A medical antibacterial nano nitrile glove and its preparation method

Abstract

The present invention discloses a medical antibacterial nano nitrile glove and a preparation method thereof, belonging to the technical field of medical gloves, and is used to solve the technical problems of poor mechanical strength and poor antibacterial property when preparing medical gloves by blending nitrile rubber with other rubber materials in the prior art; the present invention includes antibacterial composite nitrile rubber, chlorinated butyl rubber, microcapsule nano enhancer, anti-aging agent, vulcanization aid and plasticizer. Among them, inorganic materials are ground to different particle sizes and divided into mother particles and son particles. The mother particles and son particles are processed through a micro-nano particle compounding system to obtain composite spherical particles with an inner and outer layer structure. The composite spherical particles are coated with a wall material to prepare a microcapsule nano enhancer. Cyanuric chloride enriches cinnamic acid and then composites with nitrile rubber to improve the antibacterial property of nitrile rubber. The medical antibacterial nano nitrile glove prepared in the present invention has excellent mechanical properties and antibacterial property.

Description

Technical Field

[0001] The present invention relates to the technical field of medical gloves, and specifically relates to a medical antibacterial nano nitrile glove and a preparation method thereof. Background Art

[0002] Rubber is the general term for all polymer elastomers. Through the vulcanization process, linear polymer materials are chemically cross-linked to form three-dimensional network polymer materials, that is, the mixed rubber of various raw rubbers is transformed into vulcanized rubber. As a high-elastic polymer material, rubber has excellent air permeability resistance, resistance to various chemical media, and electrical insulation properties. These properties make rubber an important industrial material that cannot be replaced in polymer materials, such as various tires, wire and cable, rubber hoses, medical gloves, and sealing rubber fittings.

[0003] In addition, rubber can be used, blended, and compounded with a variety of material substances, thereby being modified to obtain good comprehensive properties. For example, by adding inorganic materials and blending with different varieties of rubber, the mechanical properties of rubber itself can be improved.

[0004] Patent application CN103554565A discloses a medical glove prepared by blending natural rubber and nitrile rubber and a preparation method thereof, which is to mix natural rubber latex, nitrile rubber latex, stabilizer, sulfur, zinc oxide, titanium dioxide, and alkaline filler, etc., to prepare a medical glove prepared by blending natural rubber and nitrile rubber; however, there is a problem of uneven distribution of the alkaline filler in the rubber matrix. When improving the mechanical strength of the prepared medical glove, the mechanical properties such as the elongation at break and tensile strength of the prepared medical glove are damaged. In addition, the medical glove itself needs to have certain antibacterial properties.

[0005] Patent application CN112812261A discloses a preparation method of a waterborne polyurethane emulsion and a nitrile rubber-polyurethane composite glove. The waterborne polyurethane emulsion therein is a cationic antibacterial waterborne polyurethane, and phenolic acid is introduced into the waterborne polyurethane to form a quaternary ammonium salt structure to improve the antibacterial efficacy of the prepared composite glove; however, the waterborne polyurethane emulsion and nitrile rubber only improve the compatibility of the two basic materials through hydrogen bonds and electrostatic interactions between cations and anions, and fail to improve the integrity of the prepared glove, that is, the mechanical properties of the prepared composite glove cannot be improved. Therefore, how to prepare a rubber glove with excellent mechanical properties and antibacterial properties is still a technical problem that needs to be solved urgently. In view of the technical defects in this regard, a solution is now proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a preparation method of a medical antibacterial nano nitrile glove, which is used to solve the problems that when preparing medical gloves by blending different varieties of rubber such as nitrile rubber in the prior art, the inorganic fillers added are unevenly distributed in the rubber matrix, reducing the elongation at break and tensile strength of the prepared medical gloves. In addition, the antibacterial performance of medical gloves is also a technical problem that urgently needs to be solved.

[0007] The purpose of the present invention can be achieved by the following technical solutions: A medical antibacterial nano nitrile glove, comprising the following components by weight: 60-80 parts of antibacterial composite nitrile rubber, 20-40 parts of chlorinated butyl rubber, 5-10 parts of microcapsule nano enhancer, 2-3 parts of anti-aging agent, 2-5 parts of vulcanization aid, and 5-10 parts of plasticizer.

