ARTICLE
glass reaction vessels were covered with Al foil to avoid
thermal and UV initiated polymerization.
ACHA), 2.32–2.25 (m, 4H, ACH2A), 2.10–2.00 (m, 2H,
ACH2A); 19F NMR (283 MHz, CDCl3) d ꢂ70.9 (s, ACF3, 3F),
ꢂ119.0 (dd, cis-CF¼¼CF2, 2F, Fa), ꢂ125.6 (dd, trans-CF¼¼CF2,
1,1-Bis(4-(1,2,2-trifluorovinyloxy)phenyl)-2,2,2-
trifluoroethyl Acrylate (M1)
2F, Fb), ꢂ134.1 (dd, ACF¼¼CF2, 2F, Fc) (Jab ¼ 95.4 Hz, Jac
¼
59.2 Hz, Jbc ¼ 108.5 Hz); 13C NMR (75.5 MHz, CDCl3)
d 171.5, 155.3, 147.0 (td, ACF¼¼CF2, 1J ¼ 274.0, 2J ¼ 66.5
Hz), 133.5 (dt, ACF¼¼CF2, 1J ¼ 257.3 Hz, 2J ¼ 47.2 Hz),
132.4, 130.3, 126.0, 122.1, 115.5, 84.3 (q, J ¼ 28.9 Hz,
ACF3), 38.7, 25.0, 18.4; HRMS (ESI–TOF) (m/z) [M þ Na]þ
calcd. for C23H15O4F9, 549.0724; found, 549.0750.
M1 was obtained as a pale yellow oil in 65% yield. ATR–
FTIR (neat) t 3024, 1830, 1753, 1630, 1606, 1508, 1314,
1165, 827; 1H NMR (300 MHz, CDCl3) d 7.50–7.48 (d, J ¼
8.9 Hz, 4H), 7.14–7.11 (d, J ¼ 8.9 Hz, 4H), 6.52–6.46 (d, 1H,
ACH¼¼CH2), 6.28–6.19 (d, 1H, trans-CH¼¼CH2), 5.98–5.95 (d,
1H, cis-CH¼¼CH2); 19F NMR (283 MHz, CDCl3) d ꢂ71.2 (s,
ACF3, 3F), ꢂ119.0 (dd, cis-CF¼¼CF2, 2F, Fa), ꢂ125.5 (dd,
[1,1-Bis(4-(1,2,2-trifluorovinyloxy)phenyl)-2,2,2-
trifluoroethyl]-6-bromohexanoate (M5)
trans-CF¼¼CF2, 2F, Fb), ꢂ134.2 (dd, ACF¼¼CF2, 2F, Fc) (Jab
¼
95.4 Hz, Jac ¼ 59.2 Hz, Jbc ¼ 111.8 Hz); 13C NMR (75.5 MHz,
M5 was obtained as a pale yellow oil in 45% yield. ATR–
FTIR (neat) t 3043, 2958, 2930, 1830, 1768, 1610, 1508,
1
2
CDCl3) d 162.5, 155.4, 146.9 (td, ACF¼¼CF2, J ¼ 274.0, J ¼
1
2
1
66.5 Hz), 133.1 (dt, ACF¼¼CF2, J ¼ 257.3 Hz, J ¼ 47.2 Hz),
133.0, 131.7, 130.5, 128.1, 125.9, 122.1, 115.5, 85.3 (q, J ¼
28.9 Hz, ACF3); HRMS (ESI–TOF) (m/z) [M þ Na]þ calcd. for
1314, 1165, 828; H NMR (300 MHz, CDCl3) d 7.45–7.48 (d,
J ¼ 8.9 Hz, 4H), 7.14–7.11 (d, J ¼ 8.9 Hz, 4H), 3.39 (t, J ¼
6.5 Hz, 2H, ACH2Br), 2.51 (t, J ¼ 7.2 Hz, 2H, ACOCH2A),
1.88–1.83 (m, 2H, ACH2A), 1.60–1.55 (m, 2H, ACH2A),
1.40–1.38 (m, 2H, ACH2A); 19F NMR (282.8 MHz, CDCl3) d
ꢂ70.9 (s, ACF3, 3F), ꢂ119.0 (dd, cis-CF¼¼CF2, 2F, Fa), ꢂ125.5
(dd, trans-CF¼¼CF2, 2F, Fb), ꢂ134.1 (dd, ACF¼¼CF2, 2F, Fc)
(Jab ¼ 95.4 Hz, Jac ¼ 59.2 Hz, Jbc ¼ 108.5 Hz); 13C NMR
C21H11O4F9, 521.0411; found, 521.042.
