Renewable (semi)aromatic polyesters from symmetrical vanillin-based dimers

Llevot, Audrey; Grau, Étienne; Carlotti, Stéphane; Grelier, Stéphane; Cramail, Henri

doi:10.1039/c5py00824g

Cited by 138 publications

(100 citation statements)

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“…At the same time, the thermal properties can be tuned depending on the erythritol ( E ) feed, the nature of the dialdehyde, and the balance tetraol. The T g values match or exceed those of many other bioaromatic polymers, such as the polyester reported from the condensation of dimethyl succinate and methylated/reduced bis‐vanillin, which bears a T g of 68 °C …”

Section: Resultssupporting

confidence: 61%

Sustainable polyacetals from erythritol and bioaromatics

Rostagno

Price

Pemba

et al. 2016

J of Applied Polymer Sci

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The polymerization of biorenewable molecules to polymers with hydrolyzable main‐chain functionality is one approach to identifying sustainable replacements for common, environmentally unsound packaging plastics. Bioaromatic polyacetals were synthesized via acid‐catalyzed acetal formation from dialdehydes and tetraols. Ethylene linked dialdehyde monomers VV and SS were constructed from bioaromatics vanillin and syringaldehyde, respectively. Tetraol monomers included biogenic erythritol (E), along with pentaerythritol (P), and ditrimethylolpropane (D). Four copolymer series were prepared with varying tetraol content: E/P‐VV; E/D‐VV; E/P‐SS; and E/D‐SS. Number average molecular weights (Mn) ranged from 1,400 to 27,100 Da. Generally, the copolymerization yields were inversely proportional to the feed fraction of erythritol (E), implying that tetraols P and D react more readily. The materials were typically amorphous and exhibited glass transition temperatures (Tg) ranging from 57 to 159 °C, suitably mimicking the Tg values of several commodity plastics. The syringaldehyde‐based copolymers exhibited a higher Tg range (71–159 °C) than the vanillin‐based copolymers (57–110 °C). Accelerated degradation studies in aqueous HCl (3 M, 6 M, concentrated) over 24 h showed that degradation (Mn decrease) was proportional to the acid concentration. A one‐year degradation study of E50/D50‐SS (from 50% feed of erythritol) in seawater, deionized water, tap water, or pH 5 buffer showed no Mn decrease; but in pH 1 buffer, the decrease was 40% (18,800 to 11,200). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44089.

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Section: Resultssupporting

confidence: 61%

Sustainable polyacetals from erythritol and bioaromatics

Rostagno

Price

Pemba

et al. 2016

J of Applied Polymer Sci

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“…On the other hand, semiaromatic polyesters, such as poly(ethylene terephthalate) (PET), have extensive commercial applications because of their good thermal properties; they have T g values typically around 70–80 °C and melting point ( T m ) values typically in excess of 200 °C . The monomer terephthalic acid (TPA) is typically produced from fossil resources, and various studies have recently been performed in which substitutes that can afford improved/different properties and improved sustainability have been investigated .…”

Section: Introductionmentioning

confidence: 99%

Towards Sustainable High‐Performance Thermoplastics: Synthesis, Characterization, and Enzymatic Hydrolysis of Bisguaiacol‐Based Polyesters

et al. 2018

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The utilization of wood-derived building blocks (xylochemicals) to replace fossil-based precursors is an attractive research subject of modern polymer science. Here, we demonstrate that bisguaiacol (BG), a lignin-derived bisphenol analogue, can be used to prepare biobased polyesters with remarkable thermal properties. BG was treated with different activated diacids to investigate the effect of co-monomer structures on the physical properties of the products. Namely, derivatives of adipic acid, succinic acid, and 2,5-furandicarboxylic acid were used. Moreover, a terephthalic acid derivative was used for comparison purposes. The products were characterized by H NMR spectroscopy, attenuated total reflectance FTIR spectroscopy, gel-permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry to assess their structural and thermal properties in detail. The polymers showed glass-transition temperatures ranging up to 160 °C and thermal stabilities in excess of 300 °C. Furthermore, the susceptibility of the polyester to enzymatic hydrolysis was investigated to assess the potential for further surface functionalization and/or recycling and biodegradation. Indeed, hydrolysis with two different enzymes from the bacteria Thermobifida cellulosilytica led to the release of monomers, as quantified by HPLC. The results of this study indicate that our new polyesters represent promising renewable and biodegradable alternatives to petroleum-based polyesters currently employed in the plastics industry, specifically for applications in which high-temperature stability is essential to ensure overall system integrity.

