CN101768856A - Super hydrophobic cotton fabric and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of water-repellent finishing and processing of textiles, and in particular relates to a super-hydrophobic cotton fabric and a preparation method thereof. The preparation method of the described super-hydrophobic cotton fabric is characterized in that the cotton fibers on the fabric are first epoxidized and modified, and then the cotton fabric is treated with aminated nano-silica and epoxidized nano-silica successively. Carry out padding to improve the roughness of the fabric surface, and finally use low surface energy substances to hydrophobize the fabric. The contact angle between the prepared cotton fabric and water droplets exceeds 150°. This method utilizes the epoxy groups of cotton fibers, nanometer two The covalent reaction between the amino groups on the silica and the epoxy groups on the nano-silica makes the rough surface constructed have good fastness, and the constructed surface has a large number of silanol and epoxy groups. The group is conducive to the chemical combination of low surface energy substances and the surface, so the superhydrophobic performance of the prepared fabric has excellent stability.

Description

A kind of superhydrophobic cotton fabric and preparation method thereof

technical field

The invention belongs to the field of water-repellent finishing and processing of textiles, and in particular relates to a preparation method of super-hydrophobic cotton fabrics.

Background technique

Superhydrophobic functional textiles not only have important applications in industrial production, medical and military products, but also have a wide range of applications in daily life. In order to utilize the self-cleaning effect of the superhydrophobic surface, Chinese patent CN 1242114C discloses nano self-cleaning cashmere or products and its preparation method, Chinese patent CN 1277019C discloses nano self-cleaning silk and products, and Chinese patent CN 1824884A discloses nano-functional The preparation method of self-cleaning suit fabric and ready-made clothing products of materials, Chinese patent CN100334291C discloses the preparation method of down jacket fabric with self-cleaning function, these patents use nano particles to build rough structure, and use organic fluorine finishing agent to impregnate and coat the fabric Or spray, which gives the fabric both hydrophobic and oleophobic properties. Chinese patent CN 101397754A discloses a preparation method of fluorine-free superhydrophobic cotton fabric, which uses silica sol to pad cotton fabric, and then obtains superhydrophobic cotton fabric through non-fluoroalkane treatment.

The preparation of superhydrophobic surfaces requires the construction of micro-nano rough structures on the one hand, and the reduction of the surface energy of rough surfaces on the other. Although there are many methods for preparing superhydrophobic textiles, these methods rarely mention micro-nano rough structures. The bonding relationship between the surface and the substrate, less mentions the stability of the superhydrophobic properties of the prepared superhydrophobic fabrics.

Contents of the invention

The object of the present invention is superhydrophobic cotton fabric and preparation method thereof.

In order to achieve the above object, the technical scheme adopted in the present invention is: first carry out epoxidized modification to the cotton fiber on the cotton fabric, then use aminated nano-silica and epoxidized nano-silica to modify the cotton fabric successively. Padding is carried out, and finally the fabric is obtained by padding the fabric with low surface energy substances.

The epoxidation modification method of said cotton fiber is: put 2g cotton fabric into 100mL mass concentration and be 5% sodium hydroxide solution, add the epichlorohydrin of 5～10mL under constant stirring, control reaction temperature is React at 40-60°C for 5-10 hours, take out the fabric, wash it with water until it is neutral, and then dry it to obtain epoxylated cotton fabric;

The preparation method of said aminated nano-silica and epoxidized nano-silica is:

Mix 12mL tetraethyl orthosilicate and 80mL methanol to obtain mixed solution A, mix 30mL ammonia water with a mass concentration of 25% to 28% and 320mL methanol to obtain mixed solution B, and then add mixed solution A to the mixed solution dropwise under stirring Reaction in B for 3 to 10 hours to obtain a methanol solution of nano silicon dioxide;

Add 0.5-2mL of a mixed solution of 3-aminopropyltriethoxysilane and 5mL of methanol dropwise to 200mL of nano-silica methanol solution, and continue the reaction for 8-24 hours to obtain aminated nano-silica;

Add 0.5-2mL of a mixed solution of 3-glycidyl ether propyltrimethoxysilane and 5mL of methanol dropwise into 200mL of nano-silica methanol solution, and continue the reaction for 8-24 hours to obtain epoxylated nano-silica .

