CN114195933B - 纸张增厚剂制备方法及增厚纸张浆料制备方法 - Google Patents

纸张增厚剂制备方法及增厚纸张浆料制备方法 Download PDF

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CN114195933B
CN114195933B CN202111589841.7A CN202111589841A CN114195933B CN 114195933 B CN114195933 B CN 114195933B CN 202111589841 A CN202111589841 A CN 202111589841A CN 114195933 B CN114195933 B CN 114195933B
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冯宇
杨以仁
高莉燕
陈叶
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Abstract

本发明提供了纸张增厚剂制备方法及增厚纸张浆料制备方法，纸张增厚剂的制备方法，包括下述重量份的组分：90～99份N‑异丙基丙烯酰胺单体I；1～10份甲基丙烯酸二甲氨乙酯阳离子型单体II；0～2份甲叉双丙烯酰胺交联剂III；0～6份甲基丙烯酸阴离子型单体IV；相对于现有技术，本发明有绿色环保、操作简单、适用于工业化生产的特点，具有较好的应用前景。

Description

纸张增厚剂制备方法及增厚纸张浆料制备方法
技术领域
本发明涉及有机高分子领域，尤其涉及纸张增厚剂制备方法及增厚纸张浆料制备方法。
背景技术
近年来，高松厚纸的需求在不断增长。书籍用纸一般多注重易翻度与触感等性质，特别是使用这些高松厚纸印制的书籍与印刷品提供了纸厚但质轻的特性。在森林资源有效地利用上，高松厚纸可以减少纸浆使用量降低环境污染负荷。高松厚纸(低密度纸)主要有以下几种方法：添加多价醇与脂肪酸酯化合物柔软化剂(CN100392182C)，或是低密度剂如：聚羟烷基添加物、非离子界面活性剂、多价醇与脂肪酸酯化合物。
聚N-异丙基丙烯酰胺(PNIPAm)为一种温敏感聚合物，在加入交联剂后会形成三维的网路结构，故选用阳离子型丙烯酰胺聚合物与带负电荷的纸浆纤维结合，借由聚N-异丙基丙烯酰胺的三维网路结构提供纸张松厚的空间，本发明提供一种阳离子型丙烯酰胺聚合物的制备方法，适合用于制造松厚纸的纸张增厚剂。
综上所述，亟需一种操作简单、适用于工业化生产的纸张增厚剂的阳离子型丙烯酰胺聚合物的制备方法。
发明内容
本发明要解决的技术问题是：
提供了一种张增厚剂制备方法及增厚纸张浆料制备方法，制备过程中，增厚剂的添加需要在阳性淀粉之前，增厚剂聚合物1为阳离子型聚合物(正电荷)，可与带负电荷的纸张纤维充分结合达到增厚的目的；阳性淀粉(正电荷)可以将纤维(负电荷)与纤维之间链合；相对于现有技术，本发明有绿色环保、操作简单、适用于工业化生产的特点，具有较好的应用前景。
为了达到上述目的，本发明采用了以下技术方案：
一种纸张增厚剂的制备方法，
包括下述重量份的组分：
90～99份N-异丙基丙烯酰胺单体I；
1～10份甲基丙烯酸二甲氨乙酯阳离子型单体II；
0～2份甲叉双丙烯酰胺交联剂III；
0～6份甲基丙烯酸阴离子型单体IV；
Figure BDA0003429479160000021
纸张增厚剂的制备步骤如下：
将丙烯酰胺单体I、单体II或单体IV、交联剂III和溶剂放入反应瓶中，加入起始剂，在反应温度为0～100℃条件下反应数小时，即得到丙烯酰胺聚合物。
作为本方案的进一步改进，所述反应溶剂为水，N,N-二甲基甲酰胺的任意一种或几种。
作为本方案的进一步改进，所述反应溶剂为水。
作为本方案的进一步改进，所述起始剂为过硫酸钾，偶氮二异丁腈中的任意一种或几种。
作为本方案的进一步改进，所述反应温度为0～100℃。
作为本方案的进一步改进，所述反应温度为15～35℃。
一种增厚纸张浆料制备方法，包括下述步骤：
S1：浆料的配置，重量份的下述组分进行混合
50份游离度为450ml的漂白硫酸盐阔叶木浆、10份游离度为460ml的漂白硫酸盐针叶木浆、10份损纸与30份阔叶木漂白化学热磨机械浆混合后，散浆30分钟；
S2手抄纸的制备
依序添加下述重量份的组分：
Figure BDA0003429479160000031
每个试剂添加间后搅拌10分钟，即制得增厚纸张浆料。
作为本方案的进一步改进，所述上胶剂为烷基烯酮二聚体；所述填料为重质碳酸钙；所述滤水助剂为阳离子聚丙烯酰胺；所述助留剂为聚合氯化铝。
与现有技术相比，本发明具备下述有益效果：
a)所述滤水助剂为高分子量低电荷密度的阳离子聚丙烯酰胺；所述助留剂为聚合氯化铝；
b)上胶剂为AKD，即烷基烯酮二聚体。保持纸张的尺寸稳定性，防止收缩，同时可降低纸的吸水量和吸油墨量，增进纸的光滑性、印刷适应性，提高纸的质量；
