Exploring Multiple Hydrogen Bonding and Ionic Bonding in the Design of Supramolecular Polymers

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Virginia Tech


Supramolecular polymers represent a family of polymeric materials that are held together with dynamic, noncovalent interactions. In contrast to conventional functional polymers that usually have high melt-viscosity due to their covalent nature and chain entanglement, supramolecular polymers combine excellent physical properties with low melt-viscosity, allowing for less energy-intensive processability and recyclability. Dynamic bonding with multiple binding sites, such as multiple hydrogen bonding or multiple ionic bonding, exhibits much stronger binding strength compared to the counterparts containing only a single binding site, thereby allowing for enhanced mechanical integrity to the polymers and facilitate self-assembly. This dissertation focuses on the design of novel supramolecular polymers building from the doubly-charged or quadruple hydrogen bonding (QHB) scaffolds utilizing chain-growth polymerization or step-growth polymerization, as well as elucidate the structure-property-morphology relationships of the polymers.

A 2-step nucleophilic substitution reaction afforded a series of 1,4-diazabicyclo[2.2.2]octane (DABCO)-based styrenic monomers with two pairs of charged groups. An optimized 2-step reversible-addition-fragmentation chain-transfer (RAFT) polymerization synthesized ABA triblock thermoplastic elastomers (TPEs) with a low Tg poly (n-butyl acrylate) central block and a high Tg external charged blocks. Strong ionic interactions between doubly-charged units drove molecular self-assembly to form densely packed, hierarchical microstructures, which contributed to a robust, crosslinked physical network that allows the polymer to retain thermomechanical integrity until degradation. High-resolution single-crystal X-ray diffraction (SCXRD) coupled with powder X-ray diffraction (PXRD) further disclosed a detailed 3-D structural information of molecular arrangement and ion distribution within the charged phase through comparing DABCO-salt monomer single-crystal structure and the corresponding homopolymer XRD pattern. It was found that the physical properties of the DABCO-salt copolymers not only relied on their charge content and architectures but also dependent on their electrostatically-bonded counterions. The size and structure of the counterion determined the strength of dipole-dipole interaction, which significantly impact on thermal property, (thermo)mechanical performance, water affinity, and microstructure.

A cytosine-functionalized monomer, cytosine acrylate (CyA), allowed the synthesis of acrylic ABA triblock TPEs with pendant nucleobase moieties in the external blocks and a low Tg central polymer matrix through RAFT polymerization. Post-functionalization of cytosine (Cyt) bidentate hydrogen bonding sites with alkyl isocyanate, allowed the formation of ureido-cytosine (UCyt) groups in the external block that were readily dimerized through QHB interactions. The UCyt units in the external block enhanced mechanical strength and induced stronger phase-separation of the block copolymers compared to the corresponding Cyt-containing TPE analogs. Facile conventional free-radical polymerization using CyA and subsequent post-functionalization enabled accessibility to random copolymers containing pendant UCyt QHB moieties in the soft polymer matrix. The synergy of the flexible polymer matrix and the dynamic character of QHB groups contributed to the ultra-high elasticity of the polymer and rapid self-healing properties. QHB interactions enabled efficient mechanical recovery upon deformation by facilitating elastic chain retraction to regenerate the original physical network. Finally, one-pot step-growth polymerization through chain extending a novel bis-Cyt monomer and a commercially available polyether diamine using a di-isocyanate extender afforded segmented polyurea series for extrusion additive manufacturing. The molecular design of the polyureas featured soft segments containing flexible polyether chain and a relatively weak urea hydrogen bonding sites in the soft segment and rigid UCyt hydrogen bonding groups in the hard segment. The reversible characteristics of QHB enabled low viscosity at the processing temperature while providing mechanical integrity after processing and reinforced bonding between the interlayers, which contributed to the remarkable strength, elasticity, toughness, and interlayer adhesion of the printed parts.



Supramolecular polymer, noncovalent interactions, hydrogen bonding, ionic interaction, ureido-cytosine, DABCO salt, self-assembly, structure-property relationships, block copolymer, thermoplastic elastomer