Cationic hydrophilic treatment agent as well as preparation method and application thereof
By chemically reacting the main chain cationic polymer with aminosilane coupling agent, superhydrophilic treatment agents for surfaces such as photovoltaic panels were prepared, which solved the problem that the prior art was difficult to realize the superhydrophilic characteristics of the material surface, and realized the Efficient self-cleaning and dirt removal.
Patent Information
- Application Number
- CN202411476226.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-22
- Publication Date
- 2025-02-11
AI Technical Summary
The prior art is difficult to achieve super hydrophilic properties of the material surface, which makes it difficult to achieve efficient self-cleaning and dirt removal on surfaces such as photovoltaic panels.
By chemically reacting the backbone cationic polymer with an aminosilane coupling agent, a surface silanization treatment agent based on backbone cationic polymer is designed and prepared for superhydrophilic treatment of solid material surfaces.
The superhydrophilic characteristics of the material surface are achieved, and the water droplet contact angle is less than 10°, which significantly improves the hydrophilicity and adhesion of the material surface, which can achieve superhydrophilic characteristics and improves the self-cleaning ability of surfaces such as photovoltaic panels.
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Figure CN119409965A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of polymer preparation and relates to a cationic hydrophilic treatment agent and a preparation method and application thereof. Background Art
[0002] Particles and dust in the air accumulate on the surface of photovoltaic modules, which will affect the light absorption efficiency of photovoltaic panels and significantly reduce the output power of photovoltaic modules. To ensure that photovoltaic modules have good output characteristics, their surfaces must be kept clean. Therefore, countries are paying more and more attention to the cleaning technology of photovoltaic module surfaces. Among them, the hydrophilic and hydrophobic modification of the surface of photovoltaic panels to give the material surface self-cleaning properties is a common focus of academic and industrial circles.
[0003] Surface wettability is an important issue of great concern to both academia and industry. Wettability is usually characterized by the contact angle (CA) of a water droplet. Generally speaking, surfaces with CA < 90° are considered hydrophilic, surfaces with CA > 90° are considered hydrophobic, surfaces with CA > 150° are called super-hydrophobic surfaces, and surfaces with CA < 10° are called super-hydrophilic surfaces. Super-hydrophilic surfaces have great application potential in real life, including self-cleaning, anti-fog, anti-icing, and oil-water separation. When the surface of a material reaches the "super-hydrophilic" state, water droplets can completely diffuse on the surface of the solid material, and water exists on the surface in the form of a thin film rather than water droplets. At the same time, the dirt on the surface can be easily transported and carried away by this diffused water layer.
[0004] Surface silanization agents, also known as silane coupling agents, are a class of organic silicon compounds that contain both hydrolyzable groups and non-hydrolyzable groups in the molecule, and their general structural formula is Y—CH2SiRnX(3-n). Among them, X is an easily hydrolyzed organic functional group, such as chloro, methoxy, ethoxy, etc.; Y is a non-hydrolyzable organic functional group, such as vinyl, epoxy, amino, long-chain alkyl, perfluoro long-chain alkyl, etc. These surface silanization agents can be used as crosslinkers, thickeners and primers for organic silicone adhesives, and can also be used to modify the surface of solid materials, giving the material surface antistatic, anti-corrosion, anticoagulant, antibacterial properties and unique hydrophilic and hydrophobic properties. At present, there are many literature reports and commercial products on silanization agents for surface hydrophobic and oleophobic modification, such as long-chain alkyl silanes that can be used to treat the surface hydrophobic and perfluoro long-chain alkyl silanes that can be used to treat the surface oleophobic. Silylation reagents that can achieve efficient hydrophilic treatment of surfaces are very rare. Although small molecule silicone compounds containing carboxyl or amino groups have certain hydrophilicity, the number of carboxyl or amino groups contained in a single small silicone molecule is very limited (generally 1 to 3), and carboxyl or amino groups are not very good hydrophilic groups. After they are modified on the solid surface, the hydrophilicity of the resulting solid surface is difficult to guarantee, and the super-hydrophilic property of the material surface cannot be achieved.
