玉米油基热固性树脂的制备及其应用研究
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摘要
本课题选用玉米油为原材料,进行热固性树脂及以这种树脂为基体的复合材料的开发和研究,制备出了性能较好的热固性树脂,其复合材料可部分取代传统不饱和聚酯基复合材料,可满足一般需求,为实际生产应用提供了理论基础。由于传统的矿物资源是不可再生资源,并且不可降解,所以以天然植物油作为代替石油合成聚合物是十分必要的。
本文首先将玉米油进行甘油化反应合成了玉米油单甘酯,作为下一步与酸酐的聚酯化反应进行树脂制备的基础。通过对甘油与玉米油配比、反应温度、反应时间、催化剂量等几个因素来对甘油化反应进行优化以达到最大的产量。反应产物通过红外光谱进行了表征,得到的最佳反应条件为:甘油与玉米油配比3:1、反应温度230℃、反应时间5h、催化剂氢氧化钙的质量分数1%。
接下来玉米油单甘酯与马来酸酐在质量比2:3、1%对苯二酚和1%二甲基咪唑、80℃水浴以及氮气保护条件下反应得到玉米油马来酸单酯,然后按相应的比例与苯乙烯和过氧化苯甲酰,在一定温度的水浴中固化,即得到玉米油基热固性树脂。通过对树脂形态的观察初步确定了大致的反应条件,反应物进一步通过热失重分析表征了其热稳定性,通过动态力学分析表征了其模量,通过综合考虑确定了最佳的反应条件为:玉米油马来酸单酯与苯乙烯、BPO的质量比6.7:3.0:0.3,固化温度90℃,反应时间1h。
最后通过手糊成型制备玻纤织物/玉米油热固树脂复合材料,讨论了玻纤织物与玉米油基树脂质量比、温度以及热压时间等因素对复合材料拉伸性能的影响,并确定了最佳热压工艺。结果表明:玻纤织物与玉米油基树脂质量比5:5,在模压温度为110℃,压力10MPa、热压时间2h有最好的拉伸性能。
本文还采用有限元分析法对复合材料的拉伸过程进行了模拟。利用有限元分析软件ANSYS对复合材料做了一定的理想化处理,简化了模拟的过程,在一定程度上与复合材料的拉伸结果相吻合。
In this work, corn oil was choused as the raw material for thermosetting resins and the composites based on the resin, during some researches, we got the thermosetting resin which had good mechanical properties, and the composites could partially replace the conventional unsaturated polyester composites, it could meet the general requirements for the practical application, and it provided for a theoretical basis. As the traditional minerals are non-renewable resources, and the burning of these minerals would lead to environmental pollution in the atmosphere, so it is very necessary to use the natural oils to synthesis polymer instead of petroleum.
First of all, corn oil and glycerin were synthesized to be corn oil monoglyceride (COMG) prepared for the next step reaction with the anhydride as the foundation of making thermosetting resins. By optimizing reaction factors of glycerolysis like glycerol and corn oil ratio, reaction temperature, reaction time, catalyst amount to achieve maximum yield. Reaction products were characterized by IR, and optimum reaction conditions were: 3:1 ratio of glycerol and corn oily, reaction temperature 230℃, reaction time 5 hours, the catalyst mass fraction of calcium hydroxide, 1%.
Next, corn oil monoglyceride (COMG) and maleic anhydride in the mass ratio of 2:3, 1% hydroquinone and 1% dimethyl-imidazole, 80℃water bath and under the protection of nitrogen were reacted to be corn oil maleic anhydride (COMA), then with appropriate ratio of styrene and benzoyl peroxide (BPO), certain temperature water bath, thermosetting resins were synthesized. Through the morphology of the resin, we could largely confirm initial reaction conditions, and further the thermosetting resins’thermal stability were characterized by weight loss of thermal stability (TG), their modulus were characterized by dynamic mechanical analysis (DMA), by considering, the optimum reaction conditions were: corn oil and styrene maleic acid monoester, BPO mass ratio of 6.7:3.0:0.3, curing temperature 90℃, reaction time 1 hour.
Finally, glass cloth / corn oil thermosetting resin composites were made by hand lay-up preparation, the effect of weight ratio, temperature and pressing time on properties of composites were discussed, and the optimum hot pressing processes were confirmed. The results showed that: the molding temperature is 110℃, pressure of 10MPa, pressing time of 2 hours has the best tensile properties.
In this paper also, the tensile process was simulated by using the finite element analysis (FEA). Finite element analysis software, ANSYS, the conditions were idealized, it could simplifies the simulation process, to a certain extent, the results of tensile and simulation were the similar.
