CN117025044A - 具有双重抗菌作用的聚丙烯酸酯皮革涂饰剂的制备方法 - Google Patents
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Abstract
本发明提供了一种具有双重抗菌作用的聚丙烯酸酯皮革涂饰剂的制备方法，其特征在于是在表面活性剂的乳化作用下将丙烯酸酯共聚单体、抗菌功能性单体制备成预乳化液，然后再通过引发剂引发抗菌功能性单体与丙烯酸酯单体发生共聚反应而制得。本发明所选用的抗菌功能性单体包括抗菌黏附性能的薄荷醇衍生物单体和含有碳碳双键的季鏻盐单体两大类。季鏻盐抗菌单体有着优异的杀菌性能，薄荷醇类衍生物为天然来源，有很好的抗菌黏附性能。本专利通过巧妙的设计和合适的聚合方法将两种不同抗菌功效的抗菌单体在分子水平引入聚丙烯酸酯，制得的聚丙烯酸酯皮革涂饰剂既具有杀菌性能，同时具备抗微生物黏附性能。
Description
技术领域
本发明涉及抗菌材料研究领域和水性皮革用涂饰材料开发领域，具体涉及一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂的制备方法。
背景技术
皮革是指以原有结构大致完整的生皮为原料，经过一系列的物理、化学加工而制成的一种具有良好的物理机械性能、穿着舒适性能和降解稳定性的生物材料，因其优异的舒适性、高透气性和耐久性而被广泛应用于日常生活中。据估计，皮革制品的贸易额每年达1000亿美元，表明皮革工业在全球经济中发挥着关键作用。但是皮革产品由于含有丰富的蛋白质、脂肪等，相比于其他材料更容易受到微生物的侵害。此外，皮革加工过程中添加的各种助剂以及其表面附着汗液、皮脂等人体分泌物也会为微生物的黏附、生长和增殖提供有利条件，最终导致生物膜的形成，并且在保存和运输过程也会受湿热环境影响而经常发生霉变。皮革表面产生的生物膜会导致许多不良问题，如变色、产生难闻的气味、损坏产品，甚至还会有皮肤感染的风险。因此，抑制微生物在皮革表面的黏附和增殖一直是人们关注的问题。
为了解决这一问题，在皮革涂饰工艺中使用抗菌聚合物涂层是一种非常有效的策略。皮革表面涂饰是改善革的外观和物性、赋予其抗菌防霉等功能防护性和高附加值的重要工段。为减小环境压力，如今绝大部分新型材料的开发已从溶剂型材料转变到环保的水性材料。水性聚丙烯酸酯乳液具有优异的成膜性、粘接性、耐候性、保光保色性，且价廉、安全、环保，已成为皮革涂饰材料中应用最为广泛的一类成膜物质。在现有的成品革防霉方法中，最有效和最主要的方法是向皮革涂饰用水性聚丙烯酸酯乳液中添加杀菌防霉剂。但物理共混方法只适合短期防护，在使用过程中皮革表面的小分子杀菌防霉剂会逐步发生迁移和游离而丧失功效。因此，从毒性角度考虑，将毒性小的有机抗菌剂和聚丙烯酸酯结合起来合成具有抗菌性能的聚丙烯酸酯将是抗菌聚丙烯酸酯的发展方向，且此种方法由于抗菌单体是在分子水平上引入聚丙烯酸酯基体中，可赋予聚丙烯酸酯永久的抗菌性能。
另一方面，目前大多数制备抗菌皮革涂层的策略都侧重于通过添加杀菌剂或抗生素对涂层进行改性。这些方法旨在杀死附着在皮革表面的微生物。然而，一个重要的问题是涂层表面很容易被死亡的微生物残留覆盖，这会阻止杀菌成分与其他活菌的相互作用，最终导致抗菌失效。因此，人们逐渐认识到开发抗微生物黏附的新型涂料是防止生物污染的有效策略，该策略的抗菌机制与传统杀菌机制不同，主要是通过防止微生物在材料表面的黏附从而阻止其生长繁殖。但对于微抗生物黏附皮革涂层来说，长期完全地预防微生物粘附是很难实现的。因此，结合杀菌和抗菌黏附作用的抗菌皮革涂料是一种很有应用前景的可有效预防微生物污染的方法。
季鏻盐是一种与季铵盐结构相似的化合物。相比于季铵盐，其具有更高效、广谱的杀菌性，毒性低，有良好的配伍性和更宽的 pH 使用范围 (pH 2~12)，弥补了季铵盐稳定性差且只有在碱性条件下才表现出较高杀菌性能的缺点。本发明方法是将不同结构的季鏻盐从分子水平上引入到聚合物涂层中并保留其持久的杀菌功效，可赋予聚丙烯酸酯永久的抗菌性能。为了解决小分子抗菌剂在抗菌过程中的释放对人体和环境造成污染的问题，近年来，科研工作者将抗菌基团通过聚合反应，制备高分子抗菌剂或者通过化学键将小分子抗菌剂引入到性能稳定的高分子基体内得到有抗菌作用的高分子材料或者制品，这将成为研究和开发抗菌高分子的热点。郭启良等用季鏻盐不饱和单体（烯丙基三苯基溴化膦）对聚氨酯丙烯酸酯进行改性(PUA)，通过共聚合制得抗菌性良好的 PUA 材料。Li等将三苯基膦引入到环氧橡胶主链中，对环氧橡胶开环和季鏻化改性，引入具有抗菌活性的季鏻盐后，得到具有持久的抗菌效果的橡胶制品。Tom等利用点击化学反应，将叠氮季鏻盐接枝到聚酯上，制备的聚酯材料可作为食品包装材料，具有良好的抗菌性。
