Acrylated Epoxidized Soybean Oil Research Articles

Coating applications to natural fiber composites to improve their physical, surface and water absorption characters

Natural (organic) fibers are used in reinforced composites and natural fiber composites (NFCs). These fibers have advantages over synthetic fiber composites such as high mechanical properties, lower densities and biodegradability. However, one major disadvantage of NFCs is their hydrophilicity. In this study, we report a method to prepare dried distillers grains with solubles (DDGS)-flax composites which can be subsequently coated with acrylated epoxidized soybean oil (AESO) and polymerized by UV light with Irgacure®819 initiator. The physical, mechanical and water resistance properties of coated DDGS-flax composites were compared to the untreated samples. Results showed that water resistance property was improved by AESO coating. The surface roughness, color and mechanical properties of coated DDGS-flax composites only slightly differed from untreated composites.

Environmentally Friendly Compatibilizers from Soybean Oil for Ternary Blends of Poly(lactic acid)-PLA, Poly(ε-caprolactone)-PCL and Poly(3-hydroxybutyrate)-PHB.

Ternary blends of poly(lactic acid) (PLA), poly(3-hydroxybutyrate) (PHB) and poly(ε-caprolactone) (PCL) with a constant weight percentage of 60%, 10% and 30% respectively were compatibilized with soybean oil derivatives epoxidized soybean oil (ESO), maleinized soybean oil (MSO) and acrylated epoxidized soybean oil (AESO). The potential compatibilization effects of the soybean oil-derivatives was characterized in terms of mechanical, thermal and thermomechanical properties. The effects on morphology were studied by field emission scanning electron microscopy (FESEM). All three soybean oil-based compatibilizers led to a noticeable increase in toughness with a remarkable improvement in elongation at break. On the other hand, both the tensile modulus and strength decreased, but in a lower extent to a typical plasticization effect. Although phase separation occurred, all three soybean oil derivatives led somewhat to compatibilization through reaction between terminal hydroxyl groups in all three biopolyesters (PLA, PHB and PCL) and the readily reactive groups in the soybean oil derivatives, that is, epoxy, maleic anhydride and acrylic/epoxy functionalities. In particular, the addition of 5 parts per hundred parts of the blend (phr) of ESO gave the maximum elongation at break while the same amount of MSO and AESO gave the maximum toughness, measured through Charpy’s impact tests. In general, the herein-developed materials widen the potential of ternary PLA formulations by a cost effective blending method with PHB and PCL and compatibilization with vegetable oil-based additives.

Enhancement of the mechanical and thermal properties of injection-molded polylactide parts by the addition of acrylated epoxidized soybean oil

This work reports the effect of acrylated epoxidized soybean oil (AESO) addition on the mechanical, thermal, and thermomechanical properties of polylactide (PLA) parts obtained by injection molding. To this end, AESO, a chemically multi-functionalized vegetable oil, was incorporated into PLA during melt processing. The PLA parts with AESO contents in the 2.5–7.5wt% range showed a remarkable enhancement in both elongation at break and impact-absorbed energy while their tensile and flexural strength as well as thermomechanical properties were maintained or slightly improved. Additionally, the AESO-containing PLA parts presented higher thermal stability and lower crystallinity. The improvement achieved was ascribed to a dual effect of plasticization in combination with a chain-extension and/or cross-linking process of the PLA chains by the highly reactive acrylate and epoxy groups present in AESO. The use of AESO thus represents an environmentally friendly solution to obtain toughened PLA materials of high interest in, for instance, rigid packaging, automotive or building and construction applications.

Preparation and Evaluation of Green Composites from Microcrystalline Cellulose and a Soybean-Oil Derivative.

The present work aimed at developing fully green composites from renewable materials, i.e., acrylated epoxidized soybean oil (AESO) and microcrystalline cellulose (MCC) by a solution casting method. The reinforcing effect of MCC on AESO resins was optimized by adjusting MCC loading from 20 to 40 wt % in terms of physical, mechanical, and thermal properties as well as water absorption of the resulting MCC/AESO composites. The interaction between MCC and AESO was characterized by Fourier transform infrared (FTIR) analysis, which revealed possible hydrogen bonds between the –OH groups of MCC along with the polar components of AESO including C=O, –OH, and epoxy groups. This was further evidenced by a benign interfacial adhesion between MCC and AESO resins as revealed by scanning electron microscope (SEM) analysis. The incorporation of MCC into AESO resins significantly increased the density, hardness, flexural strength, and flexural modulus of the MCC/AESO composites, indicative of a significant reinforcing effect of MCC on AESO resins. The composite with 30 wt % MCC obtained the highest physical and mechanical properties due to the good dispersion and interfacial interaction between MCC and AESO matrix; the density, hardness, flexural strength, and flexural modulus of the composite were 15.7%, 25.0%, 57.2%, and 129.7% higher than those of pure AESO resin, respectively. However, the water resistance at room temperature and 100 °C of the composites were dramatically decreased due to the inherent hydrophilicity of MCC.

