supplemental information co-oligomeric surfactant … s10: electron impact (ei) quadrople mass...
TRANSCRIPT
Supplemental Information
A new oligo(hexafluoropropylene oxide)-b-oligo(ethylene oxide) block co-oligomeric surfactant obtained by radical reactions
Jiří Lapčík 1,2, Olinda Gimello2, Vincent Ladmiral2, Bruno Ameduri2*, and Chadron Mark Friesen3*
1Department of Organic Chemistry, Institute of Chemical Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic, 2Ingenierie et Architectures Macromoleculaires, Institut Charles Gerhardt, Ecole Nationale Superieure de Chimie de Montpellier (UMR5253-CNRS), 8, rue de l’Ecole Normale, 34296 Montpellier Cedex 1, France; 3Department of Chemistry, Trinity Western University, Langley, British Columbia, V2Y 1Y1, Canada
E-Mail: [email protected]
Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2014
Supporting Information S2
Table of Contents
Figure S1: 1H-NMR spectrum of Allyl-PEG-OCH3..........................................................................................4Figure S2: 13C-NMR spectrum of Allyl-PEG-OCH3. ........................................................................................5Figure S3: 1H-NMR spectrum of C6F13CH2CHICH2OH initiated by TBPPI.......................................................6Figure S4. 1H-NMR spectrum of allyl alcohol (CH2=CHCH2OH). ...................................................................7Figure S5: 19F-NMR spectrum of C6F13CH2CHICH2OH initiated by TBPPI. .....................................................8Figure S6: 19F-NMR spectrum of 1-iodo-perfluorohexane (C6F13I)...............................................................9Figure S7: 13C-NMR spectrum of C6F13CH2CHICH2OH initiated by TBPPI....................................................10Figure S8: 13C-NMR spectrum of 1-iodo-perfluorohexane (C6F13I). ...........................................................11Figure S9: 13C-NMR spectrum of allyl alcohol (CH2=CHCH2OH). ................................................................12Figure S10: Electron Impact (EI) Quadrople Mass Spectrum of C6F13CH2CHICH2OH..................................13Figure S11: 1H-NMR spectrum of C6F13CH2CHICH2O(CH2CH2O)9.5CH3 (37.4% purity). ................................14Figure S12: 19F-NMR spectrum of C6F13CH2CHICH2O(CH2CH2O)9.5CH3 ........................................................15Figure S13: 13C-NMR spectrum of C6F13CH2CHICH2O(CH2CH2O)9.5CH3........................................................16Figure S14. Gas Chromatography/mass spectrometry of the reaction of C6F13I with BPO. (A) Chromatograpy of products, (B) Mass Spectrum of C6F13PhI where 126, 253, and 522 m/z are PhCF2+, IPhCF2+, and C6F13PhI, respectively.............................................................................................................17Figure S15: Electron Impact (EI) Quadrople Mass Spectrum of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane (F[CF(CF3)CF2O]8.9CF(CF3)CF2I). ............................................................................18Figure S16: Electron Impact (EI) Quadrople Mass Spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2OH.....................................................................................................................................................................19Figure S17: 1H-NMR spectrum of F[CF(CF3)CF2O]9.6CF(CF3)CF2CH2CHICH2OH initiated by TBPPI. ..............20Figure S18: 1H-NMR spectrum of F[CF(CF3)CF2O]8.9 CF(CF3)CF2CH2CHICH2OH initiated by AIBN. ..............21Figure S19: 19F-NMR spectrum of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane(F[CF(CF3)CF2O]8.9CF(CF3)CF2I). .............................................................................22Figure S20: 19F-NMR spectrum of F[CF(CF3)CF2O]8.9 CF(CF3)CF2CH2CHICH2OH initiated by TBPPI. ............23Figure S21: 13C-NMR spectrum of F[CF(CF3)CF2O]8.9 CF(CF3)CF2CH2CHICH2OH initiated by TBPPI. ............24Figure S22: 13C-NMR spectrum of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane(F[CF(CF3)CF2O]8.9CF(CF3)CF2I). .............................................................................25Figure S23: Negative Mode, Atmospheric pressure Solids Analysis Probe (ASAP) mass spectrum (MS) of 1-iodo-2-oligo(hexafluoropropylene oxide) perfluoropropane (F[CF(CF3)CF2O]8.9CF(CF3)CF2I)..................26Figure S24: Matrix assisted laser desorption ionization-time-of-flight mass spectrum (MALDI-TOF-MS) of 1-iodo-2-oligo(hexafluoropropylene oxide) perfluoropropane (F[CF(CF3)CF2O]8.9-CF(CF3)CF2I).................27Figure S25: Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrum (MS) of F[CF(CF3)CF2O]8.9 CF(CF3)CF2CH2CHICH2OH initiated by TBPPI................................................................................................28Figure S26. Matrix assisted laser desorption ionization (Positive ion mode)-time of flight- mass spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2OH (using as matrix DCTB and LiCl as the cationizing agent) ....29Figure S27: 1H-NMR spectrum of the reaction of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane(F[CF(CF3)CF2O]8.9CF(CF3)CF2I)with benzoyl peroxide initiated by BPO................30
Supporting Information S3
