Preparation and application of perfluoropolyether reactive nonionic surfactant

Abstract

The invention discloses preparation and application of a perfluoropolyether reactive nonionic surfactant, and solves the problems that perfluoropolyether surfactants in the prior art are poor in environmental protection property and single in function, and reactivity and compatibility are difficult to consider at the same time. The preparation method comprises the following steps: taking Y-type perfluoropolyether alcohol as a raw material, carrying out ring opening on the Y-type perfluoropolyether alcohol and allyl glycidyl ether to prepare an intermediate, and reacting the intermediate with ethylene oxide to prepare the perfluoropolyether reactive nonionic surfactant product. The perfluoropolyether reactive nonionic surfactant obtained by the invention takes an allyl ether segment as a functional chain segment and a polyethylene glycol segment as a hydrophilic chain segment, is good in environmental protection property, not only has the effects of reducing surface tension and improving leveling property, but also can enable a coating to have excellent water and oil resistance and wear resistance after being cured through reaction.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, and in particular to the preparation and application of a perfluoropolyether reactive nonionic surfactant. Background Art

[0002] Fluorocarbon surfactants are increasingly attracting widespread attention due to their special properties of "three highs and two hates", namely high surface activity, high heat stability, high chemical stability, and both water and oil repellency. Fluorocarbon surfactants are also the type with the highest surface activity among all surfactants currently available.

[0003] Like hydrocarbon surfactants, fluorocarbon surfactants can also be divided into four categories according to their dissociation properties: cationic, anionic, amphoteric and nonionic. Nonionic fluorocarbon surfactants will not ionize in aqueous solution and are insensitive to the acidity and alkalinity of the solution and electrolytes. At the same time, the fluorocarbon chain is chemically stable and can be used in strong acid and alkaline environments. Nonionic fluorocarbon surfactants have better compatibility with water and organic solvents, so they are often used as dispersants and leveling agents in coatings, dyes, inks and other fields.

[0004] The most widely used nonionic fluorocarbon surfactants are perfluoroalkyls. For example, Chinese patent CN106832256 A discloses a method for preparing a fluorinated nonionic surfactant, which is prepared by reacting a perfluoroalkyl iodide with a polyoxyethylene ether containing a vinyl or propylene group. However, the nonionic fluorocarbon surfactant prepared by this method contains perfluorooctyl or perfluorohexyl, which are among the most difficult organic pollutants to degrade in the world, have high bioaccumulation and multi-organ toxicity to the human body, and have poor environmental performance; and the nonionic fluorocarbon surfactant is not reactive.

[0005] Chinese patent CN 115725065 A uses perfluoropolyether carboxylic acid as raw material. This patent avoids the use of perfluorooctanoic acid or perfluorohexanoic acid. A perfluoropolyether nonionic surfactant is obtained by esterification of perfluoropolyether carboxylic acid with polyethylene glycol raw materials. However, this nonionic fluorocarbon surfactant is also not reactive.

[0006] Chinese patents CN 116217916 A, CN 112552478 A, CN 109679483 A, CN106243337A, etc. prepare reactive perfluoropolyether functional monomers, which can be used as UV curing coating additives to make the coating surface waterproof and oil-proof, anti-fingerprint, and scratch-resistant. Although the above perfluoropolyether functional monomers are reactive, they do not have the ability to significantly reduce the surface tension of the system, are not suitable as surfactants, and have poor compatibility with the system.

[0007] It can be seen that the perfluoropolyether products in the prior art have the problems of poor environmental performance and single function. In the field of UV-curing coatings, it is urgent to develop a product that has both functional reactivity and can be firmly bonded to the surface to make it anti-fouling and wear-resistant, and can also be used as an additive to improve the leveling and dispersibility of UV coatings, so as to overcome the many deficiencies and shortcomings in the prior art. Summary of the invention

[0008] The purpose of the present invention is to provide a preparation and application of a perfluoropolyether reactive nonionic surfactant to solve the above problems. The present invention uses Y-type perfluoropolyether alcohol as a raw material (Y-type perfluoropolyether acyl fluoride produced by our company is prepared by esterification and reduction), and allyl glycidyl ether is ring-opened to prepare an intermediate, and then reacted with ethylene oxide to prepare a perfluoropolyether reactive nonionic surfactant. The perfluoropolyether reactive nonionic surfactant uses an allyl ether segment as a functional segment and a polyethylene glycol segment as a hydrophilic segment, so it has the effect of reducing surface tension and improving leveling, and can also make the coating have excellent waterproof and oil-proof properties and wear resistance after curing through reaction.

[0009] The present invention is achieved through the following technical solutions: A perfluoropolyether reactive nonionic surfactant having the structure , where Rf is a Y-type perfluoropolyether , the values ​​of x, m, and n are positive integers.

