微胶囊化聚磷酸铵在聚氨酯弹性体中阻燃及协效性的研究
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摘要
聚氨酯弹性体以其优异的力学及化学性能得到了广泛应用,但是它的易燃性一定程度上限制了它的应用。聚氨酯弹性体的阻燃研究是聚氨酯弹性体研究的重要方向,通过熔融共混的方式制备膨胀型阻燃聚氨酯弹性体复合材料是解决聚氨酯弹性体易燃性的最简单有效方式。
本论文对常用阻燃剂及其在聚氨酯弹性体中的应用进行了广泛调研。以氢氧化铝等氢氧化物为代表的添加型阻燃剂在聚氨酯弹性体中的应用研究仍占主体地位。聚氨酯弹性体阻燃主要存在以下问题:(1)为获得良好的阻燃效果,阻燃剂的添加量过大;(2)阻燃后的材料的各方面使用性能下降严重;(3)反应型阻燃成本代价过大。
针对以上问题,我们考虑在聚氨酯弹性体中应用低毒低烟的聚磷酸铵(APP)作为阻燃剂,为改善材料的使用性能,对聚磷酸铵进行一定的改性处理。为降低阻燃添加剂使用量,进一步探讨了阻燃剂与协效剂磷酸硼/焦磷酸铁对聚氨酯弹性体的燃烧及热降解过程的影响。结果表明,磷酸硼/焦磷酸铁能够与阻燃剂在聚氨酯弹性体中起到明显的协同阻燃作用。同时对阻燃聚氨酯弹性体的热降解动力学进行了探讨。本文的主要研究工作如下:
(1)通过原位聚合制备聚氨酯微胶囊化聚磷酸铵(MAPP),熔融共混制备阻燃聚氨酯弹性体,并通过垂直燃烧(UL-94)与极限氧指数(LOI)考察阻燃剂的阻燃性能,确定了聚磷酸铵(APP)以及MAPP阻燃聚氨酯弹性体的最小添加量均为25wt%。
(2)筛选出含硼化合物磷酸硼与过渡金属化合物焦磷酸铁为协效剂,考察两种化合物与MAPP在聚氨酯弹性体中的协同阻燃作用。采用极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热仪(CONE)、微型燃烧量热仪(MCC)以及扫描电镜(SEM)分析方法对几种阻燃体系的燃烧性能及炭层结构进行研究。UL-94测试结果表明磷酸硼与焦磷酸铁对聚氨酯弹性体材料阻燃级别的提高均有明显作用,能够大大降低通过UL-94 V-0级别阻燃剂的添加量,其中,焦磷酸铁协效阻燃体系能够更大程度减少阻燃剂的用量;LOI测试表明两种协效剂对氧指数的提高均有一定的作用;CONE及MCC测试表明材料的热释放速率进一步降低,阻燃效率及协效效率提高;从炭渣的数码照片与SEM看,磷酸硼与焦磷酸铁的加入提高了炭层的连续性与致密性。
(3)通过热重分析(TGA)与实时傅里叶变换红外光谱(RTFTIR)分析协同阻燃体系的热稳定性及热氧化降解特性。从热失重分析以及实时傅里叶变换红外光谱的结果看,磷酸硼与焦磷酸铁的加入都提高了材料在高温区间的热稳定性。但是它们的协同阻燃作用存在一定差别:磷酸硼在400℃之后分解生成的B-O基团与APP释放的磷酸铵加热条件下形成了“盐桥”作用而促进了磷氮炭层的生成,同时,释放的硼酸覆盖在炭层表面,加强了炭层的稳定性,并通过吸附材料分解产生的可燃性气体在复合材料表面形成强还原性的气体氛围,使炭层更加质密,不易被破坏,更有效地发挥隔热、隔氧同时防止熔融滴落的作用,提高材料的阻燃性能;焦磷酸铁同样可以在燃烧过程中形成“盐桥”作用,促进磷氮炭层生成,但同时铁元素能够起到捕捉自由基的作用,中止燃烧反应的进行,从而避免材料的进一步燃烧分解。
(4)通过比较几组阻燃聚氨酯弹性体体系,最终选取阻燃效率最高的磷酸硼协效体系与焦磷酸铁协效体系进行热降解动力学对比研究。研究结果表明,磷酸硼能够赋予阻燃体系更高的反应活化能,更好的保护聚氨酯弹性体材料,减小其发生火灾的危险性。
Thermoplastic polyurethane (TPU) is one of the most versatile engineering thermoplastics with elastomeric properties. Due to its excellent physical properties, chemical resistance, abrasion resistance and good adhesion, TPU has been widely used incoatings and films. However, its flammability and melt dripping nature restricts its applications, it is therefore important to improve flame retardancy of TPU. The intumescent flame retardant (IFR) system is an effective strategy to impart polymeric materials with improved flame retardancy.