[0008] Further, the preparation method of the antibacterial composite nitrile rubber comprises the following steps:

[0009] S1. Mix cinnamic acid, cyanuric chloride, sodium carbonate, and ethanol evenly to obtain a premix; react the premix at 50-60 °C for 2-3 h, then raise the temperature to 70-75 °C and react at this temperature for 2-3 h; then raise the temperature to 80-90 °C and evaporate the ethanol solvent to obtain a solid modified antibacterial agent;

[0010] Using ethanol as a solvent and sodium carbonate as a nucleophile, a nucleophilic substitution reaction occurs between the carboxyl group in cinnamic acid and the chloride ion in cyanuric chloride to form a corresponding esterified product, which is the prepared modified antibacterial agent.

[0011] The reaction formula of cinnamic acid and cyanuric chloride is as follows:

[0012]

[0013] S2. Add the modified antibacterial agent and nitrile rubber to a two-roll mill for uniform dispersion to obtain a mixture; add the mixture to a two-roll open mill for plasticization to obtain antibacterial composite nitrile rubber.

[0014] The modified antibacterial agent and nitrile rubber are physically and uniformly dispersed in a two-roll mill in advance to obtain a mixture. Under high-temperature conditions, due to the presence of unsaturated double bonds in both the modified antibacterial agent and nitrile rubber, a polymerization reaction occurs to prepare antibacterial composite nitrile rubber.

[0015] Further, in step S1, the dosage ratio of cinnamic acid, cyanuric chloride, sodium carbonate, and ethanol is 50-60 g: 18 g: 5 g: 250 mL; in step S2, the dosage ratio of the modified antibacterial agent and nitrile rubber is 1-5 g: 50 g, the plasticization temperature is 120-150 °C, and the plasticization time is 5-10 min.

[0016] Further, the preparation method of the microcapsule nano-enhancer comprises the following steps:

[0017] A1. Grind heavy calcium carbonate until it reaches 300 - 500 μm to obtain mother particles; mix wollastonite and dolomite and grind them until they reach 30 - 50 μm to obtain daughter particles; add the mother particles and daughter particles to a micro-nano particle compounding system for compounding and spheroidization treatment to obtain composite spherical particles.

[0018] Using heavy calcium carbonate as the mother particles and the mixture of wollastonite and dolomite as the daughter particles, after grinding, the diameter ratio of the mother particles to the daughter particles is 10:1. Then add the mother particles and daughter particles to the micro-nano particle compounding system to prepare composite spherical particles.

[0019] A2. React methanol and trichlorosilane at 20 - 30 °C for 2 - 3 h to obtain a product; the product splits, and the fraction of polymethoxysilane is intercepted.

[0020] Methanol and trichlorosilane undergo alcoholysis reaction to prepare polymethoxysilane with different numbers of methoxy groups.

[0021] The reaction formula of methanol and trichlorosilane is as follows:

[0022]

[0023] A3. Mix gelatin and deionized water, heat and stir until completely dissolved; then add casein and polymethoxysilane to obtain a mixed liquid; add 1 mol / L NaOH solution dropwise to the mixed liquid to adjust the pH value of the mixed liquid to 8 - 9 to completely dissolve casein. First, react at 80 - 90 °C for 2 - 3 h, and then let it stand at room temperature for 24 h to obtain a wall material solution.

[0024] Using gelatin and casein as the wall material of the prepared microcapsule nano-enhancer; among them, polymethoxysilane undergoes hydrolysis reaction in the wall material solution to obtain silanol, and silanol can undergo esterification reaction with the carboxyl groups of amino acids in gelatin and casein. After standing for a period of time, a wall material solution modified by a coupling agent is obtained.

[0025] S4. Add the composite spherical particles to the wall material solution, then use 1 mol / L citric acid to adjust the pH value of the wall material solution to 2 - 3, and use spray drying to prepare a nano-level microcapsule enhancer.

[0026] The present invention adopts the spray drying method, using the composite spherical particles as the core material and the wall material to coat the composite spherical particles to prepare a nano-level microcapsule enhancer.

[0027] Further, in step A1, by weight, the dosage ratio of wollastonite to dolomite is 1:1, and the dosage ratio of the mother particles to the daughter particles is 2:1; the rotor speed of the PCS system is 2000 - 3000 r / min, and the processing duration is 10 - 20 min.

