The C.oleifera oil processing industry generates large amounts of solid wastes,including C.oleifera shell(COS)and C.oleifera cake(COC).Distinct from generally acknowledged lignocellulosic biomass(corn stover,bamboo,bi...The C.oleifera oil processing industry generates large amounts of solid wastes,including C.oleifera shell(COS)and C.oleifera cake(COC).Distinct from generally acknowledged lignocellulosic biomass(corn stover,bamboo,birch,etc.),Camellia wastes contain diverse bioactive substances in addition to the abundant lignocellulosic components,and thus,the biorefinery utilization of C.oleifera processing byproducts involves complicated processing technologies.This reviewfirst summarizes various technologies for extracting and converting the main components in C.oleifera oil processing byproducts into value-added chemicals and biobased materials,as well as their potential applications.Microwave,ultrasound,and Soxhlet extractions are compared for the extraction of functional bioactive components(tannin,flavonoid,saponin,etc.),while solvothermal conversion and pyrolysis are discussed for the conversion of lignocellulosic components into value-added chemicals.The application areas of these chemicals according to their properties are introduced in detail,including utilizing antioxidant and anti-in-flammatory properties of the bioactive substances for the specific application,as well as drop-in chemicals for the substitution of unrenewable fossil fuel-derived products.In addition to chemical production,biochar fabricated from COS and its applications in thefields of adsorption,supercapacitor,soil remediation and wood composites are comprehensively reviewed and discussed.Finally,based on the compositions and structural characteristics of C.oleifera byproducts,the development of full-component valorization strategies and the expansion of the appli-cationfields are proposed.展开更多
The curing process of two biobased adhesives:pine tanninhexamine(TH)and organosolv lignin non-isocyanate polyurethane(NIPU),suitable for interior nonstructural use,were compared with commercial urea-formaldehyde(UF)ad...The curing process of two biobased adhesives:pine tanninhexamine(TH)and organosolv lignin non-isocyanate polyurethane(NIPU),suitable for interior nonstructural use,were compared with commercial urea-formaldehyde(UF)adhesive.Changes in chemical structure before and after the curing process were observed with Fouriertransform infrared spectroscopy(FTIR).The process of adhesive curing was monitored with differential scanning calorimetry(DSC)and the automated bonding evaluation system(ABES).Both DSC and ABES measurements confirmed UF as the fastest and NIPU as the slowest curing adhesive observed.Taking into account the ABES results,the optimal pressing parameters for the TH adhesive would be 4 min at 175℃,for the NIPU adhesive 7 min at 200℃and for the UF 1.5 min at 100℃.Strong linear correlation was observed between mechanical and chemical curing for the UF and NIPU adhesives,whereas lower correlation was observed for the TH adhesive.At all observed adhesives,the DSC measurements were underestimating the curing process determined by ABES in the first part and overestimating it at the end.The underestimation was the most evident with the TH adhesive and the less with the UF adhesive.When comparing the uncured and cured FTIR spectra of all three types of adhesives,a drastic decrease in the characteristic band of-OH groups at 3330–3400 cm^(−1)and an increase in the signal intensity at 2920 cm^(−1)of aliphatic-CH2-groups were observed.For the UF adhesive,the C=O stretching frequency has shifted from 1632 cm^(−1)for uncured to three different bands at 1766,1701,and 1655 cm^(−1)for cured UF.The sharp band for phenolic alcohols at 1236 cm^(−1)of C–O stretch and hydroxyl O–H functional group at 1009 cm^(−1)and at 684 cm^(−1)of uncured TH adhesive diminished during curing,which indicates that a crosslinking reaction occurs via-OH groups.The peak of the C=O group of urethane bridges at 1697 cm^(−1)for uncured NIPU shifted to lower wavenumber at 1633 cm^(−1)for cured NIPU.展开更多
Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in ...Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor.The conversion achieved nearly 100%within 5 h under the reaction temperature,the mass ratio of catalyst to fatty acid methyl esters(FAMEs),and isobutanol to FAMEs total molar ratio of 180℃,0.4%(mass),and 5.4:1,respectively.In addition,kinetic model of the transesterification reaction was developed at 150–190℃.The calculated activation energy was 48.93 kJ·mol^(-1).Then,the epoxidation of obtained fatty acid isobutyl esters(FABEs)was conducted in the presence of formic acid and hydrogen peroxide.The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate(DOP)and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters(Ep-FAMEs).The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP.In addition,the extraction resistance and migration stability of Ep-FABEs were better than those of EpFAMEs.Overall,the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.展开更多
New fully biobased polyether/esters have been synthesized by a one-pot polymerization reaction of ricinoleic acid(RA),vanillic acid(VA)and ethylene carbonate(EC).In particular,EC selectively reacts with the phenolic g...New fully biobased polyether/esters have been synthesized by a one-pot polymerization reaction of ricinoleic acid(RA),vanillic acid(VA)and ethylene carbonate(EC).In particular,EC selectively reacts with the phenolic group of VA to obtain in-situ 4-(2-hydroxyethoxy)-3-methoxybenzoate(EV),suitable for subsequent copolymerization with RA.The procedure was carried out in a single step,without any solvent.Chemical structure and thermal properties of the new materials were studied in order to explore relationships between composition and final performances.The combination of EV,bearing a rigid aromatic structure,with RA,characterized by high flexibility and potential biocidal activity,allows the production of a novel class of fully biobased aliphatic-aromatic polymers presenting tuneable thermal properties and suitable for a range of applications,for example,in active packaging and biomedical fields.展开更多
Polyhydroxyurethanes(PHUs)have received considerable attention in the last decade as potential alternatives to traditional phosgene-based polyurethanes(PUs).The development of suitable 5CC(five membered-ring cyclic ca...Polyhydroxyurethanes(PHUs)have received considerable attention in the last decade as potential alternatives to traditional phosgene-based polyurethanes(PUs).The development of suitable 5CC(five membered-ring cyclic carbonate)precursors bearing multiple carbonate moieties(multi-5CCs)is a key requisite for preparing PHUs by polyaddition reaction with bis-or polyamines.Producing sustainable PHUs from CO_(2)-based five-membered cyclic carbonates(5CCs)obtained from biobased epoxides is a valuable strategy to bridge CO_(2) utilization and the upcycling of renewable substrates.In this context,while many multi-5CC monomers reported in the literature are oil-based,recent efforts have led to the development of a large variety of multifunctional 5CCs that are produced by the combination of CO_(2) and renewable resources such as fatty acids and vegetable oils,lignin,terpenes,and sugars.In this work,recent crucial advances(2019—2023)on PHUs prepared from bis-and multi-5CCs produced from CO_(2) and(partially/potentially)biobased substrates are reviewed with respect to their synthesis,thermal and mechanical properties,and their recent,emerging applications.展开更多
