Antibacterial heat accumulating temperature regulating phase change fiber material and preparation method thereof

Abstract

The application provides an antibacterial heat storage temperature regulating phase change fiber material and a preparation method thereof. The antibacterial heat storage temperature regulating phase change fiber material comprises a fiber base material and an antibacterial phase change material, the fiber base material is polyester fiber and nylon 1012, the antibacterial phase change material comprises an antibacterial material, a phase change material and a dispersing agent, and the dispersing agent is a mixture of sodium dodecyl benzene sulfonate and polyvinyl alcohol. The preparation method provided by the application is direct and efficient, the obtained antibacterial heat storage temperature regulating phase change fiber material still has long antibacterial performance and temperature regulating performance even after long-time placement, and can be used for the production of special textiles such as protective clothing, outdoor clothing and mountaineering clothing to cope with extreme use environments.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of fiber material preparation, and relates to an antibacterial heat storage temperature regulating phase change fiber material and a preparation method thereof. BACKGROUND

[0002] Fiber material is a structured material formed by textile processing of fibrous substances. According to the source and composition, it can be divided into natural fibers and synthetic fibers. Common synthetic fibers include polyester fiber (polyester), polyamide fiber (polyamide or nylon), polypropylene fiber (polypropylene), etc. Due to the excellent physical and chemical properties of synthetic fibers, such as high strength, wear resistance, corrosion resistance, etc., they have been widely used in various fields.

[0003] With the development of science and technology and the improvement of people's living standards, people's demand for clothing textiles is becoming more and more personalized and functional. Single-function synthetic fiber materials cannot meet people's requirements for specific clothing, such as mountaineering clothes. Because clothes will adsorb some microorganisms during mountaineering, and people are also prone to sweating after intense exercise, the fiber materials in the clothes absorb the sweat and sebum produced by human metabolism to provide sufficient nutrients for the growth of microorganisms, breed bacteria and produce odor, affecting comfort. In addition, the external environment temperature changes greatly during mountaineering, and the evaporation of sweat will also accelerate the heat loss from the body surface, leading to a rapid drop in body temperature. This rapid change in body temperature can weaken the body's immunity, easily leading to cold and fever, affecting the health of mountaineers. Therefore, it is of great significance to develop a fiber material with antibacterial and heat storage temperature regulating functions for making mountaineering clothes and other clothes for extreme use environments.

[0004] In the prior art, fiber materials with antibacterial and heat storage temperature regulating functions usually contain fiber substrates, phase change materials and antibacterial materials, etc. The phase change material can be applied in the fields of energy storage and temperature control by absorbing and releasing a large amount of latent heat during the phase change, and the introduction of the phase change material into the fiber substrate can meet the demand for fabric temperature control. The antibacterial phase change material exists in the form of antibacterial phase change capsules, which not only has antibacterial properties, but also can meet the demand for fabric temperature control. However, this method has the disadvantages of low core material coating rate, limited amount of antibacterial agent, etc., which greatly reduces the antibacterial rate of microcapsules and cannot achieve long-term antibacterial effect under repeated washing conditions. In addition, the fiber substrate is mainly polyester fiber (polyester) because polyester fiber has high strength and elasticity, and is not easy to break or deform when subjected to external force, and has good wear resistance. However, there is a problem that the wear of polyester fiber is accelerated when it is used frequently and rubbed, which shortens the service life and limits the expansion of its application field.

[0005] The patent with publication number "CN114990730A" discloses a graphene-white graphene skin-core structure phase change polyester composite fiber. This material uses polyester chip as fiber base material, white graphene material as antibacterial agent, and alkane energy storage material as phase change material. The prepared composite fiber has antibacterial and temperature regulation functions. Although the functional weakening does not occur with the increase of washing times, there are problems such as reduction of antibacterial effect and temperature regulation performance when used after long-term storage. Therefore, how to develop a direct and efficient antibacterial heat storage temperature regulation fiber material that can not only have long-term antibacterial effect but also ensure the compatibility between materials and fully play the role of various components for making mountaineering clothes and other clothes to cope with various extreme application scenarios and meet people's pursuit of clothing individualization and functionalization is a problem to be solved by the present application. SUMMARY

[0006] The present application aims to provide an antibacterial heat storage temperature regulation phase change fiber material, which comprises the following components: fiber base material and antibacterial phase change material; wherein the preparation raw materials of the antibacterial phase change material comprise antibacterial material, phase change material and dispersant, and the dispersant is a mixture of polyvinyl alcohol and sodium dodecyl benzene sulfonate with a mass ratio of 1:(1-3).

