ArticlePublisher preview available

Mild, rapid and efficient etherification of cellulose

Authors:
Jingxuan You at Chinese Academy of Sciences
Jingxuan You
Xin Zhang
Xin Zhang
Xin Zhang
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Qinyong Mi at Chinese Academy of Sciences
Qinyong Mi
Jinming Zhang at Chinese Academy of Sciences
Jinming Zhang
Show all 6 authorsHide
Read publisher preview
Download citation
To read the full-text of this research, you can request a copy directly from the authors.

Abstract and Figures

Etherification of cellulose is of significant importance to construct cellulose-based materials. However, the homogeneous and controllable etherification of cellulose is difficult to achieve. Herein, we systematically demonstrated that mild, rapid and efficient etherification of cellulose was realized in tetra-n-butylphosphonium hydroxide ([P4,4,4,4]OH) aqueous solution, including Williamson etherification reaction, Michael addition reaction, and hydroxyalkylation reaction. A series of cellulose ethers with different substituents and degrees of substitution (DS) were easily and controllably synthesized, including ethyl cellulose, cyanoethyl cellulose, hydroxypropyl cellulose and quaternized cellulose. More interestingly, both the Williamson etherification and hydroxyalkylation reaction were conducted in 15 min at 25–60 °C which are rapid and efficient. The DS and performance of the resultant cellulose ethers were regulated over a wide range by changing the reaction conditions. The solvent [P4,4,4,4]OH aqueous solution could be successfully recovered after a three-steps process of extraction with CHCl3, anion exchange and concentration. Graphical abstract
Figures - available from: Cellulose
This content is subject to copyright. Terms and conditions apply.
A preview of this full-text is provided by Springer Nature.
Learn more
Content available from Cellulose
This content is subject to copyright. Terms and conditions apply.
Vol.: (0123456789)
1 3
Cellulose (2022) 29:9583–9596
https://doi.org/10.1007/s10570-022-04879-x
ORIGINAL RESEARCH
Mild, rapid andefficient etherification ofcellulose
JingxuanYou· XinZhang· QinyongMi·
JinmingZhang· JinWu· JunZhang
Received: 7 July 2022 / Accepted: 1 October 2022 / Published online: 13 October 2022
© The Author(s), under exclusive licence to Springer Nature B.V. 2022
ethyl cellulose, cyanoethyl cellulose, hydroxypro-
pyl cellulose and quaternized cellulose. More inter-
estingly, both the Williamson etherification and
hydroxyalkylation reaction were conducted in 15min
at 25–60 °C which are rapid and efficient. The DS
and performance of the resultant cellulose ethers were
regulated over a wide range by changing the reaction
conditions. The solvent [P4,4,4,4]OH aqueous solution
could be successfully recovered after a three-steps
process of extraction with CHCl3, anion exchange
and concentration.
Abstract Etherification of cellulose is of significant
importance to construct cellulose-based materials.
However, the homogeneous and controllable etheri-
fication of cellulose is difficult to achieve. Herein,
we systematically demonstrated that mild, rapid and
efficient etherification of cellulose was realized in
tetra-n-butylphosphonium hydroxide ([P4,4,4,4]OH)
aqueous solution, including Williamson etherifica-
tion reaction, Michael addition reaction, and hydroxy-
alkylation reaction. A series of cellulose ethers with
different substituents and degrees of substitution (DS)
were easily and controllably synthesized, including
Supplementary Information The online version
contains supplementary material available at https:// doi.
org/ 10. 1007/ s10570- 022- 04879-x.
