Table 4. Ethylene Polymerization of C1 at 0–80 °Ca.
| entry | temp (°C) | time (min) | yield (g) | productivity (kg mol–1Ni h) | TOF (103)(h–1) | Mnb (kg mol–1) | Đb | Tmc (°C) | B/1000Cd | branching distribution (%)f | |||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Me | Et | Pr | Bu | Am | Lg | ||||||||||
| 1 | 0 | 30 | 1.1 | 440 | 15.7 | 65.1 | 1.65 | 127.8 | 5 | 100 | 0 | 0 | 0 | 0 | 0 |
| 2 | 20 | 10 | 2.4 | 2880 | 102.9 | 11.4 | 1.93 | 108.6 | 25 | 94.3 | 3.5 | 2.2 | 0 | 0 | 0 |
| 3 | 40 | 10 | 1.8 | 2160 | 77.1 | 3.7 | 1.66 | 64.4 | 56(46)e | 80.0 | 4.7 | 2.9 | 2.6 | 2.1 | 7.6 |
| 4 | 60 | 10 | 2.2 | 2640 | 94.3 | 2.0 | 1.51 | 9.3 | 95(72)e | 74.0 | 6.2 | 4.1 | 2.6 | 3.4 | 9.7 |
| 5 | 80 | 10 | 0.7 | 840 | 30.0 | 1.0 | 1.74 | –23.6 | 127(81)e | 66.4 | 7.5 | 4.5 | 2.8 | 6.6 | 12.1 |
a
Conditions: 5 μmol of Ni catalyst, 10 equiv of B(C6F5)3, 400 psi ethylene, 45 mL of toluene.
b
Determined by GPC in 1,2,4-trichlorobenzene at 160 °C using polystyrene calibration.
c
Determined by differential scanning calorimetry.
d
Determined by 1H NMR in D2-tetrachloroethane at 125 °C.
e
Branching density corrected for saturated end groups.
f
Determined by 13C NMR in D2-tetrachloroethane at 125 °C. Percentages of branch length determined from relative intensity ratios of methyl (1B1, 1B2, 1B3), methylene (2B4, 3B5) or methine (brB4+) signals of the respective branch. TOF = Turnover Frequency, Mn = Number-Average Molecular Weight, Đ = Dispersity, Tm = Melting Temperature, Me = Methyl, Et = Ethyl, Pr = Propyl, Bu = Butyl, Am = Amyl, Lg = Large.