Figure S28: 1H-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by AIBN............................................................................................................................................................31Figure S29: 19F-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by BPO. ............................................................................................................................................................32Figure S30: 13C-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by AIBN............................................................................................................................................................33Figure S31: Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrum (MS) of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by BPO................................................34Figure S32: Matrix assisted laser desorption ionization-time-of-flight mass spectrum (MALDI-TOF-MS) of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by BPO................................................35Figure S33. Comparison of the 19F-NMR expansions of the reaction C6F13I with the initiator (TBPPi, AIBN, BPO) and initiator with allyl alcohol. ..........................................................................................................36Figure S34. Comparison of the 19F-NMR expansions of the reaction of C6F13I with the initiator (TBPPi, AIBN, BPO) and initiator with ally-O-PEG-OCH3..........................................................................................37Figure S35. Comparison of the 19F-NMR expansions of the reaction of oligo(HFPO)-CF(CF3)CF2I with the initiator (TBPPi, AIBN, BPO) and initiator with ally-O-PEG-OCH3................................................................38Figure S36: 13C-NMR spectrum , Attached Proton Test (APT), of 1-iodo-2-methyl-3-[2-(poly(hexafluoro-propylene oxide) perfluoropropyl]-propane. A side reaction of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane (F[CF(CF3)CF2O]8.9CF(CF3)CF2I) with TBPPI. ..........................................................39Figure S37: Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrum (MS) of 1-iodo-2-methyl-3-[2-(poly(hexafluoropropylene oxide)perfluoropropyl]-propane, side reaction of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane (F[CF(CF3)CF2O]8.9CF(CF3)CF2I) with TBPPI. ..............40Figure S38: 1H-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CH2CH2O(CH2CH2O)9.5CH3.....................41Figure S39: 19F-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CH2CH2O(CH2CH2O)9.5CH3. ...................42Figure S40: 13C-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CH2CH2O(CH2CH2O)9.5CH3 ...................43Figure S41. Positive mode atmospheric pressure solids analysis probe (ASAP) mass spectrum (MS) of oligo(HFPO)-CH2CH2CH2-oligo(PEG)............................................................................................................44Figure S42. Positive ion mode MALDI-TOF-MS spectrum of oligo(HFPO)-CF2CH2CH2CH2-oligo(PEG) (using as matrix DCTB and LiCl as the cationizing agent), 1807 m/z is x =8 and y = 5. The insert expansion m/z between 1850 and 2100 displays 166 m/z-repeat unit for HFPO [CF(CF3)CF2O] and 44 m/z-repeat unit of ethylene oxide (CH2CH2O). .........................................................................................................................45Figure S43: Surface Tension measurement of ammonium perfluorooctanoate (C7F15C(O)O-NH4
+), CMC = 3.77 g/L. ......................................................................................................................................................46Figure S44: Positive mode atmospheric pressure solids analysis probe (ASAP)-time-of-flight-mass spectrum (MS) of oligo(HFPO)-CH2CH2CH2OH, in trifluorotoluene. ...........................................................47Figure S45: Negative ion mode MALDI-TOF-MS spectrum of oligo(HFPO)- CH2CH2CH2OH, in trifluorotoluene (using as matrix DCTB and LiCl as the cationizing agent).................................................48
Supporting Information S4
6.0 5.5 5.0 4.5 4.0 3.5Chemical Shift (ppm)
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
OO
8.5
Ha
Hb
Hc
HaHb
Hc
1 2
3O
4
56
1
6
54
2-3
Figure S1: 1H-NMR spectrum of Allyl-PEG-OCH3.
1H NMR (400 MHz, C6D6, 25°C) = 5.85 (ddt, CHaHb=CHcCH2-, 3JHcHb(trans)=17.34 Hz, 3J HcHa(cis)=10.36 Hz, 3JHcH(CH2)=5.81 Hz, 1H), 5.20 (ddt, CHaHb=CHcCH2-, 2JHbHa=1.77 Hz, 3JHbHc(trans)=17.18 Hz, 4JHbH(CH2)=1.77 Hz, 1H), 5.11 (dm, CHaHb=CHcCH2-,3JHaHc(cis)=10.36 Hz, 1H), 3.96 (dm, CHaHb=CHcCH2O-, 3JH(CH2)Hc=5.56 Hz, 2H), 3.53 (t, -OCH2CH2OCH3, 3JHH=5.5 Hz, 2H), 3.55-3.61 (m,- CH2O-, 19 X 2H), 3.31 (s, -OCH3, 4JHH=0.72 Hz, 3H), 3.48 (t, -CH2OCH3, 3JHH=5.5 Hz, 2H).
Supporting Information S5
144 136 128 120 112 104 96 88 80 72 64 56 48Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
C6D62 1 8
4-6
3&7
OO
8.51
2
3
O
4
58
6
7
Figure S2: 13C-NMR spectrum of Allyl-PEG-OCH3.
13C NMR (101 MHz, C6D6, 25°C) = 135.97 (s, 1C, –CH=), 116.0 (s, 1C, =CH2), 72.07 (s, 1C, CH2-allyl), 72.07 (s, 1C, CH2–CH2–OMe), 70.74 (s, 19 X 1C, -CH2–O), 58.65 (s, 1C, CH3).
Supporting Information S6
4.0 3.5 3.0 2.5Chemical Shift (ppm)
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
F2C
CF2
F2C
CF2
F2C OH
I
F3CHd
HeHaHb
Hc
Hc
*
Hd
EtOH
He
HaHb
-OH
Figure S3: 1H-NMR spectrum of C6F13CH2CHICH2OH initiated by TBPPI.
