CN113881074A - Preparation method of thin polyurethane medical gloves - Google Patents
Preparation method of thin polyurethane medical gloves Download PDFInfo
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- CN113881074A CN113881074A CN202111361942.9A CN202111361942A CN113881074A CN 113881074 A CN113881074 A CN 113881074A CN 202111361942 A CN202111361942 A CN 202111361942A CN 113881074 A CN113881074 A CN 113881074A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 62
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000003756 stirring Methods 0.000 claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 15
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 claims description 15
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 230000001954 sterilising effect Effects 0.000 claims description 10
- 238000004659 sterilization and disinfection Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000004321 preservation Methods 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 13
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 5
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a preparation method of thin polyurethane medical gloves, which comprises the following raw materials in parts by weight: 15-35 parts of antibacterial composite material, 20-50 parts of polyurethane emulsion, 10-15 parts of surfactant and 20-80 parts of deionized water; adding a surfactant into the polyurethane emulsion, heating to 35-45 ℃, adding an antibacterial composite material, slowly adding deionized water, keeping the temperature, mixing and stirring for 3 hours to obtain a mixed emulsion; dipping the mould in the mixed emulsion for 1min, taking out, drying, curling and demoulding to obtain the medical gloves; the nano microspheres are combined with the initial material in the preparation process of the antibacterial composite material, the nano microspheres with antibacterial property are loaded due to the high porosity and high specific surface area of the antibacterial composite material, and the phenomenon of uneven distribution caused by agglomeration of the nano microspheres is prevented.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of thin polyurethane medical gloves.
Background
At present, in a plurality of industries such as medical care, food health care, electronics and the like, the requirements on the protective performance of gloves are higher and higher, the traditional gloves only comprise natural latex gloves, polyvinyl chloride gloves, butyronitrile gloves, polyethylene gloves and the like, wherein the polyethylene gloves have no elasticity and are small in use field, the strength and the elasticity of the polyvinyl chloride gloves are slightly good, the gloves are suitable for simple hand protection, the gloves with the best elasticity only comprise the natural latex gloves and the butyronitrile gloves, and the butyronitrile gloves do not contain protein in the natural latex gloves, so that the wearing glove allergy can not be caused, and the gloves gradually replace the natural latex gloves. But the butyronitrile gloves with the best comprehensive performance are limited in use due to the defects of sulfur, easy breakage and the like. At present, most medical gloves such as natural latex gloves and butyronitrile gloves contain double bond groups, so that a radiation disinfection method cannot be adopted, otherwise, the gloves are easy to age, and therefore, the medical gloves with excellent antibacterial performance are produced, and the medical gloves have excellent mechanical performance and are problems to be solved urgently.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of thin polyurethane medical gloves.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a thin polyurethane medical glove comprises the following steps:
step S1, weighing the following raw materials in parts by weight: 15-35 parts of antibacterial composite material, 20-50 parts of polyurethane emulsion, 10-15 parts of surfactant and 20-80 parts of deionized water;
step S2, adding a surfactant into the polyurethane emulsion, heating to 35-45 ℃, adding the antibacterial composite material, slowly adding deionized water, keeping the temperature, mixing and stirring for 3 hours to obtain mixed emulsion;
and step S3, dipping the mold in the mixed emulsion for 1min, taking out, drying, curling and demolding to obtain the medical glove.
