Selective oxidation of kraft lignin over zeolite‐encapsulated Co(II) [H4]salen and [H2]salen complexes

The Co([H₄]salen) and the corresponding Co([H₂]salen) complexes were encapsulated in NaY by the impregnation (IM) and flexible ligand ship‐in‐a‐botttle (SB) method for oxidation of kraft lignin to obtain chemical compounds. The neat and encapsulated complexes were characterized by XRD, FTIR, DR UV–Vis spectroscopy and BET, which showed the observed changes in the molecular structure to be correlated to the enhanced activity of the complexes. GC‐MS confirmed that the catalytic reactions of kraft lignin in the presence of peracetic acid produced major products including 2‐methoxy phenol, 2‐hydroxy benzaldehyde, 4‐hydroxy‐3,5‐dimethoxyphenyl ethanone. The encapsulated complexes exhibited improved reactivity compared to the corresponding neat complexes. Additionally, there was a greater improvement in TOF value for complexes upon IM‐immobilization as compared to SB‐immobilization. The improved salen, that is, [H₄]salen, was beneficial to the enhancement of catalytic activity as compared to [H₂]salen, as revealed by the high TOF values due to the incorporation of a modified coordination environment of the central cobalt cation by C=N hydrogenation. Actually, Co([H₄]salen)/IM was proved to be most active. Lignin conversion and TOF were high over the neat cobalt complexes when using 100% H₂O as the solvent, and the values were high over the corresponding encapsulated analogues when using 80% H₂O + 20% CH₃OH as the solvent. It can be found that encapsulation and hydrogenation of the complexes can improve the selectivity to 2‐methoxy phenol in the oxidation of kraft lignin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40809.     

Preparation and analysis of poly(l-lactic acid) composites with oligo(d-lactic acid)-grafted cellulose

α-Cellulose extracted from jute fiber was grafted with oligo( d -lactic acid) (ODLA) via a graft polycondensation reaction in the presence of para-toluene sulfonic acid and potassium persulfate in toluene at 130 °C for 9 h under 380 mmHg. ODLA was synthesized by the ring-opening polymerization of d -lactides in the presence of stannous octoate (0.03 wt % lactide) and d -lactic acid at 140 °C for 10 h. Composites of poly( l -lactic acid) (PLLA) with the ODLA-grafted α-cellulose were prepared by the solution-mixing and film-casting methods. The grafting of ODLA onto α-cellulose was confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). The analysis of the composites was performed with FTIR spectroscopy, SEM, wide-angle X-ray diffraction, and thermogravimetric analysis. The distribution of the grafted α-cellulose in the composites was uniform and showed better compatibility with PLLA through intermolecular hydrogen bonding. Only homocrystalline structures of PLLA were present in the composites, and the thermal stability increased with increasing percentage of grafted α-cellulose. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47424.     

Sustainable bionanocomposite from d,l‐lactide/δ‐valerolactone triblock and bionanowhiskers: Preparation,characterization, and properties

Bionanocomposites were prepared using d ,l ‐lactide–δ‐valerolactone–d ,l ‐lactide triblock and unmodified and modified cellulose nanowhiskers (CNs) at different loadings (0, 2, 4, 8 wt %). Poly(δ‐valerolactone) chains were grafted on CNs for modification. These were characterized by various techniques. The broadening of OH (hydroxyl) stretching region and the presence of low‐intensity peaks at 1064 cm^?1 for C? O/C? C stretching vibration and 1426 cm^?1 for bending vibration of CH₂ group_, were evident in Fourier transform infrared spectra of the nanocomposites. The increase in crystallinity was noticed as the amount of nanowhiskers was increased. The nanowhiskers having the width in the range of 80–300 nm were uniformly dispersed in the triblock matrix. The tensile strength and modulus increased by 130% and 50% respectively at 8 wt % of filler loading. The storage modulus, loss modulus, complex viscosity, and tan δ values increased with increased filler loading. Further improvement in mechanical properties was observed with the modified CNs. The modulus mapping from atomic force microscopy confirmed the effective reinforcement behavior of the nanowhiskers. Scaffold fabrication using the bionanocomposite exhibited porous nature, having a homogeneous dispersion of CNs on the surface of the scaffold. The 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay confirmed the suitability of the composite material for scaffold application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 135, 46035.     