1,1-Bis(4-(1,2,2-trifluorovinyloxy)phenyl)-2,2,2-
trifluoroethyl Methacrylate (M2)
M2 was obtained as a pale yellow oil in 60% yield. ATR–
FTIR (neat) t 3024, 1832, 1753, 1636, 1610, 1508, 1315,
1165, 827; 1H NMR (300 MHz, CDCl3) d 7.50–7.47 (d, J ¼
8.9 Hz, 4H), 7.14–7.11 (d, J ¼ 8.9 Hz, 4H), 6.28 (s, cis-
CH¼¼CH2, 1H), 5.73 (s, trans-CH¼¼CH2, 1H), 1.98 (s,
AC(CH3)¼¼CH2, 3H); 19F NMR (283 MHz, CDCl3) d ꢂ71.2 (s,
ACF3, 3F), ꢂ119.0 (dd, cis-CF¼¼CF2, 2F, Fa), ꢂ125.6 (dd,
1
(75.5 MHz, CDCl3) d 169.7, 155.3, 147.6 (td, ACF¼¼CF2, J ¼
274.0, 2J ¼ 66.5 Hz), 133.5 (dt, ACF¼¼CF2, 1J ¼ 257.3 Hz,
2J ¼ 47.2 Hz), 132.2, 130.4, 125.9, 122.1, 115.5, 84.6 (q, J ¼
28.9 Hz, ACF3), 34.9, 33.3, 32.4, 27.5, 23.9; HRMS (ESI–TOF)
(m/z) [M þ Na]þ calcd. for C24H18O4F9Br, 643.0142; found,
643.0157.
trans-CF¼¼CF2, 2F, Fb), ꢂ134.1 (dd, ACF¼¼CF2, 2F, Fc) (Jab
¼
95.4 Hz, Jac ¼ 59.2 Hz, Jbc ¼ 108.5 Hz); 13C NMR (75.5 MHz,
General Polymerization and Copolymerization Procedure
Specified amounts of monomers were charged in a glass am-
poule previously flame-dried under vacuum. The ampoule
was vacuum sealed and then placed in a sand bath pre-
heated to 165 ꢀC or 175 ꢀC for 48 h. After cooling to room
temperature, the ampoule was then cracked and the crude
solid was dissolved into a minimum amount of THF and
then precipitated into a large excess of methanol, vacuum fil-
tered, washed liberally with MeOH, and dried in a vacuum
1
2
CDCl3) d 163.7, 155.4, 146.7, (td, ACF¼¼CF2, J ¼ 274.0, J ¼
66.5 Hz), 136.2, 133.7 (dt, ACF¼¼CF2, 1J ¼ 257.3 Hz, 2J ¼
47.2 Hz), 131.8, 130.5, 127.5, 126.0, 122.1, 115.5, 85.3 (q,
J ¼ 28.9 Hz, ACF3); GC–EIMS (70 eV) m/z (% relative inten-
sity) 512 (15, Mþ), 427 (30), 232 (30), 183 (35), 183 (35),
104 (10), 69 (100).
