Preparation and characterization of poly（D,L-lactide） and its porous biomaterials

1　INTRODUCTIONPolylactides(PLA) have become very impor tant biomedical materials due to the combination oftheir bioresorbable, biocompatible, biodegradableand mechanical properties. They have been widelyused in drug controllable release, surgical suture,orthopedics bone internal fixation and tissue engi neering[1 5]. 2 methods are currently available forPLA synthesis: polycondensation ( condensationpolymerization) of lactic acids(direct method) andring opening polymeriz…     

Synthesis and Characterization of Poly （L-lactide-co-glycolide）

Poly （ l- lactide- co-glycolide ） （ PLGA ） with different compositions was prepared using stannous octaoate as catalyst by bulk ring-opening copolymerization of l-lactide and glycolide. The structure and properties of the PLGA copolymers were cbaracterized by means of attenuated total reflectance-Fourier transform infrared （ATR-FTIR）, ^1H NMR, differential scanning calorimeter （ DSC and X-ray diffraction （XRD） methods, The experimented results indicate that the synthetic conditions and the composition of copolymers have art obvious influence on the structure of PLGA copolymers, The degradation rate of eopolymers increased with the increasing of the glycolide component in the copolymers.     

丙交酯的制备及其开环聚合

以稀土配位化合物Ｌｎ（ＣＦ３ＣＯＯ）３／Ａｌ（ｉ－Ｂｕ）３,（Ｌｎ＝Ｙ,Ｙｂ,Ｔｍ,Ｈｏ等）为催化剂进行了丙交酯的开环聚合。     

Synthesis and Characterization of Poly （L-lactide-co-ε-caprolactone） Copolymers

A series of random and block poly（ L-lactide-co-e-caprolactone ） （ PCLA ） copolymers whh different composition are prepared using stannous octaoate as catalyst.The effects of the amount of initiator on the intrinsic viscosity have been investigated. The structure of the PCLA copolymers is characterized by means of nuclear magnetic resonance（ NMR ）, Fourier transform infrared spectrum （ FTIR ）, differential scanning calorimetry （ DSC ） and X- ray diffraction （ XRD ） methods. It is shown that the synthesis condition and the composition of copolymers obrious influence on the structure of PCLA copolymers. Hydrolytic degradation of the copolymers in a PBS solution of pH 7.4 at 37.0℃ shows that the copolymers of different composhions degrade at different rates.     

Preparation of Hydroxyapatite/Polylactide Biocomposites by Absorption Process in Liquid Phase

The hydroxyapatite/polylactide biocomposites were prepared by absorption process in liquid phase. The method avoided many disadvantages, such as inaterfusion of chemical impurity substances, nonuniformity dispersal of HA in PLA, low molecular weight of PLA . HA particles were uniformly dispersed in PLA matrix, and showed well ndhesion with PLA matrix. The biocomposites have the higher mechanical properties and suitable decomposable capability.     

Biodegradable Polylactide-co-glycolide （PLGA） Thin Films Prepared by Electrospray and Pressurized Spray Deposition

PLGA thin films were prepared onto implantable devices by the electrospray and pressurized spray method. Thin films with structural gradients were obtained by controlling four parameters consisting of solution concentration, applied voltage, air pressure , and deposition time. The surface morphologies of the deposited films were observed using scanning electron microscopy （SEM）. The image analysis revealed the control factors on the preparation of PLGA thin films. The beaded structure is ensily formed with a decrease in polymer concentration while the fibrous structure is easily formed with an increuse in polymer concentration. With the increase in applied voltage, the surface morphologies changed continnously from a small amount of fibrous shape to a large fibrous one： a small amount of.fibrous shape at 10 kV, more fibers with non-uniform diameter at 20 kV, and most fibers with uniform diameter at 30 kV. Low air pressure（0.1 MPa ） corresponded to round particles while high air pressure （0.3 MPa ） corresponded to fiat particles. The change in thickness from 5.34 to 10.1μm was a result of deposition time increasing from 5 to 10 s. From our above work, films of the bead or fiber structures can be obtained by changing electrical parameters to impropvc tbe biocompntibility of the film.     

Biologically Inspired Self-assembling Synthesis of Bone-like Nano-hydroxyapatite/PLGA- （PEG-ASP）n Composite： A New Biomimetic Bone Tissue Engineering Scaffold Material

