聚合物/α-磷酸锆纳米复合材料的制备及阻燃与炭化机理研究
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摘要
α-磷酸锆(α-ZrP)是一类具有固体酸催化作用的层状化合物。本文作者结合国内外文献调研和本课题组的有关工作基础,在综述聚合物/无机物纳米复合材料的最新研究进展的基础上,将纳米复合与凝聚相的催化成炭结合,发展聚合物材料的新型阻燃技术。本文从制备具有片层阻隔作用和固体酸催化活性的α-ZrP出发,制备了低密度聚乙烯/乙烯-醋酸乙烯酯(LDPE/EVA)、聚丙烯(PP)、高抗冲聚苯乙烯(HIPS)、ABS典型聚合物/磷酸锆(α-ZrP)纳米复合材料,研究其微观结构与热稳定性、燃烧性能等之间的关系;结合热重分析和锥形量热实验,研究聚合物纳米复合材料的热解和燃烧行为,分析α-ZrP与基体中无卤阻燃剂的阻燃协效作用机理,探索制备新型阻燃材料的途径。主要研究工作如下:
1.以水热法合成层状化合物α-ZrP,以乙胺为胶体化试剂,采用“层离—插层法”获得了C16/α-ZrP插层化合物(OZrP),为制备聚合物/α-ZrP纳米复合材料提供了优良的前驱物。以溶液法制备二茂铁(Fc)插层的α-ZrP(Fc-ZrP),并尝试制备聚合物/Fc-ZrP复合材料。OZrP和Fc-ZrP的结构和形貌用X射线衍射(XRD)和透射电镜(TEM)表征,采用热重分析(TGA)研究了其热性能。
2.采用熔融共混法制备了LDPE/EVA/(ATH,OZrP)纳米复合材料。对纳米复合材料进行微观结构和形貌表征及一系列燃烧性能测试,发现LDPE/EVA/(ATH,OZrP)纳米复合材料的阻燃性能比LDPE/EVA和LDPE/EVA/ATH阻燃体系有明显提高。在燃烧过程中,OZrP的加入可以抑制基体的熔融滴落现象,并形成稳定的炭层,而只添加ATH无OZrP的阻燃体系仍存在严重的滴落现象,无稳定炭层形成。综合热释放速率峰值与点燃时间TTI、火灾性能指数FPI和火灾发展指数FGI评价材料的火灾危险性,LDPE/EVA/(ATH,OZrP)纳米复合材料的阻燃性能比聚合物纯样明显提高,火灾危险性降低。
3.采用熔融共混法制备PP/(IFR,OZrP)纳米复合材料,热重分析和SEM研究表明,添加OZrP的PP/IFR阻燃体系成炭量有所增加,燃烧后的残渣中,炭层结构更加稳固、致密。当PP基体中含有25%IFR时,复合材料的氧指数为33,垂直燃烧测试为UL-94 V-1级别,当保持添加剂总量不变,添加3%OZrP到PP/IFR体系中,氧指数增加到37,垂直燃烧达到V-0级别。IFR与OZrP间存在协效作用,合适的添加比例有利于提高复合材料的阻燃性能。
4.采用熔融共混法制备了HIPS/OZrP纳米复合材料,随着OZrP在HIPS基体中含量的增加,纳米复合材料的成炭量也逐渐增大,当复合材料中含1%OZrP时,其最大热释放速率峰值比纯样降低11%。对炭化产物的形貌和组成研究分析表明,存在石墨片和碳纳米管,这种炭层结构有利于提高材料阻燃性能。同时采用熔融共混法制备了HIPS/Fc-ZrP复合材料,Fc-ZrP由于层间距小,很难与HIPS形成具有良好插层或层离结构的纳米复合材料。燃烧后的炭化产物研究表明,Fc-ZrP对HIPS基体在燃烧过程中存在催化成炭,有助于形成石墨化结构。
5.采用熔融共混法制备了ABS/OZrP纳米复合材料,热稳定性研究表明,ABS/OZrP纳米复合材料的热稳定性比纯ABS树脂稍有提高,成炭量随着OZrP在基体树脂中的含量增加而增大。ABS/OZrP纳米复合材料炭化研究表明,在360℃的温度下炭层中存在晶化程度较高的碳材料生成:存在缺陷的多壁碳纳米管,当温度提高到500～800℃,会有更高晶化程度的多种结构与形貌的碳生成。
α-zirconium phosphate (α-ZrP) has a solid acid catalyst function. In this thesis, It would be a high efficiency flame retarding approach in polymer materials combining nanocomposites and catalyzed carbonzation on the basis of the early literatures and our group's work. Several typical polymer/OZrP nanocomposites were prepared by melting intercalation and characterized by different approaches based on the synthesis and properly organic modification ofα-ZrP. Then, the relationships between structure and property, especially thermal stability and flammability properties of the nanocomposites, using both thermogravimetric analysis (TGA) and cone calorimetry experiment, were discussed in detail. The thermal degradation of the nanocomposites was investigated by a combination of the combustion property of nanocomposites, which suggested the synergistic effect betweenα-ZrP and halogen-free flame retardants. Also, a comprehensive assessment of degradation and combustion property of the nanocomposites were carried out. The main research results as following:
1. Theα-ZrP was synthesized by hydrothermal crystallization. High-intensity ultrasound was applied to the intercalation process ofα-ZrP in organic amine solution, hexadecyltrimethyl ammonium bromide(C16)/α-ZrP intercalated compound (OZrP) was obtained by "exfoliation-intercalation method". The ferrocene intercalatedα-ZrP (Fc-ZrP) was synthesized by solution method. Structures of OZrP and Fc-ZrP were characterized by X-ray diffraction (XRD). Morphologies of OZrP and Fc-ZrP were observed by transmission electron microscopy (TEM). And the thermal property of OZrP and Fc-ZrP were measured by TGA.
