Preparation and application of super-hydrophobic film material

By introducing low surface energy organofluorine silicon and nano-TiO2 onto the surface of polystyrene, superhydrophobic thin film materials were prepared, solving the problem of poor superhydrophobicity of polystyrene thin film materials and achieving long-lasting hydrophobic effect and self-healing ability.

CN120904499BActive Publication Date: 2025-12-05NANTONG HUANENG NEW MATERIAL CO LTD
View PDF 3 Cites 0 Cited by

Patent Information

Application Number
CN202511449801.0
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-10-11
Publication Date
2025-12-05
Estimated Expiration
2045-10-11

AI Technical Summary

Technical Problem

Existing polystyrene film materials have poor superhydrophobic properties and lack durability, making them easily damaged by external forces.

Method used

Superhydrophobic thin film materials were prepared by introducing low surface energy organofluorine silicon and rough TiO2 onto the surface of polystyrene through chemical copolymerization. KH570 modified nano-titanium dioxide was copolymerized with styrene and bis(difluoromethyl)biphenyl dodecene to form micro-nano structures and molecular network structures, thereby enhancing hydrophobic properties.

Benefits of technology

The prepared superhydrophobic thin film material has durable hydrophobic properties and can self-repair after the micro-nano structure on the coating surface is damaged, maintaining excellent hydrophobic effect and improving interfacial adhesion strength and mechanical properties.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure SMS_1
    Figure SMS_1
  • Figure SMS_2
    Figure SMS_2
  • Figure SMS_3
    Figure SMS_3
Patent Text Reader

Abstract

The application relates to the technical field of thin films, and discloses preparation and application of super-hydrophobic thin film material; after nano TiO2 is treated by KH570, certain micro-nano structures are formed on the material surface, the specific surface area is increased, water drops form 'cavitation' with the material surface, water beads cannot contact the material surface, meanwhile, the dispersion of the nano particles in the matrix is promoted, the interface bonding strength is improved, the composite material is endowed with excellent mechanical properties; in addition, long-chain alkane with hydrophobic performance is grafted, can be closely connected with the polystyrene matrix by interweaving, intermolecular bonding is generated in the molecular chains, a supramolecular network structure is formed, and the hydrophobic performance is further improved; in addition, low-surface-energy substances such as organic fluorine and silicon are introduced on the material surface, so that the prepared composite material has low surface free energy, water beads cannot stay on the surface, and the super-hydrophobic effect is realized.
Need to check novelty before this filing date? Find Prior Art

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of thin films, in particular to preparation and application of super-hydrophobic thin film material. BACKGROUND

[0002] The super-hydrophobic material is a kind of bionic functional material based on the "lotus effect", the static contact angle of water droplets on the surface of the material is greater than 150 degrees, and the rolling angle is less than 10 degrees, due to the self-cleaning, waterproof, antifouling, anticorrosion and other characteristics of the super-hydrophobic material, the super-hydrophobic material has a wide application prospect in electrical appliances, chemical industry, national defense and military, etc., polystyrene is a kind of hydrophobic material, and the super-hydrophobic performance of polystyrene can expand its application to a wider range, and in recent years, the polystyrene has become a hot spot in material research.

[0003] There are usually two ways to prepare a super-hydrophobic surface: one is to construct a suitable roughness on the surface of a hydrophobic material; and the other is to modify the surface of a material with suitable roughness with a low-surface-energy chemical substance. The application patent CN115093597A discloses a preparation method of super-hydrophobic polystyrene film, a silica sol is prepared by adopting a sol-gel method, using methyl triethoxysilane as a precursor, tetraethyl orthosilicate as a precursor, anhydrous methanol as a solvent and ammonia water as a catalyst, a nanometer silica gel is prepared, and then a non-solvent induced phase separation principle is used, PS is used as a base material, tetrahydrofuran is used as a good solvent, anhydrous ethanol and the nanometer silica sol are used as non-solvents, and the PS super-hydrophobic film is prepared on a glass substrate by adopting a drop coating method, the obtained super-hydrophobic film has large surface roughness and certain wear resistance, and the preparation process is simple, but the super-hydrophobic performance of the film is derived from the construction of the surface micro-morphology, the PS does not change chemically, and therefore the durability of the super-hydrophobicity is poor, the super-hydrophobicity is easily damaged by external force, and the super-hydrophobicity is lost; the application introduces low-surface-energy organic fluorosilicon and rough TiO2 on the surface of polystyrene by chemical copolymerization, so that the super-hydrophobic performance of the prepared polystyrene film is durable and the process is simple. SUMMARY

[0004] The application solves the technical problem of providing preparation and application of super-hydrophobic thin film material, and solves the problem of poor super-hydrophobic performance of polystyrene thin film material.

