High-adhesion protective glove and preparation method thereof

Abstract

The invention discloses a high-adhesion protective glove and a preparation method thereof. The preparation method comprises the following steps: preparing a mixed glue solution containing 60-70 parts of a butyronitrile glue solution, 1-5 parts of sulfur, 1-5 parts of a zinc-based active agent, 0.8-1.5 parts of a cross-linking agent and 10-15 parts of a modified filler; and dipping the hand mold, drying and vulcanizing. Wherein the preparation of the modified filler comprises the following steps: acidifying and roasting attapulgite, and modifying with a cationic surface active agent and a silane coupling agent in sequence; and dispersing the carbon black / graphene oxide in an oleophylic polymer monomer emulsion to polymerize to form three-dimensional particles. The modified filler is prepared by compounding the attapulgite and carbon black particles according to the ratio of 1: (0.2-1.6). The adhesive force and the wear resistance of the glove in the greasy dirt environment are remarkably improved, uniform protruding structures are formed on the microscopic surface, and the wet grabbing capacity is enhanced.

Description

Technical Field

[0001] This invention belongs to the field of polymer material modification technology, specifically, it relates to a high-adhesion protective glove and its preparation method. Background Technology

[0002] Nitrile gloves are widely used in industrial applications due to their oil resistance, but their adhesion is easily reduced in oily environments due to surface oil films. Existing improvement methods often involve adding common fillers (such as calcium carbonate and talc) or increasing the depth of surface texture, but these methods suffer from three major drawbacks: poor compatibility between fillers and rubber, leading to uneven dispersion and localized stress cracking; insufficient porosity and specific surface area of ​​traditional mineral fillers, resulting in inadequate oleophilic modification and an inability to effectively break down interfacial oil films; and the tendency of friction-enhancing fillers (such as carbon black) to agglomerate, resulting in weak bonding with rubber and rapid failure after wear. Although some studies have used attapulgite or graphene modification, the synergistic problem of pore control, surface oleophilization, and nano-reinforcing agent dispersion has not been solved. Therefore, there is an urgent need to develop a glove manufacturing technology that combines high adhesion, durable wear resistance, and adaptability to oily environments. Summary of the Invention

[0003] The purpose of this invention is to provide a high-adhesion protective glove and its preparation method, which solves the problem that existing protective gloves have poor adhesion in humid or oily environments and poor adhesion when gripping objects.

[0004] The objective of this invention can be achieved through the following technical solutions: A method for preparing a high-adhesion protective glove includes the following steps: S1. Prepare the mixed adhesive solution; S2. Immerse the hand mold in the mixed adhesive solution; S3, drying, vulcanization.

[0005] The raw materials of the mixed adhesive solution include the following components in parts by weight: The mixture contains 60-70 parts by weight of nitrile rubber, 1-5 parts by weight of vulcanizing agent, 1-5 parts by weight of activator, 0.8-1.5 parts by weight of crosslinking agent, and 10-15 parts by weight of modified filler. The crosslinking agent is one of aziridine, polyol, or polyamine, or any combination of the foregoing in any ratio; The vulcanizing agent is sulfur; The activator is one of zinc oxide, zinc carbonate and zinc stearate or any combination of the foregoing in any ratio.

[0006] The modified filler is prepared by: The first step is to acidify the attapulgite soil, specifically: The attapulgite was soaked in an acid solution, heated to 50°C-65°C and kept at that temperature for 10-15 hours. After solid-liquid separation, the solid product obtained by separation was washed with deionized water and then dried to obtain acidified attapulgite. The acid solution is nitric acid or hydrochloric acid with a mass concentration of 40%-50%; Acidification treatment can depolymerize minerals and open up pores, increase specific surface area and cation exchange capacity, and enhance the adsorption capacity of attapulgite. The second step is to calcine the acidified attapulgite at 500-800 degrees Celsius for 60-180 minutes, then remove it and let it cool naturally for later use. High-temperature calcination can destroy the structural water in attapulgite, thereby increasing its porosity and specific surface area. The third step is to add the attapulgite prepared in the second step to deionized water, stir and mix evenly to obtain an attapulgite suspension, then add a cationic surfactant to the attapulgite suspension, stir and react at a temperature of 70-90 degrees Celsius for 1.5-3 hours, then maintain the reaction temperature, add a silane coupling agent, and continue stirring and reacting for 1.5-2.5 hours. After the reaction was completed, the solid and liquid phases were separated, and the filtered solid product was washed sequentially with anhydrous ethanol and deionized water. After washing, the solid product was dried at a temperature of 100°C-115°C to obtain modified attapulgite.

[0007] The cationic surfactants include octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, etc., and the added weight of the cationic surfactants is 1%-2.5% of the attapulgite. The amount of the silane coupling agent added is 0.04%-5% of the weight of the attapulgite. In this application, attapulgite is treated by acidification and high-temperature calcination to improve its porosity and specific surface area. Then, the surface of attapulgite is treated with cationic surfactants and silane coupling agents. This can improve the interfacial compatibility between attapulgite and nitrile rubber in the subsequent preparation process, and also enhance the oleophilicity of attapulgite.

