| Name | Fluorocarbon surfactant |
| Synonyms | fluoronates Surfactant Fluorocarbon surfactant Fluorocarbon Surfactants |
| Use | Uses for light water foam extinguishing agent, ink additives, binder materials, chemical plating solution additives |
main uses
The main uses of fluorocarbon surfactants are: surfactants can be used as fire extinguishing agents for oil products due to their good surface tension reduction ability, heat resistance, and chemical resistance. For example, only adding 0.003% to gasoline and conducting normal ignition point tests can have a non-combustible effect; it can also be used as an additive for electroplating bath during chromium plating (to prevent the generation of chromium acid mist); emulsifiers, pigment dispersants, surface modifiers such as plastics and rubber, metal surface detergents, hydrophobic agents such as fibers and paper, oil repellent and scale inhibitors during emulsion polymerization of fluorine-containing olefins.
1. Fluorocarbon cationic surfactants have high surface activity and stable chemical properties. It has good wetting, spreading, leveling and corrosion inhibition effects. It is used as spreading agent, leveling agent, wetting agent, oil sealing cloth, corrosion inhibitor, metal polishing aid, photographic development, leakage detection solution, etc.
2, fluorocarbon anionic surfactant has wetting, emulsifying, foaming and diffusion properties. Stable chemical properties. Can be used as wetting agent, spreading agent, emulsifying dispersant. It is used for storage of crude oil, which can reduce the evaporation loss of oil and is also used for fire fighting.
3, perfluoroalkyl sulfonate fluorocarbon surfactant has high surface activity, the lowest surface tension can reach 20mN/m, and it has the functions of wetting, foaming, washing and dispersion. It can be used as wetting agent, electroplating bath agent, metal and plastic etchant, pickling and cleaning bath, alkaline cleaning system, etc. in etching solution for manufacturing semiconductor devices.
4. The molecular structure of zwitterionic fluorocarbon surfactants contains both acidic and basic groups. The type of ions it exhibits depends on the pH value of the solution, that is, it is cationic in acidic medium and anionic in alkaline medium. The acidic groups of amphoteric fluorocarbon surfactants are mainly carboxylic acid groups and sulfonic acid groups, and the basic groups are mainly amino or quaternary ammonium groups. Amphoteric fluorocarbon surfactants have excellent emulsifying properties and are used as emulsifiers in the manufacturing process of fluorocarbon materials, paper, leather and other products. For example, DuPont Zonyl FSK can be widely used in water, acid, alkali and organic polar solvents to effectively reduce the surface tension of the system. FSK can maintain stable performance in aqueous solutions with different concentrations of 0~100 ℃. If the 0.1% dosage of active ingredients is used, FSK can effectively wet Teflon fluorocarbon film. Even if the solvent acetic acid is neutralized, it will not affect the performance of FSK, so it can be applied to alkaline solutions. In addition, unlike other common surfactants, FSK is not affected by high concentration electrolytes such as acids and salts. According to different application systems, the dosage of Zonyl FSK is generally 0.01 ~ 0.2%. FSK is especially suitable for foaming agent, alkaline cleaning agent and shampoo.
Preparation method
Regarding the manufacturing method, the manufacturing methods of fluoroalkyl group include:(1) electrolytic fluorination method (3M company in the United States);(2) telomerization method (DuPont company in the United States, Asahi Nippon, Japan Daikin Industrial Company);(3) Polymerization method (ICI company in the United Kingdom, Nestlé company in Japan).
① Electrolytic fluorination (US 3M Company). The organic compounds are dissolved in inorganic hydrofluoric acid and electrolyzed under low voltage (usually 5~6V) to generate perfluorinated compounds, which can be used as the matrix to make various surfactants. The raw materials of this method are hydrocarbon compounds and anhydrous hydrofluoric acid, and the price is relatively cheap. Its products are mostly-C8F17 and-C7F15. This approach was first developed by Simons. Hydrocarbons are fluorinated to perfluorinated at the anode. Due to the large binding energy of C- F bonds, there are often a large number of side reactions of C- C bond cleavage, with many by-products and low yield of perfluorinated compounds.
