High-wear-resistance temperature-sensitive butyronitrile glove and preparation method thereof

Abstract

The invention provides a high-wear-resistance temperature-sensitive butyronitrile glove and a preparation method thereof, and belongs to the technical field of rubber, the high-wear-resistance temperature-sensitive butyronitrile glove comprises the following raw materials by mass: 100-120 parts of butyronitrile latex; 5 to 15 parts of chlorinated polyvinyl chloride; 8-12 parts of a temperature sensing material; 1.2 to 3 parts of ethanol; 0.5-2 parts of a sodium polycarboxylate dispersant; 0.3 to 1 part of sodium dodecyl benzene sulfonate; 3-5 parts of a wear-resistant additive; 1-2 parts of a vulcanizing agent; 0.5 to 1 part of accelerant; 2-3 parts of a compatibilizer; 0.5-1 part of an anti-aging agent; and 20-40 parts of pure water. According to the glove, the butyronitrile latex is used as a main raw material, and the temperature sensing material, the wear-resistant additive and other functional additives are added, so that the combination of high wear resistance and a temperature regulation function is realized, and the problems of insufficient wear resistance and poor temperature adaptability of the traditional butyronitrile glove in an extreme environment are solved.

Description

Technical Field

[0001] The present invention belongs to the field of rubber technology, and in particular relates to a highly wear-resistant and temperature-sensitive nitrile glove and a preparation method thereof. Background Art

[0002] Nitrile gloves are widely used in medical, industrial protection and other fields due to their excellent oil resistance, chemical stability and mechanical properties. However, traditional nitrile gloves still have obvious defects in extreme working environments (such as alternating high and low temperatures, high friction scenarios): First, conventional materials are difficult to adapt to temperature fluctuations. They tend to harden in low temperature environments, resulting in reduced flexibility. At high temperatures, they may cause stuffiness and discomfort, affecting the wearing experience. Secondly, although nitrile rubber itself has a certain wear resistance, it is still prone to wear and perforation under long-term mechanical friction (such as manufacturing or laboratory operations), shortening its service life and increasing replacement costs. In the existing technology, although some studies have attempted to improve temperature adaptability by adding phase change materials (PCM), direct mixing can easily lead to material leakage or uneven distribution, and most of them do not solve the wear resistance problem. Wear-resistant modifications often rely on increasing the amount of fillers, which often sacrifices the flexibility and touch of the gloves.

[0003] In recent years, microencapsulation technology has made it possible to stably apply phase change materials. However, how to make it compatible with the nitrile latex system and maintain durability remains a technical difficulty. Therefore, there is an urgent need to develop a nitrile glove with both high wear resistance and intelligent temperature sensing functions, while ensuring basic protective performance, and solving the above contradictions through material innovation and process optimization.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The first purpose of the present invention is to provide a highly wear-resistant and temperature-sensitive nitrile glove. The glove uses nitrile latex as the main raw material. By adding temperature-sensitive materials, wear-resistant additives and other functional additives, it achieves a combination of high wear resistance and temperature regulation function, solving the problems of insufficient wear resistance and poor temperature adaptability of traditional nitrile gloves in extreme environments.

[0006] The second object of the present invention is to provide a method for preparing the above-mentioned highly wear-resistant and temperature-sensitive nitrile gloves. The preparation method ensures that the components are fully cross-linked through a staged pre-vulcanization process, thereby avoiding interference with the vulcanization process by the addition of temperature-sensitive materials.

[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are adopted:

[0008] A highly wear-resistant, temperature-sensitive nitrile glove comprising the following raw materials in parts by mass:

[0009] 80-120 parts of nitrile latex;

[0010] 5-15 parts of chlorinated polyvinyl chloride;

[0011] 8-12 portions of temperature-sensitive materials;

[0012] 1.2-3 parts of ethanol;

[0013] 0.5-2 parts of polycarboxylate sodium salt dispersant;

[0014] 0.3-1 part of sodium dodecylbenzenesulfonate;

[0015] 3-5 parts of wear-resistant additives;

[0016] 1-2 parts of vulcanizing agent;

[0017] Accelerator 0.5-1 part;

[0018] 2-3 parts of compatibilizer;

[0019] Antiaging agent 0.5-1 part;

[0020] 20-40 parts of pure water;

[0021] The temperature-sensitive material is a microcapsule with a temperature memory function, the shell of which is polyurethane and the core of which is phase-change paraffin.

[0022] The present invention provides a highly wear-resistant and temperature-sensitive nitrile glove, which achieves high wear resistance and temperature sensing functions of the glove through a specifically formulated raw material combination and their synergistic effect. The present invention clearly defines the components and their mass fraction ranges, including nitrile latex (100-120 parts), chlorinated polyvinyl chloride (5-15 parts), material (8-12 parts), ethanol (1.2-3 parts), polycarboxylate sodium salt dispersant (0.5-2 parts), sodium dodecylbenzenesulfonate (0.3-1 parts), wear-resistant additive (3-5 parts), vulcanizing agent (1-2 parts), accelerator (0.5-1 part), compatibilizer (2-3 parts), antioxidant (0.5-1 part) and 20-40 parts of pure water. The temperature-sensitive material is further defined as a microcapsule with a temperature memory function, whose shell is polyurethane and whose core is phase-change paraffin. Through scientific proportioning and material selection, the present invention solves the shortcomings of traditional nitrile gloves in wear resistance and temperature adaptability.