[0007] The antibacterial phase change material of the present application uses antibacterial material as the base, and is compounded with phase change material through vacuum adsorption to obtain antibacterial phase change material. In this process, a mixture of polyvinyl alcohol and sodium dodecyl benzene sulfonate with a certain mass ratio is added as a dispersant to make the antibacterial material and the phase change material fully contact, reduce agglomeration, and uniformly disperse, which ensures that the phase change material is not easy to leak and is also beneficial to the subsequent mixing of the antibacterial phase change material and the fiber material.

[0008] As a further improvement, the fiber base material is polyester fiber and nylon 1012, which increases the wear resistance of the fiber base material.

[0009] As a further improvement, the mass ratio of the polyester fiber and the nylon 1012 is 1:1-3.

[0010] As a further improvement, the number average molecular weight of the nylon 1012 is 2000-10000, and the relative viscosity is 2-3.

[0011] As a further improvement, the phase change material includes one or more of polyethylene glycol, paraffin and n-hexadecane.

[0012] As a further improvement, the preparation method of the antibacterial phase change material comprises the following steps:

[0013] S1: preparing the antibacterial material, adding the carbon nanotubes after acid etching to the copper-containing salt solution, adding the chelating agent while stirring, setting the reaction temperature to 50-80 DEG C, slowly adding the reducing agent to the reaction solution after sufficient reaction, centrifuging the obtained mixed solution, removing the supernatant, drying the precipitate, and obtaining the antibacterial material;

[0014] S2: dispersing the antibacterial material in the aqueous solution containing the phase change material, adding the dispersing agent, ultrasonic stirring, vacuum adsorption circulation, and freeze-drying to obtain the antibacterial phase change material.

[0015] As a further improvement, the mass ratio of the antibacterial material, the phase change material and the dispersing agent is (0.8-1):1:(0.1-0.3).

[0016] In the present application, the high specific surface area of the carbon nanotubes can uniformly disperse the antibacterial agent, improve the antibacterial rate and antibacterial life, and adsorb the phase change material, thereby endowing the fiber material with the functions of heat storage and temperature adjustment.

[0017] As a further improvement, the acid etching of the carbon nanotubes is realized by the following steps: putting the dried carbon nanotubes into an acid solution with a concentration of 1-2 mol / L, setting the reaction temperature to 50-80 DEG C, stopping the reaction after stirring for 24-48 h, removing the supernatant by centrifugation, washing the obtained precipitate with deionized water, and vacuum drying at 80 DEG C to obtain the carbon nanotubes after acid etching.

[0018] As a further improvement, the copper-containing salt solution contains one or more of copper sulfate solution, copper chloride solution and copper nitrate solution. The chelating agent is one or more of disodium ethylenediaminetetraacetate, sodium tartrate and sodium tripolyphosphate.

[0019] As a further improvement, after sufficient reaction, the copper ions are reduced in situ to copper by adding the reducing agent, which is one or more of ascorbic acid solution and sodium sulfite solution. Then, the reaction solution is centrifuged, the obtained solid is washed with deionized water, and vacuum drying is performed at 60 DEG C for 12 h to obtain the antibacterial material.

[0020] As a further improvement, the above antibacterial material is put into the deionized water solution containing the phase change material, and ultrasonic stirring is performed for 1-2 h. Then, the obtained mixed solution is transferred to a vacuum pump, and vacuum adsorption is started. The vacuum degree of the vacuum adsorption is -0.08 MPa, and the filtration time is 1.5 h. Then, the vacuum pump is closed, and the environment in the vacuum pump is restored to the normal pressure state. This cycle is repeated for 3-5 times to improve the adsorption rate of the antibacterial material. The obtained solid after freeze-drying of the mixed solution after vacuum adsorption is the antibacterial phase change material.

