CN111607025A - 一种高分子季铵盐纳米胶束抗菌剂及其制备方法 - Google Patents
一种高分子季铵盐纳米胶束抗菌剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高分子季铵盐纳米胶束抗菌剂及其制备方法，包括：以阴离子开环聚合制备单端乙烯基聚硅氧烷，再与丙烯酸、乙烯基吡啶、甲基丙烯酸羟乙酯进行自由基共聚，产物进行季铵化后得到具有梳型结构的高分子季铵盐(疏水侧链、亲水主链)，能够在溶液中自组装成核‑壳结构的纳米胶束，大大增加其表面的阳离子密度和表面积，具有很好的抗菌活性。
Description
技术领域
本发明属于高分子化学合成领域，具体涉及一种高分子季铵盐纳米胶束抗菌剂及其制备方法。
背景技术
随着经济的快速发展，人们对生活品质的要求越来越高，越来越关注健康和环保，各种各样的抗菌、防霉材料应运而生，而抗菌材料关键指标在于其抗菌性持久性和无毒性。
抗菌剂分为天然抗菌剂、无机抗菌剂和有机抗菌剂。天然抗菌剂如壳聚糖、大蒜素等，来源丰富且无毒，但具有耐热性差、不稳定的缺点。相比而言，无机抗菌剂如Ag+、TiO2、ZnO等金属化合物具有良好的热稳定性、安全性，但需要外界条件激发其抗菌性能，或者价格昂贵；有机抗菌剂如季铵盐、胍盐、季磷盐等，具有长久有效抗菌的效果，近年来得到广泛的研究。特别是季铵盐类化合物，其具有两亲性结构，对于具有强致病性的ESKAPE类的细菌有显著的抑制与杀灭效果，十二烷基二甲基苄基氯化铵(苯扎氯铵)是市面上最常用的广谱抗菌剂之一。但研究表明，小分子季铵盐抗菌剂具有极强的细胞毒性与皮肤刺激性，为了增强其生物相容性，衍生出一类高分子季铵盐抗菌剂，延长亲油链段以降低分子毒性。另外，高分子季铵盐能通过分子间力(如静电作用、亲/疏水作用、氢键)形成自组装结构，提高了表面阳离子密度，加之纳米粒度的自组装加大了分子的表面积，使得该类高分子季铵盐具有很高的抗菌活性，在日化、涂料、纺织、医疗卫生等领域有广泛的应用前景。
现有技术中基于聚硅氧烷的高分子季铵盐主要通过嵌段的方式合成具有两亲性的分子链(CN108641087A)，或乙烯基硅烷与带烯丙基的叔胺共聚后进行水解交联等方法制备(Chen S,et al.,Shaped core/shell polymer nanoobjects with highantibacterial activities via block copolymer microphase separation.Polymer,2013,54,3485-3491.)，对具有梳型结构的聚硅氧烷高分子季铵盐未见有报道。
发明内容
本发明通过乙烯基单封端聚硅氧烷与季铵盐单体进行无规共聚，得到一种具有梳型结构的季铵盐聚合物，聚硅氧烷具有很强的疏水性，作为侧链能够诱导共聚物自组装成纳米胶束。
本发明的目的在于提供一种高分子季铵盐纳米胶束抗菌剂。
本发明的另一目在于是提供上述一种高分子季铵盐纳米胶束抗菌剂的制备方法。
本发明上述目的通过以下技术方案实现：
一种高分子季铵盐纳米胶束抗菌剂，其结构式如下式所示：
式中，m:n:r:t:x＝10～20:10～20:20～40:0～20:10～30；R＝CH3或C6H13。
上述高分子季铵盐纳米胶束抗菌剂的反应流程及制备方法如下：
1.单边乙烯基封端的聚硅氧烷(PDMS-vinyl)的制备
