CN111996611A - Antistatic agent and preparation method thereof - Google Patents

Abstract

The invention discloses an antistatic agent and a preparation method thereof. The preparation method of the antistatic agent is as follows: (1) graphene oxide modification: 2-5g graphene oxide is dispersed in 0.5-1.2L water, and ultrasonically dispersed for 1-3h to obtain a graphene oxide hydrosol; Add 0.3-1g modifier to the graphene oxide hydrosol, and stir for 10-40min; after filtering and washing, vacuum-drying at 20-70°C for 5-12h to obtain modified graphene oxide; (2) chemical reduction: Dissolve 2-5g of reducing agent in 0.5-1.2L of water, add 1-2g of the above modified graphene oxide, stir in a water bath at 70-110°C for 1-3h; after filtering and washing, vacuum at 40-80°C Dry for 8‑15h. In the present invention, the modified graphene oxide composite material is used as the antistatic agent, and the antistatic performance is improved while the antibacterial effect is improved; the cationic quaternary ammonium salt modifier is added to further improve the antibacterial performance.

Description

Antistatic agent and preparation method thereof

technical field

The present invention relates to an antistatic agent and a preparation method thereof.

Background technique

Textile materials are electrical insulator materials, especially synthetic fibers such as polyester, acrylic, and polyvinyl chloride, which have poor hygroscopic properties and usually high specific resistance. Therefore, in the process of textile processing, the close contact and friction between fibers or between fibers and machine parts, as well as the mutual contact and friction of processed textiles, will cause the transfer of charges and the generation of static electricity.

The existence of static electricity will affect the quality of the product and the wearing performance of the fabric at light level, and the discharge will produce sparks and cause fires, resulting in serious consequences. In some special environments and workplaces, such as the electronics industry, the medical and health industry, and flammable and explosive places such as gas stations and mines, the use of antistatic fabrics is particularly important. At present, adding a surfactant to the surface of the molded fiber to obtain an antistatic fabric is the most conventional and convenient method, but with the increase of the number of washings, the antistatic effect will gradually decrease. Therefore, it is of far-reaching significance to develop antistatic fabrics with strong and durable antistatic properties.

SUMMARY OF THE INVENTION

The antistatic agent is added to the polymer in the molten state, and then spin-spun to make the fiber, and the antistatic fabric obtained by processing generally has good antistatic durability. Carbon-based materials have many advantages such as low density, stable structure, and low price, and have the potential to be used as antistatic agents. The surface of the graphene oxide material contains oxygen-containing functional groups such as hydroxyl and carboxyl groups, which endow it with good modifiability and can be combined with a variety of materials in a covalent or non-covalent manner. After the reduction treatment, the oxygen-containing functional groups on the surface of graphene oxide are reduced, and the original sp ² hybrid structure of the graphene material and the delocalized π bond structure formed by carbon atoms are repaired. The electrical conductivity can be significantly improved. When graphene oxide is reduced, there is still the possibility of being re-oxidized in the subsequent processing. Therefore, in the process of reducing graphene oxide, if the establishment of an anti-oxidation mechanism can be taken into account, it may be a material for the preparation of durable antistatic properties. a new idea.

Based on the above research background and thinking, the technical scheme adopted in the present invention is:

A preparation method of an antistatic agent, comprising the following steps:

(1) Graphene oxide modification: 2-5g graphene oxide is dispersed in 0.5-1.2L water, and ultrasonically dispersed for 1-3h to obtain a graphene oxide hydrosol; 0.3-1g is added to the graphene oxide hydrosol Modifier, stirring for 10-40min; after filtration and washing, vacuum drying at 20-70°C for 5-12h to obtain modified graphene oxide;

(2) Chemical reduction: dissolve 2-5g of reducing agent in 0.5-1.2L of water, add 1-2g of the above modified graphene oxide, stir in a water bath at 70-110°C for 1-3h; Vacuum dry at 40-80°C for 8-15h.

The modifier is one or both of glycerol monostearate and octadecyldimethylbenzyl ammonium chloride.

Preferably, the modifier is a mixture of glycerol monostearate and octadecyldimethylbenzylammonium chloride in a weight ratio of (1-3):(1-3).

The reducing agent is any one of tea polyphenols, vitamin C, sodium citrate and sodium borohydride.

An antistatic agent prepared by any one of the above methods.

