Synthesis of bio‐based internal and external cross‐linkers based on tannic acid for preparation of antibacterial superabsorbents

Recent researches focus on the synthesis of new cross‐linkers from natural resources. In the current work, functionalized tannic acid was employed as a replacement of petroleum‐based cross‐linkers because of its outstanding biochemical properties. Alkene‐ and epoxy‐functionalized tannic acids were synthesized as internal and external cross‐linkers, respectively. Cross‐linker structures were characterized with Ft‐IR and ¹HNMR analysis. Different amounts, as well as different numbers of alkene functional group, were incorporated during the superabsorbent synthesis. Moreover, the internal cross‐linked superabsorbent was surface cross‐linked with different amounts of epoxy‐functionalized tannic acid and increased the absorbency under load about 10 g g^?1. Free absorption properties in water and saline solution, absorbency under load, and rheological properties of superabsorbents were investigated. In addition, the antibacterial activity of the internal and external cross‐linked superabsorbent was studied against Escherichia coli and Staphylococcus aureus bacteria via different methods and compared with that of conventional superabsorbent.     

Synthesis and properties of bio‐based polyurethanes bearing hydroxy groups derived from alditols

Four kinds of bio‐based polyurethanes bearing hydroxy groups in the pendants were synthesized by the polyaddition of D ‐mannitol‐ and D,L ‐erythritol‐derived diols (1,2:5,6‐di‐O‐isopropylidene‐D ‐mannitol and 1,2‐O‐isopropylidene‐D,L ‐erythritol) with hexamethylene diisocyanate and methyl (S)‐2,6‐diisocyanatohexanoate and the subsequent deprotection of the isopropylidene groups. They were hydrolyzed much more quickly than the corresponding protected polyurethanes at 50 °C and pH 7.0, although their hydrolytic degradation rate was lower than that of polyurethanes with saccharic and glucuronic lactone groups, which had been reported in our previous articles. The introduction of D ‐mannitol units to the polyether‐polyurethanes containing poly(oxytetramethylene) glycol units also enhanced their hydrolyzibility. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Development of toughened bio‐based epoxy with epoxidized linseed oil as reactive diluent and cured with bio‐renewable crosslinker

In the current work, renewable resourced toughened epoxy blend has been developed using epoxidized linseed oil (ELO) and bio‐based crosslinker. Epoxidation of linseed oil was confirmed through FTIR and ¹H NMR spectra. The ELO bio‐resin was blended at different compositions (10, 20, and 30 phr) with a petroleum‐based epoxy (DGEBA) as reactive diluent to reduce the viscosity for better processibility and cured with cardanol‐derived phenalkamine to overcome the brittleness. The flow behavior of the neat epoxy and modified bio‐epoxy resin blend systems was analyzed by Cross model at low and high shear rates. The tensile and impact behavior studies revealed that the toughened bio‐epoxy blend with 20 to 30 phr of ELO showed moderate stiffness with much higher elongation at break 7% to 13%. Incorporation of higher amount of ELO (20 to 30 phr) increases enthalpy of curing without affecting peak temperature of curing. The thermal degradation behavior of the ELO based blends exhibits similar trend as neat epoxy. The higher intensity or broadened loss tangent curve of bio‐epoxy blends revealed higher damping ability. FE‐SEM analysis showed a rough and rippled surface of bio‐based epoxy blends ensuring effective toughening. Reduced viscosity of resin due to maximum possible incorporation of bio‐resin and use of phenalkamine as curing agent leads to an eco‐friendly toughened epoxy and can be useful for specific coating and structural application.     

Flame retardant and toughening behaviors of bio‐based DOPO‐containing curing agent in epoxy thermoset

Based on bio‐based furfural, a phosphorus‐containing curing agent (FPD) was successfully synthesized, via the addition reaction between 9,10‐dihydro‐9‐oxa‐10 phosphaphenanthrene‐10‐oxide (DOPO) and furfural‐derived Schiff base. Then, as co‐curing agent, FPD was used to prepare flame retardant epoxy thermosets (EP) cured by 4, 4′‐diaminodiphenyl methane. The incorporated FPD improved the flame retardancy and toughness of epoxy thermoset, simultaneously. When 5 wt% FPD was added into EP, the FPD/EP achieved 35.7% limited oxygen index (LOI) value and passed UL94 V‐0 rating, meanwhile. In FPD/EP thermoset, the incorporated FPD reduced the thermal decomposition rate, increased the charring capacity, and inhibited the combustion intensity of epoxy thermoset. Through gas‐phase and condensed‐phase actions in weakening fuel supply, suppressing volatile combustion, and enhancing charring barrier effect, FPD decreased the heat release of burning epoxy thermoset, significantly. For the outstanding effectiveness on both flame retardancy and toughness, the study on FPD provides a promising way to manufacture high‐performance epoxy thermoset.     

