Table 1. Ethylene Polymerization Catalyzed by Vanadium(V) Dichloro Complexes Containing WCA-NHC Ligands (1–5)–Al Cocatalysts (Ethylene 8 atm, 25 °C, 10 Min)a.
| run | V cat. (μmol) | Al cocat. (μmol) | Al/Vb | yield/mg | activityc | TOFd/min | Mne × 10–4 | Mw/Mne |
|---|---|---|---|---|---|---|---|---|
| 1f | 1 (1.0) | d-MAO (500) | 500 | 6 | 35 | 21 | ||
| 2e | 2 (1.0) | d-MAO (100) | 100 | 8 | 48 | 29 | ||
| 3f | 3 (1.0) | d-MAO (200) | 200 | 264 | 1580 | 939 | 1.53 | 1.93 |
| 4f | 3 (1.0) | d-MAO (500) | 500 | 137 | 824 | 490 | ||
| 5 | 4 (1.0) | d-MAO (100) | 500 | 17 | 102 | 61 | ||
| 6 | 5 (1.0) | d-MAO (200) | 200 | 895 | 4210 | 2500 | ||
| 7 | 5 (0.2) | d-MAO (100) | 500 | 14 | 420 | 250 | ||
| 8 | 5 (0.2) | d-MAO (200) | 1000 | 136 | 4080 | 2420 | ||
| 9 | 5 (0.2) | d-MAO (400) | 2000 | 664 | 19 900 | 11 800 | ||
| 10 | 5 (0.2) | d-MAO (600) | 3000 | 645 | 19 500 | 11 600 | 9.46 | 1.56 |
| 11g | C (1.0) | d-MAO (2500) | 2500 | 488 | 2930 | 1740 | 175 | 1.64 |
| 12f | 3 (0.2) | AliBu3 (10.0) | 50 | 365 | 11 000 | 6540 | 1.80 | 1.76 |
| 13f | 3 (0.2) | AliBu3 (20.0) | 100 | 161 | 4830 | 2870 | ||
| 14f,h | 3 (0.2) | Et2AlCl (500) | 2500 | 65.8 | 1970 | 1170 | ||
| 15 | 4 (1.0) | AliBu3 (100) | 100 | 95 | 570 | 339 | ||
| 16 | 4 (1.0) | AliBu3 (200) | 200 | 99 | 594 | 353 | ||
| 17 | 5 (0.2) | AliBu3 (10.0) | 50 | 13 | 390 | 232 | 5.11 | 1.42 |
| 18 | 5 (0.2) | AliBu3 (20.0) | 100 | 67 | 2010 | 1190 | ||
| 19 | 5 (0.2) | AliBu3 (40.0) | 200 | 187 | 5610 | 3330 | ||
| 20 | 5 (0.2) | AliBu3 (200) | 100 | 223 | 6690 | 3970 | ||
| 21 | 5 (0.2) | AliBu3 (400) | 200 | 390 | 11 700 | 6950 | ||
| 22 | 5 (0.1) | AliBu3 (400) | 400 | 263 | 15 780 | 9380 | ||
| 23 | 5 (0.1) | AliBu3 (600) | 600 | 373 | 22 380 | 13 300 | ||
| 24 | 5 (0.02) | AliBu3 (400) | 2000 | 157 | 47 100 | 28 000 | ||
| 25 | 5 (0.02) | AliBu3 (500) | 2500 | 220 | 66 000 | 39 200 | 13.7 | 2.35 |
| 26 | 5 (0.02) | AliBu3 (550) | 2750 | 187 | 56 100 | 33 300 | ||
| 27 | 5 (0.02) | AliBu3 (600) | 3000 | 59 | 17 700 | 10 500 | ||
| 28g,h | C (0.05) | Me2AlCl (250) | 5000 | 229 | 27 500 | 16 300 | (898)i | |
| 29g,h | C (0.01) | iBu2AlCl (250) | 25 000 | 108 | 64 800 | 38 500 | (1250)i |
a
Conditions: toluene 30 mL, d-MAO [used as a white solid prepared from TMAO (Tosoh Finechem Co., Ltd.) by removing toluene and AlMe3] or AliBu3.
b
Al/V molar ratio.
c
Activity in kg-PE/mol-V·h.
d
TOF (min–1) = (molar amount of ethylene reacted)/(mol-V)·(min).
e
GPC data in o-dichlorobenzene vs polystyrene standards.
f
Cited from ref (47).
h
Conducted at 0 °C.
i
Molecular weight by viscosity.45