Preparation and process optimization of lignin-based phenolic resin

doi:10.16085/j.issn.1000-6613.2023-0755

Abstract

Abstract:

The enzymatic hydrolysis lignin obtained from biorefinery industry retains the structural characteristics of the original lignin with rich active groups such as alcohol hydroxyl and phenolic hydroxyl, which can be used in the preparation of phenolic resin. The purity, alcohol hydroxylic group and the phenolic hydroxyl group were investigated for the synthesis and application properties of phenol-formaldehyde resin (PF). Limited by the complexity of the lignin structure,the reaction process could not be effectively tracked and optimized. The preparation process of lignin-PF was optimized by online ReactIR equipment, and the change pattern of formaldehyde amount in the system was studied by the infrared absorption peak of 1020cm^-1. The results showed that adding formaldehyde and sodium hydroxide in a multistep reaction with the system pH above 10.5 promoted the synthesis of the phenolic resin. When the ideal polymerization temperature was controlled at 88—95℃ and the maximum amount of lignin was added at 60%,the bonding strength of phenolic resin adhesive (0.90MPa) and the lowest formaldehyde release (0.142mg/L) could reach the E0 and I specified standard.

Key words: biorefinery, enzymatic hydrolysis lignin, phenol-formaldehyde resin, adhesive, online ReactIR

摘要：

生物炼制工业中得到的酶解木质素较好地保留了原有木质素的结构特性，具有丰富的醇羟基和酚羟基等活性基团，可应用于生物基酚醛树脂的制备。本文对酶解木质素进行纯度、醇羟基和酚羟基结构表征，并替代部分苯酚用于酚醛树脂（PF）的合成及应用性能的研究。受限于木质素结构的复杂程度，无法有效确定反应进程并优化，提出通过在线红外光谱仪实时记录关键峰变化来实现跟踪木质素基酚醛树脂的制备过程。以1020cm^-1附近红外吸收峰研究体系中甲醛量的变化规律，优化木质素酚醛树脂工艺条件。结果表明，采用多步反应形式添加甲醛和氢氧化钠控制反应体系pH大于10.5，有利于酚醛树脂的合成；制备过程中理想聚合温度控制在88~95℃，木质素添加量最大可达到60%，制得酚醛树脂胶黏剂用于胶合板制备，胶合强度达到0.90MPa，甲醛释放量低至0.142mg/L，均满足E0级Ⅰ类胶合板要求。

关键词: 生物炼制, 酶解木质素, 酚醛树脂, 胶黏剂, 在线红外

CLC Number:

TQ353.6

BAI Yuli, BAI Fudong, ZHANG Lei, SUN Qimei, LI Xiuzheng. Preparation and process optimization of lignin-based phenolic resin[J]. Chemical Industry and Engineering Progress, 2024, 43(2): 1033-1038.

白毓黎, 白富栋, 张雷, 孙启梅, 李秀峥. 木质素基酚醛树脂的制备和过程优化[J]. 化工进展, 2024, 43(2): 1033-1038.

Figures/Tables 8

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实验	测定羟值 /mg KOH·g^-1	酸值 /mg KOH·g^-1	校正后羟值 /mg KOH·g^-1	木质素质量分数 /%	酚羟基含量 /mmol·g^-1
平行实验1	47.7	20.2	67.9	90.2	3.12
平行实验2	49.2	22.0	71.2	89.3	3.01
平行实验3	49.5	21.9	71.4	89.5	2.74
平均值	48.8	21.4	70.2	89.7	2.96

实验	测定羟值 /mg KOH·g^-1	酸值 /mg KOH·g^-1	校正后羟值 /mg KOH·g^-1	木质素质量分数 /%	酚羟基含量 /mmol·g^-1
平行实验1	47.7	20.2	67.9	90.2	3.12
平行实验2	49.2	22.0	71.2	89.3	3.01
平行实验3	49.5	21.9	71.4	89.5	2.74
平均值	48.8	21.4	70.2	89.7	2.96

聚合温度 /℃	黏度 /mPa·s	pH	固体质量分数/%	游离甲醛质量分数/%	游离苯酚质量分数/%
82~90	35.6	12.37	44.6	0.04	0.07
87~95	238.9	12.08	45.0	0.08	0.08
90~98	1210.0	11.92	45.1	0.04	0.05

聚合温度 /℃	黏度 /mPa·s	pH	固体质量分数/%	游离甲醛质量分数/%	游离苯酚质量分数/%
82~90	35.6	12.37	44.6	0.04	0.07
87~95	238.9	12.08	45.0	0.08	0.08
90~98	1210.0	11.92	45.1	0.04	0.05

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