Electronic Tuning of Sterically Encumbered 2-(Arylimino)Pyridine-Nickel Ethylene Polymerization Catalysts by Para-Group Modification
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis and Characterization of L1–L5 and Their Complexes Ni1–Ni5
2.2. Catalytic Evaluation for Ethylene Polymerization
2.2.1. Co-Catalyst Screening
2.2.2. Ethylene Polymerization Using Ni1–Ni5 in the Presence of EtAlCl2
2.2.3. Ethylene Polymerization Using Ni1–Ni5 in the Presence of MMAO
2.2.4. Microstructural Studies of the Polyethylenes
2.2.5. Comparison between Current and Reported Analogues Precatalysts
3. Experimental Section
3.1. General Consideration
3.2. Synthesis of 2-{(2,6-(CH(C6H4-p-F)2)2-4-RC6H2)N=CMe}C5H4N (L1 − L5)
3.2.1. R = Me (L1)
3.2.2. R = Et (L2)
3.2.3. R = i-Pr (L3)
3.2.4. R = F (L4)
3.2.5. R = OCF3 (L5)
3.3. Synthesis of [2-{(2,6-(CH(C6H4-p-F)2)2-4-RC6H2)N=CMe}C5H4N]NiBr2 (Ni1 − Ni5)
3.3.1. R = Me (Ni1)
3.3.2. R = Et (Ni2)
3.3.3. R = i-Pr (Ni3)
3.3.4. R = F (Ni4)
3.3.5. R = OCF3 (Ni5)
3.4. Ethylene Polymerization Evaluation
3.4.1. The Polymerizations at PC2H4 = 5 or 10 atm Were Performed in a Stainless Steel Autoclave (250 mL Capacity) Equipped with a Mechanical Stirrer and an Ethylene Pressure and Temperature Control System
3.4.2. Polymerizations at PC2H4 = 1 atm
3.5. X-ray Crystallographic Studies
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Ni5 | Ni4’ | ||
---|---|---|---|
Bond lengths (Å) | |||
Ni1-Br1 | 2.5196 (8) | Ni1-Br1 | 2.5176 (5) |
Ni1-Br2 | 2.3857 (8) | Ni1-N1 | 2.020 (4) |
Ni1-N1 | 2.042 (3) | Ni1-N2 | 2.365 (3) |
Ni1-N2 | 2.055 (3) | N2-C6 | 1.286 (6) |
N2-C6 | 1.298 (5) | N2-C8 | 1.449 (5) |
N2-C8 | 1.438 (5) | ||
O1-C47 | 1.312( 5) | ||
Bond angles (o) | |||
N1-Ni1-N2 | 79.24 (13) | N1-Ni1-N2 | 75.86 (14) |
Br2-Ni1-Br1 | 128.92 (3) | N1-Ni1-Br1 | 90.96 (10) |
Br2-Ni1-Br1i | 95.80 (3) | N2-Ni1-Br1 | 91.92 (9) |
Br1-Ni1-Br1i | 84.55 (3) | N1i-Ni1-Br1 | 89.04 (10) |
N2-Ni1-Br2 | 110.91 (10) | N2i-Ni1-Br1 | 88.08 (9) |
N2-Ni1-Br1 | 119.64 (10) | N1-Ni1-N2i | 104.14 (14) |
N2-Ni1-Br1i | 97.98 (10) | N1-Ni1-N1i | 180.00 (19) |
N1-Ni1-Br2 | 91.29 (10) | N2i-Ni1-N2 | 180.00 (16) |
Run | Co-cat. | Al:Ni | Activity b | Mwc | Mw/Mnc | Tm (°C) d |
---|---|---|---|---|---|---|
1 | EASC | 400 | 2.71 | 3.70 | 2.27 | 57.5 |
2 | Et2AlCl | 400 | 2.67 | 3.27 | 2.11 | 62.2 |
3 | EtAlCl2 | 400 | 2.86 | 4.76 | 2.56 | 68.8 |
4 | MAO | 2000 | 2.31 | 5.36 | 2.23 | 65.4 |
5 | MMAO | 2000 | 2.51 | 3.68 | 2.25 | 73.4 |
Run | Precat. | T (°C) | t (min) | Al:Ni | Activity b | Mwc | Mw/Mnc | Tm (°C) d |
---|---|---|---|---|---|---|---|---|
1 | Ni1 | 30 | 30 | 300 | 1.37 | 5.22 | 2.68 | 67.4 |
2 | Ni1 | 30 | 30 | 400 | 2.86 | 4.76 | 2.56 | 68.8 |
3 | Ni1 | 30 | 30 | 450 | 3.10 | 4.84 | 2.88 | 69.8 |
4 | Ni1 | 30 | 30 | 500 | 3.20 | 5.39 | 2.65 | 67.8 |
5 | Ni1 | 30 | 30 | 550 | 2.65 | 4.53 | 2.64 | 66.1 |
