Hyperbranched fluorocarbon surfactant and method for preparing the same

Abstract

The application discloses a hyperbranched fluorocarbon surfactant and a preparation method thereof. The fluorocarbon surfactant is prepared by using an iodine-substituted alkane as a substrate and through addition, ring opening, quaternary ammonium, Grignard reaction, borohydride oxidation and other steps. The fluorocarbon surfactant has both hydrophilic groups and hydrophobic groups. The fluorocarbon surfactant with the structure has excellent surface performance. When the fluorocarbon surfactant is compounded with other materials into a foam fire extinguishing agent, the fluorocarbon surfactant can effectively isolate the combustion from air, and plays a role of rapid fire extinguishing.

Description

Technical Field

[0001] This invention relates to a hyperbranched fluorocarbon surfactant and its preparation method, belonging to the field of surfactant technology. Background Technology

[0002] With the continuous development of science and technology and various irregular human behaviors, fires are occurring frequently, seriously threatening people's lives and property. Therefore, the development of highly efficient fire extinguishing agents is particularly important. As research into fire extinguishing methods progresses, attention has gradually shifted to special surfactants, namely fluorocarbon surfactants. Fluorocarbon surfactants are surfactants with outstanding performance; their unique "high hydrophobicity, high hydrophilicity, and high hydration" properties make them widely used in fire protection and other fields. Currently, most mainstream fluorocarbon surfactants on the market are composed of eight carbon atoms, thus exhibiting strong hydrophobicity. Therefore, developing a fluorocarbon surfactant with good hydrophilic properties is a pressing issue that needs to be addressed. Summary of the Invention

[0003] To address the problems of existing fluorocarbon surfactants, this invention provides a hyperbranched fluorocarbon surfactant and its preparation method. Starting from perfluoroalkyl iodine, the synthesis of fluorinated compounds can be expanded through hyperbranching reactions using platinum-based catalysts, increasing the hydrophilicity of the product. This structured compound exhibits excellent hydrophilicity while maintaining superior surface tension and good fire extinguishing performance.

[0004] The technical solution to achieve the objective of this invention is: a hyperbranched fluorocarbon surfactant having the following structure:

[0005]

[0006] Preferably, the above-mentioned hyperbranched fluorocarbon surfactant has the following structure:

[0007]

[0008] The preparation method of the above-mentioned hyperbranched fluorocarbon surfactant includes:

[0009] (1) The step of preparing compound a by reacting iodoalkane and allyl bromide under nitrogen protection.

[0010]

[0011] (2) The step of preparing compound b by reacting compound a and trichlorosilane under nitrogen protection with a castor catalyst via hyperbranching.

[0012]

[0013] (3) The step of quaternizing compound b with the ring-opening product of allyl glycidyl ether to obtain the target product fluorocarbon surfactant c.

[0014]

[0015] Furthermore, in step (1), the reaction temperature is 80℃, the reaction time is 4h, and the molar ratio of iodoalkane to allyl bromide is 1.1:1.

[0016] Furthermore, in step (2), the reaction is carried out at room temperature for 8 hours, the amount of caster catalyst added is 3% of the mass of compound a, and the molar ratio of trichlorosilane to compound a is 1.1:1.

[0017] Furthermore, in step (3), the reaction temperature is 82℃, the reaction is kept at this temperature for 3 hours, and the molar ratio of compound b to allyl glycidyl ether is 1.1:1.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] (1) Compared with commercially available fluorocarbon surfactants, the present invention has a shorter fluorocarbon chain, thus greatly reducing the harm to the environment.

[0020] (2) While having a shorter fluorocarbon chain, its performance is far superior to that of fluorocarbon surfactants with the same chain length.

[0021] (3) Due to the introduction of a new catalyst during synthesis, the conversion rate is higher than that of traditional synthesis methods. Attached Figure Description

[0022] Figure 1 The NMR spectrum of the product in Example 1 is shown.

[0023] Figure 2 The NMR spectrum of the product in Example 2 is shown.

[0024] Figure 3 The NMR spectrum of the product in Example 3 is shown. Detailed Implementation

[0025] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0026] This invention can prepare a fluorocarbon surfactant with a hydrophilic group at one end and a hydrophobic group at the other end by means of iodoalkane addition, ring opening, quaternization reaction, borohydride oxidation, Grignard reaction and other steps. Hyperbranched fluorocarbon surfactants can be prepared by repeated hydrosilylation and Grignard reaction.

