阅读说明：本技术 一种自清洁汽车内饰复合皮革的制备方法 (Preparation method of self-cleaning automotive interior composite leather ) 是由 刘澍 于 2019-10-25 设计创作，主要内容包括：一种自清洁汽车内饰复合皮革的制备方法,包括交联型聚硅氧烷杂化材料的制备、复合皮革的制备；所述交联型聚硅氧烷杂化材料的制备,包括如下步骤：(1)聚氨丙基/甲基倍半硅氧烷纳米球的合成、(2)疏水性交联聚硅氧烷的合成、(3)杂化交联聚硅氧烷乳液的制备。本发明所述的自清洁汽车内饰复合皮革的制备方法,制备方法简单,用交联型聚硅氧烷杂化材料通过喷涂法处理皮革表面,充分发挥交联型聚硅氧烷杂化材料的低表面能和交联成膜特性,获得了环保型、耐干擦和透湿性的复合皮革,并且拒水、拒油性从而达到自清洁目的,增加了使用寿命,应用前景广泛。(A preparation method of self-cleaning automotive interior composite leather comprises the steps of preparing a cross-linked polysiloxane hybrid material and preparing the composite leather; the preparation method of the cross-linked polysiloxane hybrid material comprises the following steps: (1) synthesis of polyaminopropyl/methylsilsesquioxane nanospheres, (2) synthesis of hydrophobic cross-linked polysiloxane, and (3) preparation of hybrid cross-linked polysiloxane emulsion. The preparation method of the self-cleaning automotive interior composite leather is simple, the leather surface is treated by the cross-linked polysiloxane hybrid material through a spraying method, the low surface energy and the cross-linked film forming property of the cross-linked polysiloxane hybrid material are fully exerted, the environment-friendly, dry-wiping-resistant and moisture-permeable composite leather is obtained, and the water and oil repellency is realized, so that the self-cleaning purpose is achieved, the service life is prolonged, and the application prospect is wide.)

1. A preparation method of self-cleaning automotive interior composite leather is characterized by comprising the steps of preparing a cross-linked polysiloxane hybrid material and preparing the composite leather; the preparation method of the cross-linked polysiloxane hybrid material comprises the following steps:

(1) the synthesis of the polyaminopropyl/methyl silsesquioxane nanospheres comprises the steps of adding deionized water, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether and NaOH into a reactor, stirring for 0.5 ~ 1h at room temperature, then dropwise adding a mixed monomer of methyl triethoxysilane and gamma-aminopropyl triethoxysilane into the system, and reacting for 20 ~ 24h under heat preservation after dropwise adding to obtain a mixed emulsion;

(2) synthesizing hydrophobic cross-linked polysiloxane, namely adding octamethylcyclotetrasiloxane, methyltriethoxysilane and tetramethyltetravinylcyclotetrasiloxane into a reactor, fully stirring to obtain a silicon hydroxyl-terminated vinyl side group polysiloxane intermediate, continuously adding hydrogenated silicone oil and an isopropanol solvent, starting to dropwise add a catalyst after fully stirring uniformly, reacting for 3 ~ 4h, and removing the solvent to obtain the hydrophobic cross-linked polysiloxane;

(3) and (2) preparing the hybrid cross-linked polysiloxane emulsion, namely adding the polyaminopropyl/methyl silsesquioxane nanospheres, the hydrophobic cross-linked polysiloxane, the PAMSQ and the composite emulsifier into a reactor at room temperature, fully and uniformly stirring, then dropwise adding deionized water, and adjusting the pH value to 6 ~ 6.5.5 to obtain the hybrid cross-linked polysiloxane emulsion.

2. The method for preparing self-cleaning automotive interior composite leather according to claim 1, wherein the preparation of the composite leather comprises the following steps:

(1) pretreatment: the surface of the leather is lightly wiped by using the cleansing liquid;

(2) and (3) spraying, namely diluting the hybrid cross-linked polysiloxane emulsion to a dispersion liquid with the solid content of 0.6 percent ~ 1.2.2 percent, respectively spraying the leather twice in the longitudinal direction and the transverse direction by using spraying equipment, and drying to obtain the composite leather.

