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CN-121974835-A - Safe preparation method, product and application of short fluorocarbon alkyl sulfobetaine surfactant

CN121974835ACN 121974835 ACN121974835 ACN 121974835ACN-121974835-A

Abstract

The invention relates to the technical field of chemical material preparation, and in particular discloses a safe preparation method, a product and application of a short fluorocarbon alkyl sulfobetaine surfactant, comprising the following steps of (1) reacting epoxy chloropropane with secondary amine in a solvent system I to obtain an intermediate 1; in a solvent system II, the intermediate 1 reacts with sodium hydrosulfide or hydrate thereof to obtain an intermediate 2, the intermediate 2 reacts with short fluorocarbon alkyl iodide to obtain perfluoroalkyl thioether propyl tertiary amine, and the perfluoroalkyl thioether propyl tertiary amine is sulfonated to obtain the short fluorocarbon alkyl sulfobetaine surfactant. According to the invention, by designing a synthetic route which avoids using high-risk reagents, the safety and operability of the process are obviously improved, and the sulfobetaine surfactant with excellent acid, alkali and salt chemical stability and excellent surface activity is successfully prepared, so that the key material and the safe and reliable preparation process are provided for the development of new-generation high-efficiency environment-friendly fire extinguishing agents.

Inventors

  • CHEN CHAO
  • ZHONG WANG
  • ZHANG JIANHUA
  • LI JIHUI
  • ZHANG YUHONG

Assignees

  • 成都科宏达化学有限责任公司

Dates

Publication Date
20260505
Application Date
20260403

Claims (10)

  1. 1. A safe preparation method of a short fluorocarbon alkyl sulfobetaine surfactant, which is characterized by comprising the following steps: (1) In the solvent system I, epichlorohydrin reacts with secondary amine to obtain an intermediate 1; (2) In the solvent system II, the intermediate 1 reacts with sodium hydrosulfide or hydrate thereof to obtain an intermediate 2; (3) Reacting the intermediate 2 with short fluorocarbon alkyl iodide to obtain perfluoroalkyl thioether propyl tertiary amine, wherein the structure of the short fluorocarbon alkyl iodide is C n F 2n+1 C m H 2m I, n is an integer of 2-6, and m is an integer of 1-8; (4) Sulfonation treatment is carried out on perfluoroalkyl thioether propyl tertiary amine to obtain a short fluorocarbon alkyl sulfobetaine surfactant; r1 and R2 are each independently C1-C4 alkyl, or R1 and R2 together form C2-C6 carbocyclylalkyl or carbocyclylalkyl containing oxygen/sulfur heteroatoms, both ends of the carbocyclylalkyl being linked to the N atom to form a cyclic secondary amine structure, R3 being H, OH or C1-C3 alkyl.
  2. 2. The safe process for preparing a short fluorocarbon alkyl sulfobetaine surfactant of claim 1, wherein the secondary amine in step (1) comprises at least one of dimethylamine, diethylamine, piperidine or morpholine.
  3. 3. The process for the safe preparation of a short fluorocarbon alkyl sulfobetaine surfactant according to claim 1, wherein in step (1), the molar ratio of epichlorohydrin to secondary amine is 1:1 to 1.2, and/or in step (2), the molar ratio of intermediate 1 to sodium hydrosulfide is 1:1 to 1.5.
  4. 4. The safe preparation method of a short fluorocarbon alkyl sulfobetaine surfactant according to claim 1, wherein the sulfonating agent in step (4) is selected from one or more of sodium 3-chloro-2-hydroxy propane sulfonate, 1, 3-propane sultone, 2-methyl-1, 3-propane sultone or 2-ethyl-1, 3-propane sultone.
  5. 5. The safe preparation method of the short fluorocarbon alkyl sulfobetaine surfactant according to claim 1, wherein in the step (3), the molar ratio of the intermediate 2 to the short fluorocarbon alkyl iodide is 1:1-1.2.
  6. 6. The safe process for preparing a short fluorocarbon alkyl sulfobetaine surfactant of claim 1, wherein in step (4), the molar ratio of perfluoroalkyl thioether propyl tertiary amine to sulfonating agent is from 1:1 to 2.
  7. 7. The safe preparation method of the short fluorocarbon alkyl sulfobetaine surfactant according to claim 1, wherein the steps (1) to (4) of the preparation method are all carried out in an organic solvent, the organic solvent comprises at least one of acetonitrile, acetone, tetrahydrofuran, N-dimethylformamide or dimethyl sulfoxide, the reaction of the step (4) is carried out in a mixed solvent of the organic solvent and water, and the pH value of the system is controlled to be 7.0-9.0 in the reaction process.
  8. 8. A short fluorocarbon alkyl sulfobetaine surfactant prepared by the safe preparation process of any one of claims 1-7, characterized by having the following general structure: Rf-A-B-C; Wherein Rf is a C2-C6 linear or branched perfluoroalkyl group; a is a C1-C8 alkylene group; b is-SCH 2 CH (OH) N (R1) (R2) -; c is-CH 2 CH(R3)CH 2 SO 3 - .
  9. 9. The short fluorocarbon alkyl sulfobetaine surfactant of claim 8 wherein R1 and R2 in the B group together form a C2-C6 carbocyclic alkyl group having one or two heteroatoms selected from oxygen, sulfur, which may be the same or different, inserted therein.
  10. 10. A fire extinguishing composition comprising a short fluorocarbon alkyl sulfobetaine surfactant according to claim 8 or 9.

