Cool-feeling capsule as well as preparation method and application thereof

Abstract

The invention discloses a cool feeling capsule, a preparation method and application thereof. The capsule is prepared from the following main raw materials: 10-15 parts of a cool feeling aid, 20-60 parts of an organic solvent, 1-8 parts of an emulsifier, 9-20 parts of polymethyl methacrylate, 2-5 parts of an ethylene-vinyl acetate copolymer and 80-120 parts of dimethylformamide. According to the technical scheme, the obtained cool-feeling capsule and the fiber product applying the cool-feeling capsule have the advantages of being resistant to water washing, capable of continuously giving out cool feeling and resistant to high temperature.

Description

Technical Field

[0001] The present application relates to the technical field of textile materials, and in particular to a cooling capsule, a preparation method and application thereof. Background Art

[0002] In the field of modern textile materials, cool fabrics have attracted much attention because they can provide users with a comfortable wearing experience. However, the existing cool fabric technology has many problems that need to be solved.

[0003] Traditional cool fabrics mainly achieve the cooling function by impregnating cooling agents. This method has serious limitations. During the washing process, the cooling agent is easily washed away by water, resulting in the inability to maintain the cooling performance for a long time. This makes the washability of traditional cool fabrics poor, which not only affects the overall performance of the cool fabrics, but also greatly shortens their service life. Moreover, even without washing, the cooling intensity of traditional cool fabrics is unsatisfactory. This is mainly because traditional fabrics have poor thermal and moisture conductivity and cannot effectively conduct heat and moisture away, thus affecting the cooling effect.

[0004] In actual use, fibers are affected by external factors such as ultraviolet rays. Ultraviolet rays damage fibers in many ways. On the one hand, it directly destroys the structure of the fiber, thereby reducing the cooling performance; on the other hand, ultraviolet rays also trigger oxidation reactions inside the fiber, causing the molecular structure inside the fiber to be easily oxidized and degraded, which not only causes the overall performance of the fiber to decline, accelerates the aging and performance decline of the fiber, but also has a negative impact on the cooling performance. However, existing technologies lack effective measures to resist such damage to cooling fibers caused by ultraviolet rays.

[0005] From the perspective of multifunctional synergy, the existing cool fiber technology has not been able to integrate multiple functions well. For example, there is a lack of effective synergy between the cool feeling and antibacterial, heat and moisture conductivity and other functions. Although the cool mineral fiber jade powder fiber has a certain cool feeling, it is lacking in antibacterial properties; at the same time, it does not fully utilize the synergy in thermal conductivity to enhance the cool effect. Moreover, in terms of coolness and UV resistance, there is a lack of synergy between antioxidants and coolness, and technical means to improve both UV resistance and coolness.

[0006] To sum up, the existing cool fabric technology has many problems in terms of washability, cool strength, UV resistance, anti-oxidation and multi-functional synergy, which makes it difficult to meet people's demand for high-performance cool fibers. This provides space for the research and development of new cool and UV-resistant fibers. Summary of the invention

[0007] In view of the deficiencies in the prior art, the present application provides a cooling capsule that is washable, can continuously emit a cool feeling and is resistant to high temperatures.

[0008] In order to solve the above technical problems, the technical solution adopted in the present application is: a cooling capsule, the main raw materials for preparing the capsule include: 10-15 parts of a cooling aid, 20-60 parts of an organic solvent, 1-8 parts of an emulsifier, 9-20 parts of polymethyl methacrylate (PMMA), 2-5 parts of ethylene-vinyl acetate copolymer (EVA), and 80-120 parts of dimethylformamide (DMF).

[0009] Furthermore, the mass ratio of the cooling agent to the organic solvent is 1:2-4.

[0010] Furthermore, the mass fraction ratio of the sum of the polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA) to dimethylformamide (DMF) is 0.15-0.2:1.

[0011] Furthermore, the mass ratio of the polymethyl methacrylate (PMMA) to the ethylene-vinyl acetate copolymer (EVA) is 3-5:1.

[0012] Furthermore, the cooling agent is one or more of xylitol, ice-feeling silicone oil, menthol, menthone, eucalyptol, polypropylene glycol (PPG), polyethylene glycol (PEG), polyethylene glycol-600 (PEG-600), pentaerythritol, and N-n-alkyl-p-menthane carboxamide (N-(4-methylbenzyl)-p-menthane-3-carboxamide).

[0013] Furthermore, the organic solvent is one or more of n-propanol, ethyl acetate, toluene and dichloromethane.

[0014] Furthermore, the emulsifier is anionic such as sodium dodecylbenzene sulfonate (SDBS), sodium dodecyl sulfate (SDS); cationic such as cetyltrimethylammonium bromide (CTAB); zwitterionic such as lecithin; non-ionic such as polysorbate-80 (Tween-80) or one or more thereof.

[0015] The present application also provides a method for preparing the above-mentioned cooling capsule, the preparation steps comprising:

[0016] S1 weighs the raw materials: 10-15 parts of cooling agent, 20-60 parts of organic solvent, 1-8 parts of emulsifier, 9-20 parts of polymethyl methacrylate (PMMA), 2-5 parts of ethylene-vinyl acetate copolymer (EVA), and 80-120 parts of dimethylformamide (DMF);

[0017] S2 core material preparation: add the cooling agent to the organic solvent, stir at room temperature for 45-60 minutes, and the stirring speed is 300-350r / min, so that the cooling agent is fully dissolved in the organic solvent to form a core material solution;

[0018] S3 wall material preparation: adding a blend formed by mixing polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA) into dimethylformamide (DMF), stirring at 50-60° C. for 1.5-2 h until completely dissolved to form a wall material solution;

[0019] S4 emulsion preparation: adding the emulsifier to the wall material solution obtained in S3, increasing the stirring speed to 800-1000 rpm, stirring for 20-30 min, and adjusting the pH of the emulsion to 9-10 with weak alkaline ammonia water;

[0020] Preparation of S5 nanocapsule matrix: Slowly pour the wall material solution containing emulsifier into the core material solution, and at the same time reduce the stirring speed to 100-120 rpm, heat the temperature to 60-70°C, react for 2-3h, and continuously maintain the reaction pH at 9-10 to obtain a gel-like solid nanocapsule matrix.

[0021] S6 Preparation of high temperature resistant and cool nanocapsules: The nanocapsule matrix obtained in S5 was washed with ethanol for 3-4 times, and vacuum dried to obtain high temperature resistant and cool nanocapsule powder.

[0022] Furthermore, the amount of the emulsifier added in S6 is 0.6-9% of the mass of the wall material solution, and more preferably 3.4%.

[0023] Furthermore, the vacuum drying in S6 is carried out by gradually increasing the temperature. In the first stage, the temperature is increased to 50-80°C at a rate of 5°C / min and maintained for 1-3h; in the second stage, the temperature is increased to 85-100°C at a rate of 3°C / min and maintained for 1-3h; in the third stage, the temperature is increased to 100-150°C at a rate of 1°C / min and maintained for 0.5-2h.

[0024] Furthermore, the vacuum drying in S6 adopts a staged heating drying method. In the first stage, the temperature is increased to 60°C at a rate of 5°C / min and maintained for 2 hours; in the second stage, the temperature is increased to 90°C at a rate of 3°C / min and maintained for 2 hours; in the third stage, the temperature is increased to 120°C at a rate of 1°C / min and maintained for 1 hour.

[0025] Furthermore, the size of the cooling capsules prepared by S6 is controlled at 1-5 μm, and the thickness of the wall material is 0.1-0.3 μm.

[0026] The present application provides an application of the above-mentioned cool capsule in a modified graphene oxide cool anti-ultraviolet masterbatch. The raw materials for preparing the masterbatch include: 0.5-2 parts of a silane coupling agent, 0.5-10 parts of graphene oxide powder, 0.5-1.5 parts of a dispersant, 0.3-1 parts of an antioxidant, 5-10 parts of cool mineral fibers, 15-25 parts of cool capsules (i.e., the cool capsules prepared above), and 100-200 parts of fiber-forming polymer slices.