往封闭充满氮气的反应釜中，注入六甲基环三硅氧烷(D3)和等体积干燥的四氢呋喃，以及计量的正丁基锂(n-BuLi)引发剂，在-1～3℃下反应24h后往反应釜中注射计量的氯硅烷，继续搅拌1h，终止反应。挥发溶剂，抽滤以除去析出的氯化锂，得到无色透明的液体产物(PDMS-vinyl)。
所述氯硅烷为符合结构式R2SiClCH2CHCH2的硅氧烷，如烯丙基二己基氯硅烷、烯丙基二甲基氯硅烷等。
所述D3、n-BuLi、氯硅烷的投料摩尔比为4～9:1:1.1。
2.无规共聚物P(PDMS-co-AA-co-VP-co-HEMA)的制备
按比例称取各原料，将PDMS-vinyl、丙烯酸(AA)、乙烯吡啶(4-VP)、甲基丙烯酸羟乙酯(HEMA)放入反应釜中，加入N,N-二甲基甲酰胺(DMF)，充分搅拌10min后加入引发剂偶氮二异丁腈(AIBN)，升温至60～70℃反应5h，挥发溶剂，得到具有梳型结构的无规共聚物P(PDMS-co-AA-co-VP-co-HEMA)。
所述PDMS-vinyl、AA、4-VP、HEMA的投料摩尔比为10～20:10～20:20～40:0～20，AIBN的投入量为单体总质量的0.1～0.3％。
3.季铵化P(PDMS-co-AA-co-QA-co-HEMA)的制备
在装有冷凝回流装置、恒压滴液漏斗、氮气保护装置和搅拌桨的三口烧瓶中，投入无规共聚物和两倍体积乙醇溶液充分搅拌溶解，升温至60～90℃后开始滴加氯化苄(BC)，滴加完毕后，保温反应10h。蒸发溶剂，用水:石油醚＝1:1的混合溶剂洗涤产物3次，即得到一种具有梳型结构的高分子季铵盐P(PDMS-co-AA-co-QA-co-HEMA)。
所述BC的投料量为P(PDMS-co-AA-co-VP-co-HEMA)中4-VP摩尔量的3倍。
4.季铵盐纳米胶束的制备
将2mg P(PDMS-co-AA-co-QA-co-HEMA)溶于4ml四氢呋喃中，搅拌至完全溶解后转至透析袋中(截留分子量为3500Da)，在1L去离子水中透析24h，通过孔径为0.45μm的过滤网过滤，得到季铵盐纳米胶束溶液。
与现有技术相比，本发明具有如下优点和有益效果：
P(PDMS-co-AA-co-QA-co-HEMA)具有梳型结构，以疏水链为侧链，亲水链为主链，在溶液中能够自组装成核-壳结构的纳米胶束。纳米尺度的季铵盐胶束表面具有较高的阳离子密度，且有较大的表面积，使得抗菌活性大大提高。
附图说明：
图1为实施例1P(PDMS-co-AA-co-VP-co-HEMA)的红外光谱。
图2为实施例1对应的PDMS-vinyl和P(PDMS-co-AA-co-VP-co-HEMA)的GPC图谱。
图3为实施例1纳米胶束的TEM图。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
分别对实施例1～4和对比例1以及广谱抗菌剂苯扎氯铵进行如下测试，结果列于表1：
数均分子量(Mn)：Waters 515-2414型凝胶渗透色谱仪，流动相为氯仿，流速为1mL/min，检测器温度为35℃，柱温为40℃，标样为窄分布的聚苯乙烯(PS)。
临界胶束浓度(CMC)：以去离子水为溶剂，采用电导率法测定并推导。胶束粒径及其分布：采用Beckman CoulterN4 Plus粒径分析仪测定纳米胶束尺寸和粒径分布，将合成步骤(4)透析得到的聚合物胶束水溶液加入到比色皿中，在25℃测量其尺寸及其分布。
