Dynamic covalent polymer networks (DCPN) have historically attracted attention for their unique roles in chemical recycling and self-healing, which are both relevant for sustainable societal development. Efforts in these directions have intensified in the past decade with notable progress in newly discovered dynamic covalent chemistry, fundamental material concepts, and extension toward emerging applications including energy and electronic devices. Beyond that, the values of DCPN in discovering/designing functional properties not offered by classical thermoplastic and thermoset polymers have recently gained traction. In particular, the dynamic bond exchangeability of DCPN has shown unparalleled design versatility in various areas including shape-shifting materials/devices, artificial muscles, and microfabrication. Going beyond this basic bond exchangeability, various molecular mechanisms to manipulate network topologies (topological transformation) have led to opportunities to program polymers, with notable concepts such as living networks and topological isomerization. In this review, we provide an overview of the above progress with particular focuses on molecular design strategies for the exploitation of functional material properties. Based on this, we point out the remaining issues and offer perspectives on how this class of materials can shape the future in ways that are complementary with classical thermoplastic and thermoset polymers.

Dynamic Covalent Polymer Networks: A Molecular Platform for Designing Functions beyond Chemical Recycling and Self-Healing.

https://pubs.rsc.org/en/content/articlepdf/2019/py/c9py01260e

Dynamic covalent chemistry in polymer networks: a mechanistic perspective

Polyurethanes (PUs) have many applications resulting from their preeminent properties, but being commonly used toxic catalysts, and the lack of processability for PU thermosets cause limitations Herein, we report a new class of the PU-like dynamic covalent polymers, poly(oxime-urethanes) (POUs), which are prepared from the uncatalyzed polyaddition of multifunctional oximes and hexamethylene diisocyanate (HDI) at ambient temperature Kinetics studies reveal that almost complete polymerization (∼99% conversion) can be achieved in 3 h at 30 °C in dichloromethane (DCM), the most effective among the solvents evaluated, producing linear POUs with comparable molecular weights to the catalyzed PUs We find that the oxime-carbamate structures are reversible at about 100 °C through oxime-enabled transcarbamoylation via a thermally dissociative mechanism The cross-linked POUs based on oxime–carbamate bonds show efficient catalyst-free healable/recyclable properties Density functional theory (DFT) calculations sug

Oxime-Based and Catalyst-Free Dynamic Covalent Polyurethanes

Dynamic covalent networks are polymer networks that contain a dynamic covalent bond which allows them to be reprocessable, remoldable, and recyclable as well as exhibit crack healing or stress-relaxation properties. A key component of these materials is the nature of the dynamic covalent bond, which in addition to chemical composition and architecture can be used to dramatically alter the physical properties of these networks. The aim of this study is to understand the impact of steric hindrance of N-alkyl substituents and network connectivity in poly(alkylurea–urethane) dynamic network films. In these materials, the dynamic bond is the hindered alkyl urea moiety, whose dynamic behavior is dictated by the sterics of the alkyl substituent. Networks were prepared by the noncatalyzed curing reaction of aminoethanol compounds of varying substituents with a trifunctional isocyanate cross-linker and varying amounts of a monofunctional capping agent. Thermomechanical properties and FTIR studies show the impact o...

Effect of Sterics and Degree of Cross-Linking on the Mechanical Properties of Dynamic Poly(alkylurea–urethane) Networks

Herein we report a polymerization-induced self-assembly (PISA) process with ring-opening metathesis polymerization (ROMP). We utilize a peptide-based norbornenyl monomer as a hydrophobic unit to provide a range of nanostructures at room temperature yet at high solids concentrations of 20 wt % in combination with an oligoethylene glycol based norbornenyl monomer. Evaluation of the polymerizations under mild conditions highlight that good control is maintained along with high monomer conversion of greater than 99%, indicating that the living polymerization is unaffected during the PISA process. The demonstration broadens the scope of the PISA process to a new living polymerization methodology toward the development of easily accessible and highly functionalized nanostructures in situ.

ROMPISA: Ring-Opening Metathesis Polymerization-Induced Self-Assembly

https://pubs.rsc.org/en/content/articlepdf/2016/PY/C6PY01776B

Blocked isocyanates: from analytical and experimental considerations to non-polyurethane applications

https://pubs.rsc.org/en/content/articlepdf/2016/PY/C6PY00263C

Use of complementary nucleobase-containing synthetic polymers to prepare complex self-assembled morphologies in water

https://pubs.rsc.org/en/content/articlepdf/2017/py/c7py00219j

Marianne S. Rolph

Papers

Blocked isocyanates: from analytical and experimental considerations to non-polyurethane applications

Use of complementary nucleobase-containing synthetic polymers to prepare complex self-assembled morphologies in water

The hydrolytic behavior of N,N′-(dimethylamino)ethyl acrylate-functionalized polymeric stars

The application of blocked isocyanate chemistry in the development of tunable thermoresponsive crosslinkers