發(fā)布時間：2018-05-02 19:17

  本文選題：聚氨酯膜 + 甲苯�。� 參考：《武漢紡織大學(xué)》2017年碩士論文

【摘要】：聚氨酯是由硬段相和軟段相組成的高分子材料,其性能主要取決于軟硬段的相結(jié)構(gòu)和微相分離程度。聚氨酯中的硬段是由強(qiáng)極性和剛性的氨基甲酸酯等基團(tuán)組成,由于其內(nèi)聚能大,分子間形成的氫鍵使其聚集在一起形成硬段區(qū);而極性較弱的聚醚段或聚酯段等聚集在一起形成軟段區(qū)。蜘蛛絲由于其高強(qiáng)高韌的性能引起了廣泛的研究,研究者認(rèn)為蜘蛛絲高強(qiáng)高韌的原因是由于蜘蛛絲中含有完全結(jié)晶區(qū)、準(zhǔn)結(jié)晶區(qū)以及無定形區(qū)三相結(jié)構(gòu)。有人對聚氨酯在不同溶劑下的溶脹狀態(tài)做了研究,發(fā)現(xiàn)溶劑可以減小聚氨酯分子鏈中硬段區(qū)的氫鍵作用,會造成聚氨酯的強(qiáng)力降低,斷裂伸長率增加。通過對比聚氨酯的分子結(jié)構(gòu)和蜘蛛絲的分子結(jié)構(gòu),本文采用甲苯作為溶劑溶脹聚氨酯,使得聚氨酯中小部分的硬段介于硬段和軟段之間,來模擬蜘蛛絲的三相結(jié)構(gòu)。通過上述方式制得的聚氨酯材料與純DMF為溶劑濕法成型的聚氨酯材料相比,在強(qiáng)力和伸長方面有顯著提高,與純DMF為溶劑干法成型的聚氨酯材料相比,斷裂伸長率和斷裂功有顯著提高。本文采用甲苯與DMF二元溶劑制備聚氨酯材料,主要開展以下三個方面的工作:第一,通過改變二元溶劑中甲苯與DMF的比例,制備出了聚氨酯干法膜。通過掃描電鏡觀察不同比例溶劑體系制備出的膜的橫截面,發(fā)現(xiàn)不同比例溶劑體系所制備的聚氨酯膜與DMF為單一溶劑制備出的聚氨酯干法膜的截面均較為致密,無明顯差異,且其力學(xué)性能相似。第二,采用二元溶劑兩步法制備出了聚氨酯膜,通過掃描電鏡、紅外光譜、熱學(xué)性能、熱力學(xué)性能和力學(xué)性能測試對不同比例二元溶劑兩步法制備的聚氨酯膜的結(jié)構(gòu)和性能進(jìn)行了表征。通過膜截面的掃描電鏡圖可知,隨著二元溶劑中甲苯比例的增加,聚氨酯膜的表面更加光滑,橫截面更加致密;通過傅里葉紅外光譜分析可知,在3300cm-1附近的吸收峰向高波段略有偏移且峰變寬,表明隨著二元溶劑中甲苯比例的增加,聚氨酯膜的硬段中的氫鍵減弱;通過DSC和DMA的測試可知,當(dāng)二元溶劑中甲苯比例為30%時,聚氨酯材料的玻璃化轉(zhuǎn)變溫度最低,表明聚氨酯材料的軟鏈段變得更軟了;通過力學(xué)性能測試可知,當(dāng)二元溶劑中甲苯比例為30%時,聚氨酯膜的拉伸應(yīng)力,拉伸應(yīng)變和斷裂功最大,分別為27.72MPa,2034.18%和10.25J,是單一溶劑DMF濕法制備的聚氨酯膜拉伸應(yīng)力的6.45倍,拉伸應(yīng)變的3.18倍,斷裂功的8.47倍。通過與二元溶劑制備的干法膜對比可知,二元溶劑兩步法制備的聚氨酯膜約為干法膜拉伸應(yīng)變的2.11倍,斷裂功的2倍,而拉伸應(yīng)力有所降低,是干法拉伸應(yīng)力的78.26%。第三,通過采用二元溶劑兩步法制備出了聚氨酯纖維,通過掃描電鏡和力學(xué)性能測試對不同比例二元溶劑兩步法制備的聚氨酯纖維的結(jié)構(gòu)和性能進(jìn)行了表征。通過膜截面的掃描電鏡圖可知,隨著二元溶劑中甲苯比例的增加,聚氨酯纖維的橫截面更加致密;通過力學(xué)性能測試可知,隨著二元溶劑中甲苯比例的增加,纖維的力學(xué)性能具有較大的提高,且當(dāng)甲苯比例為30%時,聚氨酯纖維的斷裂伸長率達(dá)到最大。
[Abstract]:Polyurethane is a polymer material composed of hard segment phase and soft segment. Its properties mainly depend on the phase structure and phase separation degree of the soft and hard segments. The hard segments in the polyurethane are composed of strong and rigid carbamate groups. Because of their large cohesive energy and hydrogen bonds formed by intermolecular hydrogen bonds, the hard segments are formed together to form a hard segment. The weak polyether segments or polyester segments gather together to form a soft segment together. Spider silk has been widely studied because of its high strength and toughness. The reasons for the high strength and toughness of the spider silk are due to the three phase structure of the spider silk, which contains the complete crystalline area, the quasi crystalline area and the amorphous region. The swelling state has been studied. It is found that the solvent can reduce the hydrogen bond in the hard segment of the polyurethane chain, resulting in the strength reduction of the polyurethane and the increase of the elongation at break. By comparing the molecular structure of the polyurethane and the molecular structure of the spider silk, the toluene is used as solvent to expand the polyurethane to make the hard segments of the medium and small parts of the polyurethane. Between the hard segment and the soft segment, the three phase structure of the spider silk is simulated. The polyurethane material obtained by the above method is significantly improved in strength and elongation compared with the pure DMF for the solvent wet forming of the polyurethane. Compared with the pure DMF as the solvent based polyurethane, the breaking