壳聚糖-羟基磷灰石复合微球对聚乳酸力学与热稳定性能的影响
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摘要
以四水硝酸钙与磷酸氢二铵为原料,采用共沉淀法制备了壳聚糖-羟基磷灰石(CS-HA)复合微球,并通过熔融共混法将其与聚乳酸(PLA)复合制得PLA/CS-HA复合材料,同时分析了CS-HA复合微球的结构以及PLA/CS-HA复合材料的性能。结果表明:CS已成功与HA复合,制得具有自组装微球结构的CS-HA复合物。当CS-HA复合微球添加量为5%时,PLA/CS-HA复合材料的弯曲强度较纯PLA提高了15.1%,较同填充量的PLA/HA复合材料提高了13.5%,而拉伸强度和冲击强度较纯PLA略有降低。此外,当CS-HA复合微球添加量为5%时,PLA/CS-HA复合材料的5%质量损失温度和失重速率峰值温度较纯PLA分别提高了33.1和22.2℃,说明CS-HA复合微球的加入提高了PLA的热稳定性;当CS-HA复合微球添加量为15%时,PLA/CS-HA复合材料的结晶度达到31.72%,较纯PLA提高了23.23%,这说明CS-HA复合微球可促进PLA的结晶。
Chitosan-hydroxyapatite(CS-HA) composite microspheres were prepared by coprecipitation method using calcium nitrate tetrahydrate and diammonium phosphate as raw materials, and the polylactic acid(PLA)/CS-HA composites were prepared by melt blending method. The structure of CS-HA composite microspheres and the properties of PLA/CS-HA composites were analyzed. The results show that: CS and HA are complexed successfully, and the CSHA composities with self-assembled microsphere structure are prepared. When the addition amount of CS-HA composite microspheres is 5%, the flexural strength of PLA/CS-HA composite is 15.1% higher than that of pure PLA, 13.5% higher than that of PLA/HA composites, but the tensile strength and impact strength are slightly lower than those of pure PLA. Moreover, when the CS-HA addition amount is 5%, the 5% mass loss temperature and the temperature of maximum weight loss rate of PLA/CS-HA composites are increased by 33.1 and 22.2℃(compared with pure PLA), respectively, indicating that the addition of CS-HA composite microspheres improves the thermal stability of PLA. The crystallinity of the PLA/CS-HA composites reaches 31.72% when the addition amount of CS-HA composite microspheres is 15%, which improved by 23.23% compared with pure PLA, indicating that the CS-HA composite microspheres can promote the crystallization of PLA.
Chitosan-hydroxyapatite(CS-HA) composite microspheres were prepared by coprecipitation method using calcium nitrate tetrahydrate and diammonium phosphate as raw materials, and the polylactic acid(PLA)/CS-HA composites were prepared by melt blending method. The structure of CS-HA composite microspheres and the properties of PLA/CS-HA composites were analyzed. The results show that: CS and HA are complexed successfully, and the CSHA composities with self-assembled microsphere structure are prepared. When the addition amount of CS-HA composite microspheres is 5%, the flexural strength of PLA/CS-HA composite is 15.1% higher than that of pure PLA, 13.5% higher than that of PLA/HA composites, but the tensile strength and impact strength are slightly lower than those of pure PLA. Moreover, when the CS-HA addition amount is 5%, the 5% mass loss temperature and the temperature of maximum weight loss rate of PLA/CS-HA composites are increased by 33.1 and 22.2℃(compared with pure PLA), respectively, indicating that the addition of CS-HA composite microspheres improves the thermal stability of PLA. The crystallinity of the PLA/CS-HA composites reaches 31.72% when the addition amount of CS-HA composite microspheres is 15%, which improved by 23.23% compared with pure PLA, indicating that the CS-HA composite microspheres can promote the crystallization of PLA.
引文
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[2]刘伯业,陈复生,何乐,等.可生物降解材料及其应用研究进展[J].塑料科技,2010,38(11):87-90.
[3]Gong T,Xie J,Liao J,et al.Nanomaterials and bone regeneration[J].Bone Research,2015,3(3):123-129.
[4]Zhou H,Lee J.Nanoscale hydroxyapatite particles for bone tissue engineering[J].Acta Biomater,2011,7(7):2 769-2 781.
[5]Shishatskaya E I,Khlusov I A,Volova T G.A hybrid PHB-hydroxyapatite composite for biomedical application:Production,in vitro and in vivo investigation[J].Journal of Biomaterials Science Polymer Edition,2006,17(5):481-498.
[6]Thein-Han W W,Misra R D.Biomimetic chitosannanohydroxyapatite composite scaffolds for bone tissue engineering[J].Acta Biomater,2009,5(4):1 182-1 197.
[7]党丽,王鹏程,吴昊,等.PLA/HA多孔生物支架的制备及性能研究[J].塑料科技,2014,42(10):87-91.
