CN112759808A - Butyronitrile latex for medical examination gloves and preparation method thereof - Google Patents
Butyronitrile latex for medical examination gloves and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the technical field of rubber, and provides butyronitrile latex for a medical examination glove and a preparation method thereof, wherein the butyronitrile latex for the medical examination glove comprises the following components: modifier, bacteriostatic agent, graphene, nitrile rubber emulsion, sulfur, curing agent, titanium dioxide, dispersant and zinc oxide. According to the invention, the nitrile rubber emulsion modified by montmorillonite after acid modification and sodium modification and graphene are used to remarkably improve the mechanical properties of the nitrile rubber latex, such as tear resistance, cut resistance and puncture resistance; in the preparation process, a bacteriostatic agent which is formed by mixing dimethomorph, nano silver modified by zeolite powder, carbon black and a silane coupling agent, titanium oxide, copper sulfate and nano indium oxide is added, so that the bacteriostatic activity of the prepared butyronitrile latex is obviously improved.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to butyronitrile latex for medical examination gloves and a preparation method thereof.
Background
The nitrile latex is latex prepared by polymerizing butadiene and acrylonitrile emulsion, and is divided into three types, namely high nitrile (35-45%), medium nitrile (25-33%) and low nitrile (20-25%) according to the mass percentage of acrylonitrile. In a plurality of industries such as medical treatment, food, electronics, photovoltaic and the like, the protection of gloves is more and more important, the main glove types are polyvinyl chloride gloves, natural rubber gloves, butyronitrile gloves and the like, wherein the butyronitrile gloves do not cause allergy of wearing gloves due to the fact that the butyronitrile gloves do not contain proteins in the natural latex gloves, and the gloves gradually replace the natural latex gloves.
The existing gloves for medical examination, which are prepared from butyronitrile latex, have the problems of poor mechanical property and poor antibacterial effect when in use.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides butyronitrile latex for a medical examination glove and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the butyronitrile latex for the medical examination glove consists of the following components in parts by weight: 3-9 parts of modifier, 5-10 parts of bacteriostatic agent, 4-8 parts of graphene, 100 parts of nitrile rubber emulsion, 0.8-1.5 parts of sulfur, 1-3 parts of curing agent, 1-2 parts of titanium dioxide, 0.01-0.04 part of dispersant and 0.5-1.2 parts of zinc oxide.
The preparation method of the modifier comprises the following steps: according to (7-11): (8-12): (3-5) weighing montmorillonite, mixed acid solution and sodium carbonate solution according to the weight ratio; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 70-80 ℃, mixing for 1-2h in an ultrasonic environment, standing, filtering and drying to obtain acid-modified montmorillonite; after being crushed, the acid-modified montmorillonite and sodium carbonate solution are led into a mixing barrel to be fully mixed for 1 to 2 hours, and then the modifier is obtained after filtration, drying and crushing.
The mixed acid solution comprises a 30% sulfuric acid solution, a 30% hydrochloric acid solution and a 40% phosphoric acid solution, and the concentrations of the sulfuric acid solution, the hydrochloric acid solution and the phosphoric acid solution are all 35-55%.
The concentration of the sodium carbonate solution is 25-55%, and the ultrasonic frequency under the ultrasonic environment is 10MHz-20 MHz.
The preparation method of the bacteriostatic agent comprises the following steps: according to the following steps of 100: (40-60): (0.5-1.2): (5-10): (2-4): (0.5-1.1): (5-9): (10-12) weighing dimethomorph, zeolite powder, nano-silver, titanium oxide, copper sulfate, nano-indium oxide, carbon black and a silane coupling agent in a weight ratio; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; and fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the antibacterial agent.
The curing agent is one of silicon boron tackifier, titanate tackifier, polyethylene glycol distearate or acrylic acid polymer.
A preparation method of butyronitrile latex for medical examination gloves comprises the following steps:
step 1: weighing the components in parts by weight;
step 2: introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 25-35 ℃, stirring and mixing for 2-3h, and vacuumizing the reaction kettle while stirring;
and step 3: introducing sulfur, a curing agent, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 40-50 ℃, and keeping the temperature to react for 0.5-1h to obtain the butyronitrile latex for the medical examination gloves.
