A functional surface modifier, its preparation method and application
By using the thiol-ene click reaction of dithiol, tetramethyldivinyldisilazane and functional reagents, functional reagents were successfully covalently grafted onto the substrate surface, solving the problems of durability and single function of hydrophobic and oleophobic materials in the prior art, and realizing simple, rapid and stable modification of substrate surface.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HANGZHOU NORMAL UNIVERSITY
- Filing Date
- 2025-09-15
- Publication Date
- 2026-07-07
AI Technical Summary
Existing methods for preparing hydrophobic and oleophobic materials suffer from poor physical durability, complex processes, and limited functionality, which restricts their application in various fields.
A functionalized surface modifier was prepared by performing a thiol-ene click reaction under ultraviolet light using dithiol, tetramethyldivinyldisilazane, a photoinitiator, and a functional reagent, and then grafting the functional reagent onto the substrate surface via covalent bonds.
It achieves simple and rapid surface modification, endowing the substrate with durable and stable hydrophobic and oleophobic properties, and is suitable for surface modification of a variety of materials, with a wide range of applications.
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Figure CN121108489B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of surface treatment technology, and particularly relates to a functionalized surface modifier, its preparation method and application. Background Technology
[0002] The contact angle of a liquid on a material surface is considered an indicator of its wetting properties. The wetting properties of a material surface are closely related to many physicochemical processes and have therefore attracted widespread attention. When the contact angle of a liquid on a material surface is greater than 90°, it can be called a hydrophobic or oleophobic material; materials possessing both hydrophobic and oleophobic properties are called dual-hydrophobic materials. The special wettability of material surfaces, such as hydrophobicity and even superhydrophobicity, has led to their widespread application in numerous fields, including construction, clothing, electronic equipment, photovoltaic power generation, and home furnishings.
[0003] In nature, it's not uncommon to observe hydrophobic or oleophobic surfaces on many animals and plants, such as fish scales, water striders, and lotus leaves. In 1997, Barthlott et al. discovered microscale papillary structures and biowax on the surface of lotus leaves exhibiting superhydrophobic properties, suggesting that the superhydrophobicity of the lotus leaf surface originates from this micro- and nano-rough surface structure and the low surface energy of the biowax. Subsequently, researchers have employed various surface chemical modification methods to prepare materials with different surface wetting properties. Currently, the preparation of materials with different wetting properties, such as hydrophobic and oleophobic properties, can be mainly divided into physical methods and chemical methods. Physical methods involve physically bonding hydrophobic and oleophobic coatings or materials to a substrate to prepare hydrophobic and oleophobic materials. For example, Wang et al. used magnetron sputtering combined with wet oxidation and fluorination to construct a transparent, bi-hydrophobic, bristle-like coating similar to the leg structure of a water strider on a glass substrate, resulting in a coating with excellent hydrophobic and oleophobic properties (Surfaces and Interfaces, 2025, 62, 106-275). Zhang et al. prepared a protective coating with fluorinated side chains, a rough structure, and high crosslinking density by reacting a fluorosilicone epoxy acrylate copolymer with a composite curing agent (European Polymer Journal, 2025, 228, 113-793). Yu et al. successfully prepared spherical stable fluorinated reverse micelles with a main-chain semi-fluorinated alternating copolymer shell using trifluorotrichloroethane as a solvent and N,N-dimethylacrylamide as a hydrophilic monomer, and then used spin coating to prepare a film with bi-hydrophobic properties on a silicon substrate (Applied Surface). Science, 2023, 614, 156199.). These methods can give the substrate excellent hydrophobic and oleophobic properties, but most of them have poor physical durability due to insufficient adhesion to the substrate.Chemical methods involve grafting modified groups onto a substrate through chemical reactions to prepare hydrophobic and oleophobic materials. For example, Gou et al. successfully constructed low surface energy hydrophobic and oleophobic fibers by conducting a thiol-ene click chemical reaction between mercaptosilane and the vinyl group of a styrene-butadiene-styrene triblock copolymer, combined with hydroxyl-terminated polydimethylsiloxane modification (Environ SciTechnol, 2024, 58(39): 17376-17385). Liu et al. prepared a hydrophobic coating on the surface of polyurethane by dopamine self-polymerization and reaction with hexamethyldisilazane (Separation and Purification). Technology, 2019, 229, 115801; Zhou et al. prepared hydrophobic materials by reacting dodecafluoroheptyl methacrylate and isocyanate methacrylate with hydroxyl groups on the substrate surface (Polymers, 2023, 15(11), 2505); Hydrophobic and oleophobic materials prepared by chemical methods have excellent hydrophobic or oleophobic abilities. At the same time, due to the chemical bonding between the modified groups and the substrate, the physical durability and chemical stability of the hydrophobic and oleophobic materials are greatly improved. However, these methods generally have problems such as long reaction time, complex process and mostly single function, which greatly limits their application in various fields.
