CN111328809B - 载季铵盐聚膦腈复合抗菌剂及其制备方法和应用 - Google Patents

载季铵盐聚膦腈复合抗菌剂及其制备方法和应用 Download PDF

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CN111328809B
CN111328809B CN202010111499.9A CN202010111499A CN111328809B CN 111328809 B CN111328809 B CN 111328809B CN 202010111499 A CN202010111499 A CN 202010111499A CN 111328809 B CN111328809 B CN 111328809B
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quaternary ammonium
ammonium salt
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polyethyleneimine
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谭绍早
邝伟聪
黄浪欢
张静娴
陈登洁
熊永强
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Jinan University
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Abstract

本发明涉及一种载季铵盐聚膦腈复合抗菌剂及其制备方法和应用。所述载季铵盐聚膦腈复合抗菌剂为200～300nm的实心微球和白色固体粉末，是以环三膦腈环交联聚乙烯亚胺微球为载体、季铵盐为活性组分，其中环三膦腈环交联聚乙烯亚胺微球含量为93.0～88.5wt.％、季铵盐含量为7.0～11.5wt.％。本发明的载季铵盐聚膦腈复合抗菌剂中活性组分季铵盐以共价键方式结合，故具有安全低毒和稳定性好的优点，可以制备成抗菌喷剂直接喷洒在材料及制品表面保持长效抗菌活性，也可以添加在塑料、橡胶、纤维、涂料、胶粘剂和纸张等材料及制品中获得长效抗菌功能。

Description

载季铵盐聚膦腈复合抗菌剂及其制备方法和应用
技术领域
本发明属于抗菌材料领域，具体涉及一种载季铵盐聚膦腈复合抗菌剂及其制备方法和应用。
背景技术
可溶性消毒剂的滥用，严重破坏了人类生存环境的微生物平衡，由此产生对人们身体健康造成极大威胁的有害微生物变种，如超级细菌等问题，故如何有效控制有害微生物感染将成为目前生态环境和抗菌领域的重要研究课题。专利号为ZL200810220350.3的中国专利公开了“抗菌高分子材料及其制备方法”，是通过将不同种类的季鏻盐插入粘土制备成复合抗菌剂，然后掺加在塑料、橡胶、合成纤维、涂料、胶粘剂和纸浆等聚合物中制备了抗菌高分子材料，虽然可以获得较好的抗菌效果，但存在季鏻盐由于溶出较快而导致无法长效抗菌的问题。专利号为ZL200910039119.9的中国专利公开了“铜-稀土复合抗菌剂及其制备方法和应用”，通过在合成磷酸锆钠和天然电气石为复合载体上负载铜离子和稀土离子，得到的复合抗菌剂含有可产生协同效应的铜离子、稀土离子和负离子三抗菌活性中心，显示抗菌谱广和抗菌效率高的特点，但负载的铜离子和稀土离子活性成分容易析出而影响其长效性。另外，上述两类无机载体类抗菌剂在有机材料中存在着难以分散的技术难题。
发明内容
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种载季铵盐聚膦腈复合抗菌剂，该材料的外观为棕黄色或浅黄色粉末，具有低毒性、良好的抗菌活性、优良的稳定性等优点。
本发明的另一目的在于提供一种载季铵盐聚膦腈复合抗菌剂的制备方法。
本发明的再一目的在于提供上述载季铵盐聚膦腈复合抗菌剂的应用。
本发明目的通过以下技术方案实现：
一种载季铵盐聚膦腈复合抗菌剂，是以环三膦腈环交联聚乙烯亚胺微球为载体、季铵盐为活性组分；所述载季铵盐聚膦腈复合抗菌剂中环三膦腈环交联聚乙烯亚胺微球含量为93.0～88.5wt.％，季铵盐含量为7.0～11.5wt.％。
进一步的，所述环三膦腈环交联聚乙烯亚胺微球结构为200～300nm的实心微球，外观为白色固体粉末；所述载季铵盐聚膦腈复合抗菌剂外观为棕黄色或浅黄色粉末。
