Adhesive properties of soy proteins modified by urea and guanidine hydrochloride

An investigation was conducted on the adhesive and water-resistance properties of soy protein isolates that were modified by varying solutions of urea (1, 3, 5, and 8 M) or guanidine hydrochloride (GH) (0.5, 1, and 3 M) and applied on walnut, cherry, and pine plywoods. Soy proteins modified by 1 and 3 M urea showed greater shear strengths than did unmodified protein. The 3 M urea modification gave soy protein the highest shear strength. Soy proteins modified with 0.5 and 1 M GH gave greater shear strengths than did the unmodified protein. The 1 M GH-modified soy protein gave the highest shear strength. Compared to the unmodified protein, the modified proteins also exhibited higher shear strengths after incubating with two cycles of alternating relative humidity, zero delamination, and higher remaining shear strengths after three cycles water soaking and drying. These results indicate that soy proteins modified with urea and GH enhance water resistance as well as adhesive strength. Secondary structures of globule proteins may enhance adhesion strength, and the exposure of hydrophobic amino acids may enhance water resistance. Proteins modified by 3 M urea or 1 M GH may have higher content of secondary structure and more exposed hydrophobic amino acids, compared with other modifications or unmodified proteins.     

Soy proteins as plywood adhesives: formulation and characterization

Soybean proteins have great potential as bio-based adhesives. The objectives of our study were to develop and characterize formaldehyde-free soybean wood adhesives with improved water resistance. Second-order response surface regression models were used to determine the effects of soy protein isolate concentration, sodium chloride, and pH on adhesive performance. All three variables affected both dry and wet strengths of bonded wood specimens. The optimum operation zone for preparing adhesives with improved water resistance is at a protein concentration of 28% and pH 5.5. Sodium chloride had negative effects on adhesive performance. Soy adhesives modified with 0.5% sodium chloride had dry strength, wet strength, and boiling strength of bonded specimens comparable to nonmodified soy adhesives. Rheological study indicated that soy adhesives exhibited shear thinning behavior. Adhesives modified with sodium chloride showed significantly lower viscosity and yield stress. Sodium chloride-modified soy adhesives formed small aggregates and had low storage moduli, suggesting reduced protein–protein interactions. These formaldehyde-free soy adhesives showed strong potential as alternatives to commercial formaldehyde-based wood adhesives.     

Modification of soy proteins and their adhesive properties on woods

Adhesive properties of trypsin-modified soy proteins (TMSP) on woods were investigated. A simple method developed in our laboratory, consisting of measuring the force required to shear the bond between glued wood pieces in the Instron universal testing machine, was used to examine adhesive strength of modified soy proteins on wood. Adhesive strength of TMSP was measured for cold-pressed (ambient temperature for 2 h) and hot-pressed (60, 80, 100, and 120°C for times varying from 0.5 to 2.5 h) woods. Of the woods examined, soft maple gave the highest strength [743 Newtons (N) at a protein glue concentration of 2 mg/cm²]. For soft maple and cold-pressing, TMSP at 2 mg/cm² gave twice the adhesive strength of unmodified protein controls, 743 vs. 340 N. Also, the adhesive strength of TMSP increased from 284 to 743 N as glue concentration was increased from 1 to 2 mg/cm². However, hot-pressing of wood pieces beyond 1 h at 120°C and 30% relative humidity resulted in decreased adhesive strengths of TMSP compared to controls. Further, adhesive strengths of hot-pressed glued wood samples decreased when the relative humidity at which they were kept for curing increased from 30 to 60%. This negative effect of increased humidity on adhesive strengths of glued wood pieces was not observed with cold-pressed TMSP.     

大豆7S与11S球蛋白尿素变性后的粘接性质研究

随着人们对环境保护意识的增加和地球有限资源的缺乏,大豆蛋白在胶粘剂工业中的应用也越来越显示出强大的吸引力,鉴于前人的研究成果,文章研究了大豆7S和11S球蛋白经过尿素变性后在松木、樱桃木和胡桃木上的粘接强度和湿润能力。结果表明在不同的木块上不同胶粘剂有不同的粘接强度和湿润性能。7S大豆蛋白尿素变性后在硬木上有较好的湿润性。1M尿素变性赋予11S蛋白的粘接强度最高,3M尿素变性后,7S蛋白在硬木上的粘接强度大于11S蛋白。蛋白质的二级结构测量表明β-折叠对于3 M尿素变性后的大豆蛋白在硬木上的粘接强度起着重要作用,而无规则卷曲是降低1 M尿素变性7S大豆蛋白粘接强度的主要因素。     

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.     

Shear strength and water resistance of modified soy protein adhesives

Soy protein polymers recently have been considered as alternatives to petroleum polymers to ease environmental pollution. The use of soy proteins as adhesives for plywood has been limited because of their low water resistance. The objective of this research was to test the water resistance of adhesives containing modified soy proteins in walnut, maple, poplar, and pine plywood applications. Gluing strength and water resistance of wood were tested by using two ASTM standard methods. Glues with modified soy proteins had stronger bond strength than those containing unmodified soy proteins. Plywood made with glue containing urea-modified proteins had higher water resistance than those bonded with glues containing alkali-modified and heat-treated proteins. After three 48-h cycles of water-soaking, followed by 48 h of air-drying, no delamination was observed for either walnut or pine specimens glued with the urea-modified soy protein adhesives. Gluing strength for wood species with smooth and oriented surface structure was lower than for those with rough, randomly oriented, surface structures. Wood species with greater expansion of dimensions during water-soaking had a higher delamination rate than those showing less expansion.     

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.     

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.     

纳米TiO_2在EP中分散性研究

采用不同方法[包括EP(环氧树脂)的pH值调节法、EP中添加改性剂法和改性剂吸附包覆纳米TiO2法等]对纳米TiO2在EP中的分散性进行了研究。结果表明:上述改性方法均能促进纳米TiO2在EP中良好分散:当EP的pH值为3时,相应胶粘剂的剪切强度比pH值未调节体系提高了11.46%;采用EP中添加改性剂法,并且当改性剂为SDBS(十二烷基苯磺酸钠)时,相应胶粘剂的剪切强度比无改性剂体系提高了6.7%;采用改性剂吸附包覆纳米TiO2法,并且当改性剂为SDS(十二烷基磺酸钠)、KH-560(硅烷偶联剂)和SDBS时,相应胶粘剂的剪切强度比无改性剂体系分别提高了41.7%(SDS)、16.4%(KH-560)和9.4%(SDBS)。     

Alkali-modified soy protein with improved adhesive and hydrophobic properties

Adhesive and hydrophobic properties of alkalimodified soy protein (AMSP) and trypsin-modified soy protein (TMSP) on wood were investigated. Modifying soy protein (i) under moderate alkaline conditions (pH 10.0 at 50°C) and (ii) with trypsin, enhanced adhesive strengths (730 and 743 N, respectively) compared with unmodified soy protein (340 N). Hydrophobicities of AMSP, TMSP, and unmodified soy protein isolate by sodium dodecyl sulfate binding and 1-anilino-8-naphthalene sulfonate methods were 7.6, 6.4, 5.0 and 39, 27, 13, respectively. Modified soy protein adhesives with higher hydrophobicities (AMSP and TMSP) had enhanced water-resistance properties.