An antibacterial bamboo charcoal fiber and its preparation method

Abstract

The present invention discloses an antibacterial bamboo charcoal fiber and a preparation method thereof. In the present invention, carboxymethyl cellulose is coated in silica, and then calcined under an inert atmosphere. The carboxymethyl cellulose forms biochar, and the positions originally occupied by the carboxymethyl cellulose form pores, increasing the specific surface area of the silica, thereby improving its adsorption performance. Then, by utilizing the adsorption of silica and biochar, polyhexamethylene biguanide hydrochloride is adsorbed on the surface and inside of the silica particles. Finally, under the cross-linking action of epichlorohydrin, the antibacterial silica particles are grafted on the surface of the bamboo charcoal fiber, thereby endowing the bamboo charcoal fiber with good antibacterial properties. At the same time, under the action of epichlorohydrin, the hydroxyl groups in the silica particles react with polyhexamethylene biguanide hydrochloride, firmly fixing the polyhexamethylene biguanide hydrochloride on the silica particles, not easily falling off, and being wash-resistant, thus playing a more long-lasting antibacterial role.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical fibers, and particularly relates to an antibacterial bamboo charcoal fiber and a preparation method thereof. Background Art

[0002] Bamboo charcoal fiber is made from bamboo as raw material through a new calcination process and new technology of high temperature with pure oxygen and nitrogen barrier delay. Its unique fiber structure design has the characteristics of moisture absorption and breathability, antibacterial and bacteriostatic, warm in winter and cool in summer, and green environmental protection.

[0003] Bamboo charcoal fiber fabrics are mainly applied to underwear products, jeans, shirts, T-shirts, socks, towels, bedding, and sports and casual wear, etc., to give full play to the excellent characteristics of bamboo charcoal fiber being natural, environmentally friendly, and multifunctional. Bamboo charcoal fiber provides a brand-new raw material for textile product development. Although bamboo charcoal fiber products have certain antibacterial properties, they still cannot meet people's requirements for antibacterial products. Therefore, it is necessary to further improve and process bamboo charcoal fiber.

[0004] Chinese patent document CN200610161811.5 discloses a manufacturing method of an antibacterial bamboo charcoal fiber yarn. Nano-zinc oxide or silver with antibacterial effects is directly bonded to bamboo fiber, and then the bamboo fiber is directly subjected to a high-temperature carbonization process to obtain an antibacterial bamboo charcoal fiber with antibacterial particles bonded on the surface. Since the antibacterial bamboo charcoal fiber is composed of bamboo charcoal, the characteristics of the antibacterial bamboo charcoal fiber are the same as those of bamboo charcoal. Therefore, the lack of antibacterial ability of the bamboo charcoal fiber can be overcome. However, the prepared bamboo charcoal fiber has insufficient durability in antibacterial property, and the antibacterial effect significantly decreases after being washed many times. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an antibacterial bamboo charcoal fiber and a preparation method thereof. The prepared bamboo charcoal fiber has the characteristics of fast antibacterial speed and long-lasting antibacterial property.

[0006] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0007] A preparation method of an antibacterial bamboo charcoal fiber includes the following steps:

[0008] (1) Treat the bamboo charcoal fiber with ammonia plasma to obtain pretreated bamboo charcoal fiber;

[0009] (2) Add emulsifier span80 to liquid paraffin, then add tetraethyl orthosilicate solution and carboxymethyl cellulose thereto, stir and mix evenly. Subsequently, dropwise add ammonia water under stirring to adjust the pH of the solution to 8 - 8.5, and silicon dioxide precipitates to form a gel. After aging, washing, dialysis, and freeze-drying, a silicon dioxide coating material is obtained;

[0010] (3) Put the silica-coated material into a muffle furnace and calcine it under an inert atmosphere to obtain a silica-coated carbon material;

[0011] (4) Add the silica-coated carbon material to a polyhexamethylene biguanide hydrochloride solution, shake and adsorb, filter, wash, and dry to obtain antibacterial silica particles;

[0012] (5) Immerse the pretreated bamboo charcoal fiber in an ethanol aqueous solution, then add antibacterial silica particles and epichlorohydrin thereto, stir and react. After the reaction is completed, wash and dry to obtain antibacterial bamboo charcoal fiber.