[0005] The technical scheme of the application is:

[0006] A preparation method of super-hydrophobic film material, the preparation method is carried out according to the following steps: adding KH570 modified nano-titanium dioxide and toluene solvent into a reaction bottle, stirring uniformly, then adding dibenzoyl peroxide, stirring, adding styrene and bis-difluoromethyl biphenyl dodecene, after the polymerization reaction is completed, cooling, toluene centrifugal washing, obtaining super-hydrophobic composite material, then adding the super-hydrophobic composite material into toluene solvent, ultrasonic dispersion, placing the obtained dispersion liquid on a glass substrate to coat a film, and obtaining the super-hydrophobic film material after standing and drying.

[0007] Further, the mass ratio of the reactants is: KH570 modified nano-titanium dioxide:dibenzoyl peroxide:styrene: bis-difluoromethyl biphenyl dodecene = (40-64) g:(6-10) g:100 g:(15-40) g.

[0008] Further, the polymerization reaction temperature is 70-90 DEG C, and the reaction time is 5-8 h.

[0009] Further, the preparation method of the bis-difluoromethyl biphenyl dodecene is carried out according to the following steps:

[0010] (1) adding 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diformyl and dichloromethane solvent into a reaction bottle, stirring uniformly, then adding diethylamine trifluoride, after the reaction is completed, pouring the reaction liquid into ice water, adjusting the pH to 8-9 with saturated sodium bicarbonate solution, standing and separating, dichloromethane extracting the aqueous phase, concentrating the organic phase, and purifying by column chromatography to obtain bis-difluoromethyl biphenyl phenol.

[0011]

[0012] (2) adding sodium hydride and dimethyl sulfoxide solvent into a reaction bottle, stirring uniformly under nitrogen atmosphere, adding bis-difluoromethyl biphenyl phenol dimethyl sulfoxide solution, stirring at 20-35 DEG C for 1-3 h, then cooling to 0-10 DEG C, adding 12-bromo-1-dodecene, and warming to react, after the reaction is completed, adding deionized water, dichloromethane extraction, concentrating the organic phase, and purifying by silica gel column chromatography to obtain bis-difluoromethyl biphenyl dodecene.

[0013]

[0014] Further, the amount ratio of the reactants and solvent in step (1) is: 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diformyl: diethylamine trifluoride: dichloromethane solvent = 1 g:(2.5-3.5) g:(8-10) mL.

[0015] Further, the reaction temperature in the step (1) is 20-35℃, and the reaction time is 2-4h.

[0016] Further, the ratio of the use amount of each reactant and solvent in the step (2) is: sodium hydride: dimethyl sulfoxide solvent: bis-difluoromethyl diphenol: 12-bromo-1-dodecene = (0.22-0.26) g: (4-8) mL: 1 g: (2.1-2.7) g.

[0017] Further, the reaction temperature in the step (2) is 40-60℃, and the reaction time is 16-24h.

[0018] Further, the preparation method of the KH570 modified nano titanium dioxide is carried out according to the following steps: adding nano titanium dioxide and ethanol solvent into a reaction bottle, stirring uniformly, adding KH570, stirring for 10-30min, then adding ammonia water, heating to 40-50℃, and reacting for 36-48h, after the reaction is completed, centrifugal washing with ethanol to obtain the KH570 modified nano titanium dioxide.

[0019] The beneficial technical effects of the present application are:

[0020] 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diformaldehyde is subjected to the action of fluorinated reagent diethylamine sulfur trifluoride to obtain bis-difluoromethyl diphenol, then 12-bromo-1-dodecene is subjected to substitution reaction with the phenolic hydroxyl group of bis-difluoromethyl diphenol to obtain bis-difluoromethyl diphenyl dodecene, then KH570 is used to modify the surface of nano TiO2 to obtain modified TiO2 with olefin end groups, finally, bis-difluoromethyl diphenyl dodecene and styrene are copolymerized to form a film to obtain a super-hydrophobic film material.

