Use of a fluorine-containing block copolymer
By preparing a fluorinated block copolymer ABA coating, the problem of using toxic solvents in existing technologies was solved, and a highly efficient hydrophobic coating was prepared in an environmentally friendly solvent, thus improving the hydrophobic properties of the substrate.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- BEIJING INST OF TECH
- Filing Date
- 2024-04-11
- Publication Date
- 2026-06-30
AI Technical Summary
Existing technologies require the use of toxic organic solvents when preparing hydrophobic surfaces, resulting in complex and environmentally unfriendly processes that make large-scale production and application difficult.
A method for preparing fluorinated block copolymer ABA was adopted, using boron trifluoride diethyl ether solution and tetrahydrofuran as catalyst and solvent. The solubility of fluoride in ethanol was improved by chemical modification, and the fluoride was applied to the surface of the substrate to form a hydrophobic coating.
This method enables the preparation of hydrophobic coatings in green solvents, improving the hydrophobic properties of the substrate. The process is simple and environmentally friendly.
Smart Images
Figure CN118240457B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the application of a fluorinated block copolymer, belonging to the field of hydrophobic coating technology. Background Technology
[0002] In the aerospace field, hydrophobic coatings on aircraft surfaces effectively prevent icing, ensuring flight performance and preventing air disasters. In the transportation sector, hydrophobic coatings prevent glass fogging, ensuring clear visibility and driving safety. In the electronics and electrical fields, hydrophobic coatings prevent water accumulation on circuit boards, preventing short circuits or rusting of electronic components. In everyday life, hydrophobic coatings can prevent food from sticking to the bottom of pots and pans. Therefore, hydrophobic surfaces have a very wide range of applications.
[0003] Currently, the approach to preparing hydrophobic surfaces is relatively unified, mainly focusing on surface microstructure and low surface energy fluorinated materials. Fluorides are poorly soluble in water and common organic solvents, but readily soluble in organofluorine solvents. Therefore, surface treatment of materials with hydrophobic surfaces requires immersion in fluorinated organic solvents. This method is considered complex and environmentally unfriendly due to the toxicity of organic solvents, limiting its application. Consequently, the development of green and environmentally friendly hydrophobic coatings using non-toxic and harmless solvents to replace volatile organic solvents is gaining popularity. Therefore, the development of hydrophobic coatings using simple and environmentally friendly processes for large-scale production and application has become a current research hotspot. Summary of the Invention
[0004] The technical problem solved by this invention is to overcome the shortcomings of the prior art and propose an application of fluorinated block copolymers, chemically modifying fluorides to increase their solubility in the green solvent ethanol, and applying them to the surface of a substrate to improve the hydrophobic properties of the substrate.
[0005] The technical solution of this invention is:
[0006] A fluorinated block copolymer, wherein the molecular formula of the fluorinated block copolymer is ABA;
[0007] Wherein, B is 1,4-bis(2',3'-epoxypropyl)perfluorobutane, and A is polypropylene glycol, with a molecular weight of 400-600 g / mol.
[0008] A method for preparing a fluorinated block copolymer, wherein the raw materials used in the method include a main raw material and an auxiliary raw material, the main raw material includes polypropylene glycol and 1,4-bis(2',3'-epoxypropyl)perfluorobutane, and the auxiliary raw materials are a catalyst and a solvent;
[0009] The catalyst is a boron trifluoride diethyl ether solution (mass concentration of 46.5%), and the solvent is tetrahydrofuran;
[0010] The specific steps include:
[0011] The first step is to stir and mix polypropylene glycol and tetrahydrofuran until a solution is obtained;
[0012] The second step is to pour the solution obtained in the first step into a three-necked flask filled with nitrogen gas, then add the boron trifluoride diethyl ether catalyst solution and stir.
[0013] The third step involves mixing 1,4-bis(2',3'-epoxypropyl)perfluorobutane and tetrahydrofuran, and then adding the mixture dropwise to the solution obtained in the second step at a flow rate of 5–20 mL / h (preferably 5–10 mL / h).
[0014] Fourth step: Place the solution obtained in the third step in an oil bath and stir at a constant temperature of 40-60℃ for 4-8 hours;
[0015] The fifth step involves evaporating the product obtained in the fourth step at room temperature for 4–6 hours, then transferring it to a vacuum oven and drying it at 60–80°C for 2–4 hours. The product is then purified by chromatography to obtain the ABA triblock copolymer.
