CN111636241B - 一种壳聚糖改性阳离子淀粉乳化剂及其制备akd乳液的方法 - Google Patents

一种壳聚糖改性阳离子淀粉乳化剂及其制备akd乳液的方法 Download PDF

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CN111636241B
CN111636241B CN202010531444.3A CN202010531444A CN111636241B CN 111636241 B CN111636241 B CN 111636241B CN 202010531444 A CN202010531444 A CN 202010531444A CN 111636241 B CN111636241 B CN 111636241B
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周建恩
周游
钟庆辉
陈兴理
毛进仙
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Abstract

本发明提供一种壳聚糖改性阳离子淀粉乳化剂及其制备AKD乳液的方法，壳聚糖改性阳离子淀粉乳化剂是由壳聚糖、阳离子淀粉和交联剂戊二醛反应得到的，包含有阳离子淀粉、壳聚糖接枝物和未参与反应的壳聚糖和阳离子淀粉。相比阳离子淀粉乳化剂，壳聚糖改性后的阳离子淀粉乳化AKD后的施胶效果更显著。采用此乳化剂制备得到的KAD该乳液具有稳定性好，乳业粒径小，环保、不含有机氯等优点，可应用于制备食品包装纸。

Description

一种壳聚糖改性阳离子淀粉乳化剂及其制备AKD乳液的方法
技术领域
本发明属于造纸AKD施胶技术领域，更具体地说，特别涉及一种壳聚糖改性阳离子淀粉乳化剂及其制备AKD乳液的方法。
背景技术
反应型中性施胶剂AKD是目前造纸厂中广泛应用的施胶试剂。但由于AKD为不溶于水的蜡体，浆内施胶或表面施胶前常需通过加入乳化剂，制得AKD乳化液后才可以应用。阳离子淀粉是一种造纸AKD施胶中广泛采用的乳化剂和稳定剂，具备价廉的优点。为更大潜力地发掘阳离子淀粉作为AKD施胶应用的潜力，各种高分子乳化剂被相继用作乳化造纸施胶剂AKD。环境保护意识的增强，使得瓜尔胶、海藻酸钠和壳聚糖等天然可再生聚合物的应用越来越广泛，成为取代不可再生生物材料的研究重点，其开发与应用受到广泛关注。
出于绿色环保的理念和造纸系统的运行特点，以廉价、应用广泛的阳离子淀粉作为乳化剂的主体，通过交联手段对其改性是有效提高其乳化性能的有效手段，但相关研究报道较少，缺少相关技术应用的研究。
发明内容
为解决背景中所面临的技术问题，本发明的目的在于提供一种壳聚糖改性阳离子淀粉乳化剂及其制备AKD乳液的方法。本发明的另一个目的是为了探寻纳米氧化锌在造纸施胶中应用的技术问题，以降低有机石化产品在造纸领域中的应用。
为了解决上述问题，本发明所采用的技术方案如下：一种壳聚糖改性阳离子淀粉乳化剂，由阳离子淀粉、壳聚糖和交联剂戊二醛制备得到的，各组分的质量份数如下：
阳离子淀粉 10份、
壳聚糖 1份、
戊二醛 1份。
进一步的，所述阳离子淀粉是采用醚化剂3-氯-2-羟丙基三甲基氯化铵作为醚化试剂制备所得。
进一步的，所述壳聚糖的粘均分子量为182260，阳离子电荷需求量为4.89meq/g，脱乙酰度为80-95％。
一种壳聚糖改性阳离子淀粉乳化剂制备AKD乳液的方法，其特征在于，具体包括以下步骤：
1)取壳聚糖溶于质量浓度1％的乙酸中，磁力搅拌使其均匀分散；
2)取阳离子淀粉在80℃糊化30分钟，然后升温至90℃，磁力搅拌下加入步骤(1)溶解制备得到的壳聚糖溶液以及交联剂，补充适量水，搅拌反应90分钟，制得改性阳离子淀粉乳化剂；
3)将以上改性乳化剂倒入熔融加热熔融后的AKD蜡液中，高速剪切搅拌使其乳化。
进一步的，步骤2)所得改性阳离子淀粉乳化剂为微黄胶体溶液，黏度为50mPa.S，固含量为3.2％，Zeta电位为5.0mV。
进一步的，步骤1)中所得的壳聚糖溶液pH值为4.5。
进一步的，步骤2)中改性阳离子淀粉乳化剂的浓度为3.0％。
进一步的，步骤3)中的蜡片加热溶解温度为65℃，剪切搅拌速率为10000r/min，搅拌时间为3分钟。
与现有技术相比，本发明具有如下有益效果：本发明所得的壳聚糖改性阳离子淀粉乳液不含有机氯，能够满足食品纸的生产要求。施胶纸的施胶效果显著改善，采用接枝手段改性阳离子淀粉对相关技术领域的补充与发展具有重要性。所制得的纳米氧化锌稳定的Pickering乳液不需使用表面活性剂，所制得的AKD乳液具有粒径分散均匀、稳定性好和施胶效果显著等优点。
具体实施方式
下面实施例对本发明的实施方式作进一步详细描述。以下实施例用于说明本发明，但不能用来限制本发明的范围。
实施例1
(1)按质量计，取1份壳聚糖溶于质量浓度1％的乙酸中，磁力搅拌使其均匀分散。
(2)按质量计，取10份阳离子淀粉在80℃糊化30分钟，然后升温至90℃，磁力搅拌下加入步骤(1)溶解制备得到的壳聚糖溶液以及交联剂，补充适量水，搅拌反应90分钟，制得改性阳离子淀粉乳化剂。
(3)将以上壳聚糖改性阳离子淀粉乳化剂，一次性倒入10份的AKD蜡片液中，10000r/min高速剪切搅拌3分钟，制得AKD乳液。
Figure GDA0002582424480000041
实施例2
(1)按质量计，取1份壳聚糖溶于质量浓度1％的乙酸中，磁力搅拌使其均匀分散。
(2)按质量计，取10份阳离子淀粉在80℃糊化30分钟，然后升温至90℃，磁力搅拌下加入步骤(1)溶解制备得到的壳聚糖溶液以及交联剂，补充适量水，搅拌反应90分钟，制得改性阳离子淀粉乳化剂。
(3)将以上壳聚糖改性阳离子淀粉乳化剂，一次性倒入15份的AKD蜡片液中，10000r/min高速剪切搅拌3分钟，制得AKD乳液。
Figure GDA0002582424480000042
实施例3
(1)按质量计，取1份壳聚糖溶于质量浓度1％的乙酸中，磁力搅拌使其均匀分散。
(2)按质量计，取10份阳离子淀粉在80℃糊化30分钟，然后升温至90℃，磁力搅拌下加入步骤(1)溶解制备得到的壳聚糖溶液以及交联剂，补充适量水，搅拌反应90分钟，制得改性阳离子淀粉乳化剂。
(3)将以上壳聚糖改性阳离子淀粉乳化剂，一次性倒入20份的AKD蜡片液中，10000r/min高速剪切搅拌3分钟，制得AKD乳液。
Figure GDA0002582424480000051
对比例
以未改性的阳离子淀粉乳化的AKD乳液为对比例。
抄纸：
将所制备的AKD乳液用去离子水稀释至一定浓度，然后用于浆内施胶，用量为0.3％(相对于绝干浆)。选用质量分数为1％的阔叶木浆，依次加入AKD乳液，500r/min搅拌1min后加入0.03％阳离子聚丙烯酰胺，然后提速至1200r/min，然后加入0.2wt％的膨润土，500r/min搅拌1min，抄造定量为60g/m2的纸张，烘箱中干燥(105℃)30min。采用标准GB/T1540-2002测定纸张的Cobb值。
Cobb值(g/m2)
对比例 31.2
实施例一 28.4
实施例二 26.5
实施例三 24.7
从表中看出，与原纸阳离子淀粉乳化剂相比，本发明所制得的壳聚糖改性阳离子淀粉乳化剂乳化AKD后，对纸张有显著增强的施胶效果。这表现在，随壳聚糖接枝用量的增加，纸张的施胶效果增强。这是因为高分子化合物壳聚糖在阳离子淀粉骨架上的接枝显著地提高了淀粉与纤维间的架桥，使阳离子淀粉与纤维间的结合位点增多。同时，AKD内酯环打开，与淀粉反应后显著地提高了其在纤维上的留着率，使纸张的施胶效果提高。
本发明的实施例是为了示例和描述起见而给出的，而并不是无遗漏的或者将本发明限于所公开的形式。很多修改和变化对于本领域的普通技术人员而言是显而易见的。选择和描述实施例是为了更好说明本发明的原理和实际应用，并且使本领域的普通技术人员能够理解本发明从而设计适于特定用途的带有各种修改的各种实施例。

