Multifunctional graphene-based PCM microcapsule fabric with intelligent temperature adjustment, antibiosis and deodorization functions as well as processing method and application of multifunctional graphene-based PCM microcapsule fabric

Abstract

The invention relates to an intelligent temperature-adjusting, antibacterial and deodorant multifunctional graphene-based PCM microcapsule fabric as well as a processing method and application thereof. A microcapsule and regenerated keratin powder are embedded in a pretreated wool fabric by polyurethane, wherein the microcapsule takes a phase change material (PCM) and graphene as core materials and takes epoxy resin as a shell material. Belongs to the technical field of functional textile processing methods. According to the invention, the polyurethane embedded graphene-based PCM microcapsule, regenerated keratin powder and anti-mite finishing agent coated fabric is adopted, so that the properties of intelligent temperature regulation, antibiosis, deodorization and the like are realized, the temperature and humidity of the fabric can be intelligently regulated according to the change of the surrounding environment, the comfort requirement of a human body is met, and the fabric can be applied to the fields of bedding articles, automobile linings, medical bandages and the like.

Description

Technical Field

[0001] The invention relates to a processing method of a microcapsule functional fabric, and in particular to a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties, a processing method and a use thereof. Background Art

[0002] In the human body-clothing-environment system, clothing plays a role in regulating the thermal balance of the human body, and the warmth of textiles is a direct factor affecting the temperature of the human body. The climate inside the clothing is between the human skin and the innermost layer of the clothing. When the climate inside the clothing is 32°C, the relative humidity is 50%, and the air flow velocity is 25cm / s, the human body feels most comfortable, so this climate is also called the standard clothing climate. Traditional clothing mainly changes the thickness of the clothing thermal insulation material to control the thermal radiation, heat conduction and convection between the human body and the external environment to maintain the stability of the climate inside the clothing. Although this method is effective, it cannot fully meet the needs of the human body. Therefore, various new types of thermal insulation and intelligent temperature-regulating clothing have been developed. People have found that some materials can undergo solid-liquid reversible changes according to the changes in the external environment temperature, absorbing or releasing heat from the external environment. People call them phase change materials, or PCM for short. Using this feature of PCM materials, when the temperature of the human clothing changes, the textile itself can automatically adjust part of the temperature, reduce the changes in the human skin temperature, and achieve thermal comfort for the human body.

[0003] Microcapsule composite spinning is one of the most advanced methods for preparing phase change fibers. A certain range of PCM is coated with some inorganic compounds or polymer compounds to form solid particles with a diameter of 1 to 100 μm under normal conditions, and then embedded inside the fiber, which can solve the leakage problem of PCM. In addition to adding microcapsules to the spinning solution to prepare phase change fibers, the PCM microcapsule emulsion can also be applied to the fabric by post-finishing methods, and the PCM microcapsule fabric can be prepared through padding, drying and other process treatments.

[0004] The present invention uses phase change material and graphene as core materials, epoxy resin as shell material to prepare graphene-based PCM microcapsules, and homemade regenerated keratin powder and anti-mite finishing agent as fillers to prepare polyurethane coatings, which are attached to wool fabrics using a two-immersion and two-rolling method to finally obtain a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing functions. The fabric has the functions of intelligent two-way temperature regulation, skin-friendly softness, antibacterial and deodorizing functions, and can be applied to bedding, automobile linings, medical bandages, etc. to achieve thermal balance between the human body and the surrounding environment. Summary of the invention

[0005] The purpose of the present invention is to provide a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties, a processing method and its use, which can not only sense the temperature changes in the human body's surrounding environment, absorb heat or release heat to achieve human body thermal balance, but also have antibacterial and deodorizing properties, effectively inhibit the spread of bacteria, and maintain a comfortable and healthy environment around the human body.

