Fluorine-free anti-dissolution foam extinguishing agent and preparation method thereof

Abstract

The invention belongs to the technical field of fire extinguishing agents, and particularly relates to a fluoride-free anti-dissolution foam fire extinguishing agent and a preparation method thereof. The invention aims to solve the problem that an existing fluoride-free foam extinguishing agent is poor in polar organic matter fire extinguishing effect. The preparation method comprises the following steps: mixing lauryl alcohol polyoxyethylene ether and polyethylene glycol to prepare a main surfactant, and mixing the main surfactant with an auxiliary surfactant consisting of an addition copolymer of isooctanol and nonyl phenol to obtain a compound surfactant; the fluorine-free film-forming polymer is prepared from a hydrophilic monomer, a hydrophobic monomer and a functional monomer through random copolymerization; the compound surfactant, the fluoride-free film-forming polymer, the solvent and the film-forming agent are mixed and then subjected to defoaming post-treatment to obtain the fluoride-free solubility-resistant foam extinguishing agent. The fire extinguishing agent product prepared by the invention has good solvent resistance on the basis of not containing fluorine element, and has a good effect on the occasion of extinguishing polar organic matter fire disasters.

Description

Technical Field

[0001] The present invention belongs to the technical field of fire extinguishing agents, and particularly relates to a fluorine-free alcohol-resistant foam fire extinguishing agent and a preparation method thereof. Background Art

[0002] In the technical field of fire extinguishing agents, aqueous film-forming foam fire extinguishing agents have attracted much attention because they can quickly suppress fires caused by flammable liquids and other substances. Traditional aqueous film-forming foam fire extinguishing agents rely on perfluoro and polyfluoroalkyl substances to maintain their excellent performance and ensure their ability to form a water film on the surface of combustibles, thereby achieving rapid and efficient fire extinguishing. Although fluorine-containing foam fire extinguishing agents are efficient and fast, with excellent spreading and flame retardancy, the fluorine-containing components therein are prone to cause environmental pollution and increase the health risks of operators.

[0003] In order to address the limitations and environmental problems brought by traditional fluorine-containing foam fire extinguishing agents, fluorine-free foam fire extinguishing agents have made certain developments in recent years. Compared with traditional fluorine-containing foam fire extinguishing agents, fluorine-free foam fire extinguishing agents use new types of surfactants and halogen-free additives, significantly reducing the risk of environmental pollution. Although fluorine-free foam fire extinguishing agents have significant advantages in terms of environmental protection, there are still some key problems in their performance. In extinguishing hydrocarbon organic fires, the film-forming speed of fluorine-free foam fire extinguishing agents is relatively slow, making it difficult to quickly control the fire; in extinguishing polar organic fires, the foam and protective film generated by fluorine-free foam fire extinguishing agents are easily dissolved quickly, resulting in a deteriorated fire extinguishing effect.

[0004] Currently, the poor effect of existing fluorine-free foam fire extinguishing agents in extinguishing polar organic fires remains an important problem faced by the industry.

[0005] Therefore, a fluorine-free alcohol-resistant foam fire extinguishing agent and a preparation method thereof are proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a fluorine-free alcohol-resistant foam fire extinguishing agent and a preparation method thereof. The present invention prepares a main surfactant by mixing lauryl alcohol polyoxyethylene ether and polyethylene glycol, and mixes it with an auxiliary surfactant composed of an addition copolymer of isooctanol and nonylphenol to obtain a compound surfactant; a fluorine-free film-forming polymer is prepared by random copolymerization of a hydrophilic monomer, a hydrophobic monomer and a functional monomer; the compound surfactant, the fluorine-free film-forming polymer, a solvent and a film-forming agent are mixed and then subjected to defoaming post-treatment to obtain a fluorine-free alcohol-resistant foam fire extinguishing agent.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] A fluorine-free alcohol-resistant foam fire extinguishing agent and a preparation method thereof, comprising the following steps:

[0009] Unless otherwise specified, the parts in the present invention refer to parts by mass, and the average molecular weight refers to the number-average molecular weight.

[0010] Mix lauryl alcohol polyoxyethylene ether and polyethylene glycol to obtain the main surfactant.

[0011] Among them, the added mass ratio of lauryl alcohol polyoxyethylene ether to polyethylene glycol is 20:1 - 2.7; the average molecular weight of lauryl alcohol polyoxyethylene ether is 2000; the average molecular weight of polyethylene glycol is 500.