[0028] Further, in step A2, the dosage ratio of methanol to trichlorosilane is 96 g:100 - 135 g; in step A3, the dosage ratio of gelatin, deionized water, casein, and polymethoxysilane is 15 g:300 mL:5 g:10 - 20 g; in step A4, the dosage ratio of the composite spherical particles to the wall material solution is 50 - 60 g:100 mL.

[0029] As another aspect of the present invention, a preparation method of a medical antibacterial nano - nitrile glove includes the following steps:

[0030] B1. Add the antibacterial composite nitrile rubber and chlorinated butyl rubber into an open mill for mixing, and then successively add antioxidant additives, vulcanization additives, and plasticizers. Under the action of double - roll shearing, each component is in a cutting and mixing state to obtain a vulcanized rubber material;

[0031] B2. Add the vulcanized rubber material into a mold, pressurize and form it under a high - temperature vulcanizer, then take out the mold, cool it to room temperature, and demold to obtain the antibacterial composite nitrile rubber.

[0032] Further, in step B1, by weight, the dosage ratio of the antibacterial composite nitrile rubber, chlorinated butyl rubber, antioxidant additives, vulcanization additives, and plasticizers is 60 - 80:20 - 40:2 - 3:2 - 5:5 - 10; by weight, the antioxidant additives include 10 parts of naphthylamine - type antioxidant and 10 parts of keto - amine - type antioxidant. The naphthylamine - type antioxidant is any one of antioxidant A, antioxidant MB, and antioxidant NDPA; the keto - amine - type antioxidant is any one of antioxidant RD and antioxidant BLE; by weight, the vulcanization additives include 2 - 5 parts of sulfur, 0.5 part of vulcanization accelerator, and 0.5 part of vulcanization activator; the plasticizer is any one of black ointment, white ointment, or castor oil.

[0033] Further, in step B2, the vulcanization temperature is 200 °C, and the vulcanization duration is 3 - 5 min.

[0034] The medical antibacterial nano - nitrile glove prepared by the present invention includes the main materials of antibacterial composite nitrile rubber and chlorinated butyl rubber, and the added additives include antioxidant additives, vulcanization additives, and plasticizers. Among them, the vulcanization additives include sulfur, vulcanization accelerator, and vulcanization activator.

[0035] The present invention has the following beneficial effects:

[0036] 1. The medical antibacterial nano nitrile gloves prepared by the present invention use nitrile rubber and chlorinated butyl rubber as the base materials, and add microcapsule nano-enhancers to improve their mechanical properties. The microcapsule nano-enhancers use composite spherical particles as the core material and gelatin, casein, and polymethoxysilane as the wall material components. Grinding inorganic materials to the nanoscale can enhance their mechanical properties and is beneficial to uniform dispersion in the base rubber material. To avoid agglomeration of inorganic materials with tiny particle sizes in the rubber base material, the present invention prepares the inorganic materials into microcapsules. The inorganic materials are divided into mother particles and sub-particles according to the grinding particle size, and are processed through a micro-nano particle compounding system to obtain composite spherical particles with an inner and outer layer and a dense structure. Since polymethoxysilane can react with gelatin and casein, the compactness of the wall material is improved. The present invention uses the spray drying method to disperse the core material in the wall material solution. During the spray drying process, the hot air flow will quickly evaporate the water in the droplets, and the wall material will form a network structure that can both shield the core material particles and allow the water to evaporate from them, forming a dense vitreous structure. By adding microcapsule nano-enhancers, the present invention can significantly improve the mechanical properties such as tensile strength, elongation at break, and hardness of the prepared medical antibacterial nano nitrile gloves.

[0037] 2. The present invention pre-treats nitrile rubber with antibacterial modification; uses cyanuric chloride as a carrier to enrich the antibacterial substance cinnamic acid, thereby obtaining a modified antibacterial agent with improved antibacterial efficiency; both nitrile rubber and the modified antibacterial agent contain unsaturated double bonds, and are plastisized under high-temperature conditions to carry out an addition reaction, thereby preparing an antibacterial composite nitrile rubber grafted with a modified antibacterial agent. The antibacterial composite nitrile rubber and chlorinated butyl rubber are mixed and polyadded to obtain a vulcanized rubber material; the double bonds in the antibacterial composite nitrile rubber and chlorinated butyl rubber are further added to increase the structural saturation degree, thereby further improving the heat resistance and aging resistance of the vulcanized rubber material itself. By designing the proportions of related additives such as anti-aging additives, vulcanization additives, and plasticizers, the present invention prepares a medical antibacterial nano nitrile rubber with excellent mechanical properties and strong antibacterial properties. Specific embodiments

