端羧基聚乳酸的扩链、改性及其性能

以丙交酯为原料、辛酸亚锡为催化剂、丁二酸酐为改性剂,采用梯度升温法,在150℃、0.098MPa条件下采用直接熔融缩聚法合成端羧基聚乳酸共聚物P(LA/SA),接着用2,2-(1,3-亚苯基)-二 唑啉(1,3-PBO)对其进行扩链,按n(丙交酯)/n(1,3-PBO)= 1/2.4加入1,3-PBO,反应1h制得聚酰胺酯(PEA),最后将高岭土与PEA在150℃、减压条件下熔融复合改性。采用GPC、FTIR、¹H NMR、DSC、SEM等手段对聚合物的结构进行表征和性能测试,结果表明,与P(LA/SA) 相比,扩链产物PEA相对分子质量大幅度提高,重均相对分子质量高达24万,玻璃化转变温度T_g高于PLA和P(LA/SA),改性后复合材料的热稳定性能提高,结晶度降低。     

Ocular Permeability of Pirenzepine Hydrochloride Enhanced by Methoxy poly(ethylene glycol)–poly(D,L-lactide) Block Copolymer

Methoxy poly(ethylene glycol)–poly(D,L-lactide) block copolymer was tested as an ocular permeation enhancer for pirenzepine hydrochloride. The block copolymers with the methoxy poly(ethylene glycol) to poly(D,L-lactide) weight ratio of 80/20, 50/50, 40/60 were synthesized by a ring-opening polymerization procedure. In vitro transcorneal experiments demonstrated that the block copolymer 80/20 significantly enhanced the transcorneal permeation of pirenzepine at the mass ratio of 1/1.4 (pirenzepine hydrochloride/copolymer). Interaction between pirenzepine and copolymer was identified by infrared spectroscopy analysis and dialysis experiments. Ocular pharmacokinetics of pirenzepine/copolymer preparation by in vivo instillation experiments confirmed that block copolymer could enhance the ocular penetration of pirenzepine. Ocular chronic toxicity experiments of block copolymer and pirenzepine/copolymer preparation were studied on rabbits, and no significant toxicity in both groups was observed within 9 months. It could conclude that pirenzepine/copolymer preparation is effective and safe in ocular delivery of pirenzepine.     

乙基纤维素接枝L-丙交酯共聚物的制备、表征及其热性能

在辛酸亚锡催化下,成功制备了乙基纤维素与聚L-乳酸接枝共聚物。产物经GPC、FTIR、1HNMR、13CNMR表征,证实L-丙交酯在乙基纤维素残存的羟基上发生开环聚合,接枝到乙基纤维素骨架上。研究了丙交酯纯度、投料比、催化剂用量、反应时间、反应温度对接枝率的影响,并利用DSC和TG研究了接枝物的热性能。     

超临界流体技术制备5-氟尿嘧啶-吲哚美辛-聚乳酸缓释微球

为了考察药物5-氟尿嘧啶(5-Fu)与吲哚美辛(IDMC)的协同作用, 采用超临界流体强制分散溶液技术(SEDS), 以二氯甲烷/二甲亚砜为共溶剂, 制备了复合5-Fu和IDMC的L-聚乳酸(PLLA)微球。利用单因素法探索了制备复合微球的最佳外部条件, 通过表面形貌、 载药量、 粒径分布、 释放性能的检测和体外细胞实验来表征微球的各项性能。结果表明: 当共溶剂二氯甲烷/二甲亚砜比例为30∶1时, 制备该微球的优化条件为39℃、 14MPa; 微球形貌呈类球形, 粒径分布在0.5~5μm; 复合IDMC后微球具有更优良的缓释效果; 载药微球对A549细胞系增殖有明显的抑制作用, 但与复合IDMC前后微球共培养的2组细胞的相对生长速率(RGR)无显著性差异。      

电纺PLLA/PCL/PEG共混纤维膜的结构及性能

采用静电纺丝技术制备了聚乳酸（PLLA）/聚己内酯（PCL）/聚乙二醇（PEG）共混纤维膜,考察了溶剂体积比、共混物共混质量比、溶液浓度对电纺纤维形貌的影响,研究了共混纤维膜的热稳定性、结晶性、力学性能及亲水性。结果表明加入PEG有效提高了共混纤维膜的热稳定性和结晶性,提高了共混纤维膜的拉伸强度、弹性模量和亲水性能。     

