Grafting of cellulose by ring-opening polymerisation – A review

In this review, homogeneous and heterogeneous grafting from cellulose and cellulose derivatives by ring-opening polymerisation (ROP) are reported. Cellulose is biorenewable and biodegradable as well as a stiff material with a relatively low specific weight, foreseen to be an excellent replacement for synthetic materials. By utilising ROP of monomers such as ε-caprolactone or l-lactide from cellulose, composite materials with new and/or improved properties can be obtained. Grafting of solid cellulose substrates, such as cotton, microfibrillated cellulose (MFC) or cellulose nanocrystals, renders cellulose that can easily be dispersed into polymer matrices and may be used as reinforcing elements to improve mechanical and/or barrier properties of biocomposites. A surface grafted polymer can also tailor the interfacial properties between a matrix and the fibrillar structure of cellulose. When derivatives of cellulose are grafted with polymers in homogenous media, amphiphilic materials with interesting properties can be achieved, anticipated to be utilised for applications such as encapsulation and release.     

Preparation,Marriage Chemistry and Applications of Graphene Quantum Dots–Nanocellulose Composite: A Brief Review

Graphene quantum dots (GQDs) are zero-dimensional carbon-based materials, while nanocellulose is a nanomaterial that can be derived from naturally occurring cellulose polymers or renewable biomass resources. The unique geometrical, biocompatible and biodegradable properties of both these remarkable nanomaterials have caught the attention of the scientific community in terms of fundamental research aimed at advancing technology. This study reviews the preparation, marriage chemistry and applications of GQDs–nanocellulose composites. The preparation of these composites can be achieved via rapid and simple solution mixing containing known concentration of nanomaterial with a pre-defined composition ratio in a neutral pH medium. They can also be incorporated into other matrices or drop-casted onto substrates, depending on the intended application. Additionally, combining GQDs and nanocellulose has proven to impart new hybrid nanomaterials with excellent performance as well as surface functionality and, therefore, a plethora of applications. Potential applications for GQDs–nanocellulose composites include sensing or, for analytical purposes, injectable 3D printing materials, supercapacitors and light-emitting diodes. This review unlocks windows of research opportunities for GQDs–nanocellulose composites and pave the way for the synthesis and application of more innovative hybrid nanomaterials.     

Microalgae Biomass as a New Potential Source of Sustainable Green Lubricants

Lubricants are materials able to reduce friction and/or wear of any type of moving surfaces facilitating smooth operations, maintaining reliable machine functions, and reducing risks of failures while contributing to energy savings. At present, most worldwide used lubricants are derived from crude oil. However, production, usage and disposal of these lubricants have significant impact on environment and health. Hence, there is a growing pressure to reduce demand of this sort of lubricants, which has fostered development and use of green lubricants, as vegetable oil-based lubricants (biolubricants). Despite the ecological benefits of producing/using biolubricants, availability of the required raw materials and agricultural land to create a reliable chain supply is still far from being established. Recently, biomass from some microalgae species has attracted attention due to their capacity to produce high-value lipids/oils for potential lubricants production. Thus, this multidisciplinary work reviews the main chemical-physical characteristics of lubricants and the main attempts and progress on microalgae biomass production for developing oils with pertinent lubricating properties. In addition, potential microalgae strains and chemical modifications to their oils to produce lubricants for different industrial applications are identified. Finally, a guide for microalgae oil selection based on its chemical composition for specific lubricant applications is provided.     

Thermoplastic starch films with vegetable oils of Brazilian Cerrado

Starch is one of the most promising natural polymers to be abundant, cheap and biodegradable. To get thermoplastic starch (TPS) is necessary mechanical shake, high temperature and use of plasticizers. In this work, TPS films were prepared by casting from cassava starch and three different vegetable oils of Brazilian Cerrado as plasticizer: buriti, macauba and pequi. The materials were analyzed by TG, DSC and TMA. Thermal properties of oils depend on their chemical structures. Starch and vegetable oils are natural resources that can be used how alternative to producing materials that cause minor environmental impact.     