Synthesis and characterization of itaconic‐based epoxy resins

A trifunctional epoxy resin from itaconic acid (TEIA) was synthesized from a renewable resource‐based itaconic acid by allylation of itaconic acid to form diallyl itaconate by using m‐chloroperoxybenzoic acid as oxidizing agents followed by epoxidation of allylic C═C bond of diallyl itaconate methylhexahydropthalic anhydride as curing agent in the presence of 2‐methyl imidazole as a catalyst. The chemical structure of the synthesized resins was confirmed by Fourier transform infrared and nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR) spectroscopy analysis. The mechanical, thermal, and rheological performances of the TEIA were also investigated and compared with diglycidyl ether of bisphenol A and a plant‐based epoxidized soybean oil bioresin cured with the same curing agent. The higher epoxy value of 1.02, lower viscosity (0.96 Pa s at 25°C), higher mechanical, and higher curing reactivity toward methylhexahydropthalic anhydride of TEIA as compared with epoxidized soybean oil and comparable with diglycidyl ether of bisphenol A demonstrated significant evidence to design and develop a novel bio‐based epoxy resin with high performance to substitute the petroleum‐based epoxy resin.     

Synthesis and thermal properties of a bio‐based polybenzoxazine with curing promoter

A fully bio‐based benzoxazine, 3‐furfuryl‐8‐methoxy‐3,4‐dihydro‐2H‐1,3‐benzoxazine (Bzf), has been prepared using guaiacol, furfurylamine, and paraformaldehyde as raw materials. Its chemical structure has been characterized by 1H and 13C NMR, FTIR, and elemental analysis. The polymerization behavior of Bzf in the presence of methyl p‐toluenesulfonate (PTSM) has been studied by FTIR and DSC, and the thermal stability of the cured resin has been evaluated by thermogravimetric analysis. It was found that PTSM is a good promoter that serves to avoid thermal decomposition of the bio‐based monomer during the curing process at high temperature. In contrast to the situation with neat Bzf, the presence of PTSM (5 mol % for Bzf) significantly improves the polymerization behaviors, including a decrease in the polymerization temperature from 240 to 174 °C, a shortening of the time required to reach the gel point on heating at 200 °C from 47 to 20 min, and an increase in the char yield of the cured resin from 53 to 62%. Moreover, these observed experimental results on the promoting effect of PTSM are interpreted in terms of several possible mechanistic schemes, which involve a catalytic effect on the dissociation of C? O bonds in both the coordination ring‐opening reaction and the rearrangement from a phenoxy structure to a phenolic structure. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Bio‐based nanocomposites composed of photo‐cured epoxidized soybean oil and supramolecular hydroxystearic acid nanofibers

A mixture of epoxidized soybean oil (ESO), (R)‐12‐hydroxystrearic acid (HSA) and a photoinitiator for cationic polymerization in the ESO/HSA weight ratio 10/1 was heated to 100 °C and gradually cooled to room temperature to give bio‐based gelatinous material. The photo‐curing of the gel afforded a nanocomposite composed of crosslinked ESO and supramolecular HSA nanofibers. The transmission electron microscopy observation of the photo‐cured ESO/HSA revealed that dendritic clusters of HSA nanofibers are formed in the crosslinked ESO matrix. In the differential scanning calorimetry chart of the ESO/HSA, a thermal transition from the mesophase composed of supramolecular nanofibers to isotropic state was observed at 67 °C (ΔH = 22.6 J/g‐HSA), while the T_m of crystalline HSA is 77.7 °C (ΔH_m = 159 J/g‐HSA). Tensile strength at 20 °C of the ESO‐HSA was ～80% higher than that of photo‐cured ESO without HSA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 669–673, 2009     

Synthesis and properties of thermosetting polymers from a phosphorous‐containing fatty acid derivative

A new phosphorous‐containing fatty acid diepoxide was obtained from 10‐undecenoyl chloride and 10‐(2′,5′‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and crosslinked with 4,4′‐diaminodiphenylmethane and bis(m‐aminophenyl)methylphosphine oxide. The properties of the thermosetting materials were evaluated by differential scanning calorimetry, dynamic mechanical thermal analysis, thermogravimetric analysis, and limiting oxygen index (LOI). Thermal and thermooxidative degradation was studied by gas chromatography/mass spectrometry, FTIR, ³¹P magic angle spinning NMR spectroscopy, and scanning electron microscopy. LOI values indicate good flame‐retardant properties that are related to the formation of a protective phosphorous‐rich layer that slowed down the degradation and prevented it from being total. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5630–5644, 2006     

