An antifogging agent, a method for preparing the same, and use thereof
By chemically reacting a compound with a specific structure with the surface of silica to form a wash-resistant anti-fog layer, the problem of small molecule anti-fog agents being not wash-resistant and having low light transmittance is solved, achieving an anti-fog effect with high light transmittance and low fog.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2025-01-14
- Publication Date
- 2026-07-14
AI Technical Summary
Existing small-molecule surfactant antifogging agents are not resistant to rinsing, while polymeric and inorganic antifogging agents affect the light transmittance of silica, resulting in poor antifogging performance.
A compound with a specific structure is used as an antifog agent. It reacts with an anionizing reagent and chemically reacts with the plasma-treated silica surface to form an antifog layer that is washable and has high light transmittance.
It improves the washability and light transmittance of the anti-fogging agent, resulting in good water droplet spreading on the surface, low contact angle, low haze, and preferably light transmittance of over 90% and haze of less than 5%.
Smart Images
Figure CN122380973A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of interface modification technology, specifically to an antifogging agent, its preparation method, and its application. Background Technology
[0002] Fogging on material surfaces is very common. For example, fog easily forms on display devices such as bathroom glass, camera lenses, eyeglasses, mirrors, and safety goggles, severely affecting visibility and causing inconvenience and even danger in our daily lives. Liquid droplets on material surfaces cause incident light to refract and reflect in various directions, resulting in a significant reduction in luminous flux. For transparent materials, their optical properties, such as light transmittance, are significantly weakened. In fields requiring materials with excellent optical properties, the presence of condensed droplets reduces the accuracy of analytical instruments such as gas chromatographs and microscopes, and in the aerospace and automotive industries, as well as in certain surgical procedures, this directly affects safety. The problems and losses caused by fogging are difficult to quantify, and solving the fogging phenomenon will generate enormous economic and social benefits.
[0003] Anti-fogging agents are chemical agents that achieve an anti-fogging effect by altering the wetting state of water droplets on the lens surface. They are deposited on the surface of the medium where fog droplets adhere through physical or chemical action and can be small molecule surfactants, polymeric chemical agents, inorganic coatings, or their composites. For example, Chinese patent CN103013311A discloses a hydrophilic glass anti-fogging coating material, which is mainly a mixture of hydrophilic polymers and nanoparticles. The hydrophilic polymers include polyethylene glycol, vinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, etc.; Chinese patent CN113088254A discloses a long-lasting anti-fogging agent, whose raw materials, by weight, include: 70-80 parts polyglycerol, 20-30 parts fatty acids, 5-20 parts acrylate, 0.01-0.03 parts antioxidant, and 25-35 parts ethanol.
[0004] When small molecule surfactants are used as antifogging agents, they are easily washed away because they are physically adsorbed onto solid surfaces; polymer and inorganic coatings, on the other hand, reduce light transmittance. Therefore, increasing the washability of small molecule surfactants is becoming increasingly important for antifogging of material surfaces (especially silica surfaces). Summary of the Invention
[0005] To address the problems existing in the prior art where small molecule surfactant antifogging agents are not resistant to rinsing, and where polymeric and inorganic antifogging agents affect the light transmittance of silica, thus affecting their application, this invention provides an antifogging agent, its preparation method, and its application technology.
[0006] One object of the present invention is to provide an antifogging agent comprising at least one of the compounds with the structure shown in formula (I) below:
[0007]
[0008] In formula (I), R is one of H or C1-C18 hydrocarbon groups; x is an integer from 0 to 10, y is an integer from 0 to 10, m is an integer from 0 to 50, n is an integer from 0 to 50, and x, y, m, and n are not simultaneously 0; X is one of R1COOM or R2SO3M1, wherein R1 and R2 are the same or different, and are independently one of C1-C6 alkylene or phenylene groups, and M and M1 are the same or different, and are independently a cation or cationic group that balances the charge of the compound.
[0009] In a preferred embodiment of the present invention,
[0010] R is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or,
[0011] x is an integer between 0 and 5, y is an integer between 0 and 5; and / or,
[0012] x+y is an integer from 0 to 20, preferably an integer from 0 to 10, and more preferably an integer from 0 to 5; and / or,
[0013] m is an integer between 0 and 30, n is an integer between 0 and 30; and / or,
[0014] m+n is an integer from 1 to 100, preferably an integer from 2 to 50, and more preferably an integer from 7 to 30; and / or,
[0015] x+y+m+n is greater than or equal to the number of carbon atoms in R; preferably, x+y+m+n is 2-20 greater than the number of carbon atoms in R, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or any intermediate value between two values, more preferably 2-15 greater, and most preferably 3-10 greater; and / or,
[0016] M and M1 may be the same or different, and each is an independent alkali metal ion.