Regenerated cellulose aerogel: Morphology control and the application as the template for functional cellulose nanoparticles

This article focuses on controlling the morphology of regenerated cellulose aerogel (RCA) and its application as a template for the preparation of functional cellulose nanoparticles (FCNPs). RCA is prepared by lyophilizing cellulose hydrogel which is fabricated through a sol–gel method in sodium hydroxide (NaOH)/urea aqueous solution. The morphology of RCA is adjusted by varying the gelation temperature and time. With the gelation temperature and time increasing, lamellar RCA transforms into strings of cellulose nanoparticles. Subsequently, RCA with the morphology of "strings of nanoparticles" is modified through the bulk condensation of l -lactic acid and RCA. Eventually, the prepared functionalized RCA (FRCA) is dispersed in an organic solvent to obtain purified FCNPs. The results demonstrate that single FCNP can be obtained by dispersing FRCA in dimethyl sulfoxide. Moreover, the prepared FCNPs have uniform size, good thermal-stability, and increasing hydrophobicity, which are ideal candidates for polymer composites in terms of fillers.     

New biocomposite obtained using poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH) and microfibrillated cellulose

This research evaluates the effects of filler content and silanization on thermal, morphological and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH)-based composites. Microfibrillated cellulose (MFC) was obtained by a mechanical treatment of high-pressure homogenization, starting from oat hull fiber, a byproduct of the agri-food sector. MFC reinforced PHBH composites were prepared by melt compounding. SEM and FT-IR analysis showed a good dispersion of the filler in the polymeric matrix, denoting the effectiveness of the surface silanization process. The thermal stability of PHBH composites remains substantially unchanged, and the glass transition temperature marginally increases with the increase of the filler content. Furthermore, silanized MFC shows slightly reinforcing mechanical effects on PHBH composites, such as the increase of 10% of the Young modulus with an increase of the maximum tensile stress as well. This finding has an economical interest since the results showed that MFC, deriving from a byproduct, can be successfully used as filler, decreasing the cost of the bio-based compound leaving substantially unaltered its mechanical and thermal properties. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48953.     

Cassava starch‐based nanocomposites reinforced with cellulose nanofibers extracted from sisal

Cellulose nanofibers were extracted from sisal and incorporated at different concentrations (0–5%) into cassava starch to produce nanocomposites. Films' morphology, thickness, transparency, swelling degree in water, water vapor permeability (WVP) as well as thermal and mechanical properties were studied. Cellulose nanofiber addition affected neither thickness (56.637 ± 2.939 µm) nor transparency (2.97 ± 1.07 mm^?1). WVP was reduced until a cellulose nanofiber content of 3.44%. Tensile force was increased up to a nanocellulose concentration of 3.25%. Elongation was decreased linearly upon cellulose nanofiber addition. Among all films, the greatest Young's modulus was 2.2 GPa. Cellulose nanofibers were found to reduce the onset temperature of thermal degradation, although melting temperature and enthalpy were higher for the nanocomposites. Because cellulose nanofibers were able to improve key properties of the films, the results obtained here can pave the route for the development and large‐scale production of novel biodegradable packaging materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44637.     

Improvement in impact strength of modified cardanol‐bonded cellulose thermoplastic resin by adding modified silicones

The impact strength of cellulose diacetate (CDA) bonded with a modified cardanol (3‐pentadecylphenoxy acetic acid: PAA) was greatly improved up to 9 kJ/m² by adding a relatively small amount of modified silicones while suppressing a decrease in bending strength. In our recent research, this thermoplastic resin (PAA‐bonded CDA) exhibited high rigidity, glass transition temperature, and water resistance. However, its impact strength was insufficient for use in durable products. Therefore, silicones modified with polyether, amino, and epoxy groups were investigated as possible ways to improve the impact strength. The results show that adding polyether‐modified silicone (polyether silicone) with moderate polarity relative to PAA‐bonded CDA resulted in shearing deformation greatly enhances its impact strength while maintaining other properties, including glass transition temperature (T_g), water resistance, and thermoplasticity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40366.     

Preparation and characterization of transparent cellulose films using an improved cellulose dissolution process

Effective dissolution of cellulosic macromolecules is the first predominant step to prepare functional bio‐based materials with desirable properties. In this study, we developed an improved dissolution process using a freeze‐drying pretreatment to promote the dissolution of cellulose. Rheological measurements of cellulose solutions and physicochemical characterization of regenerated cellulose films (scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis) were performed. Cellulose solution prepared from 5% microcrystalline cellulose (w:v) in the solvent exhibits a Newtonian fluid character while cellulose solutions at higher concentrations show a pseudo‐plastic fluid behavior. Results from physicochemical characterization indicate that a freeze‐drying pretreatment step of cellulose leads to a complete dissolution at 5% concentration while only part of cellulose is dissolved at 10% and 15% concentrations. The results obtained indicated that the use of a freeze‐drying pretreatment step under mild conditions lead to a complete dissolution of cellulose at 5% concentration. The cellulose films prepared from 5% concentration exhibited desirable properties such as good optical transparency, crystallinity, and thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44871.     

