CN113174049B - Modified organic polysilazane modified based on long-chain alkyl compound and preparation method and application thereof - Google Patents

Abstract

The invention discloses a modified organic polysilazane modified based on a long-chain alkyl compound and a preparation method and application thereof. The preparation method comprises the following steps: under the protection of inert gas, alcohol monomers and diisocyanate monomers are uniformly mixed, and after a catalyst is added, the mixture reacts for 2 to 12 hours at the temperature of between 30 and 90 ℃ to obtain a long-chain alkyl compound containing 2 to 50 carbon atoms; the synthesized modified long-chain alkyl compound and the organic polysilazane are uniformly mixed and react for 1 to 8 hours at the temperature of between 20 and 60 ℃ to obtain the long-chain alkyl compound modified organic polysilazane. The modified organic polysilazane prepared by the invention not only has lower surface energy, but also keeps the excellent anchoring characteristic of polysilazane, can be firmly adhered to different types of substrates, and greatly simplifies the process for constructing the easy-to-clean coating. The modified organic polysilazane coating and the modified organic polysilazane/micro-nano material composite coating prepared by the method have the advantages of good hydrophobic property, easy cleaning property, chemical resistance, wear resistance and weather resistance, and show excellent durability.

Description

Modified organopolysilazane modified by long-chain alkyl compounds and preparation method thereof with application

technical field

The invention relates to a modified polysilazane, in particular to a modified organic polysilazane modified by long-chain alkyl compounds, a preparation method and application thereof, and belongs to the technical field of surface modification and coating preparation.

Background technique

其中，n为聚合度，R₁、R₂和R₃均为侧链取代基，一般为氢原子、甲基或其它有机基团。根据R₁、R₂和R₃基团的不同，聚硅氮烷具有不同的大分子结构和性能特征。聚硅氮烷主要分为两类：若侧链取代基全部都为氢原子时，则为全氢聚硅氮烷，也称为无机聚硅氮烷(PHPS)；若部分或全部氢原子被有机基团取代，则称其为有机聚硅氮烷(OPSZ)。Polysilazane is a polymer in which Si atoms and N atoms are alternately connected by covalent bonds to form a basic skeleton. The general formula is:

Wherein, n is the degree of polymerization, and R ₁ , R ₂ and R ₃ are all side chain substituents, generally hydrogen atoms, methyl groups or other organic groups. Depending on the R ₁ , R ₂ and R ₃ groups, polysilazane has different macromolecular structures and performance characteristics. Polysilazane is mainly divided into two categories: if all the side chain substituents are hydrogen atoms, it is perhydropolysilazane, also known as inorganic polysilazane (PHPS); if some or all of the hydrogen atoms are If the organic group is substituted, it is called organopolysilazane (OPSZ).

Polysilazane has high reactivity, and its molecular structure contains a large number of active Si-H and Si-N bonds, which are prone to hydrolysis to generate structurally unstable silanols, which can further undergo hydrolysis to form stable, hydrophobic The -Si-O-Si- structure. Polysilazane is very soluble in organic solvents; especially important, it has excellent anchoring effect on most substrates, which makes the cured polysilazane coating more adhesion to the substrate. High, can be used to build coatings with excellent heat resistance, chemical resistance, weather resistance, scratch resistance, transparency, etc., thus giving polysilazane coatings better performance and longer life. service life. Therefore, by appropriately modifying polysilazane by its reactivity and giving it functional properties, it can be applied to construct coatings with special properties or functions.

At present, there have been studies on the application of hydrophobically modified organopolysilazane in the field of hydrophobic coatings. Chinese invention patent application CN 105385349 A discloses a hydrophobic antifouling organic polysilazane coating and a preparation method thereof. The method uses perfluoroalkyl ethyl allyl ether to hydrophobically modify organopolysilazane through hydrosilylation reaction, and prepares a hydrophobic self-cleaning coating with better performance. However, the synthesis reaction system of the fluoride perfluoroalkyl ethyl allyl ether used in the method is complicated, the product needs to be purified, the process is cumbersome, and the synthesis cost is high; in addition, perfluoroalkyl ethyl allyl The hydrosilylation reaction between the base ether and the organopolysilazane must be carried out in the presence of a catalyst, and the catalyst remaining in the product is difficult to remove, which will have a certain impact on the performance of the product. On the other hand, some studies have found that fluorine-containing compounds are bioaccumulative and persistent, and have potential hazards to the environment and human health. These factors must hinder its practical application to some extent.

Chinese invention patent CN 105542658 A discloses an anti-fouling and anti-graffiti organic polysilazane coating and its preparation method and application. The method uses organopolysilazane, hydroxysilicone oil and diisocyanate as raw materials, and in the presence of a catalyst, under certain conditions, an organopolysilazane prepolymer is prepared through a two-step reaction; The antifouling and antigraffiti organopolysilazane coating is prepared by preparing the polymer, organic solvent and other auxiliary agents. The prepared organopolysilazane prepolymer has good hydrophobic properties and antifouling properties, and the coatings prepared therewith have excellent hydrophobic properties and can be used as good antifouling coatings. The method uses hydroxy silicone oil as an antifouling additive to prepare an antifouling and antigraffiti organopolysilazane prepolymer. However, hydroxy silicone oil is a mixture of macromolecules with different molecular structures, and the reactivity is different, so the structure and performance of the reaction product are not easy to control; the functional group of hydroxy silicone oil is relatively single, and the selectivity is less, and the reaction product can be designed Sex is limited. This increases the difficulty and technological process of synthesizing antifouling and anti-graffiti organopolysilazane prepolymer to a certain extent, thus restricting the performance and performance of organopolysilazane coatings with this prepolymer as the main material. its application.

In the reported studies, the modifiers used to prepare modified polysilazane are often fluorine- and silicon-containing organic compounds with certain reactivity. The cost of these substances is relatively high, and the selection scope is narrow, and the synthesis and application of fluorine-containing organic compounds, including fluorosilicon compounds, often cause potential harm to the environment and human health, and there are certain safety hazards. In addition, the controllability of the hydrosilylation reaction involved in these studies is poor, which is detrimental to the structure and properties of the modified polysilazane. Compared with organic compounds containing fluorine and silicon, long-chain alkyl compounds with reactivity are cheap and easy to obtain, have a wider choice of reactants, and are highly designable, and can be given materials by introducing groups with different functions at the same time. desired properties, even versatility; and long-chain alkyl groups can likewise have lower surface energies, whose hydrophobicity generally increases with the number of alkyl groups. More importantly, the reactivity of long-chain alkyl compounds is easy to control, and there are no safety issues like fluorine-containing organic compounds during their synthesis and use. It is a promising and environmentally friendly hydrophobic modified material.

However, whether it is an organic compound containing fluorine or silicon, or a long-chain alkyl compound, it is difficult to directly modify the surface of the substrate by chemical bonding due to its low surface energy and reaction limitations, which leads to its interaction with the substrate. The bonding force of the substrate is poor, and the adhesion, stability and durability of the prepared coating are also difficult to meet the requirements of practical applications. Therefore, how to make the low surface energy substance adhere firmly to the surface of the substrate is a fundamental problem that has to be faced in constructing a stable and durable hydrophobic surface. As a new class of materials with both organic and inorganic material characteristics, polysilazane has excellent anchoring effect on many substrates, and has excellent heat resistance, chemical resistance and weather resistance. Therefore, polysilazane is used. It is expected to construct a functional coating or surface with good stability and durability if appropriate modification is carried out to give it the expected functional properties.

Based on the understanding of the structure, properties and reaction characteristics of polysilazane, the use of compounds with isocyanate groups (NCO) with excellent reactivity can react with the Si-N bond of polysilazane for condensation coupling reaction It is possible to design and synthesize reactive long-chain alkyl compounds with isocyanate groups (NCO) through a reasonable and simple reaction, and then through the isocyanate groups of the reactive long-chain alkyl compounds and polysilazane large The Si-N bond on the molecular structure undergoes a condensation coupling reaction to bond the long-chain alkyl compound to the polysilazane macromolecule, thereby preparing the modified polysilazane with long-chain alkyl groups. This modified polysilazane has the hydrophobicity of long-chain alkyl compounds while maintaining the inherent anchoring properties of polysilazane. That is to say, through the combination of long-chain alkyl compounds and polysilazane macromolecules, an environmentally friendly modified polysilazane with both hydrophobicity and anchoring properties was constructed. A new technical solution is provided for the common problem that surface energy substances are difficult to adhere firmly to the surface of the substrate. The modification used is cheap and easy to obtain, has strong selectivity and designability, and can also endow polysilazane with other properties besides hydrophobicity; the modification reaction adopted has good controllability and reaction It is active, and the reaction can be carried out without the presence of catalysts and other auxiliary agents and under mild reaction conditions. The technical process for constructing a new type of modified polysilazane is simple and the cost is relatively low. The prepared modified polysilazane also has excellent hydrophobic properties, and can avoid the reactions faced in the previous modification process of polysilazane. The conditions are harsher, the cost is higher, and there are security risks. On the other hand, this technology greatly reduces the technological difficulty of surface modification with long-chain alkyl compounds as modifiers, and also broadens the application of reactive long-chain alkyl compounds in the construction of functional surfaces.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the common problem of poor adhesion between low surface energy substances and substrates, and poor durability of the constructed hydrophobic and superhydrophobic surfaces or coatings, and aims to provide a long-chain alkyl compound based Modified modified organopolysilazane and preparation method thereof; the prepared modified organopolysilazane retains the excellent anchoring properties of organopolysilazane to various substrates and the low surface energy of long-chain alkyl compounds properties or other functional properties, stable and durable functional coatings can be prepared on a variety of substrate surfaces using simple and versatile coating techniques.

