Synthesis of high-performance green nanocomposites from renewable natural oils

This paper describes preparation and properties of green nanocomposites from renewable resources. The nanocomposites were synthesized by an acid-catalyzed curing of epoxidized natural oils in the presence of silane coupling agents. The resulting nanocomposites were transparent and highly glossy. Their hardness and Young's modulus of the nanocomposite coatings improved, as compared with those only from the epoxidized natural oils. Dynamic viscoelasticity analysis and TEM observation showed the homogeneous structure of the nanocomposites. The properties of the nanocomposites were strongly affected by the structure and feed ratio of the monomers.     

Design and characterization of new advanced energetic biopolymers based on surface functionalized cellulosic materials

A new class of energetic biopolymers, which contain nitrate ester (O-NO₂) and nitramine (N-NO₂) as explosophoric groups, was successfully synthesized by surface modification of renewable pristine cellulose (PC) and microcrystalline cellulose (MCC) via epichlorohydrin-mediated amination followed by nitration process to produce new promising energetic aminated and nitrated cellulose and microcrystalline cellulose (APCN and AMCCN). Their structural, thermal, crystallinity and morphological features were examined and compared to those of the common cellulose nitrate. Furthermore, their energetic performances were evaluated by EXPLO5 V6.04 software. Experimental results confirm the successful chemical functionalization process to develop insensitive APCN and AMCCN with outstanding features such as nitrogen content of 15.01% and 15.39%, density of 1.692 g/cm³ and 1.708 g/cm³, and detonation velocity of 7526 m/s and 7752 m/s, respectively, which are significantly higher than those of the nitrated unmodified cellulosic biopolymers. The present investigation provides a suitable pathway to design new insensitive and energy-rich dense cellulosic biopolymers for potential application in high-performance solid propellants and composite explosives.

     

From fatty acid and lactone biobased monomers toward fully renewable polymer latexes

Novel waterborne polymeric materials based on renewable resource monomers have been prepared by the environmentally friendly miniemulsion polymerization of an oleic acid‐derivative monomer (MOA) and the α‐methylene‐γ‐butyrolactone (α‐MBL). The effect of the incorporation of different amounts of α‐MBL on kinetics and polymer microstructure is investigated. The estimation of the monomer reactivity ratios (r_α‐MBL = 0.49 and r_MOA = 1.26) shows the slight lower reactivity of the α‐MBL, resulting in a random copolymer moderately enriched with MOA at the beginning of the reaction. The thermal and mechanical properties of the polymers demonstrate that by incorporating the lactone it is possible to produce copolymers in a broad range of glass transition temperatures, with high thermal stability and improved mechanical properties. This study provides a new green route toward the bio‐sourced preparation of polymer latexes with tuneable properties, which can range from coatings to adhesives. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3543–3549     

Preparation of polymer nanoparticles from renewable biobased furfuryl alcohol and maleic anhydride by stabilizer‐free dispersion polymerization

The spherical polymer nanoparticles of biobased renewable monomers, furfuryl alcohol (FA) and maleic anhydride (MAn), with diameters (D_n) in the range of 120 to 500 nm have been prepared by stabilizer‐free dispersion copolymerization. In acetate or its mixture, the conversion of the monomers greatly depended on the concentration of AIBN. When the molar ratio of AIBN/monomers was 3.6% (wt), the monomer conversion could be as high as 80%. The aggregations of the solvated polymer chains formed the nuclei of the polymer particles. After the nucleation stage, both the monomer conversions and particle sizes increased steadily, while the coefficient of variation of the particle size decreased. The almost linear relationship between the D_n³ and the weight of polymer suggested that there is no significant secondary nucleation. The copolymer of FA and MAn could not dissolve in common organic solvents. Elemental analyses, FTIR and ¹³CP‐MAS spectra showed that the copolymer was close to the alternative copolymer of FA and MAn irrespective to the molar ratios of FA/MAn in monomer feed. Furthermore, the two 2,5‐ and 3,4‐dihydrofuran ring configurations exist in the copolymer and the later is the major one. The reaction of copolymer particles with triethylenetetramine confirmed the reactivity of the succinic anhydride groups at the surface of copolymer particles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Innovative materials for renewable energy