Polyurethanes(PUs)are a major family of polymers displaying a wide spectrum of physico-chemical,mechanical and structural properties for a large range of fields.They have shown suitable for biomedical applications and...Polyurethanes(PUs)are a major family of polymers displaying a wide spectrum of physico-chemical,mechanical and structural properties for a large range of fields.They have shown suitable for biomedical applications and are used in this domain since decades.The current variety of biomass available has extended the diversity of starting materials for the elaboration of new biobased macromolecular architectures,allowing the development of biobased PUs with advanced properties such as controlled biotic and abiotic degradation.In this frame,new tunable biomedical devices have been successfully designed.PU structures with precise tissue biomimicking can be obtained and are adequate for adhesion,proliferation and differentiation of many cell’s types.Moreover,new smart shape-memory PUs with adjustable shape-recovery properties have demonstrated promising results for biomedical applications such as wound healing.The fossil-based starting materials substitution for biomedical implants is slowly improving,nonetheless better renewable contents need to be achieved for most PUs to obtain biobased certifications.After a presentation of some PU generalities and an understanding of a biomaterial structure-biocompatibility relationship,recent developments of biobased PUs for non-implantable devices as well as short-and long-term implants are described in detail in this review and compared to more conventional PU structures.展开更多
Development of degradable polyester elastomers plays an important role in the applications of soft mateirals.Noncrystalline polymenthides(PMs)from menthol derived lactone monomers are excellent soft segments for prepa...Development of degradable polyester elastomers plays an important role in the applications of soft mateirals.Noncrystalline polymenthides(PMs)from menthol derived lactone monomers are excellent soft segments for preparing degradable polyester elastomers.By using cyclic trimeric phosphazene base(CTPB)as an organocatalyst,we succesfully synthesized PMs with different molecular weights(8.2 kDa to 100.7 kDa)in high yields via ring-opening polymerization(ROP)of menthide.When a CTPB/urea binary catalytic system was adopted,the polymerizations proceeded in a more controlled manner.Using glycerol as initiator,star shaped PMs with well.defined structure were synthesized and subsequently end-capped by acrylate.UV iradiation of the terminal acrylate groups in the star-shaped PMs resulted in formation of chemically cos-linked polyester elastomers without heat or other stimuli.The obtained polyester elastomers exhibit matched modulus(3.8-5.5 MPa),tensile strength(0.56-0.68 MPa),and strain at break(280%-320%)with soft body tssues,displaying great potential in biomedical applications.展开更多
Consumers prefer foods that are healthier with high quality and safety.Food packaging are de-manded to effectively extend the shelf-life,preserve the nutrients and decrease the microbial contamination during the trans...Consumers prefer foods that are healthier with high quality and safety.Food packaging are de-manded to effectively extend the shelf-life,preserve the nutrients and decrease the microbial contamination during the transport and storage of food.With the increasing concern on the envi-ronmental impacts caused by food packaging wastes,sustainable and green packaging are highly demanded to minimize the harmful effects of food packaging waste on the environment.Bio-based materials are derived from sustainable and renewable biomass,instead of finite petrochemicals.The applications of bio-based materials for food packaging are highlighted in this review.The emphasis is placed on the categories of related biobased materials,their characteristics and ad-vantages for food packaging,as well as the strategies used to improve their performances.Though a lot of trials have been done on biobased materials for food packaging,further attempts to im-prove their performances,understand the functioning mechanisms and develop greener methods for the production,processing and destiny of these bio-based materials are still highly needed for the future research.展开更多
Lignin is a natural biopolymer with a complex three-dimensional network, commercially obtained from wasteliquid of paper pulp and bioethanol production, and could be a candidate for preparation of environment-friendly...Lignin is a natural biopolymer with a complex three-dimensional network, commercially obtained from wasteliquid of paper pulp and bioethanol production, and could be a candidate for preparation of environment-friendlybio-based polyphenol material. In the present work, the demethylated wheat straw alkali lignin (D-Lig), preparedby demethylation of wheat straw alkali lignin (Lig) using an in-situ generated Lewis acid, was used to synthesizebio-based phenol formaldehyde resin adhesive (D-LPF) applied in plywood. Effects of synthetic process’s factors,including lignin substitution for phenol, NaOH concentration and molar ratio of formaldehyde to phenol, on thebonding strength and free formaldehyde content of D-LPF were investigated in detail, and the optimum syntheticprocess of D-LPF was obtained as following: Lignin substitution for phenol 60%, NaOH concentration 5.0% andmolar ratio of formaldehyde to phenol 2.0, and under the optimum reaction condition, the D-LPF presented lower free formaldehyde content (0.18%) and higher bonding strength (2.19 MPa), which was better than those ofcontaining-lignin phenol formaldehyde resin adhesive (LPF). Additionally, the curing behavior of the adhesivewas studied by differential scanning calorimetry (DSC) combined with gel time. It can be obtained that D-LPFresin adhesive had the shortest gel time, and fastest curing rate, compared with those of PF and L-PF resin adhesives. The curing kinetics data was fitted well by Kissinger model using non-isothermal DSC method, and theaverage activation energy value was 85.3 kJ/mol, slightly higher than that of commercial PF resin, while lowerthan that of LPF (90.2 kJ/mol). Finally, based on the analytical results of high temperature fourier transform infrared spectroscopy (FTIR), a possible curing mechanism of D-LPF was proposed.展开更多