[0006] The first aspect of the present invention provides a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties, which is prepared by the following method:

[0007] Step 1: preparing graphene-based PCM microcapsules by interfacial polymerization, using phase change material and graphene as core materials and epoxy resin as shell material;

[0008] Step 2: adding the graphene-based PCM microcapsules obtained in step 1, homemade regenerated keratin powder, and anti-mite finishing agent as fillers into a polyurethane adhesive to prepare a polyurethane coating containing graphene-based PCM microcapsules, regenerated keratin powder, and anti-mite finishing agent;

[0009] Step 3: The polyurethane coating described in step 2 is attached to the pre-treated wool fabric by a double-dipping and double-rolling method, and then dried, baked, washed, and dried again to obtain a multifunctional graphene-based PCM microcapsule wool fabric with intelligent temperature regulation, antibacterial and deodorizing properties.

[0010] Preferably, the graphene-based PCM microcapsules are prepared according to the following steps:

[0011] Step 1, dissolving 5 g of epoxy resin monomer bisphenol A in 15 mL of acetone solution, and then fully mixing with 1 L of aqueous solution containing an appropriate amount of dispersant gelatin to obtain an epoxidizing agent;

[0012] Step 2: dispersing a certain amount of graphene in an epoxidant under the action of ultrasonic machinery, and adding an appropriate amount of PCM such as 1-octadecyl alcohol to obtain an epoxidant mixed solution;

[0013] Step 3: Dissolve 4 g of isophorone diamine phenolic resin in 15 mL of acetone and add it to the solution in step 2 at a rate of 3 mL / min. After the mixture is ultrasonically treated for 1 h, it is gradually heated to 50° C. and continuously stirred to obtain graphene-based PCM microcapsules.

[0014] Preferably, the self-made regenerated keratin powder is prepared by dissolving the pretreated wool using a molten urea method and a low eutectic solvent method.

[0015] Preferably, the intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric is characterized in that the pretreated wool is cleaned with a detergent to remove impurities on the fiber surface, and is rinsed with distilled water and dried. 200 mL of a mixed solution of ethanol and acetone in a volume ratio of 1:1 is put into a Soxhlet extractor, and a certain amount of washed wool is extracted and degreased for 12 hours. After the extraction and degreasing is completed, the residual ethanol and acetone on the wool are washed with distilled water. Dry at 50°C for 1 hour, repeat the washing and drying, and dry and crush.

[0016] Preferably, the intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric is characterized in that the homemade regenerated keratin powder is prepared by the molten urea method as follows:

[0017] Step 1, weigh an appropriate amount of urea and heat it to 145°C to completely melt the urea into liquid;

[0018] Step 2, adding a certain amount of pretreated wool fibers to the molten urea in step 1 and fully dissolving the wool to obtain a wool keratin solution;

[0019] Step 3: Add a small amount of HCI or NaOH solution to the wool keratin solution in step 2 to adjust the pH value to 4-5, let it stand for 12 hours to obtain a solution with flocculent precipitation, stir the solution evenly, centrifuge it for purification, freeze-dry it and grind it to obtain the homemade regenerated keratin powder.

[0020] Preferably, the intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric is characterized in that the homemade regenerated keratin powder is prepared by a low eutectic solvent method as follows:

[0021] Step 1, weighing choline chloride and urea in a molar ratio of 1:2 respectively, mixing the two in a water bath, and stirring for a certain period of time to obtain a choline chloride-urea-deep eutectic solvent;

[0022] Step 2, adding an appropriate amount of pretreated wool to the choline chloride-urea-deep eutectic solvent in step 1, and adding a small amount of L-cysteine ​​and sodium dodecyl sulfate, and reacting at 110° C. for 2 hours to obtain a wool keratin solution;

[0023] Step 3: add a small amount of HCI or NaOH solution to the wool keratin solution in step 2 to adjust the pH to 4-5, let stand for 12 hours to obtain a solution with flocculent precipitation, stir the solution evenly, centrifuge, purify, freeze-dry and grind to obtain homemade regenerated keratin powder.

