Langmuir 1996,11, 466-469
466
Syntheses of Hybrid Anionic Surfactants Containing Fluorocarbon and Hydrocarbon Chains Norio Yoshino," Katsumi Hamano, and Yota Omiya Department of I n d u s t r i a l Chemistry, Faculty of Engineering, Science University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162, J a p a n
Yukishige Kondo, Atsushi Ito, and Masahiko Abe Department of Industrial and Engineering Chemistry, Faculty of Science a n d Technology, Science University of Tokyo, Yamazaki, Noda-shi, Chiba 278, J a p a n Received J u n e 20, 1994. I n F i n a l Form: November 3, 1994@
Six new hybrid anionic surfactants containing a fluorocarbon chain and a hydrocarbon chain in a molecule,
C , F ~ , + ~ C ~ H ~ C O C H ( S O ~ N(n~= ) 4Cand ~H~ 6 ,~ m+=I2,4, and 6, and C6H4 =p-phenylene), were prepared. The compounds l-(4-iodophenyl)-l-alkanoneswere prepared from the reaction of iodobenzene with corresponding alkanoyl chlorides in the presence of aluminum chloride in carbon disulfide. The compounds l-[4-(perfluoroalkyl)phenyll-l-alkanones were synthesized from l-(4-iodophenyl)-l-alkanones with corresponding perfluoroalkyl iodides in the presence of copper bronze powder in dimethyl sulfoxide. Hybrid with a anionic surfactants were obtained from the reaction of l-[4-(perfluoroalkyl)phenyl]-l-alkanones sulfur tnoxidef 1,4-dioxane complex in 1,2-dichloroethane, followed by neutralization with aqueous sodium hydroxide. These new hybrid surfactants have the ability to lower surface tension, and they can emulsify a ternary-component system of hydrocarbodwaterfperfluoropolyether oil.
Introduction
It is well-known that fluorocarbon compounds exhibit t h e properties of water a n d oil repellency, high lubricity, thermal a n d chemical stability, a n d so on. Fluorocarbon surfactants containing a fluorocarbon chain as t h e hydrophobic group display peculiar abilities, such as thermal a n d chemical stability, high surface activity, high surface modification ability, a n d low CMC (Critical Micelle C ~ n c e n t r a t i o n ) . l - ~It was reported that extremely heterogeneous micelles were formed in solutions of fluorocarbon surfactant a n d hydrocarbon surfactant mixture.6-10 Hybrid surfactants a r e composed of a hydrocarbon chain a n d a fluorocarbon chain attached to t h e same hydrophilic head group. I n 1992, a new series hybrid anionic surfactant, such as C7F1&H(OS03Na)C,Hl5, was synthesized precedingly by Wen Guo, e t ai." However, t h e surfactants slowly hydrolyzed in air through t h e adsorption of moisture. Therefore, they h a d to be stored i n a desiccator at -25°C. They also hydrolyze slowly in aqueous solution at room temperature, thus all t h e physical measurements h a d to be made within 20 h after t h e sample preparation. I n this paper, t h e results of t h e syntheses a n d characterizations of six new hybrid anionic surfactants having both a fluorocarbon chain a n d a hydrocarbon chain with @
Abstract published inAdvanceACSAbstrmts, January 1,1995.