聚膦腈具有可降解、结构可设计、生物相容性好及毒性低的优点，会因不同种类，数量和性质的基团的引入，而使得聚膦腈材料可同时具备无机材料和有机材料的优点，可以产生出数量极其丰富的衍生物，比传统聚合物具有更优异的特性，是一种理想的抗菌剂载体。
上述载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，包括以下步骤：
(1)在反应容器中先将一定量聚乙烯亚胺用乙腈或丙酮溶解，再添加一定量三乙胺并搅拌均匀，然后加入预先用一定量六氯环三磷腈与一定量乙腈或丙酮配成的溶液并封口，在适当温度下超声反应一段时间，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球白色固体粉末；
(2)在反应容器中将步骤(1)的白色固体粉末经过超声分散一段时间配制成无水乙醇悬浮液，再加入一定量环氧丙基十二烷基二甲基氯化铵，然后在适当温度下搅拌反应一段时间，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂。
优选的，步骤(1)所述聚乙烯亚胺为0.17～0.52质量份、三乙胺为2～6体积份、六氯环三磷腈为0.1～0.3质量份，步骤(2)所述环三膦腈环交联聚乙烯亚胺微球与环氧丙基十二烷基二甲基氯化铵质量比为50:16.7～150。
优选的，步骤(1)中溶解所述聚乙烯亚胺时，聚乙烯亚胺与乙腈或丙酮的质量体积比为0.17～0.52:80g/mL；溶解六氯环三磷腈时，六氯环三磷腈与乙腈或丙酮的质量体积比为0.1～0.3:80g/mL。
优选的，步骤(1)所述聚乙烯亚胺分子量Mw＝600，纯度为99％。
优选的，步骤(1)所述超声反应是指在45～60℃下超声反应8h以上，步骤(2)中所述超声分散时间为0.5h以上，步骤(2)中所述加热搅拌反应是指在60～70℃下搅拌反应12h以上。
一种载季铵盐聚膦腈复合抗菌剂的制备方法，包括以下步骤：
(1)在圆底烧瓶中先将0.17-0.52g聚乙烯亚胺(PEI)(重均分子量Mw 600，纯度99％)用80ml乙腈或丙酮溶解，再添加2-6ml三乙胺(TEA)并搅拌均匀，然后加入预先用0.1-0.3g六氯环三磷腈(HCCP)与20ml乙腈或丙酮配成的溶液并封口，在45～60℃下超声反应8h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球(PHP)白色固体粉末。
(2)在圆底烧瓶中将步骤(1)的PHP白色固体粉末经过超声分散0.5h以上配制成0.5mg/mL无水乙醇悬浮液100mL，再加入环氧丙基十二烷基二甲基氯化铵16.7-150mg，然后在60～70℃下搅拌反应12h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂(PHPD)棕黄色或浅黄色粉末。
本发明所提供的载季铵盐聚膦腈复合抗菌剂可用于在塑料、橡胶、纤维、涂料、胶粘剂和纸张中，提高抗菌性能。
与现有技术相比，本发明具有以下优点及有益效果：
1、本发明的聚膦腈共聚物载体兼具无机物的高稳定性和有机物的易分散性特点，并且很容易将抗菌活性成分负载上去。
2、本发明的载季铵盐聚膦腈复合抗菌剂中抗菌活性成分季铵盐以共价键方式结合，故具有安全低毒和稳定性好的优点。
3、本发明的载季铵盐聚膦腈复合抗菌剂既可以制备成抗菌喷剂直接喷洒在材料和制品表面保持长效抗菌活性，也可以添加在塑料、橡胶、纤维、涂料、胶粘剂和纸张等材料及制品中获得长效抗菌功能的材料及制品。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。本发明涉及的原料均可从市场上直接购买。对于未特别注明的工艺参数，可参照常规技术进行。
实施例使用的环氧丙基十二烷基二甲基氯化铵主要按照文献上的方法(Liu Y,Yang D,Li Y,et al.Synthesis and characterization of the epoxy-functionalizedquaternary ammonium chloride[J].Colloids and Surfaces A：Physicochemical andEngineering Aspects,2016,498:248-257.)制备，具体方法稍有改动：向装有滴液漏斗、温度计和回流冷凝管的三口烧瓶中加入10.67g十二烷基二甲基叔胺，当升温至60℃开始滴加23.31g环氧氯丙烷，并在此温度下滴加搅拌反应2h，然后依次经过减压蒸馏、丙酮重结晶、无水乙醚洗涤和冷冻干燥，得到环氧丙基十二烷基二甲基氯化铵(DDEAC)白色粉末。
