形状记忆聚己内酯基聚氨酯输尿管支架管的制备及性能
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摘要
本研究致力于制备一种具有形状记忆效应的聚己内酯基聚氨酯输尿管支架管。选用分子量为2000的聚己内酯二元醇(PCL-diol)为软段,异佛尔酮二异氰酸酯(IPDI)为硬段,1,4-丁二醇(BDO)为扩链剂,制备了不同软-硬段比例的聚氨酯;并进一步采用熔融挤出法制备双J型聚氨酯支架管。通过各种实验手段研究了聚己内酯基聚氨酯(PCLUs)的结构,测试分析了PCLUs支架管的相转变温度;通过拉伸及形状记忆测试研究了支架管的力学性能和形状记忆性;通过体外模拟降解实验进一步分析了支架管的降解性。随着硬段比例的增加,PCLUs力学强度大幅提高;熔融温度(T_m)由50.4℃降为37.1℃,更接近于人体温度;其形状固定率(R_f)和形状回复率(R_r)均达到了87%以上;相比于临床用不可降解输尿管支架管,本研究所制备的支架管(PCLU4)在前6周基本无降解,至30周时降解率可达90%。
A kind of poly(ε-caprolactone)-based polyurethane with PCL-diol as the soft segment and IPDI as the hard segment was prepared.Based on the above,a double-J ureteral stents was fixed up by melt extrusion.The chemical structure and crystallinity of the PCLUs were characterized,and the shape memory behavior and degradation rate were tested using bending test and in vitro degradation experiments.The results showed that the melting point of optimum PCLU4 can decrease to 37.1℃,and is closed to the human body temperature.Both the shape fixation ratio(R_f) and shape recovery ratio(R_r) can be up to 87%.In addition,the degradation rate at first 6 weeks was nearly zero,and it was up to 90%at the 30 th week.
A kind of poly(ε-caprolactone)-based polyurethane with PCL-diol as the soft segment and IPDI as the hard segment was prepared.Based on the above,a double-J ureteral stents was fixed up by melt extrusion.The chemical structure and crystallinity of the PCLUs were characterized,and the shape memory behavior and degradation rate were tested using bending test and in vitro degradation experiments.The results showed that the melting point of optimum PCLU4 can decrease to 37.1℃,and is closed to the human body temperature.Both the shape fixation ratio(R_f) and shape recovery ratio(R_r) can be up to 87%.In addition,the degradation rate at first 6 weeks was nearly zero,and it was up to 90%at the 30 th week.
引文
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[4]詹红彬,陈红.聚氨酯表面性能对其生物相容性的影响[J].材料科学与工程学报,2007,25(4):640~643.
[5]Benjamin Qi Yu Chan,Sing Shy Liow,Xian Jun Loh.OrganicInorganic Shape Memory Thermoplastic Polyurethane Based on Polycaprolactone and Polydimethylsiloxane[J].Royal Society of Chemistry Advances,2016,6(41):34946~34954.
[6]Jae Heung Yang,Byoung Chul Chun,Yong Chan Chung,et al.Comparison of Thermal/Mechanical Properties and Shape Memory Effect of Polyurethane Block-Copolymers with Planar or Bent Shape of Hard Segment[J].Polymer,2003,44(11):3251~3258.
[7]Andreas Lendlein,Robert Langer.Biodegradable Elastic Shape-Memory Polymers for Potential Biomedical Applications[J].Science,2002,296(5573):1673~1676.
[8]Xiao Shan Fan,Beng Hoon Tan,Zi Biao Li,et al.Control of PLA Stereoisomers-based Polyurethane Elastomers as Highly Efficient Shape Memory Materials[J].Sustainable Chemistry and Engineering,2017,5(1):1217~1227.
[9]Xi Feng Yang,Lin Wang,Wen Xi Wang,et al.Triple Shape Memory Effect of Star-Shaped Polyurethan[J].Applied Materials and Interfaces,2014,6(9):6545-6554.
[10]张玉芬,姜雪,武荣兰,等.改性多壁碳纳米管/聚氨酯形状记忆复合材料的制备及性能[J].材料科学与工程学报,2016,34(5):784~788.
[11]张晓华,曹亚.交联对透明聚氨酯弹性体结构与性能的影响[J].高分子材料科学与工程,2002,18(6):122~125.
[12]蓝承东.形状记忆聚氨酯的制备及性能研究[D].广州:广东工业大学,2015.
[13]张帆.形状记忆环氧树脂的制备及其复合材料性能研究[D].哈尔滨:哈尔滨工业大学,2009.
[14]Jerome A.Henry,Marc Simonet,Abhay Pandit,et al.Characterization of A Slowly Degrading Biodegradable Polyester-Urethane for Tissue Engineering Scaffolds[J].Journal of Biomedical Materials Research Part A,2007,82(3):669~679.
[15]李杰妹,黄瑞,等.傅里叶变换红外光谱技术在聚氨酯行业中的应用进展[J].化学推进剂与高分子材料,2008,6(6):30~35.
[16]石莹.细乳液体系中异氰酸酯加聚/界面水解反应的实验与模型研究[D].杭州:浙江大学,2009.
[17]Khalid Mahmood Zia,Mehdi Barikani,Mohammad Zuber,et al.Molecular Engineering of Chitin Based Polyurethane Elastomers[J].Carbohydrate Polymers,2008,74(2):149~158.
[18]黄美娜.可预防骨不连的骨修复用新型形状记忆聚氨酯-脲的研究[D].重庆:重庆大学,2010.
[19]陈国梁.PCL基和PCL/PEG基形状记忆聚氨酯的合成及结构和性能的研究[D].上海:东华大学,2008.