[0004] Therefore, how to provide a simple, stable, and durable hydrophobic and oleophobic surface modifier is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0005] To address the aforementioned technical problems, this invention proposes a simple and rapid functionalized surface modifier, its preparation method, and its application. Furthermore, addressing the issues of limited material functionality and insufficient application range in existing technologies, this invention utilizes different functional reagents to prepare functionalized surface modifiers, thereby imparting different surface wetting properties to the substrate.
[0006] To achieve the above objectives, the present invention provides the following technical solution:
[0007] A functionalized surface modifier comprises the following raw materials in parts by weight:
[0008] 25-50 parts of dithiol, 20-40 parts of tetramethyldivinyldisilazane, 0.2-1 part of photoinitiator, 25-50 parts of functional reagent, and 100 parts of organic solvent.
[0009] Beneficial Effects: In the preparation process of the functionalized surface modifier of this invention, the functional reagent and dithiol undergo a thiol-ene click reaction under ultraviolet light, grafting functional groups onto the dithiol. By controlling the ratio of the two, an excess of dithiol is achieved, leaving residual thiol groups after the thiol-ene click reaction. These excess thiol groups then undergo a thiol-ene click reaction with tetramethyldivinyldisilazane under ultraviolet light, thus perfectly preparing the functionalized surface modifier from the functional reagent, dithiol, and tetramethyldivinyldisilazane through a simple photo-click reaction. In application, the surface modification of the substrate is achieved by relying on the nucleophilic substitution reaction between the silicon-nitrogen bonds in the functionalized surface modifier and the hydroxyl groups on the substrate surface, through the formation of covalent bonds between the modifier and the substrate surface. For successful preparation and application of the functionalized surface modifier, the ratio of each substance in the preparation process must be carefully controlled to achieve the best modification effect.
[0010] Preferably, the dithiol includes aliphatic dithiols with a thiol group at the terminal position, including one or more of ethylenedithiol, propylenedithiol, butyldithiol, pentanedithiol, hexanedithiol, octanedithiol, nonanedithiol, and decandithiol.
[0011] Beneficial effects: Dithiol is the key to linking tetramethyldivinyldisilazane and functional groups. By photo-clicking one of the thiol groups with the vinyl group of tetramethyldivinyldisilazane, and photo-clicking the remaining thiol group with the carbon-carbon double bond in the functional reagent, the functional reagent can be covalently grafted onto the tetramethyldivinyldisilazane molecule under mild photo-clicking reaction conditions, thus achieving a simple and efficient preparation of functionalized surface modifiers.
[0012] Preferably, the photoinitiator includes one or more of 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
[0013] Beneficial effects: Initiators are used to initiate photoclick reactions, which are crucial for the thiol-alkene click reaction. Under ultraviolet light, the initiator molecule forms a free radical and abstracts a hydrogen atom from the thiol group to form an alkylsulfur free radical, thereby initiating the reaction and allowing it to proceed rapidly under mild conditions.
[0014] Preferably, the functional reagent includes one or more of the following: polyfluorinated esters of unsaturated carboxylic acids, long-chain aliphatic unsaturated amines, and unsaturated long-chain aliphatic alkenes;
[0015] Preferably, the polyfluoroester of the unsaturated carboxylic acid includes one or more of dodecylfluoroheptyl methacrylate, dodecylfluoroheptyl acrylate, perfluorooctyl methacrylate, and 3-perfluorohexyl-2-hydroxypropyl acrylate.
[0016] The long-chain aliphatic unsaturated amine is oleylamine;
[0017] The unsaturated long-chain aliphatic olefins include one or more of octadecene, heptadecanene, hexadecene, pentadecene, tetradecene, tridecene, dodecene, undecene, decene, nonene, octene, heptenene, and hexene.
