Investigation of the surface properties of polymeric soaps obtained by ring‐opening polymerization of epoxidized soybean oil

Epoxidized soybean oil (ESO) was converted to a polysoap (PESO) via a two‐step synthetic procedure of catalytic ring‐opening polymerization, followed by hydrolysis (HPESO) with a base. Various molecular weights of PESO and HPESO were prepared by varying the reaction temperature and/or catalyst concentration. In addition, the counter ion chemistry was varied by changing the base used for saponification. The PESO and HPESO products were carefully characterized and identified using a combination of FTIR, ¹H‐NMR, solid state ¹³C‐NMR, and GPC. The effect of HPESO polysoaps on the surface tension of water and the interfacial tension of water‐hexadecane was investigated as a function of HPESO concentration, molecular weight, and counter ion chemistry. HPESO polysoaps were effective at lowering the surface tension of water and the interfacial tension of water‐hexadecane and displayed minimum values in the range of 20–24 and 12–17 dyn/cm, respectively, at concentration of 200–250 μM. Water‐hexadecane interfacial tension was also calculated from measured surface tension data using the Antonoff, harmonic mean (HM), and geometric mean (GM) methods. Measured values agreed well with those calculated using the HM and GM methods, but not the Antonoff method. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cross-linkers control the viscoelastic properties of soybean oil-based biomaterials

Because of environmental concerns, biodegradable materials have been of increasing research interest over the last several years. Previously, we reported on a biobased material developed from epoxidized soybean oil (ESO) that displayed viscoelastic behavior similar to synthetic rubbers or plastics. In this work, the viscoelastic properties of several biomaterials made from ESO cross-linked by different amounts of two different cross-linking agents were investigated. The composites exhibited different glass transition temperatures and viscoelastic behaviors depending on the type and amount of cross-linker used. Higher glass transition temperatures and stronger viscoelastic properties of the materials were found with a greater amount of cross-linker. Comparing agent triethylene glycol diamine (TGD) with agent triethylenetriamine (TETA), we found that the material cross-linked by TETA had a higher glass transition temperature and stronger viscoelastic solid properties than the material cross-linked by the agent TGD.     

Electric stimuli responses to poly(vinyl alcohol)/chitosan interpenetrating polymer network hydrogel in NaCl solutions

An interpenetrating polymer network (IPN) hydrogel composed of poly(vinyl alcohol) (PVA) and chitosan exhibited electric‐sensitive behavior. The PVA/chitosan IPN hydrogel was synthesized by an ultraviolet (UV) irradiation method that is used in several biomedical and industrial fields. The swelling behavior of the PVA/chitosan IPN hydrogel was studied by immersion of the gel in NaCl aqueous solutions at various concentrations. The swelling ratio decreased with increasing concentration of NaCl solution. The stimuli response of the IPN hydrogel in electric fields was also investigated. When a swollen PVA/chitosan IPN was placed between a pair of electrodes, the IPN exhibited bending behavior in response to the applied electric field. The bending angle and the bending speed of the PVA/chitosan IPN increased with increasing applied voltage and concentration of NaCl aqueous solution. The PVA/chitosan IPN also showed stepwise bending behavior depending on the electric stimulus. In addition, thermal properties of PVA/chitosan IPN were investigated by differential scanning calorimetry (DSC) and dielectric analysis (DEA). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2285–2289, 2002     

Rheological investigation of poly(vinyl alcohol)/poly(N-vinyl pyrrolidone) mixtures in aqueous solution and hydrogel state

Rheological behavior of poly(vinyl alcohol) (PVA) and poly(N-vinyl pyrrolidone) (PVP) mixtures in aqueous solutions and hydrogel state was investigated. The complex dependence of the viscosity on PVA/PVP mixture composition could be attributed to cumulative effects of electrostatic interactions, hydrogen bonding or association phenomena. Physical hydrogels were prepared by freezing/thawing method and their viscoelastic properties were followed as a function of number of cryogenic cycles and aging time at 37 °C. From swelling experiments, it was observed that the diffusion of water molecules into the hydrogel pores is Fickian (for low number of cryogenic cycles) and it becomes pseudo-Fickian as the sample is submitted to more than 10 freezing/thawing cycles. PVA/PVP hydrogels obtained by physical interactions present a high degree of tailorability and they are suitable candidates for biomedical applications.     