[0024] Preferably, the intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric, and the polyurethane adhesive are prepared by the following method:

[0025] Step 1, put 100 parts by weight of polyester diol into a 500 mL round-bottom four-necked flask with a thermometer and a stirrer, and dehydrate under reduced pressure at 120° C. and 0.01 MPa vacuum for 3 h;

[0026] Step 2, cooling to 80°C, adding 80 parts by weight of toluene diisocyanate, and controlling the temperature at 84-90°C, and reacting for 4 hours; cooling again to 50°C, adding 1-3 parts by weight of dimethylolpropionic acid, and heating to 84-90°C, during which time acetone is added when the viscosity of the mixture increases, and reacting for 5 hours;

[0027] Step 3, lowering the temperature to 50°C, adding 1 to 3 parts by mass of triethylamine to form a salt, adding an appropriate amount of deionized water under high-speed stirring and shearing to disperse, and filtering to obtain a polyurethane adhesive.

[0028] Preferably, in the intelligent temperature-regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric, in the step 3, the pretreatment includes the following steps: after the rough cloth is subjected to raw repair, singeing, single boiling, scouring and drying, the wool fabric is etched by low-temperature plasma treatment to expose groups such as hydroxyl groups on the wool fiber; the rolling rate of the two-immersion and two-rolling method is 80% to 85%, the immersion time is 5 minutes, the drying conditions are 100°C for 10 minutes, and the baking conditions are 120°C for 3 minutes.

[0029] The second aspect of the present invention provides an application of a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties, including bedding. Since the phase change material in the microcapsule can store and release energy, the temperature and humidity of the bed can be kept within an ideal range, allowing people to sleep peacefully; the heat release and heat absorption of the phase change material in the car lining can keep the temperature inside the car constant, thereby regulating the temperature of the surrounding environment of the human body; the medical constant temperature bandage can prevent the local temperature of the bandage from being too high or too low, and can have a good soothing effect on the patient's physiology and psychology.

[0030] The graphene-based PCM microcapsule fabric formed by the present invention has the functions and characteristics of intelligent temperature regulation, skin-friendly softness, antibacterial and deodorizing.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1) Graphene-based PCM microcapsule fabric can not only realize intelligent two-way temperature regulation, but also has fast heat conduction speed and high temperature regulation efficiency;

[0033] 2) The polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder is skin-friendly, soft, breathable and comfortable;

[0034] 3) The graphene-based PCM microcapsule has stable structure and good durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The invention provides a processing method for the multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties;

[0036] Figure 2 The invention provides a method for preparing the waterborne polyurethane adhesive;

[0037] Figure 3 , 4 This is a schematic diagram of the final use of the multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties of the present invention. DETAILED DESCRIPTION

[0038] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0039] like Figure 1 As shown, the method for preparing multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties is as follows: by interfacial polymerization, graphene-based PCM microcapsules are prepared with phase change material and graphene as core materials and epoxy resin as shell material; the graphene-based PCM microcapsules, homemade regenerated keratin powder and anti-mite finishing agent are added to polyurethane adhesive as fillers to prepare a polyurethane coating containing graphene-based PCM microcapsules, regenerated keratin powder and anti-mite finishing agent. The polyurethane coating is attached to the pre-treated wool fabric by a two-dip and two-roll method to obtain multifunctional graphene-based PCM microcapsule wool fabric with intelligent temperature regulation, antibacterial and deodorizing properties. Figure 2 As shown in the figure, water-based polyurethane adhesive is made by reacting polyester diol, toluene diisocyanate and dimethylol propionic acid under certain temperature conditions. Figure 3 , 4 As shown, the prepared intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric has the properties of intelligent temperature regulating, antibacterial and deodorizing, and can intelligently adjust the temperature and humidity of the fabric according to the changes in the surrounding environment to meet the comfort needs of the human body. It can be used in the fields of bedding, automobile lining, medical bandages, etc. Example 1: A method for processing an intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric and its bedding fabric, characterized in that it is prepared according to the following steps:

[0040] A) dissolving 5 g of epoxy resin monomer bisphenol A in 15 mL of acetone solution, and then fully mixing with 1 L of aqueous solution containing an appropriate amount of dispersant gelatin to obtain an epoxidizing agent;

[0041] B) dispersing a certain amount of graphene in an epoxidant under ultrasonic mechanical action, and adding an appropriate amount of PCM such as 1-octadecyl alcohol to obtain an epoxidant mixed solution;

[0042] C) 4 g of isophorone diamine phenolic resin was dissolved in 15 mL of acetone and added to the solution in step B) at a rate of 3 mL / min. The mixture was ultrasonically treated for 1 h, and then gradually heated to 50° C. and stirred continuously to obtain graphene-based PCM microcapsules.

[0043] D) Weigh a certain amount of urea and heat it to 130°C to completely melt the urea into liquid;

[0044] E) adding an appropriate amount of pretreated wool fibers to the molten urea in D) and fully dissolving the wool to obtain a wool keratin solution;

[0045] F) Add a small amount of HCl or NaOH solution to the wool keratin solution in E) to adjust the pH value to 4-5, and let it stand for 12 hours to obtain a solution with flocculent precipitation. After stirring the solution evenly, centrifuge, purify, freeze-dry and grind to obtain regenerated keratin powder.

[0046] G) 100 parts by weight of polyester diol is placed in a 500 mL round-bottom four-necked flask with a thermometer and a stirrer, and dehydrated under reduced pressure at 120° C. and 0.01 MPa vacuum for 3 h; the temperature is lowered to 80° C., 80 parts by weight of toluene diisocyanate is added, and the temperature is controlled at 84-90° C., and the reaction is carried out for 4 h; the temperature is lowered to 50° C. again, 1-3 parts by weight of dimethylolpropionic acid are added, and the temperature is raised to 84-90° C. During this period, a certain amount of acetone is added when the viscosity of the mixture increases, and the reaction is carried out for 5 h; finally, the temperature is lowered to 50° C., 1-3 parts by weight of triethylamine are added to form a salt, and an appropriate amount of deionized water is added under high-speed stirring and shearing to disperse and filter to obtain a water-based polyurethane adhesive.

[0047] H) adding the anti-mite finishing agent, the prepared regenerated keratin powder and the graphene-based PCM microcapsules as fillers into the polyurethane adhesive in a certain proportion, and stirring them evenly under ultrasonic treatment to obtain a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder.

[0048] I) After the rough cloth has been subjected to raw repair, singeing, single boiling, scouring and drying, low-temperature plasma treatment is used to etch the wool fabric to a certain extent, so that groups such as hydroxyl groups on the wool fiber are exposed.

[0049] J) The wool fabric pretreated in I) is immersed in a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder, and the coating is fully contacted and bonded with the wool by a two-immersion and two-rolling method (rolling rate 80% to 85%, immersion for 5 minutes), and then dried (100°C, 10 minutes), baked (120°C, 3 minutes), fully washed with water, and dried again to obtain a multifunctional graphene-based PCM microcapsule wool fabric with intelligent temperature regulation, antibacterial and deodorizing properties, which is used as a bedding fabric.

[0050] Embodiment 2: A method for processing a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties and a car lining fabric, characterized in that the preparation is carried out according to the following steps:

[0051] A) dissolving 5 g of epoxy resin monomer bisphenol A in 15 mL of acetone solution, and then fully mixing with 1 L of aqueous solution containing an appropriate amount of dispersant gelatin to obtain an epoxidizing agent;

[0052] B) dispersing a certain amount of graphene in an epoxidant under ultrasonic mechanical action, and adding an appropriate amount of PCM such as 1-octadecyl alcohol to obtain an epoxidant mixed solution;

[0053] C) 4 g of isophorone diamine phenolic resin was dissolved in 15 mL of acetone and added to the solution in step B) at a rate of 3 mL / min. The mixture was ultrasonically treated for 1 h, and then gradually heated to 50° C. and stirred continuously to obtain graphene-based PCM microcapsules.