Beneficial effects of the present invention:

(1) The present invention adopts the method of graphene oxide modification combined with chemical reduction to obtain a novel antistatic agent. On the one hand, the selected modifier not only has antistatic properties, but its addition can effectively increase the exfoliation degree of graphene oxide, and at the same time, it can also increase the compatibility of the antistatic agent with the fiber matrix; After chemical reduction of graphene oxide, the oxygen-containing functional groups on its surface are reduced, the sp ² hybrid structure of graphene materials and the delocalized π bonds formed by carbon atoms are repaired, and the electrical conductivity is improved; in addition, the use of citric acid As a reducing agent, in addition to reducing oxygen-containing functional groups, sodium can also be combined with the selected cationic modifier through electrostatic action to protect the reduced graphene oxide and prevent it from being re-oxidized in subsequent processing steps;

(2) The present invention uses the modified graphene oxide composite material as an antistatic agent to improve the antistatic performance of the fabric while improving the antibacterial effect of the fabric; adding a cationic quaternary ammonium salt modifier further improves the antibacterial effect of the fabric performance.

Detailed ways

Graphene oxide, with a purity of 99.0 wt%, a monolayer rate of 99.0%, and a lateral dimension of 0.5 μm-10 μm, was purchased from Shanghai Carbon Source Huigu New Material Technology Co., Ltd.

Sodium citrate, CAS number: 68-04-2, was purchased from Tianjin Standard Technology Co., Ltd.

Tea polyphenols were purchased from Shanghai Haiqu Chemical Co., Ltd.

Octadecyldimethylbenzylammonium chloride, CAS number: 122-19-0, was purchased from Shanghai Xuejie Chemical Co., Ltd.

Glyceryl monostearate, CAS number: 123-94-4, was purchased from Beijing Bailingwei Technology Co., Ltd.

HH type digital display constant temperature water bath, purchased from Changzhou Guoyu Instrument Manufacturing Co., Ltd.

YK300ST ultrasonic cleaning machine was purchased from Shanghai Yingke Automation Cleaning Equipment Co., Ltd.

DZF-6020 vacuum drying oven was purchased from Shanghai Kesheng Instrument Co., Ltd.

CR22GII high-speed centrifuge was purchased from Hitachi, Japan.

CM type high-speed mixer, purchased from Shanghai Yiken Machinery Equipment Co., Ltd.

KTE-36 twin-screw granulator was purchased from Nanjing Kerke Company.

ZY type melt spinning machine, purchased from Sichuan Zhiyan Technology Co., Ltd.

LD128 Slitter Warping Machine was purchased from Longde Machinery Factory in Sheyang County.

IR-408 loom, purchased from Qingdao 168 Machinery Co., Ltd.

Example 1

A preparation method of an antistatic agent, comprising the following steps:

Disperse 2g of graphene oxide in 1L of deionized water, and ultrasonically disperse 1h under the condition that the ultrasonic frequency is 40kHz and the power is 450W to obtain a graphene oxide hydrosol; 0.5g of modifier is added to the graphene oxide hydrosol, Stir for 20 min; after filtering and washing, vacuum drying at 50° C. for 10 h to obtain modified graphene oxide.

The modifier is octadecyldimethylbenzylammonium chloride.

Example 2

Basically the same as Example 1, the only difference is:

The modifier is glycerol monostearate.

Example 3

Basically the same as Example 1, the only difference is:

The modifier is prepared by mixing glycerol monostearate and octadecyldimethylbenzyl ammonium chloride in a weight ratio of 1:1.

Example 4

A preparation method of an antistatic agent, comprising the following steps:

(1) 2g graphene oxide is dispersed in 1L deionized water, and the ultrasonic frequency is 40kHz and the power is 450W under the condition of ultrasonic dispersion 1h to obtain a graphene oxide hydrosol; 0.5g is added to the graphene oxide hydrosol to modify After filtration and washing, vacuum drying at 50°C for 10h to obtain modified graphene oxide;

(2) Dissolve 3g of reducing agent in 1L of deionized water, add 2g of the modified graphene oxide, stir in a 90°C water bath for 2h; filter and wash with water, then vacuum dry at 65°C for 12h.

The modifier is octadecyldimethylbenzylammonium chloride.

The reducing agent is sodium citrate.

Example 5

Basically the same as Example 4, the only difference is:

The modifier is glycerol monostearate.

Example 6

Basically the same as Example 4, the only difference is:

The modifier is prepared by mixing glycerol monostearate and octadecyldimethylbenzyl ammonium chloride in a weight ratio of 1:1.