J.You· X.Zhang· Q.Mi· J.Zhang(*)· J.Wu·
J.Zhang(*)
CAS Key Laboratory ofEngineering Plastics, Institute
ofChemistry, Chinese Academy ofSciences (CAS),
Beijing100190, China
e-mail: zhjm@iccas.ac.cn
J. Zhang
e-mail: jzhang@iccas.ac.cn
J.You· X.Zhang· J.Zhang
University ofChinese Academy ofSciences,
Beijing100049, China
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
... They lead to the insolubility of cellulose molecules in water and common organic solvents, such as ethanol, acetone and so on [9]. In order to enhance the solubility of cellulose and expand its application prospect, etherify groups are often introduced to improve hydrophilicity [10]. ...
Controllable Synthesis and Rheological Characterization of Hydroxypropyl Methyl Cellulose
Article
Full-text available
  • May 2024
Hydroxypropyl methyl cellulose (HPMC) with controllable viscosity average molecular mass (Mη) and degree of substitution had been successfully synthesized in this article. α-cellulose was firstly methylated to be methyl cellulose (MC) by dimethyl sulphate (DMS). Then MC was hydroxypropylated to be HPMC by propylene oxide (PO). In this way, the end capping structure that methoxy group connected to terminal hydroxyl group of hydroxypropyl had been avoided. FT-IR,¹H NMR and ¹³C NMR showed the successful synthesis of products with expected structure. The dilute hydrochloric acid was used to degrade HPMC to obtain a range of products with different Mη measured by ubbelohde viscometer. The rheological properties of HPMC solution with different molecular mass and concentrations were studied, including flow behavior index, thixotropy, entanglement concentration (C**), gelation temperature (Tgel), degelation temperature (Tsol). The results showed that the flow behavior index of HPMC solutions decreased with the increase of molecular mass and concentration, and gradually changed from Newtonian fluid to pseudoplastic fluid. In this article, Tgel and Tsol of HPMC both increased with the increase of molecular mass. When wt = 14%, Mη = 140 kDa, the maximum Tgel and Tsol was separately up to 70.18 °C and 46.81 °C. The effect of concentration on Tgel and Tsol was not noticeable. Tgel changed within 60 ± 2 °C and Tsol decreased from 40.56 °C to 35.72 °C as the concentration increased from 14 to 20%. These rheological studies are expected to provide data for subsequent processing and molding of HPMC capsules.
View
... Due to the shortage of nonrenewable resources and the deterioration of the environment, the importance of cellulose-based materials has increased in recent years (Onyianta et al. 2020;You et al. 2022). Cellulose is a renewable and abundant natural polymeric material that can be obtained from cotton, wood, bamboo, hemp, bagasse, straw, and many other materials (Tajima et al. 2022;Ono et al. 2022). ...
Hydrophobic and mechanical strength enhancement of hemp fabric and paper enabled by waterborne polyurethane-derived functional coating
Article
Full-text available
  • Jan 2024
  • CELLULOSE
Cellulosic-based materials such as hemp fabric and paper have combined characteristics of renewability, biodegradability, flexibility, and recyclability. However, regular products are not suitable for use in unconventional applications due to inherent limitations, and accordingly, enabling new capabilities is a necessity. To this end, the conversion of regular hemp fabric and paper into high-strength products with hydrophobic function via surface engineering was explored. The fluorinated waterborne polyurethane (FWPU) emulsions were first synthesized as functional coatings by in-situ polymerization. The structure and properties of the FWPU emulsion and film were characterized by FTIR, XRD, SEM, TG, and XPS. The results showed that the grafting of perfluorooctanol imparts WPU film excellent hydrophobicity, and the water contact angle increases from 71.2° to 105.9°. After the FWPU coating, the water contact angles of the hemp fabric and paper increase from 0° to 117.1° and 112.8°, respectively. Quite encouragingly, the coating generation of waterborne polyurethane-derived functional additives led to the increase of mechanical strength by more than 23% and 82%, in the case of qualitative filter paper and hemp fabric. Meanwhile, the folding strength of filter paper is increased by 132 times. Overall, this functionalized waterborne polyurethane coating would direct paper and hemp fabric toward diversified applications.
