CN109021199B - 一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法 - Google Patents

一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法 Download PDF

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CN109021199B
CN109021199B CN201810763923.0A CN201810763923A CN109021199B CN 109021199 B CN109021199 B CN 109021199B CN 201810763923 A CN201810763923 A CN 201810763923A CN 109021199 B CN109021199 B CN 109021199B
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quaternary ammonium
ammonium salt
diisocyanate
polyurethane
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林炜
李丽
穆畅道
李海荣
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Sichuan University
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Abstract

本发明公开了一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法。首先通过多元醇与二异氰酸酯反应得到聚氨酯预聚物，然后加入制备的含有季铵盐杀菌基团的分子扩链剂，在催化剂的作用下反应1～4 h，再加入亲水扩链剂进行分子扩链反应，最后加入中和剂中和后再水中乳化得到杀菌季铵盐/聚氨酯水性涂饰材料，含有季铵盐杀菌基团的分子扩链剂具有优异的杀菌性能，且在结构上的双羟基可以与二异氰酸酯发生缩合反应，从而可在分子水平上被引入到聚氨酯基体中，不仅保持聚氨酯涂层有较高透明度和成膜性能，而且赋予聚氨酯涂料持久的杀菌性能。

Description

一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备 方法
技术领域
本发明涉及杀菌材料研究领域和水性聚氨酯皮革涂饰材料开发领域，具体涉及一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂。
背景技术
聚氨酯(polyurethane, PU)是含有重复链段（氨基甲酸酯，-NHCOO-）的高分子材料的统称。聚氨酯是由柔性链段和刚性链段构成的嵌段共聚物，因此可通过改变聚氨酯的软硬段比例对其理化性质进行调控。聚氨酯在具有良好的力学性能的同时，结构中有与人体蛋白质是同系物的类似酰胺基团(-CONH-)和酯基团(-COOR)的结构，因此与天然皮革胶原蛋白具有优异的亲和力。目前，以水为介质的高环保、低消耗的水性聚氨酯日益得到制革工业的重视，成为目前国内外最受青睐的皮革涂饰剂。其具有成膜性能好，遮盖力强， 黏结牢固， 涂层光亮、平滑、耐水、耐磨、耐热、耐寒、耐曲折、富有弹性等优点，涂饰的产品革手感丰满、舒适，且能大大提高成品革的等级，提高皮革及其制品的使用价值和经济价值。天然皮革在适宜的温度和湿度条件下极易导致细菌及霉菌等微生物的生长和繁殖。研究表明细菌在材料表明的生长、粘附以及与细胞外基质形成生物膜是导致污损材料的根本原因。