[0021] The preparation method of the antibacterial heat storage and temperature adjustment fiber material further comprises the following steps,

[0022] The dry fiber base material and the above antibacterial phase change material are mixed, then extruded by a double screw extruder, and then melt spun to obtain an antibacterial heat storage temperature adjustment phase change fiber material.

[0023] As a further improvement, the antibacterial phase change material is mixed with the fiber base material after being dried at 100 DEG C to remove surface moisture, added to a double screw extruder for blending, granulated, then heated and melt spun, and stretched under the action of hot air to obtain an antibacterial heat storage temperature adjustment phase change fiber material; wherein the spinning temperature is 230-250 DEG C, the screw rotation speed of the spinning melt extruder in the melt spinning is 20-50 r / min, and the winding speed is 10-30 m / min.

[0024] The present application has the following advantages:

[0025] The antibacterial heat storage temperature adjustment phase change fiber material provided by the present application avoids the rupture of traditional phase change capsules at high temperatures, so that the phase change material is not easy to leak during the subsequent melt spinning process when it is compounded with fibers, the antibacterial property and heat storage temperature adjustment property of the overall material are ensured, the antibacterial performance and temperature resistance are good when used, even after multiple washes, the antibacterial life is long, and the enthalpy value is high, so that the material can be used to make mountaineering clothes and other garments to cope with various extreme application scenarios. DETAILED DESCRIPTION

[0026] The present application will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the present application and are only used to illustrate the present application, but not to limit the present application. Other combinations and various modifications within the concept of the present application can be made without departing from the spirit or scope of the present application.

[0027] In the following examples, the compound monomers and related reagents used can be purchased from the market, wherein the polyethylene glycol is purchased from Nantong Xingbaoyuan Chemical Co., Ltd. PEG-2000; the polyester fiber is purchased from Changzhou Boxia Engineering Material Co., Ltd.; the nylon 1012 and nylon 66 are purchased from Shandong Dongchen Ruishen New Material Technology Co., Ltd.; the carbon nanotube is purchased from Shenzhen Turing New Material Co., Ltd., with a brand of TL300; and the polyvinyl alcohol is purchased from Shenzhen Boshun Chemical Co., Ltd.

[0028] The preparation method of the antibacterial phase change material A-F comprises the following steps:

[0029] S1: preparing an antibacterial material, putting 5g of dried carbon nanotubes into a sulfuric acid solution with a concentration of 2mol / L and a dosage of 5mL, setting the reaction temperature to 80 DEG C, stopping the reaction after stirring for 26h, removing the supernatant liquid by centrifugation, washing the obtained precipitate with deionized water, and vacuum drying at 80 DEG C for 12h to obtain acid-etched carbon nanotubes, then adding 2g of the acid-etched carbon nanotubes 、1.3 g of copper sulfate was added to 10 mL of deionized water and stirred for 5 minutes. 1.7 g of disodium ethylenediaminetetraacetate was added. The reaction temperature was set to 70 ° C. Stirring was continued. After the reaction was completed for 24 hours, a 0.2 mol / L ascorbic acid solution was slowly added in an amount of 5 mL. The resulting mixed solution was centrifuged at a speed of 4000 r / min for 5 minutes. The supernatant was removed and the precipitate was washed with deionized water and ethanol in sequence. After washing with deionized water and ethanol for 3 times respectively, the precipitate was dried in a vacuum at 60 ° C for 12 hours to obtain an antibacterial material.

[0030] S2: The above-obtained antibacterial material, polyethylene glycol, and dispersant were added to 10 mL of deionized water, ultrasonically stirred for 3 h, and vacuum adsorption cycled 5 times with a vacuum degree of -0.1 MPa and a filtration time of 1.5 h. The antibacterial phase change material was then freeze-dried.

