CN111116859A - 一种抗菌改性水性聚氨酯的制备方法 - Google Patents

一种抗菌改性水性聚氨酯的制备方法 Download PDF

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CN111116859A
CN111116859A CN201911425875.5A CN201911425875A CN111116859A CN 111116859 A CN111116859 A CN 111116859A CN 201911425875 A CN201911425875 A CN 201911425875A CN 111116859 A CN111116859 A CN 111116859A
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mass
parts
hyperbranched polyester
silver
waterborne polyurethane
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CN111116859B (zh
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刘海龙
钱涛
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Hangzhou Jihua Polymer Materials Co ltd
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Hangzhou Jihua Polymer Materials Co ltd
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Abstract

本发明涉及新材料合成领域，公开了一种抗菌改性水性聚氨酯的制备方法，本发明先制备一种末端为羟基、分子内含羧基的超支化聚酯作为纳米银粒子制备的稳定剂和保护剂，然后与大分子多元醇混合，共同作为羟基组分，和多异氰酸酯、扩链剂等反应，制备得到具有结构型抗菌成分的水性聚氨酯，该方法制备的纳米银粒子粒径均匀，比表面积大，且被均匀、稳定地锁定于有机高分子网格中，分散性好，不易迁移，少量添加（ppm级）与水性聚氨酯结合即可达到优异长效的抗菌性。

Description

一种抗菌改性水性聚氨酯的制备方法
技术领域
本发明涉及新材料合成领域，尤其涉及一种抗菌改性水性聚氨酯的制备方法。
背景技术
水性聚氨酯是以水代替有机溶剂作为分散介质的聚氨酯体系，与传统的溶剂型聚氨酯相比，水性聚氨酯具有无毒、不易燃、对环境友好等特点，而且水性聚氨酯结构-性能的可调节性使其同时具有弹性体和塑料的性质以及优良的耐磨性和附着力等，广泛应用于皮革/合成革涂饰剂、织物涂层与整理剂、涂料、胶黏剂、纸张表面处理剂和纤维表面处理剂等领域，具有广阔的市场前景。
不过将溶剂型体系改为水性体系会遇到一些新的问题，其中水性体系在温湿度适宜环境下，面临着大量细菌等微生物繁殖的挑战，对材料的最终性能产生干扰。同时，随着社会的发展，生活水平的不断提高，人们对健康环保越来越重视，环境中微生物无处不在，一直以来，人们的生存和健康受到各种细菌的威胁。人们日常工作生活中接触到的设施、工具、器皿等很多领域都存在抗菌需求。特别是水性聚氨酯材料在用于涂层加工时，人们对其抗菌性能的要求很高。
有机系和天然系抗菌剂的耐药性差和安全性低，市场化的生产受到很大的限制，无机抗菌材料具有安全性高、杀菌性持久和化学稳定性等优点，其中银系抗菌剂因强力的抗菌效果、良好的热稳定性、持久的抗菌效果，并对细胞及组织无明显毒性，得到了广泛的应用。同时纳米材料的尺寸在纳米级别，使其具有一些特殊的性能与独特的效应，这使得纳米银系抗菌剂在抗菌中得到了很好的应用。银系抗菌成分应用于涂料、涂层、纺织品上，人体进行接触并不会有危害，也不会产生不良反应。
