CN106916529A - A kind of super-hydrophobic leather coating of durability polysilsesquioxane nano hybridization and preparation method thereof - Google Patents

Abstract

The invention relates to a durable polysilsesquioxane nano-hybrid superhydrophobic leather coating and a preparation method thereof. In this method, an anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion is firstly prepared by emulsion polymerization, and then epoxy silane, PCMSQ emulsion and hydrophobic amino silicon are used as building blocks. Yuan, using the strong electrostatic force between the ‑COO‑group on the surface of PCMSQ and the protonated ‑NH ₃ ⁺ in amino silicon to self-assemble layer by layer on the leather surface to construct a durable superhydrophobic hybrid coating, and At the same time, the invention also improves the friction resistance of the superhydrophobic hybrid coating through the action of the epoxy silane and the sheath fiber matrix. The raw materials used in the invention are easy to obtain, the preparation process is simple and feasible, green and environmentally friendly, and a large-area film can be formed. The prepared superhydrophobic coating can not only endow the leather substrate with excellent superhydrophobic performance but also have good friction resistance.

Description

A durable polysilsesquioxane nano-hybrid superhydrophobic leather coating and its preparation method

technical field

The invention belongs to the technical field of leather finishing, and in particular relates to a method for preparing a durable polysilsesquioxane nano-hybrid superhydrophobic leather coating. In the method, a durable polysilsesquioxane is prepared on the leather surface through layer-by-layer self-assembly technology. Semisiloxane nanohybrid superhydrophobic coating.

Background technique

In recent years, superhydrophobic functional leather has become one of the important directions for the development of the leather industry because of its high added value, which can significantly improve the grade of products and market competitiveness. In practice, super-hydrophobic leather not only pursues excellent super-hydrophobic performance, but also has comprehensive functions such as hygienic air permeability, water vapor permeability, wear resistance, wearing comfort, and weather resistance. How to solve the durability, hygienic and air permeability of super-hydrophobic leather puts forward higher requirements for leather-based materials, and is also a technical difficulty in the current research on the preparation of super-hydrophobic leather. Therefore, the development, promotion and application of new leather biomimetic superhydrophobic materials and their supporting processes have important practical significance.

At present, there have been a few reports on the preparation and application of bionic superhydrophobic leather surfaces. Ma Jianzhong's group sprayed hydrophobized nano-SiO ₂ on the leather surface to build a super-hydrophobic leather surface. The static contact angle of water on the surface was as high as 170.3°, but the coating affected the hygiene and air permeability of the leather itself. [Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2015, 472: 21-25]. They also loaded hydrophobic nano-silica on the leather surface through layer-by-layer self-assembly technology to construct a super-hydrophobic coating. However, the poor reactivity of traditional nano-silica resulted in poor friction resistance of the coating [CN201410366284.6]. The Shibi research group of Sichuan University and others used maleic anhydride to copolymerize with natural animal and vegetable oils, and then reacted with dodecafluoroheptanol and stearyl alcohol to prepare a fluorine-containing aqueous copolymer emulsion for leather hydrophobic fatliquor. The research found that the treated leather surface has durability, softness and good super-hydrophobic performance, and the maximum contact angle of water reaches 155°. [Journal of the Society of Leather Technologies and Chemists, 2008, 92(3): 107-113]. In addition, they also used low-temperature plasma technology to polymerize and deposit octamethylcyclotetrasiloxane (D4) on the surface of nubuck leather to prepare superhydrophobic nubuck leather. The maximum static contact angle of water on this surface is 155°, and the rolling angle is lower than 10° [China Leather, 2014, 43(5): 28-34]. However, organic fluorine materials and D4 are not environmentally friendly and have potential harm to the human body. Plasma technology requires special equipment, and has the disadvantages of high cost and difficulty in large-area film formation. The existing super-hydrophobic leather surface preparation technology is still dominated by traditional materials, and there is a lack of high-performance new materials and multi-functional super-hydrophobic leather surface preparation technologies.

As a new type of organic-inorganic hybrid material, polysilsesquioxane (PSQ) nanosphere hybrid material has excellent nano-size effect, easy structure modification and functionalization, thermal stability, physiological inertness and mechanical strength, It is an excellent substitute for traditional inorganic nano-silica materials. However, the research on the application method of polysilsesquioxane (PSQ) in this field is still lacking.