[0027] Furthermore, the silane coupling agent is one or more of 3-(N-phenylvinylmethyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride (vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, CAS No.: 34937-00-3) 40% methanol solution, 3-(1,3-dimethylbutylene)aminopropyltriethoxysilane ([3-(1,3-dimethylbutylene)aminopropyl]triethoxysilane, CAS No.: 116229-43-7), O-(vinyloxybutyl)-N-(triethoxysilylpropyl)urethane (O-(vinyloxybutyl)-N-(triethoxysilylpropyl)urea, CAS No.: 159856-61-8).

[0028] Furthermore, the graphene oxide powder is one or more of single-layer graphene oxide, double-layer graphene oxide, and multi-layer graphene oxide; it is a graphene oxide obtained by a chemical oxidation method, and is a two-dimensional material composed of graphene oxide alone or tightly stacked, with no more than 10 layers; the radial size is 0.5-15μm, and the thickness is 1-25nm.

[0029] Furthermore, the dispersant is one or more of sodium dodecylbenzene sulfonate, sodium carboxymethyl cellulose, and triethylhexyl phosphoric acid.

[0030] Furthermore, the antioxidant is a compound antioxidant formed by mixing a main antioxidant and a secondary antioxidant; the main antioxidant includes one or more of hindered phenol antioxidants 1010, 1076, 1098, and 1024; the secondary antioxidant includes phosphite antioxidants such as 168, PEP-8, 626, 9228, and PEP-36.

[0031] Furthermore, the compound antioxidant is a compound of a main antioxidant 1098 and an auxiliary antioxidant PEP-36.

[0032] Furthermore, the weight ratio of the primary antioxidant to the secondary antioxidant is 1-3:1.

[0033] Furthermore, the cool mineral fiber is one or more of jade powder fiber, mica powder fiber, pearl powder fiber, and shell powder fiber.

[0034] Furthermore, the fiber-forming polymer slices may be one or more of polyamide 6 (PA6) slices, polyamide (PA) slices, polyester (PET) slices, polyacrylonitrile (PAN) slices, and polyurethane (PU) slices.

[0035] The present application also provides a method for preparing the above-mentioned modified graphene oxide cool anti-ultraviolet masterbatch, and the preparation steps include:

[0036] (1) Mixing: First, weigh the raw materials according to the formula ratio: 0.5-2 parts of silane coupling agent, 0.5-10 parts of graphene oxide powder, 0.5-1.5 parts of dispersant, 0.3-1 parts of antioxidant, 5-10 parts of cooling mineral fiber, 15-25 parts of cooling capsule, and 100-200 parts of fiber-forming polymer slices; then add the above raw materials into a high-speed mixer, the speed of the high-speed mixer is 500-800 rpm, and the mixing time is 30-60 minutes to obtain a cooling anti-ultraviolet matrix containing modified graphene oxide;

[0037] (2) Melt coextrusion: The modified graphene oxide cool anti-ultraviolet matrix is ​​mixed and co-extruded in a twin-screw extruder. In the high shear and high temperature melt co-extrusion process, the modified graphene oxide cool anti-ultraviolet matrix melt is obtained. The extrusion temperature of the twin-screw extruder is divided into the following control areas: 1-2 zone (265-268°C), 2-10 zone (240-245°C), 11-12 zone (266-270°C), die head (270-272°C); the main engine speed is 150-400RPM, and the feed speed is 6-10HZ;

[0038] (3) Granulation: The obtained modified graphene oxide cool and anti-ultraviolet masterbatch melt is melted and co-extruded through a twin-screw extruder, and then subjected to strip drawing, water cooling, pelletizing, drying, and packaging to obtain the modified graphene oxide cool and anti-ultraviolet masterbatch.

[0039] Furthermore, the mass ratio of the graphene oxide powder to the modified graphene oxide cool and UV-resistant matrix in step (1) is controlled at 0.2-8%, more preferably 2.7%.

[0040] The present application also provides a method for preparing a modified graphene oxide cool and UV-resistant fiber using the modified graphene oxide cool and UV-resistant masterbatch, the method comprising:

[0041] (c1) Drying: Mixing the modified graphene oxide cool anti-ultraviolet masterbatch with the fiber-forming polymer slices, and putting them into a vacuum drying tower for drying, maintaining the temperature at 160-180° C. for 12-48 hours, and controlling the mass ratio of the modified graphene oxide cool anti-ultraviolet masterbatch to the mixed masterbatch in the drying tower to be 2-6%, so that the moisture content of the two after drying is less than 50 ppm;

[0042] (c2) Spinning and drawing: The dried mixed masterbatch is passed through a spinning screw extruder to form a spinning melt, which is then transferred to a spinning box for spinning. The spinneret is in a cross shape, and then subjected to heating, side-blowing cooling, drawing and bending, and winding to obtain the modified graphene oxide cool-sense UV-resistant fiber. The mass fraction of graphene oxide in the spinning melt is controlled at 0.05-0.2%. The temperature of the spinning screw extruder is 270-295°C. The aspect ratio of the micropores of the spinneret of the spinning assembly is 2:1. The side-blowing cooling temperature is 18-21°C, the side-blowing cooling humidity is 73-83%, and the side-blowing cooling speed is 0.6-0.8m / s. The drawing multiple is 3.2-3.6 times. The winding speed is 3800-4300m / min.

[0043] Furthermore, the fiber-forming polymer chips described in (c1) may be one or more of polyamide 6 (PA6) chips, polyamide (PA) chips, polyester (PET) chips, polyacrylonitrile (PAN) chips, and polyurethane (PU) chips.

[0044] Advantages and beneficial effects of this application:

[0045] 1. The antioxidant used in the masterbatch preparation process of this application is a compound antioxidant, which mainly utilizes the synergistic effect of the main antioxidant and the auxiliary antioxidant:

[0046] (1.1) Production of peroxides under ultraviolet conditions:

[0047] In polyamide 6 chips, the molecular chain contains structures such as amide bonds. When exposed to ultraviolet light, the energy of ultraviolet light is sufficient to break certain chemical bonds in the polyamide 6 molecular chain. Taking the carbon-hydrogen bond (CH) in the polyamide 6 molecular chain as an example, the ultraviolet energy can cause the CH bond to undergo homolytic cleavage reaction:

[0048] (where R is a part of the polyamide 6 molecular chain, R· is an alkyl free radical, and ·H is a hydrogen free radical)

[0049] The generated alkyl radical R· is highly reactive and will react rapidly with the surrounding oxygen molecules:

[0050] R·+O2→ROO·(generating peroxyl radicals)

[0051] The peroxyl radical ROO further reacts with the CH bond in the polyamide 6 molecular chain:

[0052] ROO·+R′-H→ROOH+R′· (wherein R′ is another part of the polyamide 6 molecular chain, ROOH is peroxide, and R′· is the newly generated alkyl free radical), thus continuously producing peroxide and triggering a chain reaction.

[0053] (1.2) Anti-ultraviolet mechanism of primary antioxidants

[0054] Structural characteristics of the main antioxidant: Main antioxidant 1098 is a hindered amine antioxidant, and the nitrogen-hydrogen (NH) bond in its molecular structure has high reactivity;

[0055] Free Radical Capture Process:

[0056] When polyamide 6 generates free radicals (such as alkyl radicals R·) under ultraviolet irradiation, the primary antioxidant 1098 can capture these free radicals. The reaction formula is as follows:

[0057] R·+NH-R→RH+N·-R′ (where R′ is the rest of the antioxidant 1098 molecule)

[0058] The main antioxidant 1098 converts free radicals into stable alkanes RH and forms relatively stable nitrogen free radicals N·-R′, thereby interrupting the chain reaction initiated by free radicals, preventing further degradation of polyamide 6, and playing an anti-ultraviolet role.

[0059] (1.3) Anti-ultraviolet mechanism of auxiliary antioxidant PEP-36

[0060] Type and function of auxiliary antioxidant PEP-36: Auxiliary antioxidant PEP-36 is a phosphite antioxidant.