纳米银粒子的制备方法主要有物理法和化学法。常用的物理法有机械球磨法、溅射法、惰性气体冷凝法、等离子体法等，这种方法制备的产品纯度较高，但采用的设备成本较高，需要消耗大量的能量使材料尺寸降低到纳米量级，并且产率较低。常用的化学法包括化学气相沉积法、电化学法、模板法、溶胶-凝胶法等，该方法的缺点是容易混入杂质，所得产品不纯，但相比物理法，具有得到的纳米材料规整均匀、利于批量生产、设备简便的优点。
纳米银的抗菌机理一般认为是接触杀菌机理，通过吸附在微生物的表面，导致细胞膜形态变化，破坏细胞膜使细胞质流出，从而杀灭微生物，从而实现更好的杀菌效果。目前一般是通过将纳米银抗菌剂添加到水性聚氨酯中，来赋予其抗菌性。然而传统方法中抗菌剂会在聚氨酯材料中发生迁移、降解等，长时间使用易造成涂层抗菌性能衰减，甚至丧失抗菌性能，使其应用具有很大的局限性。
发明内容
为了解决上述纳米银制备难以兼顾纯度和成本，以及纳米银在聚氨酯材料中性能易衰减等技术问题，本发明提供了一种抗菌改性水性聚氨酯的制备方法，本发明先制备一种末端为羟基、分子内含羧基的超支化聚酯作为纳米银粒子制备的稳定剂和保护剂，然后与大分子多元醇混合，共同作为羟基组分，和多异氰酸酯、扩链剂等反应，制备得到具有结构型抗菌成分的水性聚氨酯，该方法制备的纳米银粒子粒径均匀，比表面积大，且被均匀、稳定地锁定于有机高分子网格中，分散性好，不易迁移，少量添加(ppm级)与水性聚氨酯结合即可达到优异长效的抗菌性。
本发明的具体技术方案为：
一种抗菌改性水性聚氨酯的制备方法，包括以下步骤：
1)超支化聚酯稳定纳米银的制备：将三元醇加入到反应容器中，升温至60-80℃，至完全溶解，然后加入二元醇，升温至100-120℃，至完全溶解，加入多元酸酐，升温至140-180℃，反应至酸值为70-100mgKOH/g，即得到超支化聚酯稳定剂，三元醇、多元酸酐和二元醇的质量比为2.3-3.6∶2.9-4.6∶1；然后将其pH调节到4-6，加入硝酸银溶液，搅拌均匀后，在惰性气体保护下，缓慢滴加还原剂，室温反应4-6h后，纯化制得超支化聚酯稳定纳米银，超支化聚酯稳定剂、还原剂和硝酸银的质量比为15-35∶5-10∶1。
2)抗菌改性水性聚氨酯的制备：将1-5质量份步骤1)制备的超支化聚酯稳定纳米银与30-50质量份干燥的大分子多元醇共混，升温至50-60℃，加入15-35质量份多异氰酸酯、0.1-0.4质量份催化剂，升温至70-90℃，反应2-4h，降温至50-60℃，加入2-5质量份小分子醇类扩链剂和2-6质量份小分子亲水扩链剂，升温至70-90℃反应2-4h，降温至40-60℃，并加入10-20质量份溶剂降粘后，加入2-5质量份中和剂，反应20-40min，加入20-40质量份水和2-5质量份小分子胺类扩链剂，常温下经高速剪切乳化分散20-40min，减压蒸馏除去溶剂，即得到抗菌改性水性聚氨酯。
本发明的技术原理如下：
本发明采用超支化聚酯作为稳定剂和保护剂制备纳米银粒子，利用超支化聚酯对无机反应物的分散和包埋，其超支化网状结构可为构造有序化的无机结构提供微化学反应环境和生长空间，从而实现有机高分子相原位生长出具有尺寸、形貌和取向可控性的无机纳米银。本发明采用“A2+B3方法”(二官能度单体+三官能度单体)的方式制备超支化聚酯，三元醇具有三官能度，与有两官能度的多元酸酐进行反应，能够生成末端为羟基、分子内含有羧基(来自多元酸酐未参与醇、酸反应的羧基)的超支化聚酯。但A2和B3型单体缩聚很容易发生凝胶，且得到的聚合物分子量分布较宽，为了缓解这一现象，在体系中加入C2中间体二元醇作为中心核，同时控制多元酸酐和三元醇的比例来避免凝胶现象的产生，选用的C2单体二元醇的羟基活性较高，与三元醇相比，优先参与和二官能度的多元酸酐的反应，进而实现从一个中心核分子出发，由支化单体逐级扩散伸展形成超支化结构，控制最终产物的分散性，避免凝胶点的出现，使得制备得到的超支化聚酯结构规整，分子量分布窄。
