乙交酯/丙交酯共聚物的体内外降解行为及生物相容性研究

通过开环共聚方法合成了具有不同组成的乙交酯和Ｌ－丙交酯的共聚物（ＰＬＧＡ）,进行了聚合物在３７℃、ｐＨ７．４条件下的体外降争行为以及在大鼠体内的降解。通过粘度测定、换重、＾１Ｈ－ＮＭＲ、ＤＳＣ、Ｘ－ｒａｙ衍射等手段详细研究了ＰＬＧＡ共聚物的体内外降解行为,并对降解机理进行了探讨,通过测定组织反应观察研究了聚合物的生物相容性。结果证明：ＰＬＧＡ共聚物是一类具有良好生物相容性的生物可降解性高分子,通过     

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…     

乳酸、羟基乙酸均聚物及共聚物的合成与结构表征

本文以氯乙酸为原料制得了高纯度和高产率的乙交酯（ＧＡ），以乳酸为原料制得了丙交酯（ＬＡ），并以它们为单体制得了聚乙交酯（ＰＧＡ）、聚丙交酯（ＰＬＡ）及乙交酯（ＧＡ）和丙交酯（ＬＡ）不同配比的共聚物（ＰＧＬＡ）．用ＩＲ、ＮＭＲ、ＤＳＣ、ＴＧＡ、ＤＭＡ和Ｘ－射线衍射分析确定了该系列聚合物的结构与性质．用电导法测定了它们的降解速度，并将该系列聚合物埋入动物体内进行体内降解和病理学实验．     

乙交酯与丙交酯共聚反应和竞聚率的测定

乳酸一羟基乙酸共聚物（PLG）是一种很好的生物医用材料，具有良好的生物相容性和生物降解性，对人体无毒害，可用作医用缝合线[1]、药物缓释胶囊[2]、内固定及牙科材料等[3]．Gilding和Reed[4]在乙交酯和丙交酯共聚反应转化率较高（12．9％～16.4％）时，利用二元共聚方?..     

聚琥珀酸丁二酯的辐射交联和它的热变形行为

近年来 ,塑料废弃物污染环境的问题日趋严重 .对于环境的关心 ,已经使越来越多的科研人员对于研究环境友好化合物的发展产生了极大的兴趣 .发达国家先后制订了限制或禁止某些场合使用非降解性塑料 ,因此 ,多种可生物降解性塑料已经发展起来 .目前已经商业化的可生物降解性聚合物主要有脂肪族聚酯、聚醚、聚乙烯醇和聚多糖 .其中 ,利用化学合成法开发的可生物降解性聚合物是非常重要的 .脂肪族聚酯 ,例如聚乳酸(ＰＬＡ) .聚乙二酸 (ＰＧＡ)等被广泛地用于药物的载体[1] ,聚 (ε 己内酯 ) (ＰＣＬ)也已经被用作生产生物降解性薄膜 .脂肪族聚酯…     

聚乙二醇改性聚乳酸的研究

将丙交酯（ＤＬ ＬＡ）与聚乙二醇（ＰＥＧ）共聚得到了一系列高分子量的共聚物．用ＩＲ、１Ｈ ＮＭＲ和ＤＭＡ对它的结构和粘弹性进行了表征，并测定了其力学性能，同时对材料在加工过程中特征粘度的变化也进行了研究．结果表明，ＰＥＧ与ＬＡ的共聚物是一种三嵌段结构ＨＯ ＰＬＡ ＰＥＧ ＰＬＡ ＯＨ．当ＰＥＧ含量增加时，强度下降，伸长率增加，共聚物逐渐由脆性向韧性转变，因此用ＰＥＧ改性的ＰＬＡ是一种综合性能可调控的生物降解材料     

乳酸,羟基乙酸盐聚物及其聚物的合成与结构表征

本文以氯乙酸为原料制得了高纯度和高产率的忆较酯（ＧＡ），以乳酸为原料制得了丙交酯（ＬＡ），并以它们为单制得了聚乙交酯（ＰＧＡ）、聚丙交酯（ＰＬＡ）及忆较酯（ＧＡ）和丙交酯（ＬＡ）不同配比的共聚物（ＰＧＬＡ）＞有ＩＲ；⑽ＭＲ、ＮＭＲ、ＤＭＡ和Ｘ－射线衍射分析确定了该系列聚合物的结构与性质。用电导法测定了它们的降解速度。并将该系列聚合物埋入动物体内进行体内降解和病理学实验。     

