A heat-generating temperature-regulating fiber and a method for preparing the same

Abstract

The application relates to the technical field of fibers, and discloses a heating temperature-regulating fiber and a preparation method thereof. A light-heat material zirconium dioxide composite material is prepared, the light-heat material zirconium dioxide composite material is introduced into a phase change material as a light-heat absorbing and heating material, a light-heat storage additive with good heat resistance is prepared, the light-heat storage additive is added into polypropylene chips together with a compatible agent maleic anhydride grafted polypropylene to be melt spun, the prepared fiber has light-heat absorbing and heating and energy storage temperature-regulating performances, and because the maleic anhydride grafted polypropylene is introduced, carboxyl groups can react with epoxy groups of the light-heat storage additive under a melting condition, the maleic anhydride grafted polypropylene serves as a compatible agent to improve the compatibility among components, and the introduction of the carboxyl groups improves the moisture absorption performance of the fiber.

Description

A heating and temperature-regulating fiber and its preparation method Technical Field

[0001] This invention relates to the field of fiber technology, specifically to a heat-generating and temperature-regulating fiber and its preparation method. Background Technology

[0002] Energy storage and temperature regulation fiber is a smart fiber that can regulate temperature by absorbing, storing, and releasing heat energy through phase change materials according to changes in ambient temperature. However, traditional energy storage and temperature regulation fibers lack the ability to absorb and convert sunlight, thus failing to achieve efficient utilization of solar energy.

[0003] Photothermal conversion energy storage temperature regulation fiber, by introducing photothermal conversion materials, can actively absorb solar radiation and convert it into heat energy. This not only provides an additional, active heat source for the phase change energy storage process and broadens the application scenarios of temperature regulation fiber, but also realizes the dual functions of photothermal conversion and heat energy storage, improving the overall energy utilization efficiency and temperature regulation initiative of the fiber.

[0004] However, existing photothermal conversion energy storage and temperature regulation fibers still face several challenges in their development. First, the poor compatibility between photothermal materials and the polymer matrix makes them prone to agglomeration or phase separation during processing, affecting the mechanical properties and stability of the fibers. Second, the insufficient heat resistance of phase change materials under the high-temperature conditions of melt spinning affects the spinning effect of the fibers. Therefore, it is necessary to prepare a fiber that combines excellent photothermal conversion efficiency with energy storage and temperature regulation capabilities to improve the photothermal and temperature regulation properties of the fibers. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a heat-generating and temperature-regulating fiber and its preparation method. By preparing a graphene-supported zirconium dioxide composite material as a photothermal material, it is introduced into a phase change material as a light-absorbing and heat-generating material to form a photothermal heat storage additive with good heat resistance. This additive is then added together with maleic anhydride-grafted polypropylene as a compatibilizer and melt-spun into polypropylene chips. The resulting fiber has both light-absorbing and heat-generating properties and energy storage and temperature regulation properties. Furthermore, due to the introduction of maleic anhydride-grafted polypropylene, its carboxyl groups can react with the epoxy groups of the photothermal heat storage additive under molten conditions, acting as a compatibilizer to improve the compatibility between the components. At the same time, the introduction of carboxyl groups also improves the moisture absorption properties of the fiber.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a heat-generating and temperature-regulating fiber includes the following steps:

[0008] Step (1): Mix graphene oxide and water, and disperse by ultrasonication to obtain graphene oxide dispersion; add graphene oxide dispersion to zirconium oxychloride aqueous solution, mix by ultrasonication until uniform, react, cool after reaction, wash, freeze dry to obtain graphene-supported zirconium dioxide composite material.

[0009] The graphene-supported zirconium dioxide composite material and toluene were mixed and ultrasonically dispersed. KH570 was added and ultrasonic dispersion was continued. After the reaction was completed, the mixture was centrifuged, washed, and dried to obtain the KH570 modified graphene-supported zirconium dioxide composite material.

[0010] Step (2): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, and azobisisobutyronitrile are mixed and reacted. After the reaction is completed, paraffin is added to obtain the oil phase.

[0011] KH570 modified graphene-supported zirconium dioxide composite material was mixed with water and ultrasonically dispersed to obtain an aqueous phase;

[0012] The oil phase and the water phase were mixed, ethylene glycol dimethacrylate was added, and the reaction continued. After the reaction was completed, the mixture was filtered, washed, and dried to obtain a photothermal heat storage additive.

[0013] Step (3): Mix polypropylene chips, maleic anhydride, and benzoyl peroxide, melt and react them. After the reaction is complete, extrude and granulate to obtain maleic anhydride-grafted polypropylene.

