Mechanochemical synthesis of inverse vulcanized polymers

Yan, Peiyao; Zhao, Wei; McBride, Fiona; Cai, D.; Dale, Joseph; Hanna, Veronica; Hasell, Tom

doi:10.1038/s41467-022-32344-7

Cited by 50 publications

(56 citation statements)

References 47 publications

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“…[29][30][31] A wide range of innovative, lower-temperature processing and recycling techniques have also been explored. 29,[32][33][34][35][36] Sustainability of HSMs has been further improved by using biologically-produced olen comonomers, such as lignin derivatives, 5,6,8,9 cellulose derivatives, 37,38 starch, [39][40][41][42] raw lignocellulosic biomass, 43,44 fatty acids, [45][46][47] triglycerides, 48,49 terpenoids, 38,50 and amino acid derivatives. 51 Miscibility issues for hydrophilic olen sources during the HSM-forming reaction has been observed in some of these studies and could be addressed by using extended reaction times, adding compatibilizing agents/catalysts, or mechanochemical synthesis.…”

Section: Introductionmentioning

confidence: 99%

Durable composites by vulcanization of oleyl-esterified lignin

et al. 2023

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Section: Introductionmentioning

confidence: 99%

Durable composites by vulcanization of oleyl-esterified lignin

et al. 2023

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“…1,2,3 Since inverse vulcanization was created in 2013, 4 new crosslinkers for synthesis, and interesting intrinsic properties and unexpected applications of relevant materials have been extensively studied. Plenty of research has demonstrated that inverse vulcanized polymers have unique properties which traditional carbon-based polymers lack, such as affinity for metal, 5,6,7,8 chemically dynamic property, 9,10,11,12 ultrahigh refractive index (n>1.8) 13,14,15 et al, and they have been proved that they are able to be used in many promising applicable fields, such as antimicrobial material, 16,17 water remediation, 5,7,8,18 Li-S battery, 19,20,21 infrared thermal imaging, 22,23,24 optics throughout visible range, 15,25 and self-healing materials 12,26,27,28 .…”

Section: Introductionmentioning

confidence: 99%

Processable crosslinked terpolymers made from elemental sulfur with wide range of thermal and mechanical properties

Yan¹,

Wang²,

Dodd³

et al. 2023

Preprint

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Elemental sulfur, a by-product of the purification of crude oil, is an underused material produced in excess. Inverse vulcanization, a process that uses comonomers to stabilise polymeric sulfur to form high sulfur content (>50 wt.%, normally) polymers, has emerged as a popular strategy for transforming this waste material, elemental sulfur, into functional polymers. Inverse vulcanized polymers are intrinsically processable and recyclable, and have been demonstrated as promising for applications in many fields. If this kind of material is to be widely used in some scenarios to replace some traditional plastics, it is necessary to make them with appropriate thermal and mechanical properties that meet the basic application requirements. Mechanical properties of inverse vulcanized polymers are currently under developed; research on sulfur polymers with a wide range of thermal properties and good mechanical properties needs to be developed. Here, we report series of terpolymers copolymerized from two distinct organic comonomers and elemental sulfur to obtain polymers with a wide range of glass transition temperature (-43 °C to 45 °C) and exhibiting good mechanical properties (varying from stiff and hard to flexible and tough), by blending crosslinkers with varying feed monomer ratio and varying chain length of linear sections, which expands the application opportunities of inverse vulcanization.

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“…2 Very recently, a mechanochemical synthesis was suggested as an alternative route to inverse vulcanization. 32 Transient optical absorption measurements show that sulfur polymerization can be also achieved below 159 °C by means of photoexcitation using a laser illumination with an intensity larger than 0.21 mJ/cm 2 , although the decomposition of S 8 rings can be observed at weaker laser illumination. 33,34 understanding of the chemical and physical properties of elemental sulfur, S 8, is an important task.…”

mentioning

confidence: 99%

“…Currently, a widely used approach to develop stable sulfur polymers is to link the sulfur chains, generated upon heating above the floor temperature of sulfur, with organic comonomers, an approach referred to as inverse vulcanization . Very recently, a mechanochemical synthesis was suggested as an alternative route to inverse vulcanization . Transient optical absorption measurements show that sulfur polymerization can be also achieved below 159 °C by means of photoexcitation using a laser illumination with an intensity larger than 0.21 mJ/cm 2 , although the decomposition of S 8 rings can be observed at weaker laser illumination. , Thus, in this context, gaining a better understanding of the chemical and physical properties of elemental sulfur, S 8, is an important task.…”

mentioning

confidence: 99%

Ring-to-Chain Structural Relaxation of Elemental Sulfur upon Photoexcitation

Cho

Pratik

Pyun

et al. 2022

ACS Materials Lett.

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The emergence of high sulfur content polymeric materials and their applications in a number of important areas call for a comprehensive understanding of the chemical and physical properties of elemental sulfur. In spite of many earlier efforts, a thorough description of the electronic structure and photorelaxation pathways of the S8 ring, the thermodynamically stable structure of elemental sulfur, remains largely unexplored. It can be expected that the photoinduced homolytic processes of S8 and intermediates are analogous to those in the species observed via thermally induced processes. Here, we combine time-dependent density functional theory (TD-DFT) and highly correlated wave function STEOM-CCSD calculations to describe the photoinduced homolytic pathways in both singlet and triplet excited-state manifolds and explore the ring-to-chain relaxations. The results of our calculations indicate that, upon photoexcitation, the S8 ring undergoes a fast intersystem crossing (ISC) from the S1 state to the triplet manifold, with estimated ISC rates of over 1011 s–1 as a result of significant spin–orbit couplings. The TD-DFT geometry relaxations in the singlet and triplet excited states underline that, upon photoexcitation, an S–S bond within the S8 ring readily undergoes homolytic fragmentation, a feature that is thus also expected upon thermal excitation. Importantly, this represents the first theoretical demonstration that the molecular structure in the triplet state evolves from a ring configuration to an open chain configuration that carries a diradical character, which is consistent with the reported photoinduced polymerization processes in elemental sulfur.

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Mechanochemical synthesis of inverse vulcanized polymers

Cited by 50 publications

References 47 publications

Durable composites by vulcanization of oleyl-esterified lignin

Durable composites by vulcanization of oleyl-esterified lignin

Processable crosslinked terpolymers made from elemental sulfur with wide range of thermal and mechanical properties

Ring-to-Chain Structural Relaxation of Elemental Sulfur upon Photoexcitation

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