Further: the antibacterial composite material is prepared by the following steps:
step S11, adding calcium nitrate tetrahydrate into deionized water, stirring at a constant speed until the calcium nitrate tetrahydrate is dissolved to prepare a solution a for later use, and controlling the dosage ratio of the calcium nitrate tetrahydrate to the deionized water to be 230 g: 1000 mL; adding sodium phosphate dodecahydrate into deionized water, stirring at a constant speed until the sodium phosphate dodecahydrate is dissolved to prepare a solution b for later use, and controlling the dosage ratio of the sodium phosphate dodecahydrate to the deionized water to be 225 g: 1500 mL;
step S12, slowly dripping the solution a into the solution b, heating at 45-60 ℃, stirring at a constant speed, adjusting the pH value of the system to 10-12 after finishing dripping, carrying out ultrasonic treatment and stirring at a constant speed for 1h, continuing stirring for 20h after finishing ultrasonic treatment, then filtering, washing with deionized water until the system is neutral to prepare a primary material, and controlling the volume ratio of the solution a to the solution b to be 1: 1.5;
step S13, adding glycidyl methacrylate into a flask filled with deionized water, vacuumizing, introducing nitrogen, heating to 65-70 ℃, uniformly stirring, adding potassium persulfate, keeping the temperature and reacting for 8 hours, cooling to room temperature, adding anhydrous ethylenediamine, heating to 80 ℃, keeping the temperature and reacting for 20 hours to obtain a crude product, washing the crude product with anhydrous ethanol and deionized water for three times respectively to obtain a carrier, controlling the volume ratio of the glycidyl methacrylate to the deionized water to be 1: 20, wherein the usage amount of the anhydrous ethylenediamine is three times of the volume of the glycidyl methacrylate, and the usage amount of the potassium persulfate is 1-1.8% of the weight of the glycidyl methacrylate;
step S14, adding the carrier into deionized water, stirring at a constant speed for 15min, then sequentially adding a silver nitrate solution with the mass fraction of 20%, heating at 125 ℃, continuing to stir for 5min, adding polyvinylpyrrolidone and absolute ethyl alcohol, stirring at a constant speed for 30min, transferring to a sterilization pot, preserving heat and sterilizing at 0.25MPa and 130 ℃ for 1h, then cooling, adding the primary material, stirring at a high speed for 4h, and then cleaning with absolute ethyl alcohol for 3 times to obtain the antibacterial composite material, wherein the dosage ratio of the carrier, the silver nitrate solution, the polyvinylpyrrolidone, the absolute ethyl alcohol, the deionized water and the primary material is controlled to be 10 g: 1-2.5 g: 3 mL: 10 mL: 35-50 g.
Step S2, mixing the two solutions, reacting calcium nitrate with sodium phosphate under ultrasonic condition to generate hydroxyapatite, namely a primary material, the primary material has larger pores, then in step S3, the glycidyl methacrylate is taken as a monomer, the potassium persulfate is taken as an initiator, the ethylenediamine is added, the glycidyl methacrylate reacts with the ethylenediamine to prepare a carrier, the carrier is an aminated nano microsphere, nano silver is loaded in the carrier through a hydrothermal synthesis method in step S14 to form the nano microsphere with excellent antibacterial property, then a primary material is added to combine the nano microsphere and the primary material, the high porosity and the high specific surface area endow the nano-microsphere with excellent adsorption performance, and the nano-microsphere with antibacterial performance is loaded to prevent the phenomenon of uneven distribution caused by agglomeration.
Further: the surfactant is any one of sodium dodecyl sulfate and sodium dodecyl sulfate.
Further: the drying temperature in the step S3 is 90-100 ℃, and the drying time is 4 h.
The invention has the beneficial effects that:
the invention relates to a polyurethane medical glove, which takes polyurethane emulsion as a base material, adds an antibacterial composite material to endow the polyurethane medical glove with excellent antibacterial performance, the antibacterial composite material is prepared by mixing two solutions in step S2 in the preparation process, calcium nitrate reacts with sodium phosphate under the ultrasonic condition to generate hydroxyapatite which is a primary material, the primary material has larger pores, then glycidyl methacrylate is taken as a monomer in step S3, potassium persulfate is taken as an initiator, ethylenediamine is added, the glycidyl methacrylate reacts with ethylenediamine to prepare a carrier, the carrier is an aminated nano microsphere, then nano silver is loaded in the carrier in step S14 through a hydrothermal synthesis method to form the nano microsphere with excellent antibacterial performance, the technical problems that the nano silver is not easy to disperse and is not easy to attach to a substrate are solved, then the primary material is added, the nano microspheres are combined with the primary material, the nano microspheres with antibacterial property are loaded due to the excellent adsorption property of the primary material, and the phenomenon of uneven distribution caused by agglomeration of the nano microspheres is prevented.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The antibacterial composite material is prepared by the following steps:
step S11, adding calcium nitrate tetrahydrate into deionized water, stirring at a constant speed until the calcium nitrate tetrahydrate is dissolved to prepare a solution a for later use, and controlling the dosage ratio of the calcium nitrate tetrahydrate to the deionized water to be 230 g: 1000 mL; adding sodium phosphate dodecahydrate into deionized water, stirring at a constant speed until the sodium phosphate dodecahydrate is dissolved to prepare a solution b for later use, and controlling the dosage ratio of the sodium phosphate dodecahydrate to the deionized water to be 225 g: 1500 mL;
step S12, slowly dripping the solution a into the solution b, heating at 45 ℃, uniformly stirring, adjusting the pH value of the system to 10 after finishing dripping, carrying out ultrasonic treatment and uniformly stirring for 1h, continuously stirring for 20h after finishing ultrasonic treatment, then filtering, washing with deionized water until the system is neutral to prepare a primary material, and controlling the volume ratio of the solution a to the solution b to be 1: 1.5;
step S13, adding glycidyl methacrylate into a flask filled with deionized water, vacuumizing, introducing nitrogen, heating to 65 ℃, uniformly stirring, adding potassium persulfate, preserving heat, reacting for 8 hours, cooling to room temperature, adding anhydrous ethylenediamine, heating to 80 ℃, preserving heat, reacting for 20 hours to obtain a crude product, washing with anhydrous ethanol and deionized water for three times respectively to obtain a carrier, controlling the volume ratio of the glycidyl methacrylate to the deionized water to be 1: 20, wherein the usage amount of the anhydrous ethylenediamine is three times of the volume of the glycidyl methacrylate, and the usage amount of the potassium persulfate is 1% of the weight of the glycidyl methacrylate;
step S14, adding the carrier into deionized water, stirring at a constant speed for 15min, then sequentially adding a silver nitrate solution with the mass fraction of 20%, heating at 125 ℃, continuing to stir for 5min, adding polyvinylpyrrolidone and absolute ethyl alcohol, stirring at a constant speed for 30min, transferring to a sterilization pot, preserving heat and sterilizing at 0.25MPa and 130 ℃ for 1h, then cooling, adding the primary material, stirring at a high speed for 4h, and then cleaning with absolute ethyl alcohol for 3 times to obtain the antibacterial composite material, wherein the dosage ratio of the carrier, the silver nitrate solution, the polyvinylpyrrolidone, the absolute ethyl alcohol, the deionized water and the primary material is controlled to be 10 g: 1 g: 3 mL: 10 mL: 35 g.
Through detection, the bacteriostasis rate of the antibacterial agent in the embodiment 1 to escherichia coli is 99.7-99.9%, and the bacteriostasis rate to staphylococcus aureus is 99.3-99.6%.
Example 2
The antibacterial composite material is prepared by the following steps:
step S11, adding calcium nitrate tetrahydrate into deionized water, stirring at a constant speed until the calcium nitrate tetrahydrate is dissolved to prepare a solution a for later use, and controlling the dosage ratio of the calcium nitrate tetrahydrate to the deionized water to be 230 g: 1000 mL; adding sodium phosphate dodecahydrate into deionized water, stirring at a constant speed until the sodium phosphate dodecahydrate is dissolved to prepare a solution b for later use, and controlling the dosage ratio of the sodium phosphate dodecahydrate to the deionized water to be 225 g: 1500 mL;
step S12, slowly dripping the solution a into the solution b, heating at 50 ℃, uniformly stirring, adjusting the pH value of the system to 11 after finishing dripping, carrying out ultrasonic treatment and uniformly stirring for 1h, continuously stirring for 20h after finishing ultrasonic treatment, then filtering, washing with deionized water until the system is neutral to prepare a primary material, and controlling the volume ratio of the solution a to the solution b to be 1: 1.5;
step S13, adding glycidyl methacrylate into a flask filled with deionized water, vacuumizing, introducing nitrogen, heating to 65 ℃, uniformly stirring, adding potassium persulfate, preserving heat, reacting for 8 hours, cooling to room temperature, adding anhydrous ethylenediamine, heating to 80 ℃, preserving heat, reacting for 20 hours to obtain a crude product, washing with anhydrous ethanol and deionized water for three times respectively to obtain a carrier, controlling the volume ratio of the glycidyl methacrylate to the deionized water to be 1: 20, wherein the usage amount of the anhydrous ethylenediamine is three times of the volume of the glycidyl methacrylate, and the usage amount of the potassium persulfate is 1.5% of the weight of the glycidyl methacrylate;
step S14, adding the carrier into deionized water, stirring at a constant speed for 15min, then sequentially adding a silver nitrate solution with the mass fraction of 20%, heating at 125 ℃, continuing to stir for 5min, adding polyvinylpyrrolidone and absolute ethyl alcohol, stirring at a constant speed for 30min, transferring to a sterilization pot, preserving heat and sterilizing at 0.25MPa and 130 ℃ for 1h, then cooling, adding the primary material, stirring at a high speed for 4h, and then cleaning with absolute ethyl alcohol for 3 times to obtain the antibacterial composite material, wherein the dosage ratio of the carrier, the silver nitrate solution, the polyvinylpyrrolidone, the absolute ethyl alcohol, the deionized water and the primary material is controlled to be 10 g: 2 g: 3 mL: 10 mL: 40 g.
Through detection, the bacteriostasis rate of the antibacterial agent in the embodiment 2 to escherichia coli is 99.8-99.9%, and the bacteriostasis rate to staphylococcus aureus is 99.3-99.5%.
