阅读说明：本技术 一种超疏水多孔壳聚糖/Ag@AgCl-TiO2复合材料及环保型口罩 (Super-hydrophobic porous chitosan/Ag @ AgCl-TiO2Composite material and environment-friendly mask ) 是由 杨连利 张卫红 郭乃妮 王晓玲 李心乐 汪银涛 何世雯 刘思雨 于 2020-06-11 设计创作，主要内容包括：本发明公开了一种超疏水多孔壳聚糖/Ag@AgCl-TiO<Sub>2</Sub>复合材料及环保型口罩,以壳聚糖为原料,聚乙烯醇为柔韧剂,硅胶为造孔剂,Ag@AgCl-TiO<Sub>2</Sub>为功能性粒子,通过疏水性纳米SiO<Sub>2</Sub>溶胶后处理,在无菌医用纱布骨架上形成具有纵横交错微纳米孔道的超疏水多孔壳聚糖/Ag@AgCl-TiO<Sub>2</Sub>复合材料。本发明口罩以该复合材料为独立拆装功能层,方便清洁及更换,该复合材料能有效抵御雾霾颗粒的吸入,有效防止细菌病毒等飞沫传播,在太阳光、紫外光等光照下具有自清洁作用,而且该材料具有超疏水性能,可防止其在呼出的弱酸性水汽中溶胀,堵塞孔道,影响呼吸。因此本发明口罩能反复使用,适用于雾霾、新冠疫情中低风险地区。(The invention discloses super-hydrophobic porous chitosan/Ag @ AgCl-TiO 2 A composite material and an environment-friendly mask are prepared from chitosan as raw material, polyvinyl alcohol as flexibilizer, silica gel as pore-forming agent, Ag @ AgCl-TiO 2 Is functional particle, prepared by hydrophobic nano SiO 2 After sol post-treatment, forming super-hydrophobic porous chitosan/Ag @ AgCl-TiO with criss-cross micro-nano pore channels on a sterile medical gauze framework 2 Composite material. The mask disclosed by the invention takes the composite material as an independent disassembly and assembly functional layer, so that the mask is convenient to clean and replace, the composite material can effectively resist the inhalation of haze particles, effectively prevent the propagation of bacteria, viruses and other droplets, has a self-cleaning effect under the illumination of sunlight, ultraviolet light and the like, and has super-hydrophobic performance, so that the mask can be prevented from swelling in exhaled weak acid water vapor, blocking pore channels and influencing respiration. Therefore, the mask can be used repeatedly and is suitable for low-risk areas in haze and new crown epidemic situations.)

1. Super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂A composite material characterized by: the composite material takes sterile medical gauze as a framework and chitosan/Ag @ AgCl-TiO₂The composite is salivation material, nano silica gel as pore-forming agent and hydrophobic nano SiO₂The sol is a super-hydrophobic water treatment agent and is prepared by the following steps:

(1) preparation of Ag @ AgCl-TiO₂Composite material

Mixing isopropyl titanate or butyl titanate and 6mol/L hydrochloric acid to ensure that titanium ions and H in the mixed solution⁺Stirring for 2-4 hours at room temperature, stirring for 2-5 hours in a constant-temperature water bath at 60-80 ℃, aging for 20-30 hours at room temperature, filtering, washing with deionized water, drying, calcining the dried solid for 3-4 hours at 600-700 ℃, and obtaining TiO₂(ii) a Adding TiO into the mixture₂Dispersing in deionized water, and adding 0.1mol/L AgNO₃Aqueous solution of TiO₂Mass of (A) and AgNO₃The molar weight ratio of 1g to 0.5-1.5 mmol, stirring at room temperature for 20-30 min, adding 0.1mol/L hydrochloric acid, stirring for 20-30 min, filtering, washing with deionized water, drying, dispersing the obtained solid product in 40% volume fraction ethanol water solution, and using wavelength lambda to obtain the final product>Irradiating 400nm visible light for 20-30 minutes to reduce partial Ag⁺Forming Ag simple substance, filtering and drying to obtain Ag @ AgCl-TiO₂A complex;

or adding 0.1mol/L hydrochloric acid into the solution,stirring for 20-30 minutes, and then adding the Ag of the glucose reduction part⁺Forming Ag simple substance, filtering and drying to obtain Ag @ AgCl-TiO₂A complex;