[0014] Photothermal heat storage additives, maleic anhydride-grafted polypropylene, and polypropylene chips are melt-blended, extruded and pelletized, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0015] Preferably, in step (1), the mass ratio of graphene oxide to zirconium oxychloride is 2-5:5-8; the hydrothermal reaction conditions are: hydrothermal reaction at a pH of 8-10 and a temperature of 160-200℃ for 0.5-4 hours.

[0016] Preferably, in step (1), the mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 is 2:15-25:0.1-0.2; the reaction conditions are: reaction at 70-80℃ for 30-60 min.

[0017] Preferably, in step (2), the mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 50-60:80-85:8-12:30-35:4-5:200-220; the reaction conditions are: stirring at 55-65℃ for 20-30 min.

[0018] Preferably, in step (2): the mass ratio of KH570 modified graphene-supported zirconium dioxide composite material to water is 30-40:160-180; the mass ratio of mixed oil phase, water phase, and ethylene glycol dimethacrylate is 80:100:1.3-1.5; the reaction conditions are: shear emulsification at 15000-20000 rpm and 50-60℃ for 2-5 minutes, then heating to 70-80℃ and continuing the reaction in a nitrogen atmosphere for 4-6 hours.

[0019] Preferably, in step (3): the mass ratio of polypropylene chips, maleic anhydride and benzoyl peroxide is 100:3:0.6-0.8; the melting reaction conditions are: melting reaction in a twin-screw extruder for 5-10 minutes, with temperatures of 180-190℃ in zone 1, 190-200℃ in zones 2 and 3, and 180-190℃ in zone 4.

[0020] Preferably, in step (3): the mass ratio of photothermal heat storage additive, maleic anhydride grafted polypropylene, and polypropylene chips is 8-12:40:48-52; the melt spinning conditions are: spinning temperature is 160-170℃ in zone 1, 180-190℃ in zone 2, 190-200℃ in zone 3, and 180-190℃ in zone 4; spinning speed is 400-600m / min; drawing temperature is 130℃, and the drawing ratio is 3-5 times.

[0021] Preferably, a heat-regulating fiber is prepared using the heat-regulating fiber preparation method described above.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] This invention prepares a graphene-supported zirconium dioxide composite material for photothermal applications. This composite material is then introduced into a phase change material as a light-absorbing and heat-generating material to create a photothermal heat storage additive with good heat resistance. This additive is then added to polypropylene chips along with a maleic anhydride-grafted polypropylene compatibilizer for melt spinning. The resulting fiber possesses both light-absorbing and heat-generating properties as well as energy storage and temperature regulation capabilities. Furthermore, due to the introduction of maleic anhydride-grafted polypropylene, its carboxyl groups can react with the epoxy groups of the photothermal heat storage additive under molten conditions, acting as a compatibilizer to improve the compatibility between the components. At the same time, the introduction of carboxyl groups also improves the moisture absorption properties of the fiber.

[0024] In this invention, a hydrothermal method is used to composite zirconium dioxide with graphene oxide to produce a graphene-supported zirconium dioxide composite material with higher far-infrared emissivity. After grafting carbon-carbon double bonds onto the surface of KH570, this composite material is copolymerized with styrene, methyl methacrylate, butyl acrylate, and glycidyl methacrylate as the polymer shell, and paraffin wax as the phase change material core layer. A photothermal heat storage additive is prepared using the Pickering emulsion method. The introduction of styrene monomer and KH570-modified graphene-supported zirconium dioxide composite material synergistically improves the heat resistance of the material and enhances its stability during melt spinning. The introduction of glycidyl methacrylate endows the photothermal heat storage additive with epoxy functional groups, which can react with the carboxyl groups in maleic anhydride-grafted polypropylene under molten conditions to form chemical bonds, thereby improving the dispersibility and compatibility of the photothermal heat storage additive in polypropylene fibers. Attached Figure Description

[0025] Figure 1 is a bar chart of the moisture regain of the heat-regulating fibers prepared in the embodiments and comparative examples of the present invention during performance testing.

[0026] Figure 2 is a line graph of the far-infrared emissivity of the heat-regulating fibers prepared in the embodiments and comparative examples of the present invention during performance testing. Detailed Implementation

[0027] The present invention will be further illustrated below through specific embodiments. The following embodiments are specific implementations of the present invention, but the implementation of the present invention is not limited to the following embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and are included within the protection scope of the present invention.

