Preparation method and application of imidazolium salt graphene modified nylon fiber

Abstract

The invention relates to the technical field of fiber fabrics, and discloses an imidazolium salt graphene modified nylon fiber, alkyl chlorinated graphene and introduced long-chain alkyl chloride react with tertiary amine of 1-dodecyl imidazole to generate imidazolium salt, so that the long-chain alkyl imidazolium salt is grafted to the surface of graphene to obtain imidazolium salt modified graphene, and the imidazolium salt modified nylon fiber is prepared by the following steps: reacting the long-chain alkyl chloride with the tertiary amine of 1-dodecyl imidazole; the graphene grafted long-chain alkyl imidazolium salt is used as a functional filler and is blended with nylon 6 for melt spinning, the imidazolium salt graphene modified nylon fiber is obtained, the graphene grafted long-chain alkyl imidazolium salt has excellent antibacterial performance and has obvious inhibiting and killing effects on escherichia coli, and under synergistic modification of graphene and imidazolium salt, the antibacterial property of the graphene grafted long-chain alkyl imidazolium salt is greatly improved. The nylon 6 fiber is endowed with excellent antibacterial property and comprehensive mechanical property, so that the nylon 6 fiber has better application in the fields of antibacterial fabrics, medical fibers and the like.

Description

Technical Field

[0001] The invention relates to the technical field of fiber fabrics, and in particular to a preparation method and application of imidazole salt graphene modified nylon fiber. Background Art

[0002] Nylon fiber has the advantages of good wear resistance, dyeability, high mechanical strength, good weather resistance, etc. It can be used as fiber fabric to make blankets, clothing, tents and other textile products. It is widely used in people's daily life and industrial production. In order to expand the practical application of nylon fiber, it is necessary to modify the nylon fiber. Improving the antibacterial property and mechanical strength of nylon fiber has always been a research hotspot. Combining nylon fiber with nanomaterials can effectively enhance the comprehensive performance of the material.

[0003] Graphene is a new type of two-dimensional carbon nanomaterial with advantages such as good mechanical properties and strong thermal stability. Graphene has good chemical modifiability. Patent CN102431997B "Graphene oxide with antibacterial and anticoagulant functions and its preparation method" discloses the controllable synthesis of amino-modified graphene oxide with amine compounds, which has good antibacterial and anticoagulant effects. Therefore, antibacterial small molecules are modified into graphene, and then nylon fibers are modified to improve the antibacterial and other comprehensive properties of nylon fiber materials, thereby expanding the application of nylon fibers in clothing fabrics, medical antibacterial fibers, etc. Summary of the invention

[0004] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a preparation method and application of imidazole salt graphene modified nylon fiber, which gives the nylon fiber excellent antibacterial properties and is better used in antibacterial fiber fabrics.

[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: a method for preparing imidazole salt graphene modified nylon fiber, the preparation method comprising the following steps: (1) 100 parts (by mass) of hydroxylated graphene are ultrasonically dispersed in toluene solvent, 60-250 parts of 3-isocyanatobenzoyl chloride and 12-60 parts of catalyst pyridine are added, and esterification reaction is carried out at 25-40 °C for 3-8 h. After the reaction, centrifugation is performed, and the graphene is washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0006] (2) 100 parts (by mass) of isocyanate-modified graphene are ultrasonically dispersed in toluene, 80-300 parts of 8-chloro-1-octanol and 0.5-2.5 parts of dibutyltin dilaurate as a catalyst are added, and the mixture is heated for reaction. After the reaction, the mixture is centrifuged and washed with dichloromethane and acetone to obtain alkyl chloride graphene.

[0007] (3) ultrasonically dispersing 100 parts (by mass) of alkyl chloride graphene into a mixed solvent, adding 45-200 parts of 1-dodecyl imidazole, heating to react, centrifuging after the reaction, washing with dichloromethane and ethanol to obtain imidazole salt graphene.

[0008] (4) Nylon 6 and imidazole graphene are mixed, added into a spinning machine, melt-spinned at 230-260°C, and then the spun fibers are pulled and stretched to obtain imidazole graphene-modified nylon fibers.

[0009] Preferably, the reaction temperature in step (2) is 70-90°C and the reaction time is 6-18 h.

[0010] Preferably, the mixed solvent in step (3) is 100 parts (by volume) of ethyl acetate and 20-60 parts of toluene.

[0011] Preferably, the reaction temperature in step (3) is 90-130° C. and the reaction time is 24-72 h.

[0012] Preferably, in step (4), nylon 6 is 100 parts (by mass) and imidazole salt graphene is 0.2-1.5 parts.