The material in the reaction kettle is heated by microwave, and the frequency of the microwave is 2400-.
Montmorillonite which is sequentially subjected to acid modification and sodium modification is selected as a modifier of the nitrile-butadiene rubber emulsion and the graphene, and when the montmorillonite is modified by a mixed acid solution, cations such as K, Na, Ca, Mg and the like among montmorillonite layers are converted into acid soluble salts to be dissolved out, so that the original interlayer binding force is weakened, interlayer lattices are cracked, and the interlayer spacing is enlarged, so that the specific surface area and the adsorption capacity after modification are obviously increased; the specific surface area of the montmorillonite modified by acidification is increased, the aperture is also increased, and the montmorillonite modified by acidification has stronger adsorbability and chemical activity and very high adsorption and catalysis performances; the acid-modified montmorillonite is mixed with a sodium carbonate solution, part of the acid-modified montmorillonite is subjected to sodium modification, and the sodium-based montmorillonite has better expansibility and cation exchange property than calcium-based montmorillonite, and has dispersibility, viscosity, lubricity, thermal stability, higher heat-humidity pressure strength and higher compressive strength in an aqueous medium; and partial montmorillonite which is not subjected to sodium modification has the effect of a catalyst besides the effect of modification when modifying the nitrile-butadiene rubber emulsion and the graphene, so that the efficiency of modifying the nitrile-butadiene rubber emulsion and the graphene is improved.
The nitrile-butadiene rubber emulsion and the graphene modified by the montmorillonite after acid modification and sodium modification obviously improve the mechanical properties of the nitrile-butadiene rubber emulsion, such as tear resistance, cut resistance and puncture resistance.
In the preparation process, a bacteriostatic agent which is formed by mixing dimethomorph, nano silver modified by zeolite powder, carbon black and a silane coupling agent, titanium oxide, copper sulfate and nano indium oxide is added, so that the bacteriostatic activity of the prepared butyronitrile latex is obviously improved.
Detailed Description
The technical solutions in the embodiments of the present invention are 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.
The nitrile latex is latex prepared by polymerizing butadiene and acrylonitrile emulsion, and is divided into three types, namely high nitrile (35-45%), medium nitrile (25-33%) and low nitrile (20-25%) according to the mass percentage of acrylonitrile. In a plurality of industries such as medical treatment, food, electronics, photovoltaic and the like, the protection of gloves is more and more important, the main glove types are polyvinyl chloride gloves, natural rubber gloves, butyronitrile gloves and the like, wherein the butyronitrile gloves do not cause allergy of wearing gloves due to the fact that the butyronitrile gloves do not contain proteins in the natural latex gloves, and the gloves gradually replace the natural latex gloves. The existing gloves for medical examination, which are prepared from butyronitrile latex, have the problems of poor mechanical property and poor antibacterial effect when in use. In order to solve the technical problem, the invention provides a butyronitrile latex for a medical examination glove, which comprises the following components in parts by weight: 3-9 parts of modifier, 5-10 parts of bacteriostatic agent, 4-8 parts of graphene, 100 parts of nitrile rubber emulsion, 0.8-1.5 parts of sulfur, 1-3 parts of curing agent, 1-2 parts of titanium dioxide, 0.01-0.04 part of dispersant and 0.5-1.2 parts of zinc oxide.
In the embodiment of the invention, the butyronitrile latex for the medical examination glove is composed of the following components in parts by weight: 3-9 parts of modifier, 5-10 parts of bacteriostatic agent, 4-8 parts of graphene, 100 parts of nitrile rubber emulsion, 0.8-1.5 parts of sulfur, 1-3 parts of curing agent, 1-2 parts of titanium dioxide, 0.01-0.04 part of dispersant and 0.5-1.2 parts of zinc oxide.
