Cost-Effective Synthesis of High Molecular Weight Biobased Polycarbonate via Melt Polymerization of Isosorbide and Dimethyl Carbonate

Abstract

Green synthesis of poly­(isosorbide carbonate) (PIC) with remarkable properties is a huge challenge in industrial applications due to low molecular weight and harsh reaction conditions. We reported a novel pathway to synthesize high molecular weight PIC through melt polymerization of isosorbide (ISB) and dimethyl carbonate (DMC), which are derived from the biomass and CO2, respectively. The effects of metal ion-containing compound catalyst on chemical structures, terminal groups, and molecular weight of PIC in the process of melt polycondensation were studied. Compared with the best reported catalyst lithium acetylacetonate, the weight-average molecular weight (M w) of PIC was increased by using our preferred catalyst sodium tert-butoxide from 46 500 to 55 100 with the ISB conversion up to 99.0%, and the reaction time was decreased from 12 h to only 2.5 h, as far as we know, which is the highest M w value and the most efficient catalyst achieved by one-step method. According to the results of the experiment and simulation, we found that high catalytic performance was ascribed to the weak interaction energy of anion–cation of catalyst and the strong proton acceptance ability of the anion of the catalyst. Meanwhile, increasing the interaction energy of anion–cation of the catalyst could inhibit the occurrence of the methylation side reaction and interestingly the activated endohydroxyl groups of ISB were found to be more easily methylated. Finally, based on the captured and detected intermediates of the two-stages of the reaction, a possible mechanim for the synergetic effects of cation–anion through hydrogen bond formation was proposed.

En Route to CO2-Based (a)Cyclic Carbonates and Polycarbonates from Alcohols Substrates by Direct and Indirect Approaches

“…In this regard, a large range of catalysts was tested to selectively activate the endo or exo alcohol moieties and to prevent reactivity disparities that would considerably limit the molar mass of the PC. Among them, metal salts [202], metal alkoxides [203,204], inorganic carbonates [205], ionic liquids [206][207][208][209][210][211][212][213], organic bases [214] and others [215][216][217][218] enabled the facile construction of defect-free PCs derived from isosorbide with Mn values in the range of 14,000 to 55,000 g/mol. Carbonate metathesis polymerization principle catalyzed by K 2 CO 3 .…”

High Performance Biomass-Based Polyimides for Flexible Electronic Applications

“…In this study, we report a series of novel biobased PIs, PI­(ISBA-CBDA), PI­(ISBA-PMDA), and PI (ISBA-BPDA), prepared from a bioderived diamine, (3 R ,6 S )-hexahydrofuro­[3,2- b ]­furan-3,6-diyl bis­(4-aminobenzoate) (ISBA), and three dianhydrides of pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyl-tetracarboxylic acid dianhydride (BPDA), and cyclobutane-1,2,3,4-tetracarboxylic dianhydride (CBDA), which served as the substrate or dielectric for OFET devices. ISBA was derived from biobased isosorbide (ISB) and could be produced in a large scale. − Also, the dianhydride of CBDA can be simply obtained from fumaric acid, which is extracted from the biosource of Fumaria officinalis. − Furthermore, four Co-PIs of PI­(ISBA-C m B n ) with mole ratios of CBDA/BPDA, 95/5, 90/10, 85/15, and 80/20, were prepared to tune the thermal and mechanical properties for the electronic device applications, as shown in Scheme . The thermal, mechanical, optical, and dielectric properties of the studied biobased PIs were systematically investigated.…”

Synthesis and melt-spinning of partly bio-based thermoplastic poly(cycloacetal-urethane)s toward sustainable textiles

“…PlantBottle TM by Coca Cola), polylactic acid (PLA), 54,55 as well as many other sugar-based new polymers. 38,52,[56][57][58][59][60][61][62][63][64][65][66][67][68] Recently, a sugar-based platform molecule, 5-hydroxymethylfurfural (HMF), 69,70 was used to fabricate PAUs toward coating applications. 47 However, these PAUs were not readily suitable for textile investigations due to the relatively low thermal stability of the monomer, the presence of crosslinking, and the lack of flexible segments (as in Elastane fibres).…”