腰果酚的改性及其在呋喃树脂防腐材料性能优化上的应用

发布时间：2018-04-25 08:52

本文选题：腰果酚 + 化学改性　；参考：《安徽工程大学》2015年硕士论文

【摘要】：呋喃树脂在多种树脂中的混溶性都较好,而且耐存贮。呋喃树脂经过交联固化以后,不含有活泼的官能团,所以一般情况下其与腐蚀介质不会发生反应,因此,经交联固化后的呋喃树脂具有优良耐蚀、耐热及阻燃性能。但是与此同时,呋喃树脂也存在很多缺陷,例如：冲击强度低,固化物柔韧性差、脆性大等。除此以外,呋喃树脂在固化成型的时候,生成的水分会导致树脂产生收缩及孔洞等问题,而这些问题对呋喃树脂的应用推广产生了一定的影响。因此,希望研发出一种既带有柔性长链又带有活性羟甲基的新型呋喃树脂添加剂,从而对固化后的呋喃树脂起到增强增韧的效果。旦些本文设计出了两条不同的呋喃树脂添加剂的合成路线：首先以醛为改性剂,以带有柔性长链及酚羟基结构的腰果酚为母体,利用化学改性的方法对其进行改性,从而制备出带有柔性长链活性羟基的羟(苯)甲基腰果酚及线型腰果酚甲醛树脂。然后以聚乙二醇及糠醇为原料,利用化学方法用聚乙二醇对糠醇进行改性,制备出中间由聚乙二醇柔性长链连接且末端带有活性糠醇基团的聚乙二醇改性糠醇。与此同时,在制备过程考察了加料比、反应温度、反应时间等因素对羟(苯)甲基腰果酚、线型腰果酚甲醛树脂及聚乙二醇改性糠醇制备的影响,最终利用红外、热重等对它们进行了表征。最后,本次研究将制备出的这一系列新型呋喃树脂添加剂按照一定比例添加到未固化的呋喃树脂中,然后经交联固化制备出可用于相关测试的改性呋喃树脂样条。并且利用红外对改性呋喃树脂防腐材料的化学结构进行了表征,利用扫描电镜对其断面形貌进行了观察,利用热重测试仪对其耐高温性能进行测试及分析,利用万能实验机及冲击实验机对其力学性能及冲击强度进行了测定；最后对其防腐蚀性能进行了测定。研究结果表明：本次研究制备的呋喃树脂改性添加剂很好地提高了呋喃树脂防腐材料的韧性及冲击强度。在合成路线一中,以等摩尔量的甲醛与腰果酚为原料、丁二酸为催化剂,反应温度为125℃、时间为4-5h时,制备的添加剂(线型腰果酚甲醛树脂)对呋喃树脂的增强增韧效果最好。当该添加剂用量达25wt%时,改性呋喃树脂的抗拉强度由原来24MPa提高至33.6MPa,提高幅度达到40%,断裂伸长率由以前1.06%提高至4.35%,提高幅度为310%；冲击强度强度由原来的0.542KJ/m2提高至0.613KJ/m2,提高了13.1%；且树脂内部孔洞明显减少。在合成路线二中,以糠醇及分子量400的聚乙二醇为原料、盐酸为催化剂,反应温度为75℃、时间为1h时,制备的添加剂对呋喃树脂的增强增韧效果最好。当该添加剂用量达25wt%时,拉伸强度最大达到22.8 MPa,而断裂伸长率达到4.21%。并且经热重测试及分析发现,聚乙二醇改性糠醇改性呋喃树脂耐高温性能相对于呋喃树脂稍有减弱；而羟苯甲基腰果酚改性呋喃树脂及线型腰果酚甲醛树脂改性呋喃树脂则在很大程度上提升了呋喃树脂的耐高温性能,其中线型腰果酚甲醛树脂改性呋喃树脂的耐高温性能提升最大,使呋喃树脂的分解温度由230℃提升到了360℃。本次研究所制备的呋喃树脂改性添加剂在一定程度上克服了呋喃树脂防腐材料固化物柔韧性差、脆性大、冲击强度不高等缺点。最终得到的新型的呋喃树脂材料,期望能够在冶金、化工、基建工程、防腐容器等方面作为防腐蚀材料以及结构材料得到广泛地应用。
[Abstract]:Furan resin has better miscibility and storage in a variety of resins. Furan resin has no active functional groups after crosslinking curing, so in general it does not react with corrosion medium. Therefore, the furan resin after crosslinking curing has excellent corrosion resistance, heat resistance and flame retardancy. But at the same time, furan The resin also has many defects, such as low impact strength, poor flexibility and great brittleness. In addition, when furan resin is cured, the generated moisture will cause the shrinkage and hole of the resin, and these problems have a certain effect on the application of furan resin. Therefore, we hope to develop a kind of resin. A new furan resin additive with both flexible long chain and active hydroxymethyl was used to enhance the toughening effect of furan resin after curing. Two different synthetic routes of furan resin additives were designed. First, aldehyde was used as modifier, and cashew phenol with flexible long chain and phenolic hydroxyl structure was used as the mother. It was modified by chemical modification to prepare hydroxybenzyl cashew hydroxybenzol and linear cashew formaldehyde resin with flexible long chain active hydroxyl group. Then polyethylene glycol and furfuryl alcohol were used as raw materials to modify the furfuryl alcohol with polyethylene glycol. At the same time, the effects of feed ratio, reaction temperature, reaction time and other factors on the preparation of hydroxybenzyl cashew, linear cashew formaldehyde resin and polyethylene glycol modified furfuryl alcohol were investigated in the preparation process. Finally, they were characterized