A new biomimetic bone tissue engineering scaffold material, nano-HAI PLGA-（ PEG-Asp ）n composite, was synthesized by a biologically inspired self-assembling approach. A novel biodegradable PLGA- （ PEG-Asp ）n copolymer with pendant amine functional groups and enhanced hydrophilicity woo synthesized by bulk ring-opening copolymerization by DL-lactide（ DLLA） and glycolide（ GA ） with Aspartic acid （ Asp ）-Polyethylene glycol（PEG） alt-prepolymer. A Three-dimensional, porous scaffold of the PLGA-（ PEG- Asp）n copolymer was fabricated by a solvent casting , particulate leaching process. The scaffold woo then incubated in modified simulated body fluid （naSBF）. Growth of HA nanocrystals on the inner pore surfaces of the porous scaffold is confirmed by calcium ion binding analyses, SEM , mass increooe meoourements and quantification of phosphate content within scaffolds. SEM analysis demonstrated the nucleation and growth of a continuous bonelike, low crystalline carbonated HA nanocrystals on the inner pore surfaces of the PLGA- （ PEG-Asp ）n scaffolds. The amount of calcium binding, total mass and the mass of phosphate on experimental PLGA- （ PEG-Asp ） n scaffolds at different incubation times in mSBF was significantly greater than that of control PLGA scaffolds. This nano-HA/ PLGA-（ PEG- Asp ）n composite stunts some features of natural bone both in main composition and hierarchical microstrueture. The Asp- PEG alt-prepolymer modified PleA copolymer provide a controllable high surface density and distribution of anionic functional groups which would enhance nucleation and growth of bonelike mineral following exposure to mSBF. This biomimetic treatment provides a simple method for surface functionalization and sabsequent mineral nucleation and self-oosembling on bodegradable polymer scaffolds for tissue engineering.     

Ethylene Polymerization by a Novel Dinuclear Heter-oligated Titanium Complex with the Ligand of （Salicylaldiminato） （β-enaminoketonato）

The condensation of acetylacetone （CH3COCH2COCH3） with benzdine （H2N-C6H4-C6H4-NH2） yielded diimine ligand 1 [HOC（Me）C（H）（Me）C=N（p-C6H4）（C6H4-p）N= C（Me）C（H）C（Me）OH）], which was converted into sodium salts. And then the sodium salts reacted with monosalicylaldiminato titanium complex 2{[3,5-di-But′2-（O）C6H2CHN（PH）]TiCl3（THF）} in dried dichloromethane to give a new benzdine-bridged binuclear complex 3{[3,5-di-Bu′-2-（O）C6H2CHN（PH）]2 [OC（Me）C（H）（Me）C=N（p-C6H4）-（C6H4-p）N=C（Me）C（H） C（Me）]Ti2Cl4}. The complex 3 was characterized by ^1HNMR and elemental analysis. In the presence of MAO（methylaluminoxane）, the complex 3 in toluene was effective to catalyze polymerization, affording moderately high catalytic activity 1.93 × 10^5 g PE/（mol.Ti.h）]and high molecular weight polyethylene [5.63× 10^5 g/moll. The high temperature gel permeation chromatography （GPC） curve of polyethylene obtained revealed a single peak, but the molecular weight distribution （MWD = 3.21） is obviously broader than that of the similar mononuclear titanium complex. The melting points of the obtained polyethylene reaches 138 ℃, indicating that the polyethylene is of high crystallinity.     

Surface-modified biphasic calcium phosphate/poly (L-lactide) biocomposite

Biphasic calcium phosphate (BCP) powders were prepared by hydrolyzation process and surface-modified by directly grafted L-lactide (LLA) onto the surface of BCP through a chemical linkage. The grafting ratio of organic groups was 9 wt%. After surface modification, the surface of BCP powders was covered by the lamella-shaped crystal. Poly (L-lactide) was mixed with BCP to form the BCP/PLLA biocomposite. Modified BCP (mBCP) particles could be uniformly dispersed in PLLA matrix. The compressive strength of the mBCP/PLLA composite is 115 MPa, 28% higher than that of unmodified-BCP/PLLA composite. The improved mechanical strength is attributed to the enhanced adhesion between the inorganic BCP filler and the organic PLLA matrix. Funded by the Research Fund for the Doctoral Program of Higher Education of China (No. 20060610024)     

聚醚砜纤维研制

采用国产聚醚砜熔融纺丝，并对牵伸丝的取向，力学性能和机械性能进行评价。结果表明，该聚合物在３５０℃具有良好的熔融可纺性；在３０－１００℃温度范围内，随温度升高，牵伸倍数有所增加；牵伸丝力学性能与取向程度线性相关；聚醚砜牵伸丝在８０℃左右开始发生收缩，在其玻璃化转变温度附近出现明显收缩，尽寸热稳定性不理想。     

可生物降解多嵌段聚乳酸共聚物合成研究

以氧化锌为催化剂,使左旋丙交酯(LLA)与聚乙二醇(PEG600)开环共聚,得到三嵌段(HO PLLA PEG PLLA OH)预聚物;再以甲苯二异氰酸酯TD1 80为扩链剂对其进行扩链,得到多嵌段共聚物.采用核磁共振、红外光谱、凝胶渗透色谱等对目标产物的结构、分子量分布进行了表征;同时用变温红外法研究了与LLA结晶相关谱带的位置,并对其进行了归属.     

