CN114539571B - Antibacterial rubber glove raw material and preparation method thereof - Google Patents
Antibacterial rubber glove raw material and preparation method thereof Download PDFInfo
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- CN114539571B CN114539571B CN202210166847.1A CN202210166847A CN114539571B CN 114539571 B CN114539571 B CN 114539571B CN 202210166847 A CN202210166847 A CN 202210166847A CN 114539571 B CN114539571 B CN 114539571B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001971 elastomer Polymers 0.000 title abstract description 22
- 239000005060 rubber Substances 0.000 title abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 71
- 239000002105 nanoparticle Substances 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000009832 plasma treatment Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 17
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 16
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 12
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 12
- HYBCFWFWKXJYFT-UHFFFAOYSA-N 1,3-benzothiazole-2,6-diamine Chemical compound C1=C(N)C=C2SC(N)=NC2=C1 HYBCFWFWKXJYFT-UHFFFAOYSA-N 0.000 claims abstract description 11
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 108010039918 Polylysine Proteins 0.000 claims abstract description 11
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 11
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 11
- 229920000656 polylysine Polymers 0.000 claims abstract description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000001110 calcium chloride Substances 0.000 claims abstract description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- 229920002635 polyurethane Polymers 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 229940119177 germanium dioxide Drugs 0.000 claims description 10
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- -1 hexanediol N-methylpyrrolidone Chemical compound 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 description 11
- 230000001580 bacterial effect Effects 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 229920000126 latex Polymers 0.000 description 5
- 239000004816 latex Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 241000222122 Candida albicans Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229940095731 candida albicans Drugs 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 244000141359 Malus pumila Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000021016 apples Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229940059958 centella asiatica extract Drugs 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920006174 synthetic rubber latex Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 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
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/30—Antimicrobial, e.g. antibacterial
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2500/00—Materials for garments
- A41D2500/50—Synthetic resins or rubbers
-
- 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
- C08J2307/00—Characterised by the use of natural rubber
- C08J2307/02—Latex
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- 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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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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)
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Abstract
The invention provides an antibacterial rubber glove raw material and a preparation method thereof, wherein a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia water solution are taken as raw materials, copper calcium germanate nano particles are prepared through hydrothermal reaction, and then plasma treatment is carried out to obtain modified nano particles; then dipping the modified nano particles into polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nano particles, and uniformly stirring and mixing the grafted nano particles and polyacrylic acid to prepare premix liquid; and mixing 2, 6-benzothiazole diamine, polyaspartic acid and polylysine for reaction to obtain a modified benzothiazole polymer, and finally adding the premix and the modified benzothiazole polymer into natural latex, and stirring and uniformly mixing to obtain the modified benzothiazole polymer. The raw material of the glove can be used for manufacturing the glove, has excellent antibacterial performance, certain water absorbability and good use comfort.
Description
Technical Field
The invention relates to the technical field of glove preparation, in particular to an antibacterial rubber glove raw material and a preparation method thereof.
Background
The rubber glove is widely applied to various fields of hospitals, families, electronic industries, food industries, gardening and the like, and mainly plays a role in isolating pollution and protecting hands. Traditional rubber gloves can be divided into a plurality of types according to different raw materials, such as: rubber gloves made of natural latex as a main raw material are called latex gloves, rubber gloves made of artificial synthetic latex obtained by emulsion polymerization of butadiene and acrylonitrile as a main raw material are called nitrile gloves, and rubber gloves made of artificial synthetic latex obtained by emulsion polymerization of butadiene and styrene as a main raw material are called styrene-butadiene latex. The manufacturing method of the rubber glove is different in size, the natural rubber latex or the artificial synthetic rubber latex is pre-vulcanized, then the rubber glove is demoulded after the molding process, and the finished glove can be obtained after the chlorination, the soaking and washing, the cleaning and the drying processes.
However, the raw materials of the traditional glove are the nutrient components of bacteria, so that the glove can become a breeding place for bacteria, and the health of human bodies can be endangered in the use process of the glove. Attempts have been made to directly add antibacterial substances such as nano silver and quaternary ammonium salts into raw materials of rubber gloves, but the antibacterial substances have poor compatibility with latex components, so that a good antibacterial effect is hardly exerted.
