Biobased polymer films from avocado oil extraction residue: Production and characterization

In view of the increasing interest in the use of residues from the food industry as source for packing applications, the by‐product of the mechanical extraction of avocado oil is an attractive product as it consists basically a hydrated and defatted pulp, rich in proteins, fibers. and oil. This work aims to produce biobased polymer films from avocado oil extraction residue. Seven film‐forming solutions were elaborated from puree and the additives tested were glycerol, cassava starch, and microcrystalline cellulose. The films obtained from the pure residue presented brittle behavior. All films presented low values of water vapor permeability (0.064 to 0.446 g mm m^?2·kPa^?1 h^?1) and medium water soluble fraction (43.79 to 56.92%). The films with cassava starch and glycerol presented the best results, with mechanical (tensile: 2.70 MPa; elongation: 13.7%) and thermal properties in the range typically found in the literature for biobased films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43957.     

Isothiocyanate derivatives of soybean oil triglycerides: Synthesis,characterization, and polymerization with polyols and polyamines

In this article, a novel two step synthesis of soy oil based isothiocyanate is described. Allylicaly brominated soybean oil (ABSO) was reacted first with ammonium thiocyanate in tetrahydro furan to form allylic thiocyanates. These compounds were then converted to isothiocyanated soybean oil (ITSO) by a thermal rearrangement. Conversion was found to be 70%. The structure of the ITSO was characterized by IR and ¹ H‐NMR techniques. Then ITSO was reacted with ethylene glycol, glycerol, and castor oil to produce polythiourethanes and ethylene diamine and triethylene tetra amine to produce polythioureas. Thermal properties of the products were determined by DSC and TGA techniques. DSC traces showed T_g's for ethylene glycol polythiourethane at ?39 and 58°C, for glycerol polythiourethane at ?39 and 126°C, for castor oil polythiourethane at ?38°C and ?17°C, for ethylene diamine polythiourea at ?45°C, and for triethylene tetra amine poly thiourea at ?39°C. Additionally, DSC analysis of polythioureas showed an endotherm at around 100°C. All of the polymers started to decompose around 200°C. Tensile properties of the polymers were determined. Polythiourethanes showed higher tensile strength and lower elongation when compared with their urea analogs. Stress at break values of the polymers were 1.2 MPa for glycerol polythiourethane, 0.6 MPa for ethylene glycol polythiourethane, 0.5 MPa for ethylene diamine polythiourea, and 0.9 MPa for triethylene tetra amine polythiourea polymers. Unfortunately, polymers synthesized showed poor solvent resistance. All polymers swelled and disintegrated in CH₂Cl₂ in 5 h. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of polyurethane anionomers

Un‐ionized polyurethane was obtained by the reaction of an isocyanate‐terminated urethane prepolymer, which was synthesized from 4,4′‐diphenylmethane diisocyanate and poly(oxytetramethylene)‐α,ω‐glycol, with 2,2‐bis(hydroxymethyl)propionic acid. A carboxylate‐based polyurethane anionomer was then derived from the polyurethane by the use of the sodium, potassium, or magnesium salt of acetic acid as a neutralizer. The ionomerization resulted in the following changes in the characteristics of the polyurethane: (1) an increase in the tensile strength, (2) a decrease in the glass‐transition temperature, (3) an increase in the wettability and hygroscopicity with respect to water, and (4) susceptibility to thermal decomposition. A sulfonate‐based polyurethane was also synthesized for comparison with the carboxylate‐based polyurethane. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2144–2148, 2005     

Synthesis and characterization of polymers from soybean oil and p‐dinitrosobenzene

In this study, rubbery, bio‐based thermoset polymers were synthesized from soybean oil (SO) and p‐dinitrosobenzene (DNB) via an ene reaction. Polymeric p‐dinitrosobenzene (PDNB) was synthesized from p‐quinone dioxime and was thermally depolymerized in the presence of SO. SO/PDNB polymers were synthesized by a two‐stage polymerization. During the reaction, the role of different parameters such as mol ratio of SO and PDNB, preheating temperature of SO, polymerization time, and temperature were examined. Polymerization was followed by IR spectroscopy, and the polymers obtained were characterized by dynamic mechanical analysis, thermogravimetric analysis, and differential scanning calorimetry. The polymers have glass transition temperature ranging from ?51.5°C to ?46.3°C, whereas their storage moduli are between 430 and 210 MPa at ?60°C. Thermogravimetric analysis reveals that all of the polymers have temperatures of maximum degradation around 500°C. The crosslinked network structure of the polymers was investigated by swelling behavior and surface hardness test. Methyl oleate was used as a model compound to examine the chemical structure of the products. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A simple one‐step synthesis and polymerization of plant oil triglyceride iodo isocyanates

