Graphene multifunctional fiber, preparation method therefor, and use thereof

Abstract

The present invention relates to a functional fiber, in particular to a graphene multifunctional fiber, prepared by blending a fiber main material and a graphene functional masterbatch. The weight proportion of the fiber main material is 80% to 98%, and the weight proportion of the graphene functional masterbatch is 2% to 20%. The graphene functional masterbatch comprises the following components in parts by weight: 70-90 parts of a matrix material; 1-15 parts of graphene powder; 1-15 parts of a light-absorbing and heat-insulating material; 5-15 parts of an antibacterial material; 3-15 parts of an anti-static material; 0.1-2 parts of an auxiliary agent; and 0.1-10 parts of an anti-mite material. The preparation of the graphene multifunctional fiber involves preparing a graphene multifunctional masterbatch and melt spinning. The graphene multifunctional fiber can be used for preparing wadding or plush fabric. Thus, the functionality of graphene multifunctional fiber does not decrease with use and washing, the fiber possesses permanent functional properties, and can be used as short fiber filling, spinning, or filament weaving.

Description

Graphene multifunctional fiber and preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to functional fibers, in particular to a graphene multifunctional fiber and a preparation method and application thereof. BACKGROUND

[0002] At present, with the development of society, consumers' demand for textiles is no longer just warmth and beauty, and the demand for textile functions is increasing, and the same product with multiple functions is more and more popular in the market. TECHNICAL PROBLEM

[0003] Graphene is a single-layer carbon atom material stripped from graphite, which is tightly packed into a single-layer two-dimensional honeycomb lattice structure, has excellent mechanical, optical and electrical properties, and has stable structure. Graphene material can be applied to textile products, and combined with textiles by spinning or finishing process to maximize the functions of graphene itself, such as antibacterial, anti-mite, antistatic, anti-ultraviolet and other functions. For example, Chinese patent CN108385204A discloses a graphene polyester antistatic composite fiber and a preparation method thereof, which takes polyamide fiber as the core and is coated with polyester, the polyamide fiber contains graphene, and the polyester fiber contains an antistatic agent. The composite yarn has an antistatic effect. The fiber obtained by this method has single function, and the process of composite structure fiber is complex. For example, Chinese patent CN107557900A discloses a preparation and use method of multifunctional efficient graphene functional fiber, which combines anti-mite additives, functional additives and graphene base polyester fiber together in the finishing process to form a graphene polyester composite fiber with anti-mite property and functionality. Although this method is simple in process and the fiber has multiple composite functions, the function of the fiber is prone to decline or even disappear during use. TECHNICAL SOLUTION

[0004] In view of the problem that the existing graphene-containing functional fiber decays or disappears after long-term use, the present application provides a graphene multifunctional fiber, which is prepared by blending a fiber main material and a graphene functional master batch, the weight percentage of the fiber main material is 80%~98%, and the weight percentage of the graphene functional master batch is 2%~20%; the graphene functional master batch comprises the following components in parts by weight: base material 70~90 parts, graphene powder 1~15 parts, light-absorbing heat-insulating material 1~15 parts, antibacterial material 5~15 parts, antistatic material 3~15 parts, additive 0.1~2 parts, and anti-mite material 0.1~10 parts.

[0005] Further, the fiber main material and the base material are the same high polymer material selected from one of polyester, polyamide, polypropylene or polyolefin, the master batch and the fiber material are the same material and no incompatibility occurs in the mixing process, so that the functional material is more uniformly dispersed. To ensure the spinnability, functionality and cost input of the fiber, the graphene material used in the application has less than 10 layers, the shape is sheet, the D50 particle size of the laser particle size instrument is less than 10 um, and the physical peeling method is adopted.

