CN110528111B - Preparation method of antibacterial antistatic spandex - Google Patents

Abstract

The invention discloses a preparation method of antibacterial and antistatic spandex, which comprises the steps of compounding nano carbon black with a specific DBP value with single-layer graphene oxide according to a specific proportion, reducing the graphene oxide in a heated alkaline environment to form a stable composite structure, and then mixing the stable composite structure with spandex spinning solution to obtain the spandex with antibacterial and antistatic properties. According to the invention, only a trace amount of graphene and a small amount of carbon black are added, so that the traditional spandex has excellent antistatic and antibacterial effects, and the product has the advantages of good spinnability, stable performance, low cost, small industrialization difficulty and obvious practical value.

Description

Preparation method of antibacterial antistatic spandex

Technical Field

The invention belongs to the field of chemical fiber fabrics, and particularly relates to a preparation method of antibacterial antistatic spandex.

Background

Polyurethane elastic Fiber (PU Fiber) is a Fiber made of a block copolymer containing at least 85% of Polyurethane segments, known as Spandex (Spandex) in the us name, and is favored by western europe as Elastane Fiber, which is a commercial name of Spandex in our country. Because the spandex has the characteristics of good elasticity, fine fineness, high strength, high extensibility, light specific gravity, soft hand feeling, good light resistance, excellent dyeing property and dyeing fastness and the like, the spandex is widely applied to underwear and outerwear, female clothes (swimwear, tights, panty-hose and the like), and the industrial and biomedical fields.

When the spandex is used as the noble fiber in a chemical fiber family, the price is very expensive and the spandex is prohibitively expensive and has a high and unsmooth feeling. Nowadays, with the rapid development of spandex industry in China, spandex has rapidly moved to civilization, which not only greatly expands the downstream application field, but also rapidly improves the international market competitiveness of textiles and clothing in China and promotes the rapid growth of textile outlets. In recent years, the development of the spandex industry in China is very rapid, and the capacity reaches 17 ten thousand tons by the end of 2004, and accounts for more than 40 percent of the world capacity; the productivity of spandex reaches 20 million tons, which is nearly half of the total production energy in the world, and China has become the first spandex producing country in the world. However, spandex has single variety, the technology in the industry is slower, and the product technology content is low, so the spandex falls into the embarrassing situation of self-sealing and difficult progress.

Graphene is a newly discovered star material in recent years, has numerous unequally-used properties such as mechanical properties, electrical properties, thermal properties, optical properties, catalysis, semiconductors and the like, and is considered to be an industrial monosodium glutamate material which can cause industrial upgrading. Due to the fact that the graphene has ultrahigh conductivity, after the graphene is added into spandex, multiple functions of preventing static electricity, resisting bacteria and inhibiting bacteria of spandex products and the like are hopefully achieved, and the value-added effect of the spandex is achieved. The method is limited by a plurality of factors such as cost, preparation difficulty and environmental friendliness, the single use of graphene is not an optimal choice, and the high conductivity of graphene and the low cost of carbon black are combined, so that the method is probably a shortcut for preparing the antistatic composite material. CN103832997A graphene/carbon black composite material, preparation method and application thereof adopts a graphite oxide and carbon black compounding mode to prepare the conductive composite powder, however, the preparation is complex, the cost is high, and the industrialization difficulty is large. CN107516740A "a rock black and graphene powder composite conductive agent and its preparation" adopts the method of adding carbon black into the preparation process of graphite oxide to obtain the composite conductive agent, but the oxidizing agent of graphite oxide itself may damage the carbon black structure, and the conductivity of the composite powder is difficult to ensure. CN106147185, "conductive polycarbonate-based pellet containing multi-dimensional carbon nanomaterial, and preparation method and application thereof", blends carbon black, graphene and carbon nanotube with polycarbonate to achieve the purpose of forming a conductive network together with a multi-dimensional carbon material, however, this method cannot avoid aggregation of the carbon material and cannot perform spinning treatment. How to optimize the raw materials of the graphene and the carbon black and the preparation process, the use amounts of the graphene and the carbon black are reduced to the maximum extent, and the molecular level dispersion is realized, which is a precondition for realizing the preparation of the antistatic composite fiber and is also a difficult problem which is difficult to solve at present.

