A high-efficiency antistatic agent for use in oiling agents of spandex-coated yarn and its preparation method

Abstract

The invention belongs to the technical field of antistatic agents, and specifically relates to a high-efficiency antistatic agent for a spandex coated yarn oil and a preparation method thereof. The high-efficiency antistatic agent comprises ethylene glycol, a phosphate derivative and modified graphene; the mass ratio of ethylene glycol, the phosphate derivative and the modified graphene is 5:4-5:0.8-1; the ethylene glycol in the high-efficiency antistatic agent of the invention plays the role of a stabilizer, and through reasonable proportioning, an antistatic agent with stable performance can be formed, which is used for a spandex coated yarn oil, has excellent antistatic performance, can be evenly dispersed in the spandex coated yarn oil, and has good compatibility with other components.

Description

Technical Field

[0001] The invention belongs to the technical field of antistatic agents, and particularly relates to a high-efficiency antistatic agent for spandex coated yarn oil and a preparation method thereof. Background Art

[0002] Spandex coated yarn is a stretch yarn formed by spirally coating the stretched spandex yarn with filament or staple yarn (such as polyester) in a core. As a high-performance textile material, the core yarn is spandex yarn, which gives the coated yarn excellent elasticity and resilience. The outer yarn improves the strength, wear resistance, high temperature resistance and other properties of the coated yarn. Through the coating process, the yarn has uniform yarn length, smooth surface and good gloss. Spandex coated yarn has the advantages of high elasticity, wear resistance, high temperature resistance, uniform yarn length, strength and stability, and has been widely used and recognized in textiles in many fields such as clothing, medical treatment and sports.

[0003] Spandex coated yarn oil is an oil specially used for the production of spandex coated yarn. It is mainly applied to the surface of spandex coated yarn to improve the lubricity, antistatic property, bundling property and processability of the yarn. In the production process of spandex coated yarn, the oil can also reduce the friction between the yarn and the equipment, prevent the yarn from breaking, improve the production efficiency, and give the yarn a good feel and appearance. The main components of the spandex coated yarn oil include mineral oil, silicone oil, antistatic agent, emulsifier, etc. These components are mixed through specific formulas and processes to ensure that the oil can meet the various performance requirements of spandex coated yarn production. Among them, the antistatic agent is an indispensable component of the spandex coated yarn oil. It is not only required to have excellent antistatic properties, but also to have good compatibility with other components, which helps to improve the use effect of the spandex coated yarn oil.

[0004] Chinese patent application with application number CN202310549066.5 discloses an antistatic agent for chemical fiber spinning oil and a preparation method thereof. The components of the antistatic agent include epoxy-modified silicone oil, hydroxyl-terminated polyether and phosphorus pentoxide; wherein the molar ratio of epoxy-modified silicone oil, hydroxyl-terminated polyether and phosphorus pentoxide is 1:2-3:0.5-2, phosphorus pentoxide reacts with the reaction product of epoxy-modified silicone oil and hydroxyl-terminated polyether to generate polyether silicone oil phosphate with antistatic properties, but the conductivity of the polyether silicone oil phosphate after mixing with methyl silicone oil is less than 0.500ms·cm -1 , its antistatic performance is insufficient; therefore, it is necessary to develop a high-efficiency antistatic agent suitable for spandex coated yarn oil to meet market demand. Summary of the invention

[0005] The purpose of the present invention is to provide a high-efficiency antistatic agent for spandex coated yarn oil and a preparation method thereof in view of the deficiencies in the prior art. The high-efficiency antistatic agent comprises ethylene glycol, phosphate derivatives and modified graphene, wherein ethylene glycol plays the role of a stabilizer. Through reasonable proportioning, an antistatic agent with stable performance can be formed. The antistatic agent is used for spandex coated yarn oil, has excellent antistatic performance, can be uniformly dispersed in the spandex coated yarn oil, and has good compatibility with other components.

