Cure kinetics of an epoxidized hemp oil based bioresin system

A novel epoxidized hemp oil (EHO) based bioresin was synthesized by epoxidation in situ with peroxyacetic acid. In this research the cure kinetics of an EHO based bioresin system cured with triethylenetetramine (TETA) was studied by differential scanning calorimetry using both isothermal and nonisothermal data. The results show that the curing behavior can be modeled with a modified Kamal autocatalytic model that accounts for a shift to a diffusion‐controlled reaction postvitrification. The total order of the reaction was found to decrease with an increase in temperature from ～ 5.2 at 110°C to ～ 2.4 at 120°C. Dynamic activation energies were determined from the Kissinger (51.8 kJ/mol) and Ozawa‐Flynn‐Wall (56.3 kJ/mol) methods. Activation energies determined from the autocatalytic method were 139.5 kJ/mol and ?80.5 kJ/mol. The observed negative activation energy is thought to be due to an unidentified competitive reaction that gives rise to the appearance of k₂ decreasing with increasing temperature. The agreement of fit of the model predictions with experimental values was satisfactory for all temperatures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tung oil‐based thermosetting polymers for self‐healing applications

Several bio‐renewable thermosetting polymers were successfully prepared from tung oil through cationic polymerization for the use as the healing agent in self‐healing microencapsulated applications. The tung oil triglyceride was blended with its methyl ester, which was produced by saponification followed by esterification. The changes in storage modulus, loss modulus, and glass transition temperature as functions of the methyl ester content were measured using dynamic mechanical analysis. In addition, the fraction of cross‐linked material in the polymer was calculated by Soxhlet extraction, while proton nuclear magnetic resonance, Fourier transform infrared spectroscopy and TEM were used to investigate the structure of the copolymer networks. The thermal stability of the thermosets as a function of their methyl ester blend contents was determined by thermogravimetric analysis. Finally, the adhesive properties of the thermosets were studied using compressive lap shear and the fracture surfaces were analyzed using SEM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40406.     

Cure kinetic of castor oil‐based polyurethane

This research presents the kinetic studies on the cure reactions of a new material, castor oil‐based polyurethane resin. Thermal analysis by isothermal differential scanning calorimetry was used, as a variety of factors affect its cure, including formulation and polymerization process. The kinetic reaction of this catalyzed system is described by nth order equation. Castor oil, a vegetable triglyceride, was reacted with methylene diphenyl 4,4′‐diisocyanate to produce an elastomeric matrix. The objective of this research is thermal characterization of new polyurethane that is less aggressive to humans and environment; therefore, castor oil used on the synthesis is derived from a natural and renewable resource. The activation energy measured for the castor oil‐based polyurethane resin studied in this work was about 56 kJ/mol. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Curing of epoxidized linseed oil: Investigation of the curing reaction with different hardener types

The effect of the hardener type and amount on the curing reaction and the resulting thermal and mechanical performance characteristics of epoxidized linseed oil are studied in detail. The analysis of the curing mechanism reveals that due to steric hindrance, side reactions and/or fast gelation, the optimal mixing ratio of bio-based epoxy resins and hardeners has to be determined experimentally and cannot be calculated. The investigated thermosets exhibit a glass transition temperature of 12, 54, and 145°C after curing. The overall mechanical performance of the resulting resin ranges from soft and flexible to stiff and rigid, depending on the hardener type applied, which can be utilized in the formation of epoxy composites and coatings.     

Camelina oil‐ and linseed oil‐based polymers with bisphosphonate crosslinks

Natural oils are the attractive biobased alternatives for petroleum derived chemicals in the production of polymers. A series of new biodegradable polymers based on epoxidized camelina oil was synthesized and investigated. The thermal, mechanical, swelling properties, hydrolysis, biodegradation, and bioresistance of the camelina oil‐based polymers with bisphosphonate crosslinks were studied and compared with those of the analogous polymers based on epoxidized linseed oil. The dependence of the polymer properties on the density of crosslinks was observed. The obtained results showed that the properties of the camelina oil‐based polymers are comparable with those of the linseed oil‐based polymers and that camelina oil is a promising starting material for the synthesis of polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40683.     

