Frédéric
Boschet
*a,
Georgi
Kostov
a,
Bruno
Ameduri
*a,
Andrew
Jackson
b and
Bernard
Boutevin
a
aInstitut Charles Gerhardt, Ingénierie et Architectures Macromoléculaires, UMR CNRS 5253, Ecole Nationale Supérieure de Chimie de Montpellier, 8 Rue de l'Ecole Normale, 34296, Montpellier, France. E-mail: bruno.ameduri@enscm.fr; frederic.boschet@enscm.fr
bChemtura, 1801 U.S. Highway 52 West, West Lafayette, Indiana 47906-2200, USA
First published on 17th November 2011
Original fluorinated surfactants based on 3,3,3-trifluoropropene (TFP) as alternatives to perfluorooctanoic acid (PFOA) were synthesized in three to five straightforward steps in good overall yields. First, the radical or thermal telomerization of TFP in the presence of perfluoroisopropyl iodide as the chain transfer agent led to various TFP telomers of different molecular weights. They were further chemically modified into various ionic and non-ionic surfactants. To obtain anionic surfactants, TFP telomers bearing iodine end-group was converted into allylic group on which thioglycolic acid was added under a radical or photochemical process. Non-ionic surfactants were obtained by esterification of the anionic acid with poly(ethylene glycol)monomethylether. Cationic surfactants were obtained by ethylene end-capping of the TFP telomers followed by a nucleophilic substitution by either triethylamine or pyridine. All surfactants showed good inertness to bases and acids, and satisfactory surface properties. They exhibit interesting critical micellar concentration values comparable to that of PFOA (0.06, 4.10, and 3.20 versus 3.00 g L−1).
At that point, the main companies (Arkema, Asahi Glass, Ciba, Clariant, Daikin, 3M/Dyneon, Dupont and Solvay Solexis) involved in the production of derivatives and fluorinated polymers have been joining efforts since 2005 in a consortium called the “Stewardship Program”24 that aims to reflect the future, and to seek for new alternatives to PFOA and PFOS. Indeed, these PFOA or PFOS have been synthesized from tetrafluoroethylene (TFE) telomers.1,8 Although short perfluorinated chains (C4)25 or oligo(hexafluoropropylene oxide)26–29-based surfactants have already led to original non-bioaccumulable alternatives to PFOA, it was of interest to find new derivatives.
The purpose of this article is to deal with the synthesis of cationic, anionic and non-ionic surfactants by simple and efficient modifications of fluorinated telomers obtained by iodine transfer polymerization. The concept is illustrated using the radical telomerization of 3,3,3-trifluoropropene and the chemical modifications of the resulting TFP telomers in 2–4 steps to obtain the various types of surfactants.
The synthesis of 3,3,3-trifluoropropene (TFP) was pioneered by Haszeldine43 in the early 1950s from dehydroiodination of CF3–CH2–CH2I and is now commercially available (from Great Lakes-Chemtura now DuPont). TFP has been used in telomerization with several telogens (Table 1) using various type of initiation: redox, UV, γ-radiation, thermal, or peroxides. Results show that perfluoroalkyl iodides RFI are the best telogens.1
Telogen | Initiation | Product obtained | Ref. |
---|---|---|---|
a BPO: dibenzoyl peroxide, DTBP: di-tert-butyl peroxide. | |||
