Table 4.
Syndiotactic polymerization of styrene by complexes 1–3/activator/AlR3 ternary systems.a
| t | T | Y | rrrrd | M n e | T m f | |||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| entry | Cat. | Ab | AlR3 | [Al]/[Ln] | [ST]/[Ln] | Sol. | (h) | (°C) | (%) | Ac | (%) | (105) | Mw/Mne | (°C) |
| 1 | 1 | A | AliBu3 | 10 | 500 | PhCl2 | 12 | 25 | 18 | 781 | >99 | 7 | 2.05 | 272 |
| 2 | 1 | B | AliBu3 | 10 | 500 | PhCl2 | 6 | 25 | 32 | 2777 | >99 | 9 | 2.38 | 271 |
| 3 | 1 | C | AliBu3 | 10 | 500 | PhCl2 | 24 | 25 | 7 | 152 | >99 | 3 | 2.36 | 274 |
| 4 | 2 | B | AliBu3 | 10 | 500 | PhCl2 | 24 | 25 | 6 | 130 | 54 | n.d. | n.d. | 260 |
| 5 | 3 | B | AliBu3 | 10 | 500 | PhCl2 | 24 | 25 | 23 | 499 | >99 | 9 | 2.21 | 271 |
| 7 | 1 | B | AlEt3 | 10 | 500 | PhCl2 | 24 | 25 | 10.4 | 225.66 | >99 | 0.07 | 6.42 | |
| 6 | 1 | B | AlEt3 | 10 | 500 | PhCl2 | 24 | 25 | 10 | 217 | >99 | 0.1 | 6.42 | 271 |
| 7 | 1 | A | AliBu3 | 10 | 500 | PhCl | 24 | 25 | 26 | 564 | 63 | n.d. | n.d. | 265 |
| 8 | 1 | B | AliBu3 | 10 | 500 | PhCl | 24 | 25 | 17 | 369 | 65 | n.d. | n.d. | 267 |
| 9 | 1 | B | AliBu3 | 10 | 500 | Tol | 20 | 25 | 43 | 1120 | >99 | 7 | 2.27 | 270 |
| 10 | 1 | B | AliBu3 | 10 | 500 | C2H2Cl4 | 48 | 25 | 17 | 184 | 61 | n.d. | n.d. | 265 |
| 11 | 1 | B | AliBu3 | 5 | 500 | PhCl2 | 12 | 25 | 5 | 217 | >99 | n.d. | n.d. | 272 |
| 12 | 1 | B | AliBu3 | 15 | 500 | PhCl2 | 12 | 25 | 42 | 1822 | >99 | 6 | 2.09 | 271 |
| 13 | 1 | B | AliBu3 | 10 | 500 | PhCl2 | 12 | 50 | 60 | 2604 | >99 | 5 | 2.00 | 273 |
| 14 | 1 | B | AliBu3 | 10 | 500 | PhCl2 | 12 | 70 | 59 | 2561 | >99 | 4 | 1.98 | 272 |
| 15 | 1 | B | AliBu3 | 10 | 500 | PhCl2 | 12 | 90 | 61 | 2647 | >99 | 0.1 | 18.78 | 271 |
| 16 | 1 | B | AliBu3 | 10 | 200 | PhCl2 | 12 | 25 | 41 | 712 | >99 | 5 | 2.02 | 275 |
| 17 | 1 | B | AliBu3 | 10 | 400 | PhCl2 | 12 | 25 | 35 | 1215 | >99 | 8 | 2.02 | 273 |
| 18 | 1 | B | AliBu3 | 10 | 700 | PhCl2 | 12 | 25 | 35 | 2126 | >99 | 13 | 1.49 | 271 |
| 19 | Scg | B | AliBu3 | 10 | 500 | PhCl2 | 48 | 25 | 7 | 76 | 78 | n.d. | n.d. | 268 |
| 20 | Scg | Bh | AliBu3 | 10 | 500 | PhCl2 | 12 | 25 | 9 | 390 | >99 | n.d. | n.d. | 272 |
a Conditions unless specified otherwise: 10 μmol of Ln complex, 10 μmol of activator, 5 mL of solvent. b Activator: A = [Ph3C][B(C6F5)4]; B = [PhNHMe2][B(C6F5)4]; C = B(C6F5)3. c Activity in (g of polymer)/(molLn h). d Determined by 1H and 13C NMR spectrum. e Determined by GPC in 1,2,4-trichlorobenzene at 150 °C against polystyrene standard. f Measured by DSC. g Sc = Sc(CH2SiMe3)3(THF)2. h 20 μmol of activator.