Physical and mechanical testing of essential oil-embedded cellulose ester films

Polymer films made from cellulose esters are useful for embedding plant essential oils, either for food packaging or air freshener applications. Studies and testing were done on the physical and mechanical properties of cellulose ester-based films incorporating essential oils (EO) from lemongrass (Cybopogon citratus), rosemary pepper (Lippia sidoides) and basil (Ocimum gratissimum) at concentrations of 10 and 20% (v/w). Results obtained showed that, in all films, the addition of the essential oil caused a decrease in the water vapor permeability due to the hydrophobic nature of the oil. The use of 20% of EO caused lower transparency of the films, although the change was not observed visually. Mechanical testing was done on cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate. It was found that incorporation of lemongrass, basil and rosemary pepper EO significantly affected the Young's modulus, tensile strength and elongation at break of the cellulose ester films. The results suggested that the essential oils interacted with the polymers like plasticizers. The results were confirmed with thermal and microscopic studies.     

Cellulose as matrix component of conducting films

Conjugated polymers gain growing importance as conductive materials in industrial applications in various fields of electronic devices. Cellulose with its extraordinary supramolecular structure and material properties can help to awake the possibilities for conducting polymers in interplay of the two materials. The ability of additional derivatization, the stiff and oriented molecular structure and the inherent strength, stability and film-forming properties give cellulose a complementary role to the brittle conjugated polymers, cellulose imparting the features of a stable and robust carrier component. To go forward this way, making a composite out of cellulose and conducting polymers is a prerequisite. Different strategies to form composite materials of non-derivatized cellulose and conductive organic polymers were tested. Significant differences between various mixing strategies as well as between the conducting polymers polyaniline (PAni), polypyrrole (PPy), and polythiophen (PTh) were observed. In situ synthesis of the conducting polymers in cellulose solutions and microcellulose dispersions as well as blending of pre-synthesized conducting polymers in these cellulose systems were tested. Unexpectedly, not homogenous mixtures showed best results in respect to film formation and conductivity, but composites formed by heterogeneous mixtures of the conducting polymers within a cellulose gel. Best results were obtained with finely dispersed PAni. The results support development studies towards circuitry and photo-current systems based on cellulose carriers.     

Polymers containing substituted 2-phenyl-benzoxazole side-chain groups: Synthesis and phase behavior

The synthesis of substituted 2-phenyl-benzoxazoles has been accomplished by ring closure of Schiff bases. The compounds have been used as precursors of acrylic derivatives displaying LC properties: Four comb-like homopolymers have been obtained by radical catalysis from the acrylic monomers. The polymers have been characterized by ¹H-NMR, DSC, x-ray diffraction, viscometry, and polarizing microscopy. Three of the polymers exhibit liquid crystalline properties of smectic type. © 1996 John Wiley & Sons, Inc.     

Synthesis and Characterization of Polymeric Materials from Vegetable Oils

Although the petrochemical polymers have revolutionized the technological development, the intensive use of these materials have contributed to the global pollution. In this context, researches involving ecofriendliness materials are growing up, as well as, a current interest in developing materials from inexpensive and renewable resources, such as vegetable oils. In this work, is described the synthesis of polymeric materials by thermal polymerization from linseed oil (Linum usitatissimum L.) and passion fruit oil (Passiflora edulis) and their characterization by gas chromatographic (GC), Fourier transform infrared (FTIR) spectroscopy, solubility in organic solvents, thermogravimetry (TG), differential scanning calorimetry (DSC) and Raman spectroscopy. The TG curve shows that those polymeric materials present two stages of decomposition. DSC plots of the vegetable oils showed some endothermic and exothermic transitions which are not present in the DSC curves corresponding to oil-based polymers. The Raman spectra of the polymers indicate declining of absorbance in the region of CC stretching (∼1600 cm⁻¹). This absorption was used to estimate the degree of polymerization (79% and 67.5% for linseed and passion fruit oils, respectively).     

