CN114539571A - Raw material of antibacterial rubber gloves and preparation method thereof - Google Patents
Raw material of antibacterial rubber gloves and preparation method thereof Download PDFInfo
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- CN114539571A CN114539571A CN202210166847.1A CN202210166847A CN114539571A CN 114539571 A CN114539571 A CN 114539571A CN 202210166847 A CN202210166847 A CN 202210166847A CN 114539571 A CN114539571 A CN 114539571A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 48
- 239000005060 rubber Substances 0.000 title claims abstract description 48
- 239000002994 raw material Substances 0.000 title claims abstract description 37
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 68
- 239000002105 nanoparticle Substances 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 56
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000009832 plasma treatment Methods 0.000 claims abstract description 21
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 20
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 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
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000001110 calcium chloride Substances 0.000 claims abstract description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229920002635 polyurethane Polymers 0.000 claims description 23
- 239000004814 polyurethane Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 125000005442 diisocyanate group Chemical group 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 230000010355 oscillation Effects 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 229940119177 germanium dioxide Drugs 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 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-methyl pyrrolidone Chemical compound 0.000 claims description 5
- 239000003960 organic solvent Substances 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
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 15
- 241000894006 Bacteria Species 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 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
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 229940095731 candida albicans Drugs 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
- 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
- 239000000047 product Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000000126 substance Substances 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
- 241000167550 Centella Species 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
- 239000002250 absorbent Substances 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
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 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
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 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
- 210000004243 sweat Anatomy 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a raw material of an antibacterial rubber glove and a preparation method thereof, which comprises the steps of firstly, taking a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia aqueous solution as raw materials, preparing copper calcium germanate nano particles through a hydrothermal reaction, and then carrying out plasma treatment to obtain modified nano particles; then, soaking the modified nanoparticles in polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nanoparticles, and then uniformly stirring the grafted nanoparticles and polyacrylic acid to prepare premixed liquid; and mixing and reacting the 2, 6-benzothiazole diamine with polyaspartic acid and polylysine to obtain a modified benzothiazole polymer, and finally adding the premixed solution and the modified benzothiazole polymer into the natural latex, and stirring and uniformly mixing to obtain the modified benzothiazole polymer. The raw materials of the rubber gloves prepared by the invention can be used for manufacturing rubber gloves, and have excellent antibacterial performance, certain water absorption 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 gloves are widely applied to various fields of hospitals, families, electronic industries, food industries, gardening and the like, and mainly play roles in isolating pollution and protecting hands. The traditional rubber gloves can be divided into a plurality of types according to different raw materials, such as: rubber gloves made from natural latex as a main raw material are called latex gloves, rubber gloves made from synthetic latex obtained by emulsion polymerization of butadiene and acrylonitrile as a main raw material are called nitrile gloves, and rubber gloves made from 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 gloves is different in great similarity, firstly natural latex or artificial synthetic latex is pre-vulcanized, then demoulding is carried out after a forming procedure, and then the finished product gloves can be obtained after chlorination, soaking, washing and drying procedures are respectively carried out.
However, the raw materials of the existing rubber gloves are nutrient components of bacteria, so the rubber gloves can become a place for breeding and breeding bacteria, and the health of human bodies can be damaged in the using process of the rubber gloves. People try to add antibacterial components, such as nano silver, quaternary ammonium salts and other antibacterial substances, directly into the raw materials of the rubber gloves, but the antibacterial substances have poor compatibility with the latex components and are difficult to exert better antibacterial effect.
Patent application CN103980566A discloses a rubber glove with an antibacterial function, which is prepared from natural rubber, nitrile rubber, emulsified liquid paraffin, colloidal sulfur, zinc oxide, an accelerator and an antibacterial active ingredient as raw materials, wherein the antibacterial active ingredient is composed of a fructus momordicae extract and a centella extract. The antibacterial active ingredients in the patent technology also adopt a direct adding method, the compatibility problem still exists, and the finally obtained rubber gloves have unsatisfactory bacteriostasis rate to staphylococcus aureus, candida albicans and escherichia coli.