Patent application CN103980566a discloses a rubber glove with antibacterial function, which is prepared from natural rubber, nitrile rubber, emulsified liquid paraffin, colloidal sulfur, zinc oxide, an accelerator and antibacterial active ingredients, wherein the antibacterial active ingredients consist of fructus momordicae extract and centella asiatica extract. The antibacterial active ingredients in the technology of the patent also adopt a direct adding method, still have the problem of the compatibility, and the finally obtained rubber glove has unsatisfactory antibacterial rate on staphylococcus aureus, candida albicans and escherichia coli.
In addition, the traditional rubber glove does not absorb sweat, has poor use experience, and is easier to cause bacterial breeding.
Disclosure of Invention
The invention aims to provide an antibacterial rubber glove raw material and a preparation method thereof, which have excellent antibacterial performance, certain water absorbability and good use comfort.
In order to achieve the above purpose, the invention is realized by the following scheme:
the preparation method of the antibacterial glove raw material comprises the following specific steps:
(1) Firstly, preparing copper calcium germanate nano particles by taking a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia water solution as raw materials through hydrothermal reaction, and then performing plasma treatment to obtain modified nano particles;
(2) Then reacting diisocyanate prepolymer with pyromellitic anhydride as raw materials to prepare multi-carboxyl polyurethane, and uniformly dispersing the multi-carboxyl polyurethane in an organic solvent to obtain polyurethane dispersion liquid;
(3) Then dipping the modified nano particles into polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nano particles, and uniformly stirring and mixing the grafted nano particles and polyacrylic acid to prepare premix liquid;
(4) And mixing 2, 6-benzothiazole diamine, polyaspartic acid and polylysine for reaction to obtain a modified benzothiazole polymer, and finally adding 4-6 parts by weight of premix and 8-10 parts by weight of modified benzothiazole polymer into 55-65 parts by weight of natural latex, and stirring and uniformly mixing to obtain the glove raw material.
Preferably, in the step (1), the preparation method of the copper calcium germanate nano particles comprises the following steps of: adding 8-10 parts of germanium dioxide into 50-55 parts of water, stirring and uniformly mixing, and then dropwise adding an ammonia water solution with the mass concentration of 25-28% until the ammonia water solution is completely dissolved to obtain a germanium-containing ammonia water solution; then adding 12-15 parts of copper chloride solution with the mass concentration of 30-40% and 2-3 parts of calcium chloride solution with the mass concentration of 30-40% into nitric acid solution with the mass concentration of 3-4%, stirring and mixing uniformly, then dropwise adding aqueous ammonia solution containing germanium, stirring and mixing uniformly, adjusting pH= 9 ～ 10,300 ～ 500W, and carrying out ultrasonic oscillation for 50-60 minutes; and (3) carrying out hydrothermal reaction for 13-15 hours at 180-200 ℃, cooling, centrifuging to obtain precipitate, washing and drying to obtain the copper calcium germanate nano particles.
Preferably, in the step (1), the process conditions of the plasma treatment are as follows: the plasma treatment is carried out for 150-160 s at 20MHz and 150W, the treatment atmosphere is ammonia, and the pressure of the ammonia is 20-30 Pa.
Preferably, in the step (2), the preparation method of the polycarboxy polyurethane comprises the following steps in parts by weight: firstly adding 33-35 parts of toluene diisocyanate into 35-40 parts of N-methylpyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, then adding 1-2 parts of dibutyltin dilaurate, heating to 150-160 ℃, slowly dropwise adding 15-16 parts of hexanediol-N-methylpyrrolidone mixed solution, and after dropwise adding, keeping the temperature and stirring for 2-3 hours to obtain diisocyanate prepolymer; naturally cooling to room temperature, adding 15-17 parts of pyromellitic anhydride into the diisocyanate prepolymer, stirring for 2-3 hours at room temperature, heating to 50-60 ℃, and stirring for reacting for 8-10 hours to obtain a reaction solution; and finally, slowly dripping the reaction solution into 50-60 parts of absolute ethyl alcohol, washing, centrifuging and taking the solid to obtain the polycarboxy polyurethane.
