羧基聚硅氧烷和羟基聚硅氧烷的合成表征及对聚碳酸酯的阻燃研究
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摘要
高分子材料的广泛应用正带动着阻燃剂的迅速发展。随着阻燃技术向环保化、低毒化、高效化的方向发展,环境友好型阻燃技术已经发展成为阻燃材料研究的主要方向之一。有机聚硅氧烷正是一类理想的环境友好型有机硅阻燃剂,其引入聚合物后的热分解及燃烧过程主要释放的二氧化硅(Si02)及其他含硅产物几乎对环境没有污染,且含硅阻燃聚合物燃烧时少烟低毒、火焰传播速度慢。因此,有机聚硅氧烷在聚合物的阻燃应用研究方面引起了工业界和广大研究者的浓厚兴趣。
本文在大量文献调研的基础上,对有机聚硅氧烷、聚碳酸酯的概况以及常用阻燃剂的研究进展进行了综述。同时,本文以甲基二乙氧基氢硅烷(含一定量的三乙氧基氢硅烷)、丙烯酸、丙烯醇为原料合成了含有羧基和羟基的聚硅氧烷固体微粒,对其结构进行了表征分析。另外,本研究还采用熔融共混法制备了分别含有两种含碳官能团聚硅氧烷的PC复合材料,考察了复合材料的热分解过程、燃烧行为和力学性能,初步探讨了其阻燃机理。本论文归纳起来包括以下内容。
(1)有机硅中间体(Organic Silicone Intermediate,简称OSI)衍生物的合成与影响因素的研究。
以甲基二乙氧基氢硅烷(含三乙氧基氢硅烷)分别与丙烯酸和丙烯醇进行硅氢加成反应,合成出含有羧基和羟基的有机硅中间体OSI-COOH和OSI-OH,讨论了时间、温度、物料摩尔比对中间体产率的影响,得出了较为合理的实验条件：对于OSI-COOH,Si-H与C=C的比例为1.2：1,温度为85℃,反应时间24h；对于OSI-OH, Si-H与C=C的比例为2.0：1,温度为90℃,反应时间20h,产率分别为97.86%和95.48%。
(2)羧基聚硅氧烷(Carboxyl-Polysiloxane,简称POS-COOH)和羟基聚硅氧烷(Hydroxyl-Polysiloxane,简称POS-OH)的合成与表征。
以合成的有机硅中间体OSI-COOH和OSI-OH为原料,通过水解缩聚合成出羧基聚硅氧烷(POS-COOH)和羟基聚硅氧烷(POS-OH).反应条件为40-50%的硫酸水溶液,30-35℃下,反应1-2h,产率分别为88.92%和92.77%。用傅立叶红外光谱(FTIR),硅核磁共振谱(29Si-NMR),扫描电子显微镜(SEM),透射电子显微镜(TEM)以及X射线衍射光谱仪(XRD)进行结构分析表征；通过在氮气中的热重分析(TGA),对两种功能聚硅氧烷的热性能进行研究。
(3)聚碳酸酯(polycarbonate,简称PC)复合材料的制备,阻燃性、热稳定性和力学性能的研究。
将POS-COOH和POS-OH分别与PC共混制成阻燃PC复合材料,LOI和UL-94测、试结果表明二者能够较好地起到阻燃作用,LO1分别提高到32.3和31.1,能通过UL-94V1级测试。TGA结果表明,阻燃剂的加入提高了PC高温下的热稳定性,PC的起始分解温度分别提高了43.5℃和33.8℃,最大分解速率温度分别提高了31.1℃和30.6℃,阻燃剂还起到了成炭的作用。力学测试结果表明,阻燃剂可以提高PC的拉伸性能和弯曲性能,但会恶化冲击性能。
Wide applications of polymer materials are driving the rapid development of flame retardants. As the technology of flame retardant developing to the direction of environmental protection, low toxicity and high efficiency, environment-friendly fire retardants have become one main research direction of flame retardant technology. Organic polysiloxane is just one of the ideal environmental-friendly flame retardants. The thermal degradation and combustion products of organic polysiloxane after introduced into the polymers are SiO2 and other silicon-containing compounds, which are almost environmentally friendly. Moreover, low concentration of smoke and toxic gas will be released during the combustion of silicon-containing polymers, and the propagation of flame is slow. So the application of organic polysiloxane in polymer flame retardants has attracted the researchers very much.