本发明所设计合成的超支化聚酯稳定剂带有多种官能团，利于和银粒子结合。制备条件温和、绿色：用“一步加料法”合成(醇、酸单体一次性加入)，并且不需外加催化剂，可以不用或少用溶剂、常压、温度适中。将制备得到的超支化聚酯稳定纳米银作为羟基组分，和多异氰酸酯、扩链剂等反应，通过二次扩链使得纳米银粒子与聚氨酯大分子链之间产生微观网络互穿结构，使两者之间的结合更为紧密，同时也使得纳米银均匀锁定在有机高分子网格中，分散性好，不易迁移。因此最终制备得到的抗菌改性水性聚氨酯具有结构型的抗菌成分，少量添加即可达到优异长效的抗菌性。
本发明的反应原理示意如图1所示。
作为优选，步骤1)中，所述的三元醇选自三羟甲基丙烷、三羟甲基乙烷中的一种或两种。
作为优选，步骤1)中，所述的二元醇选自1，4-环己烷二甲醇和新戊二醇中的一种或两种。
作为优选，步骤1)中，所述的多元酸酐选自偏苯三酸酐和均苯四甲酸酐中的一种或两种。
作为优选，步骤1)中，所述的还原剂选自维生素C、抗坏血酸和柠檬酸纳中的一种或多种。
作为优选，步骤2)中，所述的大分多元醇为聚酯多元醇和/或聚醚多元醇；所述聚酯多元醇选自分子量为1000或2000的聚己二酸丁二醇酯、聚碳酸酯，所述聚醚多元醇选自分子量为1000或2000的聚丙二醇、聚四氢呋喃二醇。
作为优选，步骤2)中，所述多异氰酸酯选自对苯二异氰酸酯、1，5-萘二异氰酸酯和二苯基甲烷二异氰酸酯中的一种或多种；所述催化剂选自有机铋、有机锌。
作为优选，步骤2)中，所述小分子醇类扩链剂选自1，4-丁二醇、新戊二醇中的一种，所述小分子亲水扩链剂选自2，2-二羟甲基丙酸、2，2-二羟甲基丁酸。
作为优选，步骤2)中，所述溶剂选自丙酮、丁酮、四氢呋喃；所述中和剂选自三乙胺、三乙醇胺；所述小分子胺类扩链剂选自异佛尔酮二胺、二乙烯三胺。
与现有技术对比，本发明的有益效果是：
1、通过控制多元酸酐和三元醇的比例及引入二元醇作为中心核的方式，实现“A2+B3方法”以“一步加料法”的方式制备具有结构规整、分子量分布窄的富含羟基、羧基官能团超支化聚酯稳定剂，制备条件温和、绿色；制备的纳米银粒子粒径均匀，分散稳定性好。
2、超支化聚酯稳定纳米银的端基为羟基，作为羟基组分和异氰酸酯反应，进而以键接的方式将抗菌成分引入到聚氨酯大分子链中。尤其是通过二次扩链使得纳米银粒子与聚氨酯大分子链之间产生微观网络互穿结构，使两者之间的结合更为紧密，同时也使得纳米银均匀锁定在有机高分子网格中，分散性好，不易迁移。因此最终制备得到的抗菌改性水性聚氨酯具有结构型的抗菌成分，少量添加即可使赋予聚氨酯的抗菌性不易衰减。
3、本发明的合成方法简单、方便、易于工业化，得到的树脂成膜后耐候性、耐化学试剂性及抗菌性佳，与涂覆基质附着力好，能够在玻璃、PVC板材和金属板材等多种表面使用。
附图说明
图1为本发明的反应原理示意图。
具体实施方式
下面结合实施例对本发明作进一步的描述。
总实施例
一种抗菌改性水性聚氨酯的制备方法，包括以下步骤：
1)超支化聚酯稳定纳米银的制备：将三元醇加入到反应瓶中，升温至60-80℃，至完全溶解，然后加入二元醇，升温至100-120℃，至完全溶解，加入多元酸酐，升温至140-180℃，反应至酸值为70-100mgKOH/g，即得到超支化聚酯稳定剂，三元醇、多元酸酐和二元醇的质量比为2.3-3.6∶2.9-4.6∶1；然后将其pH调节到4-6，加入硝酸银溶液，搅拌均匀后，在氮气保护下，缓慢滴加新配置的还原剂，室温反应4-6h后，纯化制得超支化聚酯稳定纳米银，超支化聚酯稳定剂、还原剂和硝酸银的质量比为15-35∶5-10∶1。
