Glycerol citrate polyesters produced through heating without catalysis

The influence of various heating methods without catalysis to prepare polyesters from citric acid : glycerol blends were studied. In the presence of short-term microwave treatments, i.e., 60 s at 1200 W, blends of glycerol and citric acid invariably formed solid amorphous polyesters. Fourier transform infrared spectroscopy showed that citric acid and glycerol blends can form highly stable polymers composed of ester bonds. The glycerol citrate polyester polymers exhibited the least degradation in water, more in acid solutions (0.1–1.0M HCl), and the most deterioration in strong alkaline solutions (0.1–1.0M NaOH) after 72 h soakings. Polyesters of glycerol and citric acid were studied with differential scanning calorimetry and thermal gravimetric analysis. The polyesters were found to be thermally stable (up to 313°C). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on glass transition temperature of mono and bilayer protein films plasticized by glycerol and olive oil

Thermomechanical and thermal properties of whey protein, maize prolamin protein (zein), and the laminated whey protein–zein films were studied. The dynamic mechanical (thermal) analysis (DMTA) results showed that the single zein film had higher T_g than single whey protein and zein–whey laminated films. The shift in the T_g values of films from 31.2°C in whey protein film and 88.5°C in the zein film to 82.8°C in the laminated whey protein–zein films may be implied some interaction formation between the two polymers. The small tan δ peaks were observed at ?50°C in zein–glycerol films and at ?22.37°C in the whey protein films and can be related to β‐relaxation phenomena or presence of glycerol rich region in polymer matrix. Zein‐olive oil and zein–whey protein–olive oil films showed tan δ peaks corresponded the T_g values at 113.8, and 92.4°C, respectively. Thus, replacing of glycerol with olive oil in film composition increased T_g. A good correspondence was obtained when DSC results were compared with the tan δ peaks in DMTA measurements. DSC thermograms suggested that plasticizers and biopolymers remained a homogeneous material throughout the cooling and heating cycle. The results showed that T_g of zein–glycerol films predicted by Couchman and Karasz equation is very close to value obtained by DSC experiments. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure and properties of soy protein films plasticized with hydroxyamine

Two kinds of transparent films of soy protein were successfully prepared by plasticizing with diethanolamine (DEA) and triethanolamin (TEA). The films were hot pressed at 140°C and 20 MPa, and characterized with Fourier transform infrared spectroscopy, scanning electron microscope, ultraviolet–visible spectrometer, differential scanning calorimetry (DSC), thermogravimetric analysis, and tensile testing. The results indicated that films with triethanolamine plasticizers possessed better optical transmittance (more than 80% at 800 nm) than those with diethanolamine and glycerol. All of the sheets exhibited only one T_g in DSC curves. Moreover, the soy protein plastics with TEA had higher thermal stability and mechanical properties, as well as lower water uptake than those with DEA and glycerol, as a result of the strong interaction between TEA and protein molecules. The soy protein materials will be promising for the application in the fields of package and container, substituting for the nongreen polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on the cure kinetics of chitosan‐glutamic acid using glutaraldehyde as crosslinker through differential scanning calorimeter

The curing of chitosan‐glutamic acid with glutaraldehyde as curing agent in the presence of chlorpheniramine maleate (CPM) is carried out with the help of differential scanning calorimeter (DSC). The effect of concentration of chitosan and percentage of crosslinker on the curing of chitosan‐glutamic acid is studied at a heating rate of 5°C/min. Cure kinetics are measured by the DSC using scans from 25 to 220°C at four different heating rates (3, 5, 7, and 10°C/min) and it is observed that the crosslinking of chitosan‐glutamic acid is an exothermic process which results in a positive peak in the DSC thermograms. The activation energy (E_α) is determined by Flynn, Wall, and Ozawa method for curing of the samples. An increase in activation energy (E_α) is observed with the extent of conversion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of soy protein isolate/poly(vinyl alcohol) blend “green” films: Compatibility,mechanical properties,and thermal stability