[0008] Due to the excellent oleophilic properties of attapulgite, it can reduce the thickness of the oil film at the glove-object interface, thereby improving the glove's gripping ability in oily environments and enhancing the adhesion between the object and the glove.

[0009] The fourth step is to prepare a polymer monomer emulsion, wherein the monomers in the polymer monomer emulsion are lipophilic monomers; Carbon black was added to the polymer monomer emulsion and ultrasonically treated for 10-25 minutes. Then, graphene oxide dispersion was added and ultrasonically treated for another 10-25 minutes to obtain a mixed system of carbon black-graphene oxide-polymer monomer emulsion. An initiator is added to the mixture to initiate monomer polymerization. After polymerization is complete, the solid product is obtained by filtration. The solid product is then washed with deionized water and anhydrous ethanol in sequence, and then dried at a temperature of 50-65 degrees Celsius to obtain modified carbon black.

[0010] The fifth step is to uniformly mix the modified attapulgite and modified carbon black at a weight ratio of 1:0.2-1.6 to obtain the modified filler.

[0011] In the preparation of the modified carbon black, a polymer monomer emulsion is used as a medium to uniformly disperse carbon black and graphene oxide. Then, an initiator is added to initiate a polymerization reaction, forming three-dimensional particles of carbon black, graphene oxide, and polymer. The graphene and carbon black in these three-dimensional particles enhance the abrasion resistance of the gloves and create a microstructure with uniformly distributed protrusions on the glove surface, thereby improving surface friction. Furthermore, the preparation of the three-dimensional particle structure ensures the uniform distribution of carbon black and graphene oxide in the raw materials. In addition, by adding nano-silica to the raw materials, the wet friction coefficient of the glove surface can be improved.

[0012] The amount of nano silica added is 0.6%-2% of the weight of nitrile adhesive. When adding nano silica, the surface of nano silica can be modified by silane coupling agent to improve its interfacial compatibility with polymer materials and ensure its uniform dispersion in adhesive.

[0013] The beneficial effects of this invention are: 1. This invention significantly improves the wear resistance, wet friction coefficient and surface adhesion of rubber products, enhances the adsorption force on various materials, and exhibits excellent grip performance, especially in oily environments, effectively preventing surface slippage.

[0014] 2. In this application, attapulgite is treated by acidification and high-temperature calcination to improve its porosity and specific surface area. Then, the attapulgite is surface-treated with cationic surfactants and silane coupling agents. This can improve the interfacial compatibility between attapulgite and nitrile rubber in the subsequent preparation process, and also enhance the oleophilicity of attapulgite, thereby reducing the thickness of the oil film at the glove-object interface, improving the gripping ability of the glove in oily environments, and enhancing the adhesion between the object and the glove.

[0015] 3. The modified carbon black uses a polymer monomer emulsion as a medium, in which carbon black and graphene oxide are uniformly dispersed. Then, an initiator is added to initiate a polymerization reaction, forming three-dimensional particles of carbon black-graphene oxide-polymer particles. In these three-dimensional particles, graphene and carbon black enhance the abrasion resistance of the gloves and create a microstructure with uniformly distributed protrusions on the glove surface, thereby improving surface friction. Furthermore, the preparation of the three-dimensional particle structure ensures the uniform distribution of carbon black and graphene oxide in the raw materials. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 A method for preparing a high-adhesion protective glove includes the following steps: S1. Prepare the mixed adhesive solution; S2. Immerse the hand mold in the mixed adhesive solution; S3, drying, vulcanization.

[0018] Preparation of modified fillers: Attapulgite modification: Take 100g of attapulgite and soak it in 50% hydrochloric acid, keep it at 60℃ for 12h, wash it with water and dry it. Calcination at 650℃ for 120 minutes, followed by cooling; Add 1L of deionized water and stir, then add 1.8g of octadecyltrimethylammonium chloride (react at 70℃ for 2h), then add 2g of KH-550 silane coupling agent (react at 80℃ for 2h), filter and wash, and dry at 110℃.

[0019] Carbon black modification: Add 20g of carbon black to butyl acrylate emulsion (solid content 40%) and sonicate for 15min; Add 5g of graphene oxide dispersion (2mg / mL) and sonicate for 15min. Add 0.5g of potassium persulfate, polymerize at 80℃ for 2 hours, filter and wash, then dry at 60℃.

[0020] Compound preparation: Modified attapulgite clay and carbon black particles are mixed at a ratio of 1:0.8.

[0021] Glove preparation: Mixed adhesive formulation: 65 parts nitrile rubber, 3 parts sulfur, 2 parts zinc oxide, 1.2 parts crosslinking agent (aziridine XAMA-7), 12 parts modified filler, 1.0 part nano silica (treated with KH-570); after the hand mold is impregnated with the adhesive, it is pre-baked at 100℃ for 5 min and vulcanized at 148℃ for 20 min.