[0021] The nano TiO2 treated by KH570 can make the organic phase and the inorganic phase be compounded in the nano size range, promote the dispersion of the nano particles in the matrix, improve the interface bonding strength, endow the composite material with excellent mechanical properties, and form a certain micro-nano structure on the material surface, increase the surface area, make the water droplets form "cavitation" with the material surface, so that the water droplets cannot contact the material surface; in addition, the grafting of the long-chain alkane with hydrophobic property can be closely connected with the polystyrene matrix, make the molecular chains produce intermolecular bonding, form a supramolecular network structure, and further improve the hydrophobic property; in addition, the organic fluorine, silicon and other low surface energy substances are introduced on the material surface, the bond energy of C-F and Si-O is larger than that of C-H and C-O, and the atomic electron cloud shielding of C-C bond is stronger than that of H atom, so that the prepared composite material has low surface free energy, a very thin molecular layer can be formed on the material surface, thereby reducing the surface energy, so that the water droplets cannot stay on the surface, and the hydrophobic effect is realized; after the micro-nano structure on the surface of the coating is damaged, the nano structure at the bottom of the coating remains intact, and the new coating can repair the damaged micro-nano structure, ensuring the durability of the super-hydrophobic effect of the composite material. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0023] The preparation method of the KH570 modified nano titanium dioxide is as follows: 5 g of nano titanium dioxide and 500 mL of ethanol solvent are added to a reaction bottle, stirred uniformly, 50 mL of KH570 is added, 50 mL of ammonia water is added after stirring for 20 min, the temperature is increased to 40℃, and the reaction is carried out for 36 h. After the reaction is completed, the ethanol is centrifuged and washed to obtain the KH570 modified nano titanium dioxide.

[0024] Example 1

[0025] (1) 15 g of 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diformyl and 130 mL of dichloromethane solvent are added to a reaction bottle, stirred uniformly, and then 45 g of diethylamine sulfide is added dropwise. After reaction at 35℃ for 3 h, the reaction liquid is poured into ice water, a saturated sodium bicarbonate solution is used to adjust the pH to 9, and the reaction liquid is left to separate into two layers. The dichloromethane is extracted from the water phase, the organic phase is concentrated, and column chromatography is used for purification to obtain bis-difluoromethyl biphenol.

[0026] (2) Add 2.2 g of sodium hydride and 60 mL of dimethyl sulfoxide solvent into a reaction bottle, stir uniformly under nitrogen atmosphere, add 10 g of bis-difluoromethyl diphenyl phenol dimethyl sulfoxide solution, stir at 25°C for 2 h, then cool to 5°C, add 23 g of 12-bromo-1-dodecene, warm to 50°C for 18 h, then add deionized water, dichloromethane extraction, organic phase is combined and concentrated, silica gel column chromatography purification, to obtain bis-difluoromethyl diphenyl dodecene.

[0027] (3) Add 40 g of KH570 modified nano titanium dioxide and toluene solvent into a reaction bottle, stir uniformly, then add 8 g of dibenzoyl peroxide, stir, add 100 g of styrene and 15 g of bis-difluoromethyl diphenyl dodecene, react at 85°C for 7 h, then cool, toluene centrifugal washing, to obtain super-hydrophobic composite material, then add super-hydrophobic composite material into toluene solvent, ultrasonic dispersion, the obtained dispersion liquid is coated on a glass substrate to form a film, and a super-hydrophobic film material is obtained after standing and drying.

[0028] Example 2

[0029] (1) Add 8 g of 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxaldehyde and 70 mL of dichloromethane solvent into a reaction bottle, stir uniformly, then drop 28 g of diethylamine trifluoride, react at 35°C for 4 h, then pour the reaction liquid into ice water, adjust pH to 8.5 with saturated sodium bicarbonate solution, stand and separate, dichloromethane extract the aqueous phase, concentrate the organic phase, and purify by column chromatography to obtain bis-difluoromethyl diphenyl phenol.

[0030] (2) Add 11 g of sodium hydride and 200 mL of dimethyl sulfoxide solvent into a reaction bottle, stir uniformly under nitrogen atmosphere, add 50 g of bis-difluoromethyl diphenyl phenol dimethyl sulfoxide solution, stir at 30°C for 3 h, then cool to 0°C, add 105 g of 12-bromo-1-dodecene, warm to 55°C for 20 h, then add deionized water, dichloromethane extraction, organic phase is combined and concentrated, silica gel column chromatography purification, to obtain bis-difluoromethyl diphenyl dodecene.

