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表面改性纳米羟基磷灰石及与PLLA纳米复合纤维的制备与表征

发布时间:2018-11-23 21:05
【摘要】:随着化学、材料科学、医学和生物学的迅速发展,使骨科修复材料也随之产生了巨大变革,从金属合金材料、生物惰性陶瓷材料发展到当今的生物活性材料,现在以生物活性材料为基底构建骨组织工程支架材料,然后经过组织培养发育成人体骨组织,最终实现自体组织对植入体的完全替代,将极大地减轻病人痛苦,降低医疗成本以及减少术后并发症。羟基磷灰石是一种近年来研究最为深入的生物活性材料,它是哺乳动物骨骼和牙齿的主要无机物组分,具有骨诱导性和骨传导性。但是羟基磷灰石的脆性大、韧性差,限制了其在承重部位骨的修复的应用。通过与聚合物复合,制备羟基磷灰石/聚合物复合材料,能够有效地结合羟基磷灰石的骨传导性能和聚合物的韧性等优点,但是羟基磷灰石与聚合物基体之间的界面相容性比较差,无机粒子在聚合物基体中易团聚限制了其复合材料力学性能的提高。本论文提出了对羟基磷灰石的表面进行改性来提高羟基磷灰石在聚合物基体中的分散作用,增强有机相与无机相之间的界面作用力,此外,还研究了改性羟基磷灰石与聚乳酸(PLLA)复合制备了复合纳米纤维材料,对复合纳米纤维的力学性能、可浸湿性、形貌进行了初步的研究: 第2章,利用在制备羟基磷灰石的过程中加入丙炔酸,获得表面含有活性炔基的羟基磷灰石(AHA),然后再与叠氮基改性的壳聚糖(CS-N3)发生click反应,从而获得了表面接枝壳聚糖的羟基磷灰石(HA-CS)。通过红外光谱,X射线光电子能谱对反应产物进行了鉴定。热重分析表明,壳聚糖的接枝量为8.9%。广角X射线衍射(XRD)结果表明,这种改性方法只在纳米粒子表面进行,没有破坏纳米粒子的晶体结构。改性后的羟基磷灰石的亲水性能得到了提高,能够在水中均匀分散,其生物相容性明显优于纳米羟基磷灰石。 第3章,利用γ-氨基丙基三乙氧基硅烷对纳米羟基磷灰石进行表面处理,获得表面具有活性氨基的纳米羟基磷灰石(HA-NH2),再与2-溴异丁酰溴反应得到表面含有ATRP引发剂的改性纳米羟基磷灰石(HA-Br),再引发糖烯单体2-(四乙酰基-p-D-吡喃葡萄糖)甲基丙烯酸乙酯聚合,从而在纳米羟基磷灰石的表面接枝了含糖聚合物的改性的纳米羟基磷灰石。利用静电纺丝法制备了含糖聚合物改性的羟基磷灰石/(PLLA)复合材料。通过红外光谱、核磁共振氢谱、热失重、XRD、SEM等分析手段对产物进行了表征。
[Abstract]:With the rapid development of chemistry, material science, medicine and biology, the orthopaedic repair materials have been transformed, from metal alloy materials, bio-inert ceramic materials to bioactive materials. Now using bioactive material as the substrate to construct bone tissue engineering scaffold material, and then develop into human bone tissue through tissue culture, and finally realize the complete replacement of autogenous tissue to implants, which will greatly alleviate the suffering of patients. Reduce medical costs and postoperative complications. Hydroxyapatite is a bioactive material which has been studied in recent years. Hydroxyapatite is the main inorganic component of mammalian bone and teeth. It has bone inductivity and bone conductivity. However, hydroxyapatite has a large brittleness and poor toughness, which limits the application of hydroxyapatite in bone repair. Hydroxyapatite / polymer composites were prepared by blending with polymers, which could effectively combine the bone conductivity of hydroxyapatite and the toughness of polymers. However, the interfacial compatibility between hydroxyapatite and polymer matrix is poor, and the easy agglomeration of inorganic particles in the polymer matrix limits the improvement of the mechanical properties of the composites. In this paper, the surface modification of hydroxyapatite is proposed to improve the dispersion of hydroxyapatite in polymer matrix and to enhance the interfacial force between organic phase and inorganic phase. The modified hydroxyapatite and poly (lactic acid) (PLLA) composite nanofibers were prepared. The mechanical properties, wettability and morphology of the composite nanofibers were studied. Hydroxyapatite (AHA), was obtained by adding propionic acid in the preparation of hydroxyapatite and then reacted with azido modified chitosan (CS-N3) by click. The surface grafted chitosan hydroxyapatite (HA-CS) was obtained. The reaction products were identified by IR and X-ray photoelectron spectroscopy. Thermogravimetric analysis showed that the graft amount of chitosan was 8.9. The results of wide-angle X-ray diffraction (XRD) show that the modified method only takes place on the surface of nanoparticles and does not destroy the crystal structure of nanoparticles. The hydrophilicity of the modified hydroxyapatite was improved, and the hydrophilic property of the modified hydroxyapatite was improved, and the biocompatibility of the modified hydroxyapatite was obviously better than that of nano-hydroxyapatite. In chapter 3, nano-hydroxyapatite (HA-NH2) with active amino group was obtained by surface treatment of nano-hydroxyapatite with 纬 -aminopropyl triethoxy silane. The modified nano-hydroxyapatite (HA-Br) containing ATRP initiator was obtained by reaction with 2-bromoisobutylol bromide, and then the glycosene monomer 2- (tetraacetyl-p-D-glucopyranose) ethyl methacrylate was polymerized. As a result, the surface of nano-hydroxyapatite was grafted onto sucrose polymer modified nano-hydroxyapatite. Hydroxyapatite / (PLLA) composites modified by sucrose polymer were prepared by electrostatic spinning. The products were characterized by IR, NMR, TG and XRD,SEM.
【学位授予单位】:南昌大学
【学位级别】:硕士
【学位授予年份】:2012
【分类号】:R318.08

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1 刘永磊;李鸿;吕国玉;南景天;罗小满;严永刚;;n-HA/多元氨基酸共聚物复合材料的制备和界面研究[J];功能材料;2010年04期



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