[0017] In a preferred embodiment of the present invention,
[0018] The antifogging agent further comprises at least one of the compounds with the structure shown in formula (II) below and / or at least one of the compounds with the structure shown in formula (III) below:
[0019]
[0020] In equation (II), R 1It is one of H or C1-C18 hydrocarbon groups; x1 is an integer from 0 to 10, y1 is an integer from 0 to 10, m1 is an integer from 0 to 50, n1 is an integer from 0 to 50, and x1, y1, m1, and n1 are not all 0 at the same time; X 1 It is one of R1COOM and R2SO3M1, wherein R1 and R2 are the same or different, and are independently one of C1-C6 alkylene or phenylene, and M and M1 are the same or different, and are independently a cation or cationic group that balances the charge of the compound.
[0021]
[0022] In equation (III), R 2 It is one of H or C1-C18 hydrocarbon groups; x2 is an integer from 0 to 10, y2 is an integer from 0 to 10, m2 is an integer from 0 to 50, n2 is an integer from 0 to 50, and x2, y2, m2, and n2 are not all 0 at the same time.
[0023] In a preferred embodiment of the present invention,
[0024] In equation (II), R 1 It is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or, x1 is an integer from 0 to 5, y1 is an integer from 0 to 5; and / or, x1+y1 is an integer from 0 to 20, preferably an integer from 0 to 10, more preferably an integer from 0 to 5; and / or, m1 is an integer from 0 to 30, n1 is an integer from 0 to 30; and / or, m1+n1 is an integer from 1 to 100, preferably an integer from 2 to 50, more preferably an integer from 7 to 30; and / or, x1+y1+m1+n1 is greater than or equal to R. 1 Preferably, the number of carbon atoms in x1+y1+m1+n1 is greater than that in R. 1 The number of carbon atoms is greater than 2-20, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or any intermediate value between two values, more preferably greater than 2-15, and most preferably greater than 3-10; and / or, M and M1 may be the same or different, and each is independently one of the alkali metal ions; and / or,
[0025] In equation (III), R 2It is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or, x2 is an integer from 0 to 5, y2 is an integer from 0 to 5; and / or, x2+y2 is an integer from 0 to 20, preferably an integer from 0 to 10, more preferably an integer from 0 to 5; and / or, m2 is an integer from 0 to 30, n2 is an integer from 0 to 30; and / or, m2+n2 is an integer from 1 to 100, preferably an integer from 2 to 50, more preferably an integer from 7 to 30; and / or, x2+y2+m2+n2 is greater than or equal to R. 2 The number of carbon atoms in the middle, preferably, is x² + y² + m² + n² compared to R. 2 The number of carbon atoms is greater than 2-20, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or any intermediate value between two values, more preferably greater than 2-15, and most preferably 3-10; and / or,
[0026] Based on the mass of the antifogging agent as 100%, the mass content of the compound with the structure shown in formula (I) in the antifogging agent is 80-100%, for example, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or any intermediate value between two values, preferably 80-97%, more preferably 85-97%; the mass content of the compound with the structure shown in formula (II) is 0- The content of the compound with the structure shown in formula (III) is 20%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or any intermediate value between two values, preferably 1-15%, more preferably 1-10%; the mass content of the compound is 0-10%, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or any intermediate value between two values, preferably 2-8%.
[0027] A second objective of this invention is to provide a method for preparing an antifogging agent according to one of the objectives of this invention, comprising the step of reacting at least one of the compounds with the structure shown in formula (Ⅳ) below with an anionizing agent:
[0028]
[0029] In equation (Ⅳ), R 3It is one of H or C1-C18 hydrocarbon groups; x3 is an integer from 0 to 10, y3 is an integer from 0 to 10, m3 is an integer from 0 to 50, n3 is an integer from 0 to 50, and x3, y3, m3, and n3 are not all 0 at the same time; preferably,
[0030] R 3 It is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or,
[0031] x3 is an integer between 0 and 5, y3 is an integer between 0 and 5; and / or,
[0032] x3+y3 is an integer from 0 to 20, preferably an integer from 0 to 10, and more preferably an integer from 0 to 5; and / or,
[0033] m3 is an integer between 0 and 30, n3 is an integer between 0 and 30; and / or,
[0034] m3+n3 is an integer from 1 to 100, preferably an integer from 2 to 50, and more preferably an integer from 7 to 30; and / or,
[0035] x³ + y³ + m³ + n³ is greater than or equal to R 3 The number of carbon atoms in the middle; preferably, x³+y³+m³+n³ is more than R. 3 The number of carbon atoms is greater than 2-20, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or any intermediate value between two values, more preferably greater than 2-15, and most preferably greater than 3-10.