[0054] D) Weighing a certain amount of choline chloride and urea in a molar ratio of 1:2, mixing the two in a water bath, and stirring for a certain period of time to obtain ChCl-urea DES (choline chloride-urea-deep eutectic solvent);

[0055] E) adding an appropriate amount of pretreated wool to the ChCl-urea DES in D), and adding a small amount of L-cysteine ​​and sodium dodecyl sulfate, and reacting at 110° C. for 2 h to obtain a wool keratin solution;

[0056] F) Add a small amount of HCl or NaOH solution to the wool keratin solution in E) to adjust the pH to 4-5, and let it stand for 12 hours to obtain a solution with flocculent precipitation. After stirring the solution evenly, centrifuge, purify, freeze-dry and grind to obtain regenerated keratin powder.

[0057] G) 100 parts by weight of polyester diol is placed in a 500 mL round-bottom four-necked flask with a thermometer and a stirrer, and dehydrated under reduced pressure at 120° C. and 0.01 MPa vacuum for 3 h; the temperature is lowered to 80° C., 80 parts by weight of toluene diisocyanate is added, and the temperature is controlled at 84-90° C., and the reaction is carried out for 4 h; the temperature is lowered to 50° C. again, 1-3 parts by weight of dimethylolpropionic acid are added, and the temperature is raised to 84-90° C. During this period, a certain amount of acetone is added when the viscosity of the mixture increases, and the reaction is carried out for 5 h; finally, the temperature is lowered to 50° C., 1-3 parts by weight of triethylamine are added to form a salt, and an appropriate amount of deionized water is added under high-speed stirring and shearing to disperse and filter to obtain a water-based polyurethane adhesive.

[0058] H) adding the anti-mite finishing agent, the prepared regenerated keratin powder and the graphene-based PCM microcapsules as fillers into the polyurethane adhesive in a certain proportion, and stirring them evenly under ultrasonic treatment to obtain a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder.

[0059] I) After the rough cloth has been subjected to raw repair, singeing, single boiling, scouring and drying, low-temperature plasma treatment is used to etch the wool fabric to a certain extent, so that groups such as hydroxyl groups on the wool fiber are exposed.

[0060] J) The wool fabric pretreated in I) is immersed in a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder, and the coating is fully contacted and bonded to the wool by a two-immersion and two-rolling method (rolling rate 80% to 85%, immersion for 5 minutes), and then dried (100°C, 10 minutes), baked (120°C, 3 minutes), fully washed with water, and dried again to obtain a multifunctional graphene-based PCM microcapsule wool fabric with intelligent temperature regulation, antibacterial and deodorizing properties, which is used as a fabric for automobile lining.

[0061] Embodiment 3: A method for processing a graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing functions and a medical bandage fabric thereof, characterized in that the preparation is carried out according to the following steps:

[0062] A) dissolving 5 g of epoxy resin monomer bisphenol A in 15 mL of acetone solution, and then fully mixing with 1 L of aqueous solution containing an appropriate amount of dispersant gelatin to obtain an epoxidizing agent;

[0063] B) dispersing a certain amount of graphene in an epoxidant under ultrasonic mechanical action, and adding an appropriate amount of PCM such as 1-octadecyl alcohol to obtain an epoxidant mixed solution;

[0064] C) 4 g of isophorone diamine phenolic resin was dissolved in 15 mL of acetone and added to the solution in step B) at a rate of 3 mL / min. The mixture was ultrasonically treated for 1 h, and then gradually heated to 50° C. and stirred continuously to obtain graphene-based PCM microcapsules.