[0006] Specifically, the light-absorbing heat-insulating material is one or a combination of more than one of antimony-doped tin dioxide, indium tin oxide, tungsten oxide, carbon compound, carbon nanotube or cesium tungsten bronze; the antibacterial material is organic antibacterial material and / or inorganic antibacterial material, the organic antibacterial material is polyhexamethylene guanidine, the inorganic antibacterial agent is silver-based antibacterial agent, zinc-based antibacterial agent, copper-based antibacterial agent; the auxiliary agent is coupling agent and / or dispersing agent and / or crosslinking agent, the coupling agent is one of vinyltriethoxysilane coupling agent, triisostearyl titanate isopropyl coupling agent, aluminum-titanium composite coupling agent, stearate coupling agent or phosphate coupling agent, the dispersing agent is one of pentaerythritol stearate or polyethylene wax; the anti-mite material is a kind of pyrethroid.

[0007] The preparation of the graphene multifunctional fiber of the application comprises the following steps:

[0008] 1) Preparation of graphene multifunctional master batch

[0009] The components of the graphene multifunctional master batch are weighed according to the percentage by weight, respectively placed in a vacuum drying oven, dried at a vacuum degree <100 Pa and a temperature of 120-180℃ for 8-15h, and then mixed with the base material and the coupling agent and crosslinking agent after high-speed stirring, and then extruded and cut by a double-screw extruder after uniform mixing.

[0010] 2) Preparation of graphene multifunctional fiber

[0011] The fiber main material and the graphene multifunctional master batch are weighed according to the percentage by weight, and a graphene multifunctional filament or short fiber is prepared by using a melt spinning process.

[0012] In step 2), different spinning plates can be used to prepare graphene multifunctional fibers with circular, hollow, flat, triangular, trilobal, cross-shaped or double-cross-shaped cross sections. Advantages

[0013] The beneficial effects of the present application are: 1. The graphene multifunctional fiber has the functions of light absorption, heat preservation, far infrared, antibacterial, anti-mite, anti-static, high thermal conductivity and the like; 2. The functions of the graphene multifunctional fiber will not decline with the increase of use and washing times, and have permanent functional characteristics; 3. The graphene material and each functional powder have good dispersibility in the base material during the preparation of the graphene multifunctional master batch, meet the spinning requirements of short fibers and filaments, and have wide application, and can be used for short fiber filling and spinning, and can also be used for filament weaving. BRIEF DESCRIPTION OF DRAWINGS

[0014] Fig. 1 is a hollow cross-sectional structure of the graphene multifunctional fiber of Example 1.

[0015] Fig. 2 is a flat cross-sectional structure of the graphene multifunctional fiber of Example 2.

[0016] Fig. 3 is a circular cross-sectional structure of the graphene multifunctional fiber of Example 3.

[0017] Fig. 4 is a picture of the graphene multifunctional flake of Application Example 1.

[0018] Fig. 5 is a picture of the graphene multifunctional flannel fabric of Application Example 2.

[0019] Fig. 6 is a picture of the graphene multifunctional sweat cloth of Application Example 3. Embodiment of the present application

[0020] The present application is described below in combination with examples, and the examples are only used to explain the present application and are not used to limit the scope of the present application. Example 1

[0021] A graphene multifunctional polyester fiber is prepared by melt spinning after mixing 94wt% polyester chips and 6wt% graphene multifunctional master batch, and the graphene multifunctional master batch comprises the following components in parts by weight: polyester powder 80 parts, graphene material 2 parts, antimony-doped tin dioxide 1.5 parts, polyhexamethylene biguanide 5 parts, silver-based antibacterial agent 4 parts, permethrin 1 part, ethoxylated alkyl amine antistatic agent 5 parts, vinyl triethoxysilane coupling agent 0.5 parts, pentaerythritol stearate 0.5 parts, and BASF ADR4400 crosslinking agent 0.5 parts.

[0022] The preparation method comprises the following steps:

[0023] 1. Preparation of graphene multifunctional polyester master batch

[0024] The polyester powder, graphene material, antimony-doped tin dioxide, polyhexamethylene biguanide, silver-based antibacterial agent are dried in a vacuum drying oven, with the vacuum degree controlled to be less than 100 Pa and the temperature controlled to be 150 DEG C, and dried for 12 hours. The dried graphene material, antimony-doped tin dioxide, polyhexamethylene biguanide, silver-based antibacterial agent, chlorpyrifos, ethoxylated alkyl amine, pentaerythritol stearate are mixed, and then stirred at high speed. The mixture is then mixed with the polyester powder and vinyl triethoxysilane coupling agent and crosslinking agent, stirred at high speed, and then uniformly mixed. The mixture is then heated, melted, extruded, cooled and cut into particles by a double-screw extruder, to obtain the graphene multifunctional master batch.

