Short-process synthetic strategies of sustainable isohexide-based polyesters towards higher molecular weight and commercial applicability

Wang, Yaning; Wu, Jing; E, koning Cor; Wang, Huaping

doi:10.1039/d2gc02608b

Cited by 10 publications

(8 citation statements)

References 170 publications

(323 reference statements)

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“…We presumed that isosorbide undergoes degradation during the reaction leading to volatile by-products that could not be detected by NMR. 31,32 Indeed, a difficult balance was again found between selective functionalization and degradation pathways. To decrease the functional complexity of the substrate and to understand the formation of side products, exomonobenzylated isosorbide 1 was then considered as a model substrate (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

“…This type of degradation was already reported under acidic conditions, indicating once again the selectivity challenge in functionalizing this substrate. 31,34 The cutting edge issue was to find the appropriate balance between conversion and degradation/selectivity on a substrate that is difficult to handle. The use of other strong bases such as KOH or KHMDS led to the same conclusion.…”

Section: Resultsmentioning

confidence: 99%

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Ir–Na cooperativity controls the diastereoselectivity of borrowing hydrogen C–C alkylation on isosorbide: synthesis methodology and mechanistic investigation

et al. 2023

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Ir–Na cooperativity controls the diastereoselectivity of borrowing hydrogen C–C alkylation on isosorbide: synthesis methodology and mechanistic investigation

et al. 2023

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“…In the case of melting behaviors, the melting peaks of the copolyesters were 10–15 °C lower than those of homopolyesters. When the bioderived monomers, that replace the terephthalates, had bulky and asymmetric molecular structures, crystallizations of the terephthalate units were hindered by chain packing. , The melting temperatures were typically decreased and broadened with increases of the bioderivated units and, when the contents were greater than 30–40%, most of the copolyesters exhibited amorphous characteristics (Figure S8b). Also, the Ct-diester incorporated PET copolyesters showed decreases in T m with increase of the incorporated ratio .…”

Section: Resultsmentioning

confidence: 99%

Thermally Stable Biodegradable Polyesters with Camphor and Tartaric Acid Coupled Cyclic Diester Monomers for Controlled Hydrolytic Degradations

Kang

Lee

et al. 2023

ACS Appl. Polym. Mater.

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The development of biodegradable engineering plastics is challenging, because increases in biodegradability mostly degrade other material properties, such as mechanical and thermal properties of polymers. Here, we use bioderivatives of diester monomers, dimethyl (1S,4R)-1,7,7-trimethylspiro[bicyclo[2.2.1]heptane-2,2′-[1,3]dioxolane]-4′,5′-dicarboxylate (camphor dimethyl DL-tartrate, Ct diester), for the synthesis of phthalatebased copolyesters to enhance degradability without a notable loss of thermal stability. Ct diester synthesized by acetalization of tartaric acid and camphor contains a bridged type of rigid bicycling ring with high thermal stability and controlled degradation via hydrolysis of acetal groups within the spiro-ring structure. Various alkyl-length diols of ethylene, butylene, and hexylene are copolymerized with mixtures of dimethyl phthalate (DMT) and Ct diester in a 9:1 molar ratio. The glass transition temperature and degradation temperature of the copolyesters are comparable to those of DMT-based homopolyesters. Due to decreases in crystallinity, copolyesters exhibit slight decreases in melting temperature of 10 to 20 °C, which can be advantageous for reducing processing temperatures. Notably, the copolyesters demonstrate enhanced hydrolytic degradation of 9.3 to 26.2% in pH 2 environment for 18 days, as measured by the degree of molecular weight reductions. These values are between 1.7 and 3.5 times higher than the degradation rates of their control samples of DMT-based homopolyesters under the same degradation conditions.

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“…It has gained more attention and emerged as an renewable comonomer for high-performance polymeric materials . When the highly rigid bicyclic asymmetric structure of the IS building block is incorporated into the polymer, it dramatically enhances the T g of the materials. − The comonomer feed ratios were adjusted in each case to produce PESF copolymers with T g in the range of PET. The studies demonstrated that the incorporation of FDCA, BFDCA, or IS into PESF resulted in copolyesters with significantly enhanced T g values, which makes the reported copolyesters potentially more suitable for manufacturing heat-resistant drink bottles or food packaging materials than PESF.…”

Section: Introductionmentioning

confidence: 99%

High-Barrier Biobased Copolyesters with Targeted Glass Transition Temperatures as Renewable Alternatives for PET

Ahmed

Kainulainen

Sirviö

et al. 2023

ACS Appl. Polym. Mater.

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A series of amorphous furan-based copolyesters were investigated with the goal of matching the glass transition temperature (T g ) of poly(ethylene terephthalate) (PET) while providing an enhanced O 2 barrier. The biobased copolyesters were composed of dimethyl 5,5′-sulfanediyldi(furan-2-carboxylate) (DM-SFA) with either dimethyl 2,5-furandicarboxylate (DM-FDCA) or dimethyl 2,2′-bifuran-5,5′-dicarboxylate (DM-BFDCA) as the main monomers with ethylene glycol as the diol component. The furfural-based monomers DM-SFA and DM-BFDCA in roughly equimolar ratios provided copolyesters with T g in the range of PET, while also having low O 2 and UV-light permeabilities. With the 5-hydroxymethylfurfural-based DM-FDCA monomer, DM-SFA was adjusted to be the minor comonomer in the feed in order to provide PET-like T g for the copolyester. On the other hand, the O 2 permeabilities of these copolyesters were substantially lower, although the DM-FDCA monomer lacked the UV-blocking benefits of DM-BFDCA. Finally, isosorbide (IS) was also investigated as a possible T g -enhancing comonomer in conjunction with ethylene glycol and DM-SFA. However, thermal stability of the IS-containing copolyester was found to be lower, as indicated by thermogravimetric analysis. Incomplete dissolution after polycondensation was also observed, which was consistent with cross-linking under high-temperature conditions. Additionally, melt-pressed films did not completely yield at high temperatures during dynamic mechanical analysis, which contrasted with the behavior of the DM-FDCA and DM-BFDCA copolyesters. The DM-SFA/DM-BFDCA copolyesters were identified as especially interesting materials having relatively high glass transition temperatures while being completely amorphous and providing films with low O 2 and UV-light permeabilities. They are also notable for having most of their carbon derived from the renewable platform chemical furfural.

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Short-process synthetic strategies of sustainable isohexide-based polyesters towards higher molecular weight and commercial applicability

Abstract: Isohexides (1,4:3,6-dianhydrohexitols) represent a family of bio-based heterocyclic diols attracting over 40 years’ attention from both industry and academia. Their unique properties, including high structural rigidity, high hydrophilicity and distinct...

Cited by 10 publications

References 170 publications

Ir–Na cooperativity controls the diastereoselectivity of borrowing hydrogen C–C alkylation on isosorbide: synthesis methodology and mechanistic investigation

Ir–Na cooperativity controls the diastereoselectivity of borrowing hydrogen C–C alkylation on isosorbide: synthesis methodology and mechanistic investigation

Thermally Stable Biodegradable Polyesters with Camphor and Tartaric Acid Coupled Cyclic Diester Monomers for Controlled Hydrolytic Degradations

High-Barrier Biobased Copolyesters with Targeted Glass Transition Temperatures as Renewable Alternatives for PET

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