[0031] The specific components and masses of the antibacterial material, polyethylene glycol and dispersant used in the antibacterial phase change material A are: antibacterial material: 22.5g; polyethylene glycol: 25g; dispersant: 2.5g, and the dispersant is polyvinyl alcohol and sodium dodecylbenzene sulfonate in a mass ratio of 1:1.

[0032] The specific components and mass of the antibacterial material, polyethylene glycol and dispersant used in the antibacterial phase change material B are basically the same as those of the antibacterial phase change material A. The difference is that the mass ratio of polyvinyl alcohol and sodium dodecylbenzene sulfonate in the antibacterial phase change material A is 1:1, and the dispersant is polyvinyl alcohol and sodium dodecylbenzene sulfonate in the mass ratio of 1:2.

[0033] The specific components and mass of the antibacterial material, polyethylene glycol and dispersant used in the antibacterial phase change material C are basically the same as those of the antibacterial phase change material A. The difference is that the dispersant in the antibacterial phase change material A, which is polyvinyl alcohol and sodium dodecylbenzene sulfonate in a mass ratio of 1:1, is replaced by a dispersant in which is polyvinyl alcohol and sodium dodecylbenzene sulfonate in a mass ratio of 1:3.

[0034] The specific components and mass of the antibacterial material, polyethylene glycol and dispersant used in the antibacterial phase change material D are basically the same as those of the antibacterial phase change material A. The difference is that the dispersant in the antibacterial phase change material A, which is polyvinyl alcohol and sodium dodecylbenzene sulfonate in a mass ratio of 1:1, is replaced by a dispersant consisting solely of sodium dodecylbenzene sulfonate.

[0035] The specific components and mass of the antibacterial material, polyethylene glycol and dispersant used in the antibacterial phase change material E are basically the same as those of the antibacterial phase change material A, except that the dispersant in the antibacterial phase change material A, which is polyvinyl alcohol and sodium dodecylbenzene sulfonate in a mass ratio of 1:1, is replaced by a dispersant consisting solely of polyvinyl alcohol.

[0036] The specific components and mass of the antibacterial material, polyethylene glycol and dispersant used in the antibacterial phase change material F are basically the same as those of the antibacterial phase change material A, except that the dispersant in the antibacterial phase change material A is replaced by polyvinyl alcohol and sodium dodecyl benzene sulfonate with a mass ratio of 1:1, and the dispersant is polyvinyl alcohol and sodium dodecyl benzene sulfonate with a mass ratio of 1:10.

[0037] The antibacterial heat storage and temperature regulating phase change fiber materials prepared in the following Examples 1-7 and Comparative Examples 1-3 all include the following steps:

[0038] The antibacterial phase change material and the fiber base material are mixed thoroughly after being dried at 100°C to remove surface moisture, then extruded and granulated in a twin-screw extruder, and then heated and melted to be spun, and stretched under the action of hot air to obtain an antibacterial heat storage and temperature regulating phase change fiber material; the spinning temperature is 240°C, the screw rotation speed of the spinning melt extruder is 30r / min, and the winding speed is 20m / min.

[0039] Example 1 provides an antibacterial heat storage and temperature regulating phase change fiber material, which comprises the following components: 50g of fiber base material and 50g of antibacterial phase change material A, wherein the fiber base material is polyester fiber and nylon 1012 with a mass ratio of 1:1; the number average molecular weight of the nylon 1012 is 2000, and the relative viscosity is 2.

[0040] Example 2 provides an antibacterial heat storage and temperature regulating phase change fiber material, which comprises the following components: 50g of fiber base material and 50g of antibacterial phase change material B, wherein the fiber base material is polyester fiber and nylon 1012 with a mass ratio of 1:1; the number average molecular weight of the nylon 1012 is 2000, and the relative viscosity is 2.

[0041] Example 3 provides an antibacterial heat storage and temperature regulating phase change fiber material, which comprises the following components: 50g of fiber base material and 50g of antibacterial phase change material C; the fiber base material is polyester fiber and nylon 1012 with a mass ratio of 1:1; the number average molecular weight of the nylon 1012 is 2000, and the relative viscosity is 2.

