聚(L-丙交酯)/聚(DL-丙交酯)的结晶性能及相溶性

用共溶液沉淀法制备了聚 (L 丙交酯 ) 聚 (DL 丙交酯 )共混物 (PLLA PDLLA) ,然后用成纤模压法压制成3 2mm的棒材 .用差示扫描量热法研究了共混物的结晶性能和相溶性 .结果表明 ,PLLA组分在共溶液沉淀过程中可生成结晶 ,共混物中PDLLA含量直到 30 %时 ,PLLA组分的结晶熔融温度和结晶度与纯PLLA相同 ,但PDLLA含量为 5 0 %时 ,PLLA组分的结晶熔融温度和结晶度明显下降 .由于加工成型条件的不一致性 ,共混物棒材中的PLLA组分的结晶熔融温度和结晶度呈较大的分散性 .共混物从熔体降温 ,在其后的升温DSC扫描中出现分别相应于PDLLA和PLLA的玻璃化转变 ,表明PDLLA与未结晶的PLLA形成的非晶相是不相溶的     

聚左旋乳酸/聚氧化乙烯共混物的拉伸行为及结构转变

采用熔融共混方法制备了聚左旋乳酸(PLLA)和超高分子量聚氧化乙烯(PEO)共混物, 通过差示扫描量热(DSC)、 扫描电子显微镜(SEM)和二维广角X射线散射(2D-WAXS)等方法系统研究了PEO的加入对不同温度下PLLA拉伸行为及拉伸过程中微观结构变化的影响. 结果表明, PLLA/PEO共混物为非均相体系, PEO粒子均匀分布在PLLA中形成两相结构. PEO的加入能够显著降低PLLA的玻璃化转变温度(T_g), 在25～60 ℃范围内显著提高PLLA的拉伸性能. 在60 ℃拉伸时, PEO的加入提高了PLLA在拉伸过程中的结晶和形变能力. 在80 ℃拉伸时, 共混物的拉伸断裂伸长率下降, 但共混物的结晶速度仍高于纯PLLA样品.     

取向模压成型技术增强聚乳酸力学性能的研究

以取向模压成型制备了聚l -乳酸、聚dl -乳酸骨折内固定棒 (Φ =3 .2mm)。与通常的熔融成型相比 ,新的成型技术可以成倍地提高内固定材料的初始力学强度 ,其中聚l -乳酸棒的弯曲强度达 2 63±1 1MPa,聚 dl-乳酸棒的弯曲强度达 1 72± 4MPa。SEM观察显示取向后聚 l-乳酸棒的纵向纤化程度高 ,冲击断面有大量纤维尾端 ;取向后聚dl -乳酸棒弯曲断裂时呈韧性断裂。而熔融模压成型的聚l -乳酸及聚dl -乳酸棒弯曲断裂时呈脆性断裂特征。     

HDI作为扩链剂合成含PLLA和PBS链段的聚酯氨酯

以数均分子量为6350g/mol端羟基聚L-乳酸(PLLA-OH)与10500g/mol端羟基聚丁二酸丁二酯(PBS-OH)为预聚物,六亚甲基二异氰酸酯(HDI)为扩链剂,通过熔融反应制备了分子量高达30×104g/mol的可完全生物降解聚酯氨酯(PEU).研究了异氰酸根(NCO)与羟基比例对扩链反应的影响.结果表明,当[NCO]/[OH]=1∶1时,扩链效果最好,PEU分子量最大;PEU分子量随着预聚物中PBS含量增大而提高.通过核磁共振谱(1H-NMR)确定了PEU的结构与组成,并对聚酯氨酯进行了凝胶渗透色谱(GPC)、差示扫描量热(DSC)、热重分析(TGA)以及拉伸性能测试.DSC结果显示,扩链后PEU的结晶主要由PBS链段产生,而PLLA链段几乎不结晶;TGA结果表明,PEU的热降解分两步进行,第一步为PEU中PLLA链段的热降解,第二段为其中PBS链段的降解;拉伸测试结果表明,PBS与PLLA的共聚能够制备拉伸强度与断裂伸长率优异的聚合物材料.     

