CN106633808A - 一种蛋壳粉基合成纸的制备方法 - Google Patents

一种蛋壳粉基合成纸的制备方法 Download PDF

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CN106633808A
CN106633808A CN201610927186.4A CN201610927186A CN106633808A CN 106633808 A CN106633808 A CN 106633808A CN 201610927186 A CN201610927186 A CN 201610927186A CN 106633808 A CN106633808 A CN 106633808A
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shell meal
synthetic paper
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eggshell
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王东东
周虎
漆志凌
刘玄
刘国清
李友凤
王南波
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Hunan University of Science and Technology
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Priority to PCT/CN2017/074020 priority patent/WO2018076578A1/zh
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Priority to US16/009,176 priority patent/US11015294B2/en
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Abstract

本发明公开了一种蛋壳粉基合成纸的制备方法。它以蛋壳和聚氨酯为主要原料，先对蛋壳进行粉碎、粗制、精制等处理，然后将其与配制的聚氨酯溶液在一定条件下搅拌混合，再通过后续的固化处理成膜得到蛋壳粉基合成纸。本发明的合成纸所使用的无机填充物为蛋壳粉，为生物质资源，取代了生产合成纸所使用的碳酸钙，一定程度上减少了对天然方解石、白垩、石灰石等自然资源的开采，这在一定意义上有助于缓解环境污染和资源浪费问题，并实现了蛋壳的回收利用，减轻了环保负担。