In addition, the existing rubber gloves are not sweat-absorbent, have poor use experience and are easy to cause bacteria breeding and multiplication.
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 absorption and good use comfort.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of raw materials of an antibacterial rubber glove comprises the following specific steps:
(1) firstly, taking a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia aqueous solution as raw materials, preparing copper calcium germanate nano particles through a hydrothermal reaction, and then carrying out plasma treatment to obtain modified nano particles;
(2) then, reacting diisocyanate prepolymer and pyromellitic dianhydride to prepare polycarboxylic polyurethane, and uniformly dispersing the polycarboxylic polyurethane in an organic solvent to obtain polyurethane dispersion liquid;
(3) then, soaking the modified nanoparticles in polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nanoparticles, and then uniformly stirring the grafted nanoparticles and polyacrylic acid to prepare premixed liquid;
(4) and mixing and reacting 2, 6-benzothiazole diamine, polyaspartic acid and polylysine to obtain a modified benzothiazole polymer, adding 4-6 parts by weight of the premixed solution and 8-10 parts by weight of the modified benzothiazole polymer into 55-65 parts by weight of natural latex, and stirring and uniformly mixing to obtain the rubber glove raw material.
Preferably, in the step (1), the preparation method of the copper calcium germanate nanoparticles comprises the following steps: 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 30-40% copper chloride solution by mass concentration and 2-3 parts of 30-40% calcium chloride solution by mass concentration into 3-4% nitric acid solution by mass concentration, uniformly stirring, dropwise adding ammonia water solution containing germanium, uniformly stirring, adjusting pH to 9-10, and carrying out ultrasonic oscillation at 300-500W for 50-60 minutes; carrying out hydrothermal reaction at 180-200 ℃ for 13-15 hours, cooling, centrifuging to obtain a precipitate, washing and drying to obtain the copper calcium germanate nanoparticles.
Preferably, in the step (1), the process conditions of the plasma treatment are as follows: and (3) performing plasma treatment for 150-160 s at 20MHz and 150W in the presence of ammonia gas at a pressure of 20-30 Pa.
Preferably, in the step (2), the preparation method of the polycarboxylic polyurethane comprises the following steps in parts by weight: firstly, adding 33-35 parts of toluene diisocyanate into 35-40 parts of N-methyl pyrrolidone, uniformly stirring and dispersing, transferring to a reaction kettle, then adding 1-2 parts of dibutyltin dilaurate, heating to 150-160 ℃, then slowly dropwise adding 15-16 parts of hexanediol-N-methyl pyrrolidone mixed solution, and after dropwise adding, keeping the temperature and stirring for 2-3 hours to obtain a diisocyanate prepolymer; naturally cooling to room temperature, adding 15-17 parts of pyromellitic dianhydride 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 liquid into 50-60 parts of absolute ethyl alcohol, washing, centrifuging and taking solid to obtain the polycarboxylic polyurethane.
Preferably, in the step (2), the organic solvent is acetone, and the dosage of the acetone is 5-7 times of the mass of the polycarboxylic polyurethane.
Preferably, in the step (3), the mass ratio of the modified nanoparticles to the polyurethane dispersion is 1: 5, the technological conditions of the impregnation are as follows: 300-500W ultrasonic oscillation is carried out for 20-30 minutes.
Preferably, in the step (3), the preparation method of the premix comprises the following steps in parts by weight: firstly, stirring and uniformly mixing 2-3 parts of grafted nanoparticles, 10-12 parts of polyacrylic acid and 2-3 parts of water, then heating to 110-120 ℃, and stirring for 10-15 minutes under the condition of heat preservation to obtain a premixed solution.
Preferably, in the step (4), the preparation method of the modified benzothiazole polymer is as follows: 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 for reaction for 11-12 hours, adding 5-6 parts of polyaspartic acid and 1-2 parts of polylysine, keeping the temperature, stirring for reaction for 6-8 hours, precipitating a polymer, washing with dichloromethane, and drying at 70-80 ℃ for 15-17 hours to obtain the modified benzothiazole polymer.