[0028] Example 1

[0029] This embodiment discloses a method for preparing a heat-generating and temperature-regulating fiber, including the following steps:

[0030] Step (1): Mix graphene oxide and water at a mass ratio of 0.1:100 and ultrasonically disperse for 1 h to obtain a graphene oxide dispersion; add the graphene oxide dispersion to a 0.5 wt% zirconium oxychloride aqueous solution, ultrasonically mix for 30 min, and after mixing evenly, add 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, and perform hydrothermal reaction at 200℃ for 0.5 h. After the reaction is completed, cool to room temperature, wash, and freeze dry to obtain a graphene-supported zirconium dioxide composite material.

[0031] The mass ratio of graphene oxide to zirconium oxychloride is 2:8.

[0032] The graphene-supported zirconium dioxide composite material and toluene were mixed and ultrasonically dispersed for 40 min. KH570 was added and ultrasonic dispersion was continued for 10 min. The mixture was reacted at 80℃ for 30 min. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol, and dried at 60℃ for 12 h to obtain the KH570 modified graphene-supported zirconium dioxide composite material.

[0033] The mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 is 2:15:0.1.

[0034] Step (2): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate and azobisisobutyronitrile are mixed and stirred at 55°C for 30 min. After the reaction is completed, melted phase change paraffin is added to obtain the oil phase.

[0035] The mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 55:85:11:35:4.8:210.

[0036] KH570 modified graphene-supported zirconium dioxide composite material and water were mixed and ultrasonically dispersed at a mass ratio of 36:160 to obtain an aqueous phase;

[0037] The oil phase and water phase were mixed, and ethylene glycol dimethacrylate was added. The mixture was sheared and emulsified at 20,000 rpm and 55°C for 3 min. The temperature was then raised to 75°C and the reaction was continued for 6 h in a nitrogen atmosphere. After the reaction was completed, the precipitate was filtered, washed with water, and dried at 60°C for 12 h to obtain a photothermal heat storage additive.

[0038] The mass ratio of the oil phase, aqueous phase, and ethylene glycol dimethacrylate is 80:100:1.3.

[0039] Step (3): Mix polypropylene chips, maleic anhydride, and benzoyl peroxide in a mass ratio of 100:3:0.6 and melt-react in a twin-screw extruder for 10 min at temperatures of 185°C in zone 1, 190°C in zones 2 to 3, and 180°C in zone 4. After the reaction is complete, extrude and pelletize to obtain maleic anhydride-grafted polypropylene.

[0040] Photothermal heat storage additive, maleic anhydride-grafted polypropylene, and polypropylene chips are melt-blended at a mass ratio of 8:40:52, extruded and pelletized, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0041] The melt spinning conditions are as follows: spinning temperature is 165℃ in zone 1, 180℃ in zone 2, 190℃ in zone 3, and 185℃ in zone 4; spinning speed is 500m / min; drawing temperature is 130℃, and the drawing ratio is 3.

[0042] Example 2

[0043] This embodiment discloses a method for preparing a heat-generating and temperature-regulating fiber, including the following steps:

[0044] Step (1): Mix graphene oxide and water at a mass ratio of 0.1:100 and ultrasonically disperse for 1 h to obtain a graphene oxide dispersion; add the graphene oxide dispersion to a 0.5 wt% zirconium oxychloride aqueous solution, ultrasonically mix for 30 min, and after mixing evenly, add 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, and perform hydrothermal reaction at 200℃ for 0.5 h. After the reaction is completed, cool to room temperature, wash, and freeze dry to obtain a graphene-supported zirconium dioxide composite material.

[0045] The mass ratio of graphene oxide to zirconium oxychloride is 2:8.

[0046] The graphene-supported zirconium dioxide composite material and toluene were mixed and ultrasonically dispersed for 40 min. KH570 was added and ultrasonic dispersion was continued for 10 min. The mixture was reacted at 80℃ for 30 min. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol, and dried at 60℃ for 12 h to obtain the KH570 modified graphene-supported zirconium dioxide composite material.

[0047] The mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 is 2:20:0.15.

[0048] Step (2): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate and azobisisobutyronitrile are mixed and stirred at 55°C for 30 min. After the reaction is completed, melted phase change paraffin is added to obtain the oil phase.

[0049] The mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 55:85:11:35:4.8:210.

