CN115340627B - 一种具有抗菌功能的含季鏻盐聚丙烯酸乳液及其制备方法与应用 - Google Patents

一种具有抗菌功能的含季鏻盐聚丙烯酸乳液及其制备方法与应用 Download PDF

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CN115340627B
CN115340627B CN202210888746.5A CN202210888746A CN115340627B CN 115340627 B CN115340627 B CN 115340627B CN 202210888746 A CN202210888746 A CN 202210888746A CN 115340627 B CN115340627 B CN 115340627B
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antibacterial
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phosphonium salt
quaternary phosphonium
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CN115340627A (zh
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徐桂龙
王灵晓
唐敏
梁云
胡健
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South China University of Technology SCUT
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Abstract

本发明公开了一种具有抗菌功能的含季鏻盐聚丙烯酸乳液及其制备方法与应用，原料包括如下重量份的组分：水60.0‑90.0份，季鏻盐抗菌功能单体0.5‑4.0份，水溶性丙烯酸单体2.0‑6.0份，(甲基)丙烯酸酯单体10.0‑30.0份，多乙烯基交联单体0.2‑1.2份，功能自交联单体0.5‑3.0份，pH缓冲剂0.1‑0.5份，引发剂0.5‑3.0份。本发明采用无皂乳液合成技术，所得含季鏻盐聚丙烯酸乳液具有优良的抗菌性能，并且乳液干燥后具有优良的成膜性能。本发明的含季鏻盐聚丙烯酸乳液可推广用于水性涂料、油墨、胶黏剂以及作纺织、无纺布以及纸张等各类材料的表面抗菌及防霉处理。

Description

一种具有抗菌功能的含季鏻盐聚丙烯酸乳液及其制备方法与 应用
技术领域
本发明属于高分子聚合物抗菌剂领域，具体涉及一种具有抗菌功能的含季鏻盐聚丙烯酸乳液及其制备方法与应用。
背景技术
丙烯酸乳液是人们在日常生活中应用非常广泛的一种聚合物乳液，具有色浅、保光、保色、耐候、耐腐蚀、抗老化、性能稳定等优点，广泛应用于水性涂料、油墨、胶黏剂以及作织物、纸张等各类材料的表面的处理。因此，其相关产品被广泛应用于各个领域中。近年来，随着全球范围内流行性疾病的传播以及人们健康意识的提高，抗菌材料的研究受到人们的重视，各行各业对应用材料的抗菌性能提出了更高的要求。因此，具有抗菌功能的丙烯酸乳液在各领域材料的应用中具有良好的市场前景。
赋予丙烯酸树脂抗菌功能的方法主要有两种，一种是在丙烯酸乳液中添加抗菌剂形成添加型抗菌丙烯酸树脂，另一种是将抗菌基团通过配位或共价等结合方式接枝在高分子聚合物上形成结构型抗菌丙烯酸树脂。但是添加型抗菌丙烯酸树脂有两方面缺点：一是抗菌剂作为助剂添加，首先要解决与树脂的相容性和稳定性的问题；二是抗菌剂掺杂在树脂之中，抗菌剂仍会慢慢迁移，随着时间推移抗菌功能减弱甚至消失，并且对环境造成污染，因此这种方法的发展受到限制。而结构型抗菌丙烯酸树脂是将抗菌材料或抗菌基团接枝到聚合物高分子链结构中，因此抗菌基团不易溶出迁移，且抗菌基团变化和数量可控，具有良好的抗菌耐久性、低毒性和可控性。