[0012] Mix isooctanol and nonylphenol, and carry out addition copolymerization under the action of ethylene oxide to obtain the auxiliary surfactant.

[0013] Among them, the auxiliary surfactant is a mixture of the ring-opening addition copolymer of isooctanol and ethylene oxide and the ring-opening addition copolymer of nonylphenol and ethylene oxide. There is no covalent bond connection between the copolymerization product of isooctanol and the copolymerization product of nonylphenol. In fact, the auxiliary surfactant is a mixture of isooctyl alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether.

[0014] Among them, the added mass ratio of isooctanol to nonylphenol is 2:1.1 - 1.4.

[0015] Copolymerize hydrophilic monomers, hydrophobic monomers and functional monomers randomly to obtain a fluorine-free film-forming polymer.

[0016] Among them, the hydrophilic monomer is N-methylacrylamide; the hydrophobic monomers include ethyl methacrylate and butyl acrylate; the functional monomers include divinylbenzene and 2-acrylamido-2-methylpropanesulfonic acid.

[0017] Among them, in the hydrophobic monomers, the added mass ratio of ethyl methacrylate to butyl acrylate is 23:14; in the functional monomers, the added mass ratio of divinylbenzene to 2-acrylamido-2-methylpropanesulfonic acid is 1:2.2.

[0018] Mix 150 parts of the main surfactant and 36.5 parts of the auxiliary surfactant, add 1.1 parts of the stabilizer and 3 parts of the co-solvent to obtain the compound surfactant.

[0019] Among them, the stabilizer includes polyvinyl alcohol and sodium sulfate; the co-solvent is diethylene glycol butyl ether; the added mass ratio of polyvinyl alcohol to sodium sulfate is 3:1; the average molecular weight of polyvinyl alcohol is 25000.

[0020] Add 50 parts of the compound surfactant to 100 parts of the fluorine-free film-forming polymer, add 100 parts of the solvent and 1.5 parts of the film-forming agent, and then disperse and mix to obtain the fire extinguishing agent precursor.

[0021] Among them, the solvent includes deionized water, glycerol and ethylene glycol, and the mass ratio of deionized water, glycerol and ethylene glycol added is 20:6.4:2.6; the film-forming agent is polyvinylpyrrolidone, and its average molecular weight is 8500.

[0022] The fire extinguishing agent precursor is subjected to defoaming post-treatment to obtain a fluorine-free alcohol-resistant foam fire extinguishing agent.

[0023] Preferably, the addition copolymerization process is as follows: isooctanol and nonylphenol are dissolved in an isopropyl alcohol solution of potassium hydroxide with a mass concentration of 0.5-1 wt%, and after removing water and oxygen, it is heated to 150-170 °C under nitrogen protection, and ethylene oxide gas is introduced. The operating pressure is 0.2 MPa. After the reaction is completed, the ethylene oxide and isopropyl alcohol are removed by vacuum distillation, and the auxiliary surfactant is obtained after extraction and purification.

[0024] Preferably, the random copolymerization process is as follows: 120 parts of hydrophilic monomers and 108-135 parts of hydrophobic monomers are dispersed in water, heated to 60-80 °C, the reaction pH value is adjusted to 4-6, and 1-3 parts of potassium persulfate are added after starting stirring, and then 18-33 parts of functional monomers are added. After the reaction is completed, a fluorine-free film-forming polymer is obtained.

[0025] Preferably, the defoaming post-treatment process is as follows: the fire extinguishing agent precursor is treated at an operating pressure of 0.1 atm with an oscillation frequency of 2-5 Hz and a temperature of 40-55 °C for 24 hours, and then the pH value is adjusted to 6-7 to obtain a fluorine-free alcohol-resistant foam fire extinguishing agent.

[0026] A fluorine-free alcohol-resistant foam fire extinguishing agent includes a main surfactant, an auxiliary surfactant, a fluorine-free film-forming polymer, a stabilizer, a co-solvent, a solvent and a film-forming agent; this fluorine-free alcohol-resistant foam fire extinguishing agent can effectively extinguish polar organic substance fires. Under the fluorine-free formulation, the generated flame-retardant foam still has excellent alcohol resistance.