Improvement in impact strength of modified cardanol‐bonded cellulose thermoplastic resin by using olefin resins

Impact strength of a modified cardanol‐bonded cellulose thermoplastic resin was greatly improved by using a small amount of olefin resins. As we showed, this thermoplastic resin (3‐pentadecylphenoxy acetic acid (PAA)‐bonded cellulose diacetate (CDA): PAA‐bonded CDA) exhibited high practical properties such as bending strength, heat resistance, and water resistance. However, its impact strength was insufficient for use in durable products. We improved the impact strength of PAA‐bonded CDA by adding hydrophobic olefin resins, such as polyethylene or polypropylene, while maintaining good bending strength and breaking strain. Furthermore, the application of olefin resins also increased water resistance and fluidity. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39829.     

Fire retardant cellulose aerogel with improved strength and hydrophobic surface by one-pot method

Bio-based materials with multifunctional performance are getting immense attention nowadays for their environment friendly and renewable character. Inspired by toughening effect of graphene nanosheets and borate chemistry, a simple in-situ borate crosslinking in water and freeze-drying method was employed to fabricate a fire retarded bio-based aerogel. The structure of the material was evaluated and analysis by SEM, XRD, FTIR, Raman and XPS. Importantly, the bio-based aerogel has improved strength and adsorption properties due to unique structure. The compressive strength of rGO(reduced graphene oxide) + CMC (carboxymethyl cellulose) aerogel could reach 128 ± 2.1 kPa which is five times that of neat CMC aerogel. The bio-based aerogel can load more than 2500 times of self-weight. The adsorption capacity for organic solvents and oil of rGO+CMC aerogel is also greatly improved by a little rGO (1%) introducing due to its unique porous structure and hydrophobic nature of rGO. Additionally, rGO+CMC aerogel is also found fire resistant with relatively low thermal conductivity due to the borate and GO introduction.     

Bio‐sorbents from cassava waste biomass and its performance in removal of Pb2+ from aqueous solution

Cassava xanthogenate and their derivatives, as adsorbents to remove Pb²⁺ from aqueous solution, are studied based upon orthogonal factorial design. The structural and thermal properties, adsorption performance as well as equilibrium‐kinetics are comprehensively investigated with multiple tools, such as Fourier transform infrared spectroscopy, thermal gravimetric analysis (TGA), and UV–visible spectrum technique. The influence of multiple parameters, including initial Pb²⁺ concentrations, compositions, pH values, and temperatures, on the adsorption performance is emphasized. The crosslinked cassava xanthogenate serves as an effective bio‐sorbent to remove Pb ions from aqueous solution, allowing regeneration in dilute acid solution. The findings in this study are beneficial for the development of adsorbents from cassava waste biomass and may contribute to environment recovery in “nature‐to‐nature” manner. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39780.     

Poly(vinyl alcohol)–lignin blended resin for cellulose‐based composites

Wood has limitations in strength because of its biostructural defects, including vessels. To overcome this limitation, composite materials can be innovated by breaking wood down into cellulose and lignin and reassembling them for bio‐originating strong structural materials. In this study, an ecofriendly resin was developed that was suitable for cellulose‐based composites. To overcome the low dimensional stability of lignin and to increase its interactions with cellulose, it was blended with poly(vinyl alcohol) (PVA). The PVA–lignin resin was characterized with scanning electron microscopy, Fourier transform infrared spectroscopy, thermal analysis, mechanical tensile testing, and lap‐shear joint testing. The adhesion properties of the PVA–lignin resin increased with increasing PVA content. PVA played the role of synthetic polymer and that of linker between the cellulose and lignin, like hemicellulose does in wood. The PVA–lignin resin exhibited a high miscibility, mechanical toughness, and good adhesion properties for nanocellulose composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46655.     