Description

一种蛋壳粉基合成纸的制备方法
技术领域
本发明属于有机－无机复合材料生产技术领域，具体涉及一种蛋壳粉基合成纸的制备方法。
背景技术
合成纸，又被称为第二代纸。它是以高分子材料和无机填充物为主要原料，利用高分子界面化学原理和填充改性技术，经特殊工艺加工而成的一种新型纸张。合成纸是一种塑料新型材料产品，具有比重轻、强度大、抗撕裂，印刷性好，遮光、抗紫外线，经久耐用等特点。合成纸不仅具有与植物纤维纸张同样的书写性和印刷性，还具有塑料的核心性能，比如防水、防潮、防霉、防虫、耐折等。合成纸的生产过程污染较少，是现代纸张生产的一次重大改革。
目前，市场上合成纸所使用的无机填充物主要为碳酸钙，而碳酸钙主要来源于对矿山的开采。一方面，矿山开采中产生的废气、粉尘、废渣等，造成了大气污染、水土流失、酸雨、土壤污染等环境破坏；另一方面，矿山的开采破坏了原有的地貌景观，影响了整个地质生态***的多样性和完整性，特别是对生态环境较为脆弱的地区，其带来的影响是不可逆的，给重建生态环境带来了极大的困难。可见，矿山的开采对生态环境造成了严重的破坏和污染。因此，必须找寻一种新型无机填充物，对合成纸的组分和生产技术进行改进，才能有效地保护生态环境，从而更有利于合成纸生产技术的长远发展。
发明内容
本发明的目的在于提供一种新型的蛋壳粉基合成纸的制备方法。
本发明的技术方案为：
一种蛋壳粉基合成纸的制备方法，包括如下步骤：
（1）取适量新鲜蛋壳清洗干净，置于90~120℃干燥箱中干燥2~4h，并用磨粉机将蛋壳粉碎，得到含蛋壳膜和蛋壳粉的混合物；
（2）将步骤（1）所得含蛋壳膜和蛋壳粉的混合物以NaCl溶液浸泡2~4h，再用搅拌器搅拌30~60min并除去上清液，然后将溶液中固体不溶物置于90~120℃干燥箱中干燥3~5h，即得到去除蛋壳膜的粗制蛋壳粉；
（3）将步骤（2）所得粗制蛋壳粉用200～600目的标准筛进行筛分，得到对应目数的精制蛋壳粉,备用；
（4）将热塑型聚氨酯颗粒和N-N-二甲基甲酰胺按22～30：110的质量比加入反应器中，加热至50~80℃并搅拌使热塑型聚氨酯颗粒充分溶解在N-N-二甲基甲酰胺中，配制成聚氨酯溶液；
（5）在步骤（4）所得聚氨酯溶液中，加入步骤（3）所得精制蛋壳粉，聚氨酯溶液与精制蛋壳粉的质量比为132~140：25～50，再利用高速搅拌器搅拌均匀，得到固液混合物，然后静置5~8h消泡；
（6）将步骤（5）所得固液混合物均匀涂布于离型纸上，然后将离型纸浸入碳酸氢钠水溶液中；待固液混合物完全固化成膜后，将离型纸和膜一并放入干燥箱中，60~80℃干燥40~80min；
（7）待离型纸和膜冷却后除去离型纸，并根据实际应用需求将膜裁剪成适当尺寸，即得到蛋壳粉基合成纸。
进一步地，所述的蛋壳为鸡蛋壳、鸭蛋壳或鹅蛋壳，优选为鸡蛋壳。
进一步地，步骤（7）所得蛋壳粉基合成纸外观为白色，通过调节步骤（6）中涂布于离型纸上的固液混合物厚度控制蛋壳粉基合成纸厚度在0.10～0.25mm之间，以A4纸张面积计质量介于4.21～5.92g之间。
进一步地，所述热塑型聚氨酯材料（TPU）优选为聚醚型TPU或聚酯型TPU中的一种或两种，要求邵氏硬度为85A到95A的颗粒料。
进一步地，步骤（2）中，含蛋壳膜和蛋壳粉的混合物与NaCl溶液的质量比优选为1:5~8，更优选为1：6。
进一步地，步骤（2）中，NaCl溶液的质量百分数优选为3~6%，更优选为5%。
进一步地，步骤（5）所得固液混合物中，聚氨酯、N-N-二甲基甲酰胺、蛋壳粉的质量百分比优选如下：聚氨酯 12.1%～16.2%，N-N-二甲基甲酰胺 59.5%～68.8%，蛋壳粉 15.6%～27.5%。
进一步地，步骤（6）中，碳酸氢钠水溶液质量百分数优选为3~6%，更优选为5%，溶液温度优选为20~35℃，更优选为25℃。
本发明与现有合成纸生产技术相比，具有如下的优点：
本发明的合成纸所使用的无机填充物为蛋壳粉，为生物质资源，取代了生产合成纸所使用的碳酸钙，一定程度上减少了对天然方解石、白垩、石灰石等自然资源的开采，这在一定意义上有助于缓解环境污染和资源浪费问题，并实现了蛋壳的回收利用，减轻了环保负担。
具体实施方式
下面通过具体实施例来对本发明作进一步详细的描述，其中，所述原料均为工业化产品，设备为普通工业化的生产设备。
实施例1
取适量新鲜鸡蛋壳清洗干净，置于90℃干燥箱中干燥4 h，并用磨粉机将蛋壳粉碎，得到含有蛋壳膜和蛋壳粉的混合物；再经质量百分含量为6%的NaCl溶液浸泡2h（蛋壳膜和蛋壳粉的混合物与NaCl溶液质量比为1:5）；然后用搅拌器搅拌30min并除去上清液，将溶液中固体不溶物置于90℃干燥箱中干燥5h，得到粗制蛋壳粉；经200目标准筛筛分后得到200目精制蛋壳粉，备用；称取25千克的邵氏硬度为85A的聚醚型聚氨酯颗粒、110千克的N-N-二甲基甲酰胺加入反应器中，加热至60℃并搅拌使热塑型聚氨酯颗粒完全溶解后得到聚氨酯溶液；再加入25千克200目精制蛋壳粉，用高速搅拌器搅拌均匀得到固液混合物；静置6h消泡后，将固液混合物以一定厚度涂布于离型纸上，然后将离型纸浸入质量百分含量为3%的碳酸氢钠水溶液中(温度为35℃)；待固液混合物完全固化成膜后，将离型纸和膜一并放入干燥箱中，80℃干燥40min；通过调节涂布于离型纸上的固液混合物厚度来控制膜的总厚度为0.10mm；待离型纸和膜冷却后除去离型纸，最后根据实际应用需求将膜裁剪成适当尺寸，即得到蛋壳粉基合成纸产品。
