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evaporated and product was extracted (DCM/water). The
organic layer was dried over magnesium sulfate and purified
with silica gel column (dichloromethane). The solvent was
evaporated to afford 318 mg of 4,40-divinyl-1,10-biphenyl
(yield 92%) and 427 mg of 4,40-divinyl-p-terphenyl (yield
90%).
Then, the solvent was evaporated under a vacuum and cold
n-hexane (2 mL) was added to the remaining content to
form colorless precipitate. The precipitate was filtered off
and purified by column chromatography (silica gel 60/
hexane:DCM 5 1:5) to remove ruthenium complexes. Evapo-
ration of the solvent allowed an analytically pure sample
(white powder) to be obtained.
4,40-Divinyl-1,10-biphenyl
1H NMR (300 MHz, CDCl3, d, ppm): 5.3 (d, 2H, JHH 511.1 Hz,
-CH5CH2), 5.77 (d, 2H, JHH 517.7 Hz, -CH5CH2), 6.77 (dd,
2H, JHH 511.2, 17.5 Hz, -CH5CH2), 7.5 (d, 4H, JHH 5 8.4 Hz,
H2), 7.57 (d, 4H, JHH 5 8.4 Hz, H3); 13C NMR (75 MHz, CDCl3,
d, ppm): 114 (-CH5CH2), 126.8, 127.1, 136.2 (-CH5CH2),
Co-oligomers Spectroscopic Analysis
1A-1Ph-1
1H NMR (CDCl3, d, ppm): 0.42 (s, 6H, CH3 from terminal part),
0.5 (b s, 6H, CH3 from copolymer), 5.92 – 6.26 (m, 6H,
-CH5CH2 from terminal part), 6.52 (d, 2H, JHH 5 19.0 Hz,
5CHSi), 6.95 – 7.84 (m, 46H, 5CH-C6H4- and C6H5); 13C NMR
(CDCl3, d, ppm): 20.72 (CH3 from terminal part), 20.64 (CH3
from copolymer), 124.25 (d, J 5 6.4 Hz), 126.94, 127.32,
127.62 (t, J 5 7.5 Hz), 127.80, 127.86, 130.29, 130.43, 130.77,
130.90, 131.07, 131.99, 134.02, 134.18 (t, J 5 4.1 Hz), 136.81,
140.6, 146.08; 29Si NMR (CDCl3, d, ppm): 230.19, 230.61,
277.38, 278.26, 279.52, 279.67; isolated yield 5 92%
136.8, 140.1; MS (EI): m/z (rel. intensity – %): 206 (M1•
)
(100), 191 (7), 188 (10), 178 (12), 165 (6), 152 (7), 103
(5), 89 (4), 76 (5), 51 (3); HRMS (ESI, m/z) calcd. for
C16H14: 206.10955, found 206.10948.
4,40-Divinyl-p-terphenyl
1H NMR (300 MHz, CDCl3, d, ppm): 5.3 (d, 2H, JHH 511.1 Hz,
-CH5CH2), 5.81 (d, 2H, JHH 517.7 Hz, -CH5CH2), 6.77 (dd,
2H, JHH 511.2, 17.5 Hz, -CH5CH2), 7.5 (d, 4H, JHH 5 8.4 Hz,
H2), 7.62 (d, 4H, JHH 5 8.4 Hz, H3), 7.7 (s, 4H, H2’); 13C NMR
(75 MHz, CDCl3, d, ppm): 114 (-CH5CH2), 126.9, 127.1,
127.3, 136.4 (-CH5CH2), 136.5, 136.7, 140.0; MS (EI): m/z
(rel. intensity - %): 282 (M1•) (100), 265 (5), 252 (6), 239
(5), 225 (3), 202 (4), 179 (4), 152 (3), 141 (7), 126 (4), 77
(4), 51 (2); HRMS (ESI, m/z) calcd. for C22H18: 282.14085,
found 282.14077.