In this study,tannic acid(TA)was investigated as flame retardant agent for PLA.Different strategies to modify its thermal degradation pathway have been explored in order to improve its charring effect.The first one co...In this study,tannic acid(TA)was investigated as flame retardant agent for PLA.Different strategies to modify its thermal degradation pathway have been explored in order to improve its charring effect.The first one consists in combining TA with organomodified montmorillonite(oMMT),and enables limiting the thermo-oxidative degradation of TA and promoting the formation of an effective char layer.Flame-retardant(FR)behavior of PLA-based composition has been found to be positively impacted by this combination since a reduction of the peak of Heat Release Rate(PHRR),more important than the value recorded when oMMT and tannic acid are used separately,has been obtained.The second strategy,in which tannic acid was associated with a biosourced phosphorousbased compounds,i.e.metallic phytate salt,evidenced another alternative allowing enhancing TA flame retardant effect at 30 wt%loading content.The third and last strategy explored aims to chemically modify TA via a chemical grafting of phosphoric acid groups.This phosphorylated TA was shown to present the most effective flame-retardant(FR)effect.However,an important reduction of PLA molecular weight was observed.展开更多
Biomanufacturing,which uses renewable resources as raw materials and uses biological processes to produce energy and chemicals,has long been regarded as a production model that replaces the unsustainable fossil econom...Biomanufacturing,which uses renewable resources as raw materials and uses biological processes to produce energy and chemicals,has long been regarded as a production model that replaces the unsustainable fossil economy.The construction of non-natural and efficient biosynthesis routes of chemicals is an important goal of green biomanufacturing.Traditional methods that rely on experience are difficult to support the realization of this goal.However,with the rapid development of information technology,the intelligence of biomanufacturing has brought hope to achieve this goal.Retrobiosynthesis and computational enzyme design,as two of the main technologies in intelligent biomanufacturing,have developed rapidly in recent years and have made great achievements and some representative works have demonstrated the great value that the integration of the two fields may bring.To achieve the final integration of the two fields,it is necessary to examine the information,methods and tools from a bird’s-eye view,and to find a feasible idea and solution for establishing a connection point.For this purpose,this article briefly reviewed the main ideas,methods and tools of the two fields,and put forward views on how to achieve the integration of the two fields.展开更多
Two methods were used to produce chitosan by deacetylation of chitin which was extracted from Agaricus bisporus stipes.The first one gives chitosan 1 with low yield of 2.5%,degree of acetylation(DA)of 4%,molecular wei...Two methods were used to produce chitosan by deacetylation of chitin which was extracted from Agaricus bisporus stipes.The first one gives chitosan 1 with low yield of 2.5%,degree of acetylation(DA)of 4%,molecular weight(MW)of 2.973×10^(5)(g/mol).The second route produces chitosan 2 with higher yield of 41%,degree of acetylation(DA)of 17.23%,molecular weight(MW)of 2.939×10^(5)(g/mol).Both chitosans were characterized by XRD,FTIR,^(1)H-NMR spectroscopy nuclear magnetic resonance of proton.The molecular weight(MW)was determined by size exclusion chromatography(SEC).Thermal analysis shows that both chitosans have moisture content lower than 10%.However chitosan 2 has the less ash%which is the quality grade for chitosan medical applications.Accordingly,fungal chitosan 2 could have potential medical and agricultural applications.展开更多
In the current work,we have synthesized vegetable oil-based polyurethane-OMMT clay nanocomposite(PUNC)adhesive with the incorporation of different wt%of organically modified nanoclay(1 to 5 wt%)into the biobased polyu...In the current work,we have synthesized vegetable oil-based polyurethane-OMMT clay nanocomposite(PUNC)adhesive with the incorporation of different wt%of organically modified nanoclay(1 to 5 wt%)into the biobased polyurethane(PU)matrix through in-situ polymerization process via ultrasonication method.At the initial stage,PU adhesive was prepared using polyol and partially biobased aliphatic isocyanate,wherein polyol was derived from the transesterified castor oil using ethylene glycol.The formation of PU and PUNC adhesive was confirmed using Fourier transform infrared(FTIR)spectroscopy analysis.The tensile strength of PU with different wt%of nanoclay was determined and the analysis showed that the loading of 3 wt%of nanoclay within the PU matrix showed better performance as compared to the others.Furthermore,shear strength of PU and PUNC(3 wt%nanoclay)adhesives were determined using lap shear test,in which PUNC adhesive showed higher adhesive strength at 70°C.Subsequently,the dispersibility of OMMT nanoclay within the PU matrix along with exfoliation and amorphous structure was confirmed through wide angle X-ray diffractometer(WAXD)and transmission electron microscopy(TEM)analysis.The phase separation structure was analyzed using dynamic mechanical analysis(DMA).The analysis revealed that with the addition of organically modified nanoclay in the PU matrix,the glass transition temperature(Tg)of the damping curve was shifted towards higher temperature.展开更多
In this work, free tall oil fatty acids were epoxidized with in-situ generated peroxyacetic acid. Reaction kineticsof epoxidation was investigated by oxirane content and iodine value titrimetric determination, as well...In this work, free tall oil fatty acids were epoxidized with in-situ generated peroxyacetic acid. Reaction kineticsof epoxidation was investigated by oxirane content and iodine value titrimetric determination, as well as FTIRspectra analysis. A highly functional biobased polyol was synthesized by functionalizing epoxidized tall oilfatty acids with triethanolamine using Montmorillonite K10 as a catalyst. The obtained polyol was analyzed byFTIR and MALDI-TOF MS. The most common chemical and physical characteristics of obtained polyol weredetermined.展开更多
Food packaging materials compounded with antimicrobial additives can substantially diminish the incidence of foodborne diseases.Here,poly(L-lactic acid)(PLA)films containing sodium metabisulfite(NaM)were produced by m...Food packaging materials compounded with antimicrobial additives can substantially diminish the incidence of foodborne diseases.Here,poly(L-lactic acid)(PLA)films containing sodium metabisulfite(NaM)were produced by melt extrusion as an attempt to develop a new biodegradable material with antimicrobial properties for packaging.Life cycle assessment(LCA)simulations revealed that the environmental footprints of the PLA film did not change upon NaM addition,and that NaM is more eco-friendly than silver nanoparticles.The PLA/NaM films with NaM content varying from 0.5 to 5.0 wt.%were characterized by differential scanning calorimetry(DSC),thermogravimetric analysis(TGA),and optical and mechanical properties determinations.The optical properties were sustained after the addition of NaM,but high NaM contents degraded the light transparence of the PLA matrix at some extent.The thermal stability and tensile properties of the PLA film decreased proportionally to the NaM content,while no changes were observed on Tg,Tm and Xc,as determined by DSC.Agar diffusion tests revealed that the PLA/NaM films had no antimicrobial activity on Saccharomyces cerevisiae at 35°C,which was related to the limited migration of NaM from the glassy PLA matrix.The biodegradable PLA films compounded with NaM through melt extrusion display adequate optical,thermal,and mechanical properties to cover most food packaging applications,representing an essential step toward the development of eco-friendly packaging materials that can potentially exhibit an antimicrobially active surface.展开更多
