阅读说明：本技术 一种表面多孔结构的疏水纺织品制备方法 (Preparation method of hydrophobic textile with surface porous structure ) 是由 任学宏 孔雀 栗志广 于 2020-12-21 设计创作，主要内容包括：本发明公开了一种表面多孔结构的疏水纺织品制备方法,属于纺织品整理技术领域。所述方法是以疏水性或两亲性嵌段共聚物为成膜物质,以挥发性三氯甲烷或二氯甲烷为溶剂,将织物在溶液中浸渍一定时间,然后在一定的浓度和氛围湿度条件下,织物表面呈现微纳米级多孔结构。嵌段共聚物浓度、氛围湿度、溶剂、嵌段共聚物种类等对织物表面多孔形貌的形成发挥了重要作用。本发明得到的具有疏水性能的织物表面形貌易于调节,疏水性能良好,强力不受影响,在自清洁、油水分离、过滤膜等领域有潜在应用。(The invention discloses a preparation method of a hydrophobic textile with a surface porous structure, and belongs to the technical field of textile finishing. The method is characterized in that a hydrophobic or amphiphilic block copolymer is used as a film forming substance, volatile trichloromethane or dichloromethane is used as a solvent, the fabric is soaked in the solution for a certain time, and then the surface of the fabric presents a micro-nano porous structure under the conditions of a certain concentration and atmosphere humidity. The concentration, atmosphere and humidity, solvent, block copolymer types and the like of the block copolymer play an important role in forming the porous appearance on the surface of the fabric. The fabric with the hydrophobic property obtained by the invention has the advantages of easily adjustable surface appearance, good hydrophobic property, unaffected strength and potential application in the fields of self-cleaning, oil-water separation, filtering membranes and the like.)

1. A method for preparing hydrophobic textile, wherein said method comprises dissolving the block copolymer in solvent, make into the solution containing block copolymer, soak the fabric in this solution, then place it in the air or under the humidity condition of 70% -90% until its surface solvent is totally volatilized, get the fabric with hydrophobic performance; the solvent is a volatile organic solvent which is not mutually soluble with water.

2. The method of claim 1, wherein the block copolymer is one of a star-shaped fluorine-containing POSS block copolymer, a tadpole-shaped fluorine-containing POSS block copolymer, a polystyrene block copolymer, a polymethyl methacrylate block copolymer, and a polyethylene glycol amphiphilic block copolymer.

3. The method of claim 1 or 2, wherein the solvent comprises one of chloroform and dichloromethane.

4. The method of any one of claims 1-3, wherein the block copolymer concentration ranges from 10mg/mL to 150 mg/mL.

5. The method according to any one of claims 1 to 4, wherein the fabric is one of cotton fabric, polyester-cotton blend fabric, wool fabric, hemp fabric and silk fabric.

6. A hydrophobic fabric prepared by the method of any one of claims 1 to 5.

7. A finishing liquor characterized in that the finishing liquor comprises a block copolymer and a solvent; the solvent is a volatile organic solvent which is not mutually soluble with water; the concentration of the block copolymer ranges from 10mg/mL to 150 mg/mL.

8. A hydrophobic finish, characterized in that it consists in immersing the fabric in a finish according to claim 7, and then in air or at a humidity of between 70% and 90% until the solvent on the surface has evaporated completely.

9. The method according to claim 8, wherein the mass to volume ratio of the fabric to the finishing liquor is 1:20-80 in g/mL.

10. A method according to claim 8 or 9, characterized in that the immersion time is 5-30 min.

Technical Field

The invention relates to a preparation method of a hydrophobic textile with a porous surface structure, and belongs to the technical field of textile finishing.

Background

The hydrophobic material is designed bionically for the structure and the function of the lotus leaf surface, the contact angle on the surface of the hydrophobic material is larger than 90 degrees, the contact angle on the surface of the super-hydrophobic material is larger than 150 degrees, water drops are difficult to spread or wet on the surface of the super-hydrophobic material, and the hydrophobic material has wide application prospects in the fields of textiles, automotive interior, buildings and the like. The preparation and performance research of the super-hydrophobic material has become a research hotspot in the fields of chemistry and materials. In recent years, the super-hydrophobic textile with antifouling, self-cleaning and ventilating functions has wide prospects in the aspects of sportswear, combat uniform, down jacket, medical protective clothing and the like.

The finishing mode of the super-hydrophobic fabric mostly adopts a roll baking method, wherein the baking temperature is 140-200 ℃. The performance of the finished fabric is damaged due to the fact that the finishing auxiliary agent is attached to the surface of the finished fabric, so that the problem that how to reduce the finishing temperature of the super-hydrophobic fabric is solved, and the performance of the finished fabric cannot be greatly reduced becomes the bottleneck problem of the research.

