Structure–Property Relations in New Cyclic Galactaric Acid Derived Monomers and Polymers Therefrom: Possibilities and Challenges

Wróblewska, Aleksandra A.; Noordijk, Jurrie; Das, Nick; Gerards, Chris; Wildeman, Stefaan M. A. De; Bernaerts, Katrien V.

doi:10.1002/marc.201800077

Cited by 5 publications

(8 citation statements)

References 27 publications

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“…The TGA analysis (Figure 4b) does not show any influence of the inhibitor on the degradation profiles of the polymers. They all start to degrade above 260 • C in an inert atmosphere and show 5% weight loss above 300 • C. All curves show that even with a rigorous drying step there is still insignificant weight loss observed at 100 • C, which is in line with our previous findings regarding water sorption of GalX polyamides [14]. The TGA analysis (Figure 4b) does not show any influence of the inhibitor on the degradation profiles of the polymers.…”

Section: Polymerizationsupporting

confidence: 89%

“…A recently published series of articles exhaustively describes the synthesis of polyamides from the diethyl esters (instead of the diacids) of sugar-derived cyclic acetal monomers ( Figure 1 a R=Et) in the melt [ 5 , 14 ]. Polymers with broader dispersities (branching) or even crosslinked networks were obtained with the less-substituted acetal monomer (GalXH) while better defined polymers were obtained with the more-substituted monomer (GalXMe).…”

Section: Introductionmentioning

confidence: 99%

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Radical Formation in Sugar-Derived Acetals under Solvent-Free Conditions

et al. 2021

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The degradation of acetal derivatives of the diethylester of galactarate (GalX) was investigated by electron paramagnetic resonance (EPR) spectroscopy in the context of solvent-free, high-temperature reactions like polycondensations. It was demonstrated that less substituted cyclic acetals are prone to undergo radical degradation at higher temperatures as a result of hydrogen abstraction. The EPR observations were supported by the synthesis of GalX based polyamides via ester-amide exchange-type polycondensations in solvent-free conditions at high temperatures in the presence and in the absence of radical inhibitors. The radical degradation can be offset by the addition of a radical inhibitor. The radical is probably formed on the methylene unit between the oxygen atoms and subsequently undergoes a rearrangement.

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Section: Polymerizationsupporting

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Radical Formation in Sugar-Derived Acetals under Solvent-Free Conditions

et al. 2021

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“…Furthermore, the alkylation of amine groups is a significant side reaction, which leads to the deactivation of reactive groups and ultimately has inhibiting effect on the polymerization. 16 , 25 , 51 If aliphatic esters are used during the aminolysis the reaction time needs to be elongated. Exposition of the polymerization mixture to elevated temperatures for elongated periods results in a higher cross-linking risk for GalX, more degradation and more alkylation of the amine functional groups.…”

Section: Introductionmentioning

confidence: 99%

Solvent-Free Method for the Copolymerization of Labile Sugar-Derived Building Blocks into Polyamides

Wróblewska

Stevens

Garsten

et al. 2018

ACS Sustainable Chem. Eng.

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This research focuses on the preparation of biobased copolyamides containing biacetalized galactaric acid (GalX), namely, 2,3:4,5-di-O-isopropylidene-galactaric acid (GalXMe) and 2,3:4,5-di-O-methylene-galactaric acid (GalXH), in bulk by melt polycondensation of salt monomers. In order to allow the incorporation of temperature-sensitive sugar-derived building blocks into copolyamides at temperatures below the degradation temperature of the monomers and below their melting temperatures, a clever selection of salt monomers is required, such that the sugar-derived salt monomer dissolves in the other salt monomers. The polymerization was investigated by temperature dependent FT-IR and optical microscopy. The structure of the obtained copolyamides was elucidated by NMR and matrix-assisted laser desorption ionization-time-of-flight (MALDI-TOF) techniques. The positive outcome of this modified polycondensation method depends on the solubility of sugar-derived polyamide salts in polyamide salts of comonomers and the difference between their melting temperatures, however does not depend on the melting temperature of the used sugar-derived monomer. A variety of comonomers was screened in order to establish the underlying mechanisms of the process.

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“…The most common combination for carbohydrate-based polymers is the synthesis of copolyesters of biacetalized galactaric acid derivatives with aromatic and aliphatic diols [14,15,17,29,30,31,32,33,34], and, more recently, GalX (co)polyamides [9,35,36]. The conducted research demonstrates that the successful copolymerization gives polyesters with improved properties (i.e., higher elongation at break) than pure carbohydrate-based polymers themselves [15].…”

Section: Introductionmentioning

confidence: 99%

“…Facing this lack of relevant scientific data, we want to initiate the research concerning the improvement of the properties of carbohydrate-based synthetic polymers, which could form the basis for the material development thereof. Such polymers deserve significant attention as they can offer a wide variety of advantageous properties, such as transparency or thermal properties for material design, but also the introduction of new functionalities [35]. However, as with all polymeric materials at the beginning of their development, broad investigation is required.…”

Section: Introductionmentioning

confidence: 99%

Towards High-performance Materials Based on Carbohydrate-Derived Polyamide Blends

et al. 2019

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A bio-derived monomer called 2,3:4,5-di-O-isopropylidene-galactarate acid/ester (GalXMe) has great potential in polymer production. The unique properties of this molecule, such as its rigidity and bulkiness, contribute to the good thermal properties and appealing transparency of the material. The main problem, however, is that like other biobased materials, the polymers derived thereof are very brittle. In this study, we report on the melt blending of GalXMe polyamides (PAs) with different commercial PA grades using extrusion as well as blend characterization. Biobased PA blends showed limited to no miscibility with other polyamides. However, their incorporation resulted in strong materials with high Young moduli. The increase in modulus of the prepared GalXMe blends with commercial PAs ranged from up to 75% for blends with aliphatic polyamide composed of 1,6-diaminohexane and 1,12-dodecanedioic acid PA(6,12) to up to 82% for blends with cycloaliphatic polyamide composed of 4,4′-methylenebis(cyclohexylamine) and 1,12-dodecanedioic acid PA(PACM,12). Investigation into the mechanism of blending revealed that for some polyamides a transamidation reaction improved the blend compatibility. The thermal stability of the biobased PAs depended on which diamine was used. Polymers with aliphatic/aromatic or alicyclic diamines showed no degradation, whereas with fully aromatic diamines such as p-phenylenediamine, some degradation processes were observed under extrusion conditions (260/270 °C).

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Structure–Property Relations in New Cyclic Galactaric Acid Derived Monomers and Polymers Therefrom: Possibilities and Challenges

Cited by 5 publications

References 27 publications

Radical Formation in Sugar-Derived Acetals under Solvent-Free Conditions

Radical Formation in Sugar-Derived Acetals under Solvent-Free Conditions

Solvent-Free Method for the Copolymerization of Labile Sugar-Derived Building Blocks into Polyamides

Towards High-performance Materials Based on Carbohydrate-Derived Polyamide Blends

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