微生物污损具有生长繁殖能力，其产生的霉变等用洗涤的方法往往很难清除，且对人体健康也会造成一定的安全隐患，如引起病菌的感染等。抗菌聚氨酯通过引入阻具有杀菌作用的元素或集团，阻止细菌粘附在材料表面形成生物膜。目前，防止微生物膜形成的方法主要是制备抗细菌黏附表面和向涂料中引入具有杀菌功能的物质或官能团如银季铵盐和抗菌药物。通过引入抗菌基团对材料进行改性,通过物理改性、化学改性或复合改性的方法将抗菌剂的抗菌基团引入到聚氨酯材料中,最终实现维持材料表面清洁的目的。抗菌聚氨酯可大致分为抗吸附（防污）聚氨酯和杀菌聚氨酯，或者同时具有抗吸附和杀菌特性。抗菌聚氨酯不仅可以避免由于微生物诱导引起的腐蚀，还可以阻止病原菌在聚氨酯产品上繁衍和扩散，减少疾病，因此，研究抗菌聚氨酯具有非常重要的意义。
季铵盐不仅是一种常用阳离子表面活性剂，也是一种良好的杀菌剂和消毒剂，不但杀菌能力强，起效快，而且对皮肤刺激性小，对金属及橡胶无腐蚀性。因而被广泛应用于（农业杀菌剂、公共场所（医院、游泳池）的杀菌消毒、循环水杀菌灭藻剂、水产养殖杀菌消毒剂、医疗器械的杀菌消毒剂、畜禽舍消毒剂、赤潮杀灭剂、蓝藻杀灭剂等）等杀菌消毒领域。将季铵盐引入皮革涂饰聚合物中制备抗菌涂饰剂也已有相关报道，如专利CN 103436167 A报道了一种含有聚硅氧烷,缩水甘油和季铵盐的多功能型明胶皮革涂饰剂及制备方法。鉴于季铵盐优异的杀菌性能，将季铵盐从分子水平引入聚氨酯中来开发抗菌水性聚氨酯皮革涂饰剂有望赋予其持久的杀菌性能。
基于此，本发明公开了一种含有季铵盐杀菌基团的水性聚氨酯涂饰材料的制备方法，首先通过两步法制备了含有杀菌基团的双羟基小分子扩链剂，然后通过加成聚合反应将其引入到聚氨酯基体中从而赋予聚氨酯永久的杀菌性能，此方法未见文献和专利报道。
发明内容
本发明目的在于提供一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂，其制备方法是首先通过多元醇与二异氰酸酯反应得到聚氨酯预聚物，然后加入制备的含有季铵盐杀菌基团的分子扩链剂，在催化剂的作用下反应1～4 h，再加入亲水性扩链剂进行分子扩链反应，最后加入中和剂中和后在水中乳化得到抗菌防霉季铵盐/聚氨酯水性涂饰材料，具体步骤如下：（1）将二异氰酸酯与多元醇按照摩尔比为（1.2~7）：1加入反应器中，温度为50~90 ℃，搅拌速度500～3000 rpm，搅拌反应20～60 min，得到聚氨酯预聚物；
（2）向反应器中加入具有含有的季铵盐杀菌基团的分子扩链剂，季铵盐杀菌基团的分子扩链剂与二异氰酸酯的摩尔比为(0.01～0.50): 1, 温度为80～100℃，搅拌速度100～2000 rpm，在催化剂条件下反应1～4 h；
（3）加入亲水扩链剂二羟甲基丙酸，其与二异氰酸酯的摩尔比为(0.09～0.40):1加入到反应器，温度为60～100 ℃，搅拌速度100～2000 rpm，在催化剂条件下反应1～4 h；
（4） 向反应器中加入中和剂，温度为20～50℃，搅拌速度为500～2000 rpm，中和0.5～24 h，调节pH值为7～10。将反应产物加入一定量的去离子水中，高速搅拌10~30 min，搅拌速度为6000~10000 rpm，低速搅拌1~2 h，搅拌速度为2000-4000 rpm，将产物浓缩至固含量为15%～35%，得到含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂。
其中，含有季铵盐杀菌基团的分子扩链剂的制备方法如下：
（a）.在反应器三口烧瓶中加入一定量的氯乙酰氯、溶剂、催化剂及缚酸剂，然后用恒压滴液漏斗将有机醇缓慢加到烧瓶中，在常温下反应2~4 h，反应结束除去缚酸剂，用乙醚、乙酸乙酯或二氯甲烷萃取3次，用快速柱层析分离得到氯乙酸酯，其路线如下：
Figure 326519DEST_PATH_IMAGE002
