Crystallization behavior and crystallite morphology control of poly(L‐lactic acid) through N,N′‐bis(benzoyl)sebacic acid dihydrazide

Adding a nucleating agent is one of the best ways to accelerate the crystallization rate of poly(L ‐lactic acid) (PLLA) so as to obtain a high degree of crystallinity during the process, which will improve the heat distortion temperature of final products. In the work reported, N, N′‐bis(benzoyl)sebacic acid dihydrazide (BSAD) was synthesized and used as a nucleating agent for PLLA. Isothermal and non‐isothermal crystallization behaviors were investigated using differential scanning calorimetry (DSC). The addition of BSAD successfully enhances the crystallization rate of PLLA. A unique phase separation behavior of PLLA/BSAD blends is found from DSC as well as from polarized optical microscopy, which explains the difference of optimal BSAD concentration between isothermal and non‐isothermal crystallization. This is the first recording of a phase separation peak in PLLA/nucleating agent blends using DSC. In thermogravimetric analysis, the enhanced thermal stability indicates that there are strong hydrogen bonds between BSAD and PLLA matrix. BSAD can dissolve in PLLA melt below its melting point through intermolecular hydrogen bonding with PLLA and self‐assemble upon cooling, leading to the surface being capable of nucleating PLLA. Different phase separation temperatures can be used to control the morphology of BSAD, which finally determines the crystallite morphology of PLLA. © 2012 Society of Chemical Industry     

Catecholate complexes of zirconium: synthesis,spectroscopic characterization and polymerization studies

Varieties of new catecholate complexes containing zirconium were synthesized in high yields and purity. These derivatives are potent initiators for the ring‐opening polymerization (ROP) of rac‐lactide, l ‐lactide, ?‐caprolactone, δ‐valerolactone, rac‐β‐butyrolactone, ethylene and propylene. The number‐average molecular weights of the resulting polymers are slightly higher than the theoretical molecular weight and they have controlled molecular weight distributions. The isopropoxide moiety in these complexes is responsible for initiating the ROP. For ethylene and propylene polymerization, we were able to achieve good activity using methylaluminoxane as a co‐catalyst. © 2013 Society of Chemical Industry     

聚D,L-乳酸的合成及表征

以D，L－乳酸为单体，辛酸亚锡为催化剂，乳酸先缩聚合解聚制备了D，L－丙交酯，并以丙交酯为单体开环本体聚合制备了聚乳酸。用IR、^1H－NMR对丙交酯及聚乳酸的结构加以证实；用TG、DSC测定了聚乳酸的热分解温度和玻璃化温度。测试结果表明，环状丙交酯在辛酸亚锡催化剂作用下发生了开环反应，所得聚合物的热分解温度为233．9℃，玻璃化温度为54．4℃。     

固体超强酸SO4^2—／ZnO—SnO2／La^3＋催化合成丙交酯

研究了在乳酸合成丙交酯的实验中,以三种不同类型金属氧化物(ZnO,SnO2,La2O3)的固体超强酸作催化剂对反应产物收率,反应温度和时间的影响。实验表明,双金属固体超强酸SO2-4/ZnO-SnO2/La3+催化效果最佳。使用该催化剂,减压(5 0×103Pa)条件下在120～130℃下脱水2h生成乳酸低聚物。然后在150～210℃下分解低聚物,收集丙交酯,反应时间90min。丙交酯的平均收率达58%。     

Mechanical and Thermal Properties of Poly(L‐lactide) Incorporating Various Inorganic Fillers with Particle and Whisker Shapes

Poly(L ‐lactide) (PLLA) composites incorporating various inorganic fillers (ifR‐PLA) were prepared by the melt blending technique, and their mechanical and thermal properties were evaluated. The filler types influenced the mechanical properties of ifR‐PLA; for those incorporating particle‐ and whisker‐type fillers the tensile moduli were 3.1–3.7 and 3.7–4.5 GPa, respectively, and the flexural moduli were 4.1–4.8 and 4.8–6.1 GPa. It was found that the tensile strength and modulus, as well as the flexural modulus, of ifR‐PLA incorporating whisker‐type fillers increased in proportion to the volume percent of the fillers (V_f). The flexural strength of ifR‐PLA incorporating 9Al₂O₃ · 2B₂O₃ whiskers showed a similar increase, while that of ifR‐PLA incorporating CaCO₃ whiskers showed a decrease with increasing V_f. This difference may be because the 9Al₂O₃ · 2B₂O₃ with its large aspect ratio kept its original fibrous shape, while the CaCO₃ lost its fibrous shape during the blending process. However, the reinforcing effect of these fillers was relatively low compared with that known for the corresponding composites of the conventional polymeric materials, probably because of the poor surface adhesion of PLLA to the fillers.

Comparison of effect on storage moduli of different fillers.     