所述的三元醇选自三羟甲基丙烷、三羟甲基乙烷。所述的二元醇选自1，4-环己烷二甲醇、新戊二醇。所述的多元酸酐选自偏苯三酸酐、均苯四甲酸酐。所述的还原剂选自维生素C、抗坏血酸、柠檬酸纳。
2)抗菌改性水性聚氨酯的制备：将1-5质量份步骤1)制备的超支化聚酯稳定纳米银与30-50质量份干燥的大分子多元醇共混，升温至50-60℃，加入15-35质量份多异氰酸酯、0.1-0.4质量份催化剂，升温至70-90℃，反应2-4h，降温至50-60℃，加入2-5质量份小分子醇类扩链剂和2-6质量份小分子亲水扩链剂，升温至70-90℃反应2-4h，降温至40-60℃，并加入10-20质量份溶剂降粘后，加入2-5质量份中和剂，反应20-40min，加入20-40质量份去离子水和2-5质量份小分子胺类扩链剂，常温下经高速剪切乳化分散20-40min，减压蒸馏除去溶剂，即得到抗菌改性水性聚氨酯。
所述的大分多元醇为聚酯多元醇和/或聚醚多元醇；所述的聚酯多元醇选自分子量为1000或2000的聚己二酸丁二醇酯、聚碳酸酯，所述的聚醚多元醇选自分子量为1000或2000的聚丙二醇、聚四氢呋喃二醇。所述的多异氰酸酯选自对苯二异氰酸酯、1，5-萘二异氰酸酯、二苯基甲烷二异氰酸酯；所述的催化剂选自有机铋、有机锌。所述小分子醇类扩链剂选自1，4-丁二醇、新戊二醇中的一种，所述的小分子亲水扩链剂选自2，2-二羟甲基丙酸、2，2-二羟甲基丁酸。所述的溶剂选自丙酮、丁酮、四氢呋喃；所述的中和剂选自三乙胺、三乙醇胺；所述的小分子胺类扩链剂选自异佛尔酮二胺、二乙烯三胺。
实施例1
1)超支化聚酯稳定纳米银的制备：将三羟甲基丙烷加入到反应瓶中，升温至80℃，至完全溶解，然后加入新戊二醇，升温至120℃，至完全溶解，加入均苯四甲酸酐，升温至180℃，反应至酸值为100mgKOH/g，即得到超支化聚酯稳定剂，三羟甲基丙烷、均苯四甲酸酐和新戊二醇的质量比为3.6∶4.6∶1；然后将其pH调节到4，加入硝酸银溶液，搅拌均匀后，在氮气保护下，缓慢滴加新配置的维生素C，室温反应6h后，纯化制得超支化聚酯稳定纳米银，超支化聚酯稳定剂、维生素C和硝酸银的质量比为35∶10∶1；超支化聚酯稳定剂经GPC测试得到其数均分子量为2465，分子量分布指数为1.42。
2)抗菌改性水性聚氨酯的制备：将5质量份步骤1)制备的超支化聚酯稳定纳米银与50质量份干燥的聚己二酸丁二醇酯(分子量为1000)共混，升温至60℃，加入35质量份对苯二异氰酸酯、0.4质量份有机铋催化剂，升温至90℃，反应2h，降温至60℃，加入5质量份1，4-丁二醇和6质量份2，2-二羟甲基丙酸，升温至90℃反应2h，降温至60℃，并加入20质量份丙酮降粘后，加入5质量份三乙胺，反应20min，加入40质量份去离子水和5质量份异佛尔酮二胺，常温下经高速剪切乳化分散20min，减压蒸馏除去溶剂，即得到抗菌改性水性聚氨酯。
实施例2
1)超支化聚酯稳定纳米银的制备：将三羟甲基乙烷加入到反应瓶中，升温至60℃，至完全溶解，然后加入1，4-环己烷二甲醇，升温至100℃，至完全溶解，加入偏苯三酸酐，升温至140℃，反应至酸值为70mgKOH/g，即得到超支化聚酯稳定剂，三羟甲基乙烷、偏苯三酸酐和1，4-环己烷二甲醇的质量比为2.3∶2.9∶1；然后将其pH调节到6，加入硝酸银溶液，搅拌均匀后，在氮气保护下，缓慢滴加新配置的抗坏血酸，室温反应4h后，纯化制得超支化聚酯稳定纳米银，超支化聚酯稳定剂、抗坏血酸和硝酸银的质量比为15∶5∶1；超支化聚酯稳定剂经GPC测试得到其数均分子量为2617，分子量分布指数为1.49。
