阅读说明：本技术 防油防污自清洁功能性复合柔性材料及其制备方法 (Oil-proof antifouling self-cleaning functional composite flexible material and preparation method thereof ) 是由 李战雄 西艳妮 刘可心 孙弋 于 2020-05-23 设计创作，主要内容包括：本发明公开了一种防油防污自清洁功能性复合柔性材料及其制备方法。功能性织物中,纤维表面原位生成的球型纳米颗粒在基础织物的纤维上形成涂层,涂层中颗粒为球型结构,涂层的糙化形貌赋予了织物超疏液功能,保证涂层良好的机械性能。生产功能织物时,以四氯硅烷和氟烷基三氯硅烷作为单体,两种单体同浴处理织物,反应在室温条件下完成,生产工艺不仅简单、操作安全,通过控制处理液配方,使处理织物中纤维表面原位生成的球型颗粒其外层完全被氟烷基所包裹,从而形成具有低表面能的防护层,赋予处理织物非常优异的拒液功能和自清洁功能。硅烷与纤维表面活性基团可发生化学键合,使得生成的含氟聚硅氧烷纳米颗粒在纤维表面牢固地吸附,从而赋予涂层耐久性。(The invention discloses an oil-proof antifouling self-cleaning functional composite flexible material and a preparation method thereof. In the functional fabric, spherical nano particles generated on the surface of the fiber in situ form a coating on the fiber of the base fabric, the particles in the coating are of a spherical structure, the roughening morphology of the coating endows the fabric with a super-lyophobic function, and the good mechanical property of the coating is ensured. When the functional fabric is produced, tetrachlorosilane and fluoroalkyl trichlorosilane are used as monomers, the two monomers are used for treating the fabric in one bath, the reaction is completed at room temperature, the production process is simple and safe to operate, and the formula of the treatment solution is controlled, so that the outer layer of spherical particles generated in situ on the surface of fibers in the treated fabric is completely wrapped by fluoroalkyl, and a protective layer with low surface energy is formed, and the treated fabric is endowed with excellent liquid repellent function and self-cleaning function. Silane can be chemically bonded with the fiber surface active groups, so that the generated fluorine-containing polysiloxane nano-particles are firmly adsorbed on the fiber surface, thereby endowing the coating with durability.)

1. The oil-proof antifouling self-cleaning functional composite flexible material is characterized by comprising an oil-proof antifouling self-cleaning functional fabric, an adhesive layer and a base film; the oil-proof antifouling self-cleaning functional fabric consists of a base fabric and a coating on the surface of the base fabric; the coating is polysiloxane spherical particles wrapped by fluoroalkyl.

2. The oil-resistant, stain-resistant and self-cleaning functional composite flexible material as claimed in claim 1, wherein the fluoroalkyl group is 3,3,4,4,5,5,6, 6-nonafluorohexyl, 3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl or 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 10-heptadecafluorodecyl; the base fabric is any one of cotton fabric, hemp fabric, silk fabric, wool fabric and regenerated cellulose fiber fabric or the base fabric is regenerated cellulose non-woven fabric.

3. The oil-proof anti-fouling self-cleaning functional composite flexible material as claimed in claim 1, wherein the preparation method of the oil-proof anti-fouling self-cleaning functional composite flexible material comprises the following steps: putting the water-carrying base fabric into the working solution, stirring for reaction, and then cleaning and drying to obtain the oil-proof antifouling self-cleaning functional fabric; bonding the oil-proof antifouling self-cleaning functional fabric with the base film through an adhesive to obtain the oil-proof antifouling self-cleaning functional composite flexible material; the working solution comprises tetrachlorosilane, fluoroalkyl trichlorosilane and an organic solvent.

4. The oil-resistant, stain-resistant and self-cleaning functional composite flexible material as claimed in claim 3, wherein the water content in the water-carrying base fabric is 20% -40%.

5. The oil-resistant, anti-fouling and self-cleaning functional composite flexible material as claimed in claim 3, wherein the organic solvent is any one of petroleum ether, toluene, xylene and cyclohexane; the fluoroalkyl trichlorosilane is 3,3,4,4,5,5,6,6, 6-nonafluorohexyl trichlorosilane, 3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl trichlorosilane or 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl trichlorosilane; in the working solution, the weight percentage of the tetrachlorosilane is 0.05-0.25%, and the weight percentage of the fluoroalkyl trichlorosilane is 0.1-0.5%.

6. The oil-resistant, stain-resistant and self-cleaning functional composite flexible material as claimed in claim 3, wherein the base film is a plastic film.

