Thermodynamics of polymerization of heterocyclic compounds part V. The heat capacity, entropy, enthalpy and free energy of 1,3-dioxolan and poly-1,3-dioxolan

Clegg, G. A.; Melia, Tom

doi:10.1016/0032-3861(69)90127-x

Cited by 29 publications

(6 citation statements)

References 21 publications

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“… a Lin 4000 and Lin9000 correspond to linear polyDXL with M n = 4000 and 9000; Net4000 and Net9000 correspond to polyDXL networks with M c = 4000 and 9000. b The values for the crystalline fraction (χ c ) are based on the melting enthalpy of 100% crystalline polyDXL, which is known to be 231 J/g . Indium was used as calibration standard. …”

Section: Resultsmentioning

confidence: 99%

Solid-State NMR Study of the Multiphase Behavior of Linear and Cross-Linked Poly(1,3-dioxolane)

Prez¹,

Goethals²,

Adriaensens³

et al. 1996

Macromolecules

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The multiphase behavior of poly(1,3-dioxolane) (polyDXL) in linear and network forms as a function of molecular weight and cross-link density of the samples was investigated by high-resolution solid-state 13C NMR. The ability to introduce two acrylate end groups and to control the molecular weight of the polymer provided a unique way to synthesize polyDXL networks with molecular weights varying from 4000 to 9000 between the cross-links. Besides an elastomeric phase and a crystalline phase, the existence of a third phase with intermediate molecular mobility could be shown for cross-linked polyDXL. This could be realized by making use of different techniques, such as T 1 ρ H studies at well-selected contact times and careful Lorentzian deconvolution of the acetal 13C CP/MAS resonance lines. In these OCH2O resonances, the peak of the interphase is situated around 96 ppm, at about the same chemical shift as that of the elastomeric phase, but it has a broader bandwidth due to increased spin diffusion. The crystalline component having the broadest bandwidth is positioned around 93.4 ppm. While the introduction of cross-links clearly is attributed to the development of an interphase, T 1 ρ H studies demonstrated that the limited molecular mobility of this phase is independent of the cross-link density of the samples. The presence of such a noncrystalline, immobile interphase between the crystalline and elastomeric regions could not be demonstrated for linear polyDXL with a molecular weight range of 4000−9000.

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Section: Resultsmentioning

confidence: 99%

Solid-State NMR Study of the Multiphase Behavior of Linear and Cross-Linked Poly(1,3-dioxolane)

Prez¹,

Goethals²,

Adriaensens³

et al. 1996

Macromolecules

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“…In addition to the above modeling and experimental work on 1,3-dioxolane chemical kinetics, the standard enthalpies of formation, standard entropies, and heat capacities of 1,3-dioxolane are available in the literature. Pihlaja and Heikkilä determined the standard enthalpies of formation of 1,3-dioxolane, 2-methyl-1,3-dioxolane, and 2,4-dimethyl-1,3-dioxolane via combustion calorimetry.…”

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

“…In addition to the above modeling and experimental work on 1,3-dioxolane chemical kinetics, the standard enthalpies of formation, 12 standard entropies, 13 and heat capacities 14 dioxolane, 2-methyl-1,3-dioxolane, and 2,4-dimethyl-1,3-dioxolane via combustion calorimetry. Clegg and Melia 13 obtained the standard entropies of 1,3-dioxolane and its polymers calorimetrically. Dorofeeva 14 provided a collection of thermodynamic properties of oxygenated cyclic compounds, which included 1,3-dioxolane heat capacities for temperatures from 50 to 1500 K. An investigation of the combustion of dioxolane derivatives does not exist to date.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Pihlaja and Heikkilä determined the standard enthalpies of formation of 1,3-dioxolane, 2-methyl-1,3-dioxolane, and 2,4-dimethyl-1,3-dioxolane via combustion calorimetry. Clegg and Melia obtained the standard entropies of 1,3-dioxolane and its polymers calorimetrically. Dorofeeva provided a collection of thermodynamic properties of oxygenated cyclic compounds, which included 1,3-dioxolane heat capacities for temperatures from 50 to 1500 K.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Investigation of Key Properties of the Pyrolysis of Methyl, Ethyl, and Dimethyl Dioxolane Isomers

2022

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Cyclic acetals are considered as carbon-neutral fuels that can be produced from biomass and renewable electricity. Recent investigations on 1,3-dioxolane, a five-membered cyclic acetal, revealed that unimolecular decomposition through H-atom migration within the ring governs thermal decomposition. For methyl-and ethyl-substituted dioxolane compounds, very limited information on thermodynamic, transport, bond dissociation, and thermal decomposition properties is available. The present study remedies this lack of information by providing these properties for methyl-, ethyl-, and dimethyl-substituted dioxolanes in a systematic manner. While adding substituents to the dioxolane ring has only a minor effect on the bond dissociation energies, the barrier heights for H-atom migration are clearly affected by the position of the substituents. Notably, the corresponding transition states are preferably in the boat ring configuration. However, two of the substituted dioxolanes do not allow for this configuration because of their respective bonding structures, resulting in larger barrier heights. The properties provided here will aid the detailed chemical kinetic modeling of substituted dioxolane combustion chemistry.

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Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds

Léonard

1999

The Wiley Database of Polymer Properties

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Thermodynamics of polymerization of heterocyclic compounds part V. The heat capacity, entropy, enthalpy and free energy of 1,3-dioxolan and poly-1,3-dioxolan

Cited by 29 publications

References 21 publications

Solid-State NMR Study of the Multiphase Behavior of Linear and Cross-Linked Poly(1,3-dioxolane)

Solid-State NMR Study of the Multiphase Behavior of Linear and Cross-Linked Poly(1,3-dioxolane)

Theoretical Investigation of Key Properties of the Pyrolysis of Methyl, Ethyl, and Dimethyl Dioxolane Isomers

Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds

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