纳米羟基磷灰石的表面改性及其复合材料的制备

发布时间：2018-09-02 08:37

【摘要】：羟基磷灰石(HA), Ca10(PO4)6(OH)2,哺乳动物体内骨骼、牙齿等硬组织的主要无机成分,有良好的骨传导性和骨诱导性。聚乳酸(PLLA),在为数众多的聚合物中被证明为最具研究热点的可降解聚多酯,具有良好的生物可降解性、生物相容性和机械性能,通过生物体可被降解为体内三羧酸循环产物。本文主要研究两种HA的表面改性方法和制备了羟基磷灰石/聚乳酸复合材料,这种材料兼具了二者的优点,既具有生物降解性又具有骨传导性,可应用于骨组织工程支架材料中。 1.聚L-苯丙氨酸(PPha)对羟基磷灰石表面改性。首先,我们通过HA和γ-氨丙基三乙氧基硅烷反应得到表面氨基化的羟基磷灰石(HAAPS)。其次,HAAPS引发L-苯丙氨酸的N-羰基环内酸酐开环聚合得到表面接枝聚L-苯丙氨酸的羟基磷灰石。合成结果通过FTIR, TGA, XRD表征。通过控制不同的反应时间和比例,HA表面的聚L-苯丙氨酸(PPha-g-HA)接枝率为20.26%-38.92%。XRD分析证实经过表面改性的HA并没很好的有改变HA的专属性能。MTT显示PPha-g-HA具有很好的生物相容性,在骨组织工程具有很好的应用前景。 2.聚(Nε-苄氧羰基-L-赖氨酸)(PLys(z))对羟基磷灰石的表面改性。将制得的HAAPS引发Nε-苄氧羰基-L-赖氨酸的N-羰基环内酸酐(Lys(z)-NCA)开环聚合得到表面接枝聚(Nε-苄氧羰基赖氨酸)的HA (Poly(N-ε-Z-L-Lysine)-g-HA)(PLys(z)-g-HA)。合成过程通过FTIR, TGA, XRD检测,相较于HA和HAAPS,红外图中表面接枝聚Nε-苄氧羰基赖氨酸羟基磷灰石PLys(z)-g-HA在1649cm-1和1709cm-1多出了两个吸收峰,分别为酰胺Ⅰ带的羰基振动峰和酯基的羰基振动峰,从一方面证明了聚(Nε-苄氧羰基-L-赖氨酸)接枝在了HA表面。同时,从TGA的数据分析中可以看到通过控制不同的反应时间和比例,PLys(z)-g-HA接枝率为5.9%至28.99%进一步论证了我们的结论。从XRD和MTT中可以得出(PLys(z)-g-HA)没有改性HA的专属性能和无毒性,甚至在低浓度的情况下可以促进细胞的增殖。 3.PLys(z)-g-HA和聚L-乳酸(PLLA)复合材料的制备。采用相分离的方法制备了不同PLys(z)-g-HA浓度的复合材料。DSC用来表征PLys(z)-g-HA对PLLA结晶性能的影响。从PLLA和PLys(z)-g-HA/PLLA复合材料的热分析表明,PLys(z)-g-HA可以提高PLLA的热学稳定性能；改性的PLys(z)-g-HA在复合材料中起到成核剂的作用,能够加快PLLA的结晶速度。
[Abstract]:Hydroxyapatite (HA), Ca10 (PO4) 6 (OH) 2 is the main inorganic component of hard tissues such as bone and teeth in mammals. It has good bone conductivity and bone induction. Polylactic acid (PLLA),) has been proved to be the most popular biodegradable polyester among many polymers. It has good biodegradability, biocompatibility and mechanical properties. It can be degraded into tricarboxylic acid cycle product by organism. In this paper, the surface modification methods of two kinds of HA and the preparation of hydroxyapatite / polylactic acid composite were studied. This material has the advantages of both biodegradability and bone conductivity. It can be used in bone tissue engineering scaffold material. 1. Surface modification of hydroxyapatite by poly (L-phenylalanine) (PPha). First of all, we obtained the surface amino hydroxyapatite (HAAPS). By the reaction of HA and 纬 -aminopropyl triethoxy silane. Secondly, HAAPS initiated ring-opening polymerization of L-phenylalanine with N-carbonyl anhydride to obtain surface grafted L-phenylalanine hydroxyapatite. The synthesis results were characterized by FTIR, TGA, XRD. The 20.26%-38.92%.XRD analysis of poly (L-phenylalanine) (PPha-g-HA) grafted on HA with different reaction time and ratio showed that the modified HA did not change the specific properties of HA. The results showed that PPha-g-HA had good biocompatibility. It has a good application prospect in bone tissue engineering. 2. Surface Modification of hydroxyapatite by Poly (N 蔚-benzoxycarbonyl-L-lysine) (PLys (z). The HAAPS initiated ring opening polymerization of N 蔚 -benzyloxycarbonyl-L-lysine (N-carbonyl anhydride (Lys (z) -NCA) to obtain HA (Poly (N- 蔚 -Z-L-Lysine) -g-HA) (PLys (z) -g-HA on the surface of N 蔚 -benzyloxycarbonyl lysine. Compared with the surface grafted N 蔚 benzoxy carbonyl lysine hydroxyapatite PLys (z) g-HA in HA and HAAPS, infrared images, there are two absorption peaks in 1649cm-1 and 1709cm-1, which are the carbonyl vibrational peaks of amide I band and the carbonyl vibrational peak of ester group, respectively. On one hand, it is proved that poly (N 蔚 -benzyloxycarbonyl-L-lysine) grafted on the surface of HA. At the same time, from the data analysis of TGA, it can be seen that our conclusion is further demonstrated by controlling the different reaction time and proportion of PLys (z) -g-HA grafting rate ranging from 5.9% to 28.99%. From XRD and MTT, it can be concluded that (PLys (z) -g-HA has no specific property and nontoxicity of modified HA, and can even promote cell proliferation at low concentration. The preparation of 3.PLys (z) -g-HA and Poly (L-lactic acid) (PLLA) composites. The composites with different PLys (z) concentration were prepared by phase separation method. The effect of PLys (z) on the crystallization properties of PLLA was investigated. The thermal analysis of PLLA and PLys (z) -g-HA / PLLA composites shows that PLLA (z) -g-HA can improve the thermal stability of PLLA, and the modified PLys (z) -g-HA acts as a nucleating agent in the composites, which can accelerate the crystallization rate of PLLA.
【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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