Methanolysis of Poly(lactic Acid) Using Catalyst Mixtures and the Kinetics of Methyl Lactate Production

Journal article

Lamberti, Fabio M., Roman-Ramirez, L., Dove, A. and Wood, J. (2022). Methanolysis of Poly(lactic Acid) Using Catalyst Mixtures and the Kinetics of Methyl Lactate Production. Polymers. 14 (9), p. e1763. https://doi.org/10.3390/polym14091763
AuthorsLamberti, Fabio M., Roman-Ramirez, L., Dove, A. and Wood, J.
AbstractPolylactic acid (PLA) is a leading bioplastic of which the market share is predicted to increase in the future; its growing production capacity means its end-of-life treatment is becoming increasingly important. One beneficial disposal route for PLA is its chemical recycling via alcoholysis. The alcoholysis of PLA leads to the generation of value-added products alkyl lactates; this route also has potential for a circular economy. In this work, PLA was chemically recycled via methanolysis to generate methyl lactate (MeLa). Four commercially available catalysts were investigated: zinc acetate dihydrate (Zn(OAc)2), magnesium acetate tetrahydrate (Mg(OAc)2), 4-(dimethylamino)pyridine (DMAP), and triazabicyclodecene (TBD). Dual catalyst experiments displayed an increase in reactivity when Zn(OAc)2 was paired with TBD or DMAP, or when Mg(OAc)2 was paired with TBD. Zn(OAc)2 coupled with TBD displayed the greatest reactivity. Out of the single catalyst reactions, Zn(OAc)2 exhibited the highest activity: a higher mol% was found to increase reaction rate but plateaued at 4 mol%, and a higher equivalent of methanol was found to increase the reaction rate, but plateaued at 17 equivalents. PLA methanolysis was modelled as a two-step reversible reaction; the activation energies were estimated at: Ea1 = 25.23 kJ∙mol−1, Ea2 = 34.16 kJ∙mol−1 and Ea-2 = 47.93 kJ∙mol−1.
Keywordsmethanolysis; poly(lactic acid); chemical recycling; zinc acetate dihydrate; magnesium acetate tetrahydrate; 4-(dimethylamino)pyridine; triazabicyclodecene; alcoholysis; dual catalysts
Year2022
JournalPolymers
Journal citation14 (9), p. e1763
PublisherMDPI
ISSN2073-4360
Digital Object Identifier (DOI)https://doi.org/10.3390/polym14091763
Funder/ClientEngineering and Physical Sciences Research Council
Publication dates
Online26 Apr 2022
Publication process dates
Accepted21 Apr 2022
Deposited29 Apr 2022
Publisher's version
License
File Access Level
Open
Licensehttps://creativecommons.org/licenses/by/4.0/
Permalink -

https://openresearch.lsbu.ac.uk/item/8zx06

Download files

Publisher's version
polymers-14-01763.pdf
License: CC BY 4.0
File access level: Open

  • 73
    total views
  • 72
    total downloads
  • 0
    views this month
  • 0
    downloads this month