[0061] Peroxide decomposition process: When peroxide ROOH exists in the system, the auxiliary antioxidant PEP-36 plays a role.

[0062] The reaction formula is: (RO)3P+ROOH→(RO)3P=O+ROH

[0063] The auxiliary antioxidant PEP-36 decomposes peroxides, reducing the possibility of further decomposition of peroxides to produce free radicals, thereby inhibiting the photooxidative degradation of polyamide 6 and playing an anti-ultraviolet role.

[0064] (1.4) Synergistic mechanism of primary antioxidant 1098 and secondary antioxidant PEP-36

[0065] Free radical capture at the initial stage of the reaction (mainly antioxidant 1098):

[0066] In the process of preparing modified graphene cool anti-ultraviolet masterbatch and polyamide fiber, when ultraviolet rays irradiate polyamide 6 chips to induce the generation of alkyl free radicals R·, the main antioxidant 1098 plays a role first.

[0067] According to the reaction formula R·+NH-R′→RH+N·-R′, the primary antioxidant 1098 quickly captures free radicals, reduces the initial concentration of free radicals in the system, and thus inhibits the further development of the chain reaction initiated by free radicals.

[0068] Peroxide decomposition (mainly auxiliary antioxidant PEP-36):

[0069] Although the primary antioxidant 1098 captures a portion of free radicals, some free radicals still react with oxygen to generate peroxide ROOH.

[0070] At this time, the secondary antioxidant PEP-36 begins to work, decomposing the peroxide according to the reaction formula (RO)3P+ROOH→(RO)3P=O+ROH. This step prevents the peroxide from further decomposing to produce new free radicals, thereby further inhibiting the degradation of polyamide 6.

[0071] Overall synergistic effect: In the entire process of preparing modified graphene cool anti-UV masterbatch and modified graphene cool anti-UV polyamide fiber, the main antioxidant and the auxiliary antioxidant work synergistically; the main antioxidant focuses on capturing free radicals and reducing the reactions caused by free radicals from the source; the auxiliary antioxidant focuses on decomposing peroxides and preventing peroxides from generating new free radicals; the two cooperate with each other to comprehensively protect the fiber from oxidative degradation caused by ultraviolet rays and jointly improve the fiber's anti-UV performance.

[0072] 2. This application prepares a new high temperature resistant cool nanocapsule

[0073] (2.1) Structural innovation

[0074] Internal space structure of capsule: The high temperature resistant cooling nanocapsules of the present application have reserved space for the cooling agent inside the capsule through a special drying process. During the drying process, the organic solvent evaporates, while the high temperature resistant cooling agent remains, forming a loose structure, which allows the cooling agent to expand freely inside the capsule. Compared with the traditional cooling agent impregnated fiber, this structure can better protect the cooling agent and avoid losing the cooling function due to squeezing during processing or use.

[0075] Microporous structure of wall material: The wall material is a blend of PMMA and EVA, and the wall material has a microporous structure after drying; this microporous structure is formed by solvent volatilization and molecular arrangement during the condensation of the wall material; the presence of micropores enables the capsule to gradually release the cooling factor as the temperature rises in summer, achieving long-term and controllable cooling, which is a structural feature that traditional cooling fabrics do not have; in the wall material solution, when the solvent begins to evaporate, the concentration of wall material molecules (PMMA and EVA) increases relatively. Since the interaction between the solvent and the wall material molecules is different from the interaction between the wall material molecules, as the solvent continues to evaporate, the system will phase separate; from a thermodynamic point of view, the free energy of the system will change. According to the Flory-Huggins theory, for the polymer-solvent system, the mixing free energy ΔGm can be expressed as: Where k is the Boltzmann constant, T is the temperature, n1 and n2 are the molar numbers of solvent and wall material molecules, respectively. and are the volume fractions of solvent and wall material molecules, respectively, and γ is the Flory-Huggins interaction parameter; when the solvent evaporates, When ΔGm reaches a certain value, the system will undergo phase separation, forming a phase rich in wall material molecules and a phase rich in solvent. After the solvent evaporates, the space left by the solvent-rich phase forms micropores.

[0076] (2.2) Preparation process innovation

[0077] Emulsification and capsule formation process: In the emulsification process, the emulsification conditions are precisely controlled by selecting a suitable emulsifier (SDBS) and adjusting the pH value with weak alkaline ammonia water. In the preparation process of the nanocapsule matrix, the efficient and stable preparation of the capsule is achieved by controlling the speed of pouring the wall material solution into the core material solution, the stirring speed, the reaction temperature and time. This preparation process can precisely control the structure and performance of the capsule, and has higher controllability and stability compared to the traditional cooling agent impregnation process.

[0078] Drying process: The drying method adopts a staged heating method. In the first stage, the temperature is raised to 60℃ at a rate of 5℃ / min and maintained for 2h; in the second stage, the temperature is raised to 90℃ at a rate of 3℃ / min and maintained for 2h; in the third stage, the temperature is raised to 120℃ at a rate of 1℃ / min and maintained for 1h. This drying process can ensure the complete evaporation of the organic solvent and reserve space for the cooling agent to form an ideal loose structure. It is a key process step to achieve the special structure inside the capsule. The traditional drying process is difficult to achieve this effect.

[0079] (2.3) Performance improvement innovation

[0080] Improved washability: This application uses high-temperature resistant cool nanocapsules with high-temperature resistant wall materials and cool agents as core materials, which are melted into masterbatches through twin screws, and finally the capsules and fibers are integrated through spinning. During the washing process, since the cool agent is wrapped inside the capsule, it is not easy to be washed away by water, which greatly improves the number of wash durability; while traditional fibers impregnated with cool agents are prone to loss of cool agents during washing, and cannot maintain cool properties for a long time. This application fundamentally solves the problem of traditional cool fabrics being not washable, and improves the overall performance and service life of cool fabrics.

[0081] Improved long-term cooling effect: Since the microporous structure of the capsule wall material can gradually release the cooling factor as the temperature changes, and the special spatial structure of the cooling agent inside the capsule ensures the effectiveness of the cooling agent, the cooling effect of the fiber prepared in the present application is more long-lasting; compared with traditional fibers impregnated with cooling agents, the cooling effect will not disappear quickly after washing or using for a period of time, and can continue to provide users with a cooling experience.

[0082] 3. This application uses silane coupling agent to modify graphene oxide

[0083] Hydrolysis of silane coupling agent: Under the high temperature (265℃) environment of the twin screw, the moisture contained in the substrate (polyamide 6 chips, etc.) is released. The trimethoxysilane group (-Si(OCH3)3) in the silane coupling agent 3-(N-phenylvinylmethyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride has high activity and undergoes hydrolysis under the action of water; the hydrolysis reaction formula is: Si(OCH3)3-R-NH2+3H2O→Si(OH)3-R-NH2+3CH3OH (where R is the organic connecting part of the silane coupling agent).

[0084] Graphene oxide modification: The silanol group (-Si-OH) produced by the hydrolyzed silane coupling agent undergoes a condensation reaction with the abundant hydroxyl groups (-OH) on the surface of graphene oxide (GO). The reaction formula is: nSi(OH)3-R-NH2+GO-OH→GO-O-Si-(OH) 3-n (O-GO) n -R-NH2+(n-1)H2O; through this reaction, the silane coupling agent is successfully grafted onto the surface of graphene oxide, changing the surface properties of graphene oxide.

[0085] Mechanism of grafting onto substrate: The amino groups (-NH2) on the modified graphene oxide undergo condensation reaction with the carboxyl groups (-COOH) in the polyamide 6 slice (substrate). The reaction formula is:

[0086] PA6-COOH+NH2-Si-···-GO→PA6-CO-NH-Si-···-GO+H2O.

[0087] Traditional graphene oxide is easy to agglomerate in the matrix material due to its own high specific surface area and strong van der Waals force. The silane coupling agent used in this application introduces organic groups on its surface by reacting with the hydroxyl groups on the surface of graphene oxide. These organic groups increase the compatibility of graphene oxide with the surrounding medium polyamide 6 slices, thereby effectively overcoming the agglomeration phenomenon and making graphene oxide uniformly dispersed in the system.