In this study, a novel and simple route for the synthesis of the iodine isocyanate (INCO) adduct of soybean oil triglycerides is described. Soybean oil iodo isocyanate (ISONCO) was synthesized by the reaction of iodine isocyanate and soybean oil at room temperature. ISONCO was then polymerized with polyols, such as, castor oil, pentamethylene glycol, and glycerol to give the corresponding polyurethanes and with polyamines, such as, ethylene diamine, hexamethylene diamine, and triethylene tetramine to give corresponding polyureas. The structures of the monomer and the polymers were determined by FTIR and ¹H‐NMR analyses. Thermal properties of the polymers were determined by DSC and TGA. Thermal degradation of the polyurethanes started at 150°C. Stability of the polyureas was higher than polyurethanes. Almost all polymers showed a T_g around ?50°C. The mechanical properties of the polymers were determined by tensile tests. Among the polymers synthesized, castor oil polyurethane showed the highest elongation at break and the lowest tensile strength of 140 KPa. The highest tensile strength of 900 KPa was observed in the pentamethylene glycol polyurethanes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Flexible polyurethane foams modified with biobased polyols: Synthesis and physical‐chemical characterization

A series of flexible polyurethane foams with different polyol compositions were synthesized through the replacement of a portion of the petroleum‐based polyether polyol with biobased polyols, namely, glycerol (GLY) and hydroxylated methyl esters (HMETO). HMETO was synthesized by the alkaline transesterification of tung oil (TO; obtaining GLY as a byproduct) and the subsequent hydroxylation of the obtained methyl esters with performic acid generated in situ. FTIR spectroscopy, ¹H‐NMR, and different analytical procedures indicated that the hydroxyl content increased significantly and the molecular weight decreased with respect to those of the TO after the two reaction steps. The characterization of the obtained foams, achieved through the measurement of the characteristic reaction times, thermal and dynamic mechanical analysis, scanning electronic microscopy, and density measurements, is reported and discussed. The most important changes in the modified foams were found with the addition of GLY to the formulation; this led to an increased foam density and storage rubbery modulus, which were associated with a higher crosslinking density because of the decrease in the chain length between crosslinking points. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43831.     

Synthesis and characterization of bio-based polyesters derived from 1,10-decanediol

Two kinds of bio-based polyesters were synthesized from 1,10-decanediol (DD), dimethyl terephthalate (DMT) or 2,6-naphthalene dicarboxylic acid (NDCA). Chemical structure, thermal properties and crystal structures, tensile properties and rheological properties were investigated. The glass transition temperature and melting temperature of poly(decamethylene 2,6-naphthalate) (PDN) are higher than that of poly(decamethylene terephthalate) (PDT). Differential scanning calorimetry and wide-angle X-ray diffraction results suggested that PDT and PDN were semi-crystalline polymers. Equilibrium melting points of PDT and PDN were 129.5°C and 167.1°C, respectively. Compared with PDT, PDN exhibited the higher tensile strength (36.8 MPa) and lower elongation at break (224%) and the complex viscosity of PDN is more sensitive to temperature and oscillation frequency. Compared with the current available bio-based plastic poly(butylene succinate) (PBS), PDT and PDN exhibit higher melting temperature, faster crystallization rate and comparable tensile properties.     