7. The oil-resistant, stain-resistant and self-cleaning functional composite flexible material as claimed in claim 3, wherein the drying temperature is 40-110 ℃ and the drying time is 30 minutes-6 hours.

8. A preparation method of an oil-proof, anti-fouling and self-cleaning functional composite flexible material is characterized by comprising the following steps: putting the water-carrying base fabric into the working solution, stirring for reaction, and then cleaning and drying to obtain the oil-proof antifouling self-cleaning functional fabric; bonding the oil-proof antifouling self-cleaning functional fabric with the base film through an adhesive to obtain the oil-proof antifouling self-cleaning functional composite flexible material; the working solution comprises tetrachlorosilane, fluoroalkyl trichlorosilane and an organic solvent.

9. The preparation method of the oil-proof stain-proof self-cleaning functional composite flexible material according to claim 8, wherein in the stirring reaction, the stirring speed is 30-80 r/min, and the reaction time is 1-10 hours.

10. The preparation method of the oil-proof stain-proof self-cleaning functional composite flexible material as claimed in claim 8, wherein the weight percentage of the tetrachlorosilane is 0.05-0.25%, and the weight percentage of the fluoroalkyl trichlorosilane is 0.1-0.5%.

Technical Field

The invention relates to a functional flexible material and a preparation method thereof, in particular to an oil-proof, anti-fouling and self-cleaning fabric and a preparation method thereof.

Background

The flexible material has wide application field, especially can be used for wrapping and covering regular and irregular objects, and has important value in the industrial and civil fields. Fluorine atoms have extremely strong electronegativity and smaller atomic radius, so that carbon-fluorine bonds (C-F) have higher bond energy and can be firmly combined, and therefore, the fluorine-containing compound has extremely low surface free energy, excellent stability and heat resistance and is widely applied to the fields of papermaking, textiles, surface coatings, new energy sources and the like.

The fluorine-containing acrylate polymer emulsion is used and is finished on the fabric in a padding baking mode, and a layer of low surface energy film is formed on the surface of the fabric fiber, so that the hydrophobic and oleophobic performance is provided. Fabrics composed of fibers with a micron-scale Roughness morphology, with The fiber Surface completely coated with a polymer film forming a smooth coating, and The film layer and fibers forming a classic Wenzel Surface (Wenzel, Robert n. Surface roughnessand Contact angle. The Journal of medical and colloidal Chemistry 1949, 53(9): 1466-. However, it is difficult for the Wenzel surface to have super-hydrophobic and super-oleophobic properties, and only when the roughness structure formed by the low surface energy component reaches a certain degree and the liquid contacts the surface, air is confined to the roughened surface, and the liquid droplet contacts the composite interface formed by the solid and the air, which is the Cassie surface (Cassie A B D, Baxter S. Wettability of porous surfaces of the Farady Society, 1944, 40: 546-plus 551), and the composite interface formed by the solid itself and the air contacts the liquid droplet. Since the contact angle between a liquid and air can be considered to be 180 °, the Cassie surface can provide more excellent liquid-repellent functions such as water repellency, oil repellency, and stain repellency than the Wenzel surface, although the surface chemical composition is the same.

The finishing principle of the currently marketed so-called three-proofing fabric finishing agents for water resistance, oil resistance, stain resistance and the like is that a layer of protective substance with low surface energy is covered and wrapped on the surface of the treated fiber to achieve the function of resisting prevention. Most finishes can only provide water-repellent effects, and to achieve oil-repellent and even self-cleaning functions, the fabric needs to be super-hydrophobic, so the physical morphology of the coating must be strictly regulated.

Throughout the prior art, very few flexible materials have good hydrophobic and oleophobic properties and are self-cleaning.

Disclosure of Invention

The invention discloses a method for forming a coating with a nano-morphology on the surface of a fiber aiming at the defect that the liquid repellent function provided by the prior fluorine-containing polyacrylate finishing agent when the fabric is treated is not easy to realize a super-hydrophobic function and a self-cleaning property, wherein the coating and the fiber form a micro-nano secondary roughening structure together to provide super-hydrophobic and super-oleophobic properties with excellent properties, so that the oil-proof, anti-fouling and self-cleaning functional fabric can be prepared and then is bonded with a base film to obtain a flexible composite material.

The technical scheme for realizing the purpose of the invention is as follows:

an oil-proof antifouling self-cleaning functional composite flexible material comprises an oil-proof antifouling self-cleaning functional fabric, an adhesive layer and a base film; the oil-proof antifouling self-cleaning functional fabric consists of a base fabric and a coating on the surface of the base fabric; the coating is polysiloxane spherical particles wrapped by fluoroalkyl.

