CN116496562A - 一种抗菌型聚乙烯管材及其制备方法 - Google Patents
一种抗菌型聚乙烯管材及其制备方法 Download PDFInfo
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Abstract
本发明属于聚乙烯抗菌材料领域，具体涉及一种抗菌型聚乙烯管材，包含如下重量份的组成成分：聚乙烯树脂70‑100份、有机抗菌剂0.1‑5份、润滑剂0.5‑5份、抗氧剂0.5‑3份、偶联剂1‑5份、无机填料1‑10份；所述有机抗菌剂的制备方法为：将咪唑盐单体、季鏻盐单体和酰胺类单体溶于溶剂中，在引发剂作用下聚合得到有机抗菌剂。本发明制备的聚乙烯抗菌材料具有优异抗菌性能和力学性能。
Description
技术领域
本发明属于聚乙烯抗菌材料领域，具体涉及一种抗菌型聚乙烯管材及其制备方法。
背景技术
聚乙烯树脂(PE)是由乙烯通过加聚反应而制成的分子组成、结构均最简单的一种高分子化合物。聚乙烯是通用合成树脂中产量最大的品种,而且也是应用最为广泛的品种之一。聚乙烯具有来源广、价格低、绝缘性良好及较高的化学稳定性等优点,因此其应用范围比较广。一般情况下,对与聚乙烯的抗菌改性主要是通过在基体的材料中加入抗菌物质,制备出具有一定抗菌性能的材料。抗菌剂能够阻止或抑制微生物的生长发育。
抗菌材料制备过程中核心部分是抗菌剂的选择,抗菌剂一般指细菌、霉菌等微生物物相对敏感的化学物质。抗菌剂可分为大然抗菌剂、无机抗菌剂和有机抗菌剂。有机抗菌剂种类较多,其抗菌机理也不尽相同。但普遍被承认的有机抗菌剂的作用机理有三种:一是抗菌剂作用于微生物细胞壁和细胞膜系统；二是作用于微生物细胞内的生化反应酶或其他活性物质；三是作用于微生物遗传物质或遗传微型结构。例如，季铵盐和季鏻盐是近几年研究较多的抗菌剂。该类抗菌剂带有电性较强的正电荷，可以吸附带负电荷的细菌,引起微生物细胞壁结构损害并使内容物漏出，咪唑盐可以利用其功能基团与细菌之间的静电作用的特性起来杀菌的效果。
有机抗菌剂为低分子有机抗菌剂和高分子抗菌剂，国内外对高分子抗菌剂的研究处于刚刚起歩的阶段,研究相对较少，也存在一些不足,例如有机抗菌剂相容性、耐热性差，会影响材料的力学性能和抗菌性能等。
发明内容
本发明提供一种具有优异抗菌性能和力学性能的抗菌型聚乙烯管材，具体技术方案如下：
一种抗菌型聚乙烯管材，包含如下重量份的组成成分：聚乙烯树脂70-100份、有机抗菌剂0.1-5份、润滑剂0.5-5份、抗氧剂0.5-3份、偶联剂1-5份、无机填料1-10份；
所述有机抗菌剂的制备方法为：将咪唑盐单体、季鏻盐单体和酰胺类单体溶于溶剂中，在引发剂作用下聚合得到有机抗菌剂；
优选的，所述有机抗菌剂的制备方法为：在装有搅拌子、温度计、回流冷凝管的三口烧瓶中，加入等体积的DMF与蒸馏水，再加入咪唑盐单体、季鏻盐单体和酰胺类单体混合单体，以AIBN为引发剂，在氮气保护及65℃下，反应7-9h，以四氢呋喃为沉淀剂，制得有机抗菌剂。
所述的咪唑盐单体：1-乙烯基-3-丁基咪唑氯盐或1-乙烯基-3-丁基咪唑溴盐；
所述季鏻盐单体为4-乙烯基苄基三丁基氯化鏻或4-乙烯基苄基三丁基溴化鏻；
所述酰胺类单体为丙烯酰胺；
所述的引发剂为AIBN。
所述咪唑盐单体、季鏻盐单体和酰胺类单体的摩尔比为1-5:1-5:1-5。优选为咪唑盐单体、季鏻盐单体和酰胺类单体的摩尔比为1:1:1。
所述的润滑剂为润滑剂选自白油、硬脂酸、硬脂酸镁、石蜡、PE蜡中的一种或多种；
所述的抗氧剂为酚类抗氧剂、胺类抗氧剂、亚磷酸酯类抗氧剂、含硫酯类抗氧剂中的一种或多种。
所述的无机填料为滑石粉、金刚砂或石英粉中的一种或多种。
所述的偶联剂为钛酸酯偶联剂或硅烷偶联剂中的一种或多种。
所述的抗菌型聚乙烯管材的制备方法，将配方量的各原料投入到混料机中混合均匀得混合料，并经熔融共混挤出和成型制备即可。
采用上述技术方案，本发明具有如下有益效果：
