This document summarizes research on a novel self-healing and thermoreversible rubber created through supramolecular assembly. Compound A, made of small molecules and oligomers connected by hydrogen bonds, forms a translucent plastic. Plasticizing compound A with dodecane creates compound B, a non-tacky rubber-like material with a glass transition temperature of 8°C. Rheological testing shows compound B has both elastic and viscous properties. Remarkably, compound B is able to self-heal at room temperature after being cut or broken. The researchers conclude that this new material composed of supramolecular assemblies has unique self-mending properties and high extensibility, making it potentially useful for

1. Self-healing and thermoreversible
rubber from supramolecular assembly
Founta Dimitra 994
Materials Science and Technology | University of Crete
Date : 23//06/2017

2. What is a rubber?
Rubber is an example of an elastomer type polymer,
where the polymer has the ability to return to its original
shape after being stretched or deformed.
Macromolecules connection :
These connections also prevent flow
and creep.
Covalent cross-links
Network by physical associations (ex.
Multiple hydrogen bonds)
http://www.dowcorning.com/content/discover/discoverchem
/cure-systems.aspx
“Stimuli-responsive supramolecular polymeric materials”, X.Yan, F.Wang, B.
Zheng and F. Huang, Chem Soc Rev, 22 March 2012, DOI: 10.1039/c2cs35091b

3. Supramolecular polymers
Mixing ditopic + multitopic molecules
can form a supramolecular network.
Flow or partially crystallize and behave
like plastic resins or fibres.
Solution to avoid crystallization
Mixtures of molecules bearing a variety
of strongly associating groups ( for
example dimer fatty acids)

4. Synthetic Pathway
“Self-healing and thermoreversible rubber from supramolecular assembly”, P.Cordier,F.Tournilhac, C. Souliè-Ziakovic, L.Leibler, 21 Feb 2008 , LETTERS, DOI: 10.1038/nature06669

5. Compound A
Translucent glassy plastic – Tg = 28℃
Soluble in benzyl alcohol and methanol/chloroform mixtures and
insoluble in water , with water uptake of ~ 14% w/w.
T = 160 ℃ T = 90 ℃
NMR : Compound A is made of small molecules , oligomers.
Infrared Spectroscopy : shows hydrogen bonds between
N-H and C=O groups.
“Self-healing and thermoreversible rubber from supramolecular assembly”, P.Cordier,F.Tournilhac, C.
Souliè-Ziakovic, L.Leibler, 21 Feb 2008 , LETTERS, DOI: 10.1038/nature06669 – Supplementary figures

6. Compound B
Plasticized compound A with 11% w/w dodecane Compound B – Tg = 8℃
Non-tacky, rubber-like material
Confirmation that is not crystalline:
> Differential Scanning Calorimetry (DSC)
> X-ray scattering

7. Rheological and mechanical
properties of Compound B
G’ (elastic response)
G’’ (viscous behavior)
“Self-healing and thermoreversible rubber from supramolecular assembly”, P.Cordier,F.Tournilhac, C. Souliè-Ziakovic, L.Leibler, 21 Feb 2008 , LETTERS, DOI:10.1038/nature06669

8. Self-healing at room temperature

9. Conclusion
• The supramolecular assemblies , have the unique
property of self-mending and have high extensibility.
• The circle of break and heal can take place many times.
• Depending on the different parameters, we can achieve
variation of the results.
• Re-used, recycled, easy to process.
This kind of materials, can be used in bulk and bode well
for future applications and studies.

10. Literature-References
• “Self-healing and thermoreversible rubber from supramolecular assembly”, P.Cordier,F.Tournilhac, C.
Souliè-Ziakovic, L.Leibler, 21 Feb 2008 , LETTERS, DOI: 10.1038/nature06669
• “Stimuli-responsive supramolecular polymeric materials”, X.Yan, F.Wang, B. Zheng and F. Huang, Chem
Soc Rev, 22 March 2012, DOI: 10.1039/c2cs35091b
• http://chemistry.elmhurst.edu/vchembook/403rubber.html
• “Synthesis of self-healing supramolecular rubbers from fatty acid derivatives, diethylene triamine, and
urea”, Montarnal D, Cordier P, Soulié-Ziakovic C, Tournilhac F, Leibler L, Journal of Polymer Science Part
A: Polymer Chemistry , 2008 vol: 46 (24) pp: 7925-7936 , DOI : 10.1002/pola.23094
• http://www.uio.no/studier/emner/matnat/kjemi/KJM3100/v07/undervisningsmateriale/Lecture%202.pdf
• http://www.tainstruments.com/pdf/literature/AAN013_V_1_U_Thermoplast.pdf