Acrylated epoxidized soybean oil as a styrene replacement in a dicyclopentadiene‐modified unsaturated polyester resin

Nonvolatile and nonhazardous acrylated epoxidized soybean oil (AESO) was investigated as a replacement for hazardous styrene in a commercial unsaturated polyester (UPE) resin [a mixture of styrene and a dicyclopentadiene (DCPD)‐modified UPE (DCPD–UPE)]. DCPD–UPE was prepared from ethylene glycol, diethylene glycol, maleic anhydride, and DCPD. Mixtures of AESO and DCPD–UPE [AESO–(DCPD–UPE) resins] were found to be homogeneous, easily pourable solutions at room temperature. The glass‐fiber‐reinforced composites from the AESO–(DCPD–UPE) resins were comparable or even superior to those from the mixture of styrene and DCPD–UPE in terms of the flexural and tensile strengths. The viscoelastic properties of the cured AESO–(DCPD–UPE) resins and the corresponding glass‐fiber‐reinforced composites were characterized by dynamic mechanical analysis. The viscosities and pot lives of the AESO–(DCPD–UPE) resins as a function of the temperature were studied. The curing mechanism of the AESO–(DCPD–UPE) resins is discussed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46212.     

Kinetics studies and characterization of poly(furfuryl alcohol) for use as bio‐based furan novolacs

Poly(furfuryl alcohol) (PFA) is an attractive target for the development of bio‐based novolac resins. However, control of the polycondensation reaction is not well understood and side reactions are an important factor for PFA and the development of new resins. The polymerization reactions and kinetics of furfuryl alcohol and 2‐furyl ethanol into polymeric resins are detailed in this work. Nuclear magnetic resonance spectroscopy analysis of reaction kinetics, molecular weight analysis, and rheology analysis confirm that the polymerization reaction rate of 2‐furyl ethanol is much faster than that of furfuryl alcohol because the addition of this methyl group serves to stabilize the carbocation transition state. Side reactions, such as Diels–Alder crosslinking and in particular branching, are quantified and were found to be much more prevalent in the polymerization of PFA. The glass transition temperature was measured to be 376 K for PFA and only 294 K for poly(2‐furyl ethanol). Molecular dynamics simulations showed that the alternative structure that forms in PFA that causes branching results in greater backbone rigidity causing its higher glass transition temperature. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46608.     

Oil‐spill cleanup: The influence of acetylated curaua fibers on the oil‐removal capability of magnetic composites

A magnetic resin based on cardanol, furfural, and curaua fibers was prepared and characterized. The material could be used in oil‐spill cleanup processes, because of its aromatic/aliphatic balance. The resin was prepared through bulk polycondensation of cardanol and furfural in the presence of curaua fibers and maghemite nanoparticles. Hydrophobicity of the curaua fibers was improved by acetylation, increasing the oil‐absorbing capability of the composites. The obtained magnetic composites were studied by Fourier‐transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. Degree of cure, magnetic force, and oil‐removal capability tests were also performed. The results show that the composites possess an elevated cure degree in addition to a considerable magnetic force. The materials exhibit a good oil removal capability in the presence of a magnetic field, which is improved by the use of acetylated curaua. In the best case, the composite filled with maghemite and curaua can remove 12 parts of oil from water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41732.     