[0038] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

[0039] Example 1

[0040] This example provides a preparation method for a microcapsule nano-enhancer for medical antibacterial nano nitrile gloves, including the following steps:

[0041] A1. Heavy calcium carbonate is added to a planetary ball mill for grinding, and the particle size of the heavy calcium carbonate is ground to 300 μm to obtain mother particles; by weight, 10 parts of wollastonite and 10 parts of dolomite are added to the planetary ball mill, and the particle size is ground to 30 μm to obtain sub-particles; by weight, 20 parts of the mother particles and 10 parts of the sub-particles are put into a micro-nano particle compounding system to perform compounding and spheroidization treatment on the mother particles and the sub-particles to obtain composite spherical particles. Among them, argon is used as the protective gas in the micro-nano particle compounding system, the rotor speed of the system is 2000 r / min, and the treatment duration of the system is 10 min.

[0042] A2. A 500 mL three-necked flask is respectively connected to a condenser and a magnetic stirrer. 96 g of methanol and 100 g of trichlorosilane are added to the three-necked flask, and cooling medium water is introduced into the condenser. Then the three-necked flask is heated to 20 °C and reacted for 2 h to obtain a product; the product is fractionated, and the fraction of the target product polymethoxysilane is intercepted.

[0043] A3. 15 g of gelatin and 300 mL of deionized water are added to a 500 mL beaker. The beaker is heated and stirred until the gelatin is completely dissolved, and then 5 g of casein and 10 g of polymethoxysilane are added to obtain a mixed solid-liquid; then the pH value of the mixed solid-liquid is adjusted to 8 with 1 mol / L NaOH solution to make the casein completely dissolve. First, react at 80 - 90 °C for 2 - 3 h, and then stand at room temperature for 24 h to obtain a wall material solution;

[0044] A4. 50 g of the composite spherical particles are added to 100 mL of the wall material solution, and then the pH value of the wall material solution is adjusted to 2 with 1 mol / L citric acid, and a microcapsule nano-enhancer is prepared by spray drying; during the spray drying process, the inlet air temperature is 120 °C, the feeding speed is 15 mL / min, and the air inlet volume is 1 m 3 / min.

[0045] Example 2

[0046] This example provides a preparation method of a microcapsule nano-enhancer for medical antibacterial nano nitrile gloves, including the following steps:

[0047] A1. Add heavy calcium carbonate to a planetary ball mill for grinding, grind the particle size of the heavy calcium carbonate to 400 μm to obtain mother particles; by weight, add 10 parts of wollastonite and 10 parts of dolomite to the planetary ball mill, grind the particle size to 40 μm to obtain sub-particles; by weight, add 20 parts of the mother particles and 10 parts of the sub-particles to a micro-nano particle compounding system, and perform compounding and spheroidization treatment on the mother particles and sub-particles to obtain composite spherical particles. Among them, the micro-nano particle compounding system uses argon as a protective gas, the rotor speed of the system is 2500 r / min, and the processing duration of the system is 15 min.

[0048] A2. Connect a 500 mL three-necked flask to a condenser and a magnetic stirrer. Add 96 g of methanol and 115 g of trichlorosilane to the three-necked flask, pass cooling medium water into the condenser, and then heat the three-necked flask to 25 °C and react for 2.5 h to obtain a product; fractionate the product and intercept the fraction of the target product polymethoxysilane.

[0049] A3. Add 15 g of gelatin and 300 mL of deionized water to a 500 mL beaker, heat and stir the beaker until the gelatin is completely dissolved, then add 5 g of casein and 15 g of polymethoxysilane to obtain a mixed solid-liquid; then adjust the pH value of the mixed solid-liquid to 8.3 with 1 mol / L NaOH solution to completely dissolve the casein. First, react at 80 - 90 °C for 2 - 3 h, and then let it stand at room temperature for 24 h to obtain a wall material solution;

[0050] A4. Add 53 g of the composite spherical particles to 100 mL of the wall material solution, then adjust the pH value of the wall material solution to 2.5 with 1 mol / L citric acid, and prepare a microcapsule nano-enhancer by spray drying; during the spray drying process, the inlet air temperature is 125 °C, the feeding rate is 15 mL / min, and the air intake is 2 m 3 / min.