Disclosure of Invention

Aiming at the defects that the finishing temperature of the prior hydrophobic fabric is too high, the performance of the finished fabric is reduced and the self-cleaning performance is difficult to meet the requirements, the invention aims to provide the preparation method of the super-hydrophobic porous fabric, which has mild reaction conditions, simple operation and reduced steps. The method is simple and easy to implement, the porous appearance of the fabric surface can be controlled and regulated, and the hydrophobic property is excellent.

The first object of the present invention is to provide a method for preparing a hydrophobic textile, which comprises dissolving a block copolymer in a solvent to prepare a solution containing the block copolymer, immersing a fabric in the solution, and then placing the fabric in the air or under a certain humidity until the solvent on the surface of the fabric is completely volatilized to obtain the fabric with hydrophobic property; the solvent is a volatile organic solvent which is not mutually soluble with water.

In one embodiment of the present invention, the fabric is one of cotton fabric, polyester-cotton blended fabric, wool fabric, hemp fabric and silk fabric.

In one embodiment of the present invention, the block copolymer is one of a star-type fluorine-containing POSS block copolymer, a tadpole-type fluorine-containing POSS block copolymer, a polystyrene block copolymer, a polymethyl methacrylate block copolymer, and a polyethylene glycol amphiphilic block copolymer.

In one embodiment of the invention, the molecular weight of the block copolymer is between 10000-100000 and the molecular weight distribution is < 1.5.

In one embodiment of the present invention, the solvent comprises one of chloroform and dichloromethane.

In one embodiment of the invention, the concentration of the block copolymer ranges from 10mg/mL to 150 mg/mL.

In one embodiment of the invention, the humidity range is 70% to 90%.

The second purpose of the invention is to provide a hydrophobic fabric prepared by the method. The porous pore diameter range of the fabric surface is 0.1-10 μm.

A third object of the present invention is to provide a finishing liquor comprising a block copolymer and a solvent; the solvent is a volatile organic solvent which is not mutually soluble with water.

In one embodiment of the present invention, the block copolymer is one of a star-type fluorine-containing POSS block copolymer, a tadpole-type fluorine-containing POSS block copolymer, a polystyrene block copolymer, a polymethyl methacrylate block copolymer, and a polyethylene glycol amphiphilic block copolymer.

In one embodiment of the invention, the concentration of the block copolymer ranges from 10mg/mL to 150 mg/mL.

In one embodiment of the present invention, the solvent comprises one of chloroform and dichloromethane.

The fourth purpose of the invention is to provide a hydrophobic finishing method, which is to immerse the fabric in the finishing liquid and then place the fabric in the air or under a certain humidity until the surface solvent is completely volatilized.

In one embodiment of the present invention, the fabric is one of cotton fabric, polyester-cotton blended fabric, wool fabric, hemp fabric and silk fabric.

In one embodiment of the invention, the humidity range is 70% to 90%.

In one embodiment of the invention, the immersion time is 5-30 min.

In one embodiment of the invention, the mass to volume ratio of fabric to finishing liquor is 1:20-80 in g/mL.

The invention has the beneficial effects that:

according to the invention, the textile fabric is taken as a substrate, the hydrophobic or amphiphilic block copolymer is arranged on the textile fabric, the block copolymer presents a porous structure on the surface of the textile fabric, the surface roughness is improved, the surface energy is reduced, and the textile fabric achieves the hydrophobic effect. The solvent is easy to volatilize and is immiscible with water, the solvent is quickly volatilized to generate a certain temperature gradient in the film forming process, the surface temperature of the polymer solution is sharply reduced to cause the condensation of water vapor in a high-humidity environment, and small liquid drops with the diameter of nanometer level are formed on the surface of the solution. And (3) as the volatilization-condensation process continues, the liquid drops grow and self-assemble to form an ordered array, the liquid drops are coated by the polymer to avoid the coalescence of the liquid drops, and when the solvent and the water are completely volatilized, a porous structure is formed on the surface of the fabric.

The invention uses block copolymer to prepare solution with certain concentration, and uses fabric as substrate to prepare textile fabric with porous structure, to make the surface reach super-hydrophobic property. According to the invention, the molecular weight of the polymer, the concentration of the solution, the atmosphere and humidity and the like are regulated, so that the pore size and the distribution of the pores on the surface of the fabric can be regulated, the contact angle is higher than 150 degrees, and the super-hydrophobic property is achieved. The method is simple and easy to implement, can be completed within a few minutes at normal temperature, and the obtained porous structure is regular and can be used for quickly preparing the super-hydrophobic fabric. The fabric with the porous structure prepared by the method disclosed by the invention is excellent in super-hydrophobic property and has potential application in the fields of self-cleaning, oil-water separation, filtering membranes and the like.

