Table 2. Ethylene Copolymerization with 1-Dodecene (DD), 1-Tetradecene (TD), and 1-Hexadecene (HD) by the Cp*TiCl2(O-2,6-iPr2-4-SiEt3C6H2)–MAO Catalyst Systema.
| run | cat./μmol | α-olefin | conc.b/M | E/atm | yield/mg | activityc | Mnd × 10–4 | Mw/Mnd | cont.e/mol % |
|---|---|---|---|---|---|---|---|---|---|
| 1 | 0.001 | 6 | 18.1 | 181 000 | insoluble | ||||
| 2 | 0.01 | DD | 0.75 | 2 | 329 | 329 000 | 8.9 | 1.86 | 18.2 |
| 3 | 0.0025 | DD | 0.75 | 4 | 123 | 492 000 | 11.4 | 1.81 | 15.6 |
| 4 | 0.001 | DD | 0.30 | 6 | 83.5 | 835 000 | 25.0 | 2.05 | 5.1 |
| 5 | 0.001 | DD | 0.45 | 6 | 88.9 | 889 000 | 18.5 | 1.97 | 6.6 |
| 6f | 0.001 | DD | 0.75 | 6 | 104 | 1 040 000 | 16.7 | 1.62 | 15.0 (15.5)g |
| 7 | 0.0025 | DD | 1.13 | 6 | 309 | 1 240 000 | 11.4 | 1.74 | 16.0 |
| 8 | 0.0025 | DD | 1.50 | 6 | 363 | 1 450 000 | 11.6 | 1.76 | 17.6 |
| 9 | 0.001 | DD | 0.30 | 8 | 163 | 1 630 000 | 30.1 | 2.09 | 4.0 |
| 10 | 0.001 | DD | 0.45 | 8 | 177 | 1 770 000 | 23.6 | 1.95 | 5.3 |
| 11 | 0.001 | DD | 0.60 | 8 | 177 | 1 770 000 | 20.6 | 1.96 | 6.1 |
| 12 | 0.001 | DD | 0.75 | 8 | 235 | 2 350 000 | 16.9 | 1.89 | 7.2 (8.0)g |
| 13 | 0.001 | DD | 0.90 | 8 | 283 | 2 830 000 | 14.7 | 1.98 | 8.5 |
| 14 | 1.0 | DD | 0.75 | 477 | 954 | 12.7 | 1.94 | 100 | |
| 15 | 0.01 | TD | 0.67 | 2 | 130 | 130 000 | 12.2 | 1.74 | 15.4 |
| 16 | 0.0025 | TD | 0.67 | 4 | 58.3 | 233 000 | 13.1 | 1.98 | 12.0 |
| 17 | 0.001 | TD | 0.27 | 8 | 120 | 1 200 000 | 43.5 | 2.95 | 3.0 |
| 18 | 0.001 | TD | 0.40 | 8 | 299 | 2 990 000 | 35.5 | 2.49 | 4.5 |
| 19 | 0.001 | TD | 0.27 | 6 | 387 | 3 870 000 | 29.4 | 2.31 | 4.8 |
| 20 | 0.001 | TD | 0.40 | 5 | 169 | 1 690 000 | 17.6 | 2.05 | 8.8 |
| 21 | 0.001 | TD | 0.40 | 6 | 222 | 2 220 000 | 23.4 | 2.25 | 6.3 |
| 22 | 0.001 | TD | 0.40 | 7 | 234 | 2 340 000 | 29.1 | 2.10 | 5.2 |
| 23 | 0.001 | TD | 0.54 | 6 | 207 | 2 070 000 | 18.1 | 1.95 | 8.1 |
| 24 | 0.001 | TD | 0.67 | 6 | 122 | 1 220 000 | 14.0 | 1.87 | 11.4 (12.0)g |
| 25h | 0.001 | TD | 0.67 | 6 | 136 | 1 360 000 | 16.6 | 1.96 | 10.0 |
| 26 | 0.001 | TD | 0.67 | 8 | 442 | 4 420 000 | 15.2 | 2.00 | 6.6 |
| 27 | 0.0025 | TD | 1.01 | 6 | 250 | 1 000 000 | 11.2 | 1.78 | 13.5 |
| 28 | 0.005 | TD | 1.34 | 6 | 162 | 323 000 | 12.1 | 1.97 | 15.2 |
| 29 | 1.0 | TD | 0.67 | 329 | 658 | 17.6 | 1.98 | ||
| 30 | 0.0005 | HD | 0.58 | 2 | 70.8 | 142 000 | 11.0 | 1.66 | 15.0 |
| 31 | 0.001 | HD | 0.58 | 4 | 176 | 1 760 000 | 13.8 | 1.86 | 11.4 |
| 32 | 0.0005 | HD | 0.35 | 6 | 97.1 | 1 942 000 | 25.9 | 1.98 | 6.1 |
| 33 | 0.0005 | HD | 0.58 | 6 | 95.2 | 1 900 000 | 18.7 | 1.96 | 9.7 |
| 34h | 0.0005 | HD | 0.58 | 6 | 156 | 3 120 000 | 15.2 | 1.96 | 9.3 |
| 35 | 0.001 | HD | 0.87 | 6 | 190 | 1 900 000 | 14.2 | 1.90 | 12.5 |
| 36 | 0.001 | HD | 1.16 | 6 | 257 | 2 570 000 | 14.1 | 1.83 | 14.0 |
| 37 | 0.001 | HD | 0.23 | 8 | 180 | 1 800 000 | 43.3 | 2.57 | 2.7 |
| 38 | 0.001 | HD | 0.35 | 8 | 244 | 2 440 000 | 26.9 | 2.57 | 4.4 |
| 39 | 0.0005 | HD | 0.58 | 8 | 180 | 3 600 000 | 21.4 | 1.96 | 6.4 (7.1)g |
| 40 | 1.0 | HD | 0.58 | 134 | 268 | 7.8 | 1.51 |
Conditions: total volume, 30 mL; MAO, 2.0 mmol; 6 min (runs 14, 29, 40: total 6.0 mL, 30 min); and 25 °C.
Initial concentration (mmol/mL).
Activity = kg-polymer/mol-Ti·h.
GPC data in o-dichlorobenzene vs polystyrene standards.
α-Olefin in copolymer (mol %) estimated using 1H NMR spectra (selected data are shown in SI).
Polymerization data cited from ref (31).
α-Olefin in copolymer (mol %) estimated using 13C NMR spectra (selected data are shown in SI).
Polymerization at 50 °C.