H3COCOC(CH3)2H | Peroxides | H3COCOC(CH3)2, [CH2CH(CF3)]nH | 30 |
(CH3)2C(OH)H | γ-rays (T < 90 °C) | (CH3)2C(OH), [CH2CH(CF3)]nH (n = 1, 2) | 31–34 |
C6H5CH2–Cl | Fe(CO)5 | C6H5CHX [CH2CH(CF3)]nY (n = 1, 2; X = Cl, H; Y = H, Cl) | 35 |
CCl4 | Fe(CO)5 | Cl3C[CH2CH(CF3)]nCl (n = 1–3) | 36 |
CCl4 | CuCl2/ICl | Cl3C[CH2CH(CF3)]nCl (n = 1–7) | 37 |
C6H5CH2–Br | Fe(CO)5 | C6H5CHX [CH2CH(CF3)]nY (n = 1, 2; X = Br, H; Y = H, Br) | 38,39 |
Br2CH–Br | Fe(CO)5 | Br2CH[CH2CH(CF3)]nBr (n = 1–3) | 40 |
CF3CBrHCH2CBr2[CH2CH(CF3)]2H | |||
Br2CH–Br | Peroxides | XCBr2[CH2CH(CF3)]nY (Y = X = H or Br; n = 1, 2) | 40 |
Br2CH–Br | Fe(CO)5 | BrCH2[CH2CH(CF3)]nBr (n = 1, 2) | 40 |
CBr4 | BPO | Br3C[CH2CH(CF3)]nBr (n = 1–3) | 41 |
CF3I | UV, 5 days | CF3[CH2CH(CF3)]nI (n = 1, 2) | 42 |
CF3I | 225 °C, 36 h | CF3[CH2CH(CF3)]nI (n = 1–3) | 42 |
CF3I | UV, various T | Normal and reverse monoadducts, few amounts of diadducts | 43 |
C6F13I | Δ, UV, Fe3+/benzoin or peroxides | C6F13[CH2CH(CH3)]nI (n = 1, 2) | 44 |
(CF3)2CFI | DTBP | (CF3)2CF[CH2CH(CH3)]nI (n = 1, 2) | 44 |
Cl3SiH | UV | Cl3Si[CH2CH(CF3)]nH (n = 1, 2) | 45 |
(C2H5O)2P(O)H | DTBP, 130 °C | (C2H5O)2P(O)(TFP)nH (n = 1–5) | 46–48 |
THF | DTBP, 140 °C | Monoadduct (48%) | 49 |
2-Me-1,3-dioxolane | Fe(CO)5 | 2,4-bis(TFP)-2-Me-dioxolane | 50 |
CH3SSCH3 | UV | CH3SCH2CH(CF3)SCH3 | 51 |
HBr | UV | CF3CH2CH2Br | 42 |
cyclopentadiene | 180 °C, 72 h |
exo![]() ![]() ![]() ![]() |
52 |
3,3,3-Trifluoropropene (CH2CH–CF3, TFP) and 2-iodoperfluoropropane ((CF3)2CF–I), and perfluorooctanoic acid (C7F15–COOH, PFOA) were kindly supplied by Great Lakes Chemical Corporation, now Chemtura (West Lafayette, USA). 2-Iodoperfluoropropane was treated with sodium thiosulfate and then distilled prior to use to remove impurities and molecular iodine. 1,1,1,3,3-Pentafluorobutane (Solkane® 365mfc, CF3–CH2–CF2–CH3) was kindly supplied by Solvay S.A. (Tavaux, France). tert-Butyl peroxypivalate in solution of isododecane (Trigonox® 25-C75, tBuOOC(O)tBu, TBPPi) (purity 75 wt.%), di-tert-butyl peroxide (Trigonox® B, DTBP) (purity 99%), and azobisisobutyronitrile (AIBN) (purity 99%) were gifts from Akzo Nobel (Châlons-sur-Marne, France). Ethylene (CH2
CH2, E) was purchased from Air Liquide (France).
Allyl acetate (CH2CH–CH2–O–CO–CH3), triethylamine (N(C2H5)3), pyridine, zinc dust, polyethylene glycol monomethylether (n = 13), thioglycolic acid (HSCH2CO2H), magnesium sulfate (MgSO4), hydrochloric acid, and sodium thiosulfate (Na2S2O3) were purchased from Sigma-Aldrich (Saint Quentin-Fallavier, France). Tert-butanol, 2-butanone, dichloromethane, pentane, all of analytical grade, were purchased from SDS (France). Deuterated acetone d6 was purchased from Euroiso-top (Grenoble, France) (purity >99.8%).
The adducts were already characterized by Kostov et al.44
Diadduct: (CF3)2CF(C3H3F3)2-I; 2-iodo-2H,3H,3H,4H,5H,5H-4,6-bis(trifluoromethyl)perfluoroheptane (normal adduct), 1-iodo-1H,1H,2H,3H,4H,4H-2,3,5-tris(trifluoromethyl) perfluorohexane (reverse adduct). b.p. = 68–71 °C/20 mm Hg.
19F NMR (CDCl3): −69.6, −70.9, −71.5, −72.9 (assigned to CF3 of both TFP (normal and reverse adducts), 6 F); −77.3, −78.5, −78.8 (t, (CF3)2, 6 F); −185.5, −187.2 (dt, C(F), 1 F).
