Hyperbranched fluorocarbon surfactant and preparation method thereof

Abstract

The invention discloses a hyperbranched fluorocarbon surfactant and a preparation method thereof, and the fluorocarbon surfactant with both a hydrophilic group and a hydrophobic group is prepared and synthesized by taking iodo-alkane as a substrate through the steps of addition, ring opening, quaternization, Grignard reaction, hydroboration oxidation and the like. The fluorocarbon surfactant with the structure has excellent surface performance, and when the fluorocarbon surfactant is compounded with other materials to form a foam extinguishing agent, the contact between comburent and air can be effectively isolated, so that the effect of quickly extinguishing fire is achieved.

Description

Technical Field

[0001] The invention relates to a hyperbranched fluorocarbon surfactant and a preparation method thereof, belonging to the technical field of surfactants. Background Art

[0002] With the continuous development of science and technology and various irregular behaviors of human beings, various fires emerge in an endless stream, seriously threatening the safety of people's lives and property. Therefore, it is particularly important to develop efficient fire extinguishing agents. With the advancement of research on fire extinguishing, people gradually shifted their attention to special surfactants, that is, fluorocarbon surfactants. Fluorocarbon surfactants are a type of surfactant with outstanding performance. Their unique "three highs and two hates" characteristics make them widely used in firefighting and other fields. At present, the mainstream fluorocarbon surfactants on the market are mostly composed of 8 carbons, so most of them have strong hydrophobicity, so the preparation of a fluorocarbon surfactant with good hydrophilic properties is an urgent problem to be solved. Summary of the invention

[0003] In view of the problems existing in the existing fluorocarbon surfactants, the present invention provides a hyperbranched fluorocarbon surfactant and a preparation method thereof, starting from perfluoroalkyl iodide, the synthesis can be expanded by a hyperbranching reaction with a platinum catalyst to increase the hydrophilicity of the product. The compound of this structure has excellent hydrophilic effect, still has excellent surface tension, and good fire extinguishing performance.

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

[0005]

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

[0007]

[0008] The preparation method of the hyperbranched fluorocarbon surfactant comprises:

[0009] (1) a step of preparing compound a by subjecting iodoalkyl and allyl bromide to an addition reaction under nitrogen protection,

[0010]

[0011] (2) Under nitrogen protection, compound a and trichlorosilane are subjected to a hyperbranching reaction in the presence of a Custer catalyst to prepare compound b,

[0012]

[0013] (3) a step of subjecting compound b to a quaternary amination reaction with the ring-opening product of allyl glycidyl ether to obtain a target product, a fluorocarbon surfactant c,

[0014]

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

[0016] Furthermore, in step (2), the reaction is carried out at room temperature, the reaction time is 8 hours, the amount of Custer 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° C., the reaction is kept warm 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 fluorocarbon surfactants on the market, 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) Since a new catalyst is introduced during the synthesis, the conversion rate is higher than that of the traditional synthesis method. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0024] Figure 3 It is the NMR spectrum of the product in Example 3. DETAILED DESCRIPTION

[0025] The present invention is further described below in conjunction with the accompanying drawings and embodiments.

[0026] The present invention can prepare a fluorocarbon surfactant containing a hydrophilic group at one end and a hydrophobic group at the other end by performing addition, ring opening, quaternization reaction, hydroboration oxidation, Grignard reaction and other steps on iodoalkyl, and can prepare a fluorocarbon surfactant with a hyperbranched structure by repeating hydrosilylation and Grignard reaction.

[0027] Embodiment 1:

[0028] 1. Add 44.5 g (0.1 mol) of perfluorohexyl iodide to a 250 ml four-necked flask, introduce nitrogen, and slowly drop 12 g (0.1 mol) of allyl bromide at 80 °C. After the addition is complete, continue stirring and react for 4 hours.

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

[0030] 3. Add 34.2 g (0.3 mol) of allyl glycidyl ether into a 250 ml four-necked flask, heat to 80°C under a nitrogen environment, 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 from step 3 was mixed with the product from step 2, and sodium chloroacetate dissolved in 30 ml of deionized water was directly added to the flask under a nitrogen environment at 82°C and reacted for 4 hours to obtain the final product. The obtained product was tested by nuclear magnetic resonance, and the results were as follows: Figure 1 shown.

[0032]

[0033] Embodiment 2:

[0034] 1. Add 55.3 g (0.1 mol) of 1.6 diiododecylfluorohexane into a 250 ml four-necked flask, introduce nitrogen, and slowly drop 24 g (0.2 mol) of allyl bromide at 80°C. After the dropwise addition is completed, continue to stir and react for 4 hours.