3. The preparation method of the self-cleaning automotive interior composite leather according to claim 1, wherein the mass ratio of the sodium dodecyl sulfate to the fatty alcohol-polyoxyethylene ether in the step (1) is 1: 1.

4. the method for preparing self-cleaning composite leather for automobile interiors according to claim 1, wherein the washing in step (1) is 2 times by sequentially washing with 95% ethanol and distilled water.

5. The preparation method of the self-cleaning automotive interior composite leather according to claim 1, wherein the step (2) further comprises the following steps of adding octamethylcyclotetrasiloxane, methyltriethoxysilane and tetramethyltetravinylcyclotetrasiloxane into a reactor, fully stirring, introducing nitrogen for 10 ~ 30min, heating to 90 ~ 100 ℃, adding a catalyst for reaction for 0.5 ~ 1h, continuing heating to 110 ℃, keeping the temperature for reaction for 5 ~ 6h, heating to 140 ~ 150 ℃ after the reaction is finished, decomposing the catalyst, and then distilling under reduced pressure to remove low-boiling-point substances to obtain the intermediate of the silicon hydroxyl terminated vinyl side group polysiloxane.

6. The method for preparing self-cleaning composite leather for automobile interiors according to claim 4, wherein the catalyst is tetramethylammonium hydroxide.

7. The method for preparing self-cleaning composite leather for automobile interiors according to claim 4, wherein the catalyst in step (2) is chloroplatinic acid.

8. The method for preparing self-cleaning composite leather for automotive interiors according to claim 2, wherein the cleansing liquid in step (1) is a mixture of ammonia, absolute ethyl alcohol and water.

9. The method for preparing self-cleaning automotive interior composite leather according to claim 2, wherein the drying treatment is drying at 80 ℃.

Technical Field

The invention belongs to the technical field of leather preparation, and particularly relates to a preparation method of self-cleaning automotive interior composite leather.

Background

With the continuous progress of human society, automobiles are more and more entered into the lives of people, and China has become the first automobile production country and the largest automobile consumption country all over the world. As the overall quality gap between different brands of automobiles diminishes, the key to gaining the market is not the quality of the automobile anymore but the technological level of the interior trim of the automobile. Most of the time when people and vehicles are in the vehicles, the comfort, the practicability and the design level of the automotive interior become key factors for determining the sales volume of the automobiles.

Today's automotive interior styles and culture, design, modularity, new technology safety and comfort, sustainable component technology, etc., have turned into the most direct competitiveness of automotive manufacturers. The interior product represents the image of the whole automobile, determines the reputation and the grade of the automobile, determines the intention of people to select the car, plays the functions of vibration reduction, heat insulation, sound absorption, sound insulation and the like, and plays an important role in the comfort of the car. Automotive interior has become a very promising independent industry, and is penetrating into people's automobile lives at a rapid speed.

The automobile interior material includes leather, textile, non-woven fabric, linen, flocked fabric, non-woven material and the like. Leather products are popular with people because of their softness, comfort, attractive color, beautiful and fashionable appearance, good air permeability, etc. At present, when leather is used for automotive interior, problems still exist, such as difficult cleaning, dirt resistance, water soaking deformation and the like, the attractiveness of the leather is influenced to a great extent, the service life of the leather is shortened, and the development, popularization and application of leather products are greatly restricted. This is mainly due to the fact that leather has a porous structure, contains a large amount of collagen fibers, and that proteins themselves contain various polar groups, such as-NH₂-COOH, -OH, -NH-, and-CONH-, etc.), which readily form hydrogen bonds with water molecules. Therefore, in order to prolong the service life of the automotive interior leather, increase the industrial added value of the automotive interior leather and improve the grade of the automotive interior leather, research and development of the self-cleaning automotive interior composite leather are needed.