Another object of the present invention provides the application of the modified organopolysilazane modified by long-chain alkyl compounds in constructing stable and durable hydrophobic and superhydrophobic coatings, which can impart excellent self-cleaning, Anti-fouling, anti-corrosion and other properties.

The present invention designs and synthesizes long-chain alkyl compounds with monoisocyanate end groups through the condensation reaction of alcohol monomers and diisocyanate monomers, and the number of alkyl groups can be regulated; The condensation coupling reaction between the isocyanate group and the Si-N bond on the polysilazane macromolecular structure can bond the long-chain alkyl compound to the main chain of the polysilazane macromolecule, thereby producing a long-chain alkyl compound. Novel modified polysilazane with alkyl side chains. This modification reaction has high reactivity, mild reaction conditions, simple and easy process, and good controllability; the reactive long-chain alkyl compounds as modifiers are cheap and easy to obtain, and can maintain polysilazane Excellent anchoring properties while imparting good hydrophobicity and other properties.

The novel modified polysilazane with an alkyl side chain constructed by the present invention can be directly used as a coating material to be coated on the surface of a substrate, and after curing, the long-chain alkyl compound can be stably modified on the surface of the substrate , thereby giving the coating good hydrophobicity and self-cleaning properties, as well as good durability, chemical resistance, abrasion resistance and weather resistance.

The preparation process and process of the present invention are simple and feasible, can be prepared by a simple two-step reaction, and have simple operation and good repeatability; the structure of the constructed novel modified polysilazane with alkyl side chain The structure and performance of modified polysilazane can be regulated by rationally designing the structure and functionality of the reactive long-chain alkyl compound as a modification substance, which is a great way to construct specific polysilazane. Functionally modified polysilazane provides new avenues. Among the reported materials and their preparation techniques for the construction of hydrophobic surfaces or coatings so far, the low surface energy properties of polysilazane and fluorine-free long-chain alkyl compounds that can be used as "anchor molecules" Combined, the design and preparation of modified organopolysilazane based on fluorine-free long-chain alkyl compound modification, the preparation method and its application in the construction of hydrophobic surfaces or coatings have not been reported.

The present invention combines modified polysilazane modified by long-chain alkyl compounds with micro-nano materials to prepare modified polysilazane/micro-nano composite materials; this composite material can be coated on different properties by coating The coating is constructed on the surface of the substrate, and a superhydrophobic coating with stable performance can be prepared on the surface of the substrate after only one coating and heat treatment. In the present invention, the polysilazane is hydrophobically modified with a cheap and easily available reactive long-chain alkyl compound, and the excellent mechanical and chemical stability of the polysilazane coating itself and its good anchoring effect on the substrate are retained. At the same time, make it more hydrophobic; further, by combining with micro-nano materials, a coating with a multi-level micro-nano surface structure is constructed, thereby greatly improving the hydrophobicity of the coating surface and reaching a super-hydrophobic state. The constructed modified polysilazane/micro-nanomaterial composite coating can exhibit excellent superhydrophobicity and easy-to-clean performance, as well as good durability, chemical resistance, abrasion resistance and weather resistance. In the existing related technologies, there is no report on the research on the combination of modified polysilazane and micro-nano materials to prepare a superhydrophobic coating after one-step coating.

The object of the present invention is achieved through the following technical solutions:

The modified organopolysilazane modified based on long-chain alkyl compounds is characterized in that its structural formula is:

中的一种或多种；R₁₁为含1～4个碳的直链亚烷基，R₁₂为含1～4个碳的直链烷基；R₉为-(CH₂)₆-、

R₁₀为甲基或三元、四元或五元饱和脂环，或苄基；n 是4～50的整数；x和y分别为各结构单元数占总结构单元数的分数，x+y等于1；其中，y 为键接上长链烷基化合物的结构单元占总结构单元数的分数。Wherein, the side groups R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ on the main chain are organic groups or hydrogen atoms, and R ₁ , R ₂ , R ₃ , R _4. At least one of R ₅ , R ₆ , R ₇ and R ₈ is a hydrogen atom and an organic group; the organic group is a straight or branched chain alkyl, alkenyl, alkyne containing 1 to 5 carbons base or

One or more of; R ₁₁ is a straight-chain alkylene group containing 1 to 4 carbons; R ₁₂ is a straight-chain alkylene group containing 1 to 4 carbons; R ₉ is -(CH ₂ ) ₆ -,

R ₁₀ is methyl or three-membered, four-membered or five-membered saturated alicyclic, or benzyl; n is an integer from 4 to 50; x and y are the fractions of the number of each structural unit in the total number of structural units, x+y is equal to 1; where y is the fraction of the total number of structural units to which the long-chain alkyl compound is bonded.

The preparation method of modified organopolysilazane based on long-chain alkyl compound modification comprises the following steps:

(1) Synthesis of long-chain alkyl compounds: under the protection of inert gas, add alcohol monomers and diisocyanate monomers to ether solvents, and mix them evenly; The reaction is carried out at the temperature for 2 to 12 hours to obtain a long-chain alkyl compound solution; the alcohol monomer is a long straight-chain saturated monobasic aliphatic alcohol, a long straight-chain monobasic aromatic alcohol or a long straight-chain saturated monobasic lipid Cyclic alcohol;

(2) Preparation of modified organopolysilazane based on long-chain alkyl compound modification: under inert gas protection, add organopolysilazane (OPSZ) to the long-chain alkane prepared in step (1). In the base compound solution, stir evenly; at a temperature of 20 to 60 ° C, after 1 to 8 hours of reaction, remove the solvent in the reaction system to obtain modified organopolysilazane (M-OPSZ modified by long-chain alkyl compounds). ); the structural formula of described organopolysilazane is:

中的一种或多种；R₁₁为含1～4个碳的直链亚烷基，R₁₂为含1～4个碳的直链烷基；x和y分别为各结构单元数占总结构单元数的分数，x+y等于1；其中，y为键接上长链烷基化合物的结构单元占总结构单元数的分数。Wherein, the side groups R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ on the main chain are organic groups or hydrogen atoms, and R ₁ , R ₂ , R ₃ , R _4. At least one of R ₅ , R ₆ , R ₇ and R ₈ is a hydrogen atom and an organic group; the organic group is a straight or branched chain alkyl, alkenyl, alkyne containing 1 to 5 carbons base or

One or more of these; R ₁₁ is a straight-chain alkylene group containing 1 to 4 carbons, and R ₁₂ is a straight-chain alkylene group containing 1 to 4 carbons; x and y are the total number of structural units, respectively. Fraction of the number of structural units, x+y is equal to 1; wherein, y is the fraction of the structural units bonded to the long-chain alkyl compound in the total number of structural units.

其中， R₁₀为甲基、三元、四元或五元饱和脂环，或苄基；n是4～50的整数。In order to further achieve the object of the present invention, preferably, the general structural formula of the alcohol monomer is

Wherein, R ₁₀ is methyl, three-membered, four-membered or five-membered saturated alicyclic ring, or benzyl; n is an integer of 4-50.

Preferably, the diisocyanate monomer is one of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate; the ether solvent is tetrahydrofuran, diisocyanate One or more in diethyl ether, anisole and dioxane; Described catalyst is one in dibutyltin dilaurate, tetramethylbutanediamine, triethylenediamine and triethylamine. kind.

Preferably, the molar ratio of the alcohol monomer to the isocyanate monomer is 1:1 to 1:1.1;

The amount of the ether solvent is 5 to 20 times the mass sum of the alcohol monomer and the diisocyanate monomer;

The dosage of the catalyst is 0.01-0.1 wt % of the total mass of the alcohol monomer and the diisocyanate monomer.

The mass ratio of the organopolysilazane to the long-chain alkyl compound is 1:1 to 50:1.

Preferably, the inert gas described in step (1) and step (2) is nitrogen or argon.

The application of the modified organopolysilazane modified based on long-chain alkyl compounds in constructing a stable and durable hydrophobic coating: the prepared modified organopolysilazane modified based on long-chain alkyl compounds is dissolved In an aprotic solvent, mix evenly to obtain M-OPSZ solution; or dissolve the modified organopolysilazane M-OPSZ modified based on long-chain alkyl compounds in an aprotic solvent, and mix evenly to obtain M-OPSZ solution; then add the micro-nano material to the M-OPSZ solution, and mix evenly to obtain the M-OPSZ/micro-nano material solution;

Then, by coating technology, the M-OPSZ solution is applied to the surface of the substrate or the M-OPSZ/micro-nano material solution is applied to the surface of the substrate, and cured to obtain a stable and durable hydrophobic coating.

Preferably, the micro-nano material is diatomite, montmorillonite, molybdenum disulfide, boron nitride, halloysite, hectorite, attapulgite, SiO ₂ nanoparticles, TiO ₂ nanoparticles, Al ₂ One or more _of O nanoparticles, ZnO nanoparticles, carbon nanotubes and graphene oxide;

In the M-OPSZ solution, the M-OPSZ content is 1-40wt%;

In the M-OPSZ/micro-nano material solution, the amount of the micro-nano material is 1-40 wt % of the mass of the M-OPSZ solution.

