Degradation kinetics of poly(HDDA‐<i>co</i>‐MMA)

Goswami, Ankur; Umarji, AM; Madras, Giridhar

doi:10.1002/app.32122

Cited by 11 publications

(7 citation statements)

References 28 publications

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“…The change in slopes becomes less obvious with increasing conversion due to the mobility loss in the system. This has previously been observed for pHDDA and other highly crosslinked systems 57 . Figure 11b, shows the glass transition temperature as a function of crosslinks.…”

Section: Glass Transitionsupporting

confidence: 81%

Modeling the free-radical polymerization of hexanediol diacrylate (HDDA): a molecular dynamics and graph theory approach

et al. 2018

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In the printing, coating and ink industries, photocurable systems are becoming increasingly popular and multi-functional acrylates are one of the most commonly used monomers due to their high reactivity (fast curing). In this paper, we use molecular dynamics and graph theory tools to investigate the thermo-mechanical properties and topology of hexanediol diacrylate (HDDA) polymer networks. The gel point was determined as the point where a giant component was formed. For the conditions of our simulations, we found the gel point to be around 0.18 bond conversion. A detailed analysis of the network topology showed, unexpectedly, that the flexibility of the HDDA molecules plays an important role in increasing the conversion of double bonds, while delaying the gel point. This is due to a back-biting type of reaction mechanism that promotes the formation of small cycles. The glass transition temperature for several degrees of curing was obtained from the change in the thermal expansion coefficient. For a bond conversion close to experimental values we obtained a glass transition temperature around 400 K. For the same bond conversion we estimate a Young's modulus of 3 GPa. Both of these values are in good agreement with experiments.

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Section: Glass Transitionsupporting

confidence: 81%

Modeling the free-radical polymerization of hexanediol diacrylate (HDDA): a molecular dynamics and graph theory approach

et al. 2018

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“…Several studies have investigated the thermal degradation of PMMA . PMMA shows degradation in the first stage between 160 to 240 °C (as shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…The activation energy for the final step for RAFT synthesized PMMA is 130 kJ mol −1 . In the case of radically synthesized PMMA, the activation energy for the final stage varies from 124 kJ mol −1 for PMMA of M w 100 000 g mol −1 to 200 kJ mol −1 for PMMA of M w 350 000 g mol −1 . Further, the reported activation energy varies from 100 to 320 kJ mol −1 and is also dependent on the reaction order and conversion .…”

Section: Resultsmentioning

confidence: 99%

Synthesis, characterization and thermal degradation of dual temperature‐ and pH‐sensitive RAFT‐made copolymers of N,N‐(dimethylamino)ethyl methacrylate and methyl methacrylate

Roy

Bauri

Pal

et al. 2012

Polymer International

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Poly{[(N,N‐(dimethylamino)ethyl methacrylate]‐co‐(methyl methacrylate)} copolymers of various compositions were synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization at 70 °C in N,N‐dimethylformamide. The polymer molecular weights and molecular weight distributions were obtained from size exclusion chromatography, and they indicated the controlled nature of the RAFT polymerizations; the polydispersity indices are in the range 1.1–1.3. The reactivity ratios of N,N‐(dimethylamino)ethyl methacrylate (DMAEMA) and methyl methacrylate (MMA) (rDMAEMA = 0.925 and rMMA = 0.854) were computed by the extended Kelen–Tüdös method at high conversions, using compositions obtained from 1H NMR. The pH‐ and temperature‐sensitive behaviour were studied in aqueous solution to confirm dual responsiveness of these copolymers. The thermal properties of the copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The kinetics of thermal degradation were determined by Friedmann and Chang techniques to evaluate various parameters such as the activation energy, the order and the frequency factor. © 2012 Society of Chemical Industry

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“…In order to analyze the kinetic parameters, the Friedman technique was adopted using single heating rate [42, 43]. In this technique, comparison of mass loss rate $\left( {{{d\alpha } \over {dt}}} \right)$ was used to determine the kinetic parameter, where α is fractional mass loss.…”

Section: Methodsmentioning

confidence: 99%

Thermal and sonochemical degradation kinetics of poly(n‐butyl methacrylate‐co‐alkyl acrylates): Variation of chain strength and stability with copolymer composition

Bhagat

Madras

2012

Polymer Engineering & Sci

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The thermal degradation of poly(n‐butyl methacrylate‐co‐alkyl acrylate) was compared with ultrasonic degradation. For this purpose, different compositions of poly (n‐butyl methacrylate‐co‐methyl acrylate) (PBMAMA) and a particular composition of poly(n‐butyl methacrylate‐co‐ethyl acrylate) (PBMAEA) and poly(n‐butyl methacrylate‐co‐butyl acrylate) (PBMABA) were synthesized and characterized. The thermal degradation of polymers shows that the poly(alkyl acrylates) degrade in a single stage by random chain scission and poly(n‐butyl methacrylate) degrades in two stages. The number of stages of thermal degradation of copolymers was same as the majority component of the copolymer. The activation energy corresponding to random chain scission increased and then decreased with an increase of n‐butyl methacrylate fraction in copolymer. The effect of methyl acrylate content, alkyl acrylate substituent, and solvents on the ultrasonic degradation of these copolymers was investigated. A continuous distribution kinetics model was used to determine the degradation rate coefficients. The degradation rate coefficient of PBMAMA varied nonlinearly with n‐butyl methacrylate content. The degradation of poly (n‐butyl methacrylate‐co‐alkyl acrylate) followed the order: PBMAMA < PBMAEA < PBMABA. The variation in the degradation rate constant with composition of the copolymer was discussed in relation to the competing effects of the stretching of the polymer in solution and the electron displacement in the main chain. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers

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Degradation kinetics of poly(HDDA‐co‐MMA)

Cited by 11 publications

References 28 publications

Modeling the free-radical polymerization of hexanediol diacrylate (HDDA): a molecular dynamics and graph theory approach

Modeling the free-radical polymerization of hexanediol diacrylate (HDDA): a molecular dynamics and graph theory approach

Synthesis, characterization and thermal degradation of dual temperature‐ and pH‐sensitive RAFT‐made copolymers of N,N‐(dimethylamino)ethyl methacrylate and methyl methacrylate

Thermal and sonochemical degradation kinetics of poly(n‐butyl methacrylate‐co‐alkyl acrylates): Variation of chain strength and stability with copolymer composition

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