尿素对木质素酚醛树脂胶粘剂性能的影响

考察了尿素对木质素酚醛树脂(LPF)胶粘剂性能的影响,结果表明,在LPF胶粘剂中加入质量分数2%~3%(以总溶液质量为基准,下同)尿素后,胶粘性能明显提高,胶粘强度由2.02 MPa提高到2.21 MPa,游离甲醛质量分数由0.16%降至0.05%,黏度由858 mPa.s降低至306 mPa.s。红外光谱分析表明,尿素与LPF胶粘剂中的游离甲醛反应生成了脲醛树脂,在固化过程中脲醛树脂的羟基与LPF胶粘剂的羟基发生缩合反应,提高了LPF胶粘剂的胶粘强度。     

木质素酚醛树脂胶粘剂

<正>广东食品药品职业学院与华南理工大学协作,通过控制木质素酚醛树脂在胶粘剂中的用量、pH值、NaCl(低于8.3%)和尿素(2%~3%)等,可制备出一种高固含量的木质素酚醛树脂胶粘剂。该胶粘剂除了能保持原有的高     

苯酚处理液体木质素改性酚醛树脂胶粘剂的制备及性能表征

在碱性条件下,液体木质素先经苯酚处理后替代部分苯酚对酚醛树脂进行改性,制备得到液体木质素改性酚醛树脂(LPF)胶粘剂。考察了催化剂用量(苯酚处理木质素时氢氧化钠用量)、苯酚与甲醛(P/F)的物质的量之比、聚合温度、聚合时间对LPF胶粘剂性能的影响。研究结果表明:当催化剂用量3%、n(苯酚)∶n(甲醛)=1∶1.975、聚合温度90℃、聚合时间50 min时,所制备的LPF胶粘剂的干湿胶合强度分别为3.15、1.46 MPa,较未经改性的PF胶粘剂分别提高了17.5%、8.1%,游离苯酚的含量降低至0.62%;LPF胶粘剂的游离甲醛含量为0.22%,固体含量为52.8%,黏度为125 mPa·s。红外分析结果表明,苯酚处理后的木质素可以代替苯酚与甲醛发生反应生成新的物质,该物质有可能与PF胶粘剂发生接枝共聚产生新的醚键桥接,由此也说明在制备LPF胶粘剂过程中木质素发生了化学反应。     

碱性酚化木质素结构表征及在酚醛树脂中的应用研究

采用碱催化酚化改性的方式,增加木质素反应活性位点含量,提高木质素-酚醛树脂木材胶粘剂的反应活性,同时降低树脂中无机盐的含量.将甲醛溶液分三批加入酚化木质素溶液,并在第二批加入的同时加入30％质量分数的氢氧化钠溶液,甲醛加入并反应一定时间后加入尿素,自然降温至40℃以下出料,即得碱性酚化木质素改性酚醛树脂.为证明碱性酚化...     

基于橡塑发泡材料生产过程中挥发气体冷凝料调制酚醛胶粘剂的研究

以橡塑发泡材料生产过程中挥发气体冷凝料作为(PF)酚醛树脂胶粘剂的改性剂,合成了LPF(改性酚醛树脂胶粘剂),并对LPF与PUF(尿素改性的酚醛树脂胶粘剂)的pH、固含量、凝胶时间、力学、热稳定性进行分析对比。研究结果发现:当n(酰胺)=0.7(相对于橡塑冷凝料总物质的量而言),LPF比PUF力学性能更优异,剪切强度达到30.85 MPa;LPF比PUF的开始分解温度高20℃。试验结果表明橡塑冷凝料在制备水溶性PF中可以替代尿素,实现工业废料的再利用。     

三步共聚法制备木质素基酚醛树脂胶粘剂

利用木质素部分替代苯酚,三步共聚制备了木质素基酚醛树脂胶粘剂(LPF),研究了碱浓度、醛酚比、木质素添加量对LPF的粘度、固含量、游离甲醛含量、游离苯酚含量和胶合强度的影响,并采用FT-IR、13C-NMR和TG对LPF官能团结构和热固化特性进行了表征。结果表明:采用三步共聚法分步加入甲醛溶液,更有利于羟甲基化反应和后续的缩聚反应,并且可操作性好。胶粘剂的最优制备工艺为:碱的质量分数15%(以木质素和苯酚总质量为基准);醛、酚物质的量比2.0∶1;木质素添加量为苯酚物质的量分数30%。制得的LPF胶粘剂的粘度为183.2 mPa·s,固体质量分数45.05%,游离甲酵质量分数0.22%,胶合强度0.85 MPa,均达到GB/T 14732—2006要求。木质素的添加还改善了酚醛树脂的热固化特性。     

木质素改性脲醛树脂胶粘剂合成工艺及性能研究

以木质素作为改性剂,采用正交试验法探讨了n(甲醛)∶n(尿素)、木质素加入量和木质素加入时间对UF(脲醛树脂)胶粘剂的游离甲醛含量和胶接强度的影响,并优选出制备改性UF胶粘剂的最佳工艺条件。结果表明:当n(F)∶n(U)=1.6∶1、w(木质素)=40%(相对于尿素质量而言)和前期加入木质素时,UF胶粘剂的游离甲醛含量(0.052 8%)满足室内装饰装修材料用胶粘剂中有害物质限量要求(GB 18583—2001)、胶接强度为6.65 MPa且耐水性明显提高。     

尿素和MgO改性木质素基酚醛树脂研究

以尿素和纳米氧化镁(MgO)为改性剂,利用木质素部分替代苯酚,三步共聚制备了木质素基酚醛树脂胶粘剂,系统考察了尿素添加量、MgO添加量、木质素添加量等过程参数对木质素基酚醛树脂胶粘剂的密度、黏度、固含量和游离甲醛含量的影响,并采用FTIR和DSC对木质素基酚醛树脂胶粘剂官能团结构和热固化特性进行表征。结果表明,在尿素和MgO协同催化作用下,木质素添加量可以提高到45%,并且热固化性能显著提高。     

乙醇/尿素复合改性大豆分离蛋白胶粘剂的研究

以大豆分离蛋白(SPI)含量、乙醇含量、尿素含量、交联剂含量和反应温度为试验因素,以胶粘剂的固含量、黏度、干态粘接强度和湿态粘接强度为考核指标,采用正交试验法优选出制备乙醇/尿素复合改性SPI胶粘剂的最优方案。结果表明:当w(SPI)=11%、w(乙醇)=35%、w(尿素)=4%、w(交联剂)=0.3%(均相对于SPI水溶液质量而言)和反应温度为60℃时,乙醇/尿素复合改性SPI胶粘剂的综合性能相对最好,其固含量为10.340%、黏度为52.0 Pa·s、干态粘接强度(2.540 MPa)和湿态粘接强度(1.370 MPa)均满足Ⅱ类胶合板的标准要求。     

玉米秸秆木质素改性环氧树脂的制备与性能

将玉米秸秆木质素与双酚A环氧树脂混合,于100℃下预处理1 h,以改善环氧树脂的性能。对预处理后环氧树脂的黏度进行了测试,对改性环氧树脂与聚酰胺固化后材料的力学性能、动态力学性能、热稳定性以及燃烧性能进行了综合测试,考察了不同质量分数的玉米秸秆木质素对改性环氧树脂性能的影响。结果表明:以固化体系的总质量为基准,在w(木质素)=0~7%的范围内,与未添加木质素的环氧树脂相比,随着木质素质量分数的增加,改性环氧树脂22℃下的黏度从1 220 m Pa·s增大到13 220 m Pa·s;改性环氧树脂固化物的弯曲强度随木质素质量分数的增加先升高后降低,在w(木质素)=3%时达到最大值83.2 MPa,但其冲击强度下降,由20.7 MPa降低为13.6 MPa;改性环氧树脂固化物的玻璃化转变温度(Tg)随木质素质量分数的增加而增加,w(木质素)=5%时Tg提高了4.8℃;改性环氧树脂固化物的热稳定性有所改善,w(木质素)=7%时热失重50%的温度提高13℃,同时木质素的加入能够改善环氧树脂的阻燃性能。     

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.     

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.     

不同分子量麦草碱木素性能及其对LPF胶性能的影响

应用超滤分级方法,将麦草碱木素分成3种不同分子量范围的级分。分析表明：随着分子量的降低,麦草碱木素的甲氧基含量降低,酚羟基含量升高,其反应活性随之升高;同时,羧基含量降低,其溶液表面活性升高。进一步实验结果表明,随着麦草碱木素分子量的降低,LPF胶的胶黏强度升高,游离甲醛含量和黏度降低,综合性能提高。     

Eucalyptus bark lignin substituted phenol formaldehyde adhesives: A study on optimization of reaction parameters and characterization

The major adhesive resin worldwide used in the manufacture of plywood is phenol formaldehyde resole (PF) resin. The raw material for this kind of adhesive is derived from petroleum oil. Because of rising prices of crude oil and the scarcity of petroleum products, their replacement by natural resource–based raw material has become a necessity. In the present work, the possibility of replacing phenol in PF resin with lignin was explored. The parameters for preparation of bark lignin substituted PF (LPF) adhesive, such as lignin concentration, formaldehyde to phenol molar ratio, catalyst concentration, reaction time, and reaction temperature, were optimized. It was found that up to 50 wt % of phenol can be substituted by lignin to give an LPF adhesive with better bonding strength compared to that of control PF resin. Prepared resins were characterized using IR, DSC, and TGA. IR spectra of LPF adhesive showed structural similarity with that of PF adhesives. Thermal stability of LPF adhesive was found to be lower compared to that of control PF (CPF) adhesive. DSC studies revealed a lower curing temperature for LPF resin than that for CPF resin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3514–3523, 2004     

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     

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.     

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。