乙烯焦油沥青树脂的制备及其应用性能初探
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摘要
本研究工作以乙烯焦油为原料,对苯二甲醇或三聚甲醛为交联剂,对甲基苯磺酸为催化剂,合成B阶沥青树脂。在研究过程中利用正交试验考察了原料处理前后交联剂用量、催化剂用量、反应温度、反应时间对合成沥青树脂性能的影响。通过IR、1HNMR及热失重的测试分析,初步探讨了原料处理前后B阶沥青树脂合成反应机理及其固化前后沥青树脂的耐热性,重点对β树脂含量对沥青树脂粘结性的影响进行了考察。将乙烯焦油沥青树脂和石墨进行复合,考察了该复合材料的硬度和耐热性等性能。并在制备沥青树脂的实验条件下,将酚醛树脂与沥青树脂进行复配,制得复配树脂,对复配树脂的耐热性能进行了研究。
实验结果表明,将经过正庚烷和热处理的乙烯焦油为原料,交联剂三聚甲醛占原料的14%,催化剂对甲基苯磺酸占原料的10%,反应温度140℃,反应时间3h的条件下合成的沥青树脂性能较好,且交联剂、催化剂、反应时间、反应温度等对沥青树脂的性能都有一定影响。经过热固化后,沥青树脂的耐热性得到很大提高。α树脂、β树脂和γ树脂含量的变化对乙烯焦油系沥青树脂粘结性的影响是不同的。提高β树脂含量同时降低γ树脂含量更有利于乙烯焦油系沥青树脂粘结性能的提高。沥青树脂和石墨复合后材料的粘结性得到提高,并且两段合成乙烯焦油沥青树脂石墨复合材料的耐热性好于煤沥青系和脱油沥青系沥青树脂石墨复合材料。经过和酚醛树脂复配,材料的耐热性也得到提高。
本研究为使用乙烯焦油进行沥青树脂的合成技术开发提供了理论依据。乙烯焦油沥青树脂与碳材料良好的亲和性为复合材料的研制提供了一种新型树脂粘结剂;乙烯焦油沥青树脂复合材料良好的耐热性,为沥青树脂提供了一个新的应用方向,也为乙烯焦油的利用提供了一个新的方向。
B stage pitch resin has been made from synthetic reaction under certain temperature, in which TPF and PXG used as cross-linking agents,p-toluene sulfuric acid as catalyst and ethylene bottom as raw materials. Based on orthogonal test, experiments have been carried out with various operating parameters, such as different reaction temperatures, different reaction times, the ratios of feedings to cross-linking agents, etc. Through analysis of IR, 1HNMR and weight loss, it can be known the structure, reaction mechanismof the pitch resin and the heat resistance of the cured pitch resin. Composite material has been attained with mixing the resin and graphite. Then the rate of resistance and hardness were characterized. In the experimental conditions of B stage pitch resin,combination resins has been made from the mix of pitch resin and phenolic resin.
Through orthogonal experiment the optimum conditions of the reaction were obtained: TPF is 14%, PTS is 10%, the reaction temperature is 140℃, the reaction time is 3 hours. And these conditions can influence on the performance of pitch resin. The pitch resin’s heat resistance was improved greatly after Heat-curing. Effect ofαresin content,βresin content andγresin content on the Cohesiveness of pitch resin is different. Reduction inγresin content with simultaneous increase inβresin content can improve the bond performance. The bond performance of the composite material is better than the bond performance of pitch resin. The resin contents can influence on the performance of composite materials, and the performances of resistance rate and hardness increase with the increasing of resin content. The heat resistance of ethylene bottom based pitch resin /graphite composite materials is better than deoiled asphalt or coal tar pitch based pitch resin /graphite composite materials. The heat resistance was improved through mixing of pitch resin and phenolic resin.
It can provide a theoretical basis for the synthesis of ethylene bottom based pitch resin. And using the good affinity of pitch resin and carbon materials, it can provide a new type of resin binder for composite materials. And using the good heat resistance of composite material, it can provide a new direction for the application of pitch resin and ethylene bottom.