2. LDPE/EVA/(ATH,OZrP) nanocomposites were prepared by melting interaction. It consequently exhibited better flame retardant properties than LDPE/EVA and LDPE/EVA/ATH systems. ZrP eliminated the melting-dripping phenomenon during the combustion of LDPE/EVA/(ATH,OZrP) nanocomposites and promoted formation of carbonaceous char. After evaluating peak heat release rate, ignition time(TTI), fire propagation index (FPI) and fire growth index (FGI), it indicated flame retardant properties of LDPE / EVA / (ATH, OZrP) nanocomposite had a significant improvement.
3. PP/(IFR,OZrP) nanocomposites were prepared by melting interaction. TGA and SEM revealed that it had an increasing and tighter charred residue compared with PP/IFR systems or pure PP. When the PP matrix containing 25% IFR, the LOI is 33 and UL-94 is V-1 rating. When the PP matrix containing 22.5% IFR and 2.5% OZrP, the LOI is 37 and UL-94 is V-0 rating. Combined with the analysis of charred residue of nanocomposites, and ZrP was found to be a good synergistic agent in the PP/IFR flame retardant systems and eliminated dripping of PP in the combustion. ZrP promoted the cross-linking of PP chain and reduced the release of small molecules, which was proved by the formation of graphite.
4. HIPS/OZrP nanocomposites were prepared by melting interaction. XRD and HRTEM confirmed that exfoliated or intercalated structures of HIPS/OZrP nanocomposites. TGA results showed that it exhibited an increasing charred residue in comparison with pure HIPS. It was found that the rate of heat release and mass loss rate were reduced by the formation of the nanocomposites from cone calorimetry. Combined with the analysis of structure and component in charred residue, there was carbon nanotubes and graphite in carbonaceous residue, then ZrP improved theflame-retardancy of HIPS by promotion the carbonization in HIPS matrix.
5. The thermal stability of ABS/OZrP nanocomposites via melting interactionwas investigated by TGA. ABS/OZrP nanocomposites exhibited better thermal stability and increased charred residue than pure ABS. Carbonaceous residue of ABS/OZrP nanocomposites was analyzed by HRTEM. Carbonization mechanism was discussed, and it declared that ZrP catalyzed carbonization of ABS. This result was coincident with the formation of carbon nanotubes and graphite in carbonaceous residue of ABS/OZrP nanocomposites.
1.以水热法合成层状化合物α-ZrP,以乙胺为胶体化试剂,采用“层离—插层法”获得了C16/α-ZrP插层化合物(OZrP),为制备聚合物/α-ZrP纳米复合材料提供了优良的前驱物。以溶液法制备二茂铁(Fc)插层的α-ZrP(Fc-ZrP),并尝试制备聚合物/Fc-ZrP复合材料。OZrP和Fc-ZrP的结构和形貌用X射线衍射(XRD)和透射电镜(TEM)表征,采用热重分析(TGA)研究了其热性能。
2.采用熔融共混法制备了LDPE/EVA/(ATH,OZrP)纳米复合材料。对纳米复合材料进行微观结构和形貌表征及一系列燃烧性能测试,发现LDPE/EVA/(ATH,OZrP)纳米复合材料的阻燃性能比LDPE/EVA和LDPE/EVA/ATH阻燃体系有明显提高。在燃烧过程中,OZrP的加入可以抑制基体的熔融滴落现象,并形成稳定的炭层,而只添加ATH无OZrP的阻燃体系仍存在严重的滴落现象,无稳定炭层形成。综合热释放速率峰值与点燃时间TTI、火灾性能指数FPI和火灾发展指数FGI评价材料的火灾危险性,LDPE/EVA/(ATH,OZrP)纳米复合材料的阻燃性能比聚合物纯样明显提高,火灾危险性降低。
3.采用熔融共混法制备PP/(IFR,OZrP)纳米复合材料,热重分析和SEM研究表明,添加OZrP的PP/IFR阻燃体系成炭量有所增加,燃烧后的残渣中,炭层结构更加稳固、致密。当PP基体中含有25%IFR时,复合材料的氧指数为33,垂直燃烧测试为UL-94 V-1级别,当保持添加剂总量不变,添加3%OZrP到PP/IFR体系中,氧指数增加到37,垂直燃烧达到V-0级别。IFR与OZrP间存在协效作用,合适的添加比例有利于提高复合材料的阻燃性能。
4.采用熔融共混法制备了HIPS/OZrP纳米复合材料,随着OZrP在HIPS基体中含量的增加,纳米复合材料的成炭量也逐渐增大,当复合材料中含1%OZrP时,其最大热释放速率峰值比纯样降低11%。对炭化产物的形貌和组成研究分析表明,存在石墨片和碳纳米管,这种炭层结构有利于提高材料阻燃性能。同时采用熔融共混法制备了HIPS/Fc-ZrP复合材料,Fc-ZrP由于层间距小,很难与HIPS形成具有良好插层或层离结构的纳米复合材料。燃烧后的炭化产物研究表明,Fc-ZrP对HIPS基体在燃烧过程中存在催化成炭,有助于形成石墨化结构。
5.采用熔融共混法制备了ABS/OZrP纳米复合材料,热稳定性研究表明,ABS/OZrP纳米复合材料的热稳定性比纯ABS树脂稍有提高,成炭量随着OZrP在基体树脂中的含量增加而增大。ABS/OZrP纳米复合材料炭化研究表明,在360℃的温度下炭层中存在晶化程度较高的碳材料生成:存在缺陷的多壁碳纳米管,当温度提高到500～800℃,会有更高晶化程度的多种结构与形貌的碳生成。