The antibacterial rubber glove raw material obtained by the preparation method is utilized.
The antibacterial rubber glove raw material is applied to manufacturing rubber gloves.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprises the steps of firstly, preparing copper calcium germanate nanoparticles by taking a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia aqueous solution as raw materials through a hydrothermal reaction, and then carrying out plasma treatment to obtain modified nanoparticles; then, soaking the modified nanoparticles in polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nanoparticles, and then uniformly stirring the grafted nanoparticles and polyacrylic acid to prepare premixed liquid; and finally, adding the premixed solution and the modified benzothiazole polymer into natural latex, and uniformly stirring to obtain the raw material of the rubber gloves. The raw materials of the rubber gloves prepared by the invention can be used for manufacturing rubber gloves, and have excellent antibacterial performance, certain water absorption and good use comfort.
(2) According to the invention, the premix and the modified benzothiazole polymer are added into the natural latex, so that good antibacterial property and water absorption are provided. The pre-mixed solution is obtained by mixing grafted nanoparticles and polyacrylic acid, modified nanoparticles contain copper ions, calcium ions and the like, sterilization is performed synergistically, the surface performance of the copper calcium germanate nanoparticles can be changed through plasma treatment, a certain etching effect is achieved, amino groups are introduced to form hydrogen bonds with polyurethane in the polyurethane dispersion solution, and the dispersibility of the nanoparticles in a system is improved.
(3) The polyurethane dispersion liquid is prepared by reacting diisocyanate prepolymer and pyromellitic anhydride serving as raw materials to prepare polycarboxylic polyurethane, and uniformly dispersing the polycarboxylic polyurethane in an organic solvent. The polycarboxyl structure can improve the dispersibility of the nanoparticles in a system, thereby exerting the antibacterial property and improving the water absorption property.
The modified benzothiazole polymer is obtained by mixing and reacting 2, 6-benzothiazole diamine, polyaspartic acid and polylysine, and the antibacterial property and the water absorption are further improved under the synergistic effect of the 2, 6-benzothiazole diamine, the polyaspartic acid and the polylysine.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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
A preparation method of raw materials of an antibacterial rubber glove comprises the following specific steps:
(1) firstly, adding 8g of germanium dioxide into 55g of water, uniformly stirring, and then dropwise adding an ammonia water solution with the mass concentration of 25% until the germanium-containing ammonia water solution 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, uniformly stirring, dropwise adding the obtained germanium-containing ammonia water solution, uniformly stirring, adjusting the pH value to 9, performing 500W ultrasonic oscillation for 50 minutes; carrying out hydrothermal reaction at 200 ℃ for 13 hours, cooling, centrifuging, taking precipitate, washing and drying to obtain copper calcium germanate nanoparticles, and carrying out plasma treatment on the copper calcium germanate nanoparticles to obtain modified nanoparticles;
(2) adding 35g of toluene diisocyanate into 35g N-methyl pyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, adding 2g of dibutyltin dilaurate, heating to 150 ℃, slowly dropwise adding 16g of hexanediol-N-methyl pyrrolidone mixed solution, and keeping the temperature and stirring for 2 hours after dropwise adding to obtain a diisocyanate prepolymer; naturally cooling to room temperature, adding 17g of pyromellitic anhydride into the diisocyanate prepolymer, stirring for 2 hours at room temperature, heating to 60 ℃, and stirring for reaction for 8 hours to obtain a reaction solution; finally, slowly dripping the reaction liquid into 60g of absolute ethyl alcohol, washing, centrifuging to obtain a solid to obtain polycarboxylic polyurethane, and uniformly dispersing the polycarboxylic polyurethane in acetone with the mass of 5 times that of the polycarboxylic polyurethane to obtain polyurethane dispersion liquid;
(3) then 1g of modified nanoparticles are dipped in 5g of polyurethane dispersion liquid, the solvent is volatilized to obtain grafted nanoparticles, then 3g of grafted nanoparticles, 10g of polyacrylic acid and 3g of water are uniformly stirred, heated to 110 ℃, kept warm and stirred for 15 minutes to prepare a premixed solution;
(4) then adding 8g of 2, 6-benzothiazole diamine and 3g of potassium carbonate into 130g of N-methylpyrrolidone, heating to 95 ℃, stirring for reaction for 11 hours, then adding 6g of polyaspartic acid and 1g of polylysine, keeping the temperature, stirring for reaction for 8 hours, separating out a polymer, washing by using dichloromethane, and drying at 70 ℃ for 17 hours to obtain a modified benzothiazole polymer; and finally, adding 4g of the premixed solution and 10g of the modified benzothiazole polymer into 55g of the natural latex, and uniformly stirring to obtain the rubber glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: plasma treatment is carried out for 160s at the frequency of 20MHz and 150W, the treatment atmosphere is ammonia gas, and the pressure of the ammonia gas is 20 Pa.