Preferably, the aprotic solvent is one or more of acetone, tetrahydrofuran, butyl acetate, toluene, ethyl acetate, xylene and n-hexane;

The coating technique is drop casting, dipping, spray coating, spin coating or blade coating;

The base material is one of inorganic non-metallic materials, metal materials, polymer materials and composite materials with one-dimensional, two-dimensional or three-dimensional structures;

The curing is to cure the surface coating obtained by coating at a temperature of 60-200° C. for 0.5-6 hours.

Preferably, the water droplet contact angle of the M-OPSZ solution applied to the surface of the substrate and cured to obtain a stable and durable hydrophobic coating is 104°˜110°.

Preferably, the M-OPSZ/micro-nano material solution is coated on the surface of the substrate and cured to obtain a stable and durable hydrophobic coating with a water droplet contact angle of 150°-180°.

The synthesis reaction of the long-chain alkyl compound of the present invention is shown in the reaction formula (1).

Reaction formula (1):

等；R₁₀为甲基、三元、四元或五元饱和脂环，或苄基；n是4～50的整数。Wherein, R ₉ is the group structure other than the isocyanate end group (OCN-) in the diisocyanate monomer structure used, mainly including -(CH ₂ ) ₆ -,

etc.; R ₁₀ is methyl, three-membered, four-membered or five-membered saturated alicyclic ring, or benzyl; n is an integer of 4-50.

The synthesis of the modified polysilazane modified by the long-chain alkyl compound is shown in the reaction formula (2).

Reaction formula (2):

The composite coating prepared by the modified organopolysilazane modified based on the long-chain alkyl compound and the micro-nano material in the present invention, namely the M-OPSZ/micro-nano material composite coating, has a micro-nano composite structure on the surface, and the water droplets contact the surface of the composite coating. The angle is 150°～180°, showing excellent superhydrophobicity and easy cleaning, and has good durability, chemical resistance, abrasion resistance and weather resistance.

The present invention provides a modified organopolysilazane modified based on long-chain alkyl compounds, which has both the excellent anchoring properties of organopolysilazane to various substrates and the low surface energy of long-chain alkyl substances. It is possible to construct hydrophobic or superhydrophobic coatings with excellent durability on the surface of various substrates through a simple one-step coating process, which is important for promoting the rapid construction and practical application of hydrophobic and superhydrophobic surfaces or coatings. significance and practical value.

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

(1) The present invention constructs a new type of modified polysilazane that is environmentally friendly and has both hydrophobicity and anchoring properties through the combination of long-chain alkyl compounds and polysilazane macromolecules. The common problem that the low surface energy substances are difficult to adhere firmly to the surface of the substrate provides a new technical solution.

(2) The modification used in the present invention for preparing the modified organopolysilazane modified based on the long-chain alkyl compound is a long-chain alkyl compound with high reactivity. The compound has a highly active monoisocyanate end group (NCO), and can be synthesized through a reasonable and simple reaction using cheap and readily available reactants, alcohol monomers and diisocyanate monomers. Compared with conventional low surface energy modifiers such as fluorine-containing reactive compounds, the synthesis and use of this reactive long-chain alkyl compound is safer, more environmentally friendly, and less expensive. In addition, the reactive long-chain alkyl compound used as a modifier of the present invention has strong designability, and its design and synthesis have excellent scalability, which can greatly enrich the types of reactive long-chain alkyl compounds, and Broaden its application in the construction of functional surfaces. That is to say, using a wide range of hydrocarbon and organic synthesis reactions, reactive alkyl compounds with expected reaction characteristics and functionalities that can be used as polysilazane modifiers can be designed and synthesized. In order to endow polysilazane with other properties than hydrophobicity, it provides a new strategy and method for constructing new modified polysilazane with different functionalities.

(3) The present invention utilizes the condensation coupling reaction between the isocyanate end group carried by the long-chain alkyl compound with high reactivity and the Si-N bond on the main chain structure of the polysilazane macromolecular structure, and can be used in the polymer A long alkyl side chain is bonded to the main chain of the silazane macromolecule, thereby obtaining a novel modified polysilazane modified by long-chain alkyl compounds. Compared with the hydrosilylation reaction commonly used in the construction of modified polysilazane, the modification reaction adopted in the present invention does not need to use any catalysts and other auxiliary agents, and the reaction can still be carried out under mild and simple reaction conditions, and is more efficient. High efficiency and good controllability. Therefore, the modification reaction process of polysilazane provided by the present invention is simple and feasible, with relatively low cost and high efficiency; and relatively speaking, this modification process is more environmentally friendly.

(4) The modified organopolysilazane modified by long-chain alkyl compounds prepared in the present invention can be dissolved in various aprotic solvents to obtain modified polysilazane solutions; This solution can be applied to a variety of substrate surfaces without any special treatment to produce stable hydrophobic coatings. When the modified organopolysilazane solution of low mass concentration (5wt%) is used to coat the surface of the glass substrate, the water contact angle of the obtained modified organopolysilazane coating can also reach 109.1°, Compared with the control glass surface and the unmodified organopolysilazane surface, the water contact angles were increased by 82.4° and 17°, respectively; in addition, the adhesion grade of the coating to the substrate reached grade 0, and at pH After immersion in H ₂ SO ₄ solution of 1.0 for 24 hours, the water contact angle can still reach 107.1°, showing excellent hydrophobicity, adhesion to substrates and chemical corrosion resistance, and excellent easy cleaning characteristic.

(5) The present invention combines modified polysilazane modified by long-chain alkyl compounds with micro-nano materials, and the prepared solution of modified polysilazane/micro-nano composite materials is only coated by a simple step By this method, stable superhydrophobic coatings with multi-layered micro-nano surface structures can be constructed on the surfaces of different types of substrates. The adhesion of the coating to the substrate can reach grade 0; its water droplet contact angle is 150° to 180°, showing excellent superhydrophobicity, antifouling and easy-to-clean properties, and excellent chemical resistance. , wear resistance and weather resistance. These properties can greatly extend its service life. In the existing related technologies, there is no report on the research on the combination of modified polysilazane and micro-nano materials to prepare a superhydrophobic coating after one-step coating.

Description of drawings

Figure 1 is the infrared spectrum (FTIR) of the long-chain alkyl compound CA-HDI prepared in Example 1 and its reactants, namely n-hexadecanol (CA) and hexamethylene diisocyanate (HDI).

FIG. 2 is the ¹ H NMR spectrum of the long-chain alkyl compound CA-HDI prepared in Example 1. FIG.

FIG. 3 is the infrared spectrum (FTIR) of the modified organopolysilazane CHO-10 modified with long-chain alkyl compounds prepared in Example 1 and its reactants CA-HDI and OPSZ.

4 is the ¹ H NMR spectrum of the modified organopolysilazane CHO-10 modified with long-chain alkyl compounds prepared in Example 1 and its reactants CA-HDI and OPSZ.

Figure 5(a), Figure 5(b) and Figure 5(c) are respectively the modified organopolysilazane coating CHO-10@Glass constructed on the surface of the glass substrate in Example 5 and the unmodified control Images of the resulting water droplets in contact with different surfaces when the water contact angles of the organic polysilazane-coated OPSZ@Glass and blank glass surfaces were obtained.

Fig. 6(a), Fig. 6(b) and Fig. 6(c) are respectively the modified organopolysilazane coating CHO-10@SPTE constructed on the surface of tinplate substrate in Example 5 and the unmodified control Pictures of the obtained water droplets in contact with different surfaces when the water contact angles of the organic polysilazane-coated OPSZ@SPTE and blank tinplate surfaces were obtained.

Fig. 7(a) and Fig. 7(b) are respectively the M-OPSZ/micro/nanomaterial composite coating CHO-10/DE/SiO ₂ @ constructed on two different substrate glass and tinplate surfaces in Example 5. The water contact angle of Glass and CHO-10/DE/SiO ₂ @SPTE, pictures of the resulting water droplets in contact with the surfaces of composite coatings built on different substrates.

Fig. 8(a) and Fig. 8(b) are respectively the measurement of the two coatings CHO-10@Glass and CHO-10/DE/SiO ₂ @Glass constructed on the surface of the glass substrate in Example 5 by H at pH 1.0 Photographs of the resulting water droplets in contact with two different coating surfaces, respectively, when the surface water contact angle was immersed in _2SO4 aqueous solution for ₂₄ hours.

Fig. 9(a), Fig. 9(b) and Fig. 9(c) are the scans of the M-OPSZ/micro-nanomaterial composite coating CHO-10/DE/SiO ₂ @SPTE constructed on the surface of tinplate in Example 5, respectively Electron microscope (SEM) pictures, high magnification SEM pictures of the coating parts and SEM pictures of the blank tinplate surface as a control.

Detailed ways

In order to better understand the present invention, the present invention will be further described below with reference to the accompanying drawings and embodiments, but the embodiments of the present invention are not limited thereto.

Example 1 Preparation of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

(1) Synthesis of long-chain alkyl compounds: under argon protection, 0.665g of n-hexadecanol (CA) and 0.500g of hexamethylene diisocyanate (HDI) were added to 10ml of tetrahydrofuran solvent, and mixed uniformly; Then, 0.10wt% of triethylamine was added to the total mass of the reactant monomers, and the reaction was carried out at a temperature of 50°C for 5 hours to obtain a long-chain alkyl compound solution. The product is denoted as CA-HDI, and its chemical structure is as follows shown.

