Heterogeneity of Active Sites in the Polymer Chain Transfer Reactions at Olefin Polymerization over Multisite Supported Ziegler-Natta Catalysts
Abstract
:1. Introduction
2. Materials and Methods
3. Results and Discussion
- chain transfer reactions with a cocatalyst (AlEt3) at ethylene and hexene-1 polymerization;
- chain transfer reaction with participation of α-olefins in the case of copolymerization of ethylene with α-olefins;
- chain transfer reaction with hydrogen in the polymerization of ethylene, propylene, and hexene-1, and copolymerization of ethylene with α-olefins.
3.1. Polymer Chain Transfer Reactions Involving Aluminum Trialkyls during Polymerization of Ethylene and Hexene-1 over Supported Titanium–Magnesium Catalysts
3.1.1. Chain Transfer Reactions Involving Triethylaluminum at Ethylene Polymerization
3.1.2. Chain Transfer Reactions Involving Triethylaluminum during Polymerization of Hexene-1
3.2. Chain Transfer Reaction Involving α-Olefins in the Case of Ethylene Copolymerization with α-Olefins over Supported Titanium–Magnesium Catalysts
R=CH3, C4H9
3.3. Chain Transfer Reaction with Hydrogen in the Polymerization of Ethylene, Propylene, and Hexene-1, and Copolymerization of Ethylene with α-Olefins over Supported Titanium–Magnesium Catalysts
3.3.1. The Effect of Hydrogen on the Molecular Weight and MWD of Polymers Produced during Polymerization of Ethylene, Propylene, and Hexene-1
3.3.2. The Effect of Hydrogen on the Molecular Weight and MWD of Copolymers Produced at Ethylene Copolymerization with Propylene and Hexene-1
R=CH3, C4H9; P, polymer chain
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Exp. No. | P C2H4, bar | (TEA), mmol/L | Polymer Yield 1, kgPE/g cat | Mn, kg/mol | Mw, kg/mol | Mw/Mn |
---|---|---|---|---|---|---|
1 | 1 | 2.4 | 0.4 | 39 | 430 | 11.0 |
2 | 2 | 2.4 | 1.2 | 76 | 690 | 9.1 |
3 | 4 | 2.4 | 6.1 | 145 | 690 | 4.8 |
4 | 4 | 1.2 | 6.5 | 250 | 910 | 3.6 |
5 | 4 | 4.8 | 4.7 | 93 | 580 | 6.2 |
P (C2H4), bar | 4 | 1 | |||
---|---|---|---|---|---|
Flory Component | Contribution, % | Mw, kg/mol | Contribution, % | Mw, kg/mol | |
I | 9.0 | 3000 | 6.4 | 2100 | |
II | 28.5 | 860 | 23.2 | 690 | |
III | 40.0 | 330 | 27.2 | 275 | |
IV | 21.8 | 100 | 26.7 | 100 | |
V | - | - | 12.9 | 30 | |
VI | - | - | 3.2 | 6.8 | |
Sum of components | Mw, kg/mol | 645 | 410 | ||
Mw/Mn | 4.6 | 9.2 |
(AlEt3), mmol/L | 1.2 | 4.8 | |||
---|---|---|---|---|---|
Flory Component | Contribution, % | Mw, kg/mol | Contribution, % | Mw, kg/mol | |
I | 8.9 | 3170 | 6.6 | 3500 | |
II | 34.6 | 1100 | 18.8 | 1070 | |
III | 42.5 | 470 | 38.6 | 390 | |
IV | 14.2 | 135 | 28.3 | 120 | |
V | 7.7 | 39 | |||
Sum of components | Mw, kg/mol | 905 | 590 |
Cocatalyst | |||||
---|---|---|---|---|---|
TIBA | TEA | ||||
Mw, 1 kg/mol | 2100 | 290 | |||
Mw/Mn 1 | 3.1 | 17 | |||
Flory Component | Contribution, % | Mw, kg/mol | Contribution, % | Mw, kg/mol | |
