Macromolecules, Vol. 38, No. 25, 2005
Amphiphilic Lithium Ion Conductive Materials 10411
10H), 1.32-2.23 (br m, -CH2- 10H). 13C NMR (d6-THF): δ
(ppm) 129.87 (C-2), 128.65 (C-1), 122.88 (m, -CF2-), 80.10 (C-
5), 62.89 (m, -CH2CF3), 34.33 (C-4), 32.35 (C-6), 28.06 (C-3),
26.99 (C-8), 25.23 (C-7). 31P NMR (d6-THF): δ (ppm) 17.31 (m,
3P); Mn ) 397 kDa, Mw ) 866 kDa, PDI ) 2.2.
mmol, 0.25 equiv) and monomer 7 (4.11 g, 2.9 mmol, 0.74
equiv) in CH2Cl2 (12 mL) and a solution of 1 (10.5 mg, 0.013
mmol) in CH2Cl2 (1 mL) to yield 2.25 g (45% yield) of polymer
15. Average repeat unit composition (5, 27.1%; 7, 72.9%); Mn
) 376 kDa, Mw ) 964 kDa, PDI ) 2.6.
Synthesis of polymer 10. Polymer 10 was synthesized in a
manner similar to polymer 8 using monomer 7 (2.59 g, 1.8
mmol) in CH2Cl2 (5.0 mL) and a solution of 1 (5.2 mg, 0.006
mmol) in CH2Cl2 (1 mL) to yield 0.30 g (12% yield) of polymer
Synthesis of polymer 16. Polymer 16 was synthesized in a
manner similar to polymer 8 using monomer 5 (1.45 g, 1.7
mmol, 0.40 equiv) and monomer 7 (3.54 g, 2.5 mmol, 0.60
equiv) in CH2Cl2 (4 mL) and a solution of 1 (11.9 mg, 0.014
mmol) in CH2Cl2 (1 mL) to yield 1.87 g (37% yield) of polymer
16. Average repeat unit composition (5, 39.4%; 7, 60.6%); Mn
) 155 kDa, Mw ) 255 kDa, PDI ) 1.7.
Preparation of Solid Polymer Electrolytes. Polymers
8-16 were dried under vacuum at 40 °C for 1 week before
fabrication. Each polymer (0.3 g) was combined with 10 mol
% lithium tetrafluoroborate (LiBF4) and was dissolved in THF.
The THF was removed by air evaporation in a dry environ-
ment, and the samples were subjected to a reduced pressure
(40 °C, 0.1 mmHg, 72 h) to remove any residual THF to yield
solid polymer electrolytes (SPEs) 17-25.
Preparation of Films for Static Water Contact Angle
Measurements. Polymers 8-16 were dried under vacuum at
40 °C for 1 week before fabrication. Each polymer was
combined with 10 mol % LiBF4 and was dissolved in THF (30%
(w/v)). The polymer solutions were poured onto a glass
substrate, and the THF was air-evaporated in a dry environ-
ment. Residual THF was removed under a reduced pressure
(room temperature for 24 h, 40 °C for 72 h, 0.1 mmHg).
1
10. H NMR (d6-THF): δ (ppm) 6.54 (br m, -CF2CF2H, 5H),
5.42 (br m, -CHdCH-, 2H), 4.53 (br s, -CH2CF2-, 10H), 4.02
(br m, -CH2CH(O-)CH2-, 1H), 1.04-2.14 (br m, -CH2-,
10H). 13C NMR (d6-THF): δ (ppm) 131.23 (C-2), 128.89 (C-1),
111.14 (m, -CF2-), 73.15 (C-5), 64.23 (-CF2H), 57.45 (m,
-OCH2CF2-), 36.23 (C-4), 32.14 (C-6), 31.98 (C-3), 28.12 (C-
8), 26.67 (C-7). 31P NMR (d6-THF): δ (ppm) 17.22 (m, 3P); Mn
) 455 kDa, Mw ) 819 kDa, PDI ) 1.8.