[0006] The technical solution adopted by the present invention to achieve the above-mentioned purpose is:

[0007] A high-efficiency antistatic agent for spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, a phosphate derivative and modified graphene; the mass ratio of the ethylene glycol, the phosphate derivative and the modified graphene is 5:4-5:0.8-1;

[0008] In the technical scheme of the present invention, the preparation method of the modified graphene is: add N,N-dimethylformamide and graphene oxide into a reaction container, mix evenly, add phosphate derivatives and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, heat to 55-60°C, stir and react for 4-6 hours, after the reaction is completed, cool, filter, and wash the residue repeatedly with water and ethanol in turn, and obtain modified graphene oxide after drying.

[0009] Furthermore, the mass ratio of the graphene oxide, the phosphate derivative, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:0.2-0.3:0.1-0.15.

[0010] In the technical solution of the present invention, the preparation method of the phosphate derivative is:

[0011] S1. Add chloroform, p-nitrophenylethanol and triethylamine to a reaction vessel, mix well, slowly drop epichlorohydrin, raise the temperature to 55-60°C, stir and react for 4-5h, remove chloroform after the reaction is completed, extract with water and dichloromethane, and concentrate the organic phase under reduced pressure to obtain p-nitrophenyl alkyl alcohol, the chemical structure of which is:

[0012] ;

[0013] S2. Add chloroform, p-nitrophenyl alkyl alcohol and concentrated sulfuric acid to the reaction vessel, mix well, heat to 55-60°C, slowly drop dimethyl phosphite, continue stirring to react for 3-4 hours, remove chloroform after the reaction is completed, extract with water and dichloromethane, and concentrate the organic phase under reduced pressure to obtain p-nitrophenyl phosphate, the chemical structure of which is:

[0014] ;

[0015] S3, add methanol, p-nitrophenyl phosphate and palladium carbon to the hydrogenation reaction kettle, pass 0.1 MPa hydrogen, stir and react at room temperature for 6-7h. After the reaction is completed, filter out the palladium carbon, wash with methanol, and concentrate the filtrate under reduced pressure to obtain p-aminophenyl phosphate, the chemical structural formula is:

[0016] ;

[0017] S4. Add ethanol, p-aminophenyl phosphate and dodecyl dimethyl tertiary amine to the reaction container, mix well, heat to 80°C, and reflux for 8-9 hours. After the reaction is completed, remove ethanol, extract with water and dichloromethane, and concentrate the aqueous phase under reduced pressure to obtain a phosphate derivative with the chemical formula:

[0018]

[0019] Furthermore, in step S1, the molar ratio of p-nitrophenylethanol, epichlorohydrin and triethylamine is 1:1.0-1.1:1.3-1.5.

[0020] Furthermore, in step S2, the molar ratio of p-nitrophenyl alkyl alcohol, dimethyl phosphite and concentrated sulfuric acid is 1:1.1-1.2:0.1-0.2.

[0021] Furthermore, the mass ratio of p-nitrophenyl phosphate to palladium carbon in step S3 is 1:0.1-0.15.

[0022] Furthermore, in step S4, the molar ratio of p-aminophenyl phosphate to dodecyl dimethyl tertiary amine is 1:1.0-1.1.

[0023] The present invention also provides a method for preparing a high-efficiency antistatic agent for spandex coated yarn oil, comprising the following steps: adding ethylene glycol and phosphate derivatives into a reaction container according to a mass ratio, stirring evenly, adding modified graphene, and ultrasonically dispersing evenly to obtain a high-efficiency antistatic agent.

[0024] Furthermore, in the preparation method of the above-mentioned high-efficiency antistatic agent for spandex coated yarn oil, the stirring speed is 500-600 r / min, and the stirring time is 10-20 min; the ultrasonic power is 200-300 W, and the ultrasonic time is 0.5-1 h.