(1) Barnett, J. E. G. Carbon Fluorine Compounds; Ciba Found. Symp. 1972,95. (2)Blackley, E. R.;Boyer, P. D. Biochim. Biophys. Acta 1966,16, 576. (3)Di Paule, T.;Sandorf, C. Can. J. Chem. 1974,52,3612. (4)Yoshino, N.; Komine, N.; Suzuki, J.; Arima, Y.; Hirai, H. Bull. Chem. SOC.Jpn. 1991,64, 3262. (5)Shinoda, K.; Hato, M.; Hayashi, T. J.Phys. Chem. 1972,76,909. (6)Abe, M.; Yamaguchi, T.; Sibata, Y.; Uchiyama, H.; Yoshino, N.; Ogino, K.; Christian, S. D. Colloids Surf. 1992,67,29. (7) Burkitt, S. J.;Ottewill, R. H.; Hayter, J. B.; Ingram, B. T. Colloid Polym. Sci. 1987,265,628. ( 8 ) Burkitt, S. J.; Ingram, B. T.; Ottewill, R. H. B o g . Colloid Polym. Sci. 1988,76,247. (9)Funasaki, N.;Hada, S. J . Phys. Chem. 1983,87,342. (10)Mukerjee, P.; Yang, Y. S. J.Phys. Chem. 1976,80,1388. (11)Wen Guo; Zhong Li, Fung, B. M.; O'Rear, E. A.; Harwell, J. H. J . Phys. Chem. 1992,96,6738.
0743-7463f95f2411-0466$09.00/0
a n aromatic ring in a molecule a r e reported. These surfactants a r e very stable i n t h e presence of moisture. The results of t h e Krafft point, t h e surface tension, a n d t h e thermogravimetric analysis of these surfactants a r e also reported. One of t h e important characteristics of these hybrid surfactants is that a ternary-component system, hydrocarbodwaterlperfluoropolyether oil, which a r e immiscible with each other, can emulsify under ultrasonic irradiation by using a small amount of these surfactants.
Experimental Section Almost all syntheses were carried out under an atmosphere of purified nitrogen. Materials. The reagent grade butanoyl chloride (CsH,COCl), hexanoyl chloride ( C ~ H I ~ C O Cand ~ ) , octanoyl chloride (C,HISCOC1) were purchased from Tokyo Chemical Industry Co., Ltd. and used without further purification. Iodobenzene (bp 188 "C) was obtained from Tokyo Chemical Industry Co., Ltd.and purified by distillation over calciumhydride. Perfluorobutyliodide (CflgI, bp 67°C) and perfluorohexyl iodide (CeF131, bp 119°C) were donated from Daikin Industries, Ltd. and purified by distillation. The reagent grade aluminum chloride (Kanto Chemical Co., Inc.) and copper bronze powder (Aldrich Chemical Co., Inc.) were purchased and used without further purification. Sulfur trioxide (bp 45 "C) was obtained from Nakarai Tesque, Inc. and purified by distillation. The solvents[carbon disulfide (bp 46 "C),dimethyl sulfoxide (DMSO; bp 36 "C (13 Pa)), 1,2-dichloroethane (bp 83 "C), and 1,Cdioxane (bp 101 "C)]were obtained commercially and purified by distillation over calcium hydride. Other solvents (ethanol, diethyl ether, octane, chloroform) were used without further purification. Perfluoropolyether oil [Demnum S-20; F(CFZCFZCF~~),CF&F~, average molecular weight 27001 was donated from Daikin Industries, Ltd. and used without