Synthesis of polymer 11. Polymer 11 was synthesized in a
manner similar to polymer 8 using monomer 5 (0.28 g, 0.33
mmol, 0.10 equiv) and monomer 6 (2.19 g, 3.0 mmol, 0.90
equiv) in CH2Cl2 (5.5 mL) and a solution of 1 (9.3 mg, 0.011
mmol) in CH2Cl2 (1 mL) to yield 0.88 g (35% yield) of a rubbery
gum. The average repeat unit composition was calculated from
1
1H NMR peak integration. Similar H, 13C, and 31P chemical
shifts were observed for polymers 12 and 13.
For 11, average repeat unit composition (5, 11.2%; 6, 88.8%).
1H NMR (d6-THF): δ (ppm) 5.41 (br m, -CHdCH-, 4H), 4.48
(br s, -CH2CF3-, 18H), 4.41 (m, -CH2CH(O-)CH2-, 2H), 4.01
(br m, -OCH2CH2O-, 2H), 3.63 (br m, -OCH2CH2O-, 2H),
3.59 (br m, -OCH2CH2OCH3, 2H), 3.48 (br m, -OCH2CH2-
OCH3, 2H), 3.28 (s, -OCH3, 3H), 1.35-2.62 (br m, -CH2-,
20H). 13C NMR (d6-THF): δ (ppm) 129.49 (C-2), 129.23 (C-1),
123.46 (m, -CH2CF3), 80.06 (C-5), 71.94 (-OCH2CH2O-),
70.36 (-OCH2CH2OCH3), 70.03 (-OCH2CH2OCH3), 65.94
(-OCH2CH2O-), 62.49 (-CH2CF3), 57.97 (-OCH3), 34.69 (C-
4), 34.30 (C-6), 32.45 (C-3), 27.95 (C-8), 27.01 (C-7). 31P NMR
(d6-THF): δ (ppm) 18.12 (m, 6P); Mn ) 387 kDa, Mw ) 841
kDa, PDI ) 2.2.
Acknowledgment. We thank Dr. Jared D. Bender
for his contributions to this work.
References and Notes
(1) Urquidi-Macdonald, M.; Castaneda, H.; Cannon, A. M. Elec-
trochim. Acta 2002, 47, 2495.
(2) Allcock, H. R. Chemistry and Applications of Polyphosp-
hazenes; John Wiley and Sons: Hoboken, NJ, 2003.
Synthesis of polymer 12. Polymer 12 was synthesized in a
manner similar to polymer 8 using monomer 5 (0.68 g, 0.8
mmol, 0.25 equiv) and monomer 6 (2.22 g, 2.5 mmol, 0.75
equiv) in CH2Cl2 (5.5 mL) and a solution of 1 (9.3 mg, 0.011
mmol) in CH2Cl2 (1 mL) to yield 0.90 g (36% yield) of polymer
12. Average repeat unit composition (5, 31.5%; 6, 68.5%); Mn
) 250 kDa, Mw ) 463 kDa, PDI ) 1.9.
Synthesis of polymer 13. Polymer 13 was synthesized in a
manner similar to polymer 8 using monomer 5 (1.11 g, 1.3
mmol, 0.40 equiv) and monomer 6 (1.40 g, 1.9 mmol, 0.60
equiv) in CH2Cl2 (5.5 mL) and a solution of 1 (9.3 mg, 0.011
mmol) in CH2Cl2 (1 mL) to yield 1.09 g (44% yield) of polymer
13. Average repeat unit composition (5, 44.0%; 6, 56.0%); Mn
) 279 kDa, Mw ) 632 kDa, PDI ) 2.3.
Synthesis of polymer 14. Polymer 14 was synthesized in a
manner similar to polymer 8 using monomer 5 (0.32 g, 0.37
mmol, 0.10 equiv) and monomer 7 (4.67 g, 3.3 mmol, 0.90
equiv) in CH2Cl2 (12 mL) and a solution of 1 (10.5 mg, 0.012
mmol) in CH2Cl2 (1 mL) to yield 1.51 g (30% yield) of polymer
14. Similar chemical shifts were observed for polymers 15 and
16.
(3) Allcock, H. R.; Powell, E. S.; Chang, Y.; Kim, C. Macromol-
ecules 2004, 37, 3635.