View
View
Nanocellulose-Based Hydrogels as Versatile Bio-Based Materials with Interesting Functional Properties for Tissue Engineering Applications
Article
  • May 2024
Tissue engineering has emerged as a remarkable field aiming to restore or replace damaged tissues through the use of biomimetic constructs. Among the diverse materials investigated for this purpose, nanocellulose-based...
View
Chemical modification of polysaccharides for sustainable bioplastics
Article
  • May 2024
Sustainable bioplastics have received tremendous interest due to concerns over resource shortages and environmental challenges. Polysaccharide materials, characterized by their abundant availability and excellent mechanical properties, emerge as prime candidates for sustainable bioplastics. However, the high crystallinity and the robust hydrogen bonding networks of polysaccharides profoundly impede their processing and utilization. In this regard, chemical modification serves as a powerful strategy capable of disrupting these stubborn structures, thus improving the molecular chain processability. This review explores the profound implications of chemical modification on the structural reformation of polysaccharide networks. It also offers a comprehensive examination of the strategic approach to implementing structural design and processing methods for polysaccharide-based bioplastics, spanning the entire continuum from feedstocks to products.
View
View
Photopolymerization Pattern of New Methacrylate Cellulose Acetate Derivatives
Article
Full-text available
  • Feb 2024
Polymeric photocrosslinked networks, of particular interest in the design of materials with targeted characteristics, can be easily prepared by grafting light-sensitive moieties, such as methacrylates, on polymeric chains and, after photochemical reactions, provide materials with multiple applications via photopolymerization. In this work, photopolymerizable urethane–methacrylate sequences were attached to free hydroxyl units of cellulose acetate chains in various proportions (functionalization degree from 5 to 100%) to study the properties of the resulting macromolecules and the influence of the cellulosic material structure on the double bond conversion degree. Additionally, to manipulate the properties of the photocured systems, the methacrylate-functionalized cellulose acetate derivatives were mixed with low molecular weight dimethacrylate derivatives (containing castor oil and polypropylene glycol flexible chains), and the influence of UV-curable composition on the photopolymerization parameters being studied. The achieved data reveal that the addition of dimethacrylate comonomers augmented the polymerization rates and conversion degrees, leading to polymer networks with various microstructures.
View
View
Carboxymethyl Scleroglucan Synthesized via O-Alkylation Reaction with Different Degrees of Substitution: Rheology and Thermal Stability
Article
Full-text available
  • Jan 2024
This paper presents the methodology for synthesizing and characterizing two carboxymethyl EOR-grade Scleroglucans (CMS-A and CMS-B). An O-Alkylation reaction was used to insert a hydrophilic group (monochloroacetic acid—MCAA) into the biopolymer’s anhydroglucose subunits (AGUs). The effect of the degree of the carboxymethyl substitution on the rheology and thermal stability of the Scleroglucan (SG) was also evaluated. Simultaneous thermal analysis (STA/TGA-DSC), differential scanning calorimetry (DSC), X-ray Diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Scanning Electron Microscopy, and Energy Dispersive Spectroscopy (SEM/EDS) were employed to characterize both CMS products. FTIR analysis revealed characteristic peaks corresponding to the carboxymethyl functional groups, confirming the modification. Also, SEM analysis provided insights into the structural changes in the polysaccharide after the O-Alkylation reaction. TGA results showed that the carboxymethylation of SG lowered its dehydroxylation temperature but increased its thermal stability above 300 °C. The CMS products and SG exhibited a pseudoplastic behavior; however, lower shear viscosities and relaxation times were observed for the CMS products due to the breakage of the SG triple helix for the chemical modification. Despite the viscosity results, the modified Scleroglucans are promising candidates for developing new engineering materials for EOR processes.
View
Flexible, transparent, and sustainable cellulose-based films for organic solar cell substrates
Article
  • Jan 2024
Cellulose, often considered a highly promising substitute for petroleum-based plastics, offers several compelling advantages, including abundant availability, cost-effectiveness, environmental friendliness, and biodegradability. However, its inherent highly crystalline structure and extensive...
