Anti-fouling polyester fiber and production process thereof

Abstract

The invention discloses a production process of an anti-fouling polyester fiber, and belongs to the technical field of textile fiber preparation, and the production process comprises the following steps: step S1, synergistically modifying graphene oxide and low-surface-energy organic silicon to carry out hydrophobic finishing on the polyester fiber to obtain a modified fiber; and S2, adding the modified fibers into absolute ethyl alcohol, stirring and dispersing, adjusting the pH value to 7.8-8.2 by using ammonia water, adding the modified nano microspheres, and stirring and reacting for 0.5-1 hour to obtain the anti-fouling polyester fibers. A layer of compact low-surface-energy cross-linked network and a microcosmic nanoscale coarse structure are constructed on the surface of the polyester fiber, the anti-fouling performance of the polyester fiber is effectively improved, a pH response type antibacterial structure is directly introduced into the nanometer coarse structure on the basis, a good antibacterial effect can be achieved without additionally adding an antibacterial material, and the anti-fouling performance of the polyester fiber is effectively improved. The production of bacterial biofilms is avoided, and the bacterial pollution resistance of the polyester fibers is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of textile fiber preparation, and specifically relates to a stain-resistant polyester fiber and a production process thereof. Background Art

[0002] Polyester fiber is a synthetic fiber obtained by the condensation of organic dibasic acids and diols and then spinning. Fabrics woven with polyester fibers have good wrinkle resistance and elasticity. However, due to the porous structure and high water absorption of polyester fibers themselves, their anti-fouling properties are poor, and they are difficult to clean after contamination. They require a large amount of water and detergents, resulting in waste of resources and environmental pollution.

[0003] In the prior art, when preparing anti-fouling polyester fibers, a super-hydrophobic coating is usually constructed on the surface of the polyester fibers to improve the liquid repellency of the polyester fibers to achieve an anti-fouling effect. However, the super-hydrophobic structure can only prevent a small amount of bacteria from adhering and cannot achieve a sterilization effect. In addition, as the number of bacteria continues to increase, a biofilm will form on the fiber surface, which will eventually destroy the super-hydrophobic structure of the polyester fibers and reduce the anti-fouling performance. Therefore, how to have antibacterial properties on the super-hydrophobic structure without adding additional antibacterial agents is a technical problem that needs to be solved at present. Summary of the invention

[0004] The object of the present invention is to provide a stain-resistant polyester fiber and a production process thereof to solve the problems in the background technology.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A production process for stain-resistant polyester fiber comprises the following steps:

[0007] Step S1: Hydrophobic finishing of polyester fibers

[0008] Add trimethylolpropane triacrylate to acetone, stir evenly, add vinyl-terminated polydimethylsiloxane and 2-hydroxy-2-methyl-1-phenyl-1-propanone, ultrasonically disperse, add polyester fiber, stir evenly, add modified graphene oxide, ultrasonicate for 30 minutes in an ice-water bath, take out and then perform ultraviolet curing for 2 minutes to obtain modified fiber; use trimethylolpropane triacrylate as a crosslinking agent and 2-hydroxy-2-methyl-1-phenyl-1-propanone as a photoinitiator to graft the modified graphene oxide on the surface of the polyester fiber through hydrogen bonding, and then react the thiol group on the modified graphene oxide with the vinyl-terminated polydimethylsiloxane to form a crosslinked structure through a thiol-ene reaction, so as to obtain a modified fiber with low surface energy super-hydrophobic property;

[0009] Step S2: Preparation of stain-resistant polyester fiber

[0010] The modified fiber is added to anhydrous ethanol, stirred and dispersed, and then 25wt% ammonia water is added to adjust the pH value to 7.8-8.2, and then the modified nano-microspheres are added, and the reaction is stirred for 0.5-1h to obtain the anti-fouling polyester fiber; under weak alkaline conditions, the hydrolysis of the imine bonds on the modified nano-microspheres can be prevented, and the modified nano-microspheres are loaded on the surface of the modified fiber through the hydrogen bonds formed between the amino groups on the surface of the modified nano-microspheres and the modified fiber.

[0011] Furthermore, the usage ratio of the acetone, trimethylolpropane triacrylate, vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methyl-1-phenyl-1-propanone, polyester fiber and modified graphene oxide is 120 mL: 0.02-0.03 mL: 3-6 mL: 0.01-0.02 mL: 10-15 g: 2-7 g.

[0012] Furthermore, the usage ratio of the anhydrous ethanol, the modified fiber, and the modified nano-microspheres is 90 mL: 10-15 g: 1.6-3.8 g.