[0027] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0028] 1. Through the specific components and proportions of the compounded main surfactant and auxiliary surfactant, combined with the fluorine-free film-forming polymer, the fire extinguishing ability and the ability to resist polar solvents of the fire extinguishing agent product are synergistically improved. The selection and proportion of the main surfactant and the auxiliary surfactant are optimized, which can effectively reduce the surface tension of water, is beneficial to the rapid formation and diffusion of foam, and thus quickly covers the fire source; the fluorine-free film-forming polymer can form a protective film between the foam and the polar solvent, preventing the polar solvent from destroying the foam structure and endowing the foam with excellent alcohol resistance.

[0029] 2. By means of a random copolymerization process, a hydrophilic monomer, a hydrophobic monomer, and a functional monomer are copolymerized into a polymer. Combining the components and addition ratios of the three monomers, the water solubility and film-forming property of the fluorine-free film-forming polymer are precisely adjusted. The three monomers act synergistically through the random copolymerization process, balancing the hydrophilicity-hydrophobicity and stability, and comprehensively improving the performance of the fire extinguishing agent product.

[0030] 3. Isooctanol, nonylphenol, and ethylene oxide are subjected to addition copolymerization through an addition copolymerization process to obtain an auxiliary surfactant with good wettability and stability. In the subsequent mixing process, it acts together with the film-forming agent to improve the foaming and film-forming effects of the fire extinguishing agent product. While improving the seawater resistance of the fire extinguishing agent product, it ensures that the fire extinguishing agent product has excellent performance in the occasion of extinguishing polar solvent fires.

[0031] 4. Through the defoaming post-treatment process and the combined formula of the auxiliary surfactant containing nonylphenol, the stabilizer containing polyvinyl alcohol and sodium sulfate, the foam stability of the fire extinguishing agent product is jointly ensured, the compatibility of each component is synergistically improved, and the film-forming performance of the foam is assisted to improve, thereby comprehensively enhancing the overall fire extinguishing effect of the fire extinguishing agent product. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 It is a process flow chart of the preparation of the fluorine-free alcohol-resistant foam fire extinguishing agent in the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] Next, the technical solutions of the present invention will be clearly and completely described through some examples and experimental examples. Obviously, the described examples are only a part of the examples of the present invention, rather than all the examples. Based on the examples in the present invention, all other examples obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0034] Referring to Figure 1 the process flow chart shown, the present invention provides a fluorine-free alcohol-resistant foam fire extinguishing agent and its preparation method. The technical solutions are as follows:

[0035] Example 1

[0036] Lauryl alcohol polyoxyethylene ether and polyethylene glycol are mixed to obtain the main surfactant.

[0037] Among them, the added mass ratio of lauryl alcohol polyoxyethylene ether and polyethylene glycol is 20:1.

[0038] The average molecular weight of lauryl alcohol polyoxyethylene ether is 2000; the average molecular weight of polyethylene glycol is 500.

[0039] Dissolve isooctanol and nonylphenol in an isopropanol solution of potassium hydroxide with a mass concentration of 0.5 wt%. After removing water and oxygen, heat to 150 °C under nitrogen protection, introduce ethylene oxide gas, with an operating pressure of 0.2 MPa. After the reaction is completed, distill off the ethylene oxide and isopropanol under reduced pressure, and obtain the auxiliary surfactant after extraction and purification.

[0040] Among them, the mass ratio of the added isooctanol to nonylphenol is 2:1.1.

[0041] Disperse 120 parts of hydrophilic monomers and 108 parts of hydrophobic monomers in water, heat to 60 °C, adjust the reaction pH value to 4, add 1 part of potassium persulfate after starting stirring, and then add 18 parts of functional monomers. After the reaction is completed, obtain the fluorine-free film-forming polymer.

[0042] Among them, the hydrophilic monomer is N-methylacrylamide; the hydrophobic monomers include ethyl methacrylate and butyl acrylate; the functional monomers include divinylbenzene and 2-acrylamido-2-methylpropanesulfonic acid.

[0043] Among them, in the hydrophobic monomers, the mass ratio of the added ethyl methacrylate to butyl acrylate is 23:14; in the functional monomers, the mass ratio of the added divinylbenzene to 2-acrylamido-2-methylpropanesulfonic acid is 1:2.2.

[0044] Mix 150 parts of the main surfactant and 36.5 parts of the auxiliary surfactant, add 1.1 parts of the stabilizer and 3 parts of the cosolvent to obtain the compound surfactant.