2)抗菌改性水性聚氨酯的制备：将1质量份步骤1)制备的超支化聚酯稳定纳米银与30质量份干燥的聚碳酸酯(分子量为2000)共混，升温至50℃，加入15质量份1，5-萘二异氰酸酯、0.1质量份有机锌催化剂，升温至70℃，反应4h，降温至50℃，加入2质量份新戊二醇和2质量份2，2-二羟甲基丁酸，升温至70℃反应4h，降温至40℃，并加入10质量份丁酮降粘后，加入2质量份三乙醇胺，反应40min，加入20质量份去离子水和2质量份二乙烯三胺，常温下经高速剪切乳化分散40min，减压蒸馏除去溶剂，即得到抗菌改性水性聚氨酯。
实施例3
1)超支化聚酯稳定纳米银的制备：将三羟甲基丙烷加入到反应瓶中，升温至80℃，至完全溶解，然后加入新戊二醇，升温至120℃，至完全溶解，加入偏苯三酸酐，升温至140℃，反应至酸值为70mgKOH/g，即得到超支化聚酯稳定剂，三羟甲基丙烷、偏苯三酸酐和新戊二醇的质量比为3.6∶4.1∶1；然后将其pH调节到4，加入硝酸银溶液，搅拌均匀后，在氮气保护下，缓慢滴加新配置的柠檬酸纳，室温反应4h后，纯化制得超支化聚酯稳定纳米银，超支化聚酯稳定剂、柠檬酸纳和硝酸银的质量比为20∶8∶1；超支化聚酯稳定剂经GPC测试得到其数均分子量为2590，分子量分布指数为1.51。
2)抗菌改性水性聚氨酯的制备：将3质量份步骤1)制备的超支化聚酯稳定纳米银与40质量份干燥的聚丙二醇(分子量为2000)共混，升温至60℃，加入25质量份二苯基甲烷二异氰酸酯、0.2质量份有机锌催化剂，升温至80℃，反应3h，降温至60℃，加入3质量份1，4-丁二醇和4质量份2，2-二羟甲基丁酸，升温至80℃反应3h，降温至60℃，并加入15质量份四氢呋喃降粘后，加入3质量份三乙醇胺，反应30min，加入30质量份去离子水和3质量份异佛尔酮二胺，常温下经高速剪切乳化分散30min，减压蒸馏除去溶剂，即得到抗菌改性水性聚氨酯。
实施例4
1)超支化聚酯稳定纳米银的制备：将三羟甲基丙烷加入到反应瓶中，升温至80℃，至完全溶解，然后加入1，4-环己烷二甲醇，升温至120℃，至完全溶解，加入均苯四甲酸酐，升温至160℃，反应至酸值为80mgKOH/g，即得到超支化聚酯稳定剂，三羟甲基丙烷、均苯四甲酸酐和1，4-环己烷二甲醇的质量比为2.6∶3.3∶1；然后将其pH调节到4，加入硝酸银溶液，搅拌均匀后，在氮气保护下，缓慢滴加新配置的维生素C，室温反应5h后，纯化制得超支化聚酯稳定纳米银，超支化聚酯稳定剂、维生素C和硝酸银的质量比为30∶10∶1；超支化聚酯稳定剂经GPC测试得到其数均分子量为2632，分子量分布指数为1.48。
2)抗菌改性水性聚氨酯的制备：将5质量份步骤1)制备的超支化聚酯稳定纳米银与50质量份干燥的聚四氢呋喃二醇(分子量为1000)共混，升温至60℃，加入35质量份对苯二异氰酸酯、0.3质量份有机铋催化剂，升温至90℃，反应2h，降温至60℃，加入5质量份1，4-丁二醇和6质量份2，2-二羟甲基丙酸，升温至90℃反应2h，降温至60℃，并加入20质量份丙酮降粘后，加入5质量份三乙胺，反应20min，加入40质量份去离子水和5质量份异佛尔酮二胺，常温下经高速剪切乳化分散20min，减压蒸馏除去溶剂，即得到抗菌改性水性聚氨酯。
对比例1
与实施例1的区别仅在于，未采用稳定剂，直接通过硝酸银在还原剂维生素C的作用下制备得到银粒子，再加入到水性聚氨酯反应体系中，其余步骤以及物料与组成与实施例1一致。
对比例2
与实施例1的区别仅在于，采用聚乙烯吡咯烷酮(PVP)为稳定剂制备纳米银，其余步骤以及物料与组成与实施例1一致。
对比例3
与实施例1的区别仅在于，超支化聚酯稳定纳米银在水性聚氨酯反应完成后加入，其余步骤以及物料与组成与实施例1一致。
对比例4
与实施例1的区别仅在于，步骤2)中未添加小分子胺类扩链剂异佛尔酮二胺，未进行二次扩链反应，其余步骤以及物料与组成与实施例1一致。。
对比例5
与实施例1的区别仅在于，步骤1)中制备超支化聚酯稳定剂未添加C2单体新戊二醇，制备的超支化聚酯稳定剂经GPC测试得到其数均分子量为4970，分子量分布指数为2.68，分子量分布很宽，其余步骤以及物料与组成与实施例1一致。
