Water-soluble cooling agent modified refreshing and cooling butyronitrile glove and preparation method thereof

Abstract

The invention belongs to the technical field of glove materials, and particularly relates to a water-soluble cooling agent modified refreshing cooling butyronitrile glove and a preparation method thereof. The preparation method of the water-soluble cooling agent modified refreshing and cooling butyronitrile gloves comprises the following steps: S1, mixing carboxylic butyronitrile latex, cooling filler, a cooling agent, carbon nanotubes, zinc oxide, sulfur powder, an accelerant and an anti-aging agent, and heating and stirring to obtain a rubber emulsion; and S2, pouring the rubber emulsion into a mold, carrying out pressure forming, cooling to room temperature, and demolding to obtain the water-soluble cooling agent modified refreshing cooling butyronitrile gloves. Through the synergistic effect of all the components, the contact cool feeling coefficient of the glove is increased, and meanwhile good wear resistance and mechanical performance are obtained.

Description

Technical Field

[0001] This invention belongs to the field of glove material technology, specifically relating to a water-soluble cooling agent-modified refreshing and cooling nitrile glove and its preparation method. Background Technology

[0002] In recent years, with the increasing awareness of health protection, the demand for nitrile gloves has increased significantly. Because nitrile gloves are made from synthetic latex, they do not contain protein compared to natural latex gloves, making them less likely to cause allergies. They also possess good softness, tensile strength, elongation at break, oil resistance, and wearing comfort. They can be used to make disposable thin nitrile gloves, lined work gloves, and thick nitrile gloves, and have been widely used in medical, industrial, and household fields. Carboxylated nitrile latex, as the main raw material for nitrile gloves, is a high-molecular-weight emulsion formed by the emulsion polymerization of butadiene, acrylonitrile, and methacrylic acid. Its molecular structure contains carboxyl and nitrile groups. After vulcanization, the film-formed product exhibits the aforementioned excellent properties and has long been used as the main raw material for nitrile gloves.

[0003] Cooling and refreshing nitrile gloves usually refer to traditional nitrile gloves that have been improved in terms of materials or structural design to make them cool, breathable, and moisture-wicking, thereby improving the comfort of users in high-temperature environments or long-term work. Their main advantages include: (1) improved comfort, significantly reducing stuffiness and stickiness, especially suitable for use in hot environments and long-term work; (2) keeping dry, the sweat-wicking function can keep the hands relatively dry and reduce skin problems caused by sweat soaking; (3) enhanced grip, the hands are dry, and with the anti-slip texture, it can provide a safer and more stable grip.

[0004] Nitrile gloves excel in chemical resistance, physical properties, wearing comfort, hypoallergenicity, environmental friendliness, antistatic properties, and cleanroom suitability. However, nitrile gloves are made of nitrile rubber, a material with a relatively dense molecular structure that makes it difficult for air and moisture to pass through. When worn in hot summers or high-temperature working environments, the hands may feel stuffy.

[0005] Therefore, there is an urgent need for a cool and refreshing nitrile glove that can achieve a good cooling sensation upon contact by adding a water-soluble cooling agent and working together with other modified components, while effectively improving the abrasion resistance and tensile strength of the material. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a water-soluble cooling agent-modified refreshing and cooling nitrile glove and its preparation method. The present invention involves mixing carboxylated nitrile latex, cooling filler, cooling agent, carbon nanotubes, zinc oxide, sulfur powder, accelerator, and antioxidant, heating and stirring to obtain a rubber latex. The rubber latex is then poured into a mold, pressed, cooled to room temperature, and demolded to obtain a water-soluble cooling agent-modified refreshing and cooling nitrile glove. The present invention improves the contact cooling coefficient of the glove through the synergistic effect of its components, while simultaneously achieving good abrasion resistance and mechanical properties.

[0007] In a first aspect, the present invention provides a method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove, comprising the following steps: S1. Mix carboxylated nitrile rubber latex, cooling filler, cooling agent, carbon nanotubes, zinc oxide, sulfur powder, accelerator and antioxidant, heat and stir to obtain rubber latex; S2. Pour the rubber latex into a mold, press it into shape, cool it to room temperature, and demold it to obtain water-soluble cooling agent modified refreshing and cooling nitrile gloves.