Toughening‐modified epoxy‐amine system: Cure kinetics,mechanical behavior,and shape memory performances

Shape memory epoxy resins are derived on reacting E51 with triethylenetetramine in presence of the toughening agent polypropylene glycol diglycidyl ether (PPGDGE). The curing behaviors are studied with differential scanning calorimetry. The toughening system shows a decrease in activation energy. ?esták–Berggren model is utilized to establish the kinetic equations. The fitting results prove that the equations can well describe the reactions. Tensile tests and dynamic mechanical analysis are used to analyze mechanical performances and thermodynamics. Shape memory properties are characterized by fold‐deploy tests. The elongation at break increases as the concentration of PPGDGE increases. The toughening materials have lower glass transition temperature (T_g). The fixable ratios of all systems are greater than 99.5%. The shape recovery time decreases with increasing the PPGDGE concentration. The optimal system can fully recover its original shape in about 2 min at T_g + 30°C, and exhibit the maximum fold‐deploy cycles as 13 cycles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40853.     

Cure kinetics of the cardanyl acrylate–styrene system using isothermal differential scanning calorimetry

The curing kinetics of styrene (30 wt %) and cardanyl acrylate (70 wt %), which was synthesized from cardanol and acryloyl chloride, was investigated by differential scanning calorimetry under isothermal condition. The method allows determination of the most suitable kinetic model and corresponding parameters. All kinetic parameters including the reaction order, activation energy E_a and kinetic rate constant were evaluated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2034–2039, 2002     

Synthesis and characterization of bio‐based thermosetting resins from lactic acid and glycerol

A bio‐based thermoset resin has been synthesized from glycerol reacted with lactic acid oligomers of three different chain lengths (n): 3, 7, and 10. Lactic acid was first reacted with glycerol by direct condensation and the resulting branched molecule was then end‐functionalized with methacrylic anhydride. The resins were characterized by Fourier‐transform infrared spectroscopy (FT‐IR), by ¹³C‐NMR spectroscopy to confirm the chemical structure of the resin, and by differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA) to obtain the thermal properties. The resin flow viscosities were also measured using a rheometer with different stress levels for each temperature used, as this is an important characteristic of resins that are intended to be used as a matrix in composite applications. The resin with a chain length of three had better mechanical, thermal, and rheological properties than the resins with chain lengths of seven and 10. Also, its bio‐based content of 78% and glass transition temperature of 97°C makes this resin comparable to commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40488.     

Thermophysical properties of bacterial poly(3‐hydroxybutyrate): Characterized by TMA,DSC, and TMDSC

The melting, isothermal and nonisothermal crystallization behaviors of poly(3‐hydroxybutyrate) (PHB) have been studied by means of temperature modulated differential scanning calorimetry (TMDSC) and conventional DSC. Various experimental conditions including isothermal/annealing temperatures (80, 90, 100, 105, 110, 120, 130, and 140°C), cooling rates (2, 5, 10, 20, and 50°C/min) and heating rates (5, 10, 20, 30, 40, and 50°C/min) have been investigated. The lower endothermic peak (T_m1) representing the original crystals prior to DSC scan, while the higher one (T_m2) is attributed to the melting of the crystals formed by recrystallization. Thermomechanical analysis (TMA) was used to evaluate the original melting temperature (T_melt) and glass transition temperature (T_g) as comparison to DSC analysis. The multiple melting phenomenon was ascribed to the melting‐recrystallization‐remelting mechanism of the crystallites with lower thermal stability showing at T_m1. Different models (Avrami, Jeziorny‐modified‐Avrami, Liu and Mo, and Ozawa model) were utilized to describe the crystallization kinetics. It was found that Liu and Mo's analysis and Jeziorny‐modified‐Avrami model were successful to explain the nonisothermal crystallization kinetic of PHB. The activation energies were estimated in both isothermal and nonisothermal crystallization process, which were 102 and 116 kJ/mol in respective condition. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42412.     

