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One-Pot FDCA Diester Synthesis from Mucic Acid and Their Solvent-Free Regioselective Polytransesterification for Production of Glycerol-Based Furanic Polyesters

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One-Pot FDCA Diester Synthesis from Mucic Acid and Their Solvent-Free Regioselective Polytransesterification for Production of Glycerol-Based Furanic Polyesters molecules Article One-Pot FDCA Diester Synthesis from Mucic Acid and Their Solvent-Free Regioselective Polytransesterification for Production of Glycerol-Based Furanic Polyesters Deyang Zhao 1,2, Frederic Delbecq 3 and Christophe Len 1,2,* 1 Sorbonne Universités, Université de Technologie de Compiègne, Centre de Recherches de Royallieu, CS 60319, F-60203 Compiègne CEDEX, France; [email protected] 2 PSL Research University, Chimie ParisTech, CNRS, Institute of Chemistry for Life and Health Sciences, 11 rue Pierre et Marie Curie, F-75231 Paris CEDEX 05, France 3 Ecole Supérieure de Chimie Organique et Minérale, 1 allée du Réseau Jean-Marie Buckmaster, F-60200 Compiègne, France; [email protected] * Correspondence: [email protected]; Tel.: +33-(0)638-500-976; Fax: +33-(0)344-971-591 Received: 17 February 2019; Accepted: 8 March 2019; Published: 15 March 2019 Abstract: A one pot-two step procedure for the synthesis of diethyl furan-2,5-dicarboxylate (DEFDC) starting from mucic acid without isolation of the intermediate furan dicarboxylic acid (FDCA) was studied. Then, the production of three different kinds of furan-based polyesters— polyethylene-2,5-furan dicarboxylate (PEF), polyhydropropyl-2,5-furan dicarboxylate(PHPF) and polydiglycerol-2,5-furandicarboxylate (PDGF)—was realized through a Co(Ac)2·4H2O catalyzed polytransesterification performed at 160 ◦C between DEFDC and a defined diol furan-based prepolymer or pure diglycerol. In parallel to polymerization process, an unattended regioselective 1-OH acylation of glycerol by direct microwave-heated FDCA diester transesterification led to the formation of a symmetric prepolymer ready for further polymerization and clearly identified by 2D NMR sequences. Furthermore, the synthesis of a more soluble and hydrophilic diglycerol-based furanic polyester was also achieved. The resulting biobased polymers were characterized by NMR, FT-IR spectroscopy, DSC, TGA and XRD. The morphologies of the resulted polymers were observed by FE-SEM and the purity of the material by EDX. Keywords: mucic acid dehydration; FDCA diesters; regioselective transesterification; poly-transesterification 1. Introduction Furandicarboxylic acid (FDCA) is recognized as one of the twelve building-block chemicals by the US Department of Energy. This aromatic compound is easily synthesized through the dehydration of fructose to hydroxymethylfurfural (HMF) under acidic conditions and then peroxidation using various oxidants in one-pot one-step and one-pot two-step reactions (Scheme1)[ 1–4]. The direct conversion of HMF to FDCA is technically feasible, but faces problems of cost, stability and availability. Catalytic oxidation of HMF to FDCA using homogeneous catalysis was reported but these processes were less attractive as compared with heterogeneous catalysis due to the separation and recycling problems [5–7]. Modern heterogeneous catalysts such as nanosized bimetallic catalysts could also become a good alternative for the FDCA production [5,8–10]. Using homogeneous catalyst or heterogeneous catalyst the main limitation of the process remains the cost of HMF itself. In fact, this furanic intermediate is industrially produced in moderate yields by the dehydration of hexoses (fructose and glucose) isolated as sub-units from the depolymerization of polysaccharides such as Molecules 2019, 24, 1030; doi:10.3390/molecules24061030 www.mdpi.com/journal/molecules Molecules 2019, 24, x FOR PEER REVIEW 2 of 15 Molecules 2019, 24, 1030 2 of 15 In fact, this furanic intermediate is industrially produced in moderate yields by the dehydration of hexoses (fructose and glucose) isolated as sub-units from the depolymerization of polysaccharides cellulose or starch [11,12]. Nowadays, it appears important to find more efficient pathway to access such as cellulose or starch [11,12]. Nowadays, it appears important to find more efficient pathway to FDCA analogs. One of the most promising routes should be the dehydration of mucic acid in the access FDCA analogs. One of the most promising routes should be the dehydration of mucic acid in presence of strong mineral acid (H2SO4,H3PO4, HBr) [13] or para-toluenesulfonic acid (PTSA) [14]. the presence of strong mineral acid (H2SO4, H3PO4, HBr) [13] or para-toluenesulfonic acid (PTSA) Mucic acid offers the advantage of having two carboxylic acid groups. [14]. Mucic acid offers the advantage of having two carboxylic acid groups. SchemeScheme 1.1.Different Different ways ways for thefor production the production of 2,5-furandicarboxylic of 2,5-furandicarboxylic acid starting acid from