Characteristics of electrical responsive chitosan/polyallylamine interpenetrating polymer network hydrogel

An interpenetrating polymer network (IPN) hydrogel composed of chitosan and polyallylamine exhibited electric‐sensitive behavior. The chitosan/polyallylamine IPN hydrogel was synthesized by radical polymerization using 2,2‐dimethoxy‐2‐phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The swelling behavior of the IPN was studied by immersion of the gel samples in aqueous NaCl solutions at various concentrations and pHs. The swelling ratio decreased with increasing concentration and pH of electrolyte solution. The stimuli response of the IPN hydrogel in electric fields was also investigated. When a swollen the IPN was placed between a pair of electrodes, the IPN exhibited bending behavior in response to the applied electric field. The IPN also showed stepwise bending behavior depending on the electric stimulus. In addition, thermal properties of the IPN were investigated by differential scanning calorimetry (DSC) and dielectric analysis (DEA). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2290–2295, 2002     

A potential biodegradable rubber—Viscoelastic properties of a soybean oil-based composite

Scientists are more and more interested in biodegradable materials owing to their environmental advantage. We investigated viscoelastic properties of a newly developed biomaterial made from epoxidized soybean oil (ESO). ESO cross-linked by triethylene glycol diamine exhibited viscoelastic solid properties. The storage modulus (G′) was 2×10⁴ Pa over four frequency decades. The phase angles were 14–18°. Stress relaxation measurements showed that there was no relaxation up to 500 s. From the plateau modulus we estimated that the M.W. of this cross-linked soybean oil was on the order of 10⁵. The composites of cross-linked ESO with three different fibers had 50 times higher elasticity (G′) than those without fiber. Phase shifts were the same as those of cross-linked oil without fibers, but the linear range of rheological properties was much narrower than that of the material without fibers. All these results indicated that this new biopolymer made from soybean oil exhibited strong viscoelastic solid properties similar to synthetic rubbers. These rheological properties implied that this biomaterial has high potential to replace some of the synthetic rubber and/or plastics.     

Properties of Injection Molded Composites Containing Corn Fiber and Poly(Vinyl Alcohol)

Composites based on natural polymers alone are extremely sensitive to moisture and their mechanical properties deteriorate upon the absorption of water, limiting their usefulness in practical applications. Ongoing research cooperation between USDA and the University of Pisa, Italy, has yielded several composites based on poly(vinyl alcohol) (PVA) and corn fibers (CF). In this study, variable amounts of CF and PVA were processed in the presence of both dry and liquid plasticizers, glycerol and pentaerythritol. Cornstarch was introduced in the formulation to reduce the cost and to further increase the composition of natural components in the composites. Composites made with as low as 30% PVA were injection molded into tensile bars and evaluated. The addition of starch moderately reduced the tensile properties of the composites, lowering the elongation (∼600% to 400%) and increasing Young's modulus (∼36 MPa to ∼100 MPa) while the ultimate tensile strength remained constant at about 8 MPa. Composites prepared from CF and PVA showed little change in their mechanical properties even after conditioning them at various relative humidities, or after soaking in water. Composites tested after storage for one year, at 50% relative humidity and 23°C, exhibited mechanical properties similar to those of freshly prepared composites. *Names are necessary to report factually on available data; however the USDA neither guarantees nor warrants the standards of the product and the use of the name USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Characterization of novel soybean‐oil‐based thermosensitive amphiphilic polymers for drug delivery applications

Hydrolyzed polymers of soybean oil (HPSO) and of epoxidized soybean oil (HPESO) were developed previously. Owing to their natural food origin and biocompatibility, we exploited further their potential as a drug delivery system and pharmaceutical excipients. This work aimed to investigate self‐assembly, thermal transition, interaction with various drugs and surface activity of these novel amphiphilic polymers. The critical micelle concentration of HPSO and HPESO was determined by the surface tension method. The molecular interaction between HPESO and anticancer drug doxorubicin HCl was examined. The effect of the polymers on the solution contact angle and surface energy of compressed tablets of hydrophobic drugs ibuprofen and nifedipine was measured. The thermal transition temperatures T_tr (cloud points) of the polymers in aqueous solutions increased with increasing polymer concentration. HPSO exhibited lower T_tr than HPESO. The critical micelle concentration was found to be 0.05 mg mL^?1 for HPSO and 0.08 mg mL^?1 for HPESO. Strong molecular interactions between HPESO and doxorubicin were observed. Both polymers reduced the interfacial energy and contact angles of drug tablets with more effect on ibuprofen tablets with the use of HPSO. These results suggest that the novel soybean‐oil‐based amphiphilic polymers have great potential for drug delivery and pharmaceutical formulations. Copyright © 2012 Society of Chemical Industry     

Viscoelastic properties of lupin proteins produced by ultrafiltration-diafiltration

The linear and nonlinear rheological properties of defatted lupin proteins produced by ultrafiltration-diafiltration were investigated. Five concentrations ranging from 10 to 30% of the defatted ultrafiltered-diafiltered (DUD) lupin proteins were prepared. The viscoelastic properties strongly depended on concentrations. Below 12%, the DUD lupin proteins exhibited more fluid-like behavior. At 15%, lupin proteins became more viscoelastic, and above 20%, the viscoelastic solid-like properties became stronger. Below 12%, the high-frequency behaviors of moduli were proportional to ω^1/2, as expected for a semiflexible coil. Above 20%, the high-frequency behaviors of moduli were proportional to ω^1/2, indicating a flexible coil. The nonlinear steady shear rheological properties were also concentration-dependent and showed shear-thinning behavior, which could be described by a power law constitutive model. The trend of the power law exponent shift is very consistent with the linear viscoelastic behavior change with the lupin protein concentration. These results suggest DUD lupin proteins undergo a structural change between 12 and 20%.     

Rheological study of self‐crosslinking and co‐crosslinking of ammonium zirconium carbonate and starch in aqueous solutions

Different from common hydrogel systems formed by a polymer and a crosslinker, a hydrogel consisting of both self‐crosslinkable ammonium zirconium carbonate (AZC) and co‐crosslinkable starch was investigated in this study using rheological measurements. The evolution of viscoelastic properties of AZC solutions and AZC‐starch mixtures was characterized, and the crosslinking kinetics was determined. It was found that for both AZC self‐crosslinking and AZC‐starch co‐crosslinking, the initial bond formation rate and the gel strength exhibited a power law scaling with polymer concentrations. The competition reaction between self‐crosslinking and co‐crosslinking indicates that the gelation kinetics strongly depends on the AZC concentration but less depends on starch concentration. The temperature dependence of crosslinking was described by the Arrhenius plots which demonstrate a good linearity. It was determined that the activation energy of AZC self‐crosslinking was approximately 145–151 kJ/mol, and the activation energy of AZC‐starch co‐crosslinking was 139 kJ/mol. The effect of solution pH on the crosslinking process was also studied. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of nonprotein polymers on water‐uptake properties of fish protein‐based hydrogel

The effects of nonprotein polymers on the water‐swelling properties of fish protein‐based hydrogel were studied. Inclusion of carboxymethyl cellulose (CMC), poly(ethylene glycol) (PEG), poly(vinyl alcohol) (PVA), or guar gum at a 2.5% (w/w) level in an 80% ethylenediaminetetraacetic dianhydide (EDTAD)‐modified fish protein hydrogel (10% monomer concentration) significantly decreased the extent of water uptake of the hydrogel. Among these polymers, PVA exhibited the greatest inhibitory effect. The inhibitory effect of these polymers on the water uptake of fish protein hydrogel was apparently due to the thermodynamic incompatibility of these polymers with the fish protein gel network and the consequent effect on the extent of relaxation of the crosslinked polypeptide network. In contrast, inclusion of 60% EDTAD‐modified soy protein up to a level of 40% of the total protein in the gel did not affect the extent of the equilibrium water uptake of the gel. At higher levels, however, soy protein also decreased the amount of water uptake by the gel. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 45–51, 2002     

环氧低热油的制备及其增塑性能

选用常用来合成环氧大豆油和环氧脂肪酸甲酯的大豆油为原料,运用GC-MS联用仪测定了其组成及含量,并通过酯交换、环氧化等工艺合成了具有环氧结构的环氧长短链酰基甘油酯（环氧低热油）;并对其作为聚氯乙烯增塑剂的各项性能进行了研究。结果表明,大豆油不饱和脂肪酸含量达88.5%,当其与三乙酸甘油酯在物质的量之比为1∶1的情况下可得到以二脂肪酸单乙酸酯为主要成分的低热油;此外,通过物化性能、动态热机械分析、薄膜拉伸、热重-红外-质谱及热分解动力学等手段分析,结果表明环氧低热油的玻璃化转变温度为–0.77℃,低于环氧大豆油的6.13℃;其断裂伸长率为370.56%,也高于环氧大豆油321.11%;与环氧脂肪酸甲酯相比具有更高的闪点、较少的加热减量和更优良的热稳定性。所以环氧低热油是一种较为优良的增塑剂产品。     

Electroresponsive behavior of 2‐hydroxypropyltrimethyl ammonium chloride chitosan/poly(vinyl alcohol) interpenetrating polymer network hydrogel

An interpenetrating polymer network hydrogel composed of 2‐hydroxypropyltrimethyl ammonium chloride chitosan and poly(vinyl alcohol) was prepared. Its swelling properties and electroresponsive behavior in aqueous NaCl solutions were studied. The results indicated that the water uptake ability of the hydrogel decreased with increasing ionic strength of aqueous NaCl solution. The Young's modulus, elongation at break and tensile strength of the hydrogel swollen in deionized water were 4.29 MPa, 76.5% and 3.26 MPa, respectively. The hydrogel swollen in the NaCl solution bent toward the anode under non‐contact direct current electric fields, and its bending speed and equilibrium strain increased with increasing applied voltage. The electroresponsive behavior of the hydrogel was also affected by the electrolyte concentration of external NaCl solution, and there was a critical ionic strength of 0.10 where the maximum equilibrium strain of the hydrogel occurred. By changing the direction of the applied potential cyclically, the hydrogel exhibited good reversible bending behavior. Copyright © 2011 Society of Chemical Industry     

Glycerol-modified poly(vinyl alcohol)/poly(ethylene glycol) self-healing hydrogel for artificial cartilage

Poly(vinyl alcohol) (PVA) hydrogels have shown potential applications in bionic articular cartilage due to their tissue-like viscoelasticity, good biocompatibility and low friction. However, their lack of adequate mechanical properties is a key obstacle for PVA hydrogels to replace natural cartilage. In this study, poly(ethylene glycol) (PEG) and glycerol were introduced into PVA, and a PVA/PEG–glycerol composite hydrogel was synthesized using a mixing physical crosslinking method. The mechanical properties, hydrophilicity and tribological behavior of the PVA/PEG–glycerol hydrogel were investigated by changing the concentration of glycerol in PEG. The results showed that the tensile strength of the hydrogel reached 26.6 MPa at 270% elongation at break with 20 wt% of glycerol plasticizer, which satisfied the demand of natural cartilage. In addition, the excellent hydrophilicity of glycerol provides good lubricating properties for the composite gel under dry friction. Meanwhile, self-healing and cellular immunity assays demonstrated that the composite gel could have good self-healing ability and excellent biocompatibility even in the absence of external stimuli. This study provides a new candidate material for the design of articular cartilage, which has the potential to facilitate advances in artificial joint cartilage repair. © 2022 Society of Industrial Chemistry.     

Electrochemical behavior of an interpenetrating polymer network hydrogel composed of poly(propylene glycol) and poly(acrylic acid)

An interpenetrating polymer network (IPN) hydrogel based on poly(propylene glycol) and poly(acrylic acid) was prepared by UV irradiation. The swelling behavior of the IPN hydrogel was studied by the immersion of the gel in aqueous NaCl solutions of various concentrations. The swelling ratio decreased with an increase in the NaCl concentration. The electrically sensitive behavior of the IPN hydrogel in electric fields was also investigated. The IPN hydrogel also showed a stepwise bending behavior that depended on the electric stimulus. The bending angle and bending speed of the IPN hydrogel were greatest in 0.6 wt % aqueous NaCl and increased with an increase in the applied voltage. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2301–2305, 2003     

Hydrolyzed collagen‐based hydrogel with salt and pH‐responsiveness properties

A novel hydrolyzed collagen‐based hydrogel has been prepared by grafting the binary mixture of acrylamide and 2‐acrylamido‐2‐methylpropanesulfonic acid onto the collagen backbone in the presence of a crosslinking agent. Its physicochemical properties in aqueous solution were studied. The effect of reaction variables on both gel content and swelling capacity was investigated to achieve a hydrogel with improved absorbency and gel content. The absorbency under load of optimized hydrogel was also investigated by using an absorbency under load tester at various applied pressures. The swelling ratio in various salt solutions was also determined and additionally, the swelling of hydrogels was measured in solutions with pH ranged 1–13. The synthesized hydrogel exhibited a pH‐responsiveness character so that a swelling‐collapsing pulsatile behavior was recorded at pH 2 and 8. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Di-Hydroxylated Soybean Oil Polyols with Varied Hydroxyl Values and Their Influence on UV-Curable Pressure-Sensitive Adhesives

Di-hydroxylated soybean oil (DSO) polyols with three different hydroxyl values (OHV) of 160, 240, and 285 mg KOH/g were synthesized from epoxidized soybean oils (ESO) by oxirane cleavage with water catalyzed by perchloric acid. The DSO were clear, viscous liquids at room temperature. The structure and physical properties of DSO were characterized using titration methods, Fourier-transform infrared spectroscopy (FTIR), gel permeation chromatography, rheometer, differential scanning calorimetry, and thermogravimetric analysis. The number average molecular weight of DSO160, DSO240, and DSO285 were 1,412, 1,781, and 1,899 g/mol, respectively, indicating that oligomerization occurred during DSO synthesis, which was further confirmed by FTIR. All DSO polyols exhibited non-Newtonian, shear thinning behavior. DSO with higher OHV were more viscous than those with lower OHV. All DSO were thermally stable up to 380 °C. These three DSO were formulated into pressure-sensitive adhesives (PSA) by copolymerizing with ESO using UV curing. The peel adhesion strength of the PSA was significantly affected by the OHV of DSO and DSO content. Maximal PSA adhesion strength of 4.6 N/inch was obtained with DSO285 and a DSO/ESO weight ratio of 0.75.     

Ultrasonic monitoring of the network formation in superabsorbent cellulose based hydrogels

Biodegradable hydrogels are finding increasing interest in the academic and industrial field due to their high swelling capacity and the potential for many novel applications enabled by their biodegradability. The monitoring of the hydrogel cross-linking process is a crucial step for predicting hydrogel performances in terms of degree of swelling and viscoelastic properties.In this work, the chemical cross-linking of cellulose based hydrogels has been monitored during synthesis in water by means of ultrasonic wave propagation and low frequency dynamic mechanical analysis (DMA). The effect of the cross-linker concentration on the hydrogel acoustic behaviour has been also analysed and correlated with the different elastic response developed by the macromolecular hydrogel.The results demonstrate the reliability of the ultrasonic wave propagation in the following network formation process of a superabsorbent hydrogel, being capable of following the limited changes in the physical properties of the reacting solution.     

The role of rheological premonitory of hydrogels based on cellulose nanofibers and polymethylsilsesquioxane on the physical properties of corresponding aerogels

Cellulose nanofibers (CNFs) and polymethylsilsesquioxane (PMSQ)-based aerogels (CNF/PMSQ aerogels) have been prepared by the sol–gel method. The extraction of CNFs from pine wood and formation of composite aerogel with PMSQ were confirmed by Fourier transform infrared spectroscopic and field emission scanning electron microscopic analyses. The rheological premonitory of hydrogel has been performed to predict the physical properties (i.e., density, mechanical properties) of aerogels. The variation in the precursor (methyltrimethoxysilane [MTMS]) and urea content has shown a considerable effect on the storage modulus and phase angle of the hydrogel. The variation in urea content showed a 4–8% increment in the density with a pronounced difference in aerogel's morphology. The increment in the MTMS concentration demonstrated a 10–20% enhancement in density with a minor change in morphology. The van Gurp–Palmen plot of hydrogel has represented a relationship between complex modulus and phase angle. This study establishes that hydrogel's premonitory analysis could compare aerogel's physical properties without going through drying and further analysis.     

Barley Protein Isolate: Thermal, Functional, Rheological, and Surface Properties

Barley protein isolate (BPI) was extracted in 0.015 N NaOH in a 10:1 ratio solvent:flour and was precipitated by adjusting the pH to 4.5 and freeze-dried. The thermal properties of BPI were determined using modulated differential scanning calorimetry (MDSC). BPI with 4% moisture content exhibited a glass transition (T _g) with 140 °C onset, 153 °C middle, and 165 °C end temperatures and a ΔC _p of 0.454 J/g per °C. The high moisture content sample (50%) showed a T _g at 89, 91, or 94 °C and 0.067 ΔC _p. Acetylation had no apparent effect on the foaming and emulsifying properties of protein from barley flour but exhibited the least-stable foam among BPI samples. Foaming capacities of both barley protein isolates were ∼12% less than that of acid-precipitated soy protein isolate reported in the literature. Acetylated BPI showed the highest surface hydrophobicity compared to the other samples. The surface-tension test confirmed that unmodified and modified BPI possessed surface activity. BPI phosphorous oxycloride-crosslinked was the most effective in lowering the surface tension of aqueous NaCl, while the crosslinked BPI was the least effective. The G′ value of BPI suspension was greater than G″ at all frequencies from 0.1 to 100 rad/s. The strain value at which linear behavior ceased and nonlinear behavior began ranged from 3 to 10%. Names are necessary to report factually on available data; however, the United States Department of Agriculture (USDA) neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.