CN101775743B - Method for preparing Ag-modified TiO2 composite air-purifying functional fabric in situ at low temperature - Google Patents

Abstract

The invention relates to a method for preparing Ag-modified _TiO2 composite air-purifying functional fabric in situ at low temperature, comprising: (1) ultrasonically cleaning the fabric with acetone solution, drying, and then treating it in a high-efficiency cleaning agent; (2) padding the fabric to resist Oxidation finishing solution LZQ, pre-baked, baked at 130-150°C; (3) In an inert environment, add titanium tetraisopropoxide to anhydrous alcohol, stabilizer, a mixture of anhydrous alcohol, acid and deionized water, Wetting agent; (4) impregnate the fabric into the sol, dry, remove the residual sol on the surface of the material, and then dry; (5) treat the dried fabric in boiling water, then pre-dry it at 40-50°C, and immerse it in into silver nitrate solution and irradiated under an excimer ultraviolet light source to obtain a composite air-purifying fabric. The method of the invention is simple, low in cost, free of secondary pollution and easy for industrialized production; the obtained flexible air purification material has good air purification effect.

Description

Method for preparing Ag-modified TiO2 composite air-purifying functional fabric in situ at low temperature

technical field

The invention belongs to the field of preparation of composite air-purifying functional fabrics, in particular to a method for preparing Ag-modified _TiO2 composite air-purifying functional fabrics in situ at low temperature.

Background technique

In recent years, with the rapid development of my country's economy and the improvement of people's lives, the decoration level of offices and residences is getting higher and higher. New building materials, especially chemical synthesis building materials, are widely used in high-end furniture and household appliances, and have entered the home and office. Spices, cosmetics, polishes, air fresheners, insect repellants, insecticides, detergents, etc. have also become indispensable supplies in people's lives. While people are enjoying the comfort and satisfaction brought by these products, they are constantly producing various pollutants and harmful substances, destroying indoor air quality (indoor air quality, IAQ). Building energy saving, indoor heat preservation, unified air conditioning, etc., make the living room and office space better sealed, and the pollutants generated in the room are difficult to diffuse to the outside, resulting in the deterioration of indoor air quality. These factors have all led to the continuous increase of harmful substances in indoor air no matter from the type or quantity, thus resulting in indoor air pollution.

Domestic and foreign research data in recent years have shown that urban residents spend about 80% of their time in various indoor environments every day, and sensitive groups such as the elderly and children spend longer time indoors, so indoor ambient air quality has a great impact on the human body. The health impact is very important. People who live in such buildings for a long time will experience symptoms such as headaches, respiratory infections, fatigue, lethargy, fever, nausea, skin itching, and abnormal allergies. These syndromes are collectively referred to as "sick building syndrome" (SBS) . Indoor air pollution has been listed as one of the five major factors that endanger human health in the world, and reports about indoor pollution that endanger human health are common. In just one randomized trial of 2,060 individuals, 16% suffered from work-related mucous membrane inflammation (inflammation of the eyes, nose, or throat), while 7% suffered indoors, especially in offices of these diseases. Reduced work efficiency, employee sick leave, and direct medical expenses caused by poor indoor air quality have caused a lot of economic losses. According to the detection data of the indoor air pollution level of some buildings in China, the peak concentration of formaldehyde in the indoor air can reach 0.8-1mg/m ³ in newly renovated rooms with serious pollution, exceeding the national standard limit (0.08mg/m ³ ) More than 10 times, some even as high as 0.8-1mg/m ³ . According to literature, more than 300 kinds of pollutants can be detected indoors, and the air pollution level of indoor environment is generally 2-5 times higher than that of outdoor environment, and in extreme cases, it can exceed 100 times. Poor indoor air is causing serious harm to human health. Urban residents spend about 80% of their time indoors, and the potential harm they suffer from long-term exposure to harsh indoor environments is immeasurable. With the enhancement of people's health awareness and self-protection awareness, the requirements for quality of life and indoor environment are getting higher and higher, and people begin to realize that improving the quality of indoor air is the guarantee of healthy life and work. In the past, people's attention has always been on the air pollution and treatment of the outdoor environment, but in the past ten years, the impact of indoor air quality on human health has increasingly become a common concern around the world.

