Bio-based Raw Materials Research Articles

Thermal Insulation and Sound Absorption Properties of Open-Cell Polyurethane Foams Modified with Bio-Polyol Based on Used Cooking Oil.

The main goal of this work was to evaluate the thermal insulation and sound absorption properties of open-cell rigid polyurethane foams synthesized with different contents of cooking oil-based polyol. The content of the applied bio-polyol as well as flame retardant (triethyl phosphate) in the foam formulation had a significant influence on the cellular structures of the materials. The open-cell polyurethane foams were characterized by apparent densities in the range 16–30 kg/m3. The sound absorption coefficients of the polyurethanes with various contents of bio-polyol were determined using the standing wave method (Kundt’s tube) in the frequency range of 100–6300 Hz. The effect of the content of the bio-polyol and flame retardant on the coefficient of thermal conductivity (at average temperatures of 0, 10 and 20 °C) as well as the compressive strength (at 20 and −10 °C) was analyzed. Different trends were observed in terms of the thermal insulation properties and sound absorption ability of the open-cell polyurethanes due to the addition of bio-polyol. In conclusion, it is necessary to use systems containing both petrochemical and bio-based raw materials.

Synthesis of Biobased Polycarbonate by Copolymerization of Menth-2-ene Oxide and CO2 with Exceptional Thermal Stability

There is an urgent need for biobased raw materials, which are not food relevant and could serve as the base for novel sustainable polymers. Menthol is such a potential material, which is available ...

Near-infrared light responsive shape memory polymers from bio-based benzoxazine/epoxy copolymers produced without using photothermal filler

Shape memory polymers (SMPs) that can be actuated by a near-infrared (NIR) light are of high interest due to their potential applications in biomedical field. In this work, SMPs that could be actuated by an NIR light without using any NIR photothermal filler was introduced for the first time. Benzoxazine/epoxy (V-fa/ECO) copolymers with a shape memory property were synthesized from bio-based raw materials, which were vanillin, furfurylamine, paraformaldehyde, and epoxidized castor oil. The glass transition temperature of the copolymers could be tuned from 144 to 14 °C, by increasing the ECO content from 40 to 60% by weight. The V-fa/ECO copolymers were found to exhibit a shape memory property that could be remotely actuated by an NIR laser with a wavelength of 808 nm. A high recovery ratio of 100% within a 30 s of NIR irradiation was achieved when the percent weight of ECO in the copolymers was at least 50. We found that the shape memory property of V-fa/ECO copolymers was due to their photothermal effect in the NIR region that could induce the shape recovery process. The temperature of V-fa/ECO copolymers rose from room temperature to 100 °C within a 30 s of NIR irradiation (laser power density of 2.5 W/cm2). It was proposed that the π-conjugation in benzene rings of copolymers might play role on their NIR photothermal effect, due to the π-π interactions between polymer chains. The findings of this study suggested a new way to produce NIR light responsive SMPs without using any NIR photothemal filler.

Continuous Flow Upgrading of Selected C2–C6Platform Chemicals Derived from Biomass

The ever increasing industrial production of commodity and specialty chemicals inexorably depletes the finite primary fossil resources available on Earth. The forecast of population growth over the next 3 decades is a very strong incentive for the identification of alternative primary resources other than petro-based ones. In contrast with fossil resources, renewable biomass is a virtually inexhaustible reservoir of chemical building blocks. Shifting the current industrial paradigm from almost exclusively petro-based resources to alternative bio-based raw materials requires more than vibrant political messages; it requires a profound revision of the concepts and technologies on which industrial chemical processes rely. Only a small fraction of molecules extracted from biomass bears significant chemical and commercial potentials to be considered as ubiquitous chemical platforms upon which a new, bio-based industry can thrive. Owing to its inherent assets in terms of unique process experience, scalability, and reduced environmental footprint, flow chemistry arguably has a major role to play in this context. This review covers a selection of C2 to C6 bio-based chemical platforms with existing commercial markets including polyols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, 1,4-butanediol, xylitol, and sorbitol), furanoids (furfural and 5-hydroxymethylfurfural) and carboxylic acids (lactic acid, succinic acid, fumaric acid, malic acid, itaconic acid, and levulinic acid). The aim of this review is to illustrate the various aspects of upgrading bio-based platform molecules toward commodity or specialty chemicals using new process concepts that fall under the umbrella of continuous flow technology and that could change the future perspectives of biorefineries.