[0042] Example 4 provides an antibacterial heat storage and temperature regulating phase change fiber material, which comprises the following components: 50g of fiber base material and 50g of antibacterial phase change material B; the fiber base material is polyester fiber.

[0043] Example 5 provides an antibacterial heat storage and temperature regulating phase change fiber material, which comprises the following components: 50g of fiber base material and 50g of antibacterial phase change material B; the fiber base material is nylon 1012; the number average molecular weight of the nylon 1012 is 2000, and the relative viscosity is 2.

[0044] Example 6 provides an antibacterial heat storage temperature regulating phase change fiber material, comprising the following components: 50 g of a fiber substrate and 50 g of antibacterial phase change material B; the fiber substrate is polyester fiber and nylon 1012, the mass ratio is 1:1; the number average molecular weight of the nylon 1012 is 1000, and the relative viscosity is 1.

[0045] Example 7 provides an antibacterial heat storage temperature regulating phase change fiber material, comprising the following components: 50 g of a fiber substrate and 50 g of antibacterial phase change material, the fiber substrate is polyester fiber and nylon 66, the mass ratio is 1:1; the number average molecular weight of the nylon 66 is 2000, and the relative viscosity is 2.

[0046] Comparative Example 1: The components used and the preparation method are basically the same as in Example 1, except that the antibacterial phase change material A in Example 1 is replaced by antibacterial phase change material D.

[0047] Comparative Example 2: The components used and the preparation method are basically the same as in Example 1, except that the antibacterial phase change material A in Example 1 is replaced by antibacterial phase change material E.

[0048] Comparative Example 3: The components used and the preparation method are basically the same as in Example 1, except that the antibacterial phase change material A in Example 1 is replaced by antibacterial phase change material F.

[0049] The test method is as follows:

[0050] The antibacterial heat storage temperature regulating phase change fiber materials prepared in Examples 1-7 and Comparative Examples 1-3 were placed at a temperature of 23°C and a relative air humidity of 47% for 2 months, and then tested for antibacterial performance, antibacterial washing resistance, and temperature regulating performance, according to the following specific test methods:

[0051] Antibacterial performance test: According to GB / T20944.3-2008 "Evaluation of the antibacterial properties of textiles Part 3: oscillation method", the antibacterial effect of Staphylococcus aureus (AATCC6538) and Escherichia coli (AATCC8739) on the antibacterial heat storage temperature regulating phase change fiber materials prepared in the examples and comparative examples of the present application was tested;

[0052] Antibacterial washing resistance test: At room temperature, the fabric made of such antibacterial heat storage temperature regulating fiber materials was soaked in natural soap powder (concentration of 2 g / L) for 5 min, rinsed 3 times, and then dried, which was one washing process. The above antibacterial performance test was conducted on the fabric made of such antibacterial heat storage temperature regulating fiber materials after 80 washes.

[0053] Temperature regulating performance test: The phase change latent heat of the antibacterial heat storage temperature regulating phase change fiber materials prepared in the examples and comparative examples of the present application was tested by TA2910 type differential scanning calorimeter, and the average value was taken after three repeated experiments.

[0054] The test results are shown in Table 1.

[0055] Table 1

[0056]

[0057] It can be seen from Examples 1-3 that when the mass ratio of sodium dodecyl benzene sulfonate and polyvinyl alcohol in the dispersant is in a suitable range, the antibacterial effect of the material is still high after a long time, and the enthalpy is relatively high, the temperature regulating function is good, and when the mass ratio of sodium dodecyl benzene sulfonate and polyvinyl alcohol in the dispersant is 1:2, the antibacterial property of the material to E. coli is as high as 98.1% after a long time, and the antibacterial property of the material to E. coli is still as high as 96.9% after multiple washes, the antibacterial performance is excellent, and the enthalpy is relatively high, the temperature regulating performance is excellent;

[0058] It can be seen from the comparison of Example 1 and Comparative Examples 1-3 that when the dispersant contains only one or the mass ratio of sodium dodecyl benzene sulfonate and polyvinyl alcohol in the dispersant is not in a suitable range, a relatively high antibacterial property and enthalpy cannot be obtained, and the antibacterial performance decreases greatly after multiple washes, indicating that the antibacterial material has a failure condition.