（b）.将上述制备的氯乙酸酯溶解在乙醇中，再加入一定量的N-甲基二乙醇胺，在60~120 ℃下反应6~12 h，反应结束加入沉淀剂得固体，然后再用乙醇和丙酮的混合液重结晶，得到含有季铵盐杀菌基团的分子扩链剂，其路线如下：
Figure 181343DEST_PATH_IMAGE004
所述的一种杀菌季铵盐/聚氨酯水性涂饰材料，其特征在于所述的多元醇为分子量为1000～10000的聚醚多元醇、聚乙二醇、聚酯多元醇、端羟基聚硅氧烷、端羟基聚乳酸、聚碳酸酯二醇中的一种或几种的混合物。
所述的一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂，其特征在于所述的二异氰酸酯为、异佛尔酮二异氰酸酯（IPDI）、六亚甲基二异氰酸酯（HDI）二苯基甲烷二异氰酸酯（MDI）、和赖氨酸二异氰酸酯（LDI）中的一种或几种的混合物。
所述的有机醇为长链脂肪醇辛醇、癸纯、十二醇、十四醇、十六醇、十八醇或苄醇。
所述的缚酸剂为吡啶、三乙胺或碳酸钾，催化剂为4-二甲氨基吡啶，溶剂为二氯甲烷、四氢呋喃、乙醚或丙酮中的一种，沉淀剂为乙醚、苯或者丙酮。
本发明公开了一种一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂。其制备方法首先合成季铵盐杀菌基团的双羟基小分子扩链剂，然后利用加成聚合反应将其引入到聚氨酯基体中。具有季铵盐杀菌基团的双羟基小分子扩链剂具有优异的杀菌性能，其结构上的双羟基可以与二异氰酸酯发生缩合反应从而可在分子水平上被引入到聚氨酯基体中，在保持涂层的在保持涂层的较高透明度和成膜性能的同时，可赋予聚氨酯涂料持久的杀菌性能。
具体实施案例
下面给出本发明的四个实施例，以具体说明含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法。
实施例 1
含有季铵盐杀菌基团小分子扩链剂的制备，具体操作方法如下：称取13.56 g的氯乙酰氯，二氯甲烷20 mL，27.64 g碳酸钾于三口烧瓶中，然后用恒压滴液漏斗缓慢滴加10.8g苯甲醇，常温下反应，用薄层色谱法(TLC)确定反应终点。反应结束加入适量的食盐水搅拌30 min，然后用二氯甲烷萃取3次，合并有机相用无水硫酸钠干燥，然后旋蒸除去多余的溶剂，用快速柱层析分离得到氯乙酸苄酯。称取14.76 g氯乙酸苄酯，9.53 g N-甲基二乙醇胺置于烧瓶中，然后再加入40 mL的N,N-二甲基甲酰胺(DMF)在85℃下反应，用薄层色谱法(TLC)确定反应终点，冷却，然后向混合液中加入100 mL乙醚（作为沉淀剂），冷却至室温得白色固体。再把固体溶解在乙醇中然后用乙醚再沉淀，重复3～5次，最后得双羟基季铵盐。
称取15.00 g聚碳酸酯二醇(M n=1000)于反应器中，向反应器中加入6.96 g甲苯二异氰酸酯和300 mL四氢呋喃溶剂，在氮气保护下机械搅，60 ℃下反应 1 h。加入1.50 g二羟甲基丙酸，80 ℃搅拌催化反应2 h。加入3.74 g小分子扩链剂及催化剂，80 ℃下反应24 h。加入中和剂，温度为25～60 ℃，搅拌速度为500～2000 rpm，中和2～4 h，调节pH值为3～10。将反应产物浓缩到固含量为20%～40%。将反应物加入高纯去离子水中，高速搅拌乳化0.5 h，搅拌速度为8000 rpm，得到抗菌防霉季膦盐/聚氨酯水性乳液。
实施例 2