[0065] D) Weigh a certain amount of urea and heat it to 130°C to completely melt the urea into liquid;

[0066] E) adding an appropriate amount of pretreated wool fibers to the molten urea in D) and fully dissolving the wool to obtain a wool keratin solution;

[0067] F) Add a small amount of HCl or NaOH solution to the wool keratin solution in E) to adjust the pH value to 4-5, and let it stand for 12 hours to obtain a solution with flocculent precipitation. After stirring the solution evenly, centrifuge, purify, freeze-dry and grind to obtain regenerated keratin powder.

[0068] G) 100 parts by weight of polyester diol is placed in a 500 mL round-bottom four-necked flask with a thermometer and a stirrer, and dehydrated under reduced pressure at 120° C. and 0.01 MPa vacuum for 3 h; the temperature is lowered to 80° C., 80 parts by weight of toluene diisocyanate is added, and the temperature is controlled at 84-90° C., and the reaction is carried out for 4 h; the temperature is lowered to 50° C. again, 1-3 parts by weight of dimethylolpropionic acid are added, and the temperature is raised to 84-90° C. During this period, a certain amount of acetone is added when the viscosity of the mixture increases, and the reaction is carried out for 5 h; finally, the temperature is lowered to 50° C., 1-3 parts by weight of triethylamine are added to form a salt, and an appropriate amount of deionized water is added under high-speed stirring and shearing to disperse and filter to obtain a water-based polyurethane adhesive.

[0069] H) adding the anti-mite finishing agent, the prepared regenerated keratin powder and the graphene-based PCM microcapsules as fillers into the polyurethane adhesive in a certain proportion, and stirring them evenly under ultrasonic treatment to obtain a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder.

[0070] I) After the rough cloth has been subjected to raw repair, singeing, single boiling, scouring and drying, low-temperature plasma treatment is used to etch the wool fabric to a certain extent, so that groups such as hydroxyl groups on the wool fiber are exposed.

[0071] J) The wool fabric pretreated in I) is immersed in a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder, and the coating is fully contacted and bonded to the wool using a two-immersion and two-rolling method (rolling rate 80% to 85%, immersion for 5 minutes), followed by drying (100°C, 10 minutes), baking (120°C, 3 minutes), sufficient water washing, and drying again to obtain a multifunctional graphene-based PCM microcapsule wool fabric with intelligent temperature regulation, antibacterial and deodorizing properties, which is used as a medical bandage fabric.

[0072] Embodiment 4: A method for processing a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties and a bedding fabric thereof, characterized in that the preparation is carried out according to the following steps:

[0073] A) dissolving 5 g of epoxy resin monomer bisphenol A in 15 mL of acetone solution, and then fully mixing with 1 L of aqueous solution containing an appropriate amount of dispersant gelatin to obtain an epoxidizing agent;

[0074] B) dispersing a certain amount of graphene in an epoxidant under ultrasonic mechanical action, and adding an appropriate amount of PCM such as 1-octadecyl alcohol to obtain an epoxidant mixed solution;

[0075] C) 4 g of isophorone diamine phenolic resin was dissolved in 15 mL of acetone and added to the solution in step B) at a rate of 3 mL / min. The mixture was ultrasonically treated for 1 h, and then gradually heated to 50° C. and stirred continuously to obtain graphene-based PCM microcapsules.

[0076] D) Weigh a certain amount of urea and heat it to 130°C to completely melt the urea into liquid;

[0077] E) adding an appropriate amount of pretreated wool fibers to the molten urea in D) and fully dissolving the wool to obtain a wool keratin solution;

[0078] F) Add a small amount of HCl or NaOH solution to the wool keratin solution in E) to adjust the pH value to 4-5, and let it stand for 12 hours to obtain a solution with flocculent precipitation. After stirring the solution evenly, centrifuge, purify, freeze-dry and grind to obtain regenerated keratin powder.