Behavior of cellulose liquefaction after pretreatment using ionic liquids with water mixtures

Ionic liquid (IL)‐water mixtures were applied in cellulose pretreatment experiment and the pretreated cellulose was used in subsequent phenol liquefaction process as a new application method. Cellulose recovery rate and the average molecular weight (M_w) of pretreated cellulose were investigated to understand the influence of these mixtures on cellulose structure. X‐ray diffraction, Fourier transform infrared, gel permeation chromatograph, and scanning electron microscope were used to clarify the changes of pretreated cellulose. The liquefied residues from untreated cellulose and pretreated cellulose were considered as significant index to determine the effect of IL‐water mixtures on cellulose. Moreover, liquefied residues were initially characterized by the variation of the average M_w. It was suggested that the lower M_w of cellulose obtained in IL‐water mixtures, and the crystalline structure was disrupted. So, some cracks were found on the cellulose surface obviously. The liquefied residues result suggested that the pretreated cellulose obtained the lower residues at the same time or the same amount of residues by using the less time. The behavior of cellulose liquefaction efficiency using IL‐water mixture pretreatment was discussed. The lower M_w of cellulose was the major factor, which accelerates the cellulose phenol liquefaction process efficiency. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40255.     

Synthesis of an elastic β‐cyclodextrin hydrogel cage by hydroxyethyl cellulose

Current cyclodextrin (CD) hydrogels have disadvantages, including a limited CD content, long reaction time, and complicated chemical reactions. To overcome these, a one‐pot reaction was adopted, and a concept of a β‐CD hydrogel cage was proposed. Hydroxyethyl cellulose (HEC) was used as the raw material with the adjustment of the stoichiometric relationship among the crosslinking agent of epichlorohydrin, alkali environment, and β‐CD amount, and an elastic β‐CD hydrogel cage system was established. After the β‐CD was caged, the contents of active β‐CD in hydrogel products reached 74.45 and 69.14 wt % by weight measurement and photometric titration, respectively. Furthermore, compared to the pure HEC hydrogel, the hydrogel mechanical strength improved obviously after the β‐CD was caged, and we obtained a faster water swelling rate at the same time. Finally, a hydrophobic molecule of phenolphthalein (PP) was used to evaluated the activity of caged β‐CD in the hydrogel. In addition, the absorption and release of PP by an elastic β‐CD hydrogel cage at certain time intervals were also studied. The results demonstrate that the β‐CD hydrogel cage was used as a functional molecule carrier to quickly absorb and sustain the release of PP. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44388.     

Nanocomposites of ethylene vinyl alcohol copolymer with thermally resistant cellulose nanowhiskers by melt compounding (I): Morphology and thermal properties

In this study, ethylene‐vinyl alcohol copolymer (EVOH) nanocomposites were prepared by melt compounding both plant cellulose nanowhiskers (CNW) and bacterial cellulose nanowhiskers (BCNW) as nanofillers. Electrospinning and a “dissolution precipitation” method were used as strategies for the incorporation of CNW in EVOH before melt compounding with the aim of enhancing the degree of dispersion of the nanocrystals when compared with direct melt‐mixing of the freeze‐dried product with the polymer. As revealed by morphological characterization, the proposed preincorporation methods led to a significant improvement in the dispersion of the nanofiller in the final nanocomposite films. Furthermore, it was possible to incorporate concentrations as high as 4 wt % BCNW without causing significant agglomeration of the nanofiller, whereas increasing the CNW concentration up to 3 wt % induced agglomeration. Finally, DSC studies indicated that the crystalline content was significantly reduced when the incorporation method led to a poor dispersion of the nanocrystals, whereas high‐nanofiller dispersion resulted in thermal properties similar to those of the neat EVOH. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Construction of porous cellulose tubes and the evaluations of mechanical properties and cytocompatibility

In this work, regenerated cellulose (RC) tubes with the porous structure were successfully fabricated for constructing the non-invasive detection platform of vascular microenvironment. Polyethylene oxide (PEO) as a porogen was applied to induce porous structure of cellulose tubes. Tensile and burst pressure tests were carried out to evaluate the effects of PEO molecular weight and amount on the mechanical properties of cellulose tubes. The results showed that tensile strength of RC tubes was increased with increasing PEO molecular weight. The compliance of cellulose tubes decreased with increasing the PEO content. When 120 kDa PEO was applied, the average tensile strength of RC tubes could reach 1.27 MPa. The maximum burst pressure and compliance of RC tubes could reach 488.25 ± 35 mmHg and 7.50 ± 3.7%/100 mmHg, respectively. Human umbilical vein endothelia cells (HUVECs) exhibited obvious proliferation on cellulose tubes, and the collagen coating further improve the biocompatibility. The incorporated collagen further improved adhesion of the cells and growth on cellulose tubes. This work provided a kind of cellulose-based tube material with potential application for the construction of the vitro vascular microenvironment.     

