聚雙環(huán)戊二烯泡沫復(fù)合材料的制備與性能研究
發(fā)布時間：2019-01-12 16:49
【摘要】：聚雙環(huán)戊二烯(PDCPD)是由雙環(huán)戊二烯(DCPD)通過開環(huán)移位聚合得到的一種綜合性能優(yōu)異的新型熱固性工程塑料。雙環(huán)戊二烯的開環(huán)移位聚合過程中會放出大量的熱,利用該反應(yīng)的強放熱能同時引發(fā)發(fā)泡劑發(fā)泡的特點設(shè)計出一種聚合、發(fā)泡同步可控的新型熱固性泡沫塑料以及合成方法。雙環(huán)戊二烯按照開環(huán)移位機理快速聚合的同時,發(fā)泡劑受熱產(chǎn)生氣泡穩(wěn)定在基體中形成多孔結(jié)構(gòu),多孔結(jié)構(gòu)甚至微孔結(jié)構(gòu)的產(chǎn)生將賦予材料新的性能。通過選擇發(fā)泡劑種類、合成工藝、以及同時使用多種泡沫穩(wěn)定劑可形成不同結(jié)構(gòu)不同性能的泡沫復(fù)合材料,從而可進一步擴展PDCPD材料的應(yīng)用范圍。本文在開環(huán)移位催化體系下,嘗試了多種有機、無機發(fā)泡劑,選取合適的發(fā)泡劑以化學(xué)發(fā)泡法通過前沿聚合以及同步聚合分別研究了PDCPD的聚合、發(fā)泡反應(yīng)特征,并采用同步聚合發(fā)泡的方法制備出了不同催化劑比例、不同發(fā)泡劑含量、不同模具溫度下的聚雙環(huán)戊二烯泡沫材料,以及不同納米碳酸鈣(NPCC)、丁苯橡膠(SBR)含量的聚雙環(huán)戊二烯/納米碳酸鈣/丁苯橡膠(PDCPD/NPCC/SBR)泡沫復(fù)合材料。用SEM、Nano Measurer、TG等對復(fù)合材料的結(jié)構(gòu)和熱性能進行分析和表征,用電子萬能試驗機對泡沫復(fù)合材料進行了力學(xué)性能測試。研究發(fā)現(xiàn),DCPD開環(huán)移位聚合所放出的熱能夠引發(fā)多種發(fā)泡劑發(fā)泡,但其中AIBN發(fā)泡劑不會阻聚,發(fā)泡泡孔較小、分布均勻且泡孔率較高;同步聚合發(fā)泡相對前沿聚合發(fā)泡制備的泡沫材料具有較小的泡孔以及均勻的孔徑分布,且相對光滑平整的表面;在一定的催化劑比例以及發(fā)泡溫度下,可制備出具有微孔結(jié)構(gòu)的PDCPD泡沫;另外,NPCC作為經(jīng)典成核增強劑以及SBR作為粘度穩(wěn)定劑的加入,有效的提高了發(fā)泡劑的使用濃度范圍,改善了泡沫大小與結(jié)構(gòu)分布,可制備出微孔PDCPD泡沫復(fù)合材料。在力學(xué)測試范圍內(nèi),泡沫材料的力學(xué)性能隨著AIBN含量的升高而呈現(xiàn)出遞減的趨勢,其比壓縮強度最高達到32.81 MPa/(g?cm-3);而在PDCPD/NPCC/SBR體系中,隨著NPCC或SBR含量的升高,復(fù)合材料的力學(xué)性能均出現(xiàn)先升高后降低的趨勢,在NPCC含量為6.0 wt%,SBR含量為1.5 wt%時綜合力學(xué)性能達最優(yōu),壓縮強度、彎曲強度、拉伸強度以及沖擊強度分別達到18.73 MPa,80.03MPa,28.76 MPa以及13.79 k J/m2。TG測試表明,測試范圍內(nèi),隨著NPCC含量的升高,泡沫復(fù)合材料的熱穩(wěn)定性得到明顯提升,PDCPD泡沫復(fù)合材料的分解溫度在460℃。吸水率測試結(jié)果顯示帶結(jié)皮的PDCPD泡沫浸泡超過96 h后吸水率僅為0.129%,表明泡沫材料具有較低的吸水率。對試樣導(dǎo)熱性能的進行測試,PDCPD泡沫復(fù)合材料樣本的平均導(dǎo)熱系數(shù)為0.042 W/mk,表明泡沫復(fù)合材料具有優(yōu)異的隔熱性。
[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，
本文編號：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，
本文編號：2407997
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