further purification. Measurements and Instruments. FT-IR spectra were measured in a liquid film or by a KBr disk method with a JEOL JIR-5300 spectrophotometer. Each spectrum was recorded at a resolution of 4 cm-1 with a total of 30 scans. Pulsed Fourier transform 300-MHz lH NMR was run in CDC13 or trifluoroacetic acid (TFA) with TMS as an internal standard using a Bruker AC-3OOD spectrometer at room temperature. The FTmode 280MHz 19FNMR was recorded at 27 "C on a Bruker AC-3OOD in CDC13 or TFA with CFC13 as an external standard. The assignments of the 19F NMR spectra were based on spectra
0 1995 American Chemical Society
Syntheses of Hybrid Anionic Surfactants
Langmuir, Vol. 11, No. 2, 1995 467
Perfluoroalkylationof l-(4-Iodophenyl)-l-alkanones.14 reported in the literature.12 Mass spectra (MS) were measured Synthesis of C4F&&COCsH7 (K'F4H3). Dispersions of (70 eV) with a Hitachi M-80A GC/MS spectrometer, and the data perfluorobutyl iodide (27.8 g, 80.5 mmol), 1-(4-iodophenyl)-lwere analyzed with a Hitachi M-003 data processing system. butanone (19.9 g, 72.7 mmol), copper bronze powder (24.8 g, 390 Gas chromatography (GLC) was performed with a Hitachi 663mmol), and DMSO (120 cm3) were heated a t 125 "C for 16 h with m, i.d. 1.2 mm, 30 (G-100 40m column, film thickness 2.0 x stirring in a two-necked 200-mL flask connected with a reflux FID) and the intensities were measured with a Hitachi D-2500 condenser and a three-way stopcock. Excess copper bronze chromatointegrator. Elemental analyses ofcarbon and hydrogen powder was removed by filtration. To the filtrate was added 50 were run with aYanaco CHN Corder MT-5, and those offluorine cm3 of water and 50 cm3of diethyl ether. After the mixture was were measured by potentiometric microdetermination. l 3 U1stirred for 5 min, the ether layer was separated. The ether layer trasonic operations were carried out using a Branson Ultrasonics was washed three times with 50 cm3 of water to remove DMSO Corp. Model 250 sonifier cell disruptor system (200 W, 20 kHz). and evaporated under reduced pressure. The product C 8 9 c 6 6 Krafft points were measured with a Rigaku 8240 type highCOC3H7 was obtained as a colorless liquid by distillation (18.0 sensitivity differential scanning calorimeter (DSC). The surface g, yield 68.3%): bp 58.5 "C (24 Pa); IR (cm-l) 1268-1136 (YC-F), tension was measured with a Kyowa Model CBVP-A3Wilhelmy1695 (YC-0);'H NMR (CDCl3) 6 1.02 (a, t, 3H), 1.80 (b, m, 2H), type surface tensiometer. The thermogravimetric analysis was 3.02 (c, t, 2H), 7.69 (m-protons from C4F9, d, 2H), 8.09 (0-protons measured with a Rigaku TG 8110 type thermogravimetric from C4F9, d, 2H) for CH3aCH2bCH~cCOC~H4C4Fg; 19F NMR analyzer. (CDC13)6 -81.6 (a, m, 3F), -112.0 (d, m, 2F), -123.3 (c, m, 2F), Acylation