Solvent‐free synthesis of 6‐deoxy‐6‐(ω‐aminoalkyl)amino cellulose

Cellulose p‐toluenesulfonic acid esters (TosCell) with degree of substitution (DS_Tos) between 0.8 and 1.4 were converted with ethylene diamine or tris(2‐aminoethyl)amine. In contrast to procedures published, the conversion was carried out without any solvent, i.e., the reagent (amines) was used as reaction medium yielding readily soluble products. Moreover, the absence of an additional solvent makes the recycling of both not‐consumed amine and precipitant easy. Recycling experiments proofed the possibility of reusing the isolated ethylene diamine. The DS of 6‐deoxy‐6‐(ω‐aminoalkyl)amino groups is between 0.71 and 0.93, which is in accordance with the functionalization pattern of tosyl cellulose and the ability of amines to displace primary tosylate moieties only. Attention must be paid to the precipitant used for the workup procedure; ¹³C NMR measurements revealed a formation of imine structures in case of precipitation with acetone. Precipitation in 2‐propanol did not lead to any side product. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43987.     

Nanocomposites of ethylene vinyl alcohol copolymer with thermally resistant cellulose nanowhiskers by melt compounding (II): Water barrier and mechanical properties

In the present work, the crystallinity and crystalline morphology, thermal stability, water barrier, and mechanical properties of ethylene vinyl alcohol copolymer (EVOH) nanocomposites prepared by melt compounding and incorporating both plant (CNW) and bacterial cellulose nanowhiskers (BCNW) are reported. An improvement in the water barrier performance was observed, that is, 67% permeability drop, only for the microcomposite sample incorporating 2 wt % of bacterial cellulose fibrils. No significant differences in the water‐barrier properties of the nanocomposites generated through the two studied preincorporation methods were observed despite the fact that an excellent dispersion was observed in the previous study. On the other hand, direct melt‐mixing of the freeze‐dried nanofiller with EVOH resulted in increased water permeation. The aggregation of the filler in the latter nanocomposite was also ascribed to the detrimental effect on the mechanical properties. Interestingly, by using the precipitation method, an increase in the elastic modulus and tensile strength of ～36 and 22%, respectively, was observed for a 3 wt % BCNW loading, which was thought to coincide with the percolation threshold. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Composites based on renewable materials: Polyurethane‐type matrices from forest byproduct/vegetable oil and reinforced with lignocellulosic fibers

The use of products and byproducts from the agro‐industry and forest biorefinery is essential for the development of value‐added and low environmental‐impact materials. In this study, polyurethanes were prepared using sodium lignosulfonate (NaLS) and castor oil (CO) as reagents and were used to prepare composites reinforced with lignocellulosic fibers, namely, curaua and coir fibers (30 wt %, 3 cm length, and randomly oriented). The SEM images of fractured surfaces of the composites revealed excellent adhesion at the fiber/matrix interface of both coir and curaua composites, which probably resulted from the favorable interactions between polar groups, as well as amid low polarity domains that are present in both the matrix and the reinforcements. The composites exhibited different impact/flexural and strength/flexural moduli (NaLS/CO/Curaua = 465 Jm^?1/44 MPa/2 GPa; NaLS/CO/Coir = 180 Jm^?1/25 MPa/1 GPa). The higher tensile strength/aspect ratio of the curaua fibers (485 MPa/259) compared with that of the coir fibers (120 MPa/130) most likely contributes to the enhanced performance of its composite. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of natural flours on crystallization behaviors of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

This paper investigates the effects of natural flours on the crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBH). Two types of PHBH (3‐hydroxyhexanoate [3HH] contents of 5.6 and 11.1 mol %) were used as polymer matrix. One of two natural flours (cellulose or wood) at 1 wt % was added to this PHBH matrix. Crystallization behaviors under nonisothermal conditions were characterized using differential scanning calorimetry (DSC), while those under isothermal conditions were characterized using DSC and polarized optical microscopy. The results suggested that both cellulose and wood flour addition enhanced crystallization of the PHBH containing 5.6 mol % of 3HH (i.e., increased crystallization peak temperature and degree of crystallinity under the nonisothermal conditions, as well as decreased crystallization half time under the isothermal conditions). Of the two flours, wood flour was found to have greater effects, due to its higher crystal nucleating ability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43600.