Preferably, in the step (2), the organic solvent is acetone, and the dosage of the organic solvent is 5-7 times of the mass of the polycarboxy polyurethane.
Preferably, in the step (3), the mass ratio of the modified nanoparticle to the polyurethane dispersion is 1:5, the dipping process conditions are as follows: ultrasonic oscillation of 300-500W for 20-30 min.
Preferably, in the step (3), the preparation method of the premix liquid comprises the following steps in parts by weight: firstly, uniformly stirring and mixing 2-3 parts of grafted nano particles, 10-12 parts of polyacrylic acid and 2-3 parts of water, then heating to 110-120 ℃, and carrying out heat preservation and stirring for 10-15 minutes to obtain the premix.
Preferably, in the step (4), the preparation method of the modified benzothiazole polymer comprises the following steps in parts by weight: firstly adding 8-10 parts of 2, 6-benzothiazole diamine and 2-3 parts of potassium carbonate into 130-140 parts of N-methylpyrrolidone, heating to 85-95 ℃, stirring and reacting for 11-12 hours, then adding 5-6 parts of polyaspartic acid and 1-2 parts of polylysine, keeping the temperature and stirring and reacting for 6-8 hours, separating out a polymer, washing with dichloromethane, and drying at 70-80 ℃ for 15-17 hours to obtain the modified benzothiazole polymer.
The raw material of the antibacterial rubber glove is obtained by the preparation method.
The application of the antibacterial glove raw material in manufacturing the glove is provided.
Compared with the prior art, the invention has the beneficial effects that:
(1) Firstly, preparing copper calcium germanate nano particles by taking a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia water solution as raw materials through hydrothermal reaction, and then performing plasma treatment to obtain modified nano particles; then dipping the modified nano particles into polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nano particles, and uniformly stirring and mixing the grafted nano particles and polyacrylic acid to prepare premix liquid; and mixing 2, 6-benzothiazole diamine, polyaspartic acid and polylysine for reaction to obtain a modified benzothiazole polymer, and finally adding the premixed solution and the modified benzothiazole polymer into natural latex, and stirring and uniformly mixing to obtain the glove raw material. The raw material of the glove can be used for manufacturing the glove, has excellent antibacterial performance, certain water absorbability and good use comfort.
(2) The invention adds the premix liquid and the modified benzothiazole polymer into the natural latex to endow the natural latex with good antibacterial property and water absorption. The premix is obtained by mixing grafted nano particles with polyacrylic acid, the modified nano particles contain copper ions, calcium ions and the like, the surface performance of the copper calcium germanate nano particles can be changed through plasma treatment, the premix has a certain etching effect, amino groups are introduced, hydrogen bonds are formed with polyurethane in polyurethane dispersion liquid, and the dispersibility of the nano particles in a system is improved.
(3) The polyurethane dispersion liquid is prepared by taking diisocyanate prepolymer and pyromellitic anhydride as raw materials to react to prepare the multi-carboxyl polyurethane, and uniformly dispersing the multi-carboxyl polyurethane in an organic solvent. The polycarboxy structure can improve the dispersibility of the nanoparticle in the system, thereby exerting its antibacterial property and improving water absorption.