of Iodobenzene. Synthesisof 1-(4-Iodophen-126.2 (b, m, 2F) for CF3aCF2bCF~cCF2dC66COc3H7; MS (mlz) y1)-1-butanone. To a dispersion of anhydrous aluminum (re1 intens) 366 (9) [MI+, 323 (100) [M - C3H71+,295 (4) [M chloride (31.0 g, 232 mmol) in carbon disulfide (100 cm3) was COC3H7]+, 147(27) [M - C4Fgl+. Elemental analysis for added butanoyl chloride (24.8 g, 232 mmol) slowly with stirring C14HllOF9: Found C, 45.8; H, 2.97, F 46.8. Calcd C, 45.9; H, over 1h at 0 "C in a three-necked 500-mL flask connected with 3.03, F 46.7. a reflux condenser and two dropping funnels. To this system Syntheses of C4FeC&COCsH11 (K-F~Hs),C4FsCeH4was added iodobenzene (47.5 g, 233 mmol) slowly a t 0 "C over COC7H15 (K-F4H7), C & ' I ~ C & C O C ~ H(K-FeHs), ~ c&'13c&' 2 hwith stirring. The reaction system was refluxed with stirring COCsHll (K-Fae), and C ~ $ ~ ~ C & C O C ~ H(K-FaH7). IS Syna t 46 "C for 16 h. After the reaction mixture was poured into thetic methods and purification techniques were virtually the same as those for the preparation of K-F4H3. lOO-cm3of ice-cooled water, 25 cm3of concentrated hydrochloric acid was added to the system, and the resultant mixture was K-F4Hs: colorless liquid, yield 66.3%, bp 72.5 "C (27 Pa); IR washed well with water. The organic layer was washed with (cm-1) 1263-1134 ( Y C - F ) , 1693 (YC=O); 'H NMR (CDC13) 6 0.91 10% sodium thiosulfate aqueous solution (100 cm3) and again (a, t, 3H), 1.34 (b and c, m, 4H), 1.77 (d, m, 2H), 2.98 (e, t, 2H), 7.69 (m-protons from C4F9, d, 2H), 8.11 (o-protons from C4F9, d, washed well with water. The compound 1-(4-iodophenyl)-l2H) for C H ~ " C H Z ~ C H ~ ~ C H ~ ~ C H ~ ~19F C NMR O C ~ (CDC13) H~C~F~; butanone was obtained as a white solid by fractional distillation 6 -81.6 (a, m, 3F), -112.0 (d, m, 2F), -123.3 (c, m, 2F), -126.2 (yield 44.1 g, 69.3%): bp 94 "C (40 Pa), mp 58.5 "C; IR (cm-l) (b, m, 2F) for CF3aCF2bCFzcCFzdC6H4COC5H1~; MS (mlz) re1 1676 (vc-0); lH NMR (CDC13) 6 1.00 (a, t, 3H), 1.76 (b, m, 2H), intens) 397 (17) [MI+, 323 (100) [M - CsHlll+, 295 (5) [M 2.88 (c, t, 2H), 7.68 (m-protonsfrom iodine, d, 2H), 7.84 (0-protons COC5Hlll+, 175 (12) [M - C4FgI+. Elemental analysis for from iodine, d, 2H) for CH3aCH2bCH2CCOC6H41; MS, mlz (re1 C16H150Fg: Found C, 48.8; H, 3.88; F, 43.5. Calcd C, 48.7; H, intens) 274 (6) [MI+, 231 (100) [M - C3H71f, 203 (24) [M 3.83; F, 43.4. COC3H7]+, 147 (35) [M - I]+, 104 (14) [M - C3H7 - I]+, 76 (48) K-F4H7: colorless liquid, yield 50.0%, bp 72.2 "C (20 Pa); IR [M - COC3H7 - I]+. Elemental analysis for CloH11OI: Found (cm-1) 1267-1136 (YC-F), 1693 (YC=O); 'H NMR (CDC13) 6 0.86 C, 43.5; H, 3.87. Calcd C, 43.8; H, 4.05. (a, t, 3H), 1.32 (b-e, m, 8H), 1.78 (f, m, 2H), 2.99 (g, t, 2H), 7.69 Syntheses of l-(4-Iodophenyl)-l-hexanoneand 1-(4(m-protons