Table 2 Copolymerization of heteroatom-containing α-olefins with ethylene.
Conditions: [Sc] (0.03 mmol), [Ph3C][B(C6F5)4] (0.03 mmol), monomer 1, ethylene (1 atm), toluene (50 ml) at 20°C for t hours (unless otherwise stated).
| Entry | 1 | [Sc] | 1/[Sc] | t (hour) | 3 | Yield (g) | Activity* | Mn (×103)† | Mw/Mn† | i.r. (%)‡ | Tg (°C)§ | Tm (°C)§ |
| 1 | 1i, FG = SPh | Sc-3 | 100/1 | 1.5 | 3i | 0.12 | 2.7 | 14.7 | 1.76 | 73.5 | −8 | n.o. |
| 2 | 1i | Sc-5 | 100/1 | 2 | 3i | 0.64 | 10.6 | 20.6 | 1.39 | 29.0 | −36 | 125 |
| 3 | 1i | Sc-5 | 500/1 | 20 | 3i | 1.95 | 3.3 | 57.7 | 1.92 | 44.9 | −16 | 128 |
| 4 | 1i | Sc-6 | 100/1 | 5 | 3i | 1.11 | 7.4 | 82.4 | 1.69 | 2.6 | −18 | 124 |
| 5 | 1i | Sc-6 | 500/1 | 20 | 3i | 3.48 | 5.8 | 31.7 | 1.96 | 15.7 | −19 | 119 |
| 6 | 1i | Sc-6 | 1000/1 | 20 | 3i | 4.39 | 7.3 | 17.0 | 2.38 | 38.9 | −14 | 110 |
| 7 | 1r, FG = PPh2 | Sc-5 | 100/1 | 0.33 | 3r | 1.03 | 103.2 | 54.0 | 2.20 | 9.5 | 2 | 133 |
| 8 | 1r | Sc-5 | 500/1 | 1.5 | 3r | 2.90 | 64.4 | —ǁ | —ǁ | 32.5 | 10 | 124 |
| 9 | 1b, FG = OPh | Sc-5 | 100/1 | 5 | 3b | 0 | — | — | — | — | — | — |
| 10 | 1t, FG = CH2OPh | Sc-5 | 100/1 | 0.5 | 3t | 1.36 | 90.4 | 124.9 | 2.29 | 8.7 | -40 | 127 |
| 11 | 1t | Sc-5 | 500/1 | 5 | 3t | 3.07 | 20.5 | 89.6 | 1.95 | 24.8 | −39 | 114 |
| 12 | 1t | Sc-6 | 100/1 | 5 | 3t | 1.78 | 11.8 | 154.2 | 2.71 | 3.3 | −31 | 124 |
| 13 | 1t | Sc-6 | 500/1 | 20 | 3t | 1.22 | 2.0 | 83.0 | 2.23 | 11.8 | −36 | 119 |
*103 g of copolymer per mole of Sc per hour per standard pressure of ethylene.
†Determined by GPC in 1,2-dichlorobenzene at 145°C against polystyrene standard.
‡Incorporation ratio of 1, determined by 1H NMR analysis.
§Determined by differential scanning calorimetry.
ǁNo GPC signal was observed in 1,2-dichlorobenzene at 145°C probably because of oxidation (or other reaction) of the phosphine components at high temperatures inside the GPC columns.