In the step (3), the technological conditions of impregnation are as follows: 500W ultrasonic oscillation is carried out for 20 minutes.
Example 2
A preparation method of raw materials of an antibacterial rubber glove comprises the following specific steps:
(1) firstly, adding 10g of germanium dioxide into 50g of water, uniformly stirring, and then dropwise adding an ammonia water solution with the mass concentration of 28% until the germanium-containing ammonia water solution is completely dissolved to obtain a germanium-containing ammonia water solution; then adding 12g of 40% copper chloride solution with mass concentration and 2g of 40% calcium chloride solution with mass concentration into 3% nitric acid solution with mass concentration, uniformly stirring, dropwise adding the obtained germanium-containing ammonia water solution, uniformly stirring, adjusting the pH value to 10, and carrying out ultrasonic oscillation at 300W for 60 minutes; carrying out hydrothermal reaction at 180 ℃ for 15 hours, cooling, centrifuging, taking precipitate, washing and drying to obtain copper calcium germanate nanoparticles, and carrying out plasma treatment on the copper calcium germanate nanoparticles to obtain modified nanoparticles;
(2) then adding 33g of toluene diisocyanate into 40g N-methyl pyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, adding 1g of dibutyltin dilaurate, heating to 160 ℃, then slowly dropwise adding 15g of hexanediol-N-methyl pyrrolidone mixed solution, and keeping the temperature and stirring for 3 hours after dropwise adding to obtain a diisocyanate prepolymer; naturally cooling to room temperature, adding 15g of pyromellitic anhydride into the diisocyanate prepolymer, stirring for 3 hours at room temperature, heating to 50 ℃, and stirring for reaction for 10 hours to obtain a reaction solution; finally, slowly dripping the reaction liquid into 50g of absolute ethyl alcohol, washing, centrifuging to obtain a solid to obtain polycarboxylic polyurethane, and uniformly dispersing the polycarboxylic polyurethane in acetone with the mass 7 times that of the polycarboxylic polyurethane to obtain polyurethane dispersion liquid;
(3) then 1g of modified nanoparticles are dipped in 5g of polyurethane dispersion liquid, the solvent is volatilized to obtain grafted nanoparticles, then 2g of grafted nanoparticles, 12g of polyacrylic acid and 2g of water are uniformly stirred, heated to 120 ℃, kept warm and stirred for 10 minutes to prepare a premixed solution;
(4) then adding 10g of 2, 6-benzothiazole diamine and 2g of potassium carbonate into 140g of N-methylpyrrolidone, heating to 85 ℃, stirring for reaction for 12 hours, then adding 5g of polyaspartic acid and 2g of polylysine, keeping the temperature, stirring for reaction for 6 hours, separating out a polymer, washing by using dichloromethane, and drying at 80 ℃ for 15 hours to obtain a modified benzothiazole polymer; and finally, adding 6g of the premixed solution and 8g of the modified benzothiazole polymer into 65g of natural latex, and uniformly stirring to obtain the rubber glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: plasma treatment is carried out for 150s at the frequency of 20MHz and 150W, the treatment atmosphere is ammonia gas, and the pressure of the ammonia gas is 30 Pa.