(2) preparation of Chitosan/Ag @ AgCl-TiO₂Composite material

Dissolving chitosan and polyvinyl alcohol in 2% concentration acetic acid solution to obtain 1-5% concentration solution ①, and mixing Ag @ AgCl-TiO₂Adding the compound into distilled water for uniform ultrasonic dispersion to obtain 1-5% Ag @ AgCl-TiO₂Adding glycerol into the compound suspension, continuing to perform ultrasonic treatment for 20-30 minutes, then dropwise adding the solution ① under the ultrasonic condition, reacting for 2-3 hours at 50-60 ℃, then adding nano silica gel particles, and continuing to stir for 20-30 minutes to obtain chitosan/Ag @ AgCl-TiO₂A complex;

(3) preparation of super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂Composite material

Mixing chitosan/Ag @ AgCl-TiO₂The compound is coated on sterile medical gauze at a concentration of 2.0-2.5 mL/m²Salivation, drying at 50-60 deg.C to form a film, soaking in 8-12% sodium hydroxide water solution for 40-80 min, water washing, drying, and coating with hydrophobic nanometer SiO₂Soaking in the sol for 40-80 minutes for super-hydrophobicity treatment, washing and drying to obtain the super-hydrophobic porous chitosan/Ag @ AgCl-TiO with medical gauze as a framework₂A composite material.

2. The superhydrophobic porous chitosan/Ag @ AgCl-TiO of claim 1₂A composite material characterized by: in the step (2), the addition amount of the polyvinyl alcohol is 10-20% of the mass of the chitosan.

3. The superhydrophobic porous chitosan/Ag @ AgCl-TiO of claim 1₂A composite material characterized by: in the step (2), the chitosan and Ag @ AgCl-TiO₂The mass ratio of the compound to the glycerol is 1: 0.02-0.10: 0.5-1.5.

4. The superhydrophobic porous chitosan/Ag @ AgCl-TiO of claim 1₂A composite material characterized by: in the step (2), the adding amount of the nano silica gel particles is 20-50% of the mass of the chitosan.

5. The superhydrophobic porous chitosan/Ag @ AgCl-TiO of claim 1₂A composite material characterized by: in the step (3), the hydrophobic nano SiO₂Nano SiO in sol₂The mass concentration of (A) is 2.5-3.0%.

6. An environment-friendly mask, comprising: surface course (1), bridge of the nose strip (2), bordure (3), control hangers (4), first layer back lining (5), functional layer (6), second floor back lining (7), functional layer (6) are independent dismouting structural layer, its characterized in that: the functional layer (6) is the super-hydrophobic porous chitosan/Ag @ AgCl-TiO as set forth in any one of claims 1 to 5₂A composite material.

Technical Field

The invention belongs to the technical field of articles for daily use, and particularly relates to super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂Composite material to and have prevent haze antibacterial function and environment-friendly gauze mask that can use repeatedly.

Background

The mask is one of articles which are commonly used in life, and particularly in places with serious air pollution in cities, the mask must be used for preventing haze. In recent years, diseases such as SARS, Middle East Respiratory Syndrome (MERS), avian influenza, etc. have become more contagious and have higher mortality rates. Especially, the new coronavirus pneumonia which is outbreaked at the end of 2019 brings serious threats to the life and health of people all over the world. The transmission of droplets is the main transmission path of new coronavirus, the mask can prevent the droplets from being sprayed by a patient, can prevent droplet cores containing viruses from being inhaled by a wearer, and is an important defense line for preventing respiratory infectious diseases. At present, masks used in low-and-medium-risk areas are mostly disposable medical protective masks, the consumption is huge, a large amount of material resources, human resources and the like are needed for preparing the masks, and the treatment of waste masks is also a huge problem. In particular, the material of the melt-blown layer of the medical protective mask is mostly polypropylene, tetrafluoroethylene and other refractory plastics, which brings great pressure to the environment.