Contents of the invention

The purpose of the present invention is to disclose a method for preparing a durable polysilsesquioxane nano-hybrid superhydrophobic leather coating, and obtain a hygienic, breathable and friction-resistant superhydrophobic coating on the leather surface through layer-by-layer self-assembly. coating.

In order to achieve the above object, technical solution of the present invention is achieved in that way:

A preparation method of durable polysilsesquioxane nano-hybrid superhydrophobic leather coating,

Include the following steps:

Step 1: Add aminosilane and isopropanol with a mass ratio of 5:1 into the reaction kettle, heat to 65°C, and stir for half an hour; add maleic anhydride in 5 batches, and the molar ratio of maleic anhydride to aminosilane is 1.1: 1. After the dropwise addition, keep the temperature for 3 hours, and the reaction is completed, and the carboxylated silane monomer (CTES) is obtained;

Step 2: Add sodium lauryl sulfate, AEO-3, NaOH catalyst and distilled water into the reaction kettle, stir at 15-25°C for 60 minutes; then slowly add methylsilane monomer dropwise at a rate of 20 drops/min, Continue to stir for 1.5-2.5 hours after dropping, then add carboxylated silane monomer (CTES) dropwise at the same dropping speed, and keep warm for 12 hours after dropping to prepare anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion;

Step 3: The solvent is isopropanol, and the epoxy silane bath solution with a mass fraction of 0.5-1% is adjusted to pH 5-6 with hydrochloric acid, sprayed on the leather surface, and dried at room temperature to form a film;

Step 4: Dilute the anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion prepared in step 2 to a solid content of 0.3%-0.7%, and use it to spray the treated product in step 3 For leather samples, dry at 80°C for 10 minutes;

Step 5: The solvent is isopropanol, and the pH of the hydrophobic amino silicon dispersion with a mass fraction of 0.3-1% is adjusted to 6, and the leather sample treated in step 4 is sprayed, and baked at 80°C for 10 minutes; the durability of the leather surface is obtained. Polysilsesquioxane nanohybrid superhydrophobic leather finishing.

In step 1, the aminosilane is selected from one of aminopropyltriethoxysilane (KH550) or aminopropyltrimethoxysilane.

In step 2, the methylsilane monomer is selected from one of methyltriethoxysilane (MTES) or methyltrimethoxysilane (MTMS); the mole of carboxylated silane monomer (CTES) and methylsilane monomer The ratio is 1: 3-10; the mass ratio of the total mass of the two monomers to distilled water is 1: 10-15.

In step 2, the mass ratio of sodium lauryl sulfate and AEO-3 is 1:1, and the mass ratio of the composite emulsifier and distilled water that sodium lauryl sulfate and AEO-3 are formed is 1:80-200, hydrogen The dosage of sodium oxide is 25-100mmol/L.

The prepared anionic narrowly dispersed polycarboxylate/methylsilsesquioxane (PCMSQ) hybrid material has an average particle diameter of 40-150nm and a PDI<0.2.

In Step 3, the epoxy silane is selected from γ-glycidyloxypropyltrimethoxysilane or γ-glycidyloxypropyltriethoxysilane.

In step 3 to step 5, the spraying process is alternately spraying vertically and horizontally on the leather surface, and each spraying is twice.

In Step 5, the viscosity of the hydrophobic amino silicon is 3000-8000mPa·s, the ammonia value is 0.3-0.9mmol/g, and its molecular structure is shown in the following general formula:

;

In the formula: R ₁ =(CH ₂ ) _d CH ₃ , d=9~17; R ₂ =CH ₂ CH ₂ CH ₂ NH ₂ or CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ or CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ N(CH ₃ ) ₂ .

The durable polysilsesquioxane nano-hybrid super-hydrophobic leather coating prepared by the preparation method of the durable polysilsesquioxane nano-hybrid super-hydrophobic leather finishing material.

