CN107987304B - 一种壳聚糖-聚氨酯防雾薄膜的制备方法 - Google Patents

一种壳聚糖-聚氨酯防雾薄膜的制备方法 Download PDF

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CN107987304B
CN107987304B CN201711370248.7A CN201711370248A CN107987304B CN 107987304 B CN107987304 B CN 107987304B CN 201711370248 A CN201711370248 A CN 201711370248A CN 107987304 B CN107987304 B CN 107987304B
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姚伯龙
谈敏
徐颖聪
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Abstract

本发明的目的在于提供一种壳聚糖镶嵌到聚氨酯膜上制备超亲水聚氨酯薄膜的方法。本发明的聚酯型水性聚氨酯膜表面嵌入壳聚糖，制备的薄膜表面聚集大量羟基和氨基，这样薄膜既有一定的耐水性、耐溶剂性同时具有亲水特性和自清洁、防污的功能。

Description

一种壳聚糖-聚氨酯防雾薄膜的制备方法
技术领域
本发明属于高分子材料的制备领域，具体涉及一种壳聚糖-聚氨酯防雾薄膜的制备方法
背景介绍
壳聚糖是具有多羟基、氨基等亲水基团的化合物，将其与合成高分子聚合物结合，能够大大的扩大高分子材料的应用性能，如防雾、防污、抑菌、自清洁等，尤其在防雾性能方面，有很大的应用前景，因其携带的亲水基团能大大降低膜表面的张力达到超亲水的效果，从而温差存在时水蒸气不能在冷凝析出，起到防雾的效果。壳聚糖在地球上的含量是仅次于纤维素的第二大有机高分子材料，其来源非常广泛，主要存在于甲壳纲动物虾和蟹的甲壳、昆虫的甲壳、真菌的细胞壁和植物的细胞壁中，壳聚糖作为高分子材料不仅绿色环保且价格低廉，在目前和将来都有很大的发展前景；目前有壳聚糖固定在聚丙烯膜上用于包装食品，起抑菌的效果，也有壳聚糖与聚丙烯酰胺自组装制备防雾薄膜等的应用。
聚氨酯树脂具有耐水、耐溶剂、高强度、抗撕裂、耐磨等特性的高分子材料,易于涂膜且性能强，壳聚糖-聚氨酯结合制备的薄膜在充分发挥壳聚糖亲水特性的同时兼具有聚氨酯薄膜的耐水、耐溶剂、强度高和抗撕裂的性能。
发明内容
本发明的目的在于提供一种壳聚糖镶嵌到聚氨酯膜上制备超亲水聚氨酯薄膜的方法。本发明的聚酯型水性聚氨酯膜表面嵌入壳聚糖，制备的薄膜表面聚集大量羟基和氨基，这样薄膜既有一定的耐水性、耐溶剂性同时具有亲水特性和自清洁、防污的功能。
本发明的技术方案是：
一种壳聚糖-聚氨酯防雾薄膜的制备方法，包括如下步骤：
(1)壳聚糖的提取：首先将虾壳、蟹壳的肉质、污物杂质去除，用水洗净，然后干燥；先用强碱浸泡然后用稀酸浸泡除原料中蛋白质、脂肪和无机盐；接下来进行脱色处理，采用高锰酸钾、亚硫酸氢钠进行氧化脱色；最后利用强碱进行脱乙酰基，然后过滤、水洗至中性、干燥得到壳聚糖；
(2)聚氨酯的合成:将一定量的催化剂和二异氰酸酯加入250ml三口烧瓶中将温度升至48-50℃滴加一定量的聚酯二元醇，反应3-4h当NCO达到理论值时结束，得到初聚体。再将初聚体温度控制在78-80℃，加入扩链剂反应2-3小时当NCO达到理论值后降温到60-65℃加入活性封端剂、阻聚剂保温反应3小时，当-NCO红外吸收峰完全消失时终止反应。将反应温度降至35-40℃，加入一定量的中和剂，高速剪切30min，再加入去离子水，剪切乳化30min，即得水性聚氨酯乳液；
(3)制备聚氨酯薄膜：将聚氨酯溶液加入到聚四氟乙烯槽中固化成膜；
