Crosslinking Mechanism of Soy Protein-based Adhesives based on Glyoxal and a Compound of Protein Model

The crosslinking mechanism of glyoxal and asparagine was analyzed,and the relationship between the mechanism and practical performances of soy protein-based adhesives was also discussed.It is shown that when pH=1 and 3,glyoxal reacted with asparagine in the form of major cyclic ether compounds.When pH=5,glyoxal reacted with asparagine in two structural forms of sodium glycollate and cyclic ether compounds.However,amidogens of asparagine were easy to develop protonation under acid conditions.Supplemented by the instability of cyclic ether compounds,the reaction activity and reaction degree between glyoxal and asparagine were relatively small.Under alkaline conditions,glyoxal mainly reacted with asparagine in the form of sodium glycollate.With the increase of pH,the polycondensation was more sufficient and the produced polycondensation products were more stable.The reaction mechanism between glyoxal and asparagine had strong correspondence to the practical performances of the adhesives.Glyoxal solution could develop crosslinking reactions with soy protein under both acid and alkaline conditions.Bonding strength and water resistance of the prepared soy protein-based adhesives were increased significantly.When pH>7,glyoxal had relatively high reaction activity and reaction intensity with soy protein,and the prepared adhesives had high crosslinking density and cohesion strength,showing relatively high bonding strength,water resistance and thermal stability.

Study on the Soy Protein-Based Adhesive Cross-Linked by Glyoxal

Based on the ESI-MS and ^(13)C-NMR analysis of the forms of glyoxal in acidic and alkaline solutions,the soy-based adhesive cross-linked by glyoxal was prepared in this work.The results showed that glyoxal existed in water in different forms at different pH levels.Under alkaline conditions,glyoxal transformed to glycolate through the intramolecular disproportionation reaction.Under acidic conditions,although some of glyoxal transformed to glycolate as what happened under alkaline conditions,most of glyoxal molecules existed in the form of fiveor six-membered cyclic ether structure.No ethylene tetraol or free aldehyde group was actually detected under these conditions.Although glyoxal reacted with soy protein under both acidic and alkaline conditions,alkaline conditions were more favorable for the improvement of mechanical performance and water resistance of soybased adhesives than acid conditions.

MALDI ToF Investigation of the Reaction of Soy Protein Isolate with Glutaraldehyde for Wood Adhesives

Soy protein adhesives are currently a hot research topic in the wood panels industry for the abundant raw material reserves,reasonable price and outstanding environmental features.But their poor water resistance,low bonding strength and intolerance to mold are major drawbacks,so that proper modification before use is essential.Glutaraldehyde is one of the more apt cross-linking agents for soybean protein adhesives,which can effectively improve the bonding strength and water resistance of the adhesive.Equally,glutaraldehyde is also an efficient and broad-spectrum fungicide that can significantly improve the anti-fungal properties of a soy protein adhesive.In the work presented here,matrix assisted laser desorption ionization(MALDI-ToF)mass spectrometry and Fourier transform infrared spectroscopy techniques were used to analyze the reaction mechanism of glutaraldehyde cross-linking soybean protein.The results confirmed the reaction of the aldehyde group with amino groups of the side chains and the amide groups of the peptide linkages constituting the skeletal chain of the protein.The laboratory plywood and particleboard bonded with glutaraldehyde-soy bean protein adhesives were prepared to determine the adhesive bonding properties,the dry strength,24 h cold water soaking wet strength and 3 h hot water(63°C)wet strength of plywood were 2.03,1.13 and 0.75 MPa,respectively,which satisfied the requirements of industrial production.

Soy Protein Isolate Non-Isocyanates Polyurethanes(NIPU)Wood Adhesives

Soy-protein isolate(SPI)was used to prepare non-isocyanate polyurethane(NIPU)thermosetting adhesives for wood panels by reacting it with dimethyl carbonate(DMC)and hexamethylene diamine.Both linear as well as branched oligomers were obtained and identified,indicating how such oligomer structures could further cross-link to form a hardened network.Unusual structures were observed,namely carbamic acid-derived urethane linkages coupled with lactam structures.The curing of the adhesive was followed by thermomechanical analysis(TMA).It appeared to follow a two stages process:First,at a lower temperature(maximum 130℃),the growth of linear oligomers occurred,finally forming a physically entangled network.This appeared to collapse and disentangle,causing a decrease of MOE,as the temperature increases.This appears to be due to the ever more marked Brownian movements of the linear oligomer chains with the increase of the temperature.Second,chemical cross-linking of the chains appeared to ensue,forming a hardened network.This was shown by the thermomechanical analysis(TMA)showing two distinct MOE maxima peaks,one around 130℃ and the other around 220℃,with a very marked MOE decrease between the two.Plywood panels were prepared and bonded with the SPI-NIPU wood adhesive and the results obtained are presented.The adhesive appeared to pass comfortably the requirements for dry strength of relevant standards,showing to be suitable for interior grade plywood panels.It did not pass the requirements for wet tests.However,addition of 15%of glycerol diglycidyl ether improved the wet tests results but still not enough to satisfy the standards requirements.

A Soy Protein-Based Composite Film with a Hierarchical Structure Inspired by Nacre

Soy protein-based composite film is a potential replacement for petroleum-based film with multipurpose applica-tions and cleaner production.It is difficult to improve both the tensile strength and toughness of a protein-based film without sacrificing its elongation.In this study,inspired by the hierarchical structure of nacre,a facile yet delicate strategy was developed to fabricate a novel bio-based film with excellent toughness and high strength.Triglycidylamine(TGA)crosslinked soy protein(SPI)as hard phase and thermoplastic polyurethane elastomer(TPU)as soft phase comprise an alternative lay-up hierarchical structure.The interface of these two phases is enhanced using triglycidylamine(TGA)surface-modified TPU(MTPU).The tensile strength of SPI/MTPU/TGA films increases by 392%to 7.78 MPa and their toughness increases by 391%to 8.50 MJ/m^(3) compared to soy protein/glycerol film.The proposed hierarchical structure can also be extended to other high-performance materials and polymers.

Sustainable Raw Materials in Hot Melt Adhesives: A Review

Hot-melt (HM) adhesives offer advantages over their contemporary water-based and solvent-based adhesives like low volatile organic compounds (VOCs), 100% solid, fast drying, setting etc. In recent years, to reduce their dependence on dwindling petroleum resources and due to the enormous use of HM adhesives in packaging areas that demand 100% recyclability, efforts have been devoted to making these formulations completely bio-based, sustainable and biodegradable. In this attempt, research and developments have been focused on using starch, modified starch, soy protein, polylactides, polyamides, lignin and vegetable oils as a partial/fully replacement to the petrochemical-based polymers. The huge amount of research going on in the field of bio-based polymers has still not reached its complete potential in the field of HM adhesives. In this review paper, HM adhesives based on sustainable raw materials namely starch, modified starch, polyamides, poly (lactic acid), soy protein and lignin are discussed.

尿素-乙二醛树脂改性大豆蛋白胶黏剂的制备及性能研究

以尿素-乙二醛(UG)树脂和大豆分离蛋白(SPI)为主要原料制备大豆蛋白胶(SUG),并对其固体含量、黏度、表面张力系数、接触角及胶合性能进行测试;利用XPS、FT-IR和^(13)C NMR对合成的SUG的结构进行表征;采用DSC及DMA对SUG的固化性能进行测定。研究结果表明:改性后大豆蛋白胶的固体含量、黏度、表面张力系数及接触角随着SPI添加量的增加而增大,其中黏度的变化最显著;合成大豆蛋白胶中主要含有C—C、C—O—C、C=O、C=N、C=O等官能团;结合^(13)C NMR及FT-IR分析结果,可以得出UG树脂与SPI二者之间产生了交联;当SPI用量为30 g,UG树脂用量为50 g时,制备的大豆蛋白基胶黏剂性能较佳且固化后储能模量较大,为4082 MPa,在160和180℃热压温度下制备的胶合板冷水24 h湿强度分别为1.23和1.48 MPa,热水3 h湿强度分别为1.05和1.22 MPa,远大于国家标准GB/T 9846—2015对II类胶合板的要求,且具备一定的耐沸水性能。

大豆蛋白胶黏剂低黏化改性研究进展

大豆蛋白胶黏剂以植物蛋白质大分子为主要原料,自身存在相对分子质量大、黏度高、流动性差等突出问题,同时大豆蛋白质分子结构复杂、空间位阻大,大量的高活性基团和疏水性基团被复杂大分子链段包裹遮蔽,导致大豆蛋白胶黏剂在木材表面涂布性能差、胶层界面分布不均、耐水胶合强度低,阻碍了其工业化推广和应用。文中探究了造成大豆蛋白胶黏剂高黏度的分子及超分子结构机理,并综述了国内外研究人员针对降低大豆蛋白胶黏剂黏度的最新进展。通过以物理改性、化学改性和生物改性分类归纳,发现通过改变大豆蛋白的二、三、四级结构,对复杂分子结构进行疏解,可有效降低大豆蛋白胶黏剂的黏度、延长储存期、改善界面涂布性能、提高胶合强度。

缩合单宁-PEI改性大豆蛋白胶黏剂制备及性能研究

以脱脂豆粕为原料,以环氧类树脂为交联剂,并用聚乙烯亚胺(PEI)改性缩合单宁为增强剂制备大豆蛋白基木材胶黏剂,探究缩合单宁与PEI添加比例对胶合板胶合强度的影响,并对改性后大豆蛋白胶黏剂的微观形貌、热稳定性等进行表征和分析,探讨缩合单宁改性大豆蛋白胶黏剂的增强机理。结果表明:当胶黏剂体系中缩合单宁与PEI的质量比为2∶1时,胶合板的耐水胶合强度为1.06 MPa,与未改性的相比提高了360.8%,满足GB/T 9846—2015Ⅱ类板指标要求。该胶黏剂原料为可再生资源,且具有良好的耐水性,具有工业应用的潜力。

植物油料蛋白木材胶黏剂改性的研究进展

植物油料蛋白胶黏剂具有来源广泛、无毒、可再生及制备简单等优点,但胶接强度低、耐水性能差、易霉变等问题限制了其发展和应用。综述了近年来几种主要植物油料蛋白胶黏剂如大豆蛋白胶黏剂、花生蛋白胶黏剂、棉籽蛋白胶黏剂等在木材行业的研究和应用现状,重点阐述了提高植物油料蛋白胶黏剂耐水性能的改性方法,包括物理改性、变性剂改性、接枝改性、交联改性、仿生改性、酶改性、纳米材料改性、复合改性等,指出了植物油料蛋白胶黏剂存在的问题,并对未来发展方向和应用前景进行了展望。

脱脂大豆蛋白/蔗糖-磷酸二氢铵胶黏剂的合成工艺研究

以脱脂大豆蛋白(defattedsoyprotein,DSF)、蔗糖(Sucrose)、磷酸二氢铵(ammonium dihydrogen phosphate,ADP)为主要原料,制备一种新型大豆蛋白-蔗糖基胶黏剂(DSF/SADP),探讨固体物质质量分数、脱脂大豆蛋白与蔗糖-磷酸二氢铵糖液的质量比、合成温度及合成时间对胶黏剂胶合强度的影响,分析胶黏剂的热固化行为与固化机理。在胶黏剂的优化合成工艺:固体物质质量分数70%、脱脂大豆蛋白与蔗糖-磷酸二氢铵溶液质量比1∶4、合成温度70℃、合成时间3h的条件下,热压温度为170℃,热压时间为7min时,制备三层胶合板的湿胶合强度为0.99MPa。胶黏剂不溶解率、热重分析和差示扫描量热分析的结果显示,DSF/SADP胶黏剂在热降解过程中可能伴随着缩聚反应的发生;红外光谱测试和微观形貌观察结果显示,5-羟甲基糠醛或其衍生物参与交联反应,形成的C-O-C是固化后聚合物的主要连接键;加入DSF的胶黏剂固化后表面孔洞直径减小,表面更加致密。

Preparation and Properties of Plywood Adhesives with Soy Protein Isolate Modified by SDS

The effects of mass concentration,the reaction temperature and the reaction time of soy protein isolate(SPI) and sodium dodecyl sulfate (SDS) on the adhesive strength of the modified SPI adhesives has been studied through orthogonal experiments.And the adhesive mechanism of the modified SPI adhesives was discussed.The results show that the optimum formula conditions are as follows:mass concentration of SPI was 14%,that of SDS 1%,reaction temperature 35℃and the reaction time 3 h.Under the optimum conditions, the dry adhesive strength of the modified SPI adhesives was 1.82 MPa,the wet adhesive strength was 0.82 MPa,the viscosity was 5.8 Pa·s,the solid content was 12.96%.After SDS was added into SPI, the composites of SDS-SPI were formed,the internal hydrophobic groups among the SPI molecule structure were turned out and the water resistance of the modified SPI adhesives was enhanced with an increase of the modification time.When the concentration of SDS was over a defined value,the disulfide bond was broken and the modification effect of SDS went bad.

大豆蛋白基胶黏剂的研究进展

针对大豆蛋白基胶黏剂的耐水和胶接性能的改性方法,进行了系统性总结,主要有化学改性、物理改性、防霉改性、热压参数对胶黏剂性能影响。同时指出大豆蛋白胶黏剂存在的问题,对其未来相关研究展望。

大豆蛋白作为胶粘剂应用的研究进展

大豆蛋白作为胶粘剂应用的改性方法有盐、硫化物、碱、胰蛋白酶、尿素、盐酸胍、SDS、SDBS、酰化和磷酸化法。简述了改性大豆蛋白作为胶粘剂的研究现状以及改性后的大豆蛋白应用在木板上的胶粘特性的变化情况。大豆蛋白经改性后其胶粘特性有所变化,变化情况受改性剂浓度的影响,改性后蛋白质的部分二级结构展开,胶粘强度提高,同时改性可以暴露出包埋在蛋白质内部的疏水基团,提高大豆蛋白胶粘剂的耐水性。

胶合板用SDS改性大豆分离蛋白胶粘剂的制备及性能

采用正交试验方法研究了大豆分离蛋白(SPI)及十二烷基磺酸钠(SDS)质量浓度、反应温度、反应时间对胶粘剂粘接强度的影响;并对改性产物的机理进行了探讨。结果表明:SDS改性大豆分离蛋白胶粘剂最佳工艺条件为:14%SPI、1%SDS、反应温度35℃、反应时间3 h,并测得该胶的干态粘接强度为1.82 MPa,湿态粘接强度为0.82 MPa,粘度为5.8 Pa.s,固含量为12.96%。大豆分离蛋白分子经SDS改性后形成了SDS-SPI复合物,使包围在内部的疏水性基团转而向外,改性时间增加,其耐水性增加;SDS超过某浓度后,二硫键断裂增加,改性效果变差。

大豆异黄酮对大鼠实验性粥样硬化动脉壁内粘附分子基因表达的影响

为研究大豆异黄酮在动脉粥样硬化发生过程中与细胞间粘附分子 1和血管细胞粘附分子 1基因表达之间的关系。将 60只大鼠按总胆固醇含量随机分为 6组 ,分别喂饲基础饲料、高脂饲料、高脂饲料加不同剂量大豆异黄酮和高脂饲料加设雌激素。 2 0周后处死动物 ,光学显微镜检测HE染色的主动脉壁横切面病理改变 ,免疫组织化学和Western blot法检测血管壁内细胞间粘附分子 1和血管细胞粘附分子 1蛋白 ,并运用计算机图像分析系统进行组间分析比较。结果发现 ,大鼠主动脉粥样斑块中 ,细胞间粘附分子 1和血管细胞粘附分子 1基因表达明显增加 ,大豆异黄酮可以减轻高脂饲料诱导的主动脉病理变化 ,减弱细胞间粘附分子 1和血管细胞粘附分子 1基因在主动脉内的表达。此结果提示 ,大豆异黄酮具有抗动脉粥样硬化形成作用 。

十二烷基硫酸钠对大豆基木材胶黏剂的改性作用

采用10.0g·kg-1的十二烷基硫酸钠(SDS)改性质量分数为250.0g·kg-1的大豆粉浆液,制成SDS改性大豆基木材胶黏剂(SF),运用单因素和正交试验法考察了pH值、反应温度和反应时间对改性SF胶耐水胶合强度的影响。试验结果表明,SDS改性大豆基木材胶黏剂的最佳工艺:pH8,反应温度35℃,反应时间4h。改性后的SF胶Ⅱ类耐水胶合强度为0.70MPa。由红外光谱分析可知,SDS改性使大豆蛋白质分子大量的非极性基团外露,增加了蛋白质分子的疏水性,提高了改性SF胶的耐水胶合强度。

稳定剂对大豆蛋白基胶黏剂性能的影响

本研究首先选用Na OH对大豆蛋白进行降解处理,研究了降解处理条件对降解产物黏度和甲醛反应能力的影响。在Na OH降解大豆蛋白基础之上,再选用甲醛、乙二醛、戊二醛稳定降解的大豆蛋白液,并制备刨花板,同时对刨花板相关性能进行研究。研究结果表明:(1)大豆蛋白最佳降解工艺为加碱量9%,处理温度90℃,处理时间3 h。(2)甲醛、乙二醛、戊二醛都能显著提高豆胶的储存稳定性,甲醛稳定蛋白液效率高,固化反应活化能低,刨花板内结合强度最高,考虑到甲醛稳定剂的毒性,应尽量减少使用;乙二醛稳定蛋白液效率高,固化反应活化能高,刨花板内结合强度最低,所以不适合做蛋白质降解液的稳定剂;戊二醛稳定蛋白液效率不高,固化反应活化能低,刨花板内结合强度基本达标,适合做蛋白质降解液的稳定剂,刨花板的性能可以通过改进后期的稳定工艺或优选交联剂加以改性。

戊二醛改性提高大豆胶粘剂耐水性能

以脱脂大豆粉(SF)为原料,选用十二烷基硫酸钠(SDS)和戊二醛(GA)作为改性试剂,制备出具有较好耐水性能的木材用胶粘剂,并应用于杨木胶合板,分别研究了pH值、戊二醛用量、反应时间以及最终改性胶粘剂贮存时间对耐水胶合性能及表观粘度的影响,并采用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)和傅立叶变换红外光谱(FT-IR)分析手段探讨了改性胶粘剂耐水性能增强机理。结果表明:较佳合成工艺为:pH值为12.0,GA添加量0.80wt%(基于脱脂豆粉质量),反应时间1.0 h,反应温度30.0℃。按照GB/T 9846-2004胶合板中Ⅱ类板标准检测,耐水胶合强度可达0.68MPa。SDS-PAGE谱图说明蛋白质分子间形成化学键交联,FT-IR分析表明有环状吡啶结构生成,这些可能是改性胶粘剂耐水性能提高的原因。

大豆蛋白胶粘剂的化学改性研究进展

由于石油危机和环境污染,传统的甲醛胶粘剂受到了严峻挑战,用天然可再生物质制取环保、绿色胶粘剂已成为趋势。文章就大豆蛋白胶粘剂性能、化学改性方法及其在环保型胶粘剂的应用前景进行全面描述。