The invention discloses a preparation method of the oil-proof antifouling self-cleaning functional composite flexible material, which comprises the following steps: putting the water-carrying base fabric into the working solution, stirring for reaction, and then cleaning and drying to obtain the oil-proof antifouling self-cleaning functional fabric; bonding the oil-proof antifouling self-cleaning functional fabric with the base film through an adhesive to obtain the oil-proof antifouling self-cleaning functional composite flexible material; the working solution comprises tetrachlorosilane, fluoroalkyl trichlorosilane and an organic solvent.

In the invention, the fluoroalkyl is 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, 3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl or 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyltrichlorosilane; the base fabric is any one of cotton fabric, hemp fabric, silk fabric, wool fabric and regenerated cellulose fiber fabric or the base fabric is regenerated cellulose non-woven fabric.

The invention discloses a preparation method of the oil-proof antifouling self-cleaning functional composite flexible material, which comprises the following steps:

(1) base fabric pretreatment: soaking the base fabric in water until the base fabric is completely wetted, carrying out mangling, and then placing the base fabric in a natural environment, wherein the water content of the base fabric is controlled;

(2) preparing a working solution: adding a certain amount of organic solvent into a container with a stirring device, then adding a certain amount of tetrachlorosilane and fluoroalkyl trichlorosilane, and fully stirring and dissolving to obtain working liquid;

(3) in-situ polymerization coating: putting the base fabric with water into a container, starting stirring, controlling the stirring speed, stopping the reaction after reacting for a certain time at room temperature, and stopping stirring;

(4) and (3) post-treatment: taking out the fabric from the container, washing the fabric with a certain amount of organic solvent, finally putting the fabric into an oven for drying, and obtaining the oil-proof antifouling self-cleaning fabric after drying;

(5) bonding the oil-proof antifouling self-cleaning fabric with a base film to obtain an oil-proof antifouling self-cleaning functional composite flexible material; the base film is positioned on one side surface of the oil-proof and anti-fouling self-cleaning fabric.

In the invention, the water content of the water-carrying base fabric is 20-40%.

In the invention, the working solution consists of tetrachlorosilane, fluoroalkyl trichlorosilane and an organic solvent; the organic solvent is any one of petroleum ether, toluene, xylene and cyclohexane; the fluoroalkyl trichlorosilane is 3,3,4,4,5,5,6,6, 6-nonafluorohexyl trichlorosilane, 3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctyl trichlorosilane or 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 10-heptadecafluorodecyl trichlorosilane; in the working solution, the weight percentage of the tetrachlorosilane is 0.05-0.3%, and the weight percentage of the fluoroalkyl trichlorosilane is 0.1-0.5%; preferably, in the working solution, the weight percentage of the tetrachlorosilane is 0.1-0.25%, and the weight percentage of the fluoroalkyl trichlorosilane is 0.15-0.35%.

In the invention, in the stirring reaction, the stirring speed is 30-80 r/min, and the reaction time is 1-10 hours; the drying temperature is 40-110 ℃, and the drying time is 30 minutes-6 hours.

The oil-proof antifouling self-cleaning fabric disclosed by the invention consists of fibers in a base fabric and a surface coating of the fibers, wherein the coating is formed by spherical polysiloxane particles with a roughened appearance, and the surfaces of the spherical particles are wrapped by a layer of complete fluoroalkyl; functional fabric:

in the invention, the base film is a plastic film and is an existing product, such as a PI film, a PET film and the like, and the base film is selected by a person skilled in the art according to application occasions; the adhesive is also an existing product, and can be selected by a person skilled in the art according to application occasions.

The technical scheme provided by the invention discloses the oil-proof antifouling self-cleaning fabric, which has the beneficial effects that:

1. different from the method for forming a smooth fluorine-silicon coating when the functional fabric is treated by fluoroalkyl trichlorosilane alone, the method for producing the functional fabric uses tetrachlorosilane and fluoroalkyl trichlorosilane to treat the fabric in one bath, so that the fluorine-containing polysiloxane coating with a roughened appearance is generated on the surface of the treated fiber, and the coating not only is oleophobic, but also has super-hydrophobicity and self-cleaning functions.

2. The treatment method disclosed by the invention can ensure that spherical nano particles are generated on the surface of the fiber in situ during fabric treatment, the spherical shape of the particles in the coating ensures good mechanical property and mechanical property of the coating, and the coating has durability.

