CN114539571B - Antibacterial rubber glove raw material and preparation method thereof - Google Patents

Antibacterial rubber glove raw material and preparation method thereof Download PDF

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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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姜金河
魏进国
李玉龙
周小凤
刘汉云
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Siyang Xiangyuan Medical Technology Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/02Direct processing of dispersions, e.g. latex, to articles
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00Gloves
    • A41D19/0055Plastic or rubber gloves
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00Materials specially adapted for outerwear
    • A41D31/04Materials specially adapted for outerwear characterised by special function or use
    • A41D31/30Antimicrobial, e.g. antibacterial
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D2500/00Materials for garments
    • A41D2500/50Synthetic resins or rubbers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2433/00Characterised 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
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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

Antibacterial rubber glove raw material and preparation method thereof
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.
CN202210166847.1A 2022-02-23 2022-02-23 Antibacterial rubber glove raw material and preparation method thereof Active CN114539571B (en)

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