Thermal degradation of poly(methyl methacrylate) (PMMA): modelling of DTG and TG curves

Ferriol, M.; Gentilhomme, A.; Cochez, M.; Oget, Nicolas; Mieloszynski, J. L.

doi:10.1016/s0141-3910(02)00291-4

Cited by 317 publications

(209 citation statements)

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“…Since colloidal QDs (dropped cast layers) exhibit typically a smooth wavelength red shift with temperature, the different waveguided PL measured from 25 ºC to 50 ºC can be mainly attributed to the variations of the optical (refraction index) and morphological (film roughness) properties of PMMA matrix depending on the working temperature [20]. The PMMA stability is assured since there is not weight loss at temperatures below 165 ºC and its elastic regime is up to 195 ºC [21]. Moreover, any degradation of the material through the temperature cycles repeated during several days has not been observed.…”

Section: Resultsmentioning

confidence: 99%

Temperature Sensor Based on Colloidal Quantum Dots–PMMA Nanocomposite Waveguides

et al. 2012

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Section: Resultsmentioning

confidence: 99%

Temperature Sensor Based on Colloidal Quantum Dots–PMMA Nanocomposite Waveguides

et al. 2012

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“…The discrepancies are thought to be due to MW differences: the energy barrier is indeed expected to increase with MW [38,66,67]. It is worth noting that PMMA has been selected in this study as an emblematic case where a maximum monomer yield can be achieved.…”

Section: Pyrolysis Kinetics and Thermodynamicsmentioning

confidence: 99%

“…Thus, for example, during pyrolysis of our PMMA sample the initial degradation (between 133 and 275 °C) led to 5 wt% material loss whereas the main decomposition step (between 275 and 430 °C) was responsible for 94 wt%. It is well established that PMMA decomposes predominantly to the monomer, MMA, through unzipping reactions such as end-chain beta-scission or end-chain depolymerization [37][38][39][40][41][42]. As a result, the first stage could be attributed to breakdown of weak bonds at lower temperature through random scissions while the second involves mainly end-chain reactions; this confims the dominant mechanism of unizipping at intermediate and high temperatures.…”

Section: Pyrolysis Profilesmentioning

confidence: 99%

“…202 kJ/mol ( [18]. These changes were attributed to alternations between unzipping and random scission degradation modes as a consequence of structural differences of PMMA prepared using a free radical or anionic method [39] and of resulting differences in molecular weight [38]. According to Holland et al [39] and the trends reported here (Figure 5c), the PMMA used has been prepared by anionic polymerization: it is characterized by an abundance of saturated end-groups and hence by its higher thermal stability [66].…”

Section: Pyrolysis Kinetics and Thermodynamicsmentioning

confidence: 99%

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Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Larraín

Carrier

Radović

2017

Journal of Analytical and Applied Pyrolysis

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Highlights• Global activation energy depends on conversion in pyrolysis of all polymers.• Activation energy variability is proportional to chemical complexity of polymers.• An Evans-Polanyi relationship for initiation reactions of polymer pyrolysis is proposed. AbstractRecent advances in plastics recycling confirm the high potential of pyrolysis technologies to enhance recovery and selectivity rates. Modelling the kinetics of this complex process to stimulate scaling-up opportunities remains a major challenge.This study is an attempt to develop practical quantitative reactivity indices for the pyrolysis of natural and synthetic polymers. Representative samples from both categories (coal and pine vs. PET, PE and PMMA) were selected. Their weight loss during pyrolysis was determined experimentally and analyzed using judicious lumping procedures for its initiation, propagation and termination steps. The combined experimental and theoretical approach allowed us to determine apparent activation energies using the isoconversional Friedman method; and the use of Benson's group contribution method generated reaction enthalpies for the initiation reactions. Increasing activation energies with conversion in each case indicated that bond scission proceeds in order of increasing bond strength. The greater chemical complexity of natural polymers was reflected in the higher coefficients of variability for activation energy and wider ranges of reaction enthalpies. A structure-reactivity relationship based on the Evans-Polanyi theory was used to test the hypothesis that primary pyrolysis kinetics is controlled by cleavage of weakest chemical bonds. While the results show that this approach is promising, especially if confirmed by extension to a larger data set, they also suggest the need to compare the relative kinetic importance of initiation and propagation steps in the sequence of polymer pyrolysis reactions.