(2) Preparation of modified organopolysilazane modified by long-chain alkyl compounds: under argon protection, 11.65g of organopolysilazane OPSZ was added to the CA-HDI solution prepared in step (1). , stir evenly; at 25° C., after 7 hours of reaction, remove the solvent in the reaction system to obtain the modified organopolysilazane M-OPSZ modified by long-chain alkyl compounds. In this M-OPSZ product, the mass ratio of OPSZ to the long-chain alkyl compound CA-HDI is 10:1, so it is recorded as CA-HDI@OPSZ-10, abbreviated as CHO-10.

The structure of the organopolysilazane OPSZ used in this example is:

wherein, R is a hydrogen atom and/or a methyl group. R in the structural formula of the polysilazane of the present invention is uncertain, it may be a hydrogen atom or a methyl group, or both, which may be related to the preparation process, and R has little effect on the performance of the polysilazane.

FIG. 1 is the infrared spectrum (FTIR) of the long-chain alkyl compound CA-HDI prepared in Example 1 and its reactants, namely n-hexadecanol (CA) and hexamethylene diisocyanate (HDI). Compared with the infrared spectra of the reactants CA and HDI, in the infrared spectrum of the product CA-HDI, there is no broad peak at 3329 cm ^-1 attributable to the -OH stretching vibration, indicating that the reactant CA is completely consumed; the corresponding The characteristic absorption peaks at 3318cm ^-1 and 1540cm ^-1 which belonged to N－H in carbamate appeared, and the C=O group in carbamate appeared at 1685cm ^-1 characteristic absorption peaks of the clusters. In addition, in the infrared spectrum of CA-HDI, a characteristic absorption peak at 2270 cm ^-1 also appeared attributable to the -NCO group, but the peak shape was narrowed and the peak area was significantly reduced. According to the above analysis, it can be preliminarily determined that the long-chain alkyl compound CA-HDI with the expected structure was synthesized by the described synthesis method. Infrared spectra were measured by Bruker VERTEX70 FTIR Spectrometer; solid samples were pre-dried and then prepared by KBr tablet method; liquid samples were prepared by KBr smear method.

FIG. 2 is the ¹ H NMR spectrum of the long-chain alkyl compound CA-HDI prepared in Example 1. FIG. In this ¹ H NMR spectrum, the structures at 4.04 ppm and 3.17 ppm are attributed to the reaction between the terminal hydroxyl group of CA molecule and the isocyanate terminal group of HDI molecule, respectively -CH ₂ -O-(CO)-, -( The proton peak in CO)-NH-CH ₂ -; meanwhile, the proton peak in the NCO-CH ₂ - structure attributed to the end of the CA-HDI molecule was detected at 3.31 ppm. In addition, in the ¹ H NMR spectrum of CA-HDI, the corresponding proton peaks in the molecular structure of CA-HDI appeared at different chemical shifts. Combined with the ¹ H NMR and FTIR spectra of CA-HDI and their analysis, it is proved that the hydroxyl group of the reactant CA has undergone the expected condensation reaction with the isocyanate end group of HDI, and a compound with a reactive isocyanate end group with the expected structure is obtained. Long chain alkyl compounds CA-HDI.

FIG. 3 is the infrared spectrum (FTIR) of the modified organopolysilazane CHO-10 modified with long-chain alkyl compounds prepared in Example 1 and its reactants CA-HDI and OPSZ. Compared with the FT-IR spectra of CA-HDI and OPSZ, in the FT-IR of CA-HDI@OPSZ, the characteristic absorption peak at 2270 cm ^-1 ascribed to the asymmetric stretching vibration of the -NCO group does not appear, indicating that the band CA-HDI with -NCO end group has fully participated in the reaction; correspondingly, a characteristic absorption peak at 1750cm ^-1 which is attributed to carbonyl C=O appears, which originates from the condensation coupling of CA-HDI and OPSZ The resulting structure -N-(C=O)-N-; at the same time, the characteristic absorption peaks of NH and Si-H in the OPSZ structure appeared at 3385cm ^-1 and 2130cm ^-1 respectively, and also at ^3318cm -1 A characteristic absorption peak attributable to NH in the CA-HDI structure appeared at ¹ . The above comparative analysis shows that the modified organopolysilazane CHO-10 with the expected structure was synthesized by the described synthesis method.

4 is the ¹ H NMR spectrum of the modified organopolysilazane CHO-10 modified with long-chain alkyl compounds prepared in Example 1 and its reactants CA-HDI and OPSZ. In the ¹ H NMR spectrum of CA-HDI, a proton peak in the NCO- CH ₂ -structure at the end of the CA-HDI molecule is located at 3.30 ppm, compared with that in the ¹ H NMR spectrum of CHO-10. In the figure, the signal peak at 3.31 ppm was not detected; at the same time, the protons of -CH ₂ -O-(CO)- and -(CO)-NH-CH ₂ - in the molecular structure of CA-HDI were assigned The peaks appear at 4.01 ppm and 3.13 ppm, respectively, because the electron-withdrawing isocyanate groups in the structure are completely consumed and move to the high field, that is, the chemical shift value decreases. In addition, compared with the ¹ H NMR spectrum of OPSZ, in the ¹ H NMR spectrum of CHO-10, proton peaks in the corresponding structures were detected at the corresponding chemical shifts, indicating that CHO-10 contains OPSZ molecular chain structure. This test result and its analysis show that the synthesis method can make CA-HDI and OPSZ undergo the expected condensation coupling reaction, and obtain the modified organopolysilazane CHO-10 with the expected structure.

Example 2 Preparation of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

(1) Synthesis of long-chain alkyl compounds: under argon protection, 1.110g of n-dodecanol (DA) and 1.000g of hexamethylene diisocyanate (HDI) were added to 15ml of tetrahydrofuran solvent, and mixed uniformly; Then, adding 0.05wt% of dibutyltin dilaurate accounting for the total mass of reactant monomers, and reacting at 55°C for 5.5 hours, the long-chain alkyl compound solution can be obtained, and the product is denoted as DA-HDI.

(2) Preparation of modified organopolysilazane modified by long-chain alkyl compounds: under argon protection, 25.32 g of organopolysilazane was added to the DA-HDI solution obtained in step (1), and stirred. Uniform; at a temperature of 45°C, after 3.5 hours of reaction, the solvent in the reaction system is removed to obtain a modified organopolysilazane M-OPSZ modified by a long-chain alkyl compound. In this M-OPSZ product, the mass ratio of OPSZ to long-chain alkyl compound DA-HDI is 12:1, so it is recorded as DA-HDI@OPSZ-12, or DHO-12 for short.

其中，n值为10～25。The structure of the organopolysilazane OPSZ used in this example is:

Among them, the value of n is 10-25.

The infrared spectrum of the long-chain alkyl compound DA-HDI and the modified organopolysilazane DHO-12 modified by the long-chain alkyl compound prepared in this example and their comparative analysis results are similar to Figure 1 and Figure 3, respectively. The ¹ H NMR spectra and analysis of the two are similar to those in Figure 2 and Figure 4, respectively, so they will not be repeated. Therefore, it can be confirmed that the modified organopolysilazane DHO-12 with the expected structure was synthesized by the described synthesis method.

Example 3 Preparation of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

(1) Synthesis of long-chain alkyl compounds: under nitrogen protection, 1.381 g of 7-phenyl-1-heptanol (PHA) and 1.500 g of trimethylhexamethylene diisocyanate (TDMI) were added to 20 ml of dioxane In the solvent, mix evenly; then, add tetramethylbutanediamine accounting for 0.03wt% of the total mass of the reactant monomer, and react at a temperature of 60 ° C for 5.0 hours to obtain a long-chain alkyl compound solution, and the product is recorded as: for PHA-TDMI.

(2) Preparation of modified organopolysilazane based on long-chain alkyl compound modification: under nitrogen protection, 23.50 g of organopolysilazane was added to the PHA-TDMI solution obtained in step (1), and stirred evenly ; At a temperature of 35°C, after 5.0 hours of reaction, the solvent in the reaction system is removed to obtain a modified organopolysilazane M-OPSZ modified by a long-chain alkyl compound. In this M-OPSZ product, the mass ratio of OPSZ to the long-chain alkyl compound PHA-TDMI is 8:1, so it is recorded as PHA-TDMI@OPSZ-8, or PTO-8 for short.

其中，R为氢原子和/或甲基。The structure of the organopolysilazane used in this example is

wherein, R is a hydrogen atom and/or a methyl group.

The infrared spectrum of the long-chain alkyl compound PHA-TDMI and the modified organopolysilazane PTO-8 modified by the long-chain alkyl compound prepared in this example and their comparative analysis results are similar to Figure 1 and Figure 3, respectively. The ¹ H NMR spectra and analysis of the two are similar to those in Figure 2 and Figure 4, respectively, so they will not be repeated. Therefore, it can be confirmed that the modified organopolysilazane PTO-8 with the expected structure was synthesized by the described synthesis method.

Example 4 Preparation of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

(1) Synthesis of long-chain alkyl compounds: under nitrogen protection, 0.980g of n-triacontanol (TA) and 0.500g of isophorone diisocyanate (IPDI) were added to 15ml of diethyl ether solvent, and mixed uniformly; Then, adding 0.06wt% triethylamine accounting for the total mass of the reactant monomers, and reacting at 50°C for 6.0 hours to obtain a long-chain alkyl compound solution, the product is denoted as TA-IPDI.