[0018] Beneficial effects: The functional reagents of this invention can be selected from a variety of substances. Among them, the polyfluorinated carbon chain of the polyfluorinated ester of unsaturated carboxylic acid is a functional group, which has hydrophobic and oleophobic properties and can impart excellent hydrophobic and oleophobic properties to the substrate. The amino-substituted long carbon chain of the long-chain aliphatic unsaturated amine is a functional group, which has hydrophobic properties. After acid treatment, the amino group is converted into ammonium ions with positive charge. At this time, due to the enhanced polarity of the group, it is converted into hydrophilicity, which can realize the conversion from hydrophobic to hydrophilic. Therefore, it can adjust the hydrophobicity and hydrophilicity of the substrate surface. The long carbon chain of the unsaturated aliphatic long-chain olefin is a functional group, which has hydrophobic properties and can impart excellent hydrophobicity to the substrate. By using these different functional reagents, the modifier can achieve multiple effects such as hydrophobicity, hydrophobic-hydrophilic conversion, and hydrophobic and oleophobic properties of the substrate surface.
[0019] Preferably, the organic solvent includes one or more of dichloromethane, ethyl acetate, tetrahydrofuran, toluene, and hexane.
[0020] Beneficial effects: The above solvents can ensure that the raw material components are fully mixed, making the reaction more complete.
[0021] A method for preparing a functionalized surface modifier includes the following steps:
[0022] Dithiol, functional reagent, photoinitiator and organic solvent are mixed and placed under ultraviolet light for photoclick reaction for 0.5-1.5 h. Tetramethyldivinyldisilazane is added and placed under ultraviolet light for photoclick reaction for another 0.5-1.5 h to obtain the functionalized surface modifier.
[0023] Beneficial Effects: The surface modifier prepared by this invention is mainly obtained through a thiol-ene photoclick reaction between a functional reagent and dithiol under the action of an organic solvent, a photoinitiator, and ultraviolet light, followed by a further photoclick reaction with tetramethyldivinyldisilazane. The functional reagent in this invention contains unsaturated olefin bonds. The functional group is grafted onto the dithiol using the thiol-ene photoclick reaction, and then the grafted product is reacted with tetramethyldivinyldisilazane to undergo a thiol-ene photoclick reaction. This successfully prepares a functionalized surface modifier from the functional reagent, dithiol, and tetramethyldivinyldisilazane through a simple photoclick reaction. When this surface modifier is applied to a hydroxyl-rich substrate surface, the hydroxyl groups on the substrate surface attack the silicon of tetramethyldivinyldisilazane, resulting in a nucleophilic substitution reaction. Ultimately, the functional group is covalently grafted onto the substrate surface, imparting a durable and stable modification effect to the substrate surface.
[0024] Preferably, the wavelength of the ultraviolet light is 365nm.
[0025] Preferably, the photoclick reactions are all carried out under stirring conditions, and the temperature is 10-60℃.
[0026] Beneficial effects: 365nm ultraviolet light, in combination with an initiator, is used to initiate the reaction at a temperature of 10-60℃. The reaction conditions are mild, and heating is not required.
[0027] Application of a functionalized surface modifier in regulating the wettability of material surfaces.
[0028] Beneficial effects: The wettability of a material surface can be measured by the contact angle of water on the material surface. When the water contact angle is less than 90°, the material is hydrophilic; when the water contact angle is greater than or equal to 90°, the material is hydrophobic. Some materials, such as cotton fabrics, sponges, wood, and paper, have originally hydrophilic surfaces. After covalent modification with functionalized surface modifiers, the material surfaces can acquire hydrophobicity, thereby achieving the regulation of the material surface wettability.
[0029] Preferably, the material is a material rich in hydroxyl groups on its surface, including one or more of fabrics, sponges, wood, paper, metals, and plastics.
[0030] More preferably, if the substrate surface is not rich in hydroxyl groups, the substrate can be treated in a saturated sodium hydroxide solution for 0.5-1 hour before use.