In the step (3), the technological conditions of impregnation are as follows: 300W ultrasonic oscillation for 30 minutes.
Example 3
A preparation method of raw materials of an antibacterial rubber glove comprises the following specific steps:
(1) firstly, adding 9g of germanium dioxide into 52g of water, uniformly stirring, and then dropwise adding an ammonia water solution with the mass concentration of 27% until the germanium-containing ammonia water solution is completely dissolved to obtain a germanium-containing ammonia water solution; then adding 13g of 35% copper chloride solution with mass concentration and 2.5g of 35% calcium chloride solution with mass concentration into 3.5% nitric acid solution with mass concentration, uniformly stirring, dropwise adding the obtained germanium-containing ammonia water solution, uniformly stirring, and adjusting the pH value to 9.5,400W, and carrying out ultrasonic oscillation for 55 minutes; carrying out hydrothermal reaction at 190 ℃ for 14 hours, cooling, centrifuging, taking precipitate, washing and drying to obtain copper calcium germanate nanoparticles, and carrying out plasma treatment on the copper calcium germanate nanoparticles to obtain modified nanoparticles;
(2) then adding 34g of toluene diisocyanate into 38g N-methyl pyrrolidone, stirring and dispersing uniformly, transferring to a reaction kettle, adding 1.5g of dibutyltin dilaurate, heating to 155 ℃, then slowly dropwise adding 16g of hexanediol-N-methyl pyrrolidone mixed solution, keeping the temperature and stirring for 2.5 hours after dropwise adding is finished, and obtaining a diisocyanate prepolymer; naturally cooling to room temperature, adding 16g of pyromellitic anhydride into the diisocyanate prepolymer, stirring for 2.5 hours at room temperature, heating to 55 ℃, and stirring for reaction for 9 hours to obtain reaction liquid; finally, slowly dripping the reaction liquid into 55g of absolute ethyl alcohol, washing, centrifuging to obtain a solid to obtain polycarboxylic polyurethane, and uniformly dispersing the polycarboxylic polyurethane in acetone with the mass 6 times that of the polycarboxylic polyurethane to obtain polyurethane dispersion liquid;
(3) then soaking 1g of modified nanoparticles in 5g of polyurethane dispersion liquid, volatilizing the solvent to obtain grafted nanoparticles, then uniformly stirring and mixing 2.5g of grafted nanoparticles, 11g of polyacrylic acid and 2.5g of water, heating to 115 ℃, preserving heat and stirring for 12 minutes to prepare a premixed solution;
(4) then adding 9g of 2, 6-benzothiazole diamine and 2.5g of potassium carbonate into 135g of N-methylpyrrolidone, heating to 90 ℃, stirring for reaction for 12 hours, then adding 5.5g of polyaspartic acid and 1.5g of polylysine, keeping the temperature, stirring for reaction for 7 hours, precipitating a polymer, washing with dichloromethane, and drying for 16 hours at 75 ℃ to obtain a modified benzothiazole polymer; and finally, adding 5g of the premixed solution and 9g of the modified benzothiazole polymer into 60g of natural latex, and uniformly stirring to obtain the rubber glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: and (3) performing plasma treatment for 155s at 20MHz under the condition of ammonia gas with the pressure of 25 Pa.
In the step (3), the technological conditions of impregnation are as follows: the 400W ultrasonic wave was oscillated for 25 minutes.