[0088] 4. The interaction and mechanism formula between graphene oxide and cool mineral fiber jade powder fiber used in this application

[0089] (4.1) Interaction: Graphene oxide and cool mineral fibers cooperate with each other in thermal conductivity. When the fibers are exposed to external heat, the heat is first quickly transferred to the jade powder fibers due to the high thermal conductivity of the cool mineral fibers. Since graphene oxide is in close contact with the cool mineral fibers, heat can be efficiently transferred from the cool mineral fibers to graphene oxide, and then further quickly transferred out through the two-dimensional structure of graphene oxide, forming a continuous and efficient heat conduction path.

[0090] (4.2) Mechanism formula (based on the series model of heat conduction): For heat conduction, according to Fourier's law (where Q is the heat flow, k is the thermal conductivity, A is the cross-sectional area, is the temperature gradient). Assuming that the thermal conductivity of graphene oxide is k1 and the thermal conductivity of jade powder fiber is k2, when the two are connected in series, the total thermal resistance is (L1 and L2 are the lengths of graphene oxide and jade powder fibers on the heat conduction path, respectively); when the two work together, they form a continuous heat conduction path. Compared with the heat conduction of individual graphene oxide and jade powder fibers, when they are combined together, heat can be conducted through multiple paths due to the formation of a heat conduction network, which is no longer a series conduction mode of a single material. The total thermal resistance R is reduced relative to the individual R1 or R2. According to (ΔT is the temperature difference). When the temperature difference ΔT remains unchanged, the thermal resistance R decreases, thereby increasing the heat flow Q and enhancing the cooling effect.

[0091] 5. Interaction and mechanism formula between the high temperature resistant cooling nanocapsules prepared in this application and the cross-shaped spinneret structure

[0092] (5.1) Interaction: The high temperature resistant cooling nanocapsules achieve a special distribution and function under the action of the cross-shaped spinneret. The structure of the cross-shaped spinneret enables the nanocapsules to be evenly distributed inside the fiber along the cross-shaped channel during the fiber forming process. In the hot summer, when the nanocapsules release the cooling agent, this uniform distribution is conducive to the rapid diffusion of the cooling agent in the fiber. At the same time, the cross-shaped structure increases the surface area of ​​the fiber, which helps the conduction of heat and moisture, thereby enhancing the cooling effect.

[0093] (5.2) Mechanism formula (based on the principle of diffusion and heat conduction): For the diffusion of cooling agent, according to Fick's second law (where C is the concentration, t is the time, and D is the diffusion coefficient). In the fiber structure formed by the cross-shaped spinneret, the uniform distribution of nanocapsules makes the initial concentration distribution more uniform, and because the cross-shaped structure increases the diffusion path, the diffusion coefficient D increases, thereby increasing the diffusion speed of the cooling agent. The cross-shaped structure increases the surface area A of the fiber. Under the same temperature gradient, the heat flow Q increases, which enhances the thermal conductivity and thus enhances the cool feeling.

[0094] 6. The technical solution of the present application, through the synergistic effect of various materials and structures, enables the finally prepared fiber to have good coolness, thermal conductivity, antibacterial, anti-ultraviolet properties and washability at the same time, overcoming the shortcomings of traditional fiber materials in these aspects. Through the synergistic effect of antioxidant compounding, graphene oxide, jade powder fiber and high temperature resistant cool nanocapsules, the integration of coolness and antibacterial and thermal conductivity functions is achieved, meeting people's various needs for functional textiles; the graphene oxide is modified by a specific silane coupling agent to improve the dispersibility of graphene oxide. At the same time, the addition of a dispersant further ensures the uniform dispersion of each component in the masterbatch, thereby improving the performance stability of the masterbatch and the fiber. This modification and dispersion method helps to give full play to the functions of each component, and reduces the performance defects caused by problems such as agglomeration during the preparation process; the use of a cross-shaped spinneret structure is also an important innovation of the present application. This structure cooperates with the high temperature resistant cool nanocapsules, which is not only conducive to the uniform distribution of nanocapsules in the fiber, but also improves the thermal and moisture conductivity of the fiber. By regulating the fiber microstructure through the spinneret structure, an organic combination of function and structure is achieved, providing a new idea for the preparation of high-performance cool and UV-resistant fibers. DETAILED DESCRIPTION

[0095] The following will be combined with the embodiments to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only preferred embodiments, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0096] Preparation Example 1

[0097] Preparation of high temperature resistant cooling capsules

[0098] (1) Weigh the following raw materials: 12 parts of ice-sensing silicone oil (cooling agent), 36 parts of ethyl acetate (organic solvent), 3.91 parts of sodium dodecylbenzene sulfonate (SDBS, emulsifier), 12 parts of polymethyl methacrylate (PMMA), 3 parts of ethylene-vinyl acetate copolymer (EVA), and 100 parts of dimethylformamide (DMF);

[0099] (2) Preparation of core material: Add the cooling agent to the organic solvent and stir for 60 min at room temperature at a stirring speed of 320 r / min to fully dissolve the cooling agent in the organic solvent to form a core material solution. The mass ratio of the cooling agent to the organic solvent is 1:3.

[0100] (3) Preparation of wall material: Add a blend of polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA) into dimethylformamide (DMF) and stir at 60°C for 2 h until it is completely dissolved to form a wall material solution. The mass fraction ratio of the sum of PMMA and EVA to DMF is maintained at 0.15:1, and the mass ratio of PMMA to EVA is 4:1;

[0101] (4) Preparation of emulsion: Add the emulsifier to the wall material solution, increase the stirring speed to 1000 rpm, stir for 30 min, and adjust the pH of the emulsion to 9 with weak alkaline ammonia water;

[0102] (5) Preparation of nanocapsule matrix: The wall material solution containing the emulsifier was slowly poured into the core material solution, while the stirring speed was reduced to 100 rpm, the heating temperature was increased to 60°C, the reaction time was 2.5 h, and the reaction pH was continuously maintained at 9 to obtain a gel-like solid nanocapsule matrix;

[0103] (6) Preparation of high temperature resistant cool nanocapsules: The nanocapsule matrix was washed with ethanol for 3 times, transferred to a vacuum drying oven, and gradually heated up. In the first stage, the temperature was raised to 60°C at a rate of 5°C / min and maintained for 2 hours; in the second stage, the temperature was raised to 90°C at a rate of 3°C / min and maintained for 2 hours; in the third stage, the temperature was raised to 120°C at a rate of 1°C / min and maintained for 1 hour. High temperature resistant cool nanocapsule powder was obtained. The size of the prepared cool capsule was controlled at 1-5μm, and the wall material thickness was 0.1-0.3μm.

[0104] Preparation Example 2

[0105] Preparation of high temperature resistant cooling capsules

[0106] (1) Weigh the following raw materials: 12 parts of menthol, 24 parts of n-propanol, 3.91 parts of cetyltrimethylammonium bromide, 12 parts of polymethyl methacrylate (PMMA), 3 parts of ethylene-vinyl acetate copolymer (EVA), and 100 parts of dimethylformamide (DMF);

[0107] (2) Preparation of core material: Add the cooling agent to the organic solvent, stir at room temperature for 60 min at a stirring speed of 320 r / min to fully dissolve the cooling agent in the organic solvent to form a core material solution, wherein the mass ratio of the cooling agent to the organic solvent is 1:2;

[0108] (3) Preparation of wall material: Add a blend of polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA) into dimethylformamide (DMF) and stir at 60°C for 2 h until it is completely dissolved to form a wall material solution; keep the mass fraction ratio of the sum of PMMA and EVA to DMF at 0.15:1, and the mass ratio of PMMA to EVA at 4:1;

[0109] (4) Preparation of emulsion: Add the emulsifier to the wall material solution, increase the stirring speed to 1000 rpm, stir for 30 min, and adjust the pH of the emulsion to 9 with weak alkaline ammonia water;

[0110] (5) Preparation of nanocapsule matrix: The wall material solution containing the emulsifier was slowly poured into the core material solution, while the stirring speed was reduced to 100 rpm, the heating temperature was increased to 60°C, the reaction time was 2.5 h, and the reaction pH was continuously maintained at 9 to obtain a gel-like solid nanocapsule matrix;

[0111] (6) Preparation of high temperature resistant cool nanocapsules: The nanocapsule matrix was washed with ethanol for 3 times, transferred to a vacuum drying oven, and gradually heated up. In the first stage, the temperature was raised to 60°C at a rate of 5°C / min and maintained for 2 hours; in the second stage, the temperature was raised to 90°C at a rate of 3°C / min and maintained for 2 hours; in the third stage, the temperature was raised to 120°C at a rate of 1°C / min and maintained for 1 hour. High temperature resistant cool nanocapsule powder was obtained. The size of the prepared cool capsule was controlled at 1-5μm, and the wall material thickness was 0.1-0.3μm.

