半芳香聚酰胺PA10T、PA12T和PA6T的界面聚合工艺研究
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摘要
随着耐热性材料的需求增加,半芳香聚酰胺凭借其优异的机械性能、耐热性和尺寸稳定性等优点,得到了越来越广泛应用。目前,已经工业化生产的半芳香聚酰胺品种主要有聚对苯二甲酰己二胺(PA6T)和聚对苯二甲酰壬二胺(PA9T)。其中PA6T的熔点高于其热降解温度,很难实现熔融加工成型；而PA9T的生产成本过高,这些都在一定程度上限制了它们的广泛应用。本实验室自2002年就开始了对长碳链半芳香聚酰胺的研究工作,成功开发出了一系列的新型长碳链半芳香尼龙。研究发现,PA10T和PA12T是两种综合性能优于PA6T和PA9T的耐热性聚酰胺新品种,将来有望在众多领域得到应用。
本论文以绿色环保的酰氯化试剂固体光气为原料,通过Vilsmeier反应与对苯二甲酸合成了对苯二甲酰氯,其收率可达到91.33%,测定其纯度为90.12%。深入考察了合成对苯二甲酰氯的工艺条件。并通过FT-IR、1H-NMR确认了合成的对苯二甲酰氯的化学结构。
本论文又以对苯二甲酰氯、1,10-十碳二元胺、1,12-十二碳二元胺和1,6-己二胺为反应单体通过界面聚合的方法成功合成了半芳香聚酰胺PA10T、PA12T和PA6T。并深入研究了界面聚合工艺条件对PA10T和PA6T聚合物分子量的影响规律。通过FT-IR、1H-NMR分别确认了合成出来的半芳香聚酰胺PA10T、PA12T和PA6T的化学结构。又通过固相缩聚反应进一步提高了界面聚合得到的半芳香聚酰胺PA10T、PA12T和PA6T聚合产物的分子量。使PA10T的相对粘度由1.32提高到了1.96；PA12T的相对粘度由1.27提高到1.69；PA6T的相对粘度由1.18提高到1.46。
运用DSC分析测试方法,分析了半芳香聚酰胺PA10T聚合反应条件和熔点的关系。测得PA10T的熔点为314℃,结晶温度为288℃；PA12T的熔点为302℃,结晶温度为275℃；PA6T的熔点为373℃,结晶温度为332℃。又运用TGA分别对PA10T、PA12T和PA6T的热降解过程进行了研究,研究表明它们的热分解温度都超过了400℃,且这三种半芳香聚酰胺的降解均为一步降解反应。
With the increase of heat resistant material requirements, due to the excellent mechanical properties, heat resistance and dimensional stability, semiaromatic polyamides are more and more widely used. At present only the polyhexamethylene terephthalamide (PA6T) and polynonamethylene terephthalamide (PA9T) were commercially applied. However, PA6T cannot be processed by melting method because its melting point is higher than the thermal decomposition temperature, and the production cost of PA9T is too high, which, to some extent, limit their wide application. Since2002, Our laboratory began to research work of long chain semiaromatic polyamide, and successfully developed a series of new type of long carbon chain and semiaromatic polyamides.It is found that the comprehensive performances of poly(decamethylene terepethalamide)(PA10T) and poly(dodecamethylene terephthalamide)(PA12T) are superior to these of PA6T and PA9T. And they are expected to replace PA9T in many fields in the future.
In this paper, terphthalic acid respectively reacted with triphosgene that is environmental friendly instead of traditional chlorinating agent, especially phosgene and diphosgene to synthesize terephaloyl dichloride (TPC) through Vilsmeier reaction. The yield of TPC reached91.33%, and its purity reached90.12%. We studied the synthetic technological conditions of TPC. The structure of TPC was characterized by IR Spectrum and1H-NMR.
The semiaromatic polyamides PA10T, PA12T and PA6T were prepared from reactions of TPC and three distinct cheap aliphatic diamines (1,10-decanediamine,1,12-dodecaediamine and1,6-adipic amine) through interfacial polymerization method, respectively. The interfacial polymerization conditions on PA10T and PA6T have been in-depth investigated. The structures of PA10T, PA12T and PA6T were characterized by IR Spectrun and1H-NMR, respectively. Through the solid phase polymerization, the molecular weight of PA10T, PA12T and PA6T was futher improved. The relative viscosity of PA10T increased from1.32to1.96. The relative viscosity of PA12T increased from1.27to1.69. The relative viscosity of PA6T increased from1.18to1.46.