[0025] 2. Preparation of graphene multifunctional polyester staple fiber

[0026] The polyester chip and the graphene multifunctional master batch are dried, and then controlled to enter the screw of the spinning machine by a metering pump for melting. The temperature of the first zone to the fifth zone is controlled to be 280 DEG C, 280 DEG C, 285 DEG C, 290 DEG C and 285 DEG C respectively. The melt is sprayed through the annular spinneret, dried by side blowing, bundled, wound, drawn, crimped, oiled, cut, dried and packaged, to obtain the graphene multifunctional polyester staple fiber. The staple fiber specification is 3D*64 mm, and the cross section of the staple fiber is hollow, as shown in FIG. 1. Example 2

[0027] A graphene multifunctional polyester fiber is prepared by melt spinning after mixing 95 wt% polyester chip and 5 wt% graphene multifunctional master batch. The graphene multifunctional master batch contains the following components by weight: polyester powder 79.5 parts, graphene material 1.5 parts, antimony-doped tin dioxide 2 parts, polyhexamethylene biguanide 10 parts, chlorpyrifos 0.5 parts, ethoxylated alkyl amine antistatic agent 5 parts, vinyl triethoxysilane coupling agent 0.5 parts, pentaerythritol stearate 0.5 parts, and BASF ADR4400 crosslinking agent 0.5 parts.

[0028] The preparation method comprises the following steps:

[0029] 1. Preparation of graphene multifunctional polyester master batch

[0030] The polyester powder, graphene material, antimony-doped tin dioxide and polyhexamethylene biguanide are dried in a vacuum drying oven, with the vacuum degree controlled to be less than 100 Pa and the temperature controlled to be 150 DEG C, and dried for 12 hours. The dried graphene material, antimony-doped tin dioxide and polyhexamethylene biguanide, chlorpyrifos, ethoxylated alkyl amine, pentaerythritol stearate are mixed, and then stirred at high speed. The mixture is then mixed with the polyester powder and vinyl triethoxysilane coupling agent and crosslinking agent, stirred at high speed, and then uniformly mixed. The mixture is then heated, melted, extruded, cooled and cut into particles by a double-screw extruder, to obtain the graphene multifunctional master batch.

[0031] 2. Preparation of graphene multifunctional polyester filament

[0032] The polyester chip and the graphene multifunctional master batch are dried and then controlled to enter the screw of the spinning machine through the metering pump for melting. The temperature of the first zone to the fifth zone is controlled to be 280°C, 280°C, 285°C, 290°C and 285°C respectively. The melt is sprayed through the annular spinneret. Then, the graphene multifunctional polyester filament is obtained after drying by side blowing, oiling and drafting and winding. The filament specification is 150D / 228F, the glossiness is bright, and the filament cross section is flat, as shown in FIG. 2. Example 3

[0033] A graphene multifunctional polyamide fiber is prepared by melt spinning after mixing 95wt% polyamide chips and 5wt% graphene multifunctional master batch. The graphene multifunctional master batch comprises the following components by weight: 79.7 parts of polyamide powder, 5 parts of graphene material, 0.5 parts of antimony-doped tin dioxide, 8 parts of silver-based antibacterial agent, 0.5 parts of permethrin, 5 parts of ethoxylated lauryl amine antistatic agent, 0.5 parts of vinyl triethoxysilane coupling agent, 0.5 parts of pentaerythritol stearate, and 0.3 parts of BASF ADR4400 crosslinking agent.

[0034] The preparation method comprises the following steps:

[0035] 1. Preparation of graphene multifunctional nylon master batch

[0036] The graphene material, antimony-doped tin dioxide, silver-based antibacterial agent, polyhexamethylene biguanide, permethrin, ethoxylated lauryl amine and pentaerythritol stearate are mixed and stirred at high speed. Then, the polyamide powder and the vinyl triethoxysilane coupling agent and the crosslinking agent are mixed and stirred at high speed. After uniform mixing, the mixture is heated, melted and extruded through a twin-screw extruder, cooled and granulated to prepare the graphene multifunctional master batch.