实施例1
(1)在圆底烧瓶中先将0.34g聚乙烯亚胺(PEI)(重均分子量Mw 600，纯度99％)用80ml乙腈溶解，再添加4ml三乙胺(TEA)并搅拌均匀，然后加入预先用0.2g六氯环三磷腈(HCCP)与20ml乙腈配成的溶液并封口，在50℃下超声反应8h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球(PHP)白色固体粉末。
(2)在圆底烧瓶中将步骤(1)的PHP白色固体粉末经过超声分散0.5h以上配制成0.5mg/mL无水乙醇悬浮液100mL，再加入环氧丙基十二烷基二甲基氯化铵50mg，然后在65℃下搅拌反应12h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂(PHPD)棕黄色或浅黄色粉末，其载体两交联点间的平均分子量、季铵盐含量、平均粒径和抗菌活性见表1。
实施例2
(1)在圆底烧瓶中将0.17g聚乙烯亚胺(PEI)(重均分子量Mw 600，纯度99％)用80ml乙腈或丙酮溶解，再添加2ml三乙胺(TEA)并搅拌均匀，然后加入预先用0.1g六氯环三磷腈(HCCP)与20ml乙腈或丙酮配成的溶液并封口，在45℃下超声反应8h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球(PHP)白色固体粉末。
(2)在圆底烧瓶中将步骤(1)的PHP白色固体粉末经过超声分散0.5h以上配制成0.5mg/mL无水乙醇悬浮液100mL，再加入环氧丙基十二烷基二甲基氯化铵16.7mg，然后在60℃下搅拌反应12h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂(PHPD)棕黄色或浅黄色粉末，其载体两交联点间的平均分子量、季铵盐含量、平均粒径和抗菌活性见表1。
实施例3
(1)在圆底烧瓶中先将0.52g聚乙烯亚胺(PEI)(重均分子量Mw 600，纯度99％)用80ml乙腈或丙酮溶解，再添加6ml三乙胺(TEA)并搅拌均匀，然后加入预先用0.3g六氯环三磷腈(HCCP)与20ml乙腈或丙酮配成的溶液并封口，在60℃下超声反应8h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球(PHP)白色固体粉末。
(2)在圆底烧瓶中将步骤(1)的PHP白色固体粉末经过超声分散0.5h以上配制成0.5mg/mL无水乙醇悬浮液100mL，再加入环氧丙基十二烷基二甲基氯化铵150mg，然后在70℃下搅拌反应12h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂(PHPD)棕黄色或浅黄色粉末，其载体两交联点间的平均分子量、季铵盐含量、平均粒径和抗菌活性见表1。
实施例4
(1)在圆底烧瓶中先将0.34g聚乙烯亚胺(PEI)(重均分子量Mw 600，纯度99％)用80ml丙酮溶解，再添加4ml三乙胺(TEA)并搅拌均匀，然后加入预先用0.2g六氯环三磷腈(HCCP)与20ml丙酮配成的溶液并封口，在50℃下超声反应8h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球(PHP)白色固体粉末。
(2)在圆底烧瓶中将步骤(1)的PHP白色固体粉末经过超声分散0.5h以上配制成0.5mg/mL无水乙醇悬浮液100mL，再加入环氧丙基十二烷基二甲基氯化铵50mg，然后在65℃下搅拌反应12h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂(PHPD)棕黄色或浅黄色粉末，其载体两交联点间的平均分子量、季铵盐含量、平均粒径和抗菌活性见表1。
表1实施例1～4载季铵盐聚膦腈复合抗菌剂的载体两交联点间的平均分子量、季铵盐含量、平均粒径和抗菌活性
Figure BDA0002390174480000061
注：采用元素分析(EA)测定季铵盐含量；采用溶胀平衡法测定载体的交联点平均分子量(数值越小，交联度越大)；采用振荡法的测定复合抗菌剂对大肠杆菌(ATCC25292，广东省微生物研究所提供)和金黄色葡萄球菌(ATCC6538，广东省微生物研究所提供)的抗菌活性。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

