【作者】 严永刚；

【导师】 李玉宝；

【作者基本信息】 四川大学 ， 生物医学工程， 2003， 博士

【摘要】 本论文综合聚合物的韧性和磷灰石的活性与硬度，研究了力学性能高、生物活性好的纳米磷灰石/聚合物复合材料。着重研究两类新型复合生物材料的设计、制备及性能评价。一类是纳米羟基磷灰石(HA)与聚酰胺-6(PA6)复合材料，即：另一类是纳米羟基磷灰石与聚苯硫醚-聚芳硫醚共聚物(p-PPS-m-PPSA)生物活性复合材料：其中，Ar为： 本论文首创了以纳米羟基磷灰石为主要无机成分，与聚酰胺-6和聚苯硫醚-聚芳硫醚共聚物(p-PPS-m-PPSA)形成复合材料，首次研究了纳米HA/p-PPS-m-PPSA共聚物复合材料的制备方法，并提出用RF溅射对复合材料表面进行改性的方法，得出以下结论： 1、通过开环聚合在常压下制备纳米HA/PA-6复合材料，HA含量能够达到40％，在40％范围内可以随意调配其含量；开环聚合法合成的HA/PA-6复合材料具有良好的均一性，各部分HA含量基本相同；合成的HA/PA-6复合材料具仃稳定的界面结合，HA基本保持原有晶型状态；HA在复合材料中直径为10～20纳米、长度为60～80纳米左右，在复合材料中保持其原来的结晶形貌，保持了纳米状态，均匀分布在复合材料中;HA/PA一6复合材料具有良好的热稳定性、较好的机械力学性能:纳米HA理A一6复合材料的弯曲强度和弯曲模量比PA一6有大幅度的提高，其断裂为韧性断裂。 2、PA七在SBF中的吸水率随时间延长有增大的趋势，而H刀PA一6复合材料的吸水率较PA一6低;PA一6在模拟体液(SBF)中溶胀、吸附、降解，重量变化可达到1.1%，HA想A.6复合材料的重量减少比PA6稍快，在四周内达到2%以上;在SBF中，Ca、P在PA一6表面缓慢沉积，且Ca/P比为1 .2左右，与HA中的Ca/P比例(l .67)相差较远，XRD曲线上未出现HA的特征衍射峰:HA/RA一6复合材料表面的Ca、P含量在第一周下降较快，Ca、P溶解和沉积在第二周达到平衡，C砰比向HA的理论值逼近，到第四周的时候，Ca/P比达到1 .67，与HA的理论值完全相同;随着H户以RA一6复合材料在SBF中浸泡时间的增加，其表面碳酸取代的HA逐步形成，表明该复合材料具有较好的生物活性。 3、以对二氯苯、2，4一二氛苯甲酸、硫化钠、纳米磷灰石等在N*甲基一毗咯烷酮(NMP)中加压聚合可以制备高分子量卜PPs(聚苯硫醚)、P-PPs一m一PPs、p一PPs一m一PPsA共聚物和川吻~PPs一m一PPsA共聚物复合材料;从红外光谱和X一射线衍射图谱可见，p一PPS、p一PPs一m一PPs以及p一PPs一m-PPsA共聚物树脂的结构基本相近，但具有细微的差别。 4、p一pps、p一即S一m一pps、p一pps一m一ppsA共聚物均为结晶性聚合物，HA在聚合前后晶型保持不变;p一PPS、p一PPS一m一PPS、p一PPS一m一PPSA及复合材料具有良好的热稳定性，复合材料的结晶度和熔点与HA的含量密切相关;HA在复合材料中的尺寸小于100纳米，与自然骨中的磷灰石晶体接近，为复合材料提供了生物活性，由于p一PPs一m一PPSA共聚物在200℃以下没有任何溶剂，复合材料可能作为具有生物活性的且可长期稳定植入的骨修复材料。H刀p一PPS一m一PPsA复合材料基本保持了PPS和HA的结构，二者之间有一定的结合;H刀p一PPS一m一PPSA复合材料中含有一定的亲水基团—狡基(一COOH)，HA中的ca、P、o和p一PPs一m一PPsA共聚物中的梭基具有较强的相互作用和稳定的界面结合;HA和p一PPS一m一 PPSA共聚物在材料中保持了原有的结晶形貌，HA在复合材料中的尺寸在64-75lun之间，具有无机。有机纳米复合材料结构:p一PPs一m一PPsA共聚物和H刀p一PPS一m一PPSA共聚物复合材料在sBF中表现出良好的稳定性，其亲水性大幅度提高;在SBF中复合材料表面形成了HA沉积物，四川大学博士学位论文该沉积物与复合材料中HA具有相近的结晶形貌;ca、P在p一PPS一m一PPsA共聚物和H刀p一PPs一m一PPsA共聚物复合材料表面的沉积是逐步进行的，前三周时Ca/P比的变化两者有所不同，但到四周的时候Ca/P比基本接近，都接近HA的理论Ca/P比(1 .67)。 5、三种聚合物在SBF中的吸水性顺序为:p一PPs一m一PPsA<以一66<PA一6，HA的加入使复合材料的亲水性大幅度提高，H刀p一 PPS一m一PPsA共聚物复合材料的吸水率稳定在10%左右，而HA爪A一6复合材料的吸水率相对于队一6有所下降，H户“PA一66复合材料的吸水率相对于PA一66变化不大;从p一PPS一m一PPSA、队一6和PA一66在SBF中的重量变化看，p一PPS一m一PPSA的重量变化小于0.14%，几乎不变;以一6的重量变化达到1.1%;PA一“的重量变化达到1.27%;这三类聚合物与HA的复合材料在SBF中的稳定性大概顺序为:H刀p一PPS一m一PPSA>队/PA一66>HA/PA一6;无论是p一PPS一m一PPsA共聚物还是HA/p一PPS一m一PPSA共聚物复合材料在SBF中都表现出较好的活性，表面形成了HA沉积物:从Ca、P在聚合物表面的沉积速度和组成看，这几类聚合物的活性顺序大概为:p一PPS一m一PPSA>PA一6>PA一66;从复合材料表面成分和C押比变化过程看，复合材料表面的Ca、P沉积和比例变化与新骨形成的过程相似，这说明H刀p一PPS一m一PPSA复合材料、H户“PA一6复合材料和H刀队一66复合材料均具有良好的生物活性。 6、通过R更多还原

