吡啶甜菜碱两性离子形状记忆聚氨酯的制备及性能研究

发布时间：2019-03-05 08:30

【摘要】：形状记忆聚氨酯(SMPUs)具有结构性能易于控制、温度响应范围宽等优点,作为新型智能材料备受关注。传统的SMPUs形状记忆形式单一,且长期应用于人体会引发炎症,所以需要对SMPUs进行改性。另一方面,两性离子聚合物具有超强亲水性的阴、阳离子基团,能够形成强的离子水化层,使其具有良好的生物相容性和抗生物污染的优良特性,但两性离子聚合物的智能化应用需进一步开发。本课题结合SMPUs和两性离子聚合物的结构特点与功能特性,设计制备了具有热致形状记忆、湿敏感形状记忆性能和生物相容性较好的两性离子SMPUs。首先,用聚乙二醇(Mn=4000,PEG4000)、六亚甲基二异氰酸酯(HDI)、N,N-二羟乙基异烟碱(BINA)、1,3-丙磺酸内脂(1,3-PS),合成以BINAPS-HDI作为硬段相,PEG4000作为软段相的吡啶甜菜碱型两性离子形状记忆聚氨酯(PEGZPUs),系统地对PEGZPUs的结构和性能进行研究。结果表明:PEG4000软链段在常温下具有良好的结晶性,随着BINAPS含量的增加,PEG4000的晶型逐渐变大,且PEGZPUs的拉伸强度逐渐提升,但PEGZPUs总体的拉伸强度仍然不能满足于实际应用。另外,PEGZPUs具有良好的弯曲性能和形状记忆性能。其次,以BINA-HDI为软段相,液化二苯甲烷-4,4-二异氰酸酯(L-MDI)-1,4-丁二醇(BDO)为硬段相,合成硬度含量为35wt%的SMPUs,再与1,3-PS进行两性离子化处理,合成吡啶甜菜碱型两性离子形状记忆聚氨酯(PyZPUs),系统地对PyZPUs的结构和性能进行研究。结果表明:随着BINAPS含量的增加,PyZPUs的热稳定性和热机械性能均得到了提升,且适量的BINAPS的含量对PyZPUs的形状回复率有大幅的提升。此外,PyZPUs具有良好的多重形状记忆性能、循环形状记忆性能以及湿敏感形状记忆性能。在生物相容性进行方面,发现适量的BINAPS含量对PyZPUs的生物相容性具有较好的提升。最后,为了提高SMPUs的拉伸强度和循环形状记忆性能,合成了交联结构吡啶甜菜碱型两性离子SMPUs。先用BINA和HDI合成预聚体,再用季戊四醇作为交联剂合成交联结构的SMPUs,后用1,3-PS进行两性离子化处理,合成两性离子形状记忆聚氨酯(CZPUs),系统地研究其结构和性能。结果表明:随着BINAPS含量的增加,CZPUs的形状回复率先下降后上升,最终CZPU10比CZPU0的形状回复率要高。另外,CZPUs还具有良好的多重形状记忆性能、循环形状记忆性能和湿敏感形状记忆性能。
[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.
【学位授予单位】：深圳大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB381

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