[0025] The present invention has the following beneficial effects:

[0026] In order to obtain a high-efficiency antistatic agent for a spandex coated yarn oil with better performance, the present invention firstly uses p-nitrophenylethanol as a raw material, first reacts with epichlorohydrin and dimethyl phosphite to obtain p-nitrophenyl phosphate, and after hydrogen reduction, reacts with dodecyl dimethyl tertiary amine to obtain a phosphate derivative containing an aniline group, a long-chain quaternary ammonium salt group and a phosphate group in the structure, and the long-chain quaternary ammonium salt group and the phosphate group give the phosphate derivative good dispersion stability and antistatic property; in addition, the present invention utilizes the aniline group in the structure of the phosphate derivative and the carboxyl group on the surface of graphene oxide to form a phosphate derivative in the shrinkage Under the action of the mixture 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, a condensation reaction occurs, and then the phosphate derivative molecules are grafted onto the surface of graphene oxide to obtain modified graphene. The phosphate derivative molecules can give the graphene good dispersion stability and antistatic properties. The modified graphene has good compatibility with other organic components. The present invention adds the antistatic agent containing the modified graphene to the spandex coated yarn oil, which can greatly improve the conductivity of the oil, more effectively conduct static electricity, reduce static electricity accumulation, and thus significantly improve its antistatic performance.

[0027] The high-efficiency antistatic agent provided by the present invention comprises ethylene glycol, phosphate derivatives and modified graphene, wherein ethylene glycol plays the role of a stabilizer. Through reasonable proportioning, an antistatic agent with stable performance can be formed, which is used for spandex coated yarn oil, has excellent antistatic performance, can be evenly dispersed in the spandex coated yarn oil, and has good compatibility with other components. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments; the technical features designed in different implementation modes of the present invention described below can be combined with each other as long as they do not conflict with each other; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0029] In the technical scheme of the present invention, the chemical reagents used are all commercially available, among which graphene oxide is purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; ethylene glycol CAS No. 107-21-1; N,N-dimethylformamide CAS No. 68-12-2; 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride CAS No. 25952-53-8; p-nitrophenylethanol CAS No. 100-27-6; triethylamine CAS No. 121-44-8; epichlorohydrin CAS No. 106-89-8; dimethyl phosphite CAS No. 868-85-9; concentrated sulfuric acid CAS No. 7664-93-9; dodecyl dimethyl tertiary amine CAS No. 112-18-5; chloroform CAS No. 67-66-3; ethanol CAS No. 64-17-5; methanol CAS No. 67-56-1.

[0030] Embodiment 1

[0031] This embodiment provides a method for preparing a phosphate derivative, and the synthetic route is:

[0032] ;

[0033] S1. Add 600 mL of chloroform, 20.0 g of p-nitrophenylethanol and 18.2 g of triethylamine to a reaction vessel, mix well, slowly drop 11.6 g of epichlorohydrin, and after the drop is complete, heat to 60 ° C. and stir to react for 5 hours. After the reaction is completed, remove chloroform, extract with water and dichloromethane, and concentrate the organic phase under reduced pressure to obtain 25.8 g of p-nitrophenyl alkyl alcohol; wherein the molar ratio of p-nitrophenylethanol, epichlorohydrin and triethylamine is 1:1.05:1.5;

[0034] p-Nitrophenyl alkyl alcohol: ESI (m / z): 260.7 [M+H] + , 1 H-NMR (600MHz, DMSO-d6, δppm): 8.14 (d, J=8.5Hz, 2H), 7.52 (d, J=8.5Hz, 2H), 5.37 ( s, 1H), 4.11-4.15 (m, 1H), 3.64-3.70 (m, 4H), 3.38-3.42 (m, 2H), 2.85-2.89 (m, 2H);