[0112] Preparation Example 3

[0113] Preparation of high temperature resistant cooling capsules

[0114] (1) Weigh the following raw materials: 12 parts of polyethylene glycol-600, 48 parts of dichloromethane, 3.91 parts of sodium lauryl sulfate, 12 parts of polymethyl methacrylate (PMMA), 3 parts of ethylene-vinyl acetate copolymer (EVA), and 100 parts of dimethylformamide (DMF);

[0115] (2) Preparation of core material: Add the cooling agent to the organic solvent, stir at room temperature for 60 min at a stirring speed of 320 r / min to fully dissolve the cooling agent in the organic solvent to form a core material solution, wherein the mass ratio of the cooling agent to the organic solvent is 1:4;

[0116] (3) Preparation of wall material: Add a blend of polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA) into dimethylformamide (DMF) and stir at 60°C for 2 h until it is completely dissolved to form a wall material solution. The mass fraction ratio of the sum of PMMA and EVA to DMF is maintained at 0.15:1, and the mass ratio of PMMA to EVA is 4:1;

[0117] (4) Preparation of emulsion: Add the emulsifier to the wall material solution, increase the stirring speed to 1000 rpm, stir for 30 min, and adjust the pH of the emulsion to 9 with weak alkaline ammonia water;

[0118] (5) Preparation of nanocapsule matrix: The wall material solution containing the emulsifier was slowly poured into the core material solution, while the stirring speed was reduced to 100 rpm, the heating temperature was increased to 60°C, the reaction time was 2.5 h, and the reaction pH was continuously maintained at 9 to obtain a gel-like solid nanocapsule matrix;

[0119] (6) Preparation of high temperature resistant cool nanocapsules: The nanocapsule matrix was washed with ethanol for 3 times, transferred to a vacuum drying oven, and gradually heated up. In the first stage, the temperature was raised to 60°C at a rate of 5°C / min and maintained for 2 hours; in the second stage, the temperature was raised to 90°C at a rate of 3°C / min and maintained for 2 hours; in the third stage, the temperature was raised to 120°C at a rate of 1°C / min and maintained for 1 hour. High temperature resistant cool nanocapsule powder was obtained. The size of the prepared cool capsule was controlled at 1-5μm, and the wall material thickness was 0.1-0.3μm.

[0120] Preparation Example 4

[0121] Preparation of high temperature resistant cooling capsules

[0122] (1) Weigh the following raw materials: 12 parts of polypropylene glycol, 36 parts of ethyl acetate, 4.08 parts of sodium dodecylbenzene sulfonate (SDBS), 16 parts of polymethyl methacrylate (PMMA), 4 parts of ethylene-vinyl acetate copolymer (EVA), and 100 parts of dimethylformamide (DMF);

[0123] (2) Preparation of core material: Add the cooling agent to the organic solvent and stir for 60 min at room temperature at a stirring speed of 320 r / min to fully dissolve the cooling agent in the organic solvent to form a core material solution. The mass ratio of the cooling agent to the organic solvent is 1:3.

[0124] (3) Preparation of wall material: A blend of polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA) was added to dimethylformamide (DMF) and stirred at 60°C for 2 h until completely dissolved to form a wall material solution; the mass fraction ratio of the sum of PMMA and EVA to DMF was maintained at 0.2:1, and the mass ratio of PMMA to EVA was maintained at 4:1.

[0125] (4) Preparation of emulsion: Add the emulsifier to the wall material solution, increase the stirring speed to 1000 rpm, stir for 30 min, and adjust the pH of the emulsion to 9 with weak alkaline ammonia water.

[0126] (5) Preparation of nanocapsule matrix: The wall material solution containing the emulsifier was slowly poured into the core material solution, while the stirring speed was reduced to 100 rpm, the heating temperature was increased to 60°C, the reaction time was 2.5 h, and the reaction pH was continuously maintained at 9 to obtain a gel-like solid nanocapsule matrix.

[0127] (6) Preparation of high temperature resistant cool nanocapsules: The nanocapsule matrix was washed with ethanol for 3 times, transferred to a vacuum drying oven, and gradually heated up. In the first stage, the temperature was raised to 60°C at a rate of 5°C / min and maintained for 2 hours; in the second stage, the temperature was raised to 90°C at a rate of 3°C / min and maintained for 2 hours; in the third stage, the temperature was raised to 120°C at a rate of 1°C / min and maintained for 1 hour. High temperature resistant cool nanocapsule powder was obtained. The size of the prepared cool capsule was controlled at 1-5μm, and the wall material thickness was 0.1-0.3μm.

[0128] Preparation Example 5

[0129] Preparation of high temperature resistant cooling capsules

[0130] (1) Weigh the following raw materials: 12 parts of ice-sensitive silicone oil, 36 parts of ethyl acetate, 4 parts of polysorbate 80, 14 parts of polymethyl methacrylate (PMMA), 3.5 parts of ethylene-vinyl acetate copolymer (EVA), and 100 parts of dimethylformamide (DMF);

[0131] (2) Preparation of core material: Add the cooling agent to the organic solvent and stir for 60 min at room temperature at a stirring speed of 320 r / min to fully dissolve the cooling agent in the organic solvent to form a core material solution. The mass ratio of the cooling agent to the organic solvent is 1:3.

[0132] (3) Preparation of wall material: Add a blend of polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA) into dimethylformamide (DMF) and stir at 60°C for 2 h until it is completely dissolved to form a wall material solution; keep the mass fraction ratio of the sum of PMMA and EVA to DMF at 0.175:1, and the mass ratio of PMMA to EVA at 4:1;

[0133] (4) Preparation of emulsion: Add the emulsifier to the wall material solution, increase the stirring speed to 1000 rpm, stir for 30 min, and adjust the pH of the emulsion to 9 with weak alkaline ammonia water.

[0134] (5) Preparation of nanocapsule matrix: The wall material solution containing the emulsifier was slowly poured into the core material solution, while the stirring speed was reduced to 100 rpm, the heating temperature was increased to 60°C, the reaction time was 2.5 h, and the reaction pH was continuously maintained at 9 to obtain a gel-like solid nanocapsule matrix.

[0135] (6) Preparation of high temperature resistant cool nanocapsules: The nanocapsule matrix was washed with ethanol for 3 times, transferred to a vacuum drying oven, and gradually heated up. In the first stage, the temperature was raised to 60°C at a rate of 5°C / min and maintained for 2 hours; in the second stage, the temperature was raised to 90°C at a rate of 3°C / min and maintained for 2 hours; in the third stage, the temperature was raised to 120°C at a rate of 1°C / min and maintained for 1 hour. High temperature resistant cool nanocapsule powder was obtained. The size of the prepared cool capsule was controlled at 1-5μm, and the wall material thickness was 0.1-0.3μm.