[0031] Beneficial Effects: The functionalized surface modifiers obtained in this invention can be used to modify the surfaces of different substrates through simple methods such as impregnation and spraying, achieving excellent modification effects. When using polyfluorinated esters of unsaturated carboxylic acids as functional reagents to synthesize and use surface modifiers, the material surface exhibits hydrophobic and oleophobic properties, with a water contact angle of 130°-155° and an oil contact angle of 90°-110°. When using long-chain aliphatic unsaturated amines as functional reagents to synthesize and use surface modifiers, the material surface exhibits a water contact angle of 120°-155° and hydrophobic-hydrophilic conversion properties. When using aliphatic long-chain olefins as functional reagents to synthesize and use surface modifiers, the material surface exhibits hydrophobic properties, with a water contact angle of 120°-155°. These modifiers can be widely used in waterproofing, oil resistance, corrosion resistance, stain resistance, and self-cleaning applications.
[0032] Compared with the prior art, the present invention has the following advantages and technical effects:
[0033] The functionalized surface modifier preparation method provided by this invention is simple, rapid, and efficient, requiring only two photo-click reactions. The preparation process is short and easy to manufacture. The functionalized surface modifier provided by this invention chemically modifies the substrate surface through impregnation or spraying. The silicon-nitrogen bonds in the functionalized surface modifier molecules break with the hydroxyl groups on the material surface to form new bonds, thus endowing the substrate surface with special hydrophobic, oleophobic, and hydrophobic-hydrophilic conversion properties. Compared with existing chemical modification methods for substrates, the modification process provided by this invention is simple, mild, and fast, facilitating rapid modification. Furthermore, the materials prepared using the functionalized surface modifiers provided by this invention exhibit chemical bonding between the functional groups on the surface and the substrate. When subjected to physical damage such as peeling or friction, the functional coating maintains structural stability and is not easily detached, endowing the material with durable and stable hydrophobic and oleophobic properties. The series of functionalized surface modifiers prepared by this invention are suitable for modifying the surfaces of materials with different requirements, and have a wide range of applications and promising prospects. Attached Figure Description
[0034] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:
[0035] Figure 1 FTIR images of tetramethyldivinyldisilazane, ethylenedithiol, dodecafluoroheptyl methacrylate and the functionalized surface modifier obtained in Example 1;
[0036] Figure 2 The following are the hydrophobic and oleophobic effects, water contact angle and n-hexane contact angle of the melamine sponge with hydrophobic and oleophobic properties obtained in Example 1;
[0037] Figure 3 The images show (a) the wetting state of the superhydrophobic cotton fabric obtained in Example 2, (b) the surface wetting state of the cotton fabric after acid treatment, and (c) the water contact angle.
[0038] Figure 4 The friction experiment process of the superhydrophobic cotton fabric obtained in Example 2 and the relationship between the water contact angle and the number of friction cycles are shown.
[0039] Figure 5 (a) Hydrophobic effect and (b) water contact angle of the hydrophobic wood board obtained in Example 3;
[0040] Figure 6 The hydrophobic effect and water contact angle of the hydrophobic paper obtained in Example 4 are shown in (a) and (b) respectively.
[0041] Figure 7 The hydrophobic effect of the hydrophobic melamine sponge obtained in Comparative Example 1;
[0042] Figure 8 (a) Hydrophobic effect and (b) water contact angle of the hydrophobic melamine sponge obtained in Comparative Example 2;
[0043] Figure 9 The hydrophobic effect of the hydrophobic melamine sponge obtained in Comparative Example 3 is shown. Detailed Implementation
[0044] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0045] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
[0046] Unless otherwise specified, all raw materials used in the embodiments of this invention were purchased through commercial channels;
[0047] Unless otherwise specified, room temperature or normal temperature in the embodiments of the present invention refers to 25±3℃.
[0048] Example 1
[0049] A method for preparing a functionalized surface modifier includes the following steps:
[0050] 25 parts of 1,2-ethylenedithiol, 25 parts of dodecafluoroheptyl methacrylate, 0.2 parts of 2-hydroxy-2-methylphenylacetone, and 100 parts of dichloromethane were thoroughly mixed and stirred at 25°C under 365 nm ultraviolet light for 1 h. Then, 20 parts of tetramethyldivinyldisilazane were added and stirred under 365 nm ultraviolet light for another 0.5 h to obtain a functionalized surface modifier.
