Rubbers exhibit enormous extensibility up to several hundred per cent, compared with a few per cent for ordinary solids, and have the ability to recover their original shape and dimensions on release of stress. Rubber elasticity is a property of macromolecules that are either covalently cross-linked or connected in a network by physical associations such as small glassy or crystalline domains, ionic aggregates or multiple hydrogen bonds. Covalent cross-links or strong physical associations prevent flow and creep. Here we design and synthesize molecules that associate together to form both chains and cross-links via hydrogen bonds. The system shows recoverable extensibility up to several hundred per cent and little creep under load. In striking contrast to conventional cross-linked or thermoreversible rubbers made of macromolecules, these systems, when broken or cut, can be simply repaired by bringing together fractured surfaces to self-heal at room temperature. Repaired samples recuperate their enormous extensibility. The process of breaking and healing can be repeated many times. These materials can be easily processed, re-used and recycled. Their unique self-repairing properties, the simplicity of their synthesis, their availability from renewable resources and the low cost of raw ingredients (fatty acids and urea) bode well for future applications.

Self-healing and thermoreversible rubber from supramolecular assembly

Viscoelasticity and dynamics of entangled polymers

As polymers and polymeric materials are “the” smart invention and technological driving force of the 20th century, the quest for self-healing or self-repairing polymers is strong. The concept of supramolecular self-healing materials relies on the use of noncovalent, transient bonds to generate networks, which are able to heal the damaged site, putting aspects of reversibility and dynamics of a network as crucial factors for the understanding and design of such self-healing materials. This Review describes recent examples and concepts of supramolecular polymers based on hydrogen bonding, π–π interactions, ionomers, and coordinative bonds, thus convincingly discussing the advantages and versatility of these supramolecular forces for the design and realization of self-healing polymers.

Self‐Healing Polymers via Supramolecular Forces

Supramolecular polymer networks are three-dimensional structures of crosslinked macromolecules connected by transient, non-covalent bonds; they are a fascinating class of soft materials, exhibiting properties such as stimuli-responsiveness, self-healing, and shape-memory. This critical review summarizes the current state of the art in the physical–chemical characterization of supramolecular networks and relates this knowledge to that about classical, covalently jointed and crosslinked networks. We present a separate focus on the formation, the structure, the dynamics, and the mechanics of both permanent chemical and transient supramolecular networks. Particular emphasis is placed on features such as the formation and the effect of network inhomogeneities, the manifestation of the crosslink relaxation dynamics in the macroscopic sample behavior, and the applicability of concepts developed for classical polymer melts, solutions, and networks such as the reptation model and the principle of time–temperature superposition (263 references).

Physical chemistry of supramolecular polymer networks

Random copolymers consisting of n-butyl acrylate backbones with quadruple hydrogen-bonding side chains based on 2-ureido-4[1H]-pyrimidinone (UPy) have been synthesized via controlled radical polymerization and postpolymerization functionalization. Through this synthetic strategy high UPy monomer content (15 mol %) can be reached while maintaining low polydispersity and excellent control over molecular weight, providing model reversible networks with well-defined molecular architecture. Despite low Tgs and a lack of entanglements or crystallinity, these materials behave as thermoplastic elastomers through the strong but reversible association of UPy groups. Bulk properties such as the plateau modulus, tensile modulus, and relaxation time scale are primarily determined by the average distance between UPy’s along the chain. Starting from a difunctional initiator, triblock copolymers can also be synthesized containing a homopolymer midblock and random copolymer end blocks, effectively concentrating the hydrog...

Model Transient Networks from Strongly Hydrogen-Bonded Polymers

Polybutadiene of narrow molecular weight distribution was modified using 4-phenyl-1, 2,4-triazoline-3,5-dione. The degree of modification was 1% and 2% with respect to the repeating units. Hydrogen bonding between the highly polar urazole groups thus incorporated into the polymer gives rise to the formation of a thermoreversible elastomeric network. Dynamic mechanical measurements in the temperature range between 220 and 330 K support the picture of the thermoreversible hydrogen bond interaction. The rubber elastic plateau is shifted to higher temperatures and lower frequencies. The increase in the plateau modulus cannot be attributed solely to the contribution of the network structure but is mainly a consequence of the broadening of the relaxation time spectrum in the modified samples. From the temperature dependence of the shift factors log(aT) it is concluded that the general WLF approach fails. The strong temperature dependence of the apparent activation energy of flow is a consequence of the temperature dependence of the hydrogen bond interaction.

Thermoplastic elastomers by hydrogen bonding 1. Rheological properties of modified polybutadiene

The temperature dependence of the viscoelastic properties of thermoreversible polybutadiene networks based on hydrogen bond linkages is analyzed from the logarithmic shift factors loga

 T
 . For binary hydrogen bond complexes thermorheologically simple behavior is observed. The temperature dependence of loga

 T
 is described by the Williams-Landel-Ferry (WLF) equation. The thermoreversible linkages cause an increase in the apparent activation enthalpy of flow which is related to the number of complexing sites in the polymer. Thermorheologically complex behavior is observed in a system with more complex association.

Thermoplastic elastomers by hydrogen bonding 4. Influence of hydrogen bonding on the temperature dependence of the viscoelastic properties

Oligomers as molecular probes of orientational coupling interactions in polymer melts and networks

The dynamics of hydrogen bond complex formation between functional groups which are attached to a polymer chain, is studied in the molten state. The concentration of complexes in the thermodynamic equilibrium is distorted by the application of a large oscillatory strain in the nonlinear viscoelastic regime. The relaxation back to the thermodynamic equilibrium is studied as a function of the temperature in the linear viscoelastic regime. From the mechanical response the kinetic analysis can be performed using a modified Doi-Edwards theory. Using the equilibrium constants obtained from IR-spectroscopy, the rate constants for complex formation and decomplexation are obtained. The temperature dependence is equivalent to the temperature dependence of the zero shear viscosity which implies that complex formation is a diffusion-controlled process.

R. Stadler

Papers

Thermoplastic elastomers by hydrogen bonding 1. Rheological properties of modified polybutadiene

Thermoplastic elastomers by hydrogen bonding 4. Influence of hydrogen bonding on the temperature dependence of the viscoelastic properties

Oligomers as molecular probes of orientational coupling interactions in polymer melts and networks

Dynamics of hydrogen bond complexes in polymer melts

Tetrafunctional networks with deuterated network junctions. Synthesis and characterization