[0136] Example 1

[0137] Preparation of modified graphene oxide cool anti-ultraviolet masterbatch

[0138] (1) Mixing: 1.2 parts of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride (coupling agent), 5.03 parts of monolayer graphene oxide powder, 1 part of sodium dodecylbenzene sulfonate (dispersant), 0.4 parts of primary antioxidant 1098 (antioxidant), 0.2 parts of secondary antioxidant PEP-36 (antioxidant), 7 parts of jade powder fiber (cooling mineral fiber), 15 parts of high temperature resistant cool nanocapsules in Preparation Example 1 (cooling capsules), and 150 parts of polyamide 6 slices (PA6, fiber-forming polymer slices); adding the above raw materials to a high-speed mixer at a speed of 800 rpm and a mixing time of 45 min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide; wherein the mass ratio of graphene oxide powder to modified graphene oxide cool anti-ultraviolet matrix is ​​controlled at about 2.7%;

[0139] (2) Melt coextrusion: The modified graphene oxide cool anti-ultraviolet matrix is ​​mixed and coextruded in a twin-screw extruder. In the high shear and high temperature melt coextrusion process, the modified graphene oxide cool anti-ultraviolet matrix melt is obtained. The extrusion temperature of the twin-screw extruder is divided into the following control areas: 1-2 zone (265-268°C), 2-10 zone (240-245°C), 11-12 zone (266-270°C), die head (270-272°C). The main engine speed is 200RPM (r / min), and the feed speed is 10HZ.

[0140] (3) Granulation: The obtained modified graphene oxide cool and anti-ultraviolet masterbatch melt is melted and co-extruded through a twin-screw extruder, and then subjected to strip drawing, water cooling, and pelletizing to obtain the modified graphene oxide cool and anti-ultraviolet masterbatch.

[0141] Preparation of modified graphene oxide cool and UV-resistant fibers

[0142] (c1) Drying: The modified graphene oxide cool and anti-ultraviolet masterbatch prepared above is mixed with polyamide 6 chips (PA6, fiber-forming polymer chips) and put into a vacuum drying tower for drying, maintaining the temperature at 170°C for 24 hours. The mass ratio of the modified graphene oxide cool and anti-ultraviolet masterbatch to the mixed masterbatch in the drying tower (a mixture with fiber-forming polymer chips added) is controlled to be 5%, so that the moisture content of the two after drying is less than 50 ppm.

[0143] (c2) Spinning and drawing: The dried mixed masterbatch is passed through a spinning screw extruder to form a spinning melt, which is then transferred to a spinning box for spinning. The spinneret is in a cross-shaped structure, and then heated, side-blown cooling, drawn and bent, and wound to obtain a modified graphene oxide cool anti-ultraviolet fiber; the mass fraction of graphene oxide in the spinning melt is controlled at 0.135%. The spinning screw extruder temperature is 285°C; the micropore aspect ratio of the spinning assembly spinneret is 2:1; the side-blown cooling temperature is 18°C, the side-blown cooling humidity is 75%, and the side-blown cooling speed is 0.7m / s; the drawing multiple is 3.4 times; and the winding speed is 4000m / min.

[0144] Example 2

[0145] Mixing: 1.2 parts of 3-(1,3-dimethylbutylene)aminopropyltriethoxysilane, 5.03 parts of monolayer graphene oxide powder, 1 part of sodium carboxymethyl cellulose, 0.4 parts of primary antioxidant 1098, 0.2 parts of auxiliary antioxidant PEP-36, 7 parts of mica powder fiber, 15 parts of high temperature resistant cool nanocapsules in Preparation Example 2, and 150 parts of polyamide slices. The above raw materials are added to a high-speed mixer, the speed of the high-speed mixer is 800 rpm, and the mixing time is 45min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0146] Example 3

[0147] Mixing: 1.2 parts of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, 5.03 parts of multilayer graphene oxide powder, 1 part of triethylhexyl phosphate, 0.4 parts of primary antioxidant 1098, 0.2 parts of auxiliary antioxidant PEP-36, 7 parts of pearl powder fiber, 15 parts of high temperature resistant cool nanocapsules in Preparation Example 3, and 150 parts of polyamide 6 slices (PA6). The above raw materials are added to a high-speed mixer, the speed of the high-speed mixer is 800 rpm, and the mixing time is 45min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0148] Example 4

[0149] Mixing: 1.2 parts of O-(vinyloxybutyl)-N-(triethoxysilylpropyl)urethane, 5.03 parts of double-layer graphene oxide powder, 1 part of sodium dodecylbenzene sulfonate, 0.4 parts of primary antioxidant 1098, 0.2 parts of auxiliary antioxidant PEP-36, 7 parts of shell powder fiber, 15 parts of high temperature resistant cool nanocapsules in Preparation Example 4, and 150 parts of polyurethane slices. The above raw materials are added to a high-speed mixer, the speed of the high-speed mixer is 700 rpm, and the mixing time is 50min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0150] Example 5

[0151] Mixing: 1.2 parts of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, 5.03 parts of double-layer graphene oxide powder, 1 part of sodium dodecylbenzene sulfonate, 0.4 parts of primary antioxidant 1098, 0.2 parts of auxiliary antioxidant PEP-36, 7 parts of jade powder fiber, 15 parts of high temperature resistant cool nanocapsules in Preparation Example 5, and 150 parts of polyacrylonitrile slices; add the above raw materials to a high-speed mixer, the speed of the high-speed mixer is 600 rpm, and the mixing time is 60min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0152] Example 6

[0153] Mixing: 1.2 parts of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, 5.32 parts of graphene oxide powder, 1 part of sodium dodecylbenzene sulfonate, 0.4 parts of primary antioxidant 1098, 0.2 parts of auxiliary antioxidant PEP-36, 7 parts of jade powder fiber, 25 parts of high temperature resistant cool nanocapsules in Preparation Example 5, and 150 parts of polyamide 6 slices (PA6). The above raw materials are added to a high-speed mixer, the speed of the high-speed mixer is 800 rpm, and the mixing time is 45min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0154] Example 7

[0155] Mixing: 1.2 parts of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, 5.18 parts of monolayer graphene oxide powder, 1 part of sodium dodecylbenzene sulfonate, 0.4 parts of primary antioxidant 1098, 0.2 parts of auxiliary antioxidant PEP-36, 7 parts of jade powder fiber, 20 parts of high temperature resistant cool nanocapsules in Preparation Example 5, and 150 parts of polyamide 6 slices (PA6). The above raw materials are added to a high-speed mixer, the speed of the high-speed mixer is 800 rpm, and the mixing time is 45min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0156] Comparative Example 1 (no antioxidant added)

[0157] Mixing: 1.2 parts of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, 3 parts of graphene oxide powder, 1 part of sodium dodecylbenzenesulfonate, 7 parts of jade powder fiber, 15 parts of high temperature resistant cool nanocapsules in Preparation Example 1, and 150 parts of polyamide 6 slices (PA6). The above raw materials are added to a high-speed mixer at a speed of 800 rpm for 45 minutes to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0158] Comparative Example 2 (without adding coupling agent)

[0159] Mixing: 3 parts of graphene oxide powder, 1 part of sodium dodecylbenzene sulfonate, 0.4 parts of primary antioxidant 1098, 0.2 parts of secondary antioxidant PEP-36, 7 parts of jade powder fiber, 15 parts of high temperature resistant cool nanocapsules in Preparation Example 1, and 150 parts of polyamide 6 slices (PA6). The above raw materials are added to a high-speed mixer, the speed of the high-speed mixer is 800 rpm, and the mixing time is 45min to obtain a cool anti-ultraviolet matrix containing graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0160] Comparative Example 3 (without adding cool mineral fiber)

[0161] Mixing: 1.2 parts of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, 3 parts of graphene oxide powder, 1 part of sodium dodecylbenzene sulfonate, 0.4 parts of primary antioxidant 1098, 0.2 parts of auxiliary antioxidant PEP-36, 15 parts of high temperature resistant cool nanocapsules in Preparation Example 1, and 150 parts of polyamide 6 slices (PA6). The above raw materials are added to a high-speed mixer, the speed of the high-speed mixer is 800 rpm, and the mixing time is 45min to obtain a cool anti-ultraviolet matrix containing modified graphene oxide. The subsequent steps are the same as in Example 1 to obtain the final preparation of modified graphene oxide cool anti-ultraviolet fiber.

