Controlling polymer architecture to design dynamic network materials with multiple dynamic linkers
17 Aug 2020-Vol. 5, Iss: 7, pp 1267-1276
TL;DR: In this paper, a one pot synthesis is applied to control the chain structure and architecture of multiply dynamic polymers, enabling fine tuning of materials properties by choice of polymer chain length or crosslink density.
Abstract: A one pot synthesis is applied to control the chain structure and architecture of multiply dynamic polymers, enabling fine tuning of materials properties by choice of polymer chain length or crosslink density. Macromolecules containing both non-covalent linkers based on quadruple hydrogen-bonded 2-(((6-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)hexyl)carbamoyl)oxy)ethyl methacrylate (UPyMA), and thermoresponsive dynamic covalent furan–maleimide based Diels–Alder linkers are explored. The primary polymer's architecture was controlled by reversible addition-fragmentation chain transfer (RAFT) polymerization, with the dynamic non-covalent (UPyMA) and dynamic covalent furfuryl methacrylate (FMA) units incorporated into the same backbone. The materials are crosslinked, taking advantage of the “click” chemistry properties of the furan–maleimide reaction. The polymer materials showed stimulus-responsive thermomechanical properties with a decrosslinking temperature increasing with the polymer's primary chain length and crosslink density. The polymers had good thermally promoted self-healing properties due to the dynamic covalent Diels–Alder bonds. Besides, the materials had excellent stress relaxation characteristics induced by the exchange of the hydrogen bonds in UPyMA units.
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01 Jan 2010
TL;DR: In this paper, the synthesis of a poly(methyl methacrylate) (PMMA) chain bearing Cp functionality at both chain ends and a trifunctional pyridinyldithioformate linker was reported.
Abstract: The synthesis of a novel poly(methyl methacrylate) (PMMA) chain bearing Cp functionality at both chain ends and a trifunctional pyridinyldithioformate linker molecule, which are able to rapidly and reversibly cross-link on demand within a highly accessible temperature range was reported. The ATRP initiator 1,2-bis(bromoisobutyryloxy)ethane was synthesized. Methyl methacrylate was passed through a short column of basic alumina and stored at -19°C prior to use. Copper(I) bromide (Fluka) was purified by sequential washing with sulfurous acid, acetic acid, and ethanol, followed by drying under reduced pressure. 1H NMR spectroscopy was performed using a Bruker AM 250 spectrometer at 250 MHz for hydrogen nuclei and 100 MHz for carbon nuclei. Size exclusion chromatography measurements were performed on a Polymer Laboratories. It is observed that a sharp increase in the absorbance of the system occurs at around 80 °C, corresponding to the rapid onset of debonding.
115 citations
01 Mar 2021
TL;DR: The diversity of dynamic bonds and the polymer architectures used in dynamic polymers are highlighted, with a focus on how the interplay of dynamic Bonds and polymer architecture can be used to develop advanced materials.
Abstract: Introducing dynamic and exchangeable bonds can breathe life into polymers by imparting self-healing, enhanced toughness, or adaptability to the material. Synergies between the exchangeable bonds and the polymer’s architectural features can facilitate the dynamic exchange pathways and tune the material’s thermal and mechanical properties. In recent years, numerous dynamic chemistries and architectural variations have been used to develop superior dynamic polymer materials. This article highlights the diversity of dynamic bonds and the polymer architectures used in dynamic polymers, with a focus on how the interplay of dynamic bonds and polymer architecture can be used to develop advanced materials. Finally, this article highlights how judicious choice of the polymer’s architectural features could be used to realize applications of dynamic materials.
31 citations
TL;DR: In this article, a semi-interpenetrating polymer networks (semi IPNs) with multiple dynamic linkers was constructed based on a linear copolymer of styrene and furfuryl methacrylate and boronic ester crosslinker.
Abstract: Thermoset polymers show favorable material properties, while bringing about environmental pollution due to non-reprocessing and unrecyclable. Diels–Alder (DA) chemistry or reversible exchange boronic ester bonds have been employed to fabricate recycled polymers with covalent adaptable networks (CANs). Herein, a novel type of CANs with multiple dynamic linkers (DA chemistry and boronic ester bonds) was firstly constructed based on a linear copolymer of styrene and furfuryl methacrylate and boronic ester crosslinker. Thermoplastic polyurethane is introduced into the CANs to give a semi Interpenetrating Polymer Networks (semi IPNs) to enhance the properties of the CANs. We describe the synthesis and dynamic properties of semi IPNs. Because of the DA reaction and transesterification of boronic ester bonds, the topologies of semi IPNs can be altered, contributing to the reprocessing, self-healing, welding, and shape memory behaviors of the produced polymer. Through a microinjection technique, the cut samples of the semi IPNs can be reshaped and mechanical properties of the recycled samples can be well-restored after being remolded at 190 °C for 5 min.