The relationship of the melting temperature (Tm) and the polymerization reaction condition of PA10T was analysised by DSC. It was found that the melting point of PA10T after solid phase polymerization was not much improved. The melting temperatures of PA10T, PA12T and PA6T were314℃,302℃and373℃, and their crystallization temperatures were288℃,275℃,332℃, respectively. Thermal degradation processes of PA10T, PA12T and PA6T were analysised by TGA. It was found that their thermal degradation temperatures were over400℃. It was proved that the degradation of PA10T, PA12T and PA6T was step degradation reaction.
本论文以绿色环保的酰氯化试剂固体光气为原料,通过Vilsmeier反应与对苯二甲酸合成了对苯二甲酰氯,其收率可达到91.33%,测定其纯度为90.12%。深入考察了合成对苯二甲酰氯的工艺条件。并通过FT-IR、1H-NMR确认了合成的对苯二甲酰氯的化学结构。
本论文又以对苯二甲酰氯、1,10-十碳二元胺、1,12-十二碳二元胺和1,6-己二胺为反应单体通过界面聚合的方法成功合成了半芳香聚酰胺PA10T、PA12T和PA6T。并深入研究了界面聚合工艺条件对PA10T和PA6T聚合物分子量的影响规律。通过FT-IR、1H-NMR分别确认了合成出来的半芳香聚酰胺PA10T、PA12T和PA6T的化学结构。又通过固相缩聚反应进一步提高了界面聚合得到的半芳香聚酰胺PA10T、PA12T和PA6T聚合产物的分子量。使PA10T的相对粘度由1.32提高到了1.96；PA12T的相对粘度由1.27提高到1.69；PA6T的相对粘度由1.18提高到1.46。
运用DSC分析测试方法,分析了半芳香聚酰胺PA10T聚合反应条件和熔点的关系。测得PA10T的熔点为314℃,结晶温度为288℃；PA12T的熔点为302℃,结晶温度为275℃；PA6T的熔点为373℃,结晶温度为332℃。又运用TGA分别对PA10T、PA12T和PA6T的热降解过程进行了研究,研究表明它们的热分解温度都超过了400℃,且这三种半芳香聚酰胺的降解均为一步降解反应。
With the increase of heat resistant material requirements, due to the excellent mechanical properties, heat resistance and dimensional stability, semiaromatic polyamides are more and more widely used. At present only the polyhexamethylene terephthalamide (PA6T) and polynonamethylene terephthalamide (PA9T) were commercially applied. However, PA6T cannot be processed by melting method because its melting point is higher than the thermal decomposition temperature, and the production cost of PA9T is too high, which, to some extent, limit their wide application. Since2002, Our laboratory began to research work of long chain semiaromatic polyamide, and successfully developed a series of new type of long carbon chain and semiaromatic polyamides.It is found that the comprehensive performances of poly(decamethylene terepethalamide)(PA10T) and poly(dodecamethylene terephthalamide)(PA12T) are superior to these of PA6T and PA9T. And they are expected to replace PA9T in many fields in the future.
In this paper, terphthalic acid respectively reacted with triphosgene that is environmental friendly instead of traditional chlorinating agent, especially phosgene and diphosgene to synthesize terephaloyl dichloride (TPC) through Vilsmeier reaction. The yield of TPC reached91.33%, and its purity reached90.12%. We studied the synthetic technological conditions of TPC. The structure of TPC was characterized by IR Spectrum and1H-NMR.
The semiaromatic polyamides PA10T, PA12T and PA6T were prepared from reactions of TPC and three distinct cheap aliphatic diamines (1,10-decanediamine,1,12-dodecaediamine and1,6-adipic amine) through interfacial polymerization method, respectively. The interfacial polymerization conditions on PA10T and PA6T have been in-depth investigated. The structures of PA10T, PA12T and PA6T were characterized by IR Spectrun and1H-NMR, respectively. Through the solid phase polymerization, the molecular weight of PA10T, PA12T and PA6T was futher improved. The relative viscosity of PA10T increased from1.32to1.96. The relative viscosity of PA12T increased from1.27to1.69. The relative viscosity of PA6T increased from1.18to1.46.
The relationship of the melting temperature (Tm) and the polymerization reaction condition of PA10T was analysised by DSC. It was found that the melting point of PA10T after solid phase polymerization was not much improved. The melting temperatures of PA10T, PA12T and PA6T were314℃,302℃and373℃, and their crystallization temperatures were288℃,275℃,332℃, respectively. Thermal degradation processes of PA10T, PA12T and PA6T were analysised by TGA. It was found that their thermal degradation temperatures were over400℃. It was proved that the degradation of PA10T, PA12T and PA6T was step degradation reaction.
引文
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