Catalyzed Reaction of Cellulose and Lignin with Methyltrimethoxysilane—FT-IR, 13C NMR and 29Si NMR Studies
Abstract
:1. Introduction
- complex compounds (aluminum acetylacetonate, chromium (III) acetylacetonate);
- complex compounds of metal alkoxides (complexes of aluminum sec-butanolan);
2. Materials and Methods
2.1. Materials
2.2. Silanization
2.3. FT-IR Analysis
2.4. NMR Analysis
2.5. AAS Analysis
3. Results and Discussion
3.1. FT-IR Analysis of Silanized Cellulosesilanized
3.2. FT-IR Analysis of Silanized Lignin
3.3. Cellulose 13C, 29Si NMR Study
3.4. Lignin 13C and 29Si NMR Study
3.5. AAS Study
3.6. Mechanism of Bonding
4. Conclusions
- Lignin undergoes a silanization reaction with alkoxysilanes much easier than cellulose. Cellulose silanization efficiency without a catalyst is unlikely. Higher lignin reactivity when compared with cellulose is caused by the presence of more acidic hydroxy groups. Moreover, the amorphous character of lignin makes its reactivity easier in contrast to cellulose, which presents a crystalline and amorphous structure. The reactivity was proven by FT-IR and NMR analyses. Bonds between lignin and MTMOS were identified in the reaction without catalysts. No significant influence of catalyst activity on lignin silanization reaction was observed.
- Depending on various catalysis mechanisms, diverse efficiency of cellulose silanization was observed. The highest efficiency of silanization was observed for the reaction where Al(acac)3 was used. These results were confirmed by FT-IR and AAS analyses. The silanization mechanism with the transition state of H2O and Al(acac)3 appeared to be more efficient than commonly applied acid catalysis.
- The durability of silanization of cellulose and lignin in the presence of Al(acac)3 was confirmed. T1, T2 or T3 structures on NMR spectra were observed after leaching. The results of AAS analysis confirmed, additionally, the effective silanization, where the content of silicone was higher after leaching.
Author Contributions
Funding
Conflicts of Interest
References
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Sample | Material | Methyltrimethoxysilane (MTMOS) | Ethanol | Catalyst |
---|---|---|---|---|
C | cellulose | − | − | - |
C–M | cellulose | + | + | - |
C–M–Al | cellulose | + | + | aluminum acetylacetonate (Al(acac)3) |
C–M–Ac | cellulose | + | + | acetic acid (AcOH) |
L | lignin | − | − | - |
L–M | lignin | + | + | - |
L–M–Al | lignin | + | + | Al(acac)3 |
L–M–Ac | lignin | + | + | AcOH |
Sample | Band Intensity Ratio | ||||
---|---|---|---|---|---|
770/897 Si–CH3/C–H | 1032/897 (Si–O/C–H) | 1127/897 (Si–O–C/C–H) | 1270/897 Si–CH3/C–H | 3360/897 OH/C–H | |
C | — | — | — | — | 3.72 |
C–M | 0.38 | 7.45 | 6.17 | 1.34 | 6.53 |
C–M–Al | 1.67 | 4.47 | 3.92 | 2.14 | 3.20 |
C–M–Ac | 0.49 | 4.83 | 4.13 | 1.29 | 4.03 |
Sample | LOI | TCI | HBI |
---|---|---|---|
C | 1.98 | 1.43 | 1.83 |
C–M | 1.89 | 1.26 | 3.24 |
C–M–Ac | 1.22 | 1.26 | 3.15 |
C–M–Al | 1.33 | 1.26 | 2.54 |
Sample | Band Intensity Ratio | |||||
---|---|---|---|---|---|---|
777/1510 (Si–CH3/C–HAr) | 920/1510 (Si–OH/C–HAr) | 1032/1510 (Si–O/C–HAr) | 1127/1510 (Si–O–C/C–HAr) | 1270/1510 (Si–CH3/C–HAr) | 3450/1510 (OH/C–HAr) | |
L | — | — | — | — | — | 0.69 |
L–M | 0.52 | 0.17 | 1.40 | 1.29 | 1.40 | 0.88 |
L–M–Al | 0.77 | 0.14 | 1.89 | 1.44 | 1.51 | 0.94 |
L–M–Ac | 0.89 | 0.18 | 1.98 | 1.82 | 1.73 | 0.91 |
Sample | Si (mg/g) | Sample | Si (mg/g) |
---|---|---|---|
C | 0.00 | L | 0.00 |
C–M | 3.60 | L–M | 61.22 |
C–M–Al | 61.49 | L–M–Al | 71.72 |
C–M–Ac | 34.94 | L–M–Ac | 84.07 |
C–W | 0.00 | L–W | 0.00 |
C–M–W | 0.54 | L–M–W | 57.81 |
C–M–Al–W | 70.02 | L–M–Al–W | 108.2 |
C–M–Ac–W | 16.05 | L–M–Ac–W | 76.43 |
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Siuda, J.; Perdoch, W.; Mazela, B.; Zborowska, M. Catalyzed Reaction of Cellulose and Lignin with Methyltrimethoxysilane—FT-IR, 13C NMR and 29Si NMR Studies. Materials 2019, 12, 2006. https://doi.org/10.3390/ma12122006
Siuda J, Perdoch W, Mazela B, Zborowska M. Catalyzed Reaction of Cellulose and Lignin with Methyltrimethoxysilane—FT-IR, 13C NMR and 29Si NMR Studies. Materials. 2019; 12(12):2006. https://doi.org/10.3390/ma12122006
Chicago/Turabian StyleSiuda, Joanna, Waldemar Perdoch, Bartłomiej Mazela, and Magdalena Zborowska. 2019. "Catalyzed Reaction of Cellulose and Lignin with Methyltrimethoxysilane—FT-IR, 13C NMR and 29Si NMR Studies" Materials 12, no. 12: 2006. https://doi.org/10.3390/ma12122006