In the invention, montmorillonite which is sequentially subjected to acid modification and sodium modification is selected as a modifier of the nitrile-butadiene rubber emulsion and the graphene, and when the montmorillonite is modified by a mixed acid solution, cations such as K, Na, Ca, Mg and the like among montmorillonite layers are converted into soluble salts of acid to be dissolved out, so that the original interlayer binding force is weakened, interlayer lattices are cracked, and the interlayer spacing is enlarged, so that the specific surface area and the adsorption capacity after modification are obviously increased; the specific surface area of the montmorillonite modified by acidification is increased, the aperture is also increased, and the montmorillonite modified by acidification has stronger adsorbability and chemical activity and very high adsorption and catalysis performances; the acid-modified montmorillonite is mixed with a sodium carbonate solution, part of the acid-modified montmorillonite is subjected to sodium modification, and the sodium-based montmorillonite has better expansibility and cation exchange property than calcium-based montmorillonite, and has dispersibility, viscosity, lubricity, thermal stability, higher heat-humidity pressure strength and higher compressive strength in an aqueous medium; and partial montmorillonite which is not subjected to sodium modification has the effect of a catalyst besides the effect of modification when modifying the nitrile-butadiene rubber emulsion and the graphene, so that the efficiency of modifying the nitrile-butadiene rubber emulsion and the graphene is improved.
According to the invention, the nitrile rubber emulsion and the graphene modified by the montmorillonite after acid modification and sodium modification obviously improve the mechanical properties of the nitrile rubber latex, such as tear resistance, cut resistance and puncture resistance.
In the invention, the bacteriostatic agent which is formed by mixing dimethomorph, nano silver modified by zeolite powder, carbon black and a silane coupling agent, titanium oxide, copper sulfate and nano indium oxide is added in the preparation process, so that the bacteriostatic activity of the prepared butyronitrile latex is obviously improved.
The technical effects of the nitrile rubber latex for medical examination gloves and the preparation method thereof according to the present invention will be further described with reference to the following specific examples, but the specific implementation methods mentioned in these examples are only illustrative and explanatory of the technical solution of the present invention, and do not limit the implementation scope of the present invention, and all modifications and substitutions based on the above principles should be within the protection scope of the present invention.
Example 1
Respectively mixing 35% sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution according to the weight ratio of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 8: 3, weighing montmorillonite, mixed acid solution and 25% sodium carbonate solution in percentage by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 70 ℃, mixing the montmorillonite and the mixed acid solution for 1 hour in an ultrasonic environment, standing, filtering and drying to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 10 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 1h, filtering, drying and crushing to obtain a modifier;
according to the following steps of 100: 40: 0.5: 5: 2: 0.5: 5: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 10; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 3 parts of modifier, 5 parts of bacteriostatic agent, 4 parts of graphene, 100 parts of nitrile rubber emulsion, 0.8 part of sulfur, 1 part of silicon-boron tackifier, 1 part of titanium dioxide, 0.01 part of dispersant and 0.5 part of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 25 ℃ by microwave, stirring and mixing for 2 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, silicon boron tackifier, titanium dioxide, zinc oxide, dispersant and bacteriostatic agent into a reaction kettle, fully mixing, heating to 40 ℃ by microwave, keeping the frequency of the microwave at 2400Mhz, and reacting for 0.5h to obtain the butyronitrile latex for the medical examination gloves.
Example 2
Respectively mixing 35% sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution according to the weight ratio of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 8: 3, weighing montmorillonite, mixed acid solution and 25% sodium carbonate solution in percentage by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 70 ℃, mixing the montmorillonite and the mixed acid solution for 1 hour in an ultrasonic environment, standing, filtering and drying to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 10 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 1h, filtering, drying and crushing to obtain a modifier;
according to the following steps of 100: 40: 0.5: 5: 2: 0.5: 5: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 10; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 4 parts of modifier, 6 parts of bacteriostatic agent, 5 parts of graphene, 100 parts of nitrile rubber emulsion, 0.9 part of sulfur, 1.1 parts of silicon-boron tackifier, 1.2 parts of titanium dioxide, 0.02 part of dispersant and 0.6 part of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 25 ℃ by microwave, stirring and mixing for 2 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, silicon boron tackifier, titanium dioxide, zinc oxide, dispersant and bacteriostatic agent into a reaction kettle, fully mixing, heating to 40 ℃ by microwave, keeping the frequency of the microwave at 2400Mhz, and reacting for 0.5h to obtain the butyronitrile latex for the medical examination gloves.