Drawings

FIG. 1: SEM image of cotton fabric with porous structure

FIG. 2: SEM image of cotton fabric with smooth surface structure.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

Example 1: method for preparing hydrophobic cotton fabric

0.090g of POSS block copolymer containing fluorine POSS- (PTFEMA)₈(molecular weight 13500) was dissolved in 1mL of chloroform (CHCl)₃) Preparing a solution. And completely soaking the cotton fabric in the solution, taking out the cotton fabric after 10min, immediately placing the cotton fabric in an atmosphere with the humidity of 90%, and completely volatilizing the solvent and water on the surface of the cotton fabric to obtain the cotton fabric with a porous structure. Its contact angle with water was 154.0 °.

Referring to fig. 1, the cotton fabric having a porous structure prepared in this example. The solvent selected by the invention is easy to volatilize and is immiscible with water, the solvent is quickly volatilized to generate a certain temperature gradient in the film forming process, the surface temperature of the polymer solution is rapidly reduced to cause the condensation of water vapor in a high-humidity environment, and small liquid drops with the diameter of nanometer level are formed on the surface of the solution. And (3) as the volatilization-condensation process continues, the liquid drops grow and self-assemble to form an ordered array, the liquid drops are coated by the polymer to avoid the coalescence of the liquid drops, and when the solvent and the water are completely volatilized, a porous structure is formed on the surface of the fabric.

Example 2: method for preparing hydrophobic cotton fabric

The hydrophobic cotton fabric was prepared by referring to the method of example 1 except that the addition amounts of the fluorine-containing block copolymer in example 1 were adjusted to 0.010g, 0.030g, 0.045g, 0.060g, 0.120g and 0.150g, respectively, so that the concentrations of the fluorine-containing block copolymer were 10mg/mL, 30mg/mL, 45mg/mL, 60mg/mL, 120mg/mL and 150mg/mL, respectively. The other conditions or parameters were in accordance with example 1. The contact angle, strength and air permeability of the prepared cotton fabric are shown in table 1. This shows that the concentration of the fluorine-containing POSS block copolymer has great effect on improving the surface hydrophobicity of cotton fabrics, the strength is basically kept unchanged and slightly improved, and the air permeability is reduced along with the increase of the concentration.

TABLE 1

Example 3: method for preparing hydrophobic cotton fabric

A hydrophobic cotton fabric was prepared with reference to the method of example 1 except that the humidity in example 1 was changed to 50%, 70%, and 100%, and other conditions or parameters were identical to example 1. The cellulose membrane can not form a regular porous structure when the humidity is 50% and 100%, and when the humidity is 70%, the contact angle of the cellulose membrane is 142.6 degrees, the strength is 607N, and the air permeability is 128mm · s^-1。

Example 4: method for preparing hydrophobic cotton fabric

0.090g of POSS block copolymer containing fluorine POSS- (PTFEMA)₈(molecular weight 13500) was dissolved in 1mL of chloroform (CHCl)₃) Preparing a solution. Completely soaking cotton fabric in the solution, taking out after 10min, placing in the air, and naturally volatilizing the solvent on the surface of the cotton fabric to obtain the cotton fabric with smooth surface, wherein the surface SEM image is shown in figure 2. The contact angle of the fabric to water is 138.9 degrees, which shows that the porous structure of the fabric surface plays an important role in improving the hydrophobic property of the fabric.

Comparative example 1:

the process of example 1 was followed except that chloroform was replaced with N, N-dimethylformamide and the other conditions were the same as in example 1. The results show that: the surface of the fabric is not formed with a porous structure.

Comparative example 2:

the process of example 1 is referred to with the only difference that chloroform is replaced by tetrahydrofuran and the other conditions are the same as in example 1. The results show that: the fabric surface cannot form a regular porous structure.

Comparative example 3:

the process of example 1 was followed except that the fluorinated POSS block copolymer was replaced with polyethylene glycol under the same conditions as in example 1. The results show that: the surface of the fabric is not formed with a porous structure.

TABLE 2

As can be seen from the data in tables 1 and 2, the hydrophobicity of the fabric surface has a great relationship with the concentration of the block copolymer, the atmosphere humidity and the like, and the porous structure of the fabric surface is formed in relation to the atmosphere humidity, the solvent and the copolymer type. The strength is slightly improved, and the fiber is not damaged. The air permeability is reduced to a certain extent, and is better than that of a directly film-formed fabric due to the porous structure of the surface.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.