Chinese patent application No. cn201410711207.x discloses a production process of automotive interior leather, which is to treat the surface of leather by using an aqueous treating agent so as to reduce the residue of a solvent, remove a peculiar smell, improve the environment and make the cloth surface smoother, but as people have higher and higher requirements on automotive interiors, the leather used for automotive interiors is required to have excellent self-cleaning properties such as water repellency, oil repellency and the like.

Thereby achieving self-cleaning.

Disclosure of Invention

The purpose of the invention is as follows: in order to overcome the defects, the invention aims to provide a preparation method of the self-cleaning automotive interior composite leather, the preparation method is simple, the environment-friendly, dry-wiping-resistant and moisture-permeable composite leather is prepared, and the water and oil repellency is realized, so that the self-cleaning purpose is achieved, the service life is prolonged, and the application prospect is wide.

The purpose of the invention is realized by the following technical scheme:

a preparation method of self-cleaning automotive interior composite leather is characterized by comprising the steps of preparing a cross-linked polysiloxane hybrid material and preparing the composite leather; the preparation method of the cross-linked polysiloxane hybrid material comprises the following steps:

(1) synthesis of polyaminopropyl/methylsilsesquioxane nanospheres: adding deionized water, sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether and NaOH into a reactor, stirring for 0.5-1 h at room temperature, then dropwise adding a mixed monomer of methyltriethoxysilane and gamma-aminopropyltriethoxysilane into the system, and reacting for 20-24 h under heat preservation after dropwise adding to obtain a mixed emulsion; filtering, washing, drying and grinding the mixed emulsion to obtain the polyaminopropyl/methyl silsesquioxane nanospheres;

(2) synthesis of hydrophobic crosslinked polysiloxane: adding octamethylcyclotetrasiloxane, methyltriethoxysilane and tetramethyltetravinylcyclotetrasiloxane into a reactor, and fully stirring to obtain the silicon hydroxyl-terminated vinyl side group polysiloxane intermediate; continuously adding hydrogen silicone oil and an isopropanol solvent, dropwise adding a catalyst after fully and uniformly stirring, reacting for 3-4 h, and removing the solvent to obtain the hydrophobic cross-linked polysiloxane;

(3) preparation of hybrid cross-linked polysiloxane emulsion: and at room temperature, adding the polyaminopropyl/methyl silsesquioxane nanospheres, the hydrophobic cross-linked polysiloxane, the PAMSQ and the composite emulsifier into a reactor, fully and uniformly stirring, dropwise adding deionized water, and adjusting the pH value to 6-6.5 to obtain the hybrid cross-linked polysiloxane emulsion.

The cross-linking polysiloxane hybrid material is prepared by firstly adopting a hydrolytic condensation method to prepare the nano-scale polyaminopropyl/methyl silsesquioxane nanospheres, the preparation method is simple and convenient, the cost is low, the particle size of the product is controllable, the preparation method is a green process, the polyaminopropyl/methyl silsesquioxane nanospheres have smooth surfaces, good sphericity, monodispersity and strong heat-resistant stability, and can endow leather with a nano-scale rough structure. Then, the hydrophobic comb-structure cross-linked polysiloxane is prepared by alkaline equilibration reaction. Finally, a chemically bonded cross-linked polysiloxane hybrid material is prepared through in-situ condensation between hydrosilation groups, a corresponding hybrid emulsion is prepared, the hybrid emulsion is used as a leather composite coating material, the softness, low surface energy and cross-linking film forming property of cross-linked polysiloxane and the nanoscale effect of polysilsesquioxane nanospheres are fully exerted, and the treated leather surface is endowed with comprehensive properties of super hydrophobicity, water repellency, oil repellency, water vapor permeability, dry rub resistance and the like, so that the aim of self-cleaning is fulfilled.