Example 3
The antibacterial composite material is prepared by the following steps:
step S11, adding calcium nitrate tetrahydrate into deionized water, stirring at a constant speed until the calcium nitrate tetrahydrate is dissolved to prepare a solution a for later use, and controlling the dosage ratio of the calcium nitrate tetrahydrate to the deionized water to be 230 g: 1000 mL; adding sodium phosphate dodecahydrate into deionized water, stirring at a constant speed until the sodium phosphate dodecahydrate is dissolved to prepare a solution b for later use, and controlling the dosage ratio of the sodium phosphate dodecahydrate to the deionized water to be 225 g: 1500 mL;
step S12, slowly dripping the solution a into the solution b, heating at 60 ℃, uniformly stirring, adjusting the pH value of the system to 12 after finishing dripping, carrying out ultrasonic treatment and uniformly stirring for 1h, continuously stirring for 20h after finishing ultrasonic treatment, then filtering, washing with deionized water until the system is neutral to prepare a primary material, and controlling the volume ratio of the solution a to the solution b to be 1: 1.5;
step S13, adding glycidyl methacrylate into a flask filled with deionized water, vacuumizing, introducing nitrogen, heating to 70 ℃, uniformly stirring, adding potassium persulfate, preserving heat and reacting for 8 hours, cooling to room temperature, adding anhydrous ethylenediamine, heating to 80 ℃, preserving heat and reacting for 20 hours to obtain a crude product, washing with anhydrous ethanol and deionized water for three times respectively to obtain a carrier, controlling the volume ratio of the glycidyl methacrylate to the deionized water to be 1: 20, wherein the usage amount of the anhydrous ethylenediamine is three times of the volume of the glycidyl methacrylate, and the usage amount of the potassium persulfate is 1.8% of the weight of the glycidyl methacrylate;
step S14, adding the carrier into deionized water, stirring at a constant speed for 15min, then sequentially adding a silver nitrate solution with the mass fraction of 20%, heating at 125 ℃, continuing to stir for 5min, adding polyvinylpyrrolidone and absolute ethyl alcohol, stirring at a constant speed for 30min, transferring to a sterilization pot, preserving heat and sterilizing at 0.25MPa and 130 ℃ for 1h, then cooling, adding the primary material, stirring at a high speed for 4h, and then cleaning with absolute ethyl alcohol for 3 times to obtain the antibacterial composite material, wherein the dosage ratio of the carrier, the silver nitrate solution, the polyvinylpyrrolidone, the absolute ethyl alcohol, the deionized water and the primary material is controlled to be 10 g: 2.5 g: 3 mL: 10 mL: 50 g.
Through detection, the bacteriostasis rate of the antibacterial agent in example 3 to escherichia coli is 99.7-99.8%, and the bacteriostasis rate to staphylococcus aureus is 99.5-99.6%.
Example 4
A preparation method of a thin polyurethane medical glove comprises the following steps:
step S1, weighing the following raw materials in parts by weight: 15 parts of an antibacterial composite material, 20 parts of AH-1720A polyurethane emulsion produced by the company Anda Huatai, 10 parts of sodium dodecyl sulfate and 20 parts of deionized water;
step S2, adding sodium dodecyl sulfate into polyurethane emulsion, heating to 35 ℃, adding an antibacterial composite material, slowly adding deionized water, keeping the temperature, mixing and stirring for 3 hours to obtain mixed emulsion;
and step S3, dipping the mold in the mixed emulsion for 1min, taking out, drying, curling and demolding to obtain the medical glove.
Example 5
A preparation method of a thin polyurethane medical glove comprises the following steps:
step S1, weighing the following raw materials in parts by weight: 25 parts of an antibacterial composite material, 35 parts of AH-1720A polyurethane emulsion produced by the company Anda Huatai, 12 parts of sodium dodecyl sulfate and 60 parts of deionized water;
step S2, adding sodium dodecyl sulfate into polyurethane emulsion, heating to 40 ℃, adding an antibacterial composite material, slowly adding deionized water, keeping the temperature, mixing and stirring for 3 hours to obtain mixed emulsion;
and step S3, dipping the mold in the mixed emulsion for 1min, taking out, drying, curling and demolding to obtain the medical glove.
Example 6
A preparation method of a thin polyurethane medical glove comprises the following steps:
step S1, weighing the following raw materials in parts by weight: 35 parts of an antibacterial composite material, 50 parts of AH-1720A polyurethane emulsion produced by the company Anda Huatai, 15 parts of sodium dodecyl sulfate and 80 parts of deionized water;
step S2, adding sodium dodecyl sulfate into polyurethane emulsion, heating to 45 ℃, adding an antibacterial composite material, slowly adding deionized water, keeping the temperature, mixing and stirring for 3 hours to obtain mixed emulsion;
and step S3, dipping the mold in the mixed emulsion for 1min, taking out, drying, curling and demolding to obtain the medical glove.
