Coordinative Chain Transfer Polymerization of Sustainable Terpene Monomers Using a Neodymium-Based Catalyst System
Abstract
:1. Introduction
2. Materials and Methods
2.1. Laboratory Homopolymerization Procedure
2.2. Reactor Homopolymerization Procedure
2.3. Characterization
3. Results and Discussion
3.1. Effect of [Cl]/[Nd] Ratio
3.2. Effect of [Al]/[Nd] Ratio
3.3. Effect of Temperature
3.4. Validation of CCTP Regime through Living Polymerizations (Sequential Polymerizations)
3.5. Nd-Catalyst: Efficiency and Economy in CCTP
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Entry | [Nd]:[Al]:[Cl] | [Nd]0 (μmol) | Time (min) | Yield a (%) | Ð b | ||
---|---|---|---|---|---|---|---|
Ip-1 d | 1:20:01 | 1.73 | 75 | 99 | 2600 | 1.3 | 2.7 |
Ip-2 d | 1:20:03 | 1.73 | 45 | 93 | 8000 | 1.8 | 2.3 |
My-1 e | 1:20:01 | 0.15 | 240 | 96 | 2900 | 1.6 | 6.1 |
My-2 e | 1:20:03 | 0.15 | 240 | 96 | 8300 | 3 | 2.5 |
Fa-1 e | 1:20:01 | 0.09 | 240 | 99 | 7600 | 2.3 | 4 |
Fa-2 e | 1:20:03 | 0.09 | 240 | 99 | 24,000 | 4.1 | 1.3 |
Entry a | [Nd]:[Al]:[Cl] | T (°C) | Time (min) | Yield b (%) | Ð c | Isoprene Structure (%) e | (°C) | ||||
---|---|---|---|---|---|---|---|---|---|---|---|
3,4 | 1,4-trans | 1,4-cis | |||||||||
Ip-3 | 1:15:01 | 60 | 90 | 84 | 10,900 | 1.8 | 2.6 | 3 | 15.5 | 81.5 | −68.2 |
Ip-4 | 1:20:01 | 60 | 90 | 90 | 7100 | 1.5 | 4.1 | 3 | 22.3 | 74.7 | −69.4 |
Ip-5 | 1:25:01 | 60 | 75 | 92 | 4800 | 1.4 | 6.6 | 3.2 | 27.5 | 69.3 | −69.2 |
Ip-6 | 1:30:01 | 60 | 60 | 97 | 3300 | 1.4 | 9.9 | 3 | 27 | 70 | −70.5 |
Ip-7 | 1:15:01 | 70 | 80 | 87 | 9700 | 1.5 | 3.2 | 3 | 26.5 | 70.5 | −66.4 |
Ip-8 | 1:20:01 | 70 | 80 | 93 | 6400 | 1.4 | 4.9 | 4 | 32 | 64 | −68.3 |
Ip-9 | 1:25:01 | 70 | 70 | 94 | 3800 | 1.4 | 8.2 | 3 | 34 | 63 | −69.3 |
Ip-10 | 1:30:01 | 70 | 55 | 96 | 3600 | 1.3 | 8.2 | 3 | 32 | 65 | −70.3 |
Entry a | [Nd]:[Al]:[Cl] | T (°C) | Time (min) | Yield b (%) | Ð c | β-myrcene Structure (%) e | (°C) | ||||
---|---|---|---|---|---|---|---|---|---|---|---|
3,4 | 1,4-trans | 1,4-cis | |||||||||
My-3 | 1:15:1 | 60 | 80 | 85 | 8200 | 1.5 | 2.2 | 6.3 | 3.4 | 90.3 | −68.4 |
My-4 | 1:20:1 | 60 | 75 | 90 | 4000 | 1.5 | 4.6 | 6.3 | 1.6 | 92.1 | −72.2 |
My-5 | 1:25:1 | 60 | 60 | 88 | 2900 | 1.8 | 7.3 | 6.1 | 5.6 | 87.4 | −73.7 |
My-6 | 1:30:1 | 60 | 45 | 95 | 2500 | 1.8 | 6.9 | 9.7 | 16.8 | 73.5 | −78.0 |
My-7 | 1:15:1 | 70 | 75 | 86 | 7100 | 1.3 | 2.5 | 13.0 | 4.1 | 82.9 | −69.4 |
My-8 | 1:20:1 | 70 | 65 | 89 | 3400 | 1.5 | 5.2 | 8.0 | 2.3 | 89.7 | −72.1 |
My-9 | 1:25:1 | 70 | 60 | 93 | 2500 | 1.6 | 7.6 | 8.1 | 8.7 | 83.2 | −74.3 |
My-10 | 1:30:1 | 70 | 45 | 94 | 2300 | 1.5 | 7.5 | 10.0 | 18.8 | 71.2 | −77.0 |
Entry a | [Nd]:[Al]:[Cl] | T (°C) | Time (min) | Yield b (%) | Ð c | β-farnesene Structure (%) e | (°C) | ||||
---|---|---|---|---|---|---|---|---|---|---|---|