1H NMR (CDCl3): 1.9–2.3 (m, *C–CH2–C*, 2 H); 2.3–2.7 (m, RF–CH2, 2 H); 2.6–3.2 (m, *CH(CF3)), 25% of one diastereoisomer overlapping with RF–CH2protons and 75% in the range of 2.75–3.2; negligible reverse adduct (absence of signal at 3.5, 1 H)); 4.15–4.45 (m, *CH(CF3)I, 1 H).
13C NMR (CDCl3): 130.8 (130.6), 128.0 (127.8), 125.2 (125.0), 122.4 (122.3) (q of d (coupling of two diastereoisomers), CF3 of TFP between two CH2groups in normal adduct, 1JCF = 279.7, 1 C); 128.4 (128.16), 125.66 (125.42), 122.92 (122.68), 120.18 (119.94) (q of d, CF3 adjacent to I in normal adduct, 1JCF = 276.7, 1 C); 125.04 (124.94), 122.27 (122.10), 119.39 (119.26), 116.55 (116.43), 124.79 (124.66), 121.95 (121.82), 119.11 (118.99), 116.27 (116.15) (two q of d, CF3, 1JCF = 285.7, 2JCF = 28.17, 6 C); 92.63–89.02 (d of sept, C(F), 1JCF = 207.3, 2JCF = 32.2, 1 C); 38.10, 37.8, 37.6, 37.3, 37.0, 36.7 (sext, C*H(CF3) of TFP between two CH2groups, 2JCF = 27.17, 1 C); 35.56, 33.29 (d, CH2 of TFP-I, 1 C); 27.70, 27.51, 27.29, 27.10 (two d, CH2, 2JCF = 19.1, 1 C); 19.53–18.55, 17.23–16.30 (d of q (tr/er), *CH(CF3)I, 2JCF = 29.2, 1 C).
(CF3)2CF(C3H3F3)2CH2CH(I)CH2OCOCH3; 8,9,9,9-tetrafluoro-2-iodo-4,6,8-tris(trifluoromethyl)nonyl acetate. b.p. = 78–80 °C/0.1 mm Hg
19F NMR (CDCl3): no signal at −67 (no reverse product); −70.5 to −72.77 (m, 2 × CF3 of TFP, 6 F); −77.2 to −78.75 (m, (CF3)2, 6 F); −186.4, −187.14, −187.73 (t, C(F), 1 F)
1H NMR (CDCl3): 1.6–1.9 (m, *C–CH2–*C, 2 H); 2.02–2.25 (CH3OCO, 3 H); 2.25–2.4 (CH2–CHI, 2 H); 2.3–2.5 (RF–CH2, 2 H); 2.6–3.0 (*CH(CF3), 1 H); 4.2 (m, 1 H of CH(I) + 1 H of *CH(CF3)); 4.4 (m, ester CH2OCOCH3, 2 H).
(CF3)2CFCH2CH(CF3)CH2CH(CF3)CH2CHCH2; 8,9,9,9-tetrafluoro-4,6,8-tris(trifluoromethyl)non-1-ene. b.p. = 62–65 °C/20 mmHg.
19F NMR (CDCl3): −71.7, −72.2, −72.5 (t, 2 × CF3 in TFP, 6 F); −77.7 to −78.9 (dt, (CF3)2, 6 F); −186.9, −187.4 (m, C(F), 1 F).
1H NMR (CDCl3): 1.55–2.2 (m, CH2 from *C–CH2–C*, 2 H); 2.0–2.2 (m, allylCH2, 2 H); 2.3–2.5 (m, 2 H of (CF3)2CF–CH2 + 25% of diastereoisomer *CH(CF3) from the side of (CF3)2CF–); 2.9 (m, 1 H of *CH(CF3) from the side of the allyl); 5.20 (m, CH2, 2 H); 5.7 (m, –CH
, 1 H).