c)填料为重质碳酸钙，由于重质碳酸钙的粒度组成和形态较好，有利于纸张纤维的结合和纸页的强度，同时还可以改善纸张的白度，不透明度、光泽度、平滑度、吸水性，降低造纸涂料的粘度和提高拉毛强度；
d)本发明制备过程中，增厚剂的添加需要在阳性淀粉之前，增厚剂聚合物1为阳离子型聚合物(正电荷)，可与带负电荷的纸张纤维充分结合达到增厚的目的；阳性淀粉(正电荷)可以将纤维(负电荷)与纤维之间链合；
e)相对于现有技术，本发明有绿色环保、操作简单、适用于工业化生产的特点，具有较好的应用前景。
具体实施方式
为了使本发明的目的、技术方案和优点更加清楚，以下结合实施例对本发明作进一步说明：
实施例1
聚合物1的合成
秤取5.38g的N-异丙基丙烯酰胺、0.39g的甲基丙烯酸二甲氨乙酯、58mg的甲叉双丙烯酰胺与162mg的过硫酸钾溶于200ml的去离子水中，以0.1N盐酸水溶液调整pH值～4，并对水溶液通入氮气气泡约10min去除氧气；将114mg的焦亚硫酸钠溶于约20ml的去离子水中，除脱氧气后，于室温下缓慢加入前述之溶液中，反应约15hr，制得聚合物1。
实施例2
聚合物2的合成
秤取5.38g的N-异丙基丙烯酰胺、0.39g的甲基丙烯酸二甲氨乙酯与162mg的过硫酸钾溶于200ml的去离子水中，以0.1N盐酸水溶液调整pH值～4，并对水溶液通入氮气气泡约10min去除氧气；将114mg的焦亚硫酸钠溶于约20ml的去离子水中，除脱氧气后，于室温下缓慢加入前述之溶液中，反应约15hr，制得聚合物2。
实施例3
聚合物3的合成
秤取5.38g的N-异丙基丙烯酰胺、0.18g的甲基丙烯酸、58mg的甲叉双丙烯酰胺与162mg的过硫酸钾溶于200ml的去离子水中，并对水溶液通入氮气气泡约10min去除氧气；将114mg的焦亚硫酸钠溶于40ml的去离子水中，除脱氧气后，于室温下缓慢加入前述之溶液中，反应约15，制得聚合物3。
实施例1～3中制得的聚合物低临界溶解温度的测定见表1
低临界溶解温度的测定，反应后将溶液以去离子水稀释至250g(视为2％溶液)，取20g的2％聚N-异丙基丙烯酰胺溶液以pH＝4.0醋酸缓冲溶液180g稀释与取20g的2％聚N-异丙基丙烯酰胺溶液以pH＝7.4磷酸缓冲溶液180g稀释。
表1实施例1～3中制得的聚合物低临界溶解温度的测定
聚合物1 聚合物2 聚合物3
低临界溶解温度1 / / pH＝4.31,33.2℃
低临界溶解温度2 pH＝7.93,30.8℃ pH＝7.95,33.8℃ pH＝7.88,41.1℃
手抄纸的制备
纸浆混合比例为：取漂白硫酸盐阔叶木浆(游离度：450ml)50％、漂白硫酸盐针叶木浆(游离度:460ml)10％、损纸10％与阔叶木漂白化学热磨机械浆(85/250)30％。
试剂原料添加顺序为：浆料散浆30分钟后，依序添加增厚剂、阳性淀粉、上胶剂、填料、滤水助剂与助留剂，每个试剂添加间搅拌10分钟。进行基重80g/㎡手抄纸实验，试剂原料配比如下表：
表2试剂原料配比
试剂原料 重量份
漂白硫酸盐阔叶木浆(游离度:450ml) 50
漂白硫酸盐针叶木浆(游离度:460ml) 10
损纸 10
阔叶木漂白化学热磨机械浆(85/250) 30
增厚剂(聚合物1、聚合物2或聚合物3) 1.0
阳性淀粉 1.2
上胶剂(烷基烯酮二聚体) 0.12
填料(重质碳酸钙) 20
滤水助剂(高分子量低电荷密度的阳离子聚丙烯酰胺) 0.5
助留剂(聚合氯化铝) 0.6
纸张物理性质试验结果如下表：
表3纸张物理性能试验结果
Figure BDA0003429479160000061
结果分析见表4
表4结果分析
Figure BDA0003429479160000071
由表4可知，于手抄纸湿端系统中使用阳离子型丙烯酰胺聚合物增厚剂聚合物1，并添加1.0％，可增加手抄纸的松度达14.1％。
本发明的实施例1中制得的增厚剂聚合物1为阳离子型网状聚合物，可与纸浆阴离子(淀粉分子为负电荷性质)互相结合，为网状结构在纸浆纤维之间造成孔隙，故可使纸张增厚，因与纸浆纤维作用故纸张强度的断裂长、撕裂指数、破裂指数降低；
本发明的实施例2中制得的增厚剂聚合物2为阳离子型线状聚合物，可与纸浆阴离子(淀粉分子为负电荷性质)互相结合，为线状结构在纸浆纤维之间造成孔隙较增厚剂聚合物1为差，故可使纸张增厚较低，因与纸浆纤维作用故纸张强度的断裂长、撕裂指数、破裂指数降低；
本发明实施例3中制得的增厚剂聚合物3为阴离子型网状聚合物，与纸浆阴离子(淀粉分子为负电荷性质)结合力不佳，形成孔隙较增厚剂聚合物1为差，故纸张增厚较低，因与纸浆纤维作用较差故纸张强度的断裂长、撕裂指数、破裂指数变化不大，因聚合物为水凝胶类物质，Cobb吸水率较高。
以上所述仅为本发明的优选实施方式，并非因此限制本发明的专利范围，凡是利用本发明所作的等效变换，均在本发明的专利保护范围内。