Nanoparticles of the conductive coordination polymer Ni(tto) have been synthesized under mild conditions in the presence of bio-based polyesters or polyethylene glycol acting as growth controlling agents. With polyest...Nanoparticles of the conductive coordination polymer Ni(tto) have been synthesized under mild conditions in the presence of bio-based polyesters or polyethylene glycol acting as growth controlling agents. With polyesters, aggregates of particles are observed whereas well dispersed nanoparticles are obtained with polyethylene glycol. Indeed, for a Ni2+/polyethylene glycol weight ratio of 0.031, transmission electron micrographs evidence dispersed particles exhibiting sizes in the 3 - 10 nm range. Infrared spectra for nanopowders show two CS stretching modes in the 1100 - 1190 cm−1 range, confirming the presence of the tetrathiooxalate ligand coordinated to the nickel center. The room-temperature electrical conductivity for the nanopowder prepared in the presence of polyethylene glycol is about 0.8 S∙cm−1, a decent value for tetrathiolate-based polymers. Finally, magnetic susceptibility measurements for well-dispersed Ni(tto) particles evidence a Curie-Weiss law in a large temperature range. Moreover, low temperatures measurement would confirm intra- or interchain interactions between nickel atoms within the Ni(tto) polymer chains.展开更多
A novel colourant for hair dyeing was prepared by an enzymatic reaction with (+)-catechin and its characteristics as a hair dyestuff were studied. The study is aimed at inventing the hair dyestuff that is human- and e...A novel colourant for hair dyeing was prepared by an enzymatic reaction with (+)-catechin and its characteristics as a hair dyestuff were studied. The study is aimed at inventing the hair dyestuff that is human- and eco-friendly. One potentially powerful dyestuff was obtained from (+)-catechin treated with tyrosinase after screening experiments using biobased materials. The obtained reddish orange colourant, 4-(3,4-dihydro-3α,5,7-trihydroxy-2H-1-benzopyran-2α-yl) 1,2-benzoquinone named “catechinone”, shows enough dyeability for decolourised white hair. Catechinone does not cause erythema or oedema on skin of rabbits. The colour is controlled by the addition of other biobased materials and a variety of colours of dyed hair are acquired. The fastness to light or washing for hair dyed by catechinone is high enough for practical use.展开更多
Surfactants are important chemical products,serving as emulsifiers and interfacial modifiers in the household detergents,personal care products,paints and coatings,foods,cosmetics,and pharmaceuticals industries.This r...Surfactants are important chemical products,serving as emulsifiers and interfacial modifiers in the household detergents,personal care products,paints and coatings,foods,cosmetics,and pharmaceuticals industries.This review focuses upon recent advances in research and development to improve the ecological sustainability of surfactants throughout their life cycle,including derivation from renewable resources,production using green manufacturing principles,and improved biocompatibility and biodegradability during their consumer use and disposal stages.Biobased surfactants,derived from vegetable oils,polysaccharides,proteins,phospholipids,and other renewable resources,currently comprise approximately 24%of the surfactant market,and this percentage is expected to increase,especially in Asia.The use of renewables is attractive to consumers because of reduced production of CO2,a greenhouse gas associated with climate change.Enzymes can greatly increase process sustainability,through reduced use of organic solvent,water,and energy,and reduced formation of by-products and waste products.Among the enzymes being investigated for surfactant synthesis,lipases are the most robust,due to their relatively high biocatalytic activity,operational stability and their ability to form or cleave ester,amide,and thioester bonds.For enzymes to be robust catalysts of surfactants,further research and development is needed to improve catalytic productivity,stability and reduce their purchase cost.展开更多
The biobased renewable monomer 2,5-diformylfuran is polymerised using various N-heterocyclic carbene(NHC)catalysts in dimethyl sulfoxide(DMSO)affording a low molar mass polymer.It is shown that catalyst structure as w...The biobased renewable monomer 2,5-diformylfuran is polymerised using various N-heterocyclic carbene(NHC)catalysts in dimethyl sulfoxide(DMSO)affording a low molar mass polymer.It is shown that catalyst structure as well as the temperature and time the polymerization is running have a noticeable effect on its molar mass.The obtained material is characterized by nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),differential scanning calorimetry(DSC)and X-ray diffraction(XRD).An attempt at chain extension with diamine leads to precipitation of the polymer.This new biobased polymer material might be useful as a sustainable resin.展开更多
Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, β-diketiminate yttrium complex 2, bis(phosphino)carbazolide yttrium complex 3, half-san...Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, β-diketiminate yttrium complex 2, bis(phosphino)carbazolide yttrium complex 3, half-sandwich benzyl fluorenyl scandium complex 4 and pyridyl-methylene-fluorenyl rare-metal complexes 5a–5c. Complexes 1, 4 and 5a–5c show trans-1,2-regioselectivities and high activities, of which 5c exhibits excellent isoselectivity(mmmm>99%). Conversely, complexes 2 and 3 promote β-ocimene polymerization to produce isotactic cis-1,4-polyocimenes(cis-1,4>99%, mm>95%). Diblock copolymers cis-1,4-PIP-block-cis-1,4-POc and cis-1,4-PBD-block-cis-1,4-POc are obtained in one-pot reactions of β-ocimene with isoprene and butadiene using complex 3. Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced T_(g)(from-20 ℃ to 79 ℃ and 74 ℃) and hydrophilicity.展开更多
基金The authors acknowledge the financial support from the National Natural Science Foundation of China(Grant No.32201509)Hunan Science and Technology Xiaohe Talent Support Project(2022 TJ-XH 013)+6 种基金Science and Technology Innovation Program of Hunan Province(2022RC1156,2021RC2100)State Key Laboratory of Woody Oil Resource Utilization Common Key Technology Innovation for the Green Transformation of Woody Oil(XLKY202205)State Key Laboratory of Woody Oil Resource Utilization Project(2019XK2002)Key Research and Development Program of the State Forestry and Grassland Administration(GLM[2021]95)Hunan Forestry Outstanding Youth Project(XLK202108-1)Changsha Science and Technology Project(kq2202325,kq2107022)Science and Technology Innovation Leading Talent of Hunan Province(2020RC4026).