Synthesis and Characterization of Methacrylated Eugenol as a Sustainable Reactive Diluent for a Maleinated Acrylated Epoxidized Soybean Oil Resin

This work presents a solvent-free, facile synthesis of a renewable, aromatic monomer, methacrylated eugenol (ME), from eugenol and methacrylic anhydride by the Steglich esterification reaction. The resulting ME was subsequently used as a reactive diluent to copolymerize with a commercial maleinated acrylated epoxidized soybean oil (MAESO) resin to form renewable MAESO-ME thermosets. The volatility of ME was examined, along with an analysis of viscosity and curing behavior of the MAESO-ME mixtures. The curing kinetics, thermo-mechanical properties, and thermal stabilities of the fully cured MAESO-ME thermosets with different ME proportions (0, 20, 40, 60, 80, and 100%) were systematically investigated. The results indicated that ME monomer exhibited extremely low volatility (less than 3% mass loss after being held isothermally at 30 °C for 10 h), high bio-based carbon content (BBC, 71.4%), and low viscosity (17.6 cP at 25 °C). When used with MAESO resin, viscosity of the system was considerably decreased. ...

Development of acrylated soybean oil‐based UV‐curable coatings with high impact strength from low viscosity oligomer

ABSTRACTIn recent years, more and more attention has been paid to bio‐based materials due to their sustainability and environmental friendliness. The combination of biomass and ultraviolet (UV) curing technology can reduce the dependence on petroleum products and emissions of volatile organic compounds. In this article, a new environment‐friendly UV‐curable coating with good performances was successfully prepared from acrylated soybean oil (ACSO). ACSO was obtained at low temperature without catalyst and inhibitor by reacting soybean oil‐based polyol with acryloyl chloride and characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. It was found that the UV‐curable oligomer of ACSO had lower viscosity and better ductility, compared to acrylated epoxidized soybean oil (AESO). The properties of UV‐cured films prepared by ACSO were studied and compared with films from AESO. The results showed that the ACSO‐based films were significantly improved in the adhesion and impact resistance. Furthermore, the addition of styrene could enhance the hardness and impact resistance of films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45698.

Dynamics of hyperbranched polymers derived from acrylated epoxidized soybean oil

In this article we demonstrate the role of chain architecture on the relaxation dynamics of poly(acrylated epoxidized soybean oil) (PAESO), a hyperbranched polymer, with a particular focus on the role played by intramolecular loops. PAESO is produced by reversible addition-fragmentation chain transfer (RAFT) polymerization from acrylated epoxidized soybean oil (AESO) containing an average of 2.6 polymerizable acrylic moieties per trigylceride. By adjusting the relative concentrations of solvent, monomer, and RAFT chain transfer agent, PAESO undergoes a series of both inter-molecular and intra-molecular reactions such that both molecular weight and chain architecture vary throughout the reaction. While intermolecular reactions are responsible for branching, intramolecular reactions introduce loops to the structure with altogether different consequences on chain conformations and segmental dynamics. Using dynamic shear rheology in the linear viscoelastic regime we find that Rouse/Zimm-like dynamics persist to molecular weights as high as 390 kDa and that the primary influence of looping is to strongly suppress the number of Zimm relaxation modes.

Fabrication of highly water-repelling paper by surface coating with stearic acid modified calcium carbonate particles and reactive biopolymers

Cellulose paper is the most attractive green packaging material due to its recyclability, renewability, sustainability and biodegradability. In some applications, paper with a high level of water resistance is desirable to meet specific requirements in modern packaging fields. This research aimed to develop a water-repelling paper with cost-effective and nontoxic materials. Commercial precipitated calcium carbonate (PCC) particles were modified by stearic acid (SA) and incorporated with soybean oil-based binder as a water repelling coating agent. The water-repelling efficiency of the coated paper was highly dependent on the ratio of SA/PCC as well as the binder content in the coating formula. PCC particles modified with 12wt% SA were efficient in increasing the water contact angle (WCA) of the coated paper to 146° at a coating weight of 5 g/m². The binder for the coating was synthesized with acrylated epoxidized soybean oil (AESO) through Michael addition reaction. The triglyceride structure in the polymer chain imparted good bio-degradability to the binder polymer. It was found that surface modification of PCC with stearic acid played an important role in improving the WCA of paper. A super hydrophobic paper with a WCA of 162° was fabricated with a coating formula of 60% SA-modified PCC and 40 wt% AESO-binder.