Further, the preparation method of the self-cleaning automotive interior composite leather comprises the following steps:

(1) pretreatment: the surface of the leather is lightly wiped by using the cleansing liquid;

(2) spraying: and (2) diluting the hybrid cross-linked polysiloxane emulsion to a dispersion liquid with the solid content of 0.6-1.2%, respectively spraying the leather longitudinally and transversely twice by using spraying equipment, and drying to obtain the composite leather.

The invention adopts the spraying method for treatment, and has the advantages of simple method, low cost and strong controllability.

Further, in the preparation method of the self-cleaning automotive interior composite leather, the mass ratio of the sodium dodecyl sulfate to the fatty alcohol-polyoxyethylene ether in the step (1) is 1: 1.

further, in the preparation method of the self-cleaning automotive interior composite leather, the washing in the step (1) is sequentially washed for 2 times by using 95% ethanol and distilled water respectively.

Further, the preparation method of the self-cleaning automotive interior composite leather comprises the step (2) as follows: adding octamethylcyclotetrasiloxane, methyltriethoxysilane and tetramethyltetravinylcyclotetrasiloxane into a reactor, fully stirring, introducing nitrogen for 10-30 min, heating to 90-100 ℃, adding a catalyst for reaction for 0.5-1 h, continuing to heat to 110 ℃, and keeping the temperature for reaction for 5-6 h; and after the reaction is finished, raising the temperature to 140-150 ℃, decomposing the catalyst, and then carrying out reduced pressure distillation to remove low-boiling-point substances to obtain the silicon hydroxyl terminated vinyl side group polysiloxane intermediate.

Further, in the preparation method of the self-cleaning automotive interior composite leather, the catalyst is tetramethylammonium hydroxide.

Further, in the preparation method of the self-cleaning automotive interior composite leather, the catalyst in the step (2) is chloroplatinic acid.

Further, in the preparation method of the self-cleaning automotive interior composite leather, the cleansing liquid in the step (1) is a mixture of ammonia water, absolute ethyl alcohol and water.

Further, in the preparation method of the self-cleaning automotive interior composite leather, the drying treatment is drying at 80 ℃.

Compared with the prior art, the invention has the following beneficial effects:

(1) the preparation method of the self-cleaning automotive interior composite leather is simple and reasonable, the leather surface is treated by the cross-linked polysiloxane hybrid material through a spraying method, the cost is low, the controllability is strong, the softness, the low surface energy and the cross-linked film forming property of the cross-linked polysiloxane and the nanoscale effect of the polysilsesquioxane nanospheres are fully exerted, the comprehensive performances of super hydrophobicity, water repellency, oil repellency, water vapor permeability, dry rub resistance and the like of the treated leather surface are endowed, and the purpose of self-cleaning is achieved

(2) The preparation method of the cross-linking polysiloxane hybrid material is characterized in that a hydrolytic condensation method is adopted to prepare the nano-scale polyaminopropyl/methyl silsesquioxane nanosphere, the preparation method is simple and convenient, the cost is low, the particle size of the product is controllable, the preparation method is a green process, the polyaminopropyl/methyl silsesquioxane nanosphere has smooth surface, good sphericity, monodispersity and strong heat-resistant stability, and can endow the leather surface with a nano-scale rough structure; the chemically bonded cross-linked polysiloxane hybrid material is prepared through in-situ condensation of hydrosilation groups, the cross-linked polysiloxane hybrid material can be directionally arranged on the surface of leather, aminopropyl/methyl silsesquioxane nanospheres are preferentially and uniformly adsorbed on the surface of leather fibers, the nano-scale roughness of a matrix is improved, a layer of compact hydrophobic silicon film is formed on the outermost layer of cross-linked polysiloxane, the surface energy of the matrix is reduced, and the super-hydrophobic leather surface is further obtained.

Detailed Description

The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments and specific experimental data, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.