Medical rubber gloves and preparation method thereof
By modifying the preparation process of natural latex and BHT, the tensile properties and durability of medical rubber gloves are improved, solving the problem of easy breakage of traditional medical rubber gloves, making them suitable for both medical and non-medical fields.
Patent Information
- Application Number
- CN202511303950.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-12
- Publication Date
- 2025-11-14
AI Technical Summary
Traditional medical rubber gloves have poor tensile properties, are prone to breakage and damage, affecting their effectiveness and potentially causing contamination.
Medical rubber gloves are prepared using modified natural latex and modified BHT through a specific process to enhance the tensile properties and durability of the rubber, and a polymer coating is added to improve protection.
The prepared medical rubber gloves have excellent tensile strength and durability, and are suitable for both medical and non-medical applications, meeting the requirements for high hygiene and operational flexibility.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of medical rubber glove manufacturing technology, specifically to a medical rubber glove and its manufacturing method. Background Technology
[0002] Medical gloves are essential tools for healthcare professionals in medical examinations and procedures, effectively protecting users' safety and preventing cross-contamination between caregivers and patients, as well as inflammation of patient wounds due to bacterial infection. Medical gloves are generally made of organic materials such as latex, rubber, polyvinyl chloride (PVC), and neoprene rubber, and their tensile properties are generally poor. Beyond the medical industry, non-medical industries such as food processing, electronics manufacturing, and laboratory testing are also increasingly demanding medical rubber gloves. These industries have high requirements for the hygiene, protection, and operational flexibility of gloves, and medical rubber gloves, with their superior performance, are widely used in these fields.
[0003] Natural rubber is a high-performance natural polymer. After vulcanization, it exhibits excellent cross-linking properties and good flexibility. Medical gloves made from it have good skin fit and a pleasant feel, and offer good barrier properties against most pathogens. However, in practical use, traditional medical rubber gloves are prone to breakage and damage, which can affect daily work and easily cause contamination. Therefore, based on these problems, there is an urgent need to invent a new type of medical rubber glove to meet the higher demands of the medical rubber glove manufacturing field. Summary of the Invention
[0004] This invention proposes a medical rubber glove and its preparation method, which solves the problem of poor tensile properties of natural latex in related technologies.
[0005] The technical solution of the present invention is as follows: This invention proposes a medical rubber glove and its preparation method. The medical rubber glove is prepared from the following components in parts by weight: 80-90 parts modified natural latex, 1-2 parts zinc oxide, 1-2 parts sulfur, 1-2 parts accelerator, 1-2 parts modified BHT, and 1-2 parts polymer coating.
[0006] As a further technical solution, the medical rubber gloves are manufactured through the following steps: Step A1: Mix modified natural rubber latex, zinc oxide, sulfur, accelerator, and modified BHT, raise the temperature to 120~150℃, and keep the reaction at this temperature for 4~5 minutes to obtain rubber latex. Step A2: Pour the rubber latex into the mold, press it into shape, cool it to room temperature, and demold it to obtain medical rubber gloves; Step A3: Stir the medical rubber gloves in calcium stearate solution for 10-15 minutes to obtain medical rubber gloves with a polymer coating.
[0007] As a further technical solution, the concentration of calcium stearate in the calcium stearate solution is 5 wt%.
[0008] As a further technical solution, the accelerator is zinc diethyldithiocarbamate.
[0009] As a further technical solution, the modified natural latex is prepared through the following steps: Step B1: Place NRL in a three-necked flask, add isomeric tridecyl alcohol polyoxyethylene ether, and stir for 0.5-1 h; adding acrylic acid will improve the stability of the system; add sodium bicarbonate as a buffer to adjust the pH of the system so that the reaction is carried out under neutral conditions; perform a second emulsification, stirring for 0.5-1 h, add acetone aqueous solution, and then add peroxyformic acid to carry out the reaction, controlling the reaction temperature below 10℃; after the reaction is completed, precipitate the intermediate product with anhydrous ethanol or let it stand, soak and wash the product with water, and dry it in a 50℃ constant temperature drying oven until the mass is constant; In step B1, NRL and peroxyformic acid react in a molar ratio of 1:0.5, as shown in the following reaction equation:
[0010] Step B2: Dilute the intermediate product to 20% solid content, adjust the pH to 7.0-9.0 with ammonia, purge with ammonia for 30-60 minutes, raise the reaction system to 40-50℃, and slowly add 3,3'-dithiotripropionic acid dropwise with a dropping funnel under stirring. After the addition is complete, react for 6 hours. After the reaction is complete, cool to 10℃ in an ice bath, add acetic acid to quench, and then put the reaction solution into a dialysis bag and dialyze with flowing deionized water for 48 hours to obtain modified natural latex. In step B2, the intermediate product reacts with 3,3'-dithiotripropionic acid in a molar ratio of 1:1.5, as shown in the following reaction equation:
[0011] The modified natural rubber latex prepared by this invention is produced by epoxidation modification of natural rubber latex. Some double bonds on the natural rubber latex molecular chain are oxidized to epoxy groups. After epoxidation, the polarity of the natural rubber latex increases and the intermolecular forces are enhanced, resulting in excellent air tightness, oil resistance and anti-slip properties. At the same time, it has low rolling resistance and good adhesion to other materials. Furthermore, by introducing disulfide bonds into the rubber as crosslinking points, and utilizing their weaker molecular chain confinement effect compared to vulcanized covalent bonds, the rubber material can also have good tensile properties.
