阅读说明：本技术 石墨烯过滤颗粒物呼吸器抗菌滤芯制备方法及制备的滤芯 (Preparation method of graphene filtering particulate respirator antibacterial filter element and prepared filter element ) 是由 李修兵 陈晓中 王斌 于 2020-04-08 设计创作，主要内容包括：发明涉及口罩滤芯术领域,尤其是一种石墨烯过滤颗粒物呼吸器抗菌滤芯制备方法及制备的抗菌滤芯。一种石墨烯过滤颗粒物呼吸器抗菌滤芯制备方法,包含如下步骤：步骤一、制备氧化石墨；步骤二、制备氧化石墨烯粘稠溶液；步骤三、将熔喷无纺布连续通过所得的粘稠溶液,再经轧液、辊筒烘干,制备氧化石墨烯熔喷无纺布复合膜用做口罩抗菌滤芯。这种石墨烯过滤颗粒物呼吸器抗菌滤芯制备方法及制备的滤芯利用石墨烯具有优异的吸附性能、阻隔性能和抗菌性能,将石墨烯材料用于口罩滤芯将会有效提高口罩对空气中固体颗粒物的过滤性能,同时有消除异味作用,并有良好的抗菌性能。(The invention relates to the field of mask filter core technology, in particular to a preparation method of a graphene particle filtering respirator antibacterial filter core and a prepared antibacterial filter core. A preparation method of an antibacterial filter element of a graphene filtering particulate respirator comprises the following steps: step one, preparing graphite oxide; step two, preparing a graphene oxide viscous solution; and step three, continuously passing the melt-blown non-woven fabric through the obtained viscous solution, and then carrying out liquid rolling and roller drying to prepare the graphene oxide melt-blown non-woven fabric composite membrane used as the mask antibacterial filter element. According to the preparation method of the graphene antibacterial filter element for the particulate filtering respirator and the prepared filter element, the graphene has excellent adsorption performance, barrier performance and antibacterial performance, the graphene material is used for the mask filter element, the filtering performance of the mask on solid particulate in the air can be effectively improved, meanwhile, the peculiar smell is eliminated, and the filter element has good antibacterial performance.)

1. A preparation method of an antibacterial filter element of a graphene filtering particulate respirator is characterized by comprising the following steps:

step one, preparing graphite oxide, mixing nitric acid and sulfuric acid, reducing the temperature to 5 ℃, maintaining the temperature, adding graphite, and then adding NaClO₃Continuously stirring the solution for reaction, and then filtering and washing to obtain graphite oxide;

step two, preparing a viscous graphene oxide solution, adding a nitrogen-containing compound into the graphite oxide obtained in the step one, stirring and dispersing to obtain an aminated graphene oxide solution, adding an adhesive, and stirring to obtain an aminated graphene oxide viscous solution;

and step three, continuously passing the melt-blown non-woven fabric through the viscous solution obtained in the step two, and then carrying out rolling and roller drying to prepare the graphene melt-blown non-woven fabric composite membrane used as the mask filter element.

2. The preparation method of the antibacterial filter element of the graphene filtering particulate respirator, as claimed in claim 1, is characterized in that in the first step, the volume ratio of the mixed acid of sulfuric acid and nitric acid is 1.5-2:1, the concentration of sulfuric acid is 98%, and the concentration of nitric acid is 68%.

3. The method for preparing the antibacterial filter element of the graphene filtering particulate matter respirator of claim 1, wherein NaClO is used in the step one₃The solution was saturated.

4. The method for preparing the antibacterial filter element of the graphene filtering particulate matter respirator of claim 1, wherein NaClO is used in the step one₃The addition rate of the saturated solution is 10-20 ml/min.

5. The method for preparing the antibacterial filter element of the graphene filtering particulate matter respirator of claim 1, wherein in the first step, the continuous stirring reaction time is 4-10 hours.

6. The preparation method of the antibacterial filter element of the graphene filtering particulate respirator as claimed in claim 1, wherein the mass ratio of deionized water to graphite used in the washing in the step one is 30-50:1, and the washing times are 3-5 times.

7. The method for preparing the antibacterial filter element of the graphene filtering particulate matter respirator of claim 1, wherein in the second step, the nitrogen-containing compound comprises one or more of ammonia water, uric acid, ammonium carbonate, ammonium bicarbonate and hydrazine hydrate.

8. The method for preparing the antibacterial filter element of the graphene filtering particulate matter respirator of claim 1, wherein the adhesive in the second step comprises one or more of polyvinyl alcohol, polypropylene alcohol, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diacetate and triethylene glycol diacetate.

9. The preparation method of the antibacterial filter element of the graphene filtering particulate respirator according to claim 1, wherein in the second step, the mass ratio of the addition amount of the adhesive to the aminated graphene oxide solution is 1: 1000-2000.

10. A respirator filter element prepared by the method of making a graphene filtering particulate respirator antimicrobial filter element of any of claims 1-9.

Technical Field

The invention relates to the technical field of mask filter elements, in particular to a preparation method of a graphene particle filtering respirator antibacterial filter element and a prepared filter element.