[8]Ghorbani F,Nojehdehian H,Zamanian A.Physicochemical and mechanical properties of freeze cast hydroxyapatitegelatin scaffolds with dexamethasone loaded PLGAmicrospheres for hard tissue engineering applications[J].Materials Science&Engineering C,2016,69:208-220.
[9]Kaito T,Myoui A,Takaoka K,et al.Potentiation of the activity of bone morphogenetic protein-2 in bone regeneration by a PLA-PEG/hydroxyapatite composite[J].Biomaterials,2005,26(1):73-79.
[10]Kasuga T,Ota Y,Nogami M,et al.Preparation and mechanical properties of polylactic acid composites containing hydroxyapatite fibers[J].Biomaterials,2000,22(1):19-23.
[11]Lin C C,Fu S J,Lin Y C,et al.Chitosan-coated electrospun PLA fibers for rapid mineralization of calcium phosphate[J].International Journal of Biological Macromolecules,2014,68:39-47.
[12]Verlee A,Mincke S,Stevens C V.Recent developments in antibacterial and antifungal chitosan and its derivatives[J].Carbohydrate Polymers,2017,164:268-283.
[13]Logithkumar R,Keshavnarayan A,Dhivya S,et al.A review of chitosan and its derivatives in bone tissue engineering[J].Carbohydrate Polymers,2016,151:172-188.
[14]袁华,葛芳芳,乔馨乐,等.壳聚糖-聚乳酸接枝共聚物的制备与表征[J].高分子材料科学与工程,2009,25(12):1-4.
[15]Grande R,Pessan L A,Carvalho A J F.Ternary melt blends of poly(lactic acid)/poly(vinylalcohol)-chitosan[J].Industrial Crops and Products,2015,72:159-165.
[16]Dorati R,Pisani S,Maffeis G,et al.Study on hydrophilicity and degradability of chitosan/polylactide-co-polycaprolactone nanofibre blend electrospun membrane[J].Carbohydrate Polymers,2018,199:150-160.
[17]刘淑琼,王兆礼,李冲.壳聚糖对聚乳酸/竹纤维复合材料的性能影响[J].塑料,2017,46(4):45-48,52.
[18]Cai X,Tong H,Shen X,et al.Preparation and characterization of homogeneous chitosan-polylactic acid/hydroxyapatite nanocomposite for bone tissue engineering and evaluation of its mechanical properties[J].Acta Biomater,2009,5(7):2 693-2 703.
[19]Xu T,Yang H,Yang D,et al.Polylactic acid nanofibers scaffold decorated with chitosan island-like topography for bone tissue engineering[J].ACS Applied Materials&Interfaces,2017,9(25):21 094-21 104.
[20]Jafarkhani M,Fazlali A,MoztarzadehF,et al.Mechanical and structural properties of polylactide/chitosan scaffolds reinforced with nano-calcium phosphate[J].Iranian Polymer Journal,2012,21(10):713-720.
[21]Zhang C Y,Zhang C L,Wang J F,et al.Fabrication and in vitro investigation of nanohydroxyapatite,chitosan,poly(L-lactic acid)ternary biocomposite[J].Journal of Applied Polymer Science,2013,127(3):2 152-2 159.
[22]M Roy,A Bandyopadhyay,S Bose.Induction plasma sprayed nano hydroxyapatite coatings on titanium for orthopaedic and dental implants[J].Surf Coat Technol,2011,205:2 785-2 792.
[23]Mitra T,Sailakshmi G,Gnanamani A,et al.Studieson crosslinking of succinic acid with chitosan/collagen[J].Mater Res,2013,16:755-765.
[24]M Qiu,X Wang,X Li,et al.Preparation and microanalysis of hydroxyapatite/chitosan-sodium alginate composite materials[J].Mater Rev,2013(4):60-62.
[25]Zhang Y,Venugopal J R,El-Turki A,et al.Electrospun biomimetic nanocomposite nanofibers of hydroxyapatite/chitosan for bone tissue engineering[J].Biomaterials,2008,29(32):4 314-4 322.
[26]Zou L,Zhang Y J,Liu X,et al.Biomimetic mineralization on natural and synthetic polymers to prepare hybrid scaffolds for bone tissue engineering[J].Colloids&Surfaces B:Biointerfaces,2019,178:222-229.
[27]Kai-Ping Z,Jing S,Song Y E,et al.A novel hollow hydroxyapatite microspheres/chitosan composite drug carrier for controlled release[J].Journal of Inorganic Materials,2016,31(4):434-442.
[28]潘亚妮,付亚国.改性聚乳酸/羟基磷灰石复合材料的制备及性能研究[J].化工新型材料,2015(10):88-90.
[29]Türk S,Alt?nsoy I,?elebi Efe G,et al.3D porous collagen/functionalized multiwalled carbon nanotube/chitosan/hydroxyapatite composite scaffolds for bone tissue engineering[J].Mater Sci Eng C:Mater Biol Appl,2018,92:757-768.