[0023] First, nitrile latex as a matrix material gives gloves excellent elasticity, oil resistance and chemical stability, but it still has performance limitations and insufficient wear resistance at extreme temperatures. The present invention significantly improves the chemical corrosion resistance and rigidity of the material by introducing chlorinated polyvinyl chloride. The chlorine atoms in its molecular structure can effectively resist the erosion of acids, alkalis and organic solvents, making it particularly suitable for medical and industrial protection scenarios. However, CPVC has poor compatibility with nitrile latex, and direct mixing easily leads to phase separation, thereby affecting the uniformity and mechanical properties of the product. To this end, the present invention cleverly solves this technical problem by adding maleic anhydride grafts as a compatibilizer. The maleic anhydride groups in the compatibilizer can form polar interactions with the chlorine atoms of CPVC, and its grafted chain segments have good compatibility with the molecular chains of nitrile latex, thereby constructing a stable interface layer between the two, ensuring the uniform dispersion of CPVC particles in the nitrile latex. This interface optimization not only avoids the problem of material delamination, but also significantly improves the mechanical properties of the composite system, so that the gloves maintain flexibility while enhancing wear resistance and tear resistance; the amount of nitrile latex ensures the mechanical properties and chemical stability of the gloves. Nitrile rubber itself has excellent oil resistance, tear resistance and elasticity, but pure nitrile latex is easy to harden or soften at extreme temperatures, and long-term friction will cause surface wear. Therefore, in order to solve these problems, the present invention introduces temperature-sensitive materials and wear-resistant additives, and the temperature-sensitive material adopts microencapsulation technology, with polyurethane as the shell to wrap the phase change paraffin core. At the same time, the appropriate amount of the temperature-sensitive material can effectively regulate the temperature without excessively affecting the vulcanization performance and mechanical strength of the latex. In addition, the polyurethane shell has good compatibility with nitrile latex and can be evenly dispersed in the system, while the phase change paraffin undergoes solid-liquid phase change within a specific temperature range, absorbing or releasing heat, thereby buffering the impact of ambient temperature changes on the wearer. For the present invention, this design effectively avoids the leakage or uneven distribution problems caused by the direct addition of traditional temperature-sensitive materials, and significantly improves the durability and comfort of the product.

[0024] Secondly, the introduction of wear-resistant additives further enhances the mechanical properties of the gloves. The high hardness, high specific surface area, and excellent dispersibility of the nanomaterials form a reinforced network in the nitrile latex, effectively resisting friction and puncture. The dosage range is strictly screened: too little will result in insufficient wear resistance, while too much may affect the fluidity of the rubber and the flexibility of the gloves. In addition, the synergistic effect of ethanol and sodium polycarboxylate dispersants ensures uniform dispersion of the temperature-sensitive material and wear-resistant additives, avoiding agglomeration, thereby improving the uniformity and performance stability of the product. The present invention further enhances the performance of the gloves by adding vulcanizing agents and accelerators. The dosage of these two agents directly affects the crosslinking density and vulcanization rate of the rubber, which in turn determines the strength, elasticity, and durability of the gloves.

[0025] Preferably, as a further specific embodiment, 0.1-0.3 parts of a stabilizer is further added to the temperature-sensitive material, and the stabilizer is polyvinyl pyrrolidone.

[0026] In the present invention, 0.1-0.3 parts of a stabilizer are added to the temperature-sensitive material, and it is clarified that the stabilizer is polyvinyl pyrrolidone, thereby improving the long-term stability of the temperature-sensitive material microcapsules in the nitrile latex system. In the present invention, the temperature-sensitive material adopts a microcapsule structure in which a polyurethane shell wraps a phase-change paraffin core. Although polyurethane has good compatibility with nitrile latex, during actual production and use, the microcapsules may still face the risk of physical damage or chemical degradation, especially in pre-vulcanization, mixing and stirring, and subsequent vulcanization, chlorine washing and other process links. Mechanical shear force, high temperature and chemical environment may pose a challenge to the integrity of the microcapsules. In addition, as a hydrophobic substance, phase-change paraffin also needs to ensure its interfacial stability with the aqueous nitrile latex system. If the microcapsule is damaged or the paraffin leaks, not only will the temperature-sensing function be lost, but the vulcanization process of the latex and the mechanical properties of the final product may also be affected. Therefore, in order to avoid the above problems, the present invention effectively solves the above problems by adding polyvinyl pyrrolidone. First, polyvinyl pyrrolidone is a water-soluble high molecular weight The sub-polymer has excellent film-forming properties, dispersibility and interfacial stabilization. Adding 0.1-0.3 parts of polyvinyl pyrrolidone to the temperature-sensitive material can form hydrogen bonds or van der Waals forces with the polyurethane shell through the polar groups in the polyvinyl pyrrolidone molecule, further enhancing the mechanical strength of the microcapsule shell, making it less likely to break during processes such as stirring and vulcanization. Secondly, the hydrophilic chain segment of polyvinyl pyrrolidone can form a stable protective layer in the aqueous latex system, reducing the interfacial tension between the microcapsules and the latex, thereby avoiding the agglomeration or sedimentation of the microcapsules and ensuring their uniform dispersion in the rubber compound. Polyvinyl pyrrolidone also has the effect of inhibiting phase separation, which can effectively prevent the paraffin core from migrating or leaking during temperature changes or long-term storage. Therefore, it can be seen that the amount of polyvinyl pyrrolidone added needs to be strictly controlled within an appropriate range. If the amount is too low, it is difficult to form a sufficient protective effect. If the amount is too high, the viscosity of the rubber compound may be too high due to the thickening effect of polyvinyl pyrrolidone, affecting subsequent molding processes such as leaching and lip curling.

[0027] Preferably, as a further specific embodiment, the wear-resistant additive is one or a combination of nano-silicon dioxide or nano-silicon carbide.