Compared with prior art, the beneficial effect of the present invention:

1. The present invention has successfully prepared a stable anionic, narrowly dispersed polycarboxy/methylsilsesquioxane nanosphere hybrid emulsion by means of emulsion polymerization. The reaction temperature is room temperature, solvent-free, and no complicated reaction is required equipment;

2. With the help of layer-by-layer self-assembly technology, the present invention uses electrostatic force as the driving force to prepare a polysilsesquioxane nano-hybrid superhydrophobic coating with hygienic, breathable and friction-resistant properties on the leather surface; wherein, the ring The cross-linking effect between oxysilane and leather fiber matrix improves the friction resistance of superhydrophobic coating;

3. The raw materials used in the present invention are easy to obtain, the preparation process is simple and feasible, green and environmentally friendly, and can be used for large-scale film production; the preparation method can be widely applied to various full-grain leathers and suede leathers such as cow leather, sheep leather, and pig leather. surface.

Description of drawings

Fig. 1 is the water contact angle photo (water static contact angle 158.4 °) of the superhydrophobic leather surface that the embodiment 1 of the present invention makes;

Fig. 2 is the water contact angle photo (water static contact angle 156.8 °) of the superhydrophobic leather surface that the embodiment of the present invention 2 makes;

Fig. 3 is the water contact angle photo (water static contact angle 160.1 °) of the superhydrophobic leather surface that the embodiment of the present invention 3 makes;

Fig. 4 is the SEM photo of the polysilsesquioxane hybrid superhydrophobic coating on the leather surface prepared in Example 1 of the present invention.

detailed description

The present invention will be described in further detail below in conjunction with specific implementation example and accompanying drawing, but protection scope of the present invention is not limited to the following:

A preparation method of durable polysilsesquioxane nano-hybrid superhydrophobic leather coating, comprising the following steps:

Step 1: Add aminosilane and isopropanol with a mass ratio of 5:1 into the reaction kettle, heat to 65°C, and stir for half an hour; add maleic anhydride in 5 batches, and the molar ratio of maleic anhydride to aminosilane is 1.1: 1. After the dropwise addition, keep the temperature for 3 hours, and the reaction is completed, and the carboxylated silane monomer (CTES) is obtained;

Step 2: Add sodium lauryl sulfate, AEO-3, NaOH catalyst and distilled water into the reaction kettle, stir at 15-25°C for 60 minutes; then slowly add methylsilane monomer dropwise at a rate of 20 drops/min, Continue to stir for 1.5-2.5 hours after dropping, then add carboxylated silane monomer (CTES) dropwise at the same dropping speed, and keep warm for 12 hours after dropping to prepare anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion;

Step 3: The solvent is isopropanol, and the epoxy silane bath solution with a mass fraction of 0.5-1% is adjusted to pH 5-6 with hydrochloric acid, sprayed on the leather surface, and dried at room temperature to form a film;

Step 4: Dilute the anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion prepared in step 2 to a solid content of 0.3%-0.7%, and use it to spray the treated product in step 3 For leather samples, dry at 80°C for 10 minutes;

Step 5: The solvent is isopropanol, and the pH of the hydrophobic amino silicon dispersion with a mass fraction of 0.3-1% is adjusted to 6, and the leather sample treated in step 4 is sprayed, and baked at 80°C for 10 minutes; the durability of the leather surface is obtained. Polysilsesquioxane nanohybrid superhydrophobic leather finishing.

In step 1, the aminosilane is selected from one of aminopropyltriethoxysilane (KH550) or aminopropyltrimethoxysilane.

In step 2, the methylsilane monomer is selected from one of methyltriethoxysilane or methyltrimethoxysilane; the molar ratio of carboxylated silane monomer (CTES) to methylsilane monomer is 1: 3- 10; the ratio of the total mass of the two monomers to the water mass is 1: 10-15.

In step 2, the mass ratio of sodium lauryl sulfate and AEO-3 is 1:1, and the mass ratio of the composite emulsifier and distilled water that sodium lauryl sulfate and AEO-3 are formed is 1:80-200, hydrogen The dosage of sodium oxide is 25-100mmol/L.

The prepared anionic narrowly dispersed polycarboxylate/methylsilsesquioxane (PCMSQ) hybrid material has an average particle diameter of 40-150nm and a PDI<0.2.

