Antibacterial modified lyocell fiber fabric and preparation method thereof

Abstract

The invention discloses an antibacterial modified lyocell fiber fabric and a preparation method thereof, and the preparation method comprises the following steps: cutting a lyocell fiber fabric into a certain size, and placing the cut lyocell fiber fabric in a eutectic solvent for pretreatment; and after the pretreatment is finished, adding an antibacterial agent into the deep-eutectic solvent, then adding a coupling agent, carrying out graft modification, after the reaction is finished, taking out, washing with deionized water, and finally drying to obtain the antibacterial modified lyocell fiber fabric. According to the method, the lyocell fiber fabric is used as a reaction raw material, polyhexamethylene guanidine hydrochloride is used as an antibacterial agent, glutaraldehyde is used as a coupling agent, a choline chloride-urea eutectic solvent is used as a pretreatment solvent and a subsequent reaction medium, the lyocell fiber fabric is pretreated in the eutectic solvent, the fiber surface is damaged, more active hydroxyl groups are exposed, and the surface of the fiber is subjected to surface modification; and adding a coupling agent and an antibacterial agent, so that the polyhexamethylene guanidine hydrochloride is grafted on the lyocell fiber fabric, and the antibacterial lyocell fiber fabric which is excellent in antibacterial performance, long-acting and washable is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of lyocell fiber fabrics, and particularly relates to an antibacterial modified lyocell fiber fabric and a preparation method thereof. Background Art

[0002] Lyocell fabrics offer a smooth feel and a good sheen, along with excellent toughness whether wet or dry, and possess excellent performance. However, because Lyocell fibers themselves lack antibacterial properties, bacteria and other microorganisms easily attach and grow on them. This not only causes discoloration, reduced mechanical strength, and unpleasant odors, but also has negative impacts on human health, limiting their development and high-end applications in medical and health-related fields. With the increasing demand for antibacterial Lyocell fabrics and their expanding application areas, the development of antibacterial Lyocell fabrics is necessary. Summary of the Invention

[0003] The main purpose of the present invention is to overcome the deficiencies of the prior art and provide an antibacterial modified lyocell fiber fabric and a preparation method thereof.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0006] The lyocell fiber fabric is cut into a certain size and placed in a low eutectic solvent for pretreatment. After the pretreatment, an antibacterial agent is added to the low eutectic solvent, and then a coupling agent is added to perform grafting modification. After the reaction is completed, the fabric is taken out and washed with deionized water, and finally dried to obtain an antibacterial modified lyocell fiber fabric.

[0007] Preferably, the lyocell fiber fabric is cut into a certain size, specifically, cut into 4 cm×4 cm.

[0008] Preferably, the deep eutectic solvent comprises choline chloride and urea, and the molar ratio of choline chloride to urea is 1:1.

[0009] Preferably, the mass of the deep eutectic solvent is 20 g.

[0010] Preferably, the pretreatment temperature is 30° C. to 90° C., and the pretreatment time is 20 min to 80 min.

[0011] Furthermore, the antibacterial agent is specifically polyhexamethyleneguanidine hydrochloride, which is prepared by melt polycondensation. In the polyhexamethyleneguanidine hydrochloride, the molar ratio of 1,6-hexanediamine and guanidine hydrochloride is 1:1.

[0012] Furthermore, the coupling agent is specifically glutaraldehyde.

[0013] Preferably, the molar ratio of the added glutaraldehyde to polyhexamethyleneguanidine hydrochloride is x:1, and x ranges from 1 to 8.

[0014] Preferably, the reaction temperature during graft modification is 80° C. to 120° C., and the reaction time is 10 min to 40 min.

[0015] The present invention also includes an antibacterial modified lyocell fiber fabric, which is prepared according to the preparation method provided by the present invention.

[0016] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0017] 1. The present invention uses lyocell fiber fabric as a reaction raw material, polyhexamethylene guanidine hydrochloride as an antibacterial agent, glutaraldehyde as a coupling agent, and a choline chloride-urea low eutectic solvent as a pretreatment solvent and a subsequent reaction medium. The lyocell fiber fabric is pretreated in the low eutectic solvent to destroy the fiber surface and expose more active hydroxyl groups. Glutaraldehyde and polyhexamethylene guanidine hydrochloride are then added to graft the polyhexamethylene guanidine hydrochloride onto the lyocell fiber fabric, thereby obtaining an antibacterial lyocell fiber fabric with excellent antibacterial properties and long-lasting washability, which can broaden its development and application in medical and health-related fields. The preparation method of the present invention is simple to operate and environmentally friendly, and provides an efficient and safe method for preparing long-lasting antibacterial lyocell fiber. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a schematic diagram of the preparation method of the present invention;

[0019] Figure 2 3 is an antibacterial effect diagram of the antibacterial modified lyocell fiber fabric prepared in Example 3;

[0020] Figure 3 is a schematic diagram of the antibacterial modified lyocell fiber fabric prepared in Example 6;

[0021] Figure 4 is a scanning electron microscope image of the antibacterial modified lyocell fiber fabric prepared in Example 7. DETAILED DESCRIPTION

[0022] The present invention will be described in further detail below with reference to the embodiments and drawings, but the embodiments of the present invention are not limited thereto.