[0008] As a preferred technical solution of the present invention, the conditions for heating and stirring in step S1 are: stirring speed of 100~200 r / min, temperature of 120~140℃, and time of 6~10 min.

[0009] As a preferred embodiment of the present invention, each component comprises, by weight: 90-100 parts of carboxylated nitrile latex, 8-10 parts of cooling filler, 6-9 parts of cooling agent, 4-6 parts of carbon nanotubes, 2-4 parts of zinc oxide, 2-4 parts of sulfur powder, 0.6-0.8 parts of accelerator and 0.6-0.8 parts of antioxidant.

[0010] As a preferred embodiment of the present invention, the weight parts of the carboxylated nitrile latex may be 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, or 100 parts, etc.

[0011] As a preferred embodiment of the present invention, the weight of the cooling filler can be 8 parts, 8.5 parts, 9 parts, 9.5 parts, or 10 parts, etc.

[0012] As a preferred embodiment of the present invention, the cooling agent may be present in 6, 7, 8 or 9 parts by weight, etc.

[0013] As a preferred embodiment of the present invention, the carbon nanotubes may be in the following weight proportions: 4 parts, 4.5 parts, 5 parts, 5.5 parts, or 6 parts, etc.

[0014] As a preferred embodiment of the present invention, the zinc oxide may be in the following weight proportions: 2 parts, 2.5 parts, 3 parts, 3.5 parts, or 4 parts, etc.

[0015] As a preferred embodiment of the present invention, the sulfur powder may be in the following weight proportions: 2 parts, 2.5 parts, 3 parts, 3.5 parts, or 4 parts, etc.

[0016] As a preferred embodiment of the present invention, the weight fraction of the accelerator may be 0.6 parts, 0.7 parts, or 0.8 parts, etc.

[0017] As a preferred embodiment of the present invention, the antioxidant may be present in the following quantities: 0.6 parts, 0.7 parts, or 0.8 parts by weight.

[0018] As a preferred technical solution of the present invention, the preparation method of the cooling filler is as follows: sodium carbonate, calcium chloride and polyacrylic acid are mixed and reacted to obtain mesoporous calcium carbonate; the mesoporous calcium carbonate is wet-modified using butanetetracarboxylic acid to obtain modified mesoporous calcium carbonate; the modified mesoporous calcium carbonate is vacuum-loaded using L-menthol to obtain the cooling filler.

[0019] As a preferred technical solution of the present invention, the preparation steps of the mesoporous calcium carbonate are as follows: by weight, 80-120 parts of 0.1 mol / L sodium carbonate solution and 20-30 parts of 1 g / L polyacrylic acid aqueous solution are mixed, and then 40-60 parts of 0.01 mol / L sodium dodecyl sulfonate are added. The mixture is heated to 75-85°C and stirred for 20-40 min to obtain a mixed solution. 80-120 parts of 0.1 mol / L calcium chloride solution and 20-30 parts of 1 g / L polyacrylic acid aqueous solution are mixed and then added to the mixed solution. The mixture is stirred and reacted at 75-85°C for 60-80 min. The residue is filtered, washed with deionized water, and dried to obtain mesoporous calcium carbonate.

[0020] As a preferred technical solution of the present invention, the wet modification step is as follows: by weight, 4-6 parts of butanetetracarboxylic acid are added to 80-100 parts of anhydrous ethanol and stirred evenly, then 8-10 parts of the mesoporous calcium carbonate are added, and wet modification is carried out at 70-80°C for 50-60 minutes, followed by filtration, drying, and grinding to obtain modified mesoporous calcium carbonate.

[0021] As a preferred technical solution of the present invention, the vacuum loading treatment step is as follows: by weight, 4-6 parts of L-menthol are added to 80-100 parts of anhydrous ethanol and stirred evenly, then 8-10 parts of the modified mesoporous calcium carbonate are added, and vacuum loading treatment is carried out under a vacuum degree of 5-10 Pa for 20-24 hours to obtain the cooling filler.

