Internal catalysis on the opposite side of the fence in non-isocyanate polyurethane covalent adaptable networks

Hernández, Aitor; Houck, Hannes A.; Elizalde, Fermin; Guerre, Marc; Sardón, Haritz; Prez, Filip Du

doi:10.1016/j.eurpolymj.2022.111100

Cited by 22 publications

(30 citation statements)

References 56 publications

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“…Cramer, Hillmyer, and Dichtel previously reported catalyst-free polyhydroxyurethane vitrimers based on TREN as the multifunctional monomer . Guerre, Sardon, and Du Prez proposed that exchange in these networks is internally catalyzed by the tertiary amine in TREN . While networks with amines on either the nitrogen or oxygen side of the carbamate displayed similar flow E a values in stress relaxation measurements (111–118 kJ/mol), the latter design underwent urea formation during reprocessing, suggesting that the placement of the internal catalyst can affect the prevalence of side reactions (Figure c).…”

Section: Strategies To Modulate Molecular Reactivity and Network Prop...mentioning

confidence: 96%

Structure–Reactivity–Property Relationships in Covalent Adaptable Networks

et al. 2022

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Polymer networks built out of dynamic covalent bonds offer the potential to translate the control and tunability of chemical reactions to macroscopic physical properties. Under conditions at which these reactions occur, the topology of covalent adaptable networks (CANs) can rearrange, meaning that they can flow, self-heal, be remolded, and respond to stimuli. Materials with these properties are necessary to fields ranging from sustainability to tissue engineering; thus the conditions and time scale of network rearrangement must be compatible with the intended use. The mechanical properties of CANs are based on the thermodynamics and kinetics of their constituent bonds. Therefore, strategies are needed that connect the molecular and macroscopic worlds. In this Perspective, we analyze structure−reactivity−property relationships for several classes of CANs, illustrating both general design principles and the predictive potential of linear free energy relationships (LFERs) applied to CANs. We discuss opportunities in the field to develop quantitative structure−reactivity−property relationships and open challenges.

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Section: Strategies To Modulate Molecular Reactivity and Network Prop...mentioning

confidence: 96%

Structure–Reactivity–Property Relationships in Covalent Adaptable Networks

et al. 2022

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“…Cyclic carbonates have low toxicity, show biodegradability and are reactive toward amines, which make them very attractive materials to use for NIPU synthesis . Furthermore, the absence of residual unstable chemicals commonly seen in PU enhance NIPUs with better thermal stability than conventional PU, although residuals hydroxyl groups are known to induce transcarbamoylation reactions. , To avoid pendant hydroxyl groups, ethylene carbonate can be reacted with a diamine and a diol to produce linear polyurethanes and ethylene glycol (Figure b) …”

Section: Bisfunctional Monomers Used In the Synthesis Of Commodity Th...mentioning

confidence: 99%

Polymers without Petrochemicals: Sustainable Routes to Conventional Monomers

et al. 2022

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Access to a wide range of plastic materials has been rationalized by the increased demand from growing populations and the development of high-throughput production systems. Plastic materials at low costs with reliable properties have been utilized in many everyday products. Multibillion-dollar companies are established around these plastic materials, and each polymer takes years to optimize, secure intellectual property, comply with the regulatory bodies such as the Registration, Evaluation, Authorisation and Restriction of Chemicals and the Environmental Protection Agency and develop consumer confidence. Therefore, developing a fully sustainable new plastic material with even a slightly different chemical structure is a costly and long process. Hence, the production of the common plastic materials with exactly the same chemical structures that does not require any new registration processes better reflects the reality of how to address the critical future of sustainable plastics. In this review, we have highlighted the very recent examples on the synthesis of common monomers using chemicals from sustainable feedstocks that can be used as a like-for-like substitute to prepare conventional petrochemical-free thermoplastics.

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“…97 The introduction of 1 mol% DMAP as the catalyst for promoting network rearrangements could decrease the temperatures required for reprocessing and result in recyclable PHU networks with the full recovery of mechanical properties after multiple reprocessing cycles, as proved in several PHU systems by the Torkelson group. [97][98][99] The internally catalyzed PHU networks with implanted tertiary amine groups were designed based on N-substituted eight-membered cyclic carbonates and polyetheramine, 100 in which exchange reactions between urethanes were expedited, although urea formation was also found. Shape memory polymers (SMPs) are a class of smart polymers, which can change from a programmed shape (temporary shape) to the original (permanent) state while triggered by external stimuli (e.g.…”

Section: Dynamic Covalent Polymers With Urethane Bondsmentioning

confidence: 99%