Direct one-step synthesis of a formally fully bio-based polymer from cellulose and cinnamon flavor

Hirose, Daisuke; Kusuma, Samuel Budi Wardhana; Daiki, Ina; Wada, Naoki; Takahashi, Kenji

doi:10.1039/c9gc01333d

Cited by 19 publications

(31 citation statements)

References 43 publications

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“…Our previous report confirmed that the oxidative esterification does not proceed when dimethyl sulfoxide (DMSO) is used as the solvent without IL. To investigate the influence of the IL on the reaction result, we tested ILs containing various anions (Table ).…”

Section: Results and Discussionsupporting

confidence: 73%

“… a Reaction conditions: [ROH]/[ 1 ]/[IL]/[DMSO] = 1/1/1/20 (molar ratio), 24 h, 60 °C, Ar atmosphere. b On the basis of the IR absorption band at ∼1730 cm –1 corresponding to CO stretching (Figure ). c Data in previous report (ref ). d DS side value derived from the acetate anion. …”

Section: Results and Discussionmentioning

confidence: 99%

“…Other chemicals were obtained from commercial sources and were used as-received unless otherwise stated. Fully substituted cellulose phenylpropionate for comparison was prepared using corresponding acyl donor according to a previous report …”

Section: Methodsmentioning

confidence: 99%

“…Besides cinnamaldehyde, other α,β-unsaturated aldehydes are also abundant in the essential oils of plants, such as citral, 2-hexenal, and perillaldehyde. − However, when using carboxylate-type ILs presented by commercially available 1-ethyl-3-methylimidazolium (Emim) acetate (OAc) for the esterification reaction, the anion in the IL is inevitably mixed into the polymer as an ester group due to the generation of mixed acid anhydride, ,,,, and it is difficult to completely suppress the problem of anion introduction as an ester group on the product and obtain the product polymer consisting of the full-biobased single-ester group in the strict sense. We previously developed Emim phenylpropionate (EmimPPA) as an appropriate IL for use with cinnamaldehyde to improve the appearance for the synthesis of the formally full-biobased polymer.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, the degree of substitution (DS) was also limited to ∼2.0 or lower. Thus, the optimization of ILs could bring about some improvement in both the reactivity and the scope of the substrates …”

Section: Introductionmentioning

confidence: 99%

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Direct Synthesis of Full-Biobased Cellulose Esters from Essential Oil Component α,β-Unsaturated Aldehydes

Kusuma

Hirose

Yoshizawa

et al. 2021

ACS Sustainable Chem. Eng.

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To become independent of petroleum resources, societies have to develop methods to synthesize full-biobased polymers from natural products directly. In this study, full-biobased cellulose esters were synthesized by the oxidative esterification process between cellulose and natural α,β-unsaturated aldehydes in an ionic liquid working as solvent and catalyst. The role of the ionic liquid in this cellulose-modification system was systematically investigated, and a newly designed noncarboxylate-type ionic liquid, 1-ethyl-3-methylimidazolium 2-pyridinolate (EmimOPy), was developed to prevent a serious side reaction in which the carboxylate anion of the carboxylate-type ionic liquid is introduced into the hydroxyl group of cellulose as an ester group on the products. Under optimized conditions, this oxidative esterification-reaction system in EmimOPy afforded fully substituted cellulose ester (up to the degree of substitution = 3.0). Furthermore, cellulose reacted with several types of aldehyde substrates, even biobased low-reactive α- or β-substituted unsaturated aldehydes (e.g., citral and perillaldehyde). Thus, this synthesis demonstrates excellent atom economy without using any additional catalysts or activators under metal-free conditions.

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Section: Results and Discussionsupporting

confidence: 73%

Section: Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Direct Synthesis of Full-Biobased Cellulose Esters from Essential Oil Component α,β-Unsaturated Aldehydes

Kusuma

Hirose

Yoshizawa

et al. 2021

ACS Sustainable Chem. Eng.

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Cellulose Esters, Organic

Thompson,

Masias,

Yazdi

et al. 2023

Encyclopedia of Polymer Science and Technology

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Renewable cellulose, the major structural component of plant cell walls, is one of the most abundant biopolymers on Earth, and exhibits many desirable properties including biodegradability, high stiffness, low inherent toxicity, and general compatibility with a plethora of biological tissues under many conditions. While these properties make cellulose appealing as a polymer, it is not melt‐ or solution‐processable due to its extensive inter‐ and intramolecular hydrogen bonding network that prevents softening or melting before decomposition. To circumvent this, cellulose can be converted into organic esters, generating a processable plastic material with the benefits inherent to cellulose. Organic cellulose esters have been commercially significant materials for over a century since their initial use as safety film to replace flammable nitrocellulose. Since then, the chemistry of cellulose esters has undergone dramatic growth, generating new cellulose derivatives with a wide range of properties, finding value in a wide variety of applications including industrial coatings, tissue engineering, drug delivery, optical materials, and biodegradable plastics. The polymer science of cellulose esters is an important, complex, and ever‐expanding field; herein, we will introduce and discuss the synthesis, characterization, structure–property relationships, and applications of organic cellulose esters.

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N‐Heterocyclic Carbene/Carboxylic Acid Co‐Catalysis Enables Oxidative Esterification of Demanding Aldehydes/Enals, at Low Catalyst Loading

et al. 2021

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We report the discovery that simple carboxylic acids, such as benzoic acid, boost the activity of N‐heterocyclic carbene (NHC) catalysts in the oxidative esterification of aldehydes. A simple and efficient protocol for the transformation of a wide range of sterically hindered α‐ and β‐substituted aliphatic aldehydes/enals, catalyzed by a novel and readily accessible N‐Mes‐/N‐2,4,6‐trichlorophenyl 1,2,4‐triazolium salt, and benzoic acid as co‐catalyst, was developed. A whole series of α/β‐substituted aliphatic aldehydes/enals hitherto not amenable to NHC‐catalyzed esterification could be reacted at typical catalyst loadings of 0.02–1.0 mol %. For benzaldehyde, even 0.005 mol % of NHC catalyst proved sufficient: the lowest value ever achieved in NHC catalysis. Preliminary studies point to carboxylic acid‐induced acceleration of acyl transfer from azolium enolate intermediates as the mechanistic basis of the observed effect.

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Direct one-step synthesis of a formally fully bio-based polymer from cellulose and cinnamon flavor

Abstract: Direct fully bio-based polymer synthesis by cellulose modification involving simply mixing cellulose and cinnamaldehyde “cinnamon flavor” in an ionic liquid.

Cited by 19 publications

References 43 publications

Direct Synthesis of Full-Biobased Cellulose Esters from Essential Oil Component α,β-Unsaturated Aldehydes

Direct Synthesis of Full-Biobased Cellulose Esters from Essential Oil Component α,β-Unsaturated Aldehydes

Cellulose Esters, Organic

N‐Heterocyclic Carbene/Carboxylic Acid Co‐Catalysis Enables Oxidative Esterification of Demanding Aldehydes/Enals, at Low Catalyst Loading

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