[0005] The structural formula of the commercially available product trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride is: This product is not only expensive, but also has a certain degree of hydrophilicity, but its hydrophilicity is still poor. Summary of the invention
[0006] The object of the present invention is to provide a cationic hydrophilic treatment agent with a water drop angle less than 10° and a preparation method and application thereof.
[0007] In order to achieve the above object, the technical solution of the present invention is as follows:
[0008] A cationic hydrophilic treatment agent, the raw materials of which, by weight, include 0.2-5 parts of aminosilane monomer and 1-20 parts of main chain cationic polymer; the aminosilane monomer is Wherein, R is methyl or ethyl, R' is H, CH3 or CH2CH3; the main chain cationic polymer is one or more of PC-I type, PC-II type, PC-III type or PC-IV type polymers:
[0009] PC-I type:
[0010] PC-II type:
[0011] PC-III type:
[0012] PC-IV type:
[0013] Wherein, n is an integer of 2-4, m is an integer of 2-50, and X is selected from one or more of Cl, Br, and I.
[0014] Quaternary ammonium salt cationic polymers are a kind of widely used functional polymers, which can be used as antibacterial agents, surface hydrophilic modifiers, purifiers and flocculants. Although the prior art CN 116410464 B discloses a main chain cationic polymer that can be modified by click chemistry and a preparation method thereof, the first monomer, the second monomer and the solvent are mixed, stirred and reacted at room temperature, ether is added for sedimentation, centrifuged and vacuum dried to obtain a main chain cationic polymer that can be modified by click chemistry. The preparation method of the invention has mild conditions, is simple and efficient, can be carried out at room temperature and has a fast reaction speed. The main chain cationic polymer that can be subsequently modified by click chemistry of the invention has unreacted active sites, and its aqueous solution has excellent antibacterial effect at extremely low concentrations. But its hydrophilicity is still unknown. The present invention uses the main chain cationic polymer prepared in the early stage as an important precursor, and designs and prepares a surface silanization treatment agent based on the main chain cationic polymer by chemically reacting the active halogenated alkyl group at the end of the main chain cationic polymer with the existing aminosilane coupling agent. The surface silanization treatment agent is used for super-hydrophilic treatment of the surface of solid materials, especially super-hydrophilic treatment of photovoltaic panels, to obtain a cationic hydrophilic treatment agent with a water drop angle less than 10°.
[0015] In a preferred embodiment, the aminosilane monomer is (N,N-dimethyl-3-aminopropyl)trimethoxysilane.
[0016] In a preferred embodiment, n is 2 or 3.
[0017] In a preferred embodiment, m is an integer of 5-48.
[0018] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 5 wt % of the following structure:
[0019]
[0020] Wherein, n is an integer of 2-4, m is an integer of 2-50, X is selected from one or more of Cl, Br, I, R is methyl or ethyl, and R' is H, CH3 or CH2CH3.
[0021] The active structure accounts for more than 5% of the mass proportion of the total cationic hydrophilic treatment agent, which can provide excellent hydrophilicity.
[0022] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 50 wt % of the following structure:
[0023]
[0024] Wherein, X=Br, n=3, m is 4, R is methyl, and R' is ethyl.
[0025] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 50 wt % of the following structure:
[0026]
[0027] Wherein, X=Br, n=3, m is 8, R is methyl, and R' is ethyl.
[0028] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 50 wt % of the following structure:
[0029]
[0030] Wherein, X=Br, n=3, m is 48, R is methyl, and R' is ethyl.
[0031] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 25 wt % of the following structure:
[0032]
[0033] Wherein, X=Br, n=3, m is 8, R is a methyl group, and R' is a methyl group.
[0034] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 15 wt % of the following structure:
[0035]
[0036] Wherein, X=Br, n=3, m is 4, R is methyl, and R' is methyl.
[0037] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 5 wt % of the following structure:
[0038]
[0039] X=Br, n=3, m is 4, R is methyl, and R' is methyl.
[0040] In a preferred embodiment, the cationic hydrophilic treatment agent contains no less than 15 wt % of the following structure:
[0041]
[0042] X=Br, n=3, m is 4, R is methyl, and R' is ethyl.