[0059] It can be seen from Examples 2 and 4-7 that when the fiber substrate is not a mixture of polyester fiber and nylon 1012 and the number average molecular weight and relative viscosity of nylon 1012 are not in a suitable range, even if the mass ratio of polyvinyl alcohol and sodium dodecyl benzene sulfonate in the dispersant is 1:2, the antibacterial property, antibacterial life and enthalpy are all decreased.

[0060] In summary, the antibacterial heat storage temperature regulating phase change fiber material provided by the application uses polyester fiber and nylon 1012 as the fiber substrate, and uses a dispersant with a mass ratio of polyvinyl alcohol and sodium dodecyl benzene sulfonate in a suitable range in the antibacterial phase change material, so that a multifunctional fiber material with good antibacterial performance, long antibacterial life and high enthalpy can be obtained, and when the mass ratio of polyvinyl alcohol and sodium dodecyl benzene sulfonate in the dispersant is 1:2, the antibacterial property of the antibacterial heat storage temperature regulating phase change fiber material prepared is the best, the antibacterial life is the longest, and the enthalpy is the highest.

[0061] The above embodiments are only for illustrating the technical concept and characteristics of the application, and the purpose is to enable those skilled in the art to understand the content of the application and implement it, and cannot limit the protection scope of the application, and any equivalent changes or modifications made according to the spirit and essence of the application should be covered within the protection scope of the application.

Claims

1. An antibacterial heat storage and temperature regulating phase change fiber material, characterized in that: The antibacterial heat storage and temperature regulating phase change fiber material comprises the following components: a fiber base material and an antibacterial phase change material; The raw materials for preparing the antibacterial phase change material include: antibacterial material, phase change material and dispersant, wherein the dispersant is a mixture of polyvinyl alcohol and sodium dodecylbenzene sulfonate in a mass ratio of 1:(1-3); the fiber substrate is polyester fiber and nylon 1012; the number average molecular weight of the nylon 1012 is 2000-10000 and the relative viscosity is 2-3; The phase change material includes one or more of polyethylene glycol, paraffin and n-hexadecane; The mass ratio of the antibacterial material, the phase change material and the dispersant is (0.8-1):1:(0.1-0.3); The mass ratio of the polyester fiber to nylon 1012 is 1:1-3; The preparation method of the antibacterial phase change material comprises the following steps: S1: Preparing an antibacterial material: adding acid-etched carbon nanotubes to a copper-containing salt solution, adding a chelating agent while stirring, setting the reaction temperature to 50-80°C, and after sufficient reaction, slowly adding a reducing agent to the reaction solution, centrifuging the resulting mixed solution, removing the supernatant, and drying the precipitate to obtain an antibacterial material; S2: dispersing the above antibacterial material in an aqueous solution containing a phase change material, adding a dispersant, ultrasonically stirring, vacuum adsorption cycling, and then freeze-drying to obtain the antibacterial phase change material.

2. The antibacterial heat storage and temperature regulating phase change fiber material according to claim 1, characterized in that: The copper-containing salt solution comprises one or more of copper sulfate solution, copper chloride solution and copper nitrate solution; the chelating agent comprises one or more of disodium ethylenediaminetetraacetate, sodium tartrate and sodium tripolyphosphate.

3. The method for preparing the antibacterial heat storage and temperature regulating phase change fiber material according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: fully mixing a dry fiber base material and an antibacterial phase change material, then extruding and granulating the material through a twin-screw extruder, and melt spinning the material to obtain an antibacterial heat storage and temperature regulating phase change fiber material.

4. The method for preparing the antibacterial heat storage and temperature regulating phase change fiber material according to claim 3, characterized in that: The spinning temperature in the melt spinning is 230-250° C., the screw speed of the spinning melt extruder in the melt spinning is 20-50 r / min, and the winding speed is 10-30 m / min.

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