Biobased homopolymers and amphiphilic diblock copolymers containing guaiacyl (G) or hydroxyphenyl (H) lignin derivatives synthesized by RAFT (PISA)

Abstract

In this work, we exploited guaiacyl (G) and hydroxyphenyl (H) lignin derivatives, namely 4-vinylguaiacol (4-hydroxy-3-methoxystyrene) and p-hydroxystyrene, to engineer biobased homopolymers and amphiphilic diblock copolymers. Firstly, after adequate monomers protection,...

Mechanosynthesis and Polymerization of Biosourced Styrene Derivatives Based on Building Blocks of Lignin

“…The main strategy encountered in the literature resides on the synthesis of acrylate esters on the phenol group for further polymerization. − The remaining aldehyde group offers in this case a possibility to functionalize the monomer. ,, Another way consists of converting them into styrene derivatives by changing the aldehyde of V , H , and S derivatives or conjugated carboxylic acid of ferulic acid derivatives into vinyl groups. Following this transformation, phenol moieties need to be protected, usually through an esterification reaction before radical polymerization can occur, as shown in our recent paper, followed, if needed, by a deprotection step. , Such a protection–deprotection sequence is efficient to produce polystyrenes with good thermal properties but is energy- and solvent-consuming. We will demonstrate here that a similar strategy using a vinyl derivative is possible in a simpler and more environmentally friendly way, without any deprotection step required and by mechanical activation.…”

“…18,30,31 Another way consists of converting them into styrene derivatives by changing the aldehyde 6 of V, H, and S derivatives or conjugated carboxylic acid 9 of ferulic acid derivatives into vinyl groups. Following this transformation, phenol moieties need to be protected, usually through an esterification reaction before radical polymerization can occur, as shown in our recent paper, 20 followed, if needed, by a deprotection step. 6,9 Such a protection−deprotection sequence is efficient to produce polystyrenes with good thermal properties but is energy-and solvent-consuming.…”

“…Indeed, the controlled degradation of lignin allows to produce biofuels, precursors for organic synthesis, or oligomers that can be applied to prepare functional materials. , Among those examples, the compounds obtained from lignin degradation represent a promising alternative to design biosourced polymers displaying interesting thermomechanical properties ,− thanks to the presence of aromatic cycles. Besides, we have recently shown that lignin derivatives, based on guaiacyl or hydroxyphenyl units, could lead to polystyrene-type materials using the reversible addition–fragmentation chain transfer (RAFT) radical polymerization …”

“…Besides, we have recently shown that lignin derivatives, based on guaiacyl or hydroxyphenyl units, could lead to polystyrene-type materials using the reversible addition−fragmentation chain transfer (RAFT) radical polymerization. 20 Nowadays, the depolymerization of lignin is well-mastered, and according to the degradation conditions (thermal or biological degradation, acidic or alkaline treatment, etc. ), 21,22 different classes of compounds can be selectively obtained, such as aromatic alcohols or aldehydes and carboxylic acids or hydrocarbons.…”

Temperature-Responsive Lactic Acid-Based Nanoparticles by RAFT-Mediated Polymerization-Induced Self-Assembly in Water

“…The resultant PAA- b -PMA diblock copolymer nanoparticles can be fully biobased if the AA is synthesized from renewable resources (i.e., lactic acid). Recently, the same group chain extended PAA with lignin derivatives, acetoxy-protected 4-vinylguaiacol (AcVG), and p -hydroxystyrene (AcST) by RAFT emulsion polymerization forming PAA- b -PAcVG and PAA- b -PAcST diblock copolymer nanoparticles …”