Preparation of high viscosity average molecular mass poly-L-lactide

1 INTRODUCTION In recent years, much attention has been focused on biodegradable and biocompatible polymers. Among biodegradable biomaterials, poly-L-lactide(PLLA) is a widely used polymer[1?2]. PLLA is currently used in medicine, including drug delivery systems and hard tissue scaffolds. For hard tissue scaffolds, a certain strength is demanded due to the coordination of strength loss and tissue healing rate to support loading after all degradation of the implant[3]. Many studies on c…     

Preparation ofpoly（amino-quinone） by microwave-assisted solid-state polymerization

Microwave irradiation was employed to assist the synthesis of poly(amino-quinone) (PAQ) from p-benzoquinone and diamines in solid state. The effects of power, time, and pattern (continuously or intermittently) of microwave irradiation on yield and intrinsic viscosity of PAQs were studied. It is shown that the continuous microwave irradiation at a high power leads to rapid increase of yield and a sudden halt in polymerization afterwards, due to the subsequent loss of volatile reactants at a high reaction temperature. Alternatively, the high-power microwave irradiation is applicable to raising the yield if used intermittently. In contrast, the low-power microwave irradiation favours the way of continuous exposure to ensure sufficient heat for polymerization. In both cases of high and low power, the yield and intrinsic viscosity can be further promoted by prolonging the exposure time. It is found that under a preliminarily optimized condition of intermittent irradiation at 490 W with six sequences of 5 min irradiation followed by 5 min interval, the yield and intrinsic viscosity of PAQ from p-benzoquinone and p-phenylene diamine can reach as high as 83% and 41.9 mL/g, respectively.     

PMMA胶体晶体模板法制备SiO2多孔材料

通过PMMA胶体晶体模板法制备了有序的SiO2多孔材料．首先采用两阶段加料的无皂乳液聚合方法,成功地合成了单分散的甲基丙烯酸改性聚甲基丙烯酸甲酯微球,然后将聚合合成的胶乳在一定温度下蒸发一段时间使单分散微球组装成大面积的有序胶体晶体,再以硅溶胶填充胶体晶体,经干燥后煅烧去掉PMMA胶体晶体模板等过程制备较大面积有序的SiO2多孔薄膜．粒径分析、紫外-可见光透过光谱图分析结果表明：所制备的甲基丙烯酸改性聚甲基丙烯酸甲酯微球为单分散且粒径为250nm左右．扫描电镜、热失重、红外光谱等分析结果表明：SiO2多孔材料孔洞规则排列、相互连接、较好的复制了胶体晶体的有序结构,孔径分布在250nm左右．     

聚甲基丙烯酸甲酯／蒙脱土纳米复合材料的制备与表征

以甲基丙烯酸甲酯（MMA）、蒙脱土（MMT）以及乙醇胺为主要原料,采用原位氧化还原聚合的方法制备出一种聚合物／蒙脱土纳米复合材料。采用红外光谱（FT-IR）、粉末X-射线衍射（XRD）、扫描电子显微镜（SEM）、热重（TGA）等分析手段表征所制备的纳米复合材料的结构。通过原位氧化还原聚合方法成功制备了完全剥离型复合材料和部分插层结构型复合材料。结果表明,MMT的加入显著提高了复合材料的热稳^串性能。此外,还推测出纳米复合材料的形成机理。     

两性聚羧酸类高聚物阳离子丙烯酸酯单体DAC的制备及其性能

以丙烯酸甲酯(MA)与2-氯乙醇(CE)为反应原料,通过酯交换反应制备了丙烯酸氯乙醇酯(CA)中间体,再将CA与三甲胺(TMA)水溶液反应,合成了一种用于制备两性聚羧酸类高聚物的阳离子丙烯酸酯单体(丙烯酰氧乙基三甲基氯化铵,DAC).采用FTIR和¹HNMR对DAC结构进行了表征,并考察了n(TMA)/n(CA)、催化剂用量、阻聚剂用量、反应温度和反应时间对CA转化率和DAC质量分数的影响.结果显示:最佳制备工艺条件为n(TMA)/n<     

高分子量及高规整度聚新戊酸乙烯酯的制备

本研究以新戊酸乙烯酯(VPi)为单体,偶氮二异(N-胺乙基)丁脒(ABEA)为引发剂,十二烷基硫酸钠(SDS)为乳化剂,通过低温乳液聚合法合成了高相对分子质量和高立构规整度的聚新戊酸乙烯酯(PVPi).讨论了反应温度、引发剂浓度和乳化剂浓度等因素对聚合物相对分子质量的影响.聚合物PVPi的结构用红外光谱进行了表征,相对分子质量和立构规整度分别用凝胶渗透色谱和核磁共振氢谱进行了表征.所制得的PVPi的平均聚合度为6 300,间同立构规整度为86.5%.     

准单分散阳8离子型聚甲基苯乙烯胶乳粒子的制备

采用偶氮对2－脒基丙烷盐酸盐（V－50）为引发剂通过无乳化剂乳液聚合方法制备尺寸均一的阳离子聚甲基苯乙烯（PMS）胶乳粒子。详细讨论聚合条件,如引发剂浓度、单体浓度、离子强度、搅拌速度对聚合速率、粒子尺寸及分布的影响。最终获得制备单分散无乳化剂阳离子型聚甲基苯乙烯乳粒子的方法。