薄荷醇来源于天然植物，被验证能够明显抑制多种不同类的真菌及细菌的生长，是通过作用生物质膜脂质部分，改变膜通透性来达到抗菌作用，但其杀菌抗菌性非常有限。申请人近年研究发现，具有立体化学效应的单体可对微生物细胞有识别作用，讲该类单体引入皮革聚合物基体中，制备皮革用涂层，可以赋予皮革良好的抗微生物黏附性能，从而达到抗菌防霉效果。申请人研究发现，薄荷醇具有立体化学结构，通过立体化学结构赋予材料表面较好的抗菌黏附性能。
基于此，本发明的目的是先加入表面活性剂和丙烯酸酯共聚单体形成预乳化液，再通过引发剂将具有抗菌黏附性能的薄荷醇衍生物单体和具有杀菌性能的季鏻盐单体与丙烯酸酯单体发生共聚反应，得到一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂。
发明内容
本发明提供了一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂的制备方法，其特征在于制备方法是在表面活性剂的乳化作用下将丙烯酸酯共聚单体、抗菌功能性单体制备成预乳化液，然后再通过引发剂引发抗菌功能性单体与丙烯酸酯共聚单体发生共聚反应，制备一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂，其具体制备步骤如下：
（1）向反应器中加入一定量的表面活性剂，然后加入丙烯酸酯共聚单体和抗菌功能性单体，表面活性剂用量为共聚单体总量的2~5 wt%，共聚单体与水质量比（0.4~1）:1，高速乳化分散10~30 min，搅拌速度为4000~10000 rpm，得到预乳化液；
（2）将上述预乳化液加入到具有冷凝和搅拌装置的反应器中，温度为 60~80℃，向其中滴加一定量的水溶性引发剂水溶液，控制滴加速度使得滴加时间控制在0.5~1 h，引发剂用量为共聚单体总量的0.4~1 wt%，整个反应体系中共聚单体与水的质量比为（0.2~0.5）:1；升温至75～100℃，搅拌速度500～2000 rpm，搅拌反应2～5 h，得到具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂；
所述的丙烯酸酯共聚单体包括软单体和硬单体两个组分，软单体为丙烯酸乙酯、丙烯酸正丙酯和丙烯酸正丁酯中的一种；硬单体为丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯中一种；抗菌功能性单体包括两种，一种为具有抗菌黏附性能且含碳碳双键的薄荷醇衍生物，另一种为具有碳碳双键的季鏻盐，软性单体与硬性单体的质量比为（1~3）:1，抗菌功能性单体用量为丙烯酸酯共聚单体和抗菌功能性单体总质量的10~25 wt%。
所述的一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的具有碳碳双键的季鏻盐单体为烯丙基三苯基溴化膦、(4-戊烯基)三苯基溴化膦和溴化乙烯基三苯基膦中的一种。
所述的一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的具有抗菌黏附性能的薄荷醇衍生物为异胡薄荷醇、异蒲勒醇和异薄荷醇中的一种，薄荷醇衍生物用量占抗菌功能性单体总质量的10~30%。
所述的种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的表面活性剂为烷基酚聚氧乙烯醚（OP-10）、脂肪醇聚氧乙烯醚 (AEO-10)、多元醇聚氧乙烯醚脂肪酸酯（T-20）中的一种。
所述的种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的引发剂为过硫酸铵、过硫酸钾中的一种。
本发明所选用的抗菌功能性单体包括具有抗菌黏附性能的薄荷醇衍生物单体和含有碳碳双键的季鏻盐单体两大类。季鏻盐抗菌单体有着优异的杀菌性能，薄荷醇类衍生物为天然来源，有很好的抗菌黏附性能，并具有一定的疏水性，满足皮革涂层的耐湿擦性能的要求。本专利通过巧妙的设计和合适的聚合方法将两种具有不同抗菌功效的抗菌单体在分子水平引入到聚丙烯酸酯，制得的水性聚丙烯酸酯皮革涂饰剂既具有杀菌性能，同时具备抗微生物黏附性能。
具体实施方式
下面给出本发明的三个实施例，以具体说明具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂的制备方法。
实施例1：
向反应釜中加入0.5 g烷基酚聚氧乙烯醚（OP-10）和25 g去离子水，然后加入丙烯酸酯共聚单体混合物：丙烯酸甲酯4.2 g，丙烯酸正丁酯12.85 g，烯丙基三苯基溴化膦3.41g，异胡薄荷醇0.85 g，高速乳化分散10~30 min，乳化分散速度为8000 rpm，得到预乳化液。
将上述预乳化液加入到具有冷凝和搅拌装置的250 ml三口烧瓶中，温度保存在70℃，搅拌速度1000 rpm，将0.15g引发剂过硫酸铵溶于20 g水中，过硫酸铵水溶液。向反应瓶中逐步滴加过硫酸铵水溶液，控制滴加速度，使得0.5h内滴加完毕。升温至85℃，反应3h；冷却至常温，过滤，得到具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂。