13C NMR (CDCl3): 133.21 (132.89) (d, CH2CH-, 1 C); 131.76 (131.61), 128.98 (128.83), 126.20 (126.05), 123.43 (123.28) (q, CF3 of TFP on the side of (CF3)2CF–, 1JCF = 279.7, 1 C); 131.18 (131.00), 128.40 (128.22), 125.62 (125.45), 122.84 (122.67) (q, CF3 of TFP adjacent to allyl, 1JCF = 279.7, 1 C); 125.10 (125.06), 124.82 (124.79), 122.26 (122.23), 121.98 (121.95), 116.59 (116.55), 116.30 (116.26) (two qd, (CF3)2, 1JCF = 285.7, 2JCF = 28.2, 2 C); 188.29 (118.24) (d, -CH
CH2, 1 C); 92.74–88.77 (d of sept, (CF3)2CF, 1JCF = 206.25, 2JCF = 32.2, 1 C); 40.37–39.38 (qn, *CH(CF3) adjacent to (CF3)2CFCH2–, 2JCF = 25.15, 1 C); 35.85–34.68 (qn of d, *CH(CF3) adjacent to allyl, 2JCF = 27.16, 1 C); 32.78–32.75 (d, CH2 adjacent to vinyl, 1 C); 32.10, 32.08, 31.91 (t, CH2 between 2*C, 1 C); 28.94, 27.70 (two d, CH2-CF(CF3)2, 2JCF = 19.12, 1 C).
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Fig. 1 19F NMR spectrum of RF-TFP-I telomer and its derivatives (A, B, and C surfactants) recorded in CDCl3. |
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Fig. 2 1H NMR spectrum of (CF3)2CF(C3H3F3)n(CH2)3SCH2COO(CH2CH2O)nCH3Surfactant A recorded in CDCl3. |
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Fig. 3 FTIR spectra during the esterification reaction of (CF3)2CF(C3H3F3)n(CH2)3SCH2COOH with PEO–OH leading to (CF3)2CF(C3H3F3)n(CH2)3SCH2COO(CH2CH2O)nCH3 after 3 h (upper spectrum) and 8 h (lower spectrum). |
iC3F7(TFP)2CH2CH2I b.p. = 44–46 °C/0.2 mm Hg
1H NMR (acetone d6, ppm): 3.6–3.4 (m, central –CH2C*H(CF3)–, 1H); 3.4–3.1(m, –CH2CH2I, 2H); 2.8–2.7 (m, –CH2C*H(CF3)–, 1H); 2.3–2.1, centre 2.2, (m, HA, HB in AB system RF–CH2C*H–, 2H), –(C*H–CH2C*H–, 2H) and (–CH2CH2I, 2H).
19F NMR (acetone d6, ppm; Fig. 1) δ: −69.2 and −71.6 [2 × CF3 in –CH2C*H(CF3), 6F]; −78.5 (2 × CF3 end-groups, 6F); −187 (m, CF–, 1F).
13C NMR (acetone d6, ppm) d: 130.8 (130.6); 128.0 (127.8); 125.2 (125.0); 122.4 (122.3); 1JCF = 265 Hz; q (coupling of two diastereoisomers) 2 × 1C (CF3 of TFP between two CH2groups); 128.4; 125.7; 122.9; 120.1; 125.0; 122.3; 119.4; 116.3; two q of d (1JCF = 275.7 Hz; 2JCF = 28.2 Hz; 2 × 1C from terminal (CF3)2– groups); 92.6–89.0 d of hept., 1C [C(F)], 1JCF = 207.3 Hz; 2JCF = 32.2 Hz; 40.8; 40.7; 40.5; 40.3; 35.2; 34.9, 34.3; 34.1; d of q, 2JCF = 27.2 Hz, 2×1C [C*H(CF3) of TFP between two CH2groups]; 32.5; 31.8, d, 1C [–C(F)–CH2– of TFP, 2JCF = 27.1 Hz]; 29.0; 28.9; 28.7; 28.5; q, 1C (–CH2–CH2I of E); 27.0; 26.8; 26.6; t, 1C (C*–CH2–C*) 2JCF = 19.1 Hz; 0.8; 0.0; s, 1C (–CH2–I, 2 diastereoisomers).
