阅读说明：本技术 一种无氟环保防水透气面料的制备方法 (Preparation method of fluoride-free environment-friendly waterproof breathable fabric ) 是由 吕维扬 孙继安 姚玉元 王金辉 甄建政 王燕 于 2020-11-21 设计创作，主要内容包括：本发明公开了一种防水透气面料的制备方法,具体为：在不同缓冲液条件下,将盐酸多巴胺与缓冲液混合形成稳定的盐酸多巴胺自聚体系；将面料浸入盐酸多巴胺自聚体系中,在面料表面形成纳米级薄层聚多巴胺；最后通过添加含胺低表面能物质与聚多巴胺产生反应,将含胺低表面能物质覆盖在面料表面,赋予面料防水的特性,而且面料表面形成的疏水改性层厚度调控方便,能够很好地保留面料的多孔结构。该方法反应条件温和、简单易行、耗时短、绿色无污染,合成的防水透气面料防水表面稳定、透气性良好。(The invention discloses a preparation method of a waterproof breathable fabric, which comprises the following steps: under the conditions of different buffers, dopamine hydrochloride and the buffers are mixed to form a stable dopamine hydrochloride self-polymerization system; immersing the fabric into a dopamine hydrochloride self-polymerization system to form a nano-scale thin-layer polydopamine on the surface of the fabric; and finally, amine-containing low-surface-energy substances are added to react with polydopamine, so that the amine-containing low-surface-energy substances cover the surface of the fabric, the fabric is endowed with waterproof property, the thickness of a hydrophobic modified layer formed on the surface of the fabric is convenient to regulate and control, and the porous structure of the fabric can be well maintained. The method has the advantages of mild reaction conditions, simplicity, practicability, short time consumption, greenness, no pollution, stable waterproof surface and good air permeability of the synthesized waterproof breathable fabric.)

1. A preparation method of a fluorine-free environment-friendly waterproof breathable fabric is characterized by comprising the following steps:

(1) dissolving dopamine hydrochloride in different buffer solutions with the pH value adjusted to 8.5 to obtain different dopamine hydrochloride self-polymerization systems;

(2) soaking the cleaned fabric into different dopamine hydrochloride self-polymerization systems, mixing and reacting for 1-6 h at 25-60 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain a polydopamine deposited fabric;

(3) and (3) uniformly mixing an amine-containing low-surface-energy substance with a hydroalcoholic solution, soaking the fabric deposited with the polydopamine obtained in the step (2) into the mixture, and mixing and reacting at the temperature of 25-60 ℃ for 6-12 hours to obtain the waterproof breathable fabric.

2. The preparation method of the fluorine-free environment-friendly waterproof breathable fabric according to claim 1, wherein the fabric is one of grey cloth, cotton cloth, silk cloth, wool cloth, polyester, spandex and aramid, the fabric structure of the fabric is one of knitted fabric, woven fabric and non-woven fabric, and the thickness of the fabric is 0.025 mm-0.1 mm;

the mass concentration of the dopamine hydrochloride in the total deionized water is 500-5000 mg/L;

the mass concentration of the buffer substances in the buffer solution in the total deionized water is 300-2500 mg/L;

the volume ratio of the amine-containing low surface energy substance to the hydroalcoholic solution is 1: 6.5-20;

the volume ratio of the hydroalcoholic solution is 1: 1-24;

the total deionized water is the sum of the deionized water used in the step (1);

the hydroalcoholic solution is the sum of the hydroalcoholic solutions used in the step (3).

3. The method for preparing the fluoride-free environment-friendly waterproof breathable fabric according to claim 2, wherein the buffer solution is Tris buffer solution, phosphate buffer solution and bicarbonate buffer solution.

4. The method for preparing the fluorine-free environment-friendly waterproof breathable fabric according to claim 2, wherein the amine-containing low surface energy substance is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl-gamma-aminopropyl) methyldimethoxysilane, N- (beta-aminoethyl-gamma-aminopropyl) trimethoxysilane, diethylenetriaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-diethylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N-butylaminopropyltrimethoxysilane or stearylamine.