by infrared and thermal weight. A series of new furan resin additives were added to the non curing furan resin in a certain proportion, and then the modified furan resin sample was prepared by crosslinking curing. The chemical structure of the modified furan resin anticorrosion material was characterized by infrared and the scanning electron microscope was used. The profile of the section was observed and the thermogravimetric analyzer was used to test and analyze its high temperature resistance. The mechanical properties and impact strength were measured by the universal test machine and the impact test machine. Finally, the corrosion resistance was measured. The results showed that the furan resin was modified by this study. The toughness and impact strength of furan resin anticorrosion materials are improved very well. In the synthetic route one, the additive (line type cashew formaldehyde tree fat) has the best toughening effect on furan resin when the amount of formaldehyde and cashew phenol as the raw material and the diacid as the catalyst, the reaction temperature is 125 C and the time is 4-5h. When the dosage of adding agent is 25wt%, the tensile strength of the modified furan resin is increased from original 24MPa to 33.6MPa, the increase of the tensile strength is 40%, the elongation at break is raised from 1.06% to 4.35%, and the increase is 310%. The strength of the impact strength is increased from the original 0.542KJ/m2 to 0.613KJ/m2, and is increased by 13.1%; and the inner hole of the resin is obviously reduced. The synthetic road is in the synthetic road. Xian Erzhong, with furfuryl alcohol and molecular weight 400 polyethylene glycol as raw material, hydrochloric acid as the catalyst, the reaction temperature is 75, and the time is 1H, the additive has the best strengthening and toughening effect on furan resin. When the dosage of the additive reaches 25wt%, the tensile strength is up to 22.8 MPa, and the elongation at break reaches 4.21%. and is tested by thermogravimetric analysis. It was found that the high temperature resistance of furan modified furan resin modified by polyethylene glycol was slightly weaker than that of furan resin, while hydroxybenzyl cashew modified furan resin and linear cashew formaldehyde resin modified furan resin greatly improved the high temperature resistance of furan resin, in which the furan resin modified by linear cashew formaldehyde resin modified furan resin. The high temperature resistance of the resin has been improved greatly, and the decomposition temperature of furan resin is raised from 230 to 360. The furan resin modifier prepared by this study overcomes the shortcomings of poor flexibility, large brittleness and low impact strength of furan resin anticorrosion material. The new furan resin material is finally obtained. It is expected that it can be widely used as corrosion protection material and structural material in metallurgy, chemical engineering, infrastructure projects, anticorrosive containers and so on.

【学位授予单位】：安徽工程大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB37

【参考文献】