UV-Curable Biobased Polyacrylates Based on a Multifunctional Monomer Derived from Furfural

Area of Science:

• Polymer Chemistry
• Materials Science
• Organic Chemistry

Background:

• Developing novel biobased monomers is crucial for sustainable polymer synthesis.
• 4-oxocyclopent-2-en-1-yl acrylate (4CPA) is a new biobased monomer with dual reactivity.
• Uncontrolled polymerization of 4CPA can lead to gelation due to its unsymmetrical structure.

Purpose of the Study:

• To establish controlled polymerization of 4CPA using reversible addition-fragmentation chain transfer (RAFT) polymerization.
• To explore the copolymerization behavior of 4CPA with common acrylates.
• To demonstrate the utility of 4CPA in creating functional, cross-linkable polymers.

Main Methods:

• Reversible addition-fragmentation chain transfer (RAFT) (co)polymerization of 4CPA.
• Synthesis of copolymers with lauryl acrylate (LA), methyl acrylate (MA), and isobornyl acrylate.
• Photodimerization studies of 4-oxocyclopent-2-en-1-yl acetate (1) under UV light.
• First-principles quantum mechanical simulations for structural analysis.
• UV cross-linking of copolymers and characterization of resulting films.

Main Results:

• Controlled RAFT polymerization of 4CPA yielded polymers with pendent cyclopentenone units, achieving controlled conversions without gelation.
• Copolymerization of 4CPA with LA, MA, and isobornyl acrylate resulted in high monomer conversions (63-95%).
• Model studies confirmed the [2 + 2] photocyclodimerization of the cyclopentenone unit under UV light.
• Quantum mechanical simulations supported experimental NMR findings on dimer formation.
• UV-cross-linked films from LA and MA copolymers containing 4CPA were successfully prepared and characterized.

Conclusions:

• 4CPA can be effectively polymerized using RAFT, enabling controlled synthesis of functional biobased polymers.
• The pendent cyclopentenone groups in 4CPA allow for subsequent UV-induced cross-linking via photodimerization.
• This work presents the first report of 4CPA as a monomer for biobased polymers with tunable properties via UV curing.