New biosourced alternated poly(ether)Ester-Amides (PeEA): synthesis and combined NMR/MALDI ToF MS characterization

Abstract

International audienceNew biosourced alternated poly(ether)Ester-Amides PeEA were prepared by polycondensation in solution or in bulk of unprecedented aminoalcohols based on 1,4:3,6-dianhydrohexitols (DAH) with aromatic and aliphatic diacyl chlorides (sebacoyl, terephtaloyl and isophtaloyl). Optimization of the polymerization in solution has been investigated using MALDI ToF MS and NMR spectroscopy to ascertain the structures and end chain nature of the resulting polymers. The influence of the DAH stereochemistry and the polymerization mode on the structures and thermal properties was demonstrated by MALDI ToF and complementary analytical techniques (DSC and SEC). Isomannide based polymers revealed amorphous but showed higher Tg (around 80 °C for sebacoyl and 180 °C for isophtaloyl) whereas the isosorbide based polymers were semi crystalline. Best properties were obtained in bulk using isomannide based aminoalcohol and sebacoyl chloride (Tg of 82 °C and Mw of 32 kDa, PDI = 1.41)

Synthesis and characterization of novel biosourced building blocks from isosorbide

“…In this context, while 5a had a melting point T m = 156-161 °C, we observed with Pe_EA 8 a glass transition temperature T g = 92 °C with an enthalpy recovery ΔH = 19.3184 J g −1 probably due to a physical aging, currently known in sugar chemistry. [27] Comparing with previously obtained semi-crystalline Polyester-amides PeEA [23] fully based on sebacoyl spacer (T g 72-75 °C), the thermal shown in Figure 4. We observed the presence of signals with high intensity and others with low ones corresponding respectively to the protons from the main chain of the polymer and the end chain moiety.…”

“…[23] CH 2 Cl 2 ) (or 1.68 mmol of 2,6-lutidine), and terephthaloyl chloride (0.42 mmol, 85.26 mg in 1 ml of CH 2 Cl 2 ) to afford 5c as a white solid (212 mg, 84%) (5f, brown solid, 193 mg, 77%). 5a (0.51 mmol, 330 mg) and succinic acid 6 (0.51 mmol, 61 mg) were charged into a round-bottom flask with a mechanical stirring.…”

“…[22] We recently reported the synthesis of poly(ether)esteramides (PeEA) obtained from aminoalcohols based on isosorbide and isomannide, two isomers of 1,4:3,6-dianhydrohexitols. [23] The first step involved a solvent-free S N Ar affording mononitrophenyl-dianhydrohexitol intermediate followed by a reduction reaction. The obtained polymers exhibited interesting properties allying the ester and amide bond characters but the sequences were random affecting their thermal properties.…”

Catalyst‐Free Ring Opening Synthesis of Biodegradable Poly(ester‐urethane)s Using Isosorbide Bio‐Based Initiator

“…DMAP(99%) was purchased from Merck. ( 3S,6R )‐6‐(4‐aminophenoxy)hexahydrofuro[3,2‐b]furan‐3‐ol (Is‐AA) was synthesized as described earlier . Methanol (MeOH, 99.8%) was purchased from Honeywell and 1‐methyl‐2‐pyrrolidinone (NMP, 99%) was purchased from Scharlau.…”

“…To the best of our knowledge, no other research so far has used an aminoalcohol in a catalytic amount under metal‐free conditions for the synthesis of PCLs. However, we recently developed a new platform for the synthesis of building blocks and copolymers based on aminoalcohols derived from 1,4:3,6‐dianhydrohexitols in two to three steps . this platform has enabled us to carry out the following work.…”