[0051] The functionalized surface modifiers obtained in Example 1, including tetramethyldivinyldisilazane, ethylenedithiol, dodecafluoroheptyl methacrylate, and the product obtained by FTIR analysis were analyzed using FTIR. The results are as follows: Figure 1 As shown, ethylenedithiol at 2555 cm⁻¹ -1 The absorption peak at 1595 cm⁻¹ corresponds to the stretching vibration of the SH bond in the thiol group; the absorption peak of tetramethyldivinyldisilazane at 1595 cm⁻¹ corresponds to the stretching vibration of the SH bond in the thiol group. -1 The absorption peak at 1250 cm⁻¹ corresponds to the stretching vibration of C=C. -1 The absorption peak at 925 cm⁻¹ corresponds to the bending vibration of Si-CH₃. -1 The absorption peak at 1741 cm⁻¹ corresponds to the Si-N bond; the absorption peak of dodecylfluoroheptyl methacrylate at 1741 cm⁻¹ corresponds to the Si-N bond. -1 The absorption peak at 1641 cm⁻¹ corresponds to the stretching vibration of the C=O bond. -1 The absorption peak at 1236 cm⁻¹ corresponds to the stretching vibration of C=C. -1 and 1136cm -1 The absorption peak at the point corresponds to the stretching vibration of the CF bond on the polyfluoromethyl or methylene group. The disappearance of the C=C bond and -SH absorption peaks in the surface modifier indicates that the reaction proceeded successfully.
[0052] The application of a functionalized surface modifier includes the following steps:
[0053] After immersing the melamine sponge in the functionalized surface modifier described in this embodiment for 2 hours, it is washed to obtain a melamine sponge with hydrophobic and oleophobic properties.
[0054] The liquid contact angle of the melamine sponge with hydrophobic and oleophobic properties was measured. The water contact angle was as follows: Figure 2 As shown in section (b), the result is 142°; the contact angle of n-hexane is as follows. Figure 2 In section (c), the result is 100°. For example... Figure 2 As shown in section (a), water and n-hexane droplets form spherical shapes on the surface of both hydrophobic and oleophobic melamine sponges, while droplets on the original melamine sponge surface completely penetrate into it, indicating that the use of surface modifiers can impart hydrophobic and oleophobic properties to the sponge.
[0055] Example 2
[0056] A method for preparing a functionalized surface modifier includes the following steps:
[0057] 30 parts of 1,2-ethylenedithiol, 30 parts of oleylamine, 0.2 parts of 1-hydroxycyclohexylbenzophenone, and 100 parts of toluene were thoroughly mixed and stirred at 30°C under 365 nm ultraviolet light for 0.5 h. Then, 20 parts of tetramethyldivinyldisilazane were added and stirred under 365 nm ultraviolet light for another 0.5 h to obtain a functionalized surface modifier.
[0058] The application of a functionalized surface modifier includes the following steps:
[0059] The cotton fabric is immersed in the functionalized surface modifier described in this embodiment for 2 hours and then washed to obtain a superhydrophobic cotton fabric. After being treated with an acidic solution, the surface of the superhydrophobic cotton fabric can be further converted from hydrophobic to hydrophilic.
[0060] The wettability and contact angle of the superhydrophobic cotton fabric obtained in Example 2 and the original cotton fabric were tested, and the results are as follows: Figure 3 . Figure 3 Part (a) shows the surface wetting state of the superhydrophobic cotton fabric obtained in this embodiment; as shown in section (a). Figure 3 As shown in section (c), its static water contact angle reaches 151°, exhibiting superhydrophobic properties. After treatment with a hydrobromic acid solution at pH=1, the surface wetting state of this superhydrophobic cotton fabric changed, as shown... Figure 3 In part (b), the water droplets are spread out completely, indicating that the functionalized surface modifier obtained in this embodiment can not only impart superhydrophobic properties to the surface of cotton fabric after soaking, but also enable the cotton fabric to achieve a superhydrophobic-hydrophilic conversion through acidic solution treatment.
[0061] The superhydrophobic cotton fabric obtained in Example 2 was subjected to a physical friction durability test. A 200g weight was placed on the fabric and rubbed with 500-grit sandpaper. Each cycle consisted of the fabric traveling 20cm on the sandpaper, and a total of 100 cycles were performed. The water contact angle of the fabric was tested every 10 cycles. The results are as follows: Figure 4 The friction test had no significant effect on the hydrophobicity of the superhydrophobic cotton fabric. After 100 friction tests, it still maintained its hydrophobicity and remained above 145°, indicating that the superhydrophobic cotton fabric has excellent physical friction resistance.