专利CN101168586A《一种抗菌性高分子聚合物及其制备方法》利用卤代酚基团和叔胺基团季胺化反应得到一种季胺盐抗菌剂，避免了小分子流失而使抗菌性能下降的问题。专利CN103554367A《一种含β-环糊精的卤胺类抗菌剂共聚物及其制备方法和应用》将含有双键的马来酸酐改性-β糊精卤胺化得到一种卤胺盐抗菌剂。专利CN101628952A《胍类高分子型抗菌剂的制备方法》利用功能化胍盐共聚得到一种胍类高分子抗菌剂。专利CN104371056A《丙烯酸酯基结构型抗菌乳液的制备及其应用》将含有双键的阳离子铵盐与丙烯酸酯类单体共聚制备了一种丙烯酸酯基高分子结构型抗菌乳液，具有无毒无味、安全可靠的优点。专利CN112592419A《兼具接触抗菌和防雾的丙烯酸类季铵盐薄膜制备方法》将甲基丙烯酸二甲氨基乙酯与丙烯酸丁酯共聚得到二元共聚物前驱体，然后用溴辛烷离子化制备了季铵盐聚合物，所得薄膜具有抗菌功能。专利CN106565912A《一种聚季铵盐类聚合物乳液抗菌剂及其制备方法和应用》采用阳离子季铵盐单体作为抗菌单体制备得到具有良好抗菌功能的丙烯酸乳液。
尽管在丙烯酸乳液中引入季铵盐抗菌成分是目前报道最多的方法，但是季铵盐抗菌材料的不足之处在于抗菌活性较小，长期使用容易使细菌对其产生抗药性。与之相比，含季鏻盐抗菌材料更容易吸附细菌细胞，抗菌活性更高，性能更加稳定，与一般的氧化还原剂以及酸、碱不发生反应，且低毒，在pH＝2～12均可发挥较好的抗菌效力。因此，季鏻盐抗菌材料具有更加广泛的应用前景。专利CN103739786A《高分子季鏻盐抗菌材料及其制备方法》通过接枝反应将卤代酰卤类单体键接到乙烯-乙烯醇共聚物EVOH大分子上，进一步与三烷基膦进行季鏻化反应，合成了具有季鏻盐基团的抗菌剂，具有广谱、高效、持久的抗菌功能，但其存在着成本过高，制备方法存在难以规模化使用的不足，此外，这种聚合物接枝的方法还存在接枝率不高的问题，会造成浪费以及污染。因此，高效、毒性小、环境友好型、耐久型的季鏻盐抗菌聚合物还有待开发。
发明内容
为解决现有技术的缺点和不足，本发明的首要目的在于提供一种具有抗菌功能的含季鏻盐聚丙烯酸乳液，其具有高效抗菌活性、安全绿色且不溶出、耐久性好、应用范围广等特点。
本发明的再一目的在于提供一种具有抗菌功能的含季鏻盐聚丙烯酸乳液的制备方法。通过将水溶性丙烯酸单体聚合形成水溶性聚合物而充当可聚合高分子乳化剂的作用，成功使得体系形成无皂乳液聚合体系，最终的含季鏻盐聚丙烯酸乳液不含乳化剂，可减少水体富氧污染以及对涂膜性能的负面影响，同时可以进一步提高所得抗菌乳液的抗菌性能。本发明的乳液具有优良的成膜性能，成膜后可制成聚合物涂膜，可应用于纺织物品、塑料制品、玻璃金属制品、纸张、木制品等物体表面涂膜处理，从而获得降低或杀灭细菌的效果，也可单独作为具有抗菌性能的胶粘剂。另外，起到抗菌功能作用的季鏻盐单体主要集中在乳胶粒的壳层组分，更有利于乳液成膜后季鏻盐单体组分在乳胶粒或者涂膜表面的作用，可以在较低含量下发挥优良的抗菌功能。
本发明目的通过以下技术方案实现：
一种具有抗菌功能的含季鏻盐聚丙烯酸乳液，原料包括如下重量份的组分：水60.0-90.0份，pH缓冲剂0.1-0.5份，季鏻盐抗菌功能单体0.5-4.0份，水溶性丙烯酸单体2.0-6.0份，(甲基)丙烯酸酯单体10.0-30.0份，多乙烯基交联单体0.2-1.2份，功能自交联单体0.5-3.0份，引发剂0.5-3.0份。
进一步优选地，按重量份数计，包括水60.0-90.0份，pH缓冲剂0.1-0.5份，季鏻盐抗菌功能单体0.5-2.0份，水溶性丙烯酸单体2.0-4.0份，(甲基)丙烯酸酯单体10.0-30.0份，多乙烯基交联单体0.2-1.0份，功能自交联单体0.5-2.0份，引发剂0.5-1.0份。
进一步地，所述pH缓冲剂为碳酸氢钠、碳酸钠、磷酸钾、硫酸氢钾、醋酸钠、磷酸氢二钠、磷酸二氢钾、碳酸氢铵等常规使用的缓冲剂中的一种或多种混合物。
进一步地，所述(甲基)丙烯酸酯单体为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸异冰片酯等常规丙烯酸酯单体中的一种或多种混合物。