[0016] In the first step, the ratio of polypropylene glycol to tetrahydrofuran (moles:volume) is 0.1 mol: 30-50 mL;
[0017] In the second step, the ratio (volume:molar) of the boron trifluoride diethyl ether catalyst solution to the polypropylene glycol in the first step is 3-5 mL: 0.1 mol.
[0018] In the third step, the molar-to-volume ratio of 1,4-bis(2',3'-epoxypropyl)perfluorobutane to tetrahydrofuran is 0.1 mol: 30-50 mL.
[0019] In the third step, the volume ratio of 1,4-bis(2',3'-epoxypropyl)perfluorobutane to the solution obtained in the second step is (1:0.6~1).
[0020] In the fifth step, the developing solvent used for purification by chromatography column is a mixture of tetrafluoropropanol and tetrahydrofuran, with a mass ratio of tetrafluoropropanol to tetrahydrofuran of 3:7.
[0021] An application of a fluorinated block copolymer involves applying the fluorinated block copolymer as a hydrophobic coating to the surface of a substrate, which is mainly a metal or alloy. The following example uses an aluminum substrate.
[0022] The specific steps include:
[0023] The obtained ABA fluorinated block copolymer was dissolved in ethanol, stirred evenly, and allowed to stand for 1-3 hours until the dispersion was stable. The substrate was then immersed in a beaker and stirred for 3-5 hours. The substrate was then removed and dried in a forced-air oven at 50-70℃ for 2-4 hours. After drying, a metal sheet coated with an ABA triblock copolymer was obtained.
[0024] Beneficial effects
[0025] The ABA fluorinated block copolymer of the present invention can be applied to the surface of a substrate as a hydrophobic coating. The coating operation is simple and can increase the hydrophobicity of the substrate. Attached Figure Description
[0026] Figure 1 The results are from the GPC test of polypropylene glycol.
[0027] Figure 2 The results are GPC test results for the product obtained in Example 1;
[0028] Figure 3 The GPC test results are for the product obtained in Example 2;
[0029] Figure 4 The results are GPC test results of the product obtained in Example 3;
[0030] Figure 5 The GPC test results are for the product obtained in Example 4;
[0031] Figure 6 This is a schematic diagram showing the contact angle test results of an uncoated aluminum sheet.
[0032] Figure 7 This is a schematic diagram showing the contact angle test results of the ABA copolymer-coated aluminum sheet in Example 1;
[0033] Figure 8 This is a schematic diagram showing the contact angle test results of the ABA copolymer-coated aluminum sheet in Example 2;
[0034] Figure 9 This is a schematic diagram showing the contact angle test results of the ABA copolymer-coated aluminum sheet in Example 3. Detailed Implementation
[0035] The present invention will be further illustrated by the following examples.
[0036] Example 1
[0037] First, add 0.1 mol of polypropylene glycol and 50 mL of THF to a beaker and stir for 20 minutes until completely dissolved.
[0038] The second step involves pouring the solution obtained in the first step into a three-necked flask filled with nitrogen gas, then adding 3 mL of boron trifluoride diethyl ether catalyst solution, and stirring for 10 minutes.
[0039] Third, dissolve 0.04 mol of 1,4-bis(2',3'-epoxypropyl)perfluorobutane in 30 mL of tetrahydrofuran, and add it dropwise to the polypropylene glycol solution obtained in the second step at a flow rate of 5 mL / h.
[0040] Fourth step: Place the solution obtained in the third step in an oil bath and stir at a constant temperature of 40°C for 6 hours.
[0041] Fifth, the product obtained in the fourth step was evaporated at room temperature for 6 hours, transferred to a vacuum oven and dried at 60°C for 2 hours. The product was then purified by chromatography to obtain the ABA copolymer.
[0042] GPC tests were performed on polypropylene glycol and the product obtained in Example 1, and the results are as follows: Figure 1 , Figure 2 As shown, the results indicate that the polypropylene glycol has a weight-average molecular weight of 410 g / mol and a polydispersity of 1.08; the obtained ABA copolymer has a polydispersity of 1.19 and a weight-average molecular weight of 1213 g / mol, which is close to the theoretical value. This indicates that the ABA copolymer has high purity and few by-products. The purified product was weighed and compared with the initial feed, showing a yield of 85%.