(2) Preparation of modified organopolysilazane modified by long-chain alkyl compounds: under nitrogen protection, 22.31 g of organopolysilazane was added to the TA-IPDI solution obtained in step (1), and stirred evenly ; After 2.0 hours of reaction at a temperature of 55°C, the solvent in the reaction system is removed to obtain a modified organopolysilazane M-OPSZ modified by a long-chain alkyl compound. In this M-OPSZ product, the mass ratio of OPSZ to long-chain alkyl compound TA-IPDI is 15:1, so it is recorded as TA-IPDI@OPSZ-15, or TIO-15 for short.

The structure of the organopolysilazane used in this example is:

The infrared spectrum of the long-chain alkyl compound TA-IPDI and the modified organopolysilazane TIO-15 modified by the long-chain alkyl compound prepared in this example and their comparative analysis results are similar to Figure 1 and Figure 3, respectively. The ¹ H NMR spectra and analysis of the two are similar to those in Figure 2 and Figure 4, respectively, so they will not be repeated. Therefore, it was confirmed that the modified organopolysilazane TIO-15 with the expected structure was synthesized by the described synthesis method.

Example 5 Application of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

Dissolve 0.2 g of the modified organopolysilazane CHO-10 prepared in Example 1 in 3.8 g of ethyl acetate solvent, and mix evenly to obtain a CHO-10 solution with a mass fraction of 5 wt %; (Glass) and tinplate (SPTE) as substrates, the prepared CHO-10 solution was applied to the surface of the substrate by spraying technology, and it was thermally cured at 120 ° C for 2.0 hours, that is, the surface of different substrates was obtained. The constructed modified organopolysilazane CHO-10 coatings were denoted as CHO-10@Glass and CHO-10@SPTE, respectively.

Dissolve 0.2 g of the modified organopolysilazane CHO-10 prepared in Example 1 in 3.8 g of ethyl acetate solvent, and mix evenly to obtain a CHO-10 solution with a mass fraction of 5 wt %; then add 0.05 g of silicon Altomite (DE) and 0.05g of nano-silica (SiO ₂ ) were added to the CHO-10 solution and mixed evenly to obtain a CHO-10/DE/SiO ₂ composite solution; then, glass and tinplate were used as the base materials, respectively. , the prepared CHO-10/DE/SiO ₂ composite solution was coated on the surface of the substrate by spraying technology, and it was thermally cured at 120 ° C for 2.0 hours, that is, the CHO-10/DE/SiO 2 composite solution constructed on the surface of different substrates was obtained. 10/DE/SiO ₂ composite coatings, denoted as CHO-10/DE/SiO ₂ @Glass and CHO-10/DE/SiO ₂ @SPTE, respectively.

At the same time, using the corresponding unmodified polysilazane as the coating material, the unmodified organopolysilazane coatings OPSZ@Glass and tinplate substrates were constructed by the same method, respectively. OPSZ@SPTE.

The water contact angles of the prepared different coating surfaces were measured using a DSA 100 contact angle meter from KRUSS, Germany.

Fig. 5(a), Fig. 5(b) and Fig. 5(c) respectively show the determination of the modified organopolysilazane CHO-10 coating CHO-10@Glass constructed on the glass surface used as a substrate in this example As well as the water contact angles of the unmodified organopolysilazane OPSZ coating OPSZ@Glass and the blank glass surface as a control, the obtained pictures of water droplets in contact with different surfaces. According to the test results in Figure 5, the water contact angle of the blank glass surface is only 26.7°, which is a hydrophilic surface; while the modified organopolysilazane CHO-10 coating CHO-10@Glass and The water contact angles of the unmodified organopolysilazane OPSZ-coated OPSZ@Glass surface were 109.1° and 92.7°, respectively, showing hydrophobic properties, and the hydrophobicity of the CHO-10@Glass surface was more significant.

Figure 6(a), Figure 6(b) and Figure 6(c) respectively show the determination of the modified organopolysilazane CHO-10 coating CHO-10@SPTE constructed on the surface of tinplate used as a substrate in this example As well as the water contact angles of the unmodified organopolysilazane OPSZ coating OPSZ@SPTE and the blank tinplate surface as a control, the obtained water droplets are in contact with different surfaces. According to the test results in Fig. 6, the water contact angles of the CHO-10 coating CHO-10@SPTE, the unmodified organopolysilazane OPSZ coating OPSZ@SPTE and the blank tinplate constructed on the tinplate substrate are 110.1°, 94.2° and 79.2°, CHO-10@SPTE has the same significant hydrophobicity as CHO-10@Glass. Therefore, the coatings constructed with the modified organopolysilazane CHO-10 prepared in Example 1 on different substrates all have good hydrophobicity.

Fig. 7(a) and Fig. 7(b) are respectively the measurement of the CHO-10/DE/SiO ₂ composite coating CHO-10/DE/SiO ₂ constructed on the surface of two different substrate glass and tinplate in this example. The water contact angles of @Glass and CHO-10/DE/SiO ₂ @SPTE, the images of the resulting water droplets in contact with the surfaces of CHO-10/DE/SiO ₂ composite coatings built on different substrates. According to the test results in Fig. 7, the water contact angles on the surfaces of CHO-10/DE/SiO ₂ composite coatings CHO-10/DE/SiO ₂ @Glass and CHO-10/DE/SiO ₂ @SPTE are 158.2°, respectively and 156.9°, which are much higher than the water contact angles of the corresponding modified organopolysilazane CHO-10 coatings CHO-10@Glass and CHO-10@SPTE surfaces, both exhibiting superhydrophobic properties.

Figure 8(a) and Figure 8(b) respectively show the measurement of the two coatings CHO-10@Glass and CHO-10/DE/SiO ₂ @Glass constructed on the surface of the glass substrate in this example by H with pH of 1.0 Photographs of the resulting water droplets in contact with two different coating surfaces, respectively, when the surface water contact angle was immersed in _2SO4 aqueous solution for ₂₄ hours. According to the test results in Fig. 8, after soaking in H ₂ SO ₄ aqueous solution with pH 1.0 for 24 hours, the water contact angles of the coated CHO-10@Glass and CHO-10/DE/SiO ₂ @Glass surfaces are 107.1° and 107.1°, respectively. 154.3°, which is only 2.0° and 3.9° lower than before soaking, and still maintains considerable hydrophobicity and superhydrophobicity. This result indicates that the constructed modified organopolysilazane CHO-10 coating CHO-10@Glass and the corresponding CHO-10/DE/ _SiO2 composite coating CHO-10/DE/ _SiO2 @Glass All have good chemical resistance.

According to the standard GB/T 9286-1988, the adhesion of the constructed different coatings to the substrate was measured. The test results show that the adhesion grades of the modified organopolysilazane CHO-10 coatings CHO-10@Glass and CHO-10@SPTE constructed on the surfaces of two different substrates in this example are both grade 0; corresponding The adhesion ratings of the CHO-10/DE/SiO ₂ composite coatings CHO-10/DE/SiO ₂ @Glass and CHO-10/DE/SiO ₂ @SPTE are also grade 0. This indicates that the constructed modified organopolysilazane CHO-10 still maintains the excellent anchoring properties inherent in polysilazane to different substrates.

The surface hardness of the prepared different coatings was determined according to the standard GB/T 6739-2006. The test results show that the pencil hardness of the modified organopolysilazane CHO-10 coatings CHO-10@Glass and CHO-10@SPTE constructed on the surfaces of two different substrates in this example are both 3H; the corresponding CHO The pencil hardness of -10/DE/SiO ₂ composite coatings CHO-10/DE/SiO ₂ @Glass and CHO-10/DE/SiO ₂ @SPTE are also both 3H.

The easy-to-clean performance of the hydrophobic coating was evaluated by the erasability test test of scratches on the coating surface by an oil-based marker. On the surface of the constructed modified organopolysilazane CHO-10 coatings CHO-10@Glass and CHO-10@SPTE, use an oil-based marker to make several scratches on the surface of the coating, and let it stand for a period of time. After the ink dries, wipe the ink scratches with a paper towel, and find that the ink scratches can be easily wiped off without remaining on the coating surface. This indicates that the constructed modified organopolysilazane CHO-10 coatings CHO-10@Glass and CHO-10@SPTE have good easy-to-clean properties.

The easy-cleaning performance of the hydrophobic coating was evaluated by methylene blue as a simulated contaminant on the surface of the coating to conduct a soil removal experiment. On the surface of the constructed M-OPSZ/micro-nanomaterial composite coatings CHO-10/DE/SiO ₂ @Glass and CHO-10/DE/SiO ₂ @SPTE placed at an inclination angle of 15° to the horizontal direction Quality simulated contaminant methylene blue, by adding deionized water drop by drop to the surface, the water droplets roll off the coating surface and carry away the methylene blue contamination, so that the contamination on the coating surface can be completely removed. This indicates that the constructed M-OPSZ/micro-nanomaterial composite coatings CHO-10/DE/SiO ₂ @Glass and CHO-10/DE/SiO ₂ @SPTE have good easy-cleaning properties on the surfaces.

According to the above test results, the modified organopolysilazane CHO-10 coatings constructed on different substrates and the corresponding CHO-10/DE/ _SiO2 composite CHO-10/DE/ _SiO2 coatings have excellent good adhesion, high hardness and good easy cleaning properties.

