选择磷酸三钙(TCP)为成核剂、左旋乳酸己内酯无规共聚物(PLLCA82/18)为增塑剂加入到左旋乳酸乙醇酸无规共聚物(PLLGA85/15)中,用平板硫化机热压成薄片,在130℃等温退火40min。通过万能力学实验机测试材料的力学性能,通过X射线衍射仪考察复合材料的结晶情况。结果表明:只需添加1% TCP和2% PLLCA82/18,复合材料的结晶度和拉伸强度即可得到显著改善,并且材料内部无明显缺陷产生。对复合材料进行降解实验,考察了降解过程中样品失重率和降解液pH的变化,通过扫描电镜观察降解后样品的微观形貌变化情况。降解实验结果表明复合材料的降解速率减缓,退火后材料的降解速率均加快。
Tricalcium phosphate (TCP) was used as nucleating agent and poly(L-lactic acid-co-ε-caprolactone) with monomer molar ratios of 82/18 (PLLCA82/18) was used as plasticizer,they were added into poly(L-lactic-co-glycolic acid) with monomer molar ratios of 85/15 (PLLCA85/15) simultaneously to improve its degree of crystallinity.Then the composite samples were isothermal annealed at 130℃ for 40min.The mechanical properties were tested,and the degree of crystallinity was investigated by XRD.The results shown that the crystallinity and tensile strength of the composites were significantly improved.The in vitro degradation properties were studied by investigating the mass loss of the samples and the pH of the degradation solution.The morphology of the degraded samples was observed by SEM.The results indicated that the degradation rate of the composite samples was slower than that of PLLGA85/15,and the degradation rate was faster after annealing.
[1] Gentile P,Chiono V,Carmagnola I,et al.An overview of poly(lactic-co-glycolic) acid (PLGA)-based biomaterials for bone tissue engineering[J].International Journal of Molecular Sciences.2014,15(3):3640-3659.
[2] Ansary R H,Awang M B,Rahman M M.Biodegradable poly(D,L-lactic-co-glycolic acid)-based micro/nanoparticles for sustained release of protein drugs-a review[J].Tropical Journal of Pharmaceutical Research,2014,13(7):1179-1190.
[3] Sreemanti D,Anisur Rahman K B.PLGA-loaded nanomedicines in melanoma treatment:future prospect for efficient drug delivery[J].Indian Journal of Medical Research,2016,144(2):181-193.
[4] Duan B,Wu L L,Yuan X Y,et al.Hybrid nanofibrous membranes of PLGA/chitosan fabricated via an electrospinning array[J].Journal of Biomedical Materials Research Part A,2007,83(3):868-878.
[5] 张广明.生物可降解聚乳酸己内酯无规共聚物输尿管支架管的制备及实验研究[D].成都:四川大学,2006.
[6] 祁金,熊成东,张丽芳.不同含量的NBG对NBG/PLGA复合材料等温结晶、形貌和力学性能的影响[J].西北师范大学学报(自然科学版),2016,52(6):70-77.
[7] Zhao N,Ma Z G,Li Q,et al.Effect of nucleation of tricalcium phosphate and isothermal annealing on the crystallization of poly(l-lactide-co-glycolide)[J].Journal of Polymers and the Environment,2013,21:259-265.
[8] 赵娜,张田瑶,陈和春,等.成核剂TCP对PLLGA85/15结晶度、力学性能和降解性能的影响[J].高分子材料科学与工程,2018,34(5):91-98.
[9] Li H B,Huneault M A.Effect of nucleation and plasticization on the crystallization of poly(lactic acid)[J].Polymer,2007,23:6855-6866.
[10] 令艳,张秀芹,张银芳,等.不同分子量的聚氧化乙烯对聚乳酸结晶和力学性能的影响研究[J].化工新型材料,2015,43(12):111-114.
[11] 张涵,孙志强,庞烜,等.聚乳酸/聚己内酯/聚(ε-己内酯-L-丙交酯)共聚物三元共混体系的结构与性能[J].应用化学,2016,33(9):1026-1032.
[12] 杨博,李琦,李晓露,等.右旋聚乳酸-己内酯无规共聚物对左旋聚乳酸/聚己内酯共混物的结构调控和性能[J].高分子材料科学与工程,2019,35(4):79-86.
[13] 富学宇,王利霞,赵幸一,等.聚己内酯对聚乳酸熔融结晶的影响[J].塑料工业,2020,48(5):141-144.
[14] 肖薇,陈卫星,罗春燕,等.聚己内酯对左旋聚乳酸结晶行为的影响[J].高分子材料科学与工程,2019,35(6):45-53.
[15] 桑青青,吕瑶,李赫宇,等.静电纺制备负载环丙沙星聚乳酸己内酯纳米纤维膜[J].化工新型材料,2017,45(12):176-179.
[16] 朱爱臣,王勤,王传栋,等.L-丙交酯/乙交酯/ε-己内酯共聚物在人工肠液中的降解[J].复合材料学报,2013(S1):142-146.
[17] 袁泉,徐娟娟,刘璐,等.骨支架复合材料不饱和聚磷酸酯-β-磷酸钙的体外降解行为研究[J].化学与生物工程,2015(5):14-19.
[18] 林飞.电纺聚乳酸/磷酸钙/胶原修复大鼠坐骨神经缺损的研究[D].武汉:武汉理工大学,2018.
[19] 刘士琦,袁明伟,王勃,等.聚(ε-己内酯-丙交酯)改性聚乳酸薄膜的制备及其性能研究[J].黑龙江科学,2016(16):1-3.
[20] Zhao N,Xiong Z C,Yang D J,et al.Enhanced degradation of poly(L-lactide) containing arginine,tryptophan and lysine[J].Polymer Composites,2009(30):1771-1778.
基金资助
湖北省自然科学基金项目面上项目(2011CDC064);石家庄市科学技术研究与发展计划自筹经费项目(201070881);石家庄学院科研启动基金资助项目(21BS003);石家庄市技术创新中心建设专项(198070107A);湖北理工学院校级科学研究项目(10yjz01R)