[0043] Based on the same inventive concept, the present invention also claims a method for preparing the cationic hydrophilic treatment agent, comprising the following steps:
[0044] The aminosilane monomer, the main chain cationic polymer and the solvent are uniformly mixed, reacted at 25-80° C. for 0.5-24 hours, and then a diluent is added to obtain the cationic hydrophilic treatment agent.
[0045] In a preferred embodiment, the solvent is one or more of methanol, ethanol, isopropanol, water, or a mixture of one or more of them and water.
[0046] In a preferred embodiment, the reaction time is 1-12 h, preferably 2-5 h.
[0047] In a preferred embodiment, the aminosilane monomer, the main chain cationic polymer and the solvent are mixed in a mass volume ratio of 0.2-5 g: 1-20 g: 1-100 mL.
[0048] Too little aminosilane monomer will result in poor adhesion on glass and other substrate materials. Too little main chain cationic polymer will result in poor hydrophilicity. Too little solvent will result in poor dispersion.
[0049] In a preferred embodiment, the aminosilane monomer, the main chain cationic polymer and the solvent are mixed and reacted without subsequent separation and purification, and the resulting reaction solution is directly used for superhydrophilic treatment of the solid surface after adding a diluent.
[0050] In a preferred embodiment, the diluent is one or more of methanol, ethanol, isopropanol, and water.
[0051] Based on the same inventive concept, the present invention also claims to protect the application of the cationic hydrophilic treatment agent, which includes the following steps: activating the cleaned glass substrate and coating it on the surface of the glass substrate to form a super hydrophilic coating.
[0052] In a preferred embodiment, the activation treatment is to first clean the glass substrate with ethanol, then put the glass substrate into a 0.1-10 mol / L sodium hydroxide or potassium hydroxide solution, soak for 1-30 minutes, take it out, rinse it with water, dry it and set it aside.
[0053] In a preferred embodiment, the activation treatment is to use oxygen plasma or air plasma to activate the surface of the glass substrate.
[0054] In a preferred embodiment, the coating method includes any one of dipping, spraying, roller coating or scraping.
[0055] Compared with the prior art, the present invention has the following beneficial effects:
[0056] (1) Based on the main chain cationic polymer, the present invention uses it as an important precursor, and chemically reacts the active halogenated alkyl group at the end of the main chain cationic polymer with a small molecule aminosilane coupling agent to prepare a surface silanized super hydrophilic treatment agent based on the main chain cationic polymer for the first time.
[0057] (2) The preparation method of the present invention has mild conditions, is simple and efficient.
[0058] (3) Compared with existing small-molecule organic silane reagents, the surface silane super-hydrophilic treatment agent based on the main chain cationic polymer of the present invention has a more excellent effect in constructing the hydrophilic function of the material surface, has better hydrophilicity and better adhesion, and can achieve super-hydrophilic properties that are difficult to achieve with small-molecule organic silane reagents. BRIEF DESCRIPTION OF THE DRAWINGS
[0059] Figure 1 This is a schematic diagram of the reaction process for preparing a cationic hydrophilic treatment agent according to the present invention;
[0060] Figure 2 This is the H NMR spectrum of the intermediate product B6A5 obtained in Example 1;
[0061] Figure 3 This is the H NMR spectrum of the target compound B6A5NEtSi obtained in Example 1;
[0062] Figure 4 The intermediate product B obtained in Example 2 10 H NMR spectrum of A9;
[0063] Figure 5 The target compound B obtained in Example 2 10 H NMR spectrum of A9NEtSi;
[0064] Figure 6 The intermediate product B obtained in Example 3 50 A 49 H NMR spectrum of
[0065] Figure 7 The intermediate product B obtained in Example 3 50 A 49 H NMR spectrum of NEtSi;
[0066] Figure 8 This is the H NMR spectrum of the super hydrophilic treatment agent mother solution M1 obtained in Example 4;
[0067] Fig. 9 This is a test diagram of water drop angle on the glass surface treated with the superphilic solution S1 in Example 4;
[0068] Fig.10 This is the H NMR spectrum of the intermediate product B6A5 obtained in Example 5;
[0069] Fig.11 This is a test diagram of water drop angle on the glass surface treated with the superphilic solution S2 in Example 5;
[0070] Fig.12 This is the H NMR spectrum of the intermediate product 2 obtained in Example 6;
[0071] Fig.13 This is a test diagram of water drop angle on the glass surface treated with the superphilic solution S3 in Example 6;
[0072] Fig.14 This is the H NMR spectrum of the intermediate product 3 obtained in Example 7;
[0073] Fig.15 This is a test diagram of water drop angle on the glass surface treated with the superphilic solution S4 in Example 7;
[0074] Fig.16 This is a water drop angle test diagram of the glass surface after being treated with trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride. DETAILED DESCRIPTION
[0075] The present invention will be described in detail below in conjunction with the embodiments. It should be noted that the embodiments and features in the embodiments of the present invention can be combined with each other without conflict.