In Step 3, the epoxy silane is selected from γ-glycidyloxypropyltrimethoxysilane or γ-glycidyloxypropyltriethoxysilane.

In step 3 to step 5, the spraying process is alternately spraying vertically and horizontally on the leather surface, and each spraying is twice.

In Step 5, the viscosity of the hydrophobic amino silicon is 3000-8000mPa·s, the ammonia value is 0.3-0.9mmol/g, and its molecular structure is shown in the following general formula:

;

In the formula: R ₁ =(CH ₂ ) _d CH ₃ , d=9~17; R ₂ =CH ₂ CH ₂ CH ₂ NH ₂ or CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ or CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ N(CH ₃ ) ₂ .

Describe several embodiments of the present invention in detail below:

Example 1

(1) Add 20g of KH550 and 4g of isopropanol into the reaction kettle in sequence, heat to 65°C, and stir for 30 minutes. Then, start to add 9.8g maleic anhydride in 5 batches, after the dropwise addition is completed, keep the temperature for 3 hours, and the reaction is completed, and the carboxylated silane monomer (CTES) is obtained;

(2) Accurately weigh 3.8g sodium lauryl sulfate, 3.8g AEO-3, 4.5g NaOH and 1500g distilled water, add them into the reaction kettle, and stir at room temperature (25°C) for 60min. Then, start to slowly add 120g of methylsilane monomer (MTES) dropwise, control the drop rate (20 drops/min), continue to stir for 2.0h after the drop, and then start to drop the carboxyl group prepared in step (1) at the same drop rate Silane monomer (CTES), after dropping, keep warm for 12 hours to prepare anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion (average particle size is 106.9nm, PDI is 0.20);

(3) Spray the surface of cow leather with 0.5% γ-glycidyl etheroxypropyl trimethoxysilane bath solution (solvent isopropanol, adjust pH to about 6 with hydrochloric acid) (dyeing, fatliquoring, drying and finishing ), dried at room temperature to form a film;

(4) Dilute the PCMSQ nanosphere hybrid emulsion prepared in the first step to a solid content of 0.3%-1.0%, and spray it (spray twice vertically and horizontally) on the leather sample treated in the third step. Bake at 80°C for 10 minutes;

(5) Use 0.4% hydrophobic amino silicon (R ₁ = (CH ₂ ) ₁₅ CH ₃ , R ₂ = CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ , viscosity 5800mPa·s, ammonia value 0.4 mmol/g) dispersion (solvent isopropanol, pH about 6) spray the leather sample treated in the fourth step, and bake at 80°C for 10min. Then an environmentally friendly, friction-resistant polysilsesquioxane nano-hybrid superhydrophobic coating was prepared on the leather surface;

Accompanying drawing 1 is the water contact angle photo of the superhydrophobic leather surface that this embodiment makes (water static contact angle is 158.4 °).

Example 2:

(1) Add 20g of aminopropyltrimethoxysilane and 4g of isopropanol into the reaction kettle in sequence, heat to 65°C, and stir for 30min. Then, start to add 12.0 g of maleic anhydride in 5 batches, after the dropwise addition is completed, keep the temperature for 3 hours, and the reaction is completed, and the carboxylated silane monomer (CTES) is obtained;

(2) Accurately weigh 7.4g sodium lauryl sulfate, 7.4g AEO-3, 3.2g NaOH and 1920g distilled water, add them into the reaction kettle, and stir at room temperature (25°C) for 60min. Then, start to slowly add 128g of methylsilane monomer (MTMS) dropwise, control the drop rate (20 drops/min), continue to stir for 2.0h after the drop, and then start to drop the carboxyl group prepared in step (1) at the same drop rate Silane monomer (CTES), after dripping, keep warm for 12 hours to prepare anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion (average particle size is 66.98nm, PDI is 0.181);

(3) Spray the surface of cow leather (dyed, fatliquored, dried) with 0.7% γ-glycidyl etheroxypropyl triethoxysilane bath solution (solvent isopropanol, hydrochloric acid to adjust pH to about 6) Finishing), drying at room temperature to form a film;