Disclosure of Invention

The invention aims to provide a preparation method of antibacterial and antistatic spandex aiming at the defects of the prior art. The reduced graphene oxide and the nano carbon black are uniformly dispersed in the spandex to form a conductive network, so that the conductivity can be kept unchanged even after long-term use and washing, the spandex has high durability, and the spandex is endowed with excellent antibacterial property.

The purpose of the invention is realized by the following technical scheme: the preparation method of the antibacterial antistatic spandex is characterized by comprising the following steps of:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution.

(2) Mixing the low-DBP-value nano carbon black and the high-DBP-value nano carbon black according to the mass ratio of 3-5: 1 to obtain mixed nano carbon black, adding 0.16-0.3 part by mass of the mixed nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting at 100 ℃ for 1 hour to obtain mixed dispersion liquid; the DBP value of the high-DBP-value nano carbon black is 360-400, and the DBP value of the low-DBP-value nano carbon black is 200-280.

(3) And (3) adding water to adjust the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure to remove water to obtain a second mixed liquid.

(4) And (4) uniformly mixing the second mixed solution obtained in the step (3) with 25-40% of spandex spinning solution according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

Further, the carbon-oxygen ratio of the graphene oxide in the step (1) is between 4 and 7.

The invention has the beneficial effects that:

(1) the reduced graphene oxide/nano carbon black composite structure is prepared by a one-step method. In the graphene oxide aqueous dispersion, nano carbon black is selectively enriched on the surface of the modified graphene to form a composite structure. Secondly, the carbon black with the low DBP value has a low structure degree, namely a compact structure and a few porous structures, can repair the surface defects of the modified graphene, improves the intrinsic conductivity of the modified graphene, and the carbon black with the high DBP value has a more extended microstructure and developed gaps, can extend outwards when being attached to the surface of the modified graphene, and is beneficial to interface charge transfer and formation of a conductive network. According to the invention, the optimal formula is obtained by repeatedly adjusting the proportion of the modified graphene, the high-DBP carbon black and the low-DBP carbon black, and the antistatic effect of the composite fiber is finally realized (Table 1).

(2) After the thermal reduction by sodium hydroxide, functional groups on the surface of the oxidized graphene are removed, defects are repaired, the conductivity is further improved, and the reduced graphene can still be stably and uniformly dispersed in water. The nano carbon black is attached to the surface of the reduced graphene oxide and dispersed in water together, so that the premise is provided for uniform dispersion in spandex.

(3) The graphene and nano carbon black composite structure is uniformly dispersed in spandex to form a conductive network, so that the conductivity can be kept not to be attenuated even after long-term use and washing, and the polyurethane has high durability.

(4) The addition of the graphene and the carbon black can endow the spandex fiber with properties which are not possessed originally, so that the conductivity is remarkably improved, and the spandex fiber can have antibacterial property.

(5) The graphene content in the fiber is below 0.8%, the addition amount is obviously lower than similar products and reported values in the market, the cost is low, and the industrial production is easy to realize.

In conclusion, the composite fiber obtained by the method is simple to prepare, excellent in antistatic performance, good in durability and low in cost, has remarkable advantages compared with the traditional fiber, and has wide market prospect and application value.

Drawings

Fig. 1 is a schematic view of the microscopic composition of the composite fiber, wherein 1 is a single-layer graphene sheet, 2 is a defect on the surface of graphene, 3 is low-structure-degree carbon black, and 4 is high-structure-degree carbon black.

