Mild and controlled lignin methylation with trimethyl phosphate: towards a precise control of lignin functionality

Duval, Antoine; Avérous, Luc

doi:10.1039/c9gc03890f

Cited by 39 publications

(28 citation statements)

References 32 publications

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“…The detection was performed by an Acquity refractive index (RI) detector and an Acquity TUV detector operating at 280 nm. To ensure full solubility in THF, all samples were first acetylated according to a standard protocol, [63] then dissolved in THF at 5 mg mL −1 concentration and filtered through 0.2 μm PTFE syringe filters prior to injection. The average molar masses ( M n , M w ) and dispersities ( Đ ) were calculated from a calibration with polystyrene standards.…”

Section: Methodsmentioning

confidence: 99%

“…The yield was calculated taking into account the increase in mass due to the grafting, as previously reported. [16,63] The grafting of ethylene oxide groups onto the phenolic OH groups leads to an increase of 44 g mol À 1 , whereas the grafting of ethylene carbonate groups onto the aliphatic OH leads to an increase of 88 g mol À 1 . The yield was thus calculated according to Equation (10):…”

Section: Chemical Modification Of Lignin With Ethylene Carbonate (Ec)mentioning

confidence: 99%

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Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis

et al. 2020

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Two organosolv lignins extracted during pilot runs of the Fabiola process were analyzed, fractionated and chemically modified with ethylene carbonate (EC) to produce building blocks suitable for polymer synthesis. Isolation of low dispersity fractions relied on the partial solubility of the lignins in organic solvents. Lignins solubility was first evaluated and analyzed with Hansen and Kamlet-Taft solubility parameters, showing a good correlation with the solvents dipolarity/polarizability parameter π*. The results were then used to select a sequence of solvents able to fractionate the lignins into low dispersity fractions of increasing molar masses, which were analyzed by 31 P NMR, SEC and DSC. The lignins were then reacted with EC, to convert the phenolic OH groups into primary aliphatic OH groups. The reactivity of the organosolv lignins was high, and milder reaction conditions than previously reported were sufficient to fully convert the phenolic OH groups. A gradual reduction in reactivity with increasing molar mass was evidenced and attributed to reduced solubility of high molar mass fragments in EC. Undesirable crosslinking side reactions were evidenced by SEC, but were efficiently limited thanks to a fine control of the reaction conditions, helping to maximize the benefits of the developed lignin modification with EC.

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Section: Methodsmentioning

confidence: 99%

Section: Chemical Modification Of Lignin With Ethylene Carbonate (Ec)mentioning

confidence: 99%

Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis

et al. 2020

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“…3a). 23,26,[50][51][52][53][54][55][56][57][58] Many of these chemical modifications have attempted to convert lignin macromolecules into macromonomers and subsequently graft classical monomers or polymers, and in this way, synthetize ligninbased functional polymers. 23,[26][27][28] Well-defined lignin graft copolymers can be elaborated by two main methodologies: ''grafting from'' and ''grafting to'' ( Fig.…”

Section: Roadmap To Lignin-based Smart Materialsmentioning

confidence: 99%

Lignin-based smart materials: a roadmap to processing and synthesis for current and future applications

2020

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“…DMC was a greener reagent for lignin methylation, but the modification time was up to 5 h . Afterward, Duval et al used a quick way where lignin was methylated by trimethyl phosphate (TMP) in 1 h without a solvent . This novel protocol could be applied to prepare methylated lignin for a large range of lignin-based materials.…”

Section: Chemical Modification Of Ligninmentioning

confidence: 99%

Technical Lignin Valorization in Biodegradable Polyester-Based Plastics (BPPs)

Zhou

Wang

Xiong

et al. 2021

ACS Sustainable Chem. Eng.

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Synthetic plastics have been reshaping the planet since the early 20th century. They have brought plenty of conveniences to our lives; meanwhile, plastic wastes discarded into the environment are resistant to biodegradation, accumulating in soil, water, and even in organisms. Biodegradable polyester-based plastics (BPPs), such as polylactic acid (PLA), poly(butylene adipate-co-terephthalate) (PBAT), poly(butylene succinate) (PBS), polycaprolactone (PCL), and poly(β-hydroxybutyric acid) (PHB) are considered to be ecofriendly and sustainable alternatives and have thrived rapidly in the past few decades. However, the applications of BPPs have been limited by their high prices compared to conventional plastics, while blending with lowcost fillers has been deemed to be a facile and efficient solution to the foregoing issues. Technical lignin, a class of biodegradable aromatic polymers, has been extracted/isolated at a large scale as a coproduct in the conventional paper-making and the emerging lignocellulosic biorefinery industries. The economically competitive BPP composites reinforced by coproduct lignin could not only facilitate the lignin valorization but also improve the economic viability of the lignocellulosic biorefinery. At present, the key obstacle lies in the incompatibility between lignin and BPPs resulting from self-aggregation and thermal condensation of lignin due to its polyhydroxy aromatic structures. Herein, we overviewed a series of effective approaches to promote the interaction between lignin and BPPs by adding plasticizers and blocking the hydroxyl groups. Furthermore, lignin can act as functional fillers endowing lignin/BPP composites favorable versatilities and expanding their applications in the fields of flame retardant packaging, food packaging, medical materials, outside packaging, and mulching films. In the end, we review the developments of lignin/BPP blending composites in the future and propose current problems that need to be solved.

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Mild and controlled lignin methylation with trimethyl phosphate: towards a precise control of lignin functionality

Abstract: A novel protocol for a mild, controlled and selective methylation of lignin phenolic OH groups with trimethylphosphate has been developed.

Cited by 39 publications

References 32 publications

Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis

Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis

Lignin-based smart materials: a roadmap to processing and synthesis for current and future applications

Technical Lignin Valorization in Biodegradable Polyester-Based Plastics (BPPs)

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