The modified benzothiazole polymer is obtained by mixing and reacting 2, 6-benzothiazole diamine, polyaspartic acid and polylysine, and the three are synergistic to further improve the antibacterial property and the water absorption.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the antibacterial glove raw material comprises the following specific steps:
(1) Adding 8g of germanium dioxide into 55g of water, stirring and mixing uniformly, and then dropwise adding an ammonia water solution with the mass concentration of 25% until the germanium dioxide is completely dissolved to obtain a germanium-containing ammonia water solution; then adding 15g of 30% copper chloride solution with mass concentration and 3g of 30% calcium chloride solution with mass concentration into 4% nitric acid solution with mass concentration, stirring and mixing uniformly, then dropwise adding the obtained germanium-containing ammonia water solution, stirring and mixing uniformly, adjusting pH= 9,500W, and carrying out ultrasonic oscillation for 50 minutes; carrying out hydrothermal reaction at 200 ℃ for 13 hours, cooling, centrifuging to obtain precipitate, washing, drying to obtain copper calcium germanate nano particles, and carrying out plasma treatment to the copper calcium germanate nano particles to obtain modified nano particles;
(2) Then adding 35g of toluene diisocyanate into 35g N-methylpyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, adding 2g of dibutyltin dilaurate, heating to 150 ℃, slowly dropwise adding 16g of hexanediol-N-methylpyrrolidone mixed solution, and keeping the temperature and stirring for 2 hours after the dropwise adding is finished to obtain diisocyanate prepolymer; naturally cooling to room temperature, adding 17g of pyromellitic anhydride into the diisocyanate prepolymer, stirring at room temperature for 2 hours, heating to 60 ℃, and stirring for 8 hours to obtain a reaction solution; finally, slowly dripping the reaction solution into 60g of absolute ethyl alcohol, washing, centrifuging to obtain solid, obtaining polycarboxy polyurethane, and uniformly dispersing the polycarboxy polyurethane in acetone with the mass of 5 times of that of the polycarboxy polyurethane to obtain polyurethane dispersion liquid;
(3) Then 1g of modified nano particles are immersed in 5g of polyurethane dispersion liquid, the solvent is volatilized to obtain grafted nano particles, then 3g of grafted nano particles, 10g of polyacrylic acid and 3g of water are stirred and mixed uniformly, heated to 110 ℃, and stirred for 15 minutes under heat preservation, so as to prepare premix liquid;
(4) Then adding 8g of 2, 6-benzothiazole diamine and 3g of potassium carbonate into 130g of N-methylpyrrolidone, heating to 95 ℃, stirring and reacting for 11 hours, then adding 6g of polyaspartic acid and 1g of polylysine, keeping the temperature and stirring and reacting for 8 hours, separating out a polymer, washing with methylene dichloride, and drying at 70 ℃ for 17 hours to obtain a modified benzothiazole polymer; and finally, adding 4g of premix and 10g of modified benzothiazole polymer into 55g of natural latex, and stirring and uniformly mixing to obtain the glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: the plasma treatment is carried out for 160s at 20MHz and 150W, the treatment atmosphere is ammonia, and the ammonia pressure is 20Pa.
In the step (3), the dipping process conditions are as follows: 500W ultrasonic wave was oscillated for 20 minutes.
Example 2
The preparation method of the antibacterial glove raw material comprises the following specific steps:
(1) Firstly adding 10g of germanium dioxide into 50g of water, stirring and mixing uniformly, and then dropwise adding 28% ammonia water solution with mass concentration until the germanium dioxide is completely dissolved to obtain germanium-containing ammonia water solution; then adding 12g of 40% copper chloride solution and 2g of 40% calcium chloride solution into 3% nitric acid solution, stirring and mixing uniformly, then dropwise adding the obtained germanium-containing ammonia water solution, stirring and mixing uniformly, adjusting pH= 10,300W, and oscillating for 60 minutes by ultrasonic waves; carrying out hydrothermal reaction at 180 ℃ for 15 hours, cooling, centrifuging to obtain precipitate, washing, drying to obtain copper calcium germanate nano particles, and carrying out plasma treatment to the copper calcium germanate nano particles to obtain modified nano particles;
(2) Then adding 33g of toluene diisocyanate into 40g N-methylpyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, then adding 1g of dibutyltin dilaurate, heating to 160 ℃, slowly dropwise adding 15g of hexanediol-N-methylpyrrolidone mixed solution, and after the dropwise adding is finished, keeping the temperature and stirring for 3 hours to obtain diisocyanate prepolymer; naturally cooling to room temperature, adding 15g of pyromellitic anhydride into the diisocyanate prepolymer, stirring at room temperature for 3 hours, heating to 50 ℃, and stirring for reacting for 10 hours to obtain a reaction solution; finally, slowly dripping the reaction solution into 50g of absolute ethyl alcohol, washing, centrifuging to obtain solid, obtaining polycarboxy polyurethane, and uniformly dispersing the polycarboxy polyurethane in acetone with the mass 7 times of that of the polycarboxy polyurethane to obtain polyurethane dispersion liquid;
(3) Soaking 1g of modified nano particles in 5g of polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nano particles, uniformly stirring and mixing 2g of grafted nano particles, 12g of polyacrylic acid and 2g of water, heating to 120 ℃, and carrying out heat preservation and stirring for 10 minutes to prepare a premix;
(4) Then adding 10g of 2, 6-benzothiazole diamine and 2g of potassium carbonate into 140g of N-methylpyrrolidone, heating to 85 ℃, stirring and reacting for 12 hours, then adding 5g of polyaspartic acid and 2g of polylysine, keeping the temperature and stirring and reacting for 6 hours, separating out a polymer, washing with methylene dichloride, and drying at 80 ℃ for 15 hours to obtain a modified benzothiazole polymer; and finally, adding 6g of premix and 8g of modified benzothiazole polymer into 65g of natural latex, and stirring and uniformly mixing to obtain the glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: the plasma treatment is carried out for 150s at 20MHz and 150W, the treatment atmosphere is ammonia, and the ammonia pressure is 30Pa.
