2462 Hung et al.
Macromolecules, Vol. 36, No. 7, 2003
13C{1H} NMR (CDCl3): δ 31.49, 32.72, 35.00, 100.53, 101.75,
105.09, 122.20, 122.44, 123.64, 124.35, 124.50, 125.00, 125.39,
125.756, 126.04, 126.32, 126.37, 126.50, 126.53, 126.70, 128.07,
128.20, 128.69, 128.83, 132.72, 133.35, 133.83, 139.87, 150.90.
Anal. Calcd (found) for C45H44Cl2Zr: C, 72.36 (72.01); H, 5.94
(6.17).
Ack n ow led gm en t . Financial support from BP
Amoco and a Bayer Graduate Fellowship to J .H. are
gratefully acknowledged. We thank Dave McFarland
(BP Amoco) and Peter Fox (DuPont Dow Elastomers)
for high-temperature GPC measurements.
Eth ylen e P olym er iza tion . In a 300 mL stainless steel
Parr reactor, 150 mg of MAO in 98 mL of toluene, was
equilibrated for 30 min at 20 °C, with 16 psig of ethylene
overhead pressure. A solution of metallocene (1 × 10-6 mol)
in toluene (2 mL) was injected into the reactor via ethylene
pressure. The polymerization was run for 20 min and then
quenched with methanol (10 mL). The polyethylene was
precipitated from acidified methanol, filtered, washed with
methanol, and dried under vacuum at 40 °C.
Su p p or tin g In for m a tion Ava ila ble: Tables of sequence
distributions of copolymer samples, pentad distributions of
polypropylenes, additional fractionation data, and crystal
structure data and text describing the crystal stucture deter-
mination (26 pages). This material is free of charge via the
Internet at http://pubs.acs.org.
Refer en ces a n d Notes
P r op ylen e P olym er iza tion . In a 300 mL stainless steel
Parr reactor, 150 mg of MAO in 8 mL of toluene was
equilibrated for 30 min at 20 °C, with 90 mL of liquid
propylene. A solution of metallocene (2.68 × 10-6 mol) in
toluene (2 mL) was injected into the reactor via argon pressure
(250 psig). The polymerization was run for 20 min and then
quenched with methanol (10 mL). The polypropylene was
precipitated from acidified methanol, filtered, washed with
methanol, and dried under vacuum at 40 °C.
Eth ylen e)P r op ylen e Cop olym er iza tion . In a 300 mL
stainless steel Parr reactor, 100 mg of MAO in 18 mL of
toluene was equilibrated for 30 min at 20 °C, with 100 mL of
liquid propylene and gaseous ethylene overhead pressure.
Metallocene solution (4 × 10-7 mol) in toluene (2 mL) was
injected into the reactor via ethylene pressure, and the
polymerization was run for 20 min, after which methanol (10
mL) was injected to quench the reaction. The ethylene-
propylene copolymer was precipitated from acidified methanol,
filtered, washed with methanol, and dried under vacuum at
40 °C.
(1) Scheirs, J .; Kaminsky, W. Metallocene-based Polyolefins:
Preparation, properties, and technology; J ohn Wiley & Sons
Ltd.: Chichester, England, 2000; Vol. 1.
(2) Scheirs, J .; Kaminsky, W. Metallocene-based Polyolefins:
Preparation, properties, and technology; J ohn Wiley & Sons
Ltd.: Chichester, England, 2000; Vol. 2.
(3) Mandelkern, L. In Crystallization of Polymers; McGraw-Hill,
Inc.: New York, 1964; pp 74-116.
(4) Alamo, R.; Domszy, R.; Mandelkern, L. J . Phys. Chem. 1984,
88, 6587-6595.
(5) Alamo, R. G.; Chan, E. K. M.; Mandelkern, L. Macromolecules
1992, 25, 6381-6394.
(6) Alamo, R. G.; Viers, B. D.; Mandelkern, L. Macromolecules
1993, 26, 5740-5747.
(7) Alamo, R. G.; Mandelkern, L. Thermochim. Acta 1994, 238,
155-201.
(8) Allegra, G.; Marchessault, R. H.; Bloembergen, S. J . Polym.
Sci., Part B: Polym. Phys. 1992, 30, 809-815.
(9) Ke, B. J . Polym. Sci. 1962, 61, 47-59.
(10) Flory, P. J . Principles of Polymer Chemistry; Cornell Univer-
sity Press: Ithaca, NY, 1953.
(11) Cozewith, C.; Ver Strate, G. Macromolecules 1971, 4, 482-
Eth ylen e)1-Hexen e Cop olym er iza tion . In a 300 mL
stainless steel Parr reactor, 100 mg of MAO in 35 mL 1-hexene
was equilibrated for 30 min at 20 °C, with gaseous ethylene
overhead pressure. Catalyst solution (4 × 10-7 mol) in toluene/
1-hexene (5 mL) was injected into the reactor via ethylene
pressure, and the polymerization was run for 20 min, and then
quenched with methanol (10 mL). The ethylene-hexene co-
polymer was precipitated from acidified methanol, filtered,
washed with methanol, and dried under vacuum at 40 °C.
