通过聚合接枝改性方法改善PCU材料血液相容性的研究
发布时间：2018-10-24 06:24
【摘要】：本文主要研究了通过聚合接枝改性方法接枝多种亲水性单体，改善聚碳酸酯聚氨酯材料(PCU)的表面血液相容性。实验首先通过紫外光聚合接枝改性法和表面引发原子转移自由基聚合(SI-ATRP)方法接枝仿生单体2-甲基丙烯酰氧乙基磷酸胆碱(MPC)，构建PCU材料的仿生表面，从而提高材料的血液相容性；同时比较了两种聚合接枝方法的特点以及其对改性效果的影响。然后，利用SI-ATRP方法在设计接枝链结构方面的优势，尝试设计聚乙二醇(PEG)和MPC两种典型亲水性单体的共聚改性链结构，并通过PEG链段长度控制共聚改性层的性质，从而讨论不同共聚物对材料亲水性和血液相容性的影响，分析PEG链段变化与改性层性能的关系。最后，合成了两性离子单体N,N-二甲基-N-(2-甲基丙烯酰氧乙基)-N-(3-磺丙基)铵(DMAPS)，通过其取代MPC单体，并与聚乙二醇甲基丙烯酸酯(PEGMA)共聚接枝改性PCU材料。通过SI-ATRP方法，进一步提高了材料表面的接枝密度；通过构建两种不同共聚结构，讨论了不同的改性层结构对材料表面性能的影响。 采用傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)检测方法，表征改性前后样品的化学性质的变化，从化学组成角度表征改性过程对材料表面性质的影响；通过水接触角实验和血小板吸附实验，表征改性后样品的亲水性以及血液相容性的变化，讨论了各改性方法的不同改性效果。此外，采用AFM相图分析了不同改性层的相位分布，进一步探讨不同改性链结构对改性层链段分布的影响。 实验结果表明各种改性方法均有效地改善了PCU材料的亲水性和血液相容性，与改性前相比，改性样品的水接触角明显降低。改性样品进行血小板吸附实验，，通过扫描电子显微镜(SEM)观察材料表面对血小板吸附情况，与未改性PCU材料相比，其血小板吸附数量显著减少，部分样品表面几乎无血小板吸附，说明改性效果十分理想。对不同改性样品血小板吸附结果相比较，得到了许多有意义的结论，各种改性方法呈现不同的改性特点。
[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.
【学位授予单位】：天津大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：R318.08
[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.
【学位授予单位】：天津大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：R318.08
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