【Abstract】 `Calcium phosphate is a preferred implant material due to its excellent biological properties. Because of its brittleness and fatigue, failure in the body, this kind ceramic is mainly used for unload bearing repair. To avoid its poor fatigue properties in loaded applications, HA/polymer composites were widely studied. In the first part of the dissertation, Nano-apatite/Polyamide-6 (HA/PA6) composite has been obtained by ring-opening co-polymerization method. Nano-HA content in the composite can reach 40wt%. The structure, property and biocompatibility were tested. The nano-HA in composite keeps the original morphological structure and HA particles are uniformly distributed in the PA6 matrix. The phase composition, morphology, dissolution and precipitation in SBF were characterized by XRD, FTIR, EDS and SEM. The composites have good homogeneity, and the diameter of HA in the composite is about 30-50 nanometer. The composite has good physical and mechanical property and good biocompatibility. The in vitro bioactivity of PA-6 and HA/PA-6 were studied in SBF ( simulated body fluid) . The results showed that PA-6 was not bioactive in SBF, Ca-P compound was slowly deposited on the surface of PA-6, but it was not HA. HA/PA-6 composite was chemically active in SBF, and dissolution and deposition of Ca, P ions happened during the culture in SBF. The Ca-P precipitate on the surface of HA/PA-6 composite surface was carbonated-apatite. Its weight lost by about 2% every week. This kind of composite could be one of the best potential bioactive materials for load-bearing bone, substitution or as bioengineering material.In the second part, the copolymer of poly( 1,4-phenylene sulfide)-poly (2,4-phenylene sulfide acid)[p-PPS-m-PPSA] and its nano HA composite [HA/ p-PPS-m-PPSA] has been obtained by polycondensation in 1-methly-2-pyrrolidone(NMP), and nano apatite content in the composite can reach 60wt%. The structure and property of the copolymer and its nano HA composite were studied through IR, XPS, TEM, and AFM. The copolymer has high molecular weight(n =0.467), and excellent thermal property. There is a stable interface formed betweenHA and p-PPS-m-PPSA copolymer in the composite. HA keeps the original morphological structure and crystal behavior in the composite. The composite has good homogeneity and outstanding thermal stability. HA particles are uniformly distributed in the composite. The diameter of HA in the composite is about 40-60 nanometer. The poly (2,4-phenylene sulfide acid) in copolymer can increase affinity to apatite and does not decrease the melting point and thermal stability of copolymer. The p-PPS-m-PPSA and its nano HA composite are very stable in SBF. Ca-P compound was deposited on the surface of copolymer step by step, and the Ca/P ratio of the Ca-P precipitate on the surface of the copolymer was 1.63 in the fourth week after culture in SBF, near to the stoichiometric HA. Ca-P compound was deposited more fast on the surface of HA/ p-PPS-m-PPSA composite than on the copolymer. The Ca-P precipitates both on copolymer and on composite were HA, and carbonated HAduring the incubation in SBF. The p-PPS-m-PPSA copolymer and HA/ p-PPS-m-PPSA composite were stable and bioactive in SBF.In the third part, PA-6, PA-66, p-PPS-m-PPSA, HA/PA-6, HA/PA-66 and HA/ p-PPS-m-PPSA composite were cultured in SBF. The stability of these polymers and composite was shown as following:HA/p-PPS-m-PPSA> p-PPS-m-PPSA> PA-66) HA/PA-66> PA-6>HA/PA-6HA/p-PPS-m-PPSA was the most stable material in the SBF. Its weight almost did not change in the first two weeks during the incubation in the SBF, and increased a little in the third and fourth week after carbonated the HA deposited on the surface of the composite. The HA/PA-6 composite was the most unstable material in the SBF. Its weight lost about 2% every week during the incubation in SBF. The Ca-P precipitate in SBF was much more slowly on the surface of the polymers than on the surface of composites. And there was almost no precipitate on the PA-66 surface. The order更多还原