New cholesteric liquid‐crystal epoxy resins derived from 6‐hydroxy‐2‐naphthoic acid

Liquid‐crystalline epoxy resins were synthesized from 6‐hydroxy‐2‐naphthoic acid, which was used as a mesogenic component, with phenylhydroquinone or isosorbide and via a further reaction with (6‐bromo‐1‐hexyl)glycidylether, which was used as a flexible spacer. In this way, phenylhydroquinone‐bis‐6‐[6‐(glycidyloxy)hexyloxy]2‐naphthoate (Gly A) and isosorbide‐bis‐6‐[6‐(glycidyloxy)hexyloxy]2‐naphthoate (Gly B) were obtained. Nematic elastomers were obtained by the crosslinking of Gly A with 2,4‐diaminotoluene (DAT) and 1,10‐decanedicarboxylic acid (SA). The liquid‐crystalline behavior was investigated with differential scanning calorimetry, polarizing light microscopy, and X‐ray diffractometry. Cholesteric mesophases were produced by the blending of different ratios of Gly A and Gly B, and these blends were then crosslinked with SA to produce nematic mesophases. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2847–2858, 2001     

Partially bio‐based aromatic polyimides derived from 2,5‐furandicarboxylic acid with high thermal and mechanical properties

Two novel bio‐based diamines are synthesized through introduction of renewable 2,5‐furandicarboxylic acid (2,5‐FDCA), and the corresponding aromatic polyimides (PIs) are then prepared by these diamines with commercially available aromatic dianhydrides via two‐step polycondensation. The partially bio‐based PIs possess high glass transition temperatures (T_gs) in the range from 266 to 364 °C, high thermal stability of 5% weight loss temperatures (T_5%s) over 420 °C in nitrogen and outstanding mechanical properties with tensile strengths of 79–138 MPa, tensile moduli of 2.5–5.4 GPa, and elongations at break of 3.0–12.3%. Some colorless PI films (PI‐1‐b and PI‐1‐c) with the transmittances at 450 nm over 85% are prepared. The overall properties of 2,5‐FDCA‐based PIs are comparable with petroleum‐based PI derived from isophthalic acid, displaying the potential for development of innovative bio‐based materials. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1058–1066     

Preparation of 3‐aminopropyltriethoxy silane modified cellulose microcrystalline and their applications as flame retardant and reinforcing agents in epoxy resin

Cellulose microcrystalline (CMC), a linear polysaccharide with glucosidic bond, was successfully extracted from bamboo powder and modified by 3‐aminopropyltriethoxy silane coupling agent (KH550) to prepare KH550‐CMC. The prepared KH550‐CMC, in association with ammonium polyphosphate (APP), was introduced into epoxy resin (EP) by casting process to obtain flame retardant composites. The fire performance evaluation indicated that the presence of 10‐phr APP and 5‐phr KH550‐CMC in EP achieved the maximal LOI value of 28.9%, passed the UL‐94 V‐0 rating, and significantly decreased the peak heat release rate from 1055 kW/m² of neat EP to 286 kW/m². The improved fire performance is due to the improvement of dispersity of CMC in EP matrix and formation of better char layer, thus protecting the matrix effectively. Moreover, the introduction of KH550‐CMC could also partly eliminate the negative influence of flame retardants on the mechanical properties of EP composites due to the strengthening effect of CMC and better interfacial compatibility after modification with KH550.     

Development of completely bio‐based epoxy networks derived from epoxidized linseed and castor oil cured with citric acid

Bio‐based epoxy resins were synthesized from nonedible resources like linseed oil and castor oil. Both the oils were epoxidized through in situ method and characterized via Fourier transform infrared and ¹H‐NMR. These epoxidized oils were crosslinked with citric acid without using any catalyst and their properties compared with diglycidyl ether of bisphenol A‐epoxy. The tensile strength and modulus of epoxidized linseed oil (ELO) were found to be more than those of epoxidized castor oil (ECO)‐based network. However, elongation at break of ECO was significantly higher than that of both ELO and epoxy, which reveals its improved flexibility and toughened nature. Thermogravimetric analysis revealed that the thermal degradation of ELO‐based network is similar to that of petro‐based epoxy. Dynamic mechanical analysis revealed moderate storage modulus and broader loss tangent curve of bio‐based epoxies confirming superior damping properties. Bioepoxies exhibit nearly similar contact angle as epoxy and display good chemical resistant. The preparation method does not involve the use of any toxic catalyst and more hazardous solvents, thus being eco‐friendly.     