(1)C7H15COCl + 16HF & rarr;C7F15COF + HCl (2)C8H17SO2Cl + 18HF & rarr;C8F17SO2F + HCl.
② polymerization method. The law was first proposed by the Hasgeldine. In the presence of fluorodioxane (CH3I, C2F5I) and the like, tetrafluoroethylene undergoes free radical polymerization to form a linear telomer intermediate, which is a mixture of different chain lengths and is separated as needed. Then introduce a hydrophilic group into the iodine atom to make a surfactant. This method is less than electrolytic fluorination by-products and has a high yield, but it is difficult to produce long-chain polymers and the equipment is large. Anionic, cationic, zwitterionic and non-ionic fluorocarbon surfactants can be prepared by using the polymerization reaction.
(1)CF2=CF2+C2F5I→CF3CF2CF2CF2I
(2)CF3CF2CF2CF2I+SO2Cl2→CF3(CF2)3SO2Cl
(3)CF3(CF2)3SO2Cl+HF→CF3(CF2)3SO2F
③ Gathering method. Also known as ion oligomerization. Teflon or hexafluoropropylene, in the presence of fluorine anion, anionic polymerization, the formation of C6 ~ C14 oligomers. A hydrophilic group is introduced into the double bond site of this oligomer to make a surfactant. This method is characterized by the use of relatively cheap monomers, the quantitative production of products, and easy introduction of hydrophilic groups. The disadvantage is that the perfluoroalkyl group is side-chain, and the surface activity is slightly worse than that of the linear chain.
| surfactant | The Fluorocarbon surfactant may be an anionic, cationic, amphoteric or nonionic surfactant, and is generally a mixed type. research on fluorocarbon surfactants began in the early 50's of the 20th century. In the second half of the 50's, the Southern Institute of the U. S. Department of Agriculture published oil repellent for fiber. Into the 60's hydrophobic agent and hydrophobic agent as the center of a variety of fluorocarbon surfactants have been rapid development. The Fluorocarbon surfactant is formed by replacing a hydrogen atom of an alkyl group in a molecule of a General Hydrogen-carbon type surfactant with a fluorine atom, that is, replacing a general hydrophobic group hydrogen-carbon chain with a fluorocarbon chain. If the hydrogen in the alkyl group is all replaced by a fluorine atom, it is called perfluoroalkyl. Perfluoroalkyl fluorine atom and carbon atom bonding ability (4.86 × 105J/mol), it gives the fluorocarbon surfactant with various special properties, the Fluorocarbon type surfactant is further improved in the stability of the carbon-carbon bond, and thus is more resistant to chemicals and thermally stable. The surface tension of the aqueous solution was very low (15-20)× 10-6N/cm. It has hydrophobic and oleophobic properties that are beyond the scope of other surfactants. A low surface tension means that the surface can be spread out with less work, and the formation of a thin film is easy, that is, the formation of a foam is extremely easy. In addition, due to the rapid expansion of the liquid film, The volatilization of the volatile liquid can be greatly suppressed. As the length of the fluorocarbon chain increases, its surface activity increases. When the number of carbon atoms in the hydrocarbon chain surfactant is more than 12, it shows better activity; While the fluorocarbon surfactant, when the number of carbon atoms reaches 6, It shows a good activity, and is generally the most preferred when the number of carbon atoms is 8 to 12. This information was edited by chemical book Xiaonan (2015-08-24). |