1H NMR (400 MHz, CDCl3, 25°C): = 4.31 (quin, -CH2CHICH2OH, 3JHH=6.57 Hz, 1H), 3.80, 3.74 (-CH2CHICHaHbOH, 2JHaHb=12.13 Hz, 1H), 3.78, 3.73(d, -CH2CHICHaHbOH, 2JHbHa=12.13 Hz, 1H) 3.01 (m, -CF2CHaHbCHI-, 1H), 2.65 (m, -CF2CHaHbCHI-, 1H), 2.95(-CH2OH, 1H).
Supporting Information S7
6.5 6.0 5.5 5.0 4.5 4.0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
OHHa
Hb
Hc
Hc
Hb
Hc
1
2
2
1
Figure S4. 1H-NMR spectrum of allyl alcohol (CH2=CHCH2OH).
1H NMR (400 MHz, Neat, 25°C) = 6.10 (ddt, CHaHb=CHcCH2-, 3JHcHb(trans)=16.84 Hz, 3J HcHa(cis)=10.61 Hz, 3JHcH(CH2)=5.05 Hz, 1H), 5.44 (broad, -OH, 1H), 4.22 (dt, CHaHb=CHcCH2O-, 3JH(CH2)Hc=5.31 Hz, 4JH(CH2)H(a+b) = 1.52 Hz, 2H), 5.41 (ddt, CHaHb=CHcCH2-, 2JHbHa=1.77 Hz, 3JHbHc(trans)=17.20 Hz, 4JHbH(CH2)=1.77 Hz, 1H), 5.24 (ddt, CHaHb=CHcCH2-,2JHaHb=1.52, 3JHaHc(cis)=10.54 Hz, 4JHaH(CH2)=1.52, 1H).
Supporting Information S8
-75 -80 -85 -90 -95 -100 -105 -110 -115 -120 -125 -130Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
F2C
CF2
F2C
CF2
F2C OH
I
F3C
6 4 2
5 3 16
1
5
4
32
Figure S5: 19F-NMR spectrum of C6F13CH2CHICH2OH initiated by TBPPI.
19F NMR (376.41 MHz, CDCl3, 25°C): = -81.06 ( CF3-, 3JFF=10.33, 4JFF=2.30 Hz, 3F), -126.36(m, CF3CF2(CF2)4CH2-, 2F), -123.77(m, -CF2(CF2)3CH2-, 2F), -123.05 (m, -CF2(CF2)2CH2-, 2F), -121.97(m, -CF2CF 2CH2-, 2F), -113.17, -114.20 (dm, 2JFF =144.68 Hz, 2F).
Supporting Information S9
-55 -60 -65 -70 -75 -80 -85 -90 -95 -100 -105 -110 -115 -120 -125Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
F3CCF2
F2C
CF2
F2C
CF2
I
1
2
3
4
5
6
1
6
3 4
5
2
Figure S6: 19F-NMR spectrum of 1-iodo-perfluorohexane (C6F13I).
19F NMR (376.41 MHz, neat, 25°C): = -59.19(m, CF2I, 2F), -80.19(tm, CF3-, 3JFF =9.4 Hz, 3F), -126.19(m, CF3CF2(CF2)4I, 2F), -122.79(m, -CF2(CF2)3I, 2F), -121.17 (m, -CF2(CF2)2I, 2F), -113.17(m, -CF2CF 2I, 2F)
Supporting Information S10
120 112 104 96 88 80 72 64 56 48 40 32 24Chemical Shift (ppm)
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
F2C
CF2
F2C
CF2
F2C OH
I
F3C
1 3 52 4 6 7 8 9
1&6 2-5
CDCl3
9
7
8
Figure S7: 13C-NMR spectrum of C6F13CH2CHICH2OH initiated by TBPPI.
13C NMR (101 MHz, CDCl3, 25°C) = 118.49 (qt, CF3CF2- 1JCF=288.34 Hz, 2JCF= 33.66 Hz), 117.70 (tt, -CF2CF2CH2-, 1JCF=257.61 Hz, 2JCF = 32.20 Hz), 110.87 (m, -CF2CF2CF2-, 4C), 67.78 (s, -CH2OH, 1C), 37.18 (t, -CF2CH2CHI-, 2JCF = 20.49 Hz, 1C), 20.4 (s, -CH2CHICH2OH, 1C).
Supporting Information S11
130 125 120 115 110 105 100 95 90 85Chemical Shift (ppm)
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
F3CCF2
F2C
CF2
F2C
CF2
I
1
2
3
4
5
6
C6D6
1
6
2-5
Figure S8: 13C-NMR spectrum of 1-iodo-perfluorohexane (C6F13I).
13C NMR (101 MHz, C6D6 capillary, 25°C) = 117.03 (qt, CF3CF2-, 1JCF = 287.61 Hz, 2JCF = 32.93 Hz, 1C), 110.01 (tquin, -CF2CF2CF2-, 1JCF = 275.17 Hz, 2JCF = 32.93 Hz, 1C), 109.82( tsext, CF3CF2CF2-, 1JCF = 277.37 Hz, 2JCF = 33.67 Hz, 1C), 108.49 (tquin, -CF2CF2CF2-, 1JCF = 270.78 Hz, 2JCF = 33.66 Hz, 1C), 108.36 (tquin, -CF2CF2CF2-, 1JCF = 265.66 Hz, 2JCF = 32.20 Hz, 1C), 92.97 (tt, ICF2CF2-, 1JCF = 320.54 Hz, 2JCF = 42.45 Hz, 1C).
