CN112341772A - 一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法 - Google Patents
一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法 Download PDFInfo
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Abstract
本发明公开了抗菌剂制备技术领域的一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,该载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法步骤如下:步骤一:纳米银的制备;步骤二:有机膦酸的制备;步骤三:有机膦酸锆的制备;步骤四:载银有机膦酸锆的制备;步骤五:聚乳酸、载银有机膦酸锆复合材料的制备:将聚乳酸和载银有机膦酸锆复合材料通过共混法制,本方法将合成的协同抗菌剂添加到聚乳酸中制备出具有抗菌功能的高分子复合材料。项目产品具有抗菌性能强、无毒害、力学性能优异等优点,可以应用于各个领域,市场前景十分广阔。
Description
技术领域
本发明公开了一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,具体为抗菌剂制备技术领域。
背景技术
抗菌塑料是具备抑菌和杀菌性能的新型材料,能保持材料自身的清洁,能够减少因使用塑料制品而发生的交叉感染。一般抗菌塑料的抗菌性能是由其所添加的抗菌剂所赋予的,抗菌剂是指一些微生物高度敏感、少量添加到材料中即可赋予材料抗微生物性能的化学物质,也就是说抗菌剂是能使细菌、真菌等微生物不能发育或能抑制微生物生长的物质。抗菌剂可分为无机、有机、天然和高分子抗菌剂等四类。无机抗菌剂是利用银、铜、锌、钛等金属及其离子的杀菌或抑菌能力制得的一类抗菌剂。无机抗菌剂分为两大类,一类是以无机化合物中含有抗菌性金属离子的试剂为主流,如银、铜、锌等金属离子,抗菌性最强的是银离子,此类抗菌剂根据其载体类型又可分为沸石抗菌剂、磷酸复盐抗菌剂、硅胶抗菌剂、膨润土抗菌剂、可溶性玻璃抗菌剂等。其中银系抗菌剂存在易变色、制造困难、在塑料中使用工艺复杂等难题,而且银的价格昂贵,影响制品的最终定价,且过量的银对哺乳动物细胞存在毒性;第二类是以二氧化钛为代表的具有光催化型抗菌剂,此类抗菌剂的特点是耐热性比一般无机抗菌剂高,但是必须有紫外线照射和氧气或水存在才能起杀菌作用。有机抗菌剂主要包括季胺盐类、双胍类、醇类等抗菌剂。有机抗菌剂和无机抗菌剂抑制细菌的作用不同,有机抗菌剂的主要作用机理是通过和微生物细胞膜表面阴离子结合逐渐进入细胞,或与细胞表面的巯基等基团反应,破坏蛋白质和细胞膜的合成系统,抑制微生物的繁殖。一种有机抗菌剂对微生物的毒杀和抑制性能一方面取决于该抗菌化合物所带的能够发挥毒性的基团;另一方面也与该化合物的取代基特性(如亲油性和亲水性等)、分子中各原子及基团的排列、空间排布、分子反应性能等密切相关。有机抗菌剂品种繁多,各种微生物的菌体间也各不一样,因此其作用机理随相互种类而异。但有机类抗菌剂普遍存在的问题是:耐热性差,易在溶剂环境中析出、易产生耐药性、分解产物经常有毒。天然抗菌剂主要有壳聚糖(chitosan)、山梨酸、黄姜根醇、孟宗竹提取物和日伯醇等,大都是从动植物中提炼精制的,具有耐候性优良、毒性低、使用安全等优点,其主要缺点是耐热性较差,药效持续时间短等,且加工困难,耐热性差。在研究有机抗菌剂和具有抗菌性能的天然高分子的抗菌机理后,人们根据有机抗菌剂和天然高分子抗菌剂的抗菌机理进行分子设计,将有机抗菌剂和天然抗菌剂的特点结合起来合成具有抗菌性能的高分子,通过带抗菌活性官能团的单体聚合或以接枝的方式在高分子链上引入抗菌官能团而获得抗菌性。虽然高分子类抗菌剂热稳定性好且抗菌效果显著,但其存在生产成本高、难以工业化应用的难点。近年来,有机-无机协同抗菌剂成为了研究的热点。有机-无机协同抗菌剂结合了有机和无机抗菌剂的优点,兼有有机系的强敛性、持续性与无机系的安全性、耐热性,而且价格低廉、用量少、抗菌性能高、稳定性好。