[0031] (3) Add 50 g of KH570 modified nano titanium dioxide and toluene solvent into a reaction bottle, stir uniformly, then add 9 g of dibenzoyl peroxide, stir, add 100 g of styrene and 25 g of bis-difluoromethyl diphenyl dodecene, react at 75°C for 6 h, then cool, toluene centrifugal washing, to obtain super-hydrophobic composite material, then add super-hydrophobic composite material into toluene solvent, ultrasonic dispersion, the obtained dispersion liquid is coated on a glass substrate to form a film, and a super-hydrophobic film material is obtained after standing and drying.

[0032] Example 3

[0033] (1) Into a reaction flask, 5 g of 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxaldehyde and 45 mL of dichloromethane solvent were added, stirred uniformly, then 17 g of diethylamine trifluoride was added dropwise, after 3 h of reaction at 25°C, the reaction solution was poured into ice water, the pH was adjusted to 9 with saturated sodium bicarbonate solution, and the solution was left to stand and separate into layers, the water phase was extracted with dichloromethane, the organic phase was concentrated, and column chromatography was used for purification to obtain bis-difluoromethyl biphenol.

[0034] (2) Into a reaction flask, 7.5 g of sodium hydride and 150 mL of dimethyl sulfoxide solvent were added, stirred uniformly under nitrogen atmosphere, 30 g of bis-difluoromethyl biphenol dimethyl sulfoxide solution was added, stirred for 2 h at 35°C, then cooled to 10°C, 72 g of 12-bromo-1-dodecene was added, and the temperature was raised to 60°C for 22 h of reaction, then deionized water was added, extracted with dichloromethane, the organic phase was combined and concentrated, and column chromatography was used for purification to obtain bis-difluoromethyl biphenyl dodecene.

[0035] (3) Into a reaction flask, 60 g of KH570 modified nano titanium dioxide and toluene solvent were added, stirred uniformly, then 8 g of dibenzoyl peroxide was added, stirred, 100 g of styrene and 35 g of bis-difluoromethyl biphenyl dodecene were added, and the temperature was raised to 90°C for 8 h of reaction, then cooled, washed with toluene by centrifugation, to obtain a super-hydrophobic composite material, then the super-hydrophobic composite material was added to toluene solvent, ultrasonic dispersion was performed, the obtained dispersion liquid was coated on a glass substrate to form a film, and after standing and drying, a super-hydrophobic film material was obtained.

[0036] Example 4

[0037] (1) Into a reaction flask, 25 g of 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxaldehyde and 220 mL of dichloromethane solvent were added, stirred uniformly, then 70 g of diethylamine trifluoride was added dropwise, after 3 h of reaction at 30°C, the reaction solution was poured into ice water, the pH was adjusted to 8 with saturated sodium bicarbonate solution, and the solution was left to stand and separate into layers, the water phase was extracted with dichloromethane, the organic phase was concentrated, and column chromatography was used for purification to obtain bis-difluoromethyl biphenol.

[0038] (2) Into a reaction flask, 5.2 g of sodium hydride and 100 mL of dimethyl sulfoxide solvent were added, stirred uniformly under nitrogen atmosphere, 19 g of bis-difluoromethyl biphenol dimethyl sulfoxide solution was added, stirred for 3 h at 25°C, then cooled to 0°C, 46 g of 12-bromo-1-dodecene was added, and the temperature was raised to 60°C for 18 h of reaction, then deionized water was added, extracted with dichloromethane, the organic phase was combined and concentrated, and column chromatography was used for purification to obtain bis-difluoromethyl biphenyl dodecene.

[0039] (3) 64 g of KH570 modified nano-titanium dioxide and toluene solvent were added into a reaction bottle, stirred uniformly, 9.5 g of dibenzoyl peroxide was added, stirred, 100 g of styrene and 40 g of bis-difluoromethyl biphenyl dodecene were added, after reaction at 90°C for 7 h, cooling, toluene centrifugal washing, to obtain a super-hydrophobic composite material, then the super-hydrophobic composite material was added into toluene solvent, ultrasonic dispersion, the obtained dispersion liquid was coated on a glass substrate to form a film, and after standing and drying, a super-hydrophobic film material was obtained.

[0040] Comparative Example 1

[0041] (1) 10 g of 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diformyl and 90 mL of dichloromethane solvent were added into a reaction bottle, stirred uniformly, 25 g of diethylamine sulfide was added dropwise, after reaction at 35°C for 4 h, the reaction liquid was poured into ice water, saturated sodium bicarbonate solution was used to adjust the pH to 8, standing and separating the layers, dichloromethane was used to extract the aqueous phase, the organic phase was concentrated, and column chromatography purification was performed to obtain bis-difluoromethyl biphenyl phenol.