[0036] The compound with the structure shown in formula (Ⅳ) can be prepared using the conventional preparation methods for aliphatic amine polyoxyethylene ether compounds in the prior art. The present invention preferably obtains it through the following preparation process:
[0037] Alkylamines are optionally reacted with propylene oxide in the presence of a catalyst, followed by reaction with ethylene oxide to obtain aliphatic amine polyoxyethylene ethers (i.e., compounds with the structure shown in formula (IV)); preferably,
[0038] The alkylamine has 0-18 carbon atoms in its alkyl group, preferably 6-12; and / or,
[0039] The catalyst is an alkaline catalyst, preferably at least one of potassium hydroxide and sodium hydroxide; and / or,
[0040] The catalyst is used in an amount of 0.05-5% of the weight of the alkylamine, preferably 0.5-2%; and / or,
[0041] The molar ratio of propylene oxide to alkylamine is (0-20):1; and / or,
[0042] The molar ratio of ethylene oxide to alkylamine is (1-100):1, preferably (2-50):1, more preferably (7-30):1; and / or,
[0043] The reaction temperature of alkylamines with propylene oxide is 100-180℃, preferably 140-160℃; and / or, the reaction time of alkylamines with propylene oxide is 0.5-10h, preferably 0.5-5h; and / or, the reaction pressure of alkylamines with propylene oxide is <0.40MPa; and / or,
[0044] The reaction temperature with ethylene oxide is 100-180℃, preferably 140-160℃; and / or, the time is 0.5-10h, preferably 0.5-5h; and / or, the pressure is <0.40MPa.
[0045] Preferably, the above method for preparing fatty amine polyoxyethylene ether further includes conventional post-processing steps after the reaction is completed, including but not limited to cooling the reaction product and then neutralizing, decolorizing, filtering, and dehydrating to obtain the fatty amine polyoxyethylene ether.
[0046] In a preferred embodiment of the present invention,
[0047] The anionizing agent has the general structural formula L1-R3COOM3 or L2-R4SO3M4, wherein L1 and L2 may be the same or different, and are each independently a halogen; R3 and R4 may be the same or different, and are each independently a C1-C6 alkylene or phenylene group; M3 and M4 may be the same or different, and are each independently a cation or cationic group that balances the charge of the compound, preferably an alkali metal ion; and / or,
[0048] The molar ratio of the compound with the structure shown in formula (Ⅳ) to the anionizing agent is 1:(1-2), preferably 1:(1-1.5); and / or,
[0049] The reaction temperature is 50-150℃, preferably 60-100℃; and / or the reaction time is 1-20h, preferably 2-8h.
[0050] The preparation method of the antifogging agent of the present invention further includes a post-treatment step after reacting the compound with the structure shown in formula (Ⅳ) with an anionizing reagent. The post-treatment step includes, but is not limited to, adding the reaction product to a mixed solvent of aqueous and oil phases, mixing thoroughly, allowing it to stand, then removing the lower oil phase and adding an aqueous solvent, washing several times according to the above steps, and finally removing the lower oil phase to remove the oil phase solvent to obtain the antifogging agent. All solvents are common solvents; water is preferred as the aqueous phase solvent, and dichloroethane is preferred as the oil phase solvent. The final method for removing the oil phase solvent can be rotary evaporation.
[0051] A third objective of this invention is to provide a surface anti-fogging system comprising an anti-fogging agent according to one objective of this invention or an anti-fogging agent prepared by the method according to another objective of this invention, and an optional solvent; preferably, the solvent is any solvent capable of dissolving the anti-fogging agent, such as toluene; other conventional components in the art, such as ethers, polyethylene glycol, etc., may also be added to the surface anti-fogging system, preferably with a number-average molecular weight of 300-2000, and the amount used is also conventional, sufficient to achieve sufficient dissolution of the anti-fogging agent for easy coating, and those skilled in the art can add according to actual conditions.
[0052] The fourth objective of this invention is to provide a surface modification method, comprising the steps of plasma treating a solid surface containing high-energy active groups and then immersing it in an anti-fogging agent according to one objective of this invention, an anti-fogging agent prepared by the method according to another objective of this invention, or an anti-fogging system according to another objective of this invention; preferably, the solid surface containing high-energy active groups is a solid surface containing hydroxyl groups, preferably a solid surface containing silica, and more preferably a glass and / or quartz surface.
[0053] In a preferred embodiment of the present invention,
[0054] The plasma treatment is performed in an oxygen atmosphere; and / or,
[0055] The plasma treatment time is 1-15 min, for example 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min or any intermediate value between two values, preferably 2-10 min, with a vacuum degree of 50-80 mTorr and a gas flow rate of 20-100 sccm.
[0056] In a preferred embodiment of the present invention,
[0057] The reaction time is 2-4 hours, preferably 2-3 hours; and / or the reaction temperature is 40-80°C, preferably 50-70°C.
[0058] In a preferred embodiment of the present invention,
[0059] After modification, the contact angle between water and the modified surface is 20° or less, preferably 15° or less; after rinsing with water for 2 hours, the increase in contact angle is ≤5°.
[0060] The fifth objective of this invention is to provide an anti-fogging agent according to one objective of this invention, or an anti-fogging agent obtained by the preparation method according to another objective of this invention, or a surface anti-fogging system according to another objective of this invention, or a surface modification method according to another objective of this invention, and its application in surface anti-fogging.
