聚双环戊二烯泡沫复合材料的制备与性能研究
发布时间：2019-01-12 16:49
【摘要】：聚双环戊二烯(PDCPD)是由双环戊二烯(DCPD)通过开环移位聚合得到的一种综合性能优异的新型热固性工程塑料。双环戊二烯的开环移位聚合过程中会放出大量的热,利用该反应的强放热能同时引发发泡剂发泡的特点设计出一种聚合、发泡同步可控的新型热固性泡沫塑料以及合成方法。双环戊二烯按照开环移位机理快速聚合的同时,发泡剂受热产生气泡稳定在基体中形成多孔结构,多孔结构甚至微孔结构的产生将赋予材料新的性能。通过选择发泡剂种类、合成工艺、以及同时使用多种泡沫稳定剂可形成不同结构不同性能的泡沫复合材料,从而可进一步扩展PDCPD材料的应用范围。本文在开环移位催化体系下,尝试了多种有机、无机发泡剂,选取合适的发泡剂以化学发泡法通过前沿聚合以及同步聚合分别研究了PDCPD的聚合、发泡反应特征,并采用同步聚合发泡的方法制备出了不同催化剂比例、不同发泡剂含量、不同模具温度下的聚双环戊二烯泡沫材料,以及不同纳米碳酸钙(NPCC)、丁苯橡胶(SBR)含量的聚双环戊二烯/纳米碳酸钙/丁苯橡胶(PDCPD/NPCC/SBR)泡沫复合材料。用SEM、Nano Measurer、TG等对复合材料的结构和热性能进行分析和表征,用电子万能试验机对泡沫复合材料进行了力学性能测试。研究发现,DCPD开环移位聚合所放出的热能够引发多种发泡剂发泡,但其中AIBN发泡剂不会阻聚,发泡泡孔较小、分布均匀且泡孔率较高;同步聚合发泡相对前沿聚合发泡制备的泡沫材料具有较小的泡孔以及均匀的孔径分布,且相对光滑平整的表面;在一定的催化剂比例以及发泡温度下,可制备出具有微孔结构的PDCPD泡沫;另外,NPCC作为经典成核增强剂以及SBR作为粘度稳定剂的加入,有效的提高了发泡剂的使用浓度范围,改善了泡沫大小与结构分布,可制备出微孔PDCPD泡沫复合材料。在力学测试范围内,泡沫材料的力学性能随着AIBN含量的升高而呈现出递减的趋势,其比压缩强度最高达到32.81 MPa/(g?cm-3);而在PDCPD/NPCC/SBR体系中,随着NPCC或SBR含量的升高,复合材料的力学性能均出现先升高后降低的趋势,在NPCC含量为6.0 wt%,SBR含量为1.5 wt%时综合力学性能达最优,压缩强度、弯曲强度、拉伸强度以及冲击强度分别达到18.73 MPa,80.03MPa,28.76 MPa以及13.79 k J/m2。TG测试表明,测试范围内,随着NPCC含量的升高,泡沫复合材料的热稳定性得到明显提升,PDCPD泡沫复合材料的分解温度在460℃。吸水率测试结果显示带结皮的PDCPD泡沫浸泡超过96 h后吸水率仅为0.129%,表明泡沫材料具有较低的吸水率。对试样导热性能的进行测试,PDCPD泡沫复合材料样本的平均导热系数为0.042 W/mk,表明泡沫复合材料具有优异的隔热性。
[Abstract]:Poly (dicyclopentadiene) (PDCPD) is a new type of thermosetting engineering plastics with excellent properties obtained by ring-opening shift polymerization of dicyclopentadiene (DCPD). A large amount of heat will be released during the ring-opening shift polymerization of dicyclopentadiene. A new type of thermosetting foam, which is polymerized and controlled simultaneously, and its synthesis method have been designed by using the strong exothermic heat energy of the reaction and the foaming agent foaming. At the same time of rapid polymerization of dicyclopentadiene in accordance with the ring-opening migration mechanism, bubbles produced by the foaming agent were stable and formed in the matrix. The formation of the porous structure and even the formation of the microporous structure would give the materials new properties. By selecting the type of foaming agent, synthesizing technology and using many kinds of foam stabilizers at the same time, foam composites with different structure and different properties can be formed, thus the application range of PDCPD materials can be further expanded. In this paper, a variety of organic and inorganic foaming agents were tried in the ring-opening shift catalytic system. The polymerization and foaming reaction characteristics of PDCPD were studied by chemical foaming method and simultaneous polymerization, respectively. The polydicyclopentadiene foam materials with different catalyst ratio, different foaming agent content, different mold temperature and different nanometer calcium carbonate (NPCC),) were prepared by simultaneous polymerization and foaming. Polydicyclopentadiene / nano-calcium carbonate / styrene-butadiene rubber (PDCPD/NPCC/SBR) foam composites with (SBR) content. The structure and thermal properties of the composites were analyzed and characterized by SEM,Nano Measurer,TG, and the mechanical properties of foam composites were tested by electronic universal testing machine. It is found that the heat released by DCPD ring-opening translocation polymerization can cause many foaming agents, but the foaming agent of AIBN does not prevent the polymerization, the foam pore size is small, the distribution is uniform and the foaming porosity is high. The foam materials prepared by simultaneous polymerization foaming have relatively small foam pores and uniform pore size distribution, and relatively smooth and smooth surface. PDCPD foam with micropore structure can be prepared under certain catalyst ratio and foaming temperature. In addition, the addition of NPCC as a classical nucleating enhancer and SBR as a viscosity stabilizer can effectively increase the concentration range of foaming agent, improve the size and structure distribution of foaming agent, and produce microporous PDCPD foam composites. In the range of mechanical test, the mechanical properties of foam materials show a decreasing trend with the increase of AIBN content, and the highest specific compressive strength is 32.81 MPa/ (g?cm-3). In PDCPD/NPCC/SBR system, with the increase of NPCC or SBR content, the mechanical properties of the composites increased first and then decreased. When the content of NPCC was 6.0 wt%,SBR and 1.5 wt%, the comprehensive mechanical properties were the best. The compressive strength, bending strength, tensile strength and impact strength were 18.73 MPa,80.03MPa,28.76 MPa and 13.79k J/m2.TG, respectively. The thermal stability of foam composites was improved obviously, and the decomposition temperature of PDCPD foam composites was 460 鈩，