View
Recent Progress in High‐Strength and Robust Regenerated Cellulose Materials
Article
Full-text available
High‐strength petroleum‐based materials like plastics have been widely used in various fields, but their nonbiodegradability has caused serious pollution problems. Cellulose, as the most abundant sustainable polymer, has a great chance to act as the ideal substitute for plastics due to its low cost, wide availability, biodegradability, etc. Herein, the recent achievements for developing cellulose “green” solvents and regenerated cellulose materials with high strength via the “bottom‐up” route are presented. Cellulose can be regenerated to produce films/membranes, hydrogels/aerogels, filaments/fibers, microspheres/beads, bioplastics, etc., which show potential applications in textiles, biomedicine, energy storage, packaging, etc. Importantly, these cellulose‐based materials can be biodegraded in soil and oceans, reducing environmental pollution. The cellulose solvents, dissolving mechanism, and strategies for constructing the regenerated cellulose functional materials with high strength and performances, together with the current achievements and urgent challenges are summarized, and some perspectives are also proposed. The near future will be an exciting era for high‐strength biodegradable and renewable materials. The hope is that many environmentally friendly materials with good properties and low cost will be produced for commercial use, which will be beneficial for sustainable development in the world.
View
Rapid allylation of cellulose without heating in tetra-n-butylphosphonium hydroxide aqueous solution
Article
Full-text available
  • Aug 2020
  • CELLULOSE
Allyl cellulose is an important intermediate for cellulose functionalization because of the high reactivity of the allyl group. In this work, a rapid allylation of cellulose with allyl bromide was realized under mild ambient conditions by using a cellulose solvent, tetra-n-butylphosphonium hydroxide aqueous solution, for the reaction medium. The allylation proceeded with a consecutive change in the state of the reaction system from the initial transparent liquid through a colloidal emulsion to the definitive suspension. The reaction conducted for 1 h yielded allyl cellulose showing a degree of substitution (DS) of ~ 2.0; virtually, however, the substitution to DS ≈ 1.9 was attained at the stage of 10 min elapsing. The reaction behavior was interpreted in terms of a model scheme proposed previously for cellulose benzylation using a similar reaction medium. The allyl products indexed with such a relatively high DS (> 1.8) were well soluble in various organic solvents. It was also shown that the present synthetic process gave rise to no serious degradation of the cellulose main chains nor cross-linking between the introduced allyl groups. Graphic abstract
View
Twenty-five years of cellulose chemistry: innovations in the dissolution of the biopolymer and its transformation into esters and ethers
Article
Full-text available
  • Jan 2019
  • CELLULOSE
The anniversary of the journal “Cellulose” is an opportunity to review innovations that were introduced during the past 25 years. Of these, from our perspective, the development of solvents that dissolve cellulose physically, i.e., without formation of covalent bonds is most relevant. The reasons are that cellulose can be regenerated from these media in different shapes and transformed into many important derivatives. Twenty-five years is a long time-span! As the volume of information on the applications of the above-mentioned solvents in cellulose chemistry is extensive, we made choices to reach a balance between the amount of material covered and the length of the review. Consequently, we focus on cellulose derivatization under homogeneous reaction conditions to produce selected derivatives. We dwell on the latter because a comprehensive discussion was recently published on derivatization under heterogeneous and homogeneous conditions (Heinze et al. in Cellulose derivatives, Springer, Cham, pp 259–292, 2018a). The derivatives selected are esters of organic acids, ionic and nonionic ethers because of their tremendous commercial and scientific importance. Cellulose derivatization in homogeneous media is advantageous because of much better control of product properties relative to those obtained under the heterogeneous counterparts. These properties include degree of substitution in the anhydroglucose unit and along the biopolymer back-bone, and