聚（3-羥基丁酸酯-co-4-羥基丁酸酯）基復合材料的制備與性能研究
發(fā)布時間：2018-08-20 12:39
【摘要】：聚羥基脂肪酸酯(PHA)是近年來迅速發(fā)展起來的一類生物高分子材料,由于PHA材料具有良好的生物相容性、生物可降解性和熱加工性能,被認為是最具有競爭力可替代部分傳統(tǒng)石油基塑料的一種新型材料。聚(3-羥基丁酸酯-co-4-羥基丁酸酯)[P(3,4)HB]是PHA的典型代表,自身存在著結(jié)晶速度慢、加工溫度范圍窄、斷裂伸長率低以及易燃等缺陷。本論文在對PHA基復合材料研究進展進行文獻調(diào)研的基礎上,分別利用納米二氧化硅(SiO2)和聚氨酯彈性體(PU)作為填料,制備P(3,4)HB基復合材料。通過對其力學性能、結(jié)晶性能和熱性能的研究,探索制備可生物降解聚酯增強增韌改性的新途徑。論文主要研究內(nèi)容如下:首先,采用改進的St?ber法,制備粒徑可控的200~400nm單分散SiO2微球,并利用硅烷偶聯(lián)劑KH-550對其進行表面改性,以提高其疏水性。采用熔融共混法將改性后的SiO2與P(3,4)HB進行復合,制備P(3,4)HB/SiO2復合材料,并對其力學性能和結(jié)晶性能進行研究。結(jié)果表明,添加少量的SiO2后,P(3,4)HB/SiO2復合材料的拉伸強度和模量明顯提高,且當SiO2含量為3 wt%時效果最為顯著,然而,材料的斷裂伸長率略有下降。差示掃描量熱(DSC)和偏光顯微(POM)分析結(jié)果顯示,SiO2能夠使P(3,4)HB冷結(jié)晶溫度(Tcc)降低、晶粒細化,表明SiO2對P(3,4)HB的結(jié)晶有促進作用。其次,采用一步法合成了硬段含量為45%的聚酯型PU,進而采用溶液共混法制備了P(3,4)HB/PU復合材料,并對其微觀結(jié)構(gòu)、力學性能、結(jié)晶性能和熱性能進行了測試和分析。研究結(jié)果表明,PU能夠以納米尺度分散在P(3,4)HB基體中。隨著PU含量的增加,P(3,4)HB/PU復合材料的斷裂伸長率逐漸增大,而屈服強度和彈性模量均有所降低。掃描電鏡(SEM)結(jié)果顯示,與純基體P(3,4)HB相比,復合材料的斷裂特征從典型的脆性斷裂轉(zhuǎn)變?yōu)轫g性斷裂。此外,PU的添加能提高復合材料的熱穩(wěn)定性、減緩復合材料的生物降解速率,但其球晶尺寸變大、Tcc提高,表明PU對其結(jié)晶性能有一定的阻礙作用。最后,合成了三種不同硬段含量的聚酯型PU(包括35%PU,45%PU,55%PU),并通過溶液共混法制備P(3,4)HB/PU復合材料,對比研究其增韌效果。研究結(jié)果表明,三種不同硬段含量的PU對P(3,4)HB基體均有明顯的增韌作用,且添加量越大增韌效果越顯著。相比較而言,55%PU的增韌效果最為突出,P(3,4)HB-55%PU復合材料的斷裂強度顯著提高,出現(xiàn)了應力應變曲線持續(xù)增加的現(xiàn)象;而35%PU的增韌效果較差,P(3,4)HB-35%PU復合材料的屈服強度下降的最多。三種不同硬段含量的PU均使得P(3,4)HB/PU復合材料的熱穩(wěn)定性提高,但結(jié)晶性能均有一定的下降。
[Abstract]:Polyhydroxyl fatty acid ester (PHA) is a kind of biomaterials developed rapidly in recent years. Because of its good biocompatibility, biodegradability and hot processing properties, PHA materials have been widely used in many fields. It is considered to be the most competitive alternative to some of the traditional petroleum-based plastics a new material. Poly (3-hydroxybutyrate -co-4hydroxybutyrate) [P (3Hb) HB] is a typical representative of PHA. It has some defects such as slow crystallization rate, narrow processing temperature, low elongation at break and flammability. In this paper, based on the research progress of PHA matrix composites, P _ (3O _ 4) HB matrix composites were prepared by using nano-silica (SiO2) and polyurethane elastomer (PU) as fillers, respectively. Through the study of mechanical properties, crystallization properties and thermal properties, a new way to prepare biodegradable polyester reinforced and toughened modification was explored. The main contents of this paper are as follows: firstly, the 200~400nm monodisperse SiO2 microspheres with controllable particle size were prepared by modified St?ber method, and the surface of SiO2 microspheres was modified by silane coupling agent KH-550 to improve its hydrophobicity. The modified SiO2 and P _ (3O _ 4) HB composites were prepared by melt blending method. The mechanical properties and crystallization properties of P _ (3O _ 