1,1-Bis(4-(1,2,2-trifluorovinyloxy)phenyl)-2,2,2-trifluoroethyl
Cyclopropanecarboxylate (M3)
ꢀ
M3 was obtained as a pale yellow oil in 50% yield. ATR–
FTIR (neat): t 3043, 2930, 1830, 1753, 1606, 1510, 1313,
1165, 827; 1H NMR (300 MHz, CDCl3) d 7.47–7.44 (d, J ¼
8.9 Hz, 4H), 7.14–7.11 (d, J ¼ 8.9 Hz, 4H), 1.82–1.77 (m, 1H,
ACHA), 1.04–0.93 (m, 4H, ACH2A); 19F NMR (283 MHz,
CDCl3) d ꢂ71.20 (s, ACF3, 3F), ꢂ119.0 (dd, cis-CF¼¼CF2, 2F,
Fa), ꢂ125.6 (dd, trans-CF¼¼CF2, 2F, Fb), ꢂ134.1 (dd,
ACF¼¼CF2, 2F, Fc) (Jab ¼ 95.4 Hz, Jac ¼ 59.2 Hz, Jbc ¼ 108.5
Hz); 13C NMR (75.5 MHz, CDCl3) d 171.1, 155.3, 147.3 (unre-
solved splitting of ACF¼¼CF2), 132.1, 130.4, 126.0, 122.0,
115.4, 84.5 (unresolved splitting of ACF3), 13.8, 9.0; HRMS
(ESI–TOF) (m/z) [M þ Na]þ calcd. for C22H13O4F9, 535.0568;
found, 535.0594.
oven at 60 C for 24 h.
PFCB Aryl Ether Polymer (P3)
ATR–FTIR (neat) t 3020, 1755, 1610, 1508, 1217, 955; 1H
NMR (300 MHz, CDCl3) d 7.44–7.38 (m, 4H), 7.06–7.04 (d,
J ¼ 8.3 Hz, 2H), 7.19–7.17 (d, J ¼ 8.3 Hz, 2H), 1.78–1.73 (m,
1H, ACHA), 0.96–0.90 (m, 4H, ACH2CH2A); 19F NMR (283
MHz, CDCl3) d ꢂ71.2 (s, ACF3, 3F), ꢂ119.0 (dd, residual cis-
CF¼¼CF2, 2F, Fa), ꢂ125.5 (dd, trans-CF¼¼CF2, 2F, Fb), ꢂ134.1
(dd, residual ACF¼¼CF2, 2F, Fc) (Jab ¼ 95.4 Hz, Jac ¼ 59.2 Hz,
Jbc ¼ 108.5 Hz), ꢂ127.3–(ꢂ132.7) (m, cyclobutyl-F6).
PFCB Aryl Ether Polymer (P4)
ATR–FTIR (neat) t 3020, 1750, 1608, 1508, 1217, 957; 1H
NMR (300 MHz, CDCl3) d 7.42–7.38 (m, 4H), 7.06–7.04 (d, J
¼ 6.9 Hz, 2H), 7.19–7.16 (d, J ¼ 8.6 Hz, 2H), 3.29–3.26 (m,
1H, ACHA), 2.26–2.21 (m, 4H, ACH2A), 1.98–1.85 (m, 2H,
ACH2A); 19F NMR (283 MHz, CDCl3) d ꢂ70.80 (s, ACF3, 3F),
ꢂ118.9 (dd, residual cis-CF¼¼CF2, 2F, Fa), ꢂ125.6 (dd, resid-
ual trans-CF¼¼CF2, 2F, Fb), ꢂ134.1 (dd, residual ACF¼¼CF2,
1,1-Bis(4-(1,2,2-trifluorovinyloxy)phenyl)-2,2,2-trifluoroethyl
Cyclobutanecarboxylate (M4)
M4 was obtained as a pale yellow oil in 51% yield. ATR–
FTIR (neat) t 3043, 2958, 1832, 1762, 1608, 1508, 1314,
1165, 830; 1H NMR (300 MHz, CDCl3) d 7.46–7.43 (d, J ¼
8.6 Hz, 4H), 7.13–7.10 (d, J ¼ 8.6 Hz, 4H), 3.35–3.30 (m, 1H,
FACILE ONE-POT SYNTHESIS, ZHU ET AL.
1889