实施例2：
向反应釜中加入1g烷基酚聚氧乙烯醚（OP-10）和60 g去离子水，然后加入丙烯酸酯共聚单体混合物：甲基丙烯酸甲酯8.4 g，丙烯酸乙酯25 g，(4-戊烯基)三苯基溴化膦7.77 g，异蒲勒醇3.33 g，高速乳化分散10~30 min，乳化分散速度为8000 rpm，得到预乳化液。
将上述预乳化液加入到具有冷凝和搅拌装置的250 ml三口烧瓶中，温度保存在70℃，搅拌速度1000 rpm，将0.3 g引发剂过硫酸铵溶于40 g水中，过硫酸铵水溶液。向反应瓶中逐步滴加过硫酸铵水溶液，控制滴加速度，使得0.5 h内滴加完毕。升温至85℃，反应4 h；冷却至常温，过滤，得到具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂。
实施例3：
向反应釜中加入1.5 g烷基酚聚氧乙烯醚（OP-10）和75 g去离子水，然后加入丙烯酸酯共聚单体混合物：丙烯酸正丙酯10 g，甲基丙烯酸乙酯20 g，溴化乙烯基三苯基膦3 g，异薄荷醇0.33 g，高速乳化分散10~30 min，乳化分散速度为8000 rpm，得到预乳化液。
将上述预乳化液加入到具有冷凝和搅拌装置的250 ml三口烧瓶中，温度保存在70℃，搅拌速度1000 rpm，将0.3 g引发剂过硫酸铵溶于40 g水中，过硫酸铵水溶液。向反应瓶中逐步滴加过硫酸铵水溶液，控制滴加速度，使得0.5h内滴加完毕。升温至80℃，反应5 h；冷却至常温，过滤，得到具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂。
Claims (5)
1.一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂的制备方法，其特征在于是在表面活性剂的乳化作用下将丙烯酸酯共聚单体、抗菌功能性单体制备成预乳化液，然后再通过引发剂引发抗菌功能性单体与丙烯酸酯共聚单体发生共聚反应，制备一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂，其具体制备步骤如下：
（1）向反应器中加入一定量的表面活性剂，然后加入丙烯酸酯共聚单体和抗菌功能性单体，表面活性剂用量为共聚单体总量的2~5 wt%，共聚单体与水的质量比（0.4~1）:1，高速乳化分散10~30 min，搅拌速度为4000~10000 rpm，得到预乳化液；
（2）将上述预乳化液加入到具有冷凝和搅拌装置的反应器中，温度为 60~80℃，向其中滴加一定量的水溶性引发剂水溶液，控制滴加速度使得滴加时间控制在0.5~1 h，引发剂用量为共聚单体总量的0.4~1 wt%，整个反应体系中共聚单体与水的质量比为（0.2~0.5）:1；升温至75～100℃，搅拌速度500～2000 rpm，搅拌反应2～5 h，得到具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰剂；
所述的丙烯酸酯共聚单体包括软单体和硬单体两个组分，软单体为丙烯酸乙酯、丙烯酸正丙酯和丙烯酸正丁酯中的一种；硬单体为丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯中一种；抗菌功能性单体包括两种，一种为具有抗菌黏附性能且含碳碳双键的薄荷醇衍生物，另一种为具有碳碳双键的季鏻盐；软性单体与硬性单体的质量比为（1~3）:1，抗菌功能性单体用量为丙烯酸酯共聚单体和抗菌功能性单体总质量的10~25 wt%。
2.根据权利要求1所述的一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的具有碳碳双键的季鏻盐为烯丙基三苯基溴化膦、(4-戊烯基)三苯基溴化膦和溴化乙烯基三苯基膦中的一种。
3.根据权利要求1所述的一种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的具有抗菌黏附性能的薄荷醇衍生物为异胡薄荷醇、异蒲勒醇和异薄荷醇中的一种，薄荷醇衍生物用量占抗菌功能性单体总质量的10~30%。
4. 根据权利要求1所述的种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的表面活性剂为烷基酚聚氧乙烯醚（OP-10）、脂肪醇聚氧乙烯醚 (AEO-10)、多元醇聚氧乙烯醚脂肪酸酯（T-20）中的一种。
5.根据权利要求1所述的种具有双重抗菌作用的水性聚丙烯酸酯皮革涂饰材料，其特征在于所述的引发剂为过硫酸铵、过硫酸钾中的一种。
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