[0042] (2) 2.5 g of sodium hydride and 60 mL of dimethyl sulfoxide solvent were added into a reaction bottle, stirred uniformly under nitrogen atmosphere, 10 g of bis-difluoromethyl biphenyl phenol dimethyl sulfoxide solution was added, stirred at 25°C for 3 h, then cooled to 0°C, 23 g of 12-bromo-1-dodecene was added, after reaction at 60°C for 20 h, deionized water was added, dichloromethane was used for extraction, the organic phases were combined and concentrated, and silica gel column chromatography purification was performed to obtain bis-difluoromethyl biphenyl dodecene.

[0043] (3) 100 g of styrene and toluene solvent were added into a reaction bottle, stirred uniformly, 10 g of dibenzoyl peroxide was added, stirred, 40 g of bis-difluoromethyl biphenyl dodecene was added, after reaction at 85°C for 8 h, cooling, toluene centrifugal washing, to obtain a hydrophobic composite material, then the hydrophobic composite material was added into toluene solvent, ultrasonic dispersion, the obtained dispersion liquid was coated on a glass substrate to form a film, and after standing and drying, a hydrophobic film material was obtained.

[0044] Comparative Example 2

[0045] (1) 50 g of KH570 modified nano-titanium dioxide and toluene solvent were added into a reaction bottle, stirred uniformly, 8 g of dibenzoyl peroxide was added, stirred, 100 g of styrene was added, after reaction at 80°C for 6 h, cooling, toluene centrifugal washing, to obtain a hydrophobic composite material, then the hydrophobic composite material was added into toluene solvent, ultrasonic dispersion, the obtained dispersion liquid was coated on a glass substrate to form a film, and after standing and drying, a hydrophobic film material was obtained.

[0046] Static contact angle test: The contact angle and the roll angle of water on the film were measured by a contact angle meter. The droplets were added to the film by a microsyringe, each droplet was 3-5 μL, and each sample was measured for 5 points, and the average value was taken.

[0047] Water absorption test: The prepared film was soaked in deionized water at 25°C for 24 hours at room temperature. After taking out, the water on the surface of the coating was immediately absorbed with filter paper, and accurately weighed. The average value of three measurements was taken as the result.

[0048] Water absorption (%) = (m1-m0) / m0

[0049] m0: the mass of the film before soaking, m1: the mass of the film after soaking.

[0050]

[0051] From the above table data, it can be seen that with the increase of the content of modified nano-TiO2 and organic fluorine, the contact angle of the film with water gradually increases, and the roll angle and the water absorption rate decrease. In the comparative example 1 without nano-TiO2, the contact angle of the film is 121.6°, the roll angle is 12.3°, and the water absorption rate is 8.61%, indicating that the film has certain hydrophobic property. This is because the long-chain alkane with hydrophobic property is closely connected with the substrate, so that the molecular chain produces intermolecular bonding, forming a supramolecular network structure, and improving the hydrophobic property. In the comparative example 2 without organic fluorine, the contact angle of the film with water is 113.8°, the roll angle is 18.6°, and the water absorption rate is 9.36%, indicating that the hydrophobicity of organic fluorine is good. This is because the surface energy of organic fluorine is low, the bond energy of C-F bond is larger than that of C-H bond, and the atomic electron cloud shielding of C-C bond is stronger than that of H atom. A very thin molecular layer can be formed on the surface of the material, thereby reducing the surface energy and improving the hydrophobicity of the film, but it has not reached the requirement of super-hydrophobic property.

[0052] In examples 1 to 4, both organic fluorine and organic silicon contain nano-TiO2. With the increase of the content of the three, the contact angle gradually increases, the maximum reaches 158.4°, the roll angle reaches the minimum of 3.6°, and the water absorption rate reaches the minimum of 3.54%. At this time, the super-hydrophobicity of the film is greatly improved. This is because the surface energy of organic fluorine and silicon is low, and the specific surface area of nano-titanium dioxide is large, which can increase the roughness of the film. Both contain hydrophobic materials and have suitable roughness, so the super-hydrophobicity of the material is very superior. The reason for the decrease of the contact angle and the increase of the water absorption rate is that when the nano-TiO2 is excessive, the agglomeration phenomenon is easy to occur, and the proportion of nano-TiO2 decreases, so that the surface roughness decreases.

[0053] Impact strength test: test by using combined impact testing machine, simple supported beam impact test method, prepare film sample size 50mm*10mm*3mm, pendulum mass 1J, impact speed 3m / s.