1A-2Ph-5
1H NMR (CDCl3, d, ppm): 0.48 (b s, 6H, CH3), 6.44 (d, 2H,
J
HH 5 19.1 Hz, 5CHSi), 6.88 – 7.80 (m, 50H, 5CH-(C6H4)2-
and C6H5); 13C NMR (CDCl3, d, ppm): 20.67, 124.24 (b s),
126.92, 127.54, 127.60, 127.68, 127.79, 127.87, 129.77,
130.34, 130.41, 130.63, 130.82 (t, J 5 5.7 Hz), 131.05, 131.97
(d, J 5 2.2 Hz), 134.01 (b s), 134.05, 134.07, 134.10, 134.16,
134.22, 137.72, 146.17; 29Si NMR (CDCl3, d, ppm): 230.27,
278.26, 279.46; isolated yield 5 90%
Polymer Synthesis
Metathetic copolymerization
1A-2Ph-1
1H NMR (CDCl3, d, ppm): 0.42 (s, 6H, CH3 from terminal part),
0.5 (b s, 6H, CH3 from copolymer), 5.93 – 6.26 (m, 6H, -
CH5CH2 from terminal part), 6.52 (d, 2H, JHH 5 19.2 Hz,
5CHSi), 6.77 – 7.86 (m, 46H, 5 CH-(C6H4)2- and C6H5); 13C
NMR (CDCl3, d, ppm): 20.72 (CH3 from terminal part), 20.64
(CH3 from copolymer), 124.26 (d, J 5 7.6 Hz), 126.94, 127.33,
127.61 (t, J 5 6.6 Hz), 127.81, 127.86, 130.30, 130.43, 130.75,
130.91, 131.08, 131.99, 134.03, 134.14, 134.18, 136.8, 140.61,
146.08; 29Si NMR (CDCl3, d, ppm): 230.2, 231.5, 278.26,
279.52, 279.67; isolated yield 5 94%
A 5-mL glass reactor equipped with a reflux condenser and
connected to a gas/vacuum line was charged under argon
with DDSQ-2SiVi (1B) (0.15 g, 1.13 3 1024 mol), diolefin
(1.13 3 1024 mol), and DCM (2 mL). The mixture was
warmed up in an oil bath to 45 8C and first-generation
Grubbs’ catalyst (0.0018 g, 2.48 3 1026 mol) was added to
the mixture under argon. The reaction mixture was heated
under reflux for 24 h or 5 days. Then, the solvent was
evaporated under a vacuum and cold n-hexane (2 mL) was
added to the remaining content to form white precipitate.
The precipitate was filtered off and purified by column chro-
matography (silica gel 60/hexane:DCM 5 1:5) to remove
ruthenium complexes. Evaporation of the solvent allowed an
analytically pure sample (white powder) to be obtained.
1A-3Ph-5
1H NMR (CDCl3, d, ppm): 0.49 (s, 6H, CH3), 6.52 (d, 2H,
J
HH 5 19.3 Hz, 5CHSi), 6.75 – 7.82 (m, 54H, 5CH-(C6H4)3- and
C6H5); 13C NMR (CDCl3, d, ppm): 20.72, 124.25 (b s), 126.98,
127.37, 127.61 (t, J 5 6.8 Hz), 127.79, 127.85, 130.30, 130.42,
130.52, 130.60, 130.89, 131.08, 131.99, 134.02, 134.18
(t, J 5 4.6 Hz), 136.79, 140.52, 146.10; 29Si NMR (CDCl3,
d, ppm): 230.22, 278.27, 279.51; isolated yield 5 91%
Silylative Coupling Copolycondensation
A 5-mL glass reactor, equipped with a reflux condenser and
connected to a gas/vacuum line, was charged under argon
with DDSQ-2SiVi (1A) (0.15 g, 1.24 3 1024 mol), diolefin
(1Ph, 2Ph) (1.24 3 1024 mol), and DCM or toluene for reac-
tion with 4,4’-divinyl-p-terphenyl (3 mL). The mixture was
warmed up in an oil bath to 45 8C (for reactions performed
in DCM) or 100 8C (for reactions performed in toluene) and
[RuHCl(CO)(PCy3)2] (0.0018 g, 2.48 3 1026 mol) was added
to the mixture under argon. After 5 min of the reaction cop-
per(I) chloride (0.0012 g, 1.24 3 1025 mol) was added. The
reaction mixture was heated under reflux for 24 h or 5 days.
1A-3Ph-1
1H NMR (CDCl3, d, ppm): 0.41 (s, 6H, CH3 from terminal
part), 0.5 (b s, 6H, CH3 from copolymer), 5.91 – 6.24 (m, 6H,
-CH5CH2 from terminal part), 6.51 (d, 2H, JHH 5 19.2 Hz,
5CHSi), 6.76 – 7.81 (m, 54H, 5CH-(C6H4)3- and C6H5); 13C
NMR (CDCl3, d, ppm): 20.73 (CH3 from terminal part),
20.64 (CH3 from copolymer), 124.29 (b s), 126.93, 127.32,
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2016, 54, 1044–1055
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