[0012] As a further technical solution, in step B1, the ratio of NRL, isomeric tridecyl alcohol polyoxyethylene ether, acrylic acid, sodium bicarbonate, acetone, and peroxyformic acid is 15~20g:10~15ml:2~5ml:50~60ml:30~50ml:50~80ml.
[0013] As a further technical solution, in step B2, the ratio of the intermediate product to 3,3'-dithiotripropionic acid is 25~30g:60~80ml.
[0014] As a further technical solution, the modified BHT is prepared through the following steps: Step C1: Dissolve 2,6-di-tert-butyl-p-methylphenol in carbon tetrachloride, add liquid bromine and azobisisobutyronitrile; under nitrogen protection, reflux at 70-80℃ for 3 hours, cool and filter, wash the filtrate with 5% sodium thiosulfate solution to remove residue until the aqueous phase is colorless, dry the organic phase with magnesium sulfate, and concentrate under reduced pressure to obtain intermediate product A. In step C1, 2,6-di-tert-butyl-p-methylphenol reacts with liquid bromine in a molar ratio of 1:1.05. Step C2: Dissolve intermediate product A in acetone, add calcium carbonate and potassium iodide, raise the reaction temperature to 50-60℃ and react for 6 hours; after the reaction is completed, filter to remove the solid, evaporate the acetone from the filtrate under reduced pressure, extract with ethyl acetate, dry and concentrate to obtain intermediate product B. In step C2, intermediate product A undergoes a hydrolysis reaction, with a molar ratio of 1:1.5. The reaction equation is as follows:
[0015] Step C3: Place intermediate product B in a three-necked flask, purge air with ammonia, add tetrahydrofuran and the catalyst dibutyltin dilaurate, stir to dissolve, and cool to 0°C in an ice bath; slowly add isophorone diisocyanate, and after the addition is complete, raise the temperature to 20-30°C and react for 4 hours, then quench with methanol; pour the reaction solution into 200 mL of ice-cold n-hexane to precipitate and filter; wash the solid with cold toluene; and vacuum at 40°C for 12 hours to obtain modified BHT.
[0016] In step C3, intermediate B and isophorone diisocyanate react in a molar ratio of 2:1, as shown in the following reaction equation:
[0017] The modified BHT prepared by this invention retains the characteristics of traditional hindered phenolic antioxidants. The ortho or para position of the benzene ring hydroxyl group is occupied by substituents, and its steric hindrance structure makes it easy for the hydroxyl hydrogen atom to capture free radicals, thereby terminating the polymer thermo-oxidative aging chain reaction. At the same time, the small molecule hydroxyl-containing antioxidant 2,6-di-tert-butyl-4-hydroxymethylphenol is reacted with isophorone diisocyanate to obtain a reactive hindered phenolic antioxidant containing double bonds. Because this type of antioxidant can be grafted onto the polymer molecular chain during the processing of polymer materials, it has good compatibility with polymers and is not easy to migrate or volatilize, which is beneficial for its long-term protection of polymer materials.
[0018] As a further technical solution, in step C1, the ratio of the amounts of 2,6-di-tert-butyl-p-methylphenol, carbon tetrachloride, liquid bromine, and azobisisobutyronitrile is 5~10g:50~100ml:5~10ml:0.1~0.5g.
[0019] As a further technical solution, the ratio of intermediate product A, acetone, calcium carbonate and potassium iodide in step C2 is 5~10g:30~50ml:2~5g:0.1~0.5g.
