不同结构的双环笼状含磷阻燃剂的合成及其在聚丙烯阻燃改性中的应用
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摘要
聚丙烯(PP)是全球产量最大的树脂之一,具有生产成本低,综合力学性能好,无毒、质轻、耐腐蚀、电气性能好、易加工、易于回收等诸多优点,被广泛用于包装、纺织品、建材、汽车、电子/电气、办公用品及日用品领域。但是聚丙烯氧指数低,极易燃烧,这在一些领域限制了它的发展。
膨胀型阻燃剂(IFR)是一种以磷氮碳为主要成分的“环境友好”的阻燃剂,用该阻燃剂阻燃PP时表面能生成膨胀炭层,该膨胀炭层隔热、隔氧、抑烟,并能防止产生熔滴,从而使PP具有较好的阻燃性能,越来越受到人们的青睐。针对PP易燃烧的缺点,本论文从当前研究比较活跃的膨胀型阻燃体系的阻燃化设计原理入手,对双环笼状膦/磷酸酯阻燃剂的合成、应用及阻燃机理等方面进行了较为系统而深入的研究和探讨,取得了一些创新性成果。主要内容概要如下:
1.以季戊四醇和三氯氧磷为原料,合成了阻燃中间体1-氧代-4-羟甲基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷(PEPA)。采用亲核取代的方法,以PEPA和苯膦酰二氯、硫代苯膦酰二氯为原料,合成了两种全新阻燃剂:二(1-氧代-4-亚甲氧基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷)苯基膦酸酯(BCPPO)和二(1-氧代-4-亚甲氧基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷)硫代苯基膦酸酯(BCPPS);改进了阻燃剂二(1-氧代-4-亚甲氧基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷)苯氧基磷酸酯(BCPPOO)的合成方法。研究了以上三种阻燃剂的合成路线和反应条件对产率的影响,结果表明:采用乙腈为溶剂、三乙胺为缚酸剂时,产率最高,分别为58.1% (BCPPO),73.5% (BCPPS)和61.0% (BCPPOO);采用FT-IR、1H-NMR对BCPPO、BCPPS和BCPPOO的结构进行了表征;采用TGA对三种化合物的热性能进行了研究,结果表明三者都具有优异的热稳定性和很高的残炭量。
2.分别将BCPPO、BCPPS、BCPPOO与聚磷酸铵(APP)、三聚氰胺(MA)或三聚氰胺磷酸盐(MP)以不同的配比进行复配,并用于PP的阻燃处理,经LOI和UL-94测试表明,当APP: MA: BCPPO= 3: 1: 1,APP: MP: BCPPS= 2: 1: 2和APP: MP: BCPPOO=4: 2: 9,总添加量为30wt.%时,阻燃PP的LOI值分别是30.3,31.3和27.1,均通过UL-94 V-0级。对PP/APP/MA/BCPPO和PP/APP/MP/BCPPS体系的锥形量热测试表明,膨胀型阻燃剂的加入使PP的热释放速率、质量损失速率和烟释放速率都有明显的下降,证明其具有优异的阻燃性能。
3.通过热重分析和扫描电镜对以BCPPO、BCPPS和BCPPOO为炭源的三种膨胀阻燃PP的热降解过程和燃烧残余物的形态进行了研究,探讨了不同阻燃剂的结构对膨胀PP阻燃体系阻燃性能的影响。
4.采用协同阻燃技术处理膨胀阻燃PP体系(APP:MA:BCPPO=3:1:1),结果表明:硼酸、氧化锌和醋酸镍的加入进一步提高了体系的阻燃性能。分别添加1 wt.%的硼酸、氧化锌和醋酸镍,LOI值分别是34.2,32.2和32.8。其中以硼酸为协效剂效果最好,按最佳比例将体系的总添加量降低为25wt.%时,LOI值仍可达30.4,并且可通过UL-94 V-0级测试。
5.热重分析表明,不论是在空气中还是在氮气中,膨胀阻燃PP体系的初始热分解温度都提前了,但最终的残炭量都大于纯PP,这在一定程度上有利于提高阻燃性能。通过对膨胀阻燃PP体系(APP:MA:BCPPO=3:1:1)热降解残余量的计算,发现实验值比计算理论值高,表明膨胀型阻燃剂各组分间存在着协同阻燃效果。采用Broido方法对PP/APP/MP/BCPPOO体系和纯PP的热氧化降解活化能进行了计算,表明阻燃剂的加入降低了热氧化降解活化能。
6.采用SEM、FT-IR、XPS和XRD等分析测试方法,对膨胀型阻燃PP和协效阻燃机理进行了初步探讨。结果表明阻燃PP在燃烧时都可以形成膨胀炭层,但致密的炭层是决定阻燃性能好坏的重要标准。残炭分析表明,残炭中有磷酸类物质,这类物质具有很强的脱水作用,能使成炭剂等脱水成炭形成膨胀炭层,覆盖于聚合物表面,延缓了聚合物的氧化和脱水速度,保护了基体。在所研究的协同阻燃体系中,发现添加硼酸体系的炭层质量更好,其P/C、O/C、N/C元素浓度比率的变化表明了硼酸的加入改变了成炭过程,使阻燃性能得到进一步提高。
7.对纯PP及阻燃PP体系的流变性能研究表明:在测试温度下所有试样均表现出假塑性流体的特征,表观粘度均随切变速率的增大而减小,即切力变稀行为。在同一温度下,阻燃PP比纯PP的表观粘度大,但阻燃PP各配方的表观粘度相差不大。XRD分析表明,IFR对PP的晶体结构没有影响,它们之间基本处于一种物理共混的状态。对纯PP和膨胀阻燃PP体系(APP:MA:BCPPO=3:1:1)进行了力学性能测试,结果表明IFR的加入使PP的拉伸性能、断裂伸长率和冲击强度有所下降,但弯曲强度有所提高;其力学性能与许多文献和商业产品报道的其他阻燃体系的值接近,甚至还略好。