与小分子抗菌剂物理混合相比,高分子抗菌剂杀菌效果好，推测其原因是对杀菌单体高分子化可以增加抗菌剂中正电荷的密度，从而增强其对细菌细胞表面的有效吸附；并且与基体材料的相容性较高，不容易渗出，性能稳定。
采用咪唑盐单体、季鏻盐单体和酰胺类单体共聚有机杀菌剂与PE具有优异的相容性，可提高有机抗菌剂在PE中分散均匀度，显著提高PE树脂的拉伸强度、断裂伸长率和冲击强度。
具体实施方式
下面结合具体的实施方式对本发明做进一步的解释说明。
实施例1：有机抗菌剂制备
有机共聚抗菌剂J01制备：
在装有搅拌子、温度计、回流冷凝管的三口烧瓶中，加入等体积的DMF与蒸馏水，再加入摩尔比为1∶1：1的咪唑盐单体、季鏻盐单体和酰胺类单体混合单体，以AIBN为引发剂，在氮气保护及65℃下，反应8h，以四氢呋喃为沉淀剂，制得有机抗菌剂。
所述的咪唑盐单体为1-乙烯基-3-丁基咪唑氯盐；
所述季鏻盐单体为4-乙烯基苄基三丁基氯化鏻；
所述酰胺类单体为丙烯酰胺；
合成路线如下：
有机共聚抗菌剂J02制备：
在装有搅拌子、温度计、回流冷凝管的三口烧瓶中，加入等体积的DMF与蒸馏水，再加入摩尔比为1∶1的咪唑盐单体和季鏻盐单体混合单体，以AIBN为引发剂，在氮气保护及65℃下，反应8h，以四氢呋喃为沉淀剂，制得有机抗菌剂。
所述的咪唑盐单体为1-乙烯基-3-丁基咪唑氯盐；
所述季鏻盐单体为4-乙烯基苄基三丁基氯化鏻；
合成路线如下：
有机抗菌剂H01制备：
将摩尔比为1∶1：1的咪唑盐单体、季鏻盐单体和酰胺类单体混合单体混合即可。
实施例2：PE抗菌树脂制备
制备方法：
(1)预先进行干燥处理，首先将PE树脂(HDPE，熔融指数6-9g/10min,上海麦克林)于65℃下，在电热恒温鼓风干燥箱中干燥2h，备用；
(2)预先进行手动混合，称取一定量的PE树脂500g，先加入10g白油，使得白油与PE树脂混合均匀,再加入2.5g抗氧剂1010、5g偶联剂KH560、15g纳米滑石粉，再按照质量分数为0.5％的比例称取一定量的抗菌剂，然后加入到已经混合好的PE树脂中，充分混合均匀；
(3)挤出机中进行熔融挤出，将混合均匀好的粒料通过双螺杆挤出机中挤出，然后冷却再进行切粒。其中挤出机各段的温度分别为205℃、210℃、205℃、200℃和195℃，螺杆的转速设置为115r/min。再将挤出后的颗粒放于鼓风干燥箱中干燥2h；
(4)注塑成型，将已经烘干的粒料通过注塑机分别注塑为直径圆片以及标准的测力学性能的样条，注塑后的样条放置24h之后进行各项性能测试。
表1：添加不同有机抗菌剂的PE树脂
| 树脂 | 有机抗菌剂 |
| PE抗菌树脂A | J01 |
| PE抗菌树脂B | J02 |
| PE抗菌树脂C | H01 |
| PE树脂I | 无 |
备注：PE抗菌树脂C在制备步骤(2)最后混合物中添加适量引发剂AIBN，其余不变。
实施例3：PE抗菌树脂的抗菌性能和力学性能测试
抗菌测试方法：
(1)琼脂培养基配制:将营养琼脂培养基进行15min的高温灭菌后，在无菌的培养皿中倒入灭菌之后的营养琼脂培养基，每个培养皿中注入20mL左右。待平板凝固之后，将培养皿倒置于温度为32℃的恒温培养箱中放置1d后备用。
(2)将抗菌共混物通过激光打印技术，裁剪成直径为5mm的圆片，然后将裁剪之后的圆片经过15min的紫外灯光照射。
(3)利用接种环刮取一定量的不同菌落(金黄色葡萄球菌、大肠杆菌)，将菌落放置于无菌的PBS缓冲溶液中，获得浓度为6*105cfu/mL-6*106cfu/mL的实验菌悬液。然后取无菌棉签用来蘸取制备好的菌悬液，将菌悬液尽可能的均匀涂在营养琼脂培养基平板的表面，总共涂4次，保证平板的各处均有菌悬液。最后将平皿盖盖好，在室温条件下进行干燥，干燥时间为10min。
将事先准备好的对照样片和抗菌剂样片的圆片分别粘贴在染菌的平板上。每个平板平均贴4片，用无菌镊子将样片轻轻压放，使样片与平板表面紧紧粘贴在一起。最后将平皿盖好，并且放置在温度为32℃的恒温培养箱内进行培养，经过24h之后观察抑菌环情况。
