【摘要】：本文主要研究了通過(guò)聚合接枝改性方法接枝多種親水性單體，改善聚碳酸酯聚氨酯材料(PCU)的表面血液相容性。實(shí)驗(yàn)首先通過(guò)紫外光聚合接枝改性法和表面引發(fā)原子轉(zhuǎn)移自由基聚合(SI-ATRP)方法接枝仿生單體2-甲基丙烯酰氧乙基磷酸膽堿(MPC)，構(gòu)建PCU材料的仿生表面，從而提高材料的血液相容性；同時(shí)比較了兩種聚合接枝方法的特點(diǎn)以及其對(duì)改性效果的影響。然后，利用SI-ATRP方法在設(shè)計(jì)接枝鏈結(jié)構(gòu)方面的優(yōu)勢(shì)，嘗試設(shè)計(jì)聚乙二醇(PEG)和MPC兩種典型親水性單體的共聚改性鏈結(jié)構(gòu)，并通過(guò)PEG鏈段長(zhǎng)度控制共聚改性層的性質(zhì)，從而討論不同共聚物對(duì)材料親水性和血液相容性的影響，分析PEG鏈段變化與改性層性能的關(guān)系。最后，合成了兩性離子單體N,N-二甲基-N-(2-甲基丙烯酰氧乙基)-N-(3-磺丙基)銨(DMAPS)，通過(guò)其取代MPC單體，并與聚乙二醇甲基丙烯酸酯(PEGMA)共聚接枝改性PCU材料。通過(guò)SI-ATRP方法，進(jìn)一步提高了材料表面的接枝密度；通過(guò)構(gòu)建兩種不同共聚結(jié)構(gòu)，討論了不同的改性層結(jié)構(gòu)對(duì)材料表面性能的影響。 采用傅里葉紅外光譜(FT-IR)、X射線光電子能譜(XPS)檢測(cè)方法，表征改性前后樣品的化學(xué)性質(zhì)的變化，從化學(xué)組成角度表征改性過(guò)程對(duì)材料表面性質(zhì)的影響；通過(guò)水接觸角實(shí)驗(yàn)和血小板吸附實(shí)驗(yàn)，表征改性后樣品的親水性以及血液相容性的變化，討論了各改性方法的不同改性效果。此外，采用AFM相圖分析了不同改性層的相位分布，進(jìn)一步探討不同改性鏈結(jié)構(gòu)對(duì)改性層鏈段分布的影響。 實(shí)驗(yàn)結(jié)果表明各種改性方法均有效地改善了PCU材料的親水性和血液相容性，與改性前相比，改性樣品的水接觸角明顯降低。改性樣品進(jìn)行血小板吸附實(shí)驗(yàn)，，通過(guò)掃描電子顯微鏡(SEM)觀察材料表面對(duì)血小板吸附情況，與未改性PCU材料相比，其血小板吸附數(shù)量顯著減少，部分樣品表面幾乎無(wú)血小板吸附，說(shuō)明改性效果十分理想。對(duì)不同改性樣品血小板吸附結(jié)果相比較，得到了許多有意義的結(jié)論，各種改性方法呈現(xiàn)不同的改性特點(diǎn)。
[Abstract]:In this paper, the surface blood compatibility of polycarbonate polyurethane (PCU) was improved by graft modification of many hydrophilic monomers. In this experiment, the biomimetic surface of PCU was constructed by grafting the bionic monomer 2-methacryloxy ethylcholine phosphate (2-methacryloxy ethylcholine (MPC),) with UV-photopolymerization and surface-initiated atom transfer radical polymerization (SI-ATRP), so as to improve the blood compatibility of the PCU materials. At the same time, the characteristics of two kinds of polymerization grafting methods and their influence on the modification effect were compared. Then, using the advantage of SI-ATRP method in the design of graft chain structure, the copolymerized modified chain structure of two typical hydrophilic monomers, polyethylene glycol (PEG) and MPC, was designed, and the properties of the copolymer modified layer were controlled by the length of PEG segment. The effects of different copolymers on the hydrophilicity and blood compatibility of the materials were discussed, and the relationship between the changes of PEG chain segments and the properties of the modified layers was analyzed. Finally, the amphoteric monomer Nn- dimethyl-N- (2-methacryloxy ethyl) -N- (3-sulfopropyl) ammonium (DMAPS), was synthesized by replacing MPC monomer, and the modified PCU material was copolymerized with polyethylene glycol methacrylate (PEGMA). The graft density of the material surface was further increased by SI-ATRP method, and the influence of different modified layer structure on the surface properties of the material was discussed by constructing two different copolymerization structures. Fourier transform infrared (FT-IR), X) photoelectron spectroscopy (XPS) was used to characterize the changes of the chemical properties of the samples before and after the modification, and the influence of the modification process on the surface properties of the materials was characterized from the point of view of chemical composition. The changes of hydrophilicity and blood compatibility of the modified samples were characterized by water contact angle test and platelet adsorption experiment. The different modification effects of each modification method were discussed. In addition, the phase distribution of different modified layer was analyzed by AFM phase diagram, and the influence of different modified chain structure on the segment distribution of modified layer was discussed. The experimental results showed that the hydrophilicity and blood compatibility of PCU were improved by various modification methods, and the water contact angle of the modified samples was obviously lower than that before modification. The platelet adsorption on the surface of the modified sample was observed by scanning electron microscope (SEM). Compared with the unmodified PCU, the amount of platelet adsorbed on the surface of the modified sample was significantly reduced, and almost no platelet adsorption was found on the surface of some samples. It shows that the modification effect is very ideal. Compared with the results of platelet adsorption of different modified samples, many meaningful conclusions were obtained, and various modification methods showed different modification characteristics.
【學(xué)位授予單位】：天津大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2012
【分類(lèi)號(hào)】：R318.08

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本文編號(hào)：2290578