[0028] Preferably, as a further specific embodiment, the wear-resistant additive is a combination of nano-silicon dioxide and nano-silicon carbide, and the mass ratio of the nano-silicon dioxide to the nano-silicon carbide is 1:1.

[0029] The present invention also defines the basic selection range of wear-resistant additives, namely, one or a combination of nano-silicon dioxide or nano-silicon carbide. Preferably, when the two materials are selected for composite and the mass ratio of nano-silicon dioxide and nano-silicon carbide is clearly 1:1, the effect that can be achieved is excellent. This is because in the field of wear-resistant modification of traditional nitrile gloves, there is a common technical problem of imbalance between the enhancement effect and the material performance - either simply pursue wear resistance at the expense of flexibility, or lower the protection standard to maintain the feel. Therefore, the present invention solves the above problems by introducing nano-scale reinforcing materials and optimizing their combination. Nano-silicon dioxide has unique surface effect and volume effect, and the surface-rich silicone hydroxyl groups can form a large number of physical cross-linking points with the nitrile rubber molecular chains. This cross-linking network not only significantly improves the tensile strength and tear resistance of the material, but more importantly, it can effectively slow down the friction process through the energy dissipation mechanism. The nanosilica network is resistant to external mechanical forces, so when the glove surface is rubbed, it undergoes reversible deformation rather than permanent destruction. This property makes the product exhibit excellent durability in scenarios where it is frequently worn in the medical field. However, the pure nanosilica reinforcement system still has limitations when dealing with extreme wear conditions, especially the ability to resist puncture from sharp objects needs to be improved. Therefore, in order to make the prepared gloves have better durability, the present invention uses nanosilicon carbide to replace or combine nanosilicon dioxide. Silicon carbide has a high Mohs hardness, second only to diamond. Its nanoparticles in the rubber compound act like miniature "armor", which can effectively block the cutting effect of external hard objects. In addition, silicon carbide also has excellent thermal conductivity. This property can complement the function of temperature-sensitive materials, helping to quickly transfer heat to the phase change material for storage or release, thereby enhancing the temperature regulation effect of the gloves.

[0030] When a mixture of nano-silicon dioxide and nano-silicon carbide is used as a wear-resistant additive, the specific ratio between the two achieves the best balance between the advantages of the two nanomaterials. Too high a proportion of nano-silicon carbide will cause the viscosity of the rubber to rise sharply, affecting the subsequent dipping molding; while too low a content of nano-silicon carbide will make it difficult to reflect its enhancement effect. When nano-silicon dioxide and nano-silicon carbide coexist in equal amounts, the flexible network constructed by the former and the rigid support points provided by the latter form a "rigid and flexible" composite structure, so that the nano-silicon carbide particles are evenly embedded in the three-dimensional network constructed by silica, which not only maintains the overall elastic deformation ability of the material, but also forms high-strength protective nodes locally. This structural design enables the gloves to perform well under different types of wear conditions. For repeated plane friction, the silica network plays the main protective role; for point impact or contact with sharp objects, nano-silicon carbide particles become the first line of defense.

[0031] Preferably, as a further specific embodiment, the vulcanizing agent is one of sulfur or peroxide, wherein the peroxide is bis-(tert-butylperoxyisopropyl)benzene.

[0032] The present invention also places important restrictions on the specific type of vulcanizing agent. This is because in the manufacturing process of nitrile gloves, the choice of vulcanizing agent directly determines the cross-linking network structure of the final product, which in turn affects key indicators such as its mechanical properties, elastic recovery rate, and service life. When sulfur is selected as the vulcanizing agent, its usage of 1-2 parts not only ensures the formation of sufficient cross-linking points, but also avoids the burning of the rubber material or embrittlement of the product caused by excessive sulfur. In addition, sulfur can also react with the unsaturated carbon-carbon double bonds in nitrile rubber to form a polysulfide cross-linking network. This structure gives the gloves excellent elasticity and fatigue resistance.

[0033] When the vulcanizing agent is peroxide bis-(tert-butyl peroxide isopropyl) benzene, since bis-(tert-butyl peroxide isopropyl) benzene is a high-temperature decomposition peroxide, its decomposition temperature is about 160-180°C, which just matches the final vulcanization temperature range of nitrile gloves. As a result, bis-(tert-butyl peroxide isopropyl) benzene remains stable in the pre-vulcanization stage and will not decompose prematurely to interfere with the preparation of the temperature-sensitive suspension. During the final vulcanization, a carbon-carbon bond cross-linked network can be quickly formed. This cross-linked bond is more thermally stable than a polysulfide bond, allowing the product to maintain its performance in a high-temperature environment. Most importantly, the free radicals generated by the decomposition of bis-(tert-butyl peroxide isopropyl) benzene mainly attack the α-hydrogen atoms of the rubber molecular chain without destroying the chemical structure of the polyurethane shell, thereby perfectly protecting the integrity of the temperature-sensitive microcapsules.

[0034] Preferably, as a further specific embodiment, the accelerator is one of tetramethylthiuram disulfide or zinc diethyldithiocarbamate.

[0035] The present invention also makes important restrictions on the specific types of accelerators. This is because in the manufacturing process of nitrile gloves, the selection of accelerators directly affects the vulcanization rate, cross-linking density and physical properties of the final product. Traditional accelerator systems often find it difficult to meet the dual requirements of vulcanization efficiency and temperature-sensitive material protection. The present invention successfully solves this technical problem through the scientific selection of specific accelerators, ensuring that the product will not damage the structural integrity of the temperature-sensitive microcapsules while ensuring efficient vulcanization.