[0079] G) 100 parts by weight of polyester diol is placed in a 500 mL round-bottom four-necked flask with a thermometer and a stirrer, and dehydrated under reduced pressure at 120° C. and 0.01 MPa vacuum for 3 h; the temperature is lowered to 80° C., 80 parts by weight of toluene diisocyanate is added, and the temperature is controlled at 84-90° C., and the reaction is carried out for 4 h; the temperature is lowered to 50° C. again, 1-3 parts by weight of dimethylolpropionic acid are added, and the temperature is raised to 84-90° C. During this period, a certain amount of acetone is added when the viscosity of the mixture increases, and the reaction is carried out for 5 h; finally, the temperature is lowered to 50° C., 1-3 parts by weight of triethylamine are added to form a salt, and an appropriate amount of deionized water is added under high-speed stirring and shearing to disperse and filter to obtain a water-based polyurethane adhesive.

[0080] H) adding the anti-mite finishing agent, the prepared regenerated keratin powder and the graphene-based PCM microcapsules as fillers into the polyurethane adhesive in a certain proportion, and stirring them evenly under ultrasonic treatment to obtain a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder.

[0081] I) After the rough cloth has been subjected to raw repair, singeing, single boiling, scouring and drying, low-temperature plasma treatment is used to etch the wool fabric to a certain extent, so that groups such as hydroxyl groups on the wool fiber are exposed.

[0082] J) The wool fabric pretreated in I) is immersed in a polyurethane coating containing graphene-based PCM microcapsules and regenerated keratin powder, and the coating is fully contacted and bonded with the wool by a two-immersion and two-rolling method (rolling rate 80% to 85%, immersion for 5 minutes), and then dried (100°C, 10 minutes), baked (120°C, 3 minutes), fully washed with water, and dried again to obtain a multifunctional graphene-based PCM microcapsule wool fabric with intelligent temperature regulation, antibacterial and deodorizing properties, which is used as a bedding fabric.

[0083]

Claims

1. A multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties, characterized in that: Prepared by the following method: Step 1: preparing graphene-based PCM microcapsules by interfacial polymerization, using phase change material and graphene as core materials and epoxy resin as shell material; Step 2: adding the graphene-based PCM microcapsules obtained in step 1, homemade regenerated keratin powder, and anti-mite finishing agent as fillers into a polyurethane adhesive to prepare a polyurethane coating containing graphene-based PCM microcapsules, regenerated keratin powder, and anti-mite finishing agent; Step 3: The polyurethane coating described in step 2 is attached to the pre-treated wool fabric by a double-dipping and double-rolling method, and then dried, baked, washed, and dried again to obtain a multifunctional graphene-based PCM microcapsule wool fabric with intelligent temperature regulation, antibacterial and deodorizing properties.

2. The intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric according to claim 1 is characterized in that: In step 1, graphene-based PCM microcapsules are prepared according to the following steps: Step 1, dissolving 5 g of epoxy resin monomer bisphenol A in 15 mL of acetone solution, and then fully mixing with 1 L of aqueous solution containing an appropriate amount of dispersant gelatin to obtain an epoxidizing agent; Step 2: dispersing a certain amount of graphene in an epoxidant under the action of ultrasonic machinery, and adding an appropriate amount of PCM such as 1-octadecyl alcohol to obtain an epoxidant mixed solution; Step 3: Dissolve 4 g of isophorone diamine phenolic resin in 15 mL of acetone and add it to the solution in step 2 at a rate of 3 mL / min. After the mixture is ultrasonically treated for 1 h, it is gradually heated to 50° C. and continuously stirred to obtain graphene-based PCM microcapsules.

3. The intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric according to claim 1 is characterized in that: In the step 2, the homemade regenerated keratin powder is prepared by dissolving the pretreated wool using a molten urea method and a low eutectic solvent method.