[0037] 2. Preparation of graphene multifunctional nylon filament

[0038] The polyamide chip and the graphene multifunctional master batch are dried and then controlled to enter the screw of the spinning machine through the metering pump for melting. The temperature of the first zone to the fifth zone is controlled to be 230°C, 240°C, 245°C, 260°C and 265°C respectively. The melt is sprayed through the annular spinneret. Then, the graphene multifunctional nylon filament is obtained after drying by side blowing, oiling and drafting and winding. The filament specification is 140D / 196F, the glossiness is bright, and the filament cross section is round, as shown in FIG. 3.

[0039] Comparative Example 1

[0040] A polyester staple fiber is prepared by the following method: polyester chip with a melting point of 280 DEG C is dried and then fed into a spinning machine by a metering pump to melt extrusion, the temperature of the first to fifth zones is controlled to be 280 DEG C, 285 DEG C, 285 DEG C, 290 DEG C and 285 DEG C respectively, the melt is sprayed through a round spinneret, dried by side blowing, bundled and wound, drawn, crimped, cut, oiled, cut, dried and wound to obtain the polyester staple fiber.

[0041] Comparative example 2

[0042] A polyester filament is prepared by the following method: polyester chip with a melting point of 280 DEG C is dried and then fed into a spinning machine by a metering pump to melt extrusion, the temperature of the first to fifth zones is controlled to be 280 DEG C, 285 DEG C, 285 DEG C, 290 DEG C and 285 DEG C respectively, the melt is sprayed through a round spinneret, dried by side blowing, oiled, drawn and wound to obtain the common polyester filament, the filament specification is 150D / 228F, the glossiness is bright, and the filament cross section is circular.

[0043] Comparative example 3

[0044] A nylon filament is prepared by the following method: polyamide chip with a melting point of 260 DEG C is fed into a spinning machine by a metering pump to melt extrusion, the temperature of the first to fifth zones is controlled to be 230 DEG C, 240 DEG C, 245 DEG C, 260 DEG C and 265 DEG C respectively, the melt is sprayed through a round spinneret, dried by side blowing, oiled, drawn and wound to obtain the common nylon filament, the filament specification is 140D / 196F, the glossiness is bright, and the filament cross section is circular.

[0045] I. Light absorption and heat preservation test

[0046] The graphene multifunctional polyester short fibers of Example 1 and the ordinary polyester short fibers of Comparative Example 1 were respectively filled in a 15 cm*15 cm spring shell at a filling amount of 400 g per square meter according to Japanese Standard JIS L 1926, and light absorption and heat retention tests were performed on the test sample and the comparative sample, wherein the test sample contained 30% of the short fibers of Example 1 and 70% of ordinary polyester. The flannel with a grammage of 280 g was woven according to Example 2 and Comparative Example 2, and was cut into a 15 cm*15 cm sample for light absorption and heat retention tests, wherein the test sample contained 30% of the filaments of Example 2. A thermocouple temperature sensor was placed at the center of the back of the sample, and a reflector lamp was used to irradiate the surface of the sample. The temperature change of the sample was measured after 10 minutes of light irradiation and 10 minutes of light extinction, and the temperature record is shown in Table 1. It can be seen that the temperature of Example 1 and Example 2 increased faster than that of Comparative Example 1 and Comparative Example 2 in the first 10 minutes, and the temperature of Example 1 and Example 2 decreased slower than that of Comparative Example 1 and Comparative Example 2 in the last 10 minutes, indicating that the sample containing 30% of the graphene multifunctional fibers of the application can better absorb and store the heat energy of light, and has obvious light absorption and heat retention.

