Synthesis of α-Diimine Complex Enabling Rapidly Covalent Attachment to Silica Supports and Application of Homo-/Heterogeneous Catalysts in Ethylene Polymerization
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis of α-Diimine Ligand and Complex CatA
2.2. Ethylene Polymerization with α-Diimine Nickel (II) Complex CatA
2.3. Preparation of Supported α-Diimine Nickel(II) Catalysts (S-CatA-1, S-CatA-2)
2.4. Ethylene Polymerization with Supported Catalysts (S-CatA-1, S-CatA-2)
2.5. Morphology of Polymers Obtained over Homogeneous and Heterogeneous Catalytic Systems
3. Materials and Methods
3.1. General Methods and Materials
3.2. Characterizations
3.3. Preparation of α-Diimine Nickel (II) Complex
3.4. Synthesis of Supported Catalysts S-CatA-1 and S-CatA-2
3.5. Ethylene Polymerization
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Entry | T °C | P MPa | t min | Yield g | Act. c | Tm d °C | χc e (%) | Mw e kg/mol | PDI e |
---|---|---|---|---|---|---|---|---|---|
1 | 30 | 0.5 | 30 | 0.89 | 1.77 | 120 | 16 | 332 | 2.9 |
2 | 50 | 0.5 | 30 | 3.84 | 7.68 | 107 | 6 | n.d. | n.d. |
3 | 70 | 0.5 | 30 | 3.30 | 6.60 | 94 | 2 | 136 | 2.8 |
4 | 70 | 1.0 | 30 | 4.73 | 9.46 | 110 | 5 | 439 | 2.3 |
5 b | 30 | 0.5 | 30 | 1.02 | 2.04 | 119 | 38 | 141 | 2.3 |
6 b | 50 | 0.5 | 30 | 2.73 | 5.46 | 105 | 5 | n.d. | n.d. |
7 b | 70 | 0.5 | 30 | 1.98 | 3.96 | 74 | 1 | 114 | 2.4 |
8 | 30 | 0.5 | 60 | 2.60 | 2.60 | 118 | 28 | 359 | 2.4 |
9 | 50 | 0.5 | 60 | 6.51 | 6.51 | n.d. | n.d. | n.d. | n.d. |
10 | 70 | 0.5 | 60 | 3.90 | 3.90 | 95 | 2 | 152 | 2.1 |
11 f | 70 | 0.5 | 30 | 1.42 | 2.84 | n.d. | n.d. | n.d. | n.d. |
Entry | T °C | P MPa | Branches (1000 C) | Percentage over Total Branching (%) | |||||
---|---|---|---|---|---|---|---|---|---|
Methyl | Ethyl | Propyl | Butyl | Amyl | LCB b | ||||
1 | 30 | 0.5 | 35 | 80.8 | 9.1 | 0.9 | 0 | 0 | 9.2 |
3 | 70 | 0.5 | 90 | 63.5 | 11.3 | 9.0 | 0 | 0.8 | 15.4 |
4 | 70 | 1.0 | 82 | 70.9 | 9.8 | 1.0 | 4.7 | 0.6 | 13.0 |
5 c | 30 | 0.5 | 41 | 83.4 | 4.9 | 1.7 | 2.2 | 0.7 | 7.1 |
7 c | 70 | 0.5 | 108 | 78.9 | 4.6 | 1.5 | 3.0 | 1.5 | 10.5 |
Entry | Catalyst | Ni b wt% | T °C | Act. c | Act. d | Tm e °C | χc e (%) | Mw f kg/mol | PDI f |
---|---|---|---|---|---|---|---|---|---|
1 | S-CatA-1 | 0.94 | 30 | 2.12 | 353 | 130 | 39 | 503 | 4.6 |
2 | S-CatA-1 | 0.94 | 50 | 4.02 | 641 | 125 | 23 | n.d. | n.d. |
3 | S-CatA-1 | 0.94 | 70 | 3.86 | 615 | 120 | 13 | 190 | 3.0 |
4 g | S-CatA-1 | 0.94 | 70 | 4.28 | 681 | 125 | 19 | 205 | 4.3 |
5 | S-CatA-2 | 1.41 | 30 | 3.72 | 892 | 131 | 41 | 679 | 3.3 |
6 | S-CatA-2 | 1.41 | 50 | 6.92 | 1656 | 128 | 24 | n.d. | n.d. |
7 | S-CatA-2 | 1.41 | 70 | 4.07 | 982 | 121 | 14 | 244 | 2.7 |
8 | S-CatA-2 | 1.41 | 80 | 1.38 | 265 | 120 | 9 | n.d. | n.d. |
9 g | S-CatA-2 | 1.41 | 70 | 4.51 | 1079 | 123 | 16 | 449 | 4.6 |
Entry | Catalyst | T °C | P MPa | Branches (1000C) | Percentage over Total Branching (%) | |||||
---|---|---|---|---|---|---|---|---|---|---|
Methyl | Ethyl | Propyl | Butyl | Amyl | LCB b | |||||
3 | S-CatA-1 | 70 | 0.5 | 63 | 68.6 | 9.2 | 6.2 | 1.1 | 1.3 | 13.6 |
4 | S-CatA-1 | 70 | 1.0 | 55 | 69.0 | 8.1 | 2.4 | 3.2 | 1.4 | 15.9 |
5 | S-CatA-2 | 30 | 0.5 | 34 | 68.9 | 13.8 | 3.1 | 2.0 | 2.3 | 9.9 |
7 | S-CatA-2 | 70 | 0.5 | 52 | 61.1 | 10.7 | 4.2 | 5.8 | 4.5 | 13.7 |
8 | S-CatA-2 | 80 | 0.5 | 67 | 57.8 | 11.4 | 3.7 | 3.8 | 3.1 | 20.2 |
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Zhao, X.; Hou, Y.; Ye, L.; Zong, K.; An, Q.; Liu, B.; Yang, M. Synthesis of α-Diimine Complex Enabling Rapidly Covalent Attachment to Silica Supports and Application of Homo-/Heterogeneous Catalysts in Ethylene Polymerization. Int. J. Mol. Sci. 2023, 24, 13645. https://doi.org/10.3390/ijms241713645
Zhao X, Hou Y, Ye L, Zong K, An Q, Liu B, Yang M. Synthesis of α-Diimine Complex Enabling Rapidly Covalent Attachment to Silica Supports and Application of Homo-/Heterogeneous Catalysts in Ethylene Polymerization. International Journal of Molecular Sciences. 2023; 24(17):13645. https://doi.org/10.3390/ijms241713645
Chicago/Turabian StyleZhao, Xiaobei, Yanhui Hou, Linlin Ye, Kening Zong, Qingming An, Binyuan Liu, and Min Yang. 2023. "Synthesis of α-Diimine Complex Enabling Rapidly Covalent Attachment to Silica Supports and Application of Homo-/Heterogeneous Catalysts in Ethylene Polymerization" International Journal of Molecular Sciences 24, no. 17: 13645. https://doi.org/10.3390/ijms241713645