Supporting Information S12
144 136 128 120 112 104 96 88 80 72 64 56Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
OH
1
2
3
3
2
1
Figure S9: 13C-NMR spectrum of allyl alcohol (CH2=CHCH2OH).
13C NMR (101 MHz, C6D6, 25°C) = 138.53 (s, CH2=CH2CH2OH, 1C), 115.26 (s, CH2=CH2CH2OH, 1C), 63.8(s, CH2=CH2CH2OH, 1C)
Supporting Information S13
Figure S10: Electron Impact (EI) Quadrople Mass Spectrum of C6F13CH2CHICH2OH.
504 m/z = C6F13CH2CHICH2OH
377 m/z = C6F13CH2CHICH2OH -iodide
357 m/z = C6F13CH2CHICH2OH -iodide -HF
Supporting Information S14
OO
8.5
Ha
Hb
Hc
1 2
3O
4
56
OO
8.5
I
7 2
3O
4
56
F2C
CF2
F2C
CF2
F2C
F3C89
9
Hb Ha
1
62-3
4-5
7 7'Hc
9'8
5.5 5.0 4.5 4.0 3.5 3.0 2.5Chemical Shift (ppm)
0
0.005
0.010
0.015
0.020
0.025
0.030
Figure S11: 1H-NMR spectrum of C6F13CH2CHICH2O(CH2CH2O)9.5CH3 (37.4% purity).
1H NMR (400 MHz, CDCl3, 25 oC): 4.35 (m, -CH2CHICH2OH, 1H), 3.80, 3.74 (-CH2CHICHaHbO-, 2JHaHb=10.86 Hz, 1H), 3.65, 3.64(d, -CH2CHICHaHeOH, 2JHbHa=10.86 Hz, 1H) 3.16 (s, -OCH3, 4JHH=0.72 Hz, 3H), 3.35 (t, -OCH2CH2OCH3, 3JHH=5.3 Hz, 2H), 3.33 (t, -CH2OCH3, 3JHH=6.3 Hz, 2H), 3.5-3.4 (m, -CH2O-, 19 X 2H), 3.14-3.03 (m, -CF2CHaHbCHI-, 1H), 2.70-2.59 (m, CF2CHaHbCHI-, 1H).
Supporting Information S15
OO
8.5
IO
F2C
CF2
F2C
CF2
F2C
F3C
1
2 4 6
3 5
1
-CF2I 6
2
3
4
5
-(CF2)3I
-(CF2)2I
-60 -65 -70 -75 -80 -85 -90 -95 -100 -105 -110 -115 -120 -125Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
Figure S12: 19F-NMR spectrum of C6F13CH2CHICH2O(CH2CH2O)9.5CH3
19F NMR (376.41 MHz, DMSO capillary, 25°C): = -80 (t, CF3-, 3JFF =9.4 Hz, 3F), -112.24 (d, -CFaFbCH2- , 2JFaFb=273.06 Hz, 1F),-112.83 (d, -CFaFbCH2- , 2JFbFa=273.06 Hz, 1F), 2F), -120.73 (m, -CF2CF2CH2-, 2F), -121.78(m, -CF2(CF2)2CH2-, 2F), -122.62 (m, CF2(CF2)3CH2-, 2F), -125.15 (s, CF3CF2(CF2)4CH2-); impurity: -63.78(m, CF2I, 2F), -112.59(m, -CF2CF 2I, -120.08 (m, -(CF2)2I, 2F).
Supporting Information S16
128 120 112 104 96 88 80 72 64 56 48 40 32 24 16Chemical Shift (ppm)
0
0.05
0.10
0.15
OO
8.53 4
5O
6
78
OO
8.5
I
9 4
5O
6
7 8
F2C
CF2
F2C
CF2
F2C
F3C10
11
1
2
12
8
1011
CDCl3
9
7
6
4-5
C6F13 in the noise
Figure S13: 13C-NMR spectrum of C6F13CH2CHICH2O(CH2CH2O)9.5CH3
13C NMR (101 MHz, CDCl3 capillary, 25°C) = 76.05 (s, -CHICH2O-, 1C), 71.85 (s, -CH2OMe, 1C), 70.47 (s, -OCH2-, 19 X 1C), 70.40 (s, -OCH2CH2OMe), 58.92 (s, -OCH3, 1C), 14.39 (s, -CH2CHICH2O-, 1C), 37.34 (t, 2JCF = 20.83 Hz,-CF2CH2CHI-, 1C), Impurities: 134.67 (s, 1C, –CH=), 117.05 (s, 1C, =CH2), 70.60 (s, 1C, CH2-allyl).
Supporting Information S17
(A)
I
O
HO
IC6F13
(B)
Figure S14. Gas Chromatography/mass spectrometry of the reaction of C6F13I with BPO. (A) Chromatograpy of products, (B) Mass Spectrum of C6F13PhI where 126, 253, and 522 m/z are PhCF2+, IPhCF2+, and C6F13PhI, respectively.
Supporting Information S18
Figure S15: Electron Impact (EI) Quadrople Mass Spectrum of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane (F[CF(CF3)CF2O]8.9CF(CF3)CF2I).
