Data on synthesis and characterization of new diglycerol based environmentally friendly non-isocyanate poly(hydroxyurethanes)

This article contains original experimental data, figures and methods to the preparation of non-isocyanate poly(hydroxyurethanes) by an environmentally friendly method without the use of toxic phosgene and isocyanates from bis(2,3-dihydroxypropyl)ether dicarbonate and various diamines (Tryznowski et al., Submitted for publication) [1]. Bis(2,3-dihydroxypropyl)ether dicarbonate was obtained from a one-step procedure from commercially available diglycerol. The product was characterized by 1H NMR, 13C NMR, and FTIR spectroscopies and for the first time by X-Ray diffraction measurements. Then, the bis(cyclic carbonate) monomer was used as a precursor for the synthesis of various NIPUs. The NIPUs were prepared in a non-solvent process. Spectral and thermal properties of the NIPUs are compered. Here we give the procedure in order to perform bis(2,3-dihydroxypropyl)ether dicarbonate with high yield and the procedure NIPU synthesis and the complete set of monomer and NIPU analysis (1H NMR, 13C NMR, FTIR, X-Ray).


Value of the data
The data shows one-step procedure of synthesis of five-membered bis(cyclic carbonate)-bis(2,3dihydroxypropyl)ether dicarbonate from commercially available diglycerol with high yield.
The data shows the X-Ray structure of the obtained bis(cyclic carbonate). The data shows the use of bis(2,3-dihydroxypropyl)ether dicarbonate as a monomer for the preparation of poly(hydroxyurethanes) in a reaction with various diamines by a solvent-free green route.

Instrumentation
Obtained products five-membered bis(cyclic carbonate) and NIPUs were characterized according well known methods as presented in [1].
FTIR spectra were recorded on a Biorad FTS-165 FTIR spectrometer as KBr pellets or an Bruker ALPHA FTIR spectrometer equipped with a Platinum ATR single reflection diamond ATR module. 1 H NMR and 13 C NMR spectra were recorded on a Varian VXR 400 MHz spectrometer using tetramethylsilane as an internal standard and deuterated solvents (CDCl 3 , DMSO-d 6 ) and analyzed with MestReNova v.6.2.0-7238 (Mestrelab Research S.L) software. The X-ray measurement was performed at 100(2)K on a Bruker D8 Venture Photon 100 CMOS diffractometer equipped with a mirror monochromator and a CuKα INCOATEC IμS micro-focus source (λ¼ 1. 54178 Å). The raw frame data were collected using the Bruker APEX2 program [2] while the frames were integrated with the Bruker SAINT software package [3] using a narrow-frame algorithm integration of the data and were corrected for absorption effects using the multi-scan method (SADABS) [4]. The non-hydrogen atoms were refined anisotropically. All hydrogen atoms were placed in their calculated positions and refined within the riding model. The atomic scattering factors were taken from the International Tables [5].
Bis(2,3-dihydroxypropyl)ether dicarbonate, 2 was prepared by a reaction of commercially available diglycerol (Solvay) and dimethyl carbonate (Scheme 1). The five-membered bis(cyclic carbonate) was obatined with a 79% yield in contrast to the multistep procedure described previously in the literature [6,7]. The formation of the five-membered cyclic carbonates was confirmed by FTIR spectroscopy (see Fig. 1 in Ref. [1]), 1 H NMR and 13 C NMR (Fig. 1). The structure of the product was determined by single-crystal X-Ray diffraction (Fig. 2). The thermal properties of 2 were characterized by DSC and TGA.

Synthesis of NIPU
In a typical run, NIPUs were synthesized by the reaction of five-membered bis(cyclic carbonate) 2 with various diamines (see Scheme 2 or Table 1 in Ref. [1]). 54.5 g (0.25 mol) of bis(cyclic carbonate) was placed in a 250 mL round bottom flask equipped with a mechanical stirrer and a nitrogen inlet. The solid was melted under nitrogen atmosphere at 80°C. Then 0.25 mol of an appropriate diamine (see Table 1 in Ref. [1]) was added in portions during 30 min and the temperature increased up to 150°C. The reaction mixture was stirred at this temperature for 8 h. Then the reaction mixture was cooled down and the polymers analyzed without further purification.    The obtained bis(cyclic carbonate) was used as a monomer for the synthesis of non-isocynate poly (hydroxyurethane)s via a polyaddition reaction with various diamines: aliphatic ones, oligoetherdiamines and, for comparison, aromatic diamines (Scheme 2). The polyaddition reactions were carried out by a solvent-free and catalyst-free method. The reaction of bis(cyclic carbonate) with diamines was monitored by IR spectroscopy The formation of NIPU confirmed by 1 H NMR and 13 C NMR (Fig. 3). The properties of obtained NIPU 9-NIPU 10 are showed in [1] (Table 2).