4) HB/SiO2 composites were studied. The results showed that the tensile strength and modulus of P _ (3N _ 4) HB/SiO2 composites increased obviously after adding a small amount of SiO2, and the tensile strength and modulus of P _ (3) O _ (4) HB/SiO2 composites were the most obvious when the content of SiO2 was 3 wt%. However, the elongation at break of the composites decreased slightly. The results of differential scanning calorimetry (DSC) and polarizing microscopy (POM) show that SiO2 can decrease the cold crystallization temperature (Tcc) of P _ (3O _ 4) HB and refine the grain size, indicating that SiO2 can promote the crystallization of P _ (3O _ 4) HB. Secondly, a 45% hard segment polyester-type HB/PU composite was synthesized by one-step method, and then P _ (3O _ 4) HB/PU composites were prepared by solution blending method. The microstructure, mechanical properties, crystallization properties and thermal properties of the composites were tested and analyzed. The results show that pu can be dispersed in P _ (3O _ 4) HB matrix on nanometer scale. With the increase of pu content, the elongation at break of P _ (3O _ 4) HB/PU composites increases gradually, while the yield strength and elastic modulus decrease. The results of scanning electron microscopy (SEM) showed that the fracture characteristics of the composites changed from typical brittle fracture to ductile fracture compared with pure matrix P _ (3N _ 4) HB. In addition, the addition of pu can improve the thermal stability of the composites and slow down the biodegradation rate of the composites, but the spherulite size of the composites increases with the increase of TCC, indicating that pu has a certain blocking effect on the crystallization properties of the composites. Finally, three kinds of polyester pu with different hard segment contents (including 35PU45PU55PU) were synthesized, and P (3N 4) HB/PU composites were prepared by solution blending method. The toughening effects of the composites were compared and studied. The results show that three kinds of pu with different hard segment content have obvious toughening effect on P _ (3O _ 4) HB matrix, and the more the content of pu is, the more obvious the toughening effect is. By comparison, the toughening effect of pu is the most prominent, the fracture strength of P _ (3O _ 4) HB-55%PU composites increases significantly, and the stress-strain curve increases continuously, while the yield strength of P _ (3O _ 4) HB-35%PU composites decreases the most when the toughening effect of 35%PU is worse than that of P _ (3N _ 4) HB-35%PU composites. The thermal stability of P _ (3) O _ (4) HB/PU composites was improved by three kinds of pu with different hard segment content, but the crystallization properties of P _ (3) O _ (4) HB/PU composites decreased to some extent.
