Imine based covalent adaptable networks from diacetone acrylamide polymerization DOI

Hanghang Chen,

Z. L. Hou,

Liqiong Li

et al.

Published: Oct. 17, 2024

Abstract The construction of covalent adaptable networks (CANs) without the need for post-modification, complex monomer synthesis routes, or expensive materials is highly desirable practical application dynamic chemistry. In present study, commercially available acrylate monomer, diacetone acrylamide (DAAM), was initially polymerized using a traditional radical polymerization method. Subsequently, it cross-linked with amine agents under hot-processing conditions to form aliphatic imine-based CANs. resulting exhibited glass transition temperatures (Tg) in range 95 107°C, good thermal stability, mechanical and thermomechanical properties. All samples were amenable recycling. Post-recycling, both tensile strength Young's Modulus slight deterioration, retaining approximately 80% their original results from gel content analysis structural characterization pristine recycled indicate that observed reduction properties Tg (approximately 70°C) can be attributed decrease degree cross-linking release ketone groups. Furthermore, all demonstrated degradability acidic conditions, attributable imine structure. By this facile approach prepare acrylate-based CANs, we establish an important framework polymer are reprocessable biodegradable.

Language: Английский

Malleable, Ultrastrong Antibacterial Thermosets Enabled by Guanidine Urea Structure DOI Creative Commons
Zhen Yu, Qiong Li, Yanlin Liu

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(30)

Published: June 13, 2024

Abstract Dynamic covalent polymers (DCPs) that strike a balance between high performance and rapid reconfiguration have been challenging task. For this purpose, solution is proposed in the form of new dynamic supramolecular motif—guanidine urea structure (GUAs). GUAs contain complex diverse chemical structures as well unique bonding characteristics, allowing guanidine to demonstrate advanced physical properties. Noncovalent interaction aggregates (NIAs) confirmed GUA‐DCPs through multistage H‐bonding π‐π stacking, resulting an extremely Young's modulus 14 GPa, suggesting remarkable mechanical strength. Additionally, guanamine linkages GUAs, type bond, provide resins with excellent malleability reprocessability. Guanamine metathesis validated using small molecule model compounds, temperature dependent infrared rheological behavior following dissociative exchange mechanism. Moreover, inherent photodynamic antibacterial properties are extensively verified by experiments. Even after undergoing three reprocessing cycles, rate remains above 99% 24 h, highlighting their long‐lasting effectiveness. nature, tuneable composition, combination make them promising candidates for various technological advancements.

Language: Английский

Citations

7
Integrating ex-ante and prospective life-cycle assessment for advancing the environmental impact analysis of emerging bio-based technologies DOI Creative Commons
Nariê Rinke Dias de Souza, Livia Matt, Rauno Sedrik

et al.

Sustainable Production and Consumption, Journal Year: 2023, Volume and Issue: 43, P. 319 - 332

Published: Nov. 18, 2023

Unlike the fossil-based alternatives, many emerging bio-based technologies are still at early lab or pilot scale and not representative of optimized industrial conditions. This makes a robust comparison their environmental performances via life-cycle assessment (LCA) challenging. We propose framework to combine scaling-up projections early-stage (ex-ante LCA) with influence future socio-economic scenarios (prospective LCA), using range new polymers produced from forest residues as case study. The combined takes step-by-step approach in modifying process inventories projecting them for impact assessment. In our study, climate change lab-scale processes decreases 105–471 kg CO2-eq./kg polymer 9–14 after application ex-ante LCA, highest reduction (83 %) coming identified synergies (e.g., solvent recovering). Combining prospective LCA additionally reduces up 56 % by 2050, relative results only. Other impacts decrease well, particularly freshwater eutrophication (up 99 reduction), photochemical oxidant formation (99 %), marine (98 %). secures more products conventional such it helps identification improvements both technological background supply chains that needed make systems outperform fossil counterparts. A consistent integration is instrumental prioritize research investments upscaling most promising sustainability perspective, ultimately guide sustainable transition towards circular bioeconomy.