Disclosure of Invention

The invention aims to solve the technical problems that a mask in the prior art cannot prevent haze and resist bacteria and cannot be repeatedly used and the environment is polluted by a waste mask, and provides a super-hydrophobic porous chitosan/Ag @ AgCl-TiO with a haze-preventing and antibacterial function₂The composite material and the environment-friendly mask which adopts the composite material as a functional layer have the haze-preventing and antibacterial functions and can be used repeatedly.

In order to achieve the purpose, the super-hydrophobic porous chitosan/Ag @ AgCl-TiO adopted by the invention₂The composite material takes sterile medical gauze as a framework and chitosan/Ag @ AgCl-TiO₂The composite is salivation material, nano silica gel as pore-forming agent and hydrophobic nano SiO₂The sol is a super-hydrophobic water treatment agent and is prepared by the following steps:

1. preparation of Ag @ AgCl-TiO₂Composite material

Mixing isopropyl titanate or butyl titanate and 6mol/L hydrochloric acid to ensure that titanium ions and H in the mixed solution⁺Stirring for 2-4 hours at room temperature, stirring for 2-5 hours in a constant-temperature water bath at 60-80 ℃, aging for 20-30 hours at room temperature, filtering, washing with deionized water, drying, calcining the dried solid for 3-4 hours at 600-700 ℃, and obtaining TiO₂(ii) a Adding TiO into the mixture₂Dispersing in deionized water, and adding 0.1mol/L AgNO₃Aqueous solution of TiO₂Mass of (A) and AgNO₃The molar weight ratio of 1g to 0.5-1.5 mmol, stirring at room temperature for 20-30 min, adding 0.1mol/L hydrochloric acid, stirring for 20-30 min, filtering, washing with deionized water, drying, dispersing the obtained solid product in 40% volume fraction ethanol water solution, and using wavelength lambda to obtain the final product>Irradiating 400nm visible light for 20-30 minutes to reduce partial Ag⁺Forming Ag simple substance, filtering and drying to obtain Ag @ AgCl-TiO₂A complex; or adding 0.1mol/L hydrochloric acid, stirring for 20-30 minutes, and adding Ag of a glucose reduction part⁺Forming Ag simple substance, filtering and drying to obtain Ag @ AgCl-TiO₂And (c) a complex.

2. Preparation of Chitosan/Ag @ AgCl-TiO₂Composite material

Mixing chitosan and polyvinyl alcoholDissolving in 2% acetic acid solution to obtain solution ① with chitosan concentration of 1-5%, and mixing Ag @ AgCl-TiO₂Adding the compound into distilled water for uniform ultrasonic dispersion to obtain 1-5% Ag @ AgCl-TiO₂Adding glycerol into the compound suspension, continuing to perform ultrasonic treatment for 20-30 minutes, then dropwise adding the solution ① under the ultrasonic condition, reacting for 2-3 hours at 50-60 ℃, then adding nano silica gel particles, and continuing to stir for 20-30 minutes to obtain chitosan/Ag @ AgCl-TiO₂And (c) a complex.

3. Preparation of super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂Composite material

Mixing chitosan/Ag @ AgCl-TiO₂The compound is coated on sterile medical gauze at a concentration of 2.0-2.5 mL/m²Salivation, drying at 50-60 deg.C to form a film, soaking in 8-12% sodium hydroxide water solution for 40-80 min, water washing, drying, and coating with hydrophobic nanometer SiO₂Soaking the medical gauze in the sol for 40-80 minutes for super-hydrophobic treatment, washing and drying to obtain the super-hydrophobic porous chitosan/Ag @ AgCl-TiO with the medical gauze as a framework₂A composite material.

In the step 2, the preferable addition amount of the polyvinyl alcohol is 10-20% of the mass of the chitosan, the addition amount of the nano silica gel particles is 20-50% of the mass of the chitosan, and the chitosan and the Ag @ AgCl-TiO are added₂The mass ratio of the compound to the glycerol is 1: 0.02-0.10: 0.5-1.5.