In this paper, the development of flame retardants were reviewed as well as the reserch in the flame retardant thermoplastic polyurethane and the improvement of intumescent flame retardant (IFR) systems based on many literatures and the relative works in our group firstly. The Microencapsulated ammonium polyphosphate (MAPP) with polyurethane resin and boron phosphate (BP)/ ferric pyrophosphate(FePP) were chosen to be flame retardant and synergist in the thermoplastic polyurethane, respectively. Results showed that a suitable substitution of MAPP by BP or FePP could improve flame retardancy of the TPU/MAPP composites, and TPU composites with lower MAPP/BP (or MAPP/FePP) achieving UL-94 V-0 rating. The CONE and MCC data also showed synergistic effects between BP or FePP with MAPP in the composites. Besides, the thermal degradation and the mechanism about the synergetic effects were studied.The main research results are as following:
(1) Microencapsulated ammonium polyphosphate (MAPP) with polyurethane resin has been prepared by in situ polymerization. The combination of MAPP or APP on the flammability properties of thermoplastic polyurethane (TPU) was studied by vertical burning (UL-94) tests and limiting oxygen index (LOI) tests. UL-94 results showed that the optimum mass ratio of MAPP or APP was 25% in the thermoplastic polyurethane composites.
(2) Both the boron phosphate (BP) and ferric pyrophosphate(FePP)were chosen as synergist in the flame retardant system. The combination of MAPP and synergist on the flammability properties of thermoplastic polyurethane (TPU) was studied by vertical burning (UL-94) tests, limiting oxygen index (LOI) tests, cone calorimetry (CONE) and microscale combustion calorimeter (MCC); the morphology for char residual was also observed by photographs and scanning electron microscope (SEM). Results showed that a suitable substitution of MAPP by synergist could improve the flame retardancy of the TPU/MAPP composites, and TPU composites with lower MAPP/synergist could achieving UL-94 V-0 rating. LOI of the composites also increased a little after adding synergist. The heat release rates (HRR) and weight loss rates of TPU/MAPP composites were also considerably decreased by the synergist. The CONE and MCC data showed synergistic effects between synergist and MAPP in the composites.
(3) Thermal stability was investigated by thermogravimetric analysis (TGA) and real time Fourier transform infrared (RTFTIR). Boron phosphate and ferric pyrophosphate can improve the thermal stability of the composite at higher temperature from the TGA and the RTFTIR data. They also make the char residual of the composites more compact and continuous from their photographs and SEM, but had different synergistic effects: in BP system, during heating, polyphosphoric acid produced by the elimination of ammonia from APP could attack B-O bonds. The formation of boric acid appeared in the surface of residue, and adsorb combustible gases to make a deoxidizel atmosphere, made the char structures more stable. The (PO4)3- could promoted the release of ammonia from APP. Also APP could react with [B(PO4)x]n+, which took as bridges, the formation would brought about a stabilization of the composites. In FePP system, there is also a [Fe(PO4)x]n+, brought about a stabilization char layers, ferric also can capture the free radical in the combustion reaction.
