MWNTs/Mg（OH）_2阻燃PET功能纤维的制备及其结构与性能研究
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摘要
近年来,随着人们生活水平的提高和消费意识的增强,纺织品的阻燃性能越来越引起了人们的重视。然而,目前绝大多数纺织材料均属可燃性高聚物,在燃烧过程中,不仅会产生大量的热,而且会释放出许多有毒的气体,对人民的生命财产安全构成了严重威胁。因此,研究和开发具有阻燃功能的纤维材料具有十分重要的意义。
无机阻燃剂具有阻燃效率高、热稳定性好、无毒、无腐蚀性、抑烟以及价格低廉等优点而被广泛使用。碳纳米管(CNTs)优异的物理和化学性能,被认为是一种性能优良的高聚物基复合材料添加相。聚对苯二甲酸乙二酯纤维(PET)是一种性能优异、产量最大、用途最广的合成纤维,不仅宜于民用,也宜于产业用。然而,PET的极限氧指数仅为21左右,受热易熔融、分解、燃烧,极大地限制了其更加广泛的应用领域。为此,本课题拟以MWNTs为载体制备MWNTs/Mg(OH)2复合阻燃剂,并将其应用于PET纤维,来提高PET的热稳定性能和阻燃性能。
本文先采用硝酸氧化法对多壁碳纳米管(MWNTs)进行了表面修饰,然后以酸化后的MWNTs以为载体,通过液相反向沉淀法制备了MWNTs/Mg(OH)2复合阻燃剂,并采用双螺杆挤出机制备了MWNTs/ Mg(OH)2阻燃PET母粒,最后通过熔融共混纺丝法制成了MWNTs/Mg(OH)2阻燃PET功能纤维。
采用JSM-6700F型场发射扫描电镜(SEM)观察了样品的形貌；通过JEM-2010型高分辨透射电镜(HRTEM)、Y-2000型X射线衍射仪(XRD)和FTIR1730型红外光谱测试仪(IR)表征了样品的结构；利用AA240-FS型原子吸收光谱仪测定了样品中Mg2+的含量；采用Q100型差示扫描量热仪(DSC)和TG209F1型热重分析仪(TG)测定了样品的热性能；并通过极限氧指数仪(LOI)对样品的阻燃性能进行了测试。
通过以上研究,主要得到如下结论：
(1)通过HNO3的氧化修饰,可以在MWNTs的其表面引入了-OH、-COOH等其它的基团,有助于MWNTs的化学接枝和物理包覆；
(2)经硝酸表面修饰后的MWNTs可以作为载体,通过液相反向沉淀法在其表面包覆上一层Mg(OH)2,该复合阻燃剂的起始热分解温度比纯MWNTs提高了约100℃；
(3)采用双螺杆熔融共混挤出机可以制备具有良好分散性和阻燃性能的MWNTs/Mg(OH)2阻燃PET功能纤维母粒；
(4)采用母粒熔融共混纺丝法可以纺制具有良好阻燃性能的MWNTs/Mg(OH)2阻燃PET功能纤维。
In recent years, with the continuous improvement of living standards and the continued strengthening of consume awareness, the fire resistance of textile products has attracted people's increasing attention. However, the vast majority of textile materials belong to flammable polymers, it not only generates a lot of heat and, but also release many toxic gases during the combustion process, which posed a serious threat on people's lives and property safety. Therefore, it is of great significance to research and develop the flame-retardant fiber materials.
Inorganic flame retardant which has been widely used as a high efficiency, good thermal stability, non-toxic, non-corrosive, smoke suppression and the advantages of low cost.Carbon nanotubes (CNTs) with unique structures and excellent physical and chemical properties, which has considered to be an excellent addition phase.As a synthetic fiber with excellent performance, Polyethylene terephthalate(PET) fiber is not only one of the largest output, the most widely used among all chemical fibers, but also appropriate for civilian and industrial use. However, the limiting oxygen index of PET is only 21%, which is easy to melting, decomposition, combustion during heating process, so its applications were limited greatly. Therefore, MWNTs/Mg(OH)2 compound flame retardant were prepared which MWNTs was used as carrier, then applied to PET fiber to improve the thermal stability and flame retardant properties of PET fiber in this topic.
In present paper, Multi-walled carbon nanotubes (MWNTs) were surface modified by nitric acid oxidation method firstly, and then used as carrier to prepare the MWNTs/Mg(OH)2 compound flame retardant through reverse precipitation in the liquid phase, MWNTs/Mg(OH)2 flame-retardant PET masterbatch were prepared by using twin-screw extruder, Finally, the MWNTs/Mg(OH)2 flame-retardant PET functional fibers were spun by melt blending technique.
The morphology of the samples were observed by Scanning Electron Microscopy(SEM).The structure of specimens were characterized by High-Resolution Transmission Electron Microscopy(HRTEM), X-ray diffraction(XRD) and Infrared Spectrometry(IR). The contents of magnesium cations were measured by AA240-FS atomic absorption spectrometer. The crystallinity and thermal stability of the samples were determined through differential scanning calorimeter(DSC) and thermal gravimetric analysis (TG); and flame retardant properties were tested through the limiting oxygen index meter (LOI).Through studying and discussion, the main conclusions were drawn as follows:
(1) By oxidized in nitric acid, it can be introduced -OH,-COOH, and other groups on the surface of MWNTs, which contributed to the chemical grafting and physical coating for MWNTs;
(2) The MWNTs after modified by nitric acid can be used as the carrier to prepare MWNTs/Mg(OH)2 compound flame retardant through reverse precipitation in the liquid phase,which could increased the initial thermal decomposition temperature of pure MWNTs；
(3)The PET functional masterbatch with good dispersion and flame retardant properties,which can be prepared by melt blending in twin-screw extruder;
(4)By melt blend spinning technology,PET functional fiber can be spun with good flame retardant properties.