进一步地，所述水溶性丙烯酸单体为(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯或(甲基)丙烯酰胺、(甲基)丙烯酰氧乙基三甲基氯化铵中的一种或多种混合物。
进一步地，所述引发剂为水溶性的阳离子引发剂，包括偶氮二异丁脒盐酸盐、偶氮二异丁咪唑啉盐酸盐、偶氮二氰基戊酸、偶氮二异丙基咪唑啉盐酸盐中的一种或多种混合物。
进一步地，所述多乙烯基交联单体为具有两个乙烯基或三个乙烯基的交联单体，包括二乙烯基苯、乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、邻苯二甲酸二丙烯酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三烯丙基醚、季戊四醇四烯丙基醚、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯中的一种或多种混合物。
进一步地，所述功能自交联单体为可发生自交联的功能交联单体，包括N-羟甲基丙烯酰胺、羟乙基改性丙烯酰胺、N-(异丁氧基)甲基丙烯酰胺、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷中的一种或多种混合物。
进一步地，所述季鏻盐抗菌功能单体为季膦化合物改性的(甲基)丙烯酸溴代烷基酯，结构式如下：
其中，R0为H或者甲基；R1，R2，R3为C3-C18的烷烃或苯基；X为Cl、Br、I；n为[3，18]中的任意整数，优选为6-9。式中P+和R1，R2，R3之间的空间位置关系如下所示，R1，R2，R3优选为C6-C12的烷烃或苯基。
上述一种具有抗菌功能的含季鏻盐聚丙烯酸乳液的制备方法，包括如下步骤：
(1)将0.1-0.5份pH缓冲剂和50.0-80.0份水加入到反应釜中，剩下10.0份水用于溶解引发剂形成引发剂溶液；反应釜搅拌均匀后，继续往体系中加入全部水溶性丙烯酸单体以及1/3引发剂溶液，然后升温至60-70℃反应1.0-1.5小时；
(2)往反应体系中加入1/4-1/2含量的(甲基)丙烯酸酯单体以及0.2-1.2份多乙烯基交联单体的混合物，然后继续保温2.0-3.0小时，制备得到种子乳液；
(3)继续往种子乳液中分别滴加剩余的(甲基)丙烯酸酯单体、功能自交联单体以及季鏻盐抗菌功能单体混合物以及剩下的2/3引发剂溶液，滴加时间为2-3小时，滴加结束后体系升温至75-80℃，继续保温1-2小时；然后降温至50℃以下，出料。
本发明提供的一种具有抗菌功能的含季鏻盐聚丙烯酸乳液可用于水性涂料、油墨、胶黏剂以及作纺织、无纺布以及纸张的表面抗菌及防霉处理。
和现有技术相比，本发明具有以下有益效果和优点：
(1)本发明所制备的含季鏻盐丙烯酸树脂乳液，具有高效抗菌活性、安全绿色且不溶出、耐久性好、应用范围广等优点。
(2)本发明所制备的含季鏻盐丙烯酸树脂乳液是无皂乳液聚合体系，体系不含乳化剂，可以减少水体富氧污染以及对涂膜性能的负面影响。
(3)本发明所制备的含季鏻盐丙烯酸树脂乳液，起抗菌功能作用的季鏻盐单体主要集中在乳胶粒的表面壳层组分，更有利于乳液成膜后季鏻盐单体组分在乳胶粒或者涂膜表面的作用，可以在较低含量下发挥优良的抗菌功能。
(4)本发明所制备的含季鏻盐丙烯酸树脂乳液，本身既可以作为一种高分子乳胶抗菌剂，同时干燥成膜后也可以形成具有优良抗菌功能的聚合物涂膜，可广泛应用于涂料、胶黏剂、油墨等领域，以及作为纺织材料、纸张的抗菌处理剂，具有广阔的应用前景。
附图说明
图1是本发明所述的一种具有抗菌功能的含季鏻盐聚丙烯酸乳液的制备方法流程图。
图2是实施例1-3与对比例1所制备乳液涂膜的覆膜法抗菌性能测试结果。
图3是实施例1-3与对比例1所制备乳液用于纸张表面整理后，纸张的抗菌性能测试结果。
具体实施方式
下面结合实施例和附图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。