(4)壳聚糖固定在聚氨酯上：将PU膜切片一定大小，在异丙醇中超声清洗，再用去离子水清洗干净，30℃真空干燥，然后用氧等粒子体激活膜的表面；然后将膜浸入丁烯醛溶液中半小时，用去离子水冲洗，将膜浸入壳聚糖溶液，并保持温度在4℃以下，保持反应12h，最后用体积分数为1％的冰醋酸溶液清洗壳聚糖固定膜，用NaOH中和，用去离子水冲洗，真空干燥得到壳聚糖改性聚氨酯膜；
步骤(1)中所述强碱为氢氧化钠(NaOH)、氢氧化钾(KOH)其中的至少一种；
步骤(1)中所述稀酸为盐酸(HCl)、醋酸(HAc)中至少一种；
步骤(2)中所述扩链剂为二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)中的至少一种；
步骤(2)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种；
步骤(2)中所述二异氰酸酯为甲苯二异氰酸酯(TDI)、4,4'-二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、1,6-己二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)中的至少一种；
步骤(2)中所述活性封端剂为丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟丙酯(HPA)、甲基丙烯酸羟丙酯(HPMA)、季戊四醇三丙烯酸酯(PETA)中的至少一种；
步骤(2)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种；
步骤(2)中所述聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的至少一种；
步骤(2)中所述中和剂为三乙胺；
本发明的有益效果是：通过以上反应，合成超亲水型兼具耐水、抗菌壳聚糖-聚氨酯薄膜。该种制备方法可以应用于给玻璃镜片涂布薄膜，提高镜片的防雾性能和自清洁防污性能，在一定程度还有抗菌的效果；
具体实施方式
实施例1
壳聚糖的提取：取蟹壳洗涤、晾干、粉碎。称取碎壳100g，加入2mol/L氢氧化钠溶液(400ml)，软皂(10g)，水浴80℃加热磁力持续搅拌3h，停止搅拌，然后离心30min。将壳捞出，再用2mol/L氢氧化钠溶液(400ml)，水浴80°加热磁力持续搅拌8h。将经过两次处理后的壳捞出，纱布过滤，水洗至中性，沥干。加入1mol/L的盐酸溶液(1000ml)搅拌反应30min。将壳捞出，用1mol/L的盐酸(500ml)搅拌反应1h，纱布过滤，大量水洗至中性，挤去水分，真空干燥。接下来进行脱色处理，取干燥产品，加入4倍量无水乙醇，加热回流3h。过滤，滤饼用清水漂洗后加入1‰高锰酸钾溶液(1:2)浸泡2h。过滤，滤饼再用1％亚硫酸氢钠溶液(1:2)浸泡2h，得乳白色半透明产品，真空干燥，最后进行脱乙酰处理，将产品放入装有100ml质量分数为50％氢氧化钠溶液的250ml锥形瓶中，常温磁力搅拌1h，过滤并洗涤至中性，然后真空干燥备用。
壳聚糖溶液的制备：量筒量取1ml冰醋酸，加入到装有99ml去离子水的烧杯里，并用玻璃棒搅拌均匀，既为配置好的1％的醋酸溶液，然后称取1g干燥的壳聚糖加入醋酸溶液中，玻璃棒搅拌至壳聚糖完全溶解，得到1％的壳聚糖溶液。
聚氨酯的合成：将0.03g二月桂酸二丁基锡(DTBDL)和5.62g异佛尔酮二异氰酸酯(IPDI)加入100ml三口烧瓶中将温度升至50℃，氮气氛围下滴加25g聚碳酸酯二醇，反应4小时当NCO达到理论值时结束，得到初聚体；再将初聚体温度控制在80℃，加入0.856g二羟甲基丙酸(DMPA)反应3小时当NCO达到理论值后降温到60℃加入0.829g甲基丙烯酸羟乙酯(HEMA)活性封端剂、0.01g对甲氧基苯酚、5.0g丙酮保温反应3小时，NCO达到理论值，反应停止，NCO半封端聚酯型预聚物；称取0.402g三羟甲基丙烷(TMP)和0.09g二月桂酸二丁基锡(DTBDL)加入到250ml三口烧排中将温度升至65℃，然后将NCO半封端聚酯型预聚物缓慢滴入三口烧瓶中，保温反应3h，当-NCO红外吸收峰完全消失时终止反应，将温度降至室温，加入2.60g三乙胺中和剂，高速剪切30min，再加入50.0g离子水，剪切乳化40min，减压旋蒸除去丙酮，既得水性聚氨酯乳液；