[0013] Preferably, in step (1), the ammonia plasma treatment power is 90 - 120 W, and the treatment time is 60 - 120 s.

[0014] Preferably, in step (2), the mass ratio of emulsifier span80, liquid paraffin, tetraethyl orthosilicate solution, and carboxymethyl cellulose is 0.6 - 1:80 - 100:25 - 30:1 - 1.5.

[0015] Preferably, in step (2), the mass fraction of the tetraethyl orthosilicate solution is 20 - 30%.

[0016] Preferably, in step (3), the calcination temperature is 500 - 600 °C, and the calcination time is 2 - 3 h.

[0017] Preferably, in step (4), the mass ratio of the silica-coated carbon material to the polyhexamethylene biguanide hydrochloride solution is 5 - 10:60 - 80.

[0018] Preferably, in step (5), the mass ratio of the pretreated bamboo charcoal fiber, antibacterial silica particles, and epichlorohydrin is 10 - 20:4 - 6:3 - 5.

[0019] Preferably, in step (5), the stirring reaction temperature is 40 - 60 °C, and the stirring reaction time is 2 - 3 h.

[0020] Preferably, in step (5), the mass fraction of the ethanol aqueous solution is 60 - 80%.

[0021] The present invention also provides antibacterial bamboo charcoal fiber prepared by the above preparation method.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] In the present invention, an oil-water phase emulsion system is constructed, and carboxymethyl cellulose is coated in silica to obtain a silica-coated material. Then, it is calcined under an inert atmosphere. The carboxymethyl cellulose forms biochar, and pores are formed at the positions originally occupied by the carboxymethyl cellulose, increasing the specific surface area of the silica and thus improving its adsorption performance. Then, by utilizing the adsorption of silica and biochar, polyhexamethylene biguanide hydrochloride is adsorbed on the surface and inside of the silica particles. Finally, under the cross-linking action of epichlorohydrin, the active groups on the surface of the pretreated bamboo charcoal fiber react with the antibacterial silica particles, grafting the antibacterial silica particles on the surface of the bamboo charcoal fiber, thereby endowing the bamboo charcoal fiber with good antibacterial properties. At the same time, under the action of epichlorohydrin, the hydroxyl groups in the silica particles react with polyhexamethylene biguanide hydrochloride, firmly fixing the polyhexamethylene biguanide hydrochloride on the silica particles, making it not easy to fall off and resistant to washing, thus playing a more long-lasting antibacterial role. Detailed implementation mode

[0024] The present invention will be further described in detail below through specific preferred embodiments, but the present invention is not limited to the following embodiments.

[0025] It should be noted that unless otherwise specified, the chemical reagents involved in the present invention are all purchased through commercial channels.

[0026] The bamboo charcoal fiber used in the present invention is purchased from Shaoxing Xineng Textile Technology Co., Ltd., with a fineness of 75D.

[0027] Example 1

[0028] A preparation method of antibacterial bamboo charcoal fiber includes the following steps:

[0029] (1) The bamboo charcoal fiber is treated by ammonia plasma with a treatment power of 90W and a treatment time of 120s to obtain a pretreated bamboo charcoal fiber;

[0030] (2) 0.6 g of emulsifier span80 is added to 80 g of liquid paraffin, then 25 g of tetraethyl orthosilicate solution (the mass ratio of tetraethyl orthosilicate, ethanol and water is 5:10:10) and 1 g of carboxymethyl cellulose are added thereto, stirred and mixed evenly. Subsequently, ammonia water is added dropwise under stirring to adjust the pH of the solution to 8. Silica precipitates to form a gel, which is aged, washed, dialyzed, and freeze-dried to obtain a silica-coated material;