4. The intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric according to claim 3, characterized in that: The pretreated wool is washed with detergent to remove impurities on the fiber surface, and is rinsed with distilled water and dried. A mixed solution of ethanol and acetone in a volume ratio of 1:1 is placed in a Soxhlet extractor, and the washed wool is subjected to extraction and degreasing for 12 hours. After the extraction and degreasing is completed, the residual ethanol and acetone on the wool are washed with distilled water, and dried at 50°C for 1 hour, and the washing, drying and drying are repeated.

5. The intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric according to claim 3, characterized in that: The self-made regenerated keratin powder is prepared by a molten urea method, comprising the following steps: Step 1, weigh an appropriate amount of urea and heat it to 145°C to completely melt the urea into liquid; Step 2, adding a certain amount of pretreated wool fibers to the molten urea in step 1 and fully dissolving the wool to obtain a wool keratin solution; Step 3: Add a small amount of HCI or NaOH solution to the wool keratin solution in step 2 to adjust the pH value to 4-5, let it stand for 12 hours to obtain a solution with flocculent precipitation, stir the solution evenly, centrifuge it for purification, freeze-dry it and grind it to obtain the homemade regenerated keratin powder.

6. The intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric according to claim 3, characterized in that: The self-made regenerated keratin powder is prepared by a low eutectic solvent method, comprising the following steps: Step 1, weighing choline chloride and urea in a molar ratio of 1:2 respectively, mixing the two in a water bath, and stirring for a certain period of time to obtain a choline chloride-urea-deep eutectic solvent; Step 2, adding an appropriate amount of pretreated wool to the choline chloride-urea-deep eutectic solvent in step 1, and adding a small amount of L-cysteine ​​and sodium dodecyl sulfate, and reacting at 110° C. for 2 hours to obtain a wool keratin solution; Step 3: Add a small amount of HCI or NaOH solution to the wool keratin solution in step 2 to adjust the pH to 4-5, let it stand for 12 hours to obtain a solution with flocculent precipitation, stir the solution evenly, centrifuge it for purification, freeze-dry it and grind it to obtain the homemade regenerated keratin powder.

7. The intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric according to claim 1, characterized in that: In the step 2, the polyurethane adhesive is prepared by the following method: Step 1, put 100 parts by weight of polyester diol into a 500 mL round-bottom four-necked flask with a thermometer and a stirrer, and dehydrate under reduced pressure at 120° C. and 0.01 MPa vacuum for 3 h; Step 2, cooling to 80°C, adding 80 parts by weight of toluene diisocyanate, and controlling the temperature at 84-90°C, and reacting for 4 hours; cooling again to 50°C, adding 1-3 parts by weight of dimethylolpropionic acid, and heating to 84-90°C, during which time acetone is added when the viscosity of the mixture increases, and reacting for 5 hours; Step 3, lowering the temperature to 50°C and adding 1 to 3 parts by mass of triethylamine to form a salt, adding an appropriate amount of deionized water under high-speed stirring and shearing to disperse and filter to obtain a polyurethane adhesive.

8. The intelligent temperature regulating, antibacterial and deodorizing multifunctional graphene-based PCM microcapsule fabric according to claim 1, characterized in that: In the step 3, the pretreatment includes the following steps: after the rough cloth is subjected to raw repair, singeing, single boiling, scouring and drying, the wool fabric is etched by low-temperature plasma treatment to expose the hydroxyl groups on the wool fiber; the rolling rate of the two-immersion and two-rolling method is 80% to 85%, the immersion time is 5 minutes, the drying conditions are 100°C for 10 minutes, and the baking conditions are 120°C for 3 minutes.

9. The application of a multifunctional graphene-based PCM microcapsule fabric with intelligent temperature regulation, antibacterial and deodorizing properties according to claim 1, characterized in that: This includes bedding, car liners or medical thermostatic bandages.

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