[0076] Example 1
[0077] according to Figure 1 As shown in the process, 25.67 g of 1,4-dibromo-2-butene was weighed and added to a 250 ml round-bottom bottle, and 70 ml of methanol was added to dissolve. After 1,4-dibromo-2-butene bromide was completely dissolved, a mixed solution of 13.02 g of N,N,N',N'-tetramethyl-1,3-propanediamine and 30 ml of methanol was added thereto, and the mixture was reacted at room temperature for 3 hours. After the reaction was completed, acetone was added for precipitation / centrifugation, acetone was washed / centrifuged, and finally vacuum dried to obtain 37.99 g of the intermediate product B6A5 (the product obtained 1 The HNMR characterization results are shown in Figure 2 ), yield 98.2%. 1 The H NMR spectrum was measured by an AVACNE III 400 (400 MHz) nuclear magnetic resonance instrument, deuterated water (D2O) was used as solvent, and TMS was used as internal standard. The structural formula of the intermediate product B6A5 obtained is:
[0078]
[0079] Wherein, X=Br, n=3, the double bond in the structural formula is a trans double bond, and m is calculated to be 4 according to the results of H-NMR spectrum testing.
[0080] Weigh 1.93g of the above product into a 50mL round-bottom bottle, and add 20mL of methanol to dissolve. After complete dissolution, add 0.47g of N,N-diethyl-3-aminopropyltrimethoxysilane and react at room temperature for 0.5h. After the reaction is completed, add acetone for precipitation / centrifugation, acetone for washing / centrifugation, and finally vacuum dry to obtain 2.35g of the product. 1 H NMR characterization ( 1 H NMR characterization results are shown in Figure 3 ), the product contains more than 52% by mass of the target compound B6A5NEtSi, and its structural formula is as follows:
[0081]
[0082] Wherein, X=Br, n=3, m is 4, R is methyl, and R' is ethyl.
[0083] Example 2
[0084] according to Figure 1 As shown in the process, 42.78 g of 1,4-dibromo-2-butene was weighed and added to a 250 ml round-bottom bottle, and 70 ml of methanol was added to dissolve. After 1,4-dibromo-2-butene was completely dissolved, a mixed solution of 23.44 g of N,N,N',N'-tetramethyl-1,3-propanediamine and 30 ml of methanol was added thereto, and the mixture was reacted at room temperature for 0.5 h. After the reaction was completed, acetone was added for precipitation / centrifugation, acetone was washed / centrifuged, and finally, 63.11 g of intermediate product B was obtained after vacuum drying. 10 A9 (the product obtained 1 H NMR Figure 4 ), yield 95.3%. The intermediate product B 10 The structural formula of A9 is:
[0085]
[0086] Wherein, X=Br, n=3, the double bond in the structural formula is a trans double bond, and m can be calculated to be 8 according to the results of H-NMR spectrum testing.
[0087] Weigh 3.31g of the above product into a 50ml round-bottom bottle, and add 20ml of methanol to dissolve. After complete dissolution, add 0.47g of N,N-diethyl-3-aminopropyltrimethoxysilane and react at room temperature for 2h. After the reaction is completed, add acetone for precipitation / centrifugation, acetone for washing / centrifugation, and finally vacuum dry to obtain 3.61g of the product. 1 H NMR characterization ( 1 H NMR characterization results are shown in Figure 5 ), the product contains more than 67% of the target compound B by mass fraction 10A9NEtSi, its structural formula is as follows:
[0088]
[0089] Wherein, X=Br, n=3, m is 8, R is methyl, and R' is ethyl.
