Table 3.
Monomer sequence distributions of poly(ethylene‐co‐DC)s and poly(ethylene‐co‐DD)s prepared by Cp*TiCl2(O‐2,6‐iPr2‐4‐R‐C6H2) [R=H (1), tBu (2), CHPh2 (4), CPh3 (5), SiMe3 (6), SiEt3 (7), 3,5‐Me2C6H3 (9)] −MAO catalyst systems. (ethylene 6 atm, toluene).[a]
|
run |
cat. |
comonomer |
content[b]/ |
triad sequence distribution[c] [%] |
dyads[d] [%] |
r E [e] |
r C [e] |
rE⋅r C [f] |
|||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
|
[mol %] |
EEE |
EEC+CEE |
CEC |
ECE |
CCE+ECC |
CCC |
EE |
EC+CE |
CC |
||||||
|
1 |
1 |
DC |
21.4 |
39.6 |
31.5 |
6.73 |
18.0 |
4.25 |
– |
55.3 |
42.6 |
2.12 |
3.12 |
0.12 |
0.37 |
|
12 |
5 |
DC |
21.1 |
36.0 |
34.5 |
7.62 |
15.6 |
6.20 |
– |
53.3 |
43.6 |
3.10 |
2.94 |
0.17 |
0.50 |
|
14 |
5 |
DC |
21.4 |
42.8 |
28.9 |
5.69 |
17.6 |
4.98 |
– |
57.3 |
40.3 |
2.49 |
3.41 |
0.15 |
0.51 |
|
15 |
6 |
DC |
20.1 |
43.9 |
29.9 |
4.75 |
17.5 |
4.07 |
– |
58.8 |
39.2 |
2.04 |
3.60 |
0.12 |
0.45 |
|
18 |
6 |
DC |
21.3 |
39.2 |
32.4 |
5.71 |
18.3 |
4.48 |
– |
55.4 |
42.4 |
2.24 |
3.14 |
0.13 |
0.40 |
|
22 |
7 |
DC |
21.4 |
36.4 |
34.4 |
6.94 |
17.6 |
4.67 |
– |
53.6 |
44.1 |
2.33 |
2.92 |
0.13 |
0.37 |
|
27 |
9 |
DC |
21.1 |
41.9 |
26.3 |
9.31 |
16.6 |
5.98 |
– |
55.0 |
42.0 |
2.99 |
3.14 |
0.17 |
0.54 |
|
28 |
1 |
DD |
17.6 |
47.8 |
30.6 |
3.67 |
14.9 |
3.03 |
– |
63.1 |
35.3 |
1.52 |
3.68 |
0.09 |
0.33 |
|
30 |
2 |
DD |
18.3 |
50.1 |
27.4 |
4.81 |
14.2 |
3.46 |
0.76 |
63.8 |
34.4 |
2.49 |
3.82 |
0.15 |
0.57 |
|
36 |
4 |
DD |
17.5 |
47.2 |
31.8 |
3.42 |
13.5 |
4.04 |
– |
63.1 |
34.9 |
2.02 |
3.73 |
0.12 |
0.45 |
|
40 |
6 |
DD |
16.3 |
50.4 |
29.6 |
3.28 |
14.1 |
2.62 |
– |
65.2 |
33.5 |
1.31 |
4.02 |
0.08 |
0.32 |
|
42 |
7 |
DD |
15.3 |
52.4 |
29.0 |
3.04 |
13.2 |
2.29 |
– |
66.9 |
31.9 |
1.14 |
4.32 |
0.07 |
0.32 |
|
44 |
7 |
DD |
16.7 |
46.0 |
33.0 |
3.43 |
14.5 |
3.08 |
– |
62.5 |
36.0 |
1.54 |
3.58 |
0.09 |
0.32 |
|
48 |
9 |
DD |
17.6 |
49.3 |
28.9 |
4.16 |
14.9 |
2.80 |
– |
63.7 |
34.9 |
1.40 |
3.76 |
0.08 |
0.31 |
|
49 |
9 |
DD |
17.7 |
45.9 |
30.7 |
5.30 |
14.0 |
4.13 |
– |
61.2 |
36.7 |
2.06 |
3.44 |
0.12 |
0.40 |
[a] Detailed polymerization conditions, see Tables 1 and 2, C=comonomer [1‐decene (DC), 1‐dodecene (DD)]. [b] Comonomer contents in copolymer estimated by 13C NMR spectra. [c] Calculated by 13C NMR spectra, E=ethylene, C=comonomer [DC, DD]. [d] [EE]=[EEE]+1/2[EEC+CEE], [EC]=[CEC]+[ECE]+1/2{[EEC+CEE]+[CCE+ECC]}, [CC]=[CCC]+1/2[CCE+ECC]. [e] r E= [C]0/[E]0×2[EE]/[EC+CE], r C= [E]0/[C]0×2[CC]/[EC+CE]. [f] r E⋅r C = 4[EE][CC]/[EC+CE]2.