含有季铵盐杀菌基小分子扩链剂的制备，具体操作方法如下：称取称取9.03 mL的氯乙酰氯，二氯甲烷20 mL，27.64 g碳酸钾于三口烧瓶中，然后用恒压滴液漏斗缓慢滴加13.23 g正辛醇，常温下反应，用薄层色谱法(TLC)确定反应终点，反应结束加入适量的食盐水搅拌30 min，然后用二氯甲烷萃取3次，合并有机相用无水硫酸钠干燥，然后旋蒸除去多余的溶剂，用快速柱层析分离得到氯乙酸辛酯。称取16.12 g氯乙酸辛酯,9.29 g N-甲基二乙醇胺置于烧瓶中，然后再加入40 mL 的N,N-二甲基甲酰胺(DMF)在85℃下反应，用薄层色谱法(TLC)确定反应终点，冷却，然后向混合液中加入100 mL乙醚（作为沉淀剂），冷却至室温得白色固体。再把固体溶解在乙醇中然后用乙醚再沉淀，这样重复3～5次，最后得固体双羟基季铵盐。
称取 30.00 g 聚四氢呋喃醚(Mn=2000)加入到500 mL的三口烧瓶中，真空脱水2h，温度降至60 ℃，加入10.08 g二苯基甲烷二异氰酸酯，加入300 mL四氢呋喃溶剂，在氮气保护下机械搅拌，60 ℃下反应1 h。 加入1.5 g二羟甲基丙酸，80 ℃搅拌反应2 h。加入4.63 g小分子扩链剂及催化剂，80 ℃下反应 24 h。加入中和剂，温度为25～60 ℃，搅拌速度为500～2000 rpm，中和2～4 h，调节pH值为3～10。将反应物加入高纯去离子水中，高速搅拌乳化0.5 h，搅拌速度为8000 rpm，得到抗菌防霉季膦盐/聚氨酯水性乳液，将反应产物浓缩到固含量为20%。
实施例 3
含有季铵盐杀菌基团的小分子扩链剂的制备，具体操作方法如下：取称取9.03 mL的氯乙酰氯，二氯甲烷20 mL，27.64 g碳酸钾于三口烧瓶中，然后用恒压滴液漏斗缓慢滴加正癸醇10.8 g，常温下反应，用薄层色谱法(TLC)确定反应终点，反应结束加入适量的食盐水搅拌30 min，然后用二氯甲烷萃取3次，合并有机相用无水硫酸钠干燥，然后旋蒸除去多余的溶剂，用快速柱层析分离得19.01 g氯乙酸正癸酯。称取19.01 g氯乙酸辛酯，9.65 gN-甲基二乙醇胺置于烧瓶中，然后再加入40 mL 的N,N-二甲基甲酰胺(DMF)在85 ℃下反应，用薄层色谱法(TLC)确定反应终点，冷却，然后向混合液中加入100 mL乙醚（作为沉淀剂），冷却至室温得白色固体。再把固体溶解在乙醇中然后用乙醚再沉淀，这样重复3~5次，最后得固体双羟基季铵盐。
称取30.00 g聚乙二醇(Mn=2000)，加入到500 mL的三口烧瓶中，真空脱水2 h，加入6.72 g六亚甲基二异氰酸酯（溶解在THF中），加入300 mL的THF，在氮气保护下机械搅拌，60 ℃下反应1 h。加入2.00 g二羟甲基丁酸，80 ℃搅拌反应2 h。加入4.07 g小分子扩链剂及催化剂，80 ℃下反应24 h。加入中和剂，温度为25～60 ℃，搅拌速度为500～2000 rpm，中和2～4 h，调节pH值为3～10。将反应物加入高纯去离子水中，高速搅拌乳化0.5 h，搅拌速度为8000 rpm，得到抗菌防霉季膦盐/聚氨酯水性乳液，将反应产物浓缩到固含量为30%。
实施例4
含有季铵盐杀菌基小分子扩链剂的制备，具体操作方法如下：称取9.03 mL的氯乙酰氯，二氯甲烷20 mL，27.64 g碳酸钾于三口烧瓶中，然后用恒压滴液漏斗缓慢滴加18.64g十二醇，常温下反应，用薄层色谱法(TLC)确定反应终点，反应结束加入适量的食盐水搅拌30 min，然后用二氯甲烷萃取3次，合并有机相用无水硫酸钠干燥，然后旋蒸除去多余的溶剂，用快速柱层析分离得到氯乙酸十二酯。称取20.76 g氯乙酸十二酯，9.41 g N-甲基二乙醇胺置于烧瓶中，然后再加入40 mL的N,N-二甲基甲酰胺(DMF)在85 ℃下反应，用薄层色谱法(TLC)确定反应终点，冷却，然后向混合液中加入100 mL乙醚（作为沉淀剂），冷却至室温得白色固体。再把固体溶解在乙醇中然后用乙醚再沉淀，这样重复3～5次，最后得到固体双羟基季铵盐。
