Table 2.
Polymerizations of monomer mixtures aiming for random copolymers.
|
|
Monomers |
M/CoI/Cat ratio[a] (LL+Cap(+GG): CoI:1) |
p LL [b] |
p Cap [b] |
p GG [b] |
Feed |
Incorp.[c] |
M n,theo [d] [kg mol−1] |
M n [e] [kg mol−1] |
Đ [e] |
Seq. length (LL/Cap/ GG)[f] |
R (ref. LL)[g] |
T II (CapLCap/ CapGCap)[f] |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
|
1 |
LL+Cap |
500+500 : 1 : 1 |
0.90 |
0.85 |
– |
1 : 1 |
1.00 : 0.94 |
113.4 |
24.3 |
1.57 |
1.2/1.1/– |
1.30 |
0.80/– |
|
2 |
LL+Cap |
750+250 : 1 : 1 |
0.94 |
0.68 |
– |
3 : 1 |
3.90 : 1.00 |
121.0 |
42.8 |
1.35 |
3.7/1.2/– |
1.19 |
0.64/– |
|
3 |
LL+Cap |
250+750 : 1 : 1 |
0.68 |
0.89 |
– |
1 : 3 |
1.00 : 3.12 |
100.7 |
27.6 |
1.61 |
0.8/1.5/– |
1.03 |
0.90/– |
|
4 |
LL+Cap+GG |
475+475+50 : 1 : 1 |
0.91 |
0.81 |
>0.99 |
1 : 1 : 0.10 |
1.07 : 1.00 : 0.12 |
112.0 |
36.8 |
1.37 |
1.4/1.1/0.9 |
– |
0.47/1.85 |
|
5 |
LL+Cap+GG |
450+450+100 : 1 : 1 |
0.92 |
0.75 |
>0.99 |
1 : 1 : 0.22 |
1.37 : 1.00 : 0.33 |
109.8 |
39.7 |
1.27 |
1.7/1.1/1.3 |
– |
0.47/1.67 |
|
6 |
LL+Cap+GG |
425+425+150 : 1 : 1 |
0.93 |
0.75 |
>0.99 |
1 : 1 : 0.35 |
1.20 : 1.00 : 0.46 |
110.0 |
32.6 |
1.36 |
1.5/1.2/1.1 |
– |
0.47/2.12 |
|
7 |
LL+GG |
900+100 : 1 : 1 |
0.90 |
– |
>0.99 |
1 : 0.11 |
1.00 : 0.12 |
128.4 |
42.2 |
1.32 |
3.0/–/1.5 |
– |
– |
|
8 |
Cap+GG |
900+100 : 1 : 1 |
– |
0.93 |
>0.99 |
1 : 0.11 |
1.00 : 0.09 |
107.1 |
40.4 |
1.72 |
–/2.2/0.5 |
– |
– |
[a] BnOH as co‐initiator. [b] Conversions of the individual monomers determined by 1H NMR spectroscopy of the crude polymer after 24 h of polymerization at 180 °C. [c] Incorporated ratio of the monomers determined by 1H NMR spectroscopy of the precipitated polymer. [d] Calculated by the sum for all monomers of molar mass x conversion x monomer ratio of each monomer, respectively. [e] Determined by GPC in THF. [f] Calculated in accordance with ref. [21c]. [g] Randomness factor of LL calculated in accordance with ref. [33].