本实施例中所得固液混合物中聚氨酯材料的质量百分含量为15.6%,N-N-二甲基甲酰胺的质量百分含量为68.8%,蛋壳粉的质量百分含量为15.6%。所得合成纸产品颜色为白色，厚度为0.10mm，质量（以A4纸张面积计）为4.21g。
实施例2
取适量新鲜鸡蛋壳清洗干净，置于100℃干燥箱中干燥3h，并用磨粉机将蛋壳粉碎,得到含有蛋壳膜和蛋壳粉的混合物；再经质量百分含量为5%的NaCl溶液浸泡4h（蛋壳膜和蛋壳粉的混合物与NaCl溶液质量比为1:6）；然后用搅拌器搅拌60min并除去上清液，将溶液中固体不溶物置于110℃干燥箱中干燥4h，得到粗制蛋壳粉；经325目标准筛筛分后得到325目精制蛋壳粉，备用；称取15千克的邵氏硬度为89A的聚醚型聚氨酯颗粒、15千克的邵氏硬度为89A的聚酯型聚氨酯颗粒、110千克的N-N-二甲基甲酰胺加入反应器中，加热至80℃并搅拌使热塑型聚氨酯颗粒完全溶解后得到聚氨酯溶液；再加入45千克325目精制蛋壳粉，用高速搅拌器搅拌均匀得到固液混合物；静置5h消泡后，将固液混合物以一定的厚度涂布于离型纸上，然后将离型纸浸入质量百分含量为4%的碳酸氢钠水溶液中(温度为30℃)；待固液混合物完全固化成膜后，将离型纸和膜一并放入干燥箱中，70℃干燥60 min；通过调节涂布于离型纸上的固液混合物厚度来控制膜的总厚度为0.15 mm；待离型纸和膜冷却后除去离型纸，最后根据实际应用需求将膜裁剪成适当尺寸，即得到蛋壳粉基合成纸产品。
本实施例中所得固液混合物中聚氨酯材料的质量百分含量为16.2%，N-N-二甲基甲酰胺的质量百分含量为59.5%，蛋壳粉的质量百分含量为24.3%。所得合成纸产品颜色为白色，厚度为0.15mm，质量（以A4纸张面积计）为4.93g。
实施例3
取适量新鲜鸡蛋壳清洗干净，置于110℃干燥箱中干燥3h，并用磨粉机将蛋壳粉碎,得到含有蛋壳膜和蛋壳粉的混合物；再经质量百分含量为4%的NaCl溶液浸泡2h（蛋壳膜和蛋壳粉的混合物与NaCl溶液质量比为1:7）；然后用搅拌器搅拌40min并除去上清液，将溶液中固体不溶物置于120℃干燥箱中干燥3h，得到粗制蛋壳粉；经400目标准筛筛分后得到400目精制蛋壳粉，备用；称取18千克的邵氏硬度为92A的聚醚型聚氨酯颗粒、10千克的邵氏硬度为92A的聚酯型聚氨酯颗粒、110千克的N-N-二甲基甲酰胺加入反应器中，加热至70℃并搅拌使热塑型聚氨酯颗粒完全溶解后得到聚氨酯溶液；再加入41.9千克400目精制蛋壳粉，用高速搅拌器搅拌均匀得到固液混合物；静置7h消泡后，将固液混合物以一定的厚度涂布于离型纸上，然后将离型纸浸入质量百分含量为5%的碳酸氢钠水溶液中(温度为25℃)；待固液混合物完全固化成膜后，将离型纸和膜一并放入干燥箱中，60℃干燥80min；通过调节涂布于离型纸上的固液混合物厚度来控制膜的总厚度为0.18mm；待离型纸和膜冷却后除去离型纸，最后根据实际应用需求将膜裁剪成适当尺寸，即得到蛋壳粉基合成纸产品。
本实施例中所得固液混合物中聚氨酯材料的质量百分含量为15.6%，N-N-二甲基甲酰胺的质量百分含量为61.1%，蛋壳粉的质量百分含量为23.3%。所得合成纸产品颜色为白色，厚度为0.18mm，质量（以A4纸张面积计）为5.19g。
实施例4
取适量新鲜鸡蛋壳清洗干净，置于120℃干燥箱中干燥2h，并用磨粉机将蛋壳粉碎,得到含有蛋壳膜和蛋壳粉的混合物；再经质量百分含量为3%的NaCl溶液浸泡3h（蛋壳膜和蛋壳粉的混合物与NaCl溶液质量比为1:8）；然后用搅拌器搅拌50min并除去上清液，将溶液中固体不溶物置于100℃干燥箱中干燥4h，得到粗制蛋壳粉；经600目标准筛筛分后得到600目精制蛋壳粉，备用；称取22千克的邵氏硬度为95A的聚酯型聚氨酯颗粒、110千克的N-N-二甲基甲酰胺加入反应器中，加热至50℃并搅拌使热塑型聚氨酯颗粒完全溶解后得到聚氨酯溶液；再加入50千克600目精制蛋壳粉，用高速搅拌器搅拌均匀得到固液混合物；静置8h消泡后，将固液混合物以一定的厚度涂布于离型纸上，然后将离型纸浸入质量百分含量为6%的碳酸氢钠水溶液中(温度为20℃)；待固液混合物完全固化成膜后，将离型纸和膜一并放入干燥箱中，65℃干燥53min；通过调节涂布于离型纸上的固液混合物厚度来控制膜的总厚度为0.25mm；待离型纸和膜冷却后除去离型纸，最后根据实际应用需求将膜裁剪成适当尺寸，即得到蛋壳粉基合成纸产品。
本实施例中所得固液混合物中聚氨酯材料的质量百分含量为12.1%，N-N-二甲基甲酰胺的质量百分含量为60.4%，蛋壳粉的质量百分含量为27.5%。所得合成纸产品颜色为白色，厚度为0.25mm，质量（以A4纸张面积计）为5.92g。