[0020] As a further technical solution, in step C3, the ratio of intermediate product B, tetrahydrofuran, dibutyltin dilaurate, and isophorone diisocyanate is 20~25g:100~150ml:0.5~1g:10~15g.
[0021] The working principle and beneficial effects of this invention are as follows: 1. The modified natural latex used in this invention has higher elasticity, better rubber tensile strength, and elongation at break compared to natural latex.
[0022] 2. The modified BHT used in this invention improves the durability and compatibility of traditional BHT and has environmental protection properties, providing long-term protection for polymer materials.
[0023] In summary, the medical rubber gloves prepared by this invention have good durability and tensile strength, and have important application value in the field of medical rubber glove technology. Detailed Implementation
[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0025] Example 1 Preparation of modified natural latex: Step A1: Place 15g of NRL in a three-necked flask, add 10ml of isomeric tridecyl alcohol polyoxyethylene ether, and stir for 0.5h. Add 2ml of acrylic acid to improve system stability. Add sodium bicarbonate as a buffer to adjust the pH of the system so that the reaction can proceed under neutral conditions. Perform a second emulsification, stirring for 0.5h, add acetone aqueous solution, and then add peroxyformic acid to carry out the reaction, controlling the reaction temperature below 10℃. After the reaction is complete, precipitate the intermediate product with anhydrous ethanol or allow it to stand. Soak and wash the product with water, and dry it in a 50℃ constant temperature drying oven until the mass is constant. Step A2: Dilute 25g of intermediate product to 20% solid content, adjust pH to 9.0 with ammonia, purge with ammonia for 45min, raise the reaction system to 45℃, and slowly add 60ml of 3,3'-dithiotripropionic acid dropwise using a dropping funnel under stirring. After the addition is complete, react for 6h. After the reaction is complete, cool to 10℃ in an ice bath, add acetic acid to quench, and then put the reaction solution into a dialysis bag and dialyze with flowing deionized water for 48h to obtain modified natural latex. A type of medical rubber glove is manufactured through the following steps: Step B1: Mix modified natural rubber latex, zinc oxide, sulfur, accelerator and BHT, raise the temperature to 150℃, keep the reaction at this temperature for 5 minutes to obtain rubber latex; Step B2: Pour the rubber latex into the mold, press it into shape, cool it to room temperature, and demold it to obtain medical rubber gloves; Step B3: Stir the medical rubber gloves in calcium stearate solution for 15 minutes to obtain medical rubber gloves with a polymer coating.
[0026] Example 2 Preparation of modified BHT: Step A1: Dissolve 5g of 2,6-di-tert-butyl-p-methylphenol in 50ml of carbon tetrachloride, add 5ml of liquid bromine and 0.1g of azobisisobutyronitrile; under nitrogen protection, reflux at 70℃ for 3h, cool and filter, wash the filtrate with 5wt% sodium thiosulfate solution to remove residue until the aqueous phase is colorless, dry the organic phase with magnesium sulfate, and concentrate under reduced pressure to obtain intermediate product A; Step A2: Dissolve 5g of intermediate product A in 30ml of acetone, add 2g of calcium carbonate and 0.1g of potassium iodide, raise the reaction temperature to 50℃ and react for 6h; after the reaction is completed, filter to remove the solid, evaporate the acetone from the filtrate under reduced pressure, extract with ethyl acetate, dry and concentrate to obtain intermediate product B. Step A3: Place 20g of intermediate product B in a three-necked flask, purge air with ammonia gas, add 100ml of tetrahydrofuran and 0.5g of catalyst dibutyltin dilaurate, stir to dissolve, and cool to 0℃ in an ice bath; slowly add 10g of isophorone diisocyanate, and after the addition is complete, raise the temperature to 20℃ and react for 4h, then quench with methanol; pour the reaction solution into 200mL of ice-cold n-hexane to precipitate and filter; wash the solid with cold toluene; vacuum at 40℃ for 12h to obtain modified BHT.
[0027] A type of medical rubber glove is manufactured through the following steps: Step B1: Mix natural rubber latex, zinc oxide, sulfur, accelerator, and modified BHT, raise the temperature to 150°C, and keep the reaction at that temperature for 5 minutes to obtain rubber latex. Step B2: Pour the rubber latex into the mold, press it into shape, cool it to room temperature, and demold it to obtain medical rubber gloves; Step B3: Stir the medical rubber gloves in calcium stearate solution for 15 minutes to obtain medical rubber gloves with a polymer coating.
