Plant oil renewable resources as green alternatives in polymer science

The utilization of plant oil renewable resources as raw materials for monomers and polymers is discussed and reviewed. In an age of increasing oil prices, global warming and other environmental problems (e.g. waste) the change from fossil feedstock to renewable resources can considerably contribute to a sustainable development in the future. Especially plant derived fats and oils bear a large potential for the substitution of currently used petrochemicals, since monomers, fine chemicals and polymers can be derived from these resources in a straightforward fashion. The synthesis of monomers as well as polymers from plant fats and oils has already found some industrial application and recent developments in this field offer promising new opportunities, as is shown within this contribution. (138 references.)     

UN sustainable development goals: How can sustainable/green chemistry contribute? Green chemistry as a source of sustainable innovations in the cosmetic industry

Sustainable innovation is a key-objective for our Group that has recently integrated the principles of sustainable development into all stages of a product's life cycle, from its design to consumer use. The following ambitious commitment: 100% of its products should bring an environmental (or social benefit) by 2020, will be reached, in particular, by integrating and giving a constant privilege to renewable raw materials -or ingredients-that originate from sustainable resources that fully comply with the green chemistry rules. In this short review, integration of Green Chemistry principles by our Group, strategies to identify new performing ingredients through sustainable chemistry as well as illustrative examples of innovative raw materials will be presented. With regard to the crucial respect of the environment of our planet, sustainable chemistry has become an indispensable turning point for industrial groups highly devoted to innovation.     

Green polymer chemistry: new methods of polymer synthesis using renewable starting materials

The present article reviews the recent results reported mainly from our group on “green polymer chemistry”. Characteristic important aspects of green polymer chemistry include herein, typically (1) using renewable resources as starting materials for polymer production, and (2) employing green method for the polymer synthesis. As renewable starting materials, the following materials were employed; lactic acid, itaconic anhydride, renewable plant oils, and cardanol. Polymer production using these materials contributes to mitigate the carbon dioxide emission because of their “carbon neutral” nature. As green method, lipase enzyme was mainly used for polymerization catalyst, since lipase is a natural benign catalyst, showing a specific catalysis as well as recyclable character. Polymer synthesis from these materials and the catalyst provided various value-added functional polymers, demonstrating good examples of green polymer chemistry.

     

Biomass-based green chemistry: sustainable solutions for modern economies

Abstract

Biomass and renewable raw materials are the basis and driver for an even greater alignment of industry to the principles of green chemistry and sustainability. Nature provides a remarkably wide range of renewable raw materials with varying properties and differing chemical compositions. Renewable raw materials are therefore especially interesting as alternatives to fossil resources for energy generation and as starting materials for industrial chemistry. Since various forms of biomass are also essential for human nutrition and animal feed, their use as feedstocks for other purposes must be balanced. Ideally, the biomass remaining after the nutritious components are removed can serve as a feedstock. Examples of applications that use biomass as starting materials include adhesives, textile and leather, cosmetics, cleaning agents, coatings, paints, printing inks, crop protection, lubricants and dietary supplements.     

Alkylpolyglycoside: Carbohydrate Based Surfactant

Carbohydrates are growing important renewable raw material for surfactant industry. The development of surfactants based on carbohydrate and vegetable oils is the result of the product concept based on the exclusive use of natural resources. Sugar based surfactants are gaining increased attention due to advantage with regard to performance, health of consumer and environmental compatibility compared to some standard product.

Alkylpolyglycoside (APG) is nonionic surfactant prepared from renewable raw materials namely glucose and fatty alcohol. Such products are expected to exhibit surface‐active properties due to the presence of the hydrophilic sugar moiety and the hydrophobic fatty alcohol residues. This article deals with the synthesis of alkylpolyglycoside and the study their surface active properties.

APG was prepared by using fatty alcohol varying in chain length from C8‐C18.

Effect of alkyl chain length of APG on the basic characteristics such as surface tension, interfacial tension, lime soap dispersing power, detergency, foaming, and wetting were studied.

Alkylpolyglycoside prepared from octanol, decanol, and dodecanol are water soluble and shows good surface active properties where as those prepared from long chain fatty alcohols were water insoluble and, therefore, not evaluated for their surface active properties. Incorporation of APG in toilet soap was studied.     

Oils and fats as renewable raw materials in chemistry

Oils and fats of vegetable and animal origin have been the most important renewable feedstock of the chemical industry in the past and in the present. A tremendous geographical and feedstock shift of oleochemical production has taken place from North America and Europe to southeast Asia and from tallow to palm oil. It will be important to introduce and to cultivate more and new oil plants containing fatty acids with interesting and desired properties for chemical utilization while simultaneously increasing the agricultural biodiversity. The problem of the industrial utilization of food plant oils has become more urgent with the development of the global biodiesel production. The remarkable advances made during the last decade in organic synthesis, catalysis, and biotechnology using plant oils and the basic oleochemicals derived from them will be reported, including, for example, ω‐functionalization of fatty acids containing internal double bonds, application of the olefin metathesis reaction, and de novo synthesis of fatty acids from abundantly available renewable carbon sources.     

Terpene bioconversion--how does its future look?

The usage of essential oils as such or of volatile fractions thereof is widespread in the flavor and fragrance industry to aromatize perfumery and cosmetic products, foodstuffs, and many household and pharmaceutical products. The increased market share of convenience food together with consumers' request for constant high quality and natural products have established a lasting increase in the demand for natural flavorings that cannot be satisfied by the traditional plant materials. This review summarizes selected work on terpene bioconversion/transformation and focuses on recently published papers dealing with novel strains and products, high product yields, intriguing genetic engineering approaches, and integrated bioprocesses. The future perspectives of an industrial realization of a biotechnological production of terpene-derived natural flavors are critically evaluated.     

Synthesis and Characterization of a Bio-Based Resin from Linseed Oil

Summary: The use of renewable raw materials in the polymer industries is becoming increasingly popular because of environmental concerns and the need to substitute fossil resources. Plant oils with triglyceride backbones can be chemically modified and used to synthesize polymers from renewable resources (biopolymers). In the present study, linseed oil was epoxidized using a chemo-enzymatic method based on Candida Antarctica lipase B (CALB) as a biocatalyst and the modified linseed oil was cured using maleinated linseed oil and a commercial polyamide resin. The amount of epoxidation achieved depended on the amount of lipase used and was determined by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies. With 20% (weight per weight) catalyst concentration based on the wt % of oil a degree of epoxidation of > 90% was achieved. The cross-linking reaction of epoxidized linseed oil with the maleinated linseed oil and the polyamide resin was studied using differential scanning calorimetry (DSC). DSC traces showed that an increase in epoxidation degree lead to larger values for the exothermic enthalpy integrals of the curing reactions and hence to a higher reactivity of the linseed oil towards the cross-linking agents.     

Industrial Waste Utilization for Low-Cost Production of Raw Material Oil Through Microbial Fermentation

In view of ever-growing demand of biodiesel, there is an urgent need to look for inexpensive and promising renewable raw material oils for its production. In this context, the aim of this study was to evaluate the potential use of industrial wastes for low-cost production of oils through microbial fermentation. Among the strains tested, Yarrowia lipolytica grew best and produced highest lipid when grown on decanter effluent from palm oil mill. When crude glycerol by-product from a biodiesel plant was added into the effluent as a co-substrate, Y. lipolytica produced a higher biomass of 3.21 g/L and a higher amount of lipid of 2.21 g/L which was 68 % of the dry weight. The scale up and process improvement in a 5-L bioreactor increased the biomass and lipid up to 5.53 and 2.81 g/L, respectively. A semi-continuous mode of operation was an effective mode for biomass enhancement while a fed-batch mode was effective for lipid enhancement. These yeast lipids have potential to be used as biodiesel feedstocks because of their similar fatty acid composition to that of plant oil.     

Characterization of Catalysts for Glycerol Ester Production with Various Acetylating Agents

The use of raw materials from renewable sources by industries is essential to the sustainable development of modern society. The biodiesel produced by the transesterification of vegetable oils is a less polluting diesel fuel, but large amounts of glycerol (10% of total weight of product) are generated during the production process. The scientific community and industries of the sector know that, in the future, the amount of glycerol generated can cause a serious ecologic problem. Thus, it is essential to find alternatives for the consumption of this co-product, in its crude form and/or as high value-added derivatives. This work studied obtaining triacetate from the glycerol esterification reaction that was determined by electrospray ionization–mass spectrometry and gas chromatography–mass spectrometry. The reactions were carried out with sulfuric acid, phosphotungstic acid and in the absence of catalyst, using different acetylating agents (acetic acid and acetic anhydride). The phosphotungstic acid showed satisfactory performance in the catalytic esterification of glycerol when acetic acid and acid anhydride were used. The use of acetic anhydride as the acetylating agent favors the esterification reaction, decreasing the reaction time required for obtaining glycerol triacetate.     

Formulation of Environmentally Safe Graffiti Remover Containing Esterified Plant Oils and Sugar Surfactant

The removal of graffiti or over-painting requires special attention in order to not induce the surface destruction but to also address all of the important eco-compatibility concerns. Because of the necessity to avoid the use of volatile and toxic petroleum-based solvents that are common in cleaning formulations, much attention has recently been paid to the design of a variety of sustainable formulations that are based on biodegradable raw materials. In the present contribution we propose a new approach to graffiti cleaning formulations that are composed of newly synthesized green solvents such as esterified plant oils, i.e., rapeseed oil (RO), sunflower oil (SO), or used cooking oil (UCO), ethyl lactate (EL), and alkylpolyglucosides (APGs) as surfactants. Oil PEG-8 ester solvents were synthesized through the direct esterification/transesterification of these oils using monobutyltin(IV) tris(2-ethylhexanoate) and titanium(IV) butoxide catalysts under mild process conditions. The most efficient formulations, determined by optimization through the response surface methodology (RSM) was more effective in comparison to the reference solvents such as the so-called Nitro solvent (denoting a mixture of toluene and acetone) and petroleum ether. Additionally, the optimal product was found to be effective in removing graffiti from glass, metal, or sandstone surfaces under open-field conditions in the city of Wrocław. The performed studies could be an invaluable tool for developing future green formulations for graffiti removal.     

What Does the Chemical Industry Expect from Physical and Industrial Chemistry?

Process innovation—the systematic optimization of raw materials, energy consumption and product yields—is a constant challenge for those operating plants producing vital basic and intermediate chemicals. The production processes, rather than the products themselves, exhibit life cycles and determine the profitability of downstream manufacturing. The ongoing task of interdisciplinary teams of experts is not just to develop new process routes, but, more commonly, to improve individual process steps. The impulse for this innovation arises from changes in the price and availability of raw materials, economic and environmental considerations and, last but not least, scientific and technological progress. This paper illustrates the opportunities available using examples which have already been put into practice as well as problems not yet resolved. Questions such as the use of alternative feedstocks and the switch to catalytic processes arc addressed and used to suggest novel ideals for basic research. Worthwhile projects are identified in the area of industrial oxidation, both catalytic and non-catalytic. A highly developed, systematic, computer-based method for optimizing the integration of energy flows within a plant is presented and novel measurement techniques for efficient production control and product quality are. discussed. The successful realization of such concepts requires the ability and the willingness to think in terms of new approaches to problem solving, making this an important objective for university education geared to future needs.     

Ethanol from babassu coconut starch

This study describes a pioneering industrial-scale experience by Tobasa in ethanol production from the amylaceous flour obtained by mechanical processing of the babassu mesocarp. Technical aspects related to enzymatic and fermentation processes, as well as overall economical aspects, are discussed. When produced in a small-size industrial plant (5000 L/d), babassu ethanol has a final cost of about $218/m³. The impact of raw materials, production, and processing (enzymes, steam, energy, and so on) on the final product cost is also presented. Babassu coconut ethanol can be produced at low cost, compared with traditional starchy raw materials or sugar cane. The net profitability of ethanol production is about 40% for babassu coconut and just 10% for sugar cane. If the estimated renewable babassu resources were entirely industrially used, 1 billion L/yr of ethanol could be produced, which would roughly correspond to 8% of the current Brazilian ethanol production.

     

E factors, green chemistry and catalysis: an odyssey

The development of green chemistry is traced from the introduction of the concepts of atom economy (atom utilisation) and E factors in the early 1990s. The important role of catalysis in reducing or eliminating waste is emphasised and illustrated with examples from heterogeneous catalytic oxidations with hydrogen peroxide, homogeneous catalytic oxidations and carbonylations and organocatalytic oxidations with stable N-oxy radicals. Catalytic reactions in non-conventional media, e.g. aqueous biphasic, supercritical carbon dioxide and ionic liquids, are presented. Biotransformations involving non-natural reactions of enzymes, e.g. ester ammoniolysis, and the rational design of semi-synthetic enzymes, such as vanadate phytase, are discussed. The optimisation of enzyme properties using in vitro evolution and improvement of their operational stability by immobilisation as cross-linked enzyme aggregates (CLEA) are presented. The ultimate in green chemistry is the integration of catalytic steps into a one-pot, catalytic cascade process. An example of a chemoenzymatic synthesis of an enantiomerically pure amino acid in water and a trienzymatic cascade process using a triple-decker oxynitrilase/nitrilase/amidase CLEA are discussed. Finally, catalytic conversions of renewable raw materials are examined and the biocatalytic aerobic oxidation of starch to carboxy starch is presented as an example of green chemistry in optima forma i.e. a biocompatible product from a renewable raw material using a biocatalytic air oxidation.     

Optimization of microwave-assisted hydro-distillation essential oil extracted from Rumex Crispus leaves using definitive screening design

Conversion of nonfood natural products to value-added products is an important work, which is going on worldwide. In addition, to obtain a product with better quality, a sufficient separation method is helpful to improve its utilization value by using effective, rapid and environmentally friendly techniques. Thus in this work, the microwave-assisted hydrodistillation (MAHD) process of essential oils from important natural plant Rumex Crispus leaves was investigated. The experimental design and extraction conditions were optimized using a definitive screening design. The yield of essential oils of 4.67 ± 0.02 % was investigated under the optimum conditions; 534.89 W of microwave power, 23.48 min of hydrodistillation time and 4.5 mL/g of the volume of water to plant mass ratio. Under these conditions, the essential oils were analyzed using gas chromatography-mass spectrometry (GC–MS). Results revealed that the essential oil extracted by MAHD possessed high quality as proved by its higher percentage of oxygenated compounds. In addition, α-santol (29.63 %) and β-santol (25.60 %) are the primary components of oxygenated compounds in essential oils. In conclusion, the MAHD was successfully employed to obtain mainly Oxygenated compounds-rich essential oil that may be used in several industrial applications. Subsequently, a definitive screening design may be regarded as an alternative and reliable method for the prediction of experimental parameters. It was concluded that the weeds plant (Rumex Crispus) contains a reliable quantity of oils that is extremely feasible to use and recommended as good feedstock for possible use in industrial applications.     

10 years after rio-concepts on the contribution of chemistry to a sustainable development

The principles of the United Nations Conference on Environment and Development (UNCED), held in June 1992 in Rio de Janeiro, and Agenda 21, the comprehensive plan of action for the 21st century, adopted 10 years ago by more than 170 governments, address the pressing problems of today and also aim at preparing the world for the challenges of this century. The conservation and management of resources for development are the main focus of interest, to which the sciences will have to make a considerable contribution. Natural, economic, and social sciences will have to be integrated in order to achieve this aim. In their future programs, the associations of the chemical industries in Europe, Japan, and the USA have explicitly accepted their obligation to foster a sustainable development.In this review we investigate innovations in chemistry exemplarily for such a development with regard to their ecological, economical, and social dimensions from an integrated and interdisciplinary perspective. Since base chemicals are produced in large quantities and important product lines are synthesized from them, their resource-saving production is especially important for a sustainable development. This concept has been shown, amongst others, by the example of the syntheses of propylene oxide and adipic acid. In the long run, renewable resources that are catalytically processed could replace fossil raw materials. Separation methods existing today must be improved considerably to lower material and energy consumption. Chemistry might become the pioneer of an innovative energy technique.The design of chemical products should make possible a sustainable processing and recycling and should prevent their bio-accumulation. Methods and criteria to assess their contribution to a sustainable development are necessary. The time taken to introduce the new more sustainable processes and products has to be diminished by linking their development with operational innovation management and with efficient environmental-political control procedures.     

Enhancement of the fermentation process and properties of bacterial cellulose: a review

Cellulose produced by bacteria (BC) has attracted increasing interest in view of its superior properties with respect to nanofibrillar structure, high purity and biocompatibility. Despite the intensive research, industrial production of BC has been limited, due to the low productivity, and the high cost of raw materials. This paper reviews the new approaches tried recently to get BC production feasible at large scale as the reduction in the quality of raw materials, the use of by-products and the optimization of the culture method. In addition, the new trends of enhancing specific properties of BC by varying culture conditions or by using additives have been reviewed. Thus, the paper presents how to obtain and enhance a desired property of BC for a specific use. This new approach will help researchers to develop new ideas in this field which will favour the commercialization of products made with BC and their industrial application.     

基于甘油三酸酯的高分子材料Ⅱ.乙烯基聚合物等及复合材料、杂化材料

甘油三酸酯是一种可再生资源,可以从向日葵、棉花、亚麻籽等植物中提取得到。基于甘油三酸酯制造高分子材料可通过许多方法,如缩合反应、自由基反应、阳离子聚合反应等。文章是"基于甘油三酸酯的高分子材料Ⅰ.聚酯和聚氨酯"的续篇,综述乙烯基聚合物等及复合材料、杂化材料的研究进展。     

Accelerated artificial ageing of new dimer fatty acid-based polyamides

Replacing petroleum-based raw materials with renewable resources is now a major challenge in terms of economical and environmental viewpoints. Vegetable oils are expected to be an interesting alternative to produce a new generation of bio-based polymers. Due to the possible outdoor exposure in diverse applications, knowledge of the resistance to weather of these new materials is an important issue, not only for aesthetic aspects as in rapid yellowing, but also for changes in their properties. New innovative dimer acid-based bio-polyamides (DAPA) were exposed to an artificial ageing environment produced by a UV/condensation weathering device for different times. To follow and to evaluate this material ageing, several techniques were employed to correlate the chemical modifications, with the morphology and the mechanical properties. The formation of peroxide was found to be very rapid and accompanied by high gel fraction formation and chain breaking. Infrared spectroscopy showed a build-up of carbonyl absorption in the range 1700-1780 cm⁻¹, due to primary and secondary photo-oxidation products. In correlation with these morphological evolutions and in agreement with the high decrease of fusion enthalpy by differential scanning calorimetry, X-Ray diffraction showed an amorphous solid state after ageing. Strain-stress measurements revealed a change in DAPA behaviour, varying from a ductile to an elastomeric material, before and after ageing, respectively.     

Exploration of cardanol-based phenolated and epoxidized resins by size exclusion chromatography and MALDI mass spectrometry

Cardanol and cardanol derivatives are among the most important biobased materials currently investigated in green chemistry, as renewable and promising building blocks in lieu of traditional raw materials from non renewable resources, in particular owing to the olefinic linkages on the C15 alkyl side-chain. Despite the increasing interest they arouse, analytical chemistry dedicated to cardanol and associated resins has been rarely reported in the literature, found even poorer when dealing with chromatography and mass spectrometry. In this work, a thorough molecular characterization was conducted using matrix assisted laser desorption ionization (MALDI) mass spectrometry, size exclusion chromatography (SEC), and SEC–MALDI coupling to gain insights into the composition of phenolated, epoxidized, and epoxidized phenolated cardanol. A nomenclature was proposed to properly describe the numerous species found in these materials, while simulations of the unsaturation patterns and their comparison with the detected patterns in MALDI-MS gave useful details about the phenolation treatment expected to occur on the polyunsaturated C15 side chain. Finally, the SEC–MALDI off-line coupling allowed SEC peaks to be deconvoluted by mass spectrometry and MALDI artefacts related to matrix adduction to be pointed out.