无机阻燃剂具有阻燃效率高、热稳定性好、无毒、无腐蚀性、抑烟以及价格低廉等优点而被广泛使用。碳纳米管(CNTs)优异的物理和化学性能,被认为是一种性能优良的高聚物基复合材料添加相。聚对苯二甲酸乙二酯纤维(PET)是一种性能优异、产量最大、用途最广的合成纤维,不仅宜于民用,也宜于产业用。然而,PET的极限氧指数仅为21左右,受热易熔融、分解、燃烧,极大地限制了其更加广泛的应用领域。为此,本课题拟以MWNTs为载体制备MWNTs/Mg(OH)2复合阻燃剂,并将其应用于PET纤维,来提高PET的热稳定性能和阻燃性能。
本文先采用硝酸氧化法对多壁碳纳米管(MWNTs)进行了表面修饰,然后以酸化后的MWNTs以为载体,通过液相反向沉淀法制备了MWNTs/Mg(OH)2复合阻燃剂,并采用双螺杆挤出机制备了MWNTs/ Mg(OH)2阻燃PET母粒,最后通过熔融共混纺丝法制成了MWNTs/Mg(OH)2阻燃PET功能纤维。
采用JSM-6700F型场发射扫描电镜(SEM)观察了样品的形貌；通过JEM-2010型高分辨透射电镜(HRTEM)、Y-2000型X射线衍射仪(XRD)和FTIR1730型红外光谱测试仪(IR)表征了样品的结构；利用AA240-FS型原子吸收光谱仪测定了样品中Mg2+的含量；采用Q100型差示扫描量热仪(DSC)和TG209F1型热重分析仪(TG)测定了样品的热性能；并通过极限氧指数仪(LOI)对样品的阻燃性能进行了测试。
通过以上研究,主要得到如下结论：
(1)通过HNO3的氧化修饰,可以在MWNTs的其表面引入了-OH、-COOH等其它的基团,有助于MWNTs的化学接枝和物理包覆；
(2)经硝酸表面修饰后的MWNTs可以作为载体,通过液相反向沉淀法在其表面包覆上一层Mg(OH)2,该复合阻燃剂的起始热分解温度比纯MWNTs提高了约100℃；
(3)采用双螺杆熔融共混挤出机可以制备具有良好分散性和阻燃性能的MWNTs/Mg(OH)2阻燃PET功能纤维母粒；
(4)采用母粒熔融共混纺丝法可以纺制具有良好阻燃性能的MWNTs/Mg(OH)2阻燃PET功能纤维。
In recent years, with the continuous improvement of living standards and the continued strengthening of consume awareness, the fire resistance of textile products has attracted people's increasing attention. However, the vast majority of textile materials belong to flammable polymers, it not only generates a lot of heat and, but also release many toxic gases during the combustion process, which posed a serious threat on people's lives and property safety. Therefore, it is of great significance to research and develop the flame-retardant fiber materials.
Inorganic flame retardant which has been widely used as a high efficiency, good thermal stability, non-toxic, non-corrosive, smoke suppression and the advantages of low cost.Carbon nanotubes (CNTs) with unique structures and excellent physical and chemical properties, which has considered to be an excellent addition phase.As a synthetic fiber with excellent performance, Polyethylene terephthalate(PET) fiber is not only one of the largest output, the most widely used among all chemical fibers, but also appropriate for civilian and industrial use. However, the limiting oxygen index of PET is only 21%, which is easy to melting, decomposition, combustion during heating process, so its applications were limited greatly. Therefore, MWNTs/Mg(OH)2 compound flame retardant were prepared which MWNTs was used as carrier, then applied to PET fiber to improve the thermal stability and flame retardant properties of PET fiber in this topic.
In present paper, Multi-walled carbon nanotubes (MWNTs) were surface modified by nitric acid oxidation method firstly, and then used as carrier to prepare the MWNTs/Mg(OH)2 compound flame retardant through reverse precipitation in the liquid phase, MWNTs/Mg(OH)2 flame-retardant PET masterbatch were prepared by using twin-screw extruder, Finally, the MWNTs/Mg(OH)2 flame-retardant PET functional fibers were spun by melt blending technique.
The morphology of the samples were observed by Scanning Electron Microscopy(SEM).The structure of specimens were characterized by High-Resolution Transmission Electron Microscopy(HRTEM), X-ray diffraction(XRD) and Infrared Spectrometry(IR). The contents of magnesium cations were measured by AA240-FS atomic absorption spectrometer. The crystallinity and thermal stability of the samples were determined through differential scanning calorimeter(DSC) and thermal gravimetric analysis (TG); and flame retardant properties were tested through the limiting oxygen index meter (LOI).Through studying and discussion, the main conclusions were drawn as follows:
(1) By oxidized in nitric acid, it can be introduced -OH,-COOH, and other groups on the surface of MWNTs, which contributed to the chemical grafting and physical coating for MWNTs;
(2) The MWNTs after modified by nitric acid can be used as the carrier to prepare MWNTs/Mg(OH)2 compound flame retardant through reverse precipitation in the liquid phase,which could increased the initial thermal decomposition temperature of pure MWNTs；
(3)The PET functional masterbatch with good dispersion and flame retardant properties,which can be prepared by melt blending in twin-screw extruder;
(4)By melt blend spinning technology,PET functional fiber can be spun with good flame retardant properties.
引文
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