CN111996611B - 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 comprises the following steps: (1) graphene oxide modification: dispersing 2-5g of graphene oxide in 0.5-1.2L of water, and performing ultrasonic dispersion for 1-3h to obtain graphene oxide hydrosol; adding 0.3-1g of modifier into the graphene oxide hydrosol, and stirring for 10-40min; filtering, washing with water, and vacuum drying at 20-70 deg.C for 5-12h to obtain modified graphene oxide; (2) chemical reduction: dissolving 2-5g of reducing agent in 0.5-1.2L of water, adding 1-2g of the modified graphene oxide, and stirring in a water bath at 70-110 ℃ for 1-3h; filtering, washing with water, and vacuum drying at 40-80 deg.C for 8-15 hr. According to the invention, the modified graphene oxide composite material is used as the antistatic agent, so that the antistatic performance is improved, and the antibacterial effect is improved; and the cationic quaternary ammonium salt modifier is added, so that the antibacterial performance of the antibacterial agent is further improved.

Description

Antistatic agent and preparation method thereof

technical field

The 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 fiber, and polyvinyl chloride, which have poor hygroscopic performance and usually have high specific resistance. Therefore, in the process of textile processing, the close contact and friction between fibers or 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 the slightest, and the discharge will generate sparks, which will cause fire and cause serious consequences. In some special environments and workplaces, such as electronics industry, medical and health industry, gas stations, mines and other flammable and explosive places, the use of antistatic fabrics is particularly important. At present, it is the most conventional and easiest method to add surfactants to the surface of formed fibers to obtain antistatic fabrics, but as the number of washings increases, the antistatic effect will gradually decrease. Therefore, it is of far-reaching significance to develop strong and durable antistatic fabrics.

Contents of the invention

The antistatic fabric obtained by adding the antistatic agent to the polymer in the molten state and then spinning it into fibers generally has better 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 graphene oxide material contains oxygen-containing functional groups such as hydroxyl group and carboxyl group, which endow it with good modifiable properties, and can be combined with various 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 the carbon atoms are repaired. 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 anti-oxidation mechanism can be established at the same time, it may be a good way to prepare durable antistatic performance materials. of a new idea.

Based on above research background and train of thought, the technical scheme that the present invention adopts is:

A preparation method of antistatic agent, comprising the following 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 filtering and washing with water, 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-mentioned modified graphene oxide, and stir in a water bath at 70-110°C for 1-3h; Vacuum dry at 40-80°C for 8-15h.

The modifying agent is one or both of glyceryl monostearate and stearyl dimethyl benzyl ammonium chloride.

Preferably, the modifying agent is formed by mixing glyceryl monostearate and octadecyldimethylbenzyl ammonium 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 that graphene oxide is modified and combines chemical reduction, makes 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 can also increase the compatibility between the antistatic agent and the fiber matrix; on the other hand, the improved After chemical reduction of permanent graphene oxide, the oxygen-containing functional groups on its surface are reduced, the sp ² hybrid structure of the graphene material and the delocalized π bonds formed by the carbon atoms are repaired, and the electrical conductivity is improved; in addition, using citric acid As a reducing agent, sodium, in addition to reducing oxygen-containing functional groups, can also be combined with the selected cationic modifier through electrostatic interaction 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, while improving the antistatic performance of the fabric, it improves 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, purity 99.0wt%, monolayer ratio 99.0%, lateral size 0.5 μm-10 μm, 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.

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

Glyceryl monostearate, CAS No.: 123-94-4, was purchased from Beijing Bailingwei Technology Co., Ltd.

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

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

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

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

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

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

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

The LD128 section warping machine was purchased from Longde Machinery Manufacturing Factory, Sheyang County.

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

Example 1

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

Disperse 2g of graphene oxide in 1L of deionized water, and ultrasonically disperse it for 1h under the condition of ultrasonic frequency of 40kHz and power of 450W to obtain graphene oxide hydrosol; add 0.5g modifier to the graphene oxide hydrosol, Stir for 20 minutes; filter, wash with water, and vacuum-dry at 50°C for 10 hours to obtain modified graphene oxide.

The modifying agent is octadecyl dimethyl benzyl ammonium chloride.

Example 2

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

Described modifying agent is glyceryl monostearate.

Example 3

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

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

Example 4

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

(1) Disperse 2g graphene oxide in 1L deionized water, and ultrasonically disperse it for 1h under the condition of ultrasonic frequency of 40kHz and power of 450W to obtain graphene oxide hydrosol; add 0.5g modified graphene oxide hydrosol to the graphene oxide hydrosol Stirring agent for 20 minutes; after filtering and washing with water, vacuum drying at 50°C for 10 hours to obtain modified graphene oxide;

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

The modifying agent is octadecyl dimethyl benzyl ammonium chloride.

The reducing agent is sodium citrate.

Example 5

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

Described modifying agent is glyceryl monostearate.

Example 6

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

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

Example 7

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

The reducing agent is tea polyphenols.

Comparative example 1

An antistatic agent adopts graphene oxide.

Comparative example 2

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

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

The reducing agent is sodium citrate.

Comparative example 3

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

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

(2) Disperse the reduced graphene oxide in 1L of deionized water, and ultrasonically assisted dispersion for 1h under the condition of ultrasonic frequency of 40kHz and power of 450W to obtain the reduced graphene oxide hydrosol; to the reduced graphene oxide hydrosol Add 0.5g modifier to the mixture, stir for 20min; filter and wash with water, then vacuum dry at 50°C for 10h.

The modifying agent is octadecyl dimethyl benzyl ammonium chloride.

The reducing agent is sodium citrate.