本文编号：2407997
[Abstract]:Poly (dicyclopentadiene) (PDCPD) is a new type of thermosetting engineering plastics with excellent properties obtained by ring-opening shift polymerization of dicyclopentadiene (DCPD). A large amount of heat will be released during the ring-opening shift polymerization of dicyclopentadiene. A new type of thermosetting foam, which is polymerized and controlled simultaneously, and its synthesis method have been designed by using the strong exothermic heat energy of the reaction and the foaming agent foaming. At the same time of rapid polymerization of dicyclopentadiene in accordance with the ring-opening migration mechanism, bubbles produced by the foaming agent were stable and formed in the matrix. The formation of the porous structure and even the formation of the microporous structure would give the materials new properties. By selecting the type of foaming agent, synthesizing technology and using many kinds of foam stabilizers at the same time, foam composites with different structure and different properties can be formed, thus the application range of PDCPD materials can be further expanded. In this paper, a variety of organic and inorganic foaming agents were tried in the ring-opening shift catalytic system. The polymerization and foaming reaction characteristics of PDCPD were studied by chemical foaming method and simultaneous polymerization, respectively. The polydicyclopentadiene foam materials with different catalyst ratio, different foaming agent content, different mold temperature and different nanometer calcium carbonate (NPCC),) were prepared by simultaneous polymerization and foaming. Polydicyclopentadiene / nano-calcium carbonate / styrene-butadiene rubber (PDCPD/NPCC/SBR) foam composites with (SBR) content. The structure and thermal properties of the composites were analyzed and characterized by SEM,Nano Measurer,TG, and the mechanical properties of foam composites were tested by electronic universal testing machine. It is found that the heat released by DCPD ring-opening translocation polymerization can cause many foaming agents, but the foaming agent of AIBN does not prevent the polymerization, the foam pore size is small, the distribution is uniform and the foaming porosity is high. The foam materials prepared by simultaneous polymerization foaming have relatively small foam pores and uniform pore size distribution, and relatively smooth and smooth surface. PDCPD foam with micropore structure can be prepared under certain catalyst ratio and foaming temperature. In addition, the addition of NPCC as a classical nucleating enhancer and SBR as a viscosity stabilizer can effectively increase the concentration range of foaming agent, improve the size and structure distribution of foaming agent, and produce microporous PDCPD foam composites. In the range of mechanical test, the mechanical properties of foam materials show a decreasing trend with the increase of AIBN content, and the highest specific compressive strength is 32.81 MPa/ (g?cm-3). In PDCPD/NPCC/SBR system, with the increase of NPCC or SBR content, the mechanical properties of the composites increased first and then decreased. When the content of NPCC was 6.0 wt%,SBR and 1.5 wt%, the comprehensive mechanical properties were the best. The compressive strength, bending strength, tensile strength and impact strength were 18.73 MPa,80.03MPa,28.76 MPa and 13.79k J/m2.TG, respectively. The thermal stability of foam composites was improved obviously, and the decomposition temperature of PDCPD foam composites was 460 鈩，
本文编号：2407997
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