Effects of phosphorus-containing additives on soy and cottonseed protein as wood adhesives

Soy and cottonseed proteins appear promising as sustainable and environment-friendly wood adhesives. Because of their higher cost relative to formaldehyde-based adhesives, improvement in the adhesive performance of proteins is needed. In this work, we evaluated the adhesive properties of soy and cottonseed protein formulations that included phosphorus-containing acids and esters. For cottonseed protein isolate, most of these additives improved dry adhesive strength, with methylphosphonic acid, phosphorous acid, and phosphoric acid increasing the dry strength by 47, 44, and 42%, respectively, at their optimal concentrations. For soy protein isolate, these additives did not show significant benefits. The phosphorus-containing additives also improved the hot water resistance of the cottonseed protein formulations but showed either no effect or a negative effect for the of soy protein formulations. Thus, the combination of cottonseed protein with phosphorus additives appears to be attractive as wood adhesives.     

Wood adhesive properties of cottonseed protein with denaturant additives

Most commercial wood adhesive use either formaldehyde-based resins or polyurethanes, both of which include potentially toxic chemicals in their formulations. As a result, proteins are being considered as greener and more sustainable wood adhesives. While most of the protein adhesive studies focus on soy proteins, there is also interest in exploring alternatives. In this work, testing of the adhesive performance of cottonseed protein isolate was undertaken in the presence of protein denaturants, i.e. guanidine hydrochloride (GuHCl), sodium dodecyl sulfonate (SDS), urea, and alkali. For comparison, soy protein isolate was also included in the study. At optimal dosage levels, the dry adhesive strength of cottonseed protein isolate could be enhanced by 38, 25, or 47% with SDS, GuHCl, or urea, respectively. The dry adhesive strength and hot water resistance of cottonseed protein isolate was generally superior to that of soy protein isolate, with or without the denaturants. Thus, the combination of cottonseed protein with an optimal concentration of a denaturant may be a potentially promising polymeric system for use as wood adhesives.     

Adhesion properties of soy protein with fiber cardboard

Adhesion properties of soy protein isolate (SPI) on fiber cardboard and effects of press conditions, pre-pressing drying time, and protein concentrations on gluing strength were investigated. Shear strength increased as press time, press pressure, and/or press temperature increased. The effect of temperature on shear strength became more significant at high press pressure. The shear strength of the SPI adhesive on fiber cardboard decreased by 12–25% after water soaking. Shear strength increased as pre-pressing drying time increased and reached its maximal value at about 10 min. An SPI/water ratio of 12∶100 (w/w) gave the highest gluing strength. The specimens showed complete cohesive failure (fiber cardboard failure) except for soaked specimens pressed at low press temperature, low pressure, and short press time. Specimens pressed at 25°C and 2 MPa for 5 min with pre-pressing drying time of 10 min and an SPI/water ratio of 12∶100 (w/w) had T-peel strength and tensile bonding strength of 1.15 N/mm and 0.62 MPa, respectively, without water soaking, and 1.11 N/mm and 0.24 MPa, respectively, with water soaking.     

Construction of porous cellulose tubes and the evaluations of mechanical properties and cytocompatibility

In this work, regenerated cellulose (RC) tubes with the porous structure were successfully fabricated for constructing the non-invasive detection platform of vascular microenvironment. Polyethylene oxide (PEO) as a porogen was applied to induce porous structure of cellulose tubes. Tensile and burst pressure tests were carried out to evaluate the effects of PEO molecular weight and amount on the mechanical properties of cellulose tubes. The results showed that tensile strength of RC tubes was increased with increasing PEO molecular weight. The compliance of cellulose tubes decreased with increasing the PEO content. When 120 kDa PEO was applied, the average tensile strength of RC tubes could reach 1.27 MPa. The maximum burst pressure and compliance of RC tubes could reach 488.25 ± 35 mmHg and 7.50 ± 3.7%/100 mmHg, respectively. Human umbilical vein endothelia cells (HUVECs) exhibited obvious proliferation on cellulose tubes, and the collagen coating further improve the biocompatibility. The incorporated collagen further improved adhesion of the cells and growth on cellulose tubes. This work provided a kind of cellulose-based tube material with potential application for the construction of the vitro vascular microenvironment.     

Evaluation of wood bonding performance of water-washed cottonseed meal-based adhesives with high solid contents and low press temperatures

Water-washed cottonseed meal (WCSM) has been shown as a promising bio-based wood adhesive. In this work, we tested the bonding strength of WCSM slurries with high solid contents and low press temperatures per industrial input for non-structural applications as European Standard Class D1 wood adhesives. Increasing the WCSM content from 11 to 20% and 30% did not substantially change the adhesive strength but increased the viscosity of WCSM slurries dramatically. The shear strength at break of the maple wood pairs bonded at 40 and 60 °C was lower than that of maple pairs bonded at 100 °C. However, the shear strength of the pairs bonded at lower temperatures (40 and 60 °C) could be improved by extending the press time from 20 to 120 min. Addition of citric acid (CA) improved the viscosity of the WCSM adhesive at 20% solid content, but lowered the adhesive strength. The addition of denaturing reagent sodium dodecyl sulfate (SDS) showed reverse impacts on the adhesive strength and viscosity, compared to CA addition. Based on these observations, eight adhesive slurries were formulated with 20 and 30% of WCSM, 3% of CA or SDS, or 9.6% or 19.1% of denaturing reagent guanidine hydrochloride (GdmCl), and their bonding strengths were tested. These formulations could be used as the basis for developing low temperature WCSM-based wood adhesives to meet the criteria of both operational flowability and shear strength of the domestic furniture and small utensils niche markets for forest products.     

棉籽蛋白/剑麻纤维复合材料加工、界面与性能

为了提高植物蛋白基绿色高分子材料的力学性能和热稳定性能,以棉籽蛋白（CP）为原料,在尿素变性、甘油增塑、双醛淀粉（DAS）交联的基础上,将其与取向排列的天然剑麻长纤维（SF）复合,经热压硫化加工制备得到具有优异性能的棉籽蛋白/剑麻纤维全绿色复合材料。微观结构形貌和性能分析测试表明,复合材料获得改善性能主要归功于：CP基体与SF增强相间形成的紧密界面结合、对剑麻长纤维的预浸渍处理、CP与SF生物大分子间的强氢键作用。考察了不同DAS含量对复合材料力学性能和热稳定性能的影响。拉伸、热重和差示量热分析表明,经20%（质量） DAS交联的复合材料具有最优的拉伸强度（断裂应力7.5 MPa）、模量（杨氏模量93 MPa）、热稳定性（最大分解温度328℃）和玻璃化转变温度（102℃）。     

Effects of silane and MAPE coupling agents on the properties and interfacial adhesion of wood-filled PVC/LDPE blend

Composite samples were prepared from Poly(vinyl chloride)/low-density polyethylene (PVC/LDPE) blend, compatibilized by PA20 (methyl methacrylate-co-butyl acrylate copolymer), and reinforced by different levels of rubber-wood sawdust. To improve the mechanical properties of the composites, Silane A-137 (Octyltriethoxy silane), Silane A-1100 (γ-aminopropyltriethoxy silane), or MAPE (maleic anhydride-grafted-polyethylene) were introduced. It was found that the additions of Silane A-137, Silane A-1100, and MAPE could improve tensile and impact properties of the composites, regardless of the sawdust contents. Physical or chemical interactions for all coupling agents with the wood-PVC/LDPE composites used were proposed in this work. Silane A-137 or MAPE tended to give better improvement in the mechanical properties of the composites than Silane A-1100, because of the presence of the nonpolar chain ends of Silane A-137 or MAPE molecules. Besides, the addition of either Silane A-137 and MAPE or Silane A-1100 and MAPE at different ratios into the wood-PVC/LDPE composites was also studied. The experimental results suggested that the optimum mechanical properties could be obtained using Silane A-137 : MAPE of 1% : 2% wt sawdust. The morphological and thermal properties of the composites were also examined using SEM and DMA techniques, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physical,mechanical properties,and structural characterization of konjac glucomannan-chitosan-polypeptide adhesive blends

Polypeptide was used to improve the water resistance of konjac glucomannan (KGM)-chitosan-based wood adhesives. With identical solid content, the tensile strength in wet state was increased by the addition of polypeptide and a maximum tensile strength of 2.34 MPa was reached. To examine the physical and chemical changes induced by the addition of polypeptide, the structure, viscoelasticity, morphology, and miscibility of the adhesive blends were determined by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, rheometry, and scanning electron microscopy. Results indicated improvements in mechanical properties were related to the formation of intermolecular hydrogen bonds and covalent bonds between KGM, chitosan, and polypeptide, which was enhanced by increasing the polypeptide concentration. Good miscibility existed between KGM, chitosan and polypeptide, as well as good wettability between the adhesive blends and wood veneer.     

Structure and mechanical properties of cellulose derivatives/soy protein isolate blends

Biodegradable and biocompatible composites based on soy protein isolate (SPI) and various cellulose derivatives have been prepared, and the dependence of structures and mechanical properties on the content and species of cellulose derivatives for the composites were investigated by X‐ray diffraction, differential scanning calorimetry, scanning electron microscope, and tensile test. The selected cellulose derivatives, such as methyl cellulose (MC), hydroxyethyl cellulose (HEC), and hydroxypropyl cellulose, were miscible with SPI when the content of cellulose derivatives was low, and then the isolated crystalline domains, shown as the structures of network and great aggregate, formed with an increase of cellulose derivative content. The miscible blends could produce the higher strength, and even result in the simultaneous enhancement of strength and elongation for the HEC/SPI and MC/SPI blends. Meanwhile, the moderate content of great MC domains also reinforced the materials. However, the damage of original ordered structure in SPI gave the decreased modulus. Since all the components, i.e., cellulose derivatives and soy protein, are biocompatible, the resultant composites are not only used as environment‐friendly material, but the biomedical application can be expected, especially for the tissue engineering scaffold. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal properties and adhesion strength of modified soybean storage proteins

Soy proteins have shown great potential for adhesive and resin applications. This investigation characterized the thermal and adhesive properties of the major soy protein components conglycinin (7S) and glycinin (11S) after chemical modification. These globulins were extracted from defatted soy flour, then modified with either sodium hydroxide, sodium dodecyl sulfate (SDS), or urea. Modified 7S, 11S, and mixtures of 7S and 11S at varying ratios were evaluated for gluing strength with cherry veneer plywood and for thermal denaturation using DSC. Adhesive strength and water resistance were significantly improved for all proteins modified with sodium hydroxide. Gluing strength and water resistance were improved for SDS- and ureamodified proteins containing greater portions of 7S globulins. The opposite behavior was observed for proteins containing large amounts of 11S globulins. DSC results showed that the temperatures of denaturation (T _d ) decreased for the proteins modified with sodium hydroxide or urea, whereas the T _d values of proteins modified with SDS were similar to the unmodified proteins. These results suggested that, at the concentrations studied, sodium hydroxide or urea could denature soybean protein more effectively than SDS, resulting in lower protein thermal stability. Soybean proteins with high ratios of 11S had more ordered structures, as evidenced by the high enthalpy values of protein denaturation observed in DSC measurements.     

Effects of molding temperature and pressure on properties of soy protein polymers

Because of the worldwide environmental pollution problem with petroleum polymers, soy protein polymers have been considered as alternatives for biodegradable plastics. The objective of this research was to study the curing behavior of soy protein isolates (SPIs) for that application. The molding variables of temperature, pressure, and time and curing quality factors of tensile strength, strain, and water resistance were evaluated. The maximum stress of 42.9 MPa and maximum strain of 4.61% of the specimen were obtained when SPI was molded at 150°C and 20 MPa for 5 min. The water absorption of the specimen decreased as molding temperature and time increased. Glycerol greatly improved the flexibility of the specimen but decreased its strength. For SPI with 25% glycerol added, the maximum stress and strain of about 12 MPa and 140%, respectively, were achieved when the specimen was molded at 140°C for 5 min. Molding temperature, pressure, and time are major parameters influencing the curing quality of soy protein polymers. At fixed pressure, the molding temperature and time had significant interactive effects on curing quality. At high temperature (e.g., at 150°C) it took about 3 min to reach optimum curing quality; however, at low temperature (120°C) it took about 10 min to reach optimum curing quality. The maximum strength and strain of the cured protein polymer occurred at the molding temperature close to its phase transition temperature or about 40°C below its exothermic temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2595–2602, 1999     

反应性乳化剂参与的醋丙多元共聚及其压敏胶性能研究

采用种子半连续乳液聚合法,将反应性乳化剂α-烯丙基烷基酚聚氧乙烯醚硫酸铵(HS-10)引入醋丙乳液聚合体系,制备了稳定的醋丙压敏胶乳液。红外光谱实验结果表明,HS-10参与了醋丙体系共聚合反应。所得乳液的表面张力、粒径及分布、粘度及180°剥离强度都随HS-10用量增加而减小。耐水性性能实验表明采用HS-10的醋丙压敏胶体系,吸水率仅为传统型的35．9％,较好地改善了聚合物耐水性能。     

Synthesis and properties of hydrophilic polymers,part 11: Synthesis,biodegradability, and metal complexation of copolymers of ethylenediaminetetraacetic acid dianhydride and lactose

The synthesis and characterization of poly(ethylenediaminetetraacetic acid‐co‐lactose) of high molar mass (132 kg mol^?1) is described. The polycondensate with pendant carboxylic groups was shown to be hydrolytically and microbiologically degradable by using conventional microbiological methods. The metal complexing properties of the polyester were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II), Pb(II), and Al(III) ions in aqueous solution using the liquid‐phase polymer‐based retention (LPR) method. In addition, the complexing capacity of the Cu(II)‐saturated copolymer was determined by TGA to be 182 mg g^?1 polymer. According to the retention profiles determined as a function of filtration factor by using LPR in conjunction with inductively coupled plasma spectrometry, Cr(III) and Fe(III) showed a strong interaction with this polymer under these conditions, indicated by retention values of 100% at pH 5. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2932–2939, 2007     

Adhesive properties of soy proteins modified by sodium dodecyl sulfate and sodium dodecylbenzene sulfonate

A study was conducted on adhesive and water-resistance properties of soy protein isolates modified by sodium dodecyl sulfate (SDS) (0.5, 1, and 3%) and sodium dodecylbenzene sulfonate (SDBS) (0.5, 1, and 3%) and applied on walnut, cherry, and pine plywoods. Soy proteins modified by 0.5 and 1% SDS showed greater shear strengths than did unmodified protein. One percent SDS modification had the highest shear strength within each wood type tested. Soy proteins modified with 0.5 and 1% SDBS also showed greater shear strengths than did the unmodified protein. The 1% SDBS-modified soy protein had the highest shear strength in all wood samples tested. Compared to the unmodified protein, the modified proteins also exhibited higher shear strengths after incubation with two cycles of alternating relative humidity and zero delamination rate and higher remaining shear strengths after three cycles of water soaking and drying. These results indicate that soy proteins modified with SDS and SDBS have enhanced water resistance as well as adhesive strength. Possible mechanisms for the effects of SDS and SDBS also are discussed.     

Thermal properties and adhesiveness of soy protein modified with cationic detergent

This research studied the effects of cationic detergents on the adhesiveness and thermal properties of soy protein isolate (SPI). Three cationic detergents, hexadecyltrimethyl ammonium bromide, ethylhexadecyldimethyl ammonium bromide (EDAB), and benzyldimethylhexadecyl ammonium chloride, each at concentrations of 1.3, 2.6, 5.2, and 7.8 mM, were used to modify SPI. The effect of pH at selected EDAB concentrations was also studied. Results showed that both detergent concentration and pH had significant effects on the adhesiveness of modified SPI. SPI modified with detergent at a concentration of 2.6 mM yielded the greatest dry tensile strength and water resistance, which indicated that a moderate protein denaturation might be favorable to the adhesion of SPI. Both modified and unmodified SPI showed greater adhesive strength at their optimal pH values. Modified SPI showed greatest adhesive strength at pH 7, whereas unmodified SPI showed greatest adhesive strength at pH 4.5; the tensile strength of modified SPI was greater than that of unmodified SPI. The protein-denaturation temperature and the enthalpy of modified SPI adhesives were also analyzed by using DSC. Denaturation of the native structure of SPI increased as detergent concentration increased.