Enhancing the Self‐Assembly of Step‐Growth Polymers by Narrowing Their Molar Mass Distribution: A Dynamic Bond‐Mediated Approach
Abstract
Abstract Step‐growth polymerization (SGP) typically produces polymers with exceptional versatility in terms of applications, but its inherently uncontrolled nature leads to broad molecular weight distributions ( Đ ) and consequently polymers with poor nanostructure control in comparison to chain growth polymers. In this study, we provide a solution to this long‐lasting problem by introducing a new concept, asymmetric dynamic bond mediated polymerization (ADBP). In this case, the polymerization between asymmetric and reversibly deactivated AA’‐type dielectrophiles and B 2 ‐type dinucleophiles has a preferential reaction pathway between the functionality A’ of the asymmetric AA’ monomer with B 2 . We observe that this polymerization allows us to achieve better control of the step‐growth process where in the first stage only well‐defined trimers and dimers are primarily formed up to conversion ( p ) ≤ 0.6, followed by their polymerization stage ( p ≥ 0.6). This leads to polymers with reduced Đ (<1.5), in comparison to traditional SGP, and improved molar mass control. Such technique is further exploited to prepare polyurethanes with Đ = 1.2, which exhibit the ability to form microphase‐separated domains with higher ordering, giving rise to polyurethane thermosets with superior mechanical properties compared to a traditional SGP analog.
Article Details
Authors (11)
Lucas Polo Fonseca
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Shaghayegh Hamzehlou
POLYMAT, University of the Basque Country UPV/EHU Joxe Mari Korta zentroa Tolosa Hiribidea 72 Donostia‐San Sebastián 20018 Spain
Olaia Garagarza
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Daniele Mantione
POLYMAT, University of the Basque Country UPV/EHU, Avenida Tolosa 72, Donostia-San Sebastian 20018, Spain
Aritz Lamas
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Xabier Lopez de Pariza
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Fermin Elizalde
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Marta Ximenis Campins
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Amaia Agirre
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Gabriel Perli
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry University of the Basque Country UPV/EHU Paseo Manuel de Lardizábal, 3 Donostia‐San Sebastian 20018 Spain
Haritz Sardon
POLYMAT and Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel de Lardizábal, 3, 20018 Donostia-San Sebastián, Spain