First Amphiphilic Poly(Vinylidene Fluoride-co- Controlled by Xanthate.

Transcription

1 First Amphiphilic Poly(Vinylidene Fluoride-co- 3,3,3-Trifluoropropene)-b-ligo(Vinyl Alcohol) Block opolymers as Potential Non-Persistent Fluorosurfactants from Radical Polymerization ontrolled by Xanthate. Georgi Kostov 1, Frédéric Boschet 1, Jens Buller 1, Leila Badache 1,2, tephan Brandsadter 3, and Bruno Ameduri 1* 1 Institut harles Gerhardt, Ingénierie et Architectures Macromoléculaires, UMR NR 5253, Ecole Nationale upérieure de himie de Montpellier, 8 Rue de l'ecole Normale, Montpellier, France 2 Laboratoire de ynthèse rganique; Faculté de himie; Université des ciences et de la Technologie Houari Boumediène, B.P. 32, Bab-Ezzouar- Alger -ALGERIE 3 hemtura, 1801 U.. Highway 52 West, West Lafayette, Indiana , UA upporting Information

2 Radical copolymerization of vinylidene fluoride (VDF) and 3,3,3-trifluoropropene (TFP) as the first block (Run #5 in Table 1) The autoclave was filled under vacuum with the fluorinated xanthate (19.7 g, mole) and TBPPi as the initiator (2.5 g, mole) both dissolved in 1,1,1,3,3-pentafluorobutane (80 ml). The reactor was cooled in an acetone / liquid nitrogen bath to condense TFP (13.0 g, mole) and VDF (16.0 g, mole) under weight control. The reactor was heated to 75 and the evolution of pressure and temperature were recorded. An increase of the pressure up to 23 bars followed by a small decrease to 15 bars could be observed. The reaction was stopped after 48 h, cooled to room temperature and then placed in an ice bath. After purging the unreacted monomer, the conversion of gases was determined by double weighing (27 %). After opening the autoclave, the solvent was completely removed under reduced pressure. The product showed no precipitate in chilled pentane. The product was dried under vacuum (10-2 bar, 40 ) and characterized by 1 H and 19 F NMR. The calculated yield was 47 %. 1 H NMR (Dl 3 ) δ (ppm): 1.23 (d, 3 J HH = 8.5 Hz, H 3 H 2, 3H); 1.43 (t, 3 J HH = 7.0 Hz, H 3, 3H); 2.08 ( of TFP, 4H); 2.38 (tt, 3 J HF = Hz, 3 J HH = 6.42 Hz, 6 F 13, 2H); 2.75 ( of VDF, 1H); 3.98 (t, 3 J HH = 6.50 Hz, H 3, 2H); 4.6 (m, H of TFP, 1H); 19 F NMR (Dl 3 ) δ (ppm): (m, F 3 F 2 (F 2 ) 4 -, 2F); (s, F 3 (F 2 ) 3 F 2 F 2-2F); (m, F 3 F 2 F 2 (F 2 ) 3 -, 2F); (s, F 3 (F 2 ) 4 F 2 -, 2F); (s, F 3 (F 2 ) 5 -, 3F); -69 to -72 (m, F 3 of TFP, and F 2 of VDF, 5F); (m, F 3 of TFP, 3F) Polymerization of VAc in the presence of poly(vdf-co-tfp)-xanthate as a second block (Run #14 in Table 2) The product of the first step (6.0 g, mole) was dissolved in 4 F 5 H 5 (50 ml) and charged into a two necked round bottom flask without further purification. According to the

3 number of TFP units, 8 equivalents of VAc were added (5.16 g, mole).the solution was then purged under argon for 15 minutes and heated to 75. Then, the TBPPi initiator (0.11 g, mole, 1%) was added under stirring. After 24 h, the reaction was stopped, and the solution was cooled to room temperature. The solvent was evaporated and the mixture precipitated in chilled pentane. After removing pentane, and drying under vacuum (10-2 bar, 40 ), the product (Yield = 43 wt %) was analyzed by 1 H and 19 F NMR. 1 H NMR (Dl 3 ) δ (ppm): 1.2 (d, 3 J HH = 8.5 Hz, H 3, 3H); 1.4 (t, 3 J HH = 7.0 Hz, H 3 of xanthate, 3H); 2.08 (m, 4H); 2.4 (tt, 3 J HF = Hz, 3 J HH = 6.42 Hz, 2H); 2.8 (m, of TFP and VDF, 2H); 4.0 (t, 3 J HH = 6.50 Hz,, H 3, 2H); 4.6 (m, H of TFP and VAc 5H); 4.8 (m, R F -, 2H); 19 F NMR (Dl 3 ) δ (ppm): (s, F 3 F 2 (F 2 ) 4 -, 2F); and (s, F 3 F 2 (F 2 ) 2 (F 2 ) 2 -, 4F); (s, 5 F 11 F 2 -, 2F); (s, F 3 (F 2 ) 5 -, 3F); (m, - F 2 -, 2F); (m,f 3 of TFP, 1F) Hydrolysis of PVAc (Run # 63 in Table 2) In a 250 ml two necked round bottom flask equipped with a magnetic stirring bar, condenser and rubber septum, PVAc bearing a xanthate 9 (4 g) was dissolved in ethanol (150 ml). The mixture was gently purged with nitrogen, then water (3g) and 4 (1 ml) were added. The solution was stirred for 3 days and the reaction was monitored by FTIR spectroscopy at regular intervals (12 h, 24 h, 36 h, 48 h, and 72 h.) The reaction was stopped, the solvent was evaporated and the product was dried under vacuum (10-2 bar, 40 ) and a yield of 60 % was obtained. FTIR (cm -1 ): 3434 (broad, -H), 1042 (s, -F), 995 (s)

4 Description of figure 1: The 1 H NMR spectrum (Error! Reference source not found. in main manuscript) shows the characteristic signals for both methyl groups as a triplet and a doublet centered at 1.40 ppm (f) and 1.56 ppm (c), respectively. The corresponding signal for c in the first step is high field shifted, due to the absence of the adjacent electron withdrawing bromine substituent. The triplet of triplets centered at 2.40 ppm shows the same coupling pattern as the corresponding proton a in the first step. The triplet at 3.98 ppm is assigned to protons e while the quartet centered at 4.39 ppm is typical of methyne proton d. The signals for the non equivalent protons b adjacent to the thioester may be found at the high shift of 4.61 ppm or 4.64 ppm, respectively. They show the characteristic doublet of doublets. Figure 1. 1 H NMR spectrum (recorded in Dl 3 ) of fluorinated ester 7

5 Figure F NMR spectrum (recorded in Dl 3 ) of fluorinated ester 7 and xanthate 9

6 g' GKJ-105HMF-Dl3 a-f 6 F 13 H H 3 H F 3 H F 3 h F 2 H 3 g, g' h g a h f e d c b Figure F NMR spectrum (recorded in Dl 3 ) of poly(vdf-co-tfp) fluorinated block, initiated by 5-bis(tert-butylperoxy)-2,5-dimethylhexane (Run#15 in Table 2).

7 6 F 13 a b c H H 3 d e f H F 3 g k H F 3 l F 2 m n H 3 X GKJ-105HMF-Dl3 m l+e+g n b d traces of xanthate c+f+k a Figure 4. 1 H NMR spectrum (recorded in Dl 3 ) of poly(vdf-co-tfp) fluorinated block, initiated by 5-bis(tert-butylperoxy)-2,5-dimethylhexane (Run#15 in Table 2).