[0035] S2, add 500mL chloroform, 25.0g p-nitrophenyl alkyl alcohol and 1.9g concentrated sulfuric acid to the reaction vessel, mix well, heat to 60°C, slowly drop 11.7g dimethyl phosphite, after the drop is complete, continue stirring to react for 4h, after the reaction is completed, remove chloroform, use water and dichloromethane for extraction, and concentrate the organic phase under reduced pressure to obtain 28.6g p-nitrophenyl phosphate; wherein the molar ratio of p-nitrophenyl alkyl alcohol, dimethyl phosphite and concentrated sulfuric acid is 1:1.1:0.2;

[0036] p-Nitrophenyl phosphate: ESI (m / z): 352.7 [M+H] + , 1 H-NMR (600MHz, DMSO-d6, δppm): 8.15 (d, J=8.5Hz, 2H), 7.52 (d, J=8.5Hz, 2H), 4.01-4.06 (m, 1H), 3.64-3.70 (m, 10H), 3.41-3.46 (m, 2H), 2.86-2.91 (m, 2H);

[0037] S3, add 400mL methanol, 28.0g p-nitrophenyl phosphate and 2.8g palladium carbon into the hydrogenation reactor, pass 0.1MPa hydrogen, stir and react for 7h at room temperature, after the reaction is completed, filter out the palladium carbon, wash with methanol, and concentrate the filtrate under reduced pressure to obtain 22.2g p-aminophenyl phosphate; wherein the mass ratio of p-nitrophenyl phosphate to palladium carbon is 1:0.1;

[0038] p-Aminophenylphosphoester: ESI (m / z): 322.7 [M+H] + , 1 H-NMR (600MHz, DMSO-d6, δppm): 6.92 (d, J=8.4Hz, 2H), 6.45 (d, J=8.4Hz, 2H), 4.91 ( s, 2H), 4.01-4.05 (m, 1H), 3.66-3.72 (m, 10H), 3.42-3.45 (m, 2H), 2.73-2.76 (m, 2H);

[0039] S4, add 350mL ethanol, 22.0g p-aminophenyl phosphate and 15.3g dodecyl dimethyl tertiary amine to the reaction container, mix well, heat to 80°C, reflux for 9h, after the reaction is completed, remove ethanol, extract with water and dichloromethane, and concentrate the aqueous phase under reduced pressure to obtain 30.5g phosphate derivative; wherein the molar ratio of p-aminophenyl phosphate to dodecyl dimethyl tertiary amine is 1:1.05;

[0040] Phosphate derivative: ESI (m / z): 536.2 [M+H] + , 1H-NMR (600MHz, DMSO-d6, δppm): 6.95 (d, J=8.4Hz, 2H), 6.43 (d, J=8.4Hz, 2H), 4.91 (s, 2H), 4.32-4.36 (m, 1H), 3.65-3.72 (m, 9H), 3.46-3.50 (m, 2H), 3.22-3.30 (m, 9H), 2.72-2.76 (m, 2H), 1.71-1.74 (m, 2H), 1.26-1.30 (m, 18H), 0.88 (t, J=6.9Hz, 3H).

[0041] Embodiment 2

[0042] A high-efficiency antistatic agent for spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, phosphate derivatives and modified graphene; the mass ratio of ethylene glycol, phosphate derivatives and modified graphene is 5:5:1;

[0043] The preparation method of modified graphene is as follows: N,N-dimethylformamide and graphene oxide are added into a reaction container, mixed evenly, phosphate derivatives and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added, the temperature is raised to 60°C, and the reaction is stirred for 5 hours. After the reaction is completed, the mixture is cooled and filtered, and the residue is washed repeatedly with water and ethanol in sequence, and the modified graphene oxide is obtained after drying; wherein the mass ratio of graphene oxide, phosphate derivative and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:0.3:0.15; and the amount of N,N-dimethylformamide used is 15 times the mass of graphene oxide.

[0044] A method for preparing a high-efficiency antistatic agent for spandex coated yarn oil comprises the following steps: adding ethylene glycol and a phosphate derivative into a reaction container according to a mass ratio, stirring evenly, adding modified graphene, and ultrasonically dispersing evenly to obtain a high-efficiency antistatic agent; the stirring speed is 600 r / min, the stirring time is 15 min, the ultrasonic power is 200 W, and the ultrasonic time is 1 h.