Graft polymerisation of ethyl acrylate/methyl methacrylate copolymers: A tool for the consolidation of paper-based materials

Grafting polymerisation of acrylic monomers onto cellulose chains represents a useful method of restoration for both artificially and naturally aged paper-based materials. In this paper, some results concerning the grafting polymerisation of ethyl acrylate/methyl methacrylate 75/25 wt.% copolymer onto several paper grades are reported, highlighting how the presence of fillers in the raw materials reduced the grafting yields. The consolidating and protective effects have been investigated by evaluating the mechanical properties and the wetting behaviour of the grafted samples, and comparing them with the original and aged substrates.     

Recent research progress in the synthesis,properties and applications of ferrocene‐based derivatives and polymers with azobenzene

Aromatic azobenzene derivatives are outstanding organic photochromic compounds that possess unique photochemical properties. These compounds are widely used in research and development for various applications, especially in information storage, owing to their ability to isomerize between cis (Z) and trans (E) forms under the influence of light of different wavelengths. On account of these advantages, many efforts have been made to generalize the use of azobenzene derivatives. Furthermore, ferrocene‐based polymers and derivatives are promising candidates for functional materials due to their unique redox properties. By interlinking ferrocene with azobenzene, novel functional materials can be obtained that will integrate the excellent properties of both and will provide new applications in various fields including information storage, ion recognition, molecular devices, etc. This article provides an overview of the synthesis, properties and applications of novel ferrocene‐based polymers and derivatives containing azobenzene units. Copyright © 2015 John Wiley & Sons, Ltd.     

Novel biobased photo‐crosslinked polymer networks prepared from vegetable oil and 2,5‐furan diacrylate

Novel biobased crosslinked polymer networks were prepared from vegetable oil with 2,5‐furan diacrylate as a difunctional stiffener through UV photopolymerization, and the mechanical properties of the resulting films were evaluated. The vegetable oil raw materials used were acrylated epoxidized soybean oil (AESO), acrylated castor oil (ACO), and acrylated 7,10‐dihydroxy‐8(E)‐octadecenoic acid (ADOD). 2,5‐Furan dicarboxylic acid (FDCA), which can be synthesized through the oxidative dehydration of C6 sugars, was identified by the US Department of Energy as one of 12 priority chemicals for establishing the green chemistry industry of the future. 2,5‐Furan dimethanol (bis‐hydroxymethylfuran), which can be derived from FDCA, was used as a starting material to synthesize 2,5‐furan diacrylate, which was used as a biobased comonomer along with AESO, ACO, or ADOD to form photo‐crosslinked polymer networks. The synthesis of acrylate derivatives was confirmed using FT‐IR and ¹H‐NMR spectroscopic techniques. The composition of the reaction mixture was changed to obtain crosslinked polymer networks with various mechanical properties. The addition of 2,5‐furan diacrylate increased the tensile strengths of the polymer films by up to 1.4–4.2 times relative to those obtained without the addition. These fully biobased polymers derived from vegetable oil and sugar can be used as environmentally friendly renewable materials for various applications to replace the existing petroleum‐based polymers currently used. Copyright © 2013 John Wiley & Sons, Ltd.     

Renewability is not Enough: Recent Advances in the Sustainable Synthesis of Biomass‐Derived Monomers and Polymers

Taking advantage of the structural diversity of different biomass resources, recent efforts were directed towards the synthesis of renewable monomers and polymers, either for the substitution of petroleum‐based resources or for the design of novel polymers. Not only the use of biomass, but also the development of sustainable chemical approaches is a crucial aspect for the production of sustainable materials. This review discusses the recent examples of chemical modifications and polymerizations of abundant biomass resources with a clear focus on the sustainability of the described processes. Topics such as synthetic methodology, catalysis, and development of new solvent systems or greener alternative reagents are addressed. The chemistry of vegetable oil derivatives, terpenes, lignin, carbohydrates, and sugar‐based platform chemicals was selected to highlight the trends in the active field of a sustainable use of renewable resources.     

