Table 2. Tandem synthesis of aliphatic polyesters.
| Entry | Complex | Anhydride | Epoxide | [PPNCl]/[M] | [A]/[E] | Temperature (°C) | Time (h) | Yield (%)* | Mn (g mol−1)† | PDI† |
|---|---|---|---|---|---|---|---|---|---|---|
| 1 | 1 | CA | PO | — | 15 | 30 | 24 | <5 | ND‡ | ND‡ |
| 2 | 1 | CA | PO | 1 | 15 | 30 | 24 | 100 | 16,900 | 1.2 |
| 3 | 1 | SA | PO | 1 | 13.5 | 30 | 7.5 | 82 | 5,100 | 1.1 |
| 4 | 1 | GA | PO | 1 | 13.5 | 30 | 6 | 70 | 3,700 | 1.1 |
| 5 | 1 | PA | PO | 1.5 | 13.5 | 30 | 7.5 | 76 | 5,200 | 1.3 |
| 6 | 2 | CA | PO | 1 | 15 | 30 | 20 | 68 | 9,500 | 1.2 |
| 7 | 3 | CA | PO | 1 | 15 | 30 | 6.5 | 33 | 5,700 | 1.1 |
| 8 | 4 | CA | PO | 1 | 15 | 30 | 20 | 17 | 4,300 | 1.1 |
| 9§ | 1 | CA | CHO | 2 | 1 | 70 | 36 | 26 | 8,500 | 1.2 |
| 10§ | 3 | CA | CHO | 2 | 1 | 70 | 36 | 48 | 6,300 | 1.6 |
| 11§ | 2 | CA | CHO | 2 | 1 | 70 | 36 | 59 | 8,900 | 1.3 |
| 12§ | 3 | CA | LO | 2 | 1 | 100 | 28 | 29 | 8,500 | 1.2 |
| 13§ | 2 | CA | LO | 2 | 1 | 100 | 28 | 85 | 9,700 | 1.2 |
| 14§ | 2 | CA | LO | 1 | 1 | 100 | 120 | 12 | 5,900 | 1.1 |
| 15§ | 2 | CA | LO | 5 | 1 | 100 | 24 | 74 | 10,300 | 1.3 |
| 16 | 2 | CA | LO | 5 | 10 | 100 | 9 | 100 | 8,100 | 1.3 |
| 17║ | 2 | GA | PiO | 5 | 5 | 100 | 2 | 29 | 8,400 | 1.2 |
| 18¶ |
2 |
CA |
LO |
2 |
4 |
100 |
45 |
47 |
27,000 |
1.2 |
Abbreviations: CA, camphoric anhydride; GA, glutaric anhydride; PA, pimelic anhydride; SA, succinic anhydride; .
All reactions were performed after the cyclization step with [anhydride]/[M]=100 (except for entries 17 and 18).
*As determined by the integration of 1H NMR.
†Mn and PDI (Mw/Mn) of the polymer determined by SEC-RI in tetrahydrofuran at room temperature using polystyrene standards.
‡Not determined.
§Reaction performed in toluene.
║Reaction performed with [anhydride]/[M]=200.
¶Reaction performed with [anhydride]/[M]=300.