335 m/z = CF3CF2CF2OCF(CF3)CF2+
277 m/z = +CF(CF3)CF2I
169 m/z/= CF3CF2CF2+
69 m/z = CF3+
Supporting Information S19
Figure S16: Electron Impact (EI) Quadrople Mass Spectrum of F[CF(CF3)CF2O]8.9CFCF3CF2CH2CHICH2OH.
31m/z = +CH2OH; 207 m/z = +CF(CF3)CF2CH2CHICH2OH -HI
Supporting Information S20
8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
C6D6
CFCF2
O FC
F2C
CF3
OHI
F
CF3
32
3
2
Ha
Hb
Ha Hb1
1
8.9
Figure S17: 1H-NMR spectrum of F[CF(CF3)CF2O]9.68CFCF3CF2CH2CHICH2OH initiated by TBPPI.
(TBPPI): 1H NMR (400 MHz, C6D6 capillary, 25°C): = 4.4 (s, -CH2CHICH2OH, 1H), 4.21(s,-CH2OH, 1H), 3.81 (-CH2CHICH2OH,2H), 2.98 (m, -CF2CHaHbCHI-, 1H), 2.72 (m, -CF2CHaHbCHI-, 1H).
Supporting Information S21
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
C6D6
CFCF2
O FC
F2C
CF3
OHI
F
CF3
32Ha Hb
1
8.9
Ha
Hb
3
3'
1
2
Figure S18: 1H-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2OH initiated by AIBN.
(AIBN): 1H NMR (400 MHz, C6D6 capillary, 25°C): = 4.31, 4.25 (s, -CH2CHICH2OH, 1H), 3.99(s,-CH2OH, 1H), 3.66 (-CH2CHICH2OH,2H), 2.84 (m, -CF2CHaHbCHI-, 1H), 2.54 (m, -CF2CHaHbCHI-, 1H).
Supporting Information S22
-48 -56 -64 -72 -80 -88 -96 -104 -112 -120 -128 -136 -144 -152Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30 CFCF2
O FC
F2C
CF3
ICF2
CF3
8.9
F2C
F3C
12
345
6
7
8
9
1
2
5
8
3
4,6,7
9
Figure S19: 19F-NMR spectrum of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane(F[CF(CF3)CF2O]8.9CF(CF3)CF2I).
19F NMR (376.41 MHz, C6D6, 25°C): = -59.68, -60.64(s, -CFaFbI, 2JFF =212.25 Hz, 2F), -79.15 (d, -CF(CF3)CF2I, 3JFF= 51.63Hz, 3F), -79 to -84 (-[CF(CF3)CF2O]-), -82.54 (CF3CF2CF2O-, 2F), -84.25 (s, CF3CF2CF2O- , 3F), -132.21 (s, CF3CF2CF2-, 2F), -135.51(s, -CF(CF3)CF2I, 1F), -146.72 (m, -[CF(CF3)CF2O]-, 8.9 x 1F).
Supporting Information S23
CFCF2
O FC
F2C
CF38.9
OHI
CF2
CF3
Ha Hb
F2C
F3C
1
2
3
4
5
6
7
8
9
9
25&7
-CF2H -CFH-
1
3,4,6,8
-75 -80 -85 -90 -95 -100 -105 -110 -115 -120 -125 -130 -135 -140 -145Chemical Shift (ppm)
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
0.065
Figure S20: 19F-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2OH initiated by TBPPI.
19F NMR (376.41 MHz, C6D6, 25°C): = -80 to -85 (m, CF(CF3)CF2O-), -80.15 (s, CF3CF2CF2O- , 3F), -81.80 (s, CF3CF2CF2O-, 2F), -110.92 (2JFF = 262.73Hz), -112.54 (2JFF = 237.49Hz), -113.99 (2JFF = 261.58Hz), -129.80 (s, CF3CF2CF2-, 2F), -146.80 (m, -CF(CF3)CF2-, 8.9 x 1F).
Supporting Information S24
DMSO-d6
C6D6CF
CF2
O FC
F2C
CF3
OHI
CF2
CF3F2C
F3C
1
2
3
4
5
6
7
8
9
10
11
12
1112
10
5
128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
4,1,
2
Figure S21: 13C-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2OH initiated by TBPPI.
13C NMR (101 MHz, DMSO/C6D6 capillary, 25°C) = 118.0 (qd, 1JCF =290.9, 2JCF = 28.2 Hz –OCF(CF3)CF2-), 117.6 (qt, 1JCF = 286.15 Hz, 2JCF = 32.93 Hz, CF3CF2CF2O-, 1C), 117.5 (qd, 1JCF =286.15, 2JCF = 34.40 Hz, CF3CF2CF2O, 1C), 114.7 (td,1JCF = 285.74, 2JCF = 31.26Hz,-OCF(CF3)CF2-, 8.9 x 1C), 105.2 (tsext, 1JCF= 267.03 Hz, 2JCF = 36.68 Hz, CF3CF2CF2O-, 1C), 101.8(dsext, 1JCF = 270.7, 2JCF =36.7 Hz, –OCF(CF3)CF2-), 66.32 (s, -CH2CHICH2OH, 1C), 36.52(m, -CF2CH2CHICH2OH, 1C), 18.09, 17.90(s, -CH2CHICH2OH, 1C).
Supporting Information S25
135 130 125 120 115 110 105 100 95 90 85 80Chemical Shift (ppm)
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
CFCF2
O FC
F2C
CF3
IO
CF3
8.9
F2C
CF2
12
345
67
8
9
C6D6
1
2&5
3,6,&9
8
4&7
F3C
Figure S22: 13C-NMR spectrum of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane(F[CF(CF3)CF2O]8.9CF(CF3)CF2I).
