Multifunctional Polyelectrolytes Bearing Pendant Catechol / Quinone for Energy and Environmental Applications

The discovery of 3,4-dihydroxyphenyl-L-alanine (L-DOPA), a catechol-functionalized amino acid as major component in mussel adhesion proteins, has triggered enormous interest in mussel-mimetic adhesives. The design of innovative bioinspired polymers-containing catechols has rapidly gained widespread utility in the (bio)material field, ascribed to the versatility of the catechol chemistry that allows anchoring (bio)polymers, biomolecules, nanoparticles (metals and metal oxides) and other compounds onto almost any kind of surfaces without any pre-treatment.
Amongst the various synthetic protocols to incorporate catechol functionalities into (bio)polymers, the radical polymerization of catechol-bearing vinyl monomers in their protected form has proven to be a versatile technique to impart intrinsic physico–chemical properties of the catechol pendants to polymers after appropriate deprotection. Importantly, the scope of applications of catechol-bearing polymers can potentially be drastically increased by developing controlled radical polymerization (CRP) techniques of their protected vinyl monomers. Indeed, these techniques will enable to precisely design the polymer with the appropriate structure, molar mass and functionality that fit at best the target application. When this thesis started in 2013, only very limited examples of functional catechol-bearing polymers prepared by CRP were reported.
The aim of this PhD thesis was to develop well-defined innovative catechol-containing (co)polymers that find applications in energy storage and environmental fields by employing function-oriented macromolecular engineering approaches. In this work, numerous catechol-protected monomers have been prepared and their CRP investigated to afford well-defined (co)polymers with controlled and tunable molar masses, compositions, functionalities, and architectures (homopolymers, statistical and block copolymers). The potential of these innovative catechol-containing (co)polymers was then explored for applications in energy storage (as active-material in lithium-ion half-cells) and environment (as protein fouling/antifouling coatings).