[0010] Furthermore, considering the reactivity of the perfluoropolyether reactive nonionic surfactant and the waterproof, oil-proof and wear-resistant properties of the coating after curing, the degree of polymerization x is in the range of an integer from 1 to 20, preferably an integer from 3 to 15, and more preferably an integer from 5 to 10.

[0011] Furthermore, considering the compatibility with the perfluoropolyether reactive nonionic surfactant and the surface properties and dispersibility of the coating, the value range of m is an integer of 1 to 100, preferably an integer of 5 to 50, and more preferably an integer of 10 to 20; the value range of n is an integer of 1 to 50, preferably an integer of 1 to 20, and more preferably an integer of 5 to 10; the weight average molecular weight of the Y-type perfluoropolyether is 300 to 10000 g / mol, preferably 300 to 2000 g / mol, and more preferably 500 to 1000 g / mol.

[0012] The present invention also provides a method for preparing a perfluoropolyether reactive nonionic surfactant, comprising: (1) Under nitrogen protection, perfluoropolyether alcohol and solvent 1 are added to a flask, catalyst 1 is added, and allyl glycidyl ether is slowly added dropwise. After the addition is completed, the temperature is raised to the required temperature. After a certain reaction time, the reaction is quenched, and column chromatography is performed to purify the intermediate 1; (2) The intermediate 1 is added to the reaction kettle, and the catalyst 2 is added. After heating to the required temperature, ethylene oxide gas is introduced at a certain flow rate. After the feeding is completed, the perfluoropolyether reactive nonionic surfactant is purified.

[0013] The reaction process can be expressed as follows: Among them, Rf is Y-type perfluoropolyether , the values ​​of x, m, and n are positive integers.

[0014] Furthermore, in the preparation process of the intermediate 1, the solvent 1 is a mixed solvent of a fluorinated solvent and a non-fluorinated polar aprotic solvent, and the ratio of the fluorinated solvent to the non-fluorinated polar aprotic solvent is in the range of 1:1 to 1:10, preferably 1:2 to 1:8, and more preferably 1:4 to 1:6. The fluorinated solvent is a hydrofluoroether solvent, such as one or more of HFE 7200, HFE 7300, and HFE 7500, and the non-fluorinated polar aprotic solvent is one or more of tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0015] Furthermore, in the above step (1), the catalyst 1 is a strong base, such as one or more of sodium methoxide, sodium ethoxide, and potassium tert-butoxide, and the temperature is between 60 and 120°C.

[0016] Furthermore, in the above step (2), the reaction pressure is not higher than 0.4 MPa, especially not higher than 0.3 MPa; the catalyst 2 is a weak alkaline reagent, which can be one or more of sodium carbonate, triethylamine, pyridine, DBU, DMAP, and DABCO; the temperature is 100-150° C.; the flow rate of the ethylene oxide gas is 30-100 ml / min, preferably 50-80 ml / min.

[0017] Compared with the prior art, the present invention has the following advantages and beneficial effects: 1. The present invention uses Y-type perfluoropolyether alcohol as raw material to develop a new perfluoropolyether derivative and a preparation method thereof. The prepared perfluoropolyether derivative does not contain perfluorooctyl or perfluorohexyl, has good environmental performance, and can be used as a perfluoropolyether reactive nonionic surfactant; 2. The preparation method of the perfluoropolyether reactive nonionic surfactant proposed in the present invention, the prepared perfluoropolyether reactive nonionic surfactant has good compatibility with water and conventional organic solvents, a low addition amount can significantly reduce the surface tension of the system, significantly improve the surface properties and dispersibility of the light-curing coating such as leveling, and prevent the appearance of orange peel, fish eyes and the like; 3. The perfluoropolyether reactive nonionic surfactant proposed in the present invention is reactive and can be firmly bonded to the surface of the substrate through reaction, and the coating has excellent waterproof and oil-proof properties and wear resistance after curing. When a low amount is added to the UV curing coating, the coating can have significant anti-graffiti performance; 4. The perfluoropolyether reactive nonionic surfactant proposed in the present invention has good compatibility with water and conventional organic solvents and is reactive, which solves the problem that the perfluoropolyether surfactants in the prior art have a single function and it is difficult to balance reactivity and compatibility. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical scheme and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. The illustrative embodiments of the present invention and their description are only used to explain the present invention and are not intended to limit the present invention. It should be noted that the present invention is already in the actual research and development stage.

[0019] Example 1 Under nitrogen protection, 300 g of perfluoropolyether alcohol (Mn=300 g / mol), 100 ml of HFE 7200, 900 ml of acetonitrile, and 13.6 g of sodium ethoxide were added to a 2 L strictly dried round-bottom flask, and 114 g of allyl glycidyl ether was slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred for 0.5 h, the temperature was raised to 80 °C and refluxed with stirring. After reacting for 5 h, the reaction was quenched, and the mixture was separated and purified by column chromatography to obtain 328.3 g of intermediate 1 with a yield of 79.3%.