[0051] Example 3

[0052] This example provides a preparation method of a microcapsule nano-enhancer for medical antibacterial nano nitrile gloves, including the following steps:

[0053] A1. Heavy calcium carbonate is added to a planetary ball mill for grinding, and the particle size of the heavy calcium carbonate is ground to 500 μm to obtain mother particles; by weight, 10 parts of wollastonite and 10 parts of dolomite are added to the planetary ball mill, and the particle size is ground to 50 μm to obtain sub-particles; by weight, 20 parts of the mother particles and 10 parts of the sub-particles are added to a micro-nano particle compounding system to perform compounding and spheroidization treatment on the mother particles and the sub-particles to obtain composite spherical particles. Among them, argon is used as the protective gas in the micro-nano particle compounding system, the rotor speed of the system is 3000 r / min, and the processing duration of the system is 20 min.

[0054] A2. A 500 mL three-necked flask is respectively connected to a condenser and a magnetic stirrer. 96 g of methanol and 135 g of trichlorosilane are added to the three-necked flask. Cooling medium water is introduced into the condenser, and then the temperature of the three-necked flask is raised to 30 °C and reacted for 3 h to obtain a product; the product is fractionated, and the fraction of the target product polymethoxysilane is intercepted.

[0055] A3. 15 g of gelatin and 300 mL of deionized water are added to a 500 mL beaker. The beaker is heated and stirred until the gelatin is completely dissolved, and then 5 g of casein and 20 g of polymethoxysilane are added to obtain a mixed solid-liquid; then the pH value of the mixed solid-liquid is adjusted to 9 with 1 mol / L NaOH solution to completely dissolve the casein. First, react at 90 °C for 3 h, and then stand at room temperature for 24 h to obtain a wall material solution.

[0056] A4. 60 g of the composite spherical particles are added to 100 mL of the wall material solution, and then the pH value of the wall material solution is adjusted to 3 with 1 mol / L citric acid, and a microcapsule nano-enhancer is prepared by spray drying; during the spray drying process, the inlet air temperature is 130 °C, the feeding speed is 15 mL / min, and the air inlet volume is 3 m 3 / min.

[0057] Example 4

[0058] This example provides a preparation method of an antibacterial composite nitrile rubber for medical antibacterial nano nitrile gloves, including the following steps:

[0059] S1. 50 g of cinnamic acid, 18 g of cyanuric chloride, 5 g of sodium carbonate and 250 mL of ethanol are added to a 500 mL three-necked flask. One end of the three-necked flask is connected to a stirrer, one end is connected to a thermometer, and one end is sealed. The mixture is stirred at 100 r / min at room temperature for 5 min to obtain a premix; then the three-necked flask is transferred to a water bath, reacted at 50 °C for 2 h, then heated to 70 °C and reacted at this temperature for 2 h, and then heated to 80 °C to evaporate the ethanol solvent to obtain a solid, which is the modified antibacterial agent.

[0060] S2. Mix 1 g of the modified antibacterial agent and 50 g of nitrile rubber, and achieve uniform dispersion in a two-roll mill to obtain a mixture; add the mixture to a two-roll open mill and plasticize it at 120 °C for 5 min to obtain the antibacterial composite nitrile rubber.

[0061] Example 5

[0062] This example provides a preparation method of antibacterial composite nitrile rubber for medical antibacterial nano nitrile gloves, including the following steps:

[0063] S1. Add 53 g of cinnamic acid, 18 g of cyanuric chloride, 5 g of sodium carbonate and 250 mL of ethanol to a 500 mL three-necked flask. One end of the three-necked flask is connected to a stirrer, one end is connected to a thermometer, and one end is sealed. Mix and stir at 150 r / min at room temperature for 6 min to obtain a premix; then transfer the three-necked flask to a water bath, react at 55 °C for 2.5 h, then raise the temperature to 72 °C, react at this temperature for 2.5 h, then raise the temperature to 85 °C, and evaporate the ethanol solvent to obtain a solid, which is the modified antibacterial agent.

