Graphene-modified polyester fiber and method for preparing the same

Abstract

The application belongs to the technical field of textile chemistry, and particularly relates to a graphene modified polyester fiber and a preparation method thereof. The polyester fiber has low moisture regain and poor moisture absorption, and is prone to static electricity during production and use. In view of the above problems, the application provides a graphene modified polyester fiber. In the obtained modified graphene material, graphene sheet layer structures are connected together through 3,5-bis(3-aminopropyl)benzoic acid ethyl ester and four-arm-polyethylene glycol-amino structure fragments as bridges, the agglomeration phenomenon between the graphene materials is improved, the uniform dispersibility of the modified graphene material on the surface of the polyester fiber is significantly improved, the four-arm-polyethylene glycol-amino is introduced into the modified graphene material as a rich polyether structure, the hydrophilic polyether structure can absorb or associate water molecules in the air, and a conductive water film is formed on the surface of the polyester fiber to eliminate static electricity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of textile chemistry, and particularly relates to a graphene modified polyester fiber and a preparation method thereof. BACKGROUND

[0002] Polyester fiber, also known as PET fiber, is a kind of synthetic fiber, in which each chain segment in the macromolecular chain is connected by an ester group. Polyester fiber has high heat resistance and light resistance, high breaking strength and elastic modulus, moderate resilience, and excellent heat setting effect. The fabric has good washing and wearing resistance. In addition, polyester fiber also has excellent properties such as resistance to organic solvents, resistance to soap, resistance to detergents, resistance to bleaching solution, resistance to oxidizing agents, and good corrosion resistance, and is stable to weak acid and weak base. It is widely used in home textile manufacturing and protective clothing for manufacturing industry.

[0003] High molecular materials usually lack hydrophilic groups, have poor moisture absorption, high specific resistance, and are prone to static electricity and accumulation of static electricity under the influence of factors such as friction, stretching, compression, hot air drying, etc., thereby causing adverse phenomena such as static dust collection and static discharge, and even sparks, causing fire or explosion accidents, threatening people's health and property safety.

[0004] Polyester fiber also belongs to high molecular materials, and has the problems of low moisture regain, poor moisture absorption, and easy generation of static electricity during production and use. SUMMARY

[0005] The existing problems are that polyester fiber has low moisture regain, poor moisture absorption, and is prone to static electricity during production and use. In view of the above problems, the present application provides a graphene modified polyester fiber, which comprises the following preparation steps:

[0006] (1) uniformly dispersing polyether modified graphene oxide in deionized water to obtain a modified liquid;

[0007] (2) immersing polyester fiber in the modified liquid obtained in step (1) and keeping at 50-60℃ for at least 30 min, then washing with water and drying to complete the first immersion, repeating the above immersion process at least 5 times to obtain graphene oxide modified polyester fiber;

[0008] (3) immersing the graphene oxide modified polyester fiber obtained in step (2) in a reducing liquid to reduce the oxygen-containing functional groups on the surface of graphene oxide, and then washing with water and drying to obtain graphene modified polyester fiber.

[0009] Specifically, the preparation method of the polyether modified graphene oxide comprises the following steps:

[0010] (1) acylating reaction of graphene oxide and 3,5-bis(3-aminopropyl)benzoic acid ethyl ester to obtain modified graphene oxide;

[0011] (2) The modified graphene oxide is subjected to an amidation reaction with a four-arm-polyethylene glycol-amino to obtain polyether-modified graphene oxide.

[0012] Specifically, step (1) comprises the following steps:

[0013] 20 g of graphene oxide is dispersed in 20 mL of anhydrous dichloromethane, and ultrasonic dispersion is performed until uniform. Then, 15-20 g of HATU (2-(7-azabenzotriazol)-tetramethyl urea hexafluorophosphate) and 15-20 mL of DIPEA (N,N-diisopropylethylamine) are added, and ultrasonic dispersion is performed until uniform. Then, 5-10 g of 3,5-bis(3-aminopropyl)benzoic acid ethyl ester is added, and ultrasonic dispersion is performed until uniform. The reaction is monitored by FTIR while stirring. The reaction is terminated when the amino absorption peak in the infrared spectrum disappears. The reaction product is centrifuged, washed with ethanol, and dried to obtain modified graphene oxide.