[0045] Among them, the stabilizer includes polyvinyl alcohol and sodium sulfate; the cosolvent is diethylene glycol butyl ether; the mass ratio of the added polyvinyl alcohol to sodium sulfate is 3:1.

[0046] The average molecular weight of polyvinyl alcohol is 25000.

[0047] Add 50 parts of the compound surfactant to 100 parts of the fluorine-free film-forming polymer, add 100 parts of the solvent and 1.5 parts of the film-forming agent, and then disperse and mix to obtain the fire extinguishing agent precursor.

[0048] Among them, the solvent includes deionized water, glycerol and ethylene glycol, and the mass ratio of the added deionized water, glycerol and ethylene glycol is 20:6.4:2.6; the film-forming agent is polyvinylpyrrolidone, and its average molecular weight is 8500.

[0049] Treat the fire extinguishing agent precursor at an operating pressure of 0.1 atm with an oscillation frequency of 2 Hz and a temperature of 40 °C for 24 hours, and then adjust the pH value to 6 to obtain the fluorine-free alcohol-resistant foam fire extinguishing agent.

[0050] Example 2-20 has different operating parameters from Example 1, and the changes in specific parameters are summarized in Table 1 and Table 2.

[0051] Table 1 Variation of operating parameters in Examples 1 - 20 (Part 1)

[0052]

[0053]

[0054] Table 2 Variation of operating parameters in Examples 1 - 20 (Part 2)

[0055]

[0056]

[0057] Comparative Example 1

[0058] Differing from Example 1, no co - surfactant was added, and other process parameters were the same.

[0059] Comparative Example 2

[0060] Differing from Example 1, the added mass ratio of lauryl alcohol polyoxyethylene ether and polyethylene glycol was changed to 20:5, and other process parameters were the same.

[0061] Comparative Example 3

[0062] Differing from Example 1, the addition amount of the hydrophobic monomer was changed to 60 parts, and other process parameters were the same.

[0063] Comparative Example 4

[0064] Differing from Example 6, butyl acrylate was not added, and other process parameters were the same.

[0065] Comparative Example 5

[0066] Differing from Example 6, during the random copolymerization process, the hydrophilic monomer, hydrophobic monomer, and functional monomer were added simultaneously, and other process parameters were the same.

[0067] Comparative Example 6

[0068] Differing from Example 6, 2 - acrylamido - 2 - methylpropanesulfonic acid was not added, and other process parameters were the same.

[0069] Comparative Example 7

[0070] Differing from Example 11, during the addition copolymerization process, the reaction temperature was changed to 120 °C, and other process parameters were the same.

[0071] Comparative Example 8

[0072] Differing from Example 11, isooctanol was not added, and other process parameters were the same.

[0073] Comparative Example 9

[0074] Different from Example 16, nonylphenol is not added, and other process parameters are the same.

[0075] Comparative Example 10

[0076] Different from Example 16, the stabilizer is not added, and other process parameters are the same.

[0077] Comparative Example 11

[0078] Different from Example 16, during the post-treatment of defoaming, the treatment temperature is changed to 25°C, and other process parameters are the same.

[0079] Experimental Example 1

[0080] The fire extinguishing agents prepared in Examples 1-5 and Comparative Examples 1-3 are used to extinguish the fire of organic solvents, and their fire extinguishing time and anti-burning time are tested. The test method refers to the low-concentration foam liquid part in the GB 15308-2006 standard, and the strong release method is adopted. The obtained data are summarized in Table 3.

[0081] Among them, the shorter the fire extinguishing time and the longer the anti-burning time, the better the comprehensive performance of the fire extinguishing agent product.

[0082] The organic solvent is a ternary mixture of ethanol, ethyl acetate and ether, and the mass ratio of the three is 1:1:1.

[0083] Table 3 Fire extinguishing time and anti-burning time of the fire extinguishing agent products prepared in Examples 1-5 and Comparative Examples 1-3

[0084] Fire extinguishing time (s) Fire resistance time (s) Example 1 122 752 Example 2 136 773 Example 3 127 805 Example 4 131 779 Example 5 139 792 Comparative Example 1 174 775 Comparative Example 2 146 683 Comparative Example 3 153 707

[0085] As shown in the data in Table 3, the fire extinguishing time and anti-burning time of Examples 1-5 are significantly better than those of Comparative Example 1, Comparative Example 2 and Comparative Example 3. This shows that the fire extinguishing agent products prepared in Examples 1-5 have obvious advantages in fire extinguishing ability and anti-polar solvent ability.

