羟烷基甲酰胺的合成及其塑化的热塑性淀粉性能研究
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摘要
淀粉是一种来源广泛,价格低廉、再生周期短的生物质资源,淀粉在塑化剂作用下可转变为热塑性淀粉(TPS)。热塑性淀粉是具有发展前景的一种生物降解塑料,改善热塑性淀粉性能的研究是当前的热点课题之一。
本文在文献调研的基础上,设计出在无溶剂、无催化剂条件下,以醇胺和甲酸乙酯为原料合成了系列羟烷基甲酰胺(HAF)类化合物,表征了化合物的结构。该合成方法避免了传统合成方法中使用催化剂、大量溶剂和高压条件,也减少了传统方法中过量原料的用量。该合成方法更加符合绿色化学的要求。
以HAF作为淀粉的塑化剂,系统地研究了以无毒的HAF为塑化剂制备的热塑性淀粉(HAFTPS)的性能。用红外(FT-IR)研究了塑化剂HAF与淀粉分子之间的氢键作用力,塑化剂HAF和淀粉分子间有很好的相容性。用扫描电镜(SEM)观察热塑性淀粉的微观形貌,原淀粉颗粒被破坏,形成了均一的连续相。
用X衍射(XRD)详细地研究了HAFTPS的结晶,HAFTPS结晶类型和HAF的结构有关。HAF分子酰胺氮原子仅联有一个氢原子时,相应的HAFTPS中有VA结晶形成;HAF分子酰胺氮原子没有氢原子相联时,由于塑化剂的大体积效应,相应的HAFTPS中有EH结晶形成。HAFTPS的VA结晶和EH结晶吸水后会转化成VH结晶。与传统的以甘油为塑化剂的热塑性淀粉(GTPS)进行了对比。HAFTPS的热稳定性不及GTPS的高。研究了HAFTPS的吸水性能和力学性能。以N,N-二羟乙基甲酰胺为塑化剂的热塑性淀粉(BTPS,是HAFTPS的一种)的耐水性能优于GTPS,而制备的其它的HAFTPS耐水性不及GTPS。在相对湿度(RH)44%的环境中,BTPS拉伸强度优于GTPS,而制备的其它的HAFTPS拉伸强度不及GTPS。在RH 68%的环境中BTPS断裂伸长率优于GTPS。
以HAF作为蒙脱土(MMT)活化扩层剂,采用熔融一次性挤出,制得MMT增强的HAFTPS/MMT纳米复合材料。用FT-IR研究了淀粉、HAF、MMT之间的氢键,说明三者之间有很好的相容性。用原子力显微镜(AFM)观察到HAFTPS/MMT中纳米级剥离的蒙脱土。XRD表明HAFTPS/MMT中MMT层间距扩大。MMT的添加对HAFTPS结晶类型没有影响。用热重(TG)研究了HAFTPS/MMT复合材料的热稳定性。与HAFTPS相比,HAFTPS/MMT复合材料的耐水性得到提高。MMT的添加提高了HAFTPS的拉伸强度。
Starch, a cheap polysaccharide obtained from a great variety of crops, is one of biomass resources. Thermoplastic starch (TPS) can be obtained from starch in the presence of plasticizer. TPS is a promising biodegradable plastic. It is one of key research projects to improve the properties of TPS.
In the text, a series of hydroxyalkylformamides (HAF) were synthesized from alcohol amine and ethyl formate without solvent and catalyst. These products were confirmed by FT-IR, 1H NMR, MS. There were no catalyst, no high pressure and no use of much solvent for the method compared to traditional method. The new method reduced the amount of superfluous reagent. It accorded with the principles of green chemistry.
Thermoplastic starches using nontoxic HAF as plasticizers (HAFTPS) were prepared. The properties of HAFTPS were studied. The hydrogen bond interaction between HAF and starch was proved by Fourier-transform infrared (FT-IR) spectroscopy, it demonstrated that starch and HAF had good compatibility. By scanning electron microscope (SEM), starch granules were completely disrupted and a continuous phase was obtained. The crystallinity of HAFTPS was characterized by X-ray diffraction (XRD). The HAFTPS crystallinity related to the structure of plasticizer HAF. If there was one hydrogen atom connected to nitrogen of HAF, the corresponding HAFTPS only had VA crystallinity; if there was no hydrogen atom connected to nitrogen of HAF, the corresponding HAFTPS had EH crystallinity due to the bulky plasticizer. VA and EH crystallinity could lead to VH crystallinity upon hydration. The properties of HAFTPS were compared with that of traditional thermoplastic starch using glycerol as plasticizer (GTPS). The thermal stability of HAFTPS was inferior to that of GTPS. HAFTPS water vapour absorption and mechanical properties were investigated. The water resistance of thermoplastic starch using N,N-bis(2-hydroxyethyl)formamide as the plasticizer (BTPS, one kind of HAFTPS) was better than that of GTPS, the water resistance of other prepared HAFTPS was inferior to that of GTPS. At relative humidity (RH) 44%, the tensile strength of BTPS was better than that of GTPS, whereas, the tensile strength of other HAFTPS was inferior to that of GTPS. At RH 68%, the elongation at break of BTPS was better than that of GTPS.
HAF were used as Montmorillonite (MMT) activators. MMT-reinforced HAFTPS/MMT nano composites were prepared with the method of one time extrusion. The hydrogen bond interaction among HAF, starch and MMT was proved by FT-IR, it demonstrated that starch, HAF and MMT had good compatibility. Exfoliated nano MMT in HAFTPS/MMT was found by atomic force microscopy (AFM). XRD demonstrated that d-space of MMT in HAFTPS/MMT was expanded. MMT had no influence upon the crystallinity HAFTPS. The thermal stability was examined by Thermogravimetric (TG) analysis. The water resistance and tensile strength of HAFTPS were improved by adding MMT.
