Title :

Tuning the thermal properties of l-lactide/ε-caprolactone chain shuttled copolymers via catalyst selection

Author(s) :

Mosca, Xavier [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Perchery, Lucas [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Bria, Marc [Auteur]
Centre Commun de Mesure de RMN
De Winter, Julien [Auteur]
Université de Mons / University of Mons [UMONS]
Stoclet, Gregory [Auteur]
Unité Matériaux et Transformations (UMET) - UMR 8207
Bousquet, Till [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Pelinski, Lydie [Auteur]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Bonnet, Fanny [Auteur correspondant]
Unité Matériaux et Transformations (UMET) - UMR 8207
Zinck, Philippe [Auteur correspondant]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Perchery, Lucas [Auteur]

Journal title :

Polymer Chemistry

Abbreviated title :

Polym. Chem.

Publisher :

Royal Society of Chemistry (RSC)

Publication date :

2024

ISSN :

1759-9954

HAL domain(s) :

Chimie/Matériaux
Chimie/Polymères

English abstract : [en]

Chain shuttling copolymerisation (CSP) is a synthetic strategy allowing the one-pot, one-step formation of block copolymers. Initially developed in the frame of coordinative polymerisation of olefins and conjugated dienes, ...
Show more >Chain shuttling copolymerisation (CSP) is a synthetic strategy allowing the one-pot, one-step formation of block copolymers. Initially developed in the frame of coordinative polymerisation of olefins and conjugated dienes, it was recently transferred to the ring-opening polymerisation of cyclic esters. In this contribution, we report six new catalytic systems able to perform the chain shuttling copolymerisation of L-lactide (L-LA) with ε-caprolactone (ε-CL) and to tune the thermal properties of the resulting copolymers. They are based on amino(bis)phenolate supported aluminium complexes bearing different pendant donorarms (Al(O2NL)OBn), L = NEt2 (2a), NBn2 (2b), Py (2c), Mor (2d)). A Mannich reaction allowed the ligands synthesis. The two new alkoxide complexes 2a and 2b were obtained by reaction of the protonated ligands with trimethylaluminium followed by benzyl alcohol in reasonable yield, as well as two already described compounds 2c and 2d. Initially assessed as catalysts for L-LA and ε-CL homopolymerisations and statistical copolymerisation, the aluminium compound bearing pyridine as a donor arm (2c) resulted in a high selectivity toward lactide. 2c together with yttrium and aluminium alkoxides, also known for their selectivity for lactide, were successfully assessed for the chain shuttling copolymerisation of L-LA with ε-CL in combination with the three other amino(bis)phenolate supported aluminium complexes that showed a higher selectivity toward ε-CL. Chain shuttling copolymerization via transalkoxylation between two different metals, Y and Al, is achieved for the first time, therefore extending the range and scope of cyclic esters CSP. Such an alteration of the nature of the catalysts allowed fine tuning of the thermal properties of the chain shuttled copolymer, as shown by a variation of the glass transition temperature (Tg) of the soft block over ca. 25 °C without changing the catalysts ratio and feed of the reaction.Show less >

Language :

Anglais

Peer reviewed article :

Oui

Audience :

Internationale

Popular science :

Non

ANR Project :

Copolymérisation statistique par navette d'esters cycliques, une voie d'accès à de nouveaux copolymères multiblocs à base de PLA

Administrative institution(s) :

Université de Lille
CNRS
INRAE
ENSCL

Collections :

• Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
• Unité Matériaux et Transformations (UMET) - UMR 8207

Research team(s) :

Ingénierie des Systèmes Polymères

Submission date :

2024-09-24T11:54:32Z
2024-09-25T07:17:53Z