An ionic ammonium salt short-chain fluorocarbon surfactant and a synthesis method thereof
Through the development of ionic ammonium salt short-chain fluorocarbon surfactants and simple and efficient synthesis methods, the high toxicity and environmental pollution problems of existing fluorocarbon surfactants have been solved, and the production of non-toxic and environmentally friendly low-surf tension surfactants has been achieved, with significant economic and social benefits.
Patent Information
- Application Number
- CN202310537247.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-05-14
- Publication Date
- 2025-03-25
- Estimated Expiration
- 2043-05-14
AI Technical Summary
Existing fluorocarbon surfactants such as perfluorooctanic acid and perfluorooctanane sulfonic acid are highly toxic, environmentally durable and bioaccumulative, resulting in environmental pollution, and their synthetic conditions are complex and their product surfactivity is poor.
The ionic ammonium salt short-chain fluorocarbon surfactant and its simple and efficient synthesis method were adopted to produce intermediates through the reaction of isocyanate with raw materials such as 1H, 1H, 2H, 2H-threidine-1-n-octanol, and after multiple steps of reaction, a low-surf tension surfactant without PFOS was finally obtained.
The development of non-toxic and environmentally friendly fluorocarbon surfactants has been achieved, the synthesis process has been simplified, the production cost has been reduced, and the products are not easy to accumulate biologically, do not pollute the environment, and have significant economic and social benefits.
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Abstract
Description
Technical Field
[0001] The invention relates to polymers, in particular to an ionic ammonium salt short-chain fluorocarbon surfactant and a synthesis method thereof. Background Art
[0002] Fluorocarbon surfactant (FS) is the most active surfactant among all known surfactants. Due to its special properties ("three highs" and "two hates") that are different from general surfactants, it is used in situations where general surfactants are difficult to handle, greatly broadening the application range of surfactants. Currently, it is mostly used in detergents, fire extinguishing materials, disinfection and sterilization, demisting, agriculture, national defense and other industries. This characteristic can be specifically manifested in that the minimum surface tension (γcmc) of fluorocarbon surfactant aqueous solutions is much lower than that of hydrocarbon surfactants. In terms of the ability to reduce the surface tension of liquids, the minimum surface tension of fluorocarbon surfactant aqueous solutions can reach below 20mN / m, and can even reach about 15mN / m, while the minimum γcmc of hydrocarbon surfactants can generally only reach about 30-35mN / m. It is precisely because of the outstanding low surface tension ability of fluorocarbon surfactants that their aqueous solutions can form a water film on the oil surface at lower concentrations, isolate oxygen, and absorb heat. As a result, a highly effective fire extinguishing agent for extinguishing oil fires has been developed - aqueous film-forming foam fire extinguishing agent (AFFF). Compared with the shortcomings of traditional fire extinguishing agents with a single component and a small range of applications, AFFF has diverse components and is a complex mixture of solvents (such as ethylene glycol ethers) and surfactants (especially fluorocarbon surfactants). For Class B fires: fires caused by flammable liquids or gases (such as petroleum grease, tar and solvents), this type of fire extinguishing agent has a fire extinguishing speed four times that of ordinary fire extinguishing agents and can effectively suppress Class B fires.
[0003] Traditional fluorocarbon surfactants mainly refer to perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), but relevant studies have shown that these compounds have high toxicity, environmental persistence and bioaccumulation, and cause serious pollution to the environment. Therefore, the United Nations Environment Program (EPA) listed PFOS and PFOA as persistent organic pollutants (POPs) in the Stockholm Convention on Persistent Organic Pollutants in 2009. In order to deal with the pollution problems caused by PFOS and PFOA, people began to study environmentally friendly fluorocarbon surfactants, and found in the long-term research process that short-chain fluorocarbon chain compounds have lower toxicity and bioaccumulation than long-chain fluorocarbon chain compounds. Existing institutional researchers began to study the synthesis of short-chain fluorocarbon surfactants, but the synthesis conditions are relatively complex, requiring high temperature and high pressure and other conditions, and the surface activity of the product is poor; therefore, it is imperative to synthesize a fluorocarbon surfactant that does not contain PFOS, has low surface tension, and has good compatibility with hydrocarbon surfactants. Summary of the invention
[0004] In view of the above situation, in order to overcome the defects of the prior art, the purpose of the present invention is to provide an ionic ammonium salt short-chain fluorocarbon surfactant and a synthesis method thereof. The ionic ammonium salt short-chain fluorocarbon surfactant provided by the present invention is non-toxic and does not pollute the environment, and its synthesis method is simple and efficient, and the raw materials are abundant.