Language: Английский

Citations

13
Mechanism Study on Synthesis of Biobased Polycarbonate from Diphenyl Carbonate and Isosorbide with Metal-Free Catalysts by Identifying Reactivity of endo-OH and exo-OH DOI

Junyao Shen,

Xinyi Gao,

Wenze Guo

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(12), P. 5036 - 5045

Published: March 13, 2024

Isosorbide (ISB), a promising biobased monomer with two asymmetric hydroxyl groups, however, exhibits an unsatisfying reactivity in the poly(isosorbide carbonate) (PIC) synthesis metal-free catalysts. In this work, we employed density functional theory (DFT) calculations to address existing disputes surrounding catalytic mechanisms, focusing on potential reaction pathways catalyzed by tetraethylammonium hydroxide ([TEA][OH]). Energy profiles reveal that synergistic mechanism represents energetically favorable route for PIC synthesis. Meanwhile, disclose quaternary ammonium base as catalyst precursor phenol ([TEA][Ph]) acting effective cycle. Seeking enhanced efficiency, cation modification of was conducted, and hexadecyl trimethylammonium ([HTMA][OH]) exceptional performance low energy barriers 29.1 30.0 kcal/mol exo-OH endo-OH, respectively. This aligns kinetic experiments, emphasizing superior efficiency [HTMA][OH]. The proposed model enables accurate predictions terminal group distribution. A thorough examination steric hindrance electronic effect impact pathway during transesterification offers significant insights efficient design not only polyester but also chemical recycling strategy wasted ones.

Language: Английский

Citations

5
Towards Sustainable Materials: A Review of Acylhydrazone Chemistry for Reversible Polymers DOI Creative Commons
Donya Ramimoghadam, Daniel J. Eyckens, Richard A. Evans

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(49)

Published: June 18, 2024

Transitioning towards a circular economy, extensive research has focused on dynamic covalent bonds (DCBs) to pave the way for more sustainable materials. These enable debonding and rebonding demand, as well facilitating end-of-life recycling. Acylhydrazone/hydrazone chemistry offers material with high stability under neutral basic conditions making it promising candidate materials research, though is susceptible acid degradation. However, this degradation acidic can be exploited, widely applicable in self-healing biomedical fields, potential reprocessing This review highlights studies exploring reversibility of acylhydrazone/hydrazone various polymers, altering their properties, utilizing them applications such self-healing, reprocessing, The also focuses how mechanical properties are affected by presence linkages, methods improve performance.

Language: Английский

Citations

4
Biobased Self-healable Photoluminescent Polyacylhydrazones Imparted by Supramolecular Interactions DOI

Mingze Xia,

Yi Cheng,

Jingzhao Shang

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

With the rise of circular economy, self-healing polymers have attracted significant attention for their longer lifespan and greater recyclability compared with traditional thermoplastics thermosetting polymers. However, addressing instability units to develop high-performance materials remains a challenge. Herein, we report series superior polyimine derivatives, biobased polyacylhydrazones (bio-PHys), via aldehyde-hydrazide condensation. The coexistence amide bonds imine bonds, which provide hydrogen bonding dynamics, imparts remarkable mechanical properties (tensile strength 103 MPa, elongation at break 180%) bio-PHys, along notable capabilities under glass transition temperature (Tg). Bio-PHys also exhibits potential scalable production, excellent processability, photoluminescence characteristics. We explored its application in adhesive-free laminated substrates thoroughly investigated aggregation-induced emission acylhydrazone group. Furthermore, utilized bio-PHys create recyclable smart paper anticounterfeiting dynamic information storage. This work presents novel approach developing

Language: Английский

Citations

0
Bis-spirocyclic diol monomers and polyurethanes derived from citric acid: Synthesis, properties, electrospinnability, and evaluation of chemical recyclability DOI Creative Commons
Ilme Liblikas, Olivier Bonjour,

Natalja Savest

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 163525 - 163525

Published: May 1, 2025

Language: Английский

Citations

0
Digital Light Processing 3D Printing of Isosorbide- and Vanillin-Based Ester and Ester–Imine Thermosets: Structure–Property Recyclability Relationships DOI Creative Commons
Anna Liguori,

Eugenia Oliva,

Marco Sangermano

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2023, Volume and Issue: 11(39), P. 14601 - 14613

Published: Sept. 19, 2023

Four isosorbide-based photocurable resins were designed to reveal correlations between the composition and chemical structure, digital light processing (DLP) three-dimensional (3D) printability, thermoset properties, recyclability. Especially, role of functional groups, i.e., concentration ester groups vs combination imine functionalities, in recyclability was investigated. The consisted methacrylated isosorbide alone or with vanillin a flexible Schiff-base. significantly affected their 3D printability as well physical properties resulting thermosets. results indicated potential confer rigidity thermosets some negative effects on printing quality solvent-resistance properties. An increase resin enabled us overcome these drawbacks, leading, however, lower thermal stability. replacement Schiff-base decreased networks, ensuring, other hand, improved highlighted an almost complete preservation elastic modulus after reprocessing recycling ester-imine thermosets, thanks presence two distinct dynamic covalent bonds network; functions played significant success procedure.