[0028] Example 3 Preparation of modified natural latex: Step A1: Place 15g of NRL in a three-necked flask, add 10ml of isomeric tridecyl alcohol polyoxyethylene ether, and stir for 0.5h. Add 2ml of acrylic acid to improve system stability. Add sodium bicarbonate as a buffer to adjust the pH of the system so that the reaction can proceed under neutral conditions. Perform a second emulsification, stirring for 0.5h, add acetone aqueous solution, and then add peroxyformic acid to carry out the reaction, controlling the reaction temperature below 10℃. After the reaction is complete, precipitate the intermediate product with anhydrous ethanol or allow it to stand. Soak and wash the product with water, and dry it in a 50℃ constant temperature drying oven until the mass is constant. Step A2: Dilute 25g of intermediate product to 20% solid content, adjust pH to 9.0 with ammonia, purge with ammonia for 45min, raise the reaction system to 45℃, and slowly add 60ml of 3,3'-dithiotripropionic acid dropwise using a dropping funnel under stirring. After the addition is complete, react for 6h. After the reaction is complete, cool to 10℃ in an ice bath, add acetic acid to quench, and then put the reaction solution into a dialysis bag and dialyze with flowing deionized water for 48h to obtain modified natural latex. Preparation of modified BHT: Step B1: Dissolve 5g of 2,6-di-tert-butyl-p-methylphenol in 50ml of carbon tetrachloride, add 5ml of liquid bromine and 0.1g of azobisisobutyronitrile; under nitrogen protection, reflux at 70℃ for 3h, cool and filter, wash the filtrate with 5wt% sodium thiosulfate solution to remove residue until the aqueous phase is colorless, dry the organic phase with magnesium sulfate, and concentrate under reduced pressure to obtain intermediate product A; Step B2: Dissolve 5g of intermediate product A in 30ml of acetone, add 2g of calcium carbonate and 0.1g of potassium iodide, raise the reaction temperature to 50℃ and react for 6h; after the reaction is completed, filter to remove the solid, evaporate the acetone from the filtrate under reduced pressure, extract with ethyl acetate, dry and concentrate to obtain intermediate product B. Step B3: Place 20g of intermediate product B in a three-necked flask, purge air with ammonia, add 100ml of tetrahydrofuran and 0.5g of catalyst dibutyltin dilaurate, stir to dissolve, and cool to 0℃ in an ice bath; slowly add 10g of isophorone diisocyanate, and after the addition is complete, raise the temperature to 20℃ and react for 4h, then quench with methanol; pour the reaction solution into 200mL of ice-cold n-hexane to precipitate and filter; wash the solid with cold toluene; vacuum at 40℃ for 12h to obtain modified BHT.
[0029] A type of medical rubber glove is manufactured through the following steps: Step C1: Mix modified natural rubber latex, zinc oxide, sulfur, accelerator and BHT, raise the temperature to 150℃, keep the reaction at this temperature for 5 minutes to obtain rubber latex; Step C2: Pour the rubber latex into the mold, press it into shape, cool it to room temperature, and demold it to obtain medical rubber gloves; Step C3: Stir the medical rubber gloves in calcium stearate solution for 15 minutes to obtain medical rubber gloves with a polymer coating.
[0030] Comparative Example 1 The only difference between this comparative example and Example 3 is that, in this comparative example, the modified natural latex is replaced with an equal amount of commercially available natural latex.
[0031] Comparative Example 2 The only difference between this comparative example and Example 3 is that, in this comparative example, the modified BHT is replaced with an equal amount of commercially available BHT.
[0032] Comparative Example 3 The only difference between this comparative example and Example 3 is that, in this comparative example, the modified natural latex is replaced with an equal amount of commercially available natural latex; and the modified BHT is replaced with an equal amount of commercially available BHT.
[0033] The tensile strength of modified natural rubber latex and modified BHT in Examples 1-3 and Comparative Examples 1-3 were determined according to GB10213-2006 standard. The measurement results are shown in the table below:
[0034] As shown in the table above, the modified natural latex and modified BHT prepared in the embodiments of the present invention have excellent tensile properties, which are higher than those of the comparative example. Therefore, using them as one of the raw materials makes the present invention applicable to various medical and non-medical scenarios and has important application value in the field of medical rubber glove preparation technology.
[0035] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for preparing a medical rubber glove, characterized in that, Includes the following steps: Step A1: Mix modified natural rubber latex, zinc oxide, sulfur, accelerator zinc diethyldithiocarbamate, and modified BHT, raise the temperature to 120~150℃, and keep the reaction at this temperature for 4~5 minutes to obtain rubber latex. Step A2: Pour the rubber latex into a mold, press it into shape, cool it to room temperature, and demold it to obtain a semi-finished medical rubber glove. Step A3: Stir the medical rubber gloves in a 5% calcium stearate solution for 10-15 minutes to obtain the medical rubber gloves.