from C4F9, d, 2H), 8.11 (0-protons from C4F9, d, 2H) 1odophenyl)-1-octanone.Synthetic methods and purification for CH3aCH2bCHzCCH2dCHzeCH2fCH2pCOC6H&4Fg;19F NMR techniques were virtually the same as those for the preparation (CDCl3)6 -81.7 (a, m, 3F), -112.1 (d, m, 2F), -123.3 (c, m, 2F), of 1-(4-iodophenyl)-l-butanone. -126.2 (b, m, 2F) for CF3aCF2bCFzcCF~dC6H4COC7H15; MS (mlz) The compound 1-(4-iodophenyl)-l-hexanone was obtained by (re1 intens) 422 (19) [MI+, 338 (100) [M - CsH~zl+, 323 (74) [M the reaction of hexanoyl chloride (25.6g, 190mmol), iodobenzene - C7H151+, 295 (4) [M - COC7Hi51+, 203 (10) [M - C4Fgl+. (37.3 g, 183 mmol), and aluminum chloride (24.6 g, 183 mmol) Elemental analysis for CleH190Fg: Found C, 51.1; H, 5.48; F, in 80 cm3 of carbon disulfide at 46 "C for 16 h. A white solid 40.2. Calcd C, 51.2; H, 5.53; F, 40.5. product (40.3 g, yield 73.2%) was obtained: bp 83.5 "C (25 Pa), K.F&: white solid, yield 86.1%, bp 88.5"C (49 Pa), mp 36.6 mp 62.4 "C; IR (cm-l) 1674 (vc-0); 'H NMR (CDCl3) 6 0.90 (a, "C; IR (cm-l) 1290-1145 (YC-F), 1691 (YC=O); 'H NMR (CDCld t,3H),1.30-1.42(bandc,m,4H),1.73(d,m,2H),2.93(e,t,2H), 6 1.02 (a, t, 3H), 1.78 (b, m, 2H), 2.99 (c, t, 2H), 7.70 (m-protons 7.68 (m-protons from iodine, d, 2H), 7.84 (o-protons from iodine, from C6F13, d, 2H), 8.09 (o-protons from C6F13, d, 2H) for d, 2H) for CH3aCH~bCH2cCH2dCHzeCOCsH41; MS (mlz)(re1intens) CH3aCH2bCH2CCOCsH4C6F13; 19F NMR (CDC13) 6 -81.5 (a, m, 302 (4) [MI+,231 (100) [M - CsHiil+, 203 (27) [M - COC5Hiil+, 3F),-111.6(f,m,2F),-122.0(e,m,2F),-122.4(d,m,2F),-123.4 175 (9) [M - I]+, 104 (16)[M - C5Hii - I]+,76 (55) [M - COC5Hii (c, m, 2F), -126.2 (b, m, 2F) for CF3*CFzbCFzCCFzdCFzeCFzfCsH4- I]+. Elemental analysis for C12H150I: Found C, 47.5; H, 5.13. COC3H7;MS (mlz)(re1intens) 466 (2)[MI+,423 (100)[M - C3H71+, 147 (30)[M - C6F131f. Elemental analysis for C16HllOF13: Found Calcd C, 47.7; H, 5.00. C, 41.0; H, 2.30; F, 52.7. Calcd C, 41.2; H, 2.38; F, 53.0. The compound l-(4-iodophenyl)-l-octanonewas obtained by K-F&: white solid, yield 70.1%, bp 86.5"C (21 Pa), mp 43.5 the reaction of octanoyl chloride (24.7g, 152 mmol), iodobenzene "C; IR (cm-l) 1294-1145 (YC-F), 1689 (YC=O); 'H NMR (CDC13) (31.7 g, 155 mmol), and aluminum chloride (20.1 g, 150 mmol) 6 0.91 (a, t, 3H), 1.34 (b-e, m, 4H), 1.77 (d, m, 2H), 3.01 (e, t, 2H), in 64 cm3 of carbon disulfide a t 46 "C for 16 h. A white solid 7.70 (m-protons from C6F13, d, 2H), 8.10 (0-protons from C6F13, product (35.7 g, yield 71.9%) was obtained: bp 113.5 "C (39 Pa), d, 2H) for CH3aCH2bCH2CCH2dCH2ecoc6H4c6F13; 19F NMR mp 64.0 "C; IR (cm-l) 1678 (YC=O); 'H NMR (CDCl3) 6 0.86 (a, (CDC13)6 -81.5 (a, m, 3F), -111.6 (f, m, 2F), -122.0 (e, m, 2F), t, 3H), 1.23-1.43 (b-e, m, 8H), 1.73 (f, m, 2H), 2.91 (g, t, 2H), -122.4 (d, m, 2F), -123.4 (c, m, 2F), -126.6 (b, m, 2F) for 7.67 (m-protons from iodine, d, 2H), 7.81 (0-protons from iodine, CF3aCFzbCF2cCFzdCFzeCF~fC6H4COCsH11; MS (mlz)(re1intens) d, 2H) for CH3aCHzbCH2cCHzdCHzeCH~fCH~gCOC6H41; MS ( m / z ) 494 (4) [MI+, 423 (100) [M - CsHiil+, 175 (18) [M - CsFi31+. (re1 intens) 330 (21) [MI+, 246 (100) [M - CsH131+,231 (88) [M Elemental analysis for C18H150F13: Found C, 43.7; H, 2.97; F, - C7HI5]+,203 (23) [M - COC7H15 or M - I]+, 104 (17) [M 49.8. Calcd C, 43.7; H, 3.06; F, 50.0. C7H15 - I]+, 76 (50) [M - COC7H15 - I]+. Elemental analysis K-F&: white solid, yield 67.0%, bp 102 "C (27 Pa), mp 49.7 Calcd C, 50.9; H, 5.80. for C14H1901: Found C, 50.9; H, 5.75. "C; IR (cm-l) 1288-1147 ( Y C - F ) , 1687 (~4); 'H NMR (CDC13) 6 0.91 (a, t, 3H), 1.35 (b-e, m, 8H), 1.79 (f, m, 2H), 3.01 (g, t, 2H), (12) Kushida, K.; Watanabe, A. Proton and Fluorine Nuclear Magnetic 7.72 (m-protons from C6F13, d, 2H), 8.11 (0-protons from C6F13, Resonance Spectral Data 1988 Edition; Varian Instruments Ltd. and Japan Halon Co., Ltd.: Tokyo Japan, 1988. (13) Hozumi, K.; Akimoto, N. Jpn. Anal. 1971,20,467.
(14) McLoughlin, V. C. R.; Thrower, J . Tetrahedron, 1969,25,5921.
Yoshino et al.
468 Langmuir, Vol. 11,No.2, 1995
Scheme 1 d, 2H) for CH3aCHzbCH~CCHzdCHzecHzfCHzgCOCsH4C6F13; l9F NMR (CDCl3) 6 -81.5 (a, m, 3F), -111.3 (f, m, 2F), -122.0 (e, RCH2COCl 1 0 CO-CH2R m, 2F), -122.4 (d, m, 2F), -123.4 (c, m, 2F), -126.7 (b, m, 2F) for CF3aCFzbCFzcCFzdCFzeCF~fC6H4COC7H15; MS (mlz)(re1 intens) 522 (4) [MI+,38 (100) [M - CsHizI+,423 (83) [M - C7Hi51+, 203 (13) [M - C,$'13]+. Elemental analysis for CzoH190F13: Found Iul * Rf CO-CH2R Cu I DMSO C, 46.1; H, 3.62; F, 47.0. Calcd C, 46.0; H, 3.67; F, 47.3. Syntheses of Hybrid Surfactants. Synthesis of C4FBSO3:l,4-Dioxanc C&-COCH(SOsNa)CzHa ( F a & The complex, SO$1,4-diw Rf CO-CH(SO3H)R oxane, was prepared in advance as follows:161,4-Dioxane (2.02 CHzClCH&l g, 22.9 mmol) was added slowly to a solution of sulfur trioxide (1.87 g, 23.4 mmol) in 6 cm3 of 1,2-dichloroethane at 0 "C with NaOHaq t Rf CO-CH(S03Na)R stirring. The complex was formed as a white precipitate in 1,2dichloroethane. A solution of K-F4H3 (7.33 g, 20.0 mmol) in 15 cm3 of 1,2-dichloroethane was added to the complex system at Rf = C4Fg- and C6F13-;R = C2H5-, C,H9-, and C6H,,0 "C with stirring over 30 min.16 After stirring for 3 h a t room temperature, C4FgC6H4COCH(S03H)CzH5(not isolated) was extracted twice or more with 50 cm3 of water. The water layer was neutralized with aqueous sodium hydroxide (0.5 M, 1 M = m=6 m=4 n m=2 1 mol dm-3) and dried completely. The directing hybrid surfactant F a 2 was obtained as a white solid (5.09 g, yield 54.3%) 20 '0 4 '0 by extracting it with hot ethanol: IR (cm-l) 1365-1138 (YC-F), 15 48 6