α-zirconium phosphate (α-ZrP) has a solid acid catalyst function. In this thesis, It would be a high efficiency flame retarding approach in polymer materials combining nanocomposites and catalyzed carbonzation on the basis of the early literatures and our group's work. Several typical polymer/OZrP nanocomposites were prepared by melting intercalation and characterized by different approaches based on the synthesis and properly organic modification ofα-ZrP. Then, the relationships between structure and property, especially thermal stability and flammability properties of the nanocomposites, using both thermogravimetric analysis (TGA) and cone calorimetry experiment, were discussed in detail. The thermal degradation of the nanocomposites was investigated by a combination of the combustion property of nanocomposites, which suggested the synergistic effect betweenα-ZrP and halogen-free flame retardants. Also, a comprehensive assessment of degradation and combustion property of the nanocomposites were carried out. The main research results as following:
1. Theα-ZrP was synthesized by hydrothermal crystallization. High-intensity ultrasound was applied to the intercalation process ofα-ZrP in organic amine solution, hexadecyltrimethyl ammonium bromide(C16)/α-ZrP intercalated compound (OZrP) was obtained by "exfoliation-intercalation method". The ferrocene intercalatedα-ZrP (Fc-ZrP) was synthesized by solution method. Structures of OZrP and Fc-ZrP were characterized by X-ray diffraction (XRD). Morphologies of OZrP and Fc-ZrP were observed by transmission electron microscopy (TEM). And the thermal property of OZrP and Fc-ZrP were measured by TGA.
2. LDPE/EVA/(ATH,OZrP) nanocomposites were prepared by melting interaction. It consequently exhibited better flame retardant properties than LDPE/EVA and LDPE/EVA/ATH systems. ZrP eliminated the melting-dripping phenomenon during the combustion of LDPE/EVA/(ATH,OZrP) nanocomposites and promoted formation of carbonaceous char. After evaluating peak heat release rate, ignition time(TTI), fire propagation index (FPI) and fire growth index (FGI), it indicated flame retardant properties of LDPE / EVA / (ATH, OZrP) nanocomposite had a significant improvement.
3. PP/(IFR,OZrP) nanocomposites were prepared by melting interaction. TGA and SEM revealed that it had an increasing and tighter charred residue compared with PP/IFR systems or pure PP. When the PP matrix containing 25% IFR, the LOI is 33 and UL-94 is V-1 rating. When the PP matrix containing 22.5% IFR and 2.5% OZrP, the LOI is 37 and UL-94 is V-0 rating. Combined with the analysis of charred residue of nanocomposites, and ZrP was found to be a good synergistic agent in the PP/IFR flame retardant systems and eliminated dripping of PP in the combustion. ZrP promoted the cross-linking of PP chain and reduced the release of small molecules, which was proved by the formation of graphite.
4. HIPS/OZrP nanocomposites were prepared by melting interaction. XRD and HRTEM confirmed that exfoliated or intercalated structures of HIPS/OZrP nanocomposites. TGA results showed that it exhibited an increasing charred residue in comparison with pure HIPS. It was found that the rate of heat release and mass loss rate were reduced by the formation of the nanocomposites from cone calorimetry. Combined with the analysis of structure and component in charred residue, there was carbon nanotubes and graphite in carbonaceous residue, then ZrP improved theflame-retardancy of HIPS by promotion the carbonization in HIPS matrix.
5. The thermal stability of ABS/OZrP nanocomposites via melting interactionwas investigated by TGA. ABS/OZrP nanocomposites exhibited better thermal stability and increased charred residue than pure ABS. Carbonaceous residue of ABS/OZrP nanocomposites was analyzed by HRTEM. Carbonization mechanism was discussed, and it declared that ZrP catalyzed carbonization of ABS. This result was coincident with the formation of carbon nanotubes and graphite in carbonaceous residue of ABS/OZrP nanocomposites.
引文
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