[0013] Furthermore, the modified graphene oxide is prepared by the following steps:

[0014] Add graphene oxide to dimethyl sulfoxide, mix evenly, add mercaptoethylamine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, disperse by ultrasonication, react in a water bath at 30-40°C for 22-24 hours, cool, centrifuge, wash with acetone and deionized water, and dry to obtain modified graphene oxide; use dimethyl sulfoxide as solvent and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide as cross-linking agent, condense the amino group of mercaptoethylamine with the carboxyl group on the surface of graphene oxide to obtain modified graphene oxide containing mercapto groups.

[0015] Furthermore, the usage ratio of dimethyl sulfoxide, graphene oxide, mercaptoethylamine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide is 100 mL: 6-15 g: 8-12 g: 2-3 g.

[0016] Furthermore, the modified nanospheres are prepared by the following steps:

[0017] A1. Add hollow mesoporous silica to methanol, stir and disperse, add 3-aminopropyltriethoxysilane dropwise, mix well, reflux in a nitrogen atmosphere at 120° C. for 14-16 hours, cool, filter, wash with ether and dichloromethane, and dry to obtain modified hollow mesoporous silica spheres; use 3-aminopropyltriethoxysilane as a surface treatment agent, react Si-OH on the surface of the hollow mesoporous silica with 3-aminopropyltriethoxysilane, and obtain modified hollow mesoporous silica with amino functional groups on the surface;

[0018] A2. Add citral to anhydrous ethanol, stir evenly, add modified hollow mesoporous silica balls, mix evenly, adjust the pH value to 5.8-6.2 with 10wt% hydrochloric acid, and stir the reaction at room temperature for 22-24h, then adjust the pH value to 7.8-8.2 with 20wt% ammonia water, stir the reaction for 0.5-2h, and then obtain modified nano-microspheres after centrifugation, washing and drying; under acidic conditions, citral enters the cavity of the modified hollow mesoporous silica through electrostatic adsorption, and is stored in the cavity through covalent bond connection. Under alkaline conditions, the outlet of the modified hollow mesoporous silica is covered by the reversible imine bond formed between the aldehyde group and the amino group on the citral, and pH-responsive modified nano-microspheres are obtained.

[0019] Furthermore, the usage ratio of the methanol, the hollow mesoporous silica, and the 3-aminopropyltriethoxysilane is 60 mL: 2-4 g: 1.8-3.6 mL.

[0020] Furthermore, the usage ratio of anhydrous ethanol, citral, and modified hollow mesoporous silica spheres is 60 mL: 2-6 mL: 2.3-4.3 g.

[0021] The invention discloses a stain-resistant polyester fiber, which is prepared by the above production process.

[0022] Beneficial effects of the present invention:

[0023] The surface of the modified graphene oxide of the present invention contains hydroxyl groups and thiol groups with hydrophobic properties. When mixed with polyester fibers, the hydroxyl groups can coat the modified graphene oxide on the surface of the polyester fibers through hydrogen bonding, and the thiol groups can graft organic silicon with low surface energy on the polyester fibers through thiol-ene reaction, and synergistically work with graphene oxide to form a layer of dense cross-linked network structure on the surface of the polyester fibers, thereby reducing the surface energy of the polyester fibers and giving the polyester fibers good hydrophobic properties. At the same time, the surface of the modified nano-microspheres of the present invention contains amino groups and the interior contains citral. On the one hand, the amino groups can be grafted on the surface of the modified fibers through hydrogen bonding, thereby constructing a microscopic and nano-scale rough structure on the surface of the modified fibers, and on the low surface Under the synergistic effect of energy, the super hydrophobicity of polyester fiber is further improved. When a liquid containing stains drips on the surface of polyester fiber, under the action of the super hydrophobic surface of polyester fiber, the liquid will form a complete sphere and roll off the surface of polyester fiber, thereby achieving anti-fouling effect and giving polyester fiber good liquid repellency; on the other hand, the reversible imine bond formed by amino group and aldehyde group is used as a gate to encapsulate citral, so that the modified nano-microspheres have pH-responsive antibacterial properties. When organic microorganisms such as bacteria are attached to the surface of polyester fiber, since organic microorganisms such as bacteria are acidic, the imine bond is hydrolyzed under acidic conditions, the gate is opened, and then the bacteria are eliminated through citral, giving polyester fiber excellent antibacterial properties;