[0061] Through the above technical solution, the antifogging agent system of the present invention contains both anionic and hydroxyl groups in its molecular structure. The hydroxyl groups react chemically with a plasma-treated solid surface containing high-energy active groups (such as a silica surface), grafting onto the solid surface and increasing washability. The unreacted anionic groups at the other end increase their affinity for water, allowing water droplets to spread on the solid. By controlling the degree of polymerization of oxyethylene ether and oxypropylene ether and the ratio of the number of carbon atoms in the alkyl chain, the steric hindrance of the surfactant grafting onto the solid surface and its affinity for water are controlled. After modification, the contact angle between water and the modified solid surface (such as a modified silica surface) is 20° or less, preferably 15° or less, and after 2 hours of water rinsing, the increase in contact angle is ≤5°. Attached Figure Description
[0062] Figure 1 The image shows the carbon signal obtained by SEM testing after rinsing the modified silica surface of Example 1 at a rate of 1 mL / min for 2 h.
[0063] Figure 2 The image shows the carbon signal obtained by SEM testing after rinsing the modified silica surface of Comparative Example 1 at a rate of 1 mL / min for 2 h. Detailed Implementation
[0064] The present invention will now be described in detail with reference to specific embodiments and accompanying drawings. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.
[0065] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.
[0066] In this invention, the SEM is selected from a Zeiss Merlin scanning electron microscope.
[0067] In this invention, a BYK haze meter is used to test transmittance and haze.
[0068] In this invention, the DSA100 contact angle measuring instrument is used to test the contact angle.
[0069] Example 1
[0070] 1. Synthesis of antifogging agents:
[0071] (1) Preparation of fatty amine polyoxyethylene ether:
[0072] 1 mol of decylamine was added to a reactor equipped with a condenser, a stirrer, and a gas disperser. The system temperature was heated to 90°C, and a vacuum system was activated. Dehydration was carried out under high vacuum for 1 hour. The system was then purged three times with nitrogen to remove air. The reaction temperature was then adjusted to 140°C, and 2 mol of ethylene oxide was slowly introduced, maintaining a pressure <0.40 MPa and a temperature of 140°C. The reaction was continued for 1 hour. Then, 1% (by weight) of potassium hydroxide catalyst (decylamine) was added, followed by the introduction of 13 mol of ethylene oxide. The pressure was maintained below 0.40 MPa and the temperature at 140°C, and the reaction continued for another hour. After cooling, the mixture was neutralized, decolorized, filtered, and dehydrated to obtain aliphatic amine polyoxyethylene ether. Its structural formula is as follows: Among them, R 3 C 10 H 21 x³ + y³ = 0, m³ + n³ = 15. The structural formula of the above aliphatic amine polyoxyethylene ether was calculated based on the reaction principle and the amount of raw materials added.
[0073] (2) Preparation of antifogging agent:
[0074] One mole of the obtained fatty amine polyoxyethylene ether was placed in a three-necked flask. The stirring device was turned on and the temperature was raised to 70°C. 1.1 moles of the anionizing agent sodium chloroacetate were added. After the addition was complete, the reaction was continued at 80°C for 4 hours. After post-treatment (the post-treatment included adding 100 g of water and 200 g of dichloroethane to the obtained product, stirring for 3 min and letting it stand for 30 min, taking the lower dichloroethane phase, adding 100 g of water, washing twice according to the above steps, and then removing the dichloroethane by rotary evaporation), the product was obtained, which is the anti-fogging agent of the present invention.
[0075] Liquid chromatography analysis showed that the above products contained 93% of compound (I), 5% of compound (III), and 2% of compound (II), based on mass content.
[0076] The compound of formula (I) above is:
[0077] Where R is C 10 H 21 m+n=15, X is CH2COONa;
[0078] The compound of formula (II) above is:
[0079] Where R 1 C 10 H 21 m1+n1=15, X 1 It is CH2COONa;
[0080] The compound of formula (III) above is:
[0081] Where R 2 C 10 H 21 , m2+n2=15.
[0082] 2. Anti-fogging modification of solid surfaces: The quartz surface is subjected to plasma treatment for 5 minutes in an oxygen atmosphere (vacuum degree of 80 mTorr, gas flow rate of 50 sccm), and then immersed in the above anti-fogging agent and reacted at 60℃ for 3 hours.
[0083] 3. Anti-fog surface test: After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the light transmittance was tested to be 90.4%, the water droplet contact angle on the surface was 11°, and the haze was 2.0%. Then, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h using a syringe pump. The contact angle was tested to be 14°, and the haze was 2.0%.
[0084] Comparative Example 1
[0085] The quartz plate was directly immersed in the anti-fogging agent prepared in Example 1 and left at 60°C for 3 hours. After drying, it was rinsed with deionized water at a rate of 1 mL / min for 1 minute. The transmittance was tested to be 90.5%, the water droplet contact angle on the surface was 30°, and the haze was 20%. The plate was then rinsed with deionized water at a rate of 1 mL / min for 2 hours using a syringe pump. The contact angle was tested to be 40°, and the haze was 28%.
[0086] Figure 1 The image shows the carbon signal obtained by SEM testing on the modified silica surface of Example 1 after rinsing at a rate of 1 mL / min for 2 hours; it can be seen that there is a lot of carbon signal, indicating that antifogging agent still remains on the solid surface after rinsing; Figure 2 The image shows the carbon signal obtained by SEM testing on the modified silica surface of Comparative Example 1 after rinsing at a rate of 1 mL / min for 2 h; it can be seen that there is no carbon signal, indicating that the antifogging agent has been rinsed off.