[0064] S2. Mix 2 g of the modified antibacterial agent and 50 g of nitrile rubber, and achieve uniform dispersion in a two-roll mill to obtain a mixture; add the mixture to a two-roll open mill and plasticize it at 135 °C for 8 min to obtain the antibacterial composite nitrile rubber.

[0065] Example 6

[0066] This example provides a preparation method of antibacterial composite nitrile rubber for medical antibacterial nano nitrile gloves, including the following steps:

[0067] S1. Add 60 g of cinnamic acid, 18 g of cyanuric chloride, 5 g of sodium carbonate and 250 mL of ethanol to a 500 mL three-necked flask. One end of the three-necked flask is connected to a stirrer, one end is connected to a thermometer, and one end is sealed. Mix and stir at 200 r / min at room temperature for 10 min to obtain a premix; then transfer the three-necked flask to a water bath, react at 60 °C for 3 h, then raise the temperature to 75 °C, react at this temperature for 3 h, then raise the temperature to 90 °C, and evaporate the ethanol solvent to obtain a solid, which is the modified antibacterial agent.

[0068] S2. Mix 5 g of the modified antibacterial agent and 50 g of nitrile rubber, and achieve uniform dispersion in a two-roll mill to obtain a mixture; add the mixture to a two-roll open mill and plasticize it at 150 °C for 10 min to obtain the antibacterial composite nitrile rubber.

[0069] Example 7

[0070] This example provides a preparation method of medical antibacterial nano nitrile gloves, including the following steps:

[0071] B1. By weight, add 60 parts of the antibacterial composite nitrile rubber prepared in Example 4 and 20 parts of chlorinated butyl rubber to an open mill and knead for 4 min. Then, sequentially add 5 parts of the microcapsule nano-reinforcing agent prepared in Example 1, 1 part of antioxidant A, 1 part of antioxidant RD, 1 part of sulfur, 0.25 part of the vulcanization accelerator - thiuram monosulfide, 0.25 part of the vulcanization activator - thiuram monosulfide, and 5 parts of black paste, and mix evenly to obtain a vulcanized rubber material.

[0072] B2. Add the vulcanized rubber material to a mold, and carry out pressure molding at 200 °C in a high-temperature vulcanizer for 3 min; then take out the mold, cool it to room temperature, and demold to obtain the antibacterial composite nitrile rubber.

[0073] Example 8

[0074] This example provides a preparation method of a medical antibacterial nano nitrile glove, including the following steps:

[0075] B1. By weight, add 70 parts of the antibacterial composite nitrile rubber prepared in Example 5 and 30 parts of chlorinated butyl rubber to an open mill and knead for 5 min. Then, sequentially add 8 parts of the microcapsule nano-reinforcing agent prepared in Example 2, 1 part of antioxidant NDPA, 1 part of antioxidant BLE, 1 part of sulfur, 0.25 part of the vulcanization accelerator - thiuram monosulfide, 0.25 part of the vulcanization activator - thiuram monosulfide, and 5 parts of castor oil, and mix evenly to obtain a vulcanized rubber material.

[0076] B2. Add the vulcanized rubber material to a mold, and carry out pressure molding at 200 °C in a high-temperature vulcanizer for 4 min; then take out the mold, cool it to room temperature, and demold to obtain the antibacterial composite nitrile rubber.

[0077] Example 9

[0078] This example provides a preparation method of a medical antibacterial nano nitrile glove, including the following steps:

[0079] B1. By weight, add 80 parts of the antibacterial composite nitrile rubber prepared in Example 6 and 40 parts of chlorinated butyl rubber to an open mill and knead for 5 min. Then, sequentially add 10 parts of the microcapsule nano-reinforcing agent prepared in Example 3, 1 part of antioxidant MB, 1 part of antioxidant BLE, 1 part of sulfur, 0.25 part of the vulcanization accelerator - thiuram monosulfide, 0.25 part of the vulcanization activator - thiuram monosulfide, and 5 parts of white paste, and mix evenly to obtain a vulcanized rubber material.

[0080] B2. Add the vulcanized rubber material into a mold, and carry out pressure molding at 200 °C in a high-temperature vulcanizer for 5 minutes; then take out the mold, cool it to room temperature, and demold to obtain the antibacterial composite nitrile rubber.

