本文主要研究内容
作者张娜（2019）在《可生物降解聚醚酯/聚酯型聚氨酯的制备及形状记忆性能的研究》一文中研究指出：由于形状记忆聚合物(SMPs)的不可降解性和较低的生物相容性,使其在医用植入材料的应用中受到一定限制。可生物降解形状记忆聚氨酯(SMPUs)具有回复应变高、密度低和加工简单等优点,已被提出应用于多种医疗器械。本论文主要通过设计聚氨酯的组分、控制材料的性能、改变形变的临界条件来提高在医用方面的可行性。主要分为三部分:I.形状记忆聚醚酯型聚氨酯(SMPEEU):以聚乙二醇(PEG)为引发剂、ε-已内酯(ε-CL)为单体开环聚合制得三嵌段预聚物聚已内酯-聚乙二醇-聚己内酯(PECL),通过具有有序链段的脂肪族二异氰酸酯(HBH)对预聚物直接扩链,得到PEG含量不同的具有有序硬段的SMPEEU。通过~1H NMR、FT-IR和GPC对PECL和SMPEEU的化学结构进行了表征,研究了PEG含量对材料的热性能、结晶性、力学性能、亲水性和体外降解性等理化性质的影响。结果表明,PEG的引入会降低材料的玻璃化转变温度(T_g)和结晶度。随着PEG含量由9.25 wt%增加到47.5 wt%,伸长率由483%增加到956%,拉伸强度由23.1 MPa减少到9.0 MPa。体外水解降解研究表明,SMPEEU膜破碎时间为4-12周,降解速率随PEG含量的增加而增加。采用“折叠-展开形状记忆测试”方法对形状记忆性能进行评价,PEG含量为23.4 wt%的SMPEEU-III薄膜在体温下的形变回复率为99.8%,形变回复时间为3.9 s,具有良好的形状记忆性能,经过4次折叠-展开的循环后,薄膜仍能够快速回复到初始形状。细胞毒性试验表明其体外细胞相容性良好。SMPEEU不仅具有良好的力学性能、可生物降解性、降解产物无毒和良好的细胞相容性,而且在体温下具有优异的形状回复性能,在生物医用器械材料中具有很高的应用潜力。II.形状记忆壳寡糖改性聚酯型聚氨酯(SMCPU):先以PCL和HBH为原料反应得预聚物,然后通过壳寡糖(COS)扩链,两步法制备出一类新型COS含量不同的SMCPU。研究了COS含量对材料的理化性质的影响。随着COS含量增加,拉伸强度、初始模量、表面亲水性均增大,断裂伸长率和溶胀率均减小;体外降解测试表明降解速率随COS含量增多而增大,说明可以通过调节COS的用量来调节其降解速率;“折叠-展开形状记忆测试”表明SMPCU在体温下具有良好的形状记忆性能,且随COS含量的增加(交联度的增加),形变固定率和形变回复率升高,形变回复时间减少,经过10次折叠-展开的周期后,薄膜仍能够快速回复到初始形状。另外,通过蛋白质吸附和血小板黏附研究了膜材料表面的血液相容性,结果表明COS的引入大大提升了材料抗蛋白质吸附和血小板黏附的能力,表现出良好的血液相容性。优异的力学性能、可控的降解速率、良好的血液相容性和形状记忆性能表明SMPCU在医学领域具有更广的应用范围,也为新型SMPUs材料的制备提供新的研究思路。该材料上仍含有很多活泼的羟基和未反应的胺基,可作为改性材料进一步修饰,拓宽其在生物医用材料领域的应用。III.pH敏感形状记忆聚醚酯型聚氨酯(SMPEEU-Py):首先以3-巯基-1,2-丙二醇和4-乙烯基吡啶为原料,通过迈克尔加成制备了端二羟基吡啶化合物(PyDH)。然后,以二苯基甲烷二异氰酸酯对PECL和PyDH的混合物进行扩链制备了一系列的侧链含有吡啶基团的pH敏感SMPEEU-Py。通过~1H NMR、FT-IR和GPC对PyDH和SMPEEU-Py的化学结构进行了表征,研究了PyDH含量对材料的热性能、结晶性、吸水性能、力学性能和体外降解性能的影响。不同pH值下吸水率测试表明,SMPEEU-Py具有较好的pH敏感性,PyDH含量越高,pH敏感性越好。不同pH值下体外水解降解结果表明,碱性和酸性环境下的降解速度明显高于中性环境。pH敏感形状记忆性能表明,PyDH含量为21.19 wt%的膜材料(SMPEEU-Py-1/8)在pH=1.5的环境下,形变回复率为91.7%,但形变回复时间约为25 min。SMPEEU-Py不仅具有良好的理化性能,而且具有一定的pH敏感形状记忆性能,在pH敏感药物缓释材料中具有很高的应用潜力。本论文对直链型、轻度交联型、pH敏感型的三种SMPUs材料进行了制备和研究,该研究可以为新型医用多功能性SMPUs提供新的设计和制备思路,拓宽聚氨酯材料在医学上的应用领域。
Abstract
you yu xing zhuang ji yi ju ge wu (SMPs)de bu ke jiang jie xing he jiao di de sheng wu xiang rong xing ,shi ji zai yi yong zhi ru cai liao de ying yong zhong shou dao yi ding xian zhi 。ke sheng wu jiang jie xing zhuang ji yi ju an zhi (SMPUs)ju you hui fu ying bian gao 、mi du di he jia gong jian chan deng you dian ,yi bei di chu ying yong yu duo chong yi liao qi xie 。ben lun wen zhu yao tong guo she ji ju an zhi de zu fen 、kong zhi cai liao de xing neng 、gai bian xing bian de lin jie tiao jian lai di gao zai yi yong fang mian de ke hang xing 。zhu yao fen wei san bu fen :I.xing zhuang ji yi ju mi zhi xing ju an zhi (SMPEEU):yi ju yi er chun (PEG)wei yin fa ji 、ε-yi nei zhi (ε-CL)wei chan ti kai huan ju ge zhi de san qian duan yu ju wu ju yi nei zhi -ju yi er chun -ju ji nei zhi (PECL),tong guo ju you you xu lian duan de zhi fang zu er yi qing suan zhi (HBH)dui yu ju wu zhi jie kuo lian ,de dao PEGhan liang bu tong de ju you you xu ying duan de SMPEEU。