[0043] The obtained ABA copolymer was dissolved in ethanol in a beaker, stirred evenly, and allowed to stand for 3 hours until the dispersion was stable. Then, the aluminum sheet was immersed in the beaker and stirred for another 3 hours. The aluminum sheet was then removed and dried in a 50°C forced-air oven for 2 hours. The aluminum sheet coated with ABA copolymer was then obtained.
[0044] Contact angle tests were performed on both the uncoated aluminum sheet and the aluminum sheet coated with the obtained ABA copolymer. The test results are as follows: Figure 6 and Figure 7 As shown, the contact angle of the uncoated aluminum sheet is 50.0°, while the contact angle of the ABA copolymer-coated aluminum sheet is 111.2°. This indicates that the hydrophobicity of the ABA copolymer-coated aluminum sheet is improved.
[0045] Example 2
[0046] First, add 0.1 mol of polypropylene glycol and 30 mL of THF to a beaker and stir for 20 minutes until completely dissolved.
[0047] The second step is to pour the solution into a three-necked flask filled with nitrogen, then add 3 mL of boron trifluoride diethyl ether catalyst solution and stir for 10 minutes.
[0048] Third, dissolve 0.05 mol of 1,4-bis(2',3'-epoxypropyl)perfluorobutane in 30 mL of tetrahydrofuran, and add it dropwise to the polypropylene glycol solution obtained in the second step at a flow rate of 10 mL / h.
[0049] Fourth step: Place the solution obtained in the third step in an oil bath and stir at a constant temperature of 60°C for 6 hours.
[0050] Fifth, the product obtained in the fourth step was evaporated at room temperature for 6 hours, transferred to a vacuum oven and dried at 60°C for 2 hours. The product was then purified by chromatography to obtain the ABA copolymer.
[0051] The product obtained in Example 2 was subjected to GPC testing, and the results are as follows: Figure 3 As shown, the results indicate that the polydispersity of the obtained ABA copolymer is 1.52, and the weight-average molecular weight is 1719 g / mol. The purified product was weighed and compared with the initial feed, showing a yield of 71%.
[0052] The obtained ABA copolymer was dissolved in ethanol in a beaker, stirred evenly, and allowed to stand for 3 hours until the dispersion was stable. Then, the aluminum sheet was immersed in the beaker and stirred for another 3 hours. The aluminum sheet was then removed and dried in a 50°C forced-air oven for 2 hours. The aluminum sheet coated with ABA copolymer was then obtained.
[0053] Contact angle tests were performed on all the aluminum sheets coated with the obtained ABA copolymer. The test results are as follows: Figure 8 As shown, the contact angle of the aluminum sheet coated with ABA copolymer is 60.6°, indicating that the hydrophobicity of the aluminum sheet coated with ABA copolymer is improved.
[0054] Example 3
[0055] First, add 0.1 mol of polypropylene glycol and 40 mL of THF to a beaker and stir for 20 minutes until completely dissolved.
[0056] The second step involves pouring the solution into a three-necked flask filled with nitrogen. Then, 3 mL of the boron trifluoride diethyl ether catalyst solution is added to the reaction vessel and stirred for 10 minutes.
[0057] Third, dissolve 0.05 mol of 1,4-bis(2',3'-epoxypropyl)perfluorobutane in 50 mL of tetrahydrofuran, and add it dropwise to the polypropylene glycol solution obtained in the second step at a flow rate of 5 mL / h.
[0058] Fourth, place the solution obtained in the third step in an oil bath and stir at a constant temperature of 40°C for 6 hours.
[0059] Fifth, the product obtained in the fourth step was evaporated at room temperature for 6 hours, transferred to a vacuum oven and dried at 60°C for 2 hours. The product was then purified by chromatography to obtain the ABA copolymer.
[0060] The product obtained in Example 3 was subjected to GPC testing, and the results are as follows: Figure 4 As shown, the results indicate that the polydispersity of the obtained ABA copolymer is 1.49, and the weight-average molecular weight is 1490 g / mol. The purified product was weighed and compared with the initial feed, showing a yield of 72%.
[0061] The obtained ABA copolymer was dissolved in ethanol in a beaker, stirred evenly, and allowed to stand for 3 hours until the dispersion was stable. Then, the aluminum sheet was immersed in the beaker and stirred for another 3 hours. The aluminum sheet was then removed and dried in a 50°C forced-air oven for 2 hours. The aluminum sheet coated with ABA copolymer was then obtained.