2. The method for preparing a medical rubber glove according to claim 1, characterized in that, The medical rubber gloves comprise the following raw materials in parts by weight: 80-90 parts modified natural latex, 1-2 parts zinc oxide, 1-2 parts sulfur, 1-2 parts accelerator, and 1-2 parts modified BHT.
3. The method for preparing a medical rubber glove according to claim 1, characterized in that, The modified natural latex is prepared through the following steps: Step B1: Place NRL in a three-necked flask, add isomeric tridecyl alcohol polyoxyethylene ether, and stir for 0.5-1 h; add acrylic acid, then add sodium bicarbonate, stir for 0.5-1 h, add acetone aqueous solution, and then add peroxyformic acid to react, controlling the reaction temperature below 10℃; after the reaction is complete, precipitate the intermediate product with anhydrous ethanol or let it stand, soak and wash the product with water, and dry it in a 50℃ constant temperature drying oven until the mass is constant. Step B2: Dilute the intermediate product to 20% solid content, adjust the pH to 7.0-9.0 with ammonia, purge with ammonia for 30-60 minutes, raise the reaction system to 40-50℃, and slowly add 3,3'-dithiotripropionic acid dropwise with a dropping funnel under stirring. After the addition is complete, react for 6 hours. After the reaction is complete, cool to 10℃ in an ice bath, add acetic acid to quench, and then put the reaction solution into a dialysis bag and dialyze with flowing deionized water for 48 hours to obtain modified natural latex.
4. The method for preparing a medical rubber glove according to claim 3, characterized in that, The ratio of NRL, isomeric tridecyl alcohol polyoxyethylene ether, acrylic acid, sodium bicarbonate, acetone, and peroxyformic acid used in step B1 is 15~20g:10~15ml:2~5ml:50~60ml:30~50ml:50~80ml.
5. The method for preparing a medical rubber glove according to claim 3, characterized in that, The ratio of the intermediate product to the 3,3'-dithiotripropionic acid in step B2 is 25~30g:60~80ml.
6. The method for preparing a medical rubber glove according to claim 1, characterized in that, The modified BHT is prepared through the following steps: Step C1: Dissolve 2,6-di-tert-butyl-p-methylphenol in carbon tetrachloride, add liquid bromine and azobisisobutyronitrile; under nitrogen protection, reflux at 70-80°C for 3 hours, cool and filter, wash the filtrate with 5% sodium thiosulfate solution to remove residue until the aqueous phase is colorless, dry the organic phase with magnesium sulfate, and concentrate under reduced pressure to obtain intermediate product A. Step C2: Dissolve intermediate product A in acetone, add calcium carbonate and potassium iodide, raise the reaction temperature to 50-60℃ and react for 6 hours; after the reaction is completed, filter to remove the solid, extract the filtrate with ethyl acetate under reduced pressure, dry and concentrate to obtain intermediate product B; Step C3: Place intermediate product B in a three-necked flask, purge air with ammonia, add tetrahydrofuran and the catalyst dibutyltin dilaurate, stir to dissolve, and cool to 0°C in an ice bath; slowly add isophorone diisocyanate, and after the addition is complete, raise the temperature to 20-30°C and react for 4 hours, then quench with methanol; pour the reaction solution into 200 mL of ice-cold n-hexane to precipitate and filter; wash the solid with cold toluene; and vacuum at 40°C for 12 hours to obtain modified BHT.
7. The method for preparing a medical rubber glove according to claim 6, characterized in that, The ratio of the amounts of 2,6-di-tert-butyl-p-methylphenol, carbon tetrachloride, liquid bromine, and azobisisobutyronitrile in step C1 is 5~10g:50~100ml:5~10g:0.1~0.5g.
8. The method for preparing a medical rubber glove according to claim 6, characterized in that, The ratio of intermediate product A, acetone, calcium carbonate, and potassium iodide used in step C2 is 5~10g:30~50ml:2~5g:0.1~0.5g.
9. A method for preparing a medical rubber glove according to claim 6, characterized in that, The ratio of intermediate product B, tetrahydrofuran, dibutyltin dilaurate, and isophorone diisocyanate in step C3 is 20-25g: 100-150ml: 0.5-1g: 10-15g.
10. A medical rubber glove, characterized in that, The medical rubber glove is prepared according to any one of claims 1-9.