聚氨酯薄膜的制备：称取10g聚氨酯乳液，加入0.3g1173光引发剂，超声30min使1173完全溶解，然后将乳液倒入聚四氟乙烯模板中避光静止一天，然后烘箱60℃干燥3h，然后光固化2min，既得聚氨酯薄膜，最后将膜剪成边长为2cm的正方形，放入无尘袋里面保存备用。
壳聚糖固定在聚氨酯膜上：取四片PU膜切片，标上编号PU-1、PU-2、PU-3、PU-4放入50ml异丙醇溶液中超声清洗，再用去离子水清洗干净，30℃真空干燥，然后用氧等离子体激活膜的表面；然后将膜浸入50ml丁烯醛溶液中30min，用去离子水冲洗，将膜浸入1％壳聚糖溶液，并保温4℃左右，保持反应12h，最后用1％的冰醋酸溶液清洗壳聚糖固定膜，用NaOH中和，用去离子水冲洗，真空干燥得到壳聚糖改性聚氨酯膜；
实施例2
壳聚糖的提取：取蟹壳洗涤、晾干、粉碎。称取碎壳100g，加入2mol/L氢氧化钠溶液(400ml)，软皂(10g)，水浴80°加热磁力持续搅拌3h，停止搅拌，然后离心30min。将壳捞出，再用2mol/L氢氧化钠溶液(400ml)，水浴80°加热磁力持续搅拌8h。将经过两次处理后的壳捞出，纱布过滤，水洗至中性，沥干。加入1mol/L的盐酸溶液(1000ml)搅拌反应30min。将壳捞出，用1mol/L的盐酸(500ml)搅拌反应1h，纱布过滤，大量水洗至中性，挤去水分，真空干燥。接下来进行脱色处理，取干燥产品，加入4倍量无水乙醇，加热回流3h。过滤，滤饼用清水漂洗后加入1‰高锰酸钾溶液(1:2)浸泡2h。过滤，滤饼再用1％亚硫酸氢钠溶液(1:2)浸泡2h，得乳白色半透明产品，真空干燥，最后进行脱乙酰处理，将产品放入装有100ml质量分数为50％氢氧化钠溶液的250ml锥形瓶中，常温磁力搅拌1h，过滤并洗涤至中性，然后真空干燥备用。
壳聚糖溶液的制备：量筒量取1ml冰醋酸，加入到装有99ml去离子水的烧杯里，并用玻璃棒搅拌均匀，既为配置好的1％的醋酸溶液，然后称取1g干燥的壳聚糖加入醋酸溶液中，玻璃棒搅拌至壳聚糖完全溶解，得到1％的壳聚糖溶液。
聚氨酯的合成：将0.03g二月桂酸二丁基锡(DTBDL)和5.62g异佛尔酮二异氰酸酯(IPDI)加入100ml三口烧瓶中将温度升至50℃，氮气氛围下滴加25g聚碳酸酯二醇，反应4小时当NCO达到理论值时结束，得到初聚体；再将初聚体温度控制在80℃，加入1.023g二羟甲基丁酸(DMBA)反应3小时当NCO达到理论值后降温到60℃加入5.79g季戊四醇三丙烯酸酯(PETA)活性封端剂、0.01g对甲氧基苯酚、5.0g丙酮保温反应3小时，NCO达到理论值，反应停止，NCO半封端聚酯型预聚物；称取0.402g三羟甲基丙烷(TMP)和0.09g二月桂酸二丁基锡(DTBDL)加入到250ml三口烧排中将温度升至65℃，然后将NCO半封端聚酯型预聚物缓慢滴入三口烧瓶中，保温反应3h，当-NCO红外吸收峰完全消失时终止反应，将温度降至室温，加入2.60g三乙胺中和剂，高速剪切30min，再加入50.0g离子水，剪切乳化40min，减压旋蒸除去丙酮，既得水性聚氨酯乳液；
聚氨酯薄膜的制备：称取10g聚氨酯乳液，加入0.3g1173光引发剂，超声30min使1173完全溶解，然后将乳液倒入聚四氟乙烯模板中避光静止一天，然后烘箱60℃干燥3h，然后光固化2min，既得聚氨酯薄膜，最后将膜剪成边长为2cm的正方形，放入无尘袋里面保存备用。
壳聚糖固定在聚氨酯膜上：取四片PU膜切片，标上编号PU-1、PU-2、PU-3、PU-4放入50ml异丙醇溶液中超声清洗，再用去离子水清洗干净，30℃真空干燥，然后用氧等粒子体激活膜的表面；然后将膜浸入50ml丁烯醛溶液中30min，用去离子水冲洗，将膜浸入1％壳聚糖溶液，并保温4℃左右，保持反应12h，最后用1％的冰醋酸溶液清洗壳聚糖固定膜，用NaOH中和，用去离子水冲洗，真空干燥得到壳聚糖-聚氨酯膜。