Vanillin‐derived phosphorus‐containing compounds and ammonium polyphosphate as green fire‐resistant systems for epoxy resins with balanced properties

Flame retardants from vanillin when utilized together with ammonium polyphosphate (APP) yield excellent synergistic flame retardancy toward epoxy resins. Bisphenol A epoxy resins have been widely used due to their excellent mechanical properties, chemical resistance, electrical properties, adhesion, etc., while they are flammable. Environment‐friendly and bio‐based flame retardants have captured increasing attention due to their ecological necessity. In this paper, 3 bio‐based flame retardants were synthesized from abundant and more importantly renewable vanillin, and their chemical structures were determined by ¹H NMR and ¹³C NMR. They were used together with APP (an environment‐friendly commercial flame retardant) to improve the fire resistance of bisphenol A epoxy resin. With the addition APP content of 15 phr, the modified bisphenol A epoxy resin could reach UL‐94V0 rating during vertical burning test and limit oxygen index values of above 35%, but reducing APP content to 10 phr, the flame retardancy became very poor. With the total addition content of 10 phr, the epoxy resins modified by 7 to 9 phr APP and 1 to 3 phr bio‐based flame retardants with epoxy groups or more benzene rings showed excellent flame retardancy with UL‐94V0 rating and limit oxygen index values of around 29%. The T_gs of the epoxy resins could be remained or even increased after introducing bio‐based flame retardants, as the control; those of APP alone‐modified epoxy resins compromised a lot. The green synergistic flame‐retardant systems have a great potential to be used in high‐performance materials.     

Layered silicate/epoxy nanocomposites: synthesis,characterization and properties

Novel epoxy‐clay nanocomposites have been prepared by epoxy and organoclays. Polyoxypropylene triamine (Jeffamine T‐403), primary polyethertriamine (Jeffamine T‐5000) and three types of polyoxypropylene diamine (Jeffamine D‐230, D‐400, D‐2000) with different molecular weight were used to treat Na‐montmorillonite (MMT) to form organoclays. The preparation involves the ion exchange of Na⁺ in MMT with the organic ammonium group in Jeffamine compounds. X‐ray diffraction (XRD) confirms the intercalation of these organic moieties to form Jeffamine‐MMT intercalates. Jeffamine D‐230 was used as a swelling agent for the organoclay and curing agent. It was established that the d₀₀₁ spacing of MMT in epoxy‐clay nanocomposites depends on the silicate modification. Although XRD data did not show any apparent order of the clay layers in the T5000‐MMT/epoxy nanocomposite, transmission electron microscopy (TEM) revealed the presence of multiplets with an average size of 5 nm and the average spacing between multiplets falls in the range of 100 Å. The multiplets clustered into mineral rich domains with an average size of 140 nm. Scanning electron microscopy (SEM) reveals the absence of mineral aggregate. Nanocomposites exhibit significant increase in thermal stability in comparison to the original epoxy. The effect of the organoclay on the hardness and toughness properties of crosslinked polymer matrix was studied. The hardness of all the resulting materials was enhanced with the inclusion of organoclay. A three‐fold increase in the energy required for breaking the test specimen was found for T5000‐MMT/epoxy containing 7 wt% of organoclay as compared to that of pure epoxy. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis of bio‐based poly(N‐phenylitaconimide) by atom transfer radical polymerization

Poly(N‐phenylitaconimide) (polyPhII) was prepared using initiators for continuous activator regeneration atom transfer radical polymerization of PhII using FeBr₃ complexes as catalysts. Conversion reached 69% in 24 h, yielding polyPhII with a number average molecular weight M_n = 11,900 and a molecular weight distribution M_w/M_n = 1.52. Copolymerizations of PhII with styrene at various molar ratios were performed providing a range of polyPhII‐copolySt polymers. When the copolymerization was carried out with higher [St]₀ > [PhII]₀ ratio, a one‐pot synthesis of poly(St‐alt‐PhII)‐b‐polySt was achieved. The thermal properties of the obtained copolymers were studied by differential scanning calorimetry. PolyPhII prepared by ATRP showed high glass transition temperature (T_g) of 216 °C and the poly(St‐alt‐PhII)‐b‐polySt exhibited two T_gs, at 162 and 104 °C, corresponding to a poly(St‐alt‐PhII) and polySt segments, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 822–827     

Poly(acrylic acid)‐chitosan @ tannic acid double‐network self‐healing hydrogel based on ionic coordination