非等温结晶对PLLA的热行为和形貌的影响

将聚L-乳酸(PLLA)熔化非等温熔融结晶, 采用DSC、POM、SEM等技术研究了降温速率对PLLA的热行为和形貌的影响. PLLA在低降温速率(2 ℃·min-1)下的结晶在118 ℃伴随有结晶机制的转变. 玻璃化温度和结晶度随着降温速率的降低而增大. 随着降温速率的降低, 球晶尺寸增大, 当降温速率为10 ℃·min-1 时, PLLA 为无定型材料. 采用模压成型的方法并控制降温速率制备了具有球晶结构的条状PLLA 生物材料, 与高降温速率下制备的PLLA相比,低降温速率下获得的具有球晶结构的PLLA材料的断面更光滑和致密, 但脆性增强.     

低左旋度聚丙交酯的分子结构及体外降解行为研究

以辛酸亚锡为催化剂,135℃下低左旋度的l-丙交酯([a]_(Na)~(25)=—231°)开环聚合制备了低左旋度聚(l-丙交酯)[l-PLLA]([a]_(CHCl_3)~(25)=-119.7°),并用同核去偶~1H-NMR谱表征其分子链结构。用成纤模压法制备了该聚合物的棒材(φ=3.2mm)试样,研究了其在37℃的模拟体液(SBF)中的降解行为。结果表明,l-PLLA具有良好的力学性能,其初始弯曲强度(σ_b)、剪切强度(σ_s)以及弯曲模量(E_b)虽比聚(l-丙交酯)(PLLA)低,但均比聚(dl-丙交酯)(PDLLA)高得多,且材料表现出很好的韧性,呈非晶态,其分子量下降速率和失重速率都介于PLLA和PDLLA之间,可望是一种良好的骨折内固定材料。     

乙交酯、L-丙交酯均聚物及其共聚物的制备和性能研究

以辛酸亚锡为催化剂、1,4-丁二醇为引发剂,在高温、高真空条件下本体熔融开环聚合制备了聚乙交酯(PGA)、聚L-丙交酯(PLLA)及其不同比例的共聚物(PLGA).通过红外光谱(IR)、核磁共振(1H-NMR)对聚合物的结构进行了表征,用乌氏黏度计、凝胶渗透色谱仪(GPC)、示差扫描量热仪(DSC)、热重分析仪(TGA)、X射线粉末衍射仪(XRD)、流变仪等对聚合物的特性黏数、分子量与分子量分布、热性能、结晶性、流变性能进行了研究.结果表明PLGA和PLLA具有较高的分子量和窄的分子量分布;PGA、PLLA、PLGA均具有较高的热稳定性,随着PLGA中PGA单元的增加,分解温度逐渐升高.直接熔融合成的PGA在各有机溶剂中溶解性都不理想,用二甲基亚砜(DMSO)重结晶后的PGA在六氟异丙醇(HFIP)中的溶解度增大;PGA、PLLA具有较高的结晶度,而PLGA以非晶态存在,DMSO重结晶后的PGA的结晶度降低.PGA、PLLA、PLGA的熔体均是剪切变稀流体,但PGA、PLLA具有较高的储能模量,PLGA具有较高的损耗模量.相对于PGA和PLLA,无规共聚的PLGA易纯化,并且柔性较好,更易加工,因此PLGA是更适宜的生物可降解材料.     

超高分子量聚乙烯温等静压成型工艺及性能

利用全软模温等静压成型方法成功制备出直径达120mm,高105mm的超高分子量聚乙烯柱状制件,研究了成型压力对成型性能的影响。利用扫描电镜、X射线衍射及示差扫描量热法研究了不同成型压力下结晶度的差异。结果表明:提高压力更有利于结晶,160 MPa下成型样品的熔点为143.0℃,片晶厚度为123nm,结晶度达到69.39%,抗拉强度达到36.8 MPa,缺口冲击强度达到152.3kJ/m~2,断裂伸长率达到634%。     

