CN114634610B - 一种用于纸张涂层的水性聚氨酯及其制备方法 - Google Patents

一种用于纸张涂层的水性聚氨酯及其制备方法 Download PDF

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CN114634610B
CN114634610B CN202210095716.9A CN202210095716A CN114634610B CN 114634610 B CN114634610 B CN 114634610B CN 202210095716 A CN202210095716 A CN 202210095716A CN 114634610 B CN114634610 B CN 114634610B
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戴家兵
郭文鹤
李维虎
赵曦
朱保凌
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Lanzhou Ketian Waterborne Polymer Material Co ltd
Hefei Ketian Waterborne Technology Co ltd
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Abstract

本发明涉及高分子聚合技术领域，具体涉及一种用于纸张涂层的水性聚氨酯及其制备方法。该水性聚氨酯按质量份计包括聚酯多元醇15～20份，多异氰酸酯5～8份，非离子亲水扩链剂3.5～4.5份，小分子扩链剂0.5～0.8份，异氰酸酯封端剂2～3份，聚乙烯亚胺1.9～3.7份。本发明制备的水性聚氨酯脂在纸张上具有良好的附着力，能够和纸张黏合牢固不脱层，同时还具有较高的耐热性能、耐水性能，和抗撕裂性能，能够提高纸张的综合性能。

Description

一种用于纸张涂层的水性聚氨酯及其制备方法
技术领域
本发明涉及高分子聚合技术领域，具体涉及一种用于纸张涂层的水性聚氨酯及其制备方法。
背景技术
纸张作为生活中的重要材料，广泛用于书写绘画、印刷、包装等方面。传统纸张由植物纤维制成，其抗撕裂性能、防水性能、耐磨性能、耐曲折性能都有一定局限性。
水性聚氨酯材料为环保型材料，已经在各类材料中广泛应用，水性聚氨酯材料作为纸张涂层使用，可改善纸张抗撕裂、防水耐磨、耐曲折等性能。
水性聚氨酯通过多元醇种类可分为聚酯、聚醚型。根据亲水组分可分为阴离子、阳离子以及非离子型。聚酯较聚醚有更好的耐热性能，但耐水解性能较差。离子型聚氨酯易受外界电解质的影响产生破乳在生产应用过程中使用方便性。且水性聚氨酯由于氨基甲酸酯键的极性，在纸张等有机或无机已经金属材料上具有较低的附着力。
专利CN102796237A公开了一种双羟基阳离子亲水扩链剂及其在合成阳离子水性聚氨酯分散体中的应用，具体公开了一种阳离子水性聚氨酯，虽然其制备的阳离子水性聚氨酯树脂在纸张上有较好的附着力，但阳离子水性聚氨酯树脂仍存在耐热黄变、耐水性差，有酸味等缺点，限制了其应用。
发明内容
为了解决现有技术中的问题，本发明的目的之一在于提供一种用于纸张涂层的水性聚氨酯，该水性聚氨酯具有较好的耐水耐热性能和纸张附着力。
本发明采用的技术方案为：
一种用于纸张涂层的水性聚氨酯，其特征在于，该水性聚氨酯按质量份计包括：聚酯多元醇15～20份，多异氰酸酯5～8份，非离子亲水扩链剂3.5～4.5份，小分子扩链剂0.5～0.8份，异氰酸酯封端剂2～3份，聚乙烯亚胺1.9～3.7份。
优选的，所述聚酯多元醇为聚己二酸新戊二醇酯、聚乙二醇邻苯二甲酸酐二醇中的任意一种或两种。
优选的，所述多异氰酸酯包括异佛尔酮二异氰酸酯、降冰片烷二异氰酸酯、二环己基甲烷二异氰酸酯中的任意一种或多种。
优选的，所述非离子亲水性扩链剂为三羟甲基丙烷聚乙二醇单甲醚。
优选的，所述小分子扩链剂包括1,4-环己二甲醇或1,2-环己二甲醇、1,4-丁二醇、甲基丙二醇中的任意一种或多种。
优选的，所述异氰酸酯封端剂甲基乙基酮肟。
优选的，所述聚乙烯亚胺的分子量在800～5000，胺值大于19mmol/g。
本发明的目的之二在于提供上述一种用于纸张涂层的水性聚氨酯的制备方法，该方法包括以下步骤：
S1.制备预聚体：按照所需的质量配比，将聚酯多元醇、非离子亲水扩链剂投入反应釜中，真空脱水后降温至50～60℃，加入多异氰酸酯、小分子扩链剂和丙酮并混合均匀，升温至80～85℃反应3～4h；反应结束后再次降温至50～55℃，继续加入异氰酸酯封端剂和丙酮，保温搅拌70～90min，最后加入聚乙烯亚胺搅拌2～5min，即得到所述预聚体；
S2.乳化：将S1制备的预聚体转移至乳化器中，乳化器转速1500～2000r/min条件下加入去离子水，搅拌2～5min后，将乳化器转速调至200～400r/min，继续搅拌30～60min；
S3.对S2乳化后的预聚体在40～60℃，不高于-0.08MPa的真空度下进行减压蒸馏，脱去丙酮，得到所需的水性聚氨酯。
优选的，S1中，单次丙酮的加入量为聚酯多元醇体积的5～20％；S2中，去离子水温度15～30℃，加入量为聚酯多元醇的150～400％。
本发明还提供上述一种用于纸张涂层的水性聚氨酯或利用上述一种用于纸张涂层的水性聚氨酯的制备方法制备得到的水性聚氨酯在制备纸张材料中的应用。
本发明的有益效果在于：
本发明制备的水性聚氨酯树脂，聚乙烯亚胺通过与解封后的异氰酸根发生反应