[0086] In Comparative Example 1, the auxiliary surfactant is not added, resulting in poor fire extinguishing time and anti-burning time, indicating that the auxiliary surfactant plays an important role in improving the comprehensive performance of the fire extinguishing agent product; in Comparative Example 2, the mass ratio of lauryl alcohol polyoxyethylene ether and polyethylene glycol in the main surfactant is changed to 20:5, resulting in a significant decrease in the anti-burning time, indicating that a specific ratio of the main surfactant is the key to ensuring the anti-polar solvent ability of the fire extinguishing agent product; in Comparative Example 3, the addition amount of the hydrophobic monomer is reduced, resulting in a decrease in both the fire extinguishing time and the anti-burning time, indicating that the addition amount of the hydrophobic monomer has a significant impact on improving the fire extinguishing ability and anti-polar solvent ability of the fire extinguishing agent product.

[0087] In summary, the present invention realizes the synergistic improvement of the fire extinguishing ability and the ability to resist polar solvents through the specific components and proportions of the compounded main surfactant and auxiliary surfactant, in combination with a fluorine-free film-forming polymer. The selection and proportion optimization of the main surfactant and auxiliary surfactant effectively reduce the surface tension of water, which is conducive to the rapid formation and diffusion of foam, thus quickly covering the fire source; the fluorine-free film-forming polymer can form a protective film between the foam and polar solvents, preventing the polar solvents from destroying the foam structure and endowing the foam with excellent alcohol resistance.

[0088] Experimental Example 2

[0089] Referring to Experimental Example 1, the fire extinguishing agents prepared in Examples 6-10 and Comparative Examples 4-6 were used to extinguish organic solvent fires, and their fire extinguishing times and afterburn times were tested. The obtained data are summarized in Table 4.

[0090] Table 4 Fire extinguishing times and afterburn times of the fire extinguishing agents prepared in Examples 6-10 and Comparative Examples 4-6

[0091] Fire extinguishing time (s) Fire resistance time (s) Example 6 126 765 Example 7 133 780 Example 8 124 815 Example 9 135 790 Example 10 129 760 Comparative Example 4 126 732 Comparative Example 5 160 682 Comparative Example 6 177 651

[0092] As shown in Table 4, the fire extinguishing time of Example 6 was 126 s and the afterburn time was 765 s. Its fire extinguishing performance was better than that of Comparative Example 5 and Comparative Example 6, and was basically the same as that of Comparative Example 4. The data differences between Examples 7-10 and Example 6 were small, indicating that appropriate adjustment of process parameters had little impact on the performance of the fire extinguishing agent product.

[0093] Compared with Example 6, Comparative Example 4 did not add butyl acrylate. Its fire extinguishing time and afterburn time were close to those of Example 6, indicating that under the experimental conditions, whether to add butyl acrylate had no obvious impact on the fire extinguishing performance of the fire extinguishing agent product, but its afterburn time decreased significantly; compared with Example 6, in Comparative Example 5, the hydrophilic monomer, hydrophobic monomer and functional monomer were added simultaneously during the random copolymerization process, resulting in poor fire extinguishing time and afterburn time, indicating that the specific random copolymerization process, that is, adding the hydrophilic monomer, hydrophobic monomer and functional monomer step by step, was the key to ensuring the performance of the fire extinguishing agent product; compared with Example 6, Comparative Example 6 did not add 2-acrylamido-2-methylpropanesulfonic acid, resulting in poor fire extinguishing time and afterburn time, indicating that the addition of 2-acrylamido-2-methylpropanesulfonic acid played an important role in improving the comprehensive performance of the fire extinguishing agent product.

[0094] In summary, the present invention copolymerizes hydrophilic monomers, hydrophobic monomers and functional monomers into a polymer through a random copolymerization process, and combines the components and addition proportions of the three monomers to realize the precise adjustment of the water solubility and film-forming property of the fluorine-free film-forming polymer. The three monomers act synergistically through the random copolymerization process, balance the hydrophilicity-hydrophobicity and stability, and comprehensively improve the performance of the fire extinguishing agent product.