[0036] When tetramethylthiuram disulfide is selected as the accelerator, since tetramethylthiuram disulfide, as an ultra-fast accelerator, can significantly reduce the vulcanization activation energy in the sulfur vulcanization system, allowing the vulcanization reaction to proceed efficiently under relatively mild conditions. This property is particularly important for the system containing the temperature-sensitive material of the present invention. This is because traditional high-temperature rapid vulcanization processes easily cause the microcapsules of the phase-change paraffin wax to rupture. When tetramethylthiuram disulfide is added in combination with the vulcanizing agent, the temperature-sensing function of the glove can be better protected. In addition, the dimethyldithiocarbamate produced by the decomposition of tetramethylthiuram disulfide can form coordination bonds with the cyano groups in the nitrile rubber. This additional crosslinking method not only improves the vulcanization efficiency, but also enhances the interfacial bonding between the rubber molecular chains and the nano-wear-resistant additive.

[0037] When zinc diethyldithiocarbamate is chosen as the accelerator, because it is a medium-speed accelerator with a higher decomposition temperature than tetramethylthiuram disulfide, the vulcanization reaction can be better coordinated with the production process. Therefore, during the pre-vulcanization stage, the delayed acceleration of zinc diethyldithiocarbamate can prevent premature crosslinking of the rubber compound during the pre-vulcanization process, ensuring that the temperature-sensitive suspension can be evenly dispersed in the latex system. At the same time, the zinc ions in the zinc diethyldithiocarbamate molecules can produce a special interaction with the cyanide groups in the nitrile rubber, forming a more uniform cross-linked network structure.

[0038] Preferably, as a further specific embodiment, the antioxidant is one of 2,2,4-trimethyl-1,2-dihydroquinoline polymer or N-isopropyl-N'-phenyl-p-phenylenediamine, and 0.1-0.3 parts of ultraviolet absorber are further added to the antioxidant.

[0039] Preferably, as a further specific embodiment, the compatibilizer is a maleic anhydride graft.

[0040] The present invention also limits the antioxidant system. In the traditional nitrile glove formula, the selection of antioxidants often only considers conventional thermal oxidative aging protection, while ignoring the synergistic destructive effects of multiple aging factors such as ultraviolet radiation and ozone erosion. Especially for systems containing temperature-sensitive functional materials, this single protection mode is even more insufficient. Therefore, the present invention constructs a multi-dimensional protection system through the optimization of specific antioxidants and the composite addition of ultraviolet absorbers, successfully solving the technical problem of functional degradation of temperature-sensitive nitrile gloves during long-term use.

[0041] Specifically, when 2,2,4-trimethyl-1,2-dihydroquinoline polymer is selected as an antioxidant, it is a polymeric antioxidant with the characteristics of large molecular weight and slow migration speed, and can play a long-term and stable role in rubber products. The quinoline ring in its molecular structure has the ability to capture free radicals, which can effectively interrupt the chain reaction of rubber oxidation degradation. In addition, there is a special interaction between 2,2,4-trimethyl-1,2-dihydroquinoline polymer and the polyurethane microcapsule shell. The nitrogen atom in its molecule can form a weak hydrogen bond with the carbonyl group in the polyurethane. This interaction is not Not only does it not destroy the microcapsule structure, but it can also form a protective layer on the surface of the microcapsule, significantly reducing the loss rate of the phase change material during the thermal oxidative aging process. At the same time, the present invention also adds a UV absorber to enable the prepared nitrile gloves to have UV protection function. This is because ultraviolet radiation can directly destroy the rubber molecular chain and also cause photooxidative deterioration of the phase change paraffin. Therefore, the present invention constructs a complete light-heat synergistic protection system by adding 0.1-0.3 parts of UV absorber. If the amount of UV absorber is too small, the protection effect is insufficient, and if too much is used, it may affect the vulcanization characteristics of the rubber material.

[0042] The present invention also provides a method for preparing the above-mentioned highly wear-resistant and temperature-sensitive nitrile gloves, comprising the following steps:

[0043] Dilute the temperature-sensitive material with a portion of pure water, add ethanol, polycarboxylate sodium salt dispersant and sodium dodecylbenzenesulfonate during the dilution process, and stir evenly to obtain a temperature-sensitive suspension;

[0044] Mixing butadiene-acrylonitrile latex, chlorinated polyvinyl chloride, vulcanizing agent, accelerator, compatibilizer, antioxidant and the remaining portion of pure water, stirring evenly and pre-vulcanizing for 16-18 hours to obtain a latex system;

[0045] The prepared temperature-sensitive suspension was filtered and added to the latex system, and the pre-curing was continued for 19-20 hours to obtain a mixed solution;

[0046] Add the wear-resistant additive to the mixed liquid and stir evenly to obtain the rubber compound;

[0047] The rubber material is passed through a nitrile glove production line for leaching, lip curling, vulcanization, chlorine washing, washing, drying and demoulding to obtain highly wear-resistant and temperature-sensitive nitrile gloves.

[0048] Preferably, as a further specific embodiment, the chlorine washing uses a sodium hypochlorite solution with a concentration of 5-10%, and the washing uses deionized water.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] (1) The present invention provides a highly wear-resistant and temperature-sensitive nitrile glove. The glove uses nitrile latex as the main raw material. By adding temperature-sensitive materials, wear-resistant additives and other functional additives, it achieves a combination of high wear resistance and temperature regulation function, thereby solving the problems of insufficient wear resistance and poor temperature adaptability of traditional nitrile gloves in extreme environments.