13C NMR (101 MHz, C6D6 capillary, 25°C): = 117.3 (qd, 1JCF =288.3 Hz, 2JCF = 30.7 Hz –OCF(CF3)CF2-, 8.9 x 1C), 116.86 (qt, 1JCF = 286.15 Hz, 2JCF = 32.93 Hz, CF3CF2CF2O-, 1C), 116.2(qd, 1JCF =285.4 Hz, 2JCF = 30.0 Hz, –OCF(CF3)CF2I, 1C), 115.8 (td, 1JCF =287.6, 2JCF = 28.5 Hz, -OCF(CF3)CF2O-, 8.9 x 1C), 115.35 (qd, 1JCF =286.15, 2JCF = 34.40 Hz, CF3CF2CF2O, 1C), 106.3 (tsex, 1JCF=270.1, 2JCF=40.83 Hz,CF3CF2CF2O-, 1C), 102.75 (dsext, 1JCF = 269.3, 2JCF =37.3 Hz, –OCF(CF3)CF2-), 102.65 (dsext, 1JCF = 270.78, 2JCF =39.52 Hz, –OCF(CF3)CF2I, 1C), 91.5 (td, 1JCF = 319.95 Hz, 2JCF = 33.93 Hz, –OC*F(CF3)CF2I), 91.3 (td, 1JCF = 320.71 Hz, 2JCF = 36.41 Hz, –OC*F(CF3)CF2I).
Supporting Information S26
A)
B)
Figure S23: Negative Mode, Atmospheric pressure Solids Analysis Probe (ASAP) mass spectrum (MS) of 1-iodo-2-oligo(hexafluoropropylene oxide) perfluoropropane
(F[CF(CF3)CF2O]8.9CF(CF3)CF2I). The expansion (Figure B) is the minor distribution of heavier homologues of oligo(HFPO) iodide centered around 2982 m/z (average n = 16).
Supporting Information S27
Figure S24: Matrix assisted laser desorption ionization-time-of-flight mass spectrum (MALDI-TOF-MS) of 1-iodo-2-oligo(hexafluoropropylene oxide) perfluoropropane (F[CF(CF3)CF2O]8.9-CF(CF3)CF2I).
Supporting Information S28
F(CF(CF3)CF2O)nCF(CF3)CF2CH2CHICH2+.
F(CF(CF3)CF2O)nCF(CF3)CF2CH2CHICH2+.
F(CF(CF3)CF2O)nCF(CF3)CF2CH2CH+CH2O(CH3CN)
Figure S25: Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrum (MS) of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2OH initiated by TBPPI.
Supporting Information S29
Figure S26. Matrix assisted laser desorption ionization (Positive ion mode)-time of flight- mass spectrum of F[C(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2OH (using as matrix trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) and LiCl as the cationizing agent).
Supporting Information S30
9 8 7 6 5 4 3 2 1Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
Aromatic
C6D6
Figure S27: 1H-NMR spectrum of the reaction of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane(F[CF(CF3)CF2O]8.9CF(CF3)CF2I)with benzoyl peroxide initiated by BPO.
Supporting Information S31
8 7 6 5 4 3 2 1 0
0.05
0.10
0.15
0.20CF
CF2
O FC
F2C
CF3
O
CF3
8.9
F2C
CF2
3
F3C
CDCl3 -CF2H & -CFH-
O
Ha Hb
I
OO
8.5 12
34
56
7
7
Ha Hb
1
4-5
2-3
6
Figure S28: 1H-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)8.5CH3 initiated by AIBN.
1H NMR (400 MHz, CDCl3 capillary, 25 oC): = 4.36 (b, -CHI-, 1H), 3.79 (b, -CHICH2O, 2H), 3.59 (b, -CH2O, 19 x 1H), 3.46 (b, -CH2CH2OCH3, 4H), 3.28 (s, CH3O-, 3H), 3.09 (vb, -CF2CHaHbCHI-, 1H), 2.58 (vb CF2CHaHbCHI-, 1H).
Supporting Information S32
-56 -64 -72 -80 -88 -96 -104 -112 -120 -128 -136 -144 -152Chemical Shift (ppm)
-0.010
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
0.055
0.060
CFCF2
O FC
F2C
CF3
OI
CF2
CF3F2C
F3C
1
2
3
4
5
6
7
8
9
O
-CF2I-CFH-
-CF2H
2 5,7
1
3,4,6,8
9
Figure S29: 19F-NMR spectrum of F[C(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by BPO.
19F NMR (376.41 MHz, C6D6, 25°C): = -80 to -84 (CF(CF3)CF2O-), -84.04 (CF3CF2CF2O- , 3F), -82.37 (CF3CF2CF2O-, 2F), -112 to -117.5 (b, -CF(CF3)CF2CH2CHI-, 2F), -132.03 (s, CF3CF2CF2-, 2F), -146.54 (m, -CF(CF3)CF2-, 8.9 x 1F).
Supporting Information S33
128 120 112 104 96 88 80 72 64 56 48 40 32 24 16Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
CFCF2
O FC
F2C
CF3
O
CF3
8.9
F2C
CF2
F3C OI
OO
8.5 12
34
56
7
8
C6D6
1
78
6
2
4-5
3
Figure S30: 13C-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by AIBN.
