吴志刚, 陈思成, 梁坚坤, 李利芬, 雷洪, 董霁莹. 木质素-苯酚-甲醛树脂胶黏剂的性能与合成机理[J]. 农业工程学报, 2020, 36(21): 308-315. DOI: 10.11975/j.issn.1002-6819.2020.21.037
    引用本文: 吴志刚, 陈思成, 梁坚坤, 李利芬, 雷洪, 董霁莹. 木质素-苯酚-甲醛树脂胶黏剂的性能与合成机理[J]. 农业工程学报, 2020, 36(21): 308-315. DOI: 10.11975/j.issn.1002-6819.2020.21.037
    Wu Zhigang, Chen Sicheng, Liang Jiankun, Li Lifen, Lei Hong, Dong Jiying. Properties and synthesis mechanism of lignin-phenol-formaldehyde resin[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2020, 36(21): 308-315. DOI: 10.11975/j.issn.1002-6819.2020.21.037
    Citation: Wu Zhigang, Chen Sicheng, Liang Jiankun, Li Lifen, Lei Hong, Dong Jiying. Properties and synthesis mechanism of lignin-phenol-formaldehyde resin[J]. Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE), 2020, 36(21): 308-315. DOI: 10.11975/j.issn.1002-6819.2020.21.037

    木质素-苯酚-甲醛树脂胶黏剂的性能与合成机理

    Properties and synthesis mechanism of lignin-phenol-formaldehyde resin

    • 摘要: 为了降低酚醛树脂的制备成本,该研究分别以30%、40%和50%碱木质素部分替代苯酚合成木质素-苯酚-甲醛(Lignin-Phenol-Formaldehyde, LPF)树脂胶黏剂,主要研究了其替代比对LPF树脂胶合性能、固化性能和热稳定的影响,同时探讨了LPF合成机理。结果表明:1)LPF树脂具有透明度低、固体含量大、游离甲醛较低、黏度大导致活性期短和施胶困难的特点。2)LPF制备的胶合板胶合强度随碱木质素增加呈先增加后减小的趋势,但均高于PF(Phenol-Formaldehyde)树脂,碱木质素取代苯酚量最大可达50%以上。3)DSC分析表明LPF树脂固化温度高,且随碱木质素添加量增加而升高。4)碱木质素加量过高或过低都会影响LPF的热稳定性,为40%时的热稳定性高于PF树脂。5)碱性条件下,无论是以苯酚、木质素酚环还是木质素侧链为反应起点合成LPF,羟甲基苯酚经E1cb反应机理形成亚甲基共轭结构,是合成LPF的关键。该研究工作的开展可为LPF合成工艺改进和实际应用提供进一步的科学指导。

       

      Abstract: Phenol Formaldehyde (PF) resin is the earliest industrial synthetic polymer material, which has a history of more than 100 years. PF resin adhesive are widely used in the production of outdoor wood-based panels due to their advantages such as high bonding strength, weathering resistance, good water resistance, aging resistance, and so on, and it is the second largest wood adhesive after urea-formaldehyde resin. PF has some defects, such as high production cost, dark color, hard and brittle after curing, easy cracking, low initial viscosity, high toxicity, and so on, which lead to low production efficiency and high energy consumption of wood-based panels, thus limiting its wider application. Therefore, the study of alternatives for phenol has become the focus. Lignin is similar to phenol in chemical structures, and it has the condition and potential to replace part of phenol to prepare phenol formaldehyde resin. It can reduce the cost of the preparation of PF, and increase the biomass content of PF to improve its the biodegradability, and also realize the effective utilization of lignin resources. In order to reduce the cost of phenol formaldehyde resin, 30%, 40% and 50% alkali lignin was substituted for phenol to prepare Lignin-Phenol-Formaldehyde (LPF). Effects of substitution ratios on bonding performance, curing properties and thermal stability of LPF were studied, and the synthesis mechanism of LPF was also discussed in this paper. The results indicated that: 1) Compared with phenol formaldehyde resin, LPF had low transparency, high solid content, low free formaldehyde, high viscosity and bad operation. 2) With the increase of lignin addition, the bonding strength of LPF increased and then decreased, but all generally higher than that of phenol formaldehyde resin. The ratios of lignin substitution for phenol could be up to 50%. 3) LPF resin required a higher curing temperature, and the more the lignin addition, the higher the hot-pressing temperature. 4) The lignin addition could affect the thermal stability of LPF resin, and it's thermal stability was higher than that of phenol formaldehyde resin when lignin addition was only 40%. 5) At alkaline conditions, whether phenol, lignin phenol ring or lignin side chains were used as the starting reaction points for the synthesis of LPF, forming methylene conjugate structures by reaction mechanism based on hydroxymethyl phenol was the key. In conclusion, the research has a great significance to provide further scientific guidance for the improvement of LPF synthesis process and its practical application.

       

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