外消旋丙交酯立体选择聚合研究进展

脂肪酸聚酯聚乳酸具有生物降解性和生物相容性,可用于生物医学、药物和环境材料等领域。本文综述了丙交酯聚合研究的最新进展,突出强调了催化活性高、能够控制聚合物立构规整性的丙交酯开环聚合催化剂。由于选用的催化剂和丙交酯单体的不同,聚乳酸有等规、无规、杂同、间规以及立体嵌段等不同的微观结构,不同微观结构的聚乳酸的力学、物理和降解性能不同。本文重点列举了单活性中心的铝、稀土金属和环境友好型铁、锌、镁以及不含金属的有机催化剂在外消旋丙交酯的立体选择开环聚合方面的最新进展,强调低毒性、生物相容性好的催化剂是目前研究的重点。最后指出,随着环境友好聚乳酸材料的合成和应用的增加,开发单活性中心以及无金属催化剂研究丙交酯立体选择开环聚合是今后研究的一个重要的课题。     

丙交酯开环均聚合

生物可降解脂肪族聚酯--聚丙交酯由可再生资源获得.聚丙交酯独特的物理性质使得它在包装、涂层、纤维、薄膜等方面有着广泛的应用.聚丙交酯低成本、大规模的生产及应用将极大地减轻对石油产品的依赖.高分子量的聚丙交酯主要由丙交酯开环聚合制备.本文总结了催化丙交酯开环聚合的3大类催化剂及其反应机理;综述了近年来国内外在丙交酯均聚合催化剂开发上的研究进展,并重点论述了稀土催化剂在丙交酯开环聚合中的优势及由其催化合成的聚丙交酯在生物学应用中的优点.     

稀土乙酰丙酮盐催化聚合ε－己内酯和丙交酯

稀土乙酰丙酮盐催化聚合ε－己内酯和丙交酯刘建飞，沈之茎，孙俊全（浙江大学高分子科学与工程系杭州３１００２７）关键词ε－己内酯，丙交酯，稀土乙酰丙酮盐，开环聚合聚己内酯和聚丙交酯具有良好的生物相容性，在生物医药领域有广泛用途，因而丙交酯和己内酯的催化开...     

Poly(ϵ‐caprolactone‐b‐glycolide) and poly(D,L‐lactide‐b‐glycolide) diblock copolyesters: Controlled synthesis,characterization, and colloidal dispersions

Living ω‐aluminum alkoxide poly‐ϵ‐caprolactone and poly‐D,L ‐lactide chains were synthesized by the ring‐opening polymerization of ϵ‐caprolactone (ϵ‐CL) and D,L ‐lactide (D,L ‐LA), respectively, and were used as macroinitiators for glycolide (GA) polymerization in tetrahydrofuran at 40 °C. The P(CL‐b‐GA) and P(LA‐b‐GA) diblock copolymers that formed were fractionated by the use of a selective solvent for each block and were characterized by ¹H NMR spectroscopy and differential scanning calorimetry analysis. The livingness of the operative coordination–insertion mechanism is responsible for the control of the copolyester composition, the length of the blocks, and, ultimately, the thermal behavior. Because of the inherent insolubility of the polyglycolide blocks, microphase separation occurs during the course of the sequential polymerization, resulting in a stable, colloidal, nonaqueous copolymer dispersion, as confirmed by photon correlation spectroscopy. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 294–306, 2001     

Relationship among drug delivery behavior,degradation behavior and morphology of copolylactones derived from glycolide,l‐lactide and ε‐caprolactone

A series of copolylactones was synthesized by ring‐opening copolymerization of glycolide, L ‐lactide and ?‐caprolactone, using stannous octoate as catalyst. The in vitro degradation behaviors of them were studied and data demonstrated different degradation rates which mainly depended on the compositions. Investigation of the 5‐fluorouracil (5‐Fu) release from these copolylactones revealed that the composition, degradation rate and the morphology of the polymeric matrix played an important role on the drug release kinetics. A sustained 5‐Fu release without initial time lag was obtained from random poly(lactide‐co‐glycolide‐co‐caprolactone) (r‐PGLC) drug carrier, and it differed from the cases of polylactide (PLA) or random poly(lactide‐co‐glycolide) (PLGA), which usually showed an initial time lag or biphasic drug release behavior. It was due to the low glass transition temperature (T _g) of the r‐PGLC and the drug would diffuse faster in rubbery state under the experimental temperature. Furthermore, a significant change in the drug release behavior of r‐PGLC was observed when the temperatures were changed around the T _g of the drug carrier, which implied that the drug release behavior could be regulated by adjusting the morphology of the drug carrier. Copyright © 2002 John Wiley & Sons, Ltd.     