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“…[1][2][3][4] The need for synthetic plastics, PET and PBT, increases steadily. [12][13][14] Other renewable biomass materials, such as, vegetable oils (oleic acid, 15,16 linoleic acid, 17 ricinoleic acid, 18 etc. [5][6][7] However, conventional engineered plastics (e.g.…”

Section: Introductionmentioning

confidence: 99%

Toughened aromatic poly-(decylene terephthalate) copolyesters with two renewable eugenol-based components via a random copolymerization method

Zhao

et al. 2016

Polym. Chem.

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Poly-(decylene terephthalate) PDT homopolyester and two series of thermoplastic PDT 1−x M1 x and PDT 1−x M2 x copolyesters with varying molar compositions (x = 0%, 20%, 40%, 60%, 80%, 100%) were prepared via random copolymerization of dimethyl terephthalate (DMT) and 1,10-decanediol, with renewable eugenol-based subunits providing toughener properties. These eugenol-based tougheners were synthesized via a thiol-ene click reaction and subsequent nucleophilic substitutions. The obtained copolyesters exhibit averaged molecular weights (M w s) ranging between 26 800 and 55 300 g mol −1 , together with dispersity (D) values between 1.8 and 2.2. 1 H NMR, 13 C NMR and FTIR spectroscopic analyses were carried out as structural characterization techniques. The quantitative 13 C NMR spectra of PDT 1−x M1 x indicate that the copolyesters feature random microstructures. The results from thermogravimetric analysis (TGA) show that thermal stabilities of both PDT 1−x M1 x and PDT 1−x M2 x species gradually decrease with increasing toughener contents. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were carried out in order to study the thermo-mechanical properties of the polyesters.The toughener content proves to have no significant influence on the glass transition temperatures (T g s) of the copolyesters, despite the fact that an inconspicuous T g value was observed for the PDT homopolyester. Furthermore, the gradually diminishing melting enthalpy (ΔH m ) results from a decreasing crystallinity upon increase of the toughener unit content, suggesting that the incorporation of eugenol-based tougheners into PDT reduces the crystallinity in a significant manner. Isothermal crystallization and wide X-ray diffraction (WXRD) techniques provide evidence for this conclusion as well. The amount of eugenol-based units significantly influences the observed toughening effect. Strong tenacity of the brittle PDT was realized from the tensile and impact assays, with the content of the tougheners up to 20%.Specifically, the impact strength increases up to 16.4 and 15.8 kJ m −2 for PDT 80% M1 20% and PDT 80% M2 20% , respectively. Simultaneously, the ultimate strength decreases 2.6-4.3 MPa from 16.8 MPa to 12.5-14.2 MPa and elongation at break increases from approximately 5% to 18-20%. The findings described herein prove to be particularly important from a commercial point of view to meet the strict requirements for a variety of potential applications of such polyester species in structural materials. † Electronic supplementary information (ESI) available: Additional figures and Scheme S1. See

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Renewable (semi)aromatic polyesters from symmetrical vanillin-based dimers

Cited by 138 publications

References 50 publications

Sustainable polyacetals from erythritol and bioaromatics

Sustainable polyacetals from erythritol and bioaromatics

Towards Sustainable High‐Performance Thermoplastics: Synthesis, Characterization, and Enzymatic Hydrolysis of Bisguaiacol‐Based Polyesters

Toughened aromatic poly-(decylene terephthalate) copolyesters with two renewable eugenol-based components via a random copolymerization method

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