Development and characterization of a wood adhesive using bagasse lignin

Bagasse is spent fiber left after extraction of sugar. It is mainly used as a fuel to concentrate sugarcane juice. In the present work, the possibility of preparing wood adhesives from bagasse has been explored. The parameters for the preparation of a lignin phenol formaldehyde (LPF) adhesive, (lignin concentration, formaldehyde to phenol molar ratio, catalyst concentration, reaction time and reaction temperature) have been optimized. It was found that up to 50% of phenol can be substituted by bagasse lignin to give LPF wood adhesive having better bonding strength in comparison to a control phenol formaldehyde (CPF) wood adhesive. Prepared resins were characterized using IR, DSC and TGA. IR spectra of LPF resin showed structural similarity with CPF resin. Thermal stability of LPF resin was found to be lower as compared to CPF resin. DSC studies reveal a lower curing temperature for LPF adhesive in comparison to CPF adhesive. A shelf-life study reveals that LPF exhibits consistent behavior as compared to CPF in respect to adhesive strength.     

Development and characterization of a lignin–phenol–formaldehyde wood adhesive using coffee bean shell

In the present study, the possibility of development of a wood adhesive using coffee bean shell lignin (Cbsl) has been explored. Cbsl-modified phenolic adhesive has been prepared by replacing phenol with lignin at different weight percents. The optimization of weight percent lignin incorporation was carried out with respect to mechanical properties. It was found that up to 50 wt% of phenol could be replaced by Cbsl to give lignin–phenol–formaldehyde adhesive (LPF) with improved bond strength in comparison to control phenol–formaldehyde (CPF). Optimized LPF and CPF adhesives were characterized by IR, DSC and TGA. The IR spectrum of LPF showed structural similarity to CPF. Thermal stability of LPF adhesive was found to be lower as compared to that of CPF. DSC studies revealed a higher rate of curing in the LPF adhesive.     

木质素酚醛树脂的固化动力学及机理研究

通过差示扫描量热法（Dsc）和红外光谱（IR）分别研究了木质素酚醛树脂（LPF）的固化动力学及机理。DSC分析表明,LPF的固化反应起始温度比酚醛树脂高,终止温度及活化能比酚醛树脂低,因此,LPF凝胶点比酚醛树脂高,贮存稳定性比酚醛树脂好,固化速度比酚醛树脂快;IR分析表明,LPF的固化机理与酚醛树脂相似,都是羟基之间及羟基与芳环上的氢之间的缩合反应。不同的是LPF固化后仍有部分醚键结构。     

Properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde resin

The aim of this research was to investigate the physical and mechanical properties of plywood panels bonded with ionic liquid-modified lignin–phenol–formaldehyde (LPF) resin. For this purpose, soda bagasse lignin was modified by 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid, and then, various contents of modified lignins (10, 15, and 20 wt%) were added as a substitute of phenol in phenol–formaldehyde (PF) resin synthesis. The properties of the synthesized resin were compared with those of a control PF resin. The changes in curing behavior of the resins prepared were analyzed by differential scanning calorimetry (DSC). The physical properties of the resins prepared, as well as the water absorption, thickness swelling, shear strength, and formaldehyde emission of the plywood panels bonded with these adhesives, were measured according to standard methods. DSC analysis indicated that in comparison with PF resins, curing of the LPF resin occurred at lower temperatures. The physical properties of the synthesized resins indicated that viscosity and solid content increased, while gel time and density decreased by addition of treated lignin to the PF resin. Although the panels containing resins with modified lignin yielded low formaldehyde emission, their dimensional stability was worse than those bonded with a commercial PF adhesive. The plywood prepared using IL-treated lignin PF resins has shear strength, which satisfy the requirements of the relevant standards specifications and significantly better than that of panels prepared with the control PF resin. The mechanical properties of the panels could be significantly enhanced with increased percentage of treated lignin content from 0 to 20 wt%.     

Lignin–phenol–formaldehyde resin adhesives prepared with biorefinery technical lignins

In this study, four biorefinery technical lignins were used to synthesize lignin–phenol–formaldehyde (LPF) resin adhesives with a proposed formulation that was designed based on accurate analysis of the active sites in lignin with ³¹P nuclear magnetic resonance (NMR). The properties of the LPF resin adhesives and the plywoods prepared with them were tested. The structural features and curing behavior of the LPF resin adhesives were thoroughly investigated by solution‐ and solid‐state ¹³C NMR. Results indicated that the proposed formulation exhibited favorable adaptability for all four of these technical lignins for synthesis of LPF resin adhesives. High‐performance plywood with low emissions of formaldehyde could be successfully prepared with the synthesized LPF resin adhesives. All the LPF resin adhesives exhibited similar structure and curing behavior with the commercial phenol–formaldehyde (CPF) resin adhesive. However, the LPF resin adhesives showed relatively higher curing temperatures as compared with the CPF resin adhesive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42493.     

木质素酚醛树脂与木材界面反应的研究

通过差示扫描量热法（DSC）和红外光谱（FTIR）分别研究了木质素酚醛树脂（LPF）与木粉的界面反应的动力学和机理。DSC分析表明,LPF与木粉界面反应的特征温度和活化能均明显低于酚醛树脂（PF）与木粉的界面反应;FTIR分析表明,LPF与木粉界面反应的机理为羟基之间的缩合以及羟基与芳环上氢原子之间的缩合反应,和PF与木粉界面反应机理相似。     

腰果酚制备可发性酚醛树脂的合成工艺研究

以苯酚、腰果酚、甲醛为原料,NaOH为催化剂,乙二醇为助剂,合成了可发性酚醛树脂,通过粘度,固含量,韧性测试研究了原料的配比,腰果酚替代苯酚的比例,催化剂用量,反应时间,反应温度及乙二醇用量对合成树脂性能的影响并通过IR,TG分析对树脂结构及耐热性进行了表征。结果表明,适宜的反应条件为:F/P比(甲醛与总酚物质的量比值)1.6,腰果酚替代量20%,催化剂用量1%,反应时间3 h,反应温度80℃,乙二醇质量分数10%～15%。以腰果酚制备的CPF树脂耐热性变化不明显,拉伸强度为22.34 MPa,断裂伸长率3.08%,冲击强度3.56 kJ/m2,较PF树脂有很大提高。     

麦草碱木素酚化改性及其制备LPF胶粘剂工艺研究

利用碱性条件下酚化改性的麦草碱木素代替部分苯酚制备了高木质素/苯酚比例和胶粘强度高的木质素酚醛树脂(LPF)胶粘剂.利用傅立叶红外光谱(FT-IR)和凝胶色谱(GPC)研究了麦草碱木素在碱性条件下酚化改性前后的结构变化.FT-IR分析表明,麦草碱木素发生了酚化反应,伴随着酯基的断裂和甲氧基的脱落;GPC结果显示,木质素平均分子量降低,分子量分布范围变宽.接着,研究了木质素/苯酚比例、氢氧化钠浓度、甲醛/木质素比例、酚化温度、酚化时间、缩聚温度、缩聚时间等反应工艺参数对LPF胶粘剂性能的影响,优化了麦草碱木素酚化改性制备LPF胶粘剂的反应工艺参数.最后,比较了反应工艺参数优化的LPF胶粘剂与传统PF胶粘剂的各项性能,结果显示,麦草碱木素酚化改性后代替70 % 的苯酚制备得到的LPF胶粘剂的胶粘强度与传统PF胶粘剂相近.     

Use of a methylolated softwood ammonium lignosulfonate as partial substitute of phenol in resol resins manufacture

The synthesis of lignin‐phenol‐formaldehyde (LPF) was studied to determine its optimum operating conditions. The lignin proposed as phenol substitute has been the softwood ammonium lignosulfonate. The resin synthesis was optimized by varying the methylolated lignosulfonate content, 18–52%; the sodium hydroxide to phenol‐modified lignosulfonate molar ratio, 0.3–0.94; and the formaldehyde to phenol‐modified lignosulfonate molar ratio, 1.1–3.5. The parameters employed in the characterization of LPF resins were free phenol, free formaldehyde, gel time, alkaline number, viscosity, pH, solid content, and chemical structure changes. The properties of LPF resin comply with the requirements for its utilization in plywood manufacture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 643–650, 2004     

木质素酚醛树脂胶粘剂黏度的研究

木质素胶粘剂高黏度的特征阻碍了其工业化应用,该文考察了木质素酚醛树脂(LPF)胶粘剂的pH、质量分数、氯化钠与尿素的加入、贮存时间等因素对其黏度的影响,作为对比,同时测试了这些因素对酚醛树脂胶粘剂和麦草碱木素(WSSL)碱性溶液黏度的影响。结果表明,LPF胶粘剂的黏度随着尿素的加入降低,而随着其质量分数的增加、pH的降低、氯化钠的加入急剧升高,并分别在w(LPF)=30.0%、pH=10.2、w(NaCl)=8.3%处有一个转折点;LPF胶粘剂的黏度曲线与WSSL碱性溶液相似,而与酚醛树脂胶粘剂相差较大;要制得高含量的LPF胶粘剂,其pH应大于10.2,w(NaCl)<8.3%,并且w(尿素)=2%～3%。     

Thermoplastic and moisture-dependent behavior of lignin phenol formaldehyde resins

Bonding kinetics of thermosetting adhesives is influenced by a variety of factors such as temperature, humidity, and resin properties. A comparison of lignin-based phenol formaldehyde (LPF) and phenol formaldehyde (PF) adhesive in terms of reactivity and mechanical properties referring to testing conditions (temperature, moisture of specimen) were investigated. For this purpose, two resins were manufactured aiming for similar technological resin properties. The reactivity was evaluated by B-time measurements at different temperatures and the development of bonding strength at three different conditions, testing immediately after hot pressing, after applying a cooling phase after hot pressing, or sample conditioning at standard climate. In addition, the moisture stability of the two fully cured resins was examined. The calculated reactivity index demonstrated that LPF requires more energy for curing than PF. Further results indicate that lignin as substituent for phenol in PF resin has a negative impact on its moisture resistance. Additionally, the known thermoplastic behavior of lignin could also be detected in the behavior of the cured resin. This behavior is relevant for the adhesive in use and necessitates a cooling phase before testing the bonding strength development of lignin-based adhesive systems. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48011.     

木素基酚醛树脂胶粘剂的应用性能研究

采用热化学酚化技术活化木素得到木素酚化产物,以酚化产物代替苯酚制备低成本的木素酚化液基酚醛树脂(LPF)胶粘剂。采用红外光谱(FT-IR)对LPF和传统PF的结构进行了表征,通过对比试验分析了LPF的应用性能,并对LPF胶粘剂应用性能产生的机理作了一定的探讨。结果表明:酚化后的木素参与了LPF胶粘剂的合成,并具有新的不同取代基的苯环结构;LPF胶粘剂与传统酚醛树脂(PF)胶粘剂具有相似的应用性能,前者比后者具有更低的游离酚(醛)含量(游离酚<0.12%,游离醛<0.08%)、更快的干燥速率和更低的施胶量(固含量29%时施胶量为297g/m2);另外,LPF胶粘剂具有优异的胶合性能(达到了Ⅰ类胶合板的标准要求)和储存稳定性,完全满足高性能环保型胶粘剂的使用要求。     

Microwave‐assisted hydrothermal liquefaction of lignin for the preparation of phenolic formaldehyde adhesive

This study aimed to produce phenolic formaldehyde (PF) adhesives using the liquefaction product of bagasse lignin (LPBL) as a partial substitute for petroleum‐based phenol. Lignin was extracted from bagasse using 93% acetic acid solution and was rapidly degraded in hot‐compressed water by microwave heating using oxalic acid as catalyst. The liquefaction yield reached 78.69% under the optimal reaction condition. Gas chromatography–mass spectrometry (GC/MS) analysis showed that the main chemical compounds of the liquefaction product included mono‐substituted and bis‐substituted phenols, such as 2,6‐dimethoxyphenol, 4‐hydroxybenzaldehyde, and so on. The LPBL was employed to replace a portion of phenol at varying ratios from 0 to 20 wt % in the preparation of PF adhesives. The molecular weight, viscosity, and adhesive strength of LPBL‐PF adhesives were found to be lower than those of pure PF adhesives. With the phenol replaced by LPBL up to 20%, the viscosity and adhesive strength of the resin were 4.046 Pa s and 1.017 MPa, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44510.     

Replacing 100% of phenol in phenolic adhesive formulations with lignin

Lignin, produced as a byproduct of pulp and paper and bioethanol industries, is a polyphenolic compound that has excellent potential to be used as phenol replacement in phenolic adhesive formulation. In this study, the phenol portion of phenol formaldehyde (PF) resin has been replaced by an agricultural‐based lignin, which was produced as a byproduct of a cellulosic bioethanol process through dilute‐acid pretreatment and enzymatic hydrolysis from corn stover. The PF resol resin was formulated using isolated lignin under alkaline condition. Chemical, physical, and thermal properties of the isolated lignin, PF resin and adhesive were measured using advanced analytical techniques such as Fourier transformed infrared spectroscopy (FTIR), size exclusion chromatography (SEC), phosphorous nuclear magnetic resonance spectroscopy (³¹P NMR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The developed 100% lignin‐based adhesive and a commercially formulated phenol resorcinol formaldehyde (PRF, as reference) were used to prepare single‐lap‐joint samples for mechanical testing. The plywood samples were pressed under exactly the same conditions (time, temperature, and pressure) as what recommended for the commercial PRF formulation. According to two‐way ANOVA results, statistically there was no significant difference between the shear strengths of plywood samples made with 100% lignin‐based adhesive and those made with the commercial PRF resin. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45124.     

Properties of phenol‐formaldehyde resins prepared from phenol‐liquefied lignin

In this study, alkaline lignin (AL), dealkaline lignin (DAL), and lignin sulfonate (SL) were liquefied in phenol with sulfuric acid (H₂SO₄) or hydrochloric acid (HCl) as the catalyst. The phenol‐liquefied lignins were used as raw materials to prepare resol‐type phenol‐formaldehyde resins (PF) by reacting with formalin under alkaline conditions. The results show that phenol‐liquefied lignin‐based PF resins had shorter gel time at 135°C and had lower exothermic peak temperature during DSC heat‐scanning than that of normal PF resin. The thermo‐degradation of cured phenol‐liquefied lignin‐based PF resins was divided into four temperature regions, similar to the normal PF resin. When phenol‐liquefied lignin‐based PF resins were used for manufacturing plywood, most of them had the dry, warm water soaked, and repetitive boiling water soaked bonding strength fitting in the request of CNS 1349 standard for Type 1 plywood. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

丙二酸二乙酯改性酚醛树脂胶粘剂的制备与性能研究

以甲醛和苯酚为主要原料、丙二酸二乙酯为改性剂,制备碱催化水溶性酚醛树脂(PF)胶粘剂;采用DMA(动态力学分析)法、DSC(差示扫描量热)法、FT-IR(红外光谱)法和TGA(热失重分析)法等对改性PF的性能进行了表征。结果表明:适量改性剂的引入,能有效提高改性PF胶粘剂的韧性,但其固化温度和胶合板的胶接强度下降;当w(改性剂)=0.015%(相对于苯酚质量而言)时,改性体系的固化温度下降了4℃,相应胶合板的胶接强度(>0.80 MPa)仍满足GB/T 9846—2004标准中I类胶合板的指标要求。     

棉秆焦油替代苯酚合成酚醛树脂胶粘剂的研究

采用气/质联用仪(GC/MS)对棉秆焦油的成分进行了分析,确定了62种化合物,其中酚类化合物的相对含量为25.755%。用棉秆焦油部分替代苯酚合成酚醛树脂(PF)胶粘剂,并对其性能进行了研究。实验结果表明,棉秆焦油替代量对所合成的PF胶粘剂的粘度和胶合强度等性能影响较大;当m(棉秆焦油)=25g(即苯酚替代量达到19.2%)时,所制得的PF胶粘剂的粘度适中、w(游离甲醛)<0.5%,具有较高的胶合强度,并且胶合强度达到GB/T9846-2004标准中对Ⅰ类胶合板的要求。由于棉秆焦油的加入降低了PF胶粘剂的成本,因此,该PF胶粘剂具有良好的应用前景。     

Environmentally friendly mixed tannin/lignin wood resins

We obtained lignin‐based wood adhesives satisfying the requirements of relevant international standards for the manufacture of wood particleboard. These were based on two different low‐molecular‐mass lignins. These lignin‐based wood adhesives did not use any formaldehyde in their formulation; formaldehyde was substituted with a nonvolatile nontoxic aldehyde, namely, glyoxal. The last formaldehyde present, contributed by a fortifying synthetic phenol–formaldehyde resin, was also eliminated by the substitution of the phenol–formaldehyde resin with a natural, vegetable polyflavonoid tannin extract to which no aldehyde was added. This substitution brought the total content of natural material up to 80 wt % of the total adhesive. The adhesives yielded good internal bond strength results of the panels, enough to pass relevant international standard specifications for interior‐grade panels. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Lignin-modified phenolic resin: synthesis optimization,adhesive strength,and thermal stability

Lignin-modified phenolic resin has been prepared by replacing phenol with lignin at different weight percentages. The resin synthesis was optimized by varying the molar ratio of phenol to formaldehyde, the concentration of sodium hydroxide, and the reaction time by measuring parameters such as the gelation time, flow time, solids content, pH, and specific gravity. The thermal stability of lignin-modified phenolic resin was studied by DSC, TGA, and isothermal analysis, and it was found that lignin-modified phenolic resin is thermally more stable than pure phenolic resin. The adhesive strength of lignin-modified phenolic resin was determined by the lap-shear method, which showed that the lignin-modified resin retains 78% of the adhesive strength for wood-wood systems and 86% of the adhesive strength for Al-Al systems.     

Kraft lignin in phenol formaldehyde resin. Part 1. Partial replacement of phenol by kraft lignin in phenol formaldehyde adhesives for plywood

The objective of this study was to investigate the potential for partially replacing phenol with kraft lignin in the phenol formaldehyde (PF) resin designed for application as an adhesive in the production of plywood. The kraft lignin, considered to be an environmentally friendly alternative to phenol, was precipitated from black liquor recovered from kraft pulping of softwood. Kraft lignin phenol formaldehyde (KLPF) resin was prepared in a one-step preparation with different additions of lignin. Replacing 50 wt% of the phenol with kraft lignin (50KLPF) was, under the conditions used, considered to be optimal with respect to resin viscosity, storage stability, and bonding ability. The resin consists of an integrated kraft lignin-phenol network. The hot-pressing time in the plywood manufacturing had to be increased by approximately 30% at 150°C for the 50KLPF resin compared with that normally used for PF resin, in order to comply with plywood standard demands. The mechanical properties of test samples made from KLPF resins were equal to or better than those of test samples made from PF resin only.