实验结果表明,将经过正庚烷和热处理的乙烯焦油为原料,交联剂三聚甲醛占原料的14%,催化剂对甲基苯磺酸占原料的10%,反应温度140℃,反应时间3h的条件下合成的沥青树脂性能较好,且交联剂、催化剂、反应时间、反应温度等对沥青树脂的性能都有一定影响。经过热固化后,沥青树脂的耐热性得到很大提高。α树脂、β树脂和γ树脂含量的变化对乙烯焦油系沥青树脂粘结性的影响是不同的。提高β树脂含量同时降低γ树脂含量更有利于乙烯焦油系沥青树脂粘结性能的提高。沥青树脂和石墨复合后材料的粘结性得到提高,并且两段合成乙烯焦油沥青树脂石墨复合材料的耐热性好于煤沥青系和脱油沥青系沥青树脂石墨复合材料。经过和酚醛树脂复配,材料的耐热性也得到提高。
本研究为使用乙烯焦油进行沥青树脂的合成技术开发提供了理论依据。乙烯焦油沥青树脂与碳材料良好的亲和性为复合材料的研制提供了一种新型树脂粘结剂;乙烯焦油沥青树脂复合材料良好的耐热性,为沥青树脂提供了一个新的应用方向,也为乙烯焦油的利用提供了一个新的方向。
B stage pitch resin has been made from synthetic reaction under certain temperature, in which TPF and PXG used as cross-linking agents,p-toluene sulfuric acid as catalyst and ethylene bottom as raw materials. Based on orthogonal test, experiments have been carried out with various operating parameters, such as different reaction temperatures, different reaction times, the ratios of feedings to cross-linking agents, etc. Through analysis of IR, 1HNMR and weight loss, it can be known the structure, reaction mechanismof the pitch resin and the heat resistance of the cured pitch resin. Composite material has been attained with mixing the resin and graphite. Then the rate of resistance and hardness were characterized. In the experimental conditions of B stage pitch resin,combination resins has been made from the mix of pitch resin and phenolic resin.
Through orthogonal experiment the optimum conditions of the reaction were obtained: TPF is 14%, PTS is 10%, the reaction temperature is 140℃, the reaction time is 3 hours. And these conditions can influence on the performance of pitch resin. The pitch resin’s heat resistance was improved greatly after Heat-curing. Effect ofαresin content,βresin content andγresin content on the Cohesiveness of pitch resin is different. Reduction inγresin content with simultaneous increase inβresin content can improve the bond performance. The bond performance of the composite material is better than the bond performance of pitch resin. The resin contents can influence on the performance of composite materials, and the performances of resistance rate and hardness increase with the increasing of resin content. The heat resistance of ethylene bottom based pitch resin /graphite composite materials is better than deoiled asphalt or coal tar pitch based pitch resin /graphite composite materials. The heat resistance was improved through mixing of pitch resin and phenolic resin.
It can provide a theoretical basis for the synthesis of ethylene bottom based pitch resin. And using the good affinity of pitch resin and carbon materials, it can provide a new type of resin binder for composite materials. And using the good heat resistance of composite material, it can provide a new direction for the application of pitch resin and ethylene bottom.
引文
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[3]查庆芳,吴铭铂.COPNA树脂的开发及应用[C].东营:石油大学出版社,2000:114~115
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[6]阮湘泉,刘伟昌.COPNA树脂----一种新型功能材料.化工新型材料,1997,25(8):7~10
[7]印杰,张斌.以沥青为单体的缩合多核芳香烃树脂的合成及性能研究.高分子材料科学与工程,1999(3): 27～29
[8]郭燕生,查庆芳,吴明铂等. FCC油浆的芳烃富集及COPNA树脂的合成.石油大学学报(自然科学版),2002;26(4):80～83
[9]查庆芳.煤焦油沥青树脂的开发和应用.第四届全国新型炭材料学术研讨会议文集,96～100
[10]查庆芳,张玉贞,吴明铂等.菲和苯甲醛的低温合成反应机理.石油大学学报,2001;25(5):79～83
[11]张玉贞,查庆芳.炭素与有机物的中间领域-沥青树脂的开发和应用.第七次全国石油沥青技术交流会论文集,中国石油化工集团公司沥青情报站. 2000(5)
[12]印杰、陈一东.以萘及萘酚为单体苯甲醛为交联剂的COPNA研究.高分于材料科学与工程,1995(l):29
[13]查庆芳、张玉贞等.用菲和苯甲醛合成沥青树脂的反应机理.石油大学学报(自然科学版),2001(5):81～82
[14]徐音、印杰.以萘为单体三聚甲醛为交联剂的缩合多核芳香烃树脂的合成、交联及性能研究.高分于材料科学与工程,1997,(3):27
[15]印杰、徐音.以三氧六环为交联剂的COPNA树脂的合成.高分子材料科学与工程,1996(12):24～27
[16]林起浪,李铁虎等.二乙烯基苯为交联剂COPNA树脂的研究.燃料化学学报,2001,30(2):217～222
[17]大谷杉郎等(日).新型炭产品的前驱体设计.新型炭材料,1992(2):34～35
[18]大谷杉郎,金子友彦. COPNA树脂—炭素与有机物的中间领域.新型炭材料,1992(4):1~6
[19]王茂章.煤化工与合成材料信息,1990(3)
[20]太田道也.日化志,1992:107~113
[21]大谷杉郎.金属,1989:92
[22]大谷杉郎,汪力.对新型炭的期望.新型炭材料,1990(2):1~4
[23]印杰,陈一东.以萘及萘酚为单体苯甲醛为交联剂的COPNA研究[J ] .高分子料科学与工程,1995 ( 1) :29～32
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[26]阮湘泉等.缩合多核芳烃树脂固化机理[ J ] .天津大学学报,1997 ,130 (2) :217～222
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