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“…Em geral, os polímeros apresentaram baixa estabilidade térmica (T i , Tabela 4), como previamente reportado por Ferriol et al [26] , von Lampe et al [27] e Zulfiqar et al [28] . Entretanto, é importante ressaltar que o desempenho térmico dos copolímeros de MMA, GMA e MAA pode ser ligeiramente diferente.…”

Section: Figura 2 Espectros De Atr-ir Para Os Polímeros (A) Madeiraunclassified

Compósitos polímero-madeira preparados por polimerização in situ de metil metacrilato usando aditivos bifuncionais

et al. 2015

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ResumoO presente trabalho teve por objetivo a confecção de compósitos polímero-madeira por meio de polimerização in situ de metil metacrilato (MMA), utilizando ácido metacrílico (MAA) e glicidil metacrilato (GMA) como agentes de ligação e reticulação. Amostras de madeira de guapuruvu foram impregnadas em um sistema de vácuo e pressão e polimerizadas em estufa a 90°C por 10h, usando 1,5% de peroxido de benzoíla como catalisador. Os compósitos foram caracterizados por meio de testes de absorção de água e estabilidade dimensional, molhabilidade, ATR-IR, TGA, MEV e WPG. Os espectros de ATR-IR mostraram incrementos nas bandas a 1746, 1460, e 1145 cm -1 , referentes as estruturas químicas dos polímeros dentro da madeira, confirmado posteriormente pelas imagens de MEV. A termogravimetria apontou reações químicas entre os copolímeros e a parede celular da madeira nos compósitos com GMA e MAA. Os compósitos preparados com MMA apresentaram incrementos acima de 50% nas propriedades higroscópicas e de estabilidade dimensional, entretanto a adição de GMA e MAA resultou em maiores incrementos nas mesmas propriedades, entre 66-90%. Palavras-chave: polimerização por radicais livres, Schizolobium parahyba, catálise térmica, reticulantes, agentes de ligação. AbstractWe prepared wood/polymer composites by in situ polymerization of methyl methacrylate (MMA) using glycidyl methacrylate (GMA) and methacrylic acid (MAA) as cross-linkers and coupling agents. The guapuruvu wood samples were impregnated in a vacuum/pressure system and polymerized at 90 °C for 10 h, using benzoyl peroxide at 1.5 wt % as catalyst. We characterized the composites through water uptake, dimensional stability tests, wettability, ATR-FTIR spectroscopy, TGA, SEM, and WPG. ATR-FTIR spectra showed an increase of the peaks at 1746, 1460, and 1145 cm -1 , corresponding to the chemical structures of the polymers into the pores and capillaries of the wood. This was further confirmed in the SEM images. TGA curves showed evidences for a chemical interaction between the copolymer and the wood cell wall in the composites with GMA and MAA. Hygroscopicity and dimensional stability properties of the composites prepared with MMA improved by 50%. Nevertheless, the addition of GMA and MAA resulted in additional increases for hydrophobicity and dimensional stability of the samples, ~ 66 -90%.

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Thermal degradation of poly(methyl methacrylate) (PMMA): modelling of DTG and TG curves

Cited by 317 publications

References 18 publications

Temperature Sensor Based on Colloidal Quantum Dots–PMMA Nanocomposite Waveguides

Temperature Sensor Based on Colloidal Quantum Dots–PMMA Nanocomposite Waveguides

Structure-reactivity relationship in pyrolysis of plastics: A comparison with natural polymers

Compósitos polímero-madeira preparados por polimerização in situ de metil metacrilato usando aditivos bifuncionais

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