Streamlining the conversion of biomass to polyesters: bicyclic monomers with continuous flow

Dakshinamoorthy, Deivasagayam; Lewis, Stewart P.; Cavazza, Michael; Hoover, Aaron M.; Iwig, David F.; Damodaran, Krishnan; Mathers, Robert T.

doi:10.1039/c3gc41479e

Cited by 24 publications

(29 citation statements)

References 76 publications

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“…[1][2][3][4] The quantity of plastics produced currently in the world is around 250 Mtons per year with an average annual growth rate of 10%. [8][9][10][11][12][13] The most widely used renewable raw materials for non-fuel applications in chemical industry embrace plant oils, [14][15][16] lignin, 17 polysaccharides (mainly cellulose and starch), 18 sugars, 19 suberin, 20 cutin, 21 furfural 22 and others. 6 Simultaneously, such huge consumptions bring inevitable environmental pollutions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Zhao

et al. 2015

Polym. Chem.

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Two eugenol-based aromatic dimethyl terephthalate (DMT)-like monomers were prepared via thiol-ene click reaction and subsequent nucleophilic substitution reactions with methyl chloroacetate or 1,4-dibromobutane. Two series of thermoplastic polyesters derived from renewable eugenol and linear aliphatic α,ω-diols HO-(CH2)n-OH (n = 2, 3, 4, 6, 10, 12) were successfully synthesized. These prepared polyesters have weight-average molecular weights in the range of 18500-90500 g mol -1 , and polydispersities (PDI) between 1.8 and 2.2. Their chemical structures were all accurately characterized by 1 H NMR, 13 C NMR and FTIR. The random microstructures of synthetic polyesters were also explored by 13 C NMR. The obtained polyesters all exhibit thermal stability above 330°C. More importantly, the thermal stability, the maximum degradation rate and residue weight are intimately associated with the length of the linear aliphatic α,ω-diol. Their thermo-mechanical properties were studied by the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The length of linear aliphatic α,ω-diol shows crucial influence on the glass transition temperature (Tg). With the gradually increase of the α,ω-diol length, the Tg of the synthesized polyester uniformly exhibits a tendency of decreasing. The polyesters are all amorphous materials at room temperature, whose Tg values range from -28.4 to 7.6°C. The incorporation of aromatic eugenol into the polyester chains reduces the crystallinity obviously, as well as the mechanical properties compared with conventional PET or PBT. The Young's modulus and ultimate strength are just in the range of 1.2-6.9 MPa and 0.96-3.37 MPa, respectively. On the contrary, the elongation at break reaches up to 840-1000%, indicating the excellent viscosity properties for such unmanageable viscous materials.

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Section: Introductionmentioning

confidence: 99%

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Zhao

et al. 2015

Polym. Chem.

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“…More than 200 million tons of polymers are produced annually from petroleum, almost all of which are persistent in the ecosystem, creating environmental issues such as “plastic island.” One of the most significant challenges in polymer science and industry is the production, preferably using renewable resources, and utilization of biodegradable polymers that have comparable thermal/physical properties and processibility. Aliphatic polyesters have been studied as the biodegradable sustainable polymers . Polylactide (PLA), polyhydroxyalkanoate (PHA), and poly(1,4‐butylene succinate) (PBS) are currently on the market to promote the industrial applications of sustainable polymers .…”

Section: Introductionmentioning

confidence: 99%

Branched poly(1,4-butylene carbonate-co-terephthalate)s: LDPE-like semicrystalline thermoplastics

Park

Chun

Jeon

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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Branched poly[1,4-butylene carbonate-co-terephthalate]s (PBCTs) have been synthesized by the addition of a small amount of glycerol propoxylate (1) or pentaerythritol (2) in the polycondensation of 1,4-butanediol, dimethyl carbonate, and dimethyl terephthalate. To avoid gel formation, the feed amount of 1 or 2 was carefully controlled at below 0.5 mol % for 1 and below 0.3 mol % for 2. When feed of 1 or 2 was used, a high-molecular weight melt state (M w 180,000 g/mol) was reached in a total reaction time of 5.5 to 6.5 h with a yield higher than 90%. The generated PBCTs were a semicrystalline polymer (T g 5 C and T m 120 C) when the terephthalate content (F [TPA] ) was 45 to 50 mol %. The crystallization rate

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“…In the recent years, bio‐based polymers have attracted a great deal of attention due to the environmental issues and depletion of non‐renewable resources . A large number of bio‐based polymers are already being manufactured in industry . Most of the bio‐based polymers are aliphatic or cyclo‐aliphatic in nature and are derived from vegetable oils, cellulose, or starch .…”

Section: Introductionmentioning

confidence: 99%

Partially bio‐based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based on lignin‐derived phenolic acids and aromatic dianhydrides: Synthesis, characterization, and computational studies

Kuhire

Sharma

Chakrabarty

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Two new bio-based diacylhydrazide monomers, namely, 4,4 0 -(propane-1,3-diylbis(oxy))bis(3-methoxybenzohydrazide) and 4,4 0 -(propane-1,3-diylbis(oxy))bis(3,5-dimethoxybenzohydrazide) were synthesized starting from lignin-derived phenolic acids, namely, vanillic acid and syringic acid. A series of poly(amide imide)s was synthesized by polycondensation of these diacylhydrazide monomers with commercially available aromatic dianhydrides. Poly(amide imide)s showed inherent viscosity in the range 0.44-0.56 dL g 21 and exhibited good solubility in organic solvents. Poly(amide imide)s could be cast into transparent, flexible, and tough films from their N,N-dimethylacetamide solutions. Poly(amide imide)s showed 10% weight loss in the temperature range 340-364 8C indicating their good thermal stability. Glass transition temperature (T g ) of poly(amide imides)s were measured by DSC and DMA which were in the range 201-223 8C and 214-248 8C, respectively. The T g values of poly(amide imide)s were dependent on the number methoxy substituents on aromatic rings of diacylhydrazide monomers. Molecular dynamics simulation studies revealed that chain rigidity is the dominant factor for observed trends in T g . V C 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3636-3645 The presence of functional groups in these aromatic chemicals offers interesting possibilities to use them as precursors for synthesis of useful monomers. Thus, a range bio-based monomers and polymers have been synthesized from lignin-derived aromatics, 14,25 which include (meth)acrylic polymers, 26 epoxy polymers, 27 polybenzoxazines, 28 cyanate ester resins, 29 polycarbonates, 30 polyesters, 31-34 poly(ether ester)s, 14,35 polyacetals, 36 polyurethanes, 37,38 and so forth.Aromatic poly(amide imide)s represent an important class of high performance polymers due to their excellent thermal and mechanical properties. 12,[39][40][41] The excellent properties of poly(amide imide)s are derived from their distinctive chemical structure, which combine both amide and imide Additional Supporting Information may be found in the online version of this article.

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Streamlining the conversion of biomass to polyesters: bicyclic monomers with continuous flow

Abstract: Continuous flow methodology for the multi step synthesis of biomass derived aliphatic bicyclic-anhydride monomer. Polymerization with bio-based alcohols results in renewable polyesters with good thermal stability.

Cited by 24 publications

References 76 publications

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Branched poly(1,4-butylene carbonate-co-terephthalate)s: LDPE-like semicrystalline thermoplastics

Partially bio‐based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based on lignin‐derived phenolic acids and aromatic dianhydrides: Synthesis, characterization, and computational studies

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