[0050] KH570 modified graphene-supported zirconium dioxide composite material and water were mixed and ultrasonically dispersed at a mass ratio of 36:160 to obtain an aqueous phase;

[0051] The oil phase and water phase were mixed, and ethylene glycol dimethacrylate was added. The mixture was sheared and emulsified at 20,000 rpm and 55°C for 3 min. The temperature was then raised to 75°C and the reaction was continued for 6 h in a nitrogen atmosphere. After the reaction was completed, the precipitate was filtered, washed with water, and dried at 60°C for 12 h to obtain a photothermal heat storage additive.

[0052] The mass ratio of the oil phase, aqueous phase, and ethylene glycol dimethacrylate is 80:100:1.35.

[0053] Step (3): Mix polypropylene chips, maleic anhydride, and benzoyl peroxide in a mass ratio of 100:3:0.65 and melt-react in a twin-screw extruder for 10 min at temperatures of 185°C in zone 1, 190°C in zones 2 to 3, and 180°C in zone 4. After the reaction is complete, extrude and pelletize to obtain maleic anhydride-grafted polypropylene.

[0054] Photothermal heat storage additive, maleic anhydride-grafted polypropylene, and polypropylene chips are melt-blended in a mass ratio of 9:40:51, extruded and pelletized, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0055] The melt spinning conditions are as follows: spinning temperature is 165℃ in zone 1, 180℃ in zone 2, 190℃ in zone 3, and 185℃ in zone 4; spinning speed is 500m / min; drawing temperature is 130℃, and the drawing ratio is 3.

[0056] Example 3

[0057] This embodiment discloses a method for preparing a heat-generating and temperature-regulating fiber, including the following steps:

[0058] Step (1): Mix graphene oxide and water at a mass ratio of 0.1:100 and ultrasonically disperse for 1 h to obtain a graphene oxide dispersion; add the graphene oxide dispersion to a 0.5 wt% zirconium oxychloride aqueous solution, ultrasonically mix for 30 min, and after mixing evenly, add 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, and perform hydrothermal reaction at 200℃ for 0.5 h. After the reaction is completed, cool to room temperature, wash, and freeze dry to obtain a graphene-supported zirconium dioxide composite material.

[0059] The mass ratio of graphene oxide to zirconium oxychloride is 2:8.

[0060] The graphene-supported zirconium dioxide composite material and toluene were mixed and ultrasonically dispersed for 40 min. KH570 was added and ultrasonic dispersion was continued for 10 min. The mixture was reacted at 80℃ for 30 min. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol, and dried at 60℃ for 12 h to obtain the KH570 modified graphene-supported zirconium dioxide composite material.

[0061] The mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 is 2:20:0.15.

[0062] Step (2): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate and azobisisobutyronitrile are mixed and stirred at 55°C for 30 min. After the reaction is completed, melted phase change paraffin is added to obtain the oil phase.

[0063] The mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 55:85:11:35:4.8:210.

[0064] KH570 modified graphene-supported zirconium dioxide composite material and water were mixed and ultrasonically dispersed at a mass ratio of 36:160 to obtain an aqueous phase;

[0065] The oil phase and water phase were mixed, and ethylene glycol dimethacrylate was added. The mixture was sheared and emulsified at 20,000 rpm and 55°C for 3 min. The temperature was then raised to 75°C and the reaction was continued for 6 h in a nitrogen atmosphere. After the reaction was completed, the precipitate was filtered, washed with water, and dried at 60°C for 12 h to obtain a photothermal heat storage additive.

[0066] The mass ratio of the oil phase, aqueous phase, and ethylene glycol dimethacrylate is 80:100:1.4.

[0067] Step (3): Mix polypropylene chips, maleic anhydride, and benzoyl peroxide in a mass ratio of 100:3:0.7 and melt-react in a twin-screw extruder for 10 min at temperatures of 185°C in zone 1, 190°C in zones 2 to 3, and 180°C in zone 4. After the reaction is complete, extrude and pelletize to obtain maleic anhydride-grafted polypropylene.

[0068] Photothermal heat storage additive, maleic anhydride-grafted polypropylene, and polypropylene chips are melt-blended in a mass ratio of 10:40:50, extruded and pelletized, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0069] The melt spinning conditions are as follows: spinning temperature is 165℃ in zone 1, 180℃ in zone 2, 190℃ in zone 3, and 185℃ in zone 4; spinning speed is 500m / min; drawing temperature is 130℃, and the drawing ratio is 3.