Fig. 9(a), Fig. 9(b) and Fig. 9(c), respectively, of the CHO-10/DE/SiO ₂ composite coating CHO-10/DE/SiO ₂ @SPTE constructed on the surface of tinplate in this example Scanning Electron Microscope (SEM) photo, high magnification SEM photo of the coating and the SEM photo of the blank tinplate surface as a control. It can be clearly seen from the SEM image in Fig. 9 that many micron-scale small protrusions are distributed on the surface of the composite coating CHO-10/DE/SiO ₂ @SPTE, and these protrusions originate from the composite CHO-10 that constitutes the coating. The accumulation of micro-scale diatomite and nano-silica particles in /DE/SiO ₂ forms a multi-layered micro-nano structure, so that the coating has a relatively rough surface micro-structure. The surface of the blank tinplate as a control is relatively smooth, and has no such surface microscopic features at all. The scanning electron microscope used was a field emission scanning electron microscope FE-SEM from Merlin, Germany.

Example 6 Application of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

Dissolve 0.4 g of the modified organopolysilazane DHO-12 prepared in Example 2 in 6.3 g of acetone solvent, and mix evenly to obtain a DHO-12 solution with a mass fraction of 6 wt %; ) and tinplate (SPTE) as the base material, the prepared DHO-12 solution was applied to the surface of the base material by spraying technology, and it was thermally cured at 100 ° C for 3.0 hours, that is, to obtain the structure on the surface of different base materials. The modified organopolysilazane DHO-12 coatings were denoted as DHO-12@Glass and DHO-12@SPTE, respectively.

Dissolve 0.4 g of the modified organopolysilazane DHO-12 prepared in Example 2 in 6.3 g of ethyl acetate solvent, and mix evenly to obtain a DHO-12 solution with a mass fraction of 6 wt %; then add 0.10 g of nitrogen Boronide (BN) and 0.025g nano-titanium dioxide (TiO ₂ ) were added to the DHO-12 solution and mixed uniformly to obtain a DHO-12/BN/TiO ₂ composite solution; then, using glass and tinplate as substrates, respectively, through The prepared DHO-12/BN/TiO ₂ composite solution was applied to the surface of the substrate by spraying technology, and was thermally cured at 100 °C for 3.0 hours, that is, the DHO-12/TiO composite solution constructed on the surface of different substrates was obtained. BN/ _TiO composite coatings, denoted as DHO-12/BN/TiO ₂ @Glass and DHO-12/BN/TiO ₂ @SPTE, respectively.

A DSA 100 contact angle measuring instrument from KRUSS, Germany was used to measure the water contact angles of the surfaces of the different coatings constructed in this example. The test results show that the water contact angles of the modified organopolysilazane DHO-12 coatings DHO-12@Glass and DHO-12@SPTE constructed on the surfaces of two different substrates in this example are 106.6° and 106.6°, respectively. 107.6°, which is hydrophobic; while the water contact angles of the corresponding DHO-12/BN/TiO ₂ composite coatings DHO-12/BN/TiO ₂ @Glass and DHO-12/BN/TiO ₂ @SPTE surfaces are 154.3° and 155.9°, both showing superhydrophobicity. The photos of the water droplets in contact with the surfaces of DHO-12 coatings DHO-12@Glass and DHO-12@SPTE obtained by the contact angle test are similar to Fig. 5(a) and Fig. The photos of the surface contact of DHO-12/BN/TiO ₂ @Glass and DHO-12/BN/TiO ₂ @SPTE coated with /BN/TiO ₂ composites are similar to Fig. 7(a) and Fig. 7(b), respectively , so it will not be repeated.

In addition, the water contact angle test results of the coating surface also show that the modified organopolysilazane DHO-12 coatings DHO-12@Glass and DHO-12/BN/TiO ₂ constructed on the surface of the glass substrate in this example After the composite coating DHO-12/BN/ _TiO2 @Glass was soaked in _H2SO4 aqueous solution with pH 1.0 for ₂₄ h, the water contact angles were 104.4° and 152.5°, respectively, which were slightly lower than the corresponding coating surfaces before soaking The water contact angles of , still exhibit hydrophobicity and superhydrophobicity, respectively; the corresponding water droplets and DHO-12 coating DHO-12@Glass and DHO-12/BN/TiO ₂ composite coating DHO-12/ The photographs of the surface contact of BN/TiO ₂ @Glass are similar to Fig. 8(a) and Fig. 8(b), respectively, and are not repeated. This result shows that both the constructed coatings DHO-12@Glass and DHO-12/BN/TiO ₂ @Glass have good chemical resistance properties.

According to the standard GB/T 9286-1988, the adhesion grades of DHO-12@Glass and DHO-12@SPTE of modified organopolysilazane DHO-12 coatings constructed on the surface of two different substrates in this example were measured Both are grade 0; the adhesion grades of the corresponding DHO-12/BN/TiO ₂ composite coatings DHO-12/BN/TiO ₂ @Glass and DHO-12/BN/TiO ₂ @SPTE are also grade 0. This indicates that the constructed modified organopolysilazane DHO-12 still maintains the inherent excellent anchoring properties of polysilazane to different substrates.

According to the standard GB/T 6739-2006, the pencil hardnesses of the modified organopolysilazane DHO-12 coatings DHO-12@Glass and DHO-12@SPTE constructed on the surface of two different substrates in this example were both measured. The pencil hardness of the corresponding DHO-12/BN/TiO ₂ composite coatings DHO-12/BN/TiO ₂ @Glass and DHO-12/BN/TiO ₂ @SPTE surfaces are also 3H.

Through the erasability test of the scratches of the oil-based marker on the coating surface, it was found that the modified organopolysilazane DHO-12 coatings DHO-12@Glass and DHO constructed in this example were -10@SPTE surface, ink scratches from oil-based markers can be easily wiped off and will not remain on the coating surface. This indicates that the constructed modified organopolysilazane DHO-12 coated DHO-12@Glass and DHO-12@SPTE surfaces have good easy-to-clean properties.

The easy-cleaning performance of the hydrophobic coating was evaluated by methylene blue as a simulated contaminant on the surface of the coating to conduct a soil removal experiment. A certain mass of M-OPSZ/micro-nanomaterial composite coatings DHO-12/BN/TiO 2 and DHO-12/BN/TiO 2 @SPTE were placed on the surface of the as-built M-OPSZ/micro-nanomaterial composite coating DHO-12/BN/TiO ₂ and DHO-12/BN/TiO ₂ @SPTE placed at an inclined angle of 15° to the horizontal direction. To simulate the contaminant methylene blue, by adding deionized water dropwise to the surface, the water droplets roll off the coating surface and take away the methylene blue contamination, so that the contamination on the coating surface can be completely removed. This indicates that the constructed M-OPSZ/micro-nanomaterial composite coatings DHO-12/BN/TiO ₂ @Glass and DHO-12/BN/TiO ₂ @SPTE have good easy-cleaning properties on the surfaces.

According to the above test results, the modified organopolysilazane DHO-12 coatings and the corresponding DHO-12/BN/ _TiO composite coatings constructed on different substrates have excellent adhesion, high hardness and good easy cleaning performance.

The SEM photos of the DHO-12/BN/TiO ₂ composite coating DHO-12/BN/TiO ₂ @@SPTE surface constructed on the surface of tinplate in this example are similar to those in Fig. 9(a) and Fig. 9(b), so no more repetitions. This shows that the surface of the DHO-12/BN/TiO ₂ @@SPTE coating constructed in this example also has a multi-layered micro-nano structure and similar surface microscopic features.

Example 7 Application of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

Dissolve 0.6 g of the modified organopolysilazane PTO-8 prepared in Example 3 in 3.4 g of xylene solvent, and mix well to obtain a CHO-10 solution with a mass fraction of 15 wt %; Glass) and tinplate (SPTE) as the base material, the prepared PTO-8 solution was coated on the surface of the base material by dipping technology, and it was thermally cured at 80 ° C for 5.5 hours, that is, the structure on the surface of different base materials was obtained. The modified organopolysilazane PTO-8 coatings were denoted as PTO-8@Glass and PTO-8@SPTE, respectively.

Dissolve 0.6 g of the modified organopolysilazane PTO-8 prepared in Example 3 in 1.4 g of ethyl acetate solvent, and mix evenly to obtain a PTO-8 solution with a mass fraction of 30 wt %; Molybdenum sulfide (MoS ₂ ) and 0.20 g of nano-zinc oxide (ZnO) were added to the PTO-8 solution and mixed uniformly to obtain a PTO-8/MoS ₂ /ZnO composite solution; then, using glass and tinplate as substrates, respectively, The prepared PTO-8/MoS ₂ /ZnO composite solution was coated on the surface of the substrate by the blade coating technique, and was thermally cured at 80°C for 5.5 hours, to obtain the PTO-8/MoS 2 /ZnO composite solution constructed on the surface of different substrates. 8/MoS ₂ /ZnO composite coatings, denoted as PTO-8/MoS ₂ /ZnO@Glass and PTO-8/MoS ₂ /ZnO@SPTE, respectively.

A DSA 100 contact angle measuring instrument from KRUSS, Germany was used to measure the water contact angles of the surfaces of the different coatings constructed in this example. The test results show that the water contact angles of the modified organopolysilazane PTO-8 coatings PTO-8@Glass and PTO-8@SPTE constructed on the surfaces of two different substrates in this example are 107.7° and 107.7°, respectively. 108.2°, which is hydrophobic; while the water contact angles of the corresponding PTO-8/MoS ₂ /ZnO composite coatings PTO-8/MoS ₂ /ZnO@Glass and PTO-8/MoS ₂ /ZnO@SPTE surfaces are 155.3° and 157.1°, both showing superhydrophobicity. The photos of the water droplets in contact with the surfaces of the PTO-8 coatings PTO-8@Glass and PTO-8@SPTE obtained by the contact angle test are similar to Fig. The photos of the surface contact of the /MoS ₂ /ZnO composite coating PTO-8/MoS ₂ /ZnO@Glass and PTO-8/MoS ₂ /ZnO@SPTE are similar to Fig. 7(a) and Fig. 7(b), respectively , so it will not be repeated.