发明内容
本发明的目的在于提供一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,以解决上述背景技术中提出的问题。
为实现上述目的,本发明提供如下技术方案:一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,该载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法步骤如下:
步骤一:纳米银的制备:将硝酸银溶解到乙醇中,以聚乙烯吡咯烷酮为保护剂,以抗坏血酸为还原剂将硝酸银还原制得纳米银;
步骤二:有机膦酸的制备:通过曼尼希反应合成有机膦酸;
步骤三:有机膦酸锆的制备:将ZrOCl2·8H2O溶于蒸馏水中,加热搅拌并加入有机膦酸溶液,过滤后冷冻干燥得到有机膦酸锆;
步骤四:载银有机膦酸锆的制备:将一定量有机膦酸锆分散到去离子水中,搅拌加入硝酸银在,然后将产物过滤、去离子水洗涤,冷冻干燥得到载银有机膦酸锆;
步骤五:聚乳酸、载银有机膦酸锆复合材料的制备:将聚乳酸和载银有机膦酸锆复合材料通过共混法制备。
优选的,所述步骤三有机膦酸锆采用银-甲基--N,N-二甲基膦酸锆、银-乙基--N,N-二甲基膦酸锆、银-丙基--N,N-二甲基膦酸锆、银-丁基--N,N-二甲基膦酸锆、银-己基--N,N-二甲基膦酸锆或银-辛基--N,N-二甲基膦酸锆的一种或多种。
优选的,所述步骤五中聚乳酸、载银有机膦酸锆复合材料中聚乳酸的含量在0至2wt%之间。
优选的,所述步骤三中有机膦酸锆的制备温度为90摄氏度。
优选的,所述步骤四中载银有机膦酸锆的制备温度为60摄氏度。
与现有技术相比,本发明的有益效果是:本方法选用片层膦酸锆为母体,在膦酸锆表面修饰具有抗菌功能的有机官能团生产有机膦酸锆,使母体具备一定的抗菌效果。有机官能团是通过化学键的形式与母体相连的,从而解决了有机抗菌剂易溶出的问题。再以有机膦酸锆为载体,载入纳米银,纳米银在片层之间受到约束不易团聚。随着纳米银的载入,有机抗菌剂的耐药性问题被解决。此协同抗菌剂具备了有机抗菌剂和无机抗菌剂的优点,同时克服了单一的有机抗菌剂和无机抗菌剂的缺点,使该抗菌剂更有发展潜力。最后,将合成的协同抗菌剂添加到聚乳酸中制备出具有抗菌功能的高分子复合材料。项目产品具有抗菌性能强、无毒害、力学性能优异等优点,可以应用于工业、农业、林业、水利、建筑业、纺织业、装饰材料业、食品包装业、日常环保塑料制品、文体用具、医疗卫生等各个领域,市场前景十分广阔。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,该载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法步骤如下:
步骤一:纳米银的制备:将一定量的硝酸银溶解到乙醇中,以聚乙烯吡咯烷酮为保护剂,以抗坏血酸为还原剂将硝酸银还原制得纳米银,将200mg硝酸银和0.5g聚乙烯吡咯烷酮溶解到40ml乙醇中,室温下强烈的搅拌,然后向其中逐滴滴加10mL的含有0.1mol·L-1抗坏血酸的乙醇溶液,得到银纳米粒子的胶体溶液;
步骤二:有机膦酸的制备:通过曼尼希反应合成有机膦酸,取0.2mol的H3PO3溶于水,滴加0.1mol的胺到250mL的三颈烧瓶中,在磁力搅拌下向其中缓慢滴加10mL的浓盐酸,然后加热升温,当温度升到110摄氏度时向三颈瓶中缓慢滴加100%过量的37%的甲醛溶液30mL,滴加时间在1-2h之间,滴加完毕在110摄氏度下回流3h;
步骤三:有机膦酸锆的制备:将ZrOCl2·8H2O(3.23g,0.01mol)溶于蒸馏水中,加热到90摄氏度,在强烈搅拌的条件下逐滴加入100mL含有0.01mol的有机膦酸溶液,在90摄氏度温度下搅拌反应120h得到产品,将得到的产物过滤,用去离子水洗涤直到pH=5~6,冷冻干燥得到产品;