本文首先将玉米油进行甘油化反应合成了玉米油单甘酯,作为下一步与酸酐的聚酯化反应进行树脂制备的基础。通过对甘油与玉米油配比、反应温度、反应时间、催化剂量等几个因素来对甘油化反应进行优化以达到最大的产量。反应产物通过红外光谱进行了表征,得到的最佳反应条件为:甘油与玉米油配比3:1、反应温度230℃、反应时间5h、催化剂氢氧化钙的质量分数1%。
接下来玉米油单甘酯与马来酸酐在质量比2:3、1%对苯二酚和1%二甲基咪唑、80℃水浴以及氮气保护条件下反应得到玉米油马来酸单酯,然后按相应的比例与苯乙烯和过氧化苯甲酰,在一定温度的水浴中固化,即得到玉米油基热固性树脂。通过对树脂形态的观察初步确定了大致的反应条件,反应物进一步通过热失重分析表征了其热稳定性,通过动态力学分析表征了其模量,通过综合考虑确定了最佳的反应条件为:玉米油马来酸单酯与苯乙烯、BPO的质量比6.7:3.0:0.3,固化温度90℃,反应时间1h。
最后通过手糊成型制备玻纤织物/玉米油热固树脂复合材料,讨论了玻纤织物与玉米油基树脂质量比、温度以及热压时间等因素对复合材料拉伸性能的影响,并确定了最佳热压工艺。结果表明:玻纤织物与玉米油基树脂质量比5:5,在模压温度为110℃,压力10MPa、热压时间2h有最好的拉伸性能。
本文还采用有限元分析法对复合材料的拉伸过程进行了模拟。利用有限元分析软件ANSYS对复合材料做了一定的理想化处理,简化了模拟的过程,在一定程度上与复合材料的拉伸结果相吻合。
In this work, corn oil was choused as the raw material for thermosetting resins and the composites based on the resin, during some researches, we got the thermosetting resin which had good mechanical properties, and the composites could partially replace the conventional unsaturated polyester composites, it could meet the general requirements for the practical application, and it provided for a theoretical basis. As the traditional minerals are non-renewable resources, and the burning of these minerals would lead to environmental pollution in the atmosphere, so it is very necessary to use the natural oils to synthesis polymer instead of petroleum.
First of all, corn oil and glycerin were synthesized to be corn oil monoglyceride (COMG) prepared for the next step reaction with the anhydride as the foundation of making thermosetting resins. By optimizing reaction factors of glycerolysis like glycerol and corn oil ratio, reaction temperature, reaction time, catalyst amount to achieve maximum yield. Reaction products were characterized by IR, and optimum reaction conditions were: 3:1 ratio of glycerol and corn oily, reaction temperature 230℃, reaction time 5 hours, the catalyst mass fraction of calcium hydroxide, 1%.
Next, corn oil monoglyceride (COMG) and maleic anhydride in the mass ratio of 2:3, 1% hydroquinone and 1% dimethyl-imidazole, 80℃water bath and under the protection of nitrogen were reacted to be corn oil maleic anhydride (COMA), then with appropriate ratio of styrene and benzoyl peroxide (BPO), certain temperature water bath, thermosetting resins were synthesized. Through the morphology of the resin, we could largely confirm initial reaction conditions, and further the thermosetting resins’thermal stability were characterized by weight loss of thermal stability (TG), their modulus were characterized by dynamic mechanical analysis (DMA), by considering, the optimum reaction conditions were: corn oil and styrene maleic acid monoester, BPO mass ratio of 6.7:3.0:0.3, curing temperature 90℃, reaction time 1 hour.
Finally, glass cloth / corn oil thermosetting resin composites were made by hand lay-up preparation, the effect of weight ratio, temperature and pressing time on properties of composites were discussed, and the optimum hot pressing processes were confirmed. The results showed that: the molding temperature is 110℃, pressure of 10MPa, pressing time of 2 hours has the best tensile properties.
In this paper also, the tensile process was simulated by using the finite element analysis (FEA). Finite element analysis software, ANSYS, the conditions were idealized, it could simplifies the simulation process, to a certain extent, the results of tensile and simulation were the similar.
引文
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[10]宋洪川,张无敌等.植物油燃料[J].太阳能, 2001, 16 (1): 18-19
[11]李玉芹,曾虹燕.植物油脂肪酸甲酯—生物柴油作替代燃料的意义[J].应用化工, 2006, 34 (8): 464-468
[12]肖志红,胡静波等.植物油基印刷油墨研究进展[J].中国油脂, 2004, 29 (10): 57-60
[13] Dunning E T. Drying oils in printing inks [J]. Journal of the American Oil Chemists' Society, 1959, 36 (11): 586-589
[14]齐成.植物油墨的特性和发展前景[J].今日印刷, 2006, 23 (6): 60-62
[15]余立.新型环保型植物油油墨[J].中国印刷物资商情, 2007, 16 (11): 52-53
[16] Meijer M, Creemers J, Cobben W. Relationships between the performance of low-VOC wood coatings an Part B d the dimensional changes of the wooden substrate [J]. Surface Coating International: Coatings Transactions, 2001, 84 (B1): 72-85
[17] Manfred P Schneider. Plant-oil based lubricants and hydraulic fluids [J]. Journal ofthe Science of Food and Agriculture, 2006, 86: 1769-1780
[18] Helena Wagner, Rolf Luther, Theo Mang. Lubricant base fluids based on renewable raw materials their catalytic manufacture and modification [J]. Applied Catalysis A: General, 2001, 221: 429-442
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