(4) The thermal stability and the degradation kinetics of the BP/MAPP/TPU and the FePP/MAPP/TPU systems were studied. Results showed that BP/MAPP/TPU system has a higher activation energy.
本论文对常用阻燃剂及其在聚氨酯弹性体中的应用进行了广泛调研。以氢氧化铝等氢氧化物为代表的添加型阻燃剂在聚氨酯弹性体中的应用研究仍占主体地位。聚氨酯弹性体阻燃主要存在以下问题:(1)为获得良好的阻燃效果,阻燃剂的添加量过大;(2)阻燃后的材料的各方面使用性能下降严重;(3)反应型阻燃成本代价过大。
针对以上问题,我们考虑在聚氨酯弹性体中应用低毒低烟的聚磷酸铵(APP)作为阻燃剂,为改善材料的使用性能,对聚磷酸铵进行一定的改性处理。为降低阻燃添加剂使用量,进一步探讨了阻燃剂与协效剂磷酸硼/焦磷酸铁对聚氨酯弹性体的燃烧及热降解过程的影响。结果表明,磷酸硼/焦磷酸铁能够与阻燃剂在聚氨酯弹性体中起到明显的协同阻燃作用。同时对阻燃聚氨酯弹性体的热降解动力学进行了探讨。本文的主要研究工作如下:
(1)通过原位聚合制备聚氨酯微胶囊化聚磷酸铵(MAPP),熔融共混制备阻燃聚氨酯弹性体,并通过垂直燃烧(UL-94)与极限氧指数(LOI)考察阻燃剂的阻燃性能,确定了聚磷酸铵(APP)以及MAPP阻燃聚氨酯弹性体的最小添加量均为25wt%。
(2)筛选出含硼化合物磷酸硼与过渡金属化合物焦磷酸铁为协效剂,考察两种化合物与MAPP在聚氨酯弹性体中的协同阻燃作用。采用极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热仪(CONE)、微型燃烧量热仪(MCC)以及扫描电镜(SEM)分析方法对几种阻燃体系的燃烧性能及炭层结构进行研究。UL-94测试结果表明磷酸硼与焦磷酸铁对聚氨酯弹性体材料阻燃级别的提高均有明显作用,能够大大降低通过UL-94 V-0级别阻燃剂的添加量,其中,焦磷酸铁协效阻燃体系能够更大程度减少阻燃剂的用量;LOI测试表明两种协效剂对氧指数的提高均有一定的作用;CONE及MCC测试表明材料的热释放速率进一步降低,阻燃效率及协效效率提高;从炭渣的数码照片与SEM看,磷酸硼与焦磷酸铁的加入提高了炭层的连续性与致密性。
(3)通过热重分析(TGA)与实时傅里叶变换红外光谱(RTFTIR)分析协同阻燃体系的热稳定性及热氧化降解特性。从热失重分析以及实时傅里叶变换红外光谱的结果看,磷酸硼与焦磷酸铁的加入都提高了材料在高温区间的热稳定性。但是它们的协同阻燃作用存在一定差别:磷酸硼在400℃之后分解生成的B-O基团与APP释放的磷酸铵加热条件下形成了“盐桥”作用而促进了磷氮炭层的生成,同时,释放的硼酸覆盖在炭层表面,加强了炭层的稳定性,并通过吸附材料分解产生的可燃性气体在复合材料表面形成强还原性的气体氛围,使炭层更加质密,不易被破坏,更有效地发挥隔热、隔氧同时防止熔融滴落的作用,提高材料的阻燃性能;焦磷酸铁同样可以在燃烧过程中形成“盐桥”作用,促进磷氮炭层生成,但同时铁元素能够起到捕捉自由基的作用,中止燃烧反应的进行,从而避免材料的进一步燃烧分解。
(4)通过比较几组阻燃聚氨酯弹性体体系,最终选取阻燃效率最高的磷酸硼协效体系与焦磷酸铁协效体系进行热降解动力学对比研究。研究结果表明,磷酸硼能够赋予阻燃体系更高的反应活化能,更好的保护聚氨酯弹性体材料,减小其发生火灾的危险性。
Thermoplastic polyurethane (TPU) is one of the most versatile engineering thermoplastics with elastomeric properties. Due to its excellent physical properties, chemical resistance, abrasion resistance and good adhesion, TPU has been widely used incoatings and films. However, its flammability and melt dripping nature restricts its applications, it is therefore important to improve flame retardancy of TPU. The intumescent flame retardant (IFR) system is an effective strategy to impart polymeric materials with improved flame retardancy.