[0051] (2) The present invention provides a method for preparing the above-mentioned highly wear-resistant and temperature-sensitive nitrile gloves. The preparation method ensures that the components are fully cross-linked through a staged pre-vulcanization process, thereby avoiding interference with the vulcanization process caused by the addition of temperature-sensitive materials. DETAILED DESCRIPTION

[0052] The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. However, those skilled in the art will understand that the embodiments described below are part of the embodiments of the present invention, not all of them, and are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0053] In order to more clearly illustrate the technical solutions of the present invention, specific embodiments are provided below for illustration.

[0054] Example 1

[0055] The preparation process of the highly wear-resistant and temperature-sensitive nitrile gloves of the present invention is as follows:

[0056] raw material:

[0057] 80 parts of nitrile latex;

[0058] 5 parts of chlorinated polyvinyl chloride;

[0059] 8 parts of temperature-sensitive material (microcapsules of phase-change paraffin wrapped in a polyurethane shell, 0.1 parts of polyvinyl pyrrolidone);

[0060] 1.2 parts of ethanol;

[0061] 0.5 parts of polycarboxylate sodium salt dispersant;

[0062] 0.3 parts of sodium dodecylbenzenesulfonate;

[0063] 3 parts of wear-resistant additive (nano-silicon dioxide);

[0064] 1 part of vulcanizing agent (sulfur);

[0065] 0.5 parts of accelerator (zinc diethyldithiocarbamate);

[0066] 2 parts of compatibilizer (maleic anhydride grafted compound);

[0067] 0.5 parts of antioxidant (0.4 parts of 2,2,4-trimethyl-1,2-dihydroquinoline polymer and 0.1 parts of benzotriazole ultraviolet absorber);

[0068] 20 parts of pure water;

[0069] Preparation process:

[0070] Preparation of temperature-sensing material: Microcapsules with polyurethane shells wrapped in phase-change paraffin wax were prepared by polymerization method, as follows:

[0071] Paraffin emulsification:

[0072] Heat the phase change paraffin wax to a molten state, add the emulsifier sodium lauryl sulfate and deionized water, and emulsify in a high-speed homogenizer for 10 minutes to form a paraffin wax emulsion;

[0073] Aqueous dispersion:

[0074] Slowly pour the dispersant polyvinyl alcohol into the paraffin emulsion, maintain the temperature at 40°C, and continue stirring to form a stable emulsion;

[0075] Interfacial polymerization:

[0076] Add polyurethane prepolymer (shell material diisocyanate) dropwise into the emulsion. After the addition is complete, add catalyst dibutyltin dilaurate. Heat to 60°C and react for 2 hours.

[0077] Post-processing:

[0078] After the reaction is completed, the material is cooled to room temperature, filtered, collected, washed, and dried to obtain the temperature-sensitive material.

[0079] Preparation of thermosensitive suspension:

[0080] Mix 8 parts of temperature-sensitive material (phase-change paraffin containing polyvinyl pyrrolidone wrapped in a polyurethane shell) with 8 parts of pure water, add 1.2 parts of ethanol, 0.5 parts of polycarboxylate sodium salt dispersant and 0.3 parts of sodium dodecylbenzene sulfonate, and stir for 30 minutes until uniform suspension;

[0081] Pre-vulcanization of latex system: Mix 80 parts of nitrile latex, 5 parts of chlorinated polyvinyl chloride, 1 part of sulfur, 0.5 parts of accelerator, 0.5 parts of antioxidant, 2 parts of compatibilizer and 12 parts of pure water, stir for 1 hour, and pre-vulcanize at 25℃ for 16 hours;

[0082] Preparation of mixed solution: slowly filter the temperature-sensitive suspension and add it to the pre-cured latex system, continue stirring and pre-curing for 19 hours;

[0083] Rubber preparation: add 3 parts of nano-silica and stir for 1 hour until uniform;

[0084] Glove molding: The rubber compound is injected into the glove mold, and then leached (60℃, 5min), lip rolled, vulcanized (120℃, 30min), chlorine washed (5% sodium hypochlorite solution), washed (deionized water), dried (70℃, 20min) and demoulded to obtain the finished product.

[0085] Example 2

[0086] The preparation process of the highly wear-resistant and temperature-sensitive nitrile gloves of the present invention is as follows:

[0087] raw material:

[0088] 120 parts of nitrile latex;

[0089] 15 parts of chlorinated polyvinyl chloride;

[0090] 12 parts of temperature-sensitive material (microcapsules of phase-change paraffin wrapped in a polyurethane shell, 0.3 parts of polyvinyl pyrrolidone);

[0091] 3 parts of ethanol;

[0092] 2 parts of polycarboxylate sodium salt dispersant;

[0093] 1 part of sodium dodecylbenzenesulfonate;

[0094] 5 parts of wear-resistant additive (nano-silicon carbide);

[0095] 2 parts of vulcanizing agent (sulfur);

[0096] 1 part accelerator (zinc diethyldithiocarbamate);

[0097] 3 parts of compatibilizer (maleic anhydride grafted compound);

[0098] 1 part of antioxidant (0.6 part of N-isopropyl-N'-phenyl-p-phenylenediamine and 0.3 part of benzotriazole ultraviolet absorber);

[0099] 40 parts of pure water;

[0100] Preparation process:

[0101] Preparation of temperature-sensing material: Microcapsules with polyurethane shells wrapped in phase-change paraffin wax were prepared by polymerization method, as follows:

[0102] Paraffin emulsification:

[0103] Heat the phase change paraffin wax to a molten state, add the emulsifier sodium lauryl sulfate and deionized water, and emulsify in a high-speed homogenizer for 10 minutes to form a paraffin wax emulsion;

[0104] Aqueous dispersion:

[0105] Slowly pour the dispersant polyvinyl alcohol into the paraffin emulsion, maintain the temperature at 40°C, and continue stirring to form a stable emulsion;

[0106] Interfacial polymerization:

[0107] Add polyurethane prepolymer (shell material diisocyanate) dropwise into the emulsion. After the addition is complete, add catalyst dibutyltin dilaurate. Heat to 60°C and react for 2 hours.