将本实施例1-4及对比例1-5制得的抗菌改性水性聚氨酯分别涂覆在铝板上(厚度为15～20μm)，然后对其耐冲击性、耐溶剂擦洗性、抗菌性及长效抗菌性等性能进行检测，耐冲击性测试按GB/T 1732规定进行，结果评定：4倍放大镜观察，漆膜无裂纹、皱纹及剥落现象；耐溶剂擦洗性测试按GB/T 23989中仪器擦拭法规定进行，溶剂为丁酮；抗菌性测试按ISO 22196-2011规定进行，结果评定：对金黄色葡萄球菌和大肠杆菌的抗菌效力值≥2；长效抗菌性测试通过采用丁酮对抗菌改性水性聚氨酯涂层的浸泡洗脱来模仿使用情况，抗菌性根据ISO 22196-2011规定进行测试，结果评定：洗脱50次后，抗菌效力值≥2。
表1实施例1-4以及对比例1-3产品性能测试结果：
耐冲击性 耐溶剂擦洗性 抗菌性 长效抗菌性
实施例1 合格 合格 合格 合格
实施例2 合格 合格 合格 合格
实施例3 合格 合格 合格 合格
实施例4 合格 合格 合格 合格
对比例1 不合格 不合格 合格 不合格
对比例2 不合格 合格 合格 不合格
对比例3 不合格 不合格 合格 不合格
对比例4 合格 合格 合格 不合格
对比例5 不合格 不合格 合格 不合格
经检验，对比例1未采用稳定剂，制备的银粒子粒径较大，且不均匀，大部分为μm级，加入到水性聚氨酯体系中，分散稳定性不佳，造成涂层缺陷，因此耐冲击性和耐溶剂擦洗性都不好，虽然有一定的抗菌性，经过洗脱，立即丧失；对比例2采用常用的聚合物PVP作为稳定剂，制备得到的纳米银粒子较好，但和水性聚氨酯相容性较差，制备的涂层也会出现缺陷，抗冲击性较差，不过由于是在水性聚氨酯反应前加入，聚氨酯大分子链会对其进行一定的包裹，因此耐溶剂擦洗性尚可，长效抗菌性也有所提升，但也未通过洗脱50次后的抗菌试验；对比例3的超支化聚酯稳定纳米银在水性聚氨酯反应完成后加入，并未作为羟基组分参与到聚氨酯的反应中，因此是一种添加型抗菌而非结构型抗菌，与聚氨酯体系结合较差，各项性能都较差；对比例4未采用二次扩链进一步锁定纳米银在有机高分子网络中，因此虽然耐冲击性、耐溶剂性、抗菌性能够通过测试，但经过洗脱之后银粒子会逐渐流失，因而丧失抗菌性，对比例5制备的超支化聚酯稳定剂未添加C2单体来控制超支化聚酯的分子量及其分布，制备的纳米银性能不稳定，无法稳定分散在有机相中，使得最终涂层的抗冲击性、耐溶剂性差，且很容易就被洗脱，失去抗菌性。该实施例1-4的抗菌改性水性聚氨酯相对于对比例而言，具有优异的耐冲击性、耐溶剂擦洗性、抗菌性及长效抗菌性，说明由C2单体调控的超支化聚酯稳定剂结构规整，以其稳定制备得到的纳米银分散稳定性好，作为羟基组分，引入到了聚氨酯的大分子链中，以结构型的键接方式，并经过二次扩链锁定在有机相网络中，抗菌性能既优异又长效。
本发明中所用原料、设备，若无特别说明，均为本领域的常用原料、设备；本发明中所用方法，若无特别说明，均为本领域的常规方法。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换，均仍属于本发明技术方案的保护范围。

Claims (10)

1.一种抗菌改性水性聚氨酯的制备方法，其特征在于包括以下步骤：
1）超支化聚酯稳定纳米银的制备：将三元醇加入到反应容器中，升温至60-80℃，至完全溶解，然后加入二元醇，升温至100-120℃，至完全溶解，加入多元酸酐，升温至140-180℃，反应至酸值为70-100mgKOH/g，即得到超支化聚酯稳定剂，三元醇、多元酸酐和二元醇的质量比为2.3-3.6:2.9-4.6:1；然后将其pH调节到4-6，加入硝酸银溶液，搅拌均匀后，在惰性气体保护下，缓慢滴加还原剂，室温反应4-6h后，纯化制得超支化聚酯稳定纳米银，超支化聚酯稳定剂、还原剂和硝酸银的质量比为15-35:5-10:1；