The method that said aminated nano silicon dioxide and epoxidized nano silicon dioxide pad cotton fabric is:

Immerse the epoxylated cotton fabric in the ethanol solution of aminated nano-silica with a mass concentration of 0.2-2.0%, dip and roll, bake at 60-120°C for 0.5-1h, and then immerse the fabric in a mass concentration of 0.2 ~2.0% ethanol solution of epoxidized nano-silicon dioxide, once soaked and rolled, and baked at 60~120°C for 0.5~1h.

Said low surface energy substances are long-chain (fluoro) alkyl carboxylic acids with 6 to 18 carbon atoms, long-chain (fluoro) alkyl ammonia, long-chain (fluoro) alkyl siloxanes, One or more of long-chain (fluoro)alkylsilylchlorosilanes and long-chain alkylthiols are obtained by immersing the fabric in a solution made of the above-mentioned low surface energy substances with a mass concentration of 0.5-1.5%, and drying to obtain final product.

The superhydrophobic cotton fabric made by the preparation method of the present invention has a contact angle with water droplets exceeding 150°.

The present invention utilizes the covalent reaction between the epoxy group of cotton fiber, the amino group on the nano-silica and the epoxy group on the nano-silica to make the constructed rough surface have good fastness, Moreover, the constructed surface has large silicon hydroxyl groups and epoxy groups, which is beneficial to the chemical combination of low surface energy substances and the surface, so that the superhydrophobic performance of the prepared fabric has excellent stability.

Detailed ways

Example 1: Put 2g of cotton fabric into 100mL of a mass concentration of 5% sodium hydroxide solution, add 8mL of epichlorohydrin under constant stirring, control the reaction temperature at 40°C for 10 hours, take out the fabric and wash it with water until After neutral drying, epoxylated cotton fabric is obtained;

Mix 12mL tetraethyl orthosilicate and 80mL methanol to obtain mixed solution A, mix 30mL ammonia water with a mass concentration of 26% and 320mL methanol to obtain mixed solution B, then add mixed solution A dropwise to mixed solution B under stirring to react 3h, obtain nano silicon dioxide methanol solution;

A mixed solution of 0.5mL of 3-aminopropyltriethoxysilane and 5mL of methanol was added dropwise to 200mL of nano-silica methanol solution, and the reaction was continued for 12 hours to obtain aminated nano-silica;

Add 1 mL of a mixed solution of 3-glycidyl ether propyl trimethoxysilane and 5 mL of methanol dropwise into 200 mL of nano-silica methanol solution, and continue the reaction for 12 hours to obtain epoxylated nano-silica;

Immerse the epoxy-based cotton fabric in the ethanol solution of aminated nano-silicon dioxide with a mass concentration of 1%, dip and pad, bake at 100°C for 0.5-1h, and then immerse the fabric in an epoxy solution with a mass concentration of 1%. Alkaline nano-silica ethanol solution, once dipped and rolled, baked at 100°C for 0.5-1h;

Immerse the fabric in an acetone stearate solution with a mass concentration of 0.5% for 10 minutes, remove the remaining liquid by padding, and then bake at 110° C. for 1 hour to obtain a superhydrophobic cotton fabric. Ultrasonication of the fabric in ethanol solution for 1 hour still has good superhydrophobic properties.

Example 2: Put 2g of cotton fabric into 100mL of a mass concentration of 5% sodium hydroxide solution, add 10mL of epichlorohydrin under constant stirring, control the reaction temperature at 60°C for 5 hours, take out the fabric and wash it with water until After neutral drying, epoxylated cotton fabric is obtained;

Mix 12mL tetraethyl orthosilicate and 80mL methanol to obtain mixed solution A, mix 30mL ammonia water with a mass concentration of 28% and 320mL methanol to obtain mixed solution B, and then add mixed solution A dropwise to mixed solution B under stirring to react 8h, obtain nano silicon dioxide methanol solution;

A mixed solution of 1 mL of 3-aminopropyltriethoxysilane and 5 mL of methanol was added dropwise to 200 mL of nano-silica methanol solution, and the reaction was continued for 20 hours to obtain aminated nano-silica;

Add 2 mL of a mixed solution of 3-glycidyl ether propyl trimethoxysilane and 5 mL of methanol dropwise into 200 mL of nano-silica methanol solution, and continue the reaction for 20 hours to obtain epoxylated nano-silica;

Immerse the epoxy-based cotton fabric in the ethanol solution of aminated nano-silicon dioxide with a mass concentration of 0.5%, dip and pad, bake at 60°C for 0.5-1h, and then immerse the fabric in an epoxy solution with a mass concentration of 0.5%. Alkaline nano-silica ethanol solution, once dipped and rolled, baked at 60°C for 0.5-1h;

Immerse the fabric in a 1% heptadecafluorodecyltrichlorosilane toluene solution for 1 hour, take it out and dry it at room temperature to obtain a superhydrophobic cotton fabric. Ultrasonication of the fabric in ethanol solution for 1 hour still has good superhydrophobic properties.