I | 25.4 | 4700 | 10 | 1650 | |
II | 60.1 | 1400 | 26.4 | 410 | |
III | 14.2 | 490 | 34.8 | 115 | |
IV | - | - | 24.7 | 28 | |
V | - | - | 10.4 | 6 | |
Sum of components | Mw, kg/mol | 2100 | 300 | ||
Mw/Mn | 3.1 | 16 |
Exp. No. | Comonomer | (Cα/C2), molar | Polymer Yield 1, kg/g cat | Mn, kg/mol | Mw, kg/mol | Mw/Mn | Cα 2, mol. % | Content of Double Bonds 3 | ||
---|---|---|---|---|---|---|---|---|---|---|
CH2=CHR | R1CH=CHR2 | |||||||||
1 | ─ | 0 | 1.2 | 76 | 690 | 9.1 | ─ | 0.20 | 0.06 | ─ |
2 | C3H6 | 0.18 | 4.7 | 50 | 420 | 8.4 | 2.0 | 0.14 | 0.08 | 0.04 |
3 | 0.51 | 5.5 | 57 | 360 | 6.3 | 4.9 | 0.23 | 0.14 | 0.10 | |
4 | C6H12 | 2.3 | 12.5 | 59 | 540 | 9.2 | 1.0 | 0.24 | ─ | 0.04 |
5 | 4.6 | 8.7 | 49 | 430 | 8.8 | 2.3 | 0.24 | ─ | 0.07 |
Exp. No. | H2 | Polymer Yield, kg/(gcat) | Mn, kg/mol | Mw, kg/mol | Mw/Mn |
---|---|---|---|---|---|
PP 1 1 | - | 7.1 | 34 | 310 | 9.1 |
PP 2 1 | + 3 | 17.8 | 29 | 150 | 5.2 |
PH 1 2 | - | 0.5 | 14 | 230 | 16 |
PH 2 2 | + 4 | 2.1 | 9.4 | 63 | 6.7 |
Sample 1 | PP 1 | PP 2 | |||
---|---|---|---|---|---|
H2, vol. % | ─ | 2.3 | |||
Flory Component | Contribution, % | Mw, kg/mol | Contribution, % | Mw, kg/mol | |
I | 5.5 | 7 | 11.7 | 19 | |
II | 21.6 | 32 | 37.1 | 57 | |
III | 40.3 | 110 | 37.8 | 155 | |
IV | 29.2 | 390 | 13.5 | 510 | |
V | 10.2 | 1700 | |||
Sum of components | Mw, kg/mol | 320 | 145 | ||
Mw/Mn | 12 | 4.2 |
Exp. No | Cα Content, mol % | P (H2), bar | Polymer Yield 1, Kg/gcat | Mn, kg/mol | Mw, kg/mol | Mw/Mn |
---|---|---|---|---|---|---|
EPC 1 1 | 25 | - | 1 | 23 | 190 | 8.3 |
EPC 2 2 | 21 | 0.1 | 1.4 | 17 | 99 | 5.8 |
EHC 1 3 | 2.1 | - | 3.3 | 20 | 280 | 14.0 |
EHC 2 3 | 2.1 | 0.25 | 2.0 | 24 | 110 | 4.6 |
Sample 1 | EPC 1 | EPC 2 | |||
---|---|---|---|---|---|
P (H2),bar | ─ | 0.1 | |||
Flory Component | Contribution, % | Mw, kg/mol | Contribution, % | Mw, kg/mol | |
I | 11.6 | 9 | 8.3 | 5.9 | |
II | 32.1 | 32 | 35.5 | 26 | |
III | 34.2 | 100 | 42.3 | 81 | |
IV | 21.5 | 380 | 18.3 | 300 | |
V | 6.7 | 1600 | |||
Sum of components | Mw,kg/mol | 180 | 95 | ||
Mw/Mn | 7.8 | 5.8 |
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Matsko, M.; Zakharov, V. Heterogeneity of Active Sites in the Polymer Chain Transfer Reactions at Olefin Polymerization over Multisite Supported Ziegler-Natta Catalysts. Polymers 2023, 15, 4316. https://doi.org/10.3390/polym15214316
Matsko M, Zakharov V. Heterogeneity of Active Sites in the Polymer Chain Transfer Reactions at Olefin Polymerization over Multisite Supported Ziegler-Natta Catalysts. Polymers. 2023; 15(21):4316. https://doi.org/10.3390/polym15214316
Chicago/Turabian StyleMatsko, Mikhail, and Vladimir Zakharov. 2023. "Heterogeneity of Active Sites in the Polymer Chain Transfer Reactions at Olefin Polymerization over Multisite Supported Ziegler-Natta Catalysts" Polymers 15, no. 21: 4316. https://doi.org/10.3390/polym15214316