Design of New Cardanol Derivative: Synthesis and Application as Potential Biobased Plasticizer for Poly(lactide)

A novel biobased plasticizer made of cardanol is designed for poly(lactide) (PLA). This cardanol‐derived plasticizer, i.e., methoxylated hydroxyethyl cardanol (MeCard), is synthesized through methoxylation of the double bonds on the side chain of cardanol, and characterized by ¹H NMR and mass spectrometry. The plasticization effect of MeCard on the molecular structure, morphology, thermal and mechanical properties of PLA is evaluated and compared to that of a commercial cardanol, i.e., hydroxyethyl cardanol (pCard). The plasticization efficiency of MeCard is demonstrated by a substantial decrease of the glass transition temperature and storage modulus together with a significant increase of the elongation at break as compared to neat PLA. Moreover, MeCard exhibits higher plasticization performance than pCard toward PLA. Such behavior is related to a higher miscibility and compatibility between PLA and MeCard thanks to the methoxylation of the double bonds on the side chain of cardanol as shown by SEM micrographs.

     

Electrospun poly(L‐lactide)/poly(ε‐caprolactone) blend fibers and their cellular response to adipose‐derived stem cells

Polymer blending is one of the most effective methods for providing new, desirable biocomposites for tissue‐engineering applications. In this study, electrospun poly(L ‐lactide)/poly(ε‐caprolactone) (PLLA/PCL) blend fibrous membranes with defect‐free morphology and uniform diameter were optimally prepared by a 1 : 1 ratio of PLLA/PCL blend under a solution concentration of 10 wt %, an applied voltage of 20 kV, and a tip‐to‐collector distance of 15 cm. The fibrous membranes also showed a porous structure and high ductility. Because of the rapid solidification of polymer solution during electrospinning, the crystallinity of electrospun PLLA/PCL blend fibers was much lower than that of the PLLA/PCL blend cast film. To obtain an initial understanding of biocompatibility, adipose‐derived stem cells (ADSCs) were used as seed cells to assess the cellular response, including morphology, proliferation, viability, attachment, and multilineage differentiation on the PLLA/PCL blend fibrous scaffold. Because of the good biocompatibility and nontoxic effect on ADSCs, the PLLA/PCL blend electrospun fibrous membrane provided a high‐performance scaffold for feasible application in tissue engineering using ADSCs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

丙交酯与聚乳酸的合成

以D,L-乳酸为单体,氧化锌为催化剂,将乳酸合成D,L丙交酯;再以辛酸亚锡为催化剂,使丙交酯单体开环聚合制备聚乳酸。结果表明,乳酸在130℃、氧化锌质量分数为1.1%时,其粗产品产率大于60%;丙交酯聚合时,辛酸亚锡用量为0.02 mL时,聚合温度为160℃,常压聚合5 h即可得到粘均分子质量为6.0×104的聚乳酸;测试结果表明丙交酯在辛酸亚锡作用下发生了开环反应。     

用厨房垃圾的乳酸发酵液合成丙交酯的研究

以营养丰富的厨房垃圾为原料,通过接种乳酸菌发酵,得到了乳酸含量为31.47g?L?1的厨房垃圾发酵液;用电渗析法从厨房垃圾发酵液中提取乳酸,将电渗析分离液经减压脱水浓缩至乳酸含量为70%~80%(wt),作为合成丙交酯的原料。选用氧化锌作为解聚剂,分析纯D,L-乳酸作为原料通过正交设计实验确定了生成丙交酯的最佳条件为:预聚温度150℃,预聚时间3h,解聚剂用量为1.0%(wt),解聚温度220℃;在此条件下,以厨房垃圾发酵液提取的乳酸为原料合成丙交酯,其产率为60%。该丙交酯经熔点测定、红外光谱和核磁共振分析的结果表明:用厨房垃圾的乳酸发酵液合成的丙交酯为D,L-丙交酯。本工艺不但可降低丙交酯的生产成本,而且解决了厨房垃圾的环境污染问题。     

Mixtures of poly(vinyl chloride) and copolyesters based on ε‐caprolactone and L‐lactide: Miscibility,thermal stability,and weathering resistance

Properties of the blends of Poly(vinyl chloride) (PVC) and poly(ε‐caprolactone) (PCLO) and copolyesters based on ε‐caprolactone and L‐lactide (LLA) prepared by rolling were studied. Incorporating the LLA units into the structure of PCLO the content of the crystalline phase was controlled. Miscibility of the blends was assessed using DMA, and basic mechanical properties were correlated with the type and content of the polymer plasticizer. The PVC blends containing up to 20 wt parts polyesters were miscible. The presence of the LLA units in the copolyester influenced negatively the thermal stability. On the other hand even small content of copolyester in the blend enhanced the resistivity against aging. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphological study on thermal treatment and degradation behaviors of solution-grown poly(l-lactide) single crystals

Morphological changes of solution-grown crystals (SGCs) of poly(l-lactide) (PLLA) following thermal treatment and enzymatic degradation were investigated using atomic force microscopy in terms of defects in the crystals. PLLA SGCs were grown from a dilute solution of acetonitrile at 5 °C. The obtained solution-grown monolamellar crystals have a lozenge-shaped morphology containing unique dimensions, with one side measuring 12 μm. To investigate enzymatic degradation behavior, PLLA SGCs were incubated in buffered solution with proteinase-K at 37 °C. The initial stage of enzymatic degradation of PLLA SGCs with proteinase-K occurs in loosely folding chains at the surface of the crystal. Thermally treated PLLA SGCs below the melting temperature showed an increase of the lamellar thickness of the SGCs at the treated temperature and partial surface erosion following enzyme exposure. These results indicate that less ordered chains exist throughout the lamellae and their thermal-induced chain extension makes them more susceptible to enzyme attack.     