壳聚糖与L-丙交酯接枝共聚物的均相和非均相合成

以1-丁基-3-甲基咪唑氯盐([BMIM]Cl)、1-丁基-3-甲基咪唑醋酸盐([BMIM]Ac)为均相介质,以二甲基亚砜为非均相介质,研究了L-丙交酯与壳聚糖接枝共聚物的合成,并考察其接枝反应的反应效率,利用红外光谱(FT-IR)、热重分析(TGA)、差示扫描量热仪(DSC)、X射线衍射分析(XRD)等对接枝共聚物进行了表征。结果表明,均相反应能缩短反应时间,具有更高的反应效率,且在[BMIM]Cl中更高;均相接枝共聚物趋于无定型,但其热稳定性高于非均相接枝共聚物。     

聚乳酸的溶液结晶行为

采用DSC和XRD方法研究从不同浓度对二甲苯溶液中结晶的聚乳酸的结晶行为。结果表明,从稀溶液中得到的聚乳酸具有高的结晶度,高的非等温结晶温度和快的结晶速度。     

Effect of hydrolytic degradation and dehydration on the microstructure of 50:50 poly(glycolide-co-D,L-lactide)

The effect of hydrolytic degradation on the microstructure of unoriented, random 50: 50 poly(glycolic acid-co-D ,L -lactic acid) was examined using simultaneous small and wide angle X-ray scattering (SAXS/WAXS) and differential scanning calorimetry (DSC). Samples were degraded in phosphate-buffered saline solution at 37·5°C and studied wet and after dehydration. There was no evidence of crystalline material within the sample at any stage of degradation or dehydration from either X-ray scattering or thermal analysis. Thus, chain scission does not enable crystallization of the copolymer, and the glycolic acid and lactic acid fragments formed on degradation do not crystallize, even when the samples are dehydrated. Because such fragments are clearly formed (Hakkarainen, M., Albertsson, A. C. & Karlsson, S., Polym. Deg. Stab., 52 (1996) 283), and because they are crystalline in the dry state, it must be assumed either that these species are not present in any quantity in the degrading sample and that they diffuse easily from the bulk into the surrounding medium, or that the bulk polymer prevents them from crystallizing. SAXS gave evidence of small voids within the structure. Unlike dehydrated degraded semi-crystalline samples, there is no evidence for voiding on a macroscopic scale. The number and size of the small voids in the dehydrated samples rises with degradation. The voids close as samples are heated above the glass transition temperature and the amorphous chains gain mobility. The glass transition, although clearly visible in the undegraded samples, becomes less visible by DSC on degradation. After 28 days’ degradation, there is some evidence that the structure begins to close up, perhaps as a result of reduced viscosity arising from the increased fraction of low molecular weight material. © 1998 SCI.     

Ring opening polymerization of D,L-lactide in the presence of zinc metal and zinc lactate

The polymerization of D ,L -lactide in the presence of zinc metal was investigated for low values of the monomer/catalyst ratio in order to allow end-group characterization of the growing chains by high resolution 360MHz ¹H NMR. The results showed that the polymerization was moisture sensitive and that only a fraction of zinc was active. Small quantities of a side-product were detected and identified as zinc lactate. This compound appeared to be an efficient initiator of the ring-opening polymerization in the bulk. Zinc lactate is thus proposed as the actual initiator of the polymerization of 1,4-dioxane-2,5-diones in the presence of zinc metal. A polymerization mechanism based on a cationic process co-catalysed by lactic acid is also proposed, which accounted very satisfactorily for experimental data. Initiation by zinc lactate yielded high molecular weight polymers with a high degree of conversion and rather high polymerization rates. Therefore, zinc lactate appears to be an attractive alternative to the initiations by zinc metal and stannous octoate, the latter being suspected of some toxicity. © 1998 SCI.     

Synthesis and thermal behavior of triblock copolymers from L-lactide and ethylene glycol with long center PEG block

In this study, poly(L -lactide)–poly (ethylene glycol) (PLLA–PEG) ABA triblock copolymers with the PEG mole fraction ranging from 27 to 57% have been synthesized, and their thermal properties were investigated. Differential scanning calorimetric thermograms of copolymers obtained from specimens dissolved in CH₂Cl₂ solution and precipitated with hexane exhibit no crystallization exotherms, but those cast from CHCl₃ solution show some crystallinity. Water absorption depended on the PEG content of copolymers; thus, with a PEG mole fraction of 57, the water absorption was 82%. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1949–1954, 1998