实施例
实施例1-4制备了一种具有抗菌功能的含季鏻盐聚丙烯酸乳液，具体配方见表1，通过如下步骤制备得到：
(1)将0.3份pH缓冲剂碳酸氢钠和60.0-80.0份水加入到反应釜中，剩下10.0份水用于溶解偶氮二异丁脒盐酸盐形成10mL引发剂AIBA溶液；反应釜搅拌均匀后，继续往体系中加入全部水溶性丙烯酸单体以及1/3引发剂溶液，然后升温至65℃反应1.5小时；
(2)向反应体系中加入1/3含量的(甲基)丙烯酸酯单体以及0.2-1.0份多乙烯基交联单体的混合物，然后继续保温2.0小时，制备得到种子乳液；
(3)继续往种子乳液中分别滴加剩余的(甲基)丙烯酸酯单体、功能自交联单体以及季鏻盐抗菌功能单体混合物以及剩下的2/3引发剂溶液，滴加时间为2小时，滴加结束后体系升温至75℃，继续保温1.5小时；降温至40℃以下，出料。
表1实施例1-4与对比例1-2的配方组成
从表1可以看出，实施例1-4在本发明的实施范围内，均可以形成稳定且凝胶率低的乳液。与对比例1-2相比较可以发现，对比例1的凝胶率高，稳定性不及实施例1-4，而对比例2由于第一步反应中的水溶性丙烯酸单体含量较低，无法形成足够的高分子表面活性剂以稳定乳胶粒，因此反应体系出现分层现象，并且单体味浓，转利率低。
对实施例1-4和对比例1所制备的含季鏻盐聚丙烯酸乳液进行抗菌性能测试。
测试1：乳液成膜后，通过覆膜法对涂膜进行抗菌测试。参考标准GB/T 21866-2008《抗菌涂料(漆膜)抗菌性测定法和抗菌效果》中的测试方法。选择大肠杆菌和金黄色葡萄球菌作为实验菌种。具体测试步骤为：将乳液制作为涂膜，裁成5×5cm大小，将0.4mL细菌浓度为1×106CFU/mL的细菌悬液滴加在涂膜表面，用PE覆盖膜盖在样品表面，在37℃恒温培养箱中培养24h后，用20mL的生理盐水反复冲洗样品表面，然后稀释不同倍数涂布在琼脂培养基上，在37℃恒温培养箱中培养24h后计数测定活菌数。测试结果如图1和表2所示。
测试2：将所制备的乳液用于纸张表面整理后，对处理后纸张进行抗菌性能测试。参考标准GB/T 20944.3-2008《纺织品抗菌性能的评价第3部分：振荡法》中的测试方法，选择大肠杆菌和金黄色葡萄球菌作为实验菌种。具体测试步骤为：用灭菌的接种环刮取少量细菌于生理盐水中，稀释得到浓度约为1×106CFU/mL的细菌悬液。取相同量细菌悬液加入NB培养基中(牛肉浸膏3.0g、蛋白胨10.0g、NaCl 5.0g，水定容1L)，然后加入相同量纸样置于37℃恒温培养箱中振荡培养24h，然后对培养液进行十倍稀释后，取200μL涂布在营养琼脂平板上，置于37℃恒温培养箱中培养24h后，观察菌落生长情况。测试结果如图2和表3所示。
表2实施例1-4与对比例1所制备乳液涂膜的覆膜法抗菌测试结果
表3实施例1-4与对比例1所制备乳液整理纸张的抗菌测试结果
从图2、图3以及表2、表3可以看出，随着季鏻盐抗菌功能单体的用量从0.5份增加到2.0份，所制备的丙烯酸树脂膜和经过整理的纸张对大肠杆菌和金黄色葡萄球菌的抑菌率都随之增加，其中实施例3和实施例4的抑菌率都达到了99.99％以上，实施例1的抑菌率也达到了96％以上，而对比例1由于没有添加季鏻盐抗菌功能单体，所制备的乳液涂膜不具备抗菌功能。所以，实施例1-4在本发明的实施范围内所制备的抗菌乳液成膜后具有非常优良的抗菌性能，可用作纸张的抗菌处理剂。而且，实施例1中季鏻盐抗菌功能单体的用量仅0.5份，对大肠杆菌和金黄色葡萄球菌的抗菌率分别是97.17％和98.59％，整理纸张后对大肠杆菌和金黄色葡萄球菌的抗菌率分别是96.13％和98.13％，体现了本发明的含季鏻盐丙烯酸树脂乳液可以在较低含量下发挥优良的抗菌功能。
实施例5
与实施例1基本相同，不同之处在于：步骤(1)中升温至60℃反应1.0小时，步骤(3)中升温至80℃继续保温1.0小时。
实施例6
与实施例1基本相同，不同之处在于：步骤(1)中升温至70℃反应1.0小时，步骤(2)中保温3.0小时，步骤(3)中继续保温2.0小时。
实施例7