Drug release and biocompatibility of self‐assembled micelles prepared from poly (ɛ‐caprolactone/glycolide)‐poly (ethylene glycol) block copolymers

A series of poly(?‐caprolactone/glycolide)‐poly(ethylene glycol) (P(CL/GA)‐PEG) diblock copolymers were prepared by ring opening polymerization of a mixture of ?‐caprolactone and glycolide using mPEG as macro‐initiator and stannous octoate as catalyst. Self‐assembled micelles were prepared from the copolymers using nanoprecipitation method. The micelles were spherical in shape. The micelle size was larger for copolymers with longer PEG blocks. In contrast, the critical micelle concentration of copolymers increased with decreasing the overall hydrophobic block length. Drug loading and drug release studies were performed under in vitro conditions, using paclitaxel as a hydrophobic model drug. Higher drug loading was obtained for micelles with longer poly(ε‐caprolactone) blocks. Faster drug release was obtained for micelles of mPEG2000 initiated copolymers than those of mPEG5000 initiated ones. Higher GA content in the copolymers led to faster drug release. Moreover, drug release rate was enhanced in the presence of lipase from Pseudomonas sp., indicating that drug release is facilitated by copolymer degradation. The biocompatibility of copolymers was evaluated from hemolysis, dynamic clotting time, and plasma recalcification time tests, as well as MTT assay and agar diffusion test. Data showed that copolymer micelles present outstanding hemocompatibility and cytocompatibility, thus suggesting that P(CL/GA)‐PEG micelles are promising for prolonged release of hydrophobic drugs.     

生物降解高分子——聚己内酯/聚氧乙烯/聚丙交酯三元共聚物水解行为的研究

以异辛酸亚锡为催化剂 ,通过聚乙二醇醚 (PEG)引发ε 己内酯和L 丙交酯开环聚合 ,制备了PCL/PEO/PLA三元共聚物 .研究了聚合物在 pH7 4磷酸缓冲溶液、37℃条件下的体外降解行为 .采用GPC、1H NMR、DSC和XRD技术研究了聚合物在水解降解过程中分子量、分子量分布、组成、吸水率、结晶性等的变化 .结果表明共聚物的吸水率随聚醚组分含量而增大 ;随水解材料的失重率增大 ,聚醚组分含量下降程度也加大 .此外研究还表明 :聚合物中丙交酯组分含量高时 ,聚合物的结晶结构主要由PLLA形成 .由于聚合物的水解降解首先发生在无定形区和结晶区边缘 ,随着共聚物的降解、结晶性的PLLA低聚物的生成 ,导致了共聚物的分子量呈双峰分布     

Effect of comonomer on thermal/mechanical and shape memory property of L‐lactide‐based shape‐memory copolymers

In this study, three kinds of L ‐lactide‐based copolymers, poly(lactide‐co‐glycolide) (PLGA), poly(lactide‐co‐p‐dioxanone) (PLDON) and poly(lactide‐co‐caprolactone) (PLC), were synthesized by the copolymerization of L ‐lactide (L) with glycolide (G), or p‐dioxanone (DON) or ε‐caprolactone (CL), respectively. The copolymers were easily soluble in common organic solvents. The compositions of the copolymers were determined by ¹H‐NMR. Thermal/mechanical and shape‐memory properties of the copolymers with different comonomers were compared. Moreover, the effect of the chain flexibility of the comonomers on thermal/mechanical and shape‐memory properties of the copolymers were investigated. The copolymers with appropriate lactyl content showed good shape‐memory properties where both the shape fixity rate (R_f)and the shape recovery rate (R_r) could exceed 95%. It was found that the comonomers with different flexible molecular chain have different effects on their thermal/mechanical and shape‐memory properties. Among them, PLGA has the highest mechanical strength and recovery rate while PLC copolymer has high recovery rate when the lactyl content exceeded 85% and the lowest transition temperature (T_trans). Copyright © 2007 John Wiley & Sons, Ltd.     

NMR investigation of biodegradable polyesters for medical applications

Results of NMR studies of chain microstructure in polylactide, poly(lactide‐co‐ϵ‐caprolactone), poly(lactide‐co‐glycolide) and poly(glycolide‐ϵ‐caprolactone) are presented. The appropriate conditions of polymerization: temperature, solvents, type of initiators allows moulding of the structure of obtained polyesters. Statistical analysis of growing chains helps to identify in NMR spectra signals of the random and block segments of copolyester chains. Precise control of reaction conditions allows modification of chain structures by affecting rates of transesterification. Equations allowing for quantitative determination of the role of transesterification reactions on the basis of intensities of NMR resonance lines are given. Changes in the microstructure of macromolecular chains were determined using calculated values of transesterification coefficients, degree of randomness and values of average lengths of syndiotactic or isotactic blocks in lactide homopolymers or average lengths of comonomer units in copolymers.     