[0045] Embodiment 3

[0046] A high-efficiency antistatic agent for spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, phosphate derivatives and modified graphene; the mass ratio of ethylene glycol, phosphate derivatives and modified graphene is 5:4:0.9;

[0047] The preparation method of modified graphene is as follows: N,N-dimethylformamide and graphene oxide are added into a reaction container, mixed evenly, phosphate derivatives and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added, the temperature is raised to 55°C, and the reaction is stirred for 6 hours. After the reaction is completed, the mixture is cooled and filtered, and the residue is repeatedly washed with water and ethanol in sequence, and then dried to obtain modified graphene oxide; wherein the mass ratio of graphene oxide, phosphate derivative and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:0.25:0.1; and the amount of N,N-dimethylformamide used is 15 times the mass of graphene oxide.

[0048] A method for preparing a high-efficiency antistatic agent for spandex coated yarn oil comprises the following steps: adding ethylene glycol and a phosphate derivative into a reaction container according to a mass ratio, stirring evenly, adding modified graphene, and ultrasonically dispersing evenly to obtain a high-efficiency antistatic agent; the stirring speed is 550 r / min, the stirring time is 10 min, the ultrasonic power is 300 W, and the ultrasonic time is 0.5 h.

[0049] Embodiment 4

[0050] A high-efficiency antistatic agent for spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, a phosphate derivative and modified graphene; the mass ratio of ethylene glycol, the phosphate derivative and the modified graphene is 5:4.5:0.8;

[0051] The preparation method of modified graphene is as follows: N,N-dimethylformamide and graphene oxide are added into a reaction container, mixed evenly, phosphate derivatives and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added, the temperature is raised to 60°C, and the reaction is stirred for 4 hours. After the reaction is completed, the mixture is cooled and filtered, and the residue is repeatedly washed with water and ethanol in turn, and the modified graphene oxide is obtained after drying; wherein the mass ratio of graphene oxide, phosphate derivative and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:0.2:0.13; and the amount of N,N-dimethylformamide used is 15 times the mass of graphene oxide.

[0052] A method for preparing a high-efficiency antistatic agent for spandex coated yarn oil comprises the following steps: adding ethylene glycol and a phosphate derivative into a reaction container according to a mass ratio, stirring evenly, adding modified graphene, and ultrasonically dispersing evenly to obtain a high-efficiency antistatic agent; the stirring speed is 500 r / min, the stirring time is 20 min, the ultrasonic power is 250 W, and the ultrasonic time is 0.8 h.

[0053] Embodiment 5

[0054] A high-efficiency antistatic agent for spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, phosphate derivatives and modified graphene; the mass ratio of ethylene glycol, phosphate derivatives and modified graphene is 5:5:0.8;

[0055] The preparation method of modified graphene is as follows: N,N-dimethylformamide and graphene oxide are added into a reaction container, mixed evenly, phosphate derivatives and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride are added, the temperature is raised to 58°C, and the reaction is stirred for 5 hours. After the reaction is completed, the mixture is cooled and filtered, and the residue is repeatedly washed with water and ethanol in sequence, and then dried to obtain modified graphene oxide; wherein the mass ratio of graphene oxide, phosphate derivative and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:0.3:0.1; and the amount of N,N-dimethylformamide used is 15 times the mass of graphene oxide.

[0056] A method for preparing a high-efficiency antistatic agent for spandex coated yarn oil comprises the following steps: adding ethylene glycol and a phosphate derivative into a reaction container according to a mass ratio, stirring evenly, adding modified graphene, and ultrasonically dispersing evenly to obtain a high-efficiency antistatic agent; the stirring speed is 600 r / min, the stirring time is 20 min, the ultrasonic power is 300 W, and the ultrasonic time is 1 h.