P olym er Ch a r a cter iza tion . Polymer molecular weights
and molecular weight distributions were determined by high-
temperature gel permeation chromatography (GPC) using
high-density polyethylene calibration standards. Melting point
ranges and heats of fusion were determined by differential
scanning calorimetry (DSC) using a Perkin-Elmer DSC-7. All
DSC samples were heated to 180 °C, held at that temperature
for 10 min, cooled to 20 °C at a rate of 10 °C/min, and then
aged at room temperature for 48 h. DSC scans were obtained
by heating the samples to 180 °C at a rate of 20 °C/min. The
isothermally crystallized samples were prepared and run
similarly to what was described in the literature.39 The
samples were heated to 180 °C, held at that temperature for
5 min, and then quenched. The samples were then heated to
the desired annealing temperature at a rate of 40 °C/min and
held at that temperature for 1 h, after which the samples were
quenched. The DSC scans were then obtained at a rate of 10
°C/min. 13C NMR measurements were obtained using a Varian
Unity Innova 300 MHz instrument for polymer samples (80
mg in 2 mL of o-dichlorobenzene/10 vol % benzene-d6 with Cr-
(acac)3 as a relaxation agent) at 100 °C in 10 mm NMR tubes.
The delay time between pulses was set at 5 s.
489.
(12) Cozewith, C. Macromolecules 1987, 20, 1237-1244.
(13) Galimberti, M.; Piemontesi, F.; Fusco, O. In Metallocene-
Based Polyolefins; Scheirs, J ., Kaminsky, W., Eds.; Wiley:
Chichester, England, 2000; Vol. 1; pp 309-343.
(14) Matsugi, T.; Matsui, S.; Kojoh, S.; Takagi, Y.; Inoue, Y.;
Nakano, T.; Fujita, T.; Kashiwa, N. Macromolecules 2002,
35, 4880-4887.
(15) Turner, H. W.; Hlatky, G. G.; Yang, W. H.; Gadkari, A. C.;
Licciardi, G. F. U.S. Patent 5,391,629, 1995.
(16) Choo, T. N.; Waymouth, R. M. J . Am. Chem. Soc. 2002, 124,
4188-4189.
(17) Fan, W.-H.; Leclerc, M. K.; Waymouth, R. M. J . Am. Chem.
Soc. 2001, 123, 9555.
(18) Kaminsky, W.; Beulich, I.; Arndt-Rosenau, M. Macromol.
Symp. 2001, 173, 221-225.
(19) Uozumi, T.; Ahn, C. H.; Tomisaka, M.; J in, J .; Tian, G.; Sano,
T.; Soga, K. Macromol. Chem. Phys. 2000, 201, 1748-1752.
(20) Galimberti, M.; Piemontesi, F.; Mascellani, N.; Camurati, I.;
Fusco, O.; Destro, M. Macromolecules 1999, 32, 7968-7976.
(21) Arndt, M.; Kaminsky, W.; Schauwienold, A.-M.; Weingarten,
U. Macromol. Chem. Phys. 1998, 199.
(22) J in, J . H.; Uozumi, T.; Sano, T.; Teranishi, T.; Soga, K.;
Shiono, T. Macromol. Rapid Commun. 1998, 19, 337-339.
(23) Leclerc, M. K.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl.
1998, 37, 922-925.
(24) Galimberti, M.; Piemontesi, F.; Fusco, O.; Camurati, I.;
Destro, M. Macromolecules 1998, 31, 3409-3416.
(25) Uozumi, T.; Miyazawa, K.; Sano, T.; Soga, K. Macromol.
Rapid Commun. 1997, 18, 883-889.
(26) Tagge, C. D.; Kravchenko, R. L.; Lal, T. K.; Waymouth, R.
M. Organometallics 1999, 18, 380-388.
(27) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-
219.
(28) Propylene homopolymerizations: 2, productivity ) 2480 kg/
mol Zr‚hr, [mmmm] ) 28%, Mw ) 459 000, PDI ) 3.7; 3,
productivity ) 1950 kg/mol Zr‚hr, [mmmm] ) 80%; 7,
F r a ct ion a t ion of E t h ylen e)1-Hexen e Cop olym er . A
1.01 g sample of EH copolymer was transferred into an
extraction thimble, plugged with glass wool, capped with filter
paper, and placed in a Kumagawa extractor. The fractions
were obtained by successive extractions into refluxing ether
and then heptane under nitrogen for 24 h each. The ether-
and heptane-soluble fractions were isolated by precipitation
from methanol and then dried under vacuum together with
the heptane-insoluble fraction.
productivity ) 1310 kg/mol Zr‚hr, [mmmm] ) 34%, Mw
)
370 000, PDI ) 2.8; 8, productivity ) 310 kg/mol Zr‚hr,
[mmmm] ) 24%, Mw ) 73 100, PDI ) 2.9. Ethylene homo-
polymerizations: 8, productivity ) 3450 kg/mol Zr‚hr, Mw
780 000, PDI ) 4.6.
(29) Wilmes, G.; Lin, S.; Waymouth, R. M. Macromolecules 2002,
35, 5382-5387.
)