[0022] This invention first uses sodium carbonate and calcium chloride as the main raw materials, and polyacrylic acid (PAA) and sodium dodecyl sulfonate (SDS) as crystal form regulators to prepare mesoporous calcium carbonate with good dispersibility and rich nanopores through chemical metathesis. Then, the carboxyl groups of butanetetracarboxylic acid are coordinated with calcium ions on the surface of mesoporous calcium carbonate to anchor butanetetracarboxylic acid on the particle surface, thus obtaining modified mesoporous calcium carbonate. Finally, L-menthol ethanol solution is used for vacuum loading. Under vacuum conditions, L-menthol first interacts with the carboxyl groups of butanetetracarboxylic acid, and then is gradually adsorbed into the pores under the capillary force of the mesoporous pores, and gradually crystallizes in the pores, finally obtaining a mesoporous calcium carbonate cool-feeling filler containing butanetetracarboxylic acid and L-menthol.

[0023] As a preferred embodiment of the present invention, the cooling agent is cooling agent WS-23 and cooling agent WS-12.

[0024] As a preferred embodiment of the present invention, the mass ratio of cooling agent WS-23 to cooling agent WS-12 in the cooling agent is (1~2):1.

[0025] This invention selects cooling agents WS-23 and WS-12 as compound cooling agents, and by controlling the mass ratio of the two, ensures their good synergistic effect, thereby improving the overall performance of nitrile gloves.

[0026] As a preferred embodiment of the present invention, the carbon nanotubes are modified carbon nanotubes; The modified carbon nanotubes are prepared as follows: by weight, 4-6 parts of multi-walled carbon nanotubes are added to 200-300 parts of deionized water and ground for 2-4 hours. Then, 6-8 parts of ionic liquid are added and stirred for 20-30 minutes. The mixture is then transferred to an ultrasonic disperser and ultrasonically dispersed for 2-4 hours. After vacuum drying, the modified carbon nanotubes are obtained.

[0027] As a preferred embodiment of the present invention, the ionic liquid is selected from one of 1-methylimidazolium p-toluenesulfonate, 1-ethylimidazolium p-toluenesulfonate, or 1-butylimidazolium p-toluenesulfonate.

[0028] As a preferred embodiment of the present invention, the accelerator is selected from one of accelerators ZMBT, ZDEC, and ZDBC.

[0029] As a preferred embodiment of the present invention, the antioxidant is selected from antioxidant 264, antioxidant 2246, and antioxidant 4010.

[0030] In a second aspect, the present invention provides a water-soluble cooling agent modified nitrile glove prepared by the preparation method described in the first aspect.

[0031] Compared with the prior art, the present invention has the following beneficial effects: (1) The imidazole ring and benzenesulfonate contained in the ionic liquid in the modified carbon nanotube of the present invention can undergo π–π stacking with the benzene ring structure in WS-12. At the same time, the cooling filler contains butanetetracarboxylic acid and L-menthol, which can form a multiple hydrogen bond network with the amide bond of WS-23. The multi-component synergistic formation of a dense network structure effectively improves the overall performance of nitrile gloves.

[0032] (2) In the cooling filler of the present invention, L-menthol activates cold receptors to produce a cooling sensation after contact with the skin, while the mesoporous structure load can delay the release of menthol. Combined with the good thermal conductivity of calcium carbonate, an excellent contact cooling coefficient is obtained. The main component of the cooling filler is rigid calcium carbonate, which can hinder crack propagation when evenly dispersed. At the same time, the modification of butanetetracarboxylic acid can promote the strong interfacial bonding between the filler and nitrile latex, effectively transfer stress and reduce interfacial slippage, and ultimately significantly improve the wear resistance and tensile strength of the glove.