As one of the maximal output resin, polypropylene (PP) is widely used in many fields such as housing, automobiles, electronic and electric industry, wire and cables due to its low cost, low density, low toxicity, excellent electrical resistance and ease of processing and moulding and so on. However, the flammability of PP limits its application fields.
Intumescent flame retardant (IFR) is usually composed of phosphorus, nitrogen and carbon. To impart flame retardancy of PP, IFR can afford a swelling char layer, which can provides a thermal and physical barrier to the underlying material or bulk polymer during combustion. This dissertation mainly studies the synthesis, application and flame-retardant mechanism of three kinds of phosphorus-containing caged bicyclic flame retardants. The main contents are summarized as follows: 1. As an intermediate, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane (PEPA) was synthesized from pentaerythritol and phosphorus oxychloride. Phenylphosphonic dichloride (PPD), phenylphosphonothioic dichloride (PPTD) and phenyl dichlorophosphate (PDCP) were reacted with PEPA to produce bis (2, 6, 7- trioxa- 1- phosphabicyclo [2.2.2]octane- 1- oxo- 4- hydroxymethyl) phenylphosphonate (BCPPO), bis (2, 6, 7- trioxa- 1- phosphabicyclo [2.2.2] octane- 1- oxo- 4- hydroxymethyl) phenylphosphine sulfide (BCPPS) and bis (2, 6, 7- trioxa- 1- phosphabicyclo [2.2.2] octane- 1- oxo- 4- hydroxymethyl) phenyloxyphosphine (BCPPOO), respectively. Furthermore the routines were optimized, and the structures were characterized by FT-IR and 1H-NMR. The result of TGA showed that all of BCPPO, BCPPS, and BCPPOO had good thermal stability and high residues at 600℃, respectively.
2. A large amount of flame retardant PP formulations based on BCPPO, BCPPS, BCPPOO, APP, MA or MP had been studied. Based on the results of LOI and UL-94 tests, three good flame retardant formulations were obtained: APP: MA: BCPPO= 3: 1: 1, APP: MP: BCPPS= 2: 1: 2 and APP: MP: BCPPOO= 4: 2: 9 when keeping the total loading of 30 wt.%, whose LOI values were 30.3, 31.3 and 27.1, respectively. The cone calorimeter tests showed that heat release rate (HRR), mass loss rate (MLR) and rate of smoke release (RSR) were decreased largely compared to pure PP.
