Sustainable Esterification of a Soda Lignin with Phloretic Acid
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials and Reagents
2.2. Esterification of Lignin
- the reaction time (t)
- the molar ratio between the carboxylic acid units from PA (nCOOH_PA) and the lignin aliphatic ‒OH groups determined by 31P NMR (nOHali_P2400) (n)
- the catalyst loading expressed as weight percentage (wt.%), relative to the initial amount of lignin (c)
2.3. Equipments and Characterization
3. Results
3.1. Structural Characterization of the Esterified Lignin
3.2. Optimization of the Fischer Esterification of Protobind® Lignin
- when a stoichiometric amount of reactants is used (n = 1; Table 4, rows 1,2, 5 and 6), the increase in the amount of [H] units does not exceed 28%,
- when an excess of PA is used (n = 5; Table 3, rows 3, 4, 7, 8), higher conversion yields of aliphatic ‒OH groups (~90%) and amount of [H] units are reached (~50% and 65 % for t = 12 and 48 h, respectively),
- for n = 1, the amount of [H] units is equivalent to ~ 0.9 and ~1.1 mmol g−1 (c = 0.5 and 2.5 wt.%, respectively) independent of the reaction time,
- for an excess of PA (n = 5), this amount is equivalent to ~1.6 and 1.8 mmol g−1 (t = 12 and 48, respectively) regardless of the catalyst loading.
3.3. Physicochemical Properties of Esterified Lignin
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviations
References
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Reaction Parameters | Symbol | Level | |
---|---|---|---|
−1 | +1 | ||
Time (h) | t | 12 | 48 |
Molar ratio (nCOOH_PA/nOHali_P2400 a) | n | 1 | 5 |
Catalyst loading (wt.%) | c | 0.5 | 2.5 |
Sample | [COOH] | [5-subst.] | [Gnc] | [H] | [OH]aro | [OH]ali |
---|---|---|---|---|---|---|
P2400 | 0.78 ± 0.04 | 2.12 ± 0.23 | 1.29 ± 0.22 | 0.53 ± 0.07 | 3.94 ± 0.51 | 2.00 ± 0.23 |
P2400-PA | 0.81 ± 0.03 | 1.79 ± 0.09 | 1.03 ± 0.07 | 1.81 ± 0.07 | 4.63 ± 0.22 | 0.14 ± 0.02 |
Sample | C (%) | H (%) | N (%) | S (%) | O (%) |
---|---|---|---|---|---|
P2400 | 64.44 ± 0.01 | 6.06 ± 0.14 | 0.56 ± 0.05 | 0.63 ± 0.03 | 28.31 |
P2400-PA | 67.20 ± 0.04 | 5.68 ± 0.16 | 0.65 ± 0.03 | 0.58 ± 0.01 | 25.89 |
Run | t (h) | n | c (wt.%) | a [OH]ali (mmol g−1) | b Conversion (%) | a [H] (mmol g−1) | c Response (%) |
---|---|---|---|---|---|---|---|
EL-1 | 12 | 1 | 0.5 | 0.61 ± 0.03 | 69.5 | 0.87 ± 0.02 | 17.0 |
EL-2 | 48 | 1 | 0.5 | 0.40 ± 0.06 | 80.0 | 0.96 ± 0.05 | 21.5 |
EL-3 | 12 | 5 | 0.5 | 0.33 ± 0.01 | 83.5 | 1.58 ± 0.08 | 52.5 |
EL-4 | 48 | 5 | 0.5 | 0.14 ± 0.02 | 93.0 | 1.78 ± 0.10 | 62.5 |
EL-5 | 12 | 1 | 2.5 | 0.51 ± 0.01 | 74.5 | 1.09 ± 0.17 | 28.0 |
EL-6 | 48 | 1 | 2.5 | 0.26 ± 0.08 | 87.0 | 1.04 ± 0.08 | 25.5 |
EL-7 | 12 | 5 | 2.5 | 0.19 ± 0.12 | 90.5 | 1.56 ± 0.12 | 51.5 |
EL-8 | 48 | 5 | 2.5 | 0.14 ± 0.02 | 93.0 | 1.81 ± 0.07 | 64.0 |
Sample | a δD (MPa1/2) | a δP (MPa1/2) | a δH (MPa1/2) | bMn (g mol−1) | cMw (g mol−1) | dĐ |
---|---|---|---|---|---|---|
P2400 | 18.0 | 9.4 | 16.6 | 575 | 4323 | 7.5 |
P2400-PA | 17.1 | 13.1 | 12.5 | 1570 | 8546 | 5.4 |
Sample | aTonset (°C) | a,bTmax (°C) | c Char (%) | d LOI (%) | eTg (°C) |
---|---|---|---|---|---|
P2400 | 157 | 359 | 33.9 | 31.1 | 92 |
P2400-PA | 220 | 367 | 37.6 | 32.5 | 112 |
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Adjaoud, A.; Dieden, R.; Verge, P. Sustainable Esterification of a Soda Lignin with Phloretic Acid. Polymers 2021, 13, 637. https://doi.org/10.3390/polym13040637
Adjaoud A, Dieden R, Verge P. Sustainable Esterification of a Soda Lignin with Phloretic Acid. Polymers. 2021; 13(4):637. https://doi.org/10.3390/polym13040637
Chicago/Turabian StyleAdjaoud, Antoine, Reiner Dieden, and Pierre Verge. 2021. "Sustainable Esterification of a Soda Lignin with Phloretic Acid" Polymers 13, no. 4: 637. https://doi.org/10.3390/polym13040637