[0033] (3) In the compound cooling agent of the present invention, WS-12 can generate a strong cooling sensation in a short time after contact with the skin, while WS-23 can ensure the cooling sensation through slow release, realizing a step-by-step cooling sensation experience of "instant cooling + long-lasting comfort", effectively improving the contact cooling sensation coefficient; at the same time, the benzene ring structure in WS-12 can undergo π-π conjugation with modified carbon nanotubes, and the amide bond in WS-23 can form hydrogen bonds with the cooling filler, thereby improving the wear resistance and mechanical properties of nitrile gloves by constructing a physical network structure.

[0034] (4) The carbon nanotubes of the present invention, after being modified by ionic liquid, can be uniformly dispersed in the nitrile rubber matrix to form an efficient thermally conductive network, thereby improving the contact cooling coefficient through rapid heat transfer; at the same time, the modified carbon nanotubes can effectively share and resist the effect of external friction, prevent the rubber molecular chains from being easily torn or worn away, and improve the wear resistance of the material; in addition, the well dispersed carbon nanotubes act as super strong nano-reinforcing points in the rubber matrix, restricting the slippage and orientation of the rubber molecular chains, and effectively improving the tensile strength of the gloves. Attached Figure Description

[0035] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0036] Figure 1 This is the Raman spectrum of the modified carbon nanotubes in Example 1 of the present invention. Detailed Implementation

[0037] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0038] The sources of some components in the examples and comparative examples are as follows: Sodium carbonate, CAS No. 497-19-8; Calcium chloride, CAS No. 10043-52-4; Sodium dodecyl sulfonate, CAS No. 2386-53-0; Butanetetracarboxylic acid, CAS No. 1703-58-8; L-Menthol, CAS No. 2216-51-5; Cooling agent WS-23, CAS No. 51115-67-4; Cooling agent WS-12, CAS No. 68489-09-8; 1-Methylimidazolium p-toluenesulfonate, CAS No. 63458-90-2; 1-Ethylimidazole p-toluenesulfonate, CAS No. 634922-90-0; 1-Butylimidazole p-toluenesulfonate, CAS No. 839672-91-2; Zinc oxide, CAS No. 1314-13-2; Sulfur powder, CAS No. 7704-34-9.

[0039] Example 1

[0040] This embodiment provides a method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove, comprising the following steps: S1. Mix 100 parts of carboxylated nitrile rubber latex, 10 parts of cooling filler, 9 parts of cooling agent (6 parts of cooling agent WS-23 and 3 parts of cooling agent WS-12), 6 parts of modified carbon nanotubes, 4 parts of zinc oxide, 4 parts of sulfur powder, 0.8 parts of accelerator ZMBT and 0.8 parts of antioxidant 264, heat and stir (stirring speed 200 r / min, temperature 140℃, time 6 min) to obtain rubber latex; S2. Pour the rubber latex into a mold, press it into shape, cool it to room temperature, and demold it to obtain water-soluble cooling agent modified refreshing and cooling nitrile gloves.

[0041] Preparation of the cooling filler: First, by weight, mix 120 parts of 0.1 mol / L sodium carbonate solution and 30 parts of 1 g / L polyacrylic acid aqueous solution, then add 60 parts of 0.01 mol / L sodium dodecyl sulfonate, heat to 85°C and stir for 20 min to obtain a mixture; then mix 120 parts of 0.1 mol / L calcium chloride solution and 30 parts of 1 g / L polyacrylic acid aqueous solution and add to the mixture, stir and react at 85°C for 60 min, and filter to obtain the filter media. The residue was washed with deionized water and dried to obtain mesoporous calcium carbonate. Six parts of butanetetracarboxylic acid were added to 100 parts of anhydrous ethanol and stirred evenly. Then, 10 parts of the mesoporous calcium carbonate were added, and wet modification was carried out at 80°C for 50 min. The mixture was then filtered, dried, and ground to obtain modified mesoporous calcium carbonate. Six parts of L-menthol were added to 100 parts of anhydrous ethanol and stirred evenly. Then, 10 parts of the modified mesoporous calcium carbonate were added, and vacuum loading treatment was carried out at 10 Pa for 20 h to obtain a cooling filler.

