Mariusz Tryznowski

A PS-DES immobilized ruthenium carbene: a robust and easily recyclable catalyst for olefin metathesis

The butyldiethylsilyl polystyrene (PS-DES) supported ruthenium carbene 7 is a robust, practical and easily recyclable catalyst for olefin metathesis of substituted olefins.

Synthesis, characterization and reactivity of a six-membered cyclic glycerol carbonate bearing a free hydroxyl group

Five- and six-membered cyclic carbonates have recently become popular as starting materials for the synthesis of polycarbonates via ring opening polymerization or synthesis of environmentally friendly non-isocyanate polyurethanes. In many cases a five-membered glycerol carbonate has been used in these applications. However, the simplest derivative of glycerol, a six-membered cyclic glycerol carbonate (5-hydroxy-1,3-dioxan-2-one), has not been reported so far. In this work, for the first time, we report a procedure for the synthesis of this monomer from glycerol. The product was characterized by 1H NMR, 13C NMR, and FTIR spectroscopy and X-ray diffraction measurements. Further, the synthesis of bis(2-oxo-1,3-dioxan-5-yl) sebacate, a biscyclic six-membered carbonate, was described. The reactivities of 5-hydroxy-1,3-dioxan-2-one and its biscyclic ester derivative were investigated. No ring opening polymerization of both the monomers was observed, instead an isomerization to appropriate five-membered cyclic carbonates occurred. Unfortunately, the protection of the hydroxyl group 2 with an ester type substituent does not protect it against isomerisation.

Wood adhesive application of poly(hydroxyurethane)s synthesized with a dimethyl succinate-based amide backbone

Non-isocyanate poly(hydroxyurethane)s (PHUs) made by reacting bis(cyclic carbonate)s and amines are important alternatives to conventional polyurethanes. In this work, a series of PHUs was synthesized using a solvent-free, catalyst-free method from bis(2,3-dihydroxypropyl)ether dicarbonate and 1,3-diaminopropane using differing molar ratios of dimethyl succinate to change selected properties of each PHU. The obtained PHUs were characterized by FT-IR, 1H NMR and 13C NMR spectroscopy and their thermal properties and viscosities were determined. We report the use of the obtained PHUs as wood adhesives and the work of adhesion data determined using Owens–Wendt method. The mechanical properties (strength) of different PHU–wood joints were compared. It was found that the addition of dimethyl succinate increases the hydrophobicity of coatings by increasing the water contact angle and decreasing the polar component of the surface free energy of the PHU coatings. PHUs with urethane and amide backbones were stronger than those without.

Hyperbranched polyglycerol as an additive for water-based printing ink

In this work, the application of hyperbranched polyglycerol as a performance additive for water-based printing inks is demonstrated. The hyperbranched polyglycerol, (BPG), was synthesized through anionic ring-opening polymerization from glycidol using 1-butanol as the starting material. The branched structure of BPG is presented and described. The presence of linear, dendritic and terminal units was confirmed by Moore et al. (Prog Surf Sci 88(3):213–236, 2013) 13C NMR spectroscopy. BPG was then used as a performance additive in a water-based flexographic printing ink. The impact of a small amount of hyperbranched BPG on the printing ink color was examined by studying the optical density of a full-tone area, the total color difference, ΔEab*, and the gloss of the dried ink film. The colorfastness to dry and wet rubbing of overprinted samples was studied. The investigated BPG is shown to be able to improve colorfastness to dry and wet rubbing of prints.

Novel high reactive bifunctional five- and six-membered bicyclic dicarbonate – synthesis and characterisation

Five- and six-membered bicyclic carbonates are valuable raw materials for the synthesis of environmentally friendly polymers, such as polycarbonates or non-isocyanate poly(hydroxyurethane)s. However, bicyclic diglycerol dicarbonates bearing five-membered and six-membered rings have been never reported before. In this work, for the first time, we report a simple procedure for the synthesis of this monomer from commercially available diglycerol. The product was characterised by 1H NMR, 13C NMR, FTIR spectroscopy and X-ray diffraction measurements. Next, the reactivity of the obtained bicyclic carbonate was investigated. The obtained diglycerol dicarbonate was used as a monomer for polycarbonate and non-isocyanate poly(hydroxyurethane) based on putrescine. In the homopolymerisation reaction the opening of the six-membered carbonate ring was observed, while in the polycondensation with diamine both carbonate rings open nonselectively.

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).