CN114232389A - 一种超疏水纸及其制备方法 - Google Patents

一种超疏水纸及其制备方法 Download PDF

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CN114232389A
CN114232389A CN202111589665.7A CN202111589665A CN114232389A CN 114232389 A CN114232389 A CN 114232389A CN 202111589665 A CN202111589665 A CN 202111589665A CN 114232389 A CN114232389 A CN 114232389A
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王胜丹
吉兴香
田中建
叶孟廷
吕英仁
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Qilu University of Technology
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Abstract

本发明公开了一种超疏水纸及其制备方法。该方法包括以下步骤:(1)将纳米纤维素进行脱水干燥,得到微纳米颗粒;(2)将步骤(1)所得微纳米颗粒分散于有机溶剂中,再加入低表面能的表面改性剂混合制备成涂料A液;(3)将交联剂溶于水中制备涂料B液;(4)将涂料B液涂于纸张表面后,再将涂料A液涂于纸张表面,得到静态接触角高达164°的超疏水纸。本发明通过表面涂布的方式制备一种超疏水纸,可有效提高普通纸张的疏水性能,使普通纸张具有良好的疏水性及自清洁性能,具有良好经济效益。

Description

一种超疏水纸及其制备方法
技术领域
本发明属于功能纸领域,具体涉及一种超疏水纸及其制备方法。
背景技术
润湿性是自然界普遍存在的现象,对于保持物体表面属性具有极其重要的意义。诗句“出淤泥而不染”正是描述荷叶的这种自清洁功能特性,在空气中表现为超疏水的特质,这种具有荷叶效应特性的超疏水现象通常被定义为材料表面的静态接触角大于150°,滚动角小于10°。类似荷叶效应的还有鱼类鳞片一般不会被油渍污染,寒冷的冬季里蚊子的复眼不会凝结雾状小液滴等现象。通过对材料结构的研究,确定了微米和纳米级的两层结构是使荷叶表现出超高疏水性和低粘附性的原因,证实尺度结构对材料表面润湿性的重要性。常见的提供粗糙结构的微纳米粒子有SiO2、ZnO、Fe3O4、TiO2、BiVO、CaCO3、碳纳米管等无机粒子。基于该理论,人为制造的超疏水表面新材料被应用于各个领域,为学科提供了新的研究方向和契机。
超疏水表面的制造方法常用的有蚀刻法、模板法、层层自组装、等离子体沉积、气相化学沉积、电化学法、原子层沉积、纳米颗粒沉积、溶胶凝胶法等,通过上述方法产生微/纳米涂层,然后引入低表面能物质来实现材料表面特性的控制。因此,在一定的粗糙度范围内,液体与材料表面的化学相互作用是材料液相润湿性调节的关键。纳米纤维素表面存在大量的羟基官能团,硅烷类偶联剂可以发生水解反应后再与羟基官能团发生偶联反应,从而实现低表面能化合物在材料表面的覆盖。
发明内容
本发明旨在提供一种超疏水纸及其制备方法。通过成纸二次加工的方式制备疏水纸,二次加工所需超疏水涂料以纳米纤维素为基体,为纸张提供一个具有微纳米结构的粗糙表面,由表面改性剂提供超疏水所需的低表面能。所得纸张表面的涂层具有较好的耐磨性和超疏水性。
本发明的目的通过以下技术方案实现。
一种超疏水纸的制备方法,包括以下步骤:
(1)将纳米纤维素进行浓缩脱水,得到微纳米颗粒;
(2)将步骤(1)所得微纳米颗粒分散于有机溶剂中,再加入低表面能的表面改性剂混合制备成涂料A液;
(3)将交联剂溶于水中制备涂料B液;
(4)将涂料B液涂于纸张表面后,再将涂料A液涂于纸张表面,得到超疏水纸。
优选的,步骤(1)所述纳米纤维素是纤维素原料经酶处理、机械研磨处理制备得到;所述的酶是能够使纤维结构松散的酶。
优选的,所述酶处理过程中,浆料浓度为1wt%-10wt%,pH为4.5-6,温度为45-55℃,时间为1-10h;所述酶为纤维素复合酶、纤维素内切酶、打浆酶、木聚糖酶中的一种或多种。
优选的,所述酶处理过程中,浆料浓度为5wt%,pH为5.5,温度为50℃,时间为1h;所述酶为纤维素复合酶。
优选的,所述机械研磨处理后浆料的浓度为0.5wt%-10wt%。
优选的,步骤(2)所述有机溶剂为无水乙醇、乙酸乙酯、甲苯、丙酮中的一种或多种;所述低表面能的表面改性剂为十八胺、八烷基三甲氧基硅烷和十六烷基三甲氧基硅烷中的一种或多种。
优选的,步骤(2)中,微纳米颗粒与有机溶剂的质量比为1:50-1:300。
优选的,步骤(2)中,所述微纳米颗粒与表面改性剂的质量比为2:1-1:3。
优选的,所述微纳米颗粒与表面改性剂的质量比为1:3。
优选的,步骤(3)所述交联剂为阳离子淀粉、烷基烯酮二聚体(AKD)、烯基琥珀酸酐(ASA)、聚乙烯醇和水性聚氨酯中的一种或多种;所述涂料B液中交联剂的浓度为1wt%-10wt%。
优选的,步骤(4)所述纸张包括所有适合再次施胶或涂布的纸张。
由以上任一项所述的制备方法制得的一种超疏水纸。
与现有技术相比,本发明具有如下的有益效果:
(1)本发明以酶/机械法制备的纳米纤维素为原料制备疏水剂,代替使用无机粒子来提供微纳米结构的粗糙表面,为酶/机械法制备的纳米纤维素在功能纸领域的应用提供了新的方法。
