Correlation between Self-Assembled Nanostructures and Bond Exchange Properties for Polyacrylate-Based Vitrimer-like Materials with a Trans-<i>N</i>-Alkylation Bond Exchange Mechanism

Oba, Yuta; Kimura, Takahiro; Hayashi, Mikihiro; Yamamoto, Katsuhiro

doi:10.1021/acs.macromol.1c02406

Cited by 28 publications

(26 citation statements)

References 62 publications

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“…For the practical application of the vitrimer concept, various molecular frameworks with different compatible bond exchange mechanisms have been studied, and basic physical properties, including rheological features, have been clarified based on both experimental and theoretical studies. − The development of tuning methods of the bond exchange properties should also be an important issue for the practical application. Thus far, the effects of the bond exchange catalysts (i.e., the type and amount), − cross-link density, − concentration of the bond exchangeable units, − glass-transition temperature ( T g ), and polarity of the network polymers , have been assessed. Among them, the effects of catalysts and concentration of the bond exchangeable units are related to the basis of organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

“…18−25 The development of tuning methods of the bond exchange properties should also be an important issue for the practical application. Thus far, the effects of the bond exchange catalysts (i.e., the type and amount), 26−28 cross-link density, 29−31 concentration of the bond exchangeable units, 32−34 glasstransition temperature (T g ), 35 and polarity of the network polymers 36,37 have been assessed. Among them, the effects of catalysts and concentration of the bond exchangeable units are related to the basis of organic chemistry.…”

Section: ■ Introductionmentioning

confidence: 99%

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Critical Effects of Branch Numbers at the Cross-Link Point on the Relaxation Behaviors of Transesterification Vitrimers

Isogai

Hayashi

2022

Macromolecules

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Vitrimers are functional cross-linked materials, exhibiting reprocessability, recyclability, and healability, and thus these are expected for application as sustainable materials. The functionalities of vitrimers are attributable to their associative bond exchange mechanism that is activated at a certain high temperature. The construction of a tuning method for the bond exchange properties must be useful for coming practical application of the vitrimer concept. Here, we prepare transesterification-based vitrimers via the thiol−epoxy click reaction to elucidate the essential effects of the branch numbers (f) at the cross-link point on their bond exchange properties, where f can be readily tuned via the functionality of the starting materials. The temperature-ramp creep and stress−relaxation tests then demonstrate that the vitrimer properties, such as the softening and stress−relaxation behaviors, vary depending on f. The experimental results derive some empirical relationships between f and the relaxation time and between f and activation energy of the bond exchange. In addition, the relaxation behavior of the vitrimer network with mixed f is investigated in the final section, showing the relaxation rate can be determined by the harmonic mean of relaxation time weighted by the mole fraction of the network components having different f. Overall, this study demonstrates that the design of a proper f is crucial to obtain the desired properties of vitrimers.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Critical Effects of Branch Numbers at the Cross-Link Point on the Relaxation Behaviors of Transesterification Vitrimers

Isogai

Hayashi

2022

Macromolecules

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“…In addition, the bands ranging from about 1650 to 1720 cm −1 (6.06-5.81 μm) in the Catania samples are broader and show different shapes compared to those in the Jena samples. This might point to the presence of N-H bending vibrations in addition to C = O or C = N groups caused by the presence of -NH 2 groups in the ion-irradiated samples (Bernstein et al 1995;Krasnokutski et al 2022;Oba et al 2022). However, a clear identification of the functional groups and composition of the processed organics based on the IR spectra is difficult.…”

Section: Resultsmentioning

confidence: 99%

Exploring Refractory Organics in Extraterrestrial Particles

Потапов

Palumbo

Dionnet

et al. 2022

ApJ

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The origin of organic compounds detected in meteorites and comets, some of which could have served as precursors of life on Earth, remains an open question. The aim of the present study is to make one more step in revealing the nature and composition of organic materials of extraterrestrial particles by comparing infrared spectra of laboratory-made refractory organic residues to spectra of cometary particles returned by the Stardust mission, interplanetary dust particles, and meteorites. Our results reinforce the idea of a pathway for the formation of refractory organics through energetic and thermal processing of molecular ices in the solar nebula. There is also the possibility that some of the organic material had formed already in the parental molecular cloud before it entered the solar nebula. The majority of the IR “organic” bands of the studied extraterrestrial particles can be reproduced in the spectra of the laboratory organic residues. We confirm the detection of water, nitriles, hydrocarbons, and carbonates in extraterrestrial particles and link it to the formation location of the particles in the outer regions of the solar nebula. To clarify the genesis of the species, high-sensitivity observations in combination with laboratory measurements like those presented in this paper are needed. Thus, this study presents one more piece of the puzzle of the origin of water and organic compounds on Earth and motivation for future collaborative laboratory and observational projects.

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“…Since then, the exploration of new associative dynamic reactions for vitrimer materials has drawn significant attention. Up to date, several studies have been conducted on associative dynamic chemistry, and commonly used examples include transesterification of (thio)esters, , metathesis of disulfide bonds, olefins, and silyl ethers, transamination of vinylogous urethane (or enamine-one) , and amides, , transalkylation reaction, , etc.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Dynamics of Enamine-One-Based Vitrimers through Substituent Modulation of Secondary Amine Substrates

et al. 2022

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Polymer networks embedded with dynamic covalent bonds have been demonstrated to be capable of network reconfiguration. This reprocessability is often related to the network dynamics or flowability, the precise control of which highly depends on the underlying chemistry. Particularly, vitrimer materials flow at a constant crosslinking density because of the associative dynamic chemistry involved. Here, we report the fabrication of enamine-one vitrimers through an amino-yne click reaction using secondary amine substrates. Compared with primary amines, the secondary amine-based amino-yne click reaction is mild and yields less gel content (70 vs 97%) in our curing system. By modulating the substituents of the secondary amine, we show that the activation energy of the exchange reaction increases (52–90 kJ/mol) with increasing steric hindrance (piperidyl ∼ methyl < ethyl < isopropyl < tert-butyl), and a similar trend was observed in the vitrimer networks. Interestingly, piperidine exhibits reactivities (including the yielded gel content and network dynamics) comparable to that of primary amines because of the less steric hindrance related to the constrained cyclic structure. This study not only enriches the scope of amine substrates for vitrimer fabrication but also offers a convenient means to tune the network dynamics through substrate choices or combination strategies (i.e., mixing primary and secondary amines or various secondary amines).

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Correlation between Self-Assembled Nanostructures and Bond Exchange Properties for Polyacrylate-Based Vitrimer-like Materials with a Trans-N-Alkylation Bond Exchange Mechanism

Cited by 28 publications

References 62 publications

Critical Effects of Branch Numbers at the Cross-Link Point on the Relaxation Behaviors of Transesterification Vitrimers

Critical Effects of Branch Numbers at the Cross-Link Point on the Relaxation Behaviors of Transesterification Vitrimers

Exploring Refractory Organics in Extraterrestrial Particles

Tuning the Dynamics of Enamine-One-Based Vitrimers through Substituent Modulation of Secondary Amine Substrates

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