In the step (3), the dipping process conditions are as follows: ultrasonic oscillation was performed at 300W for 30 minutes.
Example 3
The preparation method of the antibacterial glove raw material comprises the following specific steps:
(1) Adding 9g of germanium dioxide into 52g of water, stirring and mixing uniformly, and then dropwise adding an ammonia water solution with the mass concentration of 27% until the germanium dioxide is completely dissolved to obtain a germanium-containing ammonia water solution; then adding 13g of 35% copper chloride solution and 2.5g of 35% calcium chloride solution into 3.5% nitric acid solution, stirring and mixing uniformly, then dropwise adding the obtained germanium-containing ammonia water solution, stirring and mixing uniformly, adjusting pH= 9.5,400W, and oscillating for 55 minutes by ultrasonic waves; carrying out hydrothermal reaction at 190 ℃ for 14 hours, cooling, centrifuging to obtain precipitate, washing, drying to obtain copper calcium germanate nano particles, and carrying out plasma treatment to the copper calcium germanate nano particles to obtain modified nano particles;
(2) Then adding 34g of toluene diisocyanate into 38g N-methylpyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, then adding 1.5g of dibutyltin dilaurate, heating to 155 ℃, then slowly dropwise adding 16g of hexanediol-N-methylpyrrolidone mixed solution, and after the dropwise adding is finished, keeping the temperature and stirring for 2.5 hours to obtain diisocyanate prepolymer; naturally cooling to room temperature, adding 16g of pyromellitic anhydride into the diisocyanate prepolymer, stirring at room temperature for 2.5 hours, heating to 55 ℃, and stirring for reacting for 9 hours to obtain a reaction solution; finally, slowly dripping the reaction solution into 55g of absolute ethyl alcohol, washing, centrifuging to obtain solid, obtaining the polycarboxy polyurethane, and uniformly dispersing the polycarboxy polyurethane in acetone with the mass of 6 times of that of the polycarboxy polyurethane to obtain polyurethane dispersion liquid;
(3) Soaking 1g of modified nano particles in 5g of polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nano particles, uniformly stirring and mixing 2.5g of grafted nano particles, 11g of polyacrylic acid and 2.5g of water, heating to 115 ℃, and carrying out heat preservation and stirring for 12 minutes to prepare a premix;
(4) Then adding 9g of 2, 6-benzothiazole diamine and 2.5g of potassium carbonate into 135g of N-methylpyrrolidone, heating to 90 ℃, stirring and reacting for 12 hours, then adding 5.5g of polyaspartic acid and 1.5g of polylysine, keeping the temperature and stirring and reacting for 7 hours, separating out a polymer, washing by using dichloromethane, and drying at 75 ℃ for 16 hours to obtain a modified benzothiazole polymer; finally, adding 5g of premix and 9g of modified benzothiazole polymer into 60g of natural latex, and stirring and uniformly mixing to obtain the glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: the plasma treatment was carried out at 20MHz and 150W for 155s under an ammonia gas pressure of 25Pa.
In the step (3), the dipping process conditions are as follows: ultrasonic oscillation at 400W for 25 minutes.