[0014] Specifically, step (2) comprises the following steps:

[0015] 40 mg of modified graphene oxide is uniformly dispersed in deionized water to obtain a modified graphene oxide dispersion with a concentration of 1-3 mg / mL. Carboxyl activators N-hydroxysuccinimide (NHS) and 1-ethyl-(3-dimethylaminopropyl) (EDC) are added, and the mass ratio between the modified graphene oxide and the NHS and EDC is 1:1-1.2:1-1.2. The reaction is stirred at room temperature for 0.5-2 h. Then, 0.15-0.2 mol of four-arm-polyethylene glycol-amino is added, and the pH is adjusted to 4.5-6. The reaction is performed at room temperature for 12-48 h. The product is filtered, washed, and dried to obtain polyether-modified graphene oxide.

[0016] Specifically, the concentration of the modification solution is 1-10 mg / L.

[0017] Specifically, the polyester fiber is subjected to a hydrolysis pretreatment by immersing the polyester fiber in a hot alkali solution to cause a mild hydrolysis reaction on the surface of the polyester fiber.

[0018] Specifically, the immersion temperature of the hydrolysis pretreatment is not higher than 80°C.

[0019] Specifically, the immersion time of the hydrolysis pretreatment is not more than 30 min.

[0020] Specifically, the alkali in the hydrolysis pretreatment includes, but is not limited to, at least one of sodium hydroxide and potassium hydroxide.

[0021] Specifically, the concentration of the alkali solution in the hydrolysis pretreatment is 0.5-1 mol / L.

[0022] Specifically, the reducing agent in the reducing solution includes, but is not limited to, at least one of sodium borohydride, L-ascorbic acid, and sodium hyposulfite.

[0023] Specifically, the concentration of the reducing solution is 10-100 mg / L.

[0024] Specifically, the room temperature reduction time is not less than 48 h.

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

[0026] (1) The graphene modified polyester fiber obtained by the present application is loaded with modified graphene material on the surface, and the graphene sheet layer structure in the modified graphene material (specifically, the polyether modified graphene oxide after reduction in the present application) is connected by the following structural fragments introduced by 3,5-bis(3-aminopropyl)benzoic acid ethyl ester and four-arm-polyethylene glycol-amino:

[0027]

[0028] As a bridge, it improves the agglomeration phenomenon between graphene materials and significantly improves the uniform dispersibility of the modified graphene material on the surface of the polyester fiber.

[0029] (2) The four-arm-polyethylene glycol-amino introduces abundant polyether structures into the modified graphene material, and the hydrophilic polyether structure can absorb or associate water molecules in the air to form a conductive water film on the surface of the polyester fiber to eliminate static charge. The oxygen atom in the polyether structure also carries a lone pair of electrons, which has the ability to receive protons, and can achieve static dissipation effect through the transfer of internal protons.

[0030] (3) The polyether structure introduced by the four-arm-polyethylene glycol-amino is a hydrophilic group, which can improve the dispersibility of the polyether modified graphene oxide in the aqueous solution, effectively prevent the agglomeration between graphene, and facilitate the more uniform adhesion of the polyether modified graphene oxide on the surface of the polyester fiber, thereby significantly improving the antistatic performance of the graphene modified polyester fiber.

[0031] (4) The 3,5-bis(3-aminopropyl)benzoic acid ethyl ester introduces benzoic acid ethyl ester structure into the modified graphene material, significantly increases the compatibility between the modified graphene material and the polyester fiber, further improves the uniform dispersibility and adhesion of the modified graphene material on the surface of the polyester fiber, and facilitates the better antistatic effect of the modified graphene material on the surface of the polyester fiber, so that the graphene modified polyester fiber has better antistatic durability. DETAILED DESCRIPTION

[0032] The present application will be described in detail below in conjunction with the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present application, and are not a limitation on the scope of the present application.

[0033] The polyester fibers in the following examples and comparative examples of the present application are all subjected to hydrolysis pretreatment, which is to immerse the polyester fibers in 1 mol / L aqueous sodium hydroxide solution at 80℃ for 20 min, so that the polyester fibers are subjected to mild hydrolysis reaction on the surface, and the immersion bath ratio (mass ratio) of the polyester fibers to the lye is 1:40.

[0034] The four-arm-polyethylene glycol-amino in the following examples and comparative examples of the present application has the trade name ZP-60105, a molecular weight of 2000, and the brand Zzstandard.

[0035] The 3,5-bis(3-aminopropyl)ethyl benzoate in the following examples of the present application has the CAS number 714276-84-3.

[0036] The washing and drying in the following examples and comparative examples of the present application refer to repeated washing with deionized water for 3 min, and then hot air drying at 60℃.

[0037] The amino polyethylene glycol carboxyl in the comparative example of the present application has the English name NH2-PEG-COOH, a molecular weight of 2000, and the brand ponsure, trade number PS2-NCM-3K.