Blend films from nature soy protein isolates (SPI) and synthetical poly(vinyl alcohol) (PVA) compatibilized by glycerol were successfully fabricated by a solution‐casting method in this study. Properties of compatibility, mechanical properties, and thermal stability of SPI/PVA films were investigated based on the effect of the PVA concentration. XRD tests confirm that the SPI/PVA films were partially crystalline materials with peaks of 2θ = 20°. And, the addition of glycerol will insert the crystalline structure and destroy the blend microstructure of SPI/PVA. Differential scanning calorimetry (DSC) tests show that SPI/PVA blend polymers have a single glass transition temperature (T_g) between 80 and 115.0°C, which indicate that SPI and PVA have good compatibility. The tension tests show that SPI/PVA films exhibit both higher tensile strength (σ_b) and percentage elongation at break point (P.E.B.). Thermogravimetric analysis (TGA) and water solubility tests show that SPI/PVA blend polymer has more stable stability than pure SPI. All the results reflect that SPI/PVA/glycerol blend film provides a convenient and promising way to prepare soy protein plastics for practical application. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of a thermoplastic poly(glycerol sebacate) elastomer by two‐step method

A thermoplastic poly(glycerol sebacate) elastomer (TMPGS), prepared by a two‐step method for the first time, is characterized in the present work. First, non‐crosslinked poly(glycerol sebacate) (PGS) prepolymers at the 1 : 1 molar ratio of glycerol to sebacic acid were synthesized through a condensation reaction. Second, TMPGSs were achieved through prepolymers that continued to react after the addition of more sebacic acid at a total molar ratio of 2 : 2.5 (glycerol/sebacic acid). The swelling experiments demonstrated that its crosslinking density was low and that it was composed of sol and gel. Compared with our previous results, the content of sol decreased but still reached >60%. Differential scanning calorimetry (DSC) studies demonstrated that TMPGS was crystallizable and had a glass transition temperature below ?20°C, but at close to 37°C, its state altered and became almost amorphous. It was explained that both the semi‐interpenetrated polymer networks composed of sol and gel and the crystal regions imparted thermoplasticity to the elastomer. Finally, the in vitro degradation tests illuminated the degradation characteristic of TMPGS in 37°C phosphate buffered saline solution (pH = 7.4). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1412–1419, 2007     

Preparation and characterization of poly(methyl methacrylate) beads

The phase behavior of Poly(ethylene terephthalate)/Poly(ethylene‐2,6‐naphthalate)/Poly(ethylene terephthalate‐co‐ethylene‐2,6‐naphthalate) (PET/PEN/P(ET‐co‐EN)) ternary blends in molten state was evaluated from differential scanning calorimetry (DSC) and NMR results as well as optical microscopic observations. Copolymer of ethylene terephthalate and ethylene‐2,6‐naphthalate was prepared by a condensation polymerization, which was a random copolymer with an intrinsic viscosity (IV) of 0.3 dL/g. The phase diagram of the ternary blends revealed that the miscibility of ternary blends in molten state was dependent on the fraction of P(ET‐co‐EN) in the blends and holding time of the blends at high temperatures above 280°C. With increase in the holding time, the fraction of copolymer in the blends necessary to induce the immiscible to miscible transition decreased. For the blends with longer holding time at 280°C, the phase diagram in molten state was irreversible against the temperature, although a reversibility was found for the blends with short holding time of 1 min at 280°C. The irreversibility of phase behavior was not explained simply by the increase of copolymer content produced during heat treatment. Complex irreversible physical and chemical interactions between components and change of phase structure of the blend in the molten state might influence on the irreversibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on novel semi‐2‐IPNs from polyetherimide and citraconimide