<正>Fossil fuels have sustained the prosperity of human civilization for centuries since the invention of internal combustion engine during the first industrial revolution.However,several drawbacks also come along with the wide-spread adoption of fossil fuels,namely,energy shortage,environmental pollution,global warming,and so on.It is therefore highly desirable to conduct     

Characterization and biodegradability of polyester bioplastic-based green renewable composites from agricultural residues

The biodegradability, morphology, and mechanical properties of composite materials consisting of acrylic acid-grafted poly(butylene succinate adipate) (PBSA-g-AA) and agricultural residues (rice husk, RH) were evaluated. Composites containing acrylic acid-grafted PBSA (PBSA-g-AA/RH) exhibited noticeably superior mechanical properties compared with those of PBSA/RH due to greater compatibility with RH. The dispersion of RH in the PBSA-g-AA matrix was highly homogeneous as a result of ester formation, and the consequent creation of branched and cross-linked macromolecules, between the carboxyl groups of PBSA-g-AA and hydroxyl groups in RH. Each composite was subject to biodegradation tests in an Azospirillum brasilense BCRC 12270 liquid culture medium. The bacterium completely degraded both the PBSA and the PBSA-g-AA/RH composite films. Morphological observations indicated severe disruption of the film structure after 20-40 days of incubation. The PBSA-g-AA/RH (20 wt%) films were not only more biodegradable than those made of PBSA but also exhibited lower molecular weight and intrinsic viscosity, implying a strong connection between these characteristics and biodegradability.     

Synthesis of a biobased waterborne polyurethane with epichlorohydrin-modified lignin

Abstract

A series of lignin-based waterborne polyurethanes (ELWPUs) are prepared using epichlorohydrin-modified lignin (ELG) as the biobased component. The effect of ELG dosage on the performance of the dispersions was studied by particle sizing. The morphology, crystallinity, thermal behavior, water resistance and mechanical properties of the films were investigated as well. The results show that the particle size of ELWPU dispersions increased with the addition of ELG. Furthermore, the ELWPU exhibited noticeable thermal stability, desired mechanical properties and water resistance as the tensile strength of ELWPU film containing 0.25?wt% ELG increased to 40.6?MPa from 15.2?MPa and the water absorption rate decreased from 20.1 to 12.4% compared to the non-modified waterborne polyurethane. The ELG played an important role in improving the properties of the biomass-based materials.     

Synthesis of readily recyclable biobased plastics by Diels-Alder reaction

Readily recyclable biobased plastics were designed and synthesized utilizing the thermally reversible DA reaction. Furyl-telechelic poly(butylene succinate) prepolymers (PBSF(2)) were extended with bis- and tris-maleimide linkers (M(2) and M(3)) by the DA reaction in the bulk state to produce linear and network polymers, respectively. The DA reaction was able to proceed at 25-80 degrees C, at which crystalline domains of PBSF(2) were present. In the linear polymer system, the molecular weight in the reaction equilibrium was dependent on the chain length of the prepolymer, but almost independent of the reaction temperature. The cycle of DA and retro-DA reactions was repeatable with no prepolymer deterioration.     

Development of biopolymers for artificial skin substitutes and blood-compatible materials

In order to develop biomedical materials we synthesized various polymers. In this study, gelatin, synthetic poly(amino acid), chitin and chitosan were chosen as the basic materials of artificial skin, polyurethane, amino acid, silicone and N-vinyl-2-pyrrolidone were chosen as the basic materials of blood-compatible materials.     

Production of anode matrices from renewable vegetable raw materials, including agricultural waste

Carbon modifications (anode matrices) were produced from renewable vegetable raw materials, agricultural crop waste, by pyrolysis in a quartz reactor without access of oxygen at 900°C, as well as by mechanical synthesis, and their characteristics were examined.     

Synthesis and properties of renewable nonisocyanate polyurethanes (NIPUs) from dimethylcarbonate

Novel fully renewable AA‐BB type nonisocyanate polyurethanes (NIPUs) were synthesized using the transurethanization approach. Dicarbamate monomers were prepared by the reaction of a diamine with an excess of dimethylcarbonate (DMC), in presence of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) as catalyst. Then, the dicarbamate was reacted with a diol to afford the polymer, in presence of TBD or K₂CO₃ as catalyst. Several renewable diamines and diols were tested. The two steps were conducted under neat conditions. The obtained materials exhibited T_g values varying from ?38 to 42 ° C, T_m values varying from 42 to 204 °C , and thermal stabilities above 200 ° C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1351–1359     

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.)     