[0038] Example 1

[0039] A graphene modified polyester fiber is prepared by the following steps:

[0040] (1) uniformly dispersing polyether modified graphene oxide in deionized water to obtain a modified liquid, and the concentration of the modified liquid is 1 mg / L;

[0041] (2) immersing the polyester fibers in the modified liquid obtained in step (1) at 50℃ for 30 min, the concentration of the modified liquid is 1 mg / L, the immersion bath ratio (mass ratio) of the polyester fibers to the modified liquid is 1:30, after washing and drying, one immersion is completed, and the above immersion process is repeated 5 times to obtain graphene oxide modified polyester fibers;

[0042] (3) immersing the graphene oxide modified polyester fibers obtained in step (2) in a reducing liquid, the reducing liquid is an aqueous sodium borohydride solution with a concentration of 10 mg / L, the immersion bath ratio (mass ratio) of the graphene oxide modified polyester fibers to the reducing liquid is 1:30, and the reduction is carried out at room temperature for 48 h, after the reduction is completed, the graphene modified polyester fibers are obtained after washing and drying.

[0043] The preparation method of the polyether modified graphene oxide is as follows:

[0044] (1) 20 g of graphene oxide was dispersed in 20 mL of anhydrous dichloromethane, ultrasonic dispersion was uniform, 15 g of HATU and 15 mL of DIPEA were added, ultrasonic dispersion was uniform, 5 g of 3,5-bis(3-aminopropyl) ethyl benzoate was added, ultrasonic dispersion was uniform, the reaction was monitored by FTIR while stirring, the reaction was stirred at room temperature until the amino absorption peak in the reaction system disappeared in the infrared spectrum, the reaction was completed, the reaction product was centrifuged, washed with ethanol, and dried to obtain modified graphene oxide;

[0045] (2) 40 mg of modified graphene oxide was uniformly dispersed in deionized water to obtain a modified graphene oxide dispersion with a concentration of 1 mg / mL, carboxyl activators NHS and EDC were added, the mass ratio of the modified graphene oxide to NHS and EDC was 1:1:1, the reaction was stirred at room temperature for 0.5 h, 300 g of four-arm-polyethylene glycol-amino was added, the pH was adjusted to 4.5, and the reaction was carried out at room temperature for 12 h, and then filtered, washed, and dried to obtain polyether-modified graphene oxide.

[0046] Example 2

[0047] A graphene-modified polyester fiber, the preparation steps of which are as follows:

[0048] (1) The polyether-modified graphene oxide was uniformly dispersed in deionized water to obtain a modified solution, and the concentration of the modified solution was 5 mg / L;

[0049] (2) The polyester fiber was immersed in the modified solution obtained in step (1), and the concentration of the modified solution was 5 mg / L, the polyester fiber was immersed in the modified solution at a bath ratio (mass ratio) of 1.5:50 at 50°C for 30 min, and then washed with water and dried to complete one immersion, and the above immersion process was repeated 5 times to obtain graphene-modified polyester fiber.

[0050] (3) The graphene-modified polyester fiber obtained in step (2) was immersed in a reducing solution, the reducing solution was an aqueous L-ascorbic acid solution with a concentration of 50 mg / L, the graphene-modified polyester fiber was immersed in the reducing solution at a bath ratio (mass ratio) of 1.5:50, and the reduction was carried out at room temperature for 48 h, and then the graphene-modified polyester fiber was obtained after washing with water and drying.

[0051] The preparation method of the polyether-modified graphene oxide is as follows:

[0052] (1) 20 g of graphene oxide was dispersed in 20 mL of anhydrous dichloromethane, ultrasonic dispersion was uniform, 18 g of HATU and 20 mL of DIPEA were added, ultrasonic dispersion was uniform, 7 g of 3,5-bis(3-aminopropyl) ethyl benzoate was added, ultrasonic dispersion was uniform, the reaction was monitored by FTIR while stirring, the reaction was stirred at room temperature until the amino absorption peak in the reaction system disappeared in the infrared spectrum, the reaction was completed, the reaction product was centrifuged, washed with ethanol, and dried to obtain modified graphene oxide;

[0053] (2) 40 mg of modified graphene oxide was uniformly dispersed in deionized water to obtain a modified graphene oxide dispersion liquid with a concentration of 2 mg / mL, carboxyl activators NHS and EDC were added, the mass ratio between the modified graphene oxide, NHS and EDC was 1:1.2:1.2, the reaction was stirred at room temperature for 1 h, 300 g of four-arm-polyethylene glycol-amino was added, the pH was adjusted to 4.5, the reaction was carried out at room temperature for 12 h, and then filtration, washing and drying were carried out to obtain polyether-modified graphene oxide.