Therefore, the control of indoor air pollution, especially the removal of organic pollutants in indoor air, has become a research hotspot for scientific and technological workers at home and abroad. At present, the methods for removing indoor air pollutants mainly include: physical adsorption method, chemical neutralization method, photocatalytic method, air negative ion method, etc. However, the above methods have disadvantages such as adsorption saturation, complex manufacture, high cost, and inability to regenerate and use. Considering that the flexible substrate (fibrous material) as a carrier has the special properties of large surface area, easy processing and molding, enriching pollutants and diluting decomposition products, the photocatalyst is loaded on the flexible substrate to prepare flexible air purification materials. The current preparation methods are: padding method and coating method. These two methods have problems such as the photocatalyst being covered by the adhesive, serious agglomeration, low catalytic efficiency, and easy photooxidative degradation of the flexible substrate. Since flexible substrates are not resistant to high temperatures, the use of photocatalysts deposited on flexible substrates and then crystal form conversion is limited.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing Ag-modified _TiO2 composite air-purifying functional fabric in situ at low temperature. The method is simple, low in cost, free of secondary pollution, and easy to industrialized production; The purification effect is good.

A kind of low-temperature in-situ preparation of Ag modification _TiO of the present invention The method for composite air-purifying functional fabrics, comprising:

(1) Pretreatment

Use acetone solution to ultrasonically clean the fabric for 30-50 minutes, dry at 20-30°C for 12-16 hours, then treat it in the high-efficiency cleaning agent Kieralon OL (BASF) solution at 40-45°C for 20-30 minutes, and dry at 80-85°C 30～45min;

(2) Anti-photooxidative protective finishing of fabrics

Take the pretreated fabric padding anti-oxidation finishing solution LZQ for 30-50 minutes, take it out, pre-bake it at 70-80°C, and then heat it up to 130-150°C for 2-4 minutes; the composition of the LZQ finishing solution is, 1-3 % Tween 80, 4-10% nano-hydroxyapatite MP40, 3-8% tetraerythritol ester, 6-10% octyltrimethoxysilane and 69-86% water;

(3) Under an inert environment, slowly add 0.02 to 0.15 mol of titanium tetraisopropoxide into 30 to 50 ml of anhydrous alcohol under stirring, then add 0.01 to 0.03 mol of stabilizer, and stir at 200 to 300 rpm for 1 to 4 minutes. Then continue to add 20-100ml of anhydrous alcohol, acid and deionized water mixed solution with a volume ratio of 30:1:5-60:1:1.5, stir for 40-100min, add a wetting agent, and obtain a low-temperature precursor sol;

(4) In situ synthesis on the surface of the fabric

Soak the fabric treated in step (2) into the sol of step (3) for 3-10 minutes, then dry it at 65-70°C to remove the residual sol on the surface of the material, and then dry it at 90-95°C for 3-8 minutes ;

(5) post-processing

The dried fabric is treated in boiling water at 90-100°C for 2-4 hours, then pre-dried at 40-50°C, then immersed in 0.001-0.01mol/L silver nitrate solution for 1-3min, and then exposed to excimer ultraviolet light source Under irradiation for 3-6 minutes, a composite air-purifying fabric is obtained.

The fabric of the step (1) is a non-woven fabric, a woven fabric or a knitted fabric.

The fibers of the fabric are selected from cotton fiber, hemp fiber, polyimide fiber, activated carbon fiber, polyester fiber, polypropylene fiber, bamboo fiber, silk fiber, wool fiber, soybean protein fiber, milk protein fiber, nylon fiber One or two blended fibers.

The alcohol in the step (3) is isopropanol, isobutanol or isopentyl glycol.

The acid in the step (3) is hydrochloric acid, nitric acid, sulfuric acid or acetic acid.

The wetting agent in the step (3) is Tween 80 or Triton 100, and the dosage is: owf 2% to 6%.