Comparative example 1
In comparison with example 4, the present comparative example did not include the antimicrobial composite.
Comparative example 2
This comparative example is a commercially available polyurethane medical glove from a company.
The mechanical properties of the medical gloves prepared in examples 4-6 and comparative examples 1-2 were measured by the test method of GB/T1701-2001, and the results are shown in the following table:
from the above table, it can be seen that the mechanical properties of the antibacterial composite materials added in examples 4-6 are not affected.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. A preparation method of thin polyurethane medical gloves is characterized in that: the method comprises the following steps:
step S1, weighing the following raw materials in parts by weight: 15-35 parts of antibacterial composite material, 20-50 parts of polyurethane emulsion, 10-15 parts of surfactant and 20-80 parts of deionized water;
step S2, adding a surfactant into the polyurethane emulsion, heating to 35-45 ℃, adding the antibacterial composite material, slowly adding deionized water, keeping the temperature, mixing and stirring for 3 hours to obtain mixed emulsion;
and step S3, dipping the mold in the mixed emulsion for 1min, taking out, drying, curling and demolding to obtain the medical glove.
2. The method of manufacturing a thin polyurethane medical glove according to claim 1, wherein: the antibacterial composite material is prepared by the following steps:
step S11, adding calcium nitrate tetrahydrate into deionized water, stirring at a constant speed until the calcium nitrate tetrahydrate is dissolved to prepare a solution a for later use, and controlling the dosage ratio of the calcium nitrate tetrahydrate to the deionized water to be 230 g: 1000 mL; adding sodium phosphate dodecahydrate into deionized water, stirring at a constant speed until the sodium phosphate dodecahydrate is dissolved to prepare a solution b for later use, and controlling the dosage ratio of the sodium phosphate dodecahydrate to the deionized water to be 225 g: 1500 mL;
step S12, slowly dripping the solution a into the solution b, heating at 45-60 ℃, stirring at a constant speed, adjusting the pH of the system to 10-12 after dripping is finished, carrying out ultrasonic and stirring at a constant speed for 1h, continuing stirring for 20h after ultrasonic is finished, filtering, and washing with deionized water until the system is neutral to obtain a primary material;
step S13, adding glycidyl methacrylate into a flask filled with deionized water, vacuumizing, introducing nitrogen, heating to 65-70 ℃, uniformly stirring, adding potassium persulfate, preserving heat and reacting for 8 hours, cooling to room temperature, adding anhydrous ethylenediamine, heating to 80 ℃, preserving heat and reacting for 20 hours to obtain a crude product, and washing with anhydrous ethanol and deionized water for three times to obtain a carrier;
and step S14, adding the carrier into deionized water, stirring at a constant speed for 15min, then sequentially adding a silver nitrate solution with the mass fraction of 20%, heating at 125 ℃, continuing stirring for 5min, adding polyvinylpyrrolidone and absolute ethyl alcohol, stirring at a constant speed for 30min, transferring to a sterilization pot, carrying out heat preservation sterilization at the temperature of 130 ℃ and under the pressure of 0.25MPa for 1h, then cooling, adding the primary material, stirring at a high speed for 4h, and then washing with absolute ethyl alcohol for 3 times to obtain the antibacterial composite material.
3. The method of manufacturing a thin polyurethane medical glove according to claim 2, wherein: in step S12, the volume ratio of solution a to solution b is controlled to 1: 1.5.
4. The method of manufacturing a thin polyurethane medical glove according to claim 2, wherein: in step S13, the volume ratio of the glycidyl methacrylate to the deionized water is controlled to be 1: 20, the amount of the anhydrous ethylenediamine is three times of the volume of the glycidyl methacrylate, and the amount of the potassium persulfate is 1-1.8% of the weight of the glycidyl methacrylate.
5. The method of manufacturing a thin polyurethane medical glove according to claim 2, wherein: in the step S14, the dosage ratio of the carrier, the silver nitrate solution, the polyvinylpyrrolidone, the absolute ethyl alcohol, the deionized water and the primary material is controlled to be 10 g: 1-2.5 g: 3 mL: 10 mL: 35-50 g.
6. The method of manufacturing a thin polyurethane medical glove according to claim 1, wherein: the surfactant is any one of sodium dodecyl sulfate and sodium dodecyl sulfate.
7. The method of manufacturing a thin polyurethane medical glove according to claim 1, wherein: the drying temperature in the step S3 is 90-100 ℃, and the drying time is 4 h.
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