Example 3
Sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution with the concentration of 45% are mixed according to the proportion of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps of 9: 10: 4, weighing montmorillonite, mixed acid solution and sodium carbonate solution with the concentration of 40 percent by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 75 ℃, mixing the montmorillonite and the mixed acid solution for 1.5 hours in an ultrasonic environment, standing, filtering and drying the montmorillonite to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 15 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 1.5h, filtering, drying and crushing to obtain a modifier;
according to the following steps of 100: 50: 0.75: 7: 3: 0.8: 7: 11 weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent in a weight ratio; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 6 parts of modifier, 7.5 parts of bacteriostatic agent, 6 parts of graphene, 100 parts of nitrile rubber emulsion, 1.15 parts of sulfur, 2 parts of titanate tackifier, 1.5 parts of titanium dioxide, 0.025 part of dispersant and 0.85 part of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 30 ℃ by microwave, stirring and mixing for 2.5 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, titanate tackifier, titanium dioxide, zinc oxide, dispersant and bacteriostatic agent into a reaction kettle, fully mixing, heating to 45 ℃ with microwave, wherein the frequency of the microwave is 2450Mhz, and carrying out heat preservation reaction for 0.75h to obtain the butyronitrile latex for the medical examination gloves.
Example 4
Sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution with the concentration of 55% are mixed according to the proportion of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 12: 5, weighing montmorillonite, a mixed acid solution and a sodium carbonate solution with the concentration of 55 percent by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 80 ℃, mixing the montmorillonite and the mixed acid solution for 2 hours in an ultrasonic environment, standing, filtering and drying the montmorillonite to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 20 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 2 hours, filtering, drying and crushing to obtain a modifier;
according to the following steps of 100: 60: 1.2: 10: 4: 1.1: 9: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 12; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 8 parts of modifier, 9 parts of bacteriostatic agent, 7 parts of graphene, 100 parts of nitrile rubber emulsion, 1.4 parts of sulfur, 2.8 parts of titanate tackifier, 1.8 parts of titanium dioxide, 0.03 part of dispersant and 1.1 parts of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 35 ℃ by microwave, stirring and mixing for 3 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, titanate tackifier, titanium dioxide, zinc oxide, dispersant and bacteriostatic agent into a reaction kettle, fully mixing, heating to 50 ℃ by microwave, keeping the frequency of the microwave at 2500Mhz, and reacting for 1h to obtain the butyronitrile latex for the medical examination gloves.
Example 5
Sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution with the concentration of 55% are mixed according to the proportion of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 12: 5, weighing montmorillonite, a mixed acid solution and a sodium carbonate solution with the concentration of 55 percent by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 80 ℃, mixing the montmorillonite and the mixed acid solution for 2 hours in an ultrasonic environment, standing, filtering and drying the montmorillonite to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 20 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 2 hours, filtering, drying and crushing to obtain a modifier;
according to the following steps of 100: 60: 1.2: 10: 4: 1.1: 9: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 12; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 9 parts of modifier, 10 parts of bacteriostatic agent, 8 parts of graphene, 100 parts of nitrile rubber emulsion, 1.5 parts of sulfur, 3 parts of polyethylene glycol distearate, 2 parts of titanium dioxide, 0.04 part of dispersant and 1.2 parts of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 35 ℃ by microwave, stirring and mixing for 3 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, polyethylene glycol distearate, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 50 ℃ with microwave at the frequency of 2500Mhz, and carrying out heat preservation reaction for 1h to obtain the butyronitrile latex for the medical examination gloves.