【學位授予單位】：南京林業(yè)大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ317;TB33
本文編號：2193635
[Abstract]:Polyhydroxyl fatty acid ester (PHA) is a kind of biomaterials developed rapidly in recent years. Because of its good biocompatibility, biodegradability and hot processing properties, PHA materials have been widely used in many fields. It is considered to be the most competitive alternative to some of the traditional petroleum-based plastics a new material. Poly (3-hydroxybutyrate -co-4hydroxybutyrate) [P (3Hb) HB] is a typical representative of PHA. It has some defects such as slow crystallization rate, narrow processing temperature, low elongation at break and flammability. In this paper, based on the research progress of PHA matrix composites, P _ (3O _ 4) HB matrix composites were prepared by using nano-silica (SiO2) and polyurethane elastomer (PU) as fillers, respectively. Through the study of mechanical properties, crystallization properties and thermal properties, a new way to prepare biodegradable polyester reinforced and toughened modification was explored. The main contents of this paper are as follows: firstly, the 200~400nm monodisperse SiO2 microspheres with controllable particle size were prepared by modified St?ber method, and the surface of SiO2 microspheres was modified by silane coupling agent KH-550 to improve its hydrophobicity. The modified SiO2 and P _ (3O _ 4) HB composites were prepared by melt blending method. The mechanical properties and crystallization properties of P _ (3O _ 4) HB/SiO2 composites were studied. The results showed that the tensile strength and modulus of P _ (3N _ 4) HB/SiO2 composites increased obviously after adding a small amount of SiO2, and the tensile strength and modulus of P _ (3) O _ (4) HB/SiO2 composites were the most obvious when the content of SiO2 was 3 wt%. However, the elongation at break of the composites decreased slightly. The results of differential scanning calorimetry (DSC) and polarizing microscopy (POM) show that SiO2 can decrease the cold crystallization temperature (Tcc) of P _ (3O _ 4) HB and refine the grain size, indicating that SiO2 can promote the crystallization of P _ (3O _ 4) HB. Secondly, a 45% hard segment polyester-type HB/PU composite was synthesized by one-step method, and then P _ (3O _ 4) HB/PU composites were prepared by solution blending method. The microstructure, mechanical properties, crystallization properties and thermal properties of the composites were tested and analyzed. The results show that pu can be dispersed in P _ (3O _ 4) HB matrix on nanometer scale. With the increase of pu content, the elongation at break of P _ (3O _ 4) HB/PU composites increases gradually, while the yield strength and elastic modulus decrease. The results of scanning electron microscopy (SEM) showed that the fracture characteristics of the composites changed from typical brittle fracture to ductile fracture compared with pure matrix P _ (3N _ 4) HB. In addition, the addition of pu can improve the thermal stability of the composites and slow down the biodegradation rate of the composites, but the spherulite size of the composites increases with the increase of TCC, indicating that pu has a certain blocking effect on the crystallization properties of the composites. Finally, three kinds of polyester pu with different hard segment contents (including 35PU45PU55PU) were synthesized, and P (3N 4) HB/PU composites were prepared by solution blending method. The toughening effects of the composites were compared and studied. The results show that three kinds of pu with different hard segment content have obvious toughening effect on P _ (3O _ 4) HB matrix, and the more the content of pu is, the more obvious the toughening effect is. By comparison, the toughening effect of pu is the most prominent, the fracture strength of P _ (3O _ 4) HB-55%PU composites increases significantly, and the stress-strain curve increases continuously, while the yield strength of P _ (3O _ 4) HB-35%PU composites decreases the most when the toughening effect of 35%PU is worse than that of P _ (3N _ 4) HB-35%PU composites. The thermal stability of P _ (3) O _ (4) HB/PU composites was improved by three kinds of pu with different hard segment content, but the crystallization properties of P _ (3) O _ (4) HB/PU composites decreased to some extent.
【學位授予單位】：南京林業(yè)大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ317;TB33
【參考文獻】
相關期刊論文 前9條
1 包孟如;朱桂茹;汪錳;高從X&;;單分散球形納米二氧化硅制備方法的研究進展[J];材料導報;2011年S2期
2 吳亮;吳德峰;吳蘭峰;張明;;聚乳酸/蒙脫土納米復合材料的冷結(jié)晶及熔融行為[J];高分子材料科學與工程;2007年05期
3 徐國榮;陳靜;夏春谷;;生物可降解性聚羥基脂肪酸酯的化學合成研究進展[J];化學通報;2012年03期
4 吳海艷;周莉;臧樹良;;納米二氧化硅表面改性的研究[J];礦冶;2010年04期
5 敖玉輝;周夢思;馮芳;;不同彈性體增韌聚丙烯的研究[J];化工新型材料;2014年03期
6 錢伯章;;熱塑性彈性體市場預計將年增長4.7%[J];世界橡膠工業(yè);2015年01期
7 楊伏生,周安寧,葛嶺梅,曲建林,李天良;聚合物增強增韌機理研究進展[J];中國塑料;2001年08期
8 陶杰;季學來;;聚合物納米復合材料的研究進展[J];機械制造與自動化;2006年01期
9 賈寧寧;高延敏;周超;宋東坡;;工藝因素對溶膠-凝膠法制備SiO_2微球粒徑的影響[J];武漢科技大學學報;2013年01期
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