Block and random copolymerization of ε‐caprolactone,L‐, and rac‐lactide using titanium complex derived from aminodiol ligand

A series of di‐ and triblock copolymers [poly(L ‐lactide‐b‐ε‐caprolactone), poly(D,L ‐lactide‐b‐ε‐caprolactone), poly(ε‐caprolactone‐b‐L ‐lactide), and poly(ε‐caprolactone‐b‐L ‐lactide‐b‐ε‐caprolactone)] have been synthesized successfully by sequential ring‐opening polymerization of ε‐caprolactone (ε‐CL) and lactide (LA) either by initiating PCL block growth with living PLA chain end or vice versa using titanium complexes supported by aminodiol ligands as initiators. Poly(trimethylene carbonate‐b‐ε‐caprolactone) was also prepared. A series of random copolymers with different comonomer composition were also synthesized in solution and bulk of ε‐CL and D,L ‐lactide. The chemical composition and microstructure of the copolymers suggest a random distribution with short average sequence length of both the LA and ε‐CL. Transesterification reactions played a key role in the redistribution of monomer sequence and the chain microstructures. Differential scanning calorimetry analysis of the copolymer also evidenced the random structure of the copolymer with a unique T_g. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. III. Synthesis and chain‐microstructure analysis of terpolymer obtained from L‐lactide,glycolide, and ϵ‐caprolactone initiated by zirconium(IV) acetylacetonate

Zirconium(IV) acetylacetonate [Zr(acac)₄] is a very good initiator for the terpolymerization of glycolide with L‐lactide and ?‐caprolactone. The microstructure of the obtained terpolymer was determined by NMR spectroscopy and then compared with terpolymers obtained in the presence of stanous(II) octoate [Sn(oct)₂]. Samples obtained with Zr(acac)₄ were characterized by a segmental‐chain microstructure. Apart from relatively long lactidyl microblocks, there were also segments made of random copolymer of glycolide with lactide. Such a structure is formed as a result of strong transesterification caused by active caproyl chain endings attacking the glycolidyl groups. Domination of this type of transestrification is shown. The growth of terpolymer chains and the influence of transesterification on gradual changes of the microstructure of the forming terpolymer chain were examined. Significant differences among glycolide, lactide, and the least reactive caprolactone were observed. The results of differential scanning calorimetric examinations of the obtained terpolymers are presented. Differences between the structures of random terpolymers obtained during terpolymerization initiated by Sn(oct)₂ and those obtained by Zr(acac)₄ influence their thermal properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3129–3143, 2002     

Synthesis and characterization of a novel biodegradable,thermoplastic polyurethane elastomer

A series of biodegradable, thermoplastic polyurethane elastomers poly(?‐caprolactone‐co‐lactide(polyurethane [PCLA–PU] were synthesized from a random copolymer of L ‐lactide (LA) and ?‐caprolactone (CL), hexamethylene diisocyanate, and 1,4‐butanediol. The effects of the LA/CL monomer ratio and hard‐segment content on the thermal and mechanical properties of PCLA–PUs were investigated. Gel permeation chromatography, IR, ¹³C NMR, and X‐ray diffraction were used to confirm the formation and structure of PCLA–PUs. Through differential scanning calorimetry, tensile testing, and tensile‐recovery testing, their thermal and mechanical properties were characterized. Their glass‐transition temperatures were below ?8 °C, and their soft domains became amorphous as the LA content increased. They displayed excellent mechanical properties, such as a tensile strength as high as 38 MPa, a tensile modulus as low as 10 MPa, and an elongation at break of 1300%. Therefore, they could find applications in biomedical fields, such as soft‐tissue engineering and artificial skin. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5505–5512, 2006     

Synthesis and properties of shape memory polymers of LLA,TMC, and ε‐CL terpolymers

Biodegradable polylactide (PLA) and its copolymers with shape memory properties have attracted great interests because of their important application prospects in biomedical field. In this study, random poly(L‐lactide‐co‐trimethylene carbonate‐co‐ε‐caprolactone) (LTCL) terpolymers with different molar ratio were synthesized and characterized. Monomer ε‐caprolactone (ε‐CL) was used in this study instead of glycolide in preliminary study of LTG terpolymers to investigate the transition temperature and the shape memory performance. Characterization on crystallization, mechanical properties, shape fixing, and recovery ratios of the terpolymers was conducted to investigate the correlation between crystallization and shape memory performance of LTCL terpolymers. The results are consistent with the formation of crystallized LLA segments, which could act as crosslinks, strengthened the stationary phase within the polymer matrix, and significantly improved the shape memory performance of LTCL terpolymers. For example, LTCL801010 is a crystalline polymer with high shape fixity and shape recovery ratio; its shape recovery temperature is 39°C. LTCL terpolymers with high CL content do not show shape memory performance for the rubbery at room temperature. Based on this study, PLA materials with shape memory property can be designed through the selection of monomers or the adjustment of comonomer ratio. These polymers with recovery temperature close to 37°C are expected to be used in human body such as scaffolds in tissue engineering.