Example 6
Sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution with the concentration of 55% are mixed according to the proportion of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 12: 5, weighing montmorillonite, a mixed acid solution and a sodium carbonate solution with the concentration of 55 percent by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 80 ℃, mixing the montmorillonite and the mixed acid solution for 2 hours in an ultrasonic environment, standing, filtering and drying the montmorillonite to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 20 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 2 hours, filtering, drying and crushing to obtain a modifier;
according to the following steps of 100: 60: 1.2: 10: 4: 1.1: 9: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 12; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 3 parts of modifier, 5 parts of bacteriostatic agent, 4 parts of graphene, 100 parts of nitrile rubber emulsion, 0.8 part of sulfur, 1 part of polyethylene glycol distearate, 1 part of titanium dioxide, 0.01 part of dispersant and 0.5 part of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 35 ℃ by microwave, stirring and mixing for 3 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, polyethylene glycol distearate, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 50 ℃ with microwave at the frequency of 2500Mhz, and carrying out heat preservation reaction for 1h to obtain the butyronitrile latex for the medical examination gloves.
Example 7
Respectively mixing 35% sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution according to the weight ratio of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 8: 3, weighing montmorillonite, mixed acid solution and 25% sodium carbonate solution in percentage by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 70 ℃, mixing the montmorillonite and the mixed acid solution for 1 hour in an ultrasonic environment, standing, filtering and drying to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 10 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 1h, filtering, drying and crushing to obtain a modifier;
according to the following steps of 100: 40: 0.5: 5: 2: 0.5: 5: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 10; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 9 parts of modifier, 10 parts of bacteriostatic agent, 8 parts of graphene, 100 parts of nitrile rubber emulsion, 1.5 parts of sulfur, 3 parts of polyethylene glycol distearate, 2 parts of titanium dioxide, 0.04 part of dispersant and 1.2 parts of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 25 ℃ by microwave, stirring and mixing for 2 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, polyethylene glycol distearate, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 40 ℃ by microwave, wherein the frequency of the microwave is 2400Mhz, and carrying out heat preservation reaction for 0.5h to obtain the butyronitrile latex for the medical examination gloves. .
The nitrile latex prepared in the examples 1 to 7 was added to a glove mold, dipping treatment, low-temperature vulcanization and drying, water washing, and high-temperature vulcanization and drying were carried out to produce medical gloves, and the prepared medical gloves were subjected to performance testing, and the total number of colonies (n/cfu g-1) was tested according to the method of national standard GB 4789.2-2010. And common medical gloves on the market are selected as a control group, and the test results are shown in table 1:
table 1
In summary, it can be seen from table 1 that the mechanical properties and antibacterial properties of the medical gloves produced from the nitrile rubber latex prepared in examples 1-7 of the present invention are significantly better than those of the medical gloves of the control group. The embodiments 4, 5 and 6 have better performance, and the technical scheme disclosed in the embodiment 5 is as follows: sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution with the concentration of 55% are mixed according to the proportion of 3: 3: 4 to obtain a mixed acid solution; according to the following steps: 12: 5, weighing montmorillonite, a mixed acid solution and a sodium carbonate solution with the concentration of 55 percent by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 80 ℃, mixing the montmorillonite and the mixed acid solution for 2 hours in an ultrasonic environment, standing, filtering and drying the montmorillonite to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 20 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 2 hours, filtering, drying and crushing to obtain a modifier; according to the following steps of 100: 60: 1.2: 10: 4: 1.1: 9: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 12; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent; weighing the following components in parts by weight: 9 parts of modifier, 10 parts of bacteriostatic agent, 8 parts of graphene, 100 parts of nitrile rubber emulsion, 1.5 parts of sulfur, 3 parts of curing agent, 2 parts of titanium dioxide, 0.04 part of dispersant and 1.2 parts of zinc oxide; introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 35 ℃ by microwave, stirring and mixing for 3 hours, and vacuumizing the reaction kettle while stirring; introducing sulfur, a curing agent, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 50 ℃ by using microwave, keeping the frequency of the microwave at 2500Mhz, and reacting for 1h to obtain the butyronitrile latex for the medical examination gloves.
