聚乳酸多孔微球的制备及其表征

doi:10.16085/j.issn.1000-6613.2017-1361

化工进展 ›› 2018, Vol. 37 ›› Issue (05): 1875-1880.DOI: 10.16085/j.issn.1000-6613.2017-1361

聚乳酸多孔微球的制备及其表征

刘瑞来

武夷学院福建省生态产业绿色技术重点实验室, 生态与资源工程学院, 福建武夷山 354300

收稿日期:2017-07-04 修回日期:2017-11-17 出版日期:2018-05-05 发布日期:2018-05-05
通讯作者: 刘瑞来(1984-),男,博士,副教授,主要从事功能高分子材料研究。
作者简介:刘瑞来(1984-),男,博士,副教授,主要从事功能高分子材料研究。E-mail:wyulrl@163.com。
基金资助:
国家自然科学基金（51406141）、福建省自然科学基金（2018J05092）、福建省高校产学研合作（2018Y4011）、福建省教育厅项目（JAT170595，JAT170596）、国家大学生创新性实验（201710397014）及武夷学院引进人才项目（YJ201703，YJ201704）。

Fabrication and characterization of poly(L-lactic acid) porous microspheres

LIU Ruilai

College of Ecological and Resources Engineering, Fujian Provincial Key laboratory of Eco-Industrial Green Technology, Wuyi University, Wuyishan 354300, Fujian, China

Received:2017-07-04 Revised:2017-11-17 Online:2018-05-05 Published:2018-05-05

摘要/Abstract

摘要： 以聚乳酸（PLLA）/四氢呋喃（THF）为淬火溶液，无其他添加剂条件下，通过低温淬火、萃取、洗涤和干燥得到直径为30.92μm±1.55μm的PLLA多孔微球，多孔微球由直径为0.34μm±0.06μm向外辐射的纤维组成。偏光显微镜表明多孔微球为球晶结构。XRD结果表明，多孔微球属于α晶型，晶粒尺寸大小为17.25nm。DSC结果表明，PLLA多孔微球的结晶度为36.05%。与熔融挤出造粒得到PLLA原料（结晶度小于10%）相比，低温淬火得到的多孔微球的结晶度大大提高。N₂吸附-脱附结果分析表明，多孔微球的平均孔径和孔体积分别为42.92nm和0.1135cm³/g，大部分为大孔和介孔结构，比表面积和孔隙率分别为14.18cm²/g和93.15%。采用等温DSC模拟低温淬火过程研究了PLLA在THF溶液中结晶动力学，利用Avrami方程得到Avrami指数n平均值为2.29，说明PLLA在THF溶液中为异相成核和三维生长。

关键词: 结晶, 纳米材料, 乳酸, 多孔微球, 低温淬火

Abstract: Poly (L-lactic acid) porous microspheres with diameter of 30.92μm±1.55μm were prepared from its tetrahydrofuran solution through four steps of low-temperature quenching,extraction,washing and drying while without the assistance of other additives. The microspheres were composed of radicalized nanofibers with diameter of 0.34μm±0.06μm. The polarized optical microscope observations show that the PLLA porous microspheres are spherulites,while the XRD patterns show that they belong to α form with grain size of 17.25nm. DSC results show that the crystallinity of the microspheres obtained from low-temperature quenching are 36.05%,higher than the raw PLLA prepared by the melt-extrusion. N₂ adsorption-desorption results indicate that the average pore size and volume of the microspheres are 42.92nm and 0.1135cm³/g,respectively,and most pores are macropore and mesopore. The specific surface area and porosity are 14.18m²/g and 93.15%,respectively. DSC was used to study the isothermal crystallization kinetics of PLLA in THF solutions to mimic the low-temperature quenching process. The Avrami equation was used to analyze the data. Avrami exponent n was 2.29,indicating that the nucleation and crystal growth mechanism were heterogenous nucleation and three-dimensional,respectively.

Key words: crystallization, nanomaterials, poly(L-lactic acid), porous microspheres, low-temperature quenching

中图分类号:

TQ317.3

刘瑞来. 聚乳酸多孔微球的制备及其表征[J]. 化工进展, 2018, 37(05): 1875-1880.

LIU Ruilai. Fabrication and characterization of poly(L-lactic acid) porous microspheres[J]. Chemical Industry and Engineering Progress, 2018, 37(05): 1875-1880.