文摘The C.oleifera oil processing industry generates large amounts of solid wastes,including C.oleifera shell(COS)and C.oleifera cake(COC).Distinct from generally acknowledged lignocellulosic biomass(corn stover,bamboo,birch,etc.),Camellia wastes contain diverse bioactive substances in addition to the abundant lignocellulosic components,and thus,the biorefinery utilization of C.oleifera processing byproducts involves complicated processing technologies.This reviewfirst summarizes various technologies for extracting and converting the main components in C.oleifera oil processing byproducts into value-added chemicals and biobased materials,as well as their potential applications.Microwave,ultrasound,and Soxhlet extractions are compared for the extraction of functional bioactive components(tannin,flavonoid,saponin,etc.),while solvothermal conversion and pyrolysis are discussed for the conversion of lignocellulosic components into value-added chemicals.The application areas of these chemicals according to their properties are introduced in detail,including utilizing antioxidant and anti-in-flammatory properties of the bioactive substances for the specific application,as well as drop-in chemicals for the substitution of unrenewable fossil fuel-derived products.In addition to chemical production,biochar fabricated from COS and its applications in thefields of adsorption,supercapacitor,soil remediation and wood composites are comprehensively reviewed and discussed.Finally,based on the compositions and structural characteristics of C.oleifera byproducts,the development of full-component valorization strategies and the expansion of the appli-cationfields are proposed.
基金the ERA-CoBioTech project WooBAdh(Environmentally-friendly bioadhesives from renewable resources)and by the Slovenian Ministry of Education.Science and Sport and the Slovenian Research Agency within the framework of the program P4-0015.
文摘The curing process of two biobased adhesives:pine tanninhexamine(TH)and organosolv lignin non-isocyanate polyurethane(NIPU),suitable for interior nonstructural use,were compared with commercial urea-formaldehyde(UF)adhesive.Changes in chemical structure before and after the curing process were observed with Fouriertransform infrared spectroscopy(FTIR).The process of adhesive curing was monitored with differential scanning calorimetry(DSC)and the automated bonding evaluation system(ABES).Both DSC and ABES measurements confirmed UF as the fastest and NIPU as the slowest curing adhesive observed.Taking into account the ABES results,the optimal pressing parameters for the TH adhesive would be 4 min at 175℃,for the NIPU adhesive 7 min at 200℃and for the UF 1.5 min at 100℃.Strong linear correlation was observed between mechanical and chemical curing for the UF and NIPU adhesives,whereas lower correlation was observed for the TH adhesive.At all observed adhesives,the DSC measurements were underestimating the curing process determined by ABES in the first part and overestimating it at the end.The underestimation was the most evident with the TH adhesive and the less with the UF adhesive.When comparing the uncured and cured FTIR spectra of all three types of adhesives,a drastic decrease in the characteristic band of-OH groups at 3330–3400 cm^(−1)and an increase in the signal intensity at 2920 cm^(−1)of aliphatic-CH2-groups were observed.For the UF adhesive,the C=O stretching frequency has shifted from 1632 cm^(−1)for uncured to three different bands at 1766,1701,and 1655 cm^(−1)for cured UF.The sharp band for phenolic alcohols at 1236 cm^(−1)of C–O stretch and hydroxyl O–H functional group at 1009 cm^(−1)and at 684 cm^(−1)of uncured TH adhesive diminished during curing,which indicates that a crosslinking reaction occurs via-OH groups.The peak of the C=O group of urethane bridges at 1697 cm^(−1)for uncured NIPU shifted to lower wavenumber at 1633 cm^(−1)for cured NIPU.
基金Financial support provided by the National High-tech Research and Development Program of China(2014AA022103)。
文摘Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor.The conversion achieved nearly 100%within 5 h under the reaction temperature,the mass ratio of catalyst to fatty acid methyl esters(FAMEs),and isobutanol to FAMEs total molar ratio of 180℃,0.4%(mass),and 5.4:1,respectively.In addition,kinetic model of the transesterification reaction was developed at 150–190℃.The calculated activation energy was 48.93 kJ·mol^(-1).Then,the epoxidation of obtained fatty acid isobutyl esters(FABEs)was conducted in the presence of formic acid and hydrogen peroxide.The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate(DOP)and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters(Ep-FAMEs).The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP.In addition,the extraction resistance and migration stability of Ep-FABEs were better than those of EpFAMEs.Overall,the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.