[0042] Preparation of modified carbon nanotubes: By weight, 6 parts of multi-walled carbon nanotubes were added to 300 parts of deionized water and ground for 4 hours. Then, 8 parts of ionic liquid 1-methylimidazolium p-toluenesulfonate were added and stirred for 30 minutes. The mixture was then transferred to an ultrasonic disperser and ultrasonically dispersed for 4 hours. After vacuum drying, modified carbon nanotubes were obtained.

[0043] Example 2

[0044] This embodiment provides a method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove, comprising the following steps: S1. Mix 90 parts of carboxylated nitrile rubber latex, 8 parts of cooling filler, 6 parts of cooling agent (3 parts of cooling agent WS-23 and 3 parts of cooling agent WS-12), 4 parts of modified carbon nanotubes, 2 parts of zinc oxide, 1 part of sulfur powder, 0.6 parts of accelerator ZDEC and 0.6 parts of antioxidant 2246, heat and stir (stirring speed 100 r / min, temperature 120℃, time 10 min) to obtain rubber latex; S2. Pour the rubber latex into a mold, press it into shape, cool it to room temperature, and demold it to obtain water-soluble cooling agent modified refreshing and cooling nitrile gloves.

[0045] Preparation of the cooling filler: First, by weight, mix 80 parts of 0.1 mol / L sodium carbonate solution and 20 parts of 1 g / L polyacrylic acid aqueous solution, then add 40 parts of 0.01 mol / L sodium dodecyl sulfonate, heat to 75°C and stir for 40 min to obtain a mixture; then mix 80 parts of 0.1 mol / L calcium chloride solution and 20 parts of 1 g / L polyacrylic acid aqueous solution and add to the mixture, stir and react at 75°C for 80 min, and filter to obtain the final product. The filter residue was washed with deionized water and dried to obtain mesoporous calcium carbonate. Four parts of butanetetracarboxylic acid were added to 80 parts of anhydrous ethanol and stirred evenly. Then, eight parts of the mesoporous calcium carbonate were added, and the mixture was wet-modified at 70°C for 60 min. The mixture was then filtered, dried, and ground to obtain modified mesoporous calcium carbonate. Four parts of L-menthol were added to 80 parts of anhydrous ethanol and stirred evenly. Then, eight parts of the modified mesoporous calcium carbonate were added, and the mixture was vacuum-loaded at 5 Pa for 24 h to obtain a cooling filler.

[0046] Preparation of modified carbon nanotubes: By weight, 4 parts of multi-walled carbon nanotubes were added to 200 parts of deionized water and ground for 2 hours. Then, 6 parts of ionic liquid 1-ethylimidazole p-toluenesulfonate were added and stirred for 20 minutes. The mixture was then transferred to an ultrasonic disperser and ultrasonically dispersed for 2-4 hours. After vacuum drying, modified carbon nanotubes were obtained.

[0047] Example 3

[0048] This embodiment provides a method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove, comprising the following steps: S1. Mix 95 parts of carboxylated nitrile rubber latex, 9 parts of cooling filler, 8 parts of cooling agent (5 parts of cooling agent WS-23 and 3 parts of cooling agent WS-12), 5 parts of modified carbon nanotubes, 3 parts of zinc oxide, 3 parts of sulfur powder, 0.7 parts of accelerator ZDBC and 0.7 parts of antioxidant 4010, and heat and stir (stirring speed 150 r / min, temperature 130℃, time 8 min) to obtain rubber latex; S2. Pour the rubber latex into a mold, press it into shape, cool it to room temperature, and demold it to obtain water-soluble cooling agent modified refreshing and cooling nitrile gloves.

[0049] Preparation of the cooling filler: First, by weight, mix 100 parts of 0.1 mol / L sodium carbonate solution and 25 parts of 1 g / L polyacrylic acid aqueous solution, then add 50 parts of 0.01 mol / L sodium dodecyl sulfonate, heat to 80°C and stir for 30 min to obtain a mixture; then mix 100 parts of 0.1 mol / L calcium chloride solution and 25 parts of 1 g / L polyacrylic acid aqueous solution and add to the mixture, stir and react at 80°C for 70 min, and filter to obtain... The filter residue was washed with deionized water and dried to obtain mesoporous calcium carbonate. Five parts of butanetetracarboxylic acid were added to 90 parts of anhydrous ethanol and stirred evenly. Then, 9 parts of the mesoporous calcium carbonate were added and wet-modified at 75°C for 55 min. The mixture was then filtered, dried, and ground to obtain modified mesoporous calcium carbonate. Five parts of L-menthol were added to 90 parts of anhydrous ethanol and stirred evenly. Then, 9 parts of the modified mesoporous calcium carbonate were added and vacuum-loaded at 8 Pa for 22 h to obtain a cooling filler.

