730 Macromolecules, Vol. 43, No. 2, 2010
Yu et al.
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H5)3]þ[B(C6F5)4]- (16.0 μmol), and Al(iBu)3 (800 μmol) in
2.0 mL of toluene, was added via a syringe, the ethylene gas
was fed immediately under pressure (Table 1). After polymeri-
zation was conducted for a given time (Table 1), the ethylene gas
was vented off. The viscous polymerized solution was trans-
ferred into a one-neck flask. After toluene was removed under
vacuum, unreacted HTCPD was recovered by vacuum distilla-
tion (80 °C/0.3 mmHg). The residue was dissolved in chloro-
form, and the resulting solution was filtered over a short pad of
Celite. Methanol was added to the solution to yield a white
precipitate, which was collected by filtration. The precipitate
was dried under vacuum above its Tg. The copolymer (5 mg)
was dissolved in CDCl3, and the NMR spectra were recorded
at 25 °C.
Ethylene/HTCPD Copolymerization (Large Scale). A toluene
solution of HTCPD (90 mL) was transferred into a dried bomb
reactor under a N2 atmosphere. After an activated catalyst,
which was prepared by mixing the catalyst (15.4 μmol),
[C(C6H5)3]þ[B(C6F5)4]- (61.7 μmol), and Al(iBu)3 (3.1 mmol)
in 10 mL of toluene, was added via a syringe, the ethylene gas
was charged immediately under 20 psig pressure. After poly-
merization was conducted for 90 min, the ethylene gas was
vented off. The viscous polymerized solution was treated as
described above to the filtration step.
Preparation of Film. Polymer was dissolved in CHCl3 to
obtain a thick viscous solution (15 wt %), which was filtered
using a 0.45 μm GD/X PVDF syringe filter. The viscous solution
was spread on a glass plate (25 cm ꢀ 40 cm) with a thickness
(750 μm) determined using an micrometer adjustable film
applicator. The solvent in the spread film was carefully evapo-
rated at room temperature for 1.0 h in an inert condition and
then at 100 °C for 1.0 h. After evaporation, the film thickness
was 110 μm. In case of norbornene/ethylene copolymer, some
bubbles were formed during the evaporation (Supporting
Information).
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ꢁ
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(13) Palmova, I.; Kosek, J.; Schongut, J.; Marek, M.; Stepanek, K.
ꢀ
€
Measurement of Tensile Properties. The tensile test bars
(110 mm ꢀ 15 mm) were cut from the films avoiding bubbles.
The tensile tests were performed according to the ASTM D 638
on UTM (WL2100). The drawing rate was 5 mm/min.
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Chem. 1991, 56, 6043. (d) Burgos, O.; Chavez, I.; Manríquez, J. M.;
Acknowledgment. This research was supported by the Ene-
rgy Technology Innovation Project (ETI) under the Energy
Resources Technology Development Program from Korea
Energy Management Cooperation (KEMCO) and by Priority
ResearchCenters Program through the National ResearchFoun-
dation of Korea (NRF) funded by the Ministry of Education,
Science and Technology (2009-0093826).
Alegría, S. Tetrahedron Lett. 2007, 48, 8331.
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(19) (a) Wurtz, S.; Glorius, F. Acc. Chem. Res. 2008, 41, 1523. (b)
Supporting Information Available: 1H and 13C NMR spec-
tra of HTCPD and the 13C-DEPT NMR spectra of a copolymer.
The material is available free of charge via the Internet at http://
pubs.acs.org
€
ꢀ
Clavier, H.; Correa, A.; Cavallo, L.; Escudero-Adan, E. C.; Benet-
Buchholz, J.; Slawin, A. M. Z.; Nolan, S. P. Eur. J. Inorg. Chem. 2009,
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