Comparative example
A preparation method of a rubber glove raw material comprises the following specific steps:
(1) Adding 8g of germanium dioxide into 55g of water, stirring and mixing uniformly, and then dropwise adding an ammonia water solution with the mass concentration of 25% until the germanium dioxide is completely dissolved to obtain a germanium-containing ammonia water solution; then adding 15g of 30% copper chloride solution with mass concentration and 3g of 30% calcium chloride solution with mass concentration into 4% nitric acid solution with mass concentration, stirring and mixing uniformly, then dropwise adding the obtained germanium-containing ammonia water solution, stirring and mixing uniformly, adjusting pH= 9,500W, and carrying out ultrasonic oscillation for 50 minutes; carrying out hydrothermal reaction at 200 ℃ for 13 hours, cooling, centrifuging to obtain precipitate, washing, drying to obtain copper calcium germanate nano particles, and carrying out plasma treatment to the copper calcium germanate nano particles to obtain modified nano particles;
(2) Mixing 3g modified nano particles, 10g polyacrylic acid and 3g water, heating to 110 ℃, and stirring for 15 minutes at a constant temperature to prepare a premix;
(3) Then adding 8g of 2, 6-benzothiazole diamine and 3g of potassium carbonate into 130g of N-methylpyrrolidone, heating to 95 ℃, stirring and reacting for 11 hours, then adding 1g of polylysine, keeping the temperature and stirring and reacting for 8 hours, separating out a polymer, washing with dichloromethane, and drying at 70 ℃ for 17 hours to obtain a modified benzothiazole polymer; and finally, adding 4g of premix and 10g of modified benzothiazole polymer into 55g of natural latex, and stirring and uniformly mixing to obtain the glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: the plasma treatment is carried out for 160s at 20MHz and 150W, the treatment atmosphere is ammonia, and the ammonia pressure is 20Pa.
In the step (2), the dipping process conditions are as follows: 500W ultrasonic wave was oscillated for 20 minutes.
Test examples
The raw materials of the rubber gloves obtained in examples 1 to 3 and comparative example were kneaded by an internal mixer, and then molded by a glove mold, and post-treated to prepare rubber gloves. The antibacterial property and water absorbability of the glove were examined.
The antibacterial property test method comprises the following steps: firstly taking a rubber glove sample of 2cm multiplied by 2cm for sterilization treatment, then respectively dripping staphylococcus aureus, candida albicans and escherichia coli bacterial liquid on the surface of the sterile sample, wherein the bacterial liquid concentration is 10 7 cfu/mL, the bacterial liquid dripping amount is 0.05mL/cm 2, then culturing the sample at the constant temperature of 37 ℃ for 24 hours, inoculating the diluted bacterial liquid on the sample on an agar plate containing a culture medium after the bacterial liquid is diluted by a multiple ratio, culturing the sample in a constant temperature incubator at the temperature of 37 ℃ for 24 hours, and calculating the number of living bacteria (refer to GB/T4789.2); the antibacterial ratio was calculated by dividing the number of living bacteria by the total number of bacteria. And the sterilized samples were again tested for antibacterial efficiency after being placed in a box for stacking rotten apples for 12 hours, and the results are shown in table 1.
The water absorption test method is as follows: the glove sample was taken to be 2cm×2cm, dried to constant weight m1, then immersed in 200mL of distilled water, left standing for 5 minutes, and then taken out, the surface moisture was absorbed by filter paper and weighed for m2, and then the water absorption rate r= (m 2-m 1)/m1×100%. The results are shown in Table 2.
TABLE 1 antibacterial test results
TABLE 2 Water absorption test results
| Water absorption (%) | |
| Example 1 | 12.1 |
| Example 2 | 12.2 |
| Example 3 | 12.8 |
| Comparative example | 9.5 |
As can be seen from tables 1 and 2, the glove materials obtained in examples 1 to 3 have good antibacterial properties against Staphylococcus aureus, candida albicans and Escherichia coli, and high water absorption rate for 5 minutes, indicating good sweat absorption and improved use comfort.