regioselectivity. Thus, novel cellulose derivatives were prepared that are not accessible under heterogeneous conditions. The requirement to dissolve cellulose physically is to disrupt hydrogen bonding and hydrophobic interactions. Thus, the solvents employed to dissolve cellulose are usually composed of strong electrolytes whose cations and anions interact preferentially with cellulose. These electrolytes are used pure or as solutions in water or dipolar aprotic solvents. Salient examples include LiCl/N,N-dimethylacetamide, tetra(n-butyl)ammonium fluoride·3H2O/dimethyl sulfoxide, ionic liquids, salts of quaternary amines and super-bases. We discuss briefly the essentials of each solvent in terms of its mechanism of cellulose dissolution and show the most relevant results regarding its application for obtaining esters and ethers and back the discussion with relevant references. This information is summarized at the end of the review. We hope that this historical perspective shows the innovations made since the first publication of “Cellulose” and points out to future possibilities—with potential industrial application—of this renewable raw material and its biocompatible and biodegradable derivatives. Graphical abstract Open image in new window
View
The new identity of cellulose pulp: A green silver nanoparticles support for highly efficient catalytic hydrogenation of 4-nitrophenol
Article
  • Apr 2022
  • J CLEAN PROD
The uniquely interconvertible transformation of cellulose pulp and paper shows great potential as smart materials for environment remediation. However, performing liquid-phase catalytic reactions involving hydrogenation steps under mild conditions and ambient temperature remains challenging. Herein, we report a facile and eco-friendly strategy to fabricate low-cost, highly effective, and stable pulp-supported silver nanoparticles (AgNPs/pulp). The pulp phase is used to maintain the high catalytic efficiency of the AgNPs/pulp catalyst, while the paper phase remains high stability as the filling material in the reaction column. The as-prepared AgNPs/pulp catalyst exhibits excellent catalytic activity toward NaBH4-mediated reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with a turnover frequency of 605.1 h⁻¹ and a k value of 24.9 × 10⁻³ s⁻¹ at room temperature, which outperforms most of reported cellulose-supported catalysts. Impressively, the AgNPs/pulp catalyst shows outstanding durability during a continuous operation for 72 hours. Such excellent performance can be attributed to the uniform dispersion of the AgNPs/pulp in solution and uniform distribution of Ag NPs on the fiber surface of cotton pulp, which greatly improve the accessibility of reactants and active sites as well as metal-support interactions. This work provides new insights into the understanding of catalytic hydrogenation of 4-NP, which could pave the way for rational design of novel cellulose-based catalysts in organic wastewater treatment.
View
View
Emerging materials and technologies of multi-layer film for food packaging application: A review
Article
  • Feb 2022
  • FOOD CONTROL
Food packaging is an essential component of the development in food industry, as it is capable of protecting food from physical, chemical and biological contamination. Synthetic plastic packaging is by far the most commonly used for packaging; however, it leads to considerable environmental problems. The use of biodegradable plastics derived from natural polymers can address this issue. Nevertheless, natural polymers have poor barrier properties. This review aims to provide an overview of the various polymers used in multi-layer packaging and also to explain their physical, mechanical and barrier properties in detail. Hence, the application of a multi-layer film that combines the unique features of different polymers may produce packaging materials with improved performance, such as mechanical and barrier properties. The properties of multi-layer films with different types of polymers (biomass, synthesis-derived and microbial-derived) are thoroughly discussed. The results show that the multi-layer films possessed superior properties as compared to single-layer films in term of physical, mechanical and gas barrier properties. Suggestions for future research on the compatibility of multi-layer film in packaging applications are also addressed in this review. This paper offers an overview of the development of biodegradable natural polymer multi-layer films for packaging applications in the food industry.