[0062] Example 3
[0063] A method for preparing a functionalized surface modifier includes the following steps:
[0064] 30 parts of 1,6-hexanedithiol, 30 parts of octadecene, 0.2 parts of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone and 100 parts of octadecene were thoroughly mixed and stirred at 10°C under 365 nm ultraviolet light for 0.1 h. Then, 22 parts of tetramethyldivinyldisilazane were added and stirred under 365 nm ultraviolet light for another 0.5 h to obtain a functionalized surface modifier.
[0065] The application of a functionalized surface modifier includes the following steps:
[0066] The wood board was immersed in the functionalized surface modifier described in this embodiment for 2 hours, and then washed to obtain the hydrophobic wood board.
[0067] The wetting state of water droplets on the surface of the hydrophobic wooden board obtained in this embodiment was observed, and a water contact angle test was performed. The results are as follows: Figure 5 As shown, by Figure 5 As can be seen in part (a), the water droplets on the hydrophobic wooden board are nearly spherical, and the water contact angle is as follows: Figure 5 As shown in section (b), the angle is 144°, indicating that the wood board surface has good hydrophobic properties after being modified with a surface modifier.
[0068] Example 4
[0069] A method for preparing a functionalized surface modifier includes the following steps:
[0070] 40 parts of 1,4-butanedithiol, 40 parts of octadecene, 0.2 parts of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 100 parts of tetrahydrofuran were thoroughly mixed and stirred at 50°C under 365 nm ultraviolet light for 1 h. Then, 25 parts of tetramethyldivinyldisilazane were added and stirred under 365 nm ultraviolet light for another 0.5 h to obtain a functionalized surface modifier.
[0071] The application of a functionalized surface modifier includes the following steps:
[0072] Soak wood pulp paper in a surface modifier for 2 hours, then wash to obtain hydrophobic paper.
[0073] The hydrophobic effect of the prepared hydrophobic paper was tested, and the results are as follows: Figure 6 As shown in (a), the contact angle of the droplet on the hydrophobic paper surface remained unchanged over 30 minutes, indicating its durable hydrophobicity. The water contact angle of the hydrophobic paper is as follows: Figure 6 As shown in (b) in the figure, it can reach 122°, indicating that it has good hydrophobicity.
[0074] Comparative Example 1
[0075] A surface modifier, differing from Example 1 only in that it does not include the functional reagent dodecafluoroheptyl methacrylate. All other raw materials, process steps, and parameters are the same as in Example 1.
[0076] The application of a surface modifier differs from that in Example 1 only in that a melamine sponge is immersed in the surface modifier obtained in this comparative example for 1 hour to obtain a modified melamine sponge.
[0077] Hexane stained with Sudan Red and water were dropped onto the modified melamine sponge obtained in Comparative Example 1, and the results were as follows: Figure 7 As shown, the contact angles of n-hexane and water on Comparative Example 1 are both 0°, indicating that the modified melamine sponge obtained in Comparative Example 1 has no hydrophobic or oleophobic properties.
[0078] Comparative Example 2
[0079] A surface modifier, differing from Example 1 only in that the dithiol is replaced with an equal amount of ethanethiol. All other raw materials, process steps, and parameters are the same as in Example 1.
[0080] The application of a surface modifier differs from that in Example 1 only in that the melamine sponge is immersed in the surface modifier obtained in this comparative example for 1 hour to obtain a modified melamine sponge.
[0081] Hexane stained with Sudan Red and water were dropped onto the modified melamine sponge obtained in Comparative Example 2, and the results were as follows: Figure 8 As shown in section (a), the contact angle of n-hexane on the modified melamine sponge is 0°, indicating that Comparative Example 2 has no oleophobic ability; water droplets on the surface of the modified melamine sponge obtained in Comparative Example 2 form spheres, and the water contact angle is as shown in section (a). Figure 8 As shown in section (b), the angle is 113°, indicating that the modified melamine sponge obtained in Comparative Example 2 has a certain hydrophobicity.