[0095] Experimental Example 3

[0096] Referring to the test method of Reference Experimental Example 1, the fire extinguishing agents prepared in Examples 11-15 and Comparative Examples 7-8 were used to extinguish the fire of organic solvents, and their fire extinguishing time and anti-burning time were tested. The relevant data are summarized in Table 5.

[0097] In particular, in order to verify the seawater resistance performance of the fire extinguishing agent, during the strong release of the fire extinguishing agent, seawater was sprayed towards the ignition point simultaneously. The spraying volume of seawater was 30% of the fire extinguishing agent, and the salt content of seawater was 35‰.

[0098] Table 5 Fire extinguishing time and anti-burning time of the fire extinguishing agent products prepared in Examples 11-15 and Comparative Examples 7-8

[0099] Fire extinguishing time (s) Fire resistance time (s) Example 11 130 775 Example 12 123 820 Example 13 137 785 Example 14 128 758 Example 15 132 795 Comparative Example 7 145 605 Comparative Example 8 124 628

[0100] As shown in the data of Table 5, the fire extinguishing time and anti-burning time of Examples 11-15 are better than those of Comparative Example 7 and Comparative Example 8. The difference between Comparative Example 7 and Example 11 is that during the addition copolymerization process, the reaction temperature was changed to 120°C, exceeding the reasonable range of 150-170°C, resulting in a slight increase in the fire extinguishing time of the fire extinguishing agent product prepared in Example 7 and a significant decrease in the anti-burning time. The difference between Comparative Example 8 and Example 11 is that isooctanol is not added. The absence of isooctanol reduces the wettability of the auxiliary surfactant, resulting in a significant decrease in the anti-burning time of the fire extinguishing agent product.

[0101] In summary, in the present invention, isooctanol, nonylphenol and ethylene oxide are subjected to addition copolymerization through an addition copolymerization process to obtain an auxiliary surfactant with good wettability and stability. The auxiliary surfactant acts together with the film-forming agent during the subsequent mixing process, improving the foaming and film-forming effects of the fire extinguishing agent product, thereby ensuring that the fire extinguishing agent product has excellent performance in extinguishing fires of polar solvents.

[0102] Experimental Example 4

[0103] Referring to the test method of Reference Experimental Example 1, the fire extinguishing agents prepared in Examples 16-20 and Comparative Examples 9-10 were used to extinguish the fire of organic solvents, and their fire extinguishing time and anti-burning time were tested. The relevant data are summarized in Table 6.

[0104] Additionally, the foaming multiples of the fire extinguishing agent products prepared in Examples 16-20 and Comparative Examples 9-10 were tested, and the relevant data are summarized in Table 6. The higher the foaming multiple, the better the foaming property of the fire extinguishing agent and the better the comprehensive fire extinguishing performance of the fire extinguishing agent.

[0105] Table 6 Fire extinguishing time and anti-burning time of the fire extinguishing agent products prepared in Examples 16-20 and Comparative Examples 9-10

[0106] Fire extinguishing time (s) Fire resistance time (s) Foaming multiple Example 16 127 778 63 Example 17 138 798 66 Example 18 126 810 62 Example 19 131 788 65 Example 20 124 762 63 Comparative Example 9 139 708 44 Comparative Example 10 157 769 51 Comparative Example 11 132 727 58

[0107] As shown in the data of Table 6, the fire extinguishing time, anti-burning time, and foaming multiple of Examples 16-20 are generally superior to those of Comparative Examples 9, 10, and 11. The difference between Comparative Example 9 and Example 16 is that nonylphenol is not added, significantly reducing the functionality of the co-surfactant as a foam stabilizer, further prolonging the fire extinguishing time and decreasing the anti-burning time; the difference between Comparative Example 10 and Example 16 is that the stabilizer is not added, showing similar data changes to Comparative Example 9, but the prolongation of the fire extinguishing time is more severe, and the shortening of the anti-burning time is not obvious; the difference between Comparative Example 11 and Example 16 is that during the post-treatment of defoaming, the treatment temperature is changed to 25°C, reducing the foam stability and compatibility of the fire extinguishing agent product, and reducing the film-forming performance of the fire extinguishing agent product. In terms of product performance, it is manifested as a significant decrease in the anti-burning time and a certain degree of decrease in the foaming multiple.