5. The preparation method of the fluorine-free environment-friendly waterproof breathable fabric according to claim 2, wherein the component alcohol in the hydroalcoholic solution is one of ethanol, n-propanol, n-butanol, 1-pentanol and n-hexanol.

6. The method for preparing the waterproof and breathable fabric according to any one of claims 1 to 5, wherein,

the mass concentration of the dopamine hydrochloride in the total deionized water is 1000-5000 mg/L;

the mass concentration of the buffer substances in the buffer solution in the total deionized water is 600-1800 mg/L;

the volume ratio of the amine-containing low surface energy substance to the hydroalcoholic solution is 1: 8-15;

the volume ratio of the hydroalcoholic solution is 1: 6-12.

7. The method for preparing the fluorine-free environment-friendly waterproof breathable fabric according to claim 3,

tris in the Tris buffer solution is Tris (hydroxymethyl) aminomethane;

the phosphate in the phosphate buffer solution is KH₂PO₄、Na₂HPO₄、Na₂HPO₄·12H₂O、K₂PO₄One kind of (1).

The bicarbonate in the bicarbonate buffer solution is NaHCO₃。

8. The preparation method of the fluorine-free environment-friendly waterproof breathable fabric according to claim 1, wherein in the step (2), the temperature of the water bath reaction is 25-55 ℃, and the reaction time is 1-5 hours; in the step (3), the temperature of the water bath reaction is 25-45 ℃, and the reaction time is 6-12 h.

Technical Field

The invention relates to the technical field of waterproof fabrics, in particular to a preparation method of a waterproof breathable fabric.

Background

With the rapid development of economy and the improvement of the living standard of people, the fabric with the traditional performances of skin-friendly property, flexibility and the like is difficult to meet the needs of people. In order to improve the added value of the fabric, the possibility of applying the fabric in more aspects is explored, the surface of the fabric is endowed with multiple functions, and the fabric has important research and development significance, but the development of the fabric in more fields is limited due to the characteristic that the surface of the fabric is easy to be polluted. Inspired by the lotus leaf effect, the material with the hydrophobic surface has certain self-cleaning capability and is concerned by researchers at home and abroad. Therefore, the research on the waterproof fabric is an effective way to solve the problem that the surface of the waterproof fabric is easy to be polluted, and is gradually becoming a popular research direction.

In the waterproof modification of fabrics, generally adopted coating methods, dipping methods, sol-gel methods and the like are mainly used for loading low-surface-energy substances on the fabrics through the physical combination of van der waals force or hydrogen bond acting force, and the method is simple and convenient to operate, but the mechanical durability and flexibility of products are poor, and the air permeability of the products is also greatly reduced. Based on the above disadvantages, some researchers use a polymer grafting modification method to cause a chain polymerization reaction of a polymer monomer on the surface of the fabric introduced with grafting sites, so as to form a modified fabric with a hydrophobic surface. The fabric and the functional polymer are connected in a chemical bond mode, so that the hydrophobic modified fabric obtained by the method is stable in performance and high in durability, but has the defects of complex operation and narrow applicability. Therefore, a universal and simple method is provided, so that the fabric can keep or improve the air permeability and the comfort level while performing hydrophobic modification, and the method has important application value.

Disclosure of Invention

The invention provides a preparation method of a waterproof breathable fabric, which is characterized in that under the conditions of different buffer solutions, dopamine hydrochloride is self-polymerized to quickly form a nano-scale thin-layer polydopamine on the surface of the fabric, and on the premise of keeping the breathability of the polydopamine, an amine-containing low-surface-energy substance is added to react with the polydopamine to generate Schiff base, so that the amine-containing low-surface-energy substance covers the surface of the fabric, and the fabric is endowed with a waterproof characteristic. The method has the advantages of mild reaction conditions, simplicity, practicability, short time consumption, greenness, no pollution, stable waterproof surface and good air permeability of the synthesized waterproof breathable fabric.