[0081] Comparative Example 1

[0082] When preparing the medical antibacterial nano nitrile gloves in Example 9 of the present invention, when preparing the composite nitrile rubber, cyanuric chloride-modified cinnamic acid was not used, and cinnamic acid was used to replace the modified antibacterial agent.

[0083] Comparative Example 2

[0084] When preparing the medical antibacterial nano nitrile gloves in Example 9 of the present invention, the nitrile rubber was not treated with the modified antibacterial agent.

[0085] Comparative Example 3

[0086] When preparing the medical antibacterial nano nitrile gloves in Example 9 of the present invention, when preparing the microcapsule nano enhancer, heavy calcium carbonate, wollastonite and dolomite were not added to the micro-nano particle composite system for spheroidization treatment, and heavy calcium carbonate, wollastonite and dolomite were directly used as the core material.

[0087] Comparative Example 4

[0088] When preparing the medical antibacterial nano nitrile gloves in Example 9 of the present invention, the micro-nano enhancer was not added.

[0089] Performance test:

[0090] 1. Detect the tensile strength and elongation at break of the medical antibacterial nano nitrile rubber prepared in Examples 7-9 according to GB / T528-2009; among them, the tensile rate is 500 mm / min.

[0091] 2. Test the Shore A hardness of the medical antibacterial nano nitrile rubber prepared in Examples 7-9 according to GB / T531.1-2008.

[0092] 3. Under a nitrogen environment, weigh 10 g of the medical antibacterial nano nitrile rubber prepared in Examples 7-9 and place it in a crucible, heat it from 50 °C at a rate of 10 °C / min, and use a thermogravimetric analyzer to measure the heating temperature when the mass loss rate is 50%.

[0093] 4. Detect the minimum inhibitory concentration (MIC) of the medical antibacterial nano nitrile rubber prepared in Examples 7-9 against Gram-negative bacteria. The specific test results are shown in the following table:

[0094] Table 1 - Performance detection data table

[0095]

[0096] Data analysis:

[0097] By analyzing the data in Table 1, the medical antibacterial nano nitrile gloves prepared in Examples 7-9 of the present invention all have excellent mechanical properties, which are manifested as the medical antibacterial nano nitrile gloves prepared in Examples 7-9 of the present invention having excellent tensile strength, elongation at break, hardness and thermal stability values;

[0098] However, in Comparative Example 3, the inorganic material was not processed by a micro-nano particle composite system to form a composite spherical particle with a dense inner and outer layer structure, resulting in a decline in the mechanical properties of the prepared microcapsule nano-enhancer. In Comparative Example 4, no microcapsule nano-enhancer was added, thus significantly reducing the mechanical properties of the prepared medical antibacterial nano nitrile gloves.

[0099] The medical antibacterial nano nitrile rubbers prepared in Examples 7-9 of the present invention all have excellent antibacterial properties, which are manifested as the medical antibacterial nano nitrile rubbers prepared in Examples 7-9 all having relatively small minimum inhibitory concentration values against Gram-negative bacteria;

[0100] However, in Comparative Example 1, cyanuric chloride was not used to modify cinnamic acid when preparing the composite nitrile rubber. In Comparative Example 2, the nitrile rubber was not treated with a modified antibacterial agent, both of which reduced the antibacterial performance of the prepared medical antibacterial nano nitrile gloves, manifested as an increase in the minimum inhibitory concentration value against Gram-negative bacteria.

[0101] The above content is only an example and explanation of the structure of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined by this claim book, they should all belong to the protection scope of the present invention.