Ligated anionic polymerization: An innovative elf-atochem technology for the polymerization of (meth)acrylates

Admittedly performing materials, (meth)acrylic polymers, used in a wide variety of applications, are traditionally produced by radical polymerization processes. The extension of living polymerization, originally developed for dienes and vinyl-aromatics, to (meth)acrylic polymers, would be an interesting opening to a variety of products with a large scope of properties and applications. However, this method suffers from chemical and technical limitations when applied to (meth)acrylates under the usual conditions of solvent and temperature. We report how alkoxy alkoxides-based systems combined with a recent Elf Atochem process offer attractive conditions for ultra-fast anionic polymerization of (meth)acrylates at high solid content. Applications to cost effective syndiotactic poly(methyl methacrylate) and block copolymers syntheses are described.     

Carbonaceous residues from biomass gasification as catalysts for biodiesel production

Tars and alkali ashes from biomass gasification processes currently constitute one of the major problems in biomass valorisation,generating clogging of filters and issues related with the purity of syngas production.To date,these waste residues find no useful applications and they are generally disposed upon generation in the gasification process.A detailed analysis of these residues pointed out the presence of high quantities of Ca(>30 wt%).TG experiments indicated that a treatment under air at moderate temperatures(400-800 C) decomposed the majority of carbon species,while XRD indicated the presence of a crystalline CaO phase.CaO enriched valorized materials turned out to be good heterogeneous catalysts for biodiesel production from vegetable oils,providing moderate to good activities(50%-70% after 12 h) to fatty acid methyl esters in the transesterification of sunflower oil with methanol.     

A Review of Cellulose and Cellulose Blends for Preparation of Bio-derived and Conventional Membranes,Nanostructured Thin Films,and Composites

Cellulose has been used as a raw material for the manufacture of membranes and fibers for many years. This review gives the background of the most recent methods of treating or dissolving cellulose, and its derivatives to form polymer films or membranes for a variety of applications. Indeed, some potential applications of bacterial cellulose, nanofibrillar cellulose (NFC) for films showing enhanced barrier characteristics are reviewed as well as the utilization of cellulose nanonocrystals (CNC) for production of highly oriented super strong films or thin films is discussed. Because of the success of the Lyocell process as well as the amine/metal thiocyanate solvent blends of cellulose and other polysaccharides like starch, chitosan, and other natural polymers. Consequently, the use of cellulose (or its derivatives) and another polysaccharide dissolved as a blend is also elaborated. It is our hope that the reader will want to follow up and investigate these new systems and use them to develop end use materials for all sorts of applications, from medical to water filtration, or electrogels for use in batteries.     

Green and Efficient Processing of Cinnamomum cassia Bark by Using Ionic Liquids: Extraction of Essential Oil and Construction of UV‐Resistant Composite Films from Residual Biomass

There is significant interest in the development of a sustainable and integrated process for the extraction of essential oils and separation of biopolymers by using novel and efficient solvent systems. Herein, cassia essential oil enriched in coumarin is extracted from Cinnamomum cassia bark by using a protic ionic liquid (IL), ethylammonium nitrate (EAN), through dissolution and the creation of a biphasic system with the help of diethyl ether. The process has been perfected, in terms of higher biomass dissolution ability and essential oil yield through the addition of aprotic ILs (based on the 1‐butyl‐3‐methylimidazolium (C₄mim) cation and chloride or acetate anions) to EAN. After extraction of oil, cellulose‐rich material and free lignin were regenerated from biomass–IL solutions by using a 1:1 mixture of acetone–water. The purity of the extracted essential oil and biopolymers were ascertained by means of FTIR spectroscopy, NMR spectroscopy, and GC‐MS techniques. Because lignin contains UV‐blocking chromophores, the oil‐free residual lignocellulosic material has been directly utilized to construct UV‐light‐resistant composite materials in conjunction with the biopolymer chitosan. Composite material thus obtained was processed to form biodegradable films, which were characterized for mechanical and optical properties. The films showed excellent UV‐light resistance and mechanical properties, thereby making it a material suitable for packaging and light‐sensitive applications.     

