A fully bio-based polyimine vitrimer derived from fructose

Abstract

A bio-based polyimine vitrimer containing 100% renewable carbon content has been synthesised and characterised, based on bio-based furan dialdehyde derived from fructose.

Renewable Responsive Systems Based on Original Click and Polyurethane Cross‐Linked Architectures with Advanced Properties

“…[32] Compared with conventional academic epoxidation based on meta-chloroperoxybenzoic acid as an oxidizing agent in solvent, [33] in situ epoxidation uses milder oxidizing agentsa nd globallya dheres better to green chemistry principles. The FTIR spectrum of FMOO ( Figure 1c)s hows the disappearance of the double bond at ñ = 3009 cm À1 .F rom 1 HNMR spectroscopic analysis (Figure 2c), the structure is confirmed by the disappearance of the vinyl and allyl protons at d = 5.35 and 1.99 ppm, respectively,a nd by the appearance of epoxide and protons alpha to the epoxidesa td = 2.90 and 1.45 ppm, respectively.The results of 13 CNMR spectroscopic analysisofF MOO agreedw ith the assigneds tructure (FigureS2i nt he Supporting Information).…”

“…The FTIR spectrum ( Figure 1d)e xhibits ab road stretchf or the hydroxyl groups at ñ = 3440 cm À1 .T he FO structure was furtherc onfirmed by 1 HNMR spectroscopic analysis( Figure 2d)b yt he disappearance of the epoxide protons and protons alpha to the epoxides at d = 2.90 and 1.45 ppm, respectively,a nd the appearance of the polyether backboneb etween d = 3.00 and 3.60 ppm (for detailed integration, see Figure S3 in the Supporting Information). By 13 C and DEPT 135 13 CNMR spectroscopy (Figures S4 and S5 in the Supporting Information, respectively), carbon atoms associated with the polyether backbone, correspondingt oe ther and carbon containing secondary hydroxyl groups, clearly appear. Concurring with Lligadas et al, [34] water was introduced into the oligomerization synthesis to suppress macrocyclization.…”

“…All NMR spectra were recorded on aB ruker Ascend 400 or 500 MHz spectrometer.S amples were dissolved in CDCl 3 or [D 6 ]DMSO with concentrations varying from 8-10 to 20-30 mg mL À1 for 1 Ha nd 13 CNMR spectroscopy,r espectively.T he number of scans was set to 128 for 1 HNMR spectroscopy and 2048 for 13 CNMR spectroscopy.T he calibration of 1 Ha nd 13 CNMR spectra was performed by using the chloroform signals at d = 7.26 and 77.16 ppm, respectively,and DMSO signal at d = 2.50 ppm. 31 PNMR spectroscopic analysis was performed on FO and polyester polyol samples phosphytilated with CL-TDP.C holesterol was used as an internal standard, as described in standard protocols.…”

“…Cross‐linked polymers containing reversible covalent bonds are defined as covalent adaptive networks (CANs) and can be further subdivided in two categories: dissociative and associative systems. Associative CANs consist of bond exchange between polymer chains, in which the overall cross‐linking density is preserved because a new covalent bond can only be formed if another has been broken, such as vitrimers, which can also be biobased . Dissociative CANs consist of chemical bond exchanges in which bonds are first broken and then formed again in another place.…”

“…Associative CANs consist of bond exchange betweenp olymer chains,i n which the overall cross-linking density is preservedb ecause a new covalent bond can only be formed if another has been broken, such as vitrimers, [12] which can also be biobased. [13] Dis-sociativeC ANs consist of chemical bond exchanges in which bonds are first broken and then formeda gain in another place. Reversible covalent bonds, such as the DA reaction [14] or An ew chemical architecture from oleic acid, consisting of a diol structure containing pendantf uran rings, denoted the furan oligomer (FO) was synthesized and fully characterized.…”