[0027] Example 1:

[0028] 1. Add 44.5 g (0.1 mol) of perfluorohexyl iodine to a 250 ml four-necked flask, purge with nitrogen gas, and slowly add 12 g (0.1 mol) of allyl bromide dropwise at 80 °C. After the addition is complete, continue stirring the reaction for 4 h.

[0029] 2. Add 500 ppm of caster catalyst and 12.3 g of trichlorosilane (0.91 mol, molar ratio 1.1:1) to the flask and stir the mixture under nitrogen atmosphere for 8 h.

[0030] 3. Add 34.2 g (0.3 mol) of allyl glycidyl ether to a 250 ml four-necked flask, heat to 80 °C under nitrogen atmosphere, add 33.3 g (0.3 mol) of sodium sarcosinate dropwise for about 0.5 h, and then continue the reaction for 3 h.

[0031] 4. The product obtained in step 3 was mixed with the product in step 2. Sodium chloroacetate dissolved in 30 ml of deionized water was directly added to the flask under nitrogen atmosphere at 82°C and the reaction was allowed to proceed for 4 hours to obtain the final product. The product was analyzed by NMR, and the results are as follows: Figure 1 As shown.

[0032]

[0033] Example 2:

[0034] 1. Add 55.3 g (0.1 mol) of 1,6-diiodododecylhexane to a 250 ml four-necked flask, purge with nitrogen gas, and slowly add 24 g (0.2 mol) of allyl bromide dropwise at 80 °C. After the addition is complete, continue stirring the reaction for 4 h.

[0035] 2. Add 1000 ppm of caster catalyst and 24.6 g of trichlorosilane (1.82 mol, molar ratio 1.1:1) to the flask and stir the mixture under nitrogen atmosphere for 8 h.

[0036] 3. Add 64.4 g (0.6 mol) of allyl glycidyl ether to a 250 ml four-necked flask, heat to 80 °C under nitrogen atmosphere, add 66.6 g (0.6 mol) of sodium sarcosinate dropwise for about 0.5 h, and then continue the reaction for 3 h.

[0037] 4. The product obtained in step 3 was mixed with the product from step 2. Sodium chloroacetate dissolved in 60 ml of deionized water was directly added to the flask under nitrogen atmosphere at 82°C and the reaction was allowed to proceed for 4 hours to obtain the final product. The product was analyzed by NMR, and the results are as follows: Figure 2 As shown.

[0038]

[0039] Example 3:

[0040] 1. Add 44.5 g (0.1 mol) of perfluorohexyl iodine to a 250 ml four-necked flask, purge with nitrogen gas, and slowly add 12 g (0.1 mol) of allyl bromide dropwise at 80 °C. After the addition is complete, continue stirring the reaction for 4 h.

[0041] 2. Add 500 ppm of caster catalyst and 12.3 g of trichlorosilane (0.91 mol, molar ratio 1.1:1) to the flask and stir the mixture under nitrogen atmosphere for 8 h.

[0042] 3. Slowly add 36g (0.3mol) of allyl bromide to the flask, and continue stirring the reaction for 4h after the addition is complete.

[0043] 4. Add 1500 ppm of caster catalyst and 36.9 g of trichlorosilane (2.73 mol, molar ratio 1.1:1) to the flask and stir the mixture under nitrogen atmosphere for 8 h.

[0044] 5. Add 102.6 g (0.9 mol) of allyl glycidyl ether to a 250 ml four-necked flask, heat to 80 °C under nitrogen atmosphere, add 99.9 g (0.9 mol) of sodium sarcosinate dropwise for about 0.5 h, and then continue the reaction for 3 h.

[0045] 5. The product obtained in step 5 was mixed with the product in step 4. Sodium chloroacetate dissolved in 90 ml of deionized water was directly added to the flask under nitrogen atmosphere at 82°C and the reaction was carried out for 4 hours to obtain the final product. The obtained product was analyzed by NMR, and the results are as follows: Figure 3 As shown.

[0046]

[0047] Comparative Example 1:

[0048] 1. Add 44.5 g (0.1 mol) of perfluorohexyl iodine to a 250 ml four-necked flask, purge with nitrogen gas, and slowly add 10.374 g (0.091 mol) of allyl glycidyl ether dropwise at 20 °C. After the addition is complete, continue stirring the reaction for 4 h.