14 citations
TL;DR: In this paper , the authors explored the dynamic chemistries involved in IPN materials and showed that network architectural features are as much as important as studying the dynamic chemistryistries using an IPN system with quadrupole hydrogen (H) bonding and thiol-Michael (TM) bonding.
Abstract: Dynamic materials are known for their self-healing, adhesive, and shape memory applications. Interpenetrating networks (IPNs) are types of materials that can hold dual-dynamic crosslinkers to show complementary chemical and mechanical properties. There have been a number of research studies exploring the dynamic chemistries involved in IPN materials. Not only the bond type but also the polymer network architecture play an important role in governing IPN material properties. In this study, we show that network architectural features are as much as important as studying the dynamic chemistries using an IPN system with quadrupole hydrogen (H) bonding and thiol-Michael (TM) bonding. This work varied network types, chain lengths, dynamic bond compositions, crosslink densities, and crosslink distributions within a system to explore their effects on the thermomechanical properties. The synergetic effects of H and TM bonds revealed excellent stress relaxation and self-healing at room temperature and elevated temperatures. Increment of chain length and crosslink density enhanced the strength of the materials to as high as 3.5 MPa, while the crosslink distribution boosted the creep resistance under an applied force. Furthermore, complementary H and TM bonding assisted in improving the adhesive properties in these materials to hold up to 2 kg weight with the adhered wood strips.
12 citations
TL;DR: In this paper , a flexible and recyclable bio-based memory device using fish colloid as the resistive switching layer on a polyimine substrate, which affords reliable mechanical and electrical properties under repetitive conformal deformation operation.
10 citations
References
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Wageningen University and Research Centre1, University of Cambridge2, North Carolina State University3, University of Göttingen4, Cornell University5, Leibniz Institute for Neurobiology6, Queen Mary University of London7, Northwestern University8, Georgia Institute of Technology9, University of Southern Mississippi10, Université de Montréal11, Duke University12, Clemson University13, Clarkson University14
TL;DR: This work reviews recent advances and challenges in the developments towards applications of stimuli-responsive polymeric materials that are self-assembled from nanostructured building blocks and provides a critical outline of emerging developments.
Abstract: Responsive polymer materials can adapt to surrounding environments, regulate transport of ions and molecules, change wettability and adhesion of different species on external stimuli, or convert chemical and biochemical signals into optical, electrical, thermal and mechanical signals, and vice versa. These materials are playing an increasingly important part in a diverse range of applications, such as drug delivery, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings and textiles. We review recent advances and challenges in the developments towards applications of stimuli-responsive polymeric materials that are self-assembled from nanostructured building blocks. We also provide a critical outline of emerging developments.
4,908 citations
TL;DR: The emergence of a new trend in the design of adaptive materials that involves the use of reversible chemistry to programme a response that originates at the most fundamental (molecular) level is described.
Abstract: In chemistry, some dynamic bonds can be selectively and reversibly broken and reformed in response to an environmental stimulus. This Review article discusses the incorporation of dynamic bonds, or interactions, in polymeric materials and the structural changes and macroscopic responses observed in the presence of different stimuli.
1,226 citations
TL;DR: Self-healing polymers and fiber-reinforced polymer composites possess the ability to heal in response to damage whenever and whenever it occurs in the material as mentioned in this paper, which is a remarkable property.
Abstract: Self-healing polymers and fiber-reinforced polymer composites possess the ability to heal in response to damage wherever and whenever it occurs in the material. This phenomenal material behavior is...
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TL;DR: A survey of self-healing polymers can be found in this article, where the authors review the major successful autonomic repairing mechanisms developed over the last decade and discuss several issues related to transferring these selfhealing technologies from the laboratory to real applications, such as virgin polymer property changes as a result of the added healing functionality.
Abstract: Inspired by the unique and efficient wound healing processes in biological systems, several approaches to develop synthetic polymers that can repair themselves with complete, or nearly complete, autonomy have recently been developed. This review aims to survey the rapidly expanding field of self-healing polymers by reviewing the major successful autonomic repairing mechanisms developed over the last decade. Additionally, we discuss several issues related to transferring these self-healing technologies from the laboratory to real applications, such as virgin polymer property changes as a result of the added healing functionality, healing in thin films v. bulk polymers, and healing in the presence of structural reinforcements.
1,137 citations
TL;DR: The authors summarizes the features and limitations of reversible addition-fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process from both a mechanistic and an application point of view has matured over the past 20 years.
Abstract: This Perspective summarizes the features and limitations of reversible addition–fragmentation chain transfer (RAFT) polymerization, highlighting its strengths and weaknesses, as our understanding of the process, from both a mechanistic and an application point of view, has matured over the past 20 years. It is aimed at both experts in the field and newcomers, including undergraduate and postgraduate students, as well as nonexperts in polymerization who are interested in developing their own polymeric structures by exploiting the simple setup of a RAFT polymerization.
828 citations