[0013] Preferably, the imidazolate graphene-modified nylon fiber is used in the field of antibacterial fibers and antibacterial fabrics.

[0014] 3. Beneficial technical effects Compared with the prior art, the present invention has the following beneficial technical effects: The imidazole salt graphene modified nylon fiber uses pyridine as a catalyst to catalyze the esterification reaction of the acyl chloride group of 3-isocyanatobenzoyl chloride with hydroxylated graphene to obtain isocyanate modified graphene, and then the isocyanate group introduced on the graphene surface reacts with the hydroxyl group of 8-chloro-1-octanol under the catalysis of dibutyltin dilaurate to obtain alkyl chloride graphene, and the introduced long-chain alkyl chloride reacts with the tertiary amine of 1-dodecyl imidazole to generate imidazole salt, so that the long-chain alkyl imidazole salt is grafted onto the graphene surface to obtain the imidazole salt modified graphene, and the graphene is used as a functional filler to be blended with nylon 6 for melt spinning to obtain The imidazole salt graphene modified nylon fiber, the graphene grafted long-chain alkyl imidazole salt has excellent antibacterial properties, has obvious inhibitory and killing effects on Escherichia coli, and under the synergistic modification of graphene and imidazole salt, the nylon 6 fiber is endowed with excellent antibacterial properties and comprehensive mechanical properties, so that the nylon 6 fiber has better applications in the fields of antibacterial fabrics, medical fibers, etc. In the embodiment, as the amount of imidazole salt graphene increases, the antibacterial property of nylon 6 fiber becomes better and better, but the amount of imidazole salt graphene added is too much, the antibacterial property is not significantly improved, and slowly decreases after reaching the peak value, while the control example does not add graphene containing imidazole salt, and the antibacterial property of nylon 6 fiber is greatly reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is the antibacterial zone test diagram of the embodiment and the comparative example. DETAILED DESCRIPTION

[0016] To achieve the above object, the present invention provides the following embodiments and examples: an imidazole salt graphene modified nylon fiber, the preparation method comprising the following steps: (1) 100 parts (by mass) of hydroxylated graphene are ultrasonically dispersed in toluene solvent, 60-250 parts of 3-isocyanatobenzoyl chloride and 12-60 parts of catalyst pyridine are added, and esterification reaction is carried out at 25-40 °C for 3-8 h. After the reaction, centrifugation is performed, and the graphene is washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0017] (2) 100 parts (by mass) of isocyanate-modified graphene are ultrasonically dispersed in toluene, 80-300 parts of 8-chloro-1-octanol and 0.5-2.5 parts of dibutyltin dilaurate as a catalyst are added, the mixture is heated to 70-90 °C, reacted for 6-18 h, centrifuged after the reaction, washed with dichloromethane and acetone, and alkyl chloride graphene is obtained.

[0018] (3) Ultrasonic dispersion of 100 parts (by mass) of alkyl chloride graphene in a mixed solvent of ethyl acetate and toluene, adding 45-200 parts of 1-dodecyl imidazole, heating to 90-130 °C, reacting for 24-72 h, centrifuging after the reaction, washing with dichloromethane and ethanol to obtain imidazole salt graphene.

[0019] (4) 100 parts (by mass) of nylon 6 and 0.2-1.5 parts of imidazole graphene are mixed and added into a spinning machine. Melt spinning is performed at 230-260 °C. The spun fibers are then pulled and stretched to obtain imidazole graphene-modified nylon fibers, which are used in the fields of antibacterial fibers and antibacterial fabrics.

[0020] Example 1

[0021] (1) 0.5 g of hydroxylated graphene was ultrasonically dispersed in 50 mL of toluene solvent, and 0.3 g of 3-isocyanatobenzoyl chloride and 0.06 g of catalyst pyridine were added. The esterification reaction was carried out at 25 °C for 3 h. After the reaction, the graphene was centrifuged and washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0022] (2) 0.5 g of isocyanate-modified graphene was ultrasonically dispersed in 100 mL of toluene, 0.4 g of 8-chloro-1-octanol and 0.003 g of dibutyltin dilaurate as a catalyst were added, and the mixture was heated to 70 °C and reacted for 6 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and acetone to obtain alkyl chloride graphene.

[0023] (3) Ultrasonic dispersion of 1 g of alkyl chloride graphene in a mixed solvent of 100 mL of ethyl acetate and 20 mL of toluene was performed, and 0.45 g of 1-dodecyl imidazole was added. The mixture was heated to 90 °C and reacted for 24 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and ethanol to obtain imidazole salt graphene.