[0087] Comparative Example 2
[0088] The quartz surface was subjected to plasma treatment for 5 min in an oxygen atmosphere (vacuum degree of 80 mTorr, gas flow rate of 50 sccm), and then immersed in the fatty amine polyoxyethylene ether prepared in Example 1, and reacted at 60 °C for 3 h.
[0089] After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the transmittance was measured to be 90.0%, the water droplet contact angle on the surface was 31°, and the haze was 23%. Then, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h using a syringe pump; the contact angle was measured to be 32° and the haze was 23%.
[0090] Example 2
[0091] 1. Synthesis of antifogging agents:
[0092] (1) Preparation of fatty amine polyoxyethylene ether: Except for the initial reaction with 2 mol of ethylene oxide followed by the reaction with 18 mol of ethylene oxide, all other steps were the same as in Example 1. The structural formula of the obtained fatty amine polyoxyethylene ether is as follows: Among them, R 3 C 10 H 21 x³ + y³ = 0, m³ + n³ = 20.
[0093] (2) Preparation of antifogging agent: The above-mentioned fatty amine polyoxyethylene ether was used, the anionizing agent was sodium 2-chloroethylsulfonate, and the rest were the same as in Example 1. The product obtained is the antifogging agent of the present invention.
[0094] Liquid chromatography analysis revealed that the above products contained 81% of compound (I), 4% of compound (III), and 15% of compound (II), based on mass content.
[0095] The compound of formula (I) above is:
[0096] Where R is C 10 H 21 m+n=20, X is CH2CH2SO3Na;
[0097] The compound of formula (II) above is:
[0098] R 1 C 10 H 21 m1+n1=20, X 1 It is CH2CH2SO3Na;
[0099] The compound of formula (III) above is:
[0100] Where R 2C 10 H 21 , m2+n2=20.
[0101] 2. Solid surface anti-fogging modification: The quartz surface was subjected to plasma treatment for 8 minutes in an oxygen atmosphere with a vacuum degree of 80 mTorr and a gas flow rate of 40 sccm. Then it was immersed in the above anti-fogging agent and reacted at 60°C for 2 hours.
[0102] 3. Anti-fog surface test: After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the light transmittance was tested to be 90.0%, the water droplet contact angle on the surface was 14°, and the haze was 2.1%. Then, using a syringe pump, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h. The contact angle was tested to be 18°, and the haze was 3.5%.
[0103] Example 3
[0104] 1. Synthesis of antifogging agents:
[0105] (1) Preparation of fatty amine polyoxyethylene ether: Except for replacing 1 mol of decylamine with 1 mol of dodecylamine, all other steps were the same as in Example 1. The structural formula of the obtained fatty amine polyoxyethylene ether is as follows: Among them, R 3 C 12 H 25 x³ + y³ = 0, m³ + n³ = 15.
[0106] (2) Preparation of antifogging agent: The above-mentioned fatty amine polyoxyethylene ether is used, and all other aspects are the same as in Example 1. The product obtained is the antifogging agent of the present invention.
[0107] Liquid chromatography analysis showed that the product contained 86% of compound (I), 4% of compound (III), and 10% of compound (II), based on mass content.
[0108] The compound of formula (I) above is:
[0109] Where R is C 12 H 25 m+n=15, X is CH2COONa;
[0110] The compound of formula (II) above is:
[0111] Where R 1 C 12 H 25 m1+n1=15, X 1 It is CH2COONa;
[0112] The compound of formula (III) above is:
[0113] Where R 2 C 12 H 25 , m2+n2=15.
[0114] 2. Solid surface anti-fogging modification: The quartz surface is subjected to plasma treatment for 2 minutes in an oxygen atmosphere with a vacuum degree of 50 mTorr and a gas flow rate of 80 sccm. Then it is immersed in the above anti-fogging agent and reacted at 50°C for 2 hours.
[0115] 3. Anti-fog surface test: After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the light transmittance was tested to be 90.1%, the water droplet contact angle on the surface was 13°, and the haze was 2.1%. Then, using a syringe pump, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h. The contact angle was tested to be 17°, and the haze was 2.4%.
[0116] Example 4
[0117] 1. Synthesis of antifogging agents:
[0118] (1) Preparation of fatty amine polyoxyethylene ether: Except for the initial reaction with 2 mol of ethylene oxide followed by the reaction with 6 mol of ethylene oxide, all other steps were the same as in Example 1. The structural formula of the obtained fatty amine polyoxyethylene ether is as follows:
[0119] Where R 3 C 10 H 21 x³ + y³ = 0, m³ + n³ = 8.
[0120] (2) Preparation of antifogging agent: The above-mentioned fatty amine polyoxyethylene ether is used, and all other aspects are the same as in Example 1. The product obtained is the antifogging agent of the present invention.
[0121] Liquid chromatography analysis showed that the product contained 91% of compound (I), 6% of compound (III), and 3% of compound (II), based on mass content.