13C NMR (101 MHz, C6D6, 25°C) = 118.0 (qd, 1JCF =290.9, 2JCF = 28.2 Hz –OCF(CF3)CF2-), 117.6 (qt, 1JCF = 286.15 Hz, 2JCF = 32.93 Hz, CF3CF2CF2O-, 1C), 117.5 (qd, 1JCF =286.15, 2JCF = 34.40 Hz, CF3CF2CF2O, 1C), 114.7 (td,1JCF = 285.74, 2JCF = 31.26Hz,-OCF(CF3)CF2-, 8.9 x 1C), 105.2 (tsext, 1JCF= 267.03 Hz, 2JCF = 36.68 Hz, CF3CF2CF2O-, 1C), 101.8 (dsext, 1JCF = 270.7, 2JCF =36.7 Hz, –OCF(CF3)CF2-), 76.27 (s, -CH2CHICH2O-, 1C), 72.17 (s, CH2–CH2–OMe, 2C), 70.79 (s, 19 X 1C, -CH2–O), 70.54 (s, -CH2CH2OMe, 1C) 58.65 (s, 1C, CH3), 37.65(m, -CF2CH2CHICH2O-, 1C), 14.30(s, -CH2CHICH2O-, 1C).
Supporting Information S34
Figure S31: Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrum (MS) of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by BPO.
Supporting Information S35
Figure S32: Matrix assisted laser desorption ionization-time-of-flight mass spectrum (MALDI-TOF-MS) of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CHICH2O(CH2CH2O)9.5CH3 initiated by BPO. The adduct (M+Li)+ at 1889 is x=7 and y=8. The expansion m/z between 1500 and 1900 displays 166 m/z-repeat unit for HFPO [CF(CF3)CF2O] and 44 m/z-repeat unit of ethylene oxide (CH2CH2O).
Supporting Information S36
C6F13I + Allyl-OH + TBPPI C6F13I + TBPPI
C6F13I + Allyl-OH + AIBN C6F13I + AIBN (no reaction)
C6F13I + Allyl-OH +BPO C6F13I +BPO
Figure S33. Comparison of the 19F-NMR expansions of the reaction C6F13I with the initiator (TBPPi, AIBN, BPO) and initiator with allyl alcohol.
RXN 1 RXN 21
RXN 2 RXN 22
RXN 3 RXN 24
Supporting Information S37
C6F13I + ally-O-PEG-OCH3 +TBPPI C6F13I + TBPPI
C6F13I + ally-O-PEG-OCH3+ AIBN C6F13I + AIBN (no reaction)
C6F13I + ally-O-PEG-OCH3+ BPO C6F13I +BPO
Figure S34. Comparison of the 19F-NMR expansions of the reaction of C6F13I with the initiator (TBPPi, AIBN, BPO) and initiator with ally-O-PEG-OCH3.
RXN 4
RXN 5
RXN 6
RXN 21
RXN 22
RXN 24
Supporting Information S38
10 g oligo(HFPO)-I + ally-O-PEG-OCH3+ TBPPI Oligo(HFPO)-I + TBPPI
10 g oligo(HFPO)-I + ally-O-PEG-OCH3 + AIBN Oligo(HFPO)-I +AIBN
10 g oligo(HFPO)-I + ally-O-PEG-OCH3+ BPOOligo(HFPO)-I + BPO
Figure S35. Comparison of the 19F-NMR expansions of the reaction of oligo(HFPO)-CF(CF3)CF2I with the initiator (TBPPi, AIBN, BPO) and initiator with ally-O-PEG-OCH3.
RXN 16 RXN
RXN 20
RXN 18
RXN 25
RXN 26
RXN 29
Supporting Information S39
48 46 44 42 40 38 36 34 32 30Chemical Shift (ppm)
-0.7
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6F F
C
F2C
OCF
CF2CF3
CF3
8.9
I1
2
2'
3
1
DMSO
3
2, 2'
Figure S36: 13C-NMR spectrum , Attached Proton Test (APT), of 1-iodo-2-methyl-3-[2-(poly(hexafluoro-propylene oxide) perfluoropropyl]-propane. A side reaction of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane (F[CF(CF3)CF2O]8.9CF(CF3)CF2I) with TBPPI.
13C NMR (101 MHz, C6D6, 25°C) = 47.51 (td, 2JCF = 19.0 Hz, 3JFCF = 8.1 Hz, -CF(CF3)CF2CH2C-(CH3)2I, 1C), 36.06 (s, -CF(CF3)CF2CH2C(CH3)2I, 2C), 31.98 (s, , -CF(CF3)CF2CH2C(CH3)I, 1C).
Supporting Information S40
Figure S37: Atmospheric pressure Solids Analysis Probe (ASAP) Mass Spectrum (MS) of 1-iodo-2-methyl-3-[2-(poly(hexafluoropropylene oxide)perfluoropropyl]-propane, side reaction of 1-iodo-2-oligo(hexafluoropropylene oxide)perfluoropropane (F[CF(CF3)CF2O]8.9CF(CF3)CF2I) with TBPPI.
Supporting Information S41
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
-CF2HCHCl3
CFCF2
O FC
F2C
CF3
O
CF3
8.9
F2C
CF2
F3C OO
O
8.5 12
34
56
7
8
X= H, F or Id = triplet, 1JCSn = 22.7 Hz
Sn-X
3
a c
b d
toluene
d
87
1
2-6
a
b-c
Figure S38: 1H-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CH2CH2O(CH2CH2O)9.5CH3.