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

[0036] 3. Add 64.4 g (0.6 mol) of allyl glycidyl ether into a 250 ml four-necked flask, heat to 80°C under a nitrogen environment, 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 from step 3 was mixed with the product from step 2, and sodium chloroacetate dissolved in 60 ml of deionized water was directly added to the flask under a nitrogen environment at 82°C and reacted for 4 hours to obtain the final product. The obtained product was tested by nuclear magnetic resonance, and the results were as follows: Figure 2 shown.

[0038]

[0039] Embodiment 3:

[0040] 1. Add 44.5 g (0.1 mol) of perfluorohexyl iodide to a 250 ml four-necked flask, introduce nitrogen, and slowly drop 12 g (0.1 mol) of allyl bromide at 80 °C. After the addition is complete, continue stirring and react for 4 hours.

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

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

[0043] 4. Add 1500 ppm of Custer catalyst and 36.9 g of trichlorosilane (2.73 mol, molar ratio 1.1:1) into the flask, and stir the reaction under nitrogen environment for 8 hours.

[0044] 5. Add 102.6 g (0.9 mol) of allyl glycidyl ether into a 250 ml four-necked flask, heat to 80°C under a nitrogen environment, 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 from step 5 was mixed with the product from step 4, and sodium chloroacetate dissolved in 90 ml of deionized water was directly added to the flask under a nitrogen environment at 82°C and reacted for 4 hours to obtain the final product. The obtained product was tested by nuclear magnetic resonance, and the results were as follows: Figure 3 shown.

[0046]

[0047] Comparative Example 1:

[0048] 1. Add 44.5 g (0.1 mol) of perfluorohexyl iodide into a 250 ml four-necked flask, introduce nitrogen, and slowly drop 10.374 g (0.091 mol) of allyl glycidyl ether at 20°C. After the addition is complete, continue to stir and react for 4 hours.

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

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

[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 diiododecylfluorohexane into a 250 ml four-necked flask, introduce nitrogen, and slowly drop 20.7474 g (0.182 mol) of allyl glycidyl ether at 20°C. After the addition is complete, continue stirring and reacting for 4 hours.

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

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

[0057] 4. For the reaction in step 3, add sodium chloroacetate dissolved in 60 ml of deionized water directly into the flask under a nitrogen atmosphere at 82°C and react for 4 h.

[0058]

[0059] The target product prepared in the example has better surface tension and foaming performance than the fluorocarbon surfactant whose fluorocarbon chain length is not hyperbranched and prepared in the comparative example. The specific results are shown in Tables 1 to 6.

[0060] Table 1 Surface tension of 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 Foaming ability of comparative example 1

[0070]

[0071] Table 6 Foaming ability of comparative example 2

[0072]

[0073] From Table 1 to Table 6, it can be seen that in aqueous solutions of different concentrations, the three products have better surface tension than traditional fluorocarbon surfactants, and the products with hyperbranched structures have better effects. At the same time, by comparing the foaming properties of the three products and traditional fluorocarbon surfactants in different solutions, it can be found that the products have richer foam and more stable foam, which can be maintained at a high level for a long time.

Claims

1. A hyperbranched fluorocarbon surfactant, characterized in that It has the following structure:

2. A hyperbranched fluorocarbon surfactant, characterized in that It has the following structure:

3. A method for preparing a hyperbranched fluorocarbon surfactant, characterized in that: include: (1) a step of preparing compound a by subjecting iodoalkyl and allyl bromide to an addition reaction under nitrogen protection, (2) Under nitrogen protection, compound a and trichlorosilane are subjected to a hyperbranching reaction in the presence of a Custer catalyst to prepare compound b, (3) a step of subjecting compound b to a quaternary amination reaction with the ring-opening product of allyl glycidyl ether to obtain a target product, a fluorocarbon surfactant c, 4. The method according to claim 3, characterized in that In step (1), the reaction temperature is 80° C. and the reaction time is 4 h.

5. The method according to claim 3, characterized in that The molar ratio of iodoalkyl to allyl bromide is 1.1:

1.

6. The method according to claim 3, characterized in that In step (2), the reaction is carried out at room temperature for 8 hours.

7. The method according to claim 3, characterized in that The amount of the Custer catalyst added was 3% of the mass of compound a, and the molar ratio of trichlorosilane to compound a was 1.1:

1.

8. The method according to claim 3, characterized in that In step (3), the quaternization reaction temperature is 82° C. and the reaction is kept warm for 3 hours.

9. The method according to claim 3, characterized in that The molar ratio of compound b to allyl glycidyl ether is 1.1:1.

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