[0070] Example 4

[0071] This embodiment discloses a method for preparing a heat-generating and temperature-regulating fiber, including the following steps:

[0072] Step (1): Mix graphene oxide and water at a mass ratio of 0.1:100 and ultrasonically disperse for 1 h to obtain a graphene oxide dispersion; add the graphene oxide dispersion to a 0.5 wt% zirconium oxychloride aqueous solution, ultrasonically mix for 30 min, and after mixing evenly, add 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, and perform hydrothermal reaction at 200℃ for 0.5 h. After the reaction is completed, cool to room temperature, wash, and freeze dry to obtain a graphene-supported zirconium dioxide composite material.

[0073] The mass ratio of graphene oxide to zirconium oxychloride is 2:8.

[0074] The graphene-supported zirconium dioxide composite material and toluene were mixed and ultrasonically dispersed for 40 min. KH570 was added and ultrasonic dispersion was continued for 10 min. The mixture was reacted at 80℃ for 30 min. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol, and dried at 60℃ for 12 h to obtain the KH570 modified graphene-supported zirconium dioxide composite material.

[0075] The mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 is 2:20:0.15.

[0076] Step (2): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate and azobisisobutyronitrile are mixed and stirred at 55°C for 30 min. After the reaction is completed, melted phase change paraffin is added to obtain the oil phase.

[0077] The mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 55:85:11:35:4.8:210.

[0078] KH570 modified graphene-supported zirconium dioxide composite material and water were mixed and ultrasonically dispersed at a mass ratio of 36:160 to obtain an aqueous phase;

[0079] The oil phase and water phase were mixed, and ethylene glycol dimethacrylate was added. The mixture was sheared and emulsified at 20,000 rpm and 55°C for 3 min. The temperature was then raised to 75°C and the reaction was continued for 6 h in a nitrogen atmosphere. After the reaction was completed, the precipitate was filtered, washed with water, and dried at 60°C for 12 h to obtain a photothermal heat storage additive.

[0080] The mass ratio of the oil phase, aqueous phase, and ethylene glycol dimethacrylate is 80:100:1.45.

[0081] Step (3): Mix polypropylene chips, maleic anhydride, and benzoyl peroxide in a mass ratio of 100:3:0.75 and melt-react in a twin-screw extruder for 10 min at temperatures of 185°C in zone 1, 190°C in zones 2 to 3, and 180°C in zone 4. After the reaction is complete, extrude and pelletize to obtain maleic anhydride-grafted polypropylene.

[0082] Photothermal heat storage additive, maleic anhydride-grafted polypropylene, and polypropylene chips are melt-blended in a mass ratio of 11:40:49, extruded and pelletized, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0083] The melt spinning conditions are as follows: spinning temperature is 165℃ in zone 1, 180℃ in zone 2, 190℃ in zone 3, and 185℃ in zone 4; spinning speed is 500m / min; drawing temperature is 130℃, and the drawing ratio is 3.

[0084] Example 5

[0085] This embodiment discloses a method for preparing a heat-generating and temperature-regulating fiber, including the following steps:

[0086] Step (1): Mix graphene oxide and water at a mass ratio of 0.1:100 and ultrasonically disperse for 1 h to obtain a graphene oxide dispersion; add the graphene oxide dispersion to a 0.5 wt% zirconium oxychloride aqueous solution, ultrasonically mix for 30 min, and after mixing evenly, add 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, and perform hydrothermal reaction at 200℃ for 0.5 h. After the reaction is completed, cool to room temperature, wash, and freeze dry to obtain a graphene-supported zirconium dioxide composite material.

[0087] The mass ratio of graphene oxide to zirconium oxychloride is 2:8.

[0088] The graphene-supported zirconium dioxide composite material and toluene were mixed and ultrasonically dispersed for 40 min. KH570 was added and ultrasonic dispersion was continued for 10 min. The mixture was reacted at 80℃ for 30 min. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol, and dried at 60℃ for 12 h to obtain the KH570 modified graphene-supported zirconium dioxide composite material.

[0089] The mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 is 2:25:0.2.

[0090] Step (2): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate and azobisisobutyronitrile are mixed and stirred at 55°C for 30 min. After the reaction is completed, melted phase change paraffin is added to obtain the oil phase.

[0091] The mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 55:85:11:35:4.8:210.

[0092] KH570 modified graphene-supported zirconium dioxide composite material and water were mixed and ultrasonically dispersed at a mass ratio of 36:160 to obtain an aqueous phase;

[0093] The oil phase and water phase were mixed, and ethylene glycol dimethacrylate was added. The mixture was sheared and emulsified at 20,000 rpm and 55°C for 3 min. The temperature was then raised to 75°C and the reaction was continued for 6 h in a nitrogen atmosphere. After the reaction was completed, the precipitate was filtered, washed with water, and dried at 60°C for 12 h to obtain a photothermal heat storage additive.