Further, the invention also makes systematic research on the butyronitrile latex for the medical examination glove and the process conditions in the preparation method thereof, and the following test scheme which only explains the obvious influence of the change of the process conditions on the effect of the butyronitrile latex for the medical examination glove and the preparation method thereof is all based on the process conditions of the embodiment 5, and is specifically shown in the comparative examples 1 to 4:
comparative example 1
According to the following steps: 5, weighing montmorillonite and 55% sodium carbonate solution by weight; after being crushed, montmorillonite and sodium carbonate solution are led into a mixing barrel to be fully mixed for 2 hours, and then the mixture is filtered, dried and crushed to obtain a modifier;
according to the following steps of 100: 60: 1.2: 10: 4: 1.1: 9: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 12; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 9 parts of modifier, 10 parts of bacteriostatic agent, 8 parts of graphene, 100 parts of nitrile rubber emulsion, 1.5 parts of sulfur, 3 parts of polyethylene glycol distearate, 2 parts of titanium dioxide, 0.04 part of dispersant and 1.2 parts of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 35 ℃ by microwave, stirring and mixing for 3 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, polyethylene glycol distearate, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 50 ℃ with microwave at the frequency of 2500Mhz, and carrying out heat preservation reaction for 1h to obtain the butyronitrile latex for the medical examination gloves.
Comparative example 2
Sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution with the concentration of 55% are mixed according to the proportion of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 12: 5, weighing montmorillonite, a mixed acid solution and a sodium carbonate solution with the concentration of 55 percent by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 80 ℃, mixing the montmorillonite and the mixed acid solution for 2 hours in an ultrasonic environment, standing, filtering and drying to obtain a modifier;
according to the following steps of 100: 60: 1.2: 10: 4: 1.1: 9: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 12; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 9 parts of modifier, 10 parts of bacteriostatic agent, 8 parts of graphene, 100 parts of nitrile rubber emulsion, 1.5 parts of sulfur, 3 parts of polyethylene glycol distearate, 2 parts of titanium dioxide, 0.04 part of dispersant and 1.2 parts of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 35 ℃ by microwave, stirring and mixing for 3 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, polyethylene glycol distearate, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 50 ℃ with microwave at the frequency of 2500Mhz, and carrying out heat preservation reaction for 1h to obtain the butyronitrile latex for the medical examination gloves.
Comparative example 3
According to the following steps of 100: 60: 1.2: 10: 4: 1.1: 9: weighing dimethomorph, zeolite powder, nano silver, titanium oxide, copper sulfate, nano indium oxide, carbon black and a silane coupling agent according to the weight ratio of 12; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the bacteriostatic agent;
weighing the following components in parts by weight: 9 parts of montmorillonite, 10 parts of bacteriostatic agent, 8 parts of graphene, 100 parts of nitrile rubber emulsion, 1.5 parts of sulfur, 3 parts of polyethylene glycol distearate, 2 parts of titanium dioxide, 0.04 part of dispersant and 1.2 parts of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the montmorillonite into a reaction kettle, heating the mixture to 35 ℃ by microwave, stirring and mixing the mixture for 3 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, polyethylene glycol distearate, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 50 ℃ with microwave at the frequency of 2500Mhz, and carrying out heat preservation reaction for 1h to obtain the butyronitrile latex for the medical examination gloves.
Comparative example 4
Sulfuric acid solution, hydrochloric acid solution and phosphoric acid solution with the concentration of 55% are mixed according to the proportion of 3: 3: 4 to obtain a mixed acid solution;
according to the following steps: 12: 5, weighing montmorillonite, a mixed acid solution and a sodium carbonate solution with the concentration of 55 percent by weight; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 80 ℃, mixing the montmorillonite and the mixed acid solution for 2 hours in an ultrasonic environment, standing, filtering and drying the montmorillonite to obtain acid-modified montmorillonite, wherein the ultrasonic frequency is 20 MHz; crushing acid-modified montmorillonite, introducing the crushed montmorillonite and a sodium carbonate solution into a mixing barrel, fully mixing for 2 hours, filtering, drying and crushing to obtain a modifier;
weighing the following components in parts by weight: 9 parts of modifier, 8 parts of graphene, 100 parts of nitrile rubber emulsion, 1.5 parts of sulfur, 3 parts of polyethylene glycol distearate, 2 parts of titanium dioxide, 0.04 part of dispersant and 1.2 parts of zinc oxide;
introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 35 ℃ by microwave, stirring and mixing for 3 hours, and vacuumizing the reaction kettle while stirring;
introducing sulfur, polyethylene glycol distearate, titanium dioxide, zinc oxide and a dispersing agent into a reaction kettle, fully mixing, heating to 50 ℃ by microwave, keeping the temperature and reacting for 1h to obtain the butyronitrile latex for the medical examination gloves.