Comparative example
A preparation method of a rubber glove raw material comprises the following specific steps:
(1) firstly, adding 8g of germanium dioxide into 55g of water, uniformly stirring, and then dropwise adding an ammonia water solution with the mass concentration of 25% until the germanium-containing ammonia water solution 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, uniformly stirring, dropwise adding the obtained germanium-containing ammonia water solution, uniformly stirring, adjusting the pH value to 9, performing 500W ultrasonic oscillation for 50 minutes; carrying out hydrothermal reaction at 200 ℃ for 13 hours, cooling, centrifuging, taking precipitate, washing and drying to obtain copper calcium germanate nanoparticles, and carrying out plasma treatment on the copper calcium germanate nanoparticles to obtain modified nanoparticles;
(2) then 3g of modified nano particles, 10g of polyacrylic acid and 3g of water are uniformly stirred and mixed, heated to 110 ℃, kept warm and stirred for 15 minutes to prepare a premixed solution;
(3) then adding 8g of 2, 6-benzothiazole diamine and 3g of potassium carbonate into 130g of N-methylpyrrolidone, heating to 95 ℃, stirring for reaction for 11 hours, then adding 1g of polylysine, keeping the temperature, stirring for reaction for 8 hours, separating out a polymer, washing by using dichloromethane, and drying for 17 hours at 70 ℃ to obtain a modified benzothiazole polymer; and finally, adding 4g of the premixed solution and 10g of the modified benzothiazole polymer into 55g of the natural latex, and uniformly stirring to obtain the rubber glove raw material.
In the step (1), the process conditions of the plasma treatment are as follows: plasma treatment is carried out for 160s at the frequency of 20MHz and 150W, the treatment atmosphere is ammonia gas, and the pressure of the ammonia gas is 20 Pa.
In the step (2), the technological conditions of impregnation are as follows: 500W ultrasonic oscillation is carried out for 20 minutes.
Test examples
And (3) respectively mixing the rubber glove raw materials obtained in the examples 1-3 and the comparative example by an internal mixer, then forming by using a glove model, and carrying out post-treatment to prepare the rubber gloves. And (5) inspecting the antibacterial property and the water absorption of the rubber gloves.
The antibacterial property test method comprises the following steps: sterilizing a rubber glove sample with a size of 2cm multiplied by 2cm, and dripping staphylococcus aureus, candida albicans and escherichia coli bacteria liquid with a concentration of 10 on the surface of the sterile sample7cfu/mL, the bacterial drop addition is 0.05mL/cm2Then culturing the sample at the constant temperature of 37 ℃ for 24 hours, diluting bacterial liquid on the sample by multiple times, inoculating the diluted bacterial liquid on an agar plate containing a culture medium, culturing the sample in a constant temperature incubator at the constant temperature of 37 ℃ for 24 hours, and calculating the number of live bacteria (refer to GB/T4789.2); the number of live bacteria was divided by the total bacteria number to calculate the antibacterial ratio. And the sterilized samples were again tested for antibacterial efficiency after being placed in a box in which rotten apples were piled for 12 hours, and the results are shown in table 1.
The water absorption test method is as follows: a2 cm × 2cm sample of the rubber glove is taken, dried to a constant weight m1, then immersed in 200mL of distilled water, and after standing for 5 minutes, the sample is taken out, and surface moisture is sucked off by filter paper and m2 is weighed, so that the water absorption R is (m2-m1)/m1 × 100%. The results are shown in Table 2.
TABLE 1 results of antibacterial property test
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 rubber gloves prepared from the rubber glove raw materials obtained in examples 1 to 3 have better antibacterial properties against staphylococcus aureus, candida albicans, and escherichia coli, and have a high water absorption rate in 5 minutes, which indicates that the rubber gloves have better sweat absorption and improved comfort in use.
The polyurethane dispersion liquid and the polyaspartic acid are omitted in the comparative example, the antibacterial property and the water absorption of the prepared rubber gloves are obviously poor, and the synergistic effects of the nanoparticles, the polyurethane modification, the polyaspartic acid modification treatment and the like are demonstrated, so that the antibacterial property and the water absorption of the product are jointly improved.