[0054] Example 3

[0055] A graphene-modified polyester fiber, the preparation steps of which are as follows:

[0056] (1) The polyether-modified graphene oxide was uniformly dispersed in deionized water to obtain a modified liquid, and the concentration of the modified liquid was 10 mg / L;

[0057] (2) The polyester fiber was immersed in the modified liquid obtained in step (1), and the concentration of the modified liquid was 10 mg / L, the polyester fiber was immersed in the modified liquid at a bath ratio (mass ratio) of 2:100 at 60°C for 30 min, and then washed with water and dried to complete one immersion, and the above immersion process was repeated 5 times to obtain graphene-modified polyester fiber.

[0058] (3) The graphene-modified polyester fiber obtained in step (2) was immersed in a reducing liquid, the reducing liquid was an aqueous sodium dithionite solution with a concentration of 100 mg / L, the graphene-modified polyester fiber was immersed in the reducing liquid at a bath ratio (mass ratio) of 2:100 at 95°C for 48 h, and then washed with water and dried to obtain graphene-modified polyester fiber.

[0059] The preparation method of the polyether-modified graphene oxide is as follows:

[0060] (1) 20g of graphene oxide was dispersed in 20mL of anhydrous dichloromethane and ultrasonically dispersed evenly. 20g of HATU and 20mL of DIPEA were added and ultrasonically dispersed evenly. Then 10g of ethyl 3,5-bis(3-aminopropyl)benzoate was added and ultrasonically dispersed evenly. The reaction was monitored by FTIR while stirring. The reaction was stirred at room temperature until the amino absorption peak in the reaction system disappeared in the infrared spectrum. The reaction was then completed. The reaction product was centrifuged, washed with ethanol, and dried to obtain modified graphene oxide.

[0061] (2) 40 mg of modified graphene oxide was uniformly dispersed in deionized water to obtain a modified graphene oxide dispersion with a concentration of 3 mg / mL. Carboxyl activator NHS and EDC were added. The mass ratio of the modified graphene oxide to NHS and EDC was 1:1:1. The mixture was stirred at room temperature for 2 h. 350 g of tetra-arm-polyethylene glycol-amino was added. The pH was then adjusted to 4.5 and the mixture was reacted at room temperature for 12 h. The mixture was then filtered, washed, and dried to obtain polyether-modified graphene oxide.

[0062] Comparative Example 1 is the same as Example 1, except that the preparation method of the polyether-modified graphene oxide in Comparative Example 1 is as follows:

[0063] 40 mg of graphene oxide was uniformly dispersed in deionized water to obtain a graphene oxide dispersion with a concentration of 1 mg / mL. Carboxyl activator NHS and EDC were added, with the mass ratio of graphene oxide to NHS and EDC being 1:1:1. The mixture was stirred at room temperature for 0.5 h, then 350 g of tetra-armed polyethylene glycol-amino was added. The pH was then adjusted to 4.5, and the mixture was reacted at room temperature for 12 h. After filtration, washing, and drying, polyether-modified graphene oxide was obtained.

[0064] Comparative Example 2 is the same as Example 1, except that the modified graphene oxide in Comparative Example 2 is prepared according to the following steps:

[0065] (1) 20g of graphene oxide was dispersed in 20mL of anhydrous dichloromethane and ultrasonically dispersed evenly. 15g of HATU and 15mL of DIPEA were added and ultrasonically dispersed evenly. Then 5g of ethyl 3,5-bis(3-aminopropyl)benzoate was added and ultrasonically dispersed evenly. The reaction was monitored by FTIR while stirring. The reaction was stirred at room temperature until the amino absorption peak in the reaction system disappeared in the infrared spectrum. The reaction was then completed. The reaction product was centrifuged, washed with ethanol, and dried to obtain modified graphene oxide.

[0066] (2) 40 mg of modified graphene oxide was uniformly dispersed in deionized water to obtain a modified graphene oxide dispersion with a concentration of 1 mg / mL, carboxyl activators NHS and EDC were added, the mass ratio between the modified graphene oxide and NHS, EDC was 1:1:1, and the reaction was stirred at room temperature for 0.5 h, 300 g of NH2-PEG-COOH was added, and then the pH was adjusted to 4.5, and the reaction was carried out at room temperature for 12 h, and then filtration, washing and drying were performed to obtain polyether-modified graphene oxide.