与实施例1基本相同，不同之处在于：步骤(2)中保温2.5小时，步骤(3)中升温至80℃，继续保温2.0小时。
实验结果表明实施例5-7在本发明的实施范围内，均可以形成稳定且凝胶率低的乳液。
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 (6)

1.一种具有抗菌功能的含季鏻盐聚丙烯酸乳液的制备方法，其特征在于，包括如下步骤：
（1）将 0.1-0.5份pH缓冲剂和50.0-80.0份水加入到反应釜中，剩下10.0份水用于溶解引发剂形成引发剂溶液；反应釜搅拌均匀后，继续往体系中加入全部水溶性丙烯酸单体以及1/3引发剂溶液，然后升温至 60-70℃反应1.0-1.5小时；
（2）往反应体系中加入1/4-1/2含量的（甲基）丙烯酸酯单体以及0.2-1.2份多乙烯基交联单体的混合物，然后继续保温2.0-3.0小时，制备得到种子乳液；
（3）继续往种子乳液中分别滴加剩余的（甲基）丙烯酸酯单体、功能自交联单体以及季鏻盐抗菌功能单体混合物以及剩下的2/3引发剂溶液，滴加时间为2-3小时，滴加结束后体系升温至75-80℃，继续保温1-2小时；然后降温至50℃以下，出料；
原料包括如下重量份的组分：水60.0-90.0份，pH缓冲剂0.1-0.5份，季鏻盐抗菌功能单体0.5-4.0份，水溶性丙烯酸单体2.0-6.0份，（甲基）丙烯酸酯单体10.0-30.0份，多乙烯基交联单体0.2-1.2份，功能自交联单体0.5-3.0份，引发剂0.5-3.0份；
所述水溶性丙烯酸单体为（甲基）丙烯酸羟乙酯、（甲基）丙烯酸羟丙酯或（甲基）丙烯酰胺、（甲基）丙烯酰氧乙基三甲基氯化铵中的一种或多种混合物；
所述多乙烯基交联单体为具有两个乙烯基或三个乙烯基的交联单体，包括二乙烯基苯、乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、邻苯二甲酸二丙烯酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、季戊四醇三烯丙基醚、季戊四醇四烯丙基醚、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯中的一种或多种混合物；
功能自交联单体为可发生自交联的功能交联单体，包括N-羟甲基丙烯酰胺、羟乙基改性丙烯酰胺、N-(异丁氧基)甲基丙烯酰胺、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三异丙氧基硅烷中的一种或多种混合物；
所述季鏻盐抗菌功能单体的结构式如下：
其中，R0为H或者甲基；R1，R2，R3为C3-C18的烷基或苯基；X为Cl、Br、I；n为[3,18]中的任意整数。
2.根据权利要求1所述的具有抗菌功能的含季鏻盐聚丙烯酸乳液的制备方法，其特征在于，所述 pH 缓冲剂为碳酸氢钠、碳酸钠、磷酸钾、硫酸氢钾、醋酸钠、磷酸氢二钠、磷酸二氢钾、碳酸氢铵中的一种或多种混合物。
3.根据权利要求1所述的具有抗菌功能的含季鏻盐聚丙烯酸乳液的制备方法，其特征在于，所述（甲基）丙烯酸酯单体为（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸环己酯、（甲基）丙烯酸异辛酯、（甲基）丙烯酸十二酯、（甲基）丙烯酸异冰片酯中的一种或多种混合物。
4.根据权利要求1所述的具有抗菌功能的含季鏻盐聚丙烯酸乳液的制备方法，其特征在于，所述引发剂为水溶性的阳离子引发剂，包括偶氮二异丁脒盐酸盐、偶氮二异丁咪唑啉盐酸盐、偶氮二氰基戊酸、偶氮二异丙基咪唑啉盐酸盐中的一种或多种混合物。
5.由权利要求1~4任一项所述的制备方法制备得到的一种具有抗菌功能的含季鏻盐聚丙烯酸乳液。
6.权利要求5所述的一种具有抗菌功能的含季鏻盐聚丙烯酸乳液的应用，其特征在于，用于水性涂料、油墨、胶黏剂以及作纺织、无纺布以及纸张的表面抗菌及防霉处理。
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