Synthesis of performance-advantaged polyurethanes and polyesters from biomass-derived monomers by aldol-condensation of 5-hydroxymethyl furfural and hydrogenation

Chang, Hochan; Gilcher, Elise B.; Huber, George W.; Dumesic, James A.

doi:10.1039/d1gc00899d

Cited by 27 publications

(28 citation statements)

References 35 publications

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“…Cu/Al 2 O 3 was synthesized by an ion-exchange method described elsewhere . Briefly, low soda γ alumina was suspended in water.…”

Section: Methodsmentioning

confidence: 99%

“…Cu/Al 2 O 3 was synthesized by an ionexchange method described elsewhere. 1 Briefly, low soda γ alumina was suspended in water. Tetraamminecopper(II) sulfate monohydrate corresponding to 5 weight percent of the weight of alumina support was dissolved in water with a small amount of ammonium hydroxide to solubilize the precursor.…”

Section: Methodsmentioning

confidence: 99%

“…The biomass-derived 5-hydroxymethyl furfural (HMF), aldolcondensed chemical (HMF−acetone−HMF, HAH), and its hydrogenated derivatives have shown promise as platform molecules for use as tunable, functionalized polyurethanes and polyesters as well as building blocks for further Diels−Alder reactions. 1 The selective hydrogenation of the HAH adduct to its partially and fully hydrogenated products is critical to open research avenues and develop technologies for industrial applications of this process. Equally important to the selective hydrogenation of HAH products is the increased production rate of these desired monomers at higher feed concentrations.…”

Section: ■ Introductionmentioning

confidence: 99%

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Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

et al. 2022

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We have developed lumped reaction schemes to optimize the yields of products from selective hydrogenations of HAH, a biomass-derived platform chemical produced by two-step aldol condensations of 5-hydroxymethyl furfural (H) with acetone (A). Reaction schemes consisting of 7, 9, and 11 steps were examined to describe the rates of formation of the observed products and reaction intermediates for hydrogenation of HAH over Ru and Pd catalysts, and a 3-step scheme was studied over Cu catalysts. Rate constants and activation energies were calculated using these reaction schemes, and we then apply the schemes to explore the effects of water addition on the hydrogenation pathways. The effects of water addition to isopropanol (IPA) solvents on the hydrogenation of HAH were markedly different over Pd, Ru, and Cu catalysts. Over the Pd catalyst, the addition of water to IPA increased hydrogenation rates and promoted the hydrogenation of furan rings. The addition of water to IPA yielded significant carbon losses over the Ru catalyst, and slowed hydrogenation steps over Cu, while significantly inhibiting hydrogenation of the ketone group. This behavior opened routes toward increased production rates of PHAHO (a partially hydrogenated, P, form of HAH containing a CO bond), a product in which the diene groups of the furan rings were not hydrogenated. The addition of water also allowed increased feed concentrations of HAH that were previously not possible in pure IPA solvents. The insights presented in this work provide a more mechanistic description of the hydrogenation of HAH, the behavior of specific intermediates, and the reactivity of key functional groups.

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“…Cu/Al 2 O 3 was synthesized by an ion-exchange method described elsewhere . Briefly, low soda γ alumina was suspended in water.…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

et al. 2022

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“…A promising building block can be obtained through sequential hydrolysis, isomerization, − and dehydration − of the cellulose portion of the lignocellulosic biomass to produce 5-hydroxymethylfurfuraldehyde (HMF) and furfuraldehyde (FA). HMF and FA can subsequently be converted into polymer precursors, feedstock chemicals, , and fuels. − One important upgrading route can involve coupling reactions such as aldol chemistry (i.e., reaction and condensation), as illustrated in Scheme . Aldol chemistry is a powerful method to upgrade small molecules provided that structure–function relationships can be elucidated that produce highly active catalysts.…”

