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蜜胺树脂的增韧改性及热解动力学研究

Study on Toughening Modification & Pyrolysis Kinetics of Melamine Resin

【作者】 张汉力

【导师】 宋怀俊;

【作者基本信息】 郑州大学 , 化学工艺, 2011, 硕士

【摘要】 蜜胺泡沫塑料是一种具有阻燃、吸音降噪、隔热、耐热稳定、卫生无毒、后加工性能优良的绿色环保的高性能泡沫塑料。但纯蜜胺树脂是含有刚性三嗪环结构的三维立体网络结构的热固性高聚物,交联密度大,发泡性能差,制成的泡沫体硬度较大,柔韧性较差,不易拉伸。因此,树脂韧性的提高,脆性的降低,成为开发新型发泡用蜜胺树脂的重要目标。本论文选取聚乙二醇(PEG-200)、三(2-羟乙基)异氰脲酸酯(THEIC)两种改性剂分别对蜜胺树脂进行增韧改性,以树脂体系的动力粘度作为改性树脂的评价指标,由正交实验结合单因素实验优化改性树脂的聚合工艺条件(如反应物摩尔比、反应时间、改性剂添加量、固含量等);通过红外光谱、核磁共振碳谱、热失重对改性树脂的结构、热稳定性进行表征和鉴定,并通过测定改性树脂的拉伸强度和断裂伸长率对其韧性进行表征;最后对改性树脂的热解动力学进行研究,为进一步了解发泡用蜜胺树脂的耐热性及其应用提供参考价值。实验得出,PEG改性树脂的适宜工艺条件为:体系pH值为9.5, n(F)/n(M)为2.8,固含量为75%,反应时间为50min, PEG添加量为5%;THEIC改性树脂的适宜工艺条件为:体系pH值为9.5,n(F)/n(M)为2.8,固含量为75%,反应时间为90min, THEIC添加量为10%。PEG、THEIC参与了体系反应,成功地植入蜜胺树脂的分子链中,加大了三嗪环之间的距离,可起到增韧改性的作用,但改性剂加入对树脂的耐热性能有一定的降低;当PEG添加量为5%, THEIC添加量为10%时,对应的改性树脂的拉伸强度和断裂伸长率基本达到发泡用树脂GFDA-7的要求,进一步得出适合发泡用蜜胺树脂的适宜工艺条件。得到PEG改性树脂热解动力学方程为:

【Abstract】 Melamine foam is a kind of high-performance green foam with Flame-retardant, acoustic noise, thermal insulation, heat stable, health non-toxic, easy post-processing performance.Widely used in architectural acoustics, automotive, industrial noise, industrial insulation, rail transportation, aerospace navigation, equipment installation and air conditioning systems, cleaning systems, etc.. But pure melamine resin was a thermosetting polymer, and it formed a cross-linking network structure in three dimensions, a rigidity triazine ring included in the network structure, thus resulted in that the melamine resin has a poor forming foam performance. Foam formed is hard and crisp with poor mechanical properties, low intensity, small deformation capacity, poor tensile and flex. Therefore, improvement of toughness and decreasement of brittleness were an important goal on developing new foaming melamine resin.The melamine resin which was respectively modified with PEG-200 and tri(2-hydroxyethyl)isocyanurate was studied in this paper. Dynamic viscosity of resin system is used as the evaluation index of modified resin. The orthogonal experiment and single factor experiment were used to investigate the polymerizing reaction conditions of modified resin (such as material ratio、reaction time、amount of modifier、solid content) on the polymerization reaction system; Structure and thermal stability of modified resin were characterized and identified using infrared spectroscopy, nuclear magnetic resonance carbon spectra, thermal gravimetric; Toughness was characterized through determining the tensile strength and fracture elongation of the modified resins, and the optimal reaction conditions of appropriate foaming modified resin are obtained; Finally, Through studying the pyrolysis kinetics of the modified resin, provide reference values for further understanding the heat resistance and application of the foaming melamine.The results indicate that the appropriate conditions of PEG modified resin were as follows, pH is 9.5, n(F)/n(M)=2.8, solid content is 75%, reaction time is 50min, the amount of PEG is 5%; the appropriate conditions of THEIC modified resin were as follows, pH is 9.5, n(F)/n(M)=2.8, solid content is 75%, reaction time is 90min, the amount of THEIC is 10%. PEG, THEIC were involved in the reaction system and successfully implanted melamine resin molecular chain, increased the distance between the triazine ring, the toughness of the modified resin was improved; though the fire-retardant property of the modified resin with modifier was reduced; When the amount of PEG is 5% and amount of THEIC is 10%, the related tensile strength and fracture elongation of the corresponding modified resins basically reach the requirements of foaming resin GFDA-7, and the appropriate conditions of appropriate foaming modified resin were further obtained. Kinetic equation of PEG modified resin is dα/dt=2.5368×1015 (1-α)[-1n(1-α)]-2 e-208.0769/RT.

  • 【网络出版投稿人】 郑州大学
  • 【网络出版年期】2012年 04期
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