elongation and fracture work are significantly improved. This paper uses two elements solvent of toluene and DMF to prepare the polyurethane material. The main work is to carry out the following three aspects: first, by changing the proportion of toluene and DMF in the two element solvent, the dry membrane of the polyurethane is prepared. The cross section of the film prepared by different proportion solvent system is observed by scanning electron microscope, and the different proportion of solvent system is found. The cross-sections of the polyurethane film prepared by the polyurethane film and DMF for the single solvent are relatively compact, and the mechanical properties are similar. Second, the polyurethane film is prepared by two steps of two element solvent. The scanning electron microscope, infrared spectra, thermal properties, thermodynamic properties and mechanical properties test for different ratios of two yuan dissolve to different proportions. The structure and performance of the polyurethane film prepared by the two step method are characterized. Through the scanning electron microscope diagram of the film section, it is known that the surface of the polyurethane film is more smooth and the cross section is more compact with the increase of the proportion of toluene in the two solvent. The absorption peak near the 3300cm-1 is slightly offset to the high band through the Fourier transform infrared spectrum analysis. With the increase of the peak value, the hydrogen bond in the hard segment of the polyurethane film is weakened with the increase of the ratio of toluene in the two element solvent. Through the test of DSC and DMA, the glass transition temperature of the polyurethane material is the lowest when the proportion of toluene in the two solvent is 30%, indicating that the soft chain section of the polyurethane material becomes softer. When the proportion of toluene in two solvent is 30%, the tensile stress, tensile strain and fracture work of the polyurethane film are the largest, 27.72MPa, 2034.18% and 10.25J, respectively, 6.45 times the tensile stress of the single solvent DMF wet method, 3.18 times the tensile strain and 8.47 times the breaking work. The polyurethane film prepared by the two step method of two element solvent is about 2.11 times the tensile strain of the dry process, 2 times the breaking work, and the tensile stress is reduced, it is 78.26%. third of the dry tensile stress. The polyurethane fiber is prepared by two steps of two solvent solvent. The two step method of two yuan solvent two step by the scanning electron microscope and the mechanical properties test is carried out. The structure and properties of the prepared polyurethane fibers were characterized. Through the scanning electron microscope diagram of the film section, it was found that the cross section of the polyurethane fiber was more compact with the increase of the proportion of toluene in the two solvent, and the mechanical properties of the fibers increased with the increase of the ratio of toluene in the two solvent. When the toluene ratio is 30%, the elongation at break of polyurethane fiber reaches the maximum.

【學(xué)位授予單位】：武漢紡織大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ342;TB383.2

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