[0005] The technical solution provided by the present invention is an ionic ammonium salt short-chain fluorocarbon surfactant and a synthesis method thereof. The structural formula of the ionic ammonium salt short-chain fluorocarbon surfactant is:
[0006]
[0007] The synthesis method comprises the following steps: 1. mixing isocyanate and solvent dichloromethane to obtain a first mixed solution, adding dibutyltin dilaurate to the first mixed solution to obtain a second mixed solution, adding 1H,1H,2H,2H-tridecafluoro-1-n-octanol to the second mixed solution, and reacting at 30-40°C for 0.5-1h to obtain an intermediate 1, wherein the molar ratio of 1H,1H,2H,2H-tridecafluoro-1-n-octanol to isocyanate is 1:1;
[0008] 2. React intermediate 1 and 2-(dimethylamino)ethanol at a molar ratio of 1:1 at 35-45°C for 0.5-1h to obtain intermediate 2;
[0009] 3. The intermediate 2 with a molar ratio of 1:1 was reacted with methyl iodide at 45°C for 0.5h. The final product was washed three times with petroleum ether and dried to obtain a white powdery solid, i.e., an ionic ammonium salt short-chain fluorocarbon surfactant.
[0010] The isocyanate is isophorone diisocyanate.
[0011] The isocyanate is 4,4′-diphenylmethane diisocyanate.
[0012] The isocyanate is 4,4′-dicyclohexylmethane diisocyanate.
[0013] The isocyanate is toluene diisocyanate or hexamethylene diisocyanate.
[0014] The invention is scientific and reasonable, has abundant raw materials, is green and environmentally friendly, has no pollution, is easy to produce and prepare, and the prepared ionic ammonium salt short-chain fluorocarbon surfactant does not contain PFOS and has low surface tension. In addition, the carbamate bond in the ionic ammonium salt short-chain fluorocarbon surfactant is an easy degradation point, will not cause biological accumulation, and will not pollute the environment. The invention is an innovation in the synthesis of the ionic ammonium salt short-chain fluorocarbon surfactant, and has significant economic and social benefits.
[0015] Instruction Manual
[0016] Figure 1It is the synthesis reaction diagram of intermediate 1 of the present invention;
[0017] Figure 2 It is the synthetic reaction diagram of intermediate 2 of the present invention;
[0018] Figure 3 The synthetic reaction diagram of the ionic ammonium salt short-chain fluorocarbon surfactant of the present invention;
[0019] Figure 4 A structural diagram of isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate;
[0020] Figure 5 This is the infrared detection image of the -NCO peak during the reaction of Example 1;
[0021] Figure 6 This is an infrared detection diagram of the -NCO peak during the reaction of Example 2;
[0022] Figure 7 This is an infrared detection diagram of the -NCO peak during the reaction of Example 3;
[0023] Figure 8 This is an infrared detection image of the -NCO peak during the reaction of Example 4;
[0024] Fig. 9 This is the infrared detection diagram of the -NCO peak during the reaction process of Example 5. DETAILED DESCRIPTION
[0025] The specific implementation modes of the present invention are described in detail below in combination with embodiments and specific situations.
[0026] Embodiment 1:
[0027] The structural formula of its ionic ammonium salt short-chain fluorocarbon surfactant is:
[0028]
[0029] The synthesis method comprises the following steps: 1. 1.68 g of hexamethylene diisocyanate and 10 ml of solvent dichloromethane are mixed to obtain a first mixed solution, 2 drops of dibutyltin dilaurate are added to the first mixed solution to obtain a second mixed solution, 3.64 g of 1H,1H,2H,2H-tridecafluoro-1-n-octanol is added to the second mixed solution, and the mixture is reacted at 30-40° C. for 0.5-1 h to obtain an intermediate 1;
[0030] 2. React intermediate 1 with 0.89 g of 2-(dimethylamino)ethanol at 35-45°C for 0.5-1 h to obtain intermediate 2;
[0031] 3. React the intermediate 2 with 1.42 g of methyl iodide at 45° C. for 0.5 h, wash the final product three times with petroleum ether, and dry it to obtain a white powdery solid, that is, an ionic ammonium salt short-chain fluorocarbon surfactant;
[0032] Example 2
[0033] The difference between this embodiment and embodiment 1 is that:
[0034] The synthesis method comprises the following steps: 1. 2.22 g of isophorone diisocyanate and 10 ml of solvent dichloromethane are mixed to obtain a first mixed solution, 2 drops of dibutyltin dilaurate are added to the first mixed solution to obtain a second mixed solution, 3.64 g of 1H,1H,2H,2H-tridecafluoro-1-n-octanol is added to the second mixed solution, and the mixture is reacted at 30-40° C. for 0.5-1 h to obtain an intermediate 1;
[0035] 2. React intermediate 1 with 0.89 g of 2-(dimethylamino)ethanol at 35-45°C for 0.5-1 h to obtain intermediate 2;
[0036] 3. The intermediate 2 was reacted with 1.42 g of methyl iodide at 45° C. for 0.5 h. The final product was washed three times with petroleum ether and dried to obtain a white powdery solid, i.e., an ionic ammonium salt short-chain fluorocarbon surfactant.
