Atmospheric breakdown chemistry of the new “green” solvent 2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals

Mapelli, Caterina; Schleicher, Juliette V.; Hawtin, Alex; Rankine, Conor D.; Whiting, Fiona C.; Byrne, Fergal; McElroy, Con Robert; Roman, Claudiu; Arsene, Cecilia; Olariu, Romeo Iulian; Bejan, Iustinian; Dillon, Terry J.

doi:10.5194/acp-22-14589-2022

Cited by 2 publications

(2 citation statements)

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“…15 A study of the atmospheric chemistry of TMO indicates that its environmental impact due to fugitive emissions is less than that of toluene. 16 To evaluate the potential of TMO in further industrial relevant processes, we herein investigated its potential as azeotropic solvent in the polycondensation of polyester resins.…”

Section: Introductionmentioning

confidence: 99%

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2,2,5,5-Tetramethyloxolane (TMO) Replacing Toluene as an Azeotropic Solvent for the Synthesis of Polyester Resins

Link,

Sherwood,

Day

et al. 2024

Ind. Eng. Chem. Res.

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A diverse array of chemical substances, from small molecules to macromolecules such as polyester resins for coatings applications, are synthesized in large quantities by means of condensation and polycondensation reactions. Condensation reactions starting from acids and alcohols are commonly used in industrial procedures because they utilize inexpensive starting materials and water is produced as the only byproduct. To ensure efficient removal of the water, the reaction can be conducted under reduced pressure or assisted by azeotropic solvents. For the latter, toluene is often used. In this study we were interested in exploring whether 2,2,5,5-tetramethyloxolane (TMO) also known as tetramethyl-tetrahydrofuran can be used as a safer and benign alternative to toluene. Therefore, the azeotropic polycondensation of polyester resins was examined in the presence of toluene or TMO. Furthermore, the nature of the TMO-water azeotrope and the stability of TMO under the reaction conditions were explored and compared to toluene. Results obtained showed that TMO does indeed form an azeotropic mixture and can be used as a safer alternative to toluene to efficiently remove water in polycondensation processes.

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Section: Introductionmentioning

confidence: 99%

“…The synthesis of TMO can be performed from levulinic acid (itself obtained from renewable resources) . A study of the atmospheric chemistry of TMO indicates that its environmental impact due to fugitive emissions is less than that of toluene …”

Section: Introductionmentioning

confidence: 99%

2,2,5,5-Tetramethyloxolane (TMO) Replacing Toluene as an Azeotropic Solvent for the Synthesis of Polyester Resins

Link,

Sherwood,

Day

et al. 2024

Ind. Eng. Chem. Res.

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Atmospheric oxidation of new “green” solvents – Part 2: methyl pivalate and pinacolone

Mapelli¹,

Donnelly²,

Hogan³

et al. 2023

Atmos. Chem. Phys.

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Abstract. Lab-based experimental and computational methods were used to study the atmospheric degradation of two promising “green” solvents: pinacolone, (CH3)3CC(O)CH3, and methyl pivalate, (CH3)3CC(O)OCH3. Pulsed laser photolysis coupled to pulsed laser-induced fluorescence was used to determine absolute rate coefficients (in 10−12 cm3 molec.−1 s−1) of k1(297 K) = (1.2 ± 0.2) for OH + (CH3)3CC(O)CH3 (Reaction R1) and k2(297 K) = (1.3 ± 0.2) for OH + (CH3)3CC(O)OCH3 (Reaction R2), in good agreement with one previous experimental study. Rate coefficients for both reactions were found to increase at elevated temperature, with k1(T) adequately described by k1(297–485 K) = 2.1 × 10−12 exp(-200/T) cm3 molec.−1 s−1. k2(T) exhibited more complex behaviour, with a local minimum at around 300 K. In the course of this work, k3(295–450 K) was obtained for the well-characterised reaction OH + C2H5OH (ethanol; Reaction R3), in satisfactory agreement with the evaluated literature. UV–Vis spectroscopy experiments and computational calculations were used to explore cross-sections for (CH3)3CC(O)CH3 photolysis (Reaction R4), while (CH3)3CC(O)OCH3 showed no sign of absorption over the wavelengths of interest. Absorption cross-sections for (CH3)3CC(O)CH3, σ4(λ), in the actinic region were larger, and the maximum was red-shifted compared to estimates (methyl ethyl ketone (MEK) values) used in current state-of-science models. As a consequence, we note that photolysis (Reaction R4) is likely the dominant pathway for removal of (CH3)3CC(O)CH3 from the troposphere. Nonetheless, large uncertainties remain as quantum yields φ4(λ) remain unmeasured. Lifetime estimates based upon Reactions (R1) and (R4) span the range 2–9 d and are consequently associated with a poorly constrained estimated photochemical ozone creation potential (POCPE). In accord with previous studies, (CH3)3CC(O)OCH3 did not absorb in the actinic region, allowing for straightforward calculation of an atmospheric lifetime of ≈ 9 d and a small POCPE ≈ 11.

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Atmospheric breakdown chemistry of the new “green” solvent 2,2,5,5-tetramethyloxolane via gas-phase reactions with OH and Cl radicals

Cited by 2 publications

References 45 publications

2,2,5,5-Tetramethyloxolane (TMO) Replacing Toluene as an Azeotropic Solvent for the Synthesis of Polyester Resins

2,2,5,5-Tetramethyloxolane (TMO) Replacing Toluene as an Azeotropic Solvent for the Synthesis of Polyester Resins

Atmospheric oxidation of new “green” solvents – Part 2: methyl pivalate and pinacolone

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