[0090] Example 3
[0091] according to Figure 1 As shown in the process, 21.4 g of 1,4-dibromo-2-butene was weighed and added to a 250 ml round-bottom bottle, and 70 ml of methanol was added to dissolve. After 1,4-dibromo-2-butene was completely dissolved, a mixed solution of 12.76 g of N,N,N',N'-tetramethyl-1,3-propanediamine and 30 ml of methanol was added, and the reaction was carried out at room temperature for 6 hours. After the reaction was completed, acetone was added for precipitation / centrifugation, acetone was washed / centrifuged, and finally vacuum dried to obtain 33.06 g of intermediate B. 50 A 49 (The product 1 H NMR characterization results are shown in Figure 6 ), yield 95.3%. The intermediate product B 50 A 49 The structural formula is:
[0092]
[0093] Wherein, X=Br, n=3, the double bond in the structural formula is a trans double bond, and m is calculated to be 48 according to the results of H NMR spectrum test.
[0094] Weigh 17.1g of the above product into a 50ml round-bottom bottle, and add 20ml of methanol to dissolve. After complete dissolution, add 0.47g of N,N-diethyl-3-aminopropyltrimethoxysilane and react at 50℃ for 2h. After the reaction is completed, add acetone for precipitation / centrifugation, acetone for washing / centrifugation, and finally vacuum dry to obtain 16.9g of the product. 1 H NMR characterization ( 1 H NMR characterization results are shown in Figure 7 ), the product contains more than 92% by mass of the target compound B 50 A 49 NEtSi, its structural formula is as follows:
[0095]
[0096] Wherein, X=Br, n=3, m is 48, R is methyl, and R' is ethyl.
[0097] Example 4
[0098] Weigh 3.31 g of B prepared in Example 2 10The product A9 and 0.22 g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane were dissolved in 10 mL of methanol, heated to 50 °C for 12 h, and cooled to room temperature to obtain the surface silanization super hydrophilic treatment agent mother solution M1 of type I main chain cationic polymer. 1 H NMR characterization ( 1 The H NMR characterization results are shown in Figure 8 ), M1 contains more than 30% by mass of the following compounds:
[0099]
[0100] Wherein, X=Br, n=3, the double bond in the structural formula is a trans double bond, m is calculated to be 8 according to the results of H NMR spectrum test, R is a methyl group, and R' is a methyl group.
[0101] Then, the mother solution M1 was diluted with a mixture of 180 mL of methanol and 10 mL of water to obtain a super-hydrophilic treatment agent solution S1. The glass sheet was soaked in solution S1 for 3 minutes, then taken out and dried at 80°C to obtain a glass sheet BS1. The water drop angle test showed that the water drop was fully spread on the surface of the glass sheet, and the water drop angle was 2.4°. Fig. 9 .
[0102] Example 5
[0103] according to Figure 1 As shown in the process, 2.567 g of 1,4-dibromo-2-butene was weighed into a glass bottle, and 5 mL of methanol was added to ultrasonicate it until it was completely dissolved to obtain a 1,4-dibromo-2-butene solution; then 1.3 g of N,N,N',N'-tetramethyl-1,3-propylenediamine was weighed into another glass bottle, and 5 mL of methanol and 1 mL of deionized water were added to obtain a N,N,N',N'-tetramethyl-1,3-propylenediamine solution; the N,N,N',N'-tetramethyl-1,3-propylenediamine solution was added dropwise to the 1,4-dibromo-2-butene solution; after reacting at room temperature for 12 hours, ether was added for precipitation, centrifuged three times, and vacuum dried (vacuum dried in a vacuum drying oven at 45°C for 10 hours) to obtain the intermediate product 1. The performance of the intermediate product 1 obtained was characterized. The intermediate product 1 obtained 1 H NMR details Fig.10 .
[0104] The structural formula of the intermediate product 1 obtained is:
[0105]
[0106] Wherein, X=Br, n=3, the double bond in the structural formula is a trans double bond, and m is calculated to be 4 according to the results of H-NMR spectrum testing.
