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Night-time atmospheric chemistry of methacrylates

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Abstract

Background, aim, and scope

Methacrylates are α, β-unsaturated esters that are widely used in the polymer plastics and resins production. Kinetic information of NO3 radical reactions is especially scarce and a good understanding of all the atmospheric oxidation processes of these compounds is necessary in order to determine lifetimes in the atmosphere and to evaluate the impact of these reactions on the formation of ozone and other photooxidants.

Materials and methods

The experiments have been carried out using the relative technique in a static Teflon reactor at room temperature and atmospheric pressure (N2 as bath gas) using gas chromatography (GC)-flame ionization detection (FID) as detection system. Products were analyzed using solid phase microextraction (SPME)-GC-mass spectrometry (MS) technique and Fourier transform infrared spectroscopy (FTIR) using air as bath gas.

Results

The following rate coefficients were obtained (in cm3 molecule−1 s−1): methyl methacrylate + NO3 = (3.55 ± 0.62) × 10−15, ethyl methacrylate + NO3 = (5.42 ± 1.90) × 10−15, butyl methacrylate + NO3 = (7.87 ± 3.86) × 10−15. Methylpyruvate, ethylpyruvate, and butylpyruvate/butanol were identified as main degradation products respectively in the GC-MS analysis. Nitrates compounds were also identified in the FTIR study.

Discussion

The reactivity increases with the substitution and with the chain of the alkyl group in −C(O)OR. An electrophilic addition mechanism is proposed as dominant degradation process. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for methacrylate esters is their daytime reaction with the hydroxyl radical. NO3 and ozone are the main oxidants at night time.

Recommendations and perspectives

A detailed products analysis including quantification could elucidate the mechanism for butanol generation for butyl methacrylate reaction.

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Acknowledgment

A. Tapia and M. P. Gallego-Iniesta thanks the “Ministerio de Educación y Cultura” for personal grants. This work was supported by the project ENE2007-67529-CO2-02 granted by the Ministerio de Educación y Ciencia and the project PAI06-0042-2369 granted by the Junta de Comunidades de Castilla La Mancha.

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Authors and Affiliations

  1. Departamento de Química Física, Facultad de Ciencias Químicas, Universidad de Castilla La Mancha, Avda Camilo José Cela 10, 13071, Ciudad Real, Spain

    M. Sagrario Salgado, M. Pilar Martín & Beatriz Cabañas

  2. Instituto de Tecnologías Química y Medioambiental (ITQUIMA), Laboratorio de Contaminación Atmosférica, Universidad de Castilla La Mancha, Avda Camilo José Cela 10, 13071, Ciudad Real, Spain

    M. Paz Gallego-Iniesta & Araceli Tapia

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  1. M. Sagrario Salgado
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  2. M. Paz Gallego-Iniesta
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  3. M. Pilar Martín
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  4. Araceli Tapia
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  5. Beatriz Cabañas
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Correspondence to M. Sagrario Salgado.

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Responsible editor: Euripides Stephanou

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Salgado, M.S., Gallego-Iniesta, M.P., Martín, M.P. et al. Night-time atmospheric chemistry of methacrylates. Environ Sci Pollut Res 18, 940–948 (2011). https://doi.org/10.1007/s11356-011-0448-x

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  • DOI: https://doi.org/10.1007/s11356-011-0448-x

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