6 | Ni1 | 30 | 30 | 600 | 2.45 | 4.79 | 2.70 | 66.3 |
7 | Ni1 | 20 | 30 | 500 | 2.76 | 9.59 | 3.02 | 102.1 |
8 | Ni1 | 40 | 30 | 500 | 2.23 | 3.46 | 2.57 | 58.2 |
9 | Ni1 | 50 | 30 | 500 | 0.50 | 2.63 | 2.21 | 57.4 |
10 | Ni1 | 30 | 05 | 500 | 2.81 | 4.27 | 2.18 | 63.9 |
11 | Ni1 | 30 | 15 | 500 | 3.02 | 4.97 | 2.69 | 72.1 |
12 | Ni1 | 30 | 45 | 500 | 3.06 | 5.74 | 3.42 | 68.4 |
13 | Ni1 | 30 | 60 | 500 | 2.74 | 6.18 | 3.43 | 68.9 |
14 e | Ni1 | 30 | 30 | 500 | 1.14 | 3.98 | 2.25 | 58.0 |
15 f | Ni1 | 30 | 30 | 500 | trace | - | - | - |
16 | Ni2 | 30 | 30 | 500 | 2.88 | 4.61 | 2.89 | 68.3 |
17 | Ni3 | 30 | 30 | 500 | 3.53 | 4.85 | 2.53 | 70.1 |
18 | Ni4 | 30 | 30 | 500 | 3.87 | 5.83 | 2.90 | 68.1 |
19 | Ni5 | 30 | 30 | 500 | 4.28 | 5.41 | 2.73 | 77.3 |
Run | Precat. | T (°C) | t (min) | Al:Ni | Activity b | Mwc | Mw/Mnc | Tm (°C) d |
---|---|---|---|---|---|---|---|---|
1 | Ni1 | 30 | 30 | 1500 | 0.70 | 4.14 | 2.21 | 79.1 |
2 | Ni1 | 30 | 30 | 2000 | 2.51 | 3.68 | 2.25 | 73.4 |
3 | Ni1 | 30 | 30 | 2500 | 2.40 | 3.50 | 2.24 | 72.1 |
4 | Ni1 | 30 | 30 | 3000 | 2.00 | 3.59 | 2.37 | 69.8 |
5 | Ni1 | 30 | 30 | 3500 | 1.86 | 3.72 | 2.25 | 74.9 |
6 | Ni1 | 20 | 30 | 2000 | 2.07 | 7.32 | 2.63 | 102.8 |
7 | Ni1 | 40 | 30 | 2000 | 1.18 | 2.62 | 2.26 | 63.1 |
8 | Ni1 | 50 | 30 | 2000 | 0.30 | 2.50 | 2.03 | 58.4 |
9 | Ni1 | 30 | 05 | 2000 | 1.87 | 3.30 | 2.02 | 69.1 |
10 | Ni1 | 30 | 15 | 2000 | 2.40 | 3.55 | 2.27 | 71.3 |
11 | Ni1 | 30 | 45 | 2000 | 1.76 | 3.73 | 2.19 | 76.6 |
12 | Ni1 | 30 | 60 | 2000 | 1.52 | 3.75 | 2.40 | 73.5 |
13 e | Ni1 | 30 | 30 | 2000 | 1.01 | 2.92 | 2.01 | 58.5 |
14 f | Ni1 | 30 | 30 | 2000 | trace | - | - | - |
15 | Ni2 | 30 | 30 | 2000 | 2.05 | 3.69 | 2.28 | 74.5 |
16 | Ni3 | 30 | 30 | 2000 | 2.62 | 3.49 | 2.36 | 74.4 |
17 | Ni4 | 30 | 30 | 2000 | 2.84 | 3.98 | 2.38 | 72.5 |
18 | Ni5 | 30 | 30 | 2000 | 3.15 | 3.83 | 2.38 | 77.4 |
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Hosseinzadeh, Z.; Liu, M.; Zhang, Q.; Liang, T.; Solan, G.A.; Ma, Y.; Sun, W.-H. Electronic Tuning of Sterically Encumbered 2-(Arylimino)Pyridine-Nickel Ethylene Polymerization Catalysts by Para-Group Modification. Catalysts 2022, 12, 1520. https://doi.org/10.3390/catal12121520
Hosseinzadeh Z, Liu M, Zhang Q, Liang T, Solan GA, Ma Y, Sun W-H. Electronic Tuning of Sterically Encumbered 2-(Arylimino)Pyridine-Nickel Ethylene Polymerization Catalysts by Para-Group Modification. Catalysts. 2022; 12(12):1520. https://doi.org/10.3390/catal12121520
Chicago/Turabian StyleHosseinzadeh, Zahra, Ming Liu, Qiuyue Zhang, Tongling Liang, Gregory A. Solan, Yanping Ma, and Wen-Hua Sun. 2022. "Electronic Tuning of Sterically Encumbered 2-(Arylimino)Pyridine-Nickel Ethylene Polymerization Catalysts by Para-Group Modification" Catalysts 12, no. 12: 1520. https://doi.org/10.3390/catal12121520