Detailed Description

According to the method, firstly, single-layer modified graphene and nano carbon black with different DBP values are mixed in water, so that the nano carbon black is selectively dispersed in a defect area and a conjugate area of graphene oxide, after heating reduction in an alkaline environment, oxygen-containing functional groups on the surface of the graphene oxide are removed, the defects are repaired to a certain extent, the conjugate structure of the graphene is enlarged, and the conductivity of the graphene is improved. And the reduction degree of the thermal alkali reduction is lower than that of the thermal reduction and the chemical reduction, so that the reduced graphene/nano carbon black composite structure can still be stably and uniformly dispersed in water. And then, removing water through reduced pressure distillation, directly mixing the polyurethane fiber with a polyurethane fiber spinning solution after the polyurethane fiber is dispersed in dimethylacetamide, and continuously preparing the novel polyurethane fiber material with antistatic property and antibacterial property through a wet spinning process. The carbon black with low structure degree on the graphene sheet has the purposes of repairing defects and improving conductivity, and the carbon black with high structure degree increases the interface effect of graphene and polyurethane molecules and is beneficial to the construction of a conductive network (as shown in figure 1). The product has low added graphene and nano carbon black amount, simple and easy process, small difficulty in industrial mass production and obvious market application value.

The present invention is described in detail by the following embodiments, which are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and the non-essential changes and modifications made by the person skilled in the art according to the above disclosure are within the scope of the present invention.

Example 1:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 4;

(2) adding 0.12 part by mass of low-DBP-value nano carbon black and 0.04 part by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting for 1h at 100 ℃ to obtain a mixed dispersion liquid, wherein the total weight of the mixed nano carbon black is 0.16 part by mass, the DBP value of the high-DBP-value nano carbon black is 360, and the DBP value of the low-DBP-value nano carbon black is 280;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 40% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 2:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 4;

(2) adding 0.25 part by mass of low-DBP-value nano carbon black and 0.05 part by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting at 100 ℃ for 1h to obtain a mixed dispersion liquid, wherein the total weight of the mixed nano carbon black is 0.3 part by mass, the DBP value of the high-DBP-value nano carbon black is 380, and the DBP value of the low-DBP-value nano carbon black is 240;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 40% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 3:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 7;

(2) adding 0.01 part by mass of low-DBP-value nano carbon black and 0.03 part by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting for 1h at 100 ℃ to obtain a mixed dispersion liquid, wherein the total weight of the mixed nano carbon black is 0.04 part by mass, the DBP value of the high-DBP-value nano carbon black is 380, and the DBP value of the low-DBP-value nano carbon black is 240;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 40% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 4:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 6;

(2) adding 0.5 part by mass of low-DBP-value nano carbon black and 2.5 parts by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting for 1h at 100 ℃ to obtain a mixed dispersion liquid, wherein the total weight of the mixed nano carbon black is 3 parts by mass, the DBP value of the high-DBP-value nano carbon black is 380, and the DBP value of the low-DBP-value nano carbon black is 240;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 40% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 5:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 4;

(2) adding 0.3 part by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting for 1h at 100 ℃ to obtain a mixed dispersion liquid, wherein the DBP value of the high-DBP-value nano carbon black is 400;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 40% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 6:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 4;

(2) adding 0.3 mass of low-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting for 1h at 100 ℃ to obtain a mixed dispersion liquid, wherein the DBP value of the low-DBP-value nano carbon black is 200;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 40% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 7:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 7;

(2) adding 0.25 part by mass of low-DBP-value nano carbon black and 0.05 part by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting for 1h at 100 ℃ to obtain a mixed dispersion liquid, wherein the total weight of the mixed nano carbon black is 0.3 part by mass, the DBP value of the high-DBP-value nano carbon black is 380, and the DBP value of the low-DBP-value nano carbon black is 200;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 32% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 8:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 5;

(2) adding 0.25 part by mass of low-DBP-value nano carbon black and 0.05 part by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting at 100 ℃ for 1h to obtain a mixed dispersion liquid, wherein the total weight of the mixed nano carbon black is 0.3 part by mass, the DBP value of the high-DBP-value nano carbon black is 400, and the DBP value of the low-DBP-value nano carbon black is 230;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with 25% of spandex spinning solution according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

