Premium
Organocatalysts for the Synthesis of Poly(ethylene terephthalate‐ co ‐isosorbide terephthalate): A Combined Experimental and DFT Study
Author(s) -
Stanley Nicholas,
Chenal Thomas,
Jacquel Nicolas,
SaintLoup René,
Prates Ramalho Joao Paulo,
Zinck Philippe
Publication year - 2019
Publication title -
macromolecular materials and engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.913
H-Index - 96
eISSN - 1439-2054
pISSN - 1438-7492
DOI - 10.1002/mame.201900298
Subject(s) - moiety , sulfonic acid , bifunctional , polymer chemistry , chemistry , monomer , nucleophile , ethylene , catalysis , guanidine , isosorbide , polymerization , organic chemistry , polymer
Organocatalysts are assessed for the insertion of isosorbide, a rigid, biobased diol monomer, into poly(ethylene terephthalate). A sulfonic acid (p‐toluenesulfonic acid—APTS), an amidine base (1,8‐diazabicyclo [5.4.0] undec‐7‐ene—DBU) and a guanidine base (1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene—TBD) successfully catalyze the polymerization. The reaction mechanisms are studied by density functional theory. A bifunctional activation is observed in the presence of the sulfonic acid, the carbonyl moiety being activated via the acidic proton of APTS and the alcohol via the basic oxygen. Regarding DBU, a mechanism based on a basic activation of the alcohol rather than a nucleophilic attack of the catalyst is evidenced. The difference observed between TBD and DBU is attributed to a better H‐bonding ability of the former versus the latter.