[0031] (3) The silica-coated material is placed in a muffle furnace and calcined under a nitrogen atmosphere at a calcination temperature of 500 °C and a calcination time of 3 h to obtain a silica-coated carbon material;

[0032] (4) Add 5 g of silica-coated carbon material to 60 g of a 10 wt% polyhexamethylene biguanide hydrochloride solution, shake and adsorb for 2 h, then filter, wash, and dry to obtain antibacterial silica particles;

[0033] (5) Immerse 10 g of pretreated bamboo charcoal fiber into a 60 wt% ethanol aqueous solution, then add 4 g of antibacterial silica particles and 3 g of epichlorohydrin thereto, stir and react at 40 °C for 3 h. After the reaction is completed, wash and dry to obtain antibacterial bamboo charcoal fiber.

[0034] Example 2

[0035] A preparation method of antibacterial bamboo charcoal fiber, comprising the following steps:

[0036] (1) Perform ammonia plasma treatment on bamboo charcoal fiber with a treatment power of 120 W and a treatment time of 60 s to obtain pretreated bamboo charcoal fiber;

[0037] (2) Add 1 g of emulsifier span80 to 100 g of liquid paraffin, then add 30 g of tetraethyl orthosilicate solution (the mass ratio of tetraethyl orthosilicate, ethanol, and water is 5:15:10) and 1.5 g of carboxymethyl cellulose thereto, stir and mix evenly. Subsequently, dropwise add ammonia water under stirring to adjust the pH of the solution to 8.5, and silica precipitates to form a gel. After aging, washing, dialysis, and freeze-drying, obtain silica-coated material;

[0038] (3) Put the silica-coated material into a muffle furnace and calcine it under a nitrogen atmosphere at a calcination temperature of 600 °C for 2 h to obtain silica-coated carbon material;

[0039] (4) Add 10 g of silica-coated carbon material to 80 g of a 10 wt% polyhexamethylene biguanide hydrochloride solution, shake and adsorb for 2 h, then filter, wash, and dry to obtain antibacterial silica particles;

[0040] (5) Immerse 20 g of pretreated bamboo charcoal fiber into a 60 wt% ethanol aqueous solution, then add 6 g of antibacterial silica particles and 5 g of epichlorohydrin thereto, stir and react at 60 °C for 2 h. After the reaction is completed, wash and dry to obtain antibacterial bamboo charcoal fiber.

[0041] Example 3

[0042] A preparation method of antibacterial bamboo charcoal fiber, comprising the following steps:

[0043] (1) Perform ammonia plasma treatment on bamboo charcoal fiber with a treatment power of 100 W and a treatment time of 90 s to obtain pretreated bamboo charcoal fiber;

[0044] (2) Add 0.8 g of emulsifier span80 to 90 g of liquid paraffin, then add 30 g of tetraethyl orthosilicate solution (the mass ratio of tetraethyl orthosilicate, ethanol and water is 5:15:10) and 1.2 g of carboxymethyl cellulose thereto, stir and mix evenly. Subsequently, dropwise add ammonia water under stirring to adjust the pH of the solution to 8.5. Silicon dioxide precipitates to form a gel, which is aged, washed, dialyzed, and freeze-dried to obtain a silicon dioxide-coated material;

[0045] (3) Put the silicon dioxide-coated material into a muffle furnace and calcine it under a nitrogen atmosphere. The calcination temperature is 550 °C and the calcination time is 3 h to obtain a silicon dioxide-coated carbon material;

[0046] (4) Add 8 g of the silicon dioxide-coated carbon material to 80 g of a 10 wt% polyhexamethylene biguanide hydrochloride solution, oscillate and adsorb for 2 h, filter, wash, and dry to obtain antibacterial silicon dioxide particles;

[0047] (5) Immerse 15 g of pretreated bamboo charcoal fiber into an 80 wt% ethanol aqueous solution, then add 5 g of antibacterial silicon dioxide particles and 4 g of epichlorohydrin thereto, stir and react at 50 °C for 3 h. After the reaction is completed, wash and dry to obtain antibacterial bamboo charcoal fiber.