Export as

Related outputs

Maximizing Polypropylene Recovery from Waste Carpet Feedstock: A Solvent-Driven Pathway Towards Circular Economy
Salazar Salazar, H., Baragau, I., Lu, Z., Roman Ramirez, L. and Kellici, S. (2024). Maximizing Polypropylene Recovery from Waste Carpet Feedstock: A Solvent-Driven Pathway Towards Circular Economy. RSC Sustainability . https://doi.org/10.1039/D3SU00270E
Impact of Formulation and Slurry Properties on Lithium-ion Electrode Manufacturing
Reynolds, C., Niri, M.F., Hidalgo, M.F., Heymer, R., Roman, Luis, Alsofi, G., Khanom, H., Pye, B., Marco, J. and Kendrick, E. (2023). Impact of Formulation and Slurry Properties on Lithium-ion Electrode Manufacturing. Batteries & Supercaps. p. e202300396. https://doi.org/10.1002/batt.202300396
Vapor Equilibrium Data for the Binary Mixtures of Dimethyl Carbonate and Ethyl Methyl Carbonate in Compressed Carbon Dioxide
Jethwa, S.J., Roman Ramirez, L., Anderson, P.A. and Leeke, G.A. (2023). Vapor Equilibrium Data for the Binary Mixtures of Dimethyl Carbonate and Ethyl Methyl Carbonate in Compressed Carbon Dioxide. International Journal of Thermophysics. 44 (86). https://doi.org/10.1007/s10765-023-03186-2
Quantifying key factors for optimised manufacturing of Li-ion battery anode and cathode via artificial intelligence
Niri, M.F., Liu, K., Apachitei, G., Roman Ramirez, L., Lain, M., Widanage, D. and Marco, J. (2022). Quantifying key factors for optimised manufacturing of Li-ion battery anode and cathode via artificial intelligence. Energy and AI. 7, p. 100129. https://doi.org/10.1016/j.egyai.2021.100129
Cross-sectional analysis of lithium ion electrodes using spatial autocorrelation techniques.
Lain, M., Apachitei, G., Roman Ramirez, L., Copley, M. and Marco, James (2022). Cross-sectional analysis of lithium ion electrodes using spatial autocorrelation techniques. Physical chemistry chemical physics : PCCP. 24 (48), pp. 29999-30009. https://doi.org/10.1039/d2cp03094b
Systematic analysis of the impact of slurry coating on manufacture of Li-ion battery electrodes via explainable machine learning
Faraji Niri, M., Reynolds, C., Kendrick, E., Marco, J. and Roman Ramirez, L. (2022). Systematic analysis of the impact of slurry coating on manufacture of Li-ion battery electrodes via explainable machine learning. Energy Storage Materials. 51, pp. 223-238. https://doi.org/10.1016/j.ensm.2022.06.036
Roadmap on Li-ion battery manufacturing research
Grant, P.S., Greenwood, D., Pardikar, K., Smith, R., Entwistle, T., Middlemiss, L.A., Murray, G., Cussen, S.A., Lain, M.J., Capener, M.J., Copley, M., Reynold, C.D., Hare, S.D., Simmons, M.J.H., Kendrick, E., Zankowski, S.P., Wheeler, S., Pengcheng, Z., Slater, P.R., Zhang, Y.S., Morrison, A.R.T., Dawson, W., Li, J., Shearling, P., Brett, D.J.L., Matthews, G., Ge, R., Drummond, R., Tredenick, E., Cheng, C., Duncan, S.R., Boyce, A.M., Faraji-Niri, M., Marco, J., Roman Ramirez, L., Harper, C., Blackmore, P., Shelley, T., Mohsseni, A. and Cumming, D.J. (2022). Roadmap on Li-ion battery manufacturing research. Journal of Physics: Energy. 4 (4). https://doi.org/10.1088/2515-7655/ac8e30
Design of experiments applied to lithium-ion batteries: A literature review
Roman-Ramirez, L.A. and Marco, J. (2022). Design of experiments applied to lithium-ion batteries: A literature review. Applied Energy. 320, p. 119305. https://doi.org/10.1016/j.apenergy.2022.119305
Effect of coating operating parameters on electrode physical characteristics and final electrochemical performance of lithium-ion batteries
Roman Ramirez, L., Apachitei G., Faraji-Niri M., Lain M., Widanage D. and Marco J. (2022). Effect of coating operating parameters on electrode physical characteristics and final electrochemical performance of lithium-ion batteries. International Journal of Energy and Environmental Engineering. https://doi.org/10.1007/s40095-022-00481-w
Comparative study on the hydrogenation of naphthalene over both Al2O3‑supported Pd and NiMo catalysts against a novel LDH-derived Ni-MMO-supported Mo catalyst
Claydon, R.M., Roman Ramirez, L. and Wood, J. (2021). Comparative study on the hydrogenation of naphthalene over both Al2O3‑supported Pd and NiMo catalysts against a novel LDH-derived Ni-MMO-supported Mo catalyst. ACS Omega. 6 (30), pp. 20053-20067. https://doi.org/10.1021/acsomega.1c03083
Machine learning for optimised and clean Li-ion battery manufacturing: Revealing the dependency between electrode and cell characteristics
Niri, M.F., Liu, K., Apachitei, G., Roman Ramirez, L., Lain, M., Widanage, D. and Marco, J. (2021). Machine learning for optimised and clean Li-ion battery manufacturing: Revealing the dependency between electrode and cell characteristics. Journal of Cleaner Production. 324, p. 129272. https://doi.org/10.1016/j.jclepro.2021.129272
Understanding the effect of coating-drying operating variables on electrode physical and electrochemical properties of lithium-ion batteries
Roman Ramirez, L., Apachitei, G., Faraji-Niri, M., Lain, M., Widanage, W.D. and Marco, J. (2021). Understanding the effect of coating-drying operating variables on electrode physical and electrochemical properties of lithium-ion batteries. Journal of Power Sources. 516, p. 230689. https://doi.org/10.1016/j.jpowsour.2021.230689
