The glass transition temperatures of amorphous linear aliphatic polyesters

Shen, Jialong; Caydamli, Yavuz; Gürarslan, Alper; Li, Shanshan; Tonelli, Alan E.

doi:10.1016/j.polymer.2017.07.054

Cited by 10 publications

(10 citation statements)

References 75 publications

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“…P3466-80/20 is the closest sample to P34 in terms of ester group content. According to estimated diad probabilities 40 (64% P34; 4% P66; 16% P36; 16% P64), there is still 36% of the oher three repeating units. This significant percentage will likely provide enough flexible structural units for it to form an IC with chain folding, and thus yields a melting temperature higher than that of the pure tetragonal urea.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The linear aliphatic tetra-polyesters were synthesized by step-growth polymerization using varying amounts of each of the two diols (1,3-propanediol and 1,6-hexanediol) and the two diacids (succinic acid and adipic acid) as monomers. The detailed experimental descriptions were reported elsewhere . The tetra-polyester series were named according to nomenclature of the copolymerization of the two homopolyesters, i.e., poly(trimethylene succinate) (P34) and poly(hexamethylene adipate) (P66).…”

Section: Experimental Sectionmentioning

confidence: 99%

“…The detailed experimental descriptions were reported elsewhere. 40 The tetra-polyester series were named according to nomenclature of the copolymerization of the two homopolyesters, i.e., poly(trimethylene succinate) (P34) and poly(hexamethylene adipate) (P66). For example, P3466-20/80 represents poly(20% trimethylene succinate-co-80% hexamethylene adipate).…”

Section: ■ Introductionsmentioning

confidence: 99%

“…Recently, we synthesized a series of linear aliphatic tetra-polyesters with varying crystallizability, and some of them were completely amorphous in the bulk. In the current work, we have made polymer urea inclusion compounds (P-U-ICs) with these tetra-polyesters using a solution co-crystallization method.…”

Section: Introductionsmentioning

confidence: 99%

See 3 more Smart Citations

The Role of Polymer Crystallizability on the Formation of Polymer-Urea-Inclusion Compounds

Shen¹,

Li²,

Caydamli³

et al. 2018

Crystal Growth & Design

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Polymer-urea inclusion compounds (P-U-ICs) were formed using a series of linear aliphatic polyesters with varying crystallizabilities: from highly crystalline to wholly amorphous. The traditional hexagonal P-U-ICs were obtained irrespective of the crystallinities of the neat guest polyesters. Two distinct co-crystallization mechanisms were evident based on the observation of the change in thermal stabilities of the ICs using DSC and the crystal morphologies by SEM; one involves polymer chain folding back and forth in a lamella-like crystal structure and the other grows much like short chain molecule U-ICs absent of chain reentering different channels. For polymers with sufficient chain length, their inherent flexibility is the key factor determining the co-crystallization mechanism while their crystallizability affects the kinetics, the consequences of which are more pronounced during recrystallization from melt. The amorphicity induced by random ester group placement is an interchain property, which does not play a role in affecting IC thermal stability. Rather, increasing the average ester group content can be understood as introducing more defects in the IC crystal and therefore reduces its thermal stability. The understanding gleaned in this study provides a new avenue for designing P-U-ICs to be used in both theoretical modeling and engineering of high-performance materials.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionsmentioning

confidence: 99%

Section: Introductionsmentioning

confidence: 99%

See 2 more Smart Citations

The Role of Polymer Crystallizability on the Formation of Polymer-Urea-Inclusion Compounds

Shen¹,

Li²,

Caydamli³

et al. 2018

Crystal Growth & Design

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“…Poly(butylene adipate- ran -butylene succinate- ran -butylene fumarate) (PBASF) with different compositions of butylene adipate (BA)/butylene succinate (BS)/butylene fumarate (BF) were synthesized by a conventional two-step reaction procedure of esterification and polycondensation in a melt state. ,,, TBT and MEHQ were respectively used as a catalyst and a free radical inhibitor, both of them were added into the reacting system ahead of polycondensation with 0.5% additional amount relative to the total weight of reactants each. After the polymerization process, the product was sufficiently dissolved in adequate volume of chloroform and subsequently centrifuged at a rate of 10,000 rpm for 15 min to remove the insoluble impurities, then the clear solution was precipitated with an excess amount of cold methanol.…”

Section: Methodsmentioning

confidence: 99%

Tailoring Crystallization of Random Terpolyester: Combination of Isodimorphism and Isomorphism

et al. 2020

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Isodimorphism and isomorphism are becoming mature approaches but separately used to regulate crystallization behavior of random copolymers and thus their performances. Most of the research work is focused on binary copolymers while leaves random copolymers containing more than two kinds of comonomeric units rarely studied in which both isodimorphism and isomorphism may occur together. This experiment is realized in the terpolymers of poly(butylene adipate-ran-butylene succinate-ran-butylene fumarate) (PBASF) wherein butylene adipate (BA) displays isodimorphic behavior with either butylene succinate (BS) or butylene fumarate (BF), and BF builds an isomorphic structure with BS. When the BA content is kept almost unchanged at ∼50 mol %, PBASF can be subtly tailored from a pseudoeutectic state to only isomorphic state by increasing the BF content that suppresses the crystallizability of the PBA-rich phase but hardly affects the PBSF-rich phase. Crystallization behaviors of PBASF from both melt and quenched samples are assayed in detail by using a differential scanning calorimeter, X-ray diffractometer/scatterometer, and Fourier transformation infrared spectrometer, and the mechanism of confined crystallization is clearly unraveled, which is relied on both intersegment hydrogen-bonding interaction and physical restriction. Furthermore, a crystal phase diagram for random terpolymer of PBASF is proposed, which provides an overall guide to tailor its crystallization. This example of the strategy combining isodimorphism and isomorphism raised here sheds light on precise regulation of properties and performances of terpolymer and copolymer with more complicated chain structures.

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Conformation and Configuration

Tonelli

2023

Encyclopedia of Polymer Science and Technology

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The unique feature of polymers is the flexibility of their long chains, achieved by rotation about their many backbone bonds, which enable them to assume an extremely large number of different Conformations. This is the source of their unique material behaviors, such as rubber‐like elasticity and their time and processing dependencies. Polymer conformations and material properties depend upon their Configurations, among which are the mode of enchainment of diene monomers, regiosequences (directions of monomer insertion), the stereosequences (stereochemical arrangements of atoms in the polymer chain), co‐monomer sequences of vinyl polymers, branches, and cross‐links. Polymer configurations cannot be altered without breaking and reforming their covalent bonds. In this article, we describe how the conformational characteristics of polymers can be rigorously treated, with account explicitly taken of their configurations, and how various conformationally averaged chain properties can be connected to the behaviors of their materials to allow improved structure–property relations. As examples, because 13 C NMR resonances depend on local polymer microstructures, the average bond conformation probabilities calculated for each microstructure can be used to assign their resonances. The applied to its dilute solution (the Kerr‐Effect) is very sensitive to the Configuration/Macrostructure of the overall polymer chain. When compared to the molar Kerr constants (mK) calculated for chains possessing the microstructures determined by 13 C NMR, the Macrostructures or complete molecular architectures of polymer chains may be revealed.

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The glass transition temperatures of amorphous linear aliphatic polyesters

Cited by 10 publications

References 75 publications

The Role of Polymer Crystallizability on the Formation of Polymer-Urea-Inclusion Compounds

The Role of Polymer Crystallizability on the Formation of Polymer-Urea-Inclusion Compounds

Tailoring Crystallization of Random Terpolyester: Combination of Isodimorphism and Isomorphism

Conformation and Configuration

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