Example 3: Put 2g of cotton fabric into 100mL of a mass concentration of 5% sodium hydroxide solution, add 6mL of epichlorohydrin under constant stirring, control the reaction temperature at 50°C for 7.5 hours, take out the fabric and wash it with water until After neutral drying, epoxylated cotton fabric is obtained;

Mix 12mL tetraethyl orthosilicate and 80mL methanol to obtain mixed solution A, mix 30mL ammonia water with a mass concentration of 27% and 320mL methanol to obtain mixed solution B, and then add mixed solution A dropwise to mixed solution B under stirring to react 5h, obtain nano silicon dioxide methanol solution;

A mixed solution of 2mL of 3-aminopropyltriethoxysilane and 5mL of methanol was added dropwise to 200mL of nano-silica methanol solution, and the reaction was continued for 8 hours to obtain aminated nano-silica;

A mixed solution of 0.8 mL of 3-glycidyl ether propyl trimethoxysilane and 5 mL of methanol was added dropwise to 200 mL of nano-silica methanol solution, and the reaction was continued for 8 hours to obtain epoxidized nano-silica;

Immerse the epoxy-based cotton fabric in the ethanol solution of aminated nano-silica with a mass concentration of 0.2%, dip and pad, bake at 80°C for 0.5-1h, and then immerse the fabric in an epoxy solution with a mass concentration of 0.2%. Alkaline nano-silica ethanol solution, once dipped and rolled, baked at 80°C for 0.5-1h;

Immerse the fabric in an acetone stearate solution with a mass concentration of 1.5% for 10 minutes, remove the remaining liquid by padding, and then bake at 110° C. for 1 hour to obtain a superhydrophobic cotton fabric. Ultrasonication of the fabric in ethanol solution for 1 hour still has good superhydrophobic properties.

Example 4: Put 2g of cotton fabric into 100mL of a mass concentration of 5% sodium hydroxide solution, add 9mL of epichlorohydrin under constant stirring, control the reaction temperature at 45°C for 8 hours, take out the fabric and wash it with water until After neutral drying, epoxylated cotton fabric is obtained;

Mix 12mL tetraethyl orthosilicate and 80mL methanol to obtain mixed solution A, mix 30mL ammonia water with a mass concentration of 25% and 320mL methanol to obtain mixed solution B, and then add mixed solution A dropwise to mixed solution B under stirring to react 10h, obtain nano silicon dioxide methanol solution;

A mixed solution of 1.5mL of 3-aminopropyltriethoxysilane and 5mL of methanol was added dropwise to 200mL of nano-silica methanol solution, and the reaction was continued for 16 hours to obtain aminated nano-silica;

A mixed solution of 0.8 mL of 3-glycidyl ether propyl trimethoxysilane and 5 mL of methanol was added dropwise to 200 mL of nano-silica methanol solution, and the reaction was continued for 16 hours to obtain epoxylated nano-silica;

Dip the epoxy-based cotton fabric into the ethanol solution of aminated nano-silicon dioxide with a mass concentration of 1.5%, dip and pad, bake at 120°C for 0.5-1h, and then immerse the fabric in an epoxy solution with a mass concentration of 1.5%. Alkaline nano-silica ethanol solution, once dipped and rolled, baked at 120°C for 0.5-1h;

Immerse the fabric in a toluene solution with a mass concentration of 0.8% heptadecafluorodecyltrimethoxysilane for 1 hour, take it out and dry it at room temperature to obtain a superhydrophobic cotton fabric. Ultrasonication of the fabric in ethanol solution for 1 hour still has good superhydrophobic properties.

