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1南京林业大学本科毕业设计(论文)题 目: 多元脂肪酸改性热固性环氧沥青材料的制备和性能研究学 院: 南方学院 专 业: 化学工程与工艺 学 号: n 学生姓名: 杨亚萍 指导教师: 费宝丽 职 称: 副教授 二 O 一三 年 六 月 2摘要随着跨江大桥和高速公路建设的迅速发展,铺设路面所需沥青材料的性能研究成为各国科研人员开始探索的重点方向。环氧沥青材料作为重要的路面铺装材料中的胶黏剂,对道路建设的发展起着及其重要的作用。如何研制出性能优异的环氧沥青材料已经成为迫在眉睫的事情。另一方面,随着地球上化石资源的枯竭,人们越来越重视可再生的生物质资源开发利用研究,利用可再生生物质资源完全或部分替代不可再生的矿物资源及其衍生产品制备新型的路面材料,可为生物质资源制备新型生物质基复合材料提供了一条新的途径,对高分子材料的可持续发展具有重大意义。鉴于羧酸或酸酐类固化剂对环氧沥青具有较好的固化作用,将生物基的多元脂肪酸引入至环氧沥青体系之中可望制得一种性能优异的热固性环氧沥青材料。本文首先利用桐油与马来酸酐加成合成的桐油酸酐为原料制备了桐油三酸固化剂;而后以多聚环甲酯为原料制备了一种聚醚多元脂肪酸类固化剂。并采用力学测试、FTIR、GPC、SEM、TG等分析手段表征了所制备的多元脂肪酸及其固化后的环氧沥青材料。分别选 E51 环氧树脂、甲基四氢苯酐为基础环氧树脂和固化剂,当固化体系中的桐油三酸替代常规甲基四氢苯酐固化剂的固化功效比例为 10%时,固化物的拉伸强度为23.57MPa,弯曲强度高达 40.02MPa,但制备的沥青材料脆性较大。为此在本研究中又制备了一种具有支化结构的多聚脂肪酸固化剂,在添加 50wt%基础可饶环氧树脂且保持桐油三酸添加固化功效比例(30%)不变的情况下,当多聚脂肪酸的添加功效比例为 20%时,固化物的拉伸强度为 1.96MPa,弯曲强度高达 7.99 MPa,其断裂伸长率可达到 203.74 %;FTIR 谱图分析表明桐油三酸、多聚脂肪酸结构已完全共聚到体系之中;SEM 分析结果表明共聚材料断裂面较为平滑规整,呈明显的脆性断裂特征。TG 的分析结果表明,热固性环氧沥青材料具有良好的热稳定性,其初始分解温度均高于 330。关键词:环氧沥青;桐油三酸;多元脂肪酸;制备;固化剂3AbstractWith the development of cross river bridge and highway construction, the study on the performance of asphalt materials which used to pave a road has become an important direction of many researchers for many country. Epoxy asphalt material can be used as a adhesive of pavement material, now it has played an important role on the development of road construction. How to develop new epoxy asphalt material with excellent performance has become a popular subject. In addition, with the growing shortage of crude oil resources, considerable research effort has been devoted to develop new products using renewable biomass resources as raw materials. Using renewable resources and their derivative products to prepare a kind of new pavement materials instead of non-renewable mineral resources completely or partly could provide a new way for the preparation of new biomass-based materials. It is of great significance to the sustainable development of epoxy material. In view of the superior curing effects of polycarboxylic acid and anhydride curing agent on epoxy asphalt material, a kind of excellent epoxy asphalt material may be expected to be prepared by introducing bio-based polybasic fatty acids. In this paper, tung oil anhydride which came from DA reaction between tung oil and maleic anhydride was used as raw material to synthesize tung oil based three acids curing agent. In addition, polymerized fatty acid curing agent was also synthesized using polymerized fatty acid methyl ester as raw materials via simple hydrolysis reaction. And the prepared polybasic fatty acids and thermosetting epoxy asphalt materials which modified by polymerized fatty acid and tung oil-based three acids curing agent were characterized by mechanical test, FTIR, GPC, SEM and TG analysis. The thermosetting epoxy asphalt materials prepared in this study had excellent mechanical properties using E51 epoxy resin and methyl tetrahydrophthalic anhydride as basic epoxy resin and curing agent, respectively.And the epoxy asphalt material modified by tung oil-based three acid with 10% of curing effect replacement ratio has the highest tensile strength of 23.57MPa and bending strength of 40.03MPa. But their cured materials brittleness was too large, thus a new polymerized fatty acid curing agent was also prepared. Under the condition of 50 wt% replacement ratio of flexible epoxy and 30% of curing effect replacement ratio of tung oil-based three acid, when the curing effect replacement ratio of polymerized fatty acid was 20%, the tensile strength of prepared cured epoxy asphalt material was 1.96MPa, bending strength could reach 7.99MPa, and the breaking enlongaition could reach 203.74 %. FTIR analysis demonstrateded that polymerized fatty acid and tung oil-based three acids have been completely copolymerizated into cured system. SEM analysis showed that the cured materials fracture surface was more regular and smooth, indicating a distinct brittle fracture character. TGA results showed that the prepared thermosetting epoxy asphalt material had good thermal stability, as all samples initial thermal decomposition temperature were all above 330.Keywords:Epoxy asphalt; Tung oil-based three acids; Polymerized fatty acid; Preparation; Curing agent4第一章 前言 .61.1 引言 .61.2 研究背景 .61.3 国内外研究现状及评述 .91.4 研究意义 .101.5 创新点 .101.6 论文研究内容和研究目的 .111.6.1 研究内容 .111.6.2 研究目的 .
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