Drawings

FIG. 1 is a composite flexible material structure with oil-proof, dirt-proof and self-cleaning functions according to the present invention;

FIG. 2 is a process for in-situ polymerization of silane on the fiber surface of the oil-proof stain-resistant self-cleaning fabric according to the invention;

FIG. 3 is a surface morphology and energy spectrum test chart of the oil-repellent, stain-resistant and self-cleaning fabric prepared according to the first embodiment of the invention. Wherein, the left image is an SEM image magnified 2000 times, and the surface of the fiber is completely covered with a layer of coating consisting of spherical particles; the right graph is an energy spectrum test graph of the nano particles in the coating, and the measured spherical particle elements comprise C, O, F and Si, and the elements confirm that the surface of the polysiloxane spherical particle is covered with the fluoroalkyl;

FIG. 4 is a 2000 SEM image magnification of functional fabrics made according to example two, example three, example four, example five, example six and example seven of the present invention, wherein the inset is a 5000 SEM image magnification;

fig. 5 is an SEM image of functional fabrics prepared according to comparative example one, comparative example two and comparative example three of the present invention at 2000 x magnification. The functional fabric obtained by treating the fluorine-containing alkyl trichlorosilane alone can be seen, and a smooth coating film is covered on the fiber surface of the functional fabric; the insets are water contact angle test graphs of the functional fabrics prepared in the first comparative example, the second comparative example and the third comparative example;

FIG. 6 is a self-cleaning diagram of the functional fabric prepared by the present invention. Wherein (a) - (c) are self-cleaning diagrams of the functional fabrics prepared in the first, second and third comparative examples, and it can be seen that the dirt on the surface of the treated fabric can not leave with water and has no self-cleaning function; (d) the self-cleaning drawings of the functional fabrics prepared in the first embodiment, the sixth embodiment and the seventh embodiment of the invention show that the dirt on the surface of the fabric can be washed away with water, and the fabric has a self-cleaning function;

fig. 7 is a test chart of the contact angle of the functional fabric to tetradecane, which is 39.5 ° and is oleophilic, prepared in example ten of the present invention;

FIG. 8 is a schematic structural view of the oil-repellent, stain-resistant, and self-cleaning functional composite flexible material according to the embodiment.

Detailed Description

The invention discloses a preparation method of the oil-proof antifouling self-cleaning functional composite flexible material, which comprises the following steps:

(1) pretreatment of the fabric: soaking a base fabric in water until the base fabric is completely wetted, carrying out mangling, and then placing the base fabric in a natural environment to control the water content of the fabric;

(2) preparing a working solution: adding a certain amount of organic solvent into a container with a stirring device, then adding a certain amount of tetrachlorosilane and fluoroalkyl trichlorosilane, and fully stirring and dissolving;

(3) in-situ polymerization coating: putting the fabric with water into a container, starting stirring, controlling the stirring speed, stopping the reaction after reacting for a certain time at room temperature, and stopping stirring;

(4) and (3) post-treatment: taking out the fabric from the container, washing the fabric with a certain amount of organic solvent, finally putting the fabric into an oven for drying, and obtaining the oil-proof antifouling self-cleaning fabric after drying is finished;

(5) bonding the oil-proof antifouling self-cleaning fabric with a base film to obtain an oil-proof antifouling self-cleaning functional composite flexible material; the structure is shown in figure 1, and the base film is positioned on one side surface of the oil-proof and anti-fouling self-cleaning fabric.

In the technical scheme provided by the invention, the preparation principle of the disclosed oil-proof antifouling self-cleaning fabric is as follows: controlling the concentration of tetrachlorosilane in the treatment liquid to be 0.05-0.3% (mass concentration), and the concentration of fluoroalkyl trichlorosilane to be 0.1-0.5% (mass concentration); this ensures that the tetrachlorosilane bonds to the fiber surface and polymerizes to aggregate into a core, which then continues to grow from the fluoroalkyltrichlorosilane on the core surface (see FIG. 2). The weight ratio of the base fabric to the working solution is 1: 45-55, the outer layer of spherical particles generated in situ on the fiber surface in the processed fabric is completely wrapped by the fluoroalkyl to form a protective layer with extremely low surface energy, so that the processed fabric can have excellent liquid repellent function, super-hydrophobic function and self-cleaning function. The silane generates covalent bonding when reacting with the fiber surface, so that the generated spherical nano particles are firmly adsorbed on the fiber surface, thereby having durability.

The raw materials involved in the invention are all commercial products, the involved test method is a conventional test method, and the same cotton fabrics are adopted in the embodiment; the technical solution of the present invention is further described with reference to the accompanying drawings and examples.