Removal of malachite green by adsorbents from paper industry waste materials

The objective of this work is to study the removal of malachite green (MG) from water by adsorbents obtained from pyrolysis of two paper industry waste materials: one de-inking paper sludge (HP) and one organic sludge from virgin pulp mill (RT). Both adsorbents showed elevated MG removal. Maximum adsorption Q ₀ obtained by Langmuir equation was higher for the adsorbent from HP (HP-3, 982 mg/g) than RT (RT-3, 435 mg/g). However, K _L (Langmuir) and 1/n (Freundlich) indicated that affinity and intensity of adsorption is higher for the adsorbents from RT. Thermal analysis (TG, DTG and DTA) of adsorbents before and after MG removal was performed in N₂ atmosphere.     

Sepabeads FP series: New packing materials for industrial-scale separation of biopolymers

Summary Sepabeads FP series with a variety of anion-exhanger type functional groups have been examined as largescale chromatographic separation media for proteins. The adsorption-desorption behavior of proteins has been found to be dependent mainly on the type and partly on the content of the attached amino ligands. The effect of the attached groups are discussed using batch measurement data. It has been found that the existence of ethanol residue on the nitrogen atom incrases the hydrophilic nature of quaternary ammonium type packings and thus gives a higher protein adsorption capacity. Among weakly basic type anionexchangers, polyethyleneimine-modified packings showed very large protein capacities. Presented at HPLC '87, Amsterdam, 1987.     

Bio-based benzoxazine from renewable L-tyrosine: Synthesis,polymerization, and properties

Developing thermosets derived from renewable sources is of great importance. In this work, a fully bio-based benzoxazine monomer, 3,6-bis((3-(furan-2-ylmethyl)-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methyl)piperazine-2,5-dione (TCDPF), is conveniently synthesized from L-tyrosine cyclic dipeptide (TCDP), furfurylamine and paraformaldehyde. The chemical structure of TCDPF is confirmed by nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy (FT-IR) techniques. The curing behavior of TCDPF is investigated by differential scanning calorimetry and in situ FT-IR techniques. After temperature-programmed curing, the thermomechanical property and thermal stability of the resulting TCDPF polymer (PTCDPF) are evaluated by dynamic mechanical analysis and thermogravimetric analysis techniques, respectively. It is found that PTCDPF have excellent comprehensive performance such as high glass transition temperature (T_g = 322 °C), high thermal degradation temperature (T_5% = 342 °C, T_10% = 395 °C in N₂ atmosphere), and high char yield (CY = 51.3% at 800 °C in N₂ atmosphere). The results demonstrate that L-tyrosine is a promising bio-based raw material for preparing high performance polybenzoxazines.     

Interfaces in advanced materials

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Absorbable biopolymers derived from dimer fatty acids

A new class of aliphatic copolyanhydrides was synthesized from nonlinear hydrophobic dimers (FAD) of erucic acid and sebacic acid which possessed the desired physico-chemical and mechanical properties for use as a carrier for drugs. The polymers were synthesized by melt condensation to yield film-forming polymers with molecular weights of 250,000. The copolymer composition was determined by ¹H-NMR and gravimetric methods. In vitro degradation studies showed that these polymers degrade following a first-order kinetics with a rapid degradation in the first 10 days leaving a residue which is mostly the FAD comonomer. The drug release from the polymer also followed a first-order kinetics which correlates with the degradation process of the polymer. Drugs like carboplatin, methotrexate, tetracycline, and gentamicin were released in vitro for over 2 weeks and in some cases over 6 weeks. In vivo biocompatibility tests in rats and rabbits in the brain, muscle, and subcutaneously, demonstrated their toxicological inertness and biodegradability. The 1 : 1 copolymer of FAD : SA was selected as a carrier for various applications including a gentamicin-releasing implant which is now undergoing human clinical trials for the treatment of osteomyelitis. © 1993 John Wiley & Sons, Inc.     

Raman spectroscopy of advanced materials

Many micro-structural aspects of advanced materials and the incidence on the physical properties have been elucidated by Raman micro-spectroscopy. The potential of this technique is demonstrated with new materials interesting in both academic and industrial developments: new carbons and diamonds, superconductors, semiconductors, superhards.