In addition, the water contact angle test results of the coating surface also show that the modified organopolysilazane PTO-8 coatings PTO-8@Glass and PTO-8/MoS ₂ /ZnO constructed on the surface of the glass substrate in this example After the composite coating PTO-8/MoS ₂ /ZnO@Glass was immersed in H ₂ SO ₄ aqueous solution with pH 1.0 for 24 hours, the water contact angles were 105.2° and 151.1°, respectively, which were slightly lower than the corresponding coating surfaces before immersion. The water contact angle of , still showed hydrophobicity and superhydrophobicity, respectively; the corresponding water droplets were composited with modified organopolysilazane PTO-8 coatings PTO-8@Glass and PTO-8/MoS ₂ /ZnO The photographs of the surface contact of PTO-8/MoS 2 /ZnO@Glass coated with PTO-8/MoS ₂ /ZnO@Glass are similar to those in Fig. 8(a) and Fig. 8(b), respectively, so they are not repeated. This result indicates that both the constructed coatings PTO-8@Glass and PTO-8/MoS ₂ /ZnO@Glass have good chemical resistance.

The adhesion grades of the modified organopolysilazane PTO-8 coatings PTO-8@Glass and PTO-8@SPTE constructed on the surfaces of two different substrates in this example were measured according to the standard GB/T 9286-1988 Both are grade 0; the adhesion grades of the corresponding PTO-8/MoS ₂ /ZnO composite coatings PTO-8/MoS ₂ /ZnO@Glass and PTO-8/MoS ₂ /ZnO@SPTE are also grade 0. This indicates that the constructed modified organopolysilazane PTO-8 still maintains the inherent excellent anchoring properties of polysilazane to different substrates.

According to the standard GB/T 6739-2006, the pencil hardness of the modified organopolysilazane PTO-8 coatings PTO-8@Glass and PTO-8@SPTE constructed on the surface of two different substrates in this example were both measured. The pencil hardness of the corresponding PTO-8/MoS ₂ /ZnO composite coatings PTO-8/MoS ₂ /ZnO@Glass and PTO-8/MoS ₂ /ZnO@SPTE surfaces are also 2H.

Through the erasability test of the scratches of the oil-based marker on the coating surface, it was found that the modified organopolysilazane PTO-8 coatings PTO-8@Glass and PTO constructed in this example were -8@SPTE surface, ink scratches from oil-based markers can be easily wiped off and will not remain on the coating surface. This indicates that the constructed modified organopolysilazane PTO-8 coated PTO-8@Glass and PTO-8@SPTE surfaces have good easy-to-clean properties.

The easy-cleaning performance of the hydrophobic coating was evaluated by methylene blue as a simulated contaminant on the surface of the coating to conduct a soil removal experiment. On the surface of the constructed M-OPSZ/micro-nanomaterial composite coatings PTO-8/MoS ₂ /ZnO and PTO-8/MoS ₂ /ZnO@SPTE placed at an inclination angle of 15° from the horizontal direction, a certain mass of To simulate the contaminant methylene blue, by adding deionized water dropwise to the surface, the water droplets roll off the coating surface and take away the methylene blue contamination, so that the contamination on the coating surface can be completely removed. This indicates that the constructed M-OPSZ/micro-nanomaterial composite coatings PTO-8/MoS ₂ /ZnO@Glass and PTO-8/MoS ₂ /ZnO@SPTE surface have good easy-cleaning properties.

According to the above test results, the modified organopolysilazane PTO-8 coatings and the corresponding PTO-8/MoS ₂ /ZnO composite coatings constructed on different substrates have excellent adhesion and high hardness and good easy cleaning performance.

The SEM images of the PTO-8/MoS ₂ /ZnO composite coating PTO-8/MoS ₂ /ZnO@SPTE surface constructed on the surface of tinplate in this example are similar to those shown in Fig. 9(a) and Fig. 9(b). Repeat again. This shows that the surface of the PTO-8/MoS ₂ /ZnO@SPTE coating constructed in this example also has a multi-layered micro-nano structure and similar surface micro-morphological characteristics.

Example 8 Application of Modified Organopolysilazane Modified Based on Long Chain Alkyl Compounds

0.3 g of the modified organopolysilazane TIO-15 prepared in Example 4 was dissolved in 4.7 g of ethyl acetate solvent, and mixed evenly to obtain a TIO-15 solution with a mass fraction of 6 wt %; (Glass) and tinplate (SPTE) as substrates, the prepared TIO-15 solution was applied to the surface of the substrate by spin coating technology, and was thermally cured at 110 ° C for 2.5 hours, that is, to obtain different substrates. The modified organopolysilazane TIO-15 coatings constructed on the surface were denoted as TIO-15@Glass and TIO-15@SPTE, respectively.

Dissolve 0.3 g of the modified organopolysilazane TIO-15 prepared in Example 4 in 1.7 g of ethyl acetate solvent, and mix evenly to obtain a TIO-15 solution with a mass fraction of 30 wt %; Rockite (HNT) and 0.15g Al ₂ O ₃ nanoparticles were added to the TIO-15 solution and mixed uniformly to obtain a TIO-15/HNT/Al ₂ O ₃ composite solution; The prepared TIO-15/HNT/Al ₂ O ₃ composite solution was coated on the surface of the substrate by the drop casting technique, and it was thermally cured at 110 ° C for 2.5 hours, that is, the surface of different substrates was obtained. The constructed TIO-15/HNT/Al ₂ O ₃ composite coatings were denoted as TIO-15/HNT/Al ₂ O ₃ @Glass and TIO-15/HNT/Al ₂ O ₃ @SPTE, respectively.

A DSA 100 contact angle measuring instrument from KRUSS, Germany was used to measure the water contact angles of the surfaces of the different coatings constructed in this example. The test results show that the water contact angles of the modified organopolysilazane TIO-15 coatings TIO-15@Glass and TIO-15@SPTE constructed on the surfaces of two different substrates in this example are 107.5° and 107.5°, respectively. 108.2°, showing hydrophobicity; while the corresponding TIO-15/HNT/Al ₂ O ₃ composite coatings TIO-15/HNT/Al ₂ O ₃ @Glass and TIO-15/HNT/Al ₂ O ₃ @SPTE surfaces The water contact angles of 157.3° and 158.9°, respectively, show superhydrophobicity. The photos of the water droplets in contact with the surfaces of the TIO-15 coatings TIO-15@Glass and TIO-15@SPTE obtained by the contact angle test are similar to Fig. /HNT/Al ₂ O ₃ composite coating TIO-15/HNT/Al ₂ O ₃ @Glass and TIO-15/HNT/Al ₂ O ₃ @SPTE surface contact photos are compared with Fig. 7(a) and Figure 7(b) is similar and will not be repeated.

In addition, the test results of the water contact angle of the coating surface also show that the modified organopolysilazane TIO-15 coatings TIO-15@Glass and TIO-15/HNT/Al ₂ After the _O3 composite coating TIO- ₁₅ /HNT/ _Al2O3 @Glass was immersed in _H2SO4 aqueous solution with pH 1.0 for ₂₄ hours, the water contact angles were 105.7° and 153.6°, respectively, which were slightly lower than those before immersion. The water contact angle of the coating surface still showed hydrophobicity and superhydrophobicity, respectively. Photographs of the corresponding water droplets in contact with the surfaces of TIO-15 coated TIO-15@Glass and TIO-15/HNT/Al ₂ O ₃ composite coated TIO-15/HNT/Al ₂ O ₃ @Glass, respectively Figure 8(a) is similar to Figure 8(b) and will not be repeated. This result shows that both the constructed coatings TIO-15@Glass and TIO-15/HNT/Al ₂ O ₃ @Glass have good chemical resistance properties.

According to the standard GB/T 9286-1988, the adhesion grades of TIO-15@Glass and TIO-15@SPTE of modified organopolysilazane TIO-15 coatings constructed on the surface of two different substrates in this example were measured Both are grade 0; the adhesion grades of the corresponding TIO-15/HNT/Al ₂ O ₃ composite coatings TIO-15/HNT/Al ₂ O ₃ @Glass and TIO-15/HNT/Al ₂ O ₃ @SPTE Both are level 0. This indicates that the constructed modified organopolysilazane TIO-15 still maintains the inherent excellent anchoring properties of polysilazane to different substrates.

According to the standard GB/T 6739-2006, the pencil hardness of the modified organopolysilazane TIO-15 coatings TIO-15@Glass and TIO-15@SPTE constructed on the surface of two different substrates in this example were both measured. is 4H; the pencil hardness of the corresponding TIO-15/HNT/Al ₂ O ₃ composite coatings TIO-15/HNT/Al ₂ O ₃ @Glass and TIO-15/HNT/Al ₂ O ₃ @SPTE surfaces are also uniform is 4H.

Through the erasability test of the scratches of the oil-based marker on the coating surface, it is found that the modified organopolysilazane TIO-15 coatings TIO-15@Glass and TIO constructed in this example -15@SPTE surface, ink scratches from oil-based markers can be easily wiped off and will not remain on the coating surface. This indicates that the constructed modified organopolysilazane TIO-15 coatings TIO-15@Glass and TIO-15@SPTE have good easy-to-clean properties.