(2)相对于化学法制备纳米纤维素,本发明以酶/机械法制备纳米纤维素具有化学试剂用量少、反应条件温和等特点,该方法更易于规模化生产纳米纤维素。
(3)本发明所制备的疏水纸的静态接触角高达164°,纸张表面具有较好的自清洁性和超疏水性。
具体实施方式
下面结合实例对本发明的具体实施作进一步的具体说明,但本发明的实施方式不限于此。
本发明对所用木质纤维素原料的种类、来源并没有特殊的限制,下面以针叶木浆和浆内施胶的格拉辛原纸(接触角为93°)为例。
实施例1
(1)将60g针叶木浆料进行磨浆处理,处理后浆料浓度为10wt%;
(2)将步骤(1)处理后的浆料进行酶解,先把纤维素复合酶溶解于去离子水中,得酶解液;再用酶解液调节浆料浓度为10wt%,酶用量为25g/kg(相对于绝干浆),在pH为5.5,温度为50℃下酶解3h;
(3)将步骤(2)酶处理后的浆料进行超微粒研磨处理,研磨时加去离子水调节浆料浓度为0.2wt%;
(4)将步骤(3)所得浆料进行冷冻干燥;
(5)将步骤(4)所得的0.5g微纳米颗粒分散在200mL无水乙醇中,在35℃、150rpm下搅拌并加入十六烷基三甲氧基硅烷反应30min,进行硅烷化改性,微纳米颗粒与十六烷基三甲氧基硅烷的质量比为2:1,制备得到疏水化改性的纳米纤维素涂料;
(6)将阳离子玉米淀粉在85℃下糊化处理后在纸张表面施胶,阳离子淀粉的浓度为1wt%;
(7)将步骤(5)所得的涂料涂于步骤(6)所得的纸张表面,得到超疏水纸。
结果:所得超疏水纸的静态接触角为155°,在纸张表面施加10N的力摩擦100次后,纸张的静态接触角依然为155°,说明经过本实施例方法制备的疏水纸具有良好的疏水性和摩擦稳定性。
实施例2
(1)将60g针叶木浆料进行磨浆处理,处理后浆料浓度为10wt%;
(2)将步骤(1)处理后的浆料进行酶解,先把纤维素复合酶溶解于去离子水中,得酶解液;再用酶解液调节浆料浓度为5wt%,酶用量为50g/kg(相对于绝干浆),在pH为5.5,温度为50℃下酶解1h;
(3)将步骤(2)酶处理后的浆料进行超微粒研磨处理,研磨时加去离子水调节浆料浓度为0.5wt%;
(4)将步骤(3)所得浆料进行冷冻干燥;
(5)将步骤(4)所得的0.5g微纳米颗粒分散在200mL无水乙醇中,在35℃、150rpm下搅拌并加入十六烷基三甲氧基硅烷反应30min,进行硅烷化改性,微纳米颗粒与十六烷基三甲氧基硅烷的质量比为1:3,制备得到疏水化改性的纳米纤维素涂料;
(6)将阳离子玉米淀粉在85℃下糊化处理后在纸张表面施胶,阳离子淀粉的浓度为10wt%;
(7)将步骤(5)所得的涂料涂于步骤(6)所得的纸张表面,得到超疏水纸。
结果:所得超疏水纸的静态接触角为164°,在纸张表面施加10N的力摩擦100次后,纸张的静态接触角依然为164°,说明经过本实施例方法制备的疏水纸具有良好的疏水性和耐摩擦稳定性。
实施例3
(1)将60g针叶木浆料进行磨浆处理,处理后浆料浓度为10wt%;
(2)将步骤(1)处理后的浆料进行酶解,先把纤维素复合酶溶解于去离子水中,得酶解液;再用酶解液调节浆料浓度为1wt%,酶用量为10g/kg(相对于绝干浆),在pH为5.5,温度为50℃下酶解3h;
(3)将步骤(2)酶处理后的浆料进行超微粒研磨处理,研磨时加去离子水调节浆料浓度为1wt%;
(4)将步骤(3)所得浆料进行冷冻干燥;
(5)将步骤(4)所得的0.5g微纳米颗粒分散在200mL无水乙醇中,在35℃、150rpm下搅拌并加入十六烷基三甲氧基硅烷反应30min,进行硅烷化改性,微纳米颗粒与十六烷基三甲氧基硅烷的质量比为1:2,制备得到疏水化改性的纳米纤维素涂料;
(6)将阳离子玉米淀粉在85℃下糊化处理后在纸张表面施胶,阳离子淀粉的浓度为5wt%;
(7)将步骤(5)所得的涂料涂于步骤(6)所得的纸张表面,得到超疏水纸。
结果:所得超疏水纸的静态接触角为159°,在纸张表面施加10N的力摩擦100次后,纸张的静态接触角依然为159°,说明经过本实施例方法制备的疏水纸具有良好的疏水性和耐摩擦稳定性。
对比例1
(1)将60g针叶木浆料进行磨浆处理,处理后浆料浓度为10wt%;
(2)将步骤(1)处理后的浆料进行酶解,先把纤维素复合酶溶解于去离子水中,得酶解液;再用酶解液调节浆料浓度为1wt%,酶用量为10g/kg(相对于绝干浆),在pH为5.5,温度为50℃下酶解3h;
(3)将步骤(2)酶处理后的浆料进行超微粒研磨处理,研磨时加去离子水调节浆料浓度为1wt%;
(4)将步骤(3)所得浆料进行冷冻干燥;
(5)将步骤(4)所得的0.5g微纳米颗粒分散在200mL无水乙醇中,在35℃、150rpm下搅拌并加入十六烷基三甲氧基硅烷反应30min,进行硅烷化改性,微纳米颗粒与十六烷基三甲氧基硅烷的质量比为1:2,制备得到疏水化改性的纳米纤维素涂料;
(6)将阳离子玉米淀粉在85℃下糊化处理,阳离子淀粉的浓度为5wt%;
(7)将步骤(5)所得纳米纤维素素涂料与步骤(6)所得淀粉糊化乳液充分搅拌,混合均匀后在纸张表面涂布,得到疏水纸。
结果:所得疏水纸的静态接触角为123°,施加10N的力在纸张表面摩擦100次后,纸张的静态接触角依然为123°,说明使用本发明的方法先对纸张进行表面施胶,在纸张表面形成交联剂后再进行疏水纳米纤维素涂布,所得纸张的疏水性更佳。
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所述实施例的限制,其他的任何未背离本发明的精神实质与原理下所做的改变、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 (10)