3. The thermal degradation process and residue after combustion of three flame-retardant PP based on BCPPO, BCPPS and BCPPOO as carbonization resource were studied by TG and SEM, respectively. The influence of different structures on flame retardancy was discussed.
4. In order to improve further the flame retardancy of IFR-PP system, some potential synergistic flame retardants such as boric acid, zinc oxide and nickel acetate were added to IFR-PP systems. When small amount of boric acid was added to the BCPPO-based IFR-PP system (APP: MA: BCPPO=3: 1: 1), much better flame retardant effect was obtained than the corresponding system without boric acid. The mechanism analysis indicates that boric acid could be decomposed into boron oxide, which could paste the char and make the char more compact. However, zinc oxide and nickel acetate could react with APP to produce cross-linking materials to decrease the speed of the melt to flame area.
5. The thermal behaviors were investigated by means of TG, and the results showed that the flame retardant PP degraded ahead of pure PP under both air and nitrogen atmosphere, but the final residue was much higher than that of neat PP. The Broido method was used to calculate the activation energy of PP/APP/MP/BCPPOO system and pure PP, and the incorporation of IFR could decrease the activation energy.
6. The flame retardant mechanism of various systems was studied by means of SEM, FT-IR, XPS and XRD. Results showed that the compact char layer was a crucial factor for flame retardancy. Phosphorus-containing compounds were detected in intumescent char, and they could delay the oxidation of PP. The XRD analysis of intumescent char containing nickel acetate showed that phosphorus-nickel oxide and inorganic salts were detected.
7. A capillary rheometer was used to investigate the rheological properties of various IFR-PP systems. Both neat PP and flame-retardant PP systems exhibit the pseudoplastic flow behavior, and the apparent viscosity decreases with the increase of shear rate. At a certain temperature, the IFR-PP systems had much higher apparent viscosities than neat PP, but there were not obvious differences of apparent viscosities among various IFR-PP systems. XRD was used to investigate the crystalline behaviors of various IFR-PP systems. IFR had no effect on the crystalline structure of PP. The investigation of mechanical properties showed that the tensile strength, elongation at break and Izod impact strength of IFR-PP systems decreased, especially elongation at break, but flexural strength increased compared to those of neat PP. However, the mechanical properties of the IFR-PP systems were a little better than those of some commercial flame-retardant PP products.