Claims (8)

1.一种纸张增厚剂的制备方法，其特征在于，
包括下述重量份的组分：
90~99份 N-异丙基丙烯酰胺单体I；
1~10份 甲基丙烯酸二甲氨乙酯阳离子型单体II；
0~2份 甲叉双丙烯酰胺交联剂III；
0~6份 甲基丙烯酸阴离子型单体IV；
Figure 877987DEST_PATH_IMAGE002
纸张增厚剂的制备步骤如下：
将丙烯酰胺单体I、单体II或单体IV、交联剂III和溶剂放入反应瓶中，加入起始剂，在反应温度为0~100℃条件下反应数小时，即得到丙烯酰胺聚合物。
2.根据权利要求1所述的纸张增厚剂的制备方法，其特征在于，所述反应溶剂为水，N,N-二甲基甲酰胺的任意一种或几种。
3.根据权利要求2所述的纸张增厚剂的制备方法，其特征在于，所述反应溶剂为水。
4.根据权利要求1所述的纸张增厚剂的制备方法，其特征在于，所述起始剂为过硫酸钾，偶氮二异丁腈中的任意一种或几种。
5.根据权利要求1所述的纸张增厚剂的制备方法，其特征在于，所述反应温度为0~100℃。
6.根据权利要求5所述的纸张增厚剂的制备方法，其特征在于，所述反应温度为15~35℃。
7.一种增厚纸张浆料制备方法，其特征在于，包括下述步骤：
S1：浆料的配置，重量份的下述组分进行混合
50份游离度为450ml的漂白硫酸盐阔叶木浆、10份游离度为460ml的漂白硫酸盐针叶木浆、10份损纸与30份阔叶木漂白化学热磨机械浆混合后，散浆30分钟；
S2手抄纸的制备
依序添加下述重量份的组分：
权利要求1~6任意一项所述的纸张增厚剂的制备方法制得的增厚剂 0.5~2.5份；
阳性淀粉 0.5~2.0份；
上胶剂 0.0~1.0份；
填料 15~25份；
滤水助剂 0.0~1.0份；
助留剂 0.0~1.0份；
每个试剂添加间后搅拌10分钟，即制得增厚纸张浆料。
8.根据权利要求7所述的增厚纸张浆料制备方法，其特征在于，所述上胶剂为烷基烯酮二聚体；所述填料为重质碳酸钙；所述滤水助剂为阳离子聚丙烯酰胺；所述助留剂为聚合氯化铝。
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