步骤四:载银有机膦酸锆的制备:将一定量的有机膦酸分散到去离子水中得到10wt%的悬浊液,在搅拌条件下加入一定量的硝酸银在60摄氏度下反应3h,然后将产物过滤、去离子水洗涤,冷冻干燥得到产品;
步骤五:聚乳酸、载银有机膦酸锆复合材料的制备:将含量为0wt%的聚乳酸和载银有机膦酸锆复合材料通过共混法制备,将流变仪温度调至190摄氏度,转速调至60rpm,加料密炼10min,将所得混合物放入磨具中在190摄氏度下预热4min,然后加压到10MPa,6min后冷却。
在固体培养基表面滴加50μL细菌浓度为3×105cfumL-1金黄色葡萄球菌和大肠杆菌,用涂布环涂抹均匀,加上尺寸为1×1cm的聚乳酸、载银有机膦酸锆复合材料,在37℃下培养24小时,取出后用约50μL液体培养基冲洗,将每个冲洗液转移到不同的固体培养基上,在37℃下培养48小时,对大肠杆菌的抗菌率>80%,对金黄色葡萄球菌的抗菌率>82%。
实施例2
一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,该载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法步骤如下:
步骤一:纳米银的制备:将一定量的硝酸银溶解到乙醇中,以聚乙烯吡咯烷酮为保护剂,以抗坏血酸为还原剂将硝酸银还原制得纳米银,将200mg硝酸银和0.5g聚乙烯吡咯烷酮溶解到40ml乙醇中,室温下强烈的搅拌,然后向其中逐滴滴加10mL的含有0.1mol·L-1抗坏血酸的乙醇溶液,得到银纳米粒子的胶体溶液;
步骤二:有机膦酸的制备:通过曼尼希反应合成有机膦酸,取0.2mol的H3PO3溶于水,滴加0.1mol的胺到250mL的三颈烧瓶中,在磁力搅拌下向其中缓慢滴加10mL的浓盐酸,然后加热升温,当温度升到110摄氏度时向三颈瓶中缓慢滴加100%过量的37%的甲醛溶液30mL,滴加时间在1-2h之间,滴加完毕在110摄氏度下回流3h;
步骤三:有机膦酸锆的制备:将ZrOCl2·8H2O(3.23g,0.01mol)溶于蒸馏水中,加热到90摄氏度,在强烈搅拌的条件下逐滴加入100mL含有0.01mol的有机膦酸溶液,在90摄氏度温度下搅拌反应120h得到产品,将得到的产物过滤,用去离子水洗涤直到pH=5~6,冷冻干燥得到产品;
步骤四:载银有机膦酸锆的制备:将一定量的有机膦酸分散到去离子水中得到10wt%的悬浊液,在搅拌条件下加入一定量的硝酸银在60摄氏度下反应3h,然后将产物过滤、去离子水洗涤,冷冻干燥得到产品;
步骤五:聚乳酸、载银有机膦酸锆复合材料的制备:将含量为1wt%的聚乳酸和载银有机膦酸锆复合材料通过共混法制备,将流变仪温度调至190摄氏度,转速调至60rpm,加料密炼10min,将所得混合物放入磨具中在190摄氏度下预热4min,然后加压到10MPa,6min后冷却。
在固体培养基表面滴加50μL细菌浓度为3×105cfumL-1金黄色葡萄球菌和大肠杆菌,用涂布环涂抹均匀,加上尺寸为1×1cm的聚乳酸、载银有机膦酸锆复合材料,在37℃下培养24小时,取出后用约50μL液体培养基冲洗,将每个冲洗液转移到不同的固体培养基上,在37℃下培养48小时,对大肠杆菌的抗菌率>90%,对金黄色葡萄球菌的抗菌率>93%。
实施例3
一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,该载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法步骤如下:
步骤一:纳米银的制备:将一定量的硝酸银溶解到乙醇中,以聚乙烯吡咯烷酮为保护剂,以抗坏血酸为还原剂将硝酸银还原制得纳米银,将200mg硝酸银和0.5g聚乙烯吡咯烷酮溶解到40ml乙醇中,室温下强烈的搅拌,然后向其中逐滴滴加10mL的含有0.1mol·L-1抗坏血酸的乙醇溶液,得到银纳米粒子的胶体溶液;
步骤二:有机膦酸的制备:通过曼尼希反应合成有机膦酸,取0.2mol的H3PO3溶于水,滴加0.1mol的胺到250mL的三颈烧瓶中,在磁力搅拌下向其中缓慢滴加10mL的浓盐酸,然后加热升温,当温度升到110摄氏度时向三颈瓶中缓慢滴加100%过量的37%的甲醛溶液30mL,滴加时间在1-2h之间,滴加完毕在110摄氏度下回流3h;