[0057] Comparative Example 1

[0058] Compared with Example 2, this comparative example comprises a high-efficiency antistatic agent including ethylene glycol, a phosphate derivative and graphene oxide.

[0059] A high-efficiency antistatic agent for spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, a phosphate derivative and graphene oxide; the mass ratio of ethylene glycol, the phosphate derivative and the graphene oxide is 5:5:1;

[0060] The preparation method of a high-efficiency antistatic agent for spandex coated yarn oil is the same as that of Example 2.

[0061] Comparative Example 2

[0062] Compared with Example 2, this comparative example comprises a high-efficiency antistatic agent including ethylene glycol, dodecyl phosphate and modified graphene.

[0063] A high-efficiency antistatic agent for spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, dodecyl phosphate ester salt and modified graphene; the mass ratio of ethylene glycol, dodecyl phosphate ester salt and modified graphene is 5:5:1;

[0064] The preparation methods of modified graphene and a high-efficiency antistatic agent for spandex coated yarn oil are the same as those in Example 2.

[0065] Comparative Example 3

[0066] Compared with Example 2, this comparative example comprises a high-efficiency antistatic agent including ethylene glycol, dodecyl phosphate and graphene oxide.

[0067] A high-efficiency antistatic agent for a spandex coated yarn oil, the high-efficiency antistatic agent comprising ethylene glycol, dodecyl phosphate salt and graphene oxide; the mass ratio of ethylene glycol, dodecyl phosphate salt and graphene oxide is 5:5:1;

[0068] The preparation method of a high-efficiency antistatic agent for spandex coated yarn oil is the same as that of Example 2.

[0069] Performance Testing

[0070] 1.0 g of the high-efficiency antistatic agent prepared in the above-mentioned Examples 2 to 5 and Comparative Examples 1 to 3 was respectively added to a spandex coated yarn oil (15.0 g of propylene glycol monopalmitate, 5.0 g of propylene glycol random polyoxyethylene polyoxypropylene ether 1500, 2.0 g of propylene glycol fatty acid ester, 5.0 g of dimethyl silicone oil and 1.5 g of lauric acid polyoxyethylene ether), and the conductivity of the spandex coated yarn oil was tested; the same amount of the spandex coated yarn oil was placed in a constant temperature water bath at 30°C for 60 days, and the stability of the oil was observed. It was considered to be stable if there was no stratification or precipitation; the spandex coated yarn oil was also used in a spinning experiment of spandex coated yarn, and the static friction coefficient between the yarns, the static electricity on the yarn roll, and whether adhesion and breakage occurred at a rewinding speed of 100 m / min were measured; the test results are shown in Table 1 below.

[0071] Table 1 Performance test results

[0072]

[0073] It can be seen from the results in Table 1 that the high-efficiency antistatic agent prepared in Examples 2 to 5 of the present invention is used in the spandex coated yarn oil, has high conductivity, no adhesion or breakage during unwinding, a small static friction coefficient between yarns, and a small amount of static electricity on the yarn roll, indicating that it has excellent antistatic performance, and the antistatic agent can be evenly dispersed in the spandex coated yarn oil, with good stability, indicating that the antistatic agent has good compatibility with other components; compared with Comparative Examples 1 to 3, the phosphate derivative and modified graphene in the antistatic agent in Example 2 of the present invention can jointly improve the antistatic performance of the antistatic agent, especially the long-chain quaternary ammonium salt and phosphate group grafted on the surface of the modified graphene, which improve the dispersion stability of the modified graphene and its compatibility with other organic components, thereby greatly improving the conductivity of the oil, and can more effectively conduct static electricity and reduce static electricity accumulation.

[0074] It should be noted that, in this article, terms such as "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or apparatus.