(4) Dilute the PCMSQ nanosphere hybrid emulsion prepared in the first step to a solid content of 0.6%, spray it (spray twice vertically and horizontally) on the leather sample treated in the third step, and dry it at 80°C 10min;

(5) Use 0.6% hydrophobic amino silicon (R ₁ =(CH ₂ ) ₉ CH ₃ , R ₂ =C ₃ H ₆ NH ₂ viscosity 4500mPa·s, ammonia value 0.6mmol/g) dispersion ( Solvent isopropanol, pH about 6) Spray the leather sample treated in the fourth step, and bake at 80°C for 10 minutes. Then an environmentally friendly, friction-resistant polysilsesquioxane nano-hybrid superhydrophobic coating was prepared on the leather surface;

Accompanying drawing 2 is the photo of the water contact angle of the surface of the superhydrophobic leather prepared in this embodiment (the water static contact angle is 156.8°).

Example 3:

(1) Add 30g of aminopropyltriethoxysilane and 6g of isopropanol into the reaction kettle in sequence, heat to 65°C, and stir for 30min. Then, start to add 14.6g of maleic anhydride in 5 batches, after the dropwise addition is completed, keep the temperature for 3 hours, and the reaction is completed, and the carboxylated silane monomer (CTES) is obtained;

(2) Accurately weigh 12.3g sodium lauryl sulfate, 12.3g AEO-3, 4.5g NaOH and 2230g distilled water, add them into the reaction kettle, and stir at room temperature (25°C) for 60min. Then, start to slowly add 248.9g of methylsilane monomer (MTES) dropwise, control the drop rate (20 drops/min), continue to stir for 2.0h after the drop, and then start to add dropwise at the same drop rate. Carboxylated silane monomer (CTES), after dropping, keep warm for 12 hours to prepare anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion (average particle size 99.1nm, PDI is 0.150);

(3) Spray the surface of cow leather (dyed, fatliquored, dried and finished) with a bath solution of epoxy silane (solvent isopropanol, hydrochloric acid to adjust pH to about 6) with a mass fraction of 0.85%, and dry at room temperature to form a film;

(4) Dilute the PCMSQ nanosphere hybrid emulsion prepared in the first step to a solid content of 0.5%, spray it (spray twice vertically and horizontally) on the leather sample treated in the third step, and dry it at 80°C 10min;

(5) Use 0.8% hydrophobic amino silicon (R ₁ =(CH ₂ ) ₁₅ CH ₃ , R ₂ = CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ N(CH ₃ ) ₂ , viscosity 6500mPa·s , ammonia value 0.3mmol/g) dispersion solution (solvent isopropanol, pH about 6) spray the leather sample treated in the fourth step, and bake at 80°C for 10min. Then an environmentally friendly, friction-resistant polysilsesquioxane nano-hybrid superhydrophobic coating was prepared on the leather surface;

Accompanying drawing 3 is the photo of the water contact angle of the surface of the superhydrophobic leather prepared in this embodiment (the water static contact angle is 160.1°).

The following table 1 is the various application properties of the superhydrophobic leather made by the superhydrophobic leather coating of the present invention:

Table 1

Summarize the above table, the water static contact angle of the superhydrophobic leather prepared by the superhydrophobic leather coating of the present invention is more than 2 times higher than that of untreated leather before rubbing, and the water static contact angle of superhydrophobic leather is higher than that of untreated leather after 20 times of dry rubbing. The leather has increased by more than 7 times, and its water vapor transmission rate is still excellent on the basis of the above-mentioned improvement.

The content of the present invention is not limited to the examples listed, and any equivalent transformation of the technical solution of the present invention adopted by those of ordinary skill in the art by reading the description of the present invention is covered by the claims of the present invention.

