酚醛树脂合成和酚醛泡沫板材的制备
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摘要
近些年来,随着我国经济的不断发展,高层次建筑物越来越多,建筑安全节能是社会可持续发展所面临的一项重要任务。然而,由于传统的保温材料聚苯乙烯(PS)和聚氨酯(PU)泡沫在阻燃方面性能非常不好,遇明火甚至火星即可燃烧,而且在燃烧过程中会产生对环境和人类都具有巨大危害的有毒气体,保温材料易燃所发生的重大火灾近年来频频发生。鉴于此,防火性能优越的酚醛泡沫(PF)保温材料就应运而生。
酚醛泡沫虽具有隔热保温、难燃低烟、耐热稳定性好等诸多优点,然而其材质本身较脆易粉化、酸性较强的缺点仍不容忽视。本文针对目前市场所销售的酚醛泡沫这两大缺点,通过对制备酚醛树脂和酚醛泡沫的配方及工艺不断改进,得到了综合性能优越的酚醛泡沫保温板材,其韧性较市场上产品有所提高,产品接近中性,对墙体几乎无腐蚀性,各力学性能也完全达到了国家标准,而且该生产工艺重复性好、可控性强、生产过程不涉及高温高压等条件,非常适合工业化生产。本文主要内容如下：
1.首先,在参阅数十篇相关参考文献的基础上,本文对酚醛树脂概况、反应机理以及固化动力学、耐热性能等方面做了简要阐述。然后,本文介绍了酚醛树脂在国内外的发展及应用。最后,本文针对酚醛泡沫的概况、改性研究、发展应用以及国内外生产企业进行了分析陈述。
2.通过对影响酚醛树脂合成的因素(温度、时间、物料比、催化剂及其用量等)做系统的实验及分析,再结合后期制备酚醛泡沫所得到的反馈信息,我们掌握了合成可发性酚醛树脂的工艺,并优化得到了适合发泡的最佳配方,并对得到的酚醛树脂做了表征及测定,如FTIR、GPC等。
3.在制备出性能稳定、可发性强的酚醛树脂基础上,我们对影响发泡结果的条件做了详细的研究,主要包括发泡剂种类及用量、固化温度、固化时间、表面活性剂种类及用量、固化剂种类及用量等。在试验及综合分析的基础上,我们制备出了综合性能优越的酚醛泡沫保温板材,并对其各方面性能进行了相应的测试及表征。
4.最后,在掌握了单纯酚醛泡沫发泡技术及工艺的基础上,我们针对聚氨酯预聚体改善酚醛泡沫的韧性进行了深入研究,并详细介绍了实验结果,对改善后的酚醛泡沫做了客观的评价。
In recent years, more and more high-rise buildings are being built with the continuous development of economy. Safety and energy-saving have become important tasks for the sustainable development of society. However, since traditional insulation materials, such as polystyrene (PS) and polyurethane(PU) foam, possess poor flame-retartant performance, they will burn in case of fire or even sparks, and generate toxic gases which is harmful to the environment and human being. Fires caused by the traditional insulation materials occur frequently in recent years. It is urgent to develop new flame-retartant materials. Fortunately, PF(phenolic foam) just meets this requirement.
Phenolic foam exsists insulation, flame-retartant, low smoke, excellent heat stability and many other advantages. However, the material itself has the disadvantage of fragility, easy powder and strong acidity. In this thesis, we focused on two major drawbacks of the current market sales phenolic foam. By improving formulation and process of the preparation of phenolic resin and phenolic foam, we obtained the phenolic foam insulation board with excellent comprehensive performance. The ductility of our product is much improved compared with the products on the market. Our products are nearly neutral, avoiding corrosion to the wall. The comprehensive properties reached the national standard completely. In addition, the production process is repeatable, controllable, free of high temparature and high pressure. So this process is suitable for industrial production. The main contents of this thesis are as follows:
1. First of all, on the basis of dozens of relative references, this thesis briefly introduced the general situation of the phenolic resin, reaction mechanism, the curing kinetics and heat resistance etc. Then, this thesis described the development and application of phenolic resin. Finally, this thesis concentrated on situation, modified research, development and application of domestic and foreign manufacturers of phenolic foam analysis statements.
2. Via systematic experiments and analysis on the factors that influence the synthesis of phenolic resin (temperature, time, material ratio, catalyst and its usage), associated with the feedback information obtained by preparation of phenolic foam, we studied synthesis process for phenolic resin, and optimized the foaming formula. The as-prepared phenolic resin have been characterized by FTIR/GPC etc.
3. We developed a process to steadily produce PR suitable for foaming, and further studied the effects of conditions, such as foaming agents, curing temperature, curing time, surfactants, curing agents, on the final foam. And finally, we measured the comprehensive properties of the phenolic resin foam board according to the corresponding standard.
4. Finally, on the basis of the simple phenolic foaming technology and process, we tried to improve the ductility of PF by polyurethane prepolymers and investigated the effects in detail.