[0094] The mass ratio of the oil phase, aqueous phase, and ethylene glycol dimethacrylate is 80:100:1.5.

[0095] Step (3): Mix polypropylene chips, maleic anhydride, and benzoyl peroxide in a mass ratio of 100:3:0.8 and melt-react in a twin-screw extruder for 10 min at temperatures of 185°C in zone 1, 190°C in zones 2 to 3, and 180°C in zone 4. After the reaction is complete, extrude and pelletize to obtain maleic anhydride-grafted polypropylene.

[0096] Photothermal heat storage additive, maleic anhydride-grafted polypropylene, and polypropylene chips are melt-blended in a mass ratio of 12:40:48, extruded and pelletized, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0097] The melt spinning conditions are as follows: spinning temperature is 165℃ in zone 1, 180℃ in zone 2, 190℃ in zone 3, and 185℃ in zone 4; spinning speed is 500m / min; drawing temperature is 130℃, and the drawing ratio is 3.

[0098] Comparative Example 1

[0099] This comparative example discloses a method for preparing a heat-generating and temperature-regulating fiber, comprising the following steps:

[0100] Step (1): Mix graphene oxide and water at a mass ratio of 0.1:100 and ultrasonically disperse for 1 h to obtain a graphene oxide dispersion; add the graphene oxide dispersion to a 0.5 wt% zirconium oxychloride aqueous solution, ultrasonically mix for 30 min, and after mixing evenly, add 1 mol / L sodium hydroxide aqueous solution to adjust the pH value to 10, and perform hydrothermal reaction at 200℃ for 0.5 h. After the reaction is completed, cool to room temperature, wash, and freeze dry to obtain a graphene-supported zirconium dioxide composite material.

[0101] The mass ratio of graphene oxide to zirconium oxychloride is 2:8.

[0102] The graphene-supported zirconium dioxide composite material and toluene were mixed and ultrasonically dispersed for 40 min. KH570 was added and ultrasonic dispersion was continued for 10 min. The mixture was reacted at 80℃ for 30 min. After the reaction was completed, the precipitate was collected by centrifugation, washed with ethanol, and dried at 60℃ for 12 h to obtain the KH570 modified graphene-supported zirconium dioxide composite material.

[0103] The mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 is 2:15:0.1.

[0104] Step (2): Styrene, methyl methacrylate, butyl acrylate and azobisisobutyronitrile are mixed and stirred at 55°C for 30 min. After the reaction is completed, melted phase change paraffin is added to obtain the oil phase.

[0105] The mass ratio of styrene, methyl methacrylate, butyl acrylate, azobisisobutyronitrile, and phase change paraffin is 55:85:11:4.8:210.

[0106] KH570 modified graphene-supported zirconium dioxide composite material and water were mixed and ultrasonically dispersed at a mass ratio of 36:160 to obtain an aqueous phase;

[0107] The oil phase and water phase were mixed, and ethylene glycol dimethacrylate was added. The mixture was sheared and emulsified at 20,000 rpm and 55°C for 3 min. The temperature was then raised to 75°C and the reaction was continued for 6 h in a nitrogen atmosphere. After the reaction was completed, the precipitate was filtered, washed with water, and dried at 60°C for 12 h to obtain a photothermal heat storage additive.

[0108] The mass ratio of the oil phase, aqueous phase, and ethylene glycol dimethacrylate is 80:100:1.3.

[0109] Step (3): The photothermal heat storage additive and polypropylene chips are melt-blended at a mass ratio of 8:92, extruded and granulated, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0110] The melt spinning conditions are as follows: spinning temperature is 165℃ in zone 1, 180℃ in zone 2, 190℃ in zone 3, and 185℃ in zone 4; spinning speed is 500m / min; drawing temperature is 130℃, and the drawing ratio is 3.

[0111] Comparative Example 2

[0112] This comparative example discloses a method for preparing a heat-generating and temperature-regulating fiber, comprising the following steps:

[0113] Step (1): Mix graphene oxide and toluene, ultrasonically disperse for 40 min, add KH570, continue ultrasonic dispersion for 10 min, react at 80℃ for 30 min, after the reaction is completed, centrifuge to collect the precipitate, wash with ethanol, and dry at 60℃ for 12 h to obtain KH570 modified graphene.

[0114] The mass ratio of graphene oxide, toluene, and KH570 is 2:15:0.1.