Background

The domestic economy is in the fast development stage, people's living standard is constantly improving, and the car ownership volume is constantly rising, and industrial activity is more active, and the environment that people live on also has consequently received serious pollution, and especially the haze weather that appears in recent years and infectious disease that suddenly breaks out have seriously influenced human health. Meanwhile, fine particles in haze weather can carry a large amount of bacteria, viruses, toxic and harmful organic matters and heavy metals, the particles stay in the air for a long time, the conveying distance is long, and the harm to the health of human bodies is great. The most effective personal protection measure in haze weather is to wear the mask, and similarly, the mask and the filtering type particulate matter prevention respirator are required to be worn in some industrial and agricultural production processes so as to well protect individuals. The great particulate matter of particle diameter can only be intercepted in the air to traditional antifog haze gauze mask and filtration formula particulate matter prevention respirator, is difficult to play the guard action, and current N95 gauze mask is when guaranteeing filtration efficiency, and the air permeability is poor, and air resistance is big, can't wear for a long time, can not play antibacterial effect simultaneously.

Disclosure of Invention

In order to overcome the defects of the existing mask, the invention provides a preparation method of an antibacterial filter element of a graphene filtering particulate respirator and the prepared filter element.

The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of an antibacterial filter element of a graphene filtering particulate respirator comprises the following steps:

step one, preparing graphite oxide, mixing nitric acid and sulfuric acid, reducing the temperature to 5 ℃, maintaining the temperature, adding graphite, and then adding NaClO₃Continuously stirring the solution for reaction, and then filtering and washing to obtain graphite oxide;

step two, preparing a viscous graphene oxide solution, adding a nitrogen-containing compound into the graphite oxide obtained in the step one, stirring and dispersing to obtain an aminated graphene oxide solution, adding an adhesive, and stirring to obtain an aminated graphene oxide viscous solution;

and step three, continuously passing the melt-blown non-woven fabric through the viscous solution obtained in the step two, and then carrying out rolling and roller drying to prepare the graphene melt-blown non-woven fabric composite membrane used as the mask filter element.

According to another embodiment of the invention, the method further comprises the step of mixing sulfuric acid and nitric acid in the first step at a volume ratio of 1.5-2:1, wherein the concentration of sulfuric acid is 98% and the concentration of nitric acid is 68%.

According to another embodiment of the invention, further comprising, in the first step, NaClO₃The solution was saturated.

According to another embodiment of the invention, further comprising, in the first step, NaClO₃The addition rate of the saturated solution is 10-20 ml/min.

According to another embodiment of the invention, further comprising, in the first step, continuing to stir the reaction for 4 to 10 hours.

According to another embodiment of the invention, the mass ratio of the deionized water to the graphite used in the washing in the step one is 30-50:1, and the washing times are 3-5 times.

According to another embodiment of the invention, the nitrogen-containing compound in the second step comprises one or more of ammonia, uric acid, ammonium carbonate, ammonium bicarbonate and hydrazine hydrate.

According to another embodiment of the invention, the binder in step two further comprises one or more of polyvinyl alcohol, polypropylene alcohol, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diacetate, and triethylene glycol diacetate.

According to another embodiment of the invention, the mass ratio of the added amount of the adhesive to the aminated graphene oxide solution in the second step is 1: 1000-2000.

A mask filter element prepared by a preparation method of a graphene particulate filtering respirator antibacterial filter element.

The invention has the beneficial effects that the preparation method of the antibacterial filter element of the graphene filtering particulate respirator and the prepared filter element utilize that the graphene is a two-dimensional plane structure consisting of single-layer carbon atoms, three of four valence electrons of the carbon atoms form a honeycomb structure connected with three adjacent carbon atoms in a plane regular hexagon by using sp2 hybridized orbitals, and the special two-dimensional structure of the graphene determines that the antibacterial filter element has unique performance: the graphene has good adsorption performance, barrier performance and antibacterial performance, the filtering performance of the mask to solid particles in the air can be effectively improved by applying the graphene material to the mask filter element, and meanwhile, the graphene has the function of eliminating peculiar smell and has good antibacterial performance.

Detailed Description

A preparation method of an antibacterial filter element of a graphene filtering particulate respirator comprises the following steps:

step one, preparing graphite oxide, mixing nitric acid and sulfuric acid, reducing the temperature to 5 ℃, maintaining the temperature, adding graphite, and then adding NaClO₃And continuously stirring the solution for reaction, and then filtering and washing the solution to obtain the graphite oxide.

The mixed acid of nitric acid and sulfuric acid has strong oxidizing property, which is beneficial to the oxidation of graphite and the proceeding of intercalation reaction. A large amount of heat is released in the process of mixing the sulfuric acid and the nitric acid solution, the reaction speed with the graphite is too fast and difficult to control, and the graphite is added when the temperature of the solution is required to be reduced to 5 ℃ so as to ensure that the subsequent reaction is safely carried out. NaClO₃HClO is generated in a mixed acid system₃The graphite has strong oxidizing property, and the purpose of oxidizing and intercalating the graphite again is achieved. In the mixed acid system, the water content is very low, which is not beneficial to NaClO₃Dissolving the solid and carrying out the reaction to obtain NaClO₃The solid is dissolved in water and added to the reaction mixture in the form of a solution, which facilitates the reaction. And after the reaction is finished, fully washing the mixture to be neutral to remove inorganic impurities to obtain pure graphite oxide.