[0049] 2. Slowly add 26.39 g (0.91 mol, molar ratio 1.1:1) of tributyltin hydrogen to the flask and stir the reaction under nitrogen atmosphere for 8 h.

[0050] 3. Heat the product from step 2 to 80°C under nitrogen atmosphere, then add 11.1g (0.1mol) of sodium sarcosinate dropwise for about 0.5h, and continue the reaction for 3h.

[0051] 4. For the reaction in step 3, add sodium chloroacetate dissolved in 30 ml of deionized water directly into the flask under a nitrogen atmosphere at 82 °C and react for 4 h.

[0052]

[0053] Comparative Example 2:

[0054] 1. Add 55.3 g (0.1 mol) of 1,6-diiodododecylhexane to a 250 ml four-necked flask, purge with nitrogen gas, and slowly add 20.7474 g (0.182 mol) of allyl glycidyl ether dropwise at 20 °C. After the addition is complete, continue stirring the reaction for 4 h.

[0055] 2. Slowly add 52.78 g (0.182 mol, molar ratio 1.1:1) of tributyltin hydrogen to the flask and stir the reaction under nitrogen atmosphere for 8 h.

[0056] 3. Heat the product from step 2 to 80°C under nitrogen atmosphere, then add 22.2g (0.2mol) of sodium sarcosinate dropwise for about 0.5h, and continue the reaction for 3h.

[0057] 4. For the reaction in step 3, sodium chloroacetate dissolved in 60 ml of deionized water was directly added to the flask under nitrogen atmosphere at 82 °C and the reaction was allowed to proceed for 4 h.

[0058]

[0059] The target product prepared in the examples has superior surface tension and foaming properties compared with the fluorocarbon surfactant with unbranched fluorocarbon chain length prepared in the comparative examples. The specific results are shown in Tables 1 to 6.

[0060] Table 1 Surface tension of the examples and comparative examples

[0061]

[0062] Table 2 Foaming ability of Example 1

[0063]

[0064] Table 3 Foaming ability of Example 2

[0065]

[0066] Table 4. Foaming ability of Example 3

[0067]

[0068]

[0069] Table 5 shows the foaming ability of Comparative Example 1.

[0070]

[0071] Table 6. Foaming ability of Comparative Example 2

[0072]

[0073] As shown in Tables 1 to 6, in aqueous solutions of different concentrations, all three products exhibit superior surface tension compared to traditional fluorocarbon surfactants, with the product possessing a hyperbranched structure showing even better performance. Furthermore, a comparison of the foaming properties of the three products and traditional fluorocarbon surfactants in different solutions reveals that the products produce richer and more stable foam, which can be maintained at a higher level for an extended period.

Claims

1. A hyperbranched fluorocarbon surfactant, characterized in that, It has the following structure: ； When n = 1, R f = -CF2-CF2-CF2-CF2-CF2-CF3; When n = 2, R f = -CF2-CF2-CF2-CF2-CF2-CF2-.

2. A method for preparing a hyperbranched fluorocarbon surfactant, characterized in that, include: (1) The step of preparing compound a by reacting iodoalkane and allyl bromide under nitrogen protection. ； When n = 1, R f = -CF2-CF2-CF2-CF2-CF2-CF3, When n = 2, R f = -CF2-CF2-CF2-CF2-CF2-CF2-; (2) The step of preparing compound b by reacting compound a and trichlorosilane under nitrogen protection with a castor catalyst through hyperbranching. ； (3) The step of quaternizing compound b with the ring-opening product of allyl glycidyl ether to obtain the target product fluorocarbon surfactant c. 。 3. The method as described in claim 2, characterized in that, In step (1), the reaction temperature is 80℃ and the reaction time is 4h.

4. The method as described in claim 2, characterized in that, The molar ratio of iodoalkane to allyl bromide is 1.1:

1.

5. The method as described in claim 2, characterized in that, In step (2), the reaction is carried out at room temperature for 8 hours.

6. The method as described in claim 2, characterized in that, The amount of cassette catalyst added is 3% of the mass of compound a, and the molar ratio of trichlorosilane to compound a is 1.1:

1.

7. The method as described in claim 2, characterized in that, In step (3), the quaternization reaction temperature is 82℃, and the reaction is maintained at this temperature for 3 hours.

8. The method as described in claim 2, characterized in that, The molar ratio of compound b to allyl glycidyl ether is 1.1:1.

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