發(fā)布時(shí)間：2019-03-05 08:30

【摘要】：形狀記憶聚氨酯(SMPUs)具有結(jié)構(gòu)性能易于控制、溫度響應(yīng)范圍寬等優(yōu)點(diǎn),作為新型智能材料備受關(guān)注。傳統(tǒng)的SMPUs形狀記憶形式單一,且長(zhǎng)期應(yīng)用于人體會(huì)引發(fā)炎癥,所以需要對(duì)SMPUs進(jìn)行改性。另一方面,兩性離子聚合物具有超強(qiáng)親水性的陰、陽(yáng)離子基團(tuán),能夠形成強(qiáng)的離子水化層,使其具有良好的生物相容性和抗生物污染的優(yōu)良特性,但兩性離子聚合物的智能化應(yīng)用需進(jìn)一步開(kāi)發(fā)。本課題結(jié)合SMPUs和兩性離子聚合物的結(jié)構(gòu)特點(diǎn)與功能特性,設(shè)計(jì)制備了具有熱致形狀記憶、濕敏感形狀記憶性能和生物相容性較好的兩性離子SMPUs。首先,用聚乙二醇(Mn=4000,PEG4000)、六亞甲基二異氰酸酯(HDI)、N,N-二羥乙基異煙堿(BINA)、1,3-丙磺酸內(nèi)脂(1,3-PS),合成以BINAPS-HDI作為硬段相,PEG4000作為軟段相的吡啶甜菜堿型兩性離子形狀記憶聚氨酯(PEGZPUs),系統(tǒng)地對(duì)PEGZPUs的結(jié)構(gòu)和性能進(jìn)行研究。結(jié)果表明:PEG4000軟鏈段在常溫下具有良好的結(jié)晶性,隨著B(niǎo)INAPS含量的增加,PEG4000的晶型逐漸變大,且PEGZPUs的拉伸強(qiáng)度逐漸提升,但PEGZPUs總體的拉伸強(qiáng)度仍然不能滿足于實(shí)際應(yīng)用。另外,PEGZPUs具有良好的彎曲性能和形狀記憶性能。其次,以BINA-HDI為軟段相,液化二苯甲烷-4,4-二異氰酸酯(L-MDI)-1,4-丁二醇(BDO)為硬段相,合成硬度含量為35wt%的SMPUs,再與1,3-PS進(jìn)行兩性離子化處理,合成吡啶甜菜堿型兩性離子形狀記憶聚氨酯(PyZPUs),系統(tǒng)地對(duì)PyZPUs的結(jié)構(gòu)和性能進(jìn)行研究。結(jié)果表明:隨著B(niǎo)INAPS含量的增加,PyZPUs的熱穩(wěn)定性和熱機(jī)械性能均得到了提升,且適量的BINAPS的含量對(duì)PyZPUs的形狀回復(fù)率有大幅的提升。此外,PyZPUs具有良好的多重形狀記憶性能、循環(huán)形狀記憶性能以及濕敏感形狀記憶性能。在生物相容性進(jìn)行方面,發(fā)現(xiàn)適量的BINAPS含量對(duì)PyZPUs的生物相容性具有較好的提升。最后,為了提高SMPUs的拉伸強(qiáng)度和循環(huán)形狀記憶性能,合成了交聯(lián)結(jié)構(gòu)吡啶甜菜堿型兩性離子SMPUs。先用BINA和HDI合成預(yù)聚體,再用季戊四醇作為交聯(lián)劑合成交聯(lián)結(jié)構(gòu)的SMPUs,后用1,3-PS進(jìn)行兩性離子化處理,合成兩性離子形狀記憶聚氨酯(CZPUs),系統(tǒng)地研究其結(jié)構(gòu)和性能。結(jié)果表明:隨著B(niǎo)INAPS含量的增加,CZPUs的形狀回復(fù)率先下降后上升,最終CZPU10比CZPU0的形狀回復(fù)率要高。另外,CZPUs還具有良好的多重形狀記憶性能、循環(huán)形狀記憶性能和濕敏感形狀記憶性能。
[Abstract]:Shape memory polyurethane (SMPUs), which has the advantages of easy control of structure and properties and wide range of temperature response, has attracted much attention as a new intelligent material. The traditional form of SMPUs shape memory is single, and long-term application in human will cause inflammation, so it is necessary to modify SMPUs. On the other hand, the amphoteric polymer has super hydrophilic anionic and cationic groups, which can form a strong ionic hydration layer, which makes it have good biocompatibility and good resistance to biological pollution. But the intelligent application of amphoteric polymer needs further development. In this paper, based on the structural and functional characteristics of SMPUs and amphoteric polymers, an amphoteric SMPUs. with heat-induced shape memory, wet-sensitive shape memory and good biocompatibility was designed and prepared. First, BINAPS-HDI was synthesized by using polyethylene glycol (Mn=4000,PEG4000), hexamethylene diisocyanate (HDI), N, N-dihydroxyethyl isonicotine (BINA), 1, 3-propanesulfonic acid (1, 3 PS) as hard segment phase. The structure and properties of PEG4000 were systematically studied by using pyridine betaine amphoteric shape memory polyurethane (PEGZPUs),) as a soft segment phase. The results show that the soft chain segment of PEG4000 has good crystallinity at room temperature. With the increase of BINAPS content, the crystal structure of PEG4000 increases gradually, and the tensile strength of PEGZPUs increases gradually. However, the overall tensile strength of PEGZPUs is still not satisfied with the practical application. In addition, PEGZPUs has good bending and shape memory properties. Secondly, using BINA-HDI as soft segment phase, liquefied diphenylmethane-4,4-diisocyanate (L-MDI)-1, and 4-butanediol (BDO) as hard-segment phase, SMPUs, with 35 wt% hardness was synthesized and then ionized with 1,3-PS. The structure and properties of pyridine betaine amphoteric shape memory polyurethane (PyZPUs) were systematically studied by using pyridine betaine type amphoteric shape memory polyurethane (PyZPUs),). The results showed that with the increase of BINAPS content, the thermal stability and thermo-mechanical properties of PyZPUs were improved, and the shape recovery rate of PyZPUs was greatly improved by the appropriate content of BINAPS. In addition, PyZPUs has good performance of multiple shape memory, cyclic shape memory and wet sensitive shape memory. In the aspect of biocompatibility, it was found that appropriate amount of BINAPS could improve the biocompatibility of PyZPUs. Finally, in order to improve the tensile strength and cyclic shape memory properties of SMPUs, the crosslinked pyridine betaine amphoteric SMPUs. was synthesized. BINA and HDI were used to synthesize prepolymer, then pentaerythritol was used as cross-linking agent to synthesize cross-linked SMPUs,. The structure and properties of amphoteric shape memory polyurethane (CZPUs),) were studied systematically. The results showed that with the increase of BINAPS content, the shape recovery of CZPUs decreased at first and then increased. Finally, the shape recovery rate of CZPU10 was higher than that of CZPU0. In addition, CZPUs also has good multi-shape memory performance, cyclic shape memory performance and wet-sensitive shape memory performance.
【學(xué)位授予單位】：深圳大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB381

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