Adding the butyronitrile latex prepared in the comparative examples 1-4 into a glove mold, carrying out dipping treatment, low-temperature vulcanization drying, water washing, high-temperature vulcanization drying, producing medical gloves, carrying out performance detection on the prepared medical gloves, and detecting the total number of bacterial colonies (n/cfu. g-1) according to the method of national standard GB4789.2-2010, wherein the test results are shown in the following table 2:
TABLE 2
In summary, it can be seen from Table 2 that the nitrile rubber latex prepared in comparative examples 1-4 produced medical gloves having inferior mechanical properties and antibacterial properties to those of the medical gloves of example 5. Wherein, in the comparative example 1, the acid modification is not carried out on the montmorillonite, only the sodium modification is carried out on the montmorillonite, and the montmorillonite which is not subjected to the acid modification has poor adsorption effect and no catalysis, so that the prepared butyronitrile latex has lower mechanical property; in the comparative example 2, sodium modification is not carried out on montmorillonite, only acid modification is carried out on montmorillonite, and the montmorillonite does not have the dispersibility, viscosity, lubricity, thermal stability, higher hot-wet-pressure strength, higher compressive strength and the like after sodium modification, so that the prepared butyronitrile latex has lower mechanical property; in the comparative example 3, montmorillonite is not modified, and only ordinary montmorillonite is used as a modifier to modify the nitrile-butadiene rubber emulsion and the graphene, so that the modification effect is poor; comparative example 4 no bacteriostatic agent was added during the preparation process, resulting in poor bacteriostatic effect of the prepared nitrile latex.
In summary, according to the butyronitrile latex for medical examination gloves and the preparation method thereof provided in this embodiment, montmorillonite which is sequentially subjected to acid modification and sodium modification is selected as a modifier of the butyronitrile latex and graphene, and when the modification treatment is performed by using a mixed acid solution, cations such as K, Na, Ca, Mg and the like between montmorillonite layers are converted into acid soluble salts to be dissolved out, so that the original interlayer bonding force is weakened, interlayer lattices are cracked, and the interlayer spacing is enlarged, so that the specific surface area and the adsorption capacity after modification are significantly increased; the specific surface area of the montmorillonite modified by acidification is increased, the aperture is also increased, and the montmorillonite modified by acidification has stronger adsorbability and chemical activity and very high adsorption and catalysis performances; the acid-modified montmorillonite is mixed with a sodium carbonate solution, part of the acid-modified montmorillonite is subjected to sodium modification, and the sodium-based montmorillonite has better expansibility and cation exchange property than calcium-based montmorillonite, and has dispersibility, viscosity, lubricity, thermal stability, higher heat-humidity pressure strength and higher compressive strength in an aqueous medium; and partial montmorillonite which is not subjected to sodium modification has the effect of a catalyst besides the effect of modification when modifying the nitrile-butadiene rubber emulsion and the graphene, so that the efficiency of modifying the nitrile-butadiene rubber emulsion and the graphene is improved.
The nitrile-butadiene rubber emulsion and the graphene modified by the montmorillonite after acid modification and sodium modification obviously improve the mechanical properties of the nitrile-butadiene rubber emulsion, such as tear resistance, cut resistance and puncture resistance.
In the preparation process, a bacteriostatic agent which is formed by mixing dimethomorph, nano silver modified by zeolite powder, carbon black and a silane coupling agent, titanium oxide, copper sulfate and nano indium oxide is added, so that the bacteriostatic activity of the prepared butyronitrile latex is obviously improved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The butyronitrile latex for the medical examination glove is characterized by comprising the following components in parts by weight: 3-9 parts of modifier, 5-10 parts of bacteriostatic agent, 4-8 parts of graphene, 100 parts of nitrile rubber emulsion, 0.8-1.5 parts of sulfur, 1-3 parts of curing agent, 1-2 parts of titanium dioxide, 0.01-0.04 part of dispersant and 0.5-1.2 parts of zinc oxide.
