp with a sodium hydroxide solution, stirring uniformly, and then carrying out squeezing, ageing and yellowing treatment to obtain the cellulose pulp; the mass ratio of the cellulose pulp to the sodium hydroxide solution is 1: 2-4; the mass fraction of the sodium hydroxide solution is 20-40%;

the pressure of the squeezing treatment is 2-6 kpa, and the squeezing time is 30 min; the aging treatment specifically comprises the following steps: the temperature is 20-25 ℃, the treatment is carried out for 5-8 h, then the temperature is raised to 30-35 ℃, and the treatment is carried out for 2-4 h; the yellowing treatment specifically comprises the following steps: the temperature is 20-22 ℃, the treatment time is 30-50 min, then the temperature is increased to 25-30 ℃, and the treatment time is 20-40 min.

The invention also provides a preparation method of the conductive cellulose fiber, which comprises the following steps:

step S1, adding the conductive polymer solution into the graphene solution, mixing, stirring, and performing ultrasonic dispersion for 20-40 min;

and S2, heating the solution prepared in the step S1 to 25-30 ℃, fully stirring and mixing the solution with the cellulose pulp treatment solution, and then spinning to obtain the conductive cellulose fibers.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the preparation method of the conductive cellulose fiber, the conductivity of the conductive cellulose fiber is greatly improved by adding a certain amount of graphene on the basis of reducing the consumption of conductive polymers, and the conductivity is improved by nearly one order of magnitude after the graphene is added.

2. The invention develops the conductive cellulose fiber, which has better conductivity on the basis of ensuring the original performance of the fiber, has the functional water washing resistance, does not need a separate post-treatment process, and is safe and environment-friendly.

3. The conductive cellulose 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.

4. According to the invention, the conductive polymer material, the graphene and the titanium dioxide are compounded to form the microsphere, and the conductivity of the fiber can be obviously improved by the technology.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.

Examples 1 to 4

The embodiment provides a conductive cellulose fiber and a preparation method thereof, wherein the components and the mass percentage of the conductive cellulose fiber are shown in table 1, and the preparation method comprises the following steps:

the method comprises the following steps: dispersing the prepared graphene powder in deionized water, preparing an aqueous solution with the concentration of 0.1-5 mg/ml, and adding 0.1-1% of surfactant and 0.1-5% of alkaline reagent in the weight of the solution according to a certain proportion to adjust the solution to be neutral or weakly alkaline. Then carrying out ultrasonic treatment for 30-60 min to uniformly disperse the mixture; and (4) treating the uniformly dispersed solution by adopting a microcapsule technology.

Step two: using salicylic acid and graphene as doping agents, and synthesizing a solution containing graphene/conductive polymer material/titanium dioxide microspheres from a conductive polymer material and titanium dioxide microspheres by using a template method; the diameter of the graphene/conductive polymer material/titanium dioxide microspheres is 2-5 um; the mass ratio of the graphene to the conductive high polymer material to the titanium dioxide microspheres is 1: 0.1-5: 0.01 to 1. The conductive polymer material comprises at least one of polypyrrole, polythiophene and polyaniline; the solid content of the graphene/conductive polymer material/titanium dioxide microspheres in the conductive polymer solution is 1-20%.

Step three: and (4) adding the conductive polymer solution prepared in the step two into the graphene solution prepared in the step one, mixing, stirring by a stirrer, and performing ultrasonic dispersion for 20-40 min.

Step three: preparing cellulose pulp treating fluid, weighing 500g of cellulose pulp, mixing with 20-40% sodium hydroxide solution according to the mass ratio of 1 (2-4), and stirring for 60min by a stirrer to completely mix the cellulose pulp and the sodium hydroxide solution; putting the mixture into a squeezer for squeezing, wherein the pressure is set to be 2-6 kpa, and the squeezing time is 30 min; aging the pulp at 20-25 ℃ for 5-8 h, raising the temperature to 30-35 ℃, and aging for 2-4 h; yellowing is carried out after the aging is finished, wherein the yellowing temperature is 20-22 ℃, the yellowing time is 30-50 min, the temperature is increased to 25-30 ℃, and the yellowing time is 20-40 min; heating the conductive polymer graphene mixed water solution prepared in the second step to 25-30 ℃, and fully mixing the conductive polymer graphene mixed water solution with pulp, wherein the stirring time of a stirrer is 30-60 min, and the proportion of the graphene solid content to the cellulose solid content in the cellulose pulp treatment solution is (0.01-5%): 1, the ratio of the solid content of the conductive polymer to the solid content of cellulose in the cellulose pulp treating fluid is (1-10%): 1; and finally spinning the prepared pulp to prepare the conductive cellulose composite fiber.