[0024] The present invention constructs a layer of dense low surface energy cross-linked network and micro-nanoscale rough structure on the surface of polyester fiber, which effectively improves the anti-fouling performance of polyester fiber, and on this basis directly introduces a pH-responsive antibacterial structure into the nano-rough structure, which can achieve good antibacterial effect without the need to add additional antibacterial agents, and as the number of bacteria increases and the acidity increases, the stronger the hydrolysis of the imine bond, the stronger the antibacterial performance, which effectively avoids the production of bacterial biofilm and improves the anti-bacterial pollution performance of polyester fiber. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Example 1

[0027] This embodiment provides a modified graphene oxide, which is prepared by the following steps:

[0028] 6 g of graphene oxide was added to 100 mL of dimethyl sulfoxide and mixed evenly. 8 g of mercaptoethylamine and 2 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide were added. After ultrasonic dispersion, the mixture was stirred in a 30°C water bath for 22 h. After cooling, the mixture was centrifuged, washed with acetone and deionized water, and dried to obtain modified graphene oxide.

[0029] Example 2

[0030] This embodiment provides a modified graphene oxide, which is prepared by the following steps:

[0031] 9 g of graphene oxide was added to 100 mL of dimethyl sulfoxide and mixed evenly. 10 g of mercaptoethylamine and 2.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide were added. After ultrasonic dispersion, the mixture was stirred in a 35°C water bath for 23 h. After cooling, the mixture was centrifuged, washed with acetone and deionized water, and dried to obtain modified graphene oxide.

[0032] Example 3

[0033] This embodiment provides a modified graphene oxide, which is prepared by the following steps:

[0034] 15 g of graphene oxide was added to 100 mL of dimethyl sulfoxide and mixed evenly. 12 g of mercaptoethylamine and 3 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide were added. After ultrasonic dispersion, the mixture was stirred in a 40°C water bath for 24 h. After cooling, the mixture was centrifuged, washed with acetone and deionized water, and dried to obtain modified graphene oxide.

[0035] Example 4

[0036] This embodiment provides a modified nanosphere, which is prepared by the following steps:

[0037] A1. Add 2 g of hollow mesoporous silica to 60 mL of methanol, stir and disperse, add 1.8 mL of 3-aminopropyltriethoxysilane dropwise, mix well, reflux for 14 h at 120 °C in a nitrogen atmosphere, cool, filter, wash with ether and dichloromethane, and dry to obtain modified hollow mesoporous silica spheres;

[0038] A2. Add 2 mL of citral to 60 mL of anhydrous ethanol and stir evenly. Add 2.3 g of modified hollow mesoporous silica balls and mix evenly. Adjust the pH value to 5.8 with 10 wt % hydrochloric acid and stir the mixture at room temperature for 22 h. Adjust the pH value to 7.8 with 20 wt % ammonia water and stir the mixture for 0.5 h. Centrifuge, wash and dry the mixture to obtain modified nanospheres.

[0039] Example 5

[0040] This embodiment provides a modified nanosphere, which is prepared by the following steps:

[0041] A1. Add 3 g of hollow mesoporous silica to 60 mL of methanol, stir and disperse, dropwise add 3.6 mL of 3-aminopropyltriethoxysilane, mix well, reflux for 15 h at 120 °C in a nitrogen atmosphere, cool, filter, wash with ether and dichloromethane, and dry to obtain modified hollow mesoporous silica spheres;

[0042] A2. Add 4 mL of citral to 60 mL of anhydrous ethanol and stir evenly. Add 3.3 g of modified hollow mesoporous silica balls and mix evenly. Adjust the pH value to 6.0 with 10 wt % hydrochloric acid and stir the mixture at room temperature for 23 h. Adjust the pH value to 8.0 with 20 wt % ammonia water and stir the mixture for 1 h. Centrifuge, wash and dry the mixture to obtain modified nanospheres.

[0043] Example 6

[0044] This embodiment provides a modified nanosphere, which is prepared by the following steps:

[0045] A1. Add 4 g of hollow mesoporous silica to 60 mL of methanol, stir and disperse, add 3.6 mL of 3-aminopropyltriethoxysilane dropwise, mix well, reflux for 16 h at 120 °C in a nitrogen atmosphere, cool, filter, wash with ether and dichloromethane, and dry to obtain modified hollow mesoporous silica spheres;

[0046] A2. Add 6 mL of citral to 60 mL of anhydrous ethanol and stir evenly. Add 4.3 g of modified hollow mesoporous silica balls and mix evenly. Adjust the pH value to 6.2 with 10 wt % hydrochloric acid and stir the mixture at room temperature for 24 h. Adjust the pH value to 8.2 with 20 wt % ammonia water and stir the mixture for 2 h. Centrifuge, wash and dry the mixture to obtain modified nanospheres.