[0037] Example 3
[0038] The difference between this embodiment and embodiment 1 is that:
[0039] The synthesis method comprises the following steps: 1. 1.74 g of toluene diisocyanate and 10 ml of solvent toluene are mixed to obtain a first mixed solution, 2 drops of dibutyltin dilaurate are added to the first mixed solution to obtain a second mixed solution, 3.64 g of 1H,1H,2H,2H-tridecafluoro-1-n-octanol are added to the second mixed solution, and the mixture is reacted at 0° C. (ice bath) for 0.5 to 1 h to obtain an intermediate 1;
[0040] 2. React intermediate 1 and 0.89 g of 2-(dimethylamino)ethanol at 0°C (ice bath) for 0.5-1 h to obtain intermediate 2;
[0041] 3. The intermediate 2 was reacted with 1.42 g of methyl iodide at 0°C (ice bath) for 0.5 h. The final product was washed three times with petroleum ether and dried to obtain a white powdery solid, i.e., an ionic ammonium salt short-chain fluorocarbon surfactant.
[0042] Example 4
[0043] The difference between this embodiment and embodiment 1 is that:
[0044] The synthesis method comprises the following steps: 1. mixing 2.50 g of 4,4′-diphenylmethane diisocyanate and 10 ml of toluene solvent to obtain a first mixed solution, adding 2 drops of dibutyltin dilaurate to the first mixed solution to obtain a second mixed solution, adding 3.64 g of 1H,1H,2H,2H-tridecafluoro-1-n-octanol to the second mixed solution, and reacting at 0° C. (ice bath) for 0.5 to 1 h to obtain an intermediate 1;
[0045] 2. React intermediate 1 and 0.89 g of 2-(dimethylamino)ethanol at 0°C (ice bath) for 0.5-1 h to obtain intermediate 2;
[0046] 3. The intermediate 2 was reacted with 1.42 g of methyl iodide at 0°C (ice bath) for 0.5 h. The final product was washed three times with petroleum ether and dried to obtain a white powdery solid, i.e., an ionic ammonium salt short-chain fluorocarbon surfactant.
[0047] Example 5
[0048] The difference between this embodiment and embodiment 1 is that:
[0049] The synthesis method comprises the following steps: 1. mixing 2.62 g of 4,4′-dicyclohexylmethane diisocyanate and 10 ml of solvent dichloromethane to obtain a first mixed solution, adding 2 drops of dibutyltin dilaurate to the first mixed solution to obtain a second mixed solution, adding 3.64 g of 1H,1H,2H,2H-tridecafluoro-1-n-octanol to the second mixed solution, and reacting at 30-40° C. for 0.5-1 h to obtain an intermediate 1;
[0050] 2. React intermediate 1 with 0.89 g of 2-(dimethylamino)ethanol at 35-45°C for 0.5-1 h to obtain intermediate 2;
[0051] 3. The intermediate 2 was reacted with 1.42 g of methyl iodide at 45° C. for 0.5 h. The final product was washed three times with petroleum ether and dried to obtain a white powdery solid, i.e., an ionic ammonium salt short-chain fluorocarbon surfactant.
[0052] Figure 5-Figure 9 These are the detections of the -NCO peak during the reactions of Examples 1-5 of the present invention. At the beginning, there is an obvious absorption peak at 2270 cm-1. As the reaction proceeds, the peak gradually disappears. A new peak is generated at 1730 cm-1, which is the peak of the urethane bond, proving that a coupling reaction has occurred between the hydroxyl group and the isocyanate.
[0053] The ionic fluorocarbon surfactants prepared in Examples 1 to 5 were subjected to surface tension testing (using the platinum ring surface tension testing method, instrument model DT-102), and the results are shown in Table 1:
[0054]
[0055]
[0056] Table 1
[0057] The synthesis method of the ionic ammonium salt short-chain fluorocarbon surfactant of the present invention is simple, the reaction conditions are easy to achieve, the cost is low, and the raw materials used are sufficient and non-toxic; the ionic ammonium salt short-chain fluorocarbon surfactant prepared by the present invention does not contain PFOS and has low surface tension; in addition, the carbamate bond in the ionic ammonium salt short-chain fluorocarbon surfactant is an easily degradable point and will not cause biological accumulation, so it is environmentally friendly, is an innovation in the synthesis of the ionic ammonium salt short-chain fluorocarbon surfactant, and has significant economic and social benefits.
Claims
1. An ionic ammonium salt short-chain fluorocarbon surfactant, characterized in that: Its structural formula is:
2. The method for preparing the ionic ammonium salt short-chain fluorocarbon surfactant according to claim 1, characterized in that: The synthesis method comprises the following steps: (1) mixing isocyanate and solvent dichloromethane to obtain a first mixed solution, adding dibutyltin dilaurate to the first mixed solution to obtain a second mixed solution, adding 1H,1H,2H,2H-tridecafluoro-1-octanol to the second mixed solution, and reacting at 30-40° C. for 0.5-1h to obtain an intermediate 1, wherein the molar ratio of 1H,1H,2H,2H-tridecafluoro-1-octanol to isocyanate is 1:1; (2) reacting intermediate 1 and 2-(dimethylamino)ethanol at a molar ratio of 1:1 at 35-45°C for 0.5-1h to obtain intermediate 2; (3) reacting the intermediate 2 with iodomethane at a molar ratio of 1:1 at 45° C. for 0.5 h, washing the obtained final product three times with petroleum ether, and drying it to obtain a white powdery solid, i.e., an ionic ammonium salt short-chain fluorocarbon surfactant; The isocyanate is one of isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.