Claims (8)

1.一种蛋壳粉基合成纸的制备方法，其特征在于，包括如下步骤：
（1）取适量新鲜蛋壳清洗干净，置于90~120℃干燥箱中干燥2~4h，并用磨粉机将蛋壳粉碎，得到含蛋壳膜和蛋壳粉的混合物；
（2）将步骤（1）所得含蛋壳膜和蛋壳粉的混合物以NaCl溶液浸泡2~4h，再搅拌30~60min并除去上清液，然后将溶液中固体不溶物置于90~120℃干燥箱中干燥3~5h，即得到去除蛋壳膜的粗制蛋壳粉；
（3）将步骤（2）所得粗制蛋壳粉用200～600目的标准筛进行筛分，得到对应目数的精制蛋壳粉，备用；
（4）将热塑型聚氨酯颗粒和N-N-二甲基甲酰胺按22～30：110的质量比加入反应器中，加热至50~80℃并搅拌使热塑型聚氨酯颗粒充分溶解在N-N-二甲基甲酰胺中，配制成聚氨酯溶液；
（5）在步骤（4）所得聚氨酯溶液中，加入步骤（3）所得精制蛋壳粉，聚氨酯溶液与精制蛋壳粉的质量比为132~140：25～50，搅拌均匀，得到固液混合物，然后静置5~8 h消泡；
（6）将步骤（5）所得固液混合物均匀涂布于离型纸上，然后将离型纸浸入碳酸氢钠水溶液中；待固液混合物完全固化成膜后，将离型纸和膜一并放入干燥箱中，60~80℃干燥40~80min；
（7）待离型纸和膜冷却后除去离型纸，并根据实际应用需求将膜裁剪成适当尺寸，即得到蛋壳粉基合成纸。
2.根据权利要求1所述的蛋壳粉基合成纸的制备方法，其特征在于，所述的蛋壳为鸡蛋壳、鸭蛋壳或鹅蛋壳。
3.根据权利要求1所述的蛋壳粉基合成纸的制备方法，其特征在于，步骤（7）所得蛋壳粉基合成纸外观为白色，通过调节步骤（6）中涂布于离型纸上的固液混合物厚度控制蛋壳粉基合成纸厚度在0.10～0.25mm之间，以A4纸张面积计质量介于4.21～5.92g之间。
4.根据权利要求1所述的蛋壳粉基合成纸的制备方法，其特征在于，所述热塑型聚氨酯材料优选为聚醚型TPU或聚酯型TPU中的一种或两种，要求邵氏硬度为85A到95A的颗粒料。
5.根据权利要求1所述的蛋壳粉基合成纸的制备方法，其特征在于，步骤（2）中，含蛋壳膜和蛋壳粉的混合物与NaCl溶液的质量比为1:5~8。
6.根据权利要求1所述的蛋壳粉基合成纸的制备方法，其特征在于，步骤（2）中，NaCl溶液的质量百分数为3~6%。
7.根据权利要求1所述的蛋壳粉基合成纸的制备方法，其特征在于，步骤（5）所得固液混合物中，聚氨酯、N-N-二甲基甲酰胺、蛋壳粉的质量百分比如下：聚氨酯 12.1%～16.2%，N-N-二甲基甲酰胺 59.5%～68.8%，蛋壳粉 15.6%～27.5%。
8.根据权利要求1所述的蛋壳粉基合成纸的制备方法，其特征在于，步，步骤（6）中，碳酸氢钠水溶液质量百分数为3~6%，溶液温度为20~35℃。
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Application publication date: 20170510