The newly progress about organic polysiloxane, polycarbonate (PC) and the flame retardants uses reviewed in this dissertation were based on the investigation of a large amount of literatures. In the dissertation, two kinds of organic polysiloxane containing carboxyl and hydroxyl(POS-COOH, POS-OH) were also synthesized from methyldiethoxysilane (containing a certain amount of triethoxysilane), acrylic acid and allyl alcohol, some characterizations of these two organic polysiloxane's structure were investigated, too. In addition, two series of flame retardant PC hybrids prepared were based on PC, POS-COOH and POS-OH by melt blending method. The thermal stability, flame retardant properties of the hybrids, mechanical properties were investigated. The flame retardant mechanism of POS-COOH and POS-OH had been discussed in the paper in detail. The paper is mainly divided into some parts following:
(1) Study on preparation and impact factors of OSI-COOH and OSI-OH.
Two kinds of organic silicone intermediates containing carboxyl and hydroxyl(OSI-COOH, OSI-OH) were synthesized by hydrosilyation reaction, using methyldiethoxysilane (containing a certain amount of triethoxysilane), acrylic acid and allyl alcohol. Time, the impact of temperature and molar ratio of monomers on the yield were discussed, we obtained the most reasonable experimental conditions:for OSI-COOH, the molar ratio of Si-H and unsaturated compound was 1.2:1, the optimal reaction temperature was 85℃for 24 h; for OSI-OH, the molar ratio of Si-H and unsaturated compound was 2.0:1, the optimal reaction temperature was 90℃for 20 h, the yield were 97.86% and 95.48%.
(2) Preparation and characterization of carboxyl-polysiloxane (POS-COOH) and hydroxyl-polysiloxane (POS-OH).
Then POS-COOH and POS-OH were prepared by hydrolysis condensation reaction, using OSI-COOH and OSI-OH prepared by the reaction of the previous step, and the reactions were catalysted by sulfuric acid aqueous solution (containing 40-50% sulfuric acid) under 30-35℃for 1-2 hours, and the yield were 88.92% and 92.77%. The molecular structures of two were characterized by FTIR,29Si-NMR, SEM, TEM, XRD. We also use TGA to investigate thermal properties of them.
(3) Study on preparation, flame retardancy, thermal property and mechanical properties of polycarbonate (PC) composite materials.
POS-COOH (POS-OH) particles were well dispersed in the PC matrix and there was no chemical reaction between the POS-COOH (POS-OH) particles and PC matrix during the melt blending. The results of LOI and UL-94 test showed that POS-COOH and POS-OH played a flame-retardant effect well, LOI of the two kinds of composite materials were raised up to 32.3 and 31.1 and could pass UL-94 V1 test (3.2mm). The results of TGA showed that the addition of POS-COOH and POS-OH raised thermal stability of composite materials under high temperature. The initial decomposition temperatures of composite materials raised 43.5℃and 33.8℃; the temperatures decomposition rate raised 31.1℃and 30.6℃at maximum; POS-COOH and POS-OH also could enhance the char formation in high temperature to form stabile. The results of mechanical properties test showed that POS-COOH and POS-OH raised tensile strength and flexural strength, but reduced the izod impact strength of composite materials.
本文在大量文献调研的基础上,对有机聚硅氧烷、聚碳酸酯的概况以及常用阻燃剂的研究进展进行了综述。同时,本文以甲基二乙氧基氢硅烷(含一定量的三乙氧基氢硅烷)、丙烯酸、丙烯醇为原料合成了含有羧基和羟基的聚硅氧烷固体微粒,对其结构进行了表征分析。另外,本研究还采用熔融共混法制备了分别含有两种含碳官能团聚硅氧烷的PC复合材料,考察了复合材料的热分解过程、燃烧行为和力学性能,初步探讨了其阻燃机理。本论文归纳起来包括以下内容。
(1)有机硅中间体(Organic Silicone Intermediate,简称OSI)衍生物的合成与影响因素的研究。
以甲基二乙氧基氢硅烷(含三乙氧基氢硅烷)分别与丙烯酸和丙烯醇进行硅氢加成反应,合成出含有羧基和羟基的有机硅中间体OSI-COOH和OSI-OH,讨论了时间、温度、物料摩尔比对中间体产率的影响,得出了较为合理的实验条件：对于OSI-COOH,Si-H与C=C的比例为1.2：1,温度为85℃,反应时间24h；对于OSI-OH, Si-H与C=C的比例为2.0：1,温度为90℃,反应时间20h,产率分别为97.86%和95.48%。
(2)羧基聚硅氧烷(Carboxyl-Polysiloxane,简称POS-COOH)和羟基聚硅氧烷(Hydroxyl-Polysiloxane,简称POS-OH)的合成与表征。
以合成的有机硅中间体OSI-COOH和OSI-OH为原料,通过水解缩聚合成出羧基聚硅氧烷(POS-COOH)和羟基聚硅氧烷(POS-OH).反应条件为40-50%的硫酸水溶液,30-35℃下,反应1-2h,产率分别为88.92%和92.77%。用傅立叶红外光谱(FTIR),硅核磁共振谱(29Si-NMR),扫描电子显微镜(SEM),透射电子显微镜(TEM)以及X射线衍射光谱仪(XRD)进行结构分析表征；通过在氮气中的热重分析(TGA),对两种功能聚硅氧烷的热性能进行研究。
(3)聚碳酸酯(polycarbonate,简称PC)复合材料的制备,阻燃性、热稳定性和力学性能的研究。
将POS-COOH和POS-OH分别与PC共混制成阻燃PC复合材料,LOI和UL-94测、试结果表明二者能够较好地起到阻燃作用,LO1分别提高到32.3和31.1,能通过UL-94V1级测试。TGA结果表明,阻燃剂的加入提高了PC高温下的热稳定性,PC的起始分解温度分别提高了43.5℃和33.8℃,最大分解速率温度分别提高了31.1℃和30.6℃,阻燃剂还起到了成炭的作用。力学测试结果表明,阻燃剂可以提高PC的拉伸性能和弯曲性能,但会恶化冲击性能。