In order to solve the technical problem, the invention aims to realize that:

the invention relates to a preparation method of a fluorine-free environment-friendly waterproof breathable fabric, which comprises the following steps:

(1) dissolving dopamine hydrochloride in different buffer solutions with the pH value adjusted to 8.5 to obtain different dopamine hydrochloride self-polymerization systems;

(2) soaking the cleaned fabric into different dopamine hydrochloride self-polymerization systems, mixing and reacting for 1-6 h at 25-60 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain a polydopamine deposited fabric;

(3) and (3) uniformly mixing an amine-containing low-surface-energy substance with a hydroalcoholic solution, soaking the fabric deposited with the polydopamine obtained in the step (2) into the mixture, and mixing and reacting at the temperature of 25-60 ℃ for 6-12 hours to obtain the waterproof breathable fabric.

Preferably, the fabric is one of grey cloth, cotton cloth, silk cloth, wool cloth, terylene, spandex and aramid fiber, the fabric structure of the fabric is one of knitted fabric, woven fabric and non-woven fabric, and the thickness of the fabric is 0.025 mm-0.1 mm;

the mass concentration of the dopamine hydrochloride in the total deionized water is 500-5000 mg/L;

the mass concentration of the buffer substances in the buffer solution in the total deionized water is 300-2500 mg/L;

the volume ratio of the amine-containing low surface energy substance to the hydroalcoholic solution is 1: 6.5-20;

the volume ratio of the hydroalcoholic solution is 1: 1-24;

the total deionized water is the sum of the deionized water used in the step (1);

the hydroalcoholic solution is the sum of the hydroalcoholic solutions used in the step (3).

Preferably, the buffer is Tris buffer, phosphate buffer and bicarbonate buffer.

Preferably, the amine-containing low surface energy substance is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (beta-aminoethyl-gamma aminopropyl) methyldimethoxysilane, N- (beta-aminoethyl-gamma aminopropyl) trimethoxysilane, diethylenetriaminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-diethylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N-butylaminopropyltrimethoxysilane or stearylamine;

preferably, the component alcohol in the hydroalcoholic solution is one of ethanol, n-propanol, n-butanol, 1-pentanol and n-hexanol.

Preferably, the mass concentration of the dopamine hydrochloride in the total deionized water is 1000-5000 mg/L;

the mass concentration of the buffer substances in the buffer solution in the total deionized water is 600-1800 mg/L;

the volume ratio of the amine-containing low surface energy substance to the hydroalcoholic solution is 1: 8-15;

the volume ratio of the hydroalcoholic solution is 1: 6-12.

Preferably, Tris in the Tris buffer solution is Tris hydroxymethyl aminomethane;

the phosphate in the phosphate buffer solution is KH₂PO₄、Na₂HPO₄、Na₂HPO₄·12H₂O、K₂PO₄One of (1);

the bicarbonate in the bicarbonate buffer solution is NaHCO₃。

Preferably, in the step (2), the temperature of the water bath reaction is 25-55 ℃, and the reaction time is 1-5 h; in the step (3), the temperature of the water bath reaction is 25-45 ℃, and the reaction time is 6-12 h.

Compared with the prior art, the invention has the following advantages:

1. the preparation process of the waterproof breathable fabric is simple and easy to implement, and is green and environment-friendly. In consideration of the toxicity of the fluorine-containing monomer, the amine-containing low surface energy substance selected in the invention not only endows the fabric with waterproof performance, but also is environment-friendly. The poly-dopamine layer deposited on the surface of the fabric is also a biodegradable material.

2. The waterproof fabric has waterproof performance and good air permeability. By changing the conditions of the addition amount of dopamine hydrochloride, the water bath reaction time, the reaction temperature, the type of buffer solution and the like, the thickness and the uniformity of the deposition of the dopamine layer on the surface of the fabric are controlled, and the good air permeability of the fabric is kept.

Drawings

FIG. 1 is a water contact angle diagram of an unmodified fabric;

fig. 2 is a water contact angle diagram of the modified waterproof breathable fabric.

