Direct Evidence of Heteroleptic Complexation in the Macroscopic Dynamics of Metallo-supramolecular Polymer Networks

Mechanistic study on the metallocene-based tandem catalytic coordinative chain transfer polymerization for the synthesis of highly branched polyolefins

Abstract Creation and control of long-chain branches (LCBs) in coordination polymerization of olefins is an enduring focus of research in both academia and industry. We have recently introduced a tandem catalytic coordinative chain transfer polymerization reaction where upon the concerted function of the polymerization catalyst, the chain transfer agent (CTA), and the displacement catalyst, a highly branched microstructure can be formed. Here we introduce a new tandem catalytic system using Et(Ind)2ZrCl2 as the polymerization catalyst. Despite the optimal reaction temperature for the cooperative function of catalyst components is lower than the ideal temperature for the productivity of the …

Connectivity Defects and Collective Assemblies in Model Metallo‐Supramolecular Dual‐Network Hydrogels

Incorporation of dynamic boronate links and Ag nanoparticles into PVA hydrogels for pH-Regulated and prolonged release of methotrexate

Abstract In this study, pH-responsive hydrogels based on PVA-boronate crosslinks were prepared via a simple route and used for controlled and targeted delivery of anticancer drug methotrexate. A double network (DN) hydrogel composed of didiol-boronate/PVA complex as the first network and PVA crystallites generated by a freeze-thaw process as the second one was developed. The swelling of PVA-boronate DN hydrogels demonstrated high sensitivity to multiple stimuli including the pH, temperature, and ionic strength of the media thanks to the dynamic boronate links in the first network. Moreover, unlike previously reported hydrogels based on the boronate linkages, the new DN hydrogels preserved t…

Enhancement of metallo-supramolecular dissociation kinetics in telechelic terpyridine-capped poly(ethylene glycol) assemblies in the semi-dilute regime.

The dynamics of supramolecular polymer assemblies is governed by that of their polymeric building blocks and that of the transient bonds between them. Entrapment of such bonds by topological crowding often causes renormalization of the bond lifetimes towards prolonging. In the present study, by contrast, we show that this effect can also be inverse in the case of telechelic metallo-supramolecular polymers in semi-dilute solution. We focus on linear poly(ethylene glycols) capped by terpyridine binding motifs at both ends that can form metal–ligand coordinative bonds with various transition metal ions, thereby creating transient metallo-supramolecular assemblies of varying length and binding …

Synthesis and Characterization of Isotactic Poly(1-hexene)/Branched Polyethylene Multiblock Copolymer via Chain Shuttling Polymerization Technique

Understanding from the underlying mechanism of chain shuttling polymerization (CSP) is limited due to scarceness of successful reports and incompetence of traditional characterization techniques to distinguish blocky structures. Here, a simple synthesis approach for production of an isotactic poly(1-hexene)/branched polyethylene multiblock copolymer from a 1-hexene monomer is presented. Resulting copolymers can be easily characterized because of their solubility in most organic solvents. This novel blocky architecture is synthesized using ansa-ethylenebis(1-η5-indenyl)zirconium dichloride and α-diimine nickel(II) bromide catalysts. While the former participates in 1,2-enchainment of monomer…

Dynamic Model Metallo‐Supramolecular Dual‐Network Hydrogels with Independently Tunable Network Crosslinks

A mechanistic study on the synthesis of branched functional polyethylene through reactive co‐polymer approach

Structural analysis of linear/branched ethylene block copolymers

Dynamics of supramolecular associative polymer networks at the interplay of chain entanglement, transient chain association, and chain‐sticker clustering

The dynamic mechanical properties of supramolecular associative polymer networks depend on the average number of entanglements along the network‐forming chains, Nₑ, and on their content of associative groups, f. In addition, there may be further influence by aggregation of the associative groups into clusters, which, in turn, is influenced by the chemical structure of these groups, and again by Nₑ and f of the polymer. Therefore, the effects of these parameters are interdependent. To conceptually understand this interdependency, we study model networks in which (a) Nₑ, (b) f, and (c) the chemical structure of the associative groups are varied systematically. Each network is probed by rheolo…

Reversible Hydrogels with Switchable Diffusive Permeability

Hydrogels are polymer networks swollen in water that are characterized by soft mechanics and high permeability. This makes them good candidates for separation and membrane technologies. The diffusion is controlled by the mesh size of the network, and this can be made tunable through the introduction of thermoresponsive polymers. However, this is still a developing field. To contribute to this development, a dual dynamic network is formed composed of four-arm polyethylene glycol precursors in which each arm is functionalized with both a terpyridine moiety capable of forming reversible metal–ligand complexes along with branches of poly(N-isopropylacrylamide) (pNIPAAm), which can be swit…

Dynamics of self-healing supramolecular guanine-modified poly(n-butyl methacrylate-co-hydroxyethyl methacrylate) copolymers

Abstract Self-healing is a nature-inspired characteristic that is imparted in synthetic polymeric materials through the integration of reversible supramolecular bonds following different design concepts. Generally, the dynamics of supramolecular bonds regulates timescale of the self-healing process, specifically in polymeric systems with a homogeneous morphology. Herein, we explore the utility of guanine as a hydrogen bonding group to construct supramolecular polymeric systems based on poly (n-butyl methacrylate). For this purpose, we follow a three-step reaction approach, including a living radical copolymerization, deprotection of the functional comonomer, and grafting of the guanine grou…

Deconvolution of the Effects of Binary Associations and Collective Assemblies on the Rheological Properties of Entangled Side-Chain Supramolecular Polymer Networks