[0047]

[0048] II. Far-infrared heat re-emission property test

[0049] The graphene multifunctional polyester short fibers of Example 1 and the ordinary polyester short fibers of Comparative Example 1 were respectively filled in a 10 cm*7 cm spring shell at a filling amount of 400 g per square meter according to the evaluation standard of the Japanese Far-Infrared Association, and far-infrared heat re-emission property tests were performed on the test sample and the comparative sample, wherein the test sample contained 30% of the short fibers of Example 1 and 70% of ordinary polyester. The flannel with a grammage of 280 g was woven according to Example 2 and Comparative Example 2, and was cut into a 10 cm*7 cm sample for far-infrared heat re-emission property tests, wherein the test sample contained 30% of the filaments of Example 2. The test sample and the comparative sample were placed side by side on an inclined 45° test bench, and a hot plate (90°C) was placed parallel to the front of the sample at a distance of 15 cm. The surface temperatures of the two samples were measured by an infrared imager, as shown in Table 2. The graphene multifunctional polyester fibers of Example 1 and Example 2 both have obvious far-infrared heat properties. The graphene multifunctional fibers of the application can re-emit the far-infrared rays emitted by the human body, and have better warmth retention effect.

[0050]

[0051] III. Antibacterial property test

[0052] The antibacterial properties of the fibers of Examples 1-3 and Comparative Examples 1-3 were tested according to Japanese Standard JIS L1902, and the results are shown in Table 3. It can be seen that the fibers of Examples 1-3 have very good antibacterial properties before and after washing, because the antibacterial substances are added to the fibers by melt spinning and do not decline with the increase of use and washing times. The fibers of Comparative Examples 1-3 do not have antibacterial properties.

[0053]

[0054] Four, thermal conductivity test

[0055] The thermal conductivities of the fibers of Examples 1-3 and Comparative Examples 1-3 were tested according to the hot-wire method for determining the thermal conductivity of nonmetallic solid materials in GB / T 10297-2015, using a thermal conductivity tester in an environment with a temperature of 23±3℃ and a humidity of 55±5% RH. The thermal conductivity test results are shown in Table 4. The thermal conductivity of ordinary polyester is 0.15-0.24 W / m·K, and the thermal conductivity of ordinary nylon is 0.26-0.35 W / m·K. The thermal conductivities of the graphene multifunctional polyester staple fibers and filaments of Examples 1 and 2 are significantly reduced, indicating that the addition of functional powders and the design of hollow and flat structures in the fibers result in lower thermal conductivity and better warmth retention. The graphene multifunctional nylon filament of Example 3 has a higher thermal conductivity than ordinary nylon, which is suitable for making cool products for summer use.

[0056]

[0057] Five, antistatic test

[0058] The specific resistances of the graphene multifunctional polyester staple fibers of Example 1 and ordinary polyester staple fibers of Comparative Example 1 were tested according to the test method for specific resistance of chemical fiber staple fibers in GB / T 14342-2015. The two types of fibers were washed to remove oil before testing. The results are shown in Table 5. It can be seen that the graphene multifunctional polyester staple fibers have smaller specific resistance and better antistatic properties than ordinary polyester staple fibers.

[0059]

[0060] The fibers of Example 2 and Comparative Example 2 were woven into flannel fabrics with a weight of 280g, and the filament content in the flannel fabrics was 50wt%. The half-life and friction charging voltage of the samples were tested according to JIS L 1094, and the test results are shown in Table 6. It can be seen that the flannel fabrics woven from the graphene multifunctional polyester filaments and nylon filaments of the present application have better antistatic properties than the flannel fabrics woven from ordinary polyester filaments and nylon filaments.

[0061]

[0062] Application Example 1

[0063] A graphene multifunctional batt comprising the graphene multifunctional polyester staple fiber obtained in Example 1, the content of the graphene multifunctional staple fiber being 30wt%, and the batt being formed by opening, mixing and carding. As shown in Fig. 4.

[0064] Application Example 2

[0065] A graphene multifunctional flannel comprising the graphene multifunctional polyester filament obtained in Example 2, the graphene multifunctional polyester filament being distributed on the surface of the flannel fabric, the weight ratio being 30wt%, and the flannel being formed by a warp knitting machine. As shown in Fig. 5.

