學校代碼***** 學號************分類號O63 密級
碩士學位論文
納米羥基磷灰石表面改性及其增強PCL復合材料性能研究
學位申請人曾亮
指導教師張雪飛副教授
學院名稱化學學院
學科專業高分子化學與物理
研究方向功能高分子
二0一0年六月
Surface Modification of Hydroxyapatite Nanoparticles and Performance Study of its Reinforced PCL Composites
Candidate Liang Zeng
Supervisor Xuefei Zhang
College Chemistry
Program Polymer Chemistry & Physics
Specialization Functional Polymer
Degree Master of Science
University Xiangtan University
Date June, 2010
湘潭大學
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摘要
近年來，骨修復材料的制備逐漸成為化學、醫學以及材料學中的一項熱點。為綜合各種材料性能，研究人員進行了大量的研究，其中提出的復合材料的理念已經被廣泛接受。由于羥基磷灰石（HAP）與聚合物基質之間差的界面相容性，生物復合材料的應用受到了很大的限制。因此，如何提高磷灰石/有機復合材料中無機相與有機相間的界面相容性是骨修復材料領域中一個重要課題。為解決這些問題，可對磷灰石進行接枝改性，使其與有機相間形成過渡相以增強相容性。目前，骨修復材料領域中，接枝改性并不理想，低的接枝量及接枝率不能控制等因素制約了其進一步的應用和發展。
原子轉移自由基聚合（ATRP）是一種很有價值的聚合方式，能很容易的在材料表面接枝上結構明確的均聚物或共聚物來改善材料的表面性能。此外，由于ATRP聚合方法具有可控的鏈增長以及可聚合單體多樣等優點，在制備具有分子量可控、分子量分布窄的聚合物方面得到了廣泛應用。
本文中，我們設計了一種結合了原子轉移自由基聚合和開環聚合的羥基磷灰石納米粒子表面改性方法。該方法利用ATRP方法將一定數量的官能團引入HAP 納米粒子表面，并能通過調節引發劑和單體投料比對接枝量進行控制。論文對HAP以及接枝改性的HAP納米粒子進行了研究。具體內容摘要如下：
1、采用化學沉淀法合成HAP納米粒子，并利用α-溴代異丁酰溴與其表面羥基反應，得到用于ATRP聚合的引發劑（HAP-Br）。采用了傅里葉變換紅外光譜儀（FT-IR）、熱失重分析（TGA）、x射線衍射（XRD）及透射電鏡（TEM）對HAP及HAP-Br進行了表征。
2、利用HAP-Br引發甲基丙烯酸羥乙酯（HEMA）的ATRP聚合，得到羥基化的HAP納米粒子（HAP-PHEMA）。然后利用HAP-PHMEA引發己內酯（CL）的開環聚合，得到具有高接枝率的改性納米羥基磷灰石。所得產品采用了13C固體核磁（13C CP/MAS）、FT-IR、TGA、XRD及TEM進行了表征。
3、利用溶液共混法將改性HAP與聚己內酯（PCL）進行共混制備復合材料。采用了差示掃描量熱儀（DSC）及掃描電鏡（SEM）以及其他測試設備對材料性能進行了表征。
關鍵詞：納米羥基磷灰石；原子轉移自由基聚合；開環聚合；化學接枝改性；復合材料。
Abstract
In recent years, the preparation of bone repairing materials has been gradually become one of the m
ost important tasks in chemical, medical and materials field. In order to integrate the performance of variety materials, great progress has been made and the idea of composites materials has been accepted widely in recently years. Due to the weak interfacial compatibility between hydroxyapatite and polymer matrix, the application of biocomposites also has been limited. To solve this problem, chemic grafting modification strategy has been developed. However, becau of the low grafted amount and uncontrollable grafting efficiency,the application of hydroxyapatite has been limited in more fields.
Atom transfer radical polymerization (ATRP) is a uful polymerization method for constructing well-defined block and graft copolymers on material surface to modify their surface properties. Furthermore, ATRP is widely applied to prepare polymers with predictable molecular weights and narrow molecular weight distribution for its advantage of controlled chain growth and multiplicity of monomers.
In this paper, a novel strategy to modify hydroxyapatite nanoparticles (HAP) surface has been developed by combination of ATRP and ring opening polymerization (ROP). In this method, definite functional groups were introduced onto the HAP surface and the amount of the functional groups could be controlled by adjusting the initiator/monomer ratio. The preparation and characterization of
HAP and modified HAP were studied. The main contents were as follows:
1．HAP nanoparticles were synthesized via chemical precipitation firstly. Then, 2-bromoisobuturyl bromide (BIBB) was coupled to the surface of HAP nanoparticles directly to obtain ATRP initiator (HAP-Br). FT-IR, TGA, XRD and TEM were ud to investigate the nanoparticles of HAP and HAP-Br.
2．HAP-Br was ud to initiate the ATRP of 2-hydroxyethyl methacrylate (HEMA) to get functionalized HAP (HAP-PHEMA). The ROP of ε-caprolactone (CL) was initiated by HAP-PHEMA to obtain high grafting ratio modified HAP. The products were characterized by 13C CP/MAS, FT-IR, TGA, XRD and TEM.
3．Composite materials of polycaprolactone (PCL) reinforced by modified HAP nanoparticles were prepared via solvent blending. DSC, SEM and other instruments