[0122] The compound of formula (I) above is:
[0123] Where R is C 10 H 21 m+n=8, X is CH2COONa;
[0124] The compound of formula (II) above is:
[0125] Where R 1 C 10 H21 m1+n1=8, X 1 It is CH2COONa;
[0126] The compound of formula (III) above is:
[0127] Where R 2 C 10 H 21 , m2+n2=8.
[0128] 2. Solid surface anti-fogging modification: The quartz surface is subjected to plasma treatment for 5 minutes in an oxygen atmosphere (vacuum degree of 80 mTorr, gas flow rate of 50 sccm), and then immersed in the above anti-fogging agent and reacted at 60℃ for 3 hours.
[0129] 3. Anti-fog surface test: After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the light transmittance was tested to be 88.7%, the water droplet contact angle on the surface was 20°, and the haze was 7.5%. Then, using a syringe pump, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h. The contact angle was tested to be 25°, and the haze was 16.1%.
[0130] Example 5
[0131] 1. Synthesis of antifogging agents:
[0132] (1) Preparation of fatty amine polyoxyethylene ether: Except for the initial reaction with 2 mol of ethylene oxide followed by the reaction with 28 mol of ethylene oxide, all other steps were the same as in Example 1. The structural formula of the obtained fatty amine polyoxyethylene ether is as follows: Where R 3 C 10 H 21 x³ + y³ = 0, m³ + n³ = 30.
[0133] (2) Preparation of antifogging agent: The above-mentioned fatty amine polyoxyethylene ether is used, and all other aspects are the same as in Example 1. The product obtained is the antifogging agent of the present invention.
[0134] Liquid chromatography analysis showed that the product contained 82% of compound (I), 8% of compound (III), and 10% of compound (II), based on mass content.
[0135] The compound of formula (I) above is:
[0136] Where R is C 10 H 21 m+n=30, X is CH2COONa;
[0137] The compound of formula (II) above is:
[0138] Where R 1 C 10 H 21 m1+n1=30, X 1 It is CH2COONa;
[0139] The compound of formula (III) above is:
[0140] Where R 2 C 10 H 21 , m2+n2=30.
[0141] 2. Anti-fogging modification of solid surfaces: The quartz surface is subjected to plasma treatment for 5 minutes in an oxygen atmosphere (vacuum degree of 80 mTorr, gas flow rate of 50 sccm), and then immersed in the above anti-fogging agent and reacted at 60℃ for 3 hours.
[0142] 3. Anti-fog surface test: After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the light transmittance was tested to be 90.7%, the water droplet contact angle on the surface was 15°, and the haze was 3.1%. Then, using a syringe pump, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h. The contact angle was tested to be 19°, and the haze was 6.1%.
[0143] Example 6
[0144] Unlike Example 1, the plasma treatment time was changed to 15 minutes.
[0145] After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the transmittance was measured to be 90.0%, the water droplet contact angle on the surface was 17°, and the haze was 4.9%. Then, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h using a syringe pump; the contact angle was measured to be 22° and the haze was 8.9%.
[0146] Example 7
[0147] 1. Synthesis of antifogging agents:
[0148] (1) Preparation of fatty amine polyoxyethylene ether:
[0149] 1 mol of decylamine was added to a reactor equipped with a condenser, a stirrer, and a gas disperser. The system temperature was heated to 90°C, and a vacuum system was activated. Dehydration was carried out under high vacuum for 1 hour. The system was then purged three times with nitrogen to remove air. The reaction temperature was then adjusted to 140°C, and 2 mol of propylene oxide was slowly introduced, maintaining a pressure <0.40 MPa and a temperature of 140°C. The reaction was continued for 1 hour. Then, 1% (by weight) of potassium hydroxide catalyst (decylamine) was added, followed by the introduction of 13 mol of ethylene oxide, maintaining a pressure <0.40 MPa and a temperature of 140°C. The reaction was continued for another 1 hour. After cooling, the mixture was neutralized, decolorized, filtered, and dehydrated to obtain aliphatic amine polyoxyethylene ether. Its structural formula is as follows: Where R 3 C 10 H 21 x3+y3=2, m3+n3=13. The structural formula of the above aliphatic amine polyoxyethylene ether was calculated based on the reaction principle and the amount of raw materials added.
[0150] (2) Preparation of antifogging agent: The above-mentioned fatty amine polyoxyethylene ether is used, and all other aspects are the same as in Example 1. The product obtained is the antifogging agent of the present invention.
[0151] Liquid chromatography analysis showed that the product contained 83% of compound (I), 8% of compound (III), and 9% of compound (II), based on mass content.
[0152] The compound of formula (I) above is:
[0153] Where R is C 10 H 21 , x+y=2, m+n=13, X is CH2COONa;
[0154] The compound of formula (II) above is:
[0155] Where R 1 C 10 H 21 x1+y1=2, m1+n1=13, X 1 It is CH2COONa;
[0156] The compound of formula (III) above is:
[0157] Where R 2 C 10 H 21 x² + y² = 2, m² + n² = 13.