Claims (2)

1.一种壳聚糖-聚氨酯防雾薄膜的制备方法，包括如下步骤：
(1)壳聚糖的提取：首先将虾壳、蟹壳的肉质、污物杂质去除，用水洗净，然后干燥；先用强碱浸泡然后用稀酸浸泡除原料中蛋白质、脂肪和无机盐；接下来进行脱色处理，采用高锰酸钾、亚硫酸氢钠进行氧化脱色；最后利用强碱进行脱乙酰基，然后过滤、水洗至中性、干燥得到壳聚糖；
(2)聚氨酯的合成:将一定量的催化剂和二异氰酸酯加入250ml三口烧瓶中将温度升至48-50℃滴加一定量的聚酯二元醇，反应3-4h当NCO达到理论值时结束，得到初聚体；再将初聚体温度控制在78-80℃，加入扩链剂反应2-3小时当NCO达到理论值后降温到60-65℃加入活性封端剂、阻聚剂保温反应3小时，当-NCO红外吸收峰完全消失时终止反应；将反应温度降至35-40℃，加入一定量的中和剂，高速剪切30min，再加入去离子水，剪切乳化30min，即得水性聚氨酯乳液；
(3)制备聚氨酯薄膜：将聚氨酯乳液加入到聚四氟乙烯槽中固化成膜；
(4)壳聚糖固定在聚氨酯上：将PU膜切片一定大小，在异丙醇中超声清洗，再用去离子水清洗干净，30℃真空干燥，然后用氧等离子体激活膜的表面；然后将膜浸入丁烯醛溶液中半小时，用去离子水冲洗，将膜浸入壳聚糖溶液，并保持温度在4℃以下，保持反应12h，最后用体积分数为1％的冰醋酸溶液清洗壳聚糖固定膜，用NaOH中和，用去离子水冲洗，真空干燥得到壳聚糖改性聚氨酯膜。
2.如权利要求1所述的一种壳聚糖-聚氨酯防雾薄膜的制备方法，其特征在于：
步骤(1)中所述强碱为氢氧化钠(NaOH)、氢氧化钾(KOH)其中的至少一种；
步骤(1)中所述稀酸为盐酸(HCl)、醋酸(HAc)中至少一种；
步骤(2)中所述扩链剂为二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)中的至少一种；
步骤(2)中所述催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种；
步骤(2)中所述二异氰酸酯为甲苯二异氰酸酯(TDI)、4,4'-二苯基甲烷二异氰酸酯(MDI)、异佛尔酮二异氰酸酯(IPDI)、1,6-己二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)中的至少一种；
步骤(2)中所述活性封端剂为丙烯酸羟乙酯(HEA)、甲基丙烯酸羟乙酯(HEMA)、丙烯酸羟丙酯(HPA)、甲基丙烯酸羟丙酯(HPMA)、季戊四醇三丙烯酸酯(PETA)中的至少一种；
步骤(2)中所述阻聚剂为对苯二酚、对甲氧基苯酚中的至少一种；
步骤(2)中所述聚酯二元醇为聚碳酸酯二元醇、聚己内酯二元醇、己二酸聚酯二元醇中的至少一种；
步骤(2)中所述中和剂为三乙胺。
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