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 attributes 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 description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of raw materials of an antibacterial rubber glove is characterized by comprising the following specific steps:
(1) firstly, taking a copper chloride aqueous solution, a calcium chloride aqueous solution and a germanium-containing ammonia aqueous solution as raw materials, preparing copper calcium germanate nano particles through a hydrothermal reaction, and then carrying out plasma treatment to obtain modified nano particles;
(2) then, reacting diisocyanate prepolymer and pyromellitic dianhydride to prepare polycarboxylic polyurethane, and uniformly dispersing the polycarboxylic polyurethane in an organic solvent to obtain polyurethane dispersion liquid;
(3) then, soaking the modified nanoparticles in polyurethane dispersion liquid, volatilizing a solvent to obtain grafted nanoparticles, and then uniformly stirring the grafted nanoparticles and polyacrylic acid to prepare premixed liquid;
(4) and mixing and reacting 2, 6-benzothiazole diamine, polyaspartic acid and polylysine to obtain a modified benzothiazole polymer, adding 4-6 parts by weight of the premixed solution and 8-10 parts by weight of the modified benzothiazole polymer into 55-65 parts by weight of natural latex, and stirring and uniformly mixing to obtain the rubber glove raw material.
2. The preparation method according to claim 1, wherein in the step (1), the copper calcium germanate nanoparticles are prepared by the following steps: 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 30-40% copper chloride solution by mass concentration and 2-3 parts of 30-40% calcium chloride solution by mass concentration into 3-4% nitric acid solution by mass concentration, uniformly stirring, dropwise adding ammonia water solution containing germanium, uniformly stirring, adjusting pH to 9-10, and carrying out ultrasonic oscillation at 300-500W for 50-60 minutes; carrying out hydrothermal reaction at 180-200 ℃ for 13-15 hours, cooling, centrifuging to obtain a precipitate, washing and drying to obtain the copper calcium germanate nanoparticles.
3. The method according to claim 1, wherein in the step (1), the process conditions of the plasma treatment are as follows: and (3) performing plasma treatment for 150-160 s at 20MHz and 150W in the presence of ammonia gas at a pressure of 20-30 Pa.
4. The method according to claim 1, wherein in the step (2), the polycarboxylic polyurethane is prepared by the following method in parts by weight: firstly, adding 33-35 parts of toluene diisocyanate into 35-40 parts of N-methyl pyrrolidone, uniformly stirring and dispersing, transferring to a reaction kettle, then adding 1-2 parts of dibutyltin dilaurate, heating to 150-160 ℃, then slowly dropwise adding 15-16 parts of hexanediol-N-methyl pyrrolidone mixed solution, and after dropwise adding, keeping the temperature and stirring for 2-3 hours to obtain a diisocyanate prepolymer; naturally cooling to room temperature, adding 15-17 parts of pyromellitic dianhydride 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 liquid into 50-60 parts of absolute ethyl alcohol, washing, centrifuging and taking solid to obtain the polycarboxylic polyurethane.
5. The preparation method according to claim 1, wherein in the step (2), the organic solvent is acetone, and the amount of acetone is 5-7 times of the mass of the polycarboxylic polyurethane.
6. The preparation 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 technological conditions of the impregnation are as follows: 300-500W ultrasonic oscillation is carried out for 20-30 minutes.
7. The method according to claim 1, wherein in the step (3), the premix is prepared by the following steps in parts by weight: firstly, stirring and uniformly mixing 2-3 parts of grafted nanoparticles, 10-12 parts of polyacrylic acid and 2-3 parts of water, then heating to 110-120 ℃, and stirring for 10-15 minutes under the condition of heat preservation to obtain a premixed solution.
8. The method according to claim 1, wherein in the step (4), the modified benzothiazole polymer is prepared by the following method in parts by weight: 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 for reaction for 11-12 hours, adding 5-6 parts of polyaspartic acid and 1-2 parts of polylysine, keeping the temperature, stirring for reaction for 6-8 hours, precipitating a polymer, washing with dichloromethane, and drying at 70-80 ℃ for 15-17 hours to obtain the modified benzothiazole polymer.
9. An antibacterial rubber glove raw material obtained by the preparation method of any one of claims 1 to 8.
10. Use of the antimicrobial glove stock of claim 9 in the manufacture of a glove.
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