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.

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.

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.

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.

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.

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。

改性大豆蛋白胶黏剂制备及其应用研究进展

目前人造板生产中大量使用的甲醛基树脂胶黏剂已成为室内甲醛污染的首要来源,极大影响着人们的健康与工作、生活质量。近些年来,大豆蛋白胶黏剂因其无毒、可生物降解、成本低、加工方便等优点,在木材胶黏剂领域受到广泛的关注。然而,相较于目前广泛商用的酚醛树脂、脲醛树脂等商用的醛基胶黏剂,大豆蛋白胶黏剂存在胶合强度低、耐水性和防霉性能差等缺陷。针对上述问题,采用交联改性、共混改性、结构改性、水解酶改性和填充改性等物理化学手段对大豆蛋白胶黏剂进行功能化改性进而提升其性能是目前常用的手段。本文综述了不同的功能改性大豆蛋白胶黏剂的方法,总结了不同改性方法所存在的问题,并对其未来的发展提出展望。

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。

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。

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。

玄武岩纤维改性大豆蛋白胶黏剂性能及胶合机理

为提高大豆蛋白胶黏剂的胶合强度,开发环境友好型木材用生物质胶黏剂,采用玄武岩纤维(basalt fiber,BF)作为增强改性剂,成功制备了胶接性能优良的玄武岩纤维改性大豆蛋白胶黏剂(basalt fiber/soybean protein isolate adhesive,BF/SPIA),并对BF/SPI的胶接强度、流变特性、化学基团及形态结构进行了分析。研究结果表明:随着玄武岩纤维用量的逐步提高,改性大豆蛋白胶黏剂的力学强度呈先增加后下降的趋势。当BF质量分数为5%时,BF/SPIA干、湿状胶接强度分别达2.15和0.92 MPa。流变特性测试结果表明BF/SPI胶黏剂的剪切模量有所增加;傅里叶红外光谱(fourier infrared spectrum,FTIR)显示出改性大豆蛋白胶黏剂中亲水基团降低,Si—O键特征峰明显,BF与大豆蛋白分子间相互作用,形成新的复合结构;扫描电镜(scanning electron microscope,SEM)图谱印证了BF与SPAI两相体系融合性良好,且固化胶接界面较为致密。中试试验结果进一步表明玄武岩纤维改性大豆蛋白胶黏剂具有良好的稳定性,其湿状胶接强度可高达1.05 MPa,木材压缩率仅14.92%,实用性较强。该研究可为改性大豆蛋白胶黏剂的工业化应用及推动环保木材胶黏剂的应用进程提供理论参考。

基于模型化合物的糠醇改性大豆蛋白基胶黏剂机理研究

为了开发真正意义上的环保型大豆蛋白基胶黏剂,该文以糠醇作为交联剂,以组成蛋白质分子的二肽为起点,采用模型化合物思想研究大豆蛋白基胶黏剂的交联改性基础理论,借助核磁共振C谱和电喷雾电离质子仪分析糠醇交联改性大豆蛋白基胶黏剂的机理。同时通过检测大豆蛋白胶胶合板性能,分析大豆蛋白基胶黏剂制备基础理论与实际性能之间的关系。研究结果表明:1)糠醇与丙谷二肽的共缩聚反应和糠醇的自缩聚反应,两者为竞争关系;2)一般碱性条件下,糠醇极其稳定,两者都不明显,只有在强碱性条件下糠醇可能产生活性稍大的酰胺负离子与丙谷二肽发生一定的共缩聚,反应速率较慢,实现共缩聚的时间太长,但自缩聚反应依然不明显;3)糠醇与丙谷二肽的共缩聚反应和糠醇的自缩聚反应都需要较强的酸性,且前者低于后者,酸性太强时糠醇自缩聚占主导,酸性太弱时产生的糠醇碳正离子浓度和反应活性较弱,不利于自缩聚和共缩聚;在pH值为3时,共缩聚表现出较强的竞争性。4)糠醇与丙谷二肽共缩聚反应和糠醇自缩聚反应主要发生在酸性条件下,糠醇与丙谷二肽发生共缩聚反应位点首先是端酰胺基团,其次是伯胺,而肽键氨基由于存在较大的空间位阻导致几乎不参与反应。5)糠醇与大豆蛋白模型化合物反应机理与大豆蛋白基胶黏剂实际性能具有较强的对应性,即在pH值为3时,糠醇与大豆蛋白基胶黏剂反应程度较高,表现为较强的耐水性和热稳定性。该研究工作的开展对实现大豆蛋白基胶黏剂的科学使用,提升大豆蛋白基胶黏剂的市场竞争力具有重要意义。

基于改性大豆蛋白胶黏剂的竹刨花板性能

为了开发生物质胶黏剂及环境友好型竹刨花板,研究了基于十二烷基硫酸钠改性的大豆蛋白胶黏剂施胶量对竹刨花板物理力学性能的影响,结果表明,大豆蛋白胶黏剂的较佳施胶量为13%。通过响应曲面设计研究了热压温度、热压时间和板坯含水率对竹刨花板的力学性能及耐水性的影响,得到最优工艺参数条件为:热压温度175℃,热压时间8.5min,板坯含水率26.0%,在此条件下,静曲强度达16.8MPa,内结合强度达0.65MPa,吸水厚度膨胀率达6.7%。实验室测得竹刨花板物理力学性能指标均达到国家标准。

木材工业用大豆蛋白胶粘剂研究与应用现状

随着木材工业持续快速发展和化石资源的日益枯竭,寻找绿色环保、可再生的木材用胶粘剂已经成木材工业面临的重大课题。从大豆蛋白胶粘剂的产生、发展,大豆蛋白的结构、特性、耐水改性机理、改性方法等几个方面,综述了近年来木材用大豆蛋白胶粘剂的研究进展和发展趋势。

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。

刨花板用大豆蛋白基胶黏剂的研究

为了提高刨花板用大豆Glycine max蛋白基胶黏剂的内结合强度和耐水性,在碱、尿素共同作用的大豆蛋白与酚醛树脂共聚(SPF)反应的基础之上,研究了在共聚之前经过交联的SPF与未经过交联的SPF对刨花板力学性能和吸水厚度膨胀率的影响。结果表明:1共聚之前经过交联的SPF胶黏剂刨花板24 h吸水厚度膨胀率满足国家标准GB/T 4897.3-2003中潮湿环境下的结构用板要求(≤10.0%)。其中,酚醛预聚液作为交联剂,刨花板内结合强度值满足标准中干燥状态下使用的家具及室内装修用板要求(≥0.40 MPa)。2傅里叶变换红外光谱(FT-IR)分析表明,交联剂主要与豆胶的伯胺反应,通过加成反应接到大豆蛋白分子链上。3差示扫描量热法(DSC)分析表明,交联剂与豆胶有比较明显的交联固化峰,交联反应比较理想。

人造板用大豆蛋白胶黏剂研究进展

目前人造板用胶黏剂仍以醛类树脂胶黏剂为主导,存在人居环境甲醛污染和依赖化石资源等问题。随着人们环保意识提高、不可再生资源日益减少以及人造板环保等级要求的不断提升,以生物质资源为原料、水为分散介质的大豆蛋白胶黏剂,作为一种环保、可再生木材胶黏剂显示出巨大的发展潜力,但其耐水胶接性能差等问题仍制约其工业化应用,为木材工业研究热点之一。笔者综述了近年来国内外研究者在提高人造板用大豆蛋白胶黏剂耐水胶接性能方面的研究进展,重点介绍了提高大豆蛋白胶黏剂耐水胶接性能的改性方法,并分析了其改性机制与存在问题,包括蛋白质变性、接枝改性、酶改性、交联改性、大豆多糖改性、仿生改性、纳米材料改性、复合改性等,同时对提高大豆蛋白胶黏剂固体含量、降低黏度、改善抗霉变性能等方面研究进行了综述。探讨了大豆蛋白胶黏剂改性研究方向,并对其科学意义以及应用发展趋势进行了展望,以期为生物质木材胶黏剂的深入研究和在木材工业中的进一步推广应用提供理论与经验指导。

钠基蒙脱土增强豆胶的耐水性研究

钠基蒙脱土(Na-MMT)的加入,提高了大豆蛋白胶黏剂的预压性能、粘接强度和耐水性,当Na-MMT的加入量为大豆分离蛋白的1 wt%时,增强效果最好,可以使杨木胶合板的干强度和Ⅱ类湿强度分别提高20.5%和18.8%;利用XRD、TEM、FTIR、接触角等分析方法研究了Na-MMT增强豆胶耐水性的机理。

PVAc乳胶/改性大豆分离蛋白共混胶黏剂的制备及性能

针对大豆蛋白胶黏剂耐水性差的缺点,用尿素初步改性大豆分离蛋白(SPI),然后与白乳胶(PVAc)共混合成了共混改性大豆分离蛋白胶黏剂。采用正交实验方法考察了大豆蛋白胶与白乳胶质量比、共混时间、交联剂质量分数、交联时间对大豆蛋白胶黏剂剪切粘接强度的影响,确定了优化配比及制备工艺条件,并在此基础上采用正交试验优化了热压参数。结果表明:大豆蛋白胶与白乳胶质量比10∶1,共混时间1h,交联剂质量分数1.0%,交联时间1.5h,热压温度120℃,热压压强1.2MPa,热压时间2min/mm,涂胶量250g/m2时,测得胶黏剂的干态剪切粘接强度为2.01MPa,按照Ⅰ类胶合板标准测得湿态剪切粘接强度为1.04MPa,并对优化配方进行了结构与性能分析。

甲醛和SDBS对碱降解改性大豆蛋白胶的影响

在碱降解改性大豆蛋白胶黏剂的基础上,选取甲醛和十二烷基苯磺酸钠(SDBS)对大豆蛋白胶黏剂进行改性。结果表明,甲醛和十二烷基苯磺酸钠的添加均有助于大豆蛋白胶黏剂耐水性能的提高,但改进效果有限,且对胶合板干状强度的影响趋势不明显。制备胶合板时,甲醛和十二烷基苯磺酸钠改性大豆蛋白胶黏剂及碱降解改性大豆蛋白胶黏剂的热压工艺可以一致。