[0115] Step (2): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate and azobisisobutyronitrile are mixed and stirred at 55°C for 30 min. After the reaction is completed, melted phase change paraffin is added to obtain the oil phase.

[0116] The mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 55:85:11:35:4.8:210.

[0117] KH570 modified graphene and water were mixed and ultrasonically dispersed at a mass ratio of 36:160 to obtain an aqueous phase;

[0118] The oil phase and water phase were mixed, and ethylene glycol dimethacrylate was added. The mixture was sheared and emulsified at 20,000 rpm and 55°C for 3 min. The temperature was then raised to 75°C and the reaction was continued for 6 h in a nitrogen atmosphere. After the reaction was completed, the precipitate was filtered, washed with water, and dried at 60°C for 12 h to obtain a photothermal heat storage additive.

[0119] The mass ratio of the oil phase, aqueous phase, and ethylene glycol dimethacrylate is 80:100:1.3.

[0120] Step (3): Mix polypropylene chips, maleic anhydride, and benzoyl peroxide in a mass ratio of 100:3:0.6 and melt-react in a twin-screw extruder for 10 min at temperatures of 185°C in zone 1, 190°C in zones 2 to 3, and 180°C in zone 4. After the reaction is complete, extrude and pelletize to obtain maleic anhydride-grafted polypropylene.

[0121] Photothermal heat storage additive, maleic anhydride-grafted polypropylene, and polypropylene chips are melt-blended at a mass ratio of 8:40:52, extruded and pelletized, melt-spun in a twin-screw spinning machine, cooled and stretched to obtain heat-generating and temperature-regulating fibers.

[0122] The melt spinning conditions are as follows: spinning temperature is 165℃ in zone 1, 180℃ in zone 2, 190℃ in zone 3, and 185℃ in zone 4; spinning speed is 500m / min; drawing temperature is 130℃, and the drawing ratio is 3.

[0123] In the above examples and comparative examples: KH570 is γ-methacryloyloxypropyltrimethoxysilane; the polypropylene chips are fiber-grade polypropylene chips, item number Liaoyang Petrochemical 71735; the phase change temperature of the phase change paraffin is about 30°C.

[0124] Test case

[0125] The performance of the heat-regulating fibers prepared in Examples 1-5 and Comparative Examples 1-2 was tested. Specific test results are shown in Table 1.

[0126] Table 1

[0127]

[0128] Table 1 shows the testing of each indicator according to the following standards: Moisture regain was tested according to GB / T6503 "Test Method for Moisture Regain of Chemical Fibers"; Far-infrared heating rate was tested using a dual-frequency infrared emission tester with a wavelength range of 8-14 μm; Elongation at break was determined according to GB / T14344 "Test Method for Tensile Properties of Chemical Fiber Filaments". Enthalpy was determined according to GB / T19466.3 "Differential Scanning Calorimetry (DSC) for Plastics - Part 3: Determination of Melting and Crystallization Temperatures and Enthalpy", using a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating / cooling rate of 10 °C / min for Examples 1-5 and Comparative Examples 1-2.

[0129] As can be seen from the test results in Table 1, the fiber prepared by this invention has both light absorption and heat generation properties as well as energy storage and temperature regulation properties, and the moisture absorption properties of the fiber are also improved. This is because the photothermal heat storage additive contains graphene-supported zirconium dioxide composite material and paraffin wax phase change material, which endow the material with light absorption and heat generation properties and phase change properties; the compatibilizer maleic anhydride-grafted polypropylene used in the fiber introduces carboxyl groups, which also improves the moisture absorption properties of the fiber.

[0130] In Comparative Example 1, no maleic anhydride-grafted polypropylene was added, and no glycidyl methacrylate was added during the preparation of the photothermal heat storage additive. The compatibility of the components in the fiber was reduced, which affected the mechanical properties. Due to the lack of carboxyl groups in maleic anhydride-grafted polypropylene, the moisture absorption of the fiber was reduced. Therefore, the mechanical properties and moisture absorption of Comparative Example 1 were not as good as those of the Example.

[0131] In Comparative Example 2, the graphene oxide did not contain zirconium dioxide, and the lack of zirconium dioxide's effect on improving the far-infrared emissivity of the material resulted in Comparative Example 2 having inferior photothermal performance compared to the Example.