[0158] 2. Solid surface anti-fogging modification: The quartz surface is subjected to plasma treatment for 5 minutes in an oxygen atmosphere with a vacuum degree of 80 mTorr and a gas flow rate of 50 sccm. Then it is immersed in the above anti-fogging agent and reacted at 60°C for 3 hours.
[0159] 3. Anti-fog surface test: After the reaction, the quartz surface was rinsed with deionized water at a rate of 1 mL / min for 1 min. After drying, the light transmittance was tested to be 90.9%, the water droplet contact angle on the surface was 13°, and the haze was 2.7%. Then, the surface was rinsed with deionized water at a rate of 1 mL / min for 2 h using a syringe pump. After drying, the contact angle was tested to be 16°, and the haze was 4.0%.
[0160] As can be seen from Example 1 and Comparative Example 1, since the quartz surface of Comparative Example 1 was not subjected to plasma treatment, the hydroxyl groups in the molecular structure of the antifogging agent of the present invention could not react chemically with the quartz surface, and therefore could not be grafted onto the quartz surface, resulting in the contact angle and haze of Comparative Example 1 being inferior to those of Example 1.
[0161] As can be seen from Example 1 and Comparative Example 2, since Comparative Example 2 uses the fatty amine polyoxyethylene ether prepared in Example 1 (i.e. the raw material for preparing the antifogging agent in Example 1) as the antifogging agent for the quartz surface, the contact angle and haze of the modified quartz surface in Comparative Example 2 are also inferior to those in Example 1.
[0162] As can be seen from Examples 1-7, the antifogging agent of the present invention contains both anionic and hydroxyl groups in its molecular structure. The hydroxyl groups chemically react with the plasma-treated solid surface (such as a quartz surface) containing high-energy active groups, grafting onto the solid surface and increasing washability. The unreacted anionic groups at the other end increase the affinity for water, allowing water droplets to spread on the solid. Furthermore, by controlling the degree of polymerization of oxyethylene ether and oxypropylene ether and the ratio of the number of carbon atoms in the alkyl chain, the steric hindrance of the grafting of the antifogging agent molecule onto the solid surface containing high-energy active groups and its affinity for water can be controlled. After modification, the light transmittance is preferably above 90%, the contact angle between water and the modified solid surface is preferably below 20°, and the haze is preferably below 5%; after 2 hours of water rinsing, the increase in contact angle is preferably ≤5°.
[0163] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. An antifogging agent comprising at least one of compounds with the structure shown in formula (I): In formula (I), R is one of H or C1-C18 hydrocarbon groups; x is an integer from 0 to 10, y is an integer from 0 to 10, m is an integer from 0 to 50, and n is an integer from 0 to 50, and x, y, m, and n are not all 0 at the same time; X is one of R1COOM or R2SO3M1, wherein... R1 and R2 may be the same or different, and are independently one of C1-C6 alkylene or phenylene groups. M and M1 may be the same or different, and are independently a cation or cationic group that balances the charge of the compound.
2. The anti-fogging agent as described in claim 1, characterized in that: R is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or, x is an integer between 0 and 5, y is an integer between 0 and 5; and / or, x+y is an integer from 0 to 20, preferably an integer from 0 to 10, and more preferably an integer from 0 to 5; and / or, m is an integer between 0 and 30, n is an integer between 0 and 30; and / or, m+n is an integer from 1 to 100, preferably an integer from 2 to 50, and more preferably an integer from 7 to 30; and / or, x+y+m+n is greater than or equal to the number of carbon atoms in R; preferably, x+y+m+n is 2-20 greater than the number of carbon atoms in R, more preferably 2-15 greater; and / or, M and M1 may be the same or different, and each is an independent alkali metal ion.
3. The anti-fogging agent as described in claim 1, characterized in that: The antifogging agent further comprises at least one of the compounds with the structure shown in formula (II) below and / or at least one of the compounds with the structure shown in formula (III) below: In equation (II), R 1 It is one of H or C1-C18 hydrocarbon groups; x1 is an integer from 0 to 10, y1 is an integer from 0 to 10, m1 is an integer from 0 to 50, n1 is an integer from 0 to 50, and x1, y1, m1, and n1 are not all 0 at the same time; X 1 It is one of R1COOM and R2SO3M1, wherein R1 and R2 are the same or different, and are independently one of C1-C6 alkylene or phenylene, and M and M1 are the same or different, and are independently a cation or cationic group that balances the charge of the compound. In equation (III), R 2 It is one of H or C1-C18 hydrocarbon groups; x2 is an integer from 0 to 10, y2 is an integer from 0 to 10, m2 is an integer from 0 to 50, n2 is an integer from 0 to 50, and x2, y2, m2, and n2 are not all 0 at the same time.