Biobased blends of poly(propylene carbonate) and poly(hydroxybutyrate‐co‐hydroxyvalerate): Fabrication and characterization

Poly(propylene carbonate) (PPC), a CO₂‐based bioplastic and poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) were melt blended followed by injection molding. Fourier transform infrared spectroscopy detected an interaction between the macromolecules from the reduction in the OH peak and a shift in the C?O peak. The onset degradation temperature of the polymer blends was improved by 5% and 19% in comparison to PHBV and PPC, respectively. Blending PPC with PHBV reduced the melting and crystallization temperatures and crystallinity of the latter as observed through differential scanning calorimetry. The amorphous nature of PPC affected the thermal properties of PHBV by hindering the spherulitic growth and diluting the crystalline region. Scanning electron micrographs presented a uniform dispersion and morphology of the blends, which lead to balanced mechanical properties. Incorporating PHBV, a stiff semi‐crystalline polymer improved the dimensional stability of PPC by restricting the motion of its polymer chains. © 2016 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44420.     

Biobased epoxy resin from canola oil

Epoxidized canola oil (ECO)‐based thermoset epoxy resins were formulated with phthalic anhydride (PA) as the curing agent for different ratios of ECO to PA (1:1, 1:1.5, and 1:2 mol/mol) at curing temperatures of 155, 170, 185, and 200°C. The gelation process of the epoxy resins and the viscoelastic properties of the systems during curing were studied by rheometry, whereas the dynamic mechanical and thermal properties of the cured resins were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry. We found that the thermomechanical properties of the resins were not strongly dependent on the curing temperature of the resin, although elevated temperatures significantly accelerated the curing process. However, an increase in the curing agent (PA) amount significantly altered both the reaction rate and the thermomechanical properties of the final resin. Thus, in the ECO/PA system, the selection of the combination of the curing temperature and the molar ratios of the curing agent could be used to design thermoset resins with unique thermomechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40142.     

The activation of furfuryl alcohol polymerization by oxygen and its enhanced mechanical properties

The effect of oxygen and additional oxygen providers on furfuryl alcohol polymerization was investigated through chemical analyses and mechanical evaluation. NMR, UV–vis, Fourier transform infrared, and gas chromatography–mass spectrometry (GC–MS) results suggested that atmospheric oxygen and the further addition of an oxygen source functioned as an activator for the entire network polymerization. Interestingly, the construction of a conjugated structure on the furan linear chain, which is key to three-dimensional cross-linking, also appears to be accelerated in the presence of oxygen. Furthermore, the introduction of oxygen providers into the curing system successfully enhanced the mechanical properties of the cured furan resin.     

Synthesis,characterization, and properties of biodegradable poly(butylene succinate) modified with imide dihydric alcohol

A series of high molecular weight poly (butylene succinate) and its copolyester containing rigid imide units were synthesized in this article. The chemical structure and composition of the copolyesters were determined by ¹H NMR spectroscopy and Fourier transform infrared spectroscope (FT‐IR). The thermal properties, crystallization behavior and mechanical properties of polymers were investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide‐angle X‐ray diffraction (WAXD) and mechanical testing. The enzymatic degradation was investigated using pancreatic lipase solution. The results showed that the melting temperature (T_m) of the copolyester decreased with the increment in pyromellitic imide unit content. However, the thermal degradation temperature (5% decomposition temperature) changed little. Meanwhile, the enzymatic degradation rate of poly (butylene succinate) was enhanced. The mechanical properties showed that the tensile strength had a trend of decrease, but the elongation at break was improved with the increment in imide units. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40807.     

Hydroxymethylation and polymerization of plant oil triglycerides

The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and paraformaldehyde was used to introduce a homoallylic hydroxyl functionality on the triglyceride. Paraformaldehyde and triglyceride were reacted in the presence of a Lewis acid catalyst, ethylaluminum dichloride, and hydroxymethyl derivatives were obtained at yields of 42 and 55% for sunflower oil and soybean oil, respectively. In the next step, hydroxymethyl products were reacted with maleic anhydride at 100°C to produce the maleate half esters. The average number of maleate groups per triglycerides was found to be 1.7 for soybean oil and 1.3 for sunflower oil. In the final step, the free‐radical–initiated copolymerization of the maleinized triglycerides with styrene produced rigid polymers. Characterization of new monomers and polymers was done by ¹H‐NMR, ¹³C‐NMR, and infrared and mass spectrometries. The swelling behavior of the crosslinked network polymers was determined in different solvents. The glass‐transition temperature of the cured resin was also determined by differential scanning calorimetry to be 40°C for soybean‐based polymer and 30°C for sunflower‐based polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4037–4046, 2004     