[0102] In the description of this specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0103] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only the specific embodiments. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A medical antibacterial nano-nitrile glove, characterized in that: The invention comprises the following components in parts by weight: 60-80 parts of antibacterial composite nitrile rubber, 20-40 parts of chlorinated butyl rubber, 5-10 parts of microcapsule nano-enhancer, 2-3 parts of anti-aging aid, 2-5 parts of vulcanization aid and 5-10 parts of plasticizer; The preparation method of the antibacterial composite nitrile rubber comprises the following steps: S1. Mix cinnamic acid, cyanuric chloride, sodium carbonate and ethanol evenly to obtain a premix; react the premix at 50-60°C for 2-3h, then heat to 70-75°C, and react at this temperature for 2-3h; then heat to 80-90°C, evaporate the ethanol solvent, and obtain a solid modified antibacterial agent; S2, adding the modified antibacterial agent and the nitrile rubber to a two-roll mill and uniformly dispersing them to obtain a mixture; adding the mixture to a two-roll mill plastic to obtain an antibacterial composite nitrile rubber; The preparation method of the microcapsule nano-enhancer comprises the following steps: A1. Grinding heavy calcium carbonate to 300-500 μm to obtain mother particles; grinding wollastonite and dolomite to 30-50 μm to obtain daughter particles; adding the mother particles and daughter particles to a micro-nano particle composite system, and subjecting them to composite and spherical treatment to obtain composite spherical particles; A2, methanol and trichlorocyanuric acid silicon react at 20-30°C for 2-3h to obtain a product; the product is split and a fraction of polymethoxysilane is intercepted; A3, gelatin and deionized water are mixed, heated and stirred until completely dissolved; then casein and polymethoxysilane are added, and 1 mol / L NaOH solution is added dropwise to adjust the pH value of the mixed liquid to 8-9, so that the casein is completely dissolved to obtain a mixed solution; the mixed solution is first reacted at 80-90° C. for 2-3 hours, and then allowed to stand at room temperature for 24 hours to obtain a wall material solution; A4. Add the composite spherical particles to the wall material solution, then adjust the pH value of the wall material solution to 2-3 with 1 mol / L citric acid, and prepare a nano-scale microcapsule enhancer by spray drying.

2. A medical antibacterial nano-nitrile glove according to claim 1, characterized in that: In step S1, the dosage ratio of cinnamic acid, cyanuric chloride, sodium carbonate and ethanol is 50-60g:18g:5g:250mL; in step S2, the dosage ratio of modified antibacterial agent and nitrile rubber is 1-5g:50g; the plasticizing temperature is 120-150°C and the plasticizing time is 5-10min.

3. The medical antibacterial nano-nitrile gloves according to claim 1, characterized in that: In step A1, the ratio of wollastonite to dolomite is 10:10, and the ratio of mother particles to daughter particles is 20:10, based on parts by weight; the rotor speed of the PCS system is 2000-3000 r / min, and the processing time is 10-20 min.

4. The medical antibacterial nano-nitrile gloves according to claim 1, characterized in that: In step A2, the ratio of methanol to trichlorocyanuric acid silicon is 96g:100-135g; in step A3, the ratio of gelatin, deionized water, casein and polymethoxysilane is 15g:300mL:5g:10-20g; in step A4, the ratio of composite spherical particles to wall material solution is 50-60g:100mL.

5. A method for preparing the medical antibacterial nano-nitrile gloves according to any one of claims 1 to 4, characterized in that: The following steps are involved: B1, adding the antibacterial composite nitrile rubber and chlorinated butyl rubber into an open mill for mixing, and then sequentially adding an anti-aging agent, a vulcanizing agent and a plasticizer, and under the shearing action of a double roller, each component is in a cutting and mixing state to obtain a vulcanized rubber material; B2. Add the vulcanized rubber material into the mold, press-form it in a high-temperature vulcanizer, then take out the mold, cool it to room temperature, and demould it to obtain the antibacterial composite nitrile rubber.

6. The method for preparing a medical antibacterial nano-nitrile glove according to claim 5, characterized in that: In step B1, the amount ratio of the antibacterial composite nitrile rubber, chlorinated butyl rubber, antioxidant, vulcanization aid and plasticizer is 60-80:20-40:2-3:2-5:5-10 in parts by weight; the antioxidant includes 10 parts of naphthylamine antioxidant and 10 parts of ketoamine antioxidant in parts by weight, the naphthylamine antioxidant is any one of antioxidant A, antioxidant MB and antioxidant NDPA, and the ketoamine antioxidant includes any one of antioxidant RD and antioxidant BLE; the vulcanization aid includes 2-5 parts of sulfur, 0.5 parts of vulcanization accelerator and 0.5 parts of vulcanization activator in parts by weight, the vulcanization accelerator is thiuram monosulfide, and the vulcanization activator is zinc oxide; the plasticizer is any one of black ointment, white ointment or castor oil.

7. The method for preparing a medical antibacterial nano-nitrile glove according to claim 5, characterized in that: In step B2, the vulcanization temperature is 200° C. and the vulcanization time is 3-5 minutes.

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