膨胀型阻燃剂(IFR)是一种以磷氮碳为主要成分的“环境友好”的阻燃剂,用该阻燃剂阻燃PP时表面能生成膨胀炭层,该膨胀炭层隔热、隔氧、抑烟,并能防止产生熔滴,从而使PP具有较好的阻燃性能,越来越受到人们的青睐。针对PP易燃烧的缺点,本论文从当前研究比较活跃的膨胀型阻燃体系的阻燃化设计原理入手,对双环笼状膦/磷酸酯阻燃剂的合成、应用及阻燃机理等方面进行了较为系统而深入的研究和探讨,取得了一些创新性成果。主要内容概要如下:
1.以季戊四醇和三氯氧磷为原料,合成了阻燃中间体1-氧代-4-羟甲基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷(PEPA)。采用亲核取代的方法,以PEPA和苯膦酰二氯、硫代苯膦酰二氯为原料,合成了两种全新阻燃剂:二(1-氧代-4-亚甲氧基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷)苯基膦酸酯(BCPPO)和二(1-氧代-4-亚甲氧基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷)硫代苯基膦酸酯(BCPPS);改进了阻燃剂二(1-氧代-4-亚甲氧基-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷)苯氧基磷酸酯(BCPPOO)的合成方法。研究了以上三种阻燃剂的合成路线和反应条件对产率的影响,结果表明:采用乙腈为溶剂、三乙胺为缚酸剂时,产率最高,分别为58.1% (BCPPO),73.5% (BCPPS)和61.0% (BCPPOO);采用FT-IR、1H-NMR对BCPPO、BCPPS和BCPPOO的结构进行了表征;采用TGA对三种化合物的热性能进行了研究,结果表明三者都具有优异的热稳定性和很高的残炭量。
2.分别将BCPPO、BCPPS、BCPPOO与聚磷酸铵(APP)、三聚氰胺(MA)或三聚氰胺磷酸盐(MP)以不同的配比进行复配,并用于PP的阻燃处理,经LOI和UL-94测试表明,当APP: MA: BCPPO= 3: 1: 1,APP: MP: BCPPS= 2: 1: 2和APP: MP: BCPPOO=4: 2: 9,总添加量为30wt.%时,阻燃PP的LOI值分别是30.3,31.3和27.1,均通过UL-94 V-0级。对PP/APP/MA/BCPPO和PP/APP/MP/BCPPS体系的锥形量热测试表明,膨胀型阻燃剂的加入使PP的热释放速率、质量损失速率和烟释放速率都有明显的下降,证明其具有优异的阻燃性能。
3.通过热重分析和扫描电镜对以BCPPO、BCPPS和BCPPOO为炭源的三种膨胀阻燃PP的热降解过程和燃烧残余物的形态进行了研究,探讨了不同阻燃剂的结构对膨胀PP阻燃体系阻燃性能的影响。
4.采用协同阻燃技术处理膨胀阻燃PP体系(APP:MA:BCPPO=3:1:1),结果表明:硼酸、氧化锌和醋酸镍的加入进一步提高了体系的阻燃性能。分别添加1 wt.%的硼酸、氧化锌和醋酸镍,LOI值分别是34.2,32.2和32.8。其中以硼酸为协效剂效果最好,按最佳比例将体系的总添加量降低为25wt.%时,LOI值仍可达30.4,并且可通过UL-94 V-0级测试。
5.热重分析表明,不论是在空气中还是在氮气中,膨胀阻燃PP体系的初始热分解温度都提前了,但最终的残炭量都大于纯PP,这在一定程度上有利于提高阻燃性能。通过对膨胀阻燃PP体系(APP:MA:BCPPO=3:1:1)热降解残余量的计算,发现实验值比计算理论值高,表明膨胀型阻燃剂各组分间存在着协同阻燃效果。采用Broido方法对PP/APP/MP/BCPPOO体系和纯PP的热氧化降解活化能进行了计算,表明阻燃剂的加入降低了热氧化降解活化能。
6.采用SEM、FT-IR、XPS和XRD等分析测试方法,对膨胀型阻燃PP和协效阻燃机理进行了初步探讨。结果表明阻燃PP在燃烧时都可以形成膨胀炭层,但致密的炭层是决定阻燃性能好坏的重要标准。残炭分析表明,残炭中有磷酸类物质,这类物质具有很强的脱水作用,能使成炭剂等脱水成炭形成膨胀炭层,覆盖于聚合物表面,延缓了聚合物的氧化和脱水速度,保护了基体。在所研究的协同阻燃体系中,发现添加硼酸体系的炭层质量更好,其P/C、O/C、N/C元素浓度比率的变化表明了硼酸的加入改变了成炭过程,使阻燃性能得到进一步提高。
7.对纯PP及阻燃PP体系的流变性能研究表明:在测试温度下所有试样均表现出假塑性流体的特征,表观粘度均随切变速率的增大而减小,即切力变稀行为。在同一温度下,阻燃PP比纯PP的表观粘度大,但阻燃PP各配方的表观粘度相差不大。XRD分析表明,IFR对PP的晶体结构没有影响,它们之间基本处于一种物理共混的状态。对纯PP和膨胀阻燃PP体系(APP:MA:BCPPO=3:1:1)进行了力学性能测试,结果表明IFR的加入使PP的拉伸性能、断裂伸长率和冲击强度有所下降,但弯曲强度有所提高;其力学性能与许多文献和商业产品报道的其他阻燃体系的值接近,甚至还略好。
As one of the maximal output resin, polypropylene (PP) is widely used in many fields such as housing, automobiles, electronic and electric industry, wire and cables due to its low cost, low density, low toxicity, excellent electrical resistance and ease of processing and moulding and so on. However, the flammability of PP limits its application fields.