The stabilizer in the step (3) is triethylamine or triethanolamine; the acid is hydrochloric acid, nitric acid, sulfuric acid or acetic acid.

Irradiation conditions in the step (5): wavelength 222 or 172nm, frequency 100Hz, current 1.6A, power 1.5KW, the gap between the lamp tube and the treated fabric is 1-3cm.

The air purification material prepared by the invention can be applied to interior decoration fields such as submarines, hospital wards, automobile interior decoration, aircraft interior decoration, etc., and has broad application prospects and market prospects.

The invention directly arranges the anti-photooxidation protective layer on the fabric, then synthesizes the photocatalyst in situ on the fabric, realizes the conversion of the crystal form of the photocatalyst in boiling water, and prepares the flexible air purification material synthesized in situ at low temperature.

Beneficial effect

(1) The preparation method of the present invention is simple, low in cost, does not add new equipment, and is easy to industrialized production;

(2) The source of fiber raw materials is wide, easy to process into various shapes, and easy to use;

(3) The present invention grows semiconductor nanoparticles in situ on fiber fabrics, which not only solves the problem of dust pollution of photocatalysts in air purification, but also avoids the problem of photocatalysts falling in agglomeration efficiency on flexible substrates; flexible air purification The photocatalyst film on the surface of the material is highly hydrophilic and can form an anti-fog coating. At the same time, due to its strong oxidation, it can oxidize the pollutants on the surface and keep itself clean. The flexible material can degrade toxic gases through photocatalysis under visible light. , and change it into a non-toxic and tasteless substance, the flexible air purification material of the present invention has good air purification effect, no secondary pollution, and can be used for a long time.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

(1) Wool fabric surface pretreatment

Ultrasonic cleaning of wool fabric with acetone solution for 30 minutes, drying at room temperature 20°C for 12 hours, then treating in BASF’s high-efficiency cleaning agent Kieralon OL solution at 40°C for 20 minutes, and drying at 80°C for 30 minutes;

(2) Protective finishing of wool fabric against photooxidation

Take out the wool fabric padding fiber anti-oxidation finishing solution LZQ for 30 minutes, pre-bake at 70°C, and then heat up to 130°C for 2 minutes; the ingredients of the LZQ finishing solution are 1-3% Tween 80, 4-10% nano Hydroxyapatite MP 40, 3-8% tetraerythritol ester, 6-10% octyltrimethoxysilane and 69-86% water;

(3) Preparation of low temperature precursor

Under an inert environment, slowly add 0.02mol titanium tetraisopropoxide to 30mL isopropanol under stirring, add 0.01mol triethylamine as a stabilizer to the mixture, stir at 200rpm for 1min, and then continue to add 20mL A mixed solution containing isopropanol, hydrochloric acid, and deionized water at a volume ratio of 30:1:5 was stirred for 40 minutes, and a wetting agent Tween 80 of 2% relative to the weight of the fabric was added to obtain a low-temperature precursor sol.

(4) In situ synthesis on wool fabric surface

The wool fabric was soaked in the above sol for 3 minutes, and the impregnated flexible material was dried at 65°C to remove the residual sol on the surface of the material, and then dried at 90°C for 3 minutes.

(5) Post-processing of composite air purification functional fabrics

Boil the composite air-purifying fabric prepared in step (4) in boiling water for 2 hours, pre-dry the sample treated with boiling water at 40°C, then immerse in 0.001mol/L silver nitrate solution for 1min, and then place it in a place 1cm away from the lamp tube. The composite air-purifying fabric was obtained by irradiating for 3 minutes under an excimer ultraviolet light source with a wavelength of 222 nm.

