Thermal and Mechanical Properties of Plastics Molded from Sodium Dodecyl Sulfate-Modified Soy Protein Isolates

Soybean protein is a potential material for manufacturing of biodegradable plastics. The objective of this investigation was to characterize the thermal and mechanical properties of plastics made from sodium dodecyl sulfate (SDS)-modified soy proteins. Soy protein isolate (SPI) was prepared from defatted soy flour, modified with various concentrations of SDS, and then molded into plastics. The temperatures of denaturation of the modified soy protein increased at low SDS concentration and then decreased at high SDS concentration. At the same SDS concentration, the plastics molded from the modified soy proteins showed a similar temperature of denaturation, but a lower enthalpy of denaturation compared to the modified soy protein. Young's modulus of the plastics decreased as SDS concentration increased, and the tensile strength and strain at break of the plastics reached a maximum value at 1% SDS modification. Two glass transition temperatures were identified corresponding to the 7S and 11S globulins in SPI by dynamic mechanical analysis, and they decreased as SDS concentration increased. The SDS modification increased the water absorption of the plastics.     

厌氧-吹脱-好氧-吸附法处理酱油废水

针对酱油废水的高CODCr、高色度、高挥发酸以及含盐的特点，设计了用厌氧-吹脱-好氧-吸附法处理酱油废水的工艺。实验结果表明，该工艺对酱油废水的处理有较好的处理效果。当厌氧进水的CODCr分别为6000～8000和1500～2000mg／L，色度分别为5000和1800倍左右时，厌氧反应的水力停留时间(HRT)分别为3～4和2d，吹脱池的停留时间为16h，气水比为0．01m^3／L，好氧反应器和煤渣吸附池的停留时间分别为14～18和14～16h时，该流程对废水CODCr的总平均去除率分别达到90％和82．7％左右，对色度的总平均去除率分别为76．7％和86．5％。     

Processing and Physical Properties of Plastics Made from Soy Protein Polyester Blends

Blending soy protein with polyesters using a polyvinyllactam as a compatibilizer successfully made soy protein-based plastics. The polyesters used to produce blends included polycaprolactone (PCL) and Biomax (a commercial biodegradable polyester). The blends were processed by compounding extrusion and injection molding. Blends containing soy protein/Biomax-poly(vinyl alcohol) had tensile strengths ranging from 16–22 MPa, with samples containing larger percentages of the synthetic polymer exhibiting greater strengths. Blends made from soy protein, Biomax, and PCL had tensile strengths ranging from 27–33 MPa. All the blends had high Young's moduli but demonstrated brittle characteristics as evident from their low elongations at break, ranging from 1.8–3.1%. Plastics made from soy protein/polyester blends exhibited low water absorption and had good stability under ambient conditions relative to the plastics made from soy protein alone. Blends made from soy protein flour produced plastics with the lowest water absorption.     

Injection Molded Biocomposites from Soy Protein Based Bioplastic and Short Industrial Hemp Fiber

Biocomposites from soy based bioplastic and chopped industrial hemp fiber were fabricated using twin-screw extrusion and injection molding process. Soy based bioplastics were prepared through cooking with plasticizer and blending with biodegradable poly(ester amide). Mechanical, thermal properties and fracture surface morphology of the “green”/biocomposites were evaluated with universal testing system (UTS), dynamic mechanical analysis (DMA), Environmental Scanning Electron Microscopy (ESEM). It was found that the tensile strength and modulus, flexural strength and modulus, impact strength and heat deflection temperature of industrial hemp fiber reinforced biocomposites significantly improved. The fracture surfaces showed no signs of matrix on the fiber surface suggesting poor interfacial adhesion.     

Soybean-Oil-Based Polyisocyanurate Rigid Foams

Polyisocyanurate foams were prepared from polymeric 4,4-diphenylmethane diisocyanate (MDI), soy polyol and polypropylene oxide polyol by varying isocyanate index from 110 to 350. The higher isocyanate index produced polyisocyanurate foams with higher thermal stability, improved flame resistance, tensile strength, higher modulus, and higher glass transition. Soy-based foams displayed better thermal stability, lower flammability, higher rigidity (modulus) and higher compression strength than those based on the propylene oxide polyols of the same molecular weight and functionality.     

Viscosity of Soy Protein Plastics Determined by Screw-Driven Capillary Rheometry

Soy protein plastics are a renewable, biodegradable alternative to fossil fuel-based plastic resins. Processing of soy protein plastics using conventional methods (injection molding, extrusion) has met with some success. Viscosities of processable formulations that contain soy protein along with the necessary additives, such as glycerol and cornstarch, have not been reported, but are necessary for extrusion modeling and the design of extrusion dies. Resins consisting of soy protein isolate-cornstarch ratios of 4:1, 3:2, and 2:3 were plasticized with glycerol and soy oil, compounded in a twin screw extruder and adjusted to 10% moisture. The effects on viscosity of added sodium sulfite, a titanate coupling agent and recycling were evaluated using a screw-driven capillary rheometer at shear rates of 100–800/s. The viscosities fit a power-law model and were found to be shear thinning with power-law indices, n, of 0.18–0.46 and consistency indices, m, of 1.1 × 10⁴–1.0 × 10⁵. Power-law indices decreased and consistency indices increased with increasing soy protein-to-cornstarch ratio and in the absence of sodium sulfite. Addition of the titanate coupling agent resulted in increased power-law index and decreased consistency index. Viscosities at a shear rate of 400/s decreased with recycling, except for the 4:1 soy protein isolate to cornstarch formulation, which displayed evidence of wall slip. Power-law indices were unaffected by recycling. Viscosities in the tested shear rate range were comparable to polystyrene and low-density polyethylene indicating soy protein plastics are potential drop-in replacements for commodity resins on conventional plastics processing equipment.     

Effect of OH/NCO Molar Ratio on Properties of Soy-Based Polyurethane Networks

Polyurethane networks from soybean oil have a number of valuable properties, which are determined by their chemical composition and cross-linking density. Changing the molar ratio of reacting groups can vary the latter. In this work we have varied the NCO/OH molar ratio (isocyanate index) from 1.05 to 0.40 in a soy polyol/MDI system, and tested physical and mechanical properties. The degree of swelling in toluene increased from 52–206% by decreasing isocyanate index from 1.05–0.4. The sol fractions and network densities determined from swelling in toluene were compared with ones obtained using the network formation theory based on branching processes. The comparison of experimental sol fractions and network densities with those predicted by theory of network formation suggest that 5–10% of bonds are lost in cycles and that high entanglement contributions increase the network densities. Polymers prepared with NCO/OH ratios from 1.05–0.8 were glassy while the others were rubbery, and that was reflected in their properties. Glass transition temperature (DSC) of the networks decreased from 64–7°C, tensile strength from 47–0.3 MPa, and elongation at break increased from 7–232%. The activation energy of the glass transition, determined from dielectric spectra, varied from 222–156 kJ/mol as the molar ratio of NCO to OH groups decreased from 1.05–0.4.     

Dynamic Mechanical Properties of Soy Protein Filled Elastomers

Dynamic mechanical properties including temperature effect, stress softening, and Payne effect are studied on the elastomer composites filled with soy protein or carbon black. The comparison of protein composite with well-known carbon black composites provides further insight into the protein composites. The elastomers filled with soy protein aggregates give substantial reinforcement effect when compared with the unfilled elastomers. Approximately 400 times increase in shear elastic modulus was observed when 40% by weight of protein is incorporated into the elastomers. The sample films were cast from the particle dispersion of soy protein isolate and carboxylated styrene–butadiene latex. At the higher temperatures, the shear elastic modulus of soy protein-filled composites does not decrease as much as that of the carbon black-filled composites. The behavior of elastic and loss modulus under the oscillatory strain of different magnitude is similar to that of carbon black reinforced styrene–butadiene rubber. However, carbon black composites show a better recovery behavior after eight cycles of dynamic strain. The reduction of shear elastic modulus with dynamic strain (Payne effect) was compared with Kraus model and the fitting parameter related to the aggregate structure of the soy protein. A reasonable agreement between the theoretical model and experiment was obtained, indicating the Payne effect of the protein-related network structure in the elastomers could also be described by the kinetic agglomeration de-agglomeration mechanism.     

Wet Strength and Water Resistance of Modified Soy Protein Adhesives and Effects of Drying Treatment

Soy protein isolate (SPI) was modified using sodium dodecyl sulfate (SDS) and guanidine hydrochloride (GuHCl). Adhesion performance of the modified SPI on fiberboard was studied. The Water-soluble mass of the modified SPI adhesives was examined following modified ASTM D5570. The SDS-modified SPI containing 91% protein had a water-soluble mass of 1.7%. To be considered a water-resistant adhesive, the water-soluble mass of adhesive should be less than 2%. The wet shear strength test showed 100% cohesive failure within fiberboard, indicating that the modified SPI has good water resistance. The effect of drying treatment on adhesion performance of the SDS-modified SPI on fiberboard was then investigated. Drying treatment significantly affected the final adhesion performance. Shear strength did not change much, but the percentage of cohesive failure within fiberboard increased markedly as drying temperature increased. All the unsoaked, soaked, and wet specimens glued by the adhesives treated at 70° or 90°C had 100% cohesive failure within fiberboard. Viscosity also increased greatly with an increase in drying temperature. This information will be useful in developing low-cost adhesive processing system in the future.     

Modification of Soy Protein Plastic with Functional Monomer with Reactive Extrusion

Chemical modification of soy protein with monomers such as maleic anhydride, glycidyl methacrylate and styrene was accomplished using reactive extrusion technology. Thermal and mechanical properties of the modified soy protein plastics were characterized with differential scanning calorimetry (DSC), a dynamic mechanical analyzer (DMA) and a United Testing System load frame. It was found that the denaturation temperature and the glass transition temperature of soy protein plastic changed. In addition, the tensile properties of modified soy protein plastic improved. Attenuated total reflection Fourier transform infrared (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of modified soy proteins. A suggestion of the interaction between soy protein and functional group in functional polymers is given. Through the in-situ interaction between the polymer and soy protein plastic, the mechanical properties of the soy protein plastic can be adjusted and controlled.