In the step 3, hydrophobic nano SiO is preferable₂Nano SiO in sol₂The mass concentration of the hydrophobic nano SiO is 2.5 to 3.0 percent₂Sol preparation and characterization of silica Superhydrophobic Sol suitable for use in textiles according to the literature "Liutao, Zhang Tong, Dong Wen English, Zhang Weihong]Guangzhou chemical, 2017, 45 (22): 34-36 "by the methods disclosed in the opening paragraph.

The environment-friendly mask of the invention comprises: the functional layer is an independent disassembly and assembly structure layer and adopts the super-hydrophobic porous chitosan/Ag @ AgCl-TiO, disclosed by the invention₂Composite materialAnd (5) feeding.

The invention has the following beneficial effects:

1. the invention takes chitosan as raw material, polyvinyl alcohol as flexibilizer, nano silica gel particles as pore-forming agent, Ag @ AgCl-TiO₂As functional particles with the functions of resisting bacteria and degrading pollutants by photocatalysis, porous chitosan/Ag @ AgCl-TiO with criss-cross micro-nano pore canals are formed on a framework of the sterile medical gauze₂Composite material and by hydrophobic nano SiO₂And (4) carrying out sol post-treatment to enable the composite material to have super-hydrophobicity.

2. The invention uses super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂The functional layer of the mask is made of the composite material, the functional layer is an independent dismounting structure layer, cleaning and replacement of the functional layer are facilitated, the functional layer is provided with criss-cross micro-nano pore channels, not only can pollutants such as haze particles be effectively prevented from passing through, but also bacterial viruses can be effectively prevented from being spread, and particularly the functional layer contains a photocatalyst Ag @ AgCl-TiO₂The product has antibacterial and photocatalytic pollutant decomposing effects, and has self-cleaning effect under sunlight, ultraviolet light, etc., and can be used repeatedly. Meanwhile, the functional layer has super-hydrophobic performance, and can prevent the functional layer from swelling in weakly acidic water vapor exhaled by a person to block pore channels and influence breathing. The mask is suitable for low-risk areas with haze and new crown epidemic situations.

Drawings

Fig. 1 is a schematic view of the structure of the mask of the present invention.

Fig. 2 is a cross-sectional view of the inventive mask.

FIG. 3 is a super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂Scanning electron micrographs of the composite (magnification 50000 times).

FIG. 4 is a super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂Transmission electron micrograph of composite (magnification 100000 times).

FIG. 5 is a super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂Ultraviolet absorption spectrum of the composite material.

FIG. 6 is a super-hydrophobic porous chitosan/Ag @ AgCl-TiO₂Photograph of contact angle of composite with water.

The elements in fig. 1 illustrate: 1-mask surface layer; 2-elastic edge covering; 3-nose bridge strip; 4-hanging a lug; 5-a first layer of lining; 6-a functional layer; 7-second layer liner.

Detailed Description

The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.

Hydrophobic nano SiO 2.6% mass concentration used in the following examples₂The preparation method of the sol comprises the following steps: adding 30mL of ammonia water into 300mL of absolute ethyl alcohol, uniformly mixing, pouring into a 1000mL round-bottom flask, and magnetically stirring at room temperature, wherein the solution is marked as solution A; another 16mL of ethyl orthosilicate was added to 300mL of absolute ethanol, and the mixture was stirred uniformly and recorded as solution B. And quickly pouring the solution B into a flask in which the solution A is positioned under the condition of quick stirring, and stirring and reacting for 12 hours at room temperature to obtain light blue nano-silica sol. 200mL of absolute ethanol was added to the sol obtained above, and the resulting sol was concentrated appropriately while removing ammonia by rotary evaporation to give a final sol volume of 500 mL. Taking 100mL of sol, adjusting the pH value of the sol to be 8.5 by using glacial acetic acid or ammonia water, transferring 1.5mL of dodecyl trimethoxy silane into the sol by using a pipette, adding the mixture into a single-neck flask after uniformly stirring, placing the flask into an oil bath at the temperature of 80 ℃, stirring and refluxing for reaction for 3 hours to obtain the hydrophobic nano SiO with the mass concentration of 2.6 percent₂And (3) sol.