A series of novel semi‐2‐interpenetrating polymeric networks (semi‐2‐IPNs) were prepared through blending in solution using two different polyimides, biscitraconamic acid as a precursor of biscitraconimide (MBMI) with various proportions of polyetherimide (PEI) to achieve optimum properties. Biscitraconamic acid was prepared by reacting citraconic anhydride (CA), 3,3',4,4'‐benzophenone tetracarboxylic dianhydride (BTDA) and bis(3‐aminopropyl)phenyl phosphine (BAPPP) and it was characterized by differential scanning calorimetry (DSC), FTIR, and ¹H‐NMR spectroscopy. Both biscitraconamic acid and PEI were blended in N,N‐dimethylacetamide (DMAc) solution, casted and thermally cured up to 300°C to give semi‐2‐IPNs. The MBMI/PEI semi‐IPN systems were characterized by UV‐Vis spectroscopy, FTIR spectroscopy and thermal techniques. The phase morphology, isothermal aging, and water uptake of semi‐IPN systems have also been studied. The morphological studies on phase distribution were investigated by scanning electron microscopy (SEM). Thermal performance of MBMI/PEI semi‐IPN systems were evaluated by DSC and thermo gravimetric analysis (TGA). All the compositions of semi‐IPN polyimide system were stable up to 400°C and their thermal stability increased with increase in the content of PEI. Isothermal aging studies done at 300°C for various time periods showed good thermo‐oxidative stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(divinylbenzene) Microencapsulated Octadecane for Use as a Heat Storage Material: Influences of Microcapsule Size and Monomer/Octadecane Ratio

Poly(divinylbenzene) (PDVB) microencapsulated octadecane (OD) (PDVB/OD) used as heat storage material were prepared by suspension polymerization at 70°C using benzoyl peroxide and polyvinyl alcohol as initiator and stabilizer, respectively. The influence of microcapsule size and divinylbenzene (DVB)/OD weight ratio on the microcapsule shape and thermal properties of encapsulated OD were considered. Thermal properties and thermal stability of PDVB/OD microcapsules were determined using differential scanning calorimeter (DSC) and thermogravimetric analyzer. The optical micrographs and scanning electron micrographs showed that the microcapsules have spherical shape only in the case of 50/50 (%w/w) of DVB/OD whereas they were nonspherical with the decreasing of DVB content. However, the core materials were still well encapsulated even increasing the OD content to 70%wt. From DSC analysis, in all cases, the melting temperature of encapsulated OD (28°C) was almost the same as that of bulk OD (30°C), yet it was quite different in the case of crystallization temperature (≤ 19°C and 25°C for encapsulated and bulk OD, respectively). The latent heats of melting and crystallization of encapsulated OD, in all conditions, were reduced from those of bulk OD (242 and 247 J/g, respectively).     

Thermal behavior of transparent poly(etheretherketone)(PEEK) film

The thermal behavior of poly(etheretherketone)(PEEK) film heated in an open differential scanning calorimetry (DSC) pan at 20°C/min is distorted by relaxation of the strained film. PEEK film in a closed pan or quenched PEEK in open or closed pans shows a glass-transition temperature (T_g) around 144°C, cold crystallization (～22 J/g) at 177°C, melt-temperature (T_m) peaking at 335–340°C, with an enthalpy of fusion of 32–34 J/g, and recrystallization on cooling at 285°C, with a crystallization exotherm of about 40 J/g. The enthalpy of fusion decreases with increasing heating rate from 2–100°C/min and approaches the enthalpy of cold crystallization. With increasing heating rate, further crystallization of PEEK during the DSC scan is suppressed. With increasing cooling rate, PEEK melt crystallizes at larger supercoolings to a lesser extent. Crystallization on cooling the melt was more complete than cold crystallization and annealing on heating.     

Modification of wheat gluten with citric acid to produce superabsorbent materials

Wheat gluten was reacted with citric acid to produce natural superabsorbent materials able to absorb up to 78 times its weight in water. The properties of the modified gluten samples were characterized using Fourier Transform Infra‐red (FTIR) spectroscopy, thermogravimetric analysis, and water uptake. The reaction between gluten and citric acid was examined for gluten : citric acid ratios of 0.38 : 1 to 0.75 : 1 at temperatures from 100 to 130°C. More citric acid reacted for samples containing higher citric acid concentrations and at higher temperatures. FTIR analyses indicated the presence of carboxylate groups on the modified gluten samples, which resulted in modified samples having higher water uptake values than neat gluten. The sample with a gluten:citric acid ratio of 0.5 : 1 and reaction temperature of 120°C had the largest water uptake value. Also, all modified gluten samples had lower thermal stability than neat gluten. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

A thermal and rheological investigation during the complex cure of a two‐component thermoset polyurethane