可降解聚氨酯丙烯酸酯生物材料的制备及其表征

以端羟基聚丙交酯(PLLA)为软段,六亚甲基二异氰酸酯(HDI)和甲基丙烯酸羟乙酯(HEMA)为硬段聚合得到端基为双键的低聚物,再在UV照射下固化得到可生物降解的聚氨酯丙烯酸酯(PUA)生物组织工程材料.PLLA由1,4-丁二醇引发L-丙交酯(L-LA)开环得到.PLLA和低聚物的组成结构用NMR和GPC进行了表征.对固化聚合物PUA的热性能(DSC和TGA)、力学性能(DMA和拉伸)和亲水性(接触角和溶胀)的研究表明增加PLLA软段会增加材料的Tg,但降低材料的亲水性和交联度.PLLA500-HDI的拉伸强度为6.7 MPa,可以满足生物材料的力学性能要求.通过体外降解实验,发现增加PUA材料的软段,降解速率下降.降解16周后,PLLA500-HDI降解最快,失重15.8%,而PLLA2000-HDI的降解速率最慢,失重5.5%,可能与其微相分离的结构有关.红外(ATR)分析表明降解的PUA膜中N—H的伸缩吸收峰(3364 cm-1)变宽和C O吸收峰变尖锐,说明主链中酯键和氨基甲酸酯键都发生了水解.热失重(TGA)曲线上PLLA500-HDI和PLLA1000-HDI降解后的PUA材料热稳定性下降,而PLLA2000-HDI变化不大.此外,在SEM图中发现降解的PLLA500-HDI膜表面出现裂纹和孔洞,PLLA2000-HDI材料表面也形成相分离结构.细胞实验说明材料支持细胞的黏附,有较好的生物相容性,具有应用于组织工程的潜力.     

二氧化钛纳米棒/二氧化硅核壳粒子的制备及在聚乳酸中的应用

以三氯化钛为钛源合成了纯金红石型Ti O2纳米棒,用正硅酸乙酯对纳米Ti O2表面进行修饰,得到Si O2为壳,Ti O2为核的纳米粒子(Si O2@Ti O2),Ti O2纳米棒的平均长度约为50 nm,平均直径约为8 nm,Si O2包覆层的厚度约为4 nm,Si O2@Ti O2的最大吸收波长较Ti O2的最大吸收波长存在微弱蓝移.采用熔融共混法制备聚左旋乳酸(PLLA)/(Si O2@Ti O2)纳米复合材料.采用透射电子显微镜(TEM)、热失重分析(TGA)、差示扫描量热分析(DSC)、紫外-可见吸收光谱(UV-Vis)和二维广角X射线散射(2D-WAXS)等研究了Si O2@Ti O2的加入对PLLA耐热性能、结晶性能、紫外线屏蔽性能及拉伸性能的影响.结果表明,Si O2@Ti O2在PLLA基体中分散较好,Si O2@Ti O2提高了PLLA的热分解温度,具有异相成核的作用.PLLA/(Si O2@Ti O2)纳米复合材料薄膜在保持较高可见光透过率的同时具有优异的紫外线屏蔽性能.Si O2@Ti O2的加入使PLLA在较高温度下拉伸时能够获得更高的结晶度和取向度.     

Hydrostatic Extrusion of Poly(L-Lactide)

Poly-L-Lactide(PLLA) has been used as a bone fracture fixation material for several years. However, its mechanical properties are still not satisfied. To improve its mechanical properties, we examined the hydrostatic extrusion procedure on the PLLA rods made by Injection Molding process. The extrusion ratio was adjusted to 3, 6, 9, and 12. The molecular weight of the PLLA decreased from 260,000 to 200,000 after injection molding process, but it did not change during the hydrostatic extrusion procedure. The melting point of PLLA hydrostatic extrusion products were increased with the extrusion ratio, but the increment was not obviouse. Extrusion products having low extrusion ratio had α-form crystal in them, extrusion products having high extrusion ratio had both of α and β-form crystall in them. At extrusion temperature of 145°C, PLLA rods showed the best flowing trends in the pressure medium of PEG 400. Extrusion temperature is placed in the range of crystalline transition temperature and melting point of PLLA. At extrusion ratio 9∼12, the extrusion products showed the best mechanical properties. The highest bending strength of the extrusion product was over than 350MPa. It is far stronger than that of the human cortical bone (200MPa). SEM observations showed that the fiber structure began to appear at an extrusion ratio ER=3, and at the extrusion ratio ER=6, the chain axes of PLLA became aligned to the extrusion direction. The structure of extrusion products at the high extrusion ratio showed highly oriented fiber structure composed of micro-fibril. At high extrusion ratio tranformation from α-crystal to β-crystal was also observed.     