[0024] (4) 10 g of nylon 6 and 0.02 g of imidazole salt graphene were mixed and added into a spinning machine for melt spinning at 230 °C. The spun fibers were then pulled and stretched to obtain imidazole salt graphene-modified nylon fibers.

[0025] Example 2

[0026] (1) 0.5 g of hydroxylated graphene was ultrasonically dispersed in 80 mL of toluene solvent, and 0.5 g of 3-isocyanatobenzoyl chloride and 0.1 g of catalyst pyridine were added. The esterification reaction was carried out at 30 °C for 4 h. After the reaction, the graphene was centrifuged and washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0027] (2) Ultrasonic dispersion of 0.5 g of isocyanate-modified graphene in 100-300 mL of toluene, addition of 0.6 g of 8-chloro-1-octanol and 0.006 g of dibutyltin dilaurate as a catalyst, heating to 70 °C, reaction for 18 h, centrifugation after the reaction, washing with dichloromethane and acetone to obtain alkyl chloride graphene.

[0028] (3) Ultrasonic dispersion of 1 g of alkyl chloride graphene in a mixed solvent of 100 mL of ethyl acetate and 30 mL of toluene was performed, and 0.8 g of 1-dodecyl imidazole was added. The mixture was heated to 100 °C and reacted for 24 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and ethanol to obtain imidazole salt graphene.

[0029] (4) 10 g of nylon 6 and 0.05 g of imidazole salt graphene are mixed and added into a spinning machine for melt spinning at 230-260 °C. The spun fibers are then pulled and stretched to obtain imidazole salt graphene-modified nylon fibers.

[0030] Example 3

[0031] (1) 0.5 g of hydroxylated graphene was ultrasonically dispersed in 120 mL of toluene solvent, and 0.8 g of 3-isocyanatobenzoyl chloride and 0.15 g of catalyst pyridine were added. The esterification reaction was carried out at 30 °C for 6 h. After the reaction, the graphene was centrifuged and washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0032] (2) 0.5 g of isocyanate-modified graphene was ultrasonically dispersed in 200 mL of toluene, 1 g of 8-chloro-1-octanol and 0.08 g of dibutyltin dilaurate as a catalyst were added, heated to 80 °C, and reacted for 12 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and acetone to obtain alkyl chloride graphene.

[0033] (3) Ultrasonic dispersion of 1 g of alkyl chloride graphene in a mixed solvent of 100 mL of ethyl acetate and 40 mL of toluene was performed, and 1.2 g of 1-dodecyl imidazole was added. The mixture was heated to 120 °C and reacted for 48 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and ethanol to obtain imidazole salt graphene.

[0034] (4) 10 g of nylon 6 and 0.8 g of imidazole salt graphene were mixed and added into a spinning machine for melt spinning at 250 °C. The spun fibers were then pulled and stretched to obtain imidazole salt graphene-modified nylon fibers.

[0035] Example 4

[0036] (1) 0.5 g of hydroxylated graphene was ultrasonically dispersed in 150 mL of toluene solvent, 1 g of 3-isocyanatobenzoyl chloride and 0.24 g of catalyst pyridine were added, and the esterification reaction was carried out at 40 °C for 4 h. After the reaction, the graphene was centrifuged and washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0037] (2) Ultrasonic dispersion of 0.5 g of isocyanate-modified graphene in 100-300 mL of toluene, addition of 1.2 g of 8-chloro-1-octanol and 0.01 g of dibutyltin dilaurate as a catalyst, heating to 70-90 °C, reaction for 12 h, centrifugation after the reaction, washing with dichloromethane and acetone to obtain alkyl chloride graphene.

[0038] (3) 1 g of alkyl chloride graphene was ultrasonically dispersed in a mixed solvent of 100 mL of ethyl acetate and 50 mL of toluene, 1.6 g of 1-dodecyl imidazole was added, and the mixture was heated to 130 °C and reacted for 72 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and ethanol to obtain imidazole salt graphene.

[0039] (4) 10 g of nylon 6 and 0.12 g of imidazole salt graphene were mixed and added into a spinning machine for melt spinning at 260 °C. The spun fibers were then pulled and stretched to obtain imidazole salt graphene-modified nylon fibers.

[0040] Example 5

[0041] (1) 0.5 g of hydroxylated graphene was ultrasonically dispersed in 200 mL of toluene solvent, and 1.25 g of 3-isocyanatobenzoyl chloride and 0.3 g of catalyst pyridine were added. The esterification reaction was carried out at 40 °C for 8 h. After the reaction, the graphene was centrifuged and washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0042] (2) 0.5 g of isocyanate-modified graphene was ultrasonically dispersed in 300 mL of toluene, 1.5 g of 8-chloro-1-octanol and 0.012 g of dibutyltin dilaurate as a catalyst were added, heated to 90 °C, and reacted for 18 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and acetone to obtain alkyl chloride graphene.