酚醛泡沫虽具有隔热保温、难燃低烟、耐热稳定性好等诸多优点,然而其材质本身较脆易粉化、酸性较强的缺点仍不容忽视。本文针对目前市场所销售的酚醛泡沫这两大缺点,通过对制备酚醛树脂和酚醛泡沫的配方及工艺不断改进,得到了综合性能优越的酚醛泡沫保温板材,其韧性较市场上产品有所提高,产品接近中性,对墙体几乎无腐蚀性,各力学性能也完全达到了国家标准,而且该生产工艺重复性好、可控性强、生产过程不涉及高温高压等条件,非常适合工业化生产。本文主要内容如下：
1.首先,在参阅数十篇相关参考文献的基础上,本文对酚醛树脂概况、反应机理以及固化动力学、耐热性能等方面做了简要阐述。然后,本文介绍了酚醛树脂在国内外的发展及应用。最后,本文针对酚醛泡沫的概况、改性研究、发展应用以及国内外生产企业进行了分析陈述。
2.通过对影响酚醛树脂合成的因素(温度、时间、物料比、催化剂及其用量等)做系统的实验及分析,再结合后期制备酚醛泡沫所得到的反馈信息,我们掌握了合成可发性酚醛树脂的工艺,并优化得到了适合发泡的最佳配方,并对得到的酚醛树脂做了表征及测定,如FTIR、GPC等。
3.在制备出性能稳定、可发性强的酚醛树脂基础上,我们对影响发泡结果的条件做了详细的研究,主要包括发泡剂种类及用量、固化温度、固化时间、表面活性剂种类及用量、固化剂种类及用量等。在试验及综合分析的基础上,我们制备出了综合性能优越的酚醛泡沫保温板材,并对其各方面性能进行了相应的测试及表征。
4.最后,在掌握了单纯酚醛泡沫发泡技术及工艺的基础上,我们针对聚氨酯预聚体改善酚醛泡沫的韧性进行了深入研究,并详细介绍了实验结果,对改善后的酚醛泡沫做了客观的评价。
In recent years, more and more high-rise buildings are being built with the continuous development of economy. Safety and energy-saving have become important tasks for the sustainable development of society. However, since traditional insulation materials, such as polystyrene (PS) and polyurethane(PU) foam, possess poor flame-retartant performance, they will burn in case of fire or even sparks, and generate toxic gases which is harmful to the environment and human being. Fires caused by the traditional insulation materials occur frequently in recent years. It is urgent to develop new flame-retartant materials. Fortunately, PF(phenolic foam) just meets this requirement.
Phenolic foam exsists insulation, flame-retartant, low smoke, excellent heat stability and many other advantages. However, the material itself has the disadvantage of fragility, easy powder and strong acidity. In this thesis, we focused on two major drawbacks of the current market sales phenolic foam. By improving formulation and process of the preparation of phenolic resin and phenolic foam, we obtained the phenolic foam insulation board with excellent comprehensive performance. The ductility of our product is much improved compared with the products on the market. Our products are nearly neutral, avoiding corrosion to the wall. The comprehensive properties reached the national standard completely. In addition, the production process is repeatable, controllable, free of high temparature and high pressure. So this process is suitable for industrial production. The main contents of this thesis are as follows:
1. First of all, on the basis of dozens of relative references, this thesis briefly introduced the general situation of the phenolic resin, reaction mechanism, the curing kinetics and heat resistance etc. Then, this thesis described the development and application of phenolic resin. Finally, this thesis concentrated on situation, modified research, development and application of domestic and foreign manufacturers of phenolic foam analysis statements.
2. Via systematic experiments and analysis on the factors that influence the synthesis of phenolic resin (temperature, time, material ratio, catalyst and its usage), associated with the feedback information obtained by preparation of phenolic foam, we studied synthesis process for phenolic resin, and optimized the foaming formula. The as-prepared phenolic resin have been characterized by FTIR/GPC etc.
3. We developed a process to steadily produce PR suitable for foaming, and further studied the effects of conditions, such as foaming agents, curing temperature, curing time, surfactants, curing agents, on the final foam. And finally, we measured the comprehensive properties of the phenolic resin foam board according to the corresponding standard.
4. Finally, on the basis of the simple phenolic foaming technology and process, we tried to improve the ductility of PF by polyurethane prepolymers and investigated the effects in detail.
引文
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[2]Honga U S, Cho K.H, Cho M H,et al. Wear mechanism of multiphase friction materials with different phenolic resin matrices[J].2009.266(7-8):739～744.
[3]Hew-Der Wu, Chen-Chi M. Ma.Thermodynamic properties of the novolac type phenolic resin blended with poly(hydroxyl ether of bisphenol[J]. Polymer,1998.39(3):703～709.
[4]Ishida H.,Allen D J. Physical and mechanical characterization of nearfzero shrinkage polybenzoxazines[J]. J Polym Sci, Polym Phys,1996.34:1019～1030.
[5]Choi M H., Jeon B H., Chung I J. The effect of coupling agent on electrical and mechanical properties of carbon fiber/phenolic resin composites[J]. Polymer,2000.41:3243～3252.
[6]Choi M H, Chung I J, Lee J D. Morphology and Curing Behaviors of Phenolic Resin-Layered Silicate Nanocomposites Prepared by Melt Intercalation[J]. Chem Mater,2000.12:2977～2983.
[7]Zaks Y, Raucher D. Pearce E M,et al. Some structure-property relationships in polymer flammability:Studies of phenolic-derived[J]. J Appl Polym Sci,1982.27:913～930.
[8]Armat R, Bike S G., Chu G., Jones F N.Rheological behavior of solutions of amphiphilic acrylic copolymers in mixed solvents[J]. J. App. Polym. Sci.,1996.60:1927～1938.
[9]Higuchi M., Urakawa T, Morita M. Condensation reactions of phenolic resins.1. Kinetics and mechanisms of the base-catalyzed self-condensation of 2-hydroxymethylphenol[J]. Polymer, 2001.42:4563-4567.
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