And step two, preparing a viscous graphene oxide solution, adding a nitrogen-containing compound into the graphite oxide obtained in the step one, stirring and dispersing to obtain an aminated graphene oxide solution, adding an adhesive, and stirring to obtain the aminated graphene oxide viscous solution.

The graphite oxide layers and the edges of the graphite oxide layers contain rich oxygen-containing functional groups such as carboxyl, hydroxyl and the like, so that the graphite oxide layers and the edges of the graphite oxide layers are favorable for being combined with nitrogen-containing compounds to form aminated graphene oxide solution, the existence of oxygen-containing and nitrogen-containing functional groups is favorable for being combined with adhesives to obtain graphene oxide viscous solution, and the graphene oxide viscous solution is also favorable for being combined with melt-blown non-woven fabrics to form a membrane material with adsorption, filtration and antibacterial functions.

And step three, continuously passing the melt-blown non-woven fabric through the viscous solution obtained in the step two, and then carrying out liquid rolling and roller drying to prepare the graphene melt-blown non-woven fabric composite membrane used as the mask filter element.

And (3) continuously passing the melt-blown non-woven fabric through the viscous solution obtained in the second step to be beneficial to continuously producing a membrane material, wherein the mangling and roller drying process mainly enables the graphene oxide material to be tightly combined with the melt-blown non-woven fabric, enables the graphene oxide to be converted into graphene and is not easy to fall off.

According to another embodiment of the invention, the method further comprises the step of mixing sulfuric acid and nitric acid in the first step at a volume ratio of 1.5-2:1, wherein the concentration of sulfuric acid is 98% and the concentration of nitric acid is 68%.

The mixed acid of sulfuric acid and nitric acid can oxidize and intercalate graphite, the volume ratio of the mixed acid of sulfuric acid and nitric acid is 1.5-2:1, the reaction can be effectively realized, and the consumption of the mixed acid is relatively less.

According to another embodiment of the invention, further comprising, in the first step, NaClO₃The solution was saturated.

Adding NaClO into the mixed solution of sulfuric acid and nitric acid with low water content₃Solid, it is not completely dissolved, resulting in waste of materials and increase of washing water. With NaClO₃The unsaturated solution is not beneficial to the oxidation and intercalation reaction because the concentration of the system is reduced, and NaClO is used₃The saturated solution is prepared and added into a reaction system, so that intercalation and oxidation reactions of the graphite can be well realized.

According to another embodiment of the invention, further comprising, in the first step, NaClO₃The addition rate of the saturated solution is 10-20 ml/min.

NaClO₃If the adding speed of the saturated solution is too slow, the reaction time is too long, and the oxidation degree of the graphite is relatively deep; NaClO₃If the addition rate of the saturated solution is too high, the reaction is too violent and difficult to control.

According to another embodiment of the invention, further comprising, in the first step, continuing to stir the reaction for 4 to 10 hours.

A large amount of heat can be released in the reaction process, graphite oxidation and intercalation are not uniform due to heat accumulation, the reaction process is easy to lose control to cause danger, the system can react uniformly by continuously stirring in the reaction process, the heat is dissipated as soon as possible, and the reaction can be carried out safely and stably.

According to another embodiment of the invention, the mass ratio of the deionized water to the graphite used in the washing in the step one is 30-50:1, and the washing times are 3-5 times.

The principle of washing for many times with a small amount of water is adopted in the washing process. The mass ratio of the deionized water to the graphite is 30-50:1, so that uniform stirring can be realized, and inorganic salt impurities can be effectively dissolved and removed; the impurity removal can be effectively realized by washing for 3-5 times.

According to another embodiment of the invention, the nitrogen-containing compound in the second step comprises one or more of ammonia, uric acid, ammonium carbonate, ammonium bicarbonate and hydrazine hydrate.

According to another embodiment of the invention, the binder in step two further comprises one or more of polyvinyl alcohol, polypropylene alcohol, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diacetate, and triethylene glycol diacetate.

According to another embodiment of the invention, the mass ratio of the added amount of the adhesive to the aminated graphene oxide solution in the second step is 1: 1000-2000.

If the amount of the adhesive is too much, the solution is too viscous, which is not favorable for combining with the melt-blown non-woven fabric; too little binder addition would make the solution too dilute for bonding to the meltblown nonwoven.

A mask filter element prepared by a preparation method of a graphene particulate filtering respirator antibacterial filter element.

The antibacterial filter element prepared by the method is applied to the mask and is shown in a parameter comparison table with the current N95 mask:

the foregoing description is intended to be illustrative rather than limiting, and it will be appreciated by those skilled in the art that many modifications, variations or equivalents may be made without departing from the spirit and scope of the invention as defined in the appended claims.