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a¹H NMR of the synthesized PAFCHDM, including three possible byproducts; b¹³C NMR of PAFCHDM, which was dissolved in DMSO-d6; c DEPT spectrum of the PAFCHDM, DEPT spectroscopy is a type of carbon spectroscopy, is used to distinguish the primary carbon, secondary carbon, tertiary carbon and quaternary carbon
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In this research, bio-based polyamide (bio-PA) was synthesized from dimethyl furan-2,5-dicarboxylate and 1,3-cyclohexanedimethanamine by melt polymerization. The properties of bio-PA were analyzed by Fourier transform infrared spectrometer (FTIR), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), an...
Citations
... Full chemical characterization of the polyamides by nuclear magnetic resonance (NMR) spectroscopy ( Fig. 1c and Supplementary Figs. [1][2][3][4][5][6][7][8][9][10] and matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF-MS; Fig. 1d and Supplementary Fig. 11) be polymerized into high-molecular-weight polyamides due to intra-cyclization reactions at high temperatures. Even when direct solid-state polymerization is used to minimize these reactions, M n s of only 8 kDa are achieved 12 . ...
Sustainably producing plastics with performance properties across a variety of materials chemistries is a major challenge—especially considering that most performance materials use aromatic precursors that are still difficult to source sustainably. Here we demonstrate catalyst-free, melt polymerization of dimethyl glyoxylate xylose, a stabilized carbohydrate that can be synthesized from agricultural waste with 97% atom efficiency, into amorphous polyamides with performances comparable to fossil-based semi-aromatic alternatives. Despite the presence of a carbohydrate core, these materials retain their thermomechanical properties through multiple rounds of high-shear mechanical recycling and could be chemically recycled. Techno-economic and life-cycle analyses suggest selling prices close to those of nylon 66 with a reduction of global warming potential of up to 75%. This work illustrates the versatility of a carbohydrate moiety to impart performance that can compete with that of semi-aromatic polymers across two important materials chemistries.
... 2,5-Furandicarboxylic acid (FDCA), as a rigid monomer, is generated from biomass-derived 5-(hydroxymethyl) furfural (5-HMF) [17][18][19]. Dimethyl furan-2,5-dicarboxylate (DMFDCA) synthesized by esterification of the FDCA can often avoid the problem of decarboxylation of the FDCA in the polymerization process [20,21]. 1,4-Butanediamine (1,4-BDA) [22] and 1,5-pentanediamine (PMD) [2,23] are readily produced from biomass feedstocks. ...
Furan semi-aromatic polyamides have become a biobased substitute for existing petrochemical semi-aromatic polyamides and received more and more attention. In this study, a series of high-performance biobased furan polyamides with different diamine chain lengths (Poly(butylene furanamide) (PA4F), Poly(pentylene furanamide) (PA5F), Poly(hexamethylene furanamide) (PA6F), Poly(octamethylene furanamide) (PA8F) and Poly(dodecamethylene furanamide) (PA12F)) were successfully prepared; Except for PA4F, other resins could be synthesized by one step bulk polymerization. Meanwhile, the effect of diamine chain length was studied. Except for PA4F they were amorphous which was confirmed by IR, XRD and DSC analysis. PA12F to PA5F had high weight-average molecular weights (Mw) ranging from 34,000 to 65,500 g/mol, number-average molecular weight (Mn) ranging from 6100 to 26,300 g/mol, glass transition temperature (Tg) ranging from 89 to 138 ℃ and temperature of decomposition at 5% mass loss (Td-5%) from 357 to 408 ℃. The Tg of PA4F reached as high as 142 ℃. The tensile strength of PA12F, PA8F and PA5F was obtained for the first time, and reached up to 45, 62 and 84 MPa, respectively. The tensile strength of PA6F was also high at 74 MPa. The α relaxation temperatures of PA12F to PA5F were also high, up to 107, 136, 146 and 158 ℃, respectively.
... While the T d-max values of samples in Fig. 2e show that the T d-max value of sample 3 (620 °C) is higher than sample 2 (570 °C) and sample 1 (520 °C). The high heat resistance is directly related to the heterogeneity of sample [31,32]. ...
2,5-furandicarboxylic acid (FDCA), one of the most important building blocks, has attracted tremendous concerns, and the routes for FDCA synthesis from non-edible hemicellulose are of vital importance from the views of the circular economy. Herein, a multistep process towards hemicellulose-to-FDCA conversion is proposed, including hemicellulose-to-furfural conversion and sequential oxidation to furoic acid (FA), following with cesium furoate (FA-Cs) preparation and its direct carboxylation with carbon dioxide (CO2). The overall conversion yield of the targeted FDCA product towards the hemicellulose-to-FDCA pathway reaches 29.6%. Many efforts are made on the direct carboxylation reaction of FA-Cs with CO2 using Cs2CO3 as a catalyst. Results show that FDCA with 56.47% yield is achieved via direct carboxylation of FA-Cs at 290 °C for 12 h with 40 mL/min of flowing CO2. Different from the previous reports, it is demonstrated that drying methods of FA-Cs show significant effects on the yield and properties of the targeted FDCA product. It is found that the conventional drying method is more suitable than the vacuum drying method. From the putative reaction mechanism, the roles of CO2 and Cs2CO3 are elucidated. CO2 plays a direct role in carboxylation reaction, and excessive Cs2CO3 can deteriorate FDCA yield due to the occurrence of decomposition. Interestingly, biochar generated during carboxylation reaction is a promising potential adsorbent, which can efficiently adsorb methylene blue with a removal rate of 96% and an adsorption amount of 80 mg/g. This present work can provide an integrated strategy for both hemicellulose valorization and CO2 utilization in future.