[0023] The hydroxyl groups on the cellulose molecules in Lyocell fibers provide reaction sites for chemically grafted antimicrobial agents. However, due to the high crystallinity and orientation of Lyocell fibers, chemical accessibility is low. Therefore, to achieve grafting modification of Lyocell fibers with antimicrobial agents, it is generally necessary to roughen the surface to increase the number of active hydroxyl groups, and then graft the antimicrobial agent to achieve long-term antimicrobial functionalization of the Lyocell fibers. Low eutectic solvents can swell the fibers, disrupting the hydrogen bonds between cellulose molecules. They have a certain dissolving effect on cellulose, roughening the fiber surface, exposing more active groups, and thus enhancing its chemical accessibility. They can also serve as a subsequent reaction medium.

[0024] PHMG (polyhexamethylene guanidine hydrochloride) is a high-molecular-weight guanidine salt antimicrobial agent whose molecular structure gives it excellent antimicrobial efficacy and good water solubility. As an environmentally friendly organic antimicrobial material, this compound has the dual advantages of high bactericidal efficiency and low biotoxicity, and can meet the antimicrobial finishing and other post-finishing processing requirements of lyocell fabrics. Due to the lack of active sites for direct reaction between the hydroxyl groups in the cellulose molecule and the amino groups of PHMG, the two cannot be connected by a covalent bond. Therefore, a chemical coupling strategy is needed to graft PHMG onto the fiber to achieve long-lasting antimicrobial function. Aldehyde groups (-CHO) can be introduced, and dialdehyde compounds such as glutaraldehyde can be used as coupling agents to covalently bond the amino groups of PHMG to the hydroxyl groups of cellulose through a Schiff base reaction, thereby giving lyocell fibers long-lasting antimicrobial properties.

[0025] Example 1

[0026] like Figure 1 As shown, a method for preparing an antibacterial modified lyocell fiber fabric comprises the following steps:

[0027] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 70 °C and stirred for 60 min;

[0028] The temperature was continued to rise to 120°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 6:1 to polyhexamethyleneguanidine hydrochloride, and the mixture was sealed and stirred for 20 minutes.

[0029] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 h to obtain an antibacterial modified lyocell fiber fabric.

[0030] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0031] After testing, the antibacterial rate of the obtained antibacterial modified lyocell fiber fabric was 99.9%.

[0032] Example 2

[0033] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0034] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 90 °C and stirred for 60 min;

[0035] The temperature was continued to rise to 120°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 6:1 to polyhexamethyleneguanidine hydrochloride, and the mixture was sealed and stirred for 20 minutes.

[0036] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 hours to obtain a modified antibacterial lyocell fiber fabric.

[0037] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0038] After testing, the antibacterial rate of the obtained antibacterial modified lyocell fiber fabric was 99.9%.

[0039] Example 3

[0040] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0041] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 50 °C and stirred for 60 min;

[0042] The temperature was continued to rise to 120°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 6:1 to polyhexamethyleneguanidine hydrochloride, and the mixture was sealed and stirred for 20 minutes.

[0043] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 hours to obtain a modified antibacterial lyocell fiber fabric.

[0044] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0045] like Figure 2 The figure shows the antibacterial effect of the antibacterial modified lyocell fiber fabric. According to the test, the antibacterial rate of the antibacterial modified lyocell fiber fabric is 99.9%.

[0046] Example 4

[0047] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0048] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 50 °C and stirred for 60 min;

[0049] The temperature was continued to rise to 100°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 6:1 to polyhexamethyleneguanidine hydrochloride. The mixture was sealed and stirred for 20 minutes.

[0050] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 hours to obtain a modified antibacterial lyocell fiber fabric.

[0051] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0052] After testing, the antibacterial rate of the obtained antibacterial modified lyocell fiber fabric was 99.9%.

[0053] Example 5

[0054] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0055] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 50 °C and stirred for 60 min;

[0056] The temperature was continued to rise to 80°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 6:1 to polyhexamethyleneguanidine hydrochloride. The mixture was sealed and stirred for 20 minutes.

[0057] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 hours to obtain a modified antibacterial lyocell fiber fabric.

[0058] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0059] After testing, the antibacterial rate of the obtained antibacterial modified lyocell fiber fabric was 99.9%.

[0060] Example 6

[0061] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0062] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 50 °C and stirred for 60 min;

[0063] The temperature was continued to rise to 120°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 3:1 to polyhexamethyleneguanidine hydrochloride. The mixture was sealed and stirred for 20 minutes.

[0064] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 hours to obtain a modified antibacterial lyocell fiber fabric.