[0066] Application Example 3

[0067] A graphene multifunctional sweat cloth comprising the graphene multifunctional nylon filament obtained in Example 3, the graphene multifunctional nylon filament accounting for at least 50wt% of the multifunctional sweat cloth, and the sweat cloth being formed by a weft knitting machine. As shown in Fig. 6.

[0068] VI. Anti-mite test

[0069] According to the JIS L 1920 avoidance test method, the polyester staple fiber of Comparative Example 1 was made into a batt of the same specification as Application Example 1, the polyester filament of Comparative Example 2 was made into a flannel fabric of the same specification as Application Example 2, and the nylon filament of Comparative Example 3 was made into a sweat cloth of the same specification as Application Example 3, and an anti-mite test was performed. The test results are shown in Table 7, and it can be seen that the graphene multifunctional fiber of the present application has good anti-mite effect.

[0070]

[0071] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A graphene multifunctional fiber, characterized by, The graphene multifunctional fiber is prepared by blending a fiber main body material and a graphene functional master batch, the fiber main body material accounts for 80-98% by weight, and the graphene functional master batch accounts for 2-20% by weight; the graphene functional master batch comprises the following components in parts by weight: base material 70-90 parts, graphene powder 1-15 parts, light-absorbing heat-insulating material 1-15 parts, antibacterial material 5-15 parts, antistatic material 3-15 parts, auxiliary agent 0.1-2 parts, and anti-mite material 0.1-10 parts.

2. The graphene multifunctional fiber according to claim 1, characterized in that, The fiber main body material and the base material are the same high-molecular polymer material selected from one of polyester, polyamide, polypropylene, and polyolefin.

3. The graphene multifunctional fiber according to claim 1, wherein, The light-absorbing heat-insulating material is one or a combination of more than one of antimony-doped tin dioxide, indium tin oxide, tungsten oxide, carbon compound, carbon nanotube, and cesium tungsten bronze.

4. The graphene multifunctional fiber according to claim 1, wherein, The antibacterial material is organic antibacterial material and / or inorganic antibacterial material, the organic antibacterial material is polyhexamethylene guanidine, and the inorganic antibacterial agent is silver-based antibacterial agent, zinc-based antibacterial agent, and copper-based antibacterial agent.

5. The graphene multifunctional fiber according to any one of claims 1 to 4, characterized in that, The auxiliary agent is coupling agent and / or dispersant and / or crosslinking agent, the coupling agent is one of vinyl triethoxy silane coupling agent, triisostearyl titanate isopropyl coupling agent, aluminum-titanium composite coupling agent, stearate coupling agent, or phosphate coupling agent, and the dispersant is one of pentaerythritol stearate or polyethylene wax.

6. The graphene multifunctional fiber according to claim 5, wherein, The anti-mite material is a kind of pyrethroid.

7. A method of producing a graphene multifunctional fiber as claimed in claim 6, characterized by, The method comprises the following steps: 1) preparing a graphene multifunctional master batch The components of the graphene multifunctional master batch are weighed in percentage by weight, and are placed in a vacuum drying oven, dried at a vacuum degree of less than 100 Pa and a temperature of 120-180 ℃ for 8-15 h, and then the dried graphene powder, light-absorbing heat-insulating material, antibacterial material, antistatic material, dispersant, and anti-mite material are mixed and stirred at high speed, and then mixed with the base material and coupling agent and crosslinking agent, and then extruded and cut into particles by a double-screw extruder; 2) preparing a graphene multifunctional fiber The fiber main body material and the graphene multifunctional master batch are weighed in percentage by weight, and a melt spinning process is used to prepare graphene multifunctional filaments or short fibers.

8. The preparation method according to claim 7, characterized in that, The cross section of the obtained graphene multifunctional fiber is circular, hollow, flat, triangular, trilobal, cross-shaped, or double-cross-shaped.

9. A graphene multifunctional floe, characterized by, The graphene multifunctional fiber comprises the graphene multifunctional short fiber with a hollow cross section according to claim 8.

10. A graphene multifunctional plush fabric, characterized by, The graphene multifunctional fiber comprises the graphene multifunctional long filament with a triangular or flat cross section according to claim 8.

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