Detailed Description

The invention is further described with reference to the following figures and specific examples.

Example 1:

dissolving 0.2g of dopamine hydrochloride in 100mL of 0.01mol/L Tris buffer solution with the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking the cleaned grey cloth with a certain area into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 3.5mL of 3-aminopropyltriethoxysilane into 50mL of water-alcohol solution (water: ethanol is 1: 8), uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 6 hours at 25 ℃ to obtain the waterproof breathable fabric.

Example 2:

dissolving 0.2g of dopamine hydrochloride in 100mL of 0.01mol/L Tris buffer solution with the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking the cleaned grey cloth with a certain area into the dopamine hydrochloride self-polymerization system, and mixing and reacting for 4 hours at 35 ℃ to form a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 3.5mL of 3-aminopropyltrimethoxysilane into 50mL (water: ethanol is 1: 16) of hydroalcoholic solution, uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 7 hours at 30 ℃ to obtain the waterproof breathable fabric.

Example 3:

dissolving 0.2g of dopamine hydrochloride in 100mL of 0.01mol/L Tris buffer solution with the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking the cleaned grey cloth with a certain area into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 35 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 3.5mL of stearylamine into 50mL of hydro-alcoholic solution (water: ethanol is 1: 24), uniformly mixing, immersing the fabric deposited with the polydopamine in the hydro-alcoholic solution at 35 ℃, and mixing and reacting for 9 hours to obtain the waterproof breathable fabric.

Example 4:

dissolving 0.2g of dopamine hydrochloride in 100mL of KH2PO4 buffer solution with the pH value of 0.02mol/L and the pH value of 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking a certain area of cleaned cotton cloth into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 1.8mL of 3-aminopropyltrimethoxysilane into 50mL (water: ethanol is 1: 16) of hydroalcoholic solution, uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 6 hours at 25 ℃ to obtain the waterproof breathable fabric.

Example 5:

dissolving 0.2g of dopamine hydrochloride in 100mL of K2PO4 buffer solution with the concentration of 0.03mol/L and the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking a certain area of cleaned cotton cloth into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 5mL of 3-aminopropyltriethoxysilane into 50mL of water-alcohol solution (water: ethanol is 1: 8), uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 6 hours at 25 ℃ to obtain the waterproof breathable fabric.

Example 6:

dissolving 0.2g of dopamine hydrochloride in 100mL of NaHCO3 buffer solution with the pH value of 0.02mol/L and adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking a certain area of cleaned cotton cloth into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 5mL of stearylamine into 50mL of hydro-alcoholic solution (water: ethanol is 1: 24), uniformly mixing, immersing the fabric deposited with the polydopamine in the hydro-alcoholic solution at 35 ℃, and mixing and reacting for 9 hours to obtain the waterproof breathable fabric.

Example 7:

dissolving 0.1g of dopamine hydrochloride in 100mL of 0.01mol/L Tris buffer solution with the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking a certain area of cleaned silk cloth into the dopamine hydrochloride self-polymerization system, and carrying out mixing reaction for 2 hours at 35 ℃ to form a stable dopamine layer on the surface of the fabric to obtain the fabric with deposited dopamine;

adding 1.8mL of 3-aminopropyltrimethoxysilane into 50mL (water: n-propanol: 1: 16) of hydroalcoholic solution, uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 7 hours at 30 ℃ to obtain the waterproof and breathable fabric.

Example 8:

dissolving 0.3g of dopamine hydrochloride in 100mL of K2PO4 buffer solution with the concentration of 0.01mol/L and the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking a certain area of cleaned silk cloth into the dopamine hydrochloride self-polymerization system, and carrying out mixing reaction for 3h at 40 ℃ to form a stable dopamine layer on the surface of the fabric to obtain the fabric with deposited dopamine;

adding 5mL of 3-aminopropyltriethoxysilane into 50mL of water-alcohol solution (water: n-butyl alcohol is 1: 8), uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 6 hours at 25 ℃ to obtain the waterproof breathable fabric.