In this paper, the development of flame retardants were reviewed as well as the reserch in the flame retardant thermoplastic polyurethane and the improvement of intumescent flame retardant (IFR) systems based on many literatures and the relative works in our group firstly. The Microencapsulated ammonium polyphosphate (MAPP) with polyurethane resin and boron phosphate (BP)/ ferric pyrophosphate(FePP) were chosen to be flame retardant and synergist in the thermoplastic polyurethane, respectively. Results showed that a suitable substitution of MAPP by BP or FePP could improve flame retardancy of the TPU/MAPP composites, and TPU composites with lower MAPP/BP (or MAPP/FePP) achieving UL-94 V-0 rating. The CONE and MCC data also showed synergistic effects between BP or FePP with MAPP in the composites. Besides, the thermal degradation and the mechanism about the synergetic effects were studied.The main research results are as following:
(1) Microencapsulated ammonium polyphosphate (MAPP) with polyurethane resin has been prepared by in situ polymerization. The combination of MAPP or APP on the flammability properties of thermoplastic polyurethane (TPU) was studied by vertical burning (UL-94) tests and limiting oxygen index (LOI) tests. UL-94 results showed that the optimum mass ratio of MAPP or APP was 25% in the thermoplastic polyurethane composites.
(2) Both the boron phosphate (BP) and ferric pyrophosphate(FePP)were chosen as synergist in the flame retardant system. The combination of MAPP and synergist on the flammability properties of thermoplastic polyurethane (TPU) was studied by vertical burning (UL-94) tests, limiting oxygen index (LOI) tests, cone calorimetry (CONE) and microscale combustion calorimeter (MCC); the morphology for char residual was also observed by photographs and scanning electron microscope (SEM). Results showed that a suitable substitution of MAPP by synergist could improve the flame retardancy of the TPU/MAPP composites, and TPU composites with lower MAPP/synergist could achieving UL-94 V-0 rating. LOI of the composites also increased a little after adding synergist. The heat release rates (HRR) and weight loss rates of TPU/MAPP composites were also considerably decreased by the synergist. The CONE and MCC data showed synergistic effects between synergist and MAPP in the composites.
(3) Thermal stability was investigated by thermogravimetric analysis (TGA) and real time Fourier transform infrared (RTFTIR). Boron phosphate and ferric pyrophosphate can improve the thermal stability of the composite at higher temperature from the TGA and the RTFTIR data. They also make the char residual of the composites more compact and continuous from their photographs and SEM, but had different synergistic effects: in BP system, during heating, polyphosphoric acid produced by the elimination of ammonia from APP could attack B-O bonds. The formation of boric acid appeared in the surface of residue, and adsorb combustible gases to make a deoxidizel atmosphere, made the char structures more stable. The (PO4)3- could promoted the release of ammonia from APP. Also APP could react with [B(PO4)x]n+, which took as bridges, the formation would brought about a stabilization of the composites. In FePP system, there is also a [Fe(PO4)x]n+, brought about a stabilization char layers, ferric also can capture the free radical in the combustion reaction.
(4) The thermal stability and the degradation kinetics of the BP/MAPP/TPU and the FePP/MAPP/TPU systems were studied. Results showed that BP/MAPP/TPU system has a higher activation energy.
引文
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