TABLE 1

Comparative examples 1 to 3

Comparative examples 1 to 3 provide conductive cellulose fibers having the components and mass percentages shown in table 2, and a method for preparing the same as in example 1.

TABLE 2

Comparative example 4

This comparative example provides a conductive cellulose fiber and a method of making the same, essentially the same as example 1, except that: the conductive polymer solution in the comparative example is a polyaniline solution and does not contain graphene, a conductive polymer material and titanium dioxide microspheres.

Comparative example 5

This comparative example provides a conductive cellulose fiber and a method of making the same, essentially the same as example 1, except that: in this comparative example, the solution after uniform dispersion described in step one was not treated by the microcapsule technique.

Effect verification:

the conductive cellulose fibers obtained in the above examples and comparative examples were subjected to a performance test, and the results are shown in table 3 (unit. omega. cm).

TABLE 3

	Conductivity of electricity	Fibril conductivity
			Example 1	10⁴	10¹²
Example 2	10⁵	10¹²
			Example 3	10⁶	10¹²
Example 4	10⁶	10¹²
			Example 5	10⁷	10¹²
Comparative example 1	10¹⁰	10¹²
			Comparative example 2	10⁹	10¹²
Comparative example 3	10⁸	10¹²
			Comparative example 4	10¹¹	10¹²
Comparative example 5	10⁸	10¹²

The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.

Claims

1. The conductive cellulose fiber is characterized in that the preparation raw materials comprise the following components in percentage by mass:

85-95% of cellulose pulp treating fluid,

2 to 8 percent of graphene solution,

1% -7% of conductive polymer solution;

the mass ratio of the solid content of cellulose in the cellulose pulp treating solution to the solid content of graphene in the graphene solution to the solid content of the conductive polymer in the conductive polymer solution is 100: 2-5: 1-5;

the preparation method of the conductive polymer solution comprises the following steps:

using salicylic acid and graphene as doping agents, and synthesizing a solution containing graphene/conductive polymer material/titanium dioxide microspheres from a conductive polymer material and titanium dioxide microspheres by using a template method; the diameter of the graphene/conductive polymer material/titanium dioxide microspheres is 2-5 microns; the mass ratio of the graphene to the conductive high polymer material to the titanium dioxide microspheres is 1: 0.1-5: 0.01 to 1;

the conductive polymer material comprises at least one of polypyrrole, polythiophene and polyaniline; the solid content of graphene, the conductive polymer material and the titanium dioxide microspheres in the conductive polymer solution is 1-20%;

the preparation method of the graphene solution comprises the following steps:

s1, dispersing graphene in deionized water, adding a surfactant and an alkaline reagent to adjust the solution to be neutral or alkalescent, and then carrying out ultrasonic treatment;

2. The conductive cellulose fiber according to claim 1, wherein the concentration of graphene in deionized water is 0.1-5 mg/mL.

3. The conductive cellulose fiber according to claim 1, wherein the surfactant and the alkaline agent are added in an amount of 0.1-1% and 0.1-5% by weight of the solution, respectively;

the surfactant is one or more of polyvinyl alcohol, polyethylene glycol, sodium lignosulfonate, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl sulfate; the alkaline reagent is one or more of ammonia water, potassium hydroxide and sodium hydroxide.

4. The conductive cellulose fiber according to claim 1, wherein the graphene is prepared by a mechanical exfoliation method, a liquid phase exfoliation method, or a chemical vapor deposition method.

5. The electrically conductive cellulose fibers of claim 1, wherein the cellulose pulp treatment solution is prepared by:

6. A method for preparing electrically conductive cellulose fibres according to any one of claims 1 to 5, comprising the steps of: