【作者】 张俊；

【导师】 杜官本；

【作者基本信息】 北京林业大学 ， 木材科学与技术， 2016， 博士

【摘要】 石油资源的浪费及石油化工产品对环境的污染致使酚醛树脂材料,如胶黏剂、塑料、砂轮片及切割片的发展受限。单宁的化学结构与酚类似,且糠醇树脂具备优良的耐热耐水性能,故本论文采用黑荆树缩合单宁与糠醇合成新型单宁-糠醇树脂来替换酚醛树脂基材料。通过调控单宁与糠醇的质量比、单宁-糠醇树脂与研磨颗粒的质量比等因素来制备胶黏剂、塑料及树脂基砂轮片和切割片。从胶黏剂的胶合性能以及塑料和砂轮片的外观、力学性能方面对材料进行筛选,最终获得最佳生产工艺。同时采用基质辅助激光解吸电离飞行时间质谱、核磁共振碳谱等技术对树脂的化学结构进行表征；采用差示扫描量热仪和静态热机械分析仪对树脂的固化特性进行表征。论文主要结论如下：(1)当糠醇与黑荆树单宁质量比为3时制备的胶黏剂粘度达到：233 mPa·s。用其制备的胶合板的干、湿胶合强度分别达到了1.69 MPa及1.22 MPa。单宁-糠醇树脂具有较好的耐热性能,其玻璃转化温度可达190℃,且当温度上升到900℃时,仍然有52%的树脂未被分解。(2)糠醇与单宁在质量比为3的条件下合成的树脂固化制备的塑料表面光滑无气泡和裂痕。其硬度(20.3 daN/mm2)较酚醛塑料(12.6 daN/mm2)高,同时抗压抗拉性能也较实验室自制酚醛塑料好。(3)对黑荆树单宁-糠醇树脂基砂轮片而言,当研磨颗粒与树脂的质量比为1.5时,树脂与颗粒的结合度最高。同时,采用玻璃砂制备的单宁-糠醇砂轮片的硬度及抗压抗拉强度均优于采用氧化铝制备的砂轮片,但采用氧化铝制备的砂轮片具备更高的磨削能力,其磨削比达到了97.4%。(4)在黑荆树单宁-糠醇切割片中加入乙二醇及桐油能增加树脂的韧性。当研磨颗粒与树脂质量比为1.5时,玻璃砂颗粒制备的单宁-糠醇切割片的硬度(19.6 daN/mm2)高于氧化铝颗粒制备的切割片(18.0N/mm2),但氧化铝切割片的切割能力较玻璃砂切割片好。同时,在切割面积相同的情况下,黑荆树皮单宁-糠醇树脂基氧化铝切割片耗时(5 s)较实验室自制酚醛树脂基切割片(6 s)短。(5)按单宁-糠醇树脂与异氰酸酯质量比为5制备的树脂与单宁-糠醇树脂相比,前者具备更高的弹性模量(3789 MPa),同时胶合板的干、湿胶合强度也较单宁-糠醇树脂的高,分别为1.85 MPa、1.31 MPa。(6)异氰酸酯-单宁-糠醇树脂基砂轮片及切割片相比单宁-糠醇树脂基砂轮片及切割片具有更高的杨氏模量,其值为1.84 GPa。异氰酸酯的加入增强了砂轮片的抗水性能及树脂与研磨颗粒的结合度,提高了砂轮片的耐磨性能,其磨削比达到112.4%；同时,异氰酸酯的加入减少了材料在切割金属时所受离心力的作用。更多还原

【Abstract】 The increase of oil resource waste, the consumption and the environmental pollution caused the limit on the development of common oil chemical products, such as the phenolic adhesive, phenolic plastic, phenolic grinding wheel and chutting wheel. Especially, the chemical structure of mimosa tannin is analogous to that of phenol. Meanwhile, the furfural resin has the high abilities to resist the water and heat. Herce, in this paper, mimosa tannin and furfuryl alcohol coming from forestry and agriculture had been used to compound the nature resin in the acid condition based on the co-condensation theory. According to the regulation of the mass ratio between mimosa tannin and furfuryl alcohol, the mass ratio between resin and abrasive particles, we can obtain a new wood adhesive, thermosetting plastics, grinding wheels and cutting wheels. The best process routes were selected based on the bonding prpperty of wood adhesive and the appearance, the hardness and the mechanical properties of plastic and grinding wheel. Meanwhile, the Matrix assisted laser desorption ionization time of flight mass spectroscopy (MALDI-TOF) and nuclear magnetic resonance spectrum (NMR) were used to character and analyse the structure of resin. At the same time, the curing characteristics of resins were tested and analysed by the differential scanning calorimetry (DSC) and thermal mechanical analyzer (TMA). The main conclusions of this paper are as follows:(1) When the mass ratio of furfuryl alcohol and mimosa tannin is 3, the viscosity of adhesive is 233 mPa-s. Moreover, the dry and wet bonding strength of plywood are 1.69 MPa and 1.22 MPa. Tannin-furanic resin has excellentheat-resistant quality, the glass transition temperature of it is as high as 190℃.Especially, when the temperature increased to 900℃,the weight ratio of undecomposed cured resin still had 52%.(2) When the mass ratio of furfuryl alcohol and mimosa tannin is 3,the cured plastic surface is pretty smooth without bubbles and cracks. Moreover, its hardness (20.3 daN/mm2) is higher than that of laboratory self-made phenolic plastics(12.6 daN/mm2). Meanwhile, its mechanical properties are better than the laboratory self-made phenolic plastics.(3) For mimosa tannin-furanic resin based grinding wheels, when the mass ratio of abrasive particles and resin is 1.5, the bonding property between the resin and abrasive particle is better than other mass ratio of resin and abrasive particles. Meanwhile, the mechanical properties of tannin-furanic grinding wheels based on the glass sand were better than that of tannin-furanic grinding wheels based on aluminum oxise. But for the wear resistance, tannin-furanic grinding wheels based on aluminum oxise were better, the grinding ratio of it with aluminum oxide is 97.4.(4) The ethylene glycol and tung oil in the mimosa tannin-furanic resin can eviectively increase the toughness of grinding and cutting wheels When the mass ratio of the abrasive particle and resin is 1.5, the hardness of tannin-furanic grinding wheel based on the glass sand(19.6 daN/mm2) was higher than that of tannin-furanic grinding wheel based on aluminum oxise (18.0 daN/mm2). On the contrary, for the cutting property, tannin-furanic cutting and grinding wheel based on aluminum oxise was better caused by the irregularity sapes of aluminum oxide. Moreover, compared with the self-made phenolic resin cutting and grinding wheel, the laboratory preparation of tannin-furanicone still has an outstanding cutting performance, which took the less time (5 s) than phenolic resin cutting and grinding wheel(6 s).(5) Under the mass ratio of mimosa tannin-furanic resin and isocyanate is 5, the resin has higher elasticity modulus (3789 MPa) compared with the mimosa tannin-furanic resin. Meanwhile, the dry and wet bonding strength of plywood made with tannin-furanic-isocyanate resin are 1.85 MPa and 1.31 MPa which is higher than that of tannin-furanic resin.(6) After isocyanate modification, the grinding wheel and cutting wheel pieces based on modified resin and abrasive particles possess higher Young’s modulus which value is 1.84 GPa. For the grinding wheel, the water resistance performance of the grinding wheel is enhanced by the addition of isocyanate. Meanwhile, becaused of the improved bonding property of the resin and the abrasive particle after isocyanate modification, the wear resistance of the treated resin based grinding wheel which grinding ratio is 112.4% is better than that of grinding wheel based on untreated resin. For the relative cutting wheel, the addition of isocyanate reduced the density of the material, which leads to the decrease of the centrifugal force when the material is working.更多还原