The polyurethane dispersion liquid and polyaspartic acid are omitted in the comparative example, and the antibacterial property and the water absorption of the prepared rubber glove are obviously deteriorated, which shows that the nano particles and polyurethane modification, polyaspartic acid modification treatment and the like of the invention have synergistic effects, and the antibacterial property and the water absorption of the product are improved together.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The preparation method of the antibacterial glove raw material is characterized by comprising the following specific steps:
(1) Firstly, preparing copper calcium germanate nano particles by taking a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia water solution as raw materials through hydrothermal reaction, and then performing plasma treatment to obtain modified nano particles;
(2) Then reacting diisocyanate prepolymer with pyromellitic anhydride as raw materials to prepare multi-carboxyl polyurethane, and uniformly dispersing the multi-carboxyl polyurethane in an organic solvent to obtain polyurethane dispersion liquid;
(3) Then dipping the modified nano particles into polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nano particles, and uniformly stirring and mixing the grafted nano particles and polyacrylic acid to prepare premix liquid;
(4) Mixing 2,6 benzothiazole diamine, polyaspartic acid and polylysine for reaction to obtain a modified benzothiazole polymer, adding 4-6 parts by weight of premix and 8-10 parts by weight of modified benzothiazole polymer into 55-65 parts by weight of natural latex, and stirring and uniformly mixing to obtain the glove raw material;
In the step (1), the preparation method of the copper calcium germanate nano particles comprises the following steps of: adding 8-10 parts of germanium dioxide into 50-55 parts of water, stirring and uniformly mixing, and then dropwise adding an ammonia water solution with the mass concentration of 25-28% until the ammonia water solution is completely dissolved to obtain a germanium-containing ammonia water solution; then adding 12-15 parts of copper chloride solution with the mass concentration of 30-40% and 2-3 parts of calcium chloride solution with the mass concentration of 30-40% into nitric acid solution with the mass concentration of 3-4%, stirring and mixing uniformly, then dropwise adding aqueous ammonia solution containing germanium, stirring and mixing uniformly, adjusting pH= 9 ～ 10,300 ～ 500W, and carrying out ultrasonic oscillation for 50-60 minutes; carrying out hydrothermal reaction for 13-15 hours at 180-200 ℃, cooling, centrifuging to obtain precipitate, washing and drying to obtain copper calcium germanate nano particles;
Wherein, in the step (1), the process conditions of the plasma treatment are as follows: the plasma treatment is carried out for 150-160 s at 20MHz and 150W, the treatment atmosphere is ammonia, and the pressure of the ammonia is 20-30 Pa.
2. The process according to claim 1, wherein in the step (2), the process for producing the polycarboxy polyurethane comprises, in parts by weight: firstly adding 33-35 parts of toluene diisocyanate into 35-40 parts of N-methylpyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, then adding 1-2 parts of dibutyltin dilaurate, heating to 150-160 ℃, slowly dropwise adding 15-16 parts of hexanediol N-methylpyrrolidone mixed solution, and after dropwise adding, keeping the temperature and stirring for 2-3 hours to obtain diisocyanate prepolymer; naturally cooling to room temperature, adding 15-17 parts of pyromellitic anhydride into the diisocyanate prepolymer, stirring for 2-3 hours at room temperature, heating to 50-60 ℃, and stirring for reacting for 8-10 hours to obtain a reaction solution; and finally, slowly dripping the reaction solution into 50-60 parts of absolute ethyl alcohol, washing, centrifuging and taking the solid to obtain the polycarboxy polyurethane.
3. The method according to claim 1, wherein in the step (2), the organic solvent is acetone in an amount of 5 to 7 times the mass of the polycarboxy polyurethane.
4. The method according to claim 1, wherein in the step (3), the mass ratio of the modified nanoparticles to the polyurethane dispersion is 1:5, the dipping process conditions are as follows: ultrasonic oscillation of 300-500W for 20-30 min.
5. The method of claim 1, wherein in step (3), the premix is prepared by the following steps in parts by weight: firstly, uniformly stirring and mixing 2-3 parts of grafted nano particles, 10-12 parts of polyacrylic acid and 2-3 parts of water, then heating to 110-120 ℃, and carrying out heat preservation and stirring for 10-15 minutes to obtain the premix.