Intumescent flame retardant (IFR) is usually composed of phosphorus, nitrogen and carbon. To impart flame retardancy of PP, IFR can afford a swelling char layer, which can provides a thermal and physical barrier to the underlying material or bulk polymer during combustion. This dissertation mainly studies the synthesis, application and flame-retardant mechanism of three kinds of phosphorus-containing caged bicyclic flame retardants. The main contents are summarized as follows: 1. As an intermediate, 1-oxo-4-hydroxymethyl-2, 6, 7-trioxa-1-phosphabicyclo [2.2.2] octane (PEPA) was synthesized from pentaerythritol and phosphorus oxychloride. Phenylphosphonic dichloride (PPD), phenylphosphonothioic dichloride (PPTD) and phenyl dichlorophosphate (PDCP) were reacted with PEPA to produce bis (2, 6, 7- trioxa- 1- phosphabicyclo [2.2.2]octane- 1- oxo- 4- hydroxymethyl) phenylphosphonate (BCPPO), bis (2, 6, 7- trioxa- 1- phosphabicyclo [2.2.2] octane- 1- oxo- 4- hydroxymethyl) phenylphosphine sulfide (BCPPS) and bis (2, 6, 7- trioxa- 1- phosphabicyclo [2.2.2] octane- 1- oxo- 4- hydroxymethyl) phenyloxyphosphine (BCPPOO), respectively. Furthermore the routines were optimized, and the structures were characterized by FT-IR and 1H-NMR. The result of TGA showed that all of BCPPO, BCPPS, and BCPPOO had good thermal stability and high residues at 600℃, respectively.
2. A large amount of flame retardant PP formulations based on BCPPO, BCPPS, BCPPOO, APP, MA or MP had been studied. Based on the results of LOI and UL-94 tests, three good flame retardant formulations were obtained: APP: MA: BCPPO= 3: 1: 1, APP: MP: BCPPS= 2: 1: 2 and APP: MP: BCPPOO= 4: 2: 9 when keeping the total loading of 30 wt.%, whose LOI values were 30.3, 31.3 and 27.1, respectively. The cone calorimeter tests showed that heat release rate (HRR), mass loss rate (MLR) and rate of smoke release (RSR) were decreased largely compared to pure PP.
3. The thermal degradation process and residue after combustion of three flame-retardant PP based on BCPPO, BCPPS and BCPPOO as carbonization resource were studied by TG and SEM, respectively. The influence of different structures on flame retardancy was discussed.
4. In order to improve further the flame retardancy of IFR-PP system, some potential synergistic flame retardants such as boric acid, zinc oxide and nickel acetate were added to IFR-PP systems. When small amount of boric acid was added to the BCPPO-based IFR-PP system (APP: MA: BCPPO=3: 1: 1), much better flame retardant effect was obtained than the corresponding system without boric acid. The mechanism analysis indicates that boric acid could be decomposed into boron oxide, which could paste the char and make the char more compact. However, zinc oxide and nickel acetate could react with APP to produce cross-linking materials to decrease the speed of the melt to flame area.
5. The thermal behaviors were investigated by means of TG, and the results showed that the flame retardant PP degraded ahead of pure PP under both air and nitrogen atmosphere, but the final residue was much higher than that of neat PP. The Broido method was used to calculate the activation energy of PP/APP/MP/BCPPOO system and pure PP, and the incorporation of IFR could decrease the activation energy.
6. The flame retardant mechanism of various systems was studied by means of SEM, FT-IR, XPS and XRD. Results showed that the compact char layer was a crucial factor for flame retardancy. Phosphorus-containing compounds were detected in intumescent char, and they could delay the oxidation of PP. The XRD analysis of intumescent char containing nickel acetate showed that phosphorus-nickel oxide and inorganic salts were detected.
7. A capillary rheometer was used to investigate the rheological properties of various IFR-PP systems. Both neat PP and flame-retardant PP systems exhibit the pseudoplastic flow behavior, and the apparent viscosity decreases with the increase of shear rate. At a certain temperature, the IFR-PP systems had much higher apparent viscosities than neat PP, but there were not obvious differences of apparent viscosities among various IFR-PP systems. XRD was used to investigate the crystalline behaviors of various IFR-PP systems. IFR had no effect on the crystalline structure of PP. The investigation of mechanical properties showed that the tensile strength, elongation at break and Izod impact strength of IFR-PP systems decreased, especially elongation at break, but flexural strength increased compared to those of neat PP. However, the mechanical properties of the IFR-PP systems were a little better than those of some commercial flame-retardant PP products.
引文
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