Biobased miktoarm star copolymer from soybean oil,isosorbide, and caprolactone

Soybean oil-based macroinitiator was prepared from epoxidized soybean oil. A ¹H NMR quantitative method was utilized for the characterization of this macroinitiator. A kind of renewable carbohydrate derivate, 1,4: 3,6-Dianhydro-D-glucitol 2-acrylate 5-acetate (AAI) was prepared as the substitute monomer of styrene. Series of renewable miktoarm star copolymers initiated by soybean oil macroinitiator were obtained by atom transfer radical polymerization (ATRP) of AAI and ring-opening polymerization (ROP) of ε-caprolactone sequentially. The obtained miktoarm star block copolymers were characterized by ¹H NMR, FTIR, and DSC. The DSC results show well dependence of the thermal behaviors of these miktoarm star block copolymers on the component of the two kinds of segments. A new strategy of renewable resource utilization has been provided on polymeric materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48281.     

Synthesis and properties of soy hull‐reinforced biocomposites from conjugated soybean oil

The tensile and flexural properties of new thermosetting composites made by the free radical polymerization of a conjugated soybean oil (CSO)‐based resin reinforced with soy hulls have been determined for various resin compositions. The effects of reinforcement particle size and filler/resin ratio have been assessed. The thermal stability of the new materials has been determined by thermogravimetric analysis and the wt % of oil incorporation has been calculated after Soxhlet extraction (the extracts have been identified by ¹H‐NMR spectroscopy). The resin consists initially of 50 wt % CSO and varying amounts of divinylbenzene (DVB; 5–15 wt %), dicyclopentadiene (DCPD; 0–10 wt %), and n‐butyl methacrylate (BMA; 25–35 wt %). Two soy hull particle sizes have been tested (<177 and <425 μm) and two different filler/resin ratios have been compared (50 : 50 and 60 : 40). An appropriate cure sequence has been established by differential scanning calorimetry (DSC) analysis. The results show a decrease in the properties whenever DVB or BMA is substituted by DCPD. Also, larger particle sizes and higher filler/resin ratios are found to have a negative effect on the tensile properties of the new materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel thermosetting resins for SMC applications from linseed oil: Synthesis,characterization, and properties

New thermosetting resins for applications of sheet‐molding compounds (SMCs) were successfully synthesized from linseed oil, which is the most molecularly unsaturated of all plant oils. The carbon–carbon double bonds were opened by epoxidation, followed by acrylation, and then maleinization, which provided more crosslink sites and added acid functionality on the triglyceride molecules to develop thickening. Dynamic mechanical analysis showed that the storage modulus of these new polymers was approximately 2.5 GPa at 30°C, and the glass‐transition temperature was above 100°C. During maturation the resins reached a molding viscosity quickly and stayed stable. Mechanical tests showed a flexural strength of 100 MPa and a flexural modulus of 2.8 GPa. Thermogravimetric analysis showed a single degradation ranging from 300°C–480°C, which was a result of the carbonization of the crosslinked network. These bio‐based resins are promising as replacements of some petroleum‐based resins in the SMC industry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Organic–inorganic hybrid linseed oil‐based urethane oil wood coatings

To prepare alkoxysilane‐functionalized urethane oil (AFUO) using linseed oil, 3‐aminopropyltriethoxysilane (APTES) was first reacted with diisocyanate to obtain an NCO‐terminating oligomer. The reaction was continued by adding linseed oil glyceride to form an AFUO prepolymer. The auto‐oxidative drying coating was obtained after adding a metal dryer to the AFUO prepolymer. Urethane oil (UO) coating, as a control, was obtained by the same procedure as that for AFUO, but without containing alkoxysilane‐functional groups in the formation. Siloxane hybrid urethane oil (SHUO) wood coatings were prepared by mixing tetraethyl orthosilicate (TEOS) solutions, as an external crosslinking agent by sol–gel process, with the AFUO and UO coatings. We found that introducing of APTES into the molecular chains of the UO coating resulted in a film with superior impact and abrasion resistance, and it is the most efficient process to enhance the UO films. The addition of TEOS into AFUO coatings shortened the curing time and further improved the crosslinking density of the AFUO films; however, the physical properties like impact resistance, bending resistance, and gloss were even worse than AFUO films. Mixing of TEOS and UO coating also shorten the curing time and improved the heat resistance, lightfastness, and hardness of the UO coating. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44562.     

