Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Thermoreversible Gelation with Supramolecularly Polymerized Cross-Link Junctions

Version 1 : Received: 21 September 2023 / Approved: 22 September 2023 / Online: 25 September 2023 (06:19:34 CEST)

A peer-reviewed article of this Preprint also exists.

Tanaka, F. Thermoreversible Gelation with Supramolecularly Polymerized Cross-Link Junctions. Gels 2023, 9, 820. Tanaka, F. Thermoreversible Gelation with Supramolecularly Polymerized Cross-Link Junctions. Gels 2023, 9, 820.

Abstract

Structure and reversibility of cross-link junctions play pivotal roles in deter- mining the nature of thermoreversible gelation and dynamic mechanical prop- erties of the produced polymer networks. We attempt to explore new types of sol–gel transitions with mechanical sharpness by allowing cross-links to grow without upper bound. We consider thermoreversible gelation of the primary molecules R{Af} carrying the number f of low molecular weight functional groups (gelators) A. Gelators A are assumed to form supramolecular assemblies. Some examples are: telechelic polymers (f = 2) carrying π–π stacking benzene derivatives at their both ends, trifunctional star molecules (f = 3) bearing mul- tiple hydrogen-bonding gelators. The sol–gel transition of the primary molecules becomes sharper with the cooperativity parameter of the stepwise linear growth of the cross-links. There is a polymerization transition (crossover without singu- larity) of the junctions in the postgel region after the gel point is passed. If the gelator A tends to form supramolecular rings competitively with linear chains, there is another phase transition in the deep postgel region where the average molecular weight of the rings becomes infinite (Bose-Einstein condensation of rings). As a typical example of binary cross-links where gelators A and B form mixed junctions, we specifically consider metal-coordinated binding of ligands A by metal ions B. Two types of multi-nuclear supramolecular complexes are studied: (i) linear stacking (ladder) of the sandwich A2B units, (ii) linear train of egg-box A4B units. The average molecular weight, the gel fraction, the av- erage length of the cross-link junctions are calculated for all of these models as functions of the functionality f, the concentration of the solute molecules, and temperature. Potential candidates for the realization of these new types of thermoreversible gelation are discussed.

Keywords

thermoreversible gelation; supramolecular cross-linking; cooperative polymerization; Bose--Einstein condensation of rings; metal-coordinated supramolecules; ladder junction / egg-box junction

Subject

Chemistry and Materials Science, Polymers and Plastics

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