[0048] Example 4

[0049] A preparation method of antibacterial bamboo charcoal fiber, comprising the following steps:

[0050] (1) Perform ammonia plasma treatment on the bamboo charcoal fiber with a treatment power of 100 W and a treatment time of 120 s to obtain pretreated bamboo charcoal fiber;

[0051] (2) Add 0.7 g of emulsifier span80 to 100 g of liquid paraffin, then add 30 g of tetraethyl orthosilicate solution (the mass ratio of tetraethyl orthosilicate, ethanol and water is 5:15:10) and 1.4 g of carboxymethyl cellulose thereto, stir and mix evenly. Subsequently, dropwise add ammonia water under stirring to adjust the pH of the solution to 8.5. Silicon dioxide precipitates to form a gel, which is aged, washed, dialyzed, and freeze-dried to obtain a silicon dioxide-coated material;

[0052] (3) Put the silicon dioxide-coated material into a muffle furnace and calcine it under a nitrogen atmosphere. The calcination temperature is 580 °C and the calcination time is 3 h to obtain a silicon dioxide-coated carbon material;

[0053] (4) Add 6 g of the silicon dioxide-coated carbon material to 80 g of a 10 wt% polyhexamethylene biguanide hydrochloride solution, oscillate and adsorb for 2 h, filter, wash, and dry to obtain antibacterial silicon dioxide particles;

[0054] (5) Immerse 16 g of pretreated bamboo charcoal fiber into an aqueous ethanol solution of 80 wt%, then add 4 g of antibacterial silica particles and 4 g of epichlorohydrin thereto, and stir and react at 50 °C for 3 h. After the reaction is completed, wash and dry to obtain antibacterial bamboo charcoal fiber.

[0055] Comparative Example 1

[0056] The bamboo charcoal fiber was not treated.

[0057] Comparative Example 2

[0058] A method for preparing antibacterial bamboo charcoal fiber, comprising the following steps:

[0059] (1) Perform ammonia plasma treatment on the bamboo charcoal fiber at a treatment power of 100 W and a treatment time of 90 s to obtain pretreated bamboo charcoal fiber;

[0060] (2) Add 0.8 g of emulsifier span80 to 90 g of liquid paraffin, then add 30 g of tetraethyl orthosilicate solution (the mass ratio of tetraethyl orthosilicate, ethanol and water is 5:15:10), stir and mix evenly, and then dropwise add ammonia water under stirring to adjust the pH of the solution to 8.5. Silica precipitates to form a gel, which is aged, washed, dialyzed, and freeze-dried to obtain silica material;

[0061] (3) Add 8 g of silica material to 80 g of 10 wt% polyhexamethylene biguanide hydrochloride solution, oscillate and adsorb for 2 h, filter, wash, and dry to obtain antibacterial silica particles;

[0062] (4) Immerse 15 g of pretreated bamboo charcoal fiber into an aqueous ethanol solution of 80 wt%, then add 5 g of antibacterial silica particles and 4 g of epichlorohydrin thereto, and stir and react at 50 °C for 3 h. After the reaction is completed, wash and dry to obtain antibacterial bamboo charcoal fiber.