Synthesis of star‐shaped poly(ε‐caprolactone)‐b‐poly(L‐lactide) copolymers: From star architectures to crystalline morphologies

Hexa‐armed star‐shaped poly(ε‐caprolactone)‐block‐poly(L ‐lactide) (6sPCL‐b‐PLLA) with dipentaerythritol core were synthesized by a two‐step ring‐opening polymerization. GPC and ¹H NMR data demonstrate that the polymerization courses are under control. The molecular weight of 6sPCLs and 6sPCL‐b‐PLLAs increases with increasing molar ratio of monomer to initiator, and the molecular weight distribution is in the range of 1.03–1.10. The investigation of the melting and crystallization demonstrated that the values of crystallization temperature (T_c), melting temperature (T_m), and the degree of crystallinity (X_c) of PLLA blocks are increased with the chain length increase of PLLA in the 6sPCL‐b‐PLLA copolymers. On the contrary, the crystallization of PCL blocks dominates when the chain length of PLLA is too short. According to the results of polarized optical micrographs, both the spherulitic growth rate (G) and the spherulitic morphology are affected by the macromolecular architecture and the length of the block chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development and Comprehensive Characteristics of Thermosensitive Liquid Suppositories of Metoprolol Based on Poly(lactide-co-glycolide) Nanoparticles

Thermosensitive liquid suppositories (LSs) carrying the model antihypertensive drug metoprolol tartrate (MT) were developed and evaluated. The fundamental purpose of this work was to produce, for the first time, liquid MT suppositories based on biodegradable nanoparticles and optimize their rheological and mechanical properties for prospective rectal administration. The nanoparticle system was based on a biodegradable copolymer synthesized by ring opening polymerization (ROP) of glycolide (GL) and L,L-lactide (LLA). Biodegradable nanoparticles loaded with the model drug were produced by the o/o method at the first stage of the investigation. Depending on the concentration of the drug in the sample, from 66 to 91% of MT was released over 12 h, according to first-order kinetics. Then, thermosensitive LSs with MT-loaded biodegradable nanoparticles were obtained by a cold method and their mechanical and rheological properties were evaluated. To adjust the thermogelling and mucoadhesive properties for rectal administration, the amounts of major formulation components such as poloxamers (P407, P188), Tween 80, hydroxypropylcellulose (HPC), polyvinylpyrrolidone (PVP), and sodium alginate were optimized. The in vitro release results revealed that more than 80% of the MT was released after 12 h, following also first-order kinetics. It was discovered that the diffusion process was dominant. The drug release profile was mainly governed by the rheological and mechanical properties of the developed formulation. Such a novel, thermosensitive formulation might be an effective alternative to hypertension treatment, particularly for unconscious patients, patients with mental illnesses, geriatric patients, and children.     

利用有机催化剂合成分子量可控聚乳酸

利用有机催化剂--1,8-二氮杂双环[5.4.0]-7-十一碳烯(DBU),以异丙醇为引发剂,实现丙交酯在常温、常压下的活性开环聚合反应,合成可作为医用材料的分子量可控的聚乳酸.反应机理为有机催化剂DBU与引发剂异丙醇通过氢键形成中间体,中间体中呈负电性的氧对丙交酯羰基中的碳进行亲核进攻,使丙交酯单体通过酰氧键断裂,进行开环聚合反应.通过FT-IR和1H NMR对聚乳酸的结构进行了表征.通过调节丙交酯和异丙醇的摩尔比来调控产品聚乳酸的分子量,GPC分析表明该聚合方法能够实现聚乳酸分子量的有效控制,且聚乳酸分子量分布很窄.通过分析聚合反应时间对聚乳酸产率的影响,确定了poly-lactide-3000、polylactide-5000、polylactide-7000 和polylactide-10000的适宜聚合反应时间分别为20、30、40和50min.     

可反应性纳米二氧化硅对聚乳酸结晶行为的影响

通过熔融共混法制备了聚乳酸（PLLA）／可反应性纳米二氧化硅（RNS）复合材料,用透射电子显微镜观察RNS在PLLA基体中的分散情况,用差示扫描量热仪（DSC）和X射线衍射仪（XRD）对复合材料的非等温结晶行为进行了研究,并利用Jeziomy法和Mo法对复合材料的非等温结晶动力学进行分析。结果表明,RNS在PLLA中分散均匀,RNS的加入虽不会改变PLLA的晶型,但RNS与PLLA之间的相互作用及其异相成核能力会对聚乳酸基体的结晶速率和结晶度产生影响,导致材料结晶过程发生变化。