The composite air-purifying functional fabric prepared by the present invention and common activated carbon air-purifying materials are respectively loaded into the same type of air purifier, and under the same conditions: including space, harmful gas concentration and time are compared and tested, and the results are as follows :

Example 2

(1) Cotton fabric surface pretreatment

Ultrasonic cleaning of cotton fabrics with acetone solution for 40 minutes, drying at room temperature 25°C for 14 hours, then treating in high-efficiency cleaning agent Kieralon OL solution at 43°C for 25 minutes, drying at 83°C for 37 minutes;

(2) Protective finishing of cotton fabric against photooxidation

Take out the cotton fabric padding fiber anti-oxidation finishing solution LZQ for 40 minutes, pre-dry at 75°C, and then heat up to 140°C for 3 minutes; the LZQ finishing solution is composed of 1-3% Tween 80, 4-10% nano Hydroxyapatite MP40, 3-8% tetraerythritol ester, 6-10% octyltrimethoxysilane and 69-86% water.

(3) Preparation of low temperature precursor

Under an inert environment, slowly add 0.08mol titanium tetraisopropoxide to 40mL isobutanol under stirring, add 0.02mol triethylamine as a stabilizer to the mixture, stir at 250rpm for 2min, and then continue to add 60mL A mixed solution of isopropanol, nitric acid, and deionized water with a volume ratio of 45:1:2 was stirred for 70 minutes, and a wetting agent Tween 80 of 4% relative to the weight of the fabric was added to obtain a low-temperature precursor sol.

(4) In situ synthesis on the surface of cotton fabric

The cotton fabric was soaked in the above sol for 7 minutes, and the impregnated flexible material was dried at 67°C to remove the residual sol on the surface of the material, and then dried at 93°C for 5 minutes.

(5) Post-processing of composite air purification functional fabrics

Boil the composite air-purifying fabric prepared in step (4) in boiling water for 2 hours, pre-dry the sample treated with boiling water at 45°C, then immerse in 0.005mol/L silver nitrate solution for 3min, and then place it in a place 2cm away from the lamp tube. The composite air-purifying fabric was obtained by irradiating for 4 minutes under an excimer ultraviolet light source with a wavelength of 222 nm.

The composite air-purifying functional fabric prepared by the present invention and common activated carbon air-purifying materials are respectively loaded into the same type of air purifier, and under the same conditions: including space, harmful gas concentration and time are compared and tested, and the results are as follows :

Example 3

(1) Surface pretreatment of linen fabric

Ultrasonic cleaning of cotton fabrics with acetone solution for 50 minutes, drying at room temperature at 30°C for 16 hours, then treating in high-efficiency cleaning agent Kieralon OL solution at 45°C for 30 minutes, and drying at 85°C for 45 minutes;

(2) Protective finishing of linen fabric against photooxidation

Take out the linen fabric padding fiber anti-oxidation finishing solution LZQ for 50 minutes, pre-bake at 80°C, and then heat up to 150°C for 4 minutes; the LZQ finishing solution is composed of 1-3% Tween 80, 4-10% nano Hydroxyapatite MP40, 3-8% tetraerythritol ester, 6-10% octyltrimethoxysilane and 69-86% water.

(3) Preparation of low temperature precursor

Under an inert environment, slowly add 0.15 mol of titanium tetraisopropoxide to 50 mL of isobutanol under stirring, add 0.03 mol of triethylamine as a stabilizer to the mixture, stir at 300 rpm for 4 min, and then continue to add 100 mL of A mixed solution of isopropanol, acetic acid, and deionized water with a volume ratio of 60:1:1.5 was stirred for 100 minutes, and a wetting agent Tween 80 of 6% relative to the weight of the fabric was added to obtain a low-temperature precursor sol.

(4) In situ synthesis on the surface of flax fabric

The cotton fabric was soaked in the above sol for 10 minutes, and the impregnated flexible material was dried at 70°C to remove the residual sol on the surface of the material, and then dried at 95°C for 8 minutes.

(5) Post-processing of composite air purification functional fabrics

Boil the composite air-purifying fabric prepared in step (4) in boiling water for 2 hours, pre-dry the sample treated with boiling water at 50°C, then immerse in 0.01mol/L silver nitrate solution for 3min, and then place it in a place 2cm away from the lamp tube. The composite air-purifying fabric was obtained by irradiating for 4 minutes under an excimer ultraviolet light source with a wavelength of 222 nm.