tong guo ~1H NMR、FT-IRhe GPCdui PECLhe SMPEEUde hua xue jie gou jin hang le biao zheng ,yan jiu le PEGhan liang dui cai liao de re xing neng 、jie jing xing 、li xue xing neng 、qin shui xing he ti wai jiang jie xing deng li hua xing zhi de ying xiang 。jie guo biao ming ,PEGde yin ru hui jiang di cai liao de bo li hua zhuai bian wen du (T_g)he jie jing du 。sui zhao PEGhan liang you 9.25 wt%zeng jia dao 47.5 wt%,shen chang lv you 483%zeng jia dao 956%,la shen jiang du you 23.1 MPajian shao dao 9.0 MPa。ti wai shui jie jiang jie yan jiu biao ming ,SMPEEUmo po sui shi jian wei 4-12zhou ,jiang jie su lv sui PEGhan liang de zeng jia er zeng jia 。cai yong “she die -zhan kai xing zhuang ji yi ce shi ”fang fa dui xing zhuang ji yi xing neng jin hang ping jia ,PEGhan liang wei 23.4 wt%de SMPEEU-IIIbao mo zai ti wen xia de xing bian hui fu lv wei 99.8%,xing bian hui fu shi jian wei 3.9 s,ju you liang hao de xing zhuang ji yi xing neng ,jing guo 4ci she die -zhan kai de xun huan hou ,bao mo reng neng gou kuai su hui fu dao chu shi xing zhuang 。xi bao du xing shi yan biao ming ji ti wai xi bao xiang rong xing liang hao 。SMPEEUbu jin ju you liang hao de li xue xing neng 、ke sheng wu jiang jie xing 、jiang jie chan wu mo du he liang hao de xi bao xiang rong xing ,er ju zai ti wen xia ju you you yi de xing zhuang hui fu xing neng ,zai sheng wu yi yong qi xie cai liao zhong ju you hen gao de ying yong qian li 。II.xing zhuang ji yi ke gua tang gai xing ju zhi xing ju an zhi (SMCPU):xian yi PCLhe HBHwei yuan liao fan ying de yu ju wu ,ran hou tong guo ke gua tang (COS)kuo lian ,liang bu fa zhi bei chu yi lei xin xing COShan liang bu tong de SMCPU。yan jiu le COShan liang dui cai liao de li hua xing zhi de ying xiang 。sui zhao COShan liang zeng jia ,la shen jiang du 、chu shi mo liang 、biao mian qin shui xing jun zeng da ,duan lie shen chang lv he rong zhang lv jun jian xiao ;ti wai jiang jie ce shi biao ming jiang jie su lv sui COShan liang zeng duo er zeng da ,shui ming ke yi tong guo diao jie COSde yong liang lai diao jie ji jiang jie su lv ;“she die -zhan kai xing zhuang ji yi ce shi ”biao ming SMPCUzai ti wen xia ju you liang hao de xing zhuang ji yi xing neng ,ju sui COShan liang de zeng jia (jiao lian du de zeng jia ),xing bian gu ding lv he xing bian hui fu lv sheng gao ,xing bian hui fu shi jian jian shao ,jing guo 10ci she die -zhan kai de zhou ji hou ,bao mo reng neng gou kuai su hui fu dao chu shi xing zhuang 。