6. The method of claim 1, wherein in the step (4), the modified benzothiazole polymer is prepared by the following steps in parts by weight: firstly adding 8-10 parts of 2,6 benzothiazole diamine and 2-3 parts of potassium carbonate into 130-140 parts of N-methyl pyrrolidone, heating to 85-95 ℃, stirring and reacting for 11-12 hours, then adding 5-6 parts of polyaspartic acid and 1-2 parts of polylysine, keeping the temperature and stirring and reacting for 6-8 hours, separating out a polymer, washing by using dichloromethane, and drying for 15-17 hours at 70-80 ℃ to obtain the modified benzothiazole polymer.
7. An antibacterial glove material obtained by the production method according to any one of claims 1 to 6.
8. Use of the antibacterial glove material of claim 7 in the manufacture of a glove.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201208443D0 (en) * | 2012-05-11 | 2012-06-27 | Gros Robert T | Method of manufacturing antimicrobial examination gloves |
| CN109096505A (en) * | 2018-07-04 | 2018-12-28 | 大连理工大学 | A kind of polyurethane grafted method for improving composite material interface performance of more carboxyls |
| CN109294014A (en) * | 2018-09-01 | 2019-02-01 | 湖南博隽生物医药有限公司 | A kind of medical antibacterial gloves and preparation method thereof |
| WO2020232863A1 (en) * | 2019-05-23 | 2020-11-26 | Yu Chen | Method for preparing antibacterial and anti-wrinkle hydrogel and use thereof in textiles |
| CN112794972A (en) * | 2020-12-30 | 2021-05-14 | 广东金发科技有限公司 | Waterborne polyurethane emulsion, nitrile rubber-polyurethane composite emulsion and application thereof |
| CN113425684A (en) * | 2021-06-07 | 2021-09-24 | 江南大学 | Zinc germanate based nano material capable of performing afterglow light monitoring, slowly releasing and resisting bacteria and preparation method thereof |
| CN113563714A (en) * | 2021-07-24 | 2021-10-29 | 浙江天源网业有限公司 | Nano silver carbon antibacterial anti-mite honeycomb net material and preparation method thereof |
| CN113881074A (en) * | 2021-11-17 | 2022-01-04 | 安徽和佳医疗用品科技有限公司 | Preparation method of thin polyurethane medical gloves |
-
2022
- 2022-02-23 CN CN202210166847.1A patent/CN114539571B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201208443D0 (en) * | 2012-05-11 | 2012-06-27 | Gros Robert T | Method of manufacturing antimicrobial examination gloves |
| CN109096505A (en) * | 2018-07-04 | 2018-12-28 | 大连理工大学 | A kind of polyurethane grafted method for improving composite material interface performance of more carboxyls |
| CN109294014A (en) * | 2018-09-01 | 2019-02-01 | 湖南博隽生物医药有限公司 | A kind of medical antibacterial gloves and preparation method thereof |
| WO2020232863A1 (en) * | 2019-05-23 | 2020-11-26 | Yu Chen | Method for preparing antibacterial and anti-wrinkle hydrogel and use thereof in textiles |
| CN112794972A (en) * | 2020-12-30 | 2021-05-14 | 广东金发科技有限公司 | Waterborne polyurethane emulsion, nitrile rubber-polyurethane composite emulsion and application thereof |
| CN113425684A (en) * | 2021-06-07 | 2021-09-24 | 江南大学 | Zinc germanate based nano material capable of performing afterglow light monitoring, slowly releasing and resisting bacteria and preparation method thereof |
| CN113563714A (en) * | 2021-07-24 | 2021-10-29 | 浙江天源网业有限公司 | Nano silver carbon antibacterial anti-mite honeycomb net material and preparation method thereof |
| CN113881074A (en) * | 2021-11-17 | 2022-01-04 | 安徽和佳医疗用品科技有限公司 | Preparation method of thin polyurethane medical gloves |
Non-Patent Citations (1)
| Title |
|---|
| 皮革用有机/无机纳米杂化抗菌剂的制备和性能;王旭;梁纪宇;熊祖江;尹岳涛;;中国皮革;20180330(第04期);全文 * |
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