View
Cellulose-based fluorescent macromolecular sensors and their ability in 2, 4, 6-trinitrophenol detection
Article
  • Dec 2021
This article deals with three cellulose-based fluorescent macromolecular sensors by introducing 1,8-naphthalimide fluorophore to cellulose. First, through the etherification reaction of cellulose with BrCH2CH2NH2, –NH2 group–bearing cellulose CS 1 was obtained. Then, the –NH2 group reacts with 4-bromo-1,8-naphthalic anhydride to synthesize a naphthalimide cellulose derivative (CS 2). Finally, the recognition group was introduced by substituting Br atoms, and three cellulose fluorescent probes (CS 3, CS 4, and CS 5) were obtained eventually. Structure and fluorescence properties of the macromolecular sensors were characterized and confirmed. Fluorescence detection measurements show that these probes can be used as selective and sensitive fluorescent sensors to 2,4,6-trinitrophenol (TNP). The detection limits are 0.52 μM, 0.76 μM, and 0.81 μM, indicating good detection performance. This work provides a new method for the selective detection of TNP and also a method to enlarge the application scope of cellulose.
View
Development of Ethyl Cellulose-based Formulations: A Perspective on the Novel Technical Methods
Article
  • Apr 2020
Cellulose is known as the most abundant natural polymer and ethyl cellulose (EC) is one of its important derivatives. Recently, EC, as a non-toxic and biodegradable polymer, has attracted attention thanks to its unique properties such as oleogel formation, delivery of active component, and film-forming ability in the food and pharmaceutical sectors. EC-based oleogels have great promise for replacing with unhealthy hydrogenated oils in food products. The EC emulgel could be used as a fat replacer in different food and drug formulation and also for encapsulation of active components. EC, as a non-digestable and water-insoluble polymer, forms micro- and nano-particles with unique properties. Accordingly, this paper tries to focus on mechanistic review of different methods for the fabrication of EC-based formulations and micro/nanoparticles with emphasis on recent progress on wide range applications of the water-insoluble polymer. Additionally, different techniques are discussed in this paper including oleogelation, anti-solvent, emulsion, Pickering emulsion, and electrospinning for the preparation of EC-based formulations.
View
3D Printing Using Plant-derived Cellulose and Its Derivatives: A Review
Article
  • Sep 2018
  • CARBOHYD POLYM
Three-dimensional (3D) printing is classified as a revolutionary, disruptive manufacturing technology. Cellulose (the most abundant natural polymer) and its many derivatives have been widely studied for many applications. The combination of 3D printing with cellulose-based feedstocks is therefore of critical interest. This review highlights many studies on 3D printing applications of plant-derived cellulose and its derivatives. Potential materials include cellulose ethers/esters, microcrystalline cellulose, nanocellulosic materials, and other products. It focuses on their roles and functions in 3D printing processes and the performance of the resultant printed objects. The outlook for future work is also provided, to underscore critical issues and opportunities.
View
Pharmaceutical Applications of Cellulose Ethers and Cellulose Ether Esters
Article
  • Jun 2018
Cellulose ethers have proven to be highly useful natural-based polymers, finding application in areas including food, personal care products, oil field chemicals, construction, paper, adhesives, and textiles. They have particular value in pharmaceutical applications due to characteristics including high glass transition temperatures, high chemical and photochemical stability, solubility, limited crystallinity, hydrogen bonding capability, and low toxicity. With regard to toxicity, cellulose ethers have essentially no ability to permeate through gastrointestinal enterocytes, and many are already in formulations approved by the US Food and Drug Administration. We review pharmaceutical applications of these valuable polymers from a structure-property-function perspective, discussing each important commercial cellulose ether class; carboxymethyl cellulose, methyl cellulose, hydroxypropylcellulose, hydroxypropyl methyl cellulose, and ethyl cellulose, and cellulose ether esters including hydroxypropyl methyl cellulose acetate succinate and carboxymethyl cellulose acetate butyrate. We also summarize their syntheses, basic material properties, and key pharmaceutical applications.
View