Super‐tough biodegradable poly(vinyl alcohol)/poly(vinyl pyrrolidone) blends plasticized by glycerol and sorbitol

Tough biodegradable films were prepared using a poly(vinyl alcohol) (PVA)/poly(vinyl pyrrolidone) (PVP) (1:1) blend with plasticizers of glycerol (GLY), sorbitol (SOR), and their (one to one) mixture. We studied the effect of plasticization on the structural, thermal, and mechanical properties of the PVA/PVP blend films. Fourier transform infrared spectra indicated good miscibility of the two components due to the H‐bonding between the PVA and PVP molecules. The addition of plasticizers reduced the interaction between PVA and PVP, evidenced by an increase in the intensity of PVA diffraction peaks observed in the X‐ray diffraction (XRD) characterization. Thermal degradation of the blends increased as a function of the plasticizer used. GLY affected thermal degradation more than SOR and the mixtures. The incorporation of the plasticizers promoted the growth of PVA crystals as evidenced by XRD patterns and the enthalpy of fusion (ΔH_f) obtained by differential scanning calorimetry measurements. The introduction of SOR to the binary blend increased toughness seven times and imparted simultaneous and pronounced improvements to maximum tensile stress and elongation at break. This behavior holds out great promise for the development of a new generation of mechanically robust, yet thoroughly biodegradable materials that could effectively supplant conventional polymers in demanding applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46406.     

Crystallization and melting behavior of partially miscible six‐armed poly(l‐lactic acid)/poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) blends

The crystallization kinetics and spherulitic morphology of six‐armed poly(L‐lactic acid) (6a‐PLLA)/poly(3‐hydroxybutyrate‐co?3‐hydroxyvalerate) (PHBV) crystalline/crystalline partially miscible blends were investigated with differential scanning calorimetry and polarized optical microscopy in this study. Avrami analysis was used to describe the isothermal crystallization process of the neat polymers and their blends. The results suggest that blending had a complex influence on the crystallization rate of the two components during the isothermal crystallization process. Also, the crystallization mechanism of these blends was different from that of the neat polymers. The melting behavior of these blends was also studied after crystallization at various crystallization temperatures. The crystallization of PHBV at 125°C was difficult, so no melting peaks were found. However, it was interesting to find a weak melting peak, which arose from the PHBV component for the 20/80 6a‐PLLA/PHBV blend after crystallization at 125°C, and it is discussed in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42548.     

Optimal designs for constant‐heating‐rate differential scanning calorimetry experiments for polymerization kinetics: nth‐order kinetics

Optimal designs have been constructed for differential scanning calorimetry (DSC) experiments conducted under constant‐heating‐rate conditions for materials that are a priori assumed to follow nth‐order kinetics. Two different operating scenarios are considered, including single‐scan and multiscan DSC experiments for eight different kinetic parameter combinations representing a range of typical polymeric curing reactions. The resulting designs are studied to determine which kinetic model parameters are influential in determining the optimal design. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Applicability of biaxially oriented poly(trimethylene terephthalate) films using bio‐based 1,3‐propanediol in retort pouches

Poly(trimethylene terephthalate) (PTT) is a material that has intermediate properties between poly(ethylene terephthalate) (PET) and nylon, and produced by polymerizing bio‐based 1,3‐propanediol and terephthalic acid. In this study, the possibility of replacing existing biaxially oriented PET (OPET) and nylon 6 (ONylon) film with biaxially oriented PTT (OPTT) film is investigated to develop a more environmentally friendly retort pouch. In order to define actual problems in the retort pouch manufacturing process, food process, and distribution process, extensive examinations are conducted to study the degradation of physical properties after the in‐processing and sterilization process, the testing of pinhole resistance caused by stress, and the box level drop test. The results show OPTT film to be a promising alternative for OPET and ONylon film, to a limited extent. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46251.     

Curing copolymerization kinetics of styrene with maleated castor oil glycerides obtained from biodiesel‐derived crude glycerol

Kinetics of curing of maleated castor oil glycerides with styrene was studied by differential scanning calorimetry and rheology. The resin was synthesized from biodiesel‐derived crude glycerol. Curing rates were fitted to several empirical models (autocatalytic model, Kamal's model and a model with vitrification). The three models showed a good fitting with experimental data at conversions lower than 0.55 for temperatures ranging from 30 to 50°C. However, the model that includes vitrification showed a better fitting in the entire range of conversions and the same temperatures. At higher temperatures (50–60°C), some deviations were observed for the three models at low and high conversions. Gel times were obtained from rheological studies and the apparent activation energies were calculated thereof. Gel times were 300–2700 s. The values of apparent activation energy obtained for this castor oil‐based copolymer (47.2–52.3 kJ/mol) were within range of commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41344.     