Functionalized lactic acid macromonomers via polycondensation as an alternative to ring opening polymerization

Engineered polylactic acid (PLA) nanoparticles synthesized from oligo(lactic acid) macromonomers have been studied over the last decades for controlled drug delivery. These macromonomers are typically produced via ring-opening polymerization (ROP) of the cyclic dimer lactide, initiated by 2-hydroxyethyl methacrylate (HEMA). This reaction route, despite leading to well-defined macromonomers, relies on the production of lactide from lactic acid, which burdens the ROP overall cost for more than 30%. In this work, we report the synthesis of PLA-based macromonomers by direct polycondensation of lactic acid in the presence of HEMA as a valuable alternative to ROP. In particular, we compare the two processes side by side, focusing on the production of three HEMA-LA_n macromonomers, with n = 2, 4, and 6. Detailed kinetic models are developed for both reaction systems, and the corresponding parameters are estimated by fitting the experimental data. Through these models, the reaction kinetics as well as the time evolution of the entire chain length distributions of the products from polycondensation and ROP could be reliably predicted. This way, we demonstrated that polycondensation is a valuable alternative to ROP only for macromonomers with an average chain length of up to 4 and that ROP remains the main route to longer chains, when a strict control over the chain length distribution is required.     

聚乳酸微球的制备

以L-乳酸为原料,锡粒为催化剂,实现了丙交酯的开环聚合反应,红外光谱结果表明,合成了分子量可控的聚乳酸。以二氯甲烷为溶剂,聚乙烯醇为表面活性剂,制备了聚乳酸微球,研究了聚乙烯醇浓度对聚乳酸微球的影响。结果表明,当聚乙烯醇浓度增加时,微球半径变小,但粒径分布均匀度下降,聚乙烯醇浓度为1%时,聚乳酸成球效果较好。     

Electrospun poly(D,L)‐lactide nonwoven mats for biomedical application: Surface area shrinkage and surface entrapment

Nanofibrous poly(D,L )‐lactide mats prepared by electrospinning are useful for numerous biomedical applications. However, it was observed that these mats tend to shrink under physiological conditions. In this research, a physical entrapment method to modify the polymer surface with poly(ethylene glycol) was developed to ensure dimensional stability and to increase the hydrophilicity of the surface of the mats. Nanofiber morphology was characterized by scanning electron microscopy. Surface element analysis was performed by high resolution X‐ray photoelectron spectroscopy. Water contact angles were determined to identify surface properties before and after surface entrapment. Canine fibroblasts were prepared and seeded onto the poly(D,L)‐lactide mats, followed by cell morphology study by SEM and cell viability tests by MTT assay, which confirmed the improvement of biocompatibility by surface modification. Taking the results into account, hydrophilic and area‐stable nanofibrous nonwoven mats were successfully produced, with potential applications as in vivo biomedical material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Spray drying technique to produce controlled release formulations of zidovudine—an anti‐HIV drug

This article explores the application of spray drying technique to produce microparticles of poly(D ,L ‐lactide‐co‐glycolic acid) (PLGA), as well as di‐block copolymer of polylactic acid (PLA) and polyethylene glycol (PEG) (PLA‐PEG), containing zidovudine (AZT), an anti‐HIV drug, to achieve its controlled release over an extended period of time. Of the two polymers studied, PLGA is hydrophobic, whereas PLA‐PEG is hydrophilic and the drug, AZT is water‐soluble. Formulations were developed containing 10 and 25 wt % of AZT giving encapsulation efficiencies (EE) of 66 to 86% for PLGA and 90 to 94% for PLA‐PEG di‐block copolymer. All the formulations were characterized by Fourier transform spectroscopy (FTIR) to investigate the interaction of AZT with polymers and to characterize PLA‐PEG. NMR was also employed to confirm the formation of PLA‐PEG. X‐ray diffraction was used to understand the molecular level dispersion of AZT within the polymeric matrices, while differential scanning calorimetry was employed to assess thermal properties. Scanning electron microscopy was employed to understand the surface morphology of AZT‐loaded microparticles. In vitro release experiments performed in pH 7.4 buffer media extended the release of AZT up to 125 h with PLGA, whereas 30 h were required for releasing AZT through PLA‐PEG microparticles. Cumulative release data were fitted to an empirical equation to understand the nature of release characteristics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 000: 000–000, 2011     

Decomposition rate control of PLLA plate by heat treatment

It is difficult to control the decomposition rate and the mechanical property of scaffolds after forming the poly(L ‐lactide) (PLLA) scaffolds. The purpose of this study is to control the decomposition rate and mechanical properties of the PLLA plate after forming. We carried out accelerated decomposition experiments using the enzyme on the (PLLA) with various crystallinity, which were prepared by changing the heat treatment condition, and elucidated the relationship between the crystallinity and the decomposition rate. A high positive correlation was observed between the heat treatment temperature and the crystallinity. A high negative correlation was observed between the crystallinity and the decomposition rate. Using the obtained empirical formula, it became possible to calculate the required period to decompose a certain amount of the PLLA if the heat treatment temperature was known. Changing the crystallinity of the PLLA plate could arbitrarily control the decomposition rate of the PLLA plate after forming. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011