文摘New fully biobased polyether/esters have been synthesized by a one-pot polymerization reaction of ricinoleic acid(RA),vanillic acid(VA)and ethylene carbonate(EC).In particular,EC selectively reacts with the phenolic group of VA to obtain in-situ 4-(2-hydroxyethoxy)-3-methoxybenzoate(EV),suitable for subsequent copolymerization with RA.The procedure was carried out in a single step,without any solvent.Chemical structure and thermal properties of the new materials were studied in order to explore relationships between composition and final performances.The combination of EV,bearing a rigid aromatic structure,with RA,characterized by high flexibility and potential biocidal activity,allows the production of a novel class of fully biobased aliphatic-aromatic polymers presenting tuneable thermal properties and suitable for a range of applications,for example,in active packaging and biomedical fields.
基金the National Research Council of Thailand(grants N41A640170 and N42A650196)for research supportD.C.acknowledges funding support from the NSRF(National Science,Research and Innovation Fund)via the Program Management Unit for Human Resources&Institutional Development,Research and Innovation(grant number B05F640208).
文摘Polyhydroxyurethanes(PHUs)have received considerable attention in the last decade as potential alternatives to traditional phosgene-based polyurethanes(PUs).The development of suitable 5CC(five membered-ring cyclic carbonate)precursors bearing multiple carbonate moieties(multi-5CCs)is a key requisite for preparing PHUs by polyaddition reaction with bis-or polyamines.Producing sustainable PHUs from CO_(2)-based five-membered cyclic carbonates(5CCs)obtained from biobased epoxides is a valuable strategy to bridge CO_(2) utilization and the upcycling of renewable substrates.In this context,while many multi-5CC monomers reported in the literature are oil-based,recent efforts have led to the development of a large variety of multifunctional 5CCs that are produced by the combination of CO_(2) and renewable resources such as fatty acids and vegetable oils,lignin,terpenes,and sugars.In this work,recent crucial advances(2019—2023)on PHUs prepared from bis-and multi-5CCs produced from CO_(2) and(partially/potentially)biobased substrates are reviewed with respect to their synthesis,thermal and mechanical properties,and their recent,emerging applications.
基金The authors are grateful to ANRT and Peters Surgical for their financial support via a CIFRE grant.
文摘Polyurethanes(PUs)are a major family of polymers displaying a wide spectrum of physico-chemical,mechanical and structural properties for a large range of fields.They have shown suitable for biomedical applications and are used in this domain since decades.The current variety of biomass available has extended the diversity of starting materials for the elaboration of new biobased macromolecular architectures,allowing the development of biobased PUs with advanced properties such as controlled biotic and abiotic degradation.In this frame,new tunable biomedical devices have been successfully designed.PU structures with precise tissue biomimicking can be obtained and are adequate for adhesion,proliferation and differentiation of many cell’s types.Moreover,new smart shape-memory PUs with adjustable shape-recovery properties have demonstrated promising results for biomedical applications such as wound healing.The fossil-based starting materials substitution for biomedical implants is slowly improving,nonetheless better renewable contents need to be achieved for most PUs to obtain biobased certifications.After a presentation of some PU generalities and an understanding of a biomaterial structure-biocompatibility relationship,recent developments of biobased PUs for non-implantable devices as well as short-and long-term implants are described in detail in this review and compared to more conventional PU structures.
基金This work was financially supported by the National Natural Science Foundation of China(No.21704048)the 111 Project(No.D17004)the Taishan Scholars Constructive Engineering Foundation(No.tsqn20161031).
文摘Development of degradable polyester elastomers plays an important role in the applications of soft mateirals.Noncrystalline polymenthides(PMs)from menthol derived lactone monomers are excellent soft segments for preparing degradable polyester elastomers.By using cyclic trimeric phosphazene base(CTPB)as an organocatalyst,we succesfully synthesized PMs with different molecular weights(8.2 kDa to 100.7 kDa)in high yields via ring-opening polymerization(ROP)of menthide.When a CTPB/urea binary catalytic system was adopted,the polymerizations proceeded in a more controlled manner.Using glycerol as initiator,star shaped PMs with well.defined structure were synthesized and subsequently end-capped by acrylate.UV iradiation of the terminal acrylate groups in the star-shaped PMs resulted in formation of chemically cos-linked polyester elastomers without heat or other stimuli.The obtained polyester elastomers exhibit matched modulus(3.8-5.5 MPa),tensile strength(0.56-0.68 MPa),and strain at break(280%-320%)with soft body tssues,displaying great potential in biomedical applications.
文摘Consumers prefer foods that are healthier with high quality and safety.Food packaging are de-manded to effectively extend the shelf-life,preserve the nutrients and decrease the microbial contamination during the transport and storage of food.With the increasing concern on the envi-ronmental impacts caused by food packaging wastes,sustainable and green packaging are highly demanded to minimize the harmful effects of food packaging waste on the environment.Bio-based materials are derived from sustainable and renewable biomass,instead of finite petrochemicals.The applications of bio-based materials for food packaging are highlighted in this review.The emphasis is placed on the categories of related biobased materials,their characteristics and ad-vantages for food packaging,as well as the strategies used to improve their performances.Though a lot of trials have been done on biobased materials for food packaging,further attempts to im-prove their performances,understand the functioning mechanisms and develop greener methods for the production,processing and destiny of these bio-based materials are still highly needed for the future research.