The ethylenated TFP telomer (0.05 mol) was introduced to a 250-ml three-necked round-bottom flask equipped with a condenser and a thermometer. Pyridine or triethylamine (0.1 mol) was added dropwise in DMF or MeOH, respectively (50 mL). Then, the mixture was purged with argon for 15 min and heated up to 40 °C (or room temperature for NEt3) under stirring. After 10 h, the reaction was stopped. The crude product was cooled, and the solvent rotavaped under vacuum and then the product was precipitated from ether. RF(C3H3F3)n(CH2)2NR+I− (where NR represents a pyridinium or triethyl ammonium function) was obtained in 40–50% yield. 19F NMR spectra were similar to those of the ethylenated TFP telomers.
The objective of the present article consists in synthesizing original TFP-based surfactants by simple chemical modifications of TFP telomers,44,55,56 achieved by radical telomerization of TFP with isoperfluoropropyl iodide.44
The overall paths for the syntheses of these surfactants is described in Scheme 1. From the radical telomerization of 3,3,3-trifluoropropene (TFP), several surfactants can be obtained (anionic, cationic and non-ionic) in satisfactory yields (50% overall yields from iC3F7I). The initial step is the telomerization of 3,3,3-trifluoropropene (TFP) in the presence of perfluoroalkyl iodides ((CF3)2CFI) that was reported in patents from Great Lakes55,56 and by Kostov et al.44 The telomerization in bulk as that initiated by organic peroxides such as di-tert-butylperoxide led to TFP telomers in high yields (>80%). TFPhomopolymerization was reported to lead to poly(TFP) homopolymer but the presence of (CF3)2CFI as an efficient chain transfer agent drastically lowered DPn to achieve either monoadduct or diadduct or triadduct for a high amount of TFP in the feed. The degree of polymerization (DPn = n in (CF3)2CF–(TFP)n-I) could be tuned by the initial molar ratio [TFP]0/[((CF3)2CFI]0. The 19F NMR spectra (Fig. 1) enabled to assess DPn value from the ratio between trifluoromethyl groups of TFP units and those of the perfluoroisopropylgroup. Fig. 1 exhibits the signals of the perfluoroisopropyl end-group (two CF3 and CF centered at −77.7, −78.5, and −188.9 ppm, respectively). It also displays the signal at −72 ppm assigned to the CF3group of TFP corresponding to the normal addition of (CF3)2CF• onto TFP [(CF3)2CF–CH2CH(CF3)–] while that assigned to the reverse addition [(CF3)2CF–CH(CF3)CH2–] expected at −67 ppm was never observed, indicating a selective normal addition, at least for the first adducts.
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Scheme 1 Straightforward strategies for the preparation of 3,3,3-trifluoropropene-based cationic and non-ionic surfactants. |
The synthesis of the non-ionic surfactants was carried out in three steps. First, the preparation of RF–(TFP)x–CH2–CHCH2 allylic derivative was reported,44 and consists in the direct radical addition of RF-(TFP)x-I onto allyl acetate (Yield = 75–80%) followed by the deiododeacetalization in the presence of zinc and methanol. As for tetrafluoroethylene telomers,57 the yields were high showing a suitable electron-withdrawing effect of CHCF3group to easily generate (CF3)2CF–CH2–CH(CF3)• radical. The conversion of iodoacetate was quantitative while allylic TFP telomers were obtained 75% yield after distillation. Second, the allylic derivative was further reacted with thioglycolic acid in acetonitrile to obtain a carboxylic ω-functionalized compound (as an anionic surfactant, PFOA type). That reaction occurred either photochemically (81% yield) or in the presence of a source of radicals arising from tert-butyl peroxypivalate (73% yield). 1H NMR enabled that reaction to be monitored by the vanishing of both allyl double bond and mercaptogroups centered at 5.0–6.5 and 1.5 ppm, respectively. 19F NMR spectrum was similar to that of the precursor. Finally, the esterification with an ω-hydroxy poly(ethylene oxide) oligomer (PEO-OH) led to the formation of an original RF-(TFP)x–CH2–CH2–CH2–S–CH2–CO2–PEO non-ionic surfactant. The 1H NMR spectrum (Fig. 2) exhibits the characteristic signals centered at 4.0, 3.4, 3.3, and 3.0 assigned to the –SCH2CO2– group, ethylene oxide units, methyl end-group, and CHCF3, respectively. To ensure a complete conversion of acid into ester, the reaction was carried out in toluene and the water-toluene azeotrope was continuously distilled using a Dean–Stark apparatus at 95 °C (b.p. of water and toluene are 100 and 110 °C, respectively). The reaction was monitored by FTIR spectroscopy (Fig. 3). The vanishing of OHgroup frequency was observed at 3600 cm−1 while that at 1750 cm−1, assigned to the carbonyl of the ester, increased. The former frequency disappeared after 8 h reaction, meaning that the esterification was complete, and was confirmed visually by the absence of water-toluene azeotrope.