Wide applications of polymer materials are driving the rapid development of flame retardants. As the technology of flame retardant developing to the direction of environmental protection, low toxicity and high efficiency, environment-friendly fire retardants have become one main research direction of flame retardant technology. Organic polysiloxane is just one of the ideal environmental-friendly flame retardants. The thermal degradation and combustion products of organic polysiloxane after introduced into the polymers are SiO2 and other silicon-containing compounds, which are almost environmentally friendly. Moreover, low concentration of smoke and toxic gas will be released during the combustion of silicon-containing polymers, and the propagation of flame is slow. So the application of organic polysiloxane in polymer flame retardants has attracted the researchers very much.
The newly progress about organic polysiloxane, polycarbonate (PC) and the flame retardants uses reviewed in this dissertation were based on the investigation of a large amount of literatures. In the dissertation, two kinds of organic polysiloxane containing carboxyl and hydroxyl(POS-COOH, POS-OH) were also synthesized from methyldiethoxysilane (containing a certain amount of triethoxysilane), acrylic acid and allyl alcohol, some characterizations of these two organic polysiloxane's structure were investigated, too. In addition, two series of flame retardant PC hybrids prepared were based on PC, POS-COOH and POS-OH by melt blending method. The thermal stability, flame retardant properties of the hybrids, mechanical properties were investigated. The flame retardant mechanism of POS-COOH and POS-OH had been discussed in the paper in detail. The paper is mainly divided into some parts following:
(1) Study on preparation and impact factors of OSI-COOH and OSI-OH.
Two kinds of organic silicone intermediates containing carboxyl and hydroxyl(OSI-COOH, OSI-OH) were synthesized by hydrosilyation reaction, using methyldiethoxysilane (containing a certain amount of triethoxysilane), acrylic acid and allyl alcohol. Time, the impact of temperature and molar ratio of monomers on the yield were discussed, we obtained the most reasonable experimental conditions:for OSI-COOH, the molar ratio of Si-H and unsaturated compound was 1.2:1, the optimal reaction temperature was 85℃for 24 h; for OSI-OH, the molar ratio of Si-H and unsaturated compound was 2.0:1, the optimal reaction temperature was 90℃for 20 h, the yield were 97.86% and 95.48%.
(2) Preparation and characterization of carboxyl-polysiloxane (POS-COOH) and hydroxyl-polysiloxane (POS-OH).
Then POS-COOH and POS-OH were prepared by hydrolysis condensation reaction, using OSI-COOH and OSI-OH prepared by the reaction of the previous step, and the reactions were catalysted by sulfuric acid aqueous solution (containing 40-50% sulfuric acid) under 30-35℃for 1-2 hours, and the yield were 88.92% and 92.77%. The molecular structures of two were characterized by FTIR,29Si-NMR, SEM, TEM, XRD. We also use TGA to investigate thermal properties of them.
(3) Study on preparation, flame retardancy, thermal property and mechanical properties of polycarbonate (PC) composite materials.
POS-COOH (POS-OH) particles were well dispersed in the PC matrix and there was no chemical reaction between the POS-COOH (POS-OH) particles and PC matrix during the melt blending. The results of LOI and UL-94 test showed that POS-COOH and POS-OH played a flame-retardant effect well, LOI of the two kinds of composite materials were raised up to 32.3 and 31.1 and could pass UL-94 V1 test (3.2mm). The results of TGA showed that the addition of POS-COOH and POS-OH raised thermal stability of composite materials under high temperature. The initial decomposition temperatures of composite materials raised 43.5℃and 33.8℃; the temperatures decomposition rate raised 31.1℃and 30.6℃at maximum; POS-COOH and POS-OH also could enhance the char formation in high temperature to form stabile. The results of mechanical properties test showed that POS-COOH and POS-OH raised tensile strength and flexural strength, but reduced the izod impact strength of composite materials.
引文
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