[0082] Comparative Example 3
[0083] A surface modifier, differing from Example 1 only in that it is stirred at 25°C for 1.5 hours under visible light. All other raw materials, process steps, and parameters are the same as in Example 1.
[0084] The application of a surface modifier differs from that in Example 1 only in that the melamine sponge is immersed in the surface modifier obtained in this comparative example for 1 hour to obtain a modified melamine sponge.
[0085] Hexane stained with Sudan Red and water were dropped onto the modified melamine sponge obtained in Comparative Example 3, and the results were as follows: Figure 9As shown, the contact angle of hexane on the modified melamine sponge is 0°, indicating that the modified melamine sponge obtained in Comparative Example 3 has no oleophobic ability; the contact angle of water droplets on the surface of the modified melamine sponge obtained in Comparative Example 3 is 0°, and the water droplets quickly penetrate the sponge surface, indicating that the modified melamine sponge obtained in Comparative Example 3 does not have hydrophobic ability.
[0086] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.
Claims
1. A functionalized surface modifier, characterized in that, The ingredients include the following parts by weight: 25-50 parts of dithiol, 20-40 parts of tetramethyldivinyldisilazane, 0.2-1 part of photoinitiator, 25-50 parts of functional reagent, and 100 parts of organic solvent; wherein the functional reagent is selected from one or more of polyfluorinated esters of unsaturated carboxylic acids, long-chain aliphatic unsaturated amines, and unsaturated long-chain aliphatic alkenes. The preparation method of the functionalized surface modifier includes the following steps: Dithiol, functional reagent, photoinitiator, and organic solvent are mixed and subjected to a first photoclick reaction under ultraviolet light, allowing the dithiol to react with the functional reagent to graft functional groups, while controlling the molar amount of the dithiol to be in excess. After the reaction is completed, tetramethyldivinyldisilazane is added, and the mixture is placed under ultraviolet light again. The remaining mercapto groups after the first photoclick reaction are used to carry out a second photoclick reaction with tetramethyldivinyldisilazane to obtain the functionalized surface modifier.
2. The functionalized surface modifier according to claim 1, characterized in that, The dithiol is selected from one or more of ethylenedithiol, propylenedithiol, butyldithiol, pentanedithiol, hexanedithiol, octanedithiol, nonanedithiol, and decandithiol.
3. The functionalized surface modifier according to claim 1, characterized in that, The photoinitiator is selected from one or more of 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.
4. The functionalized surface modifier according to claim 1, characterized in that, The polyfluoroesters of the unsaturated carboxylic acid include one or more of dodecylfluoroheptyl methacrylate, dodecylfluoroheptyl acrylate, perfluorooctyl methacrylate, and 3-perfluorohexyl-2-hydroxypropyl acrylate.
5. A functionalized surface modifier according to claim 4, characterized in that, The long-chain aliphatic unsaturated amine is oleylamine; and / or, The unsaturated long-chain aliphatic olefins include one or more of octadecene, heptadecanene, hexadecene, pentadecene, tetradecene, tridecene, dodecene, undecene, decene, nonene, octene, heptenene, and hexene.
6. The functionalized surface modifier according to claim 1, characterized in that, The organic solvent includes one or more of dichloromethane, ethyl acetate, tetrahydrofuran, toluene, and hexane.
7. A method for preparing a functionalized surface modifier according to any one of claims 1-6, characterized in that, Includes the following steps: Dithiol, functional reagent, photoinitiator, and organic solvent are mixed and subjected to a first photoclick reaction under ultraviolet light for 0.5-1.5 h, allowing the dithiol to react with the functional reagent to graft functional groups, while controlling the molar amount of the dithiol to be in excess. After the reaction is completed, tetramethyldivinyldisilazane is added, and the mixture is placed under ultraviolet light again. The remaining dithiol after the first photoclick reaction is used to carry out a second photoclick reaction with tetramethyldivinyldisilazane for 0.5-1.5 h to obtain the functionalized surface modifier.
8. The method for preparing a functionalized surface modifier according to claim 7, characterized in that, The wavelength of the ultraviolet light is 365nm.
9. The method for preparing a functionalized surface modifier according to claim 7, characterized in that, Both the primary and secondary photoclick reactions were carried out under stirring conditions, and the temperature was 10-60℃.
10. The application of a functionalized surface modifier as described in any one of claims 1-6 in regulating the wettability of material surfaces.