| Main uses | The main uses of fluorocarbon surfactant are: surfactant has good ability to reduce the surface tension, heat resistance, chemical resistance, can be used as fire extinguishing agent for oil, for example, only 0.003% in gasoline, usually ignition point test, can play a non-combustible effect; can also be used as chromium plating bath additives (to prevent the generation of chromium acid mist); Fluorinated olefin emulsion polymerization emulsifier, pigment dispersant, plastic and rubber and other surface modifiers, metal surface detergent, fiber and paper and other hydrophobic agent, hydrophobic agent and scale inhibitor. 1. Fluorocarbon cationic surfactants have high surface activity and stable chemical properties. Good wetting, spreading, leveling, corrosion inhibition, used as spreading agent, leveling agent, wetting agent, Oil Seal, corrosion inhibitor, metal polishing additives, photographic development, leak detection liquid. 2. Fluorocarbon anionic surfactants have wetting, emulsifying, foaming and diffusion properties. Chemical stability. It can be used as a wetting agent, a spreading agent, and an emulsifying dispersant. For the storage of crude oil, can reduce the evaporation loss of oil, also used for fire. 3. Perfluoroalkyl sulfonate type fluorocarbon surfactant has high surface activity, the lowest surface tension can reach 20mN/m, and has wetting, foaming, washing and dispersing effects. It can be used as a wetting agent in an etching solution for manufacturing a semiconductor device, a plating bath, a metal and plastic etchant, an acid cleaning and dipping bath, an alkaline cleaning system, and the like. 4. The molecular structure of zwitterionic fluorocarbon surfactant contains both acidic and basic groups, and the type of ions it shows depends on the pH value of the solution, that is, it is cationic in acidic medium, it is anionic in alkaline medium. The acidic Group of the Amphoteric fluorocarbon surfactant is mainly a carboxylic acid group and a sulfonic acid group, and the BASIC group is mainly an amino group or a quaternary ammonium group. Amphoteric fluorocarbon surfactants have excellent emulsifying properties, used as emulsifiers in the manufacturing process of fluorocarbon materials, paper, leather and other products, such as DuPont Zonyl FSK, can be widely used in water, acid, alkali and organic polar solvents to effectively reduce the surface tension of the system. In 0~100 deg C in different concentrations of aqueous solution, FSK can maintain stable performance. FSK can effectively wet the Teflon fluorocarbon membrane if it is used in an amount of 0.1% of the active ingredient. Even if the solvent acetic acid is neutralized, the performance of FSK is not affected, and thus it can be applied to an alkaline solution. In addition, unlike other common surfactants, FSK is not affected by high-concentration electrolytes such as acids and salts. According to different application systems, the dosage of Zonyl FSK is generally 0.01 ~ 0.2%. FSK is particularly suitable for foaming agents, alkaline cleaning agents and shampoos. Figure 1 shows DuPont Zonyl FSK zwitterionic fluorocarbon surfactant. |
| preparation method | About the manufacturing method, the manufacturing method of fluoroalkyl groups are:(1) electrolytic fluorination method (3M Company, USA);(2) polymerization reaction method (Dupont, Japan Assura, Japan Industrial Corporation, Japan);(3) oligomerization method (ICI, UK, Japan). ① electrolytic fluorination (3M Company, USA). The organic compound is dissolved in inorganic hydrofluoric acid and electrolyzed at a low voltage (usually 5 to 6V) to form a perfluorinated compound, which is used as a precursor to prepare various surfactants. The raw materials of this method are hydrocarbon compounds and anhydrous hydrofluoric acid, and the values are relatively inexpensive. Its products are-C8F17,-C7F15 majority. This approach was first developed by Simons. Hydrocarbons are fluorinated to perfluorides at the anode. Since the binding energy of the C- F bond is large, there are often a large number of side reactions in which the C- C bond is broken, there are many by-products, and the yield of perfluorinated compounds is low. (1)C7H15COCl 16HF → C7F15COF HCl (2)C8H17SO2Cl 18HF → C8F17SO2F HCl. (2) the method of polymerization. This method was first proposed by Hasgeldine. Tetrafluoroethylene and the like undergo free radical polymerization in the presence of a telogen (CH3I, C2F5I), etc., to form a linear telomer intermediate, which is a mixture of different chain lengths, they were separated as needed. A surfactant is prepared by introducing a hydrophilic