1.一种载季铵盐聚膦腈复合抗菌剂，其特征在于，是以环三膦腈环交联聚乙烯亚胺微球为载体、季铵盐为活性组分；所述载季铵盐聚膦腈复合抗菌剂中环三膦腈环交联聚乙烯亚胺微球含量为93.0～88.5wt.％，季铵盐含量为7.0～11.5wt.％；所述季铵盐为环氧丙基十二烷基二甲基氯化铵。
2.根据权利要求1所述的一种载季铵盐聚膦腈复合抗菌剂，其特征在于，所述环三膦腈环交联聚乙烯亚胺微球结构为200～300nm的实心微球，外观为白色固体粉末；所述载季铵盐聚膦腈复合抗菌剂外观为棕黄色或浅黄色粉末。
3.权利要求1或2所述载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，包括以下步骤：
(1)在反应容器中先将一定量聚乙烯亚胺用乙腈或丙酮溶解，再添加一定量三乙胺并搅拌均匀，然后加入预先用一定量六氯环三磷腈与一定量乙腈或丙酮配成的溶液并封口，在适当温度下超声反应一段时间，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球白色固体粉末；
(2)在反应容器中将步骤(1)的白色固体粉末经过超声分散一段时间配制成无水乙醇悬浮液，再加入一定量环氧丙基十二烷基二甲基氯化铵，然后在适当温度下搅拌反应一段时间，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂。
4.根据权利要求3所述的一种载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，步骤(1)所述聚乙烯亚胺为0.17～0.52质量份、三乙胺为2～6体积份、六氯环三磷腈为0.1～0.3质量份，步骤(2)所述环三膦腈环交联聚乙烯亚胺微球与环氧丙基十二烷基二甲基氯化铵质量比为50:16.7～150。
5.根据权利要求3所述的一种载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，步骤(1)中溶解所述聚乙烯亚胺时，聚乙烯亚胺与乙腈或丙酮的质量体积比为0.17～0.52:80g/mL；溶解六氯环三磷腈时，六氯环三磷腈与乙腈或丙酮的质量体积比为0.1～0.3:80g/mL。
6.根据权利要求3所述的一种载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，步骤(1)所述聚乙烯亚胺分子量Mw＝600，纯度为99％。
7.根据权利要求3所述的载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，步骤(1)所述超声反应是指在45～60℃下超声反应8h以上，步骤(2)中所述超声分散时间为0.5h以上，步骤(2)中所述加热搅拌反应是指在60～70℃下搅拌反应12h以上。
8.根据权利要求3所述的一种载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，步骤(2)中，环三膦腈环交联聚乙烯亚胺微球-无水乙醇悬浮液浓度为0.5mg/mL。
9.根据权利要求3所述的一种载季铵盐聚膦腈复合抗菌剂的制备方法，其特征在于，包括以下步骤：
(1)在圆底烧瓶中先将0.17-0.52g聚乙烯亚胺用80ml乙腈或丙酮溶解，再添加2-6ml三乙胺并搅拌均匀，然后加入预先用0.1-0.3g六氯环三磷腈与20ml乙腈或丙酮配成的溶液并封口，在45～60℃下超声反应8h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和冷冻干燥工序，得到环三膦腈环交联聚乙烯亚胺微球白色固体粉末；
(2)在圆底烧瓶中将步骤(1)的白色固体粉末经过超声分散0.5h以上配制成0.5mg/mL无水乙醇悬浮液100mL，再加入环氧丙基十二烷基二甲基氯化铵16.7-150mg，然后在60～70℃下搅拌反应12h以上，最后将产物依次经过无水乙醇和水洗涤、离心分离和真空干燥工序，得到所述载季铵盐聚膦腈复合抗菌剂。
10.权利要求1或2所述载季铵盐聚膦腈复合抗菌剂在塑料、橡胶、纤维、涂料、胶粘剂和纸张领域中的应用。
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