Epoxidized pine oil‐siloxane: Crosslinking kinetic study and thermomechanical properties

In this study, a novel approach to toughen biobased epoxy polymer with different types of siloxanes was explored. Three different modified siloxanes, e.g., amine‐terminated polydimethyl siloxane (PDMS‐amine), glycidyl‐terminated polydimethyl siloxane (PDMS‐glycidyl), and glycidyl‐terminated polyhedral oligomeric silsesquioxane (POSS‐glycidyl) were used as toughening agents. The curing and kinetics of bioepoxy was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy. The mechanical, thermal, and morphological properties of the cured materials were investigated. Rheological characterization revealed that the inclusion of POSS‐glycidyl slightly increased the complex viscosity compared to the neat resin. The morphology of the cured bioresin was characterized by transmission electron microscopy and scanning electron microscopy. The inclusion of POSS‐glycidyl to bioepoxy resin resulted in a good homogeneity within the blends. The inclusion of PDMS‐amine or PDMS‐glycidyl was shown to have no effect on tensile and flexural properties of the bioresins, but led to a deterioration in the impact strength. However, the inclusion of POSS‐glycidyl enhanced the impact strength and elongation at break of the bioresins. Dynamic mechanical analysis showed that the siloxane modified epoxy decreased the storage modulus of the bioresins. The thermal properties, such as decomposition temperature, coefficient of linear thermal expansion, and heat deflection temperature were improved by inclusion of POSS‐glycidyl. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42451.     

Effect of the melt‐mixing condition on the physical property of poly(l‐lactic acid)/poly(d‐lactic acid) blends

The effect of the mixing condition in a mill‐type mixer on the thermal property and the crystal formation of the poly(l ‐lactide)/poly(d ‐lactide) blends is investigated. The blends melt‐mixed at 200 and 210 °C under application of a high shear flow tend to show a single melting peak of the stereocomplex crystal (SC) in the differential scanning calorimetry first and second heating processes without indicating the trace of the melting of homo‐chiral crystal. The mixing at an elevated temperature causes a serious thermal degradation. Further kneading of the blends at an elevated temperature higher than T_m of SC causes the transesterification between the same enatiomeric chains forming block copolymers of l ‐ and d ‐chains. This block copolymer acts as a nucleating agent of SC and the compatibilizing agent between poly(l ‐lactide) and poly(d ‐lactide) and promotes the formation of SC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45489.     

Building and origin of bio‐based bismaleimide resins with good processability,high thermal,and mechanical properties

Bio‐based high performance thermosetting resins have been urgently required by cutting‐edge fields for meeting sustainable development. A new kind of high performance thermosetting resins (BA‐n) with good processability, high thermal resistance, and mechanical properties was developed based on 4,4′‐bismaleimidodiphenylmethane (BDM) and renewable bis(5‐allyloxy)‐4‐methoxy‐2‐methylphenyl)methane (ABE) from bio‐based lignin derivative. The effect of the molar ratio of allyl to imide (n) on structures and properties of BA resins were systematically researched. BA‐n resins have much better processability, thermal, and mechanical properties than their petroleum‐based counterparts, 2,2′‐diallylbisphenol A‐modified BDM (BD‐n) resins. Compared with BD‐0.86, the best available bismaleimide (BMI) resin, BA‐0.86 not only has 6 h longer process window and 13.7 °C higher glass transition temperature, but also owns the highest flexural strength and modulus among all bio‐based allyl compound‐modified BMI resins reported. The origin behind these attractive performances of BA resins is revealed by discussing the unique crosslinked structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45947.