Table 1.
Polymerization results of MOEPA with DBU and TBD under different conditions.
| entry | Catalyst | M : I : Catalyst (molar ratios) | Conc. (g/mL) | Time (min) | Conversion (31P NMR) | Mn, Da (GPC)a | Mw/Mn (GPC)b | Mn, Da (Theor)c | Mn, Da (1H NMR)d |
|---|---|---|---|---|---|---|---|---|---|
| 1 | DBU | 50 : 1 : 1.5 | 0.5 | 15 | 1 % | N.A. | N.A. | N.A. | N.A. |
| 2 | DBU | 50 : 1 : 2.5 | 0.5 | 30 | 2 % | N.A. | N.A. | N.A. | N.A. |
| 3 | DBU | 50 : 1 : 5.0 | 0.5 | 30 | 2 % | N.A. | N.A. | N.A. | N.A. |
| 4 | TBD | 50 : 1 : 1.5 | 0.5 | 1 | 77 % | 15000 | 1.34 | 7100 | 7300 |
| 5 | TBD | 50 : 1 : 1.0 | 0.5 | 1 | 58 % | 10000 | 1.08 | 5400 | 5500 |
| 6 | TBD | 50 : 1 : 1.0 | 0.5 | 2 | 75 % | 13000 | 1.17 | 6900 | 6800 |
| 7 | TBD | 50 : 1 : 1.0 | 0.25 | 1 | 41 % | 7200 | 1.07 | 3800 | 3900 |
| 8 | TBD | 50 : 1 : 1.0 | 0.25 | 3 | 66 % | 12000 | 1.07 | 6100 | 6300 |
| 9 | TBD | 50 : 1 : 0.5 | 0.5 | 1 | 34 % | 6200 | 1.08 | 3200 | 3300 |
| 10 | TBD | 50 : 1 : 0.5 | 0.5 | 4 | 62 % | 10000 | 1.07 | 5700 | 5400 |
| 11 | TBD | 100 : 1 : 1.0 | 0.5 | 5 | 51 % | 14000 | 1.05 | 9300 | 9000 |
| 12 | TBD | 25 : 1 : 0.25 | 0.5 | 1 | 68 % | 6200 | 1.08 | 3200 | 3400 |
Entries 1–3 were under room temperature; entries 4–12 were at 0 °C. Initiator (I) was benzyl alcohol for all entries. Solvent was anhydrous dichloromethane for all entries.
a, b
Mn (GPC) and Mw/Mn (GPC) were measured by DMF GPC calibrated using polystyrene standards.
c
Mn (Theor) was calculated from the monomer to initiator ratio and corrected for the conversion.
d
Mn (1H NMR) was calculated from the monomer to initiator ratio based on 1H NMR of final polymer product.