3,4 | 1,4-trans | 1,4-cis | |||||||||
Fa-3 | 1:15:1 | 60 | 60 | 92 | 9700 | 2.9 | 3.2 | 9.4 | 1.2 | 89.4 | −75.1 |
Fa-4 | 1:20:1 | 60 | 60 | 97 | 5700 | 2.4 | 5.4 | 3.1 | 2.2 | 94.7 | −76.6 |
Fa-5 | 1:25:1 | 60 | 40 | 99 | 4500 | 2.0 | 6.8 | 3.4 | 4.7 | 91.8 | −76.9 |
Fa-6 | 1:30:1 | 60 | 30 | 99 | 3700 | 2.0 | 8.3 | 4.7 | 8.5 | 86.8 | −78.4 |
Fa-7 | 1:15:1 | 70 | 40 | 99 | 8900 | 2.0 | 3.4 | 4.0 | 1.0 | 95.0 | −75.2 |
Fa-8 | 1:20:1 | 70 | 40 | 99 | 6500 | 2.1 | 4.7 | 3.0 | 1.5 | 95.5 | −77.6 |
Fa-9 | 1:25:1 | 70 | 30 | 99 | 4800 | 1.9 | 6.4 | 3.8 | 7.2 | 89.0 | −81.6 |
Fa-10 | 1:30:1 | 70 | 30 | 99 | 3800 | 2.6 | 8.0 | 4.8 | 5.2 | 90.0 | −76.9 |
Fa-11 g | 1:25:1 | 50 | 85 | 92 | 10,500 | 2.5 | 4.9 | - | - | - | - |
Fa-12 g | 1:25:1 | 60 | 70 | 96 | 8200 | 1.8 | 6.2 | - | - | - | - |
Fa-13 g | 1:25:1 | 70 | 60 | 97 | 7800 | 1.7 | 6.6 | - | - | - | - |
Fa-14 g | 1:25:1 | 80 | 60 | 85 | 7100 | 1.6 | 7.2 | - | - | - | - |
Entry | T (K) | (L/mol min) | (L/mol min) | ||
---|---|---|---|---|---|
Ip-5 | 333 | 7.6 | 5.2 | 4400 | 3.2 |
Ip-9 | 343 | 9.6 | 9060 | ||
My-5 | 333 | 8.4 | 6.3 | 2005 | 4.6 |
My-9 | 343 | 11.1 | 2197 | ||
Fa-12 | 333 | 20.5 | 10.5 | 3554 | 3.7 |
Fa-13 | 343 | 33.3 | 4188 |
First Step | |||||||
---|---|---|---|---|---|---|---|
Entry | Time (min) | Yield (%) | Đ a | (g/mol) | (L/mol-min) | (L/mol-min) | |
Ip-11 | 30 | 99 | 1.4 | 2600 | 36,700 | 37.2 | 7.5 |
My-11 | 95 | 99 | 1.5 | 8000 | 9970 | 21.6 | 4.1 |
Fa-15 | 95 | 99 | 1.6 | 17,900 | 8150 | 39 | 2.8 |
Second Step | |||||||
Entry | Time (min) | Yield (%) | Đ a | a (g/mol) | (L/mol-min) | (L/mol-min) | b |
Ip-11 | 80 | 144 | 1.3 | 3800 | 9080 | 6.0 | 8.5 |
My-11 | 150 | 132 | 1.5 | 10,700 | 2300 | 5.1 | 4.5 |
Fa-15 | 135 | 144 | 1.5 | 22,200 | 3710 | 16.4 | 3.3 |
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Córdova, T.; Enríquez-Medrano, F.J.; Cartagena, E.M.; Villanueva, A.B.; Valencia, L.; Álvarez, E.N.C.; González, R.L.; Díaz-de-León, R. Coordinative Chain Transfer Polymerization of Sustainable Terpene Monomers Using a Neodymium-Based Catalyst System. Polymers 2022, 14, 2907. https://doi.org/10.3390/polym14142907
Córdova T, Enríquez-Medrano FJ, Cartagena EM, Villanueva AB, Valencia L, Álvarez ENC, González RL, Díaz-de-León R. Coordinative Chain Transfer Polymerization of Sustainable Terpene Monomers Using a Neodymium-Based Catalyst System. Polymers. 2022; 14(14):2907. https://doi.org/10.3390/polym14142907
Chicago/Turabian StyleCórdova, Teresa, Francisco Javier Enríquez-Medrano, Eduardo Martínez Cartagena, Arnulfo Banda Villanueva, Luis Valencia, Edgar Nazareo Cabrera Álvarez, Ricardo López González, and Ramón Díaz-de-León. 2022. "Coordinative Chain Transfer Polymerization of Sustainable Terpene Monomers Using a Neodymium-Based Catalyst System" Polymers 14, no. 14: 2907. https://doi.org/10.3390/polym14142907