group into the iodine atom. This method is less than electrolytic fluorination by-products, high yield; But it is difficult to produce long chain telomer, and the equipment scale is large. Anionic, cationic, zwitterionic and Nonionic fluorocarbon surfactants can be prepared by telomerization. (1)CF2 = CF2 C2F5I → CF3CF2CF2CF2I (2)CF3CF2CF2CF2I SO2Cl2 → CF3(CF2)3SO2Cl (3)CF3(CF2)3SO2Cl HF → CF3(CF2)3SO2F (3). Also known as ion oligomerization method. When tetrafluoroethylene or hexafluoropropylene is subjected to anionic polymerization in the presence of a fluorine anion, C6 to C14 oligomers are formed. A surfactant is prepared by introducing a hydrophilic group at the double bond site of the oligomer. This method is characterized by the use of relatively inexpensive monomers, can be quantitatively prepared products, and easy to introduce hydrophilic groups. The disadvantage is that the perfluoroalkyl groups are side-chain and slightly less surface active than the linear ones. |
| DuPont fluorocarbon surfactant | DuPont fluorocarbon surfactant is produced by the U, compared with common surfactants (such as hydrocarbons or silicones), fluorocarbon surfactants are characterized by high efficiency and stability. At very low application concentration (0.01 ~ 0.1%), it can significantly reduce the surface tension of the system (to 18dyn/cm), greatly improve the wettability and leveling of the formula, and can effectively wet, disperse low surface energy substances (e. G., Polytetrafluoroethylene). At the same time, it has excellent thermodynamic and chemical stability, and can be applied to strong acid, strong base, strong oxidizing medium and high temperature system above 250 ℃, which are incomparable to ordinary surfactants. Due to the nature of the stability of the small amount, it is generally not to affect the overall performance and stability of the formulation, and can be compatible with all kinds of other common surfactants. DuPont Zonyl FSP is a water-soluble phosphate-based anionic fluorocarbon surfactant. It can effectively reduce the surface tension of aqueous system and significantly improve the wettability of aqueous solution to solid/gas and solid/liquid interfaces. This excellent wetting ability enables FSP to be widely used in hair and personal care products, floor wax, paint and coatings, adhesives, metal protective agents and mining and mineral processing industries. This product has poor foaming properties and is actually used as a defoamer in many applications. Because of the phosphate group, it is not suitable for application in the hard water system containing multivalent cations. DuPont Zonyl FSO-100 is a non-ionic fluorocarbon surfactant, with strong surface activity, even at a concentration of 10ppm, can effectively reduce the surface tension of aqueous solution, the main application areas are as follows: 1, ink: can be compatible with the pigment in the ink, can improve the life of the metal cylinder in the printing equipment and improve the printing effect. 2, paint, coating: improve the system's anti-fouling, anti-fog, anti-ultraviolet properties, with most of the water/solvent-based formula compatibility. 3, polymer: anti-fouling, anti-fog, anti-ultraviolet, improve the internal lubricity, can be used as a filler coupling agent, and can prevent the plasticizer migration in the system; Adhesive: used for system modification, enhanced wetting capacity, compatible with most aqueous/solvent-based formulations. 4, wax, polishing agent: improve wetting, leveling, reduce shrinkage phenomenon, can be compatible with most water/solvent formulations. 5, metal/Electron: can improve the etching effect, and can be used as a plating aid and zinc battery oxidation inhibitor. 6, joint filler/putty: improve the ability of anti-fouling, anti-ultraviolet, eliminate silicone oil leakage, enhance outdoor weather resistance, can be compatible with most water-based/solvent-based formulations. |
| Application | used in light water foam extinguishing agent, ink additives, binder materials, electroless plating bath additives |