Description

Safe preparation method, product and application of short fluorocarbon alkyl sulfobetaine surfactant Technical Field The invention relates to the technical field of chemical material preparation, and particularly discloses a safe preparation method, a product and application of a short fluorocarbon alkyl sulfobetaine surfactant. Background Fluorocarbon surfactants are widely used in the industrial fields of fire protection, oil exploitation, paint, etc. because of their extremely high surface activity, excellent thermal stability and chemical inertness. Particularly in the aqueous film-forming foam extinguishing Agent (AFFF), the fluorocarbon surfactant is taken as a key component, can be rapidly spread on the surface of fuel to form a water film, has the functions of isolating air and cooling, and realizes high-efficiency fire extinguishment and anti-reburning. To circumvent the persistent environmental risk of long chain perfluorinated compounds (e.g., PFOA, PFOS), industry has turned to the development of environmentally friendly surfactants based on short fluorocarbon chains. Betaine type amphoteric fluorocarbon surfactant becomes a research hot spot due to good compatibility and environmental compatibility. Among them, sulfobetaine can maintain stable zwitterionic state in wide pH range and high electrolyte environment because of strong acidity of sulfonate group, and its chemical stability is obviously superior to that of carboxybetaine, so it has potential in fire extinguishing application in complex environment. However, existing short fluorocarbon sulfobetaine synthesis techniques still face serious challenges of process safety and economy. For example, chinese patent publication No. CN116144377a discloses a method for synthesizing fluorocarbon betaine from perfluorohexyl ethanol. Although the method realizes a short fluorocarbon chain structure, sodium hydride (NaH) is used as a strong alkali reagent in the key step. Sodium hydride reacts violently when meeting water, is inflammable and explosive, and has extremely high requirements on production equipment, operation safety and storage and transportation, thereby greatly limiting the large-scale safe production of the technology. Another known synthetic route, such as US20110092735A1, starts with perfluoroalkyl iodides, but the subsequent steps involve oxidation with highly toxic chlorine gas, which also presents significant safety and environmental risks. In addition, some processes, such as CN107903180a, result in poor atomic economy, more three wastes, and high cost due to the use of low effective amounts of raw materials or the need for multiple lengthy reactions. Therefore, there is a need for a process for preparing short fluorocarbon alkyl sulfobetaines that is safe, mild in conditions, and avoids the use of high-risk reagents. The method can reliably synthesize the sulfobetaine product with excellent surface activity and stable chemical property, so as to meet the dual requirements of the fields of high-end foam extinguishing agents and the like on the performance, safety and environmental protection. Disclosure of Invention In order to solve the problems, the invention provides a safe preparation method, a product and application of a short fluorocarbon alkyl sulfobetaine surfactant, and designs a totally new synthetic route for avoiding the use of high-risk reagents such as sodium hydride, chlorine and the like, so that the intrinsic safety and operability of the process are obviously improved, the short fluorocarbon alkyl sulfobetaine with novel structure is successfully prepared, and the product has excellent acid resistance, alkali resistance, salt chemical stability and excellent fluorocarbon chain surface activity of the sulfobetaine. In order to achieve the above purpose, the technical scheme of the invention is as follows, a safe preparation method of a short fluorocarbon alkyl sulfobetaine surfactant comprises the following steps: (1) In the solvent system I, epichlorohydrin reacts with secondary amine to obtain an intermediate 1; (2) In the solvent system II, the intermediate 1 reacts with sodium hydrosulfide or hydrate thereof to obtain an intermediate 2; (3) Reacting the intermediate 2 with short fluorocarbon alkyl iodide to obtain perfluoroalkyl thioether propyl tertiary amine, wherein the structure of the short fluorocarbon alkyl iodide is C nF2n+1-CmH2m -I, n is an integer of 2-6, and m is an integer of 1-8; (4) Sulfonation treatment is carried out on perfluoroalkyl thioether propyl tertiary amine to obtain the short fluorocarbon alkyl sulfobetaine surfactant; in each of the above reactions, R1 and R2 are each independently C1-C4 alkyl, or R1 and R2 together form C2-C6 carbocyclylalkyl or carbocyclylalkyl containing oxygen/sulfur heteroatoms, both ends of the carbocyclylalkyl being linked to the N atom to form a cyclic secondary amine structure, and R3 is H, OH or C1-C3 alkyl. The core principle of the invention is that bas