[0067] Comparative Example 3 was the same as Example 1, except that the graphene-modified polyester fiber in Comparative Example 3 did not have the reduction step of step (3) in Example 1, and the specific process was as follows:

[0068] (1) The polyether-modified graphene oxide was uniformly dispersed in deionized water to obtain a modified solution, and the concentration of the modified solution was 1 mg / L.

[0069] (2) The polyester fiber was immersed in the modified solution obtained in step (1) at 50°C for 30 min, the concentration of the modified solution was 1 mg / L, and the immersion bath ratio (mass ratio) of the polyester fiber to the modified solution was 1:30, and after water washing and drying, one immersion was completed, and the above immersion process was repeated 5 times.

[0070] Performance test

[0071] The graphene-modified polyester fibers obtained in Examples 1-3 and Comparative Examples 1-3 were tested for related properties, and the specific test results are shown in Table 1.

[0072] The test method is as follows:

[0073] Moisture regain: The graphene-modified polyester fibers obtained in Examples 1-3 and Comparative Examples 1-3 were placed in a standard atmospheric environment for conditioning, and the moisture regain was measured after reaching the moisture absorption equilibrium.

[0074] Antistatic property: According to GB / T 12703.4-2010 "Evaluation of the Static Property of Textiles Part 4: Resistivity", the surface resistivity of the sample was tested by using a YG(B)406 fabric resistivity tester, and the water washing fastness of the fabric antistatic property was evaluated by the change of the resistivity before and after 20 times of water washing of the fabric. The graphene-modified polyester fibers obtained in Examples 1-3 and Comparative Examples 1-3 were respectively made into fabrics with the same size as the test samples.

[0075] Table 1

[0076]

[0077] With the above ideal embodiments according to the present application as the inspiration, through the above description, relevant staff can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims

1. A graphene-modified polyester fiber, characterized in that, The preparation steps include the following: (1) Polyether-modified graphene oxide is uniformly dispersed in deionized water to obtain a modified solution; (2) The polyester fiber is immersed in the modified liquid obtained in step (1) and kept at 50-60°C for at least 30 minutes. After washing and drying, the immersion is completed. The above immersion process is repeated at least 5 times to obtain graphene oxide modified polyester fiber. (3) The graphene oxide modified polyester fiber obtained in step (2) is immersed in a reducing solution to reduce the oxygen-containing functional groups on the surface of graphene oxide. After washing and drying, the graphene modified polyester fiber is obtained. The preparation method of the polyether-modified graphene oxide includes the following steps: (1) 20g of graphene oxide was dispersed in 20mL of anhydrous dichloromethane and ultrasonically dispersed evenly. 15-20g of 2-(7-azabenzotriazole)-tetramethylurea hexafluorophosphate and 15-20mL of N,N-diisopropylethylamine were added and ultrasonically dispersed evenly. Then 5-10g of ethyl 3,5-bis(3-aminopropyl)benzoate was added and ultrasonically dispersed evenly. The reaction was monitored by FTIR while stirring. The reaction was stirred at room temperature until the amino absorption peak in the reaction system disappeared in the infrared spectrum. The reaction was then completed. The reaction product was centrifuged, washed with ethanol, and dried to obtain modified graphene oxide. (2) 40 mg of modified graphene oxide was uniformly dispersed in deionized water to obtain a modified graphene oxide dispersion with a concentration of 1-3 mg / mL. Carboxyl activator NHS and EDC were added. The mass ratio of the modified graphene oxide to NHS and EDC was 1:1-1.2:1-1.

2. The mixture was stirred at room temperature for 0.5-2 h. 0.15-0.2 mol of four-arm-polyethylene glycol-amino was added. The pH was then adjusted to 4.5-6. The mixture was reacted at room temperature for 12-48 h. The mixture was filtered, washed, and dried to obtain polyether-modified graphene oxide.

2. The graphene-modified polyester fiber according to claim 1, characterized in that, The concentration of the modified solution is 1-10 mg / L.

3. The graphene-modified polyester fiber according to claim 1, characterized in that, The polyester fiber undergoes a hydrolysis pretreatment, which involves immersing the polyester fiber in a hot alkaline solution to induce a mild hydrolysis reaction on the surface of the polyester fiber. The impregnation temperature of the hydrolysis pretreatment shall not exceed 80°C; The immersion time for the hydrolysis pretreatment shall not exceed 30 minutes.

4. The graphene-modified polyester fiber according to claim 3, characterized in that, The alkali used in the hydrolysis pretreatment includes at least one of sodium hydroxide and potassium hydroxide.

5. The graphene-modified polyester fiber according to claim 1, characterized in that, The reducing agent in the reducing solution includes at least one of sodium borohydride, L-ascorbic acid, and sodium dithionite.

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