参考文献

[1] CHUNG H J,PARK T G. Surface engineered and drug releasing pre-fabricated scaffolds for tissue engineering[J]. Advanced Drug Delivery Reviews,2007,59(4):249-262.
[2] HE C,NIE W,FENG W. Engineering of biomimetic nanofibrous matrices for drug delivery and tissue engineering[J]. Journal of Materials Chemistry B,2014,2(45):7828-7848.
[3] FAN J B,HUANG C,JIANG L,et al. Nanoporous microspheres:from controllable synthesis to healthcare applications[J]. Journal of Materials Chemistry B,2013,1(17):2222-2235.
[4] AMBROSCH K,MANHARDT M,LOTH T,et al. Open porous microscaffolds for cellular and tissue engineering by lipid templating[J]. Acta Biomaterialia,2012,8(3):1303-1315.
[5] LIU R L,HAN J,CHEN X J,et al. Fabrication and control of ploylactied honeycomb porous films by breath figure method[J]. Acta Polymerica Sinica,2012(3):291-298.
[6] XIAO G,YIN H,XU W,et al. Modification and cytocompatibility of biocomposited porous PLLA/HA-microspheres scaffolds[J]. Journal of Biomaterials Science:Polymer Edition,2016,27(14):1462-1475.
[7] KIM S,KO J W,PARK C B. Bio-inspired mineralization of CO₂ gas to hollow CaCO₃ microspheres and bone hydroxyapatite/polymer composites[J]. Journal of Materials Chemistry,2011,21(30):11070-11073.
[8] HU Y,ZOU S,YANG Y,et al. Facile fabrication of macroporous PLGA microspheres via double-pickering emulsion templates[J]. Macromolecular Chemistry and Physics,2015,216(7):714-720.
[9] MEEUS J,SCURR D J,AMSSOMS K,et al. Surface characteristics of spray-dried microspheres consisting of PLGA and PVP:relating the influence of heat and humidity to the thermal characteristics of these polymers[J]. Molecular Pharmaceutics,2013,10(8):3213-3224.
[10] SHIN K C,KIM B S,KIM J H,et al. A facile preparation of highly interconnected macroporous PLGA scaffolds by liquid-liquid phase separation Ⅱ[J]. Polymer,2005,46(11):3801-3808.
[11] QIU K,HE C,FENG W,et al. Doxorubicin-loaded electrospun poly(L-lactic acid)/mesoporous silica nanoparticles composite nanofibers for potential postsurgical cancer treatment[J]. Journal of Materials Chemistry B,2013,1(36):4601-4611.
[12] JIANG B,AKAR B,WALLER T M,et al. Design of a composite biomaterial system for tissue engineering applications[J]. Acta Biomaterialia,2014,10(3):1177-1186.
[13] LIU B,ZHOU X,YANG F,et al. Fabrication of uniform sized polylactone microcapsules by premix membrane emulsification for ultrasound imaging[J]. Polymer Chemistry,2014,5(5):1693-1701.
[14] KIM H D,BEA E H,KWON I C,et al. Effect of PEG-PLLA diblock copolymer on macroporous PLLA scaffolds by thermally induced phase separation[J]. Biomaterials,2004,25(12):2319-2329.
[15] BARROCA N,DANIEL-DA-SILVA A L,VILARINHO P M,et al. Tailoring the morphology of high molecular weight PLLA scaffolds through bioglass addition[J]. Acta Biomaterialia,2010,6(9):3611-3620.
[16] HE L,ZHANG Y,ZENG X,et al. Fabrication and characterization of poly(L-lactic acid) 3D nanofibrous scaffolds with controlled architecture by liquid-liquid phase separation from a ternary polymer-solvent system[J]. Polymer,2009,50(16):4128-4138.
[17] DE SANTIS P,KOVACS A J. Molecular conformation of poly(S-lactic acid)[J]. Biopolymers,1968,6(3):299-306.
[18] HOOGTEEN W,POSTEMA A R,PENNINGS A J,et al. Crystal structure,conformation and morphology of solution-spun poly (L-lactide) fibers[J]. Macromolecules,1990,23(2):634-642.
[19] ZHANG J,DUAN Y,SATO H,et al. Crystal modifications and thermal behavior of poly(L-lactic acid)revealed by infrared spectroscopy[J]. Macromolecules,2005,38(19):8012-8021.
[20] ZHANG J,TASHIRO K,TSUJI H,et al. Disorder-to-order phase transition and multiple melting behavior of poly(L-lactide) investigated by simultaneous measurements of WAXD and DSC[J]. Macromolecules,2008,41(4):1352-1357.
[21] PAN P,ZHU B,DONG T,et al. Conformational and microstructural characteristics of poly (L-lactide)during glass transition and physical aging[J]. The Journal of Chemical Physics,2008,129:184902.
[22] PYDA M,WUNDERLICH B. Reversing and nonreversing heat capacity of poly(lactic acid) in the glass transition region by TMDSC[J]. Macromolecules,2005,38(25):10472-10479.
[23] LORENZO A T,ARNAL M L,ALBUERNE J,et al. DSC isothermal polymer crystallization kinetics measurements and the use of the Avrami equation to fit the data:guidelines to avoid common problems[J]. Polymer Testing,2007,26(2):222-231.

聚乳酸多孔微球的制备及其表征

Fabrication and characterization of poly(L-lactic acid) porous microspheres

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