[0020] Add 328.3 g of intermediate 1 and 16.0 g of triethylamine into a 2 L reactor, evacuate the reactor to remove air, stir and heat to 100 ° C, introduce 200 g of ethylene oxide gas at a flow rate of 50 ml / min, and maintain the reaction pressure at no more than 0.4 MPa during the feeding process. After the feeding is completed, the product is purified to obtain 487.6 g of perfluoropolyether reactive nonionic surfactant with a yield of 92.3%.

[0021] Example 2 Under nitrogen protection, 508 g of perfluoropolyether alcohol (Mn=508 g / mol), 200 ml of HFE 7200, 800 ml of acetonitrile and 13.6 g of sodium ethoxide were added to a 2 L strictly dried round-bottom flask, and 114 g of allyl glycidyl ether was slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred for 0.5 h, the temperature was raised to 80 °C and refluxed with stirring. After reacting for 5 h, the reaction was quenched, and the mixture was separated and purified by column chromatography to obtain 511.3 g of intermediate 1 with a yield of 82.2%.

[0022] Add 511.3 g of intermediate 1 and 16.6 g of triethylamine into a 2 L reactor, evacuate the reactor to remove air, heat with stirring to raise the temperature to 120°C, and introduce 350 g of ethylene oxide gas at a flow rate of 50 ml / min. During the feeding process, the reaction pressure is maintained at no more than 0.4 MPa. After the feeding is completed, the product is purified to obtain 779.6 g of a perfluoropolyether reactive nonionic surfactant with a yield of 90.5%.

[0023] Example 3 Under nitrogen protection, 1012 g of perfluoropolyether alcohol (Mn=1012 g / mol), 300 ml of HFE 7200, 700 ml of acetonitrile and 10.8 g of sodium methoxide were added to a 2 L strictly dried round-bottom flask, and 114 g of allyl glycidyl ether was slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred for 0.5 h, the temperature was raised to 80 °C and refluxed with stirring. After reacting for 5 h, the reaction was quenched, and the mixture was separated and purified by column chromatography to obtain 876.3 g of intermediate 1 with a yield of 77.8%.

[0024] 876.3 g of intermediate 1 and 15.7 g of triethylamine were added to a 2 L reactor, the reactor was evacuated to remove air, the temperature was raised to 120°C with stirring, and 440 g of ethylene oxide gas was introduced at a flow rate of 50 ml / min. The reaction pressure was maintained at no more than 0.4 MPa during the feeding process. After the feeding was completed, the product was purified to obtain 1064.4 g of a perfluoropolyether reactive nonionic surfactant with a yield of 80.8%.

[0025] Example 4 Under nitrogen protection, 1955 g of perfluoropolyether alcohol (Mn=1955 g / mol), 500 ml of HFE 7300, 500 ml of ethylene glycol dimethyl ether, and 19.2 g of sodium tert-butoxide were added to a 5 L strictly dried round-bottom flask, and 114 g of allyl glycidyl ether was slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred for 0.5 h, the temperature was raised to 100 °C and refluxed with stirring. After reacting for 5 h, the reaction was quenched, and the mixture was separated and purified by column chromatography to obtain 1674.9 g of intermediate 1 with a yield of 81.0%.

[0026] 1674.9 g of intermediate 1 and 16.3 g of triethylamine were added to a 2L reactor, the reactor was evacuated to remove air, the temperature was raised to 120°C with stirring, and 880 g of ethylene oxide gas was introduced at a flow rate of 50 ml / min. The reaction pressure was maintained at no more than 0.4 MPa during the feeding process. After the feeding was completed, the product was purified to obtain 2136.1 g of a perfluoropolyether reactive nonionic surfactant with a yield of 83.6%.

[0027] Comparative Example 1 (Intermediate 1 in Example 3) Under nitrogen protection, 1012 g of perfluoropolyether alcohol (Mn=1012 g / mol), 300 ml of HFE 7200, 700 ml of acetonitrile and 10.8 g of sodium methoxide were added to a 2 L strictly dried round-bottom flask, and 114 g of allyl glycidyl ether was slowly added dropwise at room temperature. After the addition was completed, the mixture was stirred for 0.5 h, the temperature was raised to 80 °C and refluxed with stirring. After reacting for 5 h, the reaction was quenched, and the mixture was separated and purified by column chromatography to obtain 876.3 g of intermediate 1 with a yield of 77.8%.