Thermosetting AESO-bacterial cellulose nanocomposite foams with tailored mechanical properties obtained by Pickering emulsion templating

This study reports on the development of nanocomposite foams, prepared by Pickering emulsion templating, with promising tailored-properties, simply tunable by their composition. The selected multicomponent monomer mixtures comprise acrylated epoxidized soybean oil (AESO), 1,6-hexanediol diacrylate (HDD) and divinylbenzene (DVB), chosen by their renewable-origin or resemblance to renewable ones, and above all due to their varying stiffness or crosslinking-ability. The Pickering water-in-oil emulsions, after their fast stabilization using cyclohexane and acetylated bacterial cellulose, were used as templates for the polymeric foams production. These original materials were thermally stable up to approximately 320 °C, and had a Young's modulus varying between 3.41 and 16.39 MPa, being the highest results prompted by the use of HDD or DVB.

Synthesis of multifunctional monomers from rosin for the properties enhancement of soybean-oil based thermosets

Two kinds of rosin derivatives, (2-hydroxy-3-(methacryloyloxy)propyl 7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,4b,5,6,10,10a-decahydrophenanthrene-1-carboxylate) (HMPIDDC) and (((7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl)methyl)azanediyl)bis(2-hydroxypropane-3,1-diyl)bis(2-methylacrylate) (IDOMAHM) were synthesized under mild and easy to implement conditions. The two derivatives were employed as the rigid monomers to copolymerize with acrylated epoxidized soybean oil (AESO), as so to improve the performance of the cured resins. The chemical structures of HMPIDDC and IDOMAHM were confirmed by nuclear magnetic resonance (NMR) and Fourier Transform Infrared (FT-IR) before copolymerization. The curing behaviors of pristine AESO, AESO/HMPIDDC blend, and AESO/IDOMAHM blend were monitored by differential scanning calorimetry (DSC). Moreover, the thermal and mechanical properties of the cured resins were evaluated by universal mechanical testing, dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). The results demonstrated that after the introduction of HMPIDDC and IDOMAHM, the glass transition temperature and mechanical properties of the copolymerized resin were significantly increased. In one word, HMPIDDC and IDOMAHM showed dramatic potential to be used as bio-based compounds to improve the properties of soybean-oil based thermosets.

Photosynthesis of anticorrosive protective coatings for steel substrate based on acrylated oil containing unsaturated amino acid compounds

Novel environment friendly anticorrosive coating formulations for mild steel substrate based on acrylated oil were prepared by using unsaturated amino acid compounds. In the first, epoxidized soybean oil acrylate (ESOA) was hardened and modified by the different functionality of monomers to be used in anticorrosive coating formulations. In this article, new corrosion inhibitors were synthesized through two steps. In step one; renewable resource based palm oil was epoxidized under a well-established condition to form epoxidized triglyceride ester of palm oil (EPO). FTIR and oxirane content analysis were used to confirm the formation of the epoxidation reaction. In step two, the EPO was reacted chemically with 4-aminobenzoic acid (AB) and 2-aminoacrylic acid (AA) under controlled conditions of an inert atmosphere and high temperature to produce EPO/AB and EPO/AA adducts. The prepared adducts were characterized by FTIR-spectroscopy and oxirane content analysis. The adducts are evaluated as corrosion inhibitors via adding different concentrations of them to the ESOA coating formulations. Then all coating films were subjected to UV irradiation. Degrees of rusting, blistering, failure at scribe, and weight loss values were measured for all UV cured films, in addition to the chemical and mechanical measurements. The obtained experimental results revealed that the cured coating films containing EPO/AB inhibitor displayed higher resistance to corrosion on the mild steel substrate than EPO/AA without any effect on the mechanical and chemical properties of cured films. Also, the optimum concentration of the prepared inhibitors was to be 0.5%.

Replacement of styrene with acrylated epoxidized soybean oil in an unsaturated polyester resin from propylene glycol and maleic anhydride

ABSTRACTA nonvolatile, vegetable‐oil based chemical, acrylated epoxidized soybean oil (AESO) was investigated as a replacement of volatile and toxic styrene in one of commercial UPE resins styrene‐(PG‐MA) that is a mixture of styrene and a UPE plastic from propylene glycol and maleic anhydride (PG‐MA). Neither AESO nor PG‐MA was capable of forming a strong matrix, respectively, for glass fiber‐reinforced composites. However, a mixture of AESO and PG‐MA resulted in glass fiber‐reinforced AESO‐(PG‐MA) composites that were comparable or even superior to those from styrene‐(PG‐MA) in terms of the flexural and tensile properties. Effects of AESO contents on the mechanical and viscoelastic properties of the glass fiber‐reinforced AESO‐(PG‐MA) composites were investigated. Resin viscosity and resin pot life as a function of temperature were studied. The curing mechanism of the AESO‐(PG‐MA) resins is also discussed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45056.

