Procedure for RAFT polymerization. Trithiocarbonate termi-
nated P3HT as a macro-RAFT agent (0.10 g, ꢂ12 mmol esti-
mated by GPC result), AIBN (0.75 mg, 4.5 mmol) as an initiator,
and anhydrous toluene (2.5 mL) were mixed in a Schlenk flask
which was then purged with argon for 15 min. To this solution,
an appropriate feed ratio of styrene to acrylate monomer 2 and
anhydrous toluene (3 mL) were added and the mixture was
degassed by freeze–pump–thaw cycles (3ꢄ), and then back-filled
with dry argon. The mixture was immersed in an oil bath at 75 ꢁC
for 24 h. The polymer solution was transferred to a centrifuge
tube, precipitated with MeOH (200 mL), centrifuged, and dec-
anted. The crude product was treated with MeOH twice in the
same manner and subjected to Soxhlet extraction with hexane
(1 d). Then, the residue was redissolved in hot ethyl acetate and
filtered to remove the trace amounts of unreacted P3HT since
the P3HT was not completely soluble in ethyl acetate, and then
the filtrate was evaporated. After being redissolved in THF, the
polymer was again precipitated into hexane, centrifuged, dec-
anted, washed with MeOH, and dried in vacuo to give a viscous
concentrated in vacuo and precipitated into MeOH (200 mL).
The crude product was subjected to Soxhlet extraction with
MeOH for 1 d and hexane for 7 d. The residue was redissolved in
THF (500 mL) and filtered (five times). The filtrate was evapo-
rated and washed with hexane (twice). The crude product was
redissolved in THF (500 mL) and filtered by using a micron filter
(0.45 mm) twice, and then evaporated. The obtained residue was
redissolved in o-DCB and precipitated into hot hexane (200 mL),
which was repeated until the disappearance (TLC) of the
unreacted C60 (about five times). The product was collected and
dried to give a reddish brown polymer.
1
P3HT-b-P(S8A2)-C60. H NMR (CDCl3, 500 MHz): d ppm
7.97 (br d), 7.55–7.33 (br m), 7.17–6.91 (br m), 6.81–6.32 (br s),
4.07 (br m), 3.81–3.25 (br s), 3.07 (br s), 2.81 (br s), 2.54–2.30 (br
m), 2.19–2.02 (br m), 1.93–1.11 (br m), 0.93 (br m). 13C NMR
(CDCl3, 125.70 MHz): see ESI‡ for the spectrum.
Acknowledgements
1
reddish polymer. Representative H NMR (CDCl3, 200 MHz):
d ppm 7.97 (br d), 7.66–7.33 (br m), 7.18–6.90 (br m), 6.82–6.40
(br s), 4.07 (br m), 3.79–3.34 (br s), 3.06 (br m), 2.81 (br s), 2.44
(br m), 2.09 (br m), 1.83–1.17 (br m), 0.93 (br m).
We thank the Mitsubishi Center for Advanced Materials (MC-
CAM) for support.
P3HT-b-P(S6A4). Styrene (0.7 g, 6.73 mmol) and acrylate
monomer 2 (1.68 g, 4.48 mmol) were used, following the proce-
dure as well as purification described above.
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GPC analysis Mn ¼ 23 110 g molꢀ1, Mw ¼ 36 720 kg molꢀ1
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1
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mmol), and dry pyridine (20 mL) was placed under argon and
stirred at rt for 30 min. To the mixture, a solution of C60 (0.28 g,
0.39 mmol) in o-DCB (100 mL) was added, and the homoge-
neous reaction mixture was stirred at 70 ꢁC under argon for 2 d.
The solution was heated to reflux and the reaction allowed
to continue overnight again. The resulting mixture was
€
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5422 | J. Mater. Chem., 2009, 19, 5416–5423
This journal is ª The Royal Society of Chemistry 2009