[0162] Relevant testing standards for cool textiles: The National Organization for Standardization has issued the GB / T 35263-2017 "Testing and evaluating the instantaneous coolness of textiles upon contact". Under the experimental environment specified in this standard, a heat detection plate with a temperature higher than the test sample is placed in contact with it, and the temperature change of the heat detection plate over time is monitored, and the contact coolness coefficient q is calculated. max [J / (cm 2 ·s)]. This coefficient can characterize the instantaneous cool feeling of the test sample when it is touched, where q max The larger the value, the stronger the coolness felt by the skin; max The smaller the value, the weaker the cool feeling felt by the skin. The test steps are as follows:

[0163] 1) Cut 5 representative specimens, each with a size of approximately 200mm*200mm. When sampling, avoid defects and wrinkles that may affect the test results.

[0164] 2) Set the sample stage temperature to (20±0.5)°C and lay the sample flat on the sample stage with the fabric side in contact with the skin facing upwards.

[0165] 3) Set the temperature of the thermal detection plate to (35±0.5)°C, and the temperature difference (ΔT) with the sample stage to 15°C.

[0166] 4) When the temperature of the heat detection plate reaches the temperature set in step 2 and remains stable, cut off the heat source of the heat detection plate and quickly place it vertically on the sample so that the copper plate surface contacts the fabric. Record the measured q max The result is rounded to 3 decimal places and the unit is joule per square centimeter second [J / (cm 2 ·s)]. Result calculation: Calculate 5 samples q max The average value of the result is rounded to two decimal places according to GB / T 8170.)

[0167] The test standard for the washability of cool textiles refers to the FZ / T 73067-2020 "Contact Cool Knitted Clothing" specification. Cut a representative sample with a size of about 200mm*200mm, wash the fabric with a neutral detergent containing 1g / L, wash at about 40℃ for 30min, dehydrate in a centrifuge and dry naturally in a well-ventilated environment away from direct sunlight, and wash 0 times, 25 times, and 50 times respectively according to the above method; a in the table indicates unwashed fabric, b indicates washing 25 times, and c indicates washing 50 times.

[0168] Although there is no completely targeted national standard for testing under simulated natural light and high temperature environments, some relevant standard ideas for textile weather resistance testing can be used as reference:

[0169] 1) Cut representative samples of cool feeling textiles and ordinary textiles, the size of the sample is about 200mm*200mm. When sampling, avoid defects and wrinkles that may affect the test results.

[0170] 2) Place the two textiles in an environmental simulation box with natural light irradiation function, set the temperature to 40°C and the natural light intensity to 1000W / m 2 about.

[0171] 3) Expose continuously in the environmental simulation box for 0 days, 4 days, and 6 days, with the light exposure time set to 12 hours per day, and the temperature kept constant but without light for the rest of the time.

[0172] 4) After the samples have been exposed for the corresponding number of days, the cooling performance of each group of samples of cooling textiles and ordinary textiles shall be tested. The testing method shall refer to the standard GB / T 35263-2017 "Testing and evaluating the instantaneous cooling performance of textiles". Record the contact cooling coefficient q after treatment. max .

[0173] According to the above detection method, the performance of the samples prepared in the above examples and comparative examples of the present application was tested, and the results are shown in Table 1 below:

[0174] Table 1 Performance of samples prepared in Examples and Comparative Examples

[0175]

[0176]

[0177] Through the test results of the above embodiments and comparative examples, it can be known that the modified graphene oxide cool and UV-resistant fiber obtained by this scheme of the present application has a more ideal cool experience. After multiple washings and exposures, its qmax value is above 0.2, which is significantly better than the fiber fabric of the comparative example; the above advantages are caused by the fact that the organic solvent used in the core material solution in the capsule structure of the present application is not resistant to high temperatures and will evaporate after drying at 120°C, while the high-temperature resistant cool aid (the boiling point of the cool aid in the present application is generally 200°C and above) is mostly relatively stable and can be retained in the capsule. Due to the space formed inside the capsule, the cool aid can expand freely in the capsule; when entering the twin-screw granulation stage, the cool aid will expand in volume due to thermal expansion and contraction; if there is no reserved space inside the capsule, as the cool aid expands, the pressure inside the capsule The volume of the cooling agent will increase dramatically. If there is not enough space when the volume of the cooling agent expands, it will exert great pressure on the capsule wall, which may easily cause the capsule to rupture. The capsule prepared in the present application can effectively avoid rupture. In addition, the expansion of the cooling agent will exert a certain pressure on the capsule wall. The capsule wall is made of an organic wall material with a microporous structure. When the cooling agent expands, this pressure will cause the microporous structure of the capsule wall to change, for example, it may increase the pore size of the micropores or enhance the permeability of the wall material. In this way, the cooling factors (such as menthol molecules, etc.) inside the capsule are more easily released into the external environment through the micropores, thereby enhancing the cooling effect. In the cooling capsule prepared in the present application, in the hot summer, the ambient temperature rises and the cooling agent molecules absorb heat faster. According to the thermal principle, the increase in temperature will increase the internal energy of the molecules and intensify the molecular motion. For the cooling agent, this will increase its volatility and release the cooling factor faster; when the cooling factor is released, it will fit the human skin. Due to the volatility of the cooling factor (such as menthol molecules), they will absorb heat from the skin surface and evaporate, thereby taking away the heat from the skin surface and giving people a cool feeling; the wall material of this application is a blend of polymethyl methacrylate (PMMA) and ethylene-vinyl acetate copolymer (EVA); PMMA has good high temperature resistance and mechanical properties, and EVA can improve the flexibility and processing properties of the wall material; the dried capsule wall material has a microporous structure, because during the condensation of the wall material, the solvent evaporates and the arrangement of molecules forms tiny pores, and these micropores can gradually release the cooling factor as the temperature rises in summer; the cooling agent is resistant to high temperatures of 120°C in order to prepare the modified graphene oxide cooling anti-ultraviolet masterbatch, which does not affect its release at room temperature. At room temperature, the cooling agent will still release the cooling factor, but the release rate is slower. This is because the release of cooling factors is a process related to many factors, including the chemical composition of the cooling agent, the properties of the capsule wall, the ambient temperature, etc.At room temperature, although the temperature is low, there is still energy exchange between the cooling agent molecules and the external environment, and the cooling factor will slowly diffuse from the inside of the capsule to the outside, giving people a cool feeling. In summer, due to the increase in temperature, the molecular movement intensifies, and the release rate of the cooling factor will accelerate.

Claims

1. A cooling capsule, characterized in that: The main raw materials for preparing the capsule include: 10-15 parts of a cooling agent, 20-60 parts of an organic solvent, 1-8 parts of an emulsifier, 9-20 parts of polymethyl methacrylate, 2-5 parts of ethylene-vinyl acetate copolymer, and 80-120 parts of dimethylformamide.

2. The cooling capsule according to claim 1, characterized in that: The mass ratio of the cooling agent to the organic solvent is 1:2-4; the mass fraction ratio of the sum of the polymethyl methacrylate and the ethylene-vinyl acetate copolymer to dimethylformamide is 0.15-0.2:1; the mass ratio of the polymethyl methacrylate and the ethylene-vinyl acetate copolymer is 3-5:

1.

3. The cooling capsule according to claim 1, characterized in that: The cooling agent is one or more of xylitol, ice-feeling silicone oil, menthol, menthone, eucalyptol, polypropylene glycol, polyethylene glycol, polyethylene glycol-600, pentaerythritol, and N-n-alkyl p-menthane carboxamide (N-(4-methylbenzyl)-p-menthane-3-carboxamide).

4. The cooling capsule according to claim 1, characterized in that: The organic solvent is one or more of n-propanol, ethyl acetate, toluene and dichloromethane.