[0107] 1.9g of the intermediate product 1 and 0.42g of (N,N-dimethyl-3-aminopropyl)trimethoxysilane were dissolved in 10mL of methanol, heated to 50°C for 12h, and cooled to room temperature to obtain the surface silanization super-hydrophilic treatment agent mother solution M2 of type I main chain cationic polymer. After characterization and determination, M2 contained more than 18% (mass fraction) of the following compounds:
[0108]
[0109] X=Br, n=3, m is 4, R is methyl, and R' is methyl.
[0110] Then, the mother solution M2 was diluted with a mixture of 180 mL of methanol and 10 mL of water to obtain a super-hydrophilic treatment agent solution S2. The glass sheet was soaked in solution S2 for 3 minutes, then taken out and dried at 80°C to obtain a glass sheet BS2. The water drop angle test found that the water drop was fully spread on the surface of the glass sheet, and the water drop angle was 3.5°. Fig.11 . (N,N-dimethyl-3-aminopropyl)trimethoxysilane was directly diluted in the same way to a mass / volume concentration of 1%, 1.3%, 1.5%, 1.7%, and 2%, and the water drop angle was 60-80°.
[0111] Example 6
[0112] according to Figure 1 As shown in the process, 0.62 g of 1,4-dichloro-2-butyne was weighed into a glass bottle, and 5 mL of methanol was added to ultrasonicate it until it was completely dissolved to obtain a 1,4-dichloro-2-butyne solution; then 0.69 g of tetramethylbutylene diamine was weighed into another glass bottle, and 5 mL of methanol and 1 mL of deionized water were added to obtain a tetramethylbutylene diamine solution; the tetramethylbutylene diamine solution was added dropwise to the 1,4-dichloro-2-butyne solution; after reacting at room temperature for 12 hours, ether was added for precipitation, centrifuged three times, and vacuum dried (vacuum dried in a vacuum drying oven at 45°C for 10 hours) to obtain the intermediate product 2. The intermediate product 2 obtained 1 H NMR details Fig.12 .
[0113] The structural formula of the intermediate product 2 obtained is:
[0114]
[0115] Wherein, X=Cl, n=4, and m can be calculated to be 9 according to the results of H-NMR spectrum test.
[0116] The above 1.40g intermediate product 2 and 0.11g (N,N-dimethyl-3-aminopropyl) trimethoxysilane were dissolved in 10mL methanol, heated to 50°C for 20h, and cooled to room temperature to obtain the surface silanization super hydrophilic treatment agent mother solution M3 of type II main chain cationic polymer. After characterization and determination, M3 contained more than 9% (mass fraction) of the following compounds:
[0117]
[0118] X=Cl, n=4, m is 9, R is methyl, and R' is methyl.
[0119] Then, the mother solution M3 was diluted with a mixture of 180 mL of methanol and 10 mL of water to obtain a super-hydrophilic treatment agent solution S3. The glass sheet was soaked in solution S3 for 5 minutes, then taken out and dried at 80°C to obtain a glass sheet BS3. The water drop angle test showed that the water drop was fully spread on the surface of the glass sheet, and the water drop angle was 5.7°. Fig.13 .
[0120] Example 7
[0121] according to Figure 1 As shown in the process, 25.67 g of 1,4-dibromo-2-butene was weighed and added to a 250 mL round-bottom flask, and 70 mL of methanol was added to dissolve. After 1,4-dibromo-2-butene was completely dissolved, 17.85 g of 4,4'-bipyridine was weighed and mixed with 10 mL of methanol and 30 mL of water, and the solution was added to 1,4-dibromo-2-butene. The reaction was allowed to proceed at room temperature for 12 hours. After the reaction was completed, acetone was added for precipitation and centrifugation was performed three times to obtain intermediate product 3. The intermediate product 3 obtained 1 H NMR details Fig.14 .
[0122] The structural formula of the intermediate product 3 obtained is:
[0123]
[0124] Wherein, X=Br, m=21, the double bond in the structural formula is a trans double bond, and m can be calculated to be 21 according to the results of H-NMR spectrum testing.