Claims (3)

1. 一种壳聚糖改性阳离子淀粉乳化剂制备AKD乳液的方法，其特征在于，所述壳聚糖改性阳离子淀粉乳化剂由阳离子淀粉、壳聚糖和交联剂戊二醛制备得到的，各组分的质量份数如下：
阳离子淀粉 10 份、
壳聚糖 1 份、
戊二醛 1 份；
具体包括以下步骤：
1） 取壳聚糖溶于质量浓度1%的乙酸中，磁力搅拌使其均匀分散，所得的壳聚糖溶液pH值为4.5；
2） 取阳离子淀粉在80℃糊化30 分钟，然后升温至90℃，磁力搅拌下加入步骤(1）溶解制备得到的壳聚糖溶液以及交联剂，补充适量水，搅拌反应90分钟，制得改性阳离子淀粉乳化剂，所得改性阳离子淀粉乳化剂为微黄胶体溶液，黏度为50 mPa.S，固含量为3.2%，Zeta电位为5.0 mV；
3） 将以上改性乳化剂倒入熔融加热熔融后的AKD蜡液中，高速剪切搅拌使其乳化，蜡片加热溶解温度为 65℃，剪切搅拌速率为10000r/min，搅拌时间为3分钟。
2.根据权利要求1所述的壳聚糖改性阳离子淀粉乳化剂制备AKD乳液的方法，其特征在于，所述阳离子淀粉是采用醚化剂3-氯-2-羟丙基三甲基氯化铵作为醚化试剂制备所得。
3.根据权利要求1所述的壳聚糖改性阳离子淀粉乳化剂制备AKD乳液的方法，其特征在于，所述壳聚糖的粘均分子量为182260，阳离子电荷需求量为4.89 meq/g，脱乙酰度为80-95%。
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