4. The anti-fogging agent as described in claim 3, characterized in that: In equation (II), R 1 It is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or, x1 is an integer from 0 to 5, y1 is an integer from 0 to 5; and / or, x1+y1 is an integer from 0 to 20, preferably an integer from 0 to 10, more preferably an integer from 0 to 5; and / or, m1 is an integer from 0 to 30, n1 is an integer from 0 to 30; and / or, m1+n1 is an integer from 1 to 100, preferably an integer from 2 to 50, more preferably an integer from 7 to 30; and / or, x1+y1+m1+n1 is greater than or equal to R. 1 Preferably, the number of carbon atoms in x1+y1+m1+n1 is greater than that in R. 1 The number of carbon atoms is greater than 2-20, more preferably greater than 2-15; and / or, M and M1 may be the same or different, and are each independently one of the alkali metal ions; and / or, In equation (III), R 2 It is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or, x2 is an integer from 0 to 5, y2 is an integer from 0 to 5; and / or, x2+y2 is an integer from 0 to 20, preferably an integer from 0 to 10, more preferably an integer from 0 to 5; and / or, m2 is an integer from 0 to 30, n2 is an integer from 0 to 30; and / or, m2+n2 is an integer from 1 to 100, preferably an integer from 2 to 50, more preferably an integer from 7 to 30; and / or, x2+y2+m2+n2 is greater than or equal to R. 2 The number of carbon atoms in the middle, preferably, is x² + y² + m² + n² compared to R. 2 The number of carbon atoms is greater than 2-20, more preferably greater than 2-15; and / or, Based on the mass of the antifogging agent as 100%, the mass content of the compound with the structure shown in formula (I) in the antifogging agent is 80-100%, preferably 80-97%; the mass content of the compound with the structure shown in formula (II) is 0-20%, preferably 1-15%; and the mass content of the compound with the structure shown in formula (III) is 0-10%, preferably 2-8%.
5. A method for preparing an antifogging agent as described in any one of claims 1-4, comprising the step of reacting at least one of the compounds with the structure shown in formula (Ⅳ) below with an anionizing agent: In equation (Ⅳ), R 3 It is one of H or C1-C18 hydrocarbon groups; x3 is an integer from 0 to 10, y3 is an integer from 0 to 10, m3 is an integer from 0 to 50, n3 is an integer from 0 to 50, and x3, y3, m3, and n3 are not all 0 at the same time; preferably, R 3 It is one of C1-C18 alkyl groups, preferably one of C6-C18 alkyl groups, more preferably one of C6-C12 alkyl groups; and / or, x3 is an integer between 0 and 5, y3 is an integer between 0 and 5; and / or, x3+y3 is an integer from 0 to 20, preferably an integer from 0 to 10, and more preferably an integer from 0 to 5; and / or, m3 is an integer between 0 and 30, n3 is an integer between 0 and 30; and / or, m3+n3 is an integer from 1 to 100, preferably an integer from 2 to 50, and more preferably an integer from 7 to 30; and / or, x³ + y³ + m³ + n³ is greater than or equal to R 3 The number of carbon atoms in the middle; preferably, x³+y³+m³+n³ is more than R. 3 The number of carbon atoms is 2-20, preferably 2-15.
6. The preparation method according to claim 5, characterized in that: The anionizing agent has the general structural formula L1-R3COOM3 or L2-R4SO3M4, wherein L1 and L2 may be the same or different, and are each independently a halogen; R3 and R4 may be the same or different, and are each independently a C1-C6 alkylene or phenylene group; M3 and M4 may be the same or different, and are each independently a cation or cationic group that balances the charge of the compound, preferably an alkali metal ion; and / or, The molar ratio of the compound with the structure shown in formula (Ⅳ) to the anionizing agent is 1:(1-2), preferably 1:(1-1.5); and / or, The reaction temperature is 50-150℃, preferably 60-100℃; and / or the reaction time is 1-20h, preferably 2-8h.
7. A surface anti-fogging system comprising the anti-fogging agent according to any one of claims 1-4 or the anti-fogging agent obtained by the preparation method according to any one of claims 5-6, and optionally a solvent.
8. A surface modification method, comprising the steps of plasma treating a solid surface containing high-energy active groups and then immersing it in an anti-fogging agent according to any one of claims 1-4, an anti-fogging agent obtained by any one of claims 5-6, or an anti-fogging system according to claim 7; preferably, the solid surface containing high-energy active groups is a solid surface containing hydroxyl groups, preferably a solid surface containing silica, and more preferably a glass and / or quartz surface.
9. The surface modification method as described in claim 8, characterized in that: The plasma treatment is performed in an oxygen atmosphere; and / or, The plasma treatment time is 1-15 min, preferably 2-10 min, the vacuum degree is 50-80 mTorr, and the gas flow rate is 20-100 sccm.
10. The surface modification method as described in claim 8, characterized in that: The reaction time is 2-4 hours, preferably 2-3 hours; and / or the reaction temperature is 40-80°C, preferably 50-70°C.
11. The surface modification method according to any one of claims 8-10, characterized in that: After modification, the contact angle between water and the modified surface is 20° or less, preferably 15° or less; after rinsing with water for 2 hours, the increase in contact angle is ≤5°.
12. The application of an antifogging agent as described in any one of claims 1-4, an antifogging agent obtained by the preparation method as described in any one of claims 5-6, an antifogging system as described in claim 7, or a surface modification method as described in any one of claims 8-11 in surface antifogging.