The thermodynamic properties of β-propiolactone, its polymer, and its polymerization in the 0–400°K range

Yevstropov, A.A.; Kulagina, T. G.; Lyudvig, Ye.B.; Belen'kaya, B.G.

doi:10.1016/0032-3950(79)90164-3

Cited by 7 publications

(1 citation statement)

References 7 publications

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“…Among the methyl-substituted monomers, δ1 is the slowest to polymerize with an observed polymerization rate constant about an order of magnitude smaller than that of the unsubstituted lactone. It is likely that this effect is partially caused by the relatively low reactivity of the propagating secondary alcohol. , When the substituent position is fixed, increasing the n- alkyl length decreases the polymerization rate; however, it is worth noting that the bulk concentration also decreases as the side chain length is increased. On the basis of prior work, we expect a similar trend to hold, even if the polymerizations are conducted in solvent at fixed concentration .…”

Section: Resultsmentioning

confidence: 99%

Aliphatic Polyester Block Polymer Design

2016

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Aliphatic polyester block polymers constitute a highly useful and amazingly versatile class of self-assembled materials. Analogous to styrenic block polymers in both design and function, the property profiles of these degradable materials can be precisely tailored by altering the chemical structure of the components. Driven by this ideal, we have examined the impact of n-alkyl substituents on the polymerization thermodynamics and kinetics of substituted δ-valerolactone monomers and developed guiding design principles based on critical structure–property relationships in the resulting aliphatic polyesters. Under bulk room temperature conditions the polymerization rate depends strongly on substituent position and exhibits a more modest dependence on alkyl length (from −CH3 to −(CH2)8CH3). The enthalpy and entropy of polymerization are significantly influenced by substituent position, but both are largely insensitive to n-alkyl length. However, the physical properties of the resulting aliphatic polyesters depend much more on substituent length than on substituent position. Notably, we demonstrate that polymer entanglement molar mass and solubility parameter can be systematically tuned by changing the substituent length. We discuss how these key structure property relationships can be used to inform the design of advanced sustainable materials for future technologies important in the arena of environmentally friendly materials.

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Section: Resultsmentioning

confidence: 99%

Aliphatic Polyester Block Polymer Design

2016

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Thermochemistry and kinetics of the 2‐butanone‐4‐yl CH₃C(=O)CH₂CH₂• + O₂ reaction system

Sebbar

Bozzelli

Trimis

et al. 2019

Int J of Chemical Kinetics

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Thermochemistry and kinetic pathways on the 2-butanone-4-yl (CH 3 C(=O) CH 2 CH 2 •) + O 2 reaction system are determined. Standard enthalpies, entropies, and heat capacities are evaluated using the G3MP2B3, G3, G3MP3, CBS-QB3 ab initio methods, and the B3LYP/6-311g(d,p) density functional calculation method. The CH 3 C(=O)CH 2 CH 2 • radical + O 2 association reaction forms a chemically activated peroxy radical with 35 kcal mol −1 excess of energy. The chemically activated adduct can undergo RO−O bond dissociation, rearrangement via intramolecular hydrogen transfer reactions to form hydroperoxide-alkyl radicals, or eliminate HO 2 and OH. The hydroperoxide-alkyl radical intermediates can undergo further reactions forming ketones, cyclic ethers, OH radicals, ketene, formaldehyde, or oxiranes. A relatively new path showing a low barrier and resulting in reactive product sets involves peroxy radical attack on a carbonyl carbon atom in a cyclic transition state structure. It is shown to be important in ketones when the cyclic transition state has five or more central atoms. K E Y W O R D S ab initio, butanone oxidation, reaction pathways, thermochemistry Int J Chem Kinet. 2019;51:541-562.

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Synthesis and characterization of novel ABA type poly(Ester-ether) triblock copolymers

et al. 2019

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The thermodynamic properties of β-propiolactone, its polymer, and its polymerization in the 0–400°K range

Cited by 7 publications

References 7 publications

Aliphatic Polyester Block Polymer Design

Aliphatic Polyester Block Polymer Design

Thermochemistry and kinetics of the 2‐butanone‐4‐yl CH₃C(=O)CH₂CH₂• + O₂ reaction system

Synthesis and characterization of novel ABA type poly(Ester-ether) triblock copolymers

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The thermodynamic properties of β-propiolactone, its polymer, and its polymerization in the 0–400°K range

Cited by 7 publications

References 7 publications

Aliphatic Polyester Block Polymer Design

Aliphatic Polyester Block Polymer Design

Thermochemistry and kinetics of the 2‐butanone‐4‐yl CH3C(=O)CH2CH2• + O2 reaction system

Synthesis and characterization of novel ABA type poly(Ester-ether) triblock copolymers

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Product

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Thermochemistry and kinetics of the 2‐butanone‐4‐yl CH₃C(=O)CH₂CH₂• + O₂ reaction system