5. The cooling capsule according to claim 1, characterized in that: The emulsifier is one or more of anionic type: sodium dodecylbenzene sulfonate, sodium dodecyl sulfate; or cationic type: hexadecyltrimethylammonium bromide; or zwitterionic type: lecithin; or nonionic type: polysorbate-80.

6. A method for preparing the cooling capsule according to any one of claims 1 to 5, characterized in that: The preparation steps include: S1 weighs the raw materials: 10-15 parts of cooling agent, 20-60 parts of organic solvent, 1-8 parts of emulsifier, 9-20 parts of polymethyl methacrylate, 2-5 parts of ethylene-vinyl acetate copolymer, and 80-120 parts of dimethylformamide; S2 core material preparation: add the cooling agent to the organic solvent, stir at room temperature for 45-60 minutes, and the stirring speed is 300-350r / min, so that the cooling agent is fully dissolved in the organic solvent to form a core material solution; S3 wall material preparation: adding a blend formed by mixing polymethyl methacrylate and ethylene-vinyl acetate copolymer into dimethylformamide, stirring at 50-60°C for 1.5-2h until completely dissolved to form a wall material solution; S4 emulsion preparation: adding the emulsifier to the wall material solution obtained in S3, increasing the stirring speed to 800-1000 rpm, stirring time for 20-30 min, and adjusting the pH of the emulsion to 9-10 with weak alkaline ammonia water; S5 Preparation of nanocapsule matrix: slowly pour the wall material solution containing the emulsifier into the core material solution, while reducing the stirring speed to 100-120 rpm, heating the temperature to 60-70°C, reacting for 2-3h, and continuously maintaining the reaction pH at 9-10 to obtain a gel-like solid nanocapsule matrix; S6 Preparation of high temperature resistant and cool nanocapsules: The nanocapsule matrix obtained in S5 was washed with ethanol for 3-4 times, and vacuum dried to obtain high temperature resistant and cool nanocapsule powder.

7. The method for preparing the cooling capsule according to claim 6, characterized in that: The amount of the emulsifier added in S4 is 0.6-9% of the mass of the wall material solution.

8. The method for preparing the cooling capsule according to claim 6, characterized in that: The vacuum drying in the S6 is carried out by gradually increasing the temperature. In the first stage, the temperature is increased to 50-80°C at a rate of 5°C / min and maintained for 1-3h; in the second stage, the temperature is increased to 85-100°C at a rate of 3°C / min and maintained for 1-3h; in the third stage, the temperature is increased to 100-150°C at a rate of 1°C / min and maintained for 0.5-2h. The size of the cooling capsules prepared by the S6 is controlled at 1-5μm, and the wall material thickness is 0.1-0.3μm.

9. A modified graphene oxide cool anti-ultraviolet masterbatch prepared by using the cool capsule according to any one of claims 1 to 5, characterized in that: The raw materials for preparing the masterbatch include: 0.5-2 parts of silane coupling agent, 0.5-10 parts of graphene oxide powder, 0.5-1.5 parts of dispersant, 0.3-1 parts of antioxidant, 5-10 parts of cool mineral fiber, 15-25 parts of cool capsules and 100-200 parts of fiber-forming polymer slices.

10. The modified graphene oxide cool anti-ultraviolet masterbatch according to claim 9, characterized in that: The silane coupling agent is one or more of vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, 3-(1,3-dimethylbutylene)aminopropyltriethoxysilane, O-(vinyloxybutyl)-N-(triethoxysilylpropyl)urethane.

11. The modified graphene oxide cool anti-ultraviolet masterbatch according to claim 9, characterized in that: The graphene oxide powder is one or more of single-layer graphene oxide, double-layer graphene oxide, and multi-layer graphene oxide; it is a graphene oxide obtained by a chemical oxidation method, and is a two-dimensional material composed of single or tightly stacked graphene oxide with no more than 10 layers; the radial size is 0.5-15μm, and the thickness is 1-25nm.

12. The modified graphene oxide cool anti-ultraviolet masterbatch according to claim 9, characterized in that: The antioxidant is a compound antioxidant formed by mixing a main antioxidant and an auxiliary antioxidant; the main antioxidant includes one or more of hindered phenol antioxidants 1010, 1076, 1098, and 1024; the auxiliary antioxidant includes phosphite antioxidants such as 168, PEP-8, 626, 9228, and PEP-36.

13. The modified graphene oxide cool anti-ultraviolet masterbatch according to claim 12, characterized in that: The compound antioxidant is a main antioxidant 1098 and an auxiliary antioxidant PEP-36; the compound weight ratio of the main antioxidant to the auxiliary antioxidant is 1-3:

1.

14. The modified graphene oxide cool anti-ultraviolet masterbatch according to claim 9, characterized in that: The cool mineral fiber is one or more of jade powder fiber, mica powder fiber, pearl powder fiber and shell powder fiber.

15. A method for preparing the modified graphene oxide cool anti-ultraviolet masterbatch according to any one of claims 10 to 14, characterized in that: The preparation steps include: (1) Mixing: First, weigh the raw materials according to the formula ratio: 0.5-2 parts of silane coupling agent, 0.5-10 parts of graphene oxide powder, 0.5-1.5 parts of dispersant, 0.3-1 parts of antioxidant, 5-10 parts of cooling mineral fiber, 15-25 parts of cooling capsule, and 100-200 parts of fiber-forming polymer slices; then add the above raw materials into a high-speed mixer, the speed of the high-speed mixer is 500-800 rpm, and the mixing time is 30-60 minutes to obtain a cooling anti-ultraviolet matrix containing modified graphene oxide; (2) Melt coextrusion: The modified graphene oxide cool anti-ultraviolet matrix is ​​mixed and co-extruded in a twin-screw extruder. In the high shear and high temperature melt co-extrusion process, the modified graphene oxide cool anti-ultraviolet matrix melt is obtained. The extrusion temperature of the twin-screw extruder is divided into the following control areas: 1-2 zone 265-268°C, 2-10 zone 240-245°C, 11-12 zone 266-270°C, die head 270-272°C; the main engine speed is 150-400RPM, and the feed speed is 6-10HZ; (3) Granulation: The obtained modified graphene oxide cool and anti-ultraviolet masterbatch melt is melted and co-extruded through a twin-screw extruder, and then subjected to strip drawing, water cooling, pelletizing, drying, and packaging to obtain the modified graphene oxide cool and anti-ultraviolet masterbatch.

16. The method for preparing the modified graphene oxide cool anti-ultraviolet masterbatch according to claim 15, characterized in that: The mass ratio of the graphene oxide powder to the modified graphene oxide cool-sense anti-ultraviolet matrix in step (1) is controlled at 0.2-8%.

17. A method for preparing fiber from the modified graphene oxide cool anti-ultraviolet masterbatch according to any one of claims 10 to 14, characterized in that: The method includes: (c1) Drying: Mixing the modified graphene oxide cool anti-ultraviolet masterbatch with the fiber-forming polymer slices, and putting them into a vacuum drying tower for drying, maintaining the temperature at 160-180° C. for 12-48 hours, and controlling the mass ratio of the modified graphene oxide cool anti-ultraviolet masterbatch to the mixed masterbatch in the drying tower to be 2-6%, so that the moisture content of the two after drying is less than 50 ppm; (c2) Spinning and drawing: The dried mixed masterbatch is passed through a spinning screw extruder to form a spinning melt, which is then transferred to a spinning box for spinning. The spinneret is in a cross shape, and then subjected to heating, side-blowing cooling, drawing and bending, and winding to obtain the modified graphene oxide cool-sense UV-resistant fiber. The mass fraction of graphene oxide in the spinning melt is controlled at 0.05-0.2%. The temperature of the spinning screw extruder is 270-295°C. The aspect ratio of the micropores of the spinneret of the spinning assembly is 2:

1. The side-blowing cooling temperature is 18-21°C, the side-blowing cooling humidity is 73-83%, and the side-blowing cooling speed is 0.6-0.8m / s. The drawing multiple is 3.2-3.6 times. The winding speed is 3800-4300m / min.

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