Fluorinated surfactant

At low concentrations fluorinated surfactants are capable of lowering effectively the surface tension of aqueous solutions and non-aqueous liquids and work well in acidic, alkaline and electrochemical media as well as at elevated temperatures. Their destruction may be bound up just with the decomposition of polar groups, e.g. polyoxyethylene chain. Adsorbing with the 

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Fluorinated Surfactants Synthesis Properties Applications, Erik Kissa... 

Chemistry of Organic Fluorine Compounds II Table 7. Properties of Fluorinated Surfactants... 

De-icing compositions for the removal of ice or for prevention of its reformation on automobile windshields are prepared from 1 part polyol, 1 part alcohol, and 0.05 part fluorinated surfactant, e.g., ammonium salts of mono- and bisfluoroalkyl phosphates and their complexes with aliphatic quaternary methyl sulfates [287]. 

See, for example, Kissa E (1994) Fluorinated surfactants. M Dekker, New York (a) Mahler W, Guillon D, Scoulios A (1985) Mol Cryst Liq Cryst Lett 2 111 (b) Shin S, Collazo N, Rice SA (1992) J Chem Phys 96 1352... 

Perfluoroalkyl)ethane thiols have been used as precursors to fluorinated surfactants and products for hydro- and oligophobic finishing of substrates such as textiles and leather (1). The synthesis of 2-(perfluoroalkyl)ethane thiol and a byproduct bis-(-2-perfluoroalkylethane)-disulfide (5-10%) has been practiced via the reaction of 2-(perfluoroalkyl)ethane iodide with thiourea to form an isothiuronium salt which is cleaved with alkali or high molecular weight amine as shown in Equation 1 for 2-(perfluorohexyl)ethane iodide (1). 

Schroder, H.E (2003). Determination of fluorinated surfactants and their metabolites in sewage sludge samples by liquid chromatography with mass spectrometry and tandem mass spectrometry after pressurized liquid extraction and separation on fluorine-modified reversed-phase sorbents. J. Chromatogr. A 1020(1), 131-151. 

E Kissa, Fluorinated surfactants synthesis, properties, applications (New York Marcel Dekker, 1993). 

Jurado E (2006) Modelling the ocean atmosphere exchanges of persistent organic pollutants (POPs). PhD thesis, Universitat Politecnica de Catalunya, Barcelona, Spain Jurado E, Zaldvar JM, Marinov D, Dachs J (2007) Fate of persistent organic pollutants in the water column Does turbulent mixing matter Mar Poll Bull 57 441 151 Kissa E (2001) Fluorinated Surfactants and Repellents. Marcel Dekker Inc. 

Shepherd FM, Holzenburg A. The potential of fluorinated surfactants in membrane biochemistry. Anal Biochem 1995 224 21-27. 

Chabaud E, Barthelemy P, Mora N, Popot JL, Pucci B. Stabilization of integral membrane proteins in aqueous solution using fluorinated surfactants. Biochemie 1998 80 515-530. 

To keep the precipitating polymers in the dispersed state throughout the polymerization, requires steric stabilizers. This problem is classically tackled via copolymerization with fluoroalkylmethacrylates or the addition of fluorinated surfactants, both being only weak steric stabilizers. DeSimone el al. also applied a fluorinated block copolymer,9 proving the superb stabilization efficiency of such systems via a rather small particle size. One goal of the present chapter is therefore an investigation of our fluorinated block copolymers as steric stabilizers in low-cohesion-energy solvents. 

The trend of discovering the analytical field of environmental analysis of surfactants by LC-MS is described in detail in Chapters 2.6-2.13 and also reflected by the method collection in Chapter 3.1 (Table 3.1.1), which gives an overview on analytical determinations of surfactants in aqueous matrices. Most methods have focused on high volume surfactants and their metabolites, such as the alkylphenol ethoxylates (APEO, Chapter 2.6), linear alkylbenzene sulfonates (LAS, Chapter 2.10) and alcohol ethoxylates (AE, Chapter 2.9). Surfactants with lower consumption rates such as the cationics (Chapter 2.12) and esterquats (Chapter 2.13) or the fluorinated surfactants perfluoro alkane sulfonates (PFAS) and perfluoro alkane carboxylates (PFAC) used in fire fighting foams (Chapter 2.11) are also covered in this book, but have received less attention. 

Under RP-Cis column separation conditions, no differentiation between conventional AE and fluorinated AE in retardation behaviour could be observed. The application of a perfluorinated RP-C8 column to a mixture of standards of non-ionic fluorinated surfactants and the extracts of wastewater sludges spiked with these compounds using realistic concentrations, however, resulted in good separation of AE and fluorinated AE (cf. mass traces and TIC in Fig. 2.9.46(a), (b) or (e) and Fig. 2.9.46(c), (d) or (e), respectively) or matrix and fluorinated AE surfactants (Fig. 2.9.46(f), (g) or (h), respectively) [52]. 