To obtain the series of cationic surfactants, first ethylene end-capping of the TFP telomers was achieved. This reaction, initiated by an organic peroxide, quantitatively led to RF-(TFP)x–CH2–CH2–I in 89% yield with a quantitative conversion of (CF3)2CF(TFP)nI. This successful ethylenation was evidenced by 1H, 13C and 19F NMR spectroscopy. The chemical shifts of ethylene end-groups were centered at about 29.0, 28.9, 28.7 and 28.5 ppm for –CH2–CH2–I, 8.0 and 0.0 for –CH2–I on the 13C NMR spectrum, and 2 ppm (–CH2–CH2–I) in the 1H NMR spectrum (details are given in the experimental section). The nucleophilic substitution of RF–(TFP)x–CH2–CH2–I by either triethylamine (NEt3) or pyridine (C5H5N) at room temperature or at 40 °C, respectively, led to cationic surfactants bearing ammoniumgroups (Scheme 1) in satisfactory yield (>75%) with a slight dehydroiodination (Fig. 4 and 5). These mild experimental conditions avoid any dehydroiodination.
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Fig. 4 1H NMR spectrum of (CF3)2CF(TFP)n(CH2)2NC5H5+I− (Surfactant B) recorded in acetone d6. |
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Fig. 5 Expansion of the 1H NMR spectrum (0.8 to 3.9 ppm) of (CF3)2CF(TFP)n(CH2)2N(CH2CH3)3+I− (Surfactant C) recorded in CDCl3. |
The structures of both cationic surfactants were proved by 1H NMR spectroscopy. In the 1H NMR spectrum of surfactant B (Fig. 4) the group of signals present in the 8.1 to 9.6 ppm range (with an integral ratio of 1: 0.5: 1) was assigned to the pyridinium group. In the case of surfactant C, the 1H NMR spectrum (Fig. 5) obviously does not display any signal in the 7–9 ppm range while the signal of the ethyl group of the triethylammonium are located at 1.4 (CH3) and 3.15 ppm (CH2).
Physicochemical properties of surfactants are often searched since they can be used under hostile conditions (e.g. oil wells, acidic buffers for emulsion polymerization of tetrafluoroethylene). These surfactants exhibit good overall inertness to acids and bases especially iC3F7(TFP)(CH2)3SCH2CO2(PEO)CH3, and a satisfactory solubility in water and methanol but a poor solubility in apolar solvents, and acetone (Table 2).
Media | T/°C | Time (days) | Surfactant | ||
---|---|---|---|---|---|
A | B | C | |||
(1) Base-acid resistance | Weight losses (%) | ||||
98% H2SO4 | 25 | 7 | 0.0 | <1.2 | 0.0 |
60% HNO3 | 25 | 7 | - | >40.0 | <20 |
37% HCl | 25 | 7 | 0.0 | >15.0 | 0.0 |
40% NaOH | 25 | 7 | 0.0 | 0.0 | 0.0 |
(2) Solubility in selected solvents | Solubility (g/100mL) | ||||
Water | 25 | 3 | >10 | >10 | >10 |
Methanol | 25 | 3 | >10 | >10 | >10 |
Diethyl ether | 25 | 3 | <1 | <1 | <1 |
Benzene | 25 | 3 | <2 | <2 | <2 |
Acetone | 25 | 3 | <10 | <10 | <10 |
A: |
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B: |
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C: |
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Surface tensions of the various surfactants were assessed at different concentrations to determine the critical micellar concentration (CMC) of the surfactants in water at 25 °C. The results are displayed in Fig. 6, and the CMC values were found to be 0.06, 4.10, 3.20, and 3.00 g L−1 for surfactants A, B, C, and PFOA, respectively. It can be seen that both cationic surfactants behave like PFOA while the non ionic surfactant (A) has a higher surface tension but a lower CMC.
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Fig. 6 Surface tension versus the concentration of TFP-based surfactants compared to that of PFOA. |
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