基于甲基二乙醇胺的兩性離子形狀記憶聚氨酯的制備及性能研究
本文選題:聚氨酯 + 兩性離子 ; 參考:《深圳大學(xué)》2017年碩士論文
【摘要】:形狀記憶聚氨酯具有理想的物理化學(xué)性質(zhì),已經(jīng)成為越來(lái)越重要的智能生物材料,但因其生物相容性不理想,也限制了它們的在醫(yī)用領(lǐng)域的應(yīng)用。從而除了增加形狀記憶聚氨酯的形狀記憶功能之外,提高其生物相容性也是很有必要的。近年來(lái),兩性離子聚氨酯因其良好的生物相容性并且制備工藝簡(jiǎn)單越來(lái)越受到人們的重視。因此,本課題創(chuàng)新性的設(shè)計(jì)基于MDEA體系的形狀記憶聚氨酯,通過(guò)兩性離子化以及改性的方法,提高形狀記憶聚氨酯的生物相容性,改善其形狀記憶性能。首先通過(guò)溶液聚合制備HDI-MDEA為軟段,HDI-BDO為硬段的SMPU。采用FT-IR,~1HNMR對(duì)其結(jié)構(gòu)進(jìn)行分析,通過(guò)DSC,TGA,DMA,POM和AFM對(duì)其熱力學(xué)以及結(jié)晶性能進(jìn)行測(cè)定。研究發(fā)現(xiàn)硬段含量低于20wt%的樣品是無(wú)定形的,HDI-BDO硬段超過(guò)30wt%會(huì)形成半結(jié)晶硬相,這種形態(tài)滿足SMP的基本結(jié)構(gòu)要求。對(duì)該系列SMPU的形狀記憶測(cè)試證明,HSC為20wt%的樣品具有良好的熱誘導(dǎo)雙重形狀記憶性能,且其具有100%的形狀固定率和80%的形狀回復(fù)率。這項(xiàng)工作為設(shè)計(jì)多功能含胺形狀的記憶聚氨酯提供了一種新策略。然后以HDI,PEG6000,MDEA以及1,3-PS為原料制備SMPU-PS系列樣品。采用FT-IR,~1HNMR、XPS對(duì)其結(jié)構(gòu)進(jìn)行分析,通過(guò)DSC,TGA,DMA,POM和AFM對(duì)其熱力學(xué)以及結(jié)晶性能進(jìn)行測(cè)定。通過(guò)DMA、TGA、微機(jī)萬(wàn)能材料試驗(yàn)機(jī)等研究該系列樣品的熱穩(wěn)定性和熱機(jī)械性能;DMA形狀記憶性能研究表明SMPU-PS系列樣品均具有熱致形狀記憶性能,且隨著樣品中1,3-PS/MDEA比例增加,形狀記憶性能有所提高,但當(dāng)1,3-PS/MDEA比例過(guò)高時(shí),反而會(huì)使形狀固定率和回復(fù)率有所下降。通過(guò)熒光倒置顯微鏡、酶標(biāo)儀、SEM等研究發(fā)現(xiàn)該系列樣品的生物相容性良好。最后將SMPU-PS系列樣品經(jīng)KH560改性制備SMPU-PS-JL系列樣品,并對(duì)它的結(jié)構(gòu)與性能進(jìn)行系統(tǒng)研究。采用FT-IR對(duì)其結(jié)構(gòu)進(jìn)行分析,通過(guò)DSC,TGA,DMA,POM和AFM對(duì)其熱力學(xué)以及結(jié)晶性能進(jìn)行測(cè)定;通過(guò)DMA、TGA、微機(jī)萬(wàn)能材料試驗(yàn)機(jī)等研究該系列樣品的熱穩(wěn)定性和熱機(jī)械性能。研究發(fā)現(xiàn)該系列樣品相較于SMPU-PS系列樣品來(lái)說(shuō),其熱穩(wěn)定性和熱機(jī)械性能提高;DMA形狀記憶性能研究表明SMPU-PS-JL系列樣品的熱致形狀記憶性能先提高后降低。通過(guò)熒光倒置顯微鏡、酶標(biāo)儀、SEM等研究發(fā)現(xiàn)樣品SMPU-0.2PS-JL、SMPU-0.8PS-JL、SMPU-1PS-JL的生物相容性良好,其中樣品SMPU-0.8PS-JL的細(xì)胞相容性良好且形狀回復(fù)率也達(dá)到87%,是將形狀記憶性能和生物相容性能結(jié)合最好的樣品。
[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.
【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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