Biocatalytic Synthesis of Furan-Based Oligomer Diols with Enhanced End-Group Fidelity

Abstract

The lipase-catalyzed synthesis of furan-comprising polyester oligomer diols (α,ω-telechelic diols) is reported. Oligofuranoate diols with excellent end-group fidelity and a yield of 95% were synthesized using a solvent-free two-stage polycondensation of dimethyl furan-2,5-dicarboxylate (DMFDCA) and 1,4-cyclohexanedimethanol (1,4-CHDM) using immobilized Candida antarctica Lipase B (CalB). Recycling of immobilized CalB to further decrease the production cost is successfully demonstrated. However, it showed limitation in the product yield that decreases ±20% with each additional reuse. The synthetic procedure has been scaled up, easily opening the possibility to use the developed diols in industrial polycondensations utilizing the excellent flame retardancy property and high thermal stability typical for furan-based polymers.

A Perspective on PEF Synthesis, Properties, and End-Life

“…With a similar aim for greener roots, Loos et al reported the use of enzymes as a catalyst for the synthesis of various PEF-related polymers from dimethyl 2,5-furandicarboxylate (DMFDC) or 2,5-bis(hydroxymethyl)furan (BHMF) (Jiang et al, 2014 , 2015b ; Skoczinski et al, 2020 ) ( Scheme 2 ). A high molecular weight furanic-aliphatic polyester ( = 23.7 kg mol −1 ) was successfully obtained from polycondensation of DMFDC with 1,10-decanediol (1,10-DDO), catalyzed by an immobilized Candida antartica Lipase B (Novozyme 435 or CALB) (Jiang et al, 2015b ).…”

“…These results imply that the catalytic activity of the enzyme still depends on the structural compatibility of the active site and the monomer transition state. Furthermore, a vast array of work on the enzyme-catalyzed synthesis of other furan-based polymers was also reported (Jiang et al, 2015a , 2016 ; Maniar et al, 2018 ) including furan based polyester diols with excellent end group fidelity for further polycondensation, (e.g., polyurethanes) (Skoczinski et al, 2020 ). With regard to the sustainability of the whole polymerization process and to address the issues in conventional PEF production, these reported studies have proven their importance as powerful approaches.…”

“…Besides renewability, other aspects of green polymer chemistry have also been addressed, mainly the green synthetic roots (Loos, 2010 ) by ring opening polymerization (Carlos Morales-Huerta et al, 2016 ; Rosenboom et al, 2018 ), or enzymatic-assisted synthesis (Jiang et al, 2014 , 2015a , b , 2016 ; Maniar et al, 2018 ; Skoczinski et al, 2020 ), despite the fact that the main synthetic route typically used for PEF production is a two-stage melt polymerization approach carried out under hard conditions and using metal-catalysts (Sipos, 2010 ; De Jong et al, 2012 ; Jiang et al, 2012 ; Jong et al, 2012 ; Ma et al, 2012 ; Knoop et al, 2013 ; Codou et al, 2014 ; Matsuo et al, 2014 ; Papageorgiou et al, 2014 ; Thiyagarajan et al, 2014 ).…”

Enzymatic Synthesis of Poly(alkylene succinate)s: Influence of Reaction Conditions

“…Numerous types of polymers prepared by enzymatic polymerization have been reported, among them polyphenols by enzymatic oxidative polymerization [3], polyaniline by enzymatic catalysis in presence of hydrogen peroxide [4], polysaccharides [5,6], vinyl polymerizates (being typically chain growth polymerizates) [7], a high number of differ-ent polyesters, polythioesters, polythioetheresters, polyphosphates, or polyketoetheresters obtained by ring-opening polymerization [8][9][10][11] or by polycondensation [12][13][14]. Polyesters and polyamides attracted particular attention, reflected by various studies [1,[15][16][17][18][19][20][21][22][23][24]. An advantage of enzymatic polycondensation is the possibility to polymerize monomers with reactive groups (e.g., oxirane and aromatic OH groups, double bonds like in itaconic acid [25][26][27], which would undergo side reactions under standard polycondensation conditions) resulting in polymers opening the opportunity for polymer-analogous reactions [12,15,25].…”

Enzymatic transesterification of urethane-bond containing ester

“…Although enzymes, especially lipases, are successfully used for many reactions in organic chemistry and also for polymerizations [17][18][19][20][21][22][23][24][25][26][27][28][29], they are not used so far for industrial polyurethane synthesis, as this method is still not efficient compared with that of classical production processes. However, regarding the demand of new variable polyurethanes with new properties for different applications, the interest of enzymes as biobased and environmentally friendly catalysts steadily increases [30,31].…”