(4) Allcock, H. R.; Powell, E. S.; Maher, A. E.; Prange, R. L.; de
Denus, C. R. Macromolecules 2004, 37, 7163.
(5) Allcock, H. R.; de Denus, C. R.; Prange, R. L.; Larado, W. R.
Macromolecules 2001, 34, 2757.
(6) Allcock, H. R.; Powell, E. S.; Berda, E. B. Macromolecules
2004, 37, 5824.
(7) Allcock, H. R.; Kellam, E. C., III; Hofmann, M. A. Macromol-
ecules 2001, 34, 5140.
(8) Allcock, H. R.; Kellam, E. C., III Macromolecules 2002, 35,
40.
(9) McIntosh, M. B.; Hartle, T. J.; Taylor, J. P.; Allcock, H. R. J.
Am. Chem. Soc. 1999, 121, 884.
(10) Allcock, H. R.; McIntosh, M. B.; Hartle, T. J. Inorg. Chem.
1999, 38, 5535.
(11) Inoue, K.; Itaya, T. Bull. Chem. Soc. Jpn. 2001, 74, 1381.
(12) Gleria, M., De Jaeger, R., Eds. Applicative Aspects of Poly-
(organo phosphazenes); Nova Science Publishers: Haup-
pauge, NY, 2004; Chapter 8, pp 169-188.
(13) Allen, C. W.; Shaw, J. C.; Brown, D. E. Macromolecules 1988,
For 14, average repeat unit composition (5, 8.3%; 7, 91.7%).
1H NMR (d6-THF): δ (ppm) 6.36-6.67 (br m, -CF2CF2H, 9H),
5.43 (br m, -CHdCH-, 4H), 4.56 (br m, -CH2CF2-, 18H),
4.43 (br m, -CH2CH(O-)CH2-, 2H), 4.02 (br m, -OCH2-
CH2O- 2H), 3.64 (br m, -OCH2CH2O-, 2H), 3.57 (br m,
-OCH2CH2OCH3, 2H), 3.45 (br m, -OCH2CH2OCH3, 2H), 3.28
(s, -OCH3, 3H), 1.37-2.31 (br m, -CH2-, 20H). 13C NMR
(CDCl3): δ (ppm) 133.45 (C-2), 130.11 (C-1), 110.48 (m, -CF2-
), 80.98 (C-5), 71.94 (-OCH2CH2O-), 70.34 (-OCH2CH2-
OCH3), 70.02 (-OCH2CH2OCH3), 64.71 (-OCH2CH2O-), 62.14
(-CF2CF2H), 62.06 (-CH2CF2-), 57.96 (-OCH3), 37.45 (C-4),
34.69 (C-6), 32.57 (C-3), 27.98 (C-8), 26.74 (C-7). 31P NMR (d6-
THF): δ (ppm) 17.2 (m, 6P); Mn ) 489 kDa, Mw ) 1129 kDa,
PDI ) 2.3.
21, 2653.
(14) Inoue, K.; Kinoshita, K.; Nakahara, H.; Tanigaki, T. Macro-
molecules 1990, 23, 1227.
(15) Puyenbrock, R.; Jeckel, A. P.; van de Grampel, J. C. J. Inorg.
Organomet. Polym. 1991, 1, 105.
(16) Dez, I.; De Jaeger, R. Inorg. Organomet. Polym. 1996, 6, 111.
(17) Allcock, H. R.; Laredo, W. R.; Morford, R. V. Solid State Ionics
2001, 139, 27.
(18) Allcock, H. R.; Bender, J. D.; Morford, R. V.; Berda, E. B.
Macromolecules 2003, 36, 3563.
(19) Breslow, D. S. Prog. Polym. Sci. 1993, 18, 1141.
(20) Do¨wald, F. Z. Metal Carbenes in Organic Synthesis; Wiley-
VCH: New York, 1999.
(21) Dragutan, V.; Streck, R. Catalytic Polymerization of Cycloole-
fins: Ionic, Ziegler-Natta, and Ring-Opening Metathesis
Polymerization; Elsevier Science B.V.: Amsterdam, 2000.
Synthesis of polymer 15. Polymer 15 was synthesized in a
manner similar to polymer 8 using monomer 5 (0.83 g, 0.98