Example 9:

dissolving 0.4g of dopamine hydrochloride in 100mL of NaHCO3 buffer solution with the pH value of 0.01mol/L and being adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking a certain area of cleaned silk cloth into the dopamine hydrochloride self-polymerization system, and carrying out mixing reaction for 4 hours at 45 ℃ to form a stable dopamine layer on the surface of the fabric to obtain the fabric with deposited dopamine;

adding 3.5mL of stearylamine into 50mL of hydro-alcoholic solution (water: n-hexanol: 1: 24), uniformly mixing, immersing the fabric deposited with the polydopamine in the hydro-alcoholic solution at 35 ℃, and mixing and reacting for 9 hours to obtain the waterproof breathable fabric.

Example 10:

dissolving 0.2g of dopamine hydrochloride in 100mL of 0.01mol/L Tris buffer solution with the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking the cleaned wool cloth with a certain area into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 3.5mL of 3-aminopropylmethyldiethoxysilane into 50mL (water: ethanol ═ 1: 24) of hydroalcoholic solution, uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 6 hours at 25 ℃ to obtain the waterproof breathable fabric.

Example 11:

dissolving 0.2g of dopamine hydrochloride in 100mL of 0.01mol/L Na2HPO4 & 12H2O buffer solution with the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking the cleaned wool cloth with a certain area into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 3.5mL of 3-aminopropyltriethoxysilane into 50mL (water: 1-amyl alcohol ═ 1: 24) of hydroalcoholic solution, uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 7 hours at 30 ℃ to obtain the waterproof breathable fabric.

Example 12:

dissolving 0.2g of dopamine hydrochloride in 100mL of NaHCO3 buffer solution with the pH value of 0.01mol/L and being adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

soaking the cleaned wool cloth with a certain area into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable polydopamine layer on the surface of the fabric to obtain the polydopamine-deposited fabric;

adding 3.5mL of 3-diethylaminopropyl trimethoxy silane into 50mL of hydroalcoholic solution (water: ethanol is 1: 24), uniformly mixing, immersing the fabric deposited with polydopamine in the solution, and mixing and reacting for 9 hours at 35 ℃ to obtain the waterproof and breathable fabric.

Comparative example 1:

adding 3.5mL of 3-aminopropyltriethoxysilane into 50mL (water: ethanol ═ 1: 8) of hydroalcoholic solution, uniformly mixing, immersing the cleaned grey cloth with a certain area in the solution, mixing and reacting for 8 hours at 25 ℃, and cleaning with water and ethanol to obtain the required fabric.

Comparative example 2:

dissolving 0.2g of dopamine hydrochloride in 100mL of 0.01mol/L Tris buffer solution with the pH value adjusted to 8.5 to obtain a uniform dopamine hydrochloride self-polymerization system;

and (3) soaking the cleaned grey cloth with a certain area into the dopamine hydrochloride self-polymerization system, mixing and reacting for 3h at 25 ℃, and forming a stable dopamine layer on the surface of the fabric to obtain the required fabric.

The waterproof breathable fabrics prepared in examples 1-12 and comparative example were tested for correlation performance, and the specific performance parameters are shown in table 1.

Table 1: test result of fabric air permeability

By combining the performance evaluation of the waterproof breathable fabrics related to the examples and the comparative examples in the invention with the table 1 and fig. 1 and 2, it can be found that the contact angle between the fabric before modification and the fabric after modification is obviously compared, and better breathability is maintained. By comparison of examples, it can be found that the waterproof effect obtained by modifying the fabric by using the amine-containing low surface energy substance such as 3-aminopropyltriethoxysilane, stearylamine and the like is better than that obtained by using other amine-containing low surface energy substances. Through performance evaluation of the comparative example, the nano-scale thin-layer polydopamine disclosed by the invention can enable an amine-containing low-surface-energy substance to uniformly cover the surface of the fabric, so that the fabric is endowed with waterproof performance, and meanwhile, the waterproof grade of the fabric can be improved, and the air permeability of the fabric can be kept.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.