Biodegradable ultra high strength poly(L-lactide) rods for bone fixation

The hydrostatic molecular orientation technique was used to explore the highest mechanical improvements achievable for poly-L-lactide (PLLA). The mechanical attributes of these materials designed for bone fracture fixation devices, i.e. bending strength and modulus were measured and compared with those prepared by stretching method. The starting samples were prepared by conventional melt extrusion at 200 °C followed by hydrostatic extrusion at 140 °C using glycerin filled extruder. Uniaxially stretched rods were prepared by drawing in silicon oil at 120 °C. The physical properties of these rods are inadequate as mechanical supports in the dynamic healing process of the bone. Moreover, they underwent a marked strength deterioration when immersed in aqueous buffered solution for 90 days. On the other hand, the hydrostatic extrusion technique produced rods with progressively higher bending strength that showed only a small drop after 90 days hydrolytic degradation. Micrographs suggested a superior molecular orientation and packing, which could be associated with the improved performance. The hydrostatic extrusion technique proved to be a safe and effective approach for strengthening biodegradable polymeric materials for dynamic mechanical support in orthopedic medical devices.     

Biodegradable Polymers for Orthopedic Applications: Synthesis and Processability of Poly (l-Lactide) and Poly (Lactide-co-€-Caprolactone)

Abstract

The synthesis of poly(l-lactide) (PLLA), poly(l-lactide-co-e-caprolactone), and poly(DL-lactide-co-e-caprolactone) by ring-opening bulk polymerization was investigated. Polymerization temperature had a significant effect on the PLLA molecular weight. At 184°C a polymer with a molecular weight of only 10 × 10⁴ resulted. This was lower by a factor of 2 than that obtained at 103 and 145°C. The stannous octoate (SnOct) concentration, with a monomer/SnOct molar ratio in the range of 1,000 to 10,000, was not found to have a significant effect on the PLLA molecular weight. A heterogeneous structure in polymerized PLLA was observed. The intrinsic viscosity of poly(lactide-co-€-caprolactone), obtained at 130°C, monomer/SnOct molar ratio 5,000, and polymerization time of 30 hours, decreased with increasing €-caprolactone content within the first 9 wt% and then leveled off. Die-drawing of PLLA cylinders, for the purpose of increasing the polymer's mechanical strength, was unsuccessful due to the brittleness of the polymer. The drawability of poly(l-lactide), however, was greatly improved by copolymerization with €-caprolactone. With only 3 wt% of €-caprolactone, for example, the tensile strength of die-drawn poly(l-lactide-co-e-caprolactone) was increased by a factor of more than 3. Polymer processing temperature was also investigated. The requirement for low processing temperatures in melt manufacture of controlled release matrix devices containing thermal sensitive drugs was accomplished by three methods: through the use of low molecular weight poly(DL-lactide), adding (DL-lactic) acid oligomer to high molecular weight PDLLA, and copolymerizing DLLA with €-caprolactone. The glass transition temperatures of the modified high molecular weight PDLLA decreased significantly. Melt extrusion below 100°C could be performed.     

含4-苯基二氮杂萘酮结构共聚芳酯的合成及性能

以4-[4-(4羧基苯氧基)苯基]-2-(4-羧基苯基)二氮杂萘-1-酮(DHPZ-DA)、4,4'-二羧基二苯醚(DAPE)和2,2'-二(4-羟基苯基)丙烷(PBA)为原料,采用溶液缩聚法,合成了一系列聚芳酯,其数均分子量在1.2×104～1.7×104之间.通过FTIR和1H-NMR对聚芳酯结构进行了表征.该系列...     

PREPARATION AND PROPERTIES OF HIGH STRENGTH RODS FROM L-AND D,L-LACTIDE COPOLYMER

Starting with the L-and D,L-lactide copolymer (L:DL = 9: 1) [P(L-DL)LA] of M_w = 32.1×10~4, rods were obtainedthrough a two stage process: (1) melt-extrusion at 155℃, and (2) hot-drawing at 90℃ to various drawing ratios. Themolecular weight of P(L-DL)LA fell to 9.3×10~4 as a consequence of the production process. The crystallization andmolecular orientation of P(L-DL)LA developed as a result of the hot-drawing. The mechanical strengths of the rods increasewith the drawing ratio. The maximum for tensile strength, bending strength, bending modulus, and shear strength are329 MPa, 237 MPa, 8.8 GPa, and 157 MPa, respectively.     