称取30.00 g聚ε-己内酯二醇(Mn=2000)，加入到500 mL的三口烧瓶中，真空脱水2h，温度降至60 C，加入8.89 g异佛尔酮二异氰酸，加入300 mL THF，在氮气保护下机械搅拌，60 ℃下反应1 h。 加入1.5 g二羟甲基丙酸，80 ℃搅拌反应2 h。加入5.31 g小分子扩链剂及催化剂，80 ℃下反应24 h。加入中和剂，温度为25～60 ℃，搅拌速度为500～2000rpm，中和2～4 h，调节pH值为3～10。将反应物加入高纯去离子水中，高速搅拌乳化0.5 h，搅拌速度为8000 rpm，得到水性聚氨酯乳液，将反应产物浓缩到固含量为35%。
图1是氯乙酸酯的制备路线。
图2是以氯乙酸酯为原料，合成含有季铵盐杀菌基团的分子扩链剂的制备路线。

Claims (4)

1.一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，具体步骤如下：
（1）将二异氰酸酯与多元醇按照摩尔比为(1.2~7)：1加入反应器中，温度为50~90℃，搅拌速度500～3000rpm，搅拌反应20～60min，得到聚氨酯预聚物；
（2）向反应器中加入含有季铵盐杀菌基团的分子扩链剂，含有季铵盐杀菌基团的分子扩链剂与二异氰酸酯的摩尔比为(0.01～0.50): 1, 温度为80～100℃，搅拌速度100～2000 rpm，在催化剂条件下反应1～4 h；
（3）加入亲水扩链剂二羟甲基丙酸到反应器，其与二异氰酸酯的摩尔比为(0.09～0.40):1，温度为60～100 ℃，搅拌速度100～2000 rpm，在催化剂条件下反应1～4h；
（4）向反应器中加入中和剂，温度为20～50℃，搅拌速度为500～2000 rpm，中和0.5～24 h，调节pH值为7～10；将反应产物加入一定量的去离子水中，高速搅拌10~30 min，搅拌速度为6000~10000 rpm，低速搅拌1~2h，搅拌速度为2000~4000 rpm，将产物浓缩至固含量为15%～35%，得到含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂；
其中，含有季铵盐杀菌基团的分子扩链剂的制备方法如下：
（a）在反应器三口烧瓶中加入一定量的氯乙酰氯、溶剂、催化剂及缚酸剂，然后用恒压滴液漏斗将有机醇缓慢加到烧瓶中，在常温下反应2~4 h，反应结束除去缚酸剂，用乙醚、乙酸乙酯或二氯甲烷萃取3次，用快速柱层析分离得到氯乙酸酯，其路线如下：
Figure 199795DEST_PATH_IMAGE001
其中，所述的有机醇为C8~C18的长链脂肪醇或苄醇；所述的溶剂为二氯甲烷、四氢呋喃、乙醚或丙酮中的一种；
（b）将上述制备的氯乙酸酯溶解在乙醇中，再加入一定量的N-甲基二乙醇胺，在6~120℃下反应6~12 h，反应结束加入沉淀剂得固体，然后再用乙醇和丙酮的混合液重结晶，得到含有季铵盐杀菌基团的分子扩链剂，其路线如下：
Figure 116935DEST_PATH_IMAGE002
。
2.根据权利要求1所述的一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述的多元醇为分子量为1000～10000的聚乙二醇、端羟基聚硅氧烷、端羟基聚乳酸、聚碳酸酯二醇中的一种或几种的混合物。
3.根据权利要求1所述的一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述的二异氰酸酯为异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯和赖氨酸二异氰酸酯中的一种或几种的混合物。
4.根据权利要求1所述的一种含有季铵盐杀菌基团的水性聚氨酯皮革涂饰剂的制备方法，其特征在于，所述的缚酸剂为吡啶、三乙胺或碳酸钾中的一种，沉淀剂为乙醚、苯或者丙酮。
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