[0108] Post-processing:

[0109] After the reaction is completed, the material is cooled to room temperature, filtered, collected, washed, and dried to obtain the temperature-sensitive material.

[0110] Preparation of thermosensitive suspension:

[0111] Mix 12 parts of temperature-sensitive material (phase-change paraffin containing polyvinyl pyrrolidone wrapped in a polyurethane shell) with 12 parts of pure water, add 3 parts of ethanol, 2 parts of polycarboxylate sodium salt dispersant and 1 part of sodium dodecylbenzene sulfonate, and stir for 30 minutes until uniform suspension;

[0112] Pre-vulcanization of latex system: Mix 120 parts of nitrile latex, 15 parts of chlorinated polyvinyl chloride, 2 parts of sulfur, 1 part of accelerator, 1 part of antioxidant, 3 parts of compatibilizer and 28 parts of pure water, stir for 2 hours, and pre-vulcanize at 30℃ for 18 hours;

[0113] Preparation of mixed solution: slowly filter the temperature-sensitive suspension and add it to the pre-cured latex system, continue stirring and pre-curing for 20 hours;

[0114] Rubber compound preparation: add 5 parts of nano silicon carbide and stir for 1 hour;

[0115] Glove molding: After the rubber compound is impregnated in the mold, it is leached (70℃, 3min), lip rolled, vulcanized (130℃, 35min), chlorine washed (10% sodium hypochlorite solution), washed (deionized water), dried (80℃, 10min) and demoulding.

[0116] Example 3

[0117] The preparation process of the highly wear-resistant and temperature-sensitive nitrile gloves of the present invention is as follows:

[0118] raw material:

[0119] 110 parts of nitrile latex;

[0120] 10 parts of chlorinated polyvinyl chloride;

[0121] 10 parts of temperature-sensitive material (microcapsules of phase-change paraffin wrapped in a polyurethane shell, 0.2 parts of polyvinyl pyrrolidone);

[0122] 2 parts of ethanol;

[0123] 1 part of polycarboxylate sodium salt dispersant;

[0124] Sodium dodecyl benzene sulfonate 0.6 parts;

[0125] Wear-resistant additive 4 parts (nano-silicon dioxide and nano-silicon carbide mixed in a mass ratio of 1:1);

[0126] Vulcanizing agent 1.5 parts (bis-(tert-butyl peroxyisopropyl) benzene);

[0127] Accelerator 0.8 parts (zinc diethyl dithiocarbamate);

[0128] Compatibilizer 3 parts;

[0129] Anti-aging agent 0.8 parts (N-isopropyl-N'-phenyl-p-phenylenediamine 0.6 parts, benzotriazole ultraviolet absorber 0.2 parts);

[0130] Pure water 30 parts;

[0131] Preparation process:

[0132] Preparation of temperature-sensitive material: polyurethane shell encapsulated phase change paraffin microcapsules are prepared by polymerization, as follows:

[0133] Paraffin emulsification:

[0134] Heat the phase change paraffin to a molten state, add the emulsifier sodium dodecyl sulfate and deionized water, and emulsify in a high-speed homogenizer for 10 min to form a paraffin emulsion;

[0135] Water phase dispersion:

[0136] Slowly pour the paraffin emulsion into the dispersant polyvinyl alcohol, keep the temperature at 40℃, and continuously stir to form a stable emulsion;

[0137] Interfacial polymerization:

[0138] Add the polyurethane prepolymer (shell material diisocyanate) dropwise to the emulsion, add the catalyst dibutyltin dilaurate after the addition is complete, warm up to 60℃, and react for 2h;

[0139] Post-treatment:

[0140] After the reaction is complete, cool to room temperature, collect, wash, and dry to obtain the temperature-sensitive material;

[0141] Preparation of temperature-sensitive suspension:

[0142] Mix 10 parts of temperature-sensitive material (polyurethane shell encapsulated phase change paraffin containing polyvinylpyrrolidone) with 10 parts of pure water, add 2 parts of ethanol, 1 part of polycarboxylic acid sodium salt dispersant, and 0.6 parts of sodium dodecyl benzene sulfonate, and stir for 30 min until uniformly suspended;

[0143] Pre-vulcanization of latex system: Mix 110 parts of nitrile latex, 10 parts of chlorinated polyvinyl chloride, 1.5 parts of sulfur, 0.8 parts of accelerator, 0.8 parts of antioxidant, 3 parts of compatibilizer and 20 parts of pure water, stir for 1.5 hours, and pre-vulcanize at 28°C for 17 hours;

[0144] Preparation of mixed solution: slowly filter the temperature-sensitive suspension and add it to the pre-cured latex system, continue stirring and pre-curing for 19 hours;

[0145] Rubber compounding: Add 2 parts of nano-silicon dioxide and 2 parts of nano-silicon carbide and stir for 40 minutes;

[0146] Glove molding: After the rubber compound is impregnated and molded, it is leached (65℃, 4min), lip rolled, vulcanized (150℃, 25min), chlorine washed (8% sodium hypochlorite solution), washed (deionized water), dried (75℃, 15min) and demolded.

[0147] Comparative Example 1

[0148] The specific preparation steps are the same as those in Example 3, except that the amount of polyvinyl pyrrolidone in Example 3 is adjusted to 0.05 parts.