Surface‐modified hydroxyapatite linked by L‐lactic acid oligomer in the absence of catalyst

A new surface modification method of hydroxyapatite nanoparticles (n‐HA) by surface grafting reaction of L ‐lactic acid oligomer with carboxyl terminal (LAc oligomer) in the absence of any catalyst was developed. The LAc oligomer with a certain molecular weight was directly synthesized by condensation of L ‐lactic acid. Surface‐modified HA nanoparticles (p‐HA) were attested by Fourier transformation infrared spectroscopy, ³¹P MAS‐NMR, and thermal gravimetric analysis (TGA). The results showed that LAc oligomer could be grafted onto the n‐HA surface by forming a Ca carboxylate bond. The grafting amount of LAc oligomer was about 13.3 wt %. The p‐HA/PLLA composites showed good mechanical properties and uniform microstructure. The tensile strength and modulus of the p‐HA/PLLA composite containing 15 wt % of p‐HA were 68.7 MPa and 2.1 GPa, respectively, while those of the n‐HA/PLLA composites were 43 MPa and 1.6 GPa, respectively. The p‐HA/PLLA composites had better thermal stability than n‐HA/PLLA composites and neat PLLA had, as determined by isothermal TGA. The hydrolytic degradation behavior of the composites in phosphate buffered saline (PBS, pH 7.4) was investigated. The p‐HA/PLLA composites lost their mechanical properties more slowly than did n‐HA/PLLA composites in PBS because of their reinforced adhesion between the HA filler and PLLA matrix. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5177–5185, 2005     

聚丙交酯/聚乙二醇多嵌段共聚物的合成及其性能

聚丙交酯 (ＰＬＬＡ)由于具有良好的生物降解性和生物相容性 ,在医学领域已经得到了广泛的临床应用 ,近来又被制备成细胞支架大量应用于组织工程中[1,2 ] ,但由于其疏水性而造成细胞亲和性不好 .聚乙二醇 (ＰＥＧ)具有良好的亲水性 ,良好的生物相容性 ,但是ＰＥＧ是非降解性的 ,只有低分子量的ＰＥＧ可以被吞噬细胞所吞噬或透过肾滤膜而排出体外 ,因此 ,低分子量的ＰＥＧ常被用来与丙交酯 (Ｌ ＬＡ)共聚以改善ＰＬＬＡ支架的亲水性 .聚丙交酯 聚乙二醇共聚物 (ＰＬＥ)的三嵌段及两嵌段共聚物的合成及其性能的研究已被广泛报道[3～ 5] .研究…     

Mechanical properties and structure of the zone‐drawn poly(L‐lactic acid) fibers

The zone‐drawing (ZD) method was applied three times to the melt‐spun poly(L ‐lactic acid) (PLLA) fibers of low molecular weight (M_v = 13,100) at different temperatures under various tensions. The mechanical properties and superstructure of the ZD fibers were investigated. The resulting ZD‐3 fiber had a draw ratio of 10.5, birefringence of 37.31 × 10⁻³, and crystallinity of 37%, while an orientation factor of crystallites remarkably increased to 0.985 by the ZD‐1. The Young's modulus and tensile strength of the ZD‐3 fiber respectively attained 9.1 GPa and 275 MPa, and the dynamic storage modulus was 10.4 GPa at room temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 991–996, 1999     

振动注塑PP的拉伸蠕变研究

分别通过改变机械振动注塑机的频率(5~25 Hz)和压力(10~18 MPa)获得不同条件下成型的PP样条,然后在各种成型条件下的PP样条上分别施加相同的拉伸力(F=125 N),进行24 h拉伸蠕变实验.结果表明,在相同的振动频率(10 Hz)和不同的振动压力下成型的PP试样,其24 h蠕变量随着压力的增大而减小;在相同振动压力(12 MPa)和不同的振动频率下成型的PP试样,其24 h蠕变量随着频率的增大而增大.当振动频率达到f=10 Hz的时候,其24 h拉伸蠕变量的变化趋于平缓.同时,也对不同振动条件下注塑的PP试样进行拉伸实验,冲击实验和动态力学性能测试,讨论了成型条件对性能的影响.     

Resorbable materials of poly(L-lactide)

Poly(L-lactide) PLLA materials with various porosity in the range of 5 to 300 Μm were produced by crystallization of the polymer in presence of low molecular weight additives from solution in good solvents, followed by the diluent extraction. For the concentration of diluent in PLLA in the range of 10 to 50 per cent by weight, the pore size increased with increasing concentration of additive, while the additive was easily extracted from the polymer. For the concentration of additive in PLLA in the range of 60 to 80 per cent by weight, the pore size increased or/and decreased with increasing concentration of the additive, while the latter was hardly extractable from the polymer. Porous, resorbable tubes or rods of various diameter well accepted by living organism were produced by this method. Tracheal prostheses, pins or porous reservoirs made from PLLA or modified porous PLLA could be some of many potential application of these materials.