Example 7

Basically the same as Example 4, the only difference is:

The reducing agent is tea polyphenols.

Comparative Example 1

An antistatic agent that uses graphene oxide.

Comparative Example 2

A preparation method of an antistatic agent, comprising the following steps:

Dissolve 3g of reducing agent in 1L of deionized water, add 2g of graphene oxide, stir in a water bath at 90°C for 2h; filter and wash with water, then vacuum dry at 65°C for 12h.

The reducing agent is sodium citrate.

Comparative Example 3

A preparation method of an antistatic agent, comprising the following steps:

(1) Dissolve 3g of reducing agent in 1L of deionized water, add 2g of graphene oxide, stir in a water bath at 90°C for 2h; after filtration and washing, vacuum dry at 65°C for 12h to obtain reduced graphene oxide;

(2) Dispersing the reduced graphene oxide in 1 L of deionized water, under the condition that the ultrasonic frequency is 40kHz and the power is 450W, the ultrasonic-assisted dispersion is 1h to obtain the reduced graphene oxide hydrosol; to the reduced graphene oxide hydrosol 0.5g of modifier was added to it, stirred for 20min; after filtration, washed with water, vacuum-dried at 50°C for 10h.

The modifier is octadecyldimethylbenzylammonium chloride.

The reducing agent is sodium citrate.

Test Example 1: Antistatic Performance Test of Antistatic Agent

6.1 and 6.2 of the previous reference standard "GB/T 16801-2013 Determination of Antistatic Properties of Fabric Conditioners".

Preparation of test pieces

Test piece washing treatment

Cut a 10cm wide selvedge from the polyester cloth used for the test, and cut out a 500mm×500mm test cloth.

Dissolve soap flakes with deionized water to prepare 1 g/L soap solution based on dry sodium soap at a temperature of 40°C.

Add 2L of soap solution at 40°C to the rinser, put 20 pieces of 500mm×500mm test cloth, cover and rotate for 15min. The rotating washing method is 5 circles clockwise, 5 circles counterclockwise, rotate for 3 minutes, stop for 2 minutes, and keep the rotation rate at 20 r/min, and so on. When the time is up, the waste water is discarded, and the dehydration is carried out rapidly for 30S.

Add 2L of 40°C deionized water to the rinser, stir and rinse for 3min, rotate clockwise for 5 circles, and counterclockwise for 5 circles. Rinse like this 3 times.

test piece drying

Use plastic shackles to clamp the washed piece of cloth, clamp the two corners with plastic clamps to hang, and dry at room temperature for 3 hours. After drying, take it off, lay it flat on the filter paper, cover it with filter paper, put it in an enamel tray, dry it in an oven at 45°C for 4 hours, take it out and put it in a hygrostat and save it for later use.

Test pieces treated with conditioner test solution

Weigh the antistatic agent into a 1000mL beaker, add deionized water to prepare 850mL solution of antistatic agent sample concentration of 30.0g/L, and divide it into four 400mL beakers, each beaker 200mL sample solution, for parallel For testing.

For each sample, take 4 pieces of 500mm × 500mm test pieces, put them into 4 pieces of 200mL sample solution at room temperature and soak them for 10min, and use a glass rod to turn them from time to time. Take out the soaked test piece, hang it with plastic clips at both corners and hang it to dry for 3 hours, and then put it into a 45°C oven to dry for 4 hours.

The antistatic property test was carried out on the above-mentioned dried test pieces.

The charge surface density was measured according to the national standard GB/T 12703.2-2009 "Textile Electrostatic Test Method Part 2: Charge Surface Density".

Table 1: Antistatic performance table of antistatic agents

Surface charge density (uc/m²) Antistatic agent prepared in Example 1 4.71 Antistatic agent prepared in Example 2 4.75 The antistatic agent prepared in Example 3 3.94 The antistatic agent prepared in Example 4 1.71 The antistatic agent prepared in Example 5 2.28 The antistatic agent prepared in Example 6 1.24 The antistatic agent prepared by embodiment 7 2.03 Antistatic agent prepared in Comparative Example 1 6.04 Antistatic agent prepared in Comparative Example 2 4.95 Antistatic agent prepared in Comparative Example 3 3.58

Comparing Examples 1-3 with Comparative Example 1, it can be seen that, compared with graphene oxide, the antistatic properties of fabrics added with modified graphene oxide as antistatic agent are significantly improved. The reason may be that the surface of graphene oxide contains a large number of functional groups, such as carboxyl groups, hydroxyl groups, epoxy groups, etc., which endow it with good modifiability; the selected modifier, on the one hand, has antistatic properties, on the other hand On the one hand, its addition can produce a non-covalent effect with graphene oxide, promote the exfoliation of graphene oxide, and increase the compatibility of the antistatic agent with the fiber matrix.