[0043] (3) Ultrasonic dispersion of 1 g of alkyl chloride graphene in a mixed solvent of 100 mL of ethyl acetate and 60 mL of toluene was performed, and 2 g of 1-dodecyl imidazole was added. The mixture was heated to 130 °C and reacted for 72 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and ethanol to obtain imidazole salt graphene.

[0044] (4) 10 g of nylon 6 and 0.15 g of imidazole salt graphene were mixed and added into a spinning machine. Melt spinning was performed at 260 °C, and then the spun fibers were pulled and stretched to obtain imidazole salt graphene-modified nylon fibers.

[0045] Comparative Example 1 (1) 0.5 g of hydroxylated graphene was ultrasonically dispersed in 100 mL of toluene solvent, 0.8 g of 3-isocyanatobenzoyl chloride and 0.2 g of catalyst pyridine were added, and the esterification reaction was carried out at 25-40 °C for 8 h. After the reaction, the graphene was centrifuged and washed with dichloromethane and ethanol to obtain isocyanate-modified graphene.

[0046] (2) 0.5 g of isocyanate-modified graphene was ultrasonically dispersed in 300 mL of toluene, 1.2 g of 8-chloro-1-octanol and 0.01 g of dibutyltin dilaurate as a catalyst were added, heated to 90 °C, and reacted for 12 h. After the reaction, the mixture was centrifuged and washed with dichloromethane and acetone to obtain alkyl chloride graphene.

[0047] (3) 10 g of nylon 6 and 0.06 g of imidazole salt graphene were mixed and added to a spinning machine. Melt spinning was performed at 240 °C, and then the spun fibers were pulled and stretched to obtain graphene-modified nylon fibers.

[0048] The imidazolate-graphene-modified nylon fiber was made into a 2 mm thick film material and placed in a culture dish. Beef extract peptone medium was then added and Escherichia coli suspension was added dropwise at a concentration of 1×10 6 CFU / mL, put it in a constant temperature incubator for cultivation, and test the antibacterial properties by the inhibition zone method according to the standard of GB / T 31713-2015.

Claims

1. A method for preparing imidazole salt graphene modified nylon fiber, characterized in that: The preparation method comprises the following steps: (1) ultrasonically dispersing 100 parts (by mass) of hydroxylated graphene in toluene solvent, adding 60-250 parts of 3-isocyanatobenzoyl chloride and 12-60 parts of catalyst pyridine, carrying out esterification reaction at 25-40 °C for 3-8 h, centrifuging after the reaction, washing with dichloromethane and ethanol to obtain isocyanate-modified graphene; (2) ultrasonically dispersing 100 parts (by mass) of isocyanate-modified graphene in toluene, adding 80-300 parts of 8-chloro-1-octanol and 0.5-2.5 parts of dibutyltin dilaurate as a catalyst, heating to react, centrifuging after the reaction, washing with dichloromethane and acetone to obtain alkyl chloride graphene; (3) ultrasonically dispersing 100 parts (by mass) of alkyl chloride graphene into a mixed solvent, adding 45-200 parts of 1-dodecyl imidazole, heating to react, centrifuging after the reaction, washing with dichloromethane and ethanol to obtain imidazole salt graphene; (4) Nylon 6 and imidazole graphene are mixed, added into a spinning machine, melt-spinned at 230-260°C, and then the spun fibers are pulled and stretched to obtain imidazole graphene-modified nylon fibers.

2. The method for preparing an imidazole salt graphene modified nylon fiber according to claim 1, characterized in that: The reaction temperature in step (2) is 70-90°C and the reaction time is 6-18 h.

3. The method for preparing an imidazole salt graphene modified nylon fiber according to claim 1, characterized in that: The mixed solvent in step (3) is 100 parts (by volume) of ethyl acetate and 20-60 parts of toluene.

4. The method for preparing an imidazole salt graphene modified nylon fiber according to claim 1, characterized in that: The reaction temperature in step (3) is 90-130°C and the reaction time is 24-72 h.

5. The method for preparing an imidazole salt graphene modified nylon fiber according to claim 1, characterized in that: In the step (4), nylon 6 is 100 parts (by mass) and imidazole salt graphene is 0.2-1.5 parts.

6. An application of imidazole salt graphene modified nylon fiber, characterized in that: The imidazole salt graphene modified nylon fiber is used in the fields of antibacterial fibers and antibacterial fabrics.

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