[0063] Weave the fibers obtained in Examples 1-4 and Comparative Examples 1-2 into a fabric with a gram weight of 120 g / m 2 and then conduct antibacterial performance tests. The specific steps are as follows: Test according to the standard of GB / T 20944.1-2007. Take Staphylococcus aureus and add it to 20 mL of liquid medium, place it in a constant temperature oscillator at 37 °C for 12 h, and use the ten-fold dilution method to dilute the bacterial suspension to a viable bacteria concentration of 1×10 8Inoculum at CFU / mL; Take 250 mL Erlenmeyer flasks, add 0.5 g of the fabrics obtained in Examples 1-4 and Comparative Examples 1-2 respectively, and 70 mL of buffer solution. Set up a blank group. Add 5 mL of the inoculum to each conical flask, place them in a constant temperature shaker at 37 °C, shake at 150 r / min for 4 h, 8 h, and 16 h respectively. Dilute to an appropriate multiple by the ten-fold dilution method. Transfer 1 mL from each diluted flask to a petri dish containing solid medium, spread evenly, invert the plate and culture at 37 °C for 24 h, and calculate the antibacterial rate.

[0064] The test results are shown in the following table:

[0065]

[0066] Wash the fabrics prepared in Example 3 and Comparative Examples 1-2 30 times, and then according to the above experimental steps, test the antibacterial rate after shaking for 16 h. The test results are shown in the following table:

[0067]

[0068] Finally, it should be noted that the above examples do not limit the present invention in any form. For those skilled in the art, based on the present invention, some modifications and improvements can be made. Therefore, any modification or improvement made without departing from the spirit of the present invention falls within the scope of the present invention claimed.

Claims

1. A preparation method of antibacterial bamboo charcoal fiber, characterized in that, It includes the following steps: (1) Perform ammonia plasma treatment on bamboo charcoal fiber to obtain pretreated bamboo charcoal fiber; (2) Add emulsifier span80 to liquid paraffin, then add tetraethyl orthosilicate solution and carboxymethyl cellulose thereto, stir and mix evenly, and then dropwise add ammonia water under stirring to adjust the pH of the solution to 8 - 8.

5. Silicon dioxide precipitates to form a gel, which is aged, washed, dialyzed, and freeze-dried to obtain silicon dioxide coating material; (3) Put the silicon dioxide coating material into a muffle furnace and calcine it under an inert atmosphere to obtain silicon dioxide-coated carbon material; (4) Add the silicon dioxide-coated carbon material to a polyhexamethylene biguanide hydrochloride solution, oscillate and adsorb, filter, wash, and dry to obtain antibacterial silicon dioxide particles; (5) Immerse the pretreated bamboo charcoal fiber in an ethanol aqueous solution, then add antibacterial silicon dioxide particles and epichlorohydrin thereto, stir and react. After the reaction is completed, wash and dry to obtain antibacterial bamboo charcoal fiber.

2. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, characterized in that, In step (1), the ammonia plasma treatment power is 90 - 120 W, and the treatment time is 60 - 120 s.

3. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, characterized in that, In step (2), the mass ratio of emulsifier span80, liquid paraffin, tetraethyl orthosilicate solution, and carboxymethyl cellulose is 0.6 - 1:80 - 100:25 - 30:1 - 1.

5.

4. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, characterized in that, In step (2), the mass fraction of the tetraethyl orthosilicate solution is 20 - 30%.

5. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, characterized in that, In step (3), the calcination temperature is 500 - 600 °C, and the calcination time is 2 - 3 h.

6. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, wherein, In step (4), the mass ratio of the silicon dioxide-coated carbon material to the polyhexamethylene biguanide hydrochloride solution is 5 - 10:60 - 80.

7. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, characterized in that, In step (5), the mass ratio of the pretreated bamboo charcoal fiber, antibacterial silicon dioxide particles, and epichlorohydrin is 10 - 20:4 - 6:3 - 5.

8. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, characterized in that, In step (5), the stirring reaction temperature is 40 - 60 °C, and the stirring reaction time is 2 - 3 h.

9. The preparation method of the antibacterial bamboo charcoal fiber according to claim 1, characterized in that, In step (5), the mass fraction of the ethanol aqueous solution is 60 - 80%.

10. The antibacterial bamboo charcoal fiber prepared by the preparation method according to any one of claims 1 - 9.

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