步骤三:有机膦酸锆的制备:将ZrOCl2·8H2O(3.23g,0.01mol)溶于蒸馏水中,加热到90摄氏度,在强烈搅拌的条件下逐滴加入100mL含有0.01mol的有机膦酸溶液,在90摄氏度温度下搅拌反应120h得到产品,将得到的产物过滤,用去离子水洗涤直到pH=5~6,冷冻干燥得到产品;
步骤四:载银有机膦酸锆的制备:将一定量的有机膦酸分散到去离子水中得到10wt%的悬浊液,在搅拌条件下加入一定量的硝酸银在60摄氏度下反应3h,然后将产物过滤、去离子水洗涤,冷冻干燥得到产品;
步骤五:聚乳酸、载银有机膦酸锆复合材料的制备:将含量为2wt%的聚乳酸和载银有机膦酸锆复合材料通过共混法制备,将流变仪温度调至190摄氏度,转速调至60rpm,加料密炼10min,将所得混合物放入磨具中在190摄氏度下预热4min,然后加压到10MPa,6min后冷却。
在固体培养基表面滴加50μL细菌浓度为3×105cfumL-1金黄色葡萄球菌和大肠杆菌,用涂布环涂抹均匀,加上尺寸为1×1cm的聚乳酸、载银有机膦酸锆复合材料,在37℃下培养24小时,取出后用约50μL液体培养基冲洗,将每个冲洗液转移到不同的固体培养基上,在37℃下培养48小时,对大肠杆菌的抗菌率>95%,对金黄色葡萄球菌的抗菌率>98%。
虽然在上文中已经参考了一些实施例对本发明进行描述,然而在不脱离本发明的范围的情况下,可以对其进行各种改进并且可以用等效无替换其中的部件。尤其是,只要不存在结构冲突,本发明所披露的各个实施例中的各项特征均可通过任意方式相互结合起来使用,在本说明书中未对这些组合的情况进行穷举的描述仅仅是处于省略篇幅和节约资源的考虑。因此,本发明并不局限于文中公开的特定实施例,而且包括落入权利要求的范围内的所有技术方案。
Claims (5)
1.一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,其特征在于:该载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法步骤如下:
步骤一:纳米银的制备:将硝酸银溶解到乙醇中,以聚乙烯吡咯烷酮为保护剂,以抗坏血酸为还原剂将硝酸银还原制得纳米银;
步骤二:有机膦酸的制备:通过曼尼希反应合成有机膦酸;
步骤三:有机膦酸锆的制备:将ZrOCl2·8H2O溶于蒸馏水中,加热搅拌并加入有机膦酸溶液,过滤后冷冻干燥得到有机膦酸锆;
步骤四:载银有机膦酸锆的制备:将一定量有机膦酸锆分散到去离子水中,搅拌加入硝酸银在,然后将产物过滤、去离子水洗涤,冷冻干燥得到载银有机膦酸锆;
步骤五:聚乳酸、载银有机膦酸锆复合材料的制备:将聚乳酸和载银有机膦酸锆复合材料通过共混法制备。
2.根据权利要求1所述的一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,其特征在于:所述步骤三有机膦酸锆采用银-甲基--N,N-二甲基膦酸锆、银-乙基--N,N-二甲基膦酸锆、银-丙基--N,N-二甲基膦酸锆、银-丁基--N,N-二甲基膦酸锆、银-己基--N,N-二甲基膦酸锆或银-辛基--N,N-二甲基膦酸锆的一种或多种。
3.根据权利要求1所述的一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,其特征在于:所述步骤五中聚乳酸、载银有机膦酸锆复合材料中聚乳酸的含量在0至2wt%之间。
4.根据权利要求1所述的一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,其特征在于:所述步骤三中有机膦酸锆的制备温度为90摄氏度。
5.根据权利要求1所述的一种载银膦酸锆协同抗菌聚乳酸基生物降解材料的制备方法,其特征在于:所述步骤四中载银有机膦酸锆的制备温度为60摄氏度。
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