基金This work was supported by the National Natural Science Foundation of China(51473024)by University Science Research General Project of Jiangsu Province(16KJD430001)。
文摘Lignin is a natural biopolymer with a complex three-dimensional network, commercially obtained from wasteliquid of paper pulp and bioethanol production, and could be a candidate for preparation of environment-friendlybio-based polyphenol material. In the present work, the demethylated wheat straw alkali lignin (D-Lig), preparedby demethylation of wheat straw alkali lignin (Lig) using an in-situ generated Lewis acid, was used to synthesizebio-based phenol formaldehyde resin adhesive (D-LPF) applied in plywood. Effects of synthetic process’s factors,including lignin substitution for phenol, NaOH concentration and molar ratio of formaldehyde to phenol, on thebonding strength and free formaldehyde content of D-LPF were investigated in detail, and the optimum syntheticprocess of D-LPF was obtained as following: Lignin substitution for phenol 60%, NaOH concentration 5.0% andmolar ratio of formaldehyde to phenol 2.0, and under the optimum reaction condition, the D-LPF presented lower free formaldehyde content (0.18%) and higher bonding strength (2.19 MPa), which was better than those ofcontaining-lignin phenol formaldehyde resin adhesive (LPF). Additionally, the curing behavior of the adhesivewas studied by differential scanning calorimetry (DSC) combined with gel time. It can be obtained that D-LPFresin adhesive had the shortest gel time, and fastest curing rate, compared with those of PF and L-PF resin adhesives. The curing kinetics data was fitted well by Kissinger model using non-isothermal DSC method, and theaverage activation energy value was 85.3 kJ/mol, slightly higher than that of commercial PF resin, while lowerthan that of LPF (90.2 kJ/mol). Finally, based on the analytical results of high temperature fourier transform infrared spectroscopy (FTIR), a possible curing mechanism of D-LPF was proposed.
文摘In this study,tannic acid(TA)was investigated as flame retardant agent for PLA.Different strategies to modify its thermal degradation pathway have been explored in order to improve its charring effect.The first one consists in combining TA with organomodified montmorillonite(oMMT),and enables limiting the thermo-oxidative degradation of TA and promoting the formation of an effective char layer.Flame-retardant(FR)behavior of PLA-based composition has been found to be positively impacted by this combination since a reduction of the peak of Heat Release Rate(PHRR),more important than the value recorded when oMMT and tannic acid are used separately,has been obtained.The second strategy,in which tannic acid was associated with a biosourced phosphorousbased compounds,i.e.metallic phytate salt,evidenced another alternative allowing enhancing TA flame retardant effect at 30 wt%loading content.The third and last strategy explored aims to chemically modify TA via a chemical grafting of phosphoric acid groups.This phosphorylated TA was shown to present the most effective flame-retardant(FR)effect.However,an important reduction of PLA molecular weight was observed.
基金support from the National Nat-ural Science Foundation of China(U1663227,21861132017,21811530003,21878170).
文摘Biomanufacturing,which uses renewable resources as raw materials and uses biological processes to produce energy and chemicals,has long been regarded as a production model that replaces the unsustainable fossil economy.The construction of non-natural and efficient biosynthesis routes of chemicals is an important goal of green biomanufacturing.Traditional methods that rely on experience are difficult to support the realization of this goal.However,with the rapid development of information technology,the intelligence of biomanufacturing has brought hope to achieve this goal.Retrobiosynthesis and computational enzyme design,as two of the main technologies in intelligent biomanufacturing,have developed rapidly in recent years and have made great achievements and some representative works have demonstrated the great value that the integration of the two fields may bring.To achieve the final integration of the two fields,it is necessary to examine the information,methods and tools from a bird’s-eye view,and to find a feasible idea and solution for establishing a connection point.For this purpose,this article briefly reviewed the main ideas,methods and tools of the two fields,and put forward views on how to achieve the integration of the two fields.
文摘Two methods were used to produce chitosan by deacetylation of chitin which was extracted from Agaricus bisporus stipes.The first one gives chitosan 1 with low yield of 2.5%,degree of acetylation(DA)of 4%,molecular weight(MW)of 2.973×10^(5)(g/mol).The second route produces chitosan 2 with higher yield of 41%,degree of acetylation(DA)of 17.23%,molecular weight(MW)of 2.939×10^(5)(g/mol).Both chitosans were characterized by XRD,FTIR,^(1)H-NMR spectroscopy nuclear magnetic resonance of proton.The molecular weight(MW)was determined by size exclusion chromatography(SEC).Thermal analysis shows that both chitosans have moisture content lower than 10%.However chitosan 2 has the less ash%which is the quality grade for chitosan medical applications.Accordingly,fungal chitosan 2 could have potential medical and agricultural applications.
文摘In the current work,we have synthesized vegetable oil-based polyurethane-OMMT clay nanocomposite(PUNC)adhesive with the incorporation of different wt%of organically modified nanoclay(1 to 5 wt%)into the biobased polyurethane(PU)matrix through in-situ polymerization process via ultrasonication method.At the initial stage,PU adhesive was prepared using polyol and partially biobased aliphatic isocyanate,wherein polyol was derived from the transesterified castor oil using ethylene glycol.The formation of PU and PUNC adhesive was confirmed using Fourier transform infrared(FTIR)spectroscopy analysis.The tensile strength of PU with different wt%of nanoclay was determined and the analysis showed that the loading of 3 wt%of nanoclay within the PU matrix showed better performance as compared to the others.Furthermore,shear strength of PU and PUNC(3 wt%nanoclay)adhesives were determined using lap shear test,in which PUNC adhesive showed higher adhesive strength at 70°C.Subsequently,the dispersibility of OMMT nanoclay within the PU matrix along with exfoliation and amorphous structure was confirmed through wide angle X-ray diffractometer(WAXD)and transmission electron microscopy(TEM)analysis.The phase separation structure was analyzed using dynamic mechanical analysis(DMA).The analysis revealed that with the addition of organically modified nanoclay in the PU matrix,the glass transition temperature(Tg)of the damping curve was shifted towards higher temperature.
文摘In this work, free tall oil fatty acids were epoxidized with in-situ generated peroxyacetic acid. Reaction kineticsof epoxidation was investigated by oxirane content and iodine value titrimetric determination, as well as FTIRspectra analysis. A highly functional biobased polyol was synthesized by functionalizing epoxidized tall oilfatty acids with triethanolamine using Montmorillonite K10 as a catalyst. The obtained polyol was analyzed byFTIR and MALDI-TOF MS. The most common chemical and physical characteristics of obtained polyol weredetermined.
基金This work received financial support from the MCTIC/CNPq Universal program(Project 437501/2018-3).