[0149] Comparative Example 2

[0150] The specific preparation steps are the same as those in Example 3, except that the amount of polyvinyl pyrrolidone in Example 3 is adjusted to 1 part.

[0151] Comparative Example 3

[0152] The specific preparation steps are consistent with those in Example 3, except that the mass ratio of nano-silicon dioxide to nano-silicon carbide in Example 3 is adjusted to 0.5:1.

[0153] Comparative Example 4

[0154] The specific preparation steps are the same as those in Example 3, except that the mass ratio of nano-silicon dioxide to nano-silicon carbide in Example 3 is adjusted to 1:3.

[0155] Comparative Example 5

[0156] The specific preparation steps are the same as those in Example 3, except that the amount of the ultraviolet absorber in the antioxidant in Example 3 is adjusted to 0.01 parts.

[0157] Comparative Example 6

[0158] The specific preparation steps are the same as those in Example 3, except that the amount of the ultraviolet absorber in the antioxidant in Example 3 is adjusted to 1 part.

[0159] Comparative Example 7

[0160] The specific preparation steps are the same as those in Example 3, except that polyvinyl pyrrolidone is not added to the temperature-sensitive material.

[0161] Comparative Example 8

[0162] The specific preparation steps are the same as those in Example 3, except that no ultraviolet absorber is added to the antioxidant.

[0163] Experimental Example 1 Performance Test of Highly Wear-Resistant and Warm-Sensitive Nitrile Gloves

[0164] The gloves finally prepared in Examples 1-3 and Comparative Examples 1-8 were used as samples for testing of abrasion resistance, temperature regulation performance, tensile strength and elongation at break, performance retention after UV aging, and microcapsule integrity.

[0165] The specific testing process is as follows:

[0166] 1.1 Wear resistance test

[0167] Operation: Use Taber abrasion tester (H18 grinding wheel, 500g load);

[0168] The glove samples finally prepared in Examples 1-3 and Comparative Examples 1-8 were cut into discs with a diameter of 100 mm and fixed on a rotating platform;

[0169] Rub 1000 times at a speed of 60 r / min, and weigh the mass loss (mg) before and after wear;

[0170] Calculate the wear rate: Wear rate = (mass loss / number of frictions) × 1000;

[0171] 1.2 Temperature regulation performance

[0172] Procedure: Place the glove sample in a -10°C environmental chamber for 30 minutes and record the initial inner surface temperature (T1);

[0173] Rapidly transfer to a 50°C environmental chamber, record the temperature (T2-T6) every 5 minutes using an infrared thermal imager, and calculate the heating rate (°C / min);

[0174] Repeat 3 times and take the average value;

[0175] 1.3 Tensile strength and elongation at break

[0176] Operation: Cut the dumbbell-shaped specimen (thickness 2mm);

[0177] A universal material testing machine (tensile speed 500 mm / min) was used to record the maximum tensile force (MPa) and elongation at break (%);

[0178] 1.4 Performance retention rate after UV aging

[0179] Operation: Place the sample in a UV aging box (UVA-340 lamp, 0.76W / m 2 , 60°C) irradiation for 200h;

[0180] Tensile strength retention rate after test aging (%);

[0181] 1.5 Microcapsule integrity (leakage rate)

[0182] Method: Cut the glove samples into pieces and soak them in 50℃ ethanol for 24h;

[0183] The solution was filtered, the paraffin content was detected by gas chromatography, and the leakage rate (%) was calculated;

[0184] The final test results are shown in Table 1 below:

[0185] Table 1 Test results

[0186]

[0187] As can be seen from the above table, Examples 1-3 demonstrate the optimized formula and process effects of the high-wear-resistant and temperature-sensitive nitrile gloves of the present invention. The comprehensive performance of Example 3 is the best, and the data results obtained in Comparative Examples 1-2 show that when the amount of polyvinyl pyrrolidone in Comparative Example 1 is small, the microcapsule leakage rate at this time is as high as 4.5%, and the heating rate is significantly worse than that of Example 3, indicating that when the amount of polyvinyl pyrrolidone is insufficient, the microcapsule shell is easily broken during the vulcanization process, resulting in leakage of phase change paraffin and weakening the temperature sensing function; and when the amount of polyvinyl pyrrolidone in Comparative Example 2 is too high, although the leakage rate is low, the wear rate and tensile strength are not as good as those in Example 3. This is because excessive polyvinyl pyrrolidone increases the viscosity of the rubber, hinders the uniform dispersion of the wear-resistant additive, and affects the vulcanization efficiency. In addition, the strength retention rate of both after ultraviolet aging is lower than that of Example 3, further proving that when the amount of polyvinyl pyrrolidone deviates from the range of 0.1-0.3 parts, it is impossible to effectively cooperate with the antioxidant system;

[0188] From the data of Comparative Examples 3-4, it can be seen that when the mass ratio of nano-silicon dioxide to nano-silicon carbide in Comparative Example 3 is low, the wear rate at this time increases significantly. This is because the excessive nano-silicon carbide causes the rubber material to be too rigid, the flexibility is reduced, and the nanoparticles are unevenly dispersed; and when the mass ratio in Comparative Example 4 is too high, the wear rate further deteriorates to 16.8 mg / 1000 times, and the tensile strength is the lowest, indicating that when the proportion of nano-silicon carbide is too high, its high hardness can resist puncture, but it sacrifices the elasticity of the overall network and reduces the wear resistance. The temperature sensing performance of the two is close to that of Example 3, indicating that the thermal conductivity advantage of nano-silicon carbide can still be partially retained, but the imbalance of mechanical properties leads to a decrease in the comprehensive protection effect.