Fig. 2.9.46. (e) APCI-LC-MS(+) RIC of a mixture of standards containing a conventional AE blend (C12 and C14 homologues) and a fluorinated non-ionic surfactant blend (C F2 +i-(CH2-CH2-0)m-H n = 6 and 8) (a)-(d) selected mass traces of conventional C12 and C14 AE compounds or CB and Cg fluorinated AE compounds (h) APCI-LC-MS(-I-) RIC of wastewater sludge extract containing non-ionic fluorinated surfactants (f) and (g) selected mass traces of C6 and C8 fluorinated AE compounds extracted from sewage sludge. Gradient elution separated on perfluorinated RP-Cg column [52]. 

Despite the fact that physico-chemical and chemical degradations were not possible, the isolation of persistent metabolites of the CnF2n+i-(CH2-CH2-0)m-H compound generated by (3 and w oxidations of the terminal PEG unit of the non-ionic blend was reported, but environmental data about this type of compound are still quite rare [49]. TSI(+) ionisation results of the industrial blend Fluowet OTN have been reported in the literature [7,51]. Actual data of non-ionic fluorinated surfactants were applied using ESI- and APCI-FIA-MS(+) and -MS-MS(+), which reported the biodegradation of the non-ionic partly fluorinated alkyl ethoxylate compounds C F2 fi-(CH2-CH2-0)x-H in a lab-scale wastewater treatment process. 

E. Kissa, In M.J. Schick and F.M. Fowkes (Eds.), Fluorinated surfactants synthesis, properties, applications, Surfactant Science Series, Vol. 50, Marcel Dekker, New York, USA, 1994. 

H.Fr. Schroder, Determination of Fluorinated Surfactants and their Metabolites in Sewage Sludge Samples by LC/MS and MSre after Accelerated Solvent Extraction and Separation on Fluorine Modified RP-Phases, J. Chromatogr. A, in press. 

Partly fluorinated or perfluorinated sulfonic and carboxylic acids are compounds with excellent surface activity combined with an extreme stability against chemical or physico-chemical attacks as also described for non-ionic fluorine containing surfactant compounds. The anionic surfactants are shown with their structural formulae in Fig. 2.11.24(1)—(III). A selected ESI-FIA-MS(-) spectrum of a partly fluorinated surfactant (CF3-(CF2)4-(CH2)8-S03H, m/z 461) is presented in Fig. 2.11.25. The FIA spectrum also contains ions of the by-products CF3-(CF2)2-(CH2)8-S03H (m/z 361) and CF3-(CF2)3-(CH2)8-S03H (m/z 411). 

A mixture of these fluorinated surfactants was separated according to the method applied by Popenoe et al. [52]. For ionisation and detection, ESI-MS in the negative mode was applied. The result of LC separation is presented in the RIC in Fig. 2.11.26(a). Some of the separated compounds in the TIC and mass traces could be identified as perfluoro alkylsulfonates and perfluoro alkylcarboxylates such as... 

Kissa E (2001) Fluorinated surfactants and repellents, 2nd edn, vol 97. Marcel Dekker, New York... 

Aldonolactone-based fluorinated surfactants have also been reported [71]. 

Another approach to tissue oxygenation, which consists of administering an aqueous suspension of O2 nanobubbles osmotically stabilized by a volatile PFC (e.g., F-pentane) and a fluorinated surfactant, appears promising. Experimental proof of efficacy for this system includes survival of erythrocyte-depleted rats and pigs, and of pigs with potentially lethal hemorrhagic shock and with severe right-to-left shunt [33],... 

Fluorinated surfactants lower the surface tension of water more strongly than their nonfluorinated analogues. Fluorinated surfactants reduce the superficial pressure of water from 72 to 15-20 dyn/cm while a nonfluorinated agent only decreases the value to 25-35 dyn/cm (Table 1.6). 

Perfluoroalkyl tail Hydrocarbon linker Junction spacer Polar head Figure 6.48 Creation of fluorinated surfactant derived from a sugar. 

Fluorinated Surfactants and Repellents Second Edition, Revised and Expanded, ErikKissa... 

Poly vinylidene fluoride is polymerized under pressure at 25-150°C in an emulsion using a fluorinated surfactant to minimize chain transfer with the emulsifying agent. Ammonium persulfate is used as the initiator. The homopolymer is highly crystalline and melts at 170°C. It can be injection molded to produce articles with a tensile strength of 7000 psi (48 MPal. a modulus of elasticity in tension of 1.2 x 105 psi and a heat deflection of 3003F (149°C). 

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