lignocellulose.starting from lignocellulose. FDCA is often employed as one of the components for the preparation of linear or branched polyestersFDCA showing is often relevantemployed thermal as one and of mechanicalthe componen propertiests for the [15 preparation]. FDCA polyesters of linear express or branched good biocompatibilitypolyesters showing with relevant the human thermal body. and Thesemechanical polymers properties are expected [15]. FDCA to be polyesters useful in aexpress near future good inbiocompatibility the field of commodity with the thermoplastichuman body. These engineering polymers polymers are expected like the to well-exploited be useful in a near polyethylene future in terephthalatethe field of commodity (PET). More thermoplastic exactly, FDCA engineering is used to polymers replace the likep-terephthalic the well-exploited acid (PTA), polyethylene which is overallterephthalate an oxidation (PET). More product exactly, of p-xylene, FDCA anis used aromatic to replace compound the p-terephthalic issued from acid refined (PTA), oil. which Besides, is PEToverall is mainly an oxidation composed product of two of Y-X-Yp-xylene, type an monomers: aromatic compound PTA and ethylene issued glycolfrom refined (EG). In oil. case Besides, of EG, thisPET diolis mainly is now composed a biobased of buildingtwo Y-X-Y block type generated monomers: by PTA the biochemical and ethylene transformation glycol (EG). In of case D-xylose. of EG, Thethis polymerizationdiol is now a biobased of FDCA building or its counterparts block generated with by EG the is alreadybiochemical set up transformation in industry for of producing D-xylose. polyethylene-2,5-furanThe polymerization of FDCA dicarboxylate or its counterparts (PEF) for commercialwith EG is already applications set up suchin industry as beverage for producing bottles. Frompolyethylene-2,5-furan a physicochemical dicarboxylate point of view (PEF) PEF isfor a polyestercommercial of higherapplications glass transitionsuch as beverage and structurally bottles. ◦ lessFrom linear a physicochemical than PET due point to the of angle view ofPEF 129 is aformed polyester between of higher the glass two consecutivetransition and ester structurally function holdless linear by the than furan PET rings. due Onto the the angle other of hand, 129° form fromed a technicalbetween the point two of consecutive view, except ester the veryfunction classical hold meltingby the furan polycondensation rings. On the of other FDCA hand, mixed from with a ate diolchnical [16 ],point to access of view, to these except polymers the very the classical furanic diacidmelting need polycondensation to be activated of leadingFDCA mixed to the with formation a diol of[16], its to corresponding access to these furan-2,5-dicarboxylic polymers the furanic aciddiacid dichloride need to be (FDCC) activated [17 leading,18], but to the the process formation requires of its corresponding hazardous chlorination furan-2,5-dicarboxylic reagents such acid as phosphorousdichloride (FDCC) pentachloride [17,18], orbut thionyl the process chloride. requir Oncees hazardous the diacyl chlorination chloride derivative reagents is such formed, as itphosphorous could react withpentachloride various diolsor thionyl or diamines chloride. to formOnce theirthe diacyl respective chloride polyesters derivative and is polyamides, formed, it butcould the react main with problem various of FDCCdiols or accessibility diamines to is causedform their by therespective low solubility polyesters of FDCA and polyamides, in the common but organicthe main solvents. problem Inof comparison,FDCC accessibility the diesters is caused of FDCA by the are low easier solubility to handle of FDCA and far in morethe common soluble andorganic could solvents. react withIn comparison, various diols the diesters in presence of FDCA of catalysts are easier such to handle as tetraalkyl and far more titanates soluble [19– and21], tincould (II) react 2-ethylhexanoate with various [22diols,23 ],in antimony presence trioxideof catalysts (III) such [24–30 as] buttetraalkyl always titanates active at [19–21], temperatures tin (II) superior2-ethylhexanoate to 200 ◦C. [22,23], A recent antimony paper reported trioxide the(III) use [24–30] of 1,8-diazabicyclo but always active [5.4.0]undec-7-ene at temperatures (DBU) superior as anto organocatalyst200 °C. A recent to performpaper reported the polytransesterification the use of 1,8-diazabicyclo of FDCA [5.4.0]undec-7-ene dimethyl ester (DMFDC) (DBU) inas thean presenceorganocatalyst of EG [to31 ].perform Another the strategy polytransesterific to synthesizeation PEF involvesof FDCA the dimethyl polymerization ester (DMFDC) of a prepolymer in the namedpresence bis(hydroxyethyl)-2,5-furandicarboxylate of EG [31]. Another strategy to synt (BHEFDC)hesize PEF [32]. Thisinvolves material the ispolymerization obtained by reaction of a Molecules 2019, 24, x FOR PEER REVIEW 3
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