Example 5: Put 2g of cotton fabric into 100mL of 5% sodium hydroxide solution, add 5mL of epichlorohydrin under constant stirring, control the reaction temperature at 55°C for 6 hours, take out the fabric and wash it with water until After neutral drying, epoxylated cotton fabric is obtained;

Mix 12mL tetraethyl orthosilicate and 80mL methanol to obtain mixed solution A, mix 30mL ammonia water with a mass concentration of 28% and 320mL methanol to obtain mixed solution B, and then add mixed solution A dropwise to mixed solution B under stirring to react 7h, obtain nano silicon dioxide methanol solution;

A mixed solution of 0.8mL of 3-aminopropyltriethoxysilane and 5mL of methanol was added dropwise to 200mL of nano-silica methanol solution, and the reaction was continued for 24 hours to obtain aminated nano-silica;

A mixed solution of 1.5 mL of 3-glycidyl ether propyl trimethoxysilane and 5 mL of methanol was added dropwise to 200 mL of nano-silica methanol solution, and the reaction was continued for 24 hours to obtain epoxidized nano-silica;

Immerse the epoxy-based cotton fabric in an ethanol solution of aminated nano-silicon dioxide with a mass concentration of 2.0%, dip and roll, bake at 90°C for 0.5-1h, and then immerse the fabric in an epoxy solution with a mass concentration of 2.0%. Alkaline nano-silicon dioxide ethanol solution, once soaked and rolled, baked at 90°C for 0.5-1h;

Immerse the fabric in a 1.2% dodecyltrimethoxysilane ethanol solution for 1 hour, take it out and dry it at room temperature to obtain a superhydrophobic cotton fabric. Ultrasonication of the fabric in ethanol solution for 1 hour still has good superhydrophobic properties.

Claims (6)

1. a preparation method of superhydrophobic cotton fabric, is characterized in that: first the cotton fiber on cotton fabric is carried out epoxy-modification, then adopts amination nano-silica and epoxy-based nano-silica successively It is obtained by padding cotton fabrics, and finally padding the fabrics with low surface energy substances. 2. the preparation method of superhydrophobic cotton fabric according to claim 1 is characterized in that: the epoxidation modification method of said cotton fiber is: putting 2g cotton fabric into 100mL mass concentration is 5% hydroxide In the sodium solution, add 5-10 mL of epichlorohydrin under constant stirring, control the reaction temperature at 40-60° C. and react for 5-10 hours, take out the fabric, wash it with water until it is neutral, and then dry it to obtain epoxylated cotton fabric. 3. the preparation method of superhydrophobic cotton fabric according to claim 1, is characterized in that: the preparation method of said aminated nano silicon dioxide and epoxidized nano silicon dioxide is: Mix 12mL tetraethyl orthosilicate and 80mL methanol to obtain mixed solution A, mix 30mL ammonia water with a mass concentration of 25% to 28% and 320mL methanol to obtain mixed solution B, and then add mixed solution A to the mixed solution dropwise under stirring Reaction in B for 3 to 10 hours to obtain a methanol solution of nano silicon dioxide; Add 0.5-2mL of a mixed solution of 3-aminopropyltriethoxysilane and 5mL of methanol dropwise to 200mL of nano-silica methanol solution, and continue the reaction for 8-24 hours to obtain aminated nano-silica; Add 0.5-2mL of a mixed solution of 3-glycidyl ether propyltrimethoxysilane and 5mL of methanol dropwise into 200mL of nano-silica methanol solution, and continue the reaction for 8-24 hours to obtain epoxylated nano-silica . 4. according to the preparation method of claim 1,2 or 3 described superhydrophobic cotton fabrics, it is characterized in that: said aminated nano-silica and epoxy-based nano-silica carry out padding to cotton fabrics The method is: Immerse the epoxylated cotton fabric in the ethanol solution of aminated nano-silica with a mass concentration of 0.2-2.0%, dip and roll, bake at 60-120°C for 0.5-1h, and then immerse the fabric in a mass concentration of 0.2 ~2.0% ethanol solution of epoxidized nano-silicon dioxide, once soaked and rolled, and baked at 60~120°C for 0.5~1h. 5. the preparation method of superhydrophobic cotton fabric according to claim 1 is characterized in that: said adopting low surface energy substance is the long-chain (fluorinated) alkyl group that carbon number is 6～18 on the long carbon chain One or more of carboxylic acid, long-chain (fluoro)alkylammonia, long-chain (fluoro)alkylsiloxane, long-chain (fluoro)alkylsilchlorosilane, long-chain alkylthiol , the fabric is immersed in the solution made of the above-mentioned low surface energy substance with a mass concentration of 0.5-1.5%, taken out and dried to obtain the final product. 6. A superhydrophobic cotton fabric made according to the preparation method of the superhydrophobic cotton fabric according to claim 1, characterized in that: the contact angle between the cotton fabric and a water drop exceeds 150°.