Section: Introductionmentioning

confidence: 99%

Investigating the Impact of Microporosity of Aminosilica Catalysts in Aldol Condensation Reactions for Biomass Upgrading of 5-Hydroxymethylfurfural and Furfuraldehyde to Fuels

Chen

Brunelli

2021

Energy Fuels

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Upgrading biomass to chemicals and fuels requires development of highly active and selective catalytic materials for important reactions such as the aldol condensation. The aldol condensation is a critical step to convert small molecules such as 5-hydroxymethylfurfural (HMF) and furfuraldehyde (FA) to larger complexes that can be used for fuels or chemicals. Whereas extensive work has examined aminosilica catalytic materials for aldol chemistry, these materials have received limited attention for HMF and FA conversion in spite of the capability of these materials to catalyze reactions in a cooperative manner. In this work, important structure–function relationships are investigated that demonstrate the impact of micropores in these materials. Materials are produced using a typical method (REG) and a method that produces limited to no micropores (NMP). The materials are grafted with aminosilanes and characterized using standard techniques. It is found that materials with limited to no micropores are more active for the aldol reaction and condensation for both FA with acetone and HMF with acetone. Additionally, the materials are tested in recycle experiments that showed the NMP catalyst retained higher activity after four catalytic cycles than the REG catalyst. Overall, the results have important implications for the design of materials for upgrading biomass into chemicals and fuels.

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“…Aldol condensation is currently used to synthesize fine chemicals [5,23,24], and it holds a promising potential for development of sustainable aviation fuels [25][26][27][28] and bio-based monomers [29,30]. In addition, it is a suitable reaction for probing the acid-base character of catalysts as only the accessible, i.e., catalytically active basic sites can be reached by the reactants in both mixed oxides and reconstructed hydrotalcites.…”

Section: Introductionmentioning

confidence: 99%

On the Effect of the M3+ Origin on the Properties and Aldol Condensation Performance of MgM3+ Hydrotalcites and Mixed Oxides

et al. 2021

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Hydrotalcites (HTCs) are promising solid base catalysts to produce advanced biofuels by aldol condensation. Their main potential lies in the tunability of their acid-base properties by varying their composition. However, the relationship between the composition of hydrotalcites, their basicity, and their catalytic performance has not yet been fully revealed. Here, we investigate systematically the preparation of HTCs with the general formula of Mg6M3+2(OH)16CO3·4H2O, where M3+ stands for Al, Ga, Fe, and In, while keeping the Mg/M3+ equal to 3. We use an array of analytical methods including XRD, N2 physisorption, CO2-TPD, TGA-MS, FTIR-ATR, and SEM to assess changes in the properties and concluded that the nature of M3+ affected the HTC crystallinity. We show that the basicity of the HTC-derived mixed oxides decreased with the increase in atomic weight of M3+, which was reflected by decreased furfural conversion in its aldol condensation with acetone. We demonstrate that all MgM3+ mixed oxides can be fully rehydrated, which boosted their activity in aldol condensation. Taking all characterization results together, we conclude that the catalytic performance of the rehydrated HTCs is determined by the “host” MgO component, rather than the nature of M3+.

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Synthesis of performance-advantaged polyurethanes and polyesters from biomass-derived monomers by aldol-condensation of 5-hydroxymethyl furfural and hydrogenation

Abstract: Synthetic platform for production of biomass-derived monomers and performance-advantaged polymers with renewability, upgradability, and economic viability.

Cited by 27 publications

References 35 publications

Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

Effects of Water Addition to Isopropanol for Hydrogenation of Compounds Derived from 5-Hydroxymethyl Furfural over Pd, Ru, and Cu Catalysts

Investigating the Impact of Microporosity of Aminosilica Catalysts in Aldol Condensation Reactions for Biomass Upgrading of 5-Hydroxymethylfurfural and Furfuraldehyde to Fuels

On the Effect of the M3+ Origin on the Properties and Aldol Condensation Performance of MgM3+ Hydrotalcites and Mixed Oxides

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