[0065] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0066] like Figure 3 Shown is a schematic diagram of the prepared antibacterial modified lyocell fiber fabric.

[0067] After testing, the antibacterial rate of the obtained antibacterial modified lyocell fiber fabric was 99.9%.

[0068] Example 7

[0069] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0070] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 50 °C and stirred for 60 min;

[0071] The temperature was continued to rise to 120°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 8:1 to polyhexamethyleneguanidine hydrochloride. The mixture was sealed and stirred for 30 minutes.

[0072] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 hours to obtain a modified antibacterial lyocell fiber fabric.

[0073] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0074] like Figure 4 Shown is a scanning electron microscope image of the prepared antibacterial modified lyocell fiber fabric.

[0075] After testing, the antibacterial rate of the obtained antibacterial modified lyocell fiber fabric was 99.9%.

[0076] Example 8

[0077] A method for preparing antibacterial modified lyocell fiber fabric comprises the following steps:

[0078] Lyocell fiber fabric was cut into 4 cm × 4 cm pieces, placed in 20 g of deep eutectic solvent for pretreatment, sealed, heated to 50 °C and stirred for 60 min;

[0079] The temperature was continued to rise to 120°C, and 0.0012 mol of polyhexamethyleneguanidine hydrochloride was added to the deep eutectic solvent system. Then, glutaraldehyde was added to the deep eutectic solvent at a molar ratio of 2:1 to polyhexamethyleneguanidine hydrochloride. The mixture was sealed and stirred for 30 minutes.

[0080] After the reaction was completed, the sample was taken out and washed with deionized water, and then placed in a 60° C. oven to dry for 24 hours to obtain a modified antibacterial lyocell fiber fabric.

[0081] The deep eutectic solvent is composed of choline chloride and urea, with the molar ratio of choline chloride to urea being 1:1. The polyhexamethyleneguanidine hydrochloride is an antibacterial agent prepared by melt polycondensation, with the molar ratio of 1,6-hexanediamine to guanidine hydrochloride being 1:1. Glutaraldehyde is used as a coupling agent.

[0082] After testing, the antibacterial rate of the obtained antibacterial modified lyocell fiber fabric was 99.9%.

[0083] The present invention pre-treats the cut lyocell fiber fabric in a low eutectic solvent containing choline chloride and urea at a suitable temperature for a certain period of time, thereby destroying the fiber surface and roughening the surface to expose more hydroxyl reactive groups, thereby obtaining a lyocell fiber fabric with an optimal pre-treatment effect. Glutaraldehyde and polyhexamethylene guanidine hydrochloride are then added to the low eutectic solvent, and the fiber and the polyhexamethylene guanidine hydrochloride are connected via the glutaraldehyde, so that the fiber surface is connected to the polyhexamethylene guanidine hydrochloride, thereby effectively improving the antibacterial property of the lyocell fiber fabric. Meanwhile, after the antibacterial modification, the overall morphology of the fiber fabric is maintained in good condition, and excellent antibacterial property is exhibited in an antibacterial test, with an antibacterial rate still reaching 99.9% after 50 washes.

[0084] It should also be noted that, in this specification, 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 comprising 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. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of other identical elements in the process, method, article or apparatus comprising the element.

[0085] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing an antibacterial modified lyocell fiber fabric, characterized in that: The following steps are involved: The lyocell fiber fabric is cut into a certain size and placed in a low eutectic solvent for pretreatment. After the pretreatment, an antibacterial agent is added to the low eutectic solvent, and then a coupling agent is added to perform grafting modification. After the reaction is completed, the fabric is taken out and washed with deionized water, and finally dried to obtain an antibacterial modified lyocell fiber fabric.

2. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 1, wherein: The lyocell fiber fabric is cut into a certain size, specifically, cut into 4 cm×4 cm.

3. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 1, wherein: The deep eutectic solvent includes choline chloride and urea, and the molar ratio of choline chloride to urea is 1:

1.

4. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 1, wherein: The mass of the deep eutectic solvent is 20 g.

5. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 1, wherein: The pretreatment temperature is 30° C. to 90° C., and the pretreatment time is 20 min to 80 min.

6. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 1, wherein: The antibacterial agent is specifically polyhexamethyleneguanidine hydrochloride, which is prepared by melt polycondensation. In the polyhexamethyleneguanidine hydrochloride, the molar ratio of 1,6-hexanediamine and guanidine hydrochloride is 1:

1.

7. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 6, wherein: The coupling agent is specifically glutaraldehyde.

8. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 7, wherein: The molar ratio of the added glutaraldehyde to the polyhexamethyleneguanidine hydrochloride is x:1, and x ranges from 1 to 8.

9. The method for preparing an antibacterial modified lyocell fiber fabric according to claim 1, wherein: During the graft modification, the reaction temperature is 80° C. to 120° C., and the reaction time is 10 min to 40 min.

10. An antibacterial modified lyocell fiber fabric, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 9.

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