Example 9:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution, wherein the carbon-oxygen ratio of graphene oxide is 4;

(2) adding 0.25 part by mass of low-DBP-value nano carbon black and 0.05 part by mass of high-DBP-value nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting for 1h at 100 ℃ to obtain a mixed dispersion liquid, wherein the total weight of the mixed nano carbon black is 0.3 part by mass, the DBP value of the high-DBP-value nano carbon black is 500, and the DBP value of the low-DBP-value nano carbon black is 100;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure until the mixed dispersion liquid is almost anhydrous to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with a spandex spinning solution with the mass concentration of 40% according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

The antibacterial antistatic spandex is obtained through the steps, and the specific properties are shown in table 1.

TABLE 1 relevant parameters and composite fiber Properties of the examples

It can be seen from the comparison of examples 1 to 4 that the composite spandex with excellent conductivity and bacteriostatic rate can be obtained by selecting a proper nano carbon black proportion and a proper DBP value, the resistivity of the composite fiber is further reduced along with the increase of the addition amount of the nano carbon black in a certain range, but when the addition amount is too high (example 4), the self-aggregation phenomenon of the nano carbon black is obvious, and the spinnability of the spandex is reduced. On the other hand, when the amount of the carbon black added is too small (example 3), the effect of the carbon black is not significant, the specific resistance of the fiber is too high, and the antibacterial ratio is also lowered.

Examples 5 and 6 demonstrate that effective conductivity of the composite fibers cannot be achieved with either high-DBP or low-DBP nano-carbon black alone because of the lack of a mechanism of synergy, and only two effects of "defect repair" and "network formation" are achieved simultaneously, a significant increase in conductivity can be achieved with low carbon black addition, otherwise similar effects can still be achieved with large amounts of carbon black.

As can be seen from comparison of examples 2,7 and 8, as the concentration of the spinning solution is reduced, the addition amount of graphene/nano carbon black in the fiber is increased, the conductivity is increased, and the antibacterial property is improved.

Example 9 selects the nano carbon black with higher DBP value and lower DBP value for compounding, and the effect is still inferior to the result obtained by the claims of the present invention, which is caused by that the nano carbon black with lower DBP value has poor conductive network forming capability and poor modified graphene defect repairing effect, and the nano carbon black with too high DBP value has poor dispersion effect and is easy to agglomerate.

Claims (2)

1. The preparation method of the antibacterial antistatic spandex is characterized by comprising the following steps of:

(1) adding 0.01 part by mass of sodium hydroxide into 25 parts by mass of graphene oxide aqueous dispersion with the mass concentration of 2mg/g, and uniformly mixing and stirring to obtain a first mixed solution;

(2) mixing the low-DBP-value nano carbon black and the high-DBP-value nano carbon black according to the mass ratio of 3-5: 1 to obtain mixed nano carbon black, adding 0.16-0.3 part by mass of the mixed nano carbon black into the first mixed solution obtained in the step (1), and stirring and reacting at 100 ℃ for 1 hour to obtain mixed dispersion liquid; the DBP value of the high-DBP-value nano carbon black is 360-400, and the DBP value of the low-DBP-value nano carbon black is 200-280;

(3) washing the mixed dispersion liquid obtained in the step (2) to be neutral, adding 5 parts by mass of dimethylacetamide, heating to 70 ℃, and distilling under reduced pressure to remove water to obtain a second mixed liquid;

(4) and (4) uniformly mixing the second mixed solution obtained in the step (3) with 25-40% of spandex spinning solution according to the mass ratio of 1:5, and performing wet spinning to obtain the antibacterial and antistatic spandex.

2. The method according to claim 1, wherein the graphene oxide in step (1) has a carbon to oxygen ratio of between 4 and 7.

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