Synthesis and properties of a novel bio-based polymer from modified soybean oil

Maleated acrylated epoxidized soybean oil (MAESO) was prepared by acrylated epoxidized soybean oil (AESO) and maleic anhydride. AESO were obtained by the reaction of epoxidized soybean oil (ESO) with acrylic acid as the ring-opening reagent. The polymer was prepared by MAESO react with styrene. The structures of the products were studied by Fourier transformation infrared spectrometer (FT-IR), and were consistent with the theoretical structures. Swelling experiment indicated that the crosslinking degree increased with increasing epoxy value of ESO. Thermal properties was tested by thermo-gravimetric analysis (TG) and differential scanning calorimetry analysis (DSC), indicating that glass transition temperature (Tg) of the polymer increased with increasing epoxy value of ESO, and thermal stability of polymer have a good correlation with the crosslinking degree. Mechanical properties analysis presented that tensile strength and impact strength affected by epoxy value of ESO. With the increase of epoxy value, the tensile strength increase, while the impact strength decrease. The property of the polymer ranged from elastomer to plastic character depended on the functionality of the ESO.

High biocontent natural plant oil based UV-curable branched oligomers

Abstract A new, green approach to improve the performance and biorenewable content of natural plant oil based UV-curable materials is presented. A novel kind of soy-based UV-curable branched oligomer (ACSO) was synthesized by chemically introducing cashew nutshell liquid (CNL) onto the epoxidized soybean oil (ESBO) backbone, followed by epoxidization and acrylation. The synthesized ACSO were used to produce UV-curable films and coatings. The UV-curing behavior of ACSO was investigated using real-time IR. The properties of UV cured films were studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), tensile testing, and nanoindentation technique. Compared to coating from acrylated epoxidized soybean oil (AESO), ACSO based coating exhibited higher impact resistance, better crosshatch adhesion, and enhanced thermal and mechanical properties. Meanwhile, high biorenewable content was maintained due to the biorenewable character of CNL in ACSO. The improved coating properties can be attributed to the incorporated aromatic ring from CNL and multi-branched structure of ACSO. This approach provided a new direction to the future development of advanced bio-based UV-curable oligomers with reasonably high biorenewable content.

Itaconic Acid as a Green Alternative to Acrylic Acid for Producing a Soybean Oil-Based Thermoset: Synthesis and Properties

In this paper, itaconic acid was monomethylated with methanol to produce monomethyl itaconate, and then monomethyl itaconated epoxidized soybean oil (IESO) was obtained by melt ring-opening esterification of monomethyl itaconate with ESO. For comparison, acrylated epoxidized soybean oil (AESO) was also synthesized from ESO and acrylic acid with the same synthetic method. The chemical structures of monomethyl itaconate, IESO, and AESO were characterized in detail by differential scanning calorimetry (DSC), FTIR, and 1H NMR. The isothermal thermogravimetric analysis at 30, 60, and 90 °C indicated that monomethyl itaconate exhibited extremely low volatility even at 90 °C, while acrylic acid volatilized very fast even at 30 °C, which suggested that monomethyl itaconate could be used as a green alternative to acrylic acid. Under UV radiation, IESO showed good copolymerization ability with reactive monomers such as glycidyl methacrylate modified itaconic acid (IG), trimethylolpropane triacrylate (TMPTMA), and s...

Design of biodegradable PCL/PI films as a joining tape for grafting plant

ABSTRACTIn this study, novel eco-friendly blends based on environmental-friendly polymers and compatibilizers, such as poly(ϵ-caprolactone) (PCL), cis-1,4-polyisoprene (PI), soybean lecithin (SOLE) and acrylated-epoxidized soybean oil (AESO), have been prepared in order to suggest a biodegradable joining tool used for plant grafting in agriculture, which will be competitive from the environment and economic points of view against conventional nonbiodegradable tools. PCL/PI blends, in which the portion of PCL was 75 and 50, were mixed with a compatibilizer by a melt-blending technique. The resulting blends were investigated by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy and also their mechanical properties were determined. Afterwards, the blend films were buried in the soil. Remarkable level of weight loss was achieved in 6 weeks, ∼46%. The results showed that the addition of SOLE helped to improve the compatibility between PCL and PI due to its amphipathic property, and, besides, accelerated the weight loss of the films in soil, increasing microorganism growth on the film.