The complex cure kinetics of the reaction between oligomeric diphenylmethane diisocyanate (PMDI) and glycerol was characterized through thermal and rheological techniques. Isoconversional analysis of Differential scanning calorimetry (DSC) data resulted in the activation energy varying with conversion. Isothermal analysis gave activation energies ranging from 5 kJ/mol to 33.7 kJ/ mol, whereas nonisothermal data gave values for the activation energy ranging from 49.5 to 55 kJ/mol. Incomplete cure was evident in isothermal DSC, becoming diffusion controlled in the final stages of cure. DMA analysis on the cured material gave a glass transition temperature of 104 ± 3°C, which was evidence for vitrification of the curing system. The primary and secondary hydroxyl group reactivity was dependant on the isothermal cure temperature. Rheological studies of viscosity increase and tan δ changes with time revealed a complex cure process, with primary and secondary hydroxyl reactivity also showing dependence on isothermal cure temperatures, reflecting similar results obtained from isothermal DSC studies. The independence of tan δ on frequency was used to determine the point where the polymer formed an infinite network and was no longer able to flow, providing an overall activation energy attained at the gel point of 77.4 ± 4.4 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization and thermal stability of cellulose‐graft‐polyacryloniytrile prepared by using KMnO4/citric acid redox system

An effective condition of graft polymerization of acrylonitrile onto cellulose fiber in large volume of KMnO₄/citric acid aqueous solution was examined and the produced grafted copolymers were characterized by using SEM, NMR, FTIR, XRD, TGA, and DSC in comparison with component homopolymers. Graft yield, GY, obtained by simple weighting method was close to the value obtained by NMR analysis. Significant change of chemical structure in cellulose fiber, other than graft reaction, was not detected by NMR and FTIR measurements, whereas a decrease in the degree of crystallinity by the reaction was detected by XRD measurement. It was pointed out that thermograms for grafted samples resembles with that of cellulose at T < 370°C and become similar with that for polyacrylonitrile at T > 370°C and the mass of residue at 550°C is proportional to the content of polyacrylonitrile (GY) only. It is concluded that thermal decomposition of both polymers occurs almost independently in grafted polymers and thermal stability of cellulose fiber is not improved. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Relationship between structure and properties of modified potato starch biodegradable films

Potato starch was gelatinized in the presence of water and varying amounts of glycerol at 90°C. Starch/glycerol films were prepared by casting with water. The addition of glycerol produces a decrease in the crystallinity of the starch in the films. Starch was acetylated (with acetic acid and anhydride) and maleated (with maleic anhydride). Differential scanning calorimetric analysis revealed decrease in the glass transition temperature (T_g) with the chemical modification. The starch modification on the equilibrium moisture content was determined at 25°C. The esterifications produce a decrease in the maximum moisture sorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4313–4319, 2006     

Expanded Vermiculite/Paraffin Composite as a Solar Thermal Energy Storage Material

A solar thermal energy storage material was prepared from expanded vermiculite (EVM) and paraffin by vacuum impregnation. Samples were characterized by thermogravimetric and differential scanning calorimetry (TG‐DSC), X‐ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), scanning electron microscopy (SEM), petrographic analysis, and thermal conductivity measurements. The results indicated that EVM existed as a phlogopite structure in the EVM/paraffin composite. The composite latent heat was 137.6 J/g at the freezing temperature of 52.5°C and 135.5 J/g at the melting temperature of 48.0°C, when the paraffin content was 67%. The phlogopite structure of EVM benefited paraffin heat transfer because the composite exhibited a thermal conductivity of 0.545 W·(m·K)^?1 higher than that of paraffin. Morphology and structural changes of EVM during composite preparation were investigated. The composite exhibited excellent thermal stability and has potential application in solar thermal energy storage and solar heating.     