ling wai ,tong guo dan bai zhi xi fu he xie xiao ban nian fu yan jiu le mo cai liao biao mian de xie ye xiang rong xing ,jie guo biao ming COSde yin ru da da di sheng le cai liao kang dan bai zhi xi fu he xie xiao ban nian fu de neng li ,biao xian chu liang hao de xie ye xiang rong xing 。you yi de li xue xing neng 、ke kong de jiang jie su lv 、liang hao de xie ye xiang rong xing he xing zhuang ji yi xing neng biao ming SMPCUzai yi xue ling yu ju you geng an de ying yong fan wei ,ye wei xin xing SMPUscai liao de zhi bei di gong xin de yan jiu sai lu 。gai cai liao shang reng han you hen duo huo po de qiang ji he wei fan ying de an ji ,ke zuo wei gai xing cai liao jin yi bu xiu shi ,ta kuan ji zai sheng wu yi yong cai liao ling yu de ying yong 。III.pHmin gan xing zhuang ji yi ju mi zhi xing ju an zhi (SMPEEU-Py):shou xian yi 3-qiu ji -1,2-bing er chun he 4-yi xi ji bi ding wei yuan liao ,tong guo mai ke er jia cheng zhi bei le duan er qiang ji bi ding hua ge wu (PyDH)。ran hou ,yi er ben ji jia wan er yi qing suan zhi dui PECLhe PyDHde hun ge wu jin hang kuo lian zhi bei le yi ji lie de ce lian han you bi ding ji tuan de pHmin gan SMPEEU-Py。tong guo ~1H NMR、FT-IRhe GPCdui PyDHhe SMPEEU-Pyde hua xue jie gou jin hang le biao zheng ,yan jiu le PyDHhan liang dui cai liao de re xing neng 、jie jing xing 、xi shui xing neng 、li xue xing neng he ti wai jiang jie xing neng de ying xiang 。bu tong pHzhi xia xi shui lv ce shi biao ming ,SMPEEU-Pyju you jiao hao de pHmin gan xing ,PyDHhan liang yue gao ,pHmin gan xing yue hao 。bu tong pHzhi xia ti wai shui jie jiang jie jie guo biao ming ,jian xing he suan xing huan jing xia de jiang jie su du ming xian gao yu zhong xing huan jing 。pHmin gan xing zhuang ji yi xing neng biao ming ,PyDHhan liang wei 21.19 wt%de mo cai liao (SMPEEU-Py-1/8)zai pH=1.5de huan jing xia ,xing bian hui fu lv wei 91.7%,dan xing bian hui fu shi jian yao wei 25 min。SMPEEU-Pybu jin ju you liang hao de li hua xing neng ,er ju ju you yi ding de pHmin gan xing zhuang ji yi xing neng ,zai pHmin gan yao wu huan shi cai liao zhong ju you hen gao de ying yong qian li 。ben lun wen dui zhi lian xing 、qing du jiao lian xing 、pHmin gan xing de san chong SMPUscai liao jin hang le zhi bei he yan jiu ,gai yan jiu ke yi wei xin xing yi yong duo gong neng xing SMPUsdi gong xin de she ji he zhi bei sai lu ,ta kuan ju an zhi cai liao zai yi xue shang de ying yong ling yu 。
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论文详细介绍
论文作者分别是来自山东师范大学的张娜，发表于刊物山东师范大学2019-07-06论文，是一篇关于医用聚氨酯论文,聚已内酯论文,可生物降解论文,形状记忆性能论文,敏感论文,山东师范大学2019-07-06论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自山东师范大学2019-07-06论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：医用聚氨酯论文; 聚已内酯论文; 可生物降解论文; 形状记忆性能论文; 敏感论文; 山东师范大学2019-07-06论文;