Castor oil and PEG‐based shape memory polyurethane films for biomedical applications

A series of polyurethane film were prepared from poly(ethylene glycol) with different molecular weight (PEG 1500, 3000, and 8000) and castor oil by one‐shot bulk polymerization method. Hexamethylene diisocyanate and 1,4‐buthane diol were used as diisocyanate and chain extender, respectively. In order to characterize the samples, their density, swelling ratio, water contact angle, surface free energy, gel content, thermal, and viscoelastic properties were determined. The effect of the soft segment length (SSL) and hard segment content (HSC) of all polyurethane films on their shape memory behavior such as shape fixity (R_f) and shape recovery (R_r) rates were investigated by bending test. Direct contact and MTT tests were used for assessment of cell adhesion and proliferation. The relatively high R_f and R_r values were obtained for the samples programmed at high temperature difference. R_f increased with decreasing HSC. On the other hand, R_r tended to decrease with increasing SSL. After evaluating experimental data by a nonlinear equation, it was found that HSC is more effective parameter on shape memory property than SSL. The gel content, swelling ratio, and water contact angle of the samples were dependent on both SSL and HSC in their structures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40590.     

Biobased Polyurethane Composite Foams Reinforced with Plum Stones and Silanized Plum Stones

In the following study, ground plum stones and silanized ground plum stones were used as natural fillers for novel polyurethane (PUR) composite foams. The impact of 1, 2, and 5 wt.% of fillers on the cellular structure, foaming parameters, and mechanical, thermomechanical, and thermal properties of produced foams were assessed. The results showed that the silanization process leads to acquiring fillers with a smoother surface compared to unmodified filler. The results also showed that the morphology of the obtained materials is affected by the type and content of filler. Moreover, the modified PUR foams showed improved properties. For example, compared with the reference foam (PUR_REF), the foam with the addition of 1 wt.% of unmodified plum filler showed better mechanical properties, such as higher compressive strength (~8% improvement) and better flexural strength (~6% improvement). The addition of silanized plum filler improved the thermal stability and hydrophobic character of PUR foams. This work shows the relationship between the mechanical, thermal, and application properties of the obtained PUR composites depending on the modification of the filler used during synthesis.     

Synthesis and characterization of diethanolamine-containing glass ionomer cement

In this study, glycidyl methacrylate (GMA) diethanolamine was synthesized and incorporated into polyacid main chains, which would be used for glass ionomer cements (GICs). The polymer was prepared by the free radical polymerization of acrylic acid and itaconic acid with readily synthesized GMA diethanolamine. Effects of molecular weight, polymer content in the liquid composition, powder/liquid ratio, and aging on compressive strength and diametral tensile strength were investigated. Working and setting time, water sorption and solubility (Wsl), pH value of the immersed solution, and microhardness were also measured. The experimental GICs had comparable mechanical properties to Fuji II GICs while exhibiting less Wsl and high hydrophilicity. The results suggested that the experimental GICs held promise as biocompatible and workable cement for application. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of elastomeric,biobased, nonisocyanate polyurethane from natural rubber

Linear and crosslinked polyhydroxyurethanes (PHUs) based on natural rubber (NR) were synthesized by a polyaddition reaction without a solvent or catalyst to exploit the reactivity of diamines or triamines with dicyclic carbonate groups. Oligo‐isoprenes were obtained from the controlled oxidative degradation of NR and successive modifications of the chain ends. The syntheses of linear PHU were carried out with two approaches. The first one consisted of a reaction between amino telechelic oligo‐isoprenes and aromatic or aliphatic dicyclic carbonates. The second approach proceeded through a reaction between oligo‐isoprenes bearing cyclic carbonate chain ends and difunctional or trifunctional amines. The evolution of these reactions was studied by Fourier transform infrared spectrometry. The influence of the carbonate‐to‐amine molar ratio, the chain length of the oligo‐isoprenes, and the reaction temperatures were investigated. The thermal properties of the PHUs were studied by differential scanning calorimetry and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45427.