The properties and function of supramolecular polymer networks are determined not only by pairwise interchain transient associations but also by chain entanglement and nanoscopic phase separation of the associative groups. To unravel the impact and interplay of these different factors, we devise a set of model supramolecular polymer networks in which the number of entanglements and the density of associative groups are systematically varied. Rheological data show that by increasing the density of associative groups, the plateau modulus grows to a steady level and extends over a distinct frequency range. This is credited to the presence of binary associations with unique partner exchange tim…

Rheological modifiers based on supramolecular block copolymers: From weak associations to interconnected micelles

Abstract The rheological spectra of poly(n-butyl acrylate) in the presence of a series of P(nBA-b-HEMA) rheology modifiers show a two-step relaxation process originating from the PnBA matrix and the self-assemblies. The HEMA segments are further grafted with strong, hydrogen bonding UPy groups, which both magnifies and slows down the relaxation of the assemblies. The extents of associations are enlightened by studying thermal transitions in DSC, morphological developments by SAXS, and description of rheological properties using a tube-based model. It is revealed that a weak association tendency, due to long hydrophobic blocks, leads to the formation of double-linear or star assemblies, whil…

Dynamics of entangled supramolecular polymer networks in presence of high-order associations of strong hydrogen bonding groups

Dynamics of entangled polymer chains in the melt state are deliberately excluded in most of the studies on supramolecular polymer networks by utilizing nonentangled precursor chains. Relaxation of the system mainly depends on the dissociation of the associative groups in latter case and nonentangled chains deliver nothing to resist afterward. Conversely, in an entangled system, relaxation of polymer chains and dissociation of associative groups can occurred parallel. Supramolecular networks based on an entangled precursor polymer with different levels of strong associating ureidopyrimidinone (UPy) groups are synthesized to screen the corresponding effects on the dynamics of the system. Bina…

Bio-inspired surface modification of iron oxide nanoparticles for active stabilization in hydrogels

Biological materials employ a variety of dynamic interactions in sophisticated composite structures to function adaptively on different time and length scales. Inspired by such designs we develop a novel surface modification approach to promote dynamic interactions between nanoparticles and polymer chains in physical and double network hydrogels. Physical hydrogels are formed via reversible complexation of borate ions with poly(vinyl alcohol) (PVA) and chemical crosslinks are introduced by electron beam irradiation. Dopamine is used for surface modification of magnetic iron oxide nanoparticles (MNPs) in two different ways: the direct treatment results in anchoring via catechol groups, where…

Coordination Geometry Preference Regulates the Structure and Dynamics of Metallo-Supramolecular Polymer Networks

Metal–ligand interactions are extensively used for the development of biomimetic polymers. Macroscopic properties of such systems are closely tied to the microscopic structure and dynamics of not o...

Efficiency range of the Belousov-Zhabotinsky reaction to induce the self-organization of transient bonds in metallo-supramolecular polymeric systems.

The periodic change of the oxidation state of the metal catalyst in the oscillating Belousov-Zhabotinsky (BZ) reaction has been reported to establish a periodic organization of metallo-supramolecular bonds in polymeric systems, which results in autonomous viscosity oscillations. To appraise the possible extent of quantitative control on the viscosity oscillation features, we assess how the kinetics of the BZ reaction affects the periodic self-organization of the metal-ligand coordination, and vice versa. Our model system includes mono-, bis-, and tetra-functional polyethyleneglycol (PEG) precursors end grafted with terpyridine ligands that are complexed with ruthenium ions, which oscillate …

Analytical representation of bimodality in bivariate distribution of chain length and chemical composition of copolymers

Abstract Tuning the bimodality of microstructural features in polymers has provided novel properties and applications. A classic example is to overcome the trade-off between processability and mechanical properties in polyolefins. A recent example is to decrease the interfacial tension in blending incompatible polymers. Therefore, the development of a bimodality index (BI), especially for the chain length distribution (CLD) and the chemical composition distribution (CCD), is crucial for the quantitative design of materials. This study introduces quantitative expressions for the bimodality of univariate CLD on the linear scale, and CCD. Moreover, we develop a bimodality criterion for bivaria…

Emergence, evidence, and effect of junction clustering in supramolecular polymer materials

A significant fraction of biomaterials consists of supramolecular polymers and networks formed by non-covalent interactions between associative motifs. They typically contain complex structures in which on top of binary associations, phase-separation and aggregation of associative junctions occur. Such hierarchical assemblies have significant influences on the dynamics as well as the physical and mechanical properties of the materials. Similar to supramolecular biomaterials, aggregation of associative junctions has also been frequently reported to occur in synthetic supramolecular polymers and networks. Engineering of such secondary structures in a sense to create and control the extent of …

Control over Branching Topology by Introducing a Dual Catalytic System in Coordinative Chain Transfer Polymerization of Olefins

Coordinative polymerization brings opportunities for producing well-defined long-chain branched polyolefins specifically by using homogeneous single-site catalysts. Herein, we report a new dual cat...

Thermodynamic control over energy dissipation modes in dual-network hydrogels based on metal-ligand coordination.

Modern polymeric hydrogels use reversible bonds to mimic biological functionalities. However, true biological materials benefit from several supramolecular elements and deliver multiple functions at the same time. To approach similar creation and control of multiple different functional elements in a synthetic soft material, we develop a model dual-network hydrogel in which multiple energy dissipating modes are formed by metal–ligand coordination and regulated by their association thermodynamics. This idea is realized by using linear and tetra-arm poly(ethylene glycol) (PEG) precursors with complementary reactive end groups. The former also carries terpyridine ligands on both ends, which fo…