[0132] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing a heat-generating and temperature-regulating fiber, characterized in that, Includes the following steps: Step (1): Styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, and azobisisobutyronitrile are mixed and reacted. After the reaction is completed, paraffin is added to obtain an oil phase. KH570 modified graphene-supported zirconium dioxide composite material and water are mixed and ultrasonically dispersed to obtain an aqueous phase. The oil phase and aqueous phase are mixed, ethylene glycol dimethacrylate is added, and the reaction continues. After the reaction is completed, the mixture is filtered, washed, and dried to obtain a photothermal heat storage additive. The KH570 modified graphene-supported zirconium dioxide composite material is prepared by the following steps: S1: Graphene oxide and water are mixed and ultrasonically dispersed to obtain a graphene oxide dispersion. Add the graphene oxide dispersion to the zirconium oxychloride aqueous solution, mix evenly by ultrasonication, react, cool, wash, freeze dry to obtain graphene-supported zirconium dioxide composite material; S2, mix the graphene-supported zirconium dioxide composite material and toluene, disperse by ultrasonication, add KH570, continue to disperse by ultrasonication, react, centrifuge, wash, dry to obtain KH570 modified graphene-supported zirconium dioxide composite material; Step (2), melt blend the photothermal heat storage additive, maleic anhydride grafted polypropylene, and polypropylene chips, extrude and granulate, melt spin in a twin-screw spinning machine, cool and stretch to obtain heat-generating and temperature-regulating fibers.

2. The method for preparing a heat-generating and temperature-regulating fiber according to claim 1, characterized in that, In step (1), when preparing the KH570 modified graphene-supported zirconium dioxide composite material, the mass ratio of graphene oxide to zirconium oxychloride in S1 is 2-5:5-8; the hydrothermal reaction conditions are: hydrothermal reaction at pH 8-10 and temperature of 160-200℃ for 0.5-4h.

3. The method for preparing a heat-generating and temperature-regulating fiber according to claim 1, characterized in that, In step (1), when preparing the KH570 modified graphene-supported zirconium dioxide composite material, the mass ratio of graphene-supported zirconium dioxide composite material, toluene, and KH570 in S2 is 2:15-25:0.1-0.2; the reaction conditions are: reacting at 70-80℃ for 30-60 min.

4. The method for preparing a heat-generating and temperature-regulating fiber according to claim 1, characterized in that, In step (1), the mass ratio of styrene, methyl methacrylate, butyl acrylate, glycidyl methacrylate, azobisisobutyronitrile, and phase change paraffin is 50-60:80-85:8-12:30-35:4-5:200-220; the reaction conditions are: stirring at 55-65℃ for 20-30 min.

5. The method for preparing a heat-generating and temperature-regulating fiber according to claim 1, characterized in that, In step (1): the mass ratio of KH570 modified graphene-supported zirconium dioxide composite material to water is 30-40:160-180; the mass ratio of mixed oil phase, water phase, and ethylene glycol dimethacrylate is 80:100:1.3-1.5; the reaction conditions are: shear emulsification at 15000-20000 rpm and 50-60℃ for 2-5 minutes, then heating to 70-80℃ and continuing the reaction in a nitrogen atmosphere for 4-6 hours.

6. The method for preparing a heat-generating and temperature-regulating fiber according to claim 1, characterized in that, The maleic anhydride-grafted polypropylene in step (2) is prepared by the following steps: mixing polypropylene chips, maleic anhydride, and benzoyl peroxide, melting and reacting them, and after the reaction is completed, extruding and pelletizing them to obtain maleic anhydride-grafted polypropylene; wherein, the mass ratio of polypropylene chips, maleic anhydride, and benzoyl peroxide is 100:3:0.6-0.8; the melting reaction conditions are: melting reaction in a twin-screw extruder for 5-10 minutes, with temperatures of 180-190℃ in zone 1, 190-200℃ in zones 2 and 3, and 180-190℃ in zone 4.

7. The method for preparing a heat-generating and temperature-regulating fiber according to claim 1, characterized in that, In step (2), the mass ratio of photothermal heat storage additive, maleic anhydride grafted polypropylene, and polypropylene chips is 8-12:40:48-52.

8. The method for preparing a heat-generating and temperature-regulating fiber according to claim 1, characterized in that, In step (2), the melt spinning conditions are as follows: the spinning temperature is 160-170℃ in zone 1, 180-190℃ in zone 2, 190-200℃ in zone 3, and 180-190℃ in zone 4; the spinning speed is 400-600m / min; the drawing temperature is 130℃, and the drawing ratio is 3-5 times.

9. A heat-regulating fiber prepared by the method for preparing heat-regulating fibers as described in any one of claims 1-8.

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