1.一种超疏水纸的制备方法,其特征在于,包括以下步骤:
(1)将纳米纤维素进行脱水干燥,得到微纳米颗粒;
(2)将步骤(1)所得微纳米颗粒分散于有机溶剂中,再加入低表面能的表面改性剂混合制备成涂料A液;
(3)将交联剂溶于水中制备涂料B液;
(4)将涂料B液涂于纸张表面后,再将涂料A液涂于纸张表面,得到超疏水纸。
2.根据权利要求1所述的一种超疏水纸的制备方法,其特征在于,步骤(1)所述纳米纤维素是纤维素原料经酶处理、机械研磨处理制备得到;所述的酶是能够使纤维结构松散的酶。
3.根据权利要求2所述的一种超疏水纸的制备方法,其特征在于,所述酶处理过程中,浆料浓度为1wt%-10wt%,pH为4.5-6,温度为45-55℃,时间为1-10h;所述酶为纤维素复合酶、纤维素内切酶、打浆酶、木聚糖酶中的一种或多种。
4.根据权利要求3所述的一种超疏水纸的制备方法,其特征在于,所述酶处理过程中,浆料浓度为5wt%,pH为5.5,温度为50℃,时间为1h;所述酶为纤维素复合酶。
5.根据权利要求2所述的一种超疏水纸的制备方法,其特征在于,所述机械研磨处理后浆料的浓度为0.1wt%-1wt%。
6.根据权利要求1-5任一项所述的一种超疏水纸的制备方法,其特征在于,步骤(2)所述有机溶剂为无水乙醇、乙酸乙酯、甲苯、丙酮中的一种或多种;所述低表面能的表面改性剂为十八胺、八烷基三甲氧基硅烷和十六烷基三甲氧基硅烷中的一种或多种;所述微纳米颗粒与表面改性剂的质量比为2:1-1:3。
7.根据权利要求6所述的一种超疏水纸的制备方法,其特征在于,所述微纳米颗粒与表面改性剂的质量比为1:3。
8.根据权利要求6所述的一种超疏水纸的制备方法,其特征在于,步骤(3)所述交联剂为阳离子淀粉、AKD、ASA、聚乙烯醇和水性聚氨酯中的一种或多种;所述涂料B液中交联剂的浓度为1wt%-10wt%。
9.根据权利要求6所述的一种超疏水纸的制备方法,其特征在于,步骤(4)所述纸张包括所有适合再次施胶或涂布的纸张。
10.由权利要求1-9任一项所述的制备方法制得的一种超疏水纸。
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