Claims (9)

1. A preparation method for durable polysilsesquioxane nano-hybrid superhydrophobic leather coating, characterized in that: Include the following steps: Step 1: Add aminosilane and isopropanol with a mass ratio of 5:1 into the reaction kettle, heat to 65°C, and stir for half an hour; add maleic anhydride in 5 batches, and the molar ratio of maleic anhydride to aminosilane is 1.1: 1. After the dropwise addition, keep the temperature for 3 hours, and the reaction is completed, and the carboxylated silane monomer (CTES) is obtained; Step 2: Add sodium lauryl sulfate, AEO-3, NaOH catalyst and distilled water into the reaction kettle, stir at 15-25°C for 60 minutes; then slowly add methylsilane monomer dropwise at a rate of 20 drops/min, Continue to stir for 1.5-2.5 hours after dropping, then add carboxylated silane monomer (CTES) dropwise at the same dropping speed, and keep warm for 12 hours after dropping to prepare anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion; Step 3: The solvent is isopropanol, and the epoxy silane bath solution with a mass fraction of 0.5-1% is adjusted to pH 5-6 with hydrochloric acid, sprayed on the leather surface, and dried at room temperature to form a film; Step 4: Dilute the anionic narrowly dispersed polycarboxy/methylsilsesquioxane (PCMSQ) nanosphere hybrid emulsion prepared in step 2 to a solid content of 0.3%-0.7%, and use it to spray the treated product in step 3 For leather samples, dry at 80°C for 10 minutes; Step 5: The solvent is isopropanol, and the pH of the hydrophobic amino silicon dispersion with a mass fraction of 0.3-1% is adjusted to 6, and the leather sample treated in step 4 is sprayed, and baked at 80°C for 10 minutes; the durability of the leather surface is obtained. Polysilsesquioxane nanohybrid superhydrophobic leather finishing. 2. according to the preparation method of the described durable polysilsesquioxane nano-hybrid superhydrophobic leather coating of claim 1, it is characterized in that: In step 1, the aminosilane is selected from one of aminopropyltriethoxysilane (KH550) or aminopropyltrimethoxysilane. 3. according to the preparation method of the described durable polysilsesquioxane nano-hybrid superhydrophobic leather coating of claim 1 or 2, it is characterized in that: In step 2, the methylsilane monomer is selected from one of methyltriethoxysilane (MTES) or methyltrimethoxysilane (MTMS); the mole of carboxylated silane monomer (CTES) and methylsilane monomer The ratio is 1: 3-10; the mass ratio of the total mass of the two monomers to distilled water is 1: 10-15. 4. according to the preparation method of the described durable polysilsesquioxane nano-hybrid superhydrophobic leather coating of claim 3, it is characterized in that: In step 2, the mass ratio of sodium lauryl sulfate and AEO-3 is 1:1, and the mass ratio of the composite emulsifier and distilled water that sodium lauryl sulfate and AEO-3 are formed is 1:80-200, hydrogen The dosage of sodium oxide is 25-100mmol/L. 5. according to the preparation method of the described durable polysilsesquioxane nano-hybrid superhydrophobic leather coating of claim 4, it is characterized in that: The prepared anionic narrowly dispersed polycarboxylate/methylsilsesquioxane (PCMSQ) hybrid material has an average particle size of 40-150nm and a PDI<0.2. 6. according to the preparation method of the described durable polysilsesquioxane nano-hybrid superhydrophobic leather coating of claim 5, it is characterized in that: In Step 3, the epoxy silane is selected from γ-glycidyloxypropyltrimethoxysilane or γ-glycidyloxypropyltriethoxysilane. 7. according to the preparation method of the described durable polysilsesquioxane nano-hybrid superhydrophobic leather coating of claim 6, it is characterized in that: In step 3 to step 5, the spraying process is alternately spraying vertically and horizontally on the leather surface, and each spraying is twice. 8. according to the preparation method of the described durable polysilsesquioxane nano-hybrid superhydrophobic leather coating of claim 7, it is characterized in that: In Step 5, the viscosity of the hydrophobic amino silicon is 3000-8000mPa·s, the ammonia value is 0.3-0.9mmol/g, and its molecular structure is shown in the following general formula: ; In the formula: R ₁ =(CH ₂ ) _d CH ₃ , d=9~17; R ₂ =CH ₂ CH ₂ CH ₂ NH ₂ or CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ or CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ N(CH ₃ ) ₂ . 9. The durable polysilsesquioxane nano-hybrid super-hydrophobic leather coating prepared according to the preparation method of the durable polysilsesquioxane nano-hybrid super-hydrophobic leather finishing material according to any one of the above claims .