Supplemental Information co-oligomeric surfactant … S10: Electron Impact (EI) Quadrople Mass Spectrum of C6F13CH2CHICH2OH.....13 Figure S11: 1H-NMR spectrum of C 6F13CH2CHICH2O(CH2CH2O)9.5CH3

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


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


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).


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).


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).


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).


-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).


-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)


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).


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).


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)


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


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).


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).


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).


(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.


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+


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


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).


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).


-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).


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).


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).


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).


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).


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).


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.


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).


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.


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).


-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).


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).


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.


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).


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


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


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


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).


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.


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).


-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).


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)


Figure S41. Positive mode atmospheric pressure solids analysis probe (ASAP) mass spectrum (MS) of oligo(HFPO)-CH2CH2CH2-oligo(PEG)


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).


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.


Figure S44: Positive mode atmospheric pressure solids analysis probe (ASAP)-time-of-flight-mass spectrum (MS) of oligo(HFPO)-CH2CH2CH2OH, in trifluorotoluene.


Figure S45: Negative ion mode MALDI-TOF-MS spectrum of oligo(HFPO)CH2CH2CH2OH, in trifluorotoluene (using as matrix DCTB and LiCl as the cationizing agent).

Documents

Supplemental Information co-oligomeric surfactant … S10: Electron Impact (EI) Quadrople Mass Spectrum of C6F13CH2CHICH2OH.....13 Figure S11: 1H-NMR spectrum of C 6F13CH2CHICH2O(CH2CH2O)9.5CH3