[0075] Although the embodiments of the present application have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present application, and that the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A high-efficiency antistatic agent for spandex coated yarn oil, characterized in that: The high-efficiency antistatic agent comprises ethylene glycol, phosphate derivatives and modified graphene; the mass ratio of the ethylene glycol, phosphate derivatives and modified graphene is 5:4-5:0.8-1; The preparation method of the modified graphene is as follows: adding N,N-dimethylformamide and graphene oxide into a reaction container, mixing them evenly, adding a phosphate derivative and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, heating to 55-60° C., stirring and reacting for 4-6 hours, cooling after the reaction is completed, filtering, and washing the filter residue repeatedly with water and ethanol in sequence, and drying to obtain the modified graphene oxide; The phosphate derivative is: 。 2. The high-efficiency antistatic agent for spandex coated yarn oil according to claim 1, characterized in that: The preparation method of the phosphate derivative is: S1. Add chloroform, p-nitrophenylethanol and triethylamine to a reaction vessel, mix well, slowly drop epichlorohydrin, raise the temperature to 55-60°C, stir and react for 4-5h, remove chloroform after the reaction is completed, extract with water and dichloromethane, and concentrate the organic phase under reduced pressure to obtain p-nitrophenyl alkyl alcohol; S2, add chloroform, p-nitrophenyl alkyl alcohol and concentrated sulfuric acid to the reaction container, mix well, heat to 55-60 ° C, slowly add dimethyl phosphite dropwise, continue to stir and react for 3-4 hours, after the reaction is completed, remove chloroform, use water and dichloromethane for extraction, and concentrate the organic phase under reduced pressure to obtain p-nitrophenyl phosphate; S3, add methanol, p-nitrophenyl phosphate and palladium carbon to the hydrogenation reaction kettle, pass 0.1 MPa hydrogen, stir and react at room temperature for 6-7 hours. After the reaction is completed, filter out the palladium carbon, wash with methanol, and concentrate the filtrate under reduced pressure to obtain p-aminophenyl phosphate; S4. Add ethanol, p-aminophenyl phosphate and dodecyl dimethyl tertiary amine to the reaction container, mix well, heat to 80°C, and reflux for 8-9 hours. After the reaction is completed, remove ethanol, extract with water and dichloromethane, and concentrate the aqueous phase under reduced pressure to obtain a phosphate derivative.

3. A high-efficiency antistatic agent for spandex coated yarn oil according to claim 2, characterized in that: The molar ratio of p-nitrophenylethanol, epichlorohydrin and triethylamine in step S1 is 1:1.0-1.1:1.3-1.

5.

4. A high-efficiency antistatic agent for spandex coated yarn oil according to claim 2, characterized in that: The molar ratio of p-nitrophenyl alkyl alcohol, dimethyl phosphite and concentrated sulfuric acid in step S2 is 1:1.1-1.2:0.1-0.

2.

5. The high-efficiency antistatic agent for spandex coated yarn oil according to claim 2, characterized in that: The mass ratio of p-nitrophenyl phosphate to palladium carbon in step S3 is 1:0.1-0.

15.

6. A high-efficiency antistatic agent for spandex coated yarn oil according to claim 2, characterized in that: The molar ratio of p-aminophenyl phosphate to dodecyl dimethyl tertiary amine in step S4 is 1:1.0-1.

1.

7. The high-efficiency antistatic agent for spandex coated yarn oil according to claim 1, characterized in that: In the preparation method of modified graphene, the mass ratio of graphene oxide, phosphate derivative and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride is 1:0.2-0.3:0.1-0.

15.

8. A method for preparing a high-efficiency antistatic agent for spandex coated yarn oil according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: adding ethylene glycol and phosphate derivatives into a reaction container according to a mass ratio, stirring evenly, adding modified graphene, and uniformly dispersing by ultrasonication to obtain a high-efficiency antistatic agent.

9. The method for preparing a high-efficiency antistatic agent for spandex coated yarn oil according to claim 8, characterized in that: The stirring speed is 500-600 r / min, and the stirring time is 10-20 min; the ultrasonic power is 200-300 W, and the ultrasonic time is 0.5-1 h.

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