Biobased Thermosets Prepared from Rigid Isosorbide and Flexible Soybean Oil Derivatives

A rigid monomer, isosorbide-methacrylate (IM), was synthesized from isosorbide with methacrylate anhydride (MAA) via a solvent-free, ultrasonic-assisted method and then was used to copolymerize with acrylated epoxidized soybean oil (AESO) to formulate a biobased thermosetting resin (IM-AESO). The synthesis of IM was monitored by attenuated total reflectance Fourier transform infrared (ATR-FTIR) by tracking the changes in the functional groups of the reaction system. The AESO was further modified with MAA to replace the hydroxyl groups of AESO with methacrylate groups, generating a resin (IM-MAESO) with an improved degree of unsaturation. The chemical structure of IM and modification of AESO with MAA were characterized using 1H NMR, 13C NMR, and ATR-FTIR analyses. The miscibility of IM with AESO was predicted according to Hansen’s solubility theory and evaluated experimentally. The formulated IM-AESO and IM-MAESO resins were compared with the pure AESO and IM resins in terms of their rheological behaviors,...

Synthesis and performance of a thermosetting resin: Acrylated epoxidized soybean oil curing with a rosin‐based acrylamide

ABSTRACTA synthesized rosin‐based polymeric monomer, N‐dehydroabietic acrylamide (DHA‐AM), was introduced into an acrylated epoxidized soybean oil (AESO)/DHA‐AM system to afford a thermosetting resin through thermocuring. Different molar ratios of the thermosetting AESO/DHA‐AM samples were obtained through curing in the presence of an initiator, and the curing processes of the AESO/DHA‐AM systems were evaluated by differential scanning calorimetry. The structures and performances of the resulting thermosets were characterized by Fourier transform infrared spectroscopy, dynamic mechanical analysis, elemental analysis, thermogravimetric analysis, and contact angle (θ) analysis. The analyses showed that with increasing content of DHA‐AM introduced into the copolymer, the storage modulus, glass‐transition temperature, thermal stability, and θ values of the cured samples all increased. Moreover, the copolymers changed from hydrophilic materials to hydrophobic materials. The results also demonstrate that the rosin acid derivatives showed comparable properties to those of reported petroleum‐based rigid compounds for the preparation of soybean‐oil‐based thermosets. The presence of DHA‐AM moieties in the composite structures could expand the use of AESO into the development of heat‐resistant and hydrophobic materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44545.

ESOA modified unsaturated polyester hybrid networks: A new perspective

ABSTRACTHybrid polymer networks based on unsaturated polyester (UPE) and epoxidized soybean oil acrylate (ESOA) were synthesized by reactive blending through free radical addition polymerization reaction. ESOA was prepared by acrylation of epoxidized soybean oil (ESO). The physical, mechanical, thermal and electrical properties of the cured blends were compared with the neat resin. ESOA resin bearing reactive functional groups showed good miscibility and compatibility with the UPE resin. The co‐cured resin showed substantial upgrading in the toughness, impact resistance, thermal properties, and downgrading brittleness up to the addition of 20 wt % of ESOA content. The muddled phase structure was corroborated by Fourier transform infrared spectroscopy, scanning electron microscope, and transmission electron microscopy and proved the formation of excellent hybrid polymer network. An improvement in overall properties has been achieved without seriously affecting any other properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44345.

Effects of Cellulosic Base Sheet Pore Structure and Soybean Oil-Based Polymer Layer on Cellulosic Packaging Performance as a Barrier for Water and Water Vapor

Cellulose-based materials are good alternatives to petroleum-based materials in the packaging industry, considering their sufficient mechanical properties and sustainability; however, the barrier performances of cellulosic packaging materials against water and water vapor are generally poor due to the hydrophilic nature of cellulose. In this study, a soybean oil-based polymer was synthesized on the surface of several cellulosic materials through an acrylated-epoxidized soybean oil (AESO) reactive coating. The best conversion of the reaction was observed when a suitable reaction temperature, curing time, initiator dosing, and monomer content were selected. Five different types of cellulosic packaging materials were used as substrates for the reactive coating, and their barrier performances were investigated. The improvement in water barrier properties was indicated by the change in water droplet contact angle (CA). The water vapor permeability (WVP) of the substrates was reduced significantly after coating. The water vapor barrier properties of the coating were highly dependent on the tested substrate. A comparison of CA and WVP showed that the change in water vapor barrier did not correspond to surface hydrophobicity.