... In recent years, there are few literatures about furan polyamide. The relevant studies are primarily focus on the synthesis and properties [18][19][20][21][22][23][24][25], degradation [26], enzymatic polymerization kinetics [27] and computational study [28], foaming [29]. Some papers demonstrated furan unit inhibited crystallization due to the high density of the random hydrogen bondings and π-π stackings of furan rings [20], which caused polyamide without high heat resistance. ...
... More importantly, the end amino groups after methylation still could react with esters to form amides in solid state polycondensation, which is different from the previous literatures. Ma et al. [18] reported that the N-methylation blocks the terminal amino group and the steric hindrance increases, leads to the termination of reaction or the reduction of reaction activity, resulting in the low molecular weight of polyamide. Meanwhile, it was found that samples synthesized at high catalyst dosage in bulk polymerization had obvious end groups signals(-CH 2 -NH 2 ), especially samples PA5T-3Cat and PA5T-4Cat, which revealed higher reaction rate at high catalyst amount lead more by-product methanol being taken out of the reaction system so that leaving more end amino groups. ...
The biobased monomers have been widely used to address climate change and biodiversity loss. In this study, the high heat-resistant poly(pentamethylene terephthalamide) (PA5T) and furan copolymer poly(pentamethylene terephthalamide/pentamethylene furanamide) (PA5T/5F) were synthesized successfully. Importantly, the 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)-catalyzed bulk polymerization combining the solid state polycondensation (SSP) as a facile, green and robust route was chosen. The PA5T and PA5T/5F had high melting temperatures at 350.8 and 309.8 °C, respectively. Besides, their initial decomposition temperatures, evaluated as the temperature at 5% mass loss (T5%) were at 420.0 and 413.2 °C, respectively, higher than melting temperatures, which demonstrated that furan unit had considerable thermal stability with benzene ring and they had great melt processing without thermal decomposition. It was first found that end amino groups after side reaction of N-methylation still could react with esters to form amides in solid state polycondensation. Additionally, the non-isothermal crystallization kinetics of PA5T and PA5T/5F were systematically studied by Jeziorny method and Mo method. It is found that crystallization rate of PA5T was greater, and the crystallization activation energy of PA5T/5F determined by the differential isoconversional method of Friedman was larger at the same relative crystallinities.
The strong interaction between Ru and –NH 2 in Ru/NH 2 –Al 2 O 3 led to the formation of highly dispersed Ru and modification of its electronic properties, and consequently greatly enhanced its performance and stability.
Semi-aromatic polyamides (SAPs) synthesized from petrochemical diacids and diamines are high-performance polymers that often derive their desirable properties from a high degree of crystallinity. Attempts to develop partially renewable SAPs by replacing petrochemical diacids with biobased furan-2,5-dicarboxylic acid (FDCA) have resulted in amorphous materials or polymers with low melting temperatures. Herein, we report the development of poly(5-aminomethyl-2-furoic acid) (PAMF), a semicrystalline SAP synthesized by the polycondensation of CO2 and lignocellulose-derived monomer 5-aminomethyl-2-furoic acid (AMF). PAMF has glass-transition and melting temperatures comparable to that of commercial materials and higher than that of any previous furanic SAP. Additionally, PAMF can be copolymerized with conventional nylon 6 and is chemically recyclable. Molecular dynamics (MD) simulations suggest that differences in intramolecular hydrogen bonding explain why PAMF is semicrystalline but many FDCA-based SAPs are not.
Three bio-based isosorbide bis(acid ester)s were synthesized by condensation of isosorbide with three symmetrical cyclic anhydrides (namely, succinic, diglycolic and phthalic anhydrides). The isosorbide-based diacids were obtained in high yields (79–97%) and converted to their diacid dichloride derivatives, which were then utilized to design series of bio-based polyester and poly(ester amide)s with wide range of thermal properties. The polyesters were synthesized in o-dichlorobenzene, utilizing either cis/trans-1,4-cyclohexanediol or 1,6-hexanediol, the polyesters were obtained in high yields (78–91%), showed good thermal stabilities, excellent solubility in organic solvents and glass transition temperatures in the range of -13.7 to 102.8 °C. Additionally, a series of novel aliphatic poly(ester amide)s was synthesized interfacially by polyamidation of the isosorbide bis(diglycolic acid) or isosorbide bis(succinic acid) derivatives with either trans-1,4-diaminocyclohexane or 1,6-hexanediamine. The aliphatic poly(ester amide)s obtained showed good thermal stabilities, good solubility in organic solvents and glass transition temperatures up to 129 °C.
Biobased polymers hold the promise of addressing climate change and biodiversity loss due to deriving from renewable carbon. Dimethyl furan-2,5-dicarboxylate as a biobased monomer is potential alternative of terephthalic acid and has been widely used to produce biobased polyesters or polyamides. In this study, excellent performance of poly(decamethylene furanamide) (PA10F) was synthesized via bulk polymerization with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst. PA10F produced at 200 °C as well as 0.05 MPa, weight-average molecular weight, glass transition temperature (Tg) and initial decomposition temperature (Td-5%) were up to 62500 g/mol, 103 °C and 401 °C, respectively. Furthermore, the mechanical properties were also outstanding with the maximum tensile strength of about 54.46 MPa, elongation at break of about 138.60 %, and tensile modulus of about 1454 MPa. According to the result of X-ray diffraction analysis, the PA10F was amorphous.