The air self-purifying functional fabric prepared by the present invention and the common activated carbon air-purifying material are respectively loaded into the same type of air purifier, and under the same conditions: including space, harmful gas concentration and time are compared and tested, and the results are as follows :

Claims (8)

1. A low-temperature in-situ preparation of Ag-modified TiO The method for _composite air-purifying functional fabrics, comprising: (1) Pretreatment Use acetone solution to ultrasonically clean the fabric for 30-50 minutes, dry at 20-30°C for 12-16 hours, then treat it in high-efficiency cleaning agent Kieralon OL solution at 40-45°C for 20-30 minutes, and dry at 80-85°C 30～45min; (2) Take out the pretreated fabric padding anti-oxidation finishing solution LZQ for 30-50 minutes, pre-bake at 70-80°C, and then heat up to 130-150°C for 2-4 minutes; the composition of the LZQ finishing solution is: 1-3% Tween, 4-10% nano-hydroxyapatite, 3-8% tetraerythritol ester, 6-10% octyltrimethoxysilane and 69-86% water; (3) Under an inert environment, slowly add 0.02 to 0.15 mol of titanium tetraisopropoxide into 30 to 50 ml of anhydrous alcohol under stirring, then add 0.01 to 0.03 mol of stabilizer, and stir at 200 to 300 rpm for 1 to 4 minutes. Then continue to add 20-100ml of anhydrous alcohol, acid and deionized water mixed solution with a volume ratio of 30:1:5-60:1:1.5, stir for 40-100min, add a wetting agent, and obtain a low-temperature precursor sol; (4) Immerse the fabric treated in step (2) into the sol of step (3) for 3-10 minutes, then dry it at 65-70°C to remove the residual sol on the surface of the material, and then dry it at 90-95°C 3～8min; (5) The dried fabric is treated in boiling water at 90-100°C for 2-4 hours, then pre-dried at 40-50°C, and then immersed in 0.001-0.01mol/L silver nitrate solution for 1-3 minutes, and then in the quasi- The composite air-purifying fabric is obtained by irradiating molecular ultraviolet light for 3 to 6 minutes. 2. a kind of low temperature in-situ preparation according to claim ₁ Ag modifies TiO The method for composite air purification functional fabric, it is characterized in that: the fabric of described step (1) is nonwoven fabric, woven fabric or knitted fabric . 3. a kind of low temperature in-situ preparation according to claim ₂ Ag modifies TiO The method for composite air purification functional fabric, it is characterized in that: the fiber of described fabric is selected from cotton fiber, hemp fiber, polyimide fiber, Activated carbon fiber, polyester fiber, polypropylene fiber, bamboo fiber, one or two blended fibers of silk fiber, wool fiber, soybean protein fiber, milk protein fiber, and nylon fiber. 4. a kind of low temperature in-situ preparation according to claim 1 Ag modifies _TiO The method for composite air purification functional fabric, it is characterized in that: the alcohol in described step (3) is isopropanol, isobutanol or isopropanol pentylene glycol. 5. A low-temperature in-situ method for preparing Ag-modified _TiO2 composite air-purifying functional fabrics according to claim 1, characterized in that: the acid in the step (3) is hydrochloric acid, nitric acid, sulfuric acid or acetic acid. 6. a kind of low temperature in-situ preparation according to claim ₁ Ag modifies TiO The method for composite air purification functional fabric, it is characterized in that: the wetting agent in the described step (3) is Tween or triton, Dosage: owf 2% to 6%. 7. A kind of low-temperature in-situ preparation of Ag-modified TiO according to claim ₁ The method for the composite air-purifying functional fabric is characterized in that: the stabilizer in the step (3) is triethylamine or triethanolamine. 8. A kind of low-temperature in-situ preparation of Ag-modified TiO according to claim ₁ The method for composite air-purifying functional fabrics, characterized in that: the irradiation conditions in the step (5): wavelength 222 or 172nm, frequency 100Hz , current 1.6A, power 1.5KW, the gap between the lamp tube and the treated fabric is 1-3cm.