[0022] Example 2 The difference between this embodiment and Example 1 is that, in the preparation process of the modified filler: acidification with 45% nitric acid (55℃, 15h), calcination at 750℃ for 90min; and the amount of cationic agent used is 2.2% (hexadecyltrimethylammonium chloride). Carbon black granules:attapulgite ratio = 1:1.5; Adhesive formulation: 70 parts nitrile adhesive, 1.5 parts nano silica, the rest are the same as in Example 1.

[0023] Comparative Example Carbon black was used as the filler to replace the modified filler, and other conditions were the same as in Example 1.

[0024] Effect verification: The oil adhesion, wet friction coefficient, and abrasion resistance of the gloves were tested, and the results are shown in the table below: Test Project Example 1 Example 2 Comparative Example Oil Adhesion 38.5 42.1 22.3 wet friction coefficient 0.83 0.87 0.51 Wear resistance times 12500 14200 9800 As shown in the table above, adding the modified filler of this invention can improve the adhesion of nitrile rubber gloves when working in oily and water environments, and the modified carbon black in the modified filler can significantly improve the wear resistance of the gloves.

[0025] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a high-adhesion protective glove, characterized in that, The steps include: S1, preparing the mixed adhesive solution; S2. Immerse the hand mold in the mixed adhesive solution; S3, drying, vulcanization; The raw materials of the mixed adhesive solution include the following components in parts by weight: The mixture contains 60-70 parts by weight of nitrile rubber, 1-5 parts by weight of vulcanizing agent, 1-5 parts by weight of activator, 0.8-1.5 parts by weight of crosslinking agent, and 10-15 parts by weight of modified filler. The modified filler is prepared by: The first step is to acidify the attapulgite soil; The second step is to calcine the acidified attapulgite at 500-800 degrees Celsius for 60-180 minutes, then remove it and let it cool naturally for later use. The third step involves surface treatment of the attapulgite clay obtained in the second step using a cationic surfactant and a silane coupling agent. The fourth step is to prepare a polymer monomer emulsion, wherein the monomers in the polymer monomer emulsion are lipophilic monomers; carbon black and graphene oxide dispersions are added to the polymer monomer emulsions, and after uniform dispersion, an initiator is added. After polymerization is completed, the solid product is obtained by filtration. The solid product is washed sequentially with deionized water and anhydrous ethanol, and then dried at a temperature of 50-65 degrees Celsius to obtain modified carbon black. The fifth step is to uniformly mix the modified attapulgite and modified carbon black at a weight ratio of 1:0.2-1.6 to obtain the modified filler.

2. The method for preparing a high-adhesion protective glove according to claim 1, characterized in that, The method for acidifying attapulgite is as follows: attapulgite is soaked in an acid solution, heated to 50℃-65℃ and kept at that temperature for 10h-15h. After solid-liquid separation, the solid product obtained by separation is washed with deionized water and then dried to obtain acidified attapulgite. The acid solution is nitric acid or hydrochloric acid with a mass concentration of 40%-50%.

3. The method for preparing a high-adhesion protective glove according to claim 1, characterized in that, The surface treatment method in the third step is as follows: Add the attapulgite clay prepared in the second step to deionized water, stir and mix evenly to obtain an attapulgite clay suspension, then add a cationic surfactant to the attapulgite clay suspension, stir and react at a temperature of 70-90 degrees Celsius for 1.5-3 hours, then maintain the reaction temperature, add a silane coupling agent, and continue stirring and reacting for 1.5-2.5 hours. After the reaction was completed, the solid and liquid phases were separated, and the filtered solid product was washed sequentially with anhydrous ethanol and deionized water. After washing, the solid product was dried at a temperature of 100°C-115°C to obtain modified attapulgite.

4. The method for preparing a high-adhesion protective glove according to claim 3, characterized in that, The cationic surfactant is either octadecyltrimethylammonium chloride or hexadecyltrimethylammonium chloride.

5. The method for preparing a high-adhesion protective glove according to claim 4, characterized in that, The cationic surfactant is added at 1%-2.5% of the weight of attapulgite; the silane coupling agent is added at 0.04%-5% of the weight of attapulgite.

6. The method for preparing a high-adhesion protective glove according to claim 1, characterized in that, The crosslinking agent is one of aziridine, polyol, or polyamine, or any combination of the foregoing in any ratio.

7. The method for preparing a high-adhesion protective glove according to claim 1, characterized in that, The vulcanizing agent is sulfur.

8. The method for preparing a high-adhesion protective glove according to claim 1, characterized in that, The activator is one of zinc oxide, zinc carbonate and zinc stearate or any combination of the foregoing in any ratio.

9. The method for preparing a high-adhesion protective glove according to claim 1, characterized in that, The raw materials for the mixed adhesive also include nano-silica that has been surface-treated with a silane coupling agent.

10. A high-adhesion protective glove, characterized in that, The gloves are prepared by the preparation method according to any one of claims 1 to 9.