[0050] Preparation of modified carbon nanotubes: By weight, 5 parts of multi-walled carbon nanotubes were added to 250 parts of deionized water and ground for 3 hours. Then, 7 parts of ionic liquid 1-butylimidazolium p-toluenesulfonate were added and stirred for 25 minutes. The mixture was then transferred to an ultrasonic disperser and ultrasonically dispersed for 3 hours. After vacuum drying, modified carbon nanotubes were obtained.

[0051] Comparative Example 1 The difference between this comparative example and Example 1 is that calcium carbonate powder is used instead of the cooling filler.

[0052] Comparative Example 2 The difference between this comparative example and Example 1 is that the cooling agent is replaced with 8 parts of cooling agent WS-23 and 1 part of cooling agent WS-12.

[0053] Comparative Example 3 The difference between this comparative example and Example 1 is that the cooling agent is replaced with 1 part of cooling agent WS-23 and 8 parts of cooling agent WS-12.

[0054] Comparative Example 4 The difference between this comparative example and Example 1 is that multi-walled carbon nanotubes are used instead of modified carbon nanotubes.

[0055] The performance of the nitrile gloves provided in the above embodiments and comparative examples was tested using the following methods: (1) Cooling sensation test: The test shall be conducted in accordance with the requirements of GB / T 35263-2017.

[0056] (2) Abrasion resistance test: The test shall be conducted in accordance with the requirements of GB / T 1689-2014.

[0057] (3) Tensile strength test: The test shall be conducted in accordance with the requirements of GB / T 528-2009.

[0058] The performance test data above are shown in Table 1.

[0059] Table 1 Performance Test Results

[0060] As can be seen from the above, the present invention mixes carboxylated nitrile butadiene latex, cooling filler, cooling agent, carbon nanotubes, zinc oxide, sulfur powder, accelerator and antioxidant, heats and stirs to obtain rubber latex, then pours the rubber latex into a mold and presses it into shape, cools it to room temperature, demolds it, and obtains water-soluble cooling agent modified refreshing and cooling nitrile butadiene gloves (Examples 1 to 3), which have the best comprehensive performance.

[0061] Compared to Example 1, using calcium carbonate powder instead of the cooling filler resulted in a decrease in the contact cooling coefficient, poorer abrasion resistance, and lower tensile strength due to the lack of the cooling filler's effect (Comparative Example 1); compared to Example 1, using 8 parts of cooling agent WS-23 and 1 part of cooling agent WS-12 instead of the cooling agent resulted in an excessive amount of cooling agent WS-23 leading to poor compounding effect, thus decreasing the contact cooling coefficient, poorer abrasion resistance, and lower tensile strength (Comparative Example 2); compared to Example 1, using 1 part of cooling agent WS-23 and 8 parts of cooling agent WS-12 instead of the cooling agent resulted in an excessive amount of cooling agent WS-12 leading to poor compounding effect, thus decreasing the contact cooling coefficient, poorer abrasion resistance, and lower tensile strength (Comparative Example 3); compared to Example 1, using multi-walled carbon nanotubes instead of modified carbon nanotubes resulted in a decrease in the contact cooling coefficient, poorer abrasion resistance, and lower tensile strength due to the lack of the modified carbon nanotube's effect (Comparative Example 4).

