基于甲基二乙醇胺的两性离子形状记忆聚氨酯的制备及性能研究

发布时间：2018-05-30 04:10

本文选题：聚氨酯 + 两性离子　；参考：《深圳大学》2017年硕士论文

【摘要】：形状记忆聚氨酯具有理想的物理化学性质,已经成为越来越重要的智能生物材料,但因其生物相容性不理想,也限制了它们的在医用领域的应用。从而除了增加形状记忆聚氨酯的形状记忆功能之外,提高其生物相容性也是很有必要的。近年来,两性离子聚氨酯因其良好的生物相容性并且制备工艺简单越来越受到人们的重视。因此,本课题创新性的设计基于MDEA体系的形状记忆聚氨酯,通过两性离子化以及改性的方法,提高形状记忆聚氨酯的生物相容性,改善其形状记忆性能。首先通过溶液聚合制备HDI-MDEA为软段,HDI-BDO为硬段的SMPU。采用FT-IR,~1HNMR对其结构进行分析,通过DSC,TGA,DMA,POM和AFM对其热力学以及结晶性能进行测定。研究发现硬段含量低于20wt%的样品是无定形的,HDI-BDO硬段超过30wt%会形成半结晶硬相,这种形态满足SMP的基本结构要求。对该系列SMPU的形状记忆测试证明,HSC为20wt%的样品具有良好的热诱导双重形状记忆性能,且其具有100%的形状固定率和80%的形状回复率。这项工作为设计多功能含胺形状的记忆聚氨酯提供了一种新策略。然后以HDI,PEG6000,MDEA以及1,3-PS为原料制备SMPU-PS系列样品。采用FT-IR,~1HNMR、XPS对其结构进行分析,通过DSC,TGA,DMA,POM和AFM对其热力学以及结晶性能进行测定。通过DMA、TGA、微机万能材料试验机等研究该系列样品的热稳定性和热机械性能;DMA形状记忆性能研究表明SMPU-PS系列样品均具有热致形状记忆性能,且随着样品中1,3-PS/MDEA比例增加,形状记忆性能有所提高,但当1,3-PS/MDEA比例过高时,反而会使形状固定率和回复率有所下降。通过荧光倒置显微镜、酶标仪、SEM等研究发现该系列样品的生物相容性良好。最后将SMPU-PS系列样品经KH560改性制备SMPU-PS-JL系列样品,并对它的结构与性能进行系统研究。采用FT-IR对其结构进行分析,通过DSC,TGA,DMA,POM和AFM对其热力学以及结晶性能进行测定;通过DMA、TGA、微机万能材料试验机等研究该系列样品的热稳定性和热机械性能。研究发现该系列样品相较于SMPU-PS系列样品来说,其热稳定性和热机械性能提高;DMA形状记忆性能研究表明SMPU-PS-JL系列样品的热致形状记忆性能先提高后降低。通过荧光倒置显微镜、酶标仪、SEM等研究发现样品SMPU-0.2PS-JL、SMPU-0.8PS-JL、SMPU-1PS-JL的生物相容性良好,其中样品SMPU-0.8PS-JL的细胞相容性良好且形状回复率也达到87%,是将形状记忆性能和生物相容性能结合最好的样品。
[Abstract]:Shape memory polyurethane (SMA) has become more and more important intelligent biomaterials because of its ideal physical and chemical properties. However, due to its poor biocompatibility, its application in medical field is limited. In addition to increasing shape memory function of shape memory polyurethane, it is necessary to improve its biocompatibility. In recent years, amphoteric polyurethane has attracted more and more attention because of its good biocompatibility and simple preparation process. Therefore, the innovative design of shape memory polyurethane based on MDEA system is to improve the biocompatibility and shape memory properties of shape memory polyurethane by amphoteric ionization and modification. Firstly, SMPU with HDI-MDEA as soft segment HDI-BDO as hard segment was prepared by solution polymerization. Its structure was analyzed by FT-IR ~ 1H NMR, and its thermodynamics and crystallization properties were determined by DSC-TGAGA-DMAPOM and AFM. It is found that the samples with hard segment content less than 20wt% are amorphous HDI-BDO hard segments with more than 30wt% hard segment, which can form semi-crystalline hard phase, which meets the basic structural requirements of SMP. The shape memory test of this series of SMPU shows that the sample with 20wt% HSC has good thermal induced dual shape memory performance and has a shape fixation rate of 100% and a shape recovery rate of 80%. This work provides a new strategy for the design of multifunctional amine-shaped memory polyurethane. Then the SMPU-PS series samples were prepared by using HDIN PEG6000 MDEA and 1C 3 PS as raw materials. Its structure was analyzed by FT-IR 1H NMR-XPS, and its thermodynamics and crystallization properties were determined by DSC-TGAGA-DMAPOM and AFM. The thermal stability and thermo-mechanical properties of the samples were studied by DMA-TGA and microcomputer universal material testing machine. The results showed that all the samples of SMPU-PS series had thermo-induced shape memory properties, and the ratio of 1 ~ 3-PS- / -MDEA increased with the increase of the ratio of 1 ~ 3-PS- / -MDEA in the samples. The shape memory performance is improved, but when the ratio of 1 / 3-PS- / MDEA is too high, the shape fixation rate and the recovery rate will decrease. The biocompatibility of this series of samples was found to be good by fluorescence inverted microscope and SEM. Finally, SMPU-PS series samples were modified by KH560 to prepare SMPU-PS-JL series samples, and the structure and properties of SMPU-PS-JL series samples were systematically studied. The structure was analyzed by FT-IR, the thermodynamics and crystallization properties were determined by DSC-TGA and AFM, and the thermal stability and thermo-mechanical properties of the samples were studied by DMA-TGA and microcomputer universal material testing machine. It is found that the thermal stability and thermo-mechanical properties of the samples are improved compared with those of the SMPU-PS series. The results show that the thermo-induced shape memory properties of the SMPU-PS-JL series samples first increase and then decrease. The biocompatibility of SMPU-0.2PS-JLN SMPU-0.8PS-JLU SMPU-1PS-JL was found to be good by fluorescence inverted microscope and enzyme labeling instrument. The cell compatibility and shape recovery rate of sample SMPU-0.8PS-JL were also good, which was the best sample to combine shape memory performance with biocompatibility of SMPU-0.2PS-JLN and SMPU-1PS-JL.
【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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