Comparing Examples 4-6 with Examples 1-3, it can be found that after the modified graphene oxide is subjected to reduction treatment, the antistatic performance of the fabric is significantly improved, and the reason should be: there is a large amount of oxygen on the surface of modified graphene oxide. When the functional group is reduced, the delocalized π bond formed by the original sp ² hybridized carbon atoms of graphene is restored, which is beneficial to the improvement of electron transport and electrical conductivity.

Comparing Example 4 and Comparative Example 3, it can be found that when the graphene oxide is first reduced and then modified, the antistatic properties of the fabric are not as good as the effect of first modification and then reduction. The reason may be that the surface of graphene oxide contains a large amount of Oxygen-containing functional groups, such a structure is easier to combine with modifiers, and its synergistic effect will be more obvious.

First use octadecyldimethylbenzyl ammonium chloride to modify graphene oxide, and then use sodium citrate to reduce it, the antistatic durability of the obtained antistatic fabric is better, the reason may be: choose citric acid When sodium is used as a reducing agent and octadecyldimethylbenzyl ammonium chloride is used as a modifier, when sodium citrate reduces the oxygen-containing functional groups on the surface of graphene oxide, the remaining sodium citrate will interact with each other due to electrostatic force. The cationic octadecyldimethylbenzylammonium chloride is incorporated, thereby avoiding reoxidation of the reduced graphene oxide in subsequent processing steps. Glyceryl monostearate is a non-ionic modifier and will not have an electrostatic interaction with sodium citrate; and when tea polyphenol is used as a reducing agent, it is also difficult to interact with cationic octadecyldimethylbenzyl. Ammonium chloride produces static electricity.

The antibacterial performance test was carried out on the above-mentioned dried test pieces.

The antibacterial performance test was carried out according to the national standard GB/T 20944.3-2008, and the test strain: Escherichia coli (ATCC25922).

Table 2: Sterilization rate test result table

Escherichia coli, % Example 1 94.0 Example 2 78.5 Example 6 94.9 Comparative Example 1 74.2 Comparative Example 4 43.7

It can be seen from Table 2 that the addition of graphene and cationic quaternary ammonium salts has a positive effect on the improvement of the bacteriostatic properties of the fabric. The reason for the antibacterial properties of graphene materials may be that graphene can have a strong dispersive interaction with phospholipid molecules on bacterial cell membranes, so it can directly extract phospholipid molecules on cell membranes on a large scale to kill bacteria; cationic quaternary ammonium The mechanism of salt sterilization should be that cations can adsorb negatively charged bacterial bodies through electrostatic force, hydrogen bonding force and hydrophobic interaction with protein molecules, and accumulate on the cell wall, resulting in a chamber resistance effect, resulting in the inhibition of bacterial growth and death.

The preferred embodiments of the present invention have been described above in detail. It should be understood that those skilled in the art can make many modifications and changes according to the concept of the present invention without creative efforts. Therefore, any technical solutions that can be obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the prior art according to the concept of the present invention shall fall within the protection scope determined by the claims.

Claims (4)

1. a preparation method of antistatic agent, is characterized in that: may further comprise the steps: (1) Graphene oxide modification: disperse 2-5g graphene oxide in 0.5-1.2L water, ultrasonically disperse for 1-3h to obtain graphene oxide hydrosol; add 0.3-1g to the graphene oxide hydrosol Modifier, stirring for 10-40min; after filtration and washing, vacuum drying at 20-70°C for 5-12h to obtain modified graphene oxide; (2) Chemical reduction: dissolve 2-5g of reducing agent in 0.5-1.2L of water, add 1-2g of the above modified graphene oxide, stir in a water bath at 70-110°C for 1-3h; Vacuum dry at 40-80°C for 8-15h. 2. the preparation method of antistatic agent according to claim 1 is characterized in that: described modifier is a kind of in glyceryl monostearate and octadecyldimethylbenzyl ammonium chloride or two kinds. 3. The preparation method of antistatic agent according to claim 1, wherein the reducing agent is any one of tea polyphenols, vitamin C, sodium citrate and sodium borohydride. 4. An antistatic agent, characterized in that it is prepared by the method of any one of claims 1-3.