1H NMR (400 MHz, CDCl3 capillary, 25 oC): = 3.59 (b, -CH2O, 23 x 1H), 3.40 (s, CH3O-, 3H), 2.20 (b, -CF2CH2CH2-, 1H), 1.89 (b, -CF2CH2CH2-, 1H).
Supporting Information S42
-64 -72 -80 -88 -96 -104 -112 -120 -128 -136 -144 -152Chemical Shift (ppm)
-0.010
-0.005
0
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
CFCF2
O FC
F2C
CF3
O
CF3
8.9
F2C
CF2
F3C OO
O
8.5
2
2
1 3
4
5
6
7
89
5&7
8CF3Ph
9-CFH-
-CF2H
3,4,6
Figure S39: 19F-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CH2CH2O(CH2CH2O)9.5CH3.
19F NMR (376.41 MHz, C6D6, 25°C): = -80 to -84 (CF(CF3)CF2O-), -84.04 (CF3CF2CF2O- , 3F), -82.37 (CF3CF2CF2O-, 2F), -112 to -118 (b, -CF(CF3)CF2CH2CH2-, 2F), -131.56 (s, CF3CF2CF2-, 2F), -146.05 (m, -CF(CF3)CF2-, 9.9 x 1F).
Supporting Information S43
128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8Chemical Shift (ppm)
0
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
C6D6
CFCF2
O FC
F2C
CF3
O
CF3
8.9
F2C
CF2
F3C OO
O8.5 12
34
56
7
8
9
9
2-68
17
X= H or Id = triplet, 1JCSn = 22.7 Hz
Sn-X
3
a c
b d
a
dbc
toluene
DMSO
Figure S40: 13C-NMR spectrum of F[CF(CF3)CF2O]8.9CF(CF3)CF2CH2CH2CH2O(CH2CH2O)9.5CH3
13C NMR (101 MHz, C6D6, 25°C) = 118.0 (qd, 1JCF =290.9, 2JCF = 28.2 Hz, –OCF(CF3)CF2-), 117.6 (qt, 1JCF = 286.15 Hz, 2JCF = 32.93 Hz, CF3CF2CF2O-, 1C), 117.5 (qd, 1JCF =286.15, 2JCF = 34.40 Hz, CF3CF2CF2O, 1C), 114.7 (td,1JCF = 285.74, 2JCF = 31.26Hz,-OCF(CF3)CF2-, 8.9 x 1C), 105.2 (tsext, 1JCF= 267.03 Hz, 2JCF = 36.68 Hz, CF3CF2CF2O-, 1C), 101.8 (dsext, 1JCF = 270.7, 2JCF =36.7 Hz, –OCF(CF3)CF2-), 69.42 (bs, -CH2O-, 21 X 1C), 57.59 (s, CH3,1C), 27.80(m, -CF2CH2CH2CH2O-, 1C), 20.55 (s, -CH2CH2CH2O-, 1C). Impurities (tributyl-Sn-X): 28.98 (s, CH3CH2CH2CH2-Sn, 3C), 26.90 (s, CH3CH2CH2CH2-Sn, 3C), 18.76 (t, CH3CH2CH2CH2-Sn, 1JCSn = 20.49 Hz, 3C), 12.53 (s, CH3CH2CH2CH2-Sn, 3C)
Supporting Information S44
Figure S41. Positive mode atmospheric pressure solids analysis probe (ASAP) mass spectrum (MS) of oligo(HFPO)-CH2CH2CH2-oligo(PEG)
Supporting Information S45
1973
1885
1763
1719 18072017 2139
1675
2349
2183
1597
2427
2261
1509
1895
2515 25931465
26811387
2339
2505
2759 2847 2969
1519
3091
0.0
0.2
0.4
0.6
0.8
1.04x10
Inte
ns. [
a.u.
]
1400 1600 1800 2000 2200 2400 2600 2800 3000m/z
(x=6– 16 ; y=1-8)
19731929
1885
20172051
19131957
2035 2079
2001
165.97
44.0244.03
44.02
44.03
0.0
0.2
0.4
0.6
0.8
1.0
4x10
Inte
ns. [
a.u.
]1900 1950 2000 2050
m/z
(x ; y)
(6 ; 1)
(16 ; 4)
[ F[CF(CF3)CF2O] x CF(CF3)CF2CH2CH2CH2O(CH2CH2O)yOCH3
Figure S42. Positive ion mode MALDI-TOF-MS spectrum of oligo(HFPO)-CH2CH2CH2-oligo(PEG) (using as matrix DCTB and LiCl as the cationizing agent), 1807 m/z is x =8 and y = 5. The insert expansion m/z between 1850 and 2100 displays 166 m/z-repeat unit for HFPO [CF(CF3)CF2O] and 44 m/z-repeat unit of ethylene oxide (CH2CH2O).
Supporting Information S46
0 2 4 6 8 10 12
20
30
40
50
60
70
80 SFT (mN/m)
B
c (gL-1)
Figure S43: Surface Tension measurement of ammonium perfluorooctanoate (C7F15C(O)O-
NH4+), CMC = 3.77 g/L.
Supporting Information S47
Figure S44: Positive mode atmospheric pressure solids analysis probe (ASAP)-time-of-flight-mass spectrum (MS) of oligo(HFPO)-CH2CH2CH2OH, in trifluorotoluene.