Cellulose triacetate synthesis <i>via</i> one-pot organocatalytic transesterification and delignification of pretreated bagasse

Suzuki, Shiori; Shibata, Yoshihiko; Hirose, Daisuke; Endo, Takatsugu; Ninomiya, Kazuaki; Kakuchi, Ryohei; Takahashi, Kenji

doi:10.1039/c8ra03859g

Cited by 31 publications

(44 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recent advances achieved in our laboratory hold promise for deriving thermoplastic cellulose derivatives from biomasses (Kakuchi et al, 2017; Suzuki et al, 2018), and utilizing these materials for preparing short carbon fiber reinforced plastics (Szabó et al, 2019a). We have also shown that the adhesion between the cellulosic matrix and carbon fiber can be improved by modifying the carbon fiber surface (Szabó et al, 2018a,b, 2019b).…”

Section: Introductionmentioning

confidence: 99%

“…It follows that lignin can serve as a functional material to improve the interfacial interactions in green biobased composites. In order to further test these theories, in this study we prepare short carbon fiber reinforced composites utilizing polymers that can be potentially derived from biomasses [cellulose derivatives (Kakuchi et al, 2017; Suzuki et al, 2018) and polyamide 6 (Buntara et al, 2011; Winnacker and Rieger, 2016)] as model materials and tailor the interfacial interactions utilizing lignin as a renewable resource.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Short Carbon Fiber Reinforced Polymers: Utilizing Lignin to Engineer Potentially Sustainable Resource-Based Biocomposites

et al. 2019

Self Cite

View full text Add to dashboard Cite

Carbon fiber reinforced composites have exceptional potential to play a key role in the materials world of our future. However, their success undoubtedly depends on the extent they can contribute to advance a global sustainability objective. Utilizing polymers in these composites that can be potentially derived from biomasses would be certainly vital for next-generation manufacturing practices. Nevertheless, deep understanding and tailoring fiber-matrix interactions are crucial issues in order to design carbon fiber reinforced sustainable resource-based biocomposites. In this study, cellulose derivatives (cellulose propionate and cellulose acetate butyrate) are utilized as model polymer matrices that can be potentially fabricated from biomasses, and the mechanical properties of the prepared short carbon fiber reinforced composites are engineered by means of a functional biobased lignin coating on the fiber surface. Furthermore, polyamide 6 based composites are also prepared, the monomer of this polymer could be obtained using C6 sugars derived from lignocellulosic biomasses in the future (through 5-hydroxymethylfurfural). Lignin was successfully immobilized on the carbon fiber surface via an industrially scalable benign epoxidation reaction. The surface modification had a beneficial impact on the mechanical properties of cellulose propionate and polyamide 6 composites. Furthermore, our results also revealed that cellulose-based matrices are highly sensitive to the presence of rigid fiber segments that restrict polymer chain movements and facilitate stress development. It follows that the physicochemical properties of the cellulosic matrices (molecular weight, crystallinity), associated with polymer chain mobility, might need to be carefully considered when designing these composites. At the same time, polyamide 6 showed excellent ability to accommodate short carbon fibers without leading to a largely brittle material, in this case, a maximum tensile strength of ~136 MPa was obtained at 20 wt% fiber loading. These results were further contrasted with that of a petroleum-based polypropylene matrix exhibiting inferior mechanical properties. Our study clearly indicates that carbon fiber reinforced polymers derived and designed using biomass-derived resources can be promising green materials for a sustainable future.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Short Carbon Fiber Reinforced Polymers: Utilizing Lignin to Engineer Potentially Sustainable Resource-Based Biocomposites

et al. 2019

Self Cite

View full text Add to dashboard Cite

show abstract

“…Washed bagasse (39 wt % of cellulose, 28 wt % of hemicellulose, and 28 wt % of lignin) 15 was then dried in a vacuum oven at 70 °C until a constant weight was achieved prior to use.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…Esterification is a traditional method applied to provide thermal and/or solution processability to lignocellulose. Previous studies have shown that sustainability of the esterification process can be enhanced by the use of enzymes , and IL catalysts and also by exploiting the advantageous solubility of ILs instead of the conventional thorough pretreatment. , In our previous study, sugarcane bagasse was directly esterified using an IL as both the solvent and catalyst, successfully yielding bagasse-derived polysaccharide acetate decanoate (Cel/Hemi-AcDe) and lignin acetate decanoate (Lig-AcDe). However, Cel/Hemi-AcDe was brittle and unsuitable for thermal processing because of its high weight-average molecular weight ( M w ) of 15 × 10 5 g mol –1 .…”

Section: Introductionmentioning

confidence: 99%

Green Conversion of Total Lignocellulosic Components of Sugarcane Bagasse to Thermoplastics Through Transesterification Using Ionic Liquid