[0125] The above 7.62g intermediate product 3 and 0.12g (N,N-diethyl-3-aminopropyl) trimethoxysilane were dissolved in 30mL methanol, heated to 60°C for 15h, and cooled to room temperature to obtain the surface silanization super hydrophilic treatment agent mother solution M4 of type II main chain cationic polymer. After characterization and determination, M4 contained more than 15% (mass fraction) of the following compounds:
[0126]
[0127] X=Br, n=3, m is 21, R is methyl, and R' is ethyl.
[0128] Then, the mother solution M3 was diluted with a mixture of 730 mL of methanol and 40 mL of water to obtain a super-hydrophilic treatment agent solution S4. The glass sheet was soaked in solution S4 for 10 min, then taken out and dried at 80°C to obtain a glass sheet BS4. The water drop angle test found that the water drop was fully spread on the surface of the glass sheet, and the water drop angle was 6.7°. Fig.15 .
[0129] Comparative Example 1
[0130] Trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride was prepared into 1%, 1.3%, 1.5%, 1.7% and 2% aqueous solutions using 95% methanol aqueous solution as solvent.
[0131] The structural formula of trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride is:
[0132] The glass sheet was immersed in solution S1 for 10 minutes, then taken out and dried at 80°C to obtain glass sheet BS4. The water drop angle test showed that the water drop was spread on the surface of the glass sheet, and the water drop angle ranged from 64° to 90°. Fig.16 .
[0133] The contents explained in the above embodiments should be understood as these embodiments are only used to more clearly illustrate the present invention, and are not used to limit the scope of the present invention. After reading the present invention, various equivalent forms of modifications to the present invention by those skilled in the art all fall within the scope defined by the claims attached to this application.
Claims
1. A cationic hydrophilic treatment agent, characterized in that: The raw materials include 0.2-5 parts of aminosilane monomer and 1-20 parts of main chain cationic polymer by weight; the aminosilane monomer is Wherein, R is methyl or ethyl, R' is H, CH3 or CH2CH3; the main chain cationic polymer is one or more of PC-I type, PC-II type, PC-III type or PC-IV type polymers: PC type I: PC-II type: PC-III type: PC-IV type: Wherein, n is an integer of 2-4, m is an integer of 2-50, and X is selected from one or more of Cl, Br, and I.
2. The cationic hydrophilic treatment agent according to claim 1, characterized in that n is 2 or 3; m is an integer of 5-48.
3. The cationic hydrophilic treatment agent according to claim 1, characterized in that: The cationic hydrophilic treatment agent contains not less than 5wt% of the following structure: Wherein, n is an integer of 2-4, m is an integer of 2-50, and X is selected from one or more of Cl, Br, and I. R is methyl or ethyl, and R' is H, CH3 or CH2CH3.
4. The method for preparing a cationic hydrophilic treatment agent according to any one of claims 1 to 3, characterized in that: The following steps are involved: The aminosilane monomer, the main chain cationic polymer and the solvent are uniformly mixed, reacted at 25-80° C. for 0.5-24 hours, and then a diluent is added to obtain the cationic hydrophilic treatment agent.
5. The preparation method according to claim 4, characterized in that: The solvent is one or more of methanol, ethanol, isopropanol, water, or a mixture of one or more of them and water.
6. The preparation method according to claim 4, characterized in that: The reaction time is 1 to 12 hours.
7. The preparation method according to claim 4, characterized in that: The aminosilane monomer, the main chain cationic polymer and the solvent are mixed in a mass volume ratio of 0.2-5 g: 1-20 g: 1-100 mL.
8. The preparation method according to claim 4, characterized in that: The diluent is one or more of methanol, ethanol, isopropanol and water.
9. The use of the cationic hydrophilic treatment agent according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: activating the cleaned glass substrate and coating the surface of the glass substrate to form a super-hydrophilic coating.
10. The use according to claim 9, characterized in that: The activation treatment is to first clean the glass substrate with ethanol, then put the glass substrate into a 0.1-10 mol / L sodium hydroxide or potassium hydroxide solution, soak for 1-30 minutes, take it out, rinse it with water, dry it and set it aside; preferably, the activation treatment is to use oxygen plasma or air plasma to activate the surface of the glass substrate.