文摘Food packaging materials compounded with antimicrobial additives can substantially diminish the incidence of foodborne diseases.Here,poly(L-lactic acid)(PLA)films containing sodium metabisulfite(NaM)were produced by melt extrusion as an attempt to develop a new biodegradable material with antimicrobial properties for packaging.Life cycle assessment(LCA)simulations revealed that the environmental footprints of the PLA film did not change upon NaM addition,and that NaM is more eco-friendly than silver nanoparticles.The PLA/NaM films with NaM content varying from 0.5 to 5.0 wt.%were characterized by differential scanning calorimetry(DSC),thermogravimetric analysis(TGA),and optical and mechanical properties determinations.The optical properties were sustained after the addition of NaM,but high NaM contents degraded the light transparence of the PLA matrix at some extent.The thermal stability and tensile properties of the PLA film decreased proportionally to the NaM content,while no changes were observed on Tg,Tm and Xc,as determined by DSC.Agar diffusion tests revealed that the PLA/NaM films had no antimicrobial activity on Saccharomyces cerevisiae at 35°C,which was related to the limited migration of NaM from the glassy PLA matrix.The biodegradable PLA films compounded with NaM through melt extrusion display adequate optical,thermal,and mechanical properties to cover most food packaging applications,representing an essential step toward the development of eco-friendly packaging materials that can potentially exhibit an antimicrobially active surface.
文摘Nanoparticles of the conductive coordination polymer Ni(tto) have been synthesized under mild conditions in the presence of bio-based polyesters or polyethylene glycol acting as growth controlling agents. With polyesters, aggregates of particles are observed whereas well dispersed nanoparticles are obtained with polyethylene glycol. Indeed, for a Ni2+/polyethylene glycol weight ratio of 0.031, transmission electron micrographs evidence dispersed particles exhibiting sizes in the 3 - 10 nm range. Infrared spectra for nanopowders show two CS stretching modes in the 1100 - 1190 cm−1 range, confirming the presence of the tetrathiooxalate ligand coordinated to the nickel center. The room-temperature electrical conductivity for the nanopowder prepared in the presence of polyethylene glycol is about 0.8 S∙cm−1, a decent value for tetrathiolate-based polymers. Finally, magnetic susceptibility measurements for well-dispersed Ni(tto) particles evidence a Curie-Weiss law in a large temperature range. Moreover, low temperatures measurement would confirm intra- or interchain interactions between nickel atoms within the Ni(tto) polymer chains.
文摘A novel colourant for hair dyeing was prepared by an enzymatic reaction with (+)-catechin and its characteristics as a hair dyestuff were studied. The study is aimed at inventing the hair dyestuff that is human- and eco-friendly. One potentially powerful dyestuff was obtained from (+)-catechin treated with tyrosinase after screening experiments using biobased materials. The obtained reddish orange colourant, 4-(3,4-dihydro-3α,5,7-trihydroxy-2H-1-benzopyran-2α-yl) 1,2-benzoquinone named “catechinone”, shows enough dyeability for decolourised white hair. Catechinone does not cause erythema or oedema on skin of rabbits. The colour is controlled by the addition of other biobased materials and a variety of colours of dyed hair are acquired. The fastness to light or washing for hair dyed by catechinone is high enough for practical use.
文摘Surfactants are important chemical products,serving as emulsifiers and interfacial modifiers in the household detergents,personal care products,paints and coatings,foods,cosmetics,and pharmaceuticals industries.This review focuses upon recent advances in research and development to improve the ecological sustainability of surfactants throughout their life cycle,including derivation from renewable resources,production using green manufacturing principles,and improved biocompatibility and biodegradability during their consumer use and disposal stages.Biobased surfactants,derived from vegetable oils,polysaccharides,proteins,phospholipids,and other renewable resources,currently comprise approximately 24%of the surfactant market,and this percentage is expected to increase,especially in Asia.The use of renewables is attractive to consumers because of reduced production of CO2,a greenhouse gas associated with climate change.Enzymes can greatly increase process sustainability,through reduced use of organic solvent,water,and energy,and reduced formation of by-products and waste products.Among the enzymes being investigated for surfactant synthesis,lipases are the most robust,due to their relatively high biocatalytic activity,operational stability and their ability to form or cleave ester,amide,and thioester bonds.For enzymes to be robust catalysts of surfactants,further research and development is needed to improve catalytic productivity,stability and reduce their purchase cost.
基金This research was funded by Research Foundation-Flanders,grant number G0D5416N。
文摘The biobased renewable monomer 2,5-diformylfuran is polymerised using various N-heterocyclic carbene(NHC)catalysts in dimethyl sulfoxide(DMSO)affording a low molar mass polymer.It is shown that catalyst structure as well as the temperature and time the polymerization is running have a noticeable effect on its molar mass.The obtained material is characterized by nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),differential scanning calorimetry(DSC)and X-ray diffraction(XRD).An attempt at chain extension with diamine leads to precipitation of the polymer.This new biobased polymer material might be useful as a sustainable resin.
基金financially supported by the open research fund program of Science and Technology on Aerospace Chemical Power Laboratory (No. STACPL120221B03)the National Natural Science Foundation of China (Nos. s22175059,52073275 and U21A20279)。
文摘Coordination polymerization of renewable β-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex1, β-diketiminate yttrium complex 2, bis(phosphino)carbazolide yttrium complex 3, half-sandwich benzyl fluorenyl scandium complex 4 and pyridyl-methylene-fluorenyl rare-metal complexes 5a–5c. Complexes 1, 4 and 5a–5c show trans-1,2-regioselectivities and high activities, of which 5c exhibits excellent isoselectivity(mmmm>99%). Conversely, complexes 2 and 3 promote β-ocimene polymerization to produce isotactic cis-1,4-polyocimenes(cis-1,4>99%, mm>95%). Diblock copolymers cis-1,4-PIP-block-cis-1,4-POc and cis-1,4-PBD-block-cis-1,4-POc are obtained in one-pot reactions of β-ocimene with isoprene and butadiene using complex 3. Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced T_(g)(from-20 ℃ to 79 ℃ and 74 ℃) and hydrophilicity.