Experimental data of cathodes manufactured in a convective dryer at the pilot-plant scale, and charge and discharge capacities of half-coin lithium-ion cells.
Román-Ramírez, L.A., Apachitei, G., Faraji-Niri, M., Lain, M., Widanage, D. and Marco, J. (2021). Experimental data of cathodes manufactured in a convective dryer at the pilot-plant scale, and charge and discharge capacities of half-coin lithium-ion cells. Data in Brief. 40, p. 107720. https://doi.org/10.1016/j.dib.2021.107720
Kinetics of methyl lactate formation from the transesterification of polylactic acid catalyzed by Zn(II) complexes
Roman Ramirez, L., McKeown, P., Jones, M.D. and Wood, J. (2020). Kinetics of methyl lactate formation from the transesterification of polylactic acid catalyzed by Zn(II) complexes . ACS Omega. 5 (10), pp. 5556-5564. https://doi.org/10.1021/acsomega.0c00291
Evaluation of the Peng–Robinson and the Cubic-Plus-Association equations of state in modeling VLE of carboxylic acids with water
Roman Ramirez, L. and Leeke, G.A. (2020). Evaluation of the Peng–Robinson and the Cubic-Plus-Association equations of state in modeling VLE of carboxylic acids with water . International Journal of Thermophysics. 41 (51). https://doi.org/10.1007/s10765-020-02643-6
Chemical degradation of end-of-life poly(lactic acid) into methyl lactate by a Zn(II) complex
Roman Ramirez, L., McKeown, P., Shah, C., Abraham, J., Jones, M.D. and Wood, J. (2020). Chemical degradation of end-of-life poly(lactic acid) into methyl lactate by a Zn(II) complex. Industrial and Engineering Chemistry Research. 59 (54), pp. 11149-11156. https://doi.org/10.1021/acs.iecr.0c01122
Organocatalysis for versatile polymer degradation
Kamran, M., Davidson, M.G., Jones, M.D., Roman Ramirez, L. and Wood, J. (2020). Organocatalysis for versatile polymer degradation. Green Chemistry. 12. https://doi.org/10.1039/D0GC01252A
Kinetics of Alkyl Lactate Formation from the Alcoholysis of Poly(Lactic Acid)
Lamberti, F.M., Roman Ramirez, L., McKeown, P., Jones, M.D. and Wood, J. (2020). Kinetics of Alkyl Lactate Formation from the Alcoholysis of Poly(Lactic Acid) . Processes. 8 (2), p. 738. https://doi.org/10.3390/pr8060738
Ethyl Lactate Production from the Catalytic Depolymerisation of Post‑consumer Poly(lactic acid)
Roman Ramirez, L., Powders, M., McKeown, P., Jones, M.D. and Wood, J. (2020). Ethyl Lactate Production from the Catalytic Depolymerisation of Post‑consumer Poly(lactic acid). Journal of Polymers and the Environment. 28, pp. 2956-2964. https://doi.org/10.1007/s10924-020-01824-6
Evaluation of association schemes in the CPA and PC-SAFT equations of state in modeling VLE of organic acids + water systems
Roman Ramirez, L., Garcia-Sanchez, F. and Leeke, G.A. (2020). Evaluation of association schemes in the CPA and PC-SAFT equations of state in modeling VLE of organic acids + water systems. Chemical Engineering Communications. 208 (9), pp. 1313-1325. https://doi.org/10.1080/00986445.2020.1771323
Recycling of Bioplastics: Routes and Benefits
Lamberi, F.M., Roman Ramirez, L. and Wood, J. (2020). Recycling of Bioplastics: Routes and Benefits. Journal of Polymers and the Environment. 28, pp. 2551-2571. https://doi.org/10.1007/s10924-020-01795-8
Zinc complexes for PLA formation and chemical recycling
McKeown, P., Roman Ramirez, L., Bates, S., Wood, J. and Jones, M. (2019). Zinc complexes for PLA formation and chemical recycling . ChemSusChem. 12 (24), pp. 5233-5238. https://doi.org/10.1002/cssc.201902755
Poly(lactic acid) Degradation into Methyl Lactate Catalyzed by a Well-Defined Zn(II) Complex
Roman Ramirez, L., Mckeown, P., Jones, M.D. and Wood, J. (2019). Poly(lactic acid) Degradation into Methyl Lactate Catalyzed by a Well-Defined Zn(II) Complex. ACS Catalysis. 9 (1), pp. 409-416. https://doi.org/10.1021/acscatal.8b04863
P-x data of (acetic acid + water) at T = (412.6, 443.2, 483.2) K
Roman Ramirez, L. and Leeke, G.A. (2016). P-x data of (acetic acid + water) at T = (412.6, 443.2, 483.2) K . Journal of Chemical and Engineering Data. 61 (6), pp. 2078-2082. https://doi.org/10.1021/acs.jced.5b01104
Vapour-liquid equilibrium of propanoic acid+water at 423.2, 453.2 and 483.2K from 1.87 to 19.38bar. Experimental and modelling with PR, CPA, PC-SAFT and PCP-SAFT
Roman Ramirez, L., Garcia-Sanchez, F., Santos, R.C.D. and Leeke, G.A. (2015). Vapour-liquid equilibrium of propanoic acid+water at 423.2, 453.2 and 483.2K from 1.87 to 19.38bar. Experimental and modelling with PR, CPA, PC-SAFT and PCP-SAFT . Fluid Phase Equilibria. 388, pp. 151-159. https://doi.org/10.1016/j.fluid.2015.01.004
Modeling of asphaltene precipitation from n-alkane diluted heavy oils and bitumens using the PC-SAFT equation of state
Zúñiga-Hinojosa, M.A., Justo-Garcia, D.N., Aquino-Olivos, M.A., Roman Ramirez, L. and Garcia-Sanchez, F. (2014). Modeling of asphaltene precipitation from n-alkane diluted heavy oils and bitumens using the PC-SAFT equation of state. Fluid Phase Equilibria. 376, pp. 210-224. https://doi.org/10.1016/j.fluid.2014.06.004