Synthesis of Polyoxazolines Using Glycerol Carbonate Derivative and End Chains Functionalization via Carbonate and Isocyanate Routes

Chloé Giardi (1) , Vincent Lapinte (1) , Françoise Nielloud (1) , Jean-Marie Devoisselle (1) , Jean-Jacques Robin (1)

1 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

We report the cationic ring-opening polymerization of 2-methyl-2-oxazoline (MOx) using bio-based initiator (GCTs). The functional initiator GCTs was prepared by tosylation of the corresponding alcohol: glycerol carbonate (GC). The termination stage of the polymerization was achieved in presence of KOH and the telechelic polyoxazoline carrying five-membered cyclic carbonate and oxazolium end groups (GC-POxium) was converted to ((HO)2-POx-OH) carrying a-diol and x-hydroxyl groups. End-functionalized polyoxazolines (HO)2-POx-OH with Mn ranging from 4200 to 8400 g mol1 were synthesized. According to GPC results, the polymerizations of MOx using GCTs and other initiator coming from 1,2-isopropylidene-glycerol (Solk-Ts) were compared. On the basis of FTIR and NMR spectroscopies, the chemical modification of end chains of polyoxazolines was investigated by two alternative synthetic routes. The isocyanate route is a postpolymerization urethanization. The nucleophilic reactivity of the a-diol and x-hydroxyl groups of (HO)2-POx-OH was studied with functional isocyanate (TESPI). In the carbonate route, the electrophilic reactivity of a- and x-end groups of GC-POxium were explored with amine. It was demonstrated that during the termination stage of the polymerization in presence of allylamine both urethane linker in a-end chain was synthesized and the x-oxazolium group was converted into terminal amine. The carbonate route is an alternative to synthesize urethane without isocyanate.

Mots clés: cationic polymerization; functionalization of polymers; renewable resources; telechelics

Domaines: Polymères

Chloé Giardi, Vincent Lapinte, Françoise Nielloud, Jean-Marie Devoisselle, Jean-Jacques Robin. Synthesis of Polyoxazolines Using Glycerol Carbonate Derivative and End Chains Functionalization via Carbonate and Isocyanate Routes. Journal of Polymer Science Part A: Polymer Chemistry, 2010, 48, pp.4027-4035. ⟨10.1002/pola.24188⟩. ⟨hal-00512378⟩