Test example 1: Antistatic performance test of antistatic agent

6.1 and 6.2 in the previous reference standard "GB/T 16801-2013 Determination of antistatic properties of fabric conditioners".

Preparation of test strips

Test piece washing treatment

Cut off the 10cm wide edge of the polyester cloth used in the test, and cut out a 500mm×500mm test cloth piece.

Dissolve the soap flakes with deionized water to prepare a 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 rotation washing method is 5 turns clockwise, 5 turns counterclockwise, rotate for 3 minutes, stop for 2 minutes, keep the rotation rate at 20r/min, and repeat. When the time is up, discard the waste water, and quickly rotate and dehydrate for 30S.

Add 2L of 40°C deionized water to the rinser, agitate and rinse for 3 minutes, and rotate 5 times clockwise and 5 times counterclockwise. After the time is up, discard the waste water, and rotate quickly for 30 seconds. Rinse like this 3 times.

Test piece drying

Use plastic shackles to pick up the washed cloth, hang it with plastic clips at both corners, and let it dry at room temperature for 3 hours. Take it out after drying, put it flat on the filter paper, cover it with filter paper, put it into an enamel plate, dry it in a 45°C oven for 4 hours, take it out and put it in a humidistat, and save it for later use.

Test strips 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, divide 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 for 10min, and use a glass rod to turn it from time to time. Take out the soaked test piece, clamp the two corners with plastic clips and hang it to dry for 3 hours, and then put it in a 45°C oven to dry for 4 hours.

The antistatic performance test was carried out on the above-mentioned dried test piece.

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

Table 1: Table of antistatic properties of antistatic agents

Surface charge density (uc/m²) The antistatic agent that embodiment 1 prepares 4.71 The antistatic agent that embodiment 2 prepares 4.75 The antistatic agent that embodiment 3 prepares 3.94 The antistatic agent that embodiment 4 prepares 1.71 The antistatic agent that embodiment 5 prepares 2.28 The antistatic agent that embodiment 6 prepares 1.24 The antistatic agent that embodiment 7 prepares 2.03 The antistatic agent that comparative example 1 prepares 6.04 The antistatic agent that comparative example 2 prepares 4.95 The antistatic agent that comparative example 3 prepares 3.58

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

Comparing Examples 4-6 with Examples 1-3, it can be found that after the modified graphene oxide is reduced, the antistatic performance of the fabric is significantly improved. The reason should be that there is a large amount of oxygen on the surface of the modified graphene oxide. When the functional group is reduced, the delocalized π bond formed by the original sp ² hybridized carbon atoms of graphene can be 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 graphene oxide is first reduced and then modified, the antistatic performance of the fabric is not as good as the effect of modifying and then reducing. 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.

Firstly, octadecyl dimethyl benzyl ammonium chloride is used to modify graphene oxide, and then sodium citrate is used to reduce it. The antistatic fabric obtained has better antistatic durability. The reason may be that the choice of citric acid When sodium is used as a reducing agent and octadecyldimethylbenzyl ammonium chloride is used as a modifying agent, after sodium citrate reduces the oxygen-containing functional groups on the surface of graphene oxide, the remaining sodium citrate will interact with the Cationic octadecyldimethylbenzyl ammonium chloride was incorporated, thereby avoiding the re-oxidation of the reduced graphene oxide in subsequent processing steps. Glyceryl monostearate is a non-ionic modifier, which will not produce electrostatic interaction with sodium citrate; and when tea polyphenol is used as a reducing agent, it is also difficult to react with cationic octadecyldimethylbenzyl Ammonium chloride has an electrostatic effect.

Antibacterial property test is carried out to above-mentioned dried test piece.

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

Table 2: Test results of sterilization rate

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

According to Table 2, it can be seen that the addition of graphene and cationic quaternary ammonium salt has a positive effect on the improvement of the antibacterial performance of the fabric. The reason why graphene materials have antibacterial properties may be that: graphene can have a strong dispersion interaction with the phospholipid molecules on the bacterial cell membrane, so it can directly extract the phospholipid molecules on the cell membrane on a large scale to kill the bacteria; cationic quaternary ammonium The mechanism of salt sterilization should be that cations can adsorb negatively charged bacteria through electrostatic force, hydrogen bond force, and hydrophobic interaction with protein molecules, and gather on the cell wall, resulting in a room resistance effect, resulting in bacterial growth being inhibited and death.

The preferred specific embodiments of the present invention have been described in detail above. 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 effort. Therefore, all technical solutions that can be obtained by those skilled in the art based on the concept of the present invention through logical analysis, reasoning or limited experiments on the basis of the prior art shall be within the scope of protection defined by the claims.

Claims (2)

1. A preparation method of an antistatic agent is characterized by comprising the following steps: the method comprises the following steps:

(1) Modifying graphene oxide: dispersing 2-5g of graphene oxide in 0.5-1.2L of water, and performing ultrasonic dispersion for 1-3h to obtain graphene oxide hydrosol; adding 0.3-1g of modifier into the graphene oxide hydrosol, and stirring for 10-40min; after filtering and water washing, carrying out vacuum drying for 5-12h at 20-70 ℃ to obtain modified graphene oxide; the modifier is a mixture of glyceryl monostearate and octadecyl dimethyl benzyl ammonium chloride in a mass ratio of 1:1;

(2) Chemical reduction: dissolving 2-5g of reducing agent in 0.5-1.2L of water, adding 1-2g of the modified graphene oxide, and stirring in a water bath at 70-110 ℃ for 1-3h; filtering, washing with water, and vacuum drying at 40-80 deg.C for 8-15 hr; the reducing agent is sodium citrate.

2. An antistatic agent characterized by being prepared by the method of claim 1.