[0189] As can be seen from Comparative Example 5-6, when the amount of the ultraviolet absorber in Comparative Example 5 is low, the strength retention rate of the glove is only 80.3%, which is much lower than that of Example 3, because insufficient ultraviolet protection leads to accelerated photo-oxidation of the rubber molecular chain and the phase change paraffin; when the amount of the ultraviolet absorber in Comparative Example 6 is too high, the glove prepared has a higher performance retention rate after aging, but the wear rate and tensile strength are slightly lower than those of Example 3, because the excess ultraviolet absorber interferes with the vulcanization reaction and slightly reduces the crosslinking density;

[0190] As can be seen from the data of Comparative Example 7, when no polyvinylpyrrolidone stabilizer is added in Comparative Example 7, the microcapsule leakage rate of the glove prepared is as high as 8.3%, and the temperature rise rate is significantly deteriorated, which proves that the polyvinylpyrrolidone is indispensable for the protection of the microcapsule shell; in addition, the wear rate and tensile strength are the worst, because the leaked paraffin after the rupture of the microcapsule interferes with the vulcanization of the latex, resulting in defects in the crosslinking network; the strength retention rate after ultraviolet aging is also greatly reduced, which shows that the absence of polyvinylpyrrolidone not only affects the temperature sensing function, but also weakens the overall effectiveness of the antioxidant system;

[0191] As can be seen from the data of Comparative Example 8, when no ultraviolet absorber is added in Comparative Example 8, the strength retention rate of the glove prepared after ultraviolet aging is much lower than that of Example 3, which shows that the rubber molecular chain and the phase change paraffin are easily subjected to photo-oxidation degradation in the absence of ultraviolet protection, although the initial mechanical properties are close to those of Example 3, but the long-term durability is significantly insufficient, which highlights the necessity of the ultraviolet absorber in prolonging the service life of the glove, especially in outdoor or strong light environment.

[0192] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, but not to limit them; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions described in the foregoing examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A highly wear-resistant and temperature-sensitive nitrile glove, characterized in that: Calculated by mass, it includes the following raw materials: 80-120 parts of nitrile latex; 5-15 parts of chlorinated polyvinyl chloride; 8-12 portions of temperature-sensitive materials; 1.2-3 parts of ethanol; 0.5-2 parts of polycarboxylate sodium salt dispersant; 0.3-1 part of sodium dodecylbenzenesulfonate; 3-5 parts of wear-resistant additives; 1-2 parts of vulcanizing agent; Accelerator 0.5-1 part; 2-3 parts of compatibilizer; Antiaging agent 0.5-1 part; 20-40 parts of pure water; The temperature-sensitive material is a microcapsule with a temperature memory function, the shell of which is polyurethane and the core of which is phase-change paraffin.

2. The high wear-resistant and temperature-sensitive nitrile gloves according to claim 1, characterized in that: 0.1-0.3 parts of a stabilizer is also added to the temperature-sensitive material, and the stabilizer is polyvinyl pyrrolidone.

3. The high wear-resistant and temperature-sensitive nitrile gloves according to claim 1, characterized in that: The wear-resistant additive is one of nano-silicon dioxide and nano-silicon carbide or a combination of the two.

4. The high wear-resistant and temperature-sensitive nitrile gloves according to claim 3, characterized in that: The wear-resistant additive is a combination of nano-silicon dioxide and nano-silicon carbide, and the mass ratio of the nano-silicon dioxide to the nano-silicon carbide is 1:

1.

5. The highly wear-resistant and temperature-sensitive nitrile gloves according to claim 1, characterized in that: The vulcanizing agent is one of sulfur or peroxide, wherein the peroxide is bis-(tert-butylperoxyisopropyl)benzene.

6. The highly wear-resistant and temperature-sensitive nitrile gloves according to claim 1, characterized in that: The accelerator is one of tetramethylthiuram disulfide and zinc diethyldithiocarbamate.

7. The highly wear-resistant and temperature-sensitive nitrile gloves according to claim 1, characterized in that: The antioxidant is one of 2,2,4-trimethyl-1,2-dihydroquinoline polymer or N-isopropyl-N'-phenyl-p-phenylenediamine, and 0.1-0.3 parts of ultraviolet absorber are added to the antioxidant.

8. The high wear-resistant and temperature-sensitive nitrile gloves according to claim 1, characterized in that: The compatibilizer is a maleic anhydride grafted compound.

9. A method for preparing the highly wear-resistant, temperature-sensitive nitrile gloves according to any one of claims 1 to 8, characterized in that: The following steps are involved: Dilute the temperature-sensitive material with a portion of pure water, add ethanol, polycarboxylate sodium salt dispersant and sodium dodecylbenzenesulfonate during the dilution process, and stir evenly to obtain a temperature-sensitive suspension; Mixing butadiene-acrylonitrile latex, chlorinated polyvinyl chloride, vulcanizing agent, accelerator, compatibilizer, antioxidant and the remaining portion of pure water, stirring evenly and pre-vulcanizing for 16-18 hours to obtain a latex system; The prepared temperature-sensitive suspension was filtered and added to the latex system, and the pre-curing was continued for 19-20 hours to obtain a mixed solution; Add the wear-resistant additive to the mixed liquid and stir evenly to obtain the rubber compound; The rubber material is passed through a nitrile glove production line for leaching, lip curling, vulcanization, chlorine washing, washing, drying and demoulding to obtain highly wear-resistant and temperature-sensitive nitrile gloves.

10. The preparation method according to claim 9, characterized in that The chlorine washing adopts a sodium hypochlorite solution with a concentration of 5-10%, and the washing adopts deionized water.

Images