本文在文献调研的基础上,设计出在无溶剂、无催化剂条件下,以醇胺和甲酸乙酯为原料合成了系列羟烷基甲酰胺(HAF)类化合物,表征了化合物的结构。该合成方法避免了传统合成方法中使用催化剂、大量溶剂和高压条件,也减少了传统方法中过量原料的用量。该合成方法更加符合绿色化学的要求。
以HAF作为淀粉的塑化剂,系统地研究了以无毒的HAF为塑化剂制备的热塑性淀粉(HAFTPS)的性能。用红外(FT-IR)研究了塑化剂HAF与淀粉分子之间的氢键作用力,塑化剂HAF和淀粉分子间有很好的相容性。用扫描电镜(SEM)观察热塑性淀粉的微观形貌,原淀粉颗粒被破坏,形成了均一的连续相。
用X衍射(XRD)详细地研究了HAFTPS的结晶,HAFTPS结晶类型和HAF的结构有关。HAF分子酰胺氮原子仅联有一个氢原子时,相应的HAFTPS中有VA结晶形成;HAF分子酰胺氮原子没有氢原子相联时,由于塑化剂的大体积效应,相应的HAFTPS中有EH结晶形成。HAFTPS的VA结晶和EH结晶吸水后会转化成VH结晶。与传统的以甘油为塑化剂的热塑性淀粉(GTPS)进行了对比。HAFTPS的热稳定性不及GTPS的高。研究了HAFTPS的吸水性能和力学性能。以N,N-二羟乙基甲酰胺为塑化剂的热塑性淀粉(BTPS,是HAFTPS的一种)的耐水性能优于GTPS,而制备的其它的HAFTPS耐水性不及GTPS。在相对湿度(RH)44%的环境中,BTPS拉伸强度优于GTPS,而制备的其它的HAFTPS拉伸强度不及GTPS。在RH 68%的环境中BTPS断裂伸长率优于GTPS。
以HAF作为蒙脱土(MMT)活化扩层剂,采用熔融一次性挤出,制得MMT增强的HAFTPS/MMT纳米复合材料。用FT-IR研究了淀粉、HAF、MMT之间的氢键,说明三者之间有很好的相容性。用原子力显微镜(AFM)观察到HAFTPS/MMT中纳米级剥离的蒙脱土。XRD表明HAFTPS/MMT中MMT层间距扩大。MMT的添加对HAFTPS结晶类型没有影响。用热重(TG)研究了HAFTPS/MMT复合材料的热稳定性。与HAFTPS相比,HAFTPS/MMT复合材料的耐水性得到提高。MMT的添加提高了HAFTPS的拉伸强度。
Starch, a cheap polysaccharide obtained from a great variety of crops, is one of biomass resources. Thermoplastic starch (TPS) can be obtained from starch in the presence of plasticizer. TPS is a promising biodegradable plastic. It is one of key research projects to improve the properties of TPS.
In the text, a series of hydroxyalkylformamides (HAF) were synthesized from alcohol amine and ethyl formate without solvent and catalyst. These products were confirmed by FT-IR, 1H NMR, MS. There were no catalyst, no high pressure and no use of much solvent for the method compared to traditional method. The new method reduced the amount of superfluous reagent. It accorded with the principles of green chemistry.
Thermoplastic starches using nontoxic HAF as plasticizers (HAFTPS) were prepared. The properties of HAFTPS were studied. The hydrogen bond interaction between HAF and starch was proved by Fourier-transform infrared (FT-IR) spectroscopy, it demonstrated that starch and HAF had good compatibility. By scanning electron microscope (SEM), starch granules were completely disrupted and a continuous phase was obtained. The crystallinity of HAFTPS was characterized by X-ray diffraction (XRD). The HAFTPS crystallinity related to the structure of plasticizer HAF. If there was one hydrogen atom connected to nitrogen of HAF, the corresponding HAFTPS only had VA crystallinity; if there was no hydrogen atom connected to nitrogen of HAF, the corresponding HAFTPS had EH crystallinity due to the bulky plasticizer. VA and EH crystallinity could lead to VH crystallinity upon hydration. The properties of HAFTPS were compared with that of traditional thermoplastic starch using glycerol as plasticizer (GTPS). The thermal stability of HAFTPS was inferior to that of GTPS. HAFTPS water vapour absorption and mechanical properties were investigated. The water resistance of thermoplastic starch using N,N-bis(2-hydroxyethyl)formamide as the plasticizer (BTPS, one kind of HAFTPS) was better than that of GTPS, the water resistance of other prepared HAFTPS was inferior to that of GTPS. At relative humidity (RH) 44%, the tensile strength of BTPS was better than that of GTPS, whereas, the tensile strength of other HAFTPS was inferior to that of GTPS. At RH 68%, the elongation at break of BTPS was better than that of GTPS.
HAF were used as Montmorillonite (MMT) activators. MMT-reinforced HAFTPS/MMT nano composites were prepared with the method of one time extrusion. The hydrogen bond interaction among HAF, starch and MMT was proved by FT-IR, it demonstrated that starch, HAF and MMT had good compatibility. Exfoliated nano MMT in HAFTPS/MMT was found by atomic force microscopy (AFM). XRD demonstrated that d-space of MMT in HAFTPS/MMT was expanded. MMT had no influence upon the crystallinity HAFTPS. The thermal stability was examined by Thermogravimetric (TG) analysis. The water resistance and tensile strength of HAFTPS were improved by adding MMT.
引文
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