[0062] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove, characterized in that, Includes the following steps: S1. Mix carboxylated nitrile rubber latex, cooling filler, cooling agent, carbon nanotubes, zinc oxide, sulfur powder, accelerator and antioxidant, heat and stir to obtain rubber latex; S2. Pour the rubber latex into a mold, press it into shape, cool it to room temperature, and demold it to obtain water-soluble cooling agent modified refreshing and cooling nitrile gloves. The cooling filler is prepared by reacting sodium carbonate, calcium chloride, and polyacrylic acid to obtain mesoporous calcium carbonate; wet-modifying the mesoporous calcium carbonate with butanetetracarboxylic acid to obtain modified mesoporous calcium carbonate; and vacuum-loading the modified mesoporous calcium carbonate with L-menthol to obtain the cooling filler.

2. The preparation method of a water-soluble cooling agent modified refreshing and cooling nitrile glove according to claim 1, characterized in that, The components, by weight, include: 90-100 parts carboxylated nitrile latex, 8-10 parts cooling filler, 6-9 parts cooling agent, 4-6 parts carbon nanotubes, 2-4 parts zinc oxide, 2-4 parts sulfur powder, 0.6-0.8 parts accelerator and 0.6-0.8 parts antioxidant.

3. The method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove according to claim 1, characterized in that, The preparation steps of the mesoporous calcium carbonate are as follows: by weight, first mix 80-120 parts of 0.1 mol / L sodium carbonate solution and 20-30 parts of 1 g / L polyacrylic acid aqueous solution, then add 40-60 parts of 0.01 mol / L sodium dodecyl sulfonate, heat to 75-85℃ and stir for 20-40 min to obtain a mixed solution; mix 80-120 parts of 0.1 mol / L calcium chloride solution and 20-30 parts of 1 g / L polyacrylic acid aqueous solution and then add to the mixed solution, stir and react at 75-85℃ for 60-80 min, filter to obtain filter residue, wash with deionized water, and dry to obtain mesoporous calcium carbonate.

4. The preparation method of a water-soluble cooling agent modified refreshing and cooling nitrile glove according to claim 1, characterized in that, The wet modification steps are as follows: by weight, 4-6 parts of butanetetracarboxylic acid are added to 80-100 parts of anhydrous ethanol and stirred evenly, then 8-10 parts of the mesoporous calcium carbonate are added, and wet modification is carried out at 70-80℃ for 50-60 minutes. After filtration, drying, and grinding, modified mesoporous calcium carbonate is obtained.

5. The preparation method of a water-soluble cooling agent modified refreshing and cooling nitrile glove according to claim 1, characterized in that, The vacuum loading treatment steps are as follows: by weight, 4-6 parts of L-menthol are added to 80-100 parts of anhydrous ethanol and stirred evenly, then 8-10 parts of the modified mesoporous calcium carbonate are added, and vacuum loading treatment is carried out under a vacuum degree of 5-10 Pa for 20-24 hours to obtain the cooling filler.

6. The method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove according to claim 1, characterized in that, The cooling agents are cooling agent WS-23 and cooling agent WS-12; The mass ratio of cooling agent WS-23 to cooling agent WS-12 in the cooling agent is (1~2):

1.

7. The method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove according to claim 1, characterized in that, The carbon nanotubes are modified carbon nanotubes; The modified carbon nanotubes are prepared as follows: by weight, 4-6 parts of multi-walled carbon nanotubes are added to 200-300 parts of deionized water and ground for 2-4 hours. Then, 6-8 parts of ionic liquid are added and stirred for 20-30 minutes. The mixture is then transferred to an ultrasonic disperser and ultrasonically dispersed for 2-4 hours. After vacuum drying, the modified carbon nanotubes are obtained.

8. The method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove according to claim 7, characterized in that, The ionic liquid is selected from one of 1-methylimidazolium p-toluenesulfonate, 1-ethylimidazolium p-toluenesulfonate, or 1-butylimidazolium p-toluenesulfonate.

9. The method for preparing a water-soluble cooling agent-modified refreshing and cooling nitrile glove according to claim 1, characterized in that, The accelerator is selected from one of the following: accelerator ZMBT, accelerator ZDEC, and accelerator ZDBC.

10. A water-soluble cooling agent-modified refreshing and cooling nitrile glove, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 9.

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