[0028] Comparative Example 2 1012 g of perfluoropolyether alcohol (Mn=1012 g / mol) and 20.2 g of triethylamine were added into a 2L reactor, the reactor was evacuated to remove air, the temperature was raised to 120°C with stirring, and 440 g of ethylene oxide gas was introduced at a flow rate of 50 ml / min. The reaction pressure was maintained at no more than 0.4 MPa during the feeding process. After the feeding was completed, the product was purified to obtain 1241.9 g of perfluoropolyether reactive nonionic surfactant with a yield of 85.5%.

[0029] Test Example 1 Table 1 Surfactant performance test As can be seen from Table 1, compared with Comparative Example 1, Examples 1-4 have better solubility in water and lower surface tension, indicating that the perfluoropolyether reactive nonionic surfactant of the present invention successfully introduces ethylene oxide hydrophilic segments, increases solubility and dispersibility, and reduces surface tension.

[0030] Test Example 2 The perfluoropolyether reactive nonionic surfactant of the present invention is used as a UV curing additive: Add 0.5% to 1% concentration of the product prepared in each embodiment to the UV coating, mix well and then spin coat the coating: the rotation speed of the first coating stage is 500 rpm, and the coating is applied for 10 seconds; then the second coating stage is carried out, and the rotation speed of the second coating stage is 3000 rpm, and the coating is applied for 20 seconds.

[0031] After coating, a metal halide UV lamp was used to cure the coating in a nitrogen environment. The output power of the lamp was 80W / cm 2 , cumulative brightness 1600mj / cm 2 .

[0032] Table 2 Comparison of UV-curing coating properties As can be seen from Table 2, compared with Comparative Example 2, the UV-cured coating of the coating prepared by using the perfluoropolyether reactive nonionic surfactant in Examples 1-4 as a UV curing additive has good water-proof and oil-proof properties and wear resistance. It is confirmed that the perfluoropolyether reactive nonionic surfactant described in the present application successfully introduces the allyl ether segment, increases the reactivity, and improves the water-proof and oil-proof properties and wear resistance of the UV-cured coating.

[0033] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is 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 in the scope of protection of the present invention.

Claims

1. A perfluoropolyether reactive nonionic surfactant, characterized in that: The structure of the perfluoropolyether reactive nonionic surfactant is , where Rf is a Y-type perfluoropolyether ; The weight average molecular weight of the Y-type perfluoropolyether is 300-2000 g / mol, and the value range of x is an integer of 1-20.

2. The perfluoropolyether reactive nonionic surfactant according to claim 1, characterized in that The value range of x is an integer from 5 to 10.

3. A method for preparing a perfluoropolyether reactive nonionic surfactant as claimed in any one of claims 1 to 2, characterized in that: The steps include: (1) Under nitrogen protection, perfluoropolyether alcohol and solvent 1 are added to a flask, catalyst 1 is added, and allyl glycidyl ether is slowly added dropwise. After the addition is completed, the temperature is raised to the required temperature. After a certain reaction time, the reaction is quenched, and column chromatography is performed to purify the intermediate 1; (2) The intermediate 1 is added to the reaction kettle, and the catalyst 2 is added. After heating to the required temperature, ethylene oxide gas is introduced at a certain flow rate. After the feeding is completed, the perfluoropolyether reactive nonionic surfactant is purified.

4. The method for preparing the perfluoropolyether reactive nonionic surfactant according to claim 3, characterized in that: The solvent 1 is a mixed solvent of a fluorinated solvent and a non-fluorinated polar aprotic solvent, and the ratio of the fluorinated solvent to the non-fluorinated polar aprotic solvent in the mixed solvent is 1:1 to 1:

10.

5. The method for preparing the perfluoropolyether reactive nonionic surfactant according to claim 4, characterized in that: The fluorine-containing solvent is a hydrofluoroether solvent selected from one or more of HFE 7200, HFE 7300, and HFE 7500, and the non-fluorine polar aprotic solvent is selected from one or more of tetrahydrofuran, ethylene glycol dimethyl ether, and acetonitrile.

6. The method for preparing the perfluoropolyether reactive nonionic surfactant according to claim 3, characterized in that: The catalyst 1 is selected from one or more of sodium methoxide, sodium ethoxide and potassium tert-butoxide.

7. The method for preparing the perfluoropolyether reactive nonionic surfactant according to claim 3, characterized in that: The reaction temperature in step (1) is 60-120°C.

8. The method for preparing the perfluoropolyether reactive nonionic surfactant according to claim 3, characterized in that: In the step (2), the reaction pressure is not higher than 0.4 MPa, and the flow rate of the ethylene oxide gas is 30-100 ml / min.

9. The method for preparing the perfluoropolyether reactive nonionic surfactant according to claim 3, characterized in that: The catalyst 2 is selected from one or more of sodium carbonate, triethylamine and pyridine.

10. Use of the preparation method of the perfluoropolyether reactive nonionic surfactant according to any one of claims 3 to 9 in UV curing coatings.

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