最小抑菌浓度(MIC)：实验菌为革兰氏阴性菌大肠杆菌(Escherichia Coli，E.coli)，采用SMA5000型微量紫外-可见分光光度计测量不同浓度的含菌混合液在600nm处的吸光值(OD600)的变化曲线。测定方法：调节含菌混合液初始浓度，使初始OD600约为0.2，然后测量0～3.5h内混合菌液吸光度与时间的关系，OD600不随时间的变化而发现变化的最小浓度，即为抗菌剂的最小抑菌浓度(MIC)。
实施例1
(1)单边乙烯基封端的聚硅氧烷(PDMS-vinyl)的制备
往封闭充满氮气的反应釜中，注入D3和等体积干燥的四氢呋喃，以及n-BuLi，在0℃下反应24h后往反应釜中注射烯丙基二甲基氯硅烷，继续搅拌1h，终止反应。挥发溶剂，抽滤以除去析出的氯化锂，得到无色透明的液体产物PDMS-vinyl。
所述各原料投料摩尔比为D3:n-BuLi:烯丙基二甲基氯硅烷＝4.5:1:1.1。
(2)无规共聚物P(PDMS-co-AA-co-VP-co-HEMA)的制备
将PDMS-vinyl、AA、4-VP、HEMA放入反应釜中，加入DMF，充分搅拌10min后加入AIBN，升温至65℃反应5h，挥发溶剂，得到具有梳型结构的无规共聚物P(PDMS-co-AA-co-VP-co-HEMA)，所述PDMS-vinyl、AA、4-VP、HEMA的投料摩尔比为10:15:40:10，AIBN为单体总质量的0.2％。
参阅图1，P(PDMS-co-AA-co-VP-co-HEMA)的红外光谱如图1所示。
参阅图2，PDMS-vinyl和P(PDMS-co-AA-co-VP-co-HEMA)的GPC图谱如图2所示。
(3)P(PDMS-co-AA-co-QA-co-HEMA)的制备
在装有冷凝回流装置、恒压滴液漏斗、氮气保护装置和搅拌桨的三口烧瓶中，投入P(PDMS-co-AA-co-VP-co-HEMA)和两倍体积乙醇溶液充分搅拌溶解，升温至60～90℃后开始滴加BC，滴加完毕后，保温反应10h。蒸发溶剂，用水:石油醚＝1:1的混合溶剂洗涤产物3次，即得到一种具有梳型结构的高分子季铵盐P(PDMS-co-AA-co-QA-co-HEMA)。
所述BC的投料量为P(PDMS-co-AA-co-VP-co-HEMA)中4-VP摩尔量的3倍。
(4)季铵盐纳米胶束的制备
将2mg P(PDMS-co-AA-co-QA-co-HEMA)溶于4ml四氢呋喃中，搅拌至完全溶解后转至透析袋中(截留分子量为3500Da)，在1L去离子水中透析24h，通过孔径为0.45μm的过滤网过滤，得到季铵盐纳米胶束溶液。
参考图3，实施例1纳米胶束的TEM如图3所示。
实施例2
步骤(1)中D3、n-BuLi、烯丙基二甲基氯硅烷的投料摩尔比为6.7:1:1.1，其余与实施例1相同，。
步骤(2)中PDMS-vinyl:AA:4-VP:HEMA的投料摩尔比为10:15:40:10，AIBN的投入量为单体总质量的0.2％，其余与实施例1相同。
步骤(3)和(4)与实施例1相同。
实施例3
步骤(1)中D3、n-BuLi、烯丙基二甲基氯硅烷的投料摩尔比为4.5:1:1.1，其余与实施例1相同，。
步骤(2)中PDMS27-vinyl:AA:4-VP:HEMA的投料摩尔比为10:15:30:10，AIBN的投入量为单体总质量的0.2％，其余与实施例1相同。
步骤(3)和(4)与实施例1相同。
实施例4