[0047] Example 7

[0048] This embodiment provides a production process for anti-fouling polyester fiber, comprising the following steps:

[0049] Step S1: Hydrophobic finishing of polyester fibers

[0050] Add 0.02 mL of trimethylolpropane triacrylate to 120 mL of acetone, stir evenly, add 3 mL of vinyl-terminated polydimethylsiloxane and 0.01 mL of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and after ultrasonic dispersion, add 10 g of polyester fiber, stir evenly, add 2 g of modified graphene oxide, and ultrasonicate for 30 min in an ice-water bath. After taking out, perform UV curing for 2 min to obtain modified fiber;

[0051] Step S2: Preparation of stain-resistant polyester fiber

[0052] 10 g of modified fiber was added to 90 mL of anhydrous ethanol, and after stirring and dispersing, 25 wt % ammonia water was added to adjust the pH value to 7.8, and then 1.6 g of modified nano-microspheres were added, and the reaction was stirred for 0.5 h to obtain anti-fouling polyester fiber.

[0053] Example 8

[0054] This embodiment provides a production process for anti-fouling polyester fiber, comprising the following steps:

[0055] Step S1: Hydrophobic finishing of polyester fibers

[0056] 0.02 mL of trimethylolpropane triacrylate was added to 120 mL of acetone, and the mixture was stirred evenly. 4 mL of vinyl-terminated polydimethylsiloxane and 0.02 mL of 2-hydroxy-2-methyl-1-phenyl-1-propanone were added, and after ultrasonic dispersion, 13 g of polyester fiber was added, and after stirring evenly, 5 g of modified graphene oxide was added, and the mixture was ultrasonicated for 30 min in an ice-water bath, and then UV-cured for 2 min to obtain modified fiber.

[0057] Step S2: Preparation of stain-resistant polyester fiber

[0058] 12 g of modified fiber was added to 90 mL of anhydrous ethanol, and after stirring and dispersing, 25 wt % ammonia water was added to adjust the pH value to 8.0, and then 2.4 g of modified nano-microspheres were added, and the reaction was stirred for 0.6 h to obtain anti-fouling polyester fiber.

[0059] Example 9

[0060] This embodiment provides a production process for anti-fouling polyester fiber, comprising the following steps:

[0061] Step S1: Hydrophobic finishing of polyester fibers

[0062] Add 0.03 mL of trimethylolpropane triacrylate to 120 mL of acetone, stir evenly, add 6 mL of vinyl-terminated polydimethylsiloxane and 0.02 mL of 2-hydroxy-2-methyl-1-phenyl-1-propanone, and after ultrasonic dispersion, add 15 g of polyester fiber, stir evenly, add 7 g of modified graphene oxide, and ultrasonicate for 30 min in an ice-water bath. After taking out, perform UV curing for 2 min to obtain modified fiber;

[0063] Step S2: Preparation of stain-resistant polyester fiber

[0064] 15 g of modified fiber was added to 90 mL of anhydrous ethanol, and after stirring and dispersing, 25 wt % ammonia water was added to adjust the pH value to 8.2, and then 3.8 g of modified nano-microspheres were added, and after stirring and reacting for 1 hour, anti-fouling polyester fiber was obtained.

[0065] Comparative Example 1: Compared with Example 7, no modified graphene oxide is added, and the rest is the same.

[0066] Comparative Example 2: Compared with Example 7, the modified nano-microspheres were replaced with silicon dioxide in equal amounts, and the rest were the same.

[0067] Comparative Example 3: Compared with Example 7, the modified graphene oxide was replaced by graphene oxide in an equal amount, and the rest was the same.

[0068] Performance tests were performed on Examples 7 to 9 and Comparative Examples 1 to 3. Antifouling performance: the samples were interwoven into a fabric with a specification of 5 cm × 5 cm by warp and weft. Referring to GB / T 30159.1-2013, soy sauce contaminated liquid was dropped onto the surface of the fabric, and the shape of the droplets on the surface of the fabric was observed. The spherical shape indicated good antifouling performance. Antibacterial performance test: referring to GB / T 20944.3-2008, the antibacterial rate of Gram-negative bacteria Escherichia coli was tested. Hydrophobic performance test: referring to GB / T 4744-2013, a water permeability tester was used for testing, and the hydrostatic pressure value when the third water droplet emerged was recorded. The results are shown in Table 1:

[0069] Table 1

[0070]

[0071] It can be seen from Table 1 that the soy sauce contaminated liquid can form a complete sphere on the surface of the polyester fiber fabric prepared by modified graphene oxide and modified nano-microspheres in Examples 7-9, while the surfaces in Comparative Examples 1-3 are all hemispherical, indicating that the polyester fibers prepared in Examples 7-9 have good liquid repellency and anti-fouling properties, and the antibacterial rates are significantly greater than those in Comparative Examples 1-3, and have good anti-bacterial pollution performance; in addition, compared with Comparative Examples 1 and 2, Example 7 has higher hydrophobicity and antibacterial rate, indicating that the anti-fouling performance is better under the synergistic effect of modified graphene oxide and modified nano-microspheres.

[0072] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including 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 device.

[0073] Although embodiments of the present invention 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 invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A production process for anti-fouling polyester fiber, It is characterized in that The following steps are involved: Step S1: Hydrophobic finishing of polyester fibers Add trimethylolpropane triacrylate to acetone, stir evenly, add vinyl-terminated polydimethylsiloxane and 2-hydroxy-2-methyl-1-phenyl-1-propanone, ultrasonically disperse, add polyester fiber, stir evenly, add modified graphene oxide, ultrasonically treat for 30 minutes in an ice-water bath, take out and then perform ultraviolet curing for 2 minutes to obtain modified fiber; Step S2: Preparation of stain-resistant polyester fiber The modified fiber is added to anhydrous ethanol, stirred and dispersed, and then the pH value is adjusted to 7.8-8.2 with ammonia water. The modified nano-microspheres are then added and stirred to react for 0.5-1h to obtain the anti-fouling polyester fiber.

2. The production process of a stain-resistant polyester fiber according to claim 1, It is characterized in that The usage ratio of the acetone, trimethylolpropane triacrylate, vinyl-terminated polydimethylsiloxane, 2-hydroxy-2-methyl-1-phenyl-1-propanone, polyester fiber and modified graphene oxide is 120 mL: 0.02-0.03 mL: 3-6 mL: 0.01-0.02 mL: 10-15 g: 2-7 g.

3. The production process of a stain-resistant polyester fiber according to claim 1, It is characterized in that The usage ratio of the anhydrous ethanol, the modified fiber and the modified nano-microspheres is 90 mL: 10-15 g: 1.6-3.8 g.

4. The production process of a stain-resistant polyester fiber according to claim 1, It is characterized in that The modified graphene oxide is prepared by the following steps: Add graphene oxide to dimethyl sulfoxide, mix evenly, add mercaptoethylamine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, disperse by ultrasonication, stir and react in a 30-40°C water bath for 22-24 hours, cool, centrifuge, wash with acetone and deionized water, and dry to obtain modified graphene oxide.

5. The production process of anti-fouling polyester fiber according to claim 4, It is characterized in that The usage ratio of the dimethyl sulfoxide, graphene oxide, mercaptoethylamine and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide is 100 mL: 6-15 g: 8-12 g: 2-3 g.

6. The production process of a stain-resistant polyester fiber according to claim 1, It is characterized in that The modified nanospheres are prepared by the following steps: A1. Add hollow mesoporous silica to methanol, stir and disperse, add 3-aminopropyltriethoxysilane dropwise, mix evenly, reflux in a nitrogen atmosphere at 120° C. for 14-16 hours, cool, filter, wash with ether and dichloromethane, and dry to obtain modified hollow mesoporous silica spheres; A2. Add citral to anhydrous ethanol, stir evenly, add modified hollow mesoporous silica balls, mix evenly, adjust the pH value to 5.8-6.2 with hydrochloric acid, and stir the reaction at room temperature for 22-24 hours, then adjust the pH value to 7.8-8.2 with ammonia water, stir the reaction for 0.5-2 hours, and then obtain modified nano-microspheres after centrifugation, washing and drying.

7. The production process of anti-fouling polyester fiber according to claim 6, It is characterized in that The usage ratio of the methanol, hollow mesoporous silica and 3-aminopropyltriethoxysilane is 60 mL: 2-4 g: 1.8-3.6 mL.

8. The production process of anti-fouling polyester fiber according to claim 1, It is characterized in that The usage ratio of the anhydrous ethanol, citral and modified hollow mesoporous silica spheres is 60 mL: 2-6 mL: 2.3-4.3 g.

9. A stain-resistant polyester fiber, It is characterized in that Prepared according to the production process according to any one of claims 1 to 8.

Images