2）抗菌改性水性聚氨酯的制备：将1-5质量份步骤1）制备的超支化聚酯稳定纳米银与30-50质量份干燥的大分子多元醇共混，升温至50-60℃，加入15-35质量份多异氰酸酯、0.1-0.4质量份催化剂，升温至70-90℃，反应2-4h，降温至50-60℃，加入2-5质量份小分子醇类扩链剂和2-6质量份小分子亲水扩链剂，升温至70-90℃反应2-4h，降温至40-60℃，并加入10-20质量份溶剂降粘后，加入2-5质量份中和剂，反应20-40min，加入20-40质量份水和2-5质量份小分子胺类扩链剂，常温下经高速剪切乳化分散20-40min，减压蒸馏除去溶剂，即得到抗菌改性水性聚氨酯。
2.如权利要求1所述的制备方法，其特征在于：步骤1）中：
所述三元醇选自三羟甲基丙烷、三羟甲基乙烷中的一种或两种；和/或
所述二元醇选自1,4-环己烷二甲醇和新戊二醇中的一种或两种；和/或
所述多元酸酐选自偏苯三酸酐和均苯四甲酸酐中的一种或两种。
3.如权利要求1所述的制备方法，其特征在于：步骤1）中：所述还原剂选自维生素C、抗坏血酸和柠檬酸纳中的一种或多种。
4.如权利要求1所述的制备方法，其特征在于：步骤2）中，所述大分多元醇为聚酯多元醇和/或聚醚多元醇。
5.如权利要求4所述的制备方法，其特征在于：所述聚酯多元醇选自分子量为1000或2000的聚己二酸丁二醇酯、聚碳酸酯；所述聚醚多元醇选自分子量为1000或2000的聚丙二醇、聚四氢呋喃二醇。
6.如权利要求1所述的制备方法，其特征在于：步骤2）中，所述多异氰酸酯选自对苯二异氰酸酯、1,5-萘二异氰酸酯和二苯基甲烷二异氰酸酯中的一种或多种。
7.如权利要求1所述的制备方法，其特征在于：步骤2）中，所述催化剂选自有机铋、有机锌。
8.如权利要求1所述的制备方法，其特征在于：步骤2）中，所述小分子醇类扩链剂选自1,4-丁二醇、新戊二醇中的一种；所述小分子亲水扩链剂选自2,2-二羟甲基丙酸、2,2-二羟甲基丁酸。
9.如权利要求1所述的制备方法，其特征在于：步骤2）中，所述小分子胺类扩链剂选自异佛尔酮二胺、二乙烯三胺。
10.如权利要求1所述的制备方法，其特征在于：步骤2）中，所述溶剂选自丙酮、丁酮、四氢呋喃；所述中和剂选自三乙胺、三乙醇胺。
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CN112592470A (zh) * 2020-12-10 2021-04-02 万华化学集团股份有限公司 一种抗菌聚酯多元醇及其制备方法，及一种抗菌聚氨酯
CN113563791A (zh) * 2021-07-26 2021-10-29 安徽明能电气有限公司 一种利用金刚石粉体可控制备mpp非开挖管表面涂层的方法
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CN112592470A (zh) * 2020-12-10 2021-04-02 万华化学集团股份有限公司 一种抗菌聚酯多元醇及其制备方法，及一种抗菌聚氨酯
CN112592470B (zh) * 2020-12-10 2022-07-26 万华化学集团股份有限公司 一种抗菌聚酯多元醇及其制备方法，及一种抗菌聚氨酯
CN113563791A (zh) * 2021-07-26 2021-10-29 安徽明能电气有限公司 一种利用金刚石粉体可控制备mpp非开挖管表面涂层的方法
CN114311861A (zh) * 2021-12-28 2022-04-12 浙江东进新材料有限公司 防水抗菌复合功能面料
CN116120829A (zh) * 2023-01-09 2023-05-16 天津初心莫移科技有限责任公司 氨酯-丙烯酸酯/纳米金属阻燃抗菌涂料及其制备方法

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