Comparison of nano- and microfibrillated cellulose films

Nanocellulose is an interesting building block for functional materials and has gained considerable interest due to its mechanical robustness, large surface area and biodegradability. It can be formed into various structures such as solids, films and gels such as hydrogels and aerogels and combined with polymers or other materials to form composites. Mechanical, optical and barrier properties of nanofibrillated cellulose (NFC) and microfibrillated cellulose (MFC) films were studied in order to understand their potential for packaging and functional printing applications. Impact of raw material choice and nanocellulose production process on these properties was evaluated. MFC and NFC were produced following two different routes. NFC was produced using a chemical pretreatment followed by a high pressure homogenization, whereas MFC was produced using a mechanical treatment only. TEMPO-mediated oxidation followed by one step of high pressure (2,000 bar) homogenization seems to produce a similar type of NFC from both hardwood and softwood. NFC films showed superior mechanical and optical properties compared with MFC films; however, MFC films demonstrated better barrier properties against oxygen and water vapor. Both the MFC and NFC films were excellent barriers against mineral oil used in ordinary printing inks and dichlorobenzene, a common solvent used in functional printing inks. Barrier properties against vegetable oil were also found to be exceptionally good for both the NFC and MFC films.     

Preparation of new types of temperature-responsive cellulose derivatives

This paper reviews briefly our preliminary results concerning thermoplastic hydrogels and thermotropic aqueous gels from cellulose. Several kinds of thermoplastic hydrogels and thermotropic aqueous gels were prepared from cellulose and their thermal properties were examined. The former aims at preparing water-insoluble cellulose derivatives having a high water absorbency and a thermal flow temperature of approximately 130°C, while the later aims at preparing water-soluble cellulose derivatives which show a solubility behavior similar to that of synthetic polymers with a lower critical solution temperature (LCST) in aqueous solution. The results will be discussed in terms of the chemical structure of the prepared derivatives and their substituent distributions along the cellulose chain.     

Silyl celluloses: A new class of soluble cellulose derivatives

Two general methods for the silylation of cellulose have been developed. Silyl amides undergo silyl—proton exchange reactions with cellulose in polar solvents leading to displacement of 80–90% of the hydroxyl protons by silyl groups. The same products are obtained by reaction of the corresponding chlorosilanes with cellulose in pyridine; however, di- and trifunctional impurities present in commercial chlorosilanes have to be removed by scavenging with a carbohydrate in order to avoid crosslinking. Cellulose derivatives with trimethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, and γ-cyanopropyldimethylsilyl substituents have been prepared by both methods. The properties of the new soluble polymers are largely dependent on the nature of the silyl substituents. The silyl celluloses exhibit a relatively high degree of hydrolytic stability; methyldiphenylsilyl cellulose is hydrolytically stable even under severe conditions.     

AGRO-MATERIALS: A BIBLIOGRAPHIC REVIEW

ABSTRACT

Facing the problems of plastic recycling and fossil resources exhaustion, the use of biomass to conceive new materials appears like a reasonable solution. Two axes of research are nowadays developed: on the one hand the synthesis of biodegradable plastics, whichever the methods may be, and on the other hand the utilization of raw biopolymers, which is the object of this article. From this perspective, the “plastic” properties of natural polymers, the characteristics of the different classes of polymers, the use of charge in vegetable matrices, and the possible means of improving the durability of these agro-materials are reviewed.