(4)采用十字交叉法利用游标卡尺将对照样片和抗菌剂样片的抑菌环直径进行测量并记录，每组实验重复4次之后，取平均值。
(5)抗菌判断标准：首先对照组没有抑菌环出现，否则无效。其次，当抑菌环直径大于7mm时，材料具有抑菌效果；抑菌环直径小于或着等于7mm时，材料没有抑菌效果。
力学性能测试方法：
拉伸性能依照GB/T1040.1-2006的标准在UTM型万能材料拉伸试验机上进行分析测试，测试之后可得到共混物的拉伸强度、断裂伸长率等性能。
冲击强度依照GB/T1043.1-2008的标准在悬臂梁冲击试验机上进行分析测试。
表2：抗菌测试结果
PE抗菌树脂A具有优异的抗菌效果，推测其原因为对杀菌单体高分子化可以增加抗菌剂中正电荷的密度，从而增强其对细菌细胞表面的有效吸附。
与PE抗菌树脂C相比，PE抗菌树脂A具有优异的抗菌效果；即与小分子抗菌剂物理混合相比,高分子抗菌剂杀菌效果好并且与基体材料的相容性较高，不容易渗出,性能稳定。
表3：力学性能测试结果
PE抗菌树脂A中，采用咪唑盐单体、季鏻盐单体和酰胺类单体共聚有机杀菌剂与HDPE具有优异的相容性，可提高有机抗菌剂在HDPE中分散均匀度，显著提高PE树脂的拉伸强度、断裂伸长率和冲击强度。
PE抗菌树脂B中，采用咪唑盐单体和季鏻盐单体共聚的抗菌剂，由于咪唑盐单体和季鏻盐单体的空间位阻较大，不能实现很好的共聚。通过添加空间位阻较小、并具有一定抗菌作用的丙烯酰胺单体，与咪唑盐单体和季鏻盐单体共聚可提高有机抗菌剂与基体材料的相容性。
PE抗菌树脂C中，虽然添加引发剂，但是咪唑盐单体、季鏻盐单体和酰胺类单体与HDPE的接枝率较低，三种单体与HDPE主要以共混的形式存在，由于三种单体与HDPE相容性不好,因此力学性能有明显降低。
最后，还需要注意的是，以上列举的仅是本发明的若干个具体实施例。本领域的普通技术人员能从本发明公开的内同直接导出或联想到的所有变形，均认为是本发明的保护范围。
Claims (8)
1.一种抗菌型聚乙烯管材，其特征在于，包含如下重量份的组成成分：聚乙烯树脂70-100份、有机抗菌剂0.1-5份、润滑剂0.5-5份、抗氧剂0.5-3份、偶联剂1-5份、无机填料1-10份；
所述有机抗菌剂的制备方法为：将咪唑盐单体、季鏻盐单体和酰胺类单体溶于溶剂中，在引发剂作用下聚合得到有机抗菌剂；
所述的咪唑盐单体：1-乙烯基-3-丁基咪唑氯盐或1-乙烯基-3-丁基咪唑溴盐；所述季鏻盐单体为4-乙烯基苄基三丁基氯化鏻或4-乙烯基苄基三丁基溴化鏻；所述酰胺类单体为丙烯酰胺；所述的引发剂为AIBN。
2.根据权利要求1所述的抗菌型聚乙烯管材，其特征在于，所述咪唑盐单体、季鏻盐单体和酰胺类单体的摩尔比为1-5:1-5:1-5。
3.根据权利要求2所述的抗菌型聚乙烯管材，其特征在于，所述有机抗菌剂的制备方法为：在装有搅拌子、温度计、回流冷凝管的三口烧瓶中，加入等体积的DMF与蒸馏水，再加入咪唑盐单体、季鏻盐单体和酰胺类单体混合单体，以AIBN为引发剂，在氮气保护及65℃下，反应7-9h，以四氢呋喃为沉淀剂，制得有机抗菌剂。
4.根据权利要求1所述的抗菌型聚乙烯管材，其特征在于，所述的润滑剂为润滑剂选自白油、硬脂酸、硬脂酸镁、石蜡、PE蜡中的一种或多种。
5.根据权利要求1所述的抗菌型聚乙烯管材，其特征在于，所述的抗氧剂为酚类抗氧剂、胺类抗氧剂、亚磷酸酯类抗氧剂、含硫酯类抗氧剂中的一种或多种。
6.根据权利要求1所述的抗菌型聚乙烯管材，其特征在于，所述的无机填料为滑石粉、金刚砂或石英粉中的一种或多种。
7.根据权利要求1所述的抗菌型聚乙烯管材，其特征在于，钛酸酯偶联剂或硅烷偶联剂中的一种或多种。
8.根据权利要求1-7任一项所述的抗菌型聚乙烯管材的制备方法，其特征在于，将配方量的各原料投入到混料机中混合均匀得混合料，并经熔融共混挤出和成型制备即可。
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