In this work, poly(acrylic) acid‐chitosan @ tannic acid‐aluminum ion (PAA‐CS@TA‐Al³⁺) double‐network hydrogel was prepared via prefabrication, blending method, and Al³⁺ immersion method. The interaction between chitosan and tannic acid (CS@TA) was analyzed using Fourier transfer infrared spectra and UV‐Vis spectra. The UV‐Vis spectrum was also used to confirm the formation of ionic coordination in the gel. Then, the possible coordination modes were studied and analyzed. The microscopic pore structure and macroscopic strain behavior of the gel were analyzed using SEM and tensile testing, respectively, which verified that the tensile strength (≈32 KPa) and elongation at break (≈1700%) of the gel primarily resulted from its crosslinking structure. In addition, the gel also demonstrated a good self‐healing performance with recovery ≈92.2% at 60 minutes. Hence, the proposed novel self‐healing gel can provide inspiration for the preparation of future self‐healing gels.     

Coatings based on mucin‐tannic acid assembled multilayers. Influence of pH

Although widely used as implantable materials due to their mechanical properties, metal devices show several disadvantages, such as the lack of cellular binding sites, antibacterial properties, or lubricant properties. To this end, the development of engineered surfaces through protein coatings has been largely investigated. Due to their natural origin and complex structure which allows the formation of hydrogels, mucins have been proposed and investigated as effective coatings for metallic implants. The present study evaluates the ability of porcine gastric mucin (PGM) to form stable coatings on a model metal surface, using three buffers with different pH values, ranging from acid to alkaline, as dispersion media. Considering its large number of hydroxyl groups and its ability to form hydrogen bonds with the protein, tannic acid (TA) was used as cross‐linker. In addition to coatings' thickness and elasticity assessed through Quartz Crystal Microbalance with Dissipation monitoring (QCM‐D), the study also evaluates the interactions between PGM and TA at various pH values of the dispersion media through DLS. The corroborated results show that the neutral pH allows the best interactions between PGM and TA leading to the formation of a stable, less elastic coating when compared with that obtained using as dispersion media the other two investigated buffers. Moreover, the hydrophilicity and mechanical properties of the dried coatings were assessed through contact angle measurements and nanoindentation, respectively.     

Preparation,characterization, thermo‐mechanical,and barrier properties of exfoliated thermoplastic toughened epoxy clay ternary nanocomposites

Ternary nanocomposites are prepared by blending hydroxyl‐terminated poly ether ether ketone having pendant methyl groups (PEEKMOH) with epoxy resin along with Nanolin DK1, followed by curing with 4,4′‐diamino diphenyl sulphone. Differential scanning calorimetry shows a two‐stage cure behavior indicating the catalytic effect of the primary amine and proton, which are generated by the dissociation of organic modifier. Tensile and flexural moduli are increased while tensile strength and glass transition temperature are decreased with increase in clay concentration. Fracture toughness and strain at break are increased by 59 and 62%, respectively, with 1 phr clay loading. Transition electron microscopy and X‐ray diffraction (XRD) analysis reveal exfoliated morphology for the nanocomposites. Scanning electron micrographs show a decrease in both, domain size as well as inter domain distance of the thermoplastic phase with the addition of clay, indicating the occurrence of gelation before phase separation. Analysis of the fracture surface reveals crack path deflection and ductile fracture behavior, confirming that toughness has been improved with the addition of clay and PEEKMOH. Coefficient of thermal expansion (CTE) of the nanocomposites is decreased up to 3 phr clay loading. Oxygen gas permeability is compared with Bharadwaj's and Neilson's models. A marginal improvement in thermal stability is observed with the addition of clay. Copyright © 2009 John Wiley & Sons, Ltd.     

Strategies for synthesis of epoxy resins from oleic acid derived from food wastes

The use of biomass‐sourced chemical feedstocks creates a conflict over land use between food and fuel/chemical production. Such conflict could be reduced by making use of the annual 1.3 Pg food waste resource. Oleic acid is available from seed oils such as pumpkin, grape, avocado and mango. Its esterification with diols 1,3‐propanediol, resorcinol and orcinol was used to form diesters and the naturally occurring norspermidine was used to prepare a diamide, all under ambient conditions. These compounds were then epoxidized and polymerized. When esterification was followed by epoxidation and subsequent curing at elevated temperature with p‐phenylenediamine or diethylenetriamine, hard insoluble resins were formed. When the sequence was changed such that the epoxidized oleic acid was first reacted with cis‐1,2‐cyclohexanedicarboxylic anhydride and then esterified with orcinol and resorcinol, insoluble crosslinked polymers were also obtained. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3159–3170