The easy-cleaning performance of the hydrophobic coating was evaluated by methylene blue as a simulated contaminant on the surface of the coating to conduct a soil removal experiment. As-built M-OPSZ/micro-nanomaterial composite coatings TIO-15/HNT/Al ₂ O ₃ @Glass and TIO-15/HNT/Al ₂ O ₃ @SPTE placed at an inclined angle of 15° from the horizontal A certain quality of simulated pollutant methylene blue is placed on the surface of the coating. By adding deionized water dropwise to the surface, the water droplets roll off the coating surface and take away the methylene blue pollutants, so that the pollutants on the coating surface can be completely removed. This indicates that the constructed M-OPSZ/micro-nanomaterial composite coatings TIO-15/HNT/Al ₂ O ₃ @Glass and TIO-15/HNT/Al ₂ O ₃ @SPTE have good surface cleaning properties.

According to the above test results, the modified organopolysilazane TIO-15 coatings and the corresponding TIO-15/HNT/Al ₂ O ₃ composite coatings constructed on different substrates have excellent adhesion, high hardness and good easy cleaning properties.

The SEM photos of the TIO-15/HNT/Al ₂ O ₃ composite coating TIO-15/HNT/Al ₂ O ₃ @SPTE surface constructed on the surface of tinplate in this example are shown in Figure 9(a) and Figure 9(b) are similar, so they will not be repeated. This shows that the surface of the TIO-15/HNT/Al ₂ O ₃ @SPTE coating constructed in this example also has a multi-layered micro-nano structure and similar surface micro-morphological characteristics.

According to Examples 1 to 8 as described above, the modified organopolysilazane M-OPSZ based on the modification of long-chain alkyl compounds prepared by the present invention can maintain the excellent anchoring effect of polysilazane on most substrates. At the same time, it imparts the hydrophobicity of long-chain alkyl compounds. The coatings constructed with M-OPSZ and M-OPSZ/micro-nanomaterial composites on the surfaces of different substrates have good hydrophobicity and superhydrophobicity, respectively; and have excellent adhesion, high pencil hardness, excellent Easy cleaning properties and good chemical resistance and durability. Therefore, the modified organopolysilazane M-OPSZ based on the modification of long-chain alkyl compounds prepared in the present invention is expected to exhibit its advantages in the field of constructing hydrophobic and superhydrophobic coatings with excellent stability and durability, and Very broad application prospects.

Embodiments of the present invention are not limited by the examples. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the ideas and principles of the present invention should be equivalent substitutions, and are included in the protection scope of the present invention.

Claims (10)

1. the modified organopolysilazane modified based on long-chain alkyl compounds, is characterized in that, its structural formula is:

Wherein, the side groups R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ on the main chain are organic groups or hydrogen atoms, and R ₁ , R ₂ , R ₃ , R _4. At least one of R ₅ , R ₆ , R ₇ and R ₈ is a hydrogen atom and an organic group; the organic group is a straight or branched chain alkyl, alkenyl, alkyne containing 1 to 5 carbons base or

One or more of; R ₁₁ is a straight-chain alkylene group containing 1 to 4 carbons; R ₁₂ is a straight-chain alkylene group containing 1 to 4 carbons; R ₉ is -(CH ₂ ) ₆ -,

or

R ₁₀ is methyl, or three-membered, four-membered or five-membered saturated alicyclic ring, or benzyl; n is an integer from 4 to 50; x and y are the fractions of each structural unit in the total structural unit, x+ y is equal to 1; wherein, y is the fraction of the total number of structural units to which the long-chain alkyl compound is bonded. 2. the preparation method of modified organopolysilazane based on long-chain alkyl compound modification according to claim 1, is characterized in that comprising the following steps: (1) Synthesis of long-chain alkyl compounds: under the protection of inert gas, add alcohol monomers and diisocyanate monomers to ether solvents, and mix them evenly; The reaction is carried out at the temperature for 2 to 12 hours to obtain a long-chain alkyl compound solution; the alcohol monomer is a long straight-chain saturated monobasic aliphatic alcohol, a long straight-chain monobasic aromatic alcohol or a long straight-chain saturated monobasic lipid Cyclic alcohol; (2) Preparation of modified organopolysilazane based on long-chain alkyl compound modification: under inert gas protection, add organopolysilazane to the long-chain alkyl compound solution obtained in step (1). , stirring evenly; at a temperature of 20-60 °C, after 1-8 hours of reaction, remove the solvent in the reaction system to obtain a modified organopolysilazane modified by a long-chain alkyl compound; the organopolysilicon The structural formula of azane is:

Wherein, the side groups R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ on the main chain are organic groups or hydrogen atoms, and R ₁ , R ₂ , R ₃ , R _4. At least one of R ₅ , R ₆ , R ₇ and R ₈ is a hydrogen atom and an organic group; the organic group is a straight or branched chain alkyl, alkenyl, alkyne containing 1 to 5 carbons base or

One or more of these; R ₁₁ is a straight-chain alkylene group containing 1 to 4 carbons, and R ₁₂ is a straight-chain alkylene group containing 1 to 4 carbons; x and y are the total number of structural units, respectively. Fraction of the number of structural units, x+y is equal to 1; wherein, y is the fraction of the structural units bonded to the long-chain alkyl compound in the total number of structural units. 3. the preparation method of modified organopolysilazane based on long-chain alkyl compound modification according to claim 2, is characterized in that: the general structural formula of described alcohol monomer is:

Wherein, R ₁₀ is methyl, three-membered, four-membered or five-membered saturated alicyclic ring, or benzyl; n is an integer of 4-50. 4. the preparation method of modified organopolysilazane based on long-chain alkyl compound modification according to claim 2, is characterized in that: described diisocyanate monomer is hexamethylene diisocyanate, trimethyl A kind of in hexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate; described ether solvent is one or more in tetrahydrofuran, diethyl ether, anisole and dioxane; described The catalyst is one of dibutyltin dilaurate, tetramethylbutanediamine, triethylenediamine and triethylamine. 5. the preparation method of modified organopolysilazane based on long-chain alkyl compound modification according to claim 2, is characterized in that: the mol ratio of described alcohol monomer and isocyanate monomer is 1: 1 ~1:1.1; The amount of the ether solvent is 5 to 20 times the mass sum of the alcohol monomer and the diisocyanate monomer; The dosage of the catalyst is 0.01-0.1 wt% of the total mass of the alcohol monomer and the diisocyanate monomer; The mass ratio of the organopolysilazane to the long-chain alkyl compound is 1:1 to 50:1. 6. the preparation method of modified organopolysilazane based on long-chain alkyl compound modification according to claim 2, is characterized in that: the inert gas described in step (1) and step (2) is nitrogen or Argon. 7. the application of the modified organopolysilazane modified based on long-chain alkyl compounds according to claim 1 in the construction of a stable durable hydrophobic coating, wherein the prepared modified organopolysilazane based on long-chain alkyl compounds is modified The modified organopolysilazane is dissolved in an aprotic solvent and mixed uniformly to obtain an M-OPSZ solution; or the modified organopolysilazane M-OPSZ modified based on long-chain alkyl compounds is dissolved in an aprotic solvent , mix uniformly to obtain M-OPSZ solution, then add the micro-nano material to the M-OPSZ solution, and mix uniformly to obtain M-OPSZ/micro-nano material solution; Then, by coating technology, the M-OPSZ solution is applied to the surface of the substrate or the M-OPSZ/micro-nano material solution is applied to the surface of the substrate, and cured to obtain a stable and durable hydrophobic coating. 8. The application of the modified organopolysilazane modified by long-chain alkyl compounds according to claim 7 in constructing a stable durable hydrophobic coating, wherein the micro-nano material is diatomaceous earth , montmorillonite, molybdenum disulfide, boron nitride, halloysite, _hectorite , attapulgite, _SiO2 nanoparticles, _TiO2 nanoparticles, _Al2O3 nanoparticles, ZnO nanoparticles, carbon nanotubes and one or more of graphene oxide; In the M-OPSZ solution, the M-OPSZ content is 1-40wt%; In the M-OPSZ/micro-nano material solution, the amount of the micro-nano material is 1-40 wt % of the mass of the M-OPSZ solution. 9. The application of the modified organopolysilazane modified by long-chain alkyl compounds according to claim 7 in constructing a stable durable hydrophobic coating, wherein the aprotic solvent is acetone, tetrahydrofuran , one or more of butyl acetate, toluene, ethyl acetate, xylene and n-hexane; The coating technique is drop casting, dipping, spray coating, spin coating or blade coating; The base material is one of inorganic non-metallic materials, metal materials, polymer materials and composite materials with one-dimensional, two-dimensional or three-dimensional structures; The curing is to cure the surface coating obtained by coating at a temperature of 60-200° C. for 0.5-6 hours. 10. The application of the modified organopolysilazane modified by long-chain alkyl compounds according to claim 7 in constructing a stable and durable hydrophobic coating, wherein the M-OPSZ solution is applied to the surface of the substrate The water droplet contact angle of the stable and durable hydrophobic coating obtained by curing is 104°～110°; the M-OPSZ/micro-nano material solution is coated on the surface of the substrate and cured to obtain a stable and durable hydrophobic coating. The water droplet contact angle is 150°～ 180°.

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