步骤(1)中D3、n-BuLi、烯丙基二甲基氯硅烷的投料摩尔比为4.5:1:1.1，其余与实施例1相同，。
步骤(2)中PDMS27-vinyl:AA:4-VP:HEMA的投料摩尔比为10:15:20:10，AIBN的投入量为单体总质量的0.2％，其余与实施例1相同。
步骤(3)和(4)与实施例1相同。
对比例1
单边乙烯基封端的聚硅氧烷的投入量为0，无规共聚物中AA:4-VP:HEMA的投料摩尔比为15:40:10，按实施例1步骤(2)～(4)制备得到季铵盐溶液P(AA-co-QA-co-HEMA)。
表1.实施例1～4、对比例1和广谱抗菌剂苯扎氯铵性能测试结果
实施例1、3、4中具有不同的4-VP的投料量，从表中数据可以看出，随着无规共聚物中VP单元的数量越多，纳米抗菌剂的MIC越小，抗菌活性越高，临界胶束浓度(CMC)也越小，但由于具有相近的数均分子量，并且具有优异的亲水性，纳米抗菌剂的平均粒径变化不大。对比例1与实施例1、2相比，抗菌活性较低，CMC较高，抗菌剂粒径也较大，说明疏水链段PDMS的存在使得分子在水溶液中发生自组装行为，其表面的阳离子密度大大增强。
Claims (4)
1.一种高分子季铵盐纳米胶束抗菌剂及其制备方法，其特征在于，其结构式如式(I)所示：
式中m:n:r:t:x＝10～20:10～20:20～40:0～20:10～30；R＝CH3或C6H13。
2.一种高分子季铵盐纳米胶束抗菌剂及其制备方法，其特征在于，包括如下步骤：
(1)单边乙烯基封端的聚硅氧烷(PDMS-vinyl)的制备
在干燥四氢呋喃溶液中，以正丁基锂(n-BuLi)引发六甲基环三硅氧烷(D3)阴离子开环聚合，在-1～3℃下反应24h后注入氯硅烷终止反应；
(2)无规共聚物P(PDMS-co-AA-co-VP-co-HEMA)的制备
以偶氮二异丁腈(AIBN)为引发剂，N,N-二甲基甲酰胺(DMF)为反应溶液，PDMS-vinyl、丙烯酸(AA)、乙烯吡啶(4-VP)、甲基丙烯酸羟乙酯(HEMA)为单体进行自由基聚合反应，在60～70℃反应5h；
(3)P(PDMS-co-AA-co-QA-co-HEMA)的制备
在氮气保护下，P(PDMS-co-AA-co-VP-co-HEMA)在乙醇溶液中，与氯化苄(BC)进行季铵化反应；
(4)季铵盐纳米胶束的制备
将P(PDMS-co-AA-co-QA-co-HEMA)溶于四氢呋喃中，完全溶解后转至透析袋中(截留分子量为3500Da)，在去离子水中透析24h、过滤，得到季铵盐纳米胶束溶液。
3.根据权利要求2所述的一种高分子季铵盐纳米胶束抗菌剂及其制备方法，其特征在于：
所述步骤(1)的氯硅烷为符合结构式R2SiClCH2CHCH2的硅氧烷，可以是烯丙基二己基氯硅烷、烯丙基二甲基氯硅烷。
4.根据权利要求2所述的一种高分子季铵盐纳米胶束抗菌剂及其制备方法，其特征在于：
所述步骤(1)的D3，n-BuLi，氯硅烷的投料摩尔比为4～9:1:1.1；
所述步骤(2)的PDMS-vinyl、AA、4-VP、HEMA的投料摩尔比为10～20:10～20:20～40:0～20；
所述步骤(2)的AIBN的投料量为单体总质量的0.1～0.3％；
所述步骤(3)的BC的投料量为P(PDMS-co-AA-co-VP-co-HEMA)中4-VP摩尔量的3倍。
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