Suzuki

Hamano

Hernandez

et al. 2021

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

Considering the recent environmental problems, it is critical to minimize our dependence on fossil fuels and maximize the utilization of sustainable and abundant lignocellulosic biomass. Herein, we present a facile approach for the green conversion of sugarcane bagasse, a lignocellulose-rich agro waste, to valorized thermoplastics by utilizing its total lignocellulosic constituents. To impart adequate thermal moldability to the bagasse without sacrificing the key mechanical properties, all hydroxy (OH) groups were substituted with long- and short-chains acyl groups via one-pot and two-step reactions, allowing for a precise control of the acyl group molar ratio. The esterified bagasse with hexanoyl and acetyl groups (∼20:80, mol/mol) demonstrated an excellent melt-flowability at 180 °C, while maintaining good mechanical properties (tensile strength: 35 ± 4 MPa and Young’s modulus: 1.6 ± 0.1 GPa), which were attributed to the plasticizer effects of the introduced long-chain acyl group as well as the retained hemicellulose and lignin components. Additionally, the material properties of the esterified bagasse were desirably tunable and dependent on the type of acyl groups and lignocellulose. Thus, these findings demonstrate the potential for lignocelluloses to be used as a high value-added biomass plastic in various fields, paving the way for the use of lignocellulosic components as polymeric materials.

show abstract

“…Ionic liquids (ILs) are molten organic salts having melting points below 100 °C and are intriguing solvents for lignocellulose: some ILs such as 1-ethyl-3-methylimidazolium acetate (EmimOAc) have been reported to work as not only a solvent but also a catalyst for transesterification between hydroxy (OH) groups in lignocellulose and vinyl esters. − There have been many reports of chemical modifications of lignocellulose using ILs, for example, acetylation, − benzoylation, maleation, and phthalation. , Nevertheless, these conventional esterified lignocellulose derivatives usually contain heterogeneous lignin components, resulting in fragility and their relatively easy thermal decomposition, and thus poor injection moldability.…”

Section: Introductionmentioning

confidence: 99%

Direct Conversion of Sugarcane Bagasse into an Injection-Moldable Cellulose-Based Thermoplastic via Homogeneous Esterification with Mixed Acyl Groups

Suzuki

Hikita

Hernandez

et al. 2021

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

Recently, lignocellulosic biomass-based plastics have attracted attention as alternatives to oil-derived plastics. However, the conventional production of biomass-based plastics is a multistep process, requiring harsh pretreatment, chemical modification, and purification, resulting in high costs and environmental burden. Herein, we report the direct conversion of lignocellulosic agricultural waste, sugarcane bagasse, into an injection-moldable cellulosic thermoplastic having good mechanical properties. Specifically, the hydroxy groups in bagasse were substituted by long-/short-chain mixed acyl groups (20:80 molar ratio of decanoyl/acetyl groups) in a one-pot, two-step homogeneous transesterification reaction using the corresponding vinyl esters and an ionic liquid (1-ethyl-3-methylimidazolium acetate) as both solvent and catalyst. The lignin component in the bagasse derivative was separated by precipitation in methanol, and a mixed-ester derivative of cellulose and hemicellulose (polysaccharide acetate decanoate, PSAD) having long- and short- acyl chains was obtained. PSAD could be injection-molded at 205 °C because of the plasticizing effects of the decanoyl groups and the hemicellulose component, despite the ultrahigh weight-average molecular weight of >1.5 × 106 g mol–1. The hemicellulose derivative in PSAD yielded moderate flexibility and sufficiently high mechanical strength for its use as a thermoplastic with tensile and flexural strengths of 50 and 80 MPa, respectively.

show abstract

Cellulose triacetate synthesis via one-pot organocatalytic transesterification and delignification of pretreated bagasse

Abstract: Cellulose triacetate was synthesised by the transesterification reaction of mild acid-pretreated lignocellulosic biomass with a stable acetylating reagent in an ionic liquid, EmimOAc, which enabled the dissolution of lignocellulose as well as the organocatalytic reaction.

Cited by 31 publications

References 44 publications

Short Carbon Fiber Reinforced Polymers: Utilizing Lignin to Engineer Potentially Sustainable Resource-Based Biocomposites

Short Carbon Fiber Reinforced Polymers: Utilizing Lignin to Engineer Potentially Sustainable Resource-Based Biocomposites

Green Conversion of Total Lignocellulosic Components of Sugarcane Bagasse to Thermoplastics Through Transesterification Using Ionic Liquid

Direct Conversion of Sugarcane Bagasse into an Injection-Moldable Cellulose-Based Thermoplastic via Homogeneous Esterification with Mixed Acyl Groups

Contact Info

Product

Resources

About