Table 1.
Synthesis of branched polymers of 25 by copolymerization with 26.
| Entry a) | [25]/[26]/[Et3N] | time b) [min] | M n,theo c) [ × 104 g mol−1] | M n,app d) [ × 104 g mol−1] | Đ d) | S n |
|---|---|---|---|---|---|---|
| 1 | 250/0/1 | 5 | 5.19 | 11.22 | 3.11 | − |
| 2 | 250/3/1 | 120 f) | 5.25 | 2.41 | 3.65 | 36 |
| 3 | 250/8/1 | 120 f) | 5.36 | 1.61 | 3.54 | 15 |
| 4 | 250/15/1 | 120 f) | 5.50 | 1.43 | 3.43 | 8.1 |
| 5 | 250/3/10 | 5 | 0.53 | 0.69 | 3.36 | 16 |
| 6 | 250/8/10 | 5 | 0.54 | 0.53 | 2.96 | 10 |
| 7 | 250/15/10 | 5 | 0.56 | 0.51 | 2.72 | 6.3 |
a)
The reaction occurred at 25 °C in bulk/solventless medium;
b)
Time interval between the addition of initiator (Et3N) and the solidification of the solution;
c)
Calculated based on complete conversion as estimated through ¹H NMR spectroscopy: M n,theo = ([25] × MW 25 + [26] × MW 26 )/[Et3N] + MW Et3N;
d)
Determined by SEC with a refractive index detector calibrated against polystyrene standards;
e)
S n = DP 25 /(1 + 2 × DP 26 ), where DP is the degree of polymerization;
f)
Time interval between the addition of initiator (Et3N) and the measurement of conversion.