[0108] In summary, through the post-treatment process of defoaming and the combined formulation of a co-surfactant containing nonylphenol, a stabilizer containing polyvinyl alcohol and sodium sulfate, the foam stability of the fire extinguishing agent product is jointly ensured, the compatibility of each component is synergistically improved, and the film-forming performance of the foam is assisted to improve, thereby comprehensively enhancing the overall fire extinguishing effect of the fire extinguishing agent product.

[0109] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A preparation method of a fluorine-free alcohol-resistant foam fire extinguishing agent, characterized in that: The preparation method is as follows: Mix lauryl alcohol polyoxyethylene ether and polyethylene glycol to obtain the main surfactant; Among them, the mass ratio of the added lauryl alcohol polyoxyethylene ether to the polyethylene glycol is 20:1 - 2.7; After mixing isooctanol and nonylphenol, carry out addition copolymerization under the action of ethylene oxide gas to obtain the auxiliary surfactant; Among them, the mass ratio of the added isooctanol to the nonylphenol is 2:1.1 - 1.4; Random copolymerize the hydrophilic monomer, hydrophobic monomer and functional monomer to obtain the fluorine-free film-forming polymer; After mixing the main surfactant and the auxiliary surfactant, add a stabilizer and a co-solvent to obtain the compound surfactant; Add the compound surfactant to the fluorine-free film-forming polymer, add a solvent and a film-forming agent, and then disperse and mix to obtain the fire extinguishing agent precursor; Carry out defoaming post-treatment on the fire extinguishing agent precursor to obtain the fluorine-free alcohol-resistant foam fire extinguishing agent.

2. The preparation method of a fluorine-free alcohol-resistant foam fire extinguishing agent according to claim 1, wherein: The process of the addition copolymerization is as follows: Dissolve the isooctanol and the nonylphenol in an isopropyl alcohol solution of potassium hydroxide with a mass concentration of 0.5 - 1 wt%, remove water and oxygen, then heat to 150 - 170 °C under nitrogen protection, introduce the ethylene oxide gas, the operating pressure is 0.2 MPa, after the reaction is completed, distill off the ethylene oxide gas and the isopropyl alcohol under reduced pressure, and obtain the auxiliary surfactant after extraction and purification.

3. The preparation method of a fluorine-free alcohol-resistant foam fire extinguishing agent according to claim 1, characterized in that: The hydrophilic monomer is N-methylacrylamide; the hydrophobic monomers include ethyl methacrylate and butyl acrylate; the functional monomers include divinylbenzene and 2-acrylamido-2-methylpropanesulfonic acid.

4. The preparation method of a fluorine-free alcohol-resistant foam fire extinguishing agent according to claim 1, characterized in that: The process of the random copolymerization is as follows: By mass, disperse 120 parts of the hydrophilic monomer and 108 - 135 parts of the hydrophobic monomer in water, heat to 60 - 80 °C, adjust the reaction pH value to 4 - 6, start stirring and then add 1 - 3 parts of potassium persulfate, and then add 18 - 33 parts of the functional monomer. After the reaction is completed, obtain the fluorine-free film-forming polymer.

5. The preparation method of a fluorine-free alcohol-resistant foam fire extinguishing agent according to claim 1, characterized in that: The stabilizer includes polyvinyl alcohol and sodium sulfate; the co-solvent is diethylene glycol butyl ether; the solvent includes deionized water, glycerol and ethylene glycol, and the mass ratio of the added deionized water, glycerol and ethylene glycol is 20:6.4:2.6; the film-forming agent is polyvinylpyrrolidone.

6. The preparation method of a fluorine-free alcohol-resistant foam fire extinguishing agent according to claim 1, wherein: The process of the defoaming post-treatment is as follows: Treat the fire extinguishing agent precursor at an operating pressure of 0.1 atm with an oscillation frequency of 2 - 5 Hz and a temperature of 40 - 55 °C for 24 hours, and then adjust the pH value to 6 - 7 to obtain the fluorine-free alcohol-resistant foam fire extinguishing agent.

7. A fluorine-free alcohol-resistant foam fire extinguishing agent, characterized in that: The fluorine-free alcohol-resistant foam fire extinguishing agent includes: a main surfactant, an auxiliary surfactant, a fluorine-free film-forming polymer, a stabilizer, a co-solvent, a solvent and a film-forming agent; the fluorine-free alcohol-resistant foam fire extinguishing agent is prepared by the preparation method described in any one of claims 1 - 6.

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