Language: Английский

Citations

5
Fabrication of Dual pH/Reduction-Responsive P(CL-co-ACL)-Based Cross-Linked Polymeric Micelles for PTX Delivery DOI
Fang Chen, Li Yin,

Teng He

et al.

Langmuir, Journal Year: 2023, Volume and Issue: 39(46), P. 16358 - 16366

Published: Nov. 7, 2023

To enhance the stability of polymeric micelles and optimize their drug-controlled release ability, three disulfide-linked polyethylene glycol methyl ether methacrylate–disulfide–poly(ε-caprolactone-co-γ-amine−ε-caprolactone) (PPEGMA-SS-P(CL-co-ACL)) polymers were synthesized characterized by 1H NMR, GPC, FT-IR successfully, dual pH/reduction-responsive cross-linked prepared for paclitaxel (PTX) delivery using 2,3-dimethylmaleic anhydride (DMMA) as cross-linking agent. The PTX loading capacity (LC) encapsulation efficiency (EE) values formed PPEGMA8-SS-P(CL47-co-ACL15) achieved 23.96% 71.58%, slightly higher than those un-cross-linked micelles. Both particle sizes blank in vitro drug PTX-loaded confirmed that compared with micelles, more stable at pH 7.4 + 0 mM DTT, a cumulative 13% 120 h, while 5.0 10 DTT close to after 60 indicating successful reversible smooth cytotoxicity assay showed its had low cell cytotoxicity, both revealed certain inhibitory effect on HepG2 cells. These results from PPEGMA8-SS-P(CL47-co-DCL15) promising candidate delivery.

Language: Английский

Citations

4
Semi-Crystalline and Amorphous Polyesters Derived from Biobased Tri-Aromatic Dicarboxylates and Containing Cleavable Acylhydrazone Units for Short-Loop Chemical Recycling DOI Creative Commons
Nitin G. Valsange, Rafael Natal Lima de Menezes, Niklas Warlin

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(6), P. 2868 - 2878

Published: March 6, 2024

Recycling polymers by site-specific scission into short-chain oligomers/polymers, followed recoupling these to form the original polymer presents an energetically more favorable shorter-loop chemical recycling in comparison monomers. Here, we present synthesis and polymerization of tri-aromatic diesters prepare polyesters with acylhydrazone units as weak structural links. Two diester monomers were prepared combining methyl 5-chloromethyl-2-furoate, obtainable from 5-chloromethylfurfural, potentially biobased hydroquinone resorcinol, respectively. The two have a central phenyl ring flanked furan rings, polymerized 1,6-hexanediol 1,4-butanediol, respectively, together controlled amounts monofunctional ethyl levulinate telechelic ketone-terminated polyesters. Subsequent reactions adipic dihydrazide yielded corresponding chain-extended increased molecular weights ([η] = 0.29–0.52 dL g–1) backbone. Thermogravimetric analysis showed high thermal stability decomposition only above 275 °C. containing linear found be semi-crystalline materials melting points at 158 192 °C, while those kinked resorcinol fully amorphous glass transition temperatures 35 44 Initial investigations recyclability demonstrated that could selectively cleaved recover polyesters, which again obtain recycled properties very similar material.

Language: Английский

Citations

1
Flame‐Retardant Self‐Healing Polymers: A Review DOI Creative Commons

M. Kianfar,

Hossein Ipakchi,

Shiva Mohajer

et al.

Journal of Polymer Science, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 25, 2024

ABSTRACT Developing multifunctional flame retardants (FRs) has become a strategy to reply on needs for advanced polymers. Self‐healing polymers are an emerging class of polymeric materials, which have been upgraded progressively, and recently taken the advantage fire safety. Correspondingly, diverse industries like aerospace, automotive, construction consumer electronics benefited from flame‐retardant self‐healing underlines their increasing contribution modern technologies. The characteristics stem intricate chemical physical interactions, adopting self‐directed repair mechanisms leading eliminating need frequent replacements, subsequently lowering maintenance costs environmental impact. This review summarizes advantages with emphasis exploring highly innovative advancements among bio‐based hydrogels, aerogels, coatings, thin films, lithium‐ion batteries ionotronic skin (‐i‐skin) structures embedding sensing features smoke detection exposure warnings, further broadening application in smart technologies safety‐critical infrastructure. outcomes reports outline challenges remaining developing such multifaceted materials view lack information due limited or exclusive investigations. However, research may facilitate dehydration, thermal shielding, free radical quenching contributing retardancy performance Sustainability circular economy requirements briefly discussed, addition outlining remarks future developments.

Language: Английский

Citations

1