Stereocomplexation and morphology of enantiomeric poly(lactic acid)s with moderate‐molecular‐weight

The thermal behavior and spherulitic morphologies of poly(L ‐lactic acid) (PLLA)/poly(D ‐lactic acid) (PDLA) 1/1 blend with weight‐molecular‐weight of 10⁵ order, together with those of pure PLLA and PDLA, were investigated using differential scanning calorimetry and polarized optical microscopy. It was found that in the blend, stereocomplex crystallites could be formed exclusively or coexisted with homocrystallites depending on thermal history. Banded to nonbanded spherulitic morphological transition occurred for melt‐crystallized PLLA and PDLA, while the blend presented exclusively nonbanded spherulitic morphologies in the temperature range investigated. The spherulite growth of the blend occurred within a wider temperature range (≤180°C) compared with that of homopolymers (≤150°C), while the spherulite growth rates were comparable for both the blend and homopolymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Amorphous copolyesters based on 1,3/1,4‐cyclohexanedimethanol: Synthesis,characterization and properties

Two series of amorphous copolyesters, PETGN and PETGS, were synthesized by the copolymerization of 2,6‐naphthalene dicarboxylic acid (NDA) (0–40%), succinic acid (SA) (0–40%), 1,3/1,4‐cyclohexanedimethanol (1,3/1,4‐CHDM) (10–50%), ethylene glycol (EG), and terephthalic acid (TPA). The compositions and molecular weights of the copolyesters were determined by ¹H NMR spectroscopy and viscometry, respectively. The thermal behaviors were studied over the entire range of copolymer compositions, using DSC and TGA. The optical characteristics, heat‐shrinkable effects and tensile properties of these polymers were also determined. Experimental results indicated that the thermal, optical, tensile, and shrinkage properties of PETGN and PETGS were functions of NDA or SA content. DSC and X‐ray analysis demonstrated that both PETGN and PETGS series were amorphous. Incorporating NDA and SA influenced the T_g values of those polymers, from about 37°C for PETG₃₀S₄₀ to 89°C for PETG₃₀N₄₀. Furthermore, the shrinkage of these amorphous copolyesters was more than 40% when the heating temperature was higher than the corresponding T_g. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Formulation and properties' evaluation of PVC/(dioctyl phthalate)/(epoxidized rubber seed oil) plastigels

Epoxidized rubber seed oil (4.5% oxirane content, ERSO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. The thermal behavior of the ERSO was determined by differential scanning calorimetry. The effect of the epoxidized oil on the thermal stability of poly (vinyl chloride) (PVC) plastigels, formulated to contain dioctyl phthalate (DOP) plasticizer and various amounts of the epoxidized oil, was evaluated by using discoloration indices of the polymer samples degraded at 160°C for 30 min and thermogravimetry at a constant heating rate of 10°C/min up to 600°C. The thermal behavior of the ERSO was characterized by endothermic peaks at about 150°C, which were attributed to the formation of network structures via epoxide groups, and at temperatures above 300°C, which were due to the decomposition of the material. Up to 50% of the DOP plasticizer in the PVC plastisol formulation could be substituted by ERSO without a marked deleterious effect on the consistency of the plastigel formed. In the presence of the epoxidized oil, PVC plastigel samples showed a marked reduction in discoloration and the number of conjugated double bonds, as well as high temperatures for the attainment of specific extents of degradation. These results showed that the ERSO retarded/inhibited thermal dehydrochlorination and the formation of long (n > 6) polyene sequences in PVC plastigels. The plasticizer efficiency/permanence of ERSO in PVC/DOP plastigels was evaluated from mechanical properties' measurements, leaching/migration tests, and water vapor permeability studies. The results showed that a large proportion of DOP could be substituted by ERSO in a PVC plastisol formulation without deleterious effects on the properties of the plastigels. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

Study on the long‐term thermal‐oxidative aging behavior of polyamide 6

The long‐term thermal‐oxidative aging behavior of polyamide 6 (PA6) was studied by comparison with the stabilized sample in this work. The variation of mechanical properties of the pure and the stabilized samples of PA6 with aging time at 110°C, 130°C, and 150°C were investigated, respectively. The aging mechanism of PA6 under heat and oxygen was studied in terms of the reduced viscosity, crystallization behavior, dynamic mechanical behavior, and chemical composition through the methods of polarized light microscopy (PLM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X‐ray photoelectron energy spectrum (XPS), and so on. The results indicated that at the initial stage of aging, the molecular crosslinking reaction of PA6 dominated resulting in the increase of the mechanical strength, reduced viscosity, and the glass transition temperature of the sample. And the molecular degradation dominated in the subsequent aging process resulting in the decrease of the melting temperature, the increase of the crystallinity, and the formation of the oxides and peroxides products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008