[0062] Contact angle tests were performed on all the aluminum sheets coated with the obtained ABA copolymer. The test results are as follows: Figure 9 As shown, the contact angle of the aluminum sheet coated with ABA copolymer is 79.4°, indicating that the hydrophobicity of the aluminum sheet coated with ABA copolymer is improved.
[0063] Example 4
[0064] First, add 0.075 mol of polypropylene glycol and 40 mL of THF to a beaker and stir for 20 minutes until completely dissolved.
[0065] The second step involves pouring the solution into a three-necked flask filled with nitrogen. Then, 3 mL of the boron trifluoride diethyl ether catalyst solution is added to the reaction vessel and stirred for 10 minutes.
[0066] Third, dissolve 0.04 mol of 1,4-bis(2',3'-epoxypropyl)perfluorobutane in 30 mL of tetrahydrofuran, and add it dropwise to the polypropylene glycol solution obtained in the second step at a flow rate of 20 mL / h.
[0067] Fourth, place the solution obtained in the third step in an oil bath and stir at a constant temperature of 40°C for 6 hours.
[0068] Fifth, the product obtained in the fourth step was evaporated at room temperature for 6 hours, transferred to a vacuum oven and dried at 60°C for 2 hours. The product was then purified by chromatography to obtain the ABA copolymer.
[0069] The product obtained in Example 4 was subjected to GPC testing, and the results are as follows: Figure 5 As shown, the results indicate that the polydispersity of the obtained ABA copolymer is 1.55, and the weight-average molecular weight is 1385 g / mol. The purified product was weighed and compared with the initial feed, showing a yield of 79%.
[0070] In summary, the above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. An application of a fluorinated block copolymer, characterized in that: Fluorinated block copolymers are applied as hydrophobic coatings to the surface of substrates. The fluorinated block copolymer has the molecular formula ABA. Wherein, B is 1,4-bis(2',3'-epoxypropyl)perfluorobutane, and A is polypropylene glycol; The preparation method of the fluorinated block copolymer is as follows: The first step is to mix polypropylene glycol and tetrahydrofuran until homogeneous; The second step involves mixing the mixture obtained in the first step with the boron trifluoride diethyl ether solution under a nitrogen atmosphere. The third step involves mixing 1,4-bis(2',3'-epoxypropyl)perfluorobutane and tetrahydrofuran; The fourth step is to mix the mixture obtained in the third step with the mixture obtained in the second step. Fifth step: Place the mixture obtained in the fourth step in an oil bath and stir at a constant temperature of 40~60℃ for 4~8 hours; Step 6: Evaporate the product obtained in step 5 at room temperature for 4-6 hours, then transfer it to a vacuum oven and dry it at 60-80°C for 2-4 hours. The product is purified by chromatography to obtain ABA triblock copolymer. In the first step, the ratio of polypropylene glycol to tetrahydrofuran is 0.1 mol: 30-50 mL; In the second step, the mass concentration of the boron trifluoride diethyl ether solution is 46.5%; In the second step, the ratio of boron trifluoride ether solution to polypropylene glycol in the first step is 3-5 mL: 0.1 mol; In the third step, the ratio of 1,4-bis(2',3'-epoxypropyl)perfluorobutane to tetrahydrofuran is 0.1 mol: 30-50 mL; The volume ratio of 1,4-bis(2',3'-epoxypropyl)perfluorobutane in the third step to the mixture obtained in the second step is 1:0.6-1; In the fourth step, mixing the mixture obtained in the third step and the mixture obtained in the second step means adding the mixture obtained in the third step dropwise to the mixture obtained in the second step at a flow rate of 5-20 mL / h. In the fifth step, the developing solvent used for purification by chromatography column is a mixture of tetrafluoropropanol and tetrahydrofuran, with a mass ratio of tetrafluoropropanol to tetrahydrofuran of 3:
7. The obtained ABA triblock copolymer was dissolved in ethanol, stirred evenly, and allowed to stand for 1-3 hours until the dispersion was stable. The substrate was then impregnated for 3-5 hours. The substrate was then removed and dried in a forced-air oven at 50-70℃ for 2-4 hours. The substrate was then removed to obtain the substrate coated with the ABA triblock copolymer. The substrate is a metal or alloy; The molecular weight of the polypropylene glycol is 400-600 g / mol.