Renewable castor oil and DL-limonene derived fully bio-based vinylogous urethane vitrimers

The utilization of bio-based precursors to prepare materials is highly desirable for the consideration of sustainable energy and materials. Vitrimers have received considerable attention because of their high mechanical performance that is comparable to conventional thermosets and advantageous reprocessability that allows to be recycled. However, most vitrimers are prepared from petroleum-based raw materials, and only a few examples employ bio-based raw materials, of which most utilize transesterification dynamic chemistry that often requires external catalyst that may leach or decompose during reprocessing. Herein, we report a catalyst-free vinylogous urethane vitrimer derived from renewable castor oil and DL-limonene. Prepared vitrimer shows excellent reprocessability and shape memory properties. We also envisaged that the strategy of preparing bio-based vitrimers reported here can be generalized to other bio-based raw materials that are rich in double bonds.

Replacement of traditional unsaturated acid by bio-based itaconic acid in the preparation of isophthalic acid-based unsaturated polyester resin

Unsaturated Polyesters Resins (UPR) are largely prepared using non-renewable resources. Today the need is to make use of bio-based raw materials to reduce the use of petroleum-based chemicals, which in turn contributes to sustainability. The objective of this research was to investigate the effect of use of bio-based monomer i.e. itaconic acid for the synthesis of Unsaturated Polyester Resin (UPR) as replacement to traditional material like maleic anhydride. The synthesis of partial bio-based UPR involves the reactions of itaconic acid and maleic anhydride at different molar concentrations with isophthalic acid and neopentyl glycol were carried out. The synthesized resin was further characterized by gel permeation chromatography (GPC) and Fourier transform infrared spectroscopy (FTIR). Also, curing parameters were studied. Further synthesized UPR was processed into sheets of 3.5 mm thickness and the thermal and mechanical behaviour were tested by using dynamic mechanical experiments and thermal analysis. Substitution of maleic anhydride by itaconic acid proved to be advantageous since it offers improved mechanical properties with slight compromise of thermal properties.

Ineos is poised to make bio-PVC in Germany

Ineos is set to become one of the first companies to produce polyvinyl chloride from a biobased raw material, and not everyone thinks it’s a good idea. The feedstock Ineos has chosen is tall oil, a byproduct of papermaking. PVC is usually made by combining chlorine with ethylene obtained from fossil fuel. Ineos will substitute some tall oil for fossil-derived naphtha to produce ethylene in one of its crackers in Cologne, Germany. The firm has an agreement to source the tall oil from the Finnish paper firm UPM Biofuels. The two crackers have a combined annual output of 1.3 million metric tons (t) of ethylene, which Ineos converts into more than 4 million t of PVC, polyethylene, and other products. Ineos isn’t saying how much of that output will be based on tall oil. Ineos is branding its bio-PVC as Biovyn. It is set for use in products including food

Development of Biodegradable Packaging Materials from Bio-Based Raw Materials

Seaweed, creatures and cellulose based packaging materials are biodegradable and promising natural polymer and their films can be prepared from bio-based raw materials. This article reviews the basic information and recent developments of both seaweed, creatures, cellulose and plant based biopolymer materials as well as analyses the feasible formation of seaweed/creatures/cellulose/plant based biodegradable packaging films which possesses excellent mechanical strength and water resistance properties. Moreover, bio-based packaging films can prolong a product’s shelf life while maintaining its biodegradability. Additionally, the films show potential in contributing to the bio-economy. These type of bio-based materials exhibit interesting film-forming properties that can be used in biomedical application and for making composites for packaging. Bio-based films can be used for the large-scale applications in food packaging in place of synthetic petroleum based non-degradable packaging. Bio-based films have the potential to be used in textile and decoration paper industries also. Currently, bio packaging gains huge attention to the scientist and general people because this type packaging materials are environmental friendly products. Some of the viewpoints are highlighted for future developments and applications.

Facile fabrication, mechanical property and flame retardancy of aerogel composites based on alginate and melamine-formaldehyde

Aerogel composites based on melamine-formaldehyde (MF) and alginate (A) was fabricated with ice-templated method. The preparation process involves two cross-linking processes, in aerogel precursor at room temperature and in dried aerogel at 80 °C (100% humidity), respectively. Cross-linking was demonstrated to be very efficient for improving the mechanical property and water resistance of MF-A aerogels. The obtained aerogels have compressive moduli ranging from 1.2 MPa to 24.1 MPa. All the cross-linked aerogels display good dimensional stability when soaked in water. The morphological study of MF-A aerogels show a layered or network microstructure, with a homogeneous distribution of MF spheres. Due to low density and porous structure, MF-A aerogels have low thermal conductivity from 0.035 to 0.047 W/m K. MF-A aerogels have good thermal stability and extremely low flammability, with LOI value up to 41%. This novel aerogel from partially bio-based raw material would have promising application prospects.