[0054]

[0055] From the above table, the impact strength of the composite material is increased from 2.23kJ / m 2 to 2.99kJ / m 2 , higher than Comparative Example 1, indicating that the addition of nano-TiO2 can improve the impact strength of the composite material.

[0056] The above description is only a preferred embodiment of the present application, and is not intended to limit the present application in other forms. Any skilled person in the art can modify or change the above disclosed technical content to equivalent embodiments. However, any simple modification, equivalent change and modification of the above embodiments without departing from the technical solution of the present application, according to the technical essence of the present application, still belongs to the protection scope of the technical solution of the present application.

Claims

1. A method of preparing a superhydrophobic thin film material, characterized by, The preparation method is carried out according to the following steps: adding KH570 modified nano-titanium dioxide and toluene solvent into a reaction bottle, stirring uniformly, then adding dibenzoyl peroxide, stirring, adding styrene and bis-difluoromethyl biphenyl dodecene, after the polymerization reaction is completed, cooling, toluene centrifugal washing, obtaining the super-hydrophobic composite material, then adding the super-hydrophobic composite material into the toluene solvent, ultrasonic dispersion, obtaining the dispersion liquid, coating the film on the glass substrate, and obtaining the super-hydrophobic film material after standing and drying. The preparation method of the bis-difluoromethyl biphenyl dodecene is carried out according to the following steps: (1) adding 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diformyl and dichloromethane solvent into a reaction bottle, stirring uniformly, then adding diethylamine sulfonium trifluoride dropwise, after the reaction is completed, pouring the reaction liquid into ice water, adjusting the pH to 8-9 with saturated sodium bicarbonate solution, standing and separating, extracting the aqueous phase with dichloromethane, concentrating the organic phase, and purifying by column chromatography to obtain bis-difluoromethyl biphenyl phenol; (2) adding sodium hydride and dimethyl sulfoxide solvent into a reaction bottle, stirring uniformly under nitrogen atmosphere, adding bis-difluoromethyl biphenyl phenol dimethyl sulfoxide solution, stirring at 20-35℃ for 1-3h, then cooling to 0-10℃, adding 12-bromo-1-dodecene, and warming to react, after the reaction is completed, adding deionized water, extracting with dichloromethane, combining the organic phase and concentrating, purifying by silica gel column chromatography to obtain bis-difluoromethyl biphenyl dodecene.

2. The method of claim 1, wherein the method further comprises: The mass ratio of the reactants is: KH570 modified nano-titanium dioxide:dibenzoyl peroxide:styrene: bis-difluoromethyl biphenyl dodecene = (40-64) g:(6-10) g:100 g:(15-40) g.

3. The method of claim 1, wherein the method further comprises: The polymerization reaction temperature is 70-90℃, and the reaction time is 5-8h.

4. The method of claim 1, wherein the method further comprises: The amount ratio of the reactants and solvent in step (1) is: 4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-diformyl: diethylamine sulfonium trifluoride:dichloromethane solvent = 1 g:(2.5-3.5) g:(8-10) mL.

5. The method of claim 1, wherein the method further comprises: The reaction temperature in step (1) is 20-35℃, and the reaction time is 2-4h.

6. The method of claim 1, wherein the method further comprises: The amount ratio of the reactants and solvent in step (2) is: sodium hydride: dimethyl sulfoxide solvent: bis-difluoromethyl biphenyl phenol: 12-bromo-1-dodecene = (0.22-0.26) g:(4-8) mL:1 g:(2.1-2.7) g.

7. The method of claim 1, wherein the method further comprises: The reaction temperature in step (2) is 40-60℃, and the reaction time is 16-24h.

8. The method of claim 1, wherein the method further comprises: The preparation method of the KH570 modified nano-titanium dioxide is carried out according to the following steps: adding nano-titanium dioxide and ethanol solvent into a reaction bottle, stirring uniformly, adding KH570, stirring for 10-30min, then adding ammonia water, warming to 40-50℃ for 36-48h, after the reaction is completed, ethanol centrifugal washing, obtaining the KH570 modified nano-titanium dioxide.

Citation Information

Patent Citations

  • Preparation method of super-hydrophobic polystyrene film

    CN115093597A

  • Ultrahydrophobic polypropylene / titanium dioxide composite film and preparation method thereof

    CN102675728A

  • Titanium dioxide / polystyrene core / shell particle composite material and preparation method thereof

    CN106749790A