2. The nitrile latex for medical examination gloves according to claim 1, wherein the preparation method of the modifier comprises the following steps: according to (7-11): (8-12): (3-5) weighing montmorillonite, mixed acid solution and sodium carbonate solution according to the weight ratio; pouring montmorillonite into the mixed acid solution, heating the mixed acid solution to 70-80 ℃, mixing for 1-2h in an ultrasonic environment, standing, filtering and drying to obtain acid-modified montmorillonite; after being crushed, the acid-modified montmorillonite and sodium carbonate solution are led into a mixing barrel to be fully mixed for 1 to 2 hours, and then the modifier is obtained after filtration, drying and crushing.
3. The nitrile rubber latex for medical examination gloves according to claim 2, wherein the mixed acid solution comprises a 30% sulfuric acid solution, a 30% hydrochloric acid solution and a 40% phosphoric acid solution, and the concentrations of the sulfuric acid solution, the hydrochloric acid solution and the phosphoric acid solution are 35-55%.
4. The nitrile latex for medical examination gloves according to claim 2, wherein the concentration of the sodium carbonate solution is 25-55%, and the ultrasonic frequency in an ultrasonic environment is 10MHz-20 MHz.
5. The nitrile rubber latex for medical examination gloves according to claim 1, wherein the preparation method of the bacteriostatic agent comprises the following steps: according to the following steps of 100: (40-60): (0.5-1.2): (5-10): (2-4): (0.5-1.1): (5-9): (10-12) weighing dimethomorph, zeolite powder, nano-silver, titanium oxide, copper sulfate, nano-indium oxide, carbon black and a silane coupling agent in a weight ratio; mixing zeolite powder, carbon black, a silane coupling agent and water, heating and stirring to obtain a mixed material A; adding nano silver, titanium oxide, copper sulfate and nano indium oxide into the mixed material A, and then carrying out ultrasonic mixing to obtain a mixed material B; and fully mixing the mixed material B with dimethomorph, drying and grinding to obtain the antibacterial agent.
6. The nitrile rubber latex for medical examination gloves according to claim 1, wherein the curing agent is one of a silicon boron tackifier, a titanate tackifier, polyethylene glycol distearate or an acrylic polymer.
7. The nitrile rubber latex for the medical examination glove according to claim 1, wherein the nitrile rubber latex comprises the following components in parts by weight: 4-8 parts of modifier, 6-9 parts of bacteriostatic agent, 5-7 parts of graphene, 100 parts of nitrile rubber emulsion, 0.9-1.4 parts of sulfur, 1.1-2.8 parts of curing agent, 1.2-1.8 parts of titanium dioxide, 0.02-0.03 part of dispersant and 0.6-1.1 part of zinc oxide.
8. The nitrile rubber latex for the medical examination glove according to claim 1, wherein the nitrile rubber latex comprises the following components in parts by weight: 6 parts of modifier, 7.5 parts of bacteriostatic agent, 6 parts of graphene, 100 parts of nitrile rubber emulsion, 1.15 parts of sulfur, 2 parts of curing agent, 1.5 parts of titanium dioxide, 0.025 part of dispersant and 0.85 part of zinc oxide.
9. The process for the preparation of the nitrile latex for medical examination gloves according to any one of claims 1 to 8, comprising the following steps:
step 1: weighing the components in parts by weight;
step 2: introducing the nitrile butadiene rubber emulsion, the graphene and the modifier into a reaction kettle, heating to 25-35 ℃, stirring and mixing for 2-3h, and vacuumizing the reaction kettle while stirring;
and step 3: introducing sulfur, a curing agent, titanium dioxide, zinc oxide, a dispersing agent and a bacteriostatic agent into a reaction kettle, fully mixing, heating to 40-50 ℃, and keeping the temperature to react for 0.5-1h to obtain the butyronitrile latex for the medical examination gloves.
10. The method for preparing nitrile rubber latex for medical examination gloves as recited in claim 9, wherein the heating of the materials in the reaction kettle is microwave heating, and the frequency of the microwave is 2400-.
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