Bioeconomy: Markets, Implications, and Investment Opportunities

In order to achieve the objectives of the Paris Climate Change Agreement, the conversion of our economy, which is still dominated by fossil carbon, to the bioeconomy model must be completed by 2050. This requires a shift from oil, gas and coal to agricultural, forestry and marine raw materials and will affect the global processing chains for energy, fuels and chemicals. However, the land required for the production of raw materials is competing with the production of food and animal feed. In addition, future land use must better take into account planetary boundaries and the preservation of ecosystem services. In order to achieve economic, ecological and societal sustainability, the necessary measures must therefore be geared towards the UN’s sustainability goals. Against this background, the future bioeconomy will have to concentrate on the food, chemical and heavy fuel sectors. Important sub-areas are alternative animal protein for nutrition, feedstock efficiency in the processing of bio-based raw materials, and the expansion of the raw materials spectrum. This requires enormous investment in industrial facilities, the integration of newly emerging value chains and the necessary infrastructure. The annual global investment requirements for renewable energy, bio-based chemicals and fuels, and ecosystem services is estimated at USD 1–2 trillion over the next three decades, equivalent to about 1.3–2.6% of global GDP. This article discusses the implications and guard rails of the bioeconomy model, as well as capital needs and possible sources.

Direct Assembly of Silica Nanospheres on Halloysite Nanotubes for “Green” Ultrahydrophobic Cotton Fabrics

AbstractThis paper presents a sustainable biomimetic approach to create ultrahydrophobic cotton fabrics. Cotton fabrics are modified using biobased raw materials to create multiple scale roughness and low surface energy on their surfaces. Naturally occurring halloysite nanotubes (HNT) are modified by silanization and direct assembly of silica (SiO2) nanospheres on the surface of HNTs. HNTs “decorated” with SiO2 nanospheres are covalently bonded onto the surface of cotton fabrics, creating a durable multiple scale surface roughness. Surface modified cotton fabrics are further grafted with fatty acid without using any solvent, via esterification. The combination of the hierarchical roughness pattern created on the surface through modified HNT, and fatty acid treatment results in ultrahydrophobic fabrics with water contact angles (WCAs) above 150°. Surface topographies of modified HNT particles and chemical changes are fully characterized. Attenuated total reflectance Fourier‐transform infrared and WCA studies are used to confirm the grafting of modified HNT particles and aliphatic fatty chains on surface of fabrics. The ultrahydrophobic cotton fabrics washed for five standard laundry cycles (25 home washings) show that the ultrahydrophobicity is durable. Moreover, the ultrahydrophobic fabrics are oleophilic, making them suitable for use in oil–water separation, anti‐biofouling and packaging, and other applications apart from water repellent clothing.

The Promises and the Challenges of Biotransformations in Microflow.

The challenges of transition toward the postpetroleum world shed light on the biocatalysis as the most sustainable way for the valorization of biobased raw materials. However, its industrial exploitation strongly relies on integration with innovative technologies such as microscale processing. Microflow devices remarkably accelerate biocatalyst screening and engineering, as well as evaluation of process parameters, and intensify biocatalytic processes in multiphase systems. The inherent feature of microfluidic devices to operate in a continuous mode brings additional interest for their use in chemoenzymatic cascade systems and in connection with the downstream processing units. Further steps toward automation and analytics integration, as well as computer-assisted process development, will significantly affect the industrial implementation of biocatalysis and fulfill the promises of the bioeconomy. This review provides an overview of recent examples on implementation of microfluidic devices into various stages of biocatalytic process development comprising ultrahigh-throughput biocatalyst screening, highly efficient biocatalytic process design including specific immobilization techniques for long-term biocatalyst use, integration with other (bio)chemical steps, and/or downstreamprocessing.

Development of Microbial Oil Wax-Based Oleogel with Potential Application in Food Formulations

Bio-based wax esters derived from microbial oil have been evaluated as a novel raw material for the production of olive oil–based oleogel. The oleaginous yeast Rhodosporidium toruloides was cultivated in batch fermentation using very high polarity cane sugar as carbon source for the production of a total dry weight of 23.8 g/L with an intracellular microbial oil content of 34% (w/w). The microbial oil was enzymatically converted into oleyl and cetyl wax esters using non-commercial lipases. The highest oil to ester conversion yields for oleyl (94%) and cetyl (91.3%) wax esters were achieved at 40 °C and 50 °C, respectively. When limonene was used as green solvent in the esterification reaction, the high melting temperature cetyl wax esters were produced at 35 °C with a high conversion yield of 87.5%. Subsequently, the microbial oil–derived cetyl wax esters were used for the production of the olive oil–based oleogel. The evaluation of the physical properties (i.e., color, crystal morphology, texture, rheological, and thermal behavior) of the oleogel showed that it was rheologically and thermally suitable for applications in spreadable fat products. This study demonstrated that microbial oil derivatives could be used as novel bio-based raw materials in the preparation of oleogels with potential use in fat-based food products.

β-Myrcene/isobornyl methacrylate SG1 nitroxide-mediated controlled radical polymerization: synthesis and characterization of gradient, diblock and triblock copolymers.

β-Myrcene (My), a natural 1,3-diene, and isobornyl methacrylate (IBOMA), from partially bio-based raw materials sources, were copolymerized by nitroxide-mediated polymerization (NMP) in bulk using the SG1-based BlocBuilder™ alkoxyamine functionalized with an N-succinimidyl ester group, NHS-BlocBuilder, at T = 100 °C with initial IBOMA molar feed compositions fIBOMA,0 = 0.10–0.90. Copolymer reactivity ratios were rMy = 1.90–2.16 and rIBOMA = 0.02–0.07 using Fineman–Ross, Kelen–Tudos and non-linear least-squares fitting to the Mayo–Lewis terminal model and indicated the possibility of gradient My/IBOMA copolymers. A linear increase in molecular weight versus conversion and a low dispersity (Đ ≤ 1.41) were exhibited by My/IBOMA copolymerization with fIBOMA,0 ≤ 0.80. My-rich and IBOMA-rich copolymers were shown to have a high degree of chain-end fidelity by performing subsequent chain-extensions with IBOMA and/or My, and by 31P NMR analysis. The preparation by NMP of My/IBOMA thermoplastic elastomers (TPEs), mostly bio-sourced, was then attempted. IBOMA-My-IBOMA triblock copolymers containing a minor fraction of My or styrene (S) units in the outer hard segments (Mn = 51–95 kg mol−1, Đ = 1.91–2.23 and FIBOMA = 0.28–0.36) were synthesized using SG1-terminated poly(ethylene-stat-butylene) dialkoxyamine. The micro-phase separation was suggested by the detection of two distinct Tgs at about −60 °C and +180 °C and confirmed by atomic force microscopy (AFM). A plastic stress–strain behavior (stress at break σB = 3.90 ± 0.22 MPa, elongation at break εB = 490 ± 31%) associated to an upper service temperature of about 140 °C were also highlighted for these triblock polymers.

Concept and challenges of modern biorefineries

International R&D community and technology developers for the last decades. However, despite intense efforts, real breakthrough has not been achieved yet. This has been mainly due to a biased view, focusing solely on a certain end product – for example cellulose pulp or ethanol and considering by-products as low value waste streams for energy applications. With the new wave of lignocellulosic biomass fractionation technologies being demonstrated at a pilot scale, success stories are closer than they have ever been. Biomass fractionation to high purity intermediate building blocks of cellulose to C6 sugars and hemicellulose to C5/C6 sugars and lignin, instead of just one main product, provides a way to produce a diversity of products and establish novel bio-based value chains. Especially important is the availability of higher purity lignin for different direct drop-in or after processing (depolymerization etc.) applications, which compared to the conventional lignins derived from pulp mills or ethanol refineries provides totally new applications and perspectives to enable the increased use of biobased raw materials in various industries. A biorefinery is a facility where different low-value renewable biomass materials are the feedstock to the processes where they are transformed, in multiple steps including fractionations, separations and conversions, to several higher-value bio-based products. Examples of these products can include fibres, food, feed, fine chemicals, transportation fuels and heat. A biorefinery can be formed by a single unit or can combine several facilities targeted for a single purpose that further process products as well as by-products or wastes of combined facilities. In biorefining one can find similarities to oil refining, with the exception that in oil refining the raw material comes from fossil resources. According to the International Energy Agency ‘Biorefineries will contribute significantly to the sustainable and efficient use of biomass resources, by providing a variety of products to different markets and sectors. They also have the potential to reduce conflicts and competition over land and feedstock, but it is necessary to measure and compare the benefits of biorefineries with other possible solutions to define the most sustainable option.’1 Although it is possible to produce the same products in a biorefinery as in an oil refinery, this is not the target, which instead is to produce products which can replace the products from oil refining.

Fabrication and characterization of antibacterial and biodegradable facial tissue papers using bio-based raw materials: effect of gamma radiation

ABSTRACTChitosan (1 wt%, dissolved in 2% aqueous acetic acid solution) and Cellulose (1 wt%, dissolved in deionized water) were mixed in different proportions (5–50 wt% chitosan) and biodegradable tissue paper films were prepared by solution casting. Tensile strength (TS) and elongation at break (EB) of the 5% chitosan-containing films were found to be 6 MPa and 3.5%, respectively. However, it was observed that with the addition of chitosan the mechanical property also increased, that is, the TS of the 50% chitosan-loaded film is improved to 300%. Fifty percent chitosan-loaded films were treated under γ-radiation (1–5 kGy). At 1 kGy radiation dose, tensile strength of the chitosan-loaded cellulosic films was improved but at a dose of 2.5 kGy the strength started to decrease. The irradiated films showed better antibacterial property than non-irradiated films. The effect of the gamma ray on the molecular interactions between chitosan and cellulose was analyzed by Fourier-Transform Infrared (FTIR) spectroscopy. A degradation test of irradiated and non-irradiated films was carried out in the soil medium. The water uptake property of both films was studied and it was noticed that the non-irradiated films absorbed water more significantly than the irradiated films.

Experimentation of composites materials reinforced with vegetable fibres for the construction sector

This document describes a research project carried out in the Ph.D. course in Civil Engineering at Mediterranea University of Reggio Calabria. The project is part of a doctoral dissertation entitled “Experimentation of laminas in composites materials reinforced with vegetable fibres for the construction sector”. The research is placed in a general context of studies on advanced materials in the architectural industry, and particularly on biocomposites. The project concerned the design and the characterization of laminas in NFRP, natural fibre reinforced polymers, and it aims to obtain an environmental, economic and social sustainable material. In particular, biobased raw materials and their production process have been subject of the study.

Unprecedented Influence of Carbon Dot@TiO2 Nanohybrid on Multifaceted Attributes of Waterborne Hyperbranched Polyester Nanocomposite.

Herein, we wish to report fabrication of multifaceted environmentally friendly benign renewable resource-based waterborne hyperbranched polyester nanocomposites using three different doses of carbon dot@TiO2 nanohybrid through a facile in situ polymerization technique in the absence of solvent or additional catalyst. Carbon dot@TiO2 nanohybrid was prepared through a greener one-pot hydrothermal process from bio-based raw materials. The nanocomposites were characterized by different instrumental techniques. The thermosets of these nanocomposites are obtained by curing them with glycerol-based hyperbranched epoxy and fatty acid-based poly(amido amine). Enhancements of 6.67 folds tensile strength, 3.8 folds toughness, 1.7 folds Young’s modulus, >2.5 units gloss, and 46 °C thermal stability were observed for the thermosets by the formation of nanocomposites. The nanocomposites also showed antifogging and anti-icing properties. More interestingly, they can also be used for efficient separation of crude oil and water from their mixture. Thus, these environmentally benign polymeric materials could find applications in different fields.

Renewable aromatics advance in Texas

Anellotech, which is developing a process to make aromatic chemicals from nonfood biomass, has won $9 million in additional funding from the Japanese beverage maker Suntory. The money is part of $15 million in investor funding that Anellotech got for hitting technical milestones; it also brings Suntory’s total investment to $25 million. Anellotech said earlier this month that it has commissioned a pilot plant in Silsbee, Texas. Suntory is interested in using biobased raw materials to make its polyester beverage containers.

Fabrication and Characterization of Antibacterial and Biodegradable Facial Tissue Papers Using Bio-Based Raw Materials: Effect of Glycerin

Antibacterial facial tissue papers were prepared by solution casting method with chitosan loaded bleached cellulosic pulp. Chitosan, in the film act as an antibacterial agent. Tissue paper films were fabricated by 50% cellulose and 50% chitosan (by weight, dry basis). Mechanical properties of the films were evaluated. It was found that tensile strength (TS) and elongation at break (EB) of the 50% chitosan contain films were 24 MPa and 10.8% respectively. To increase the plasticity of the tissue paper films glycerin was added 0.4 to 2% (by weight). It was found that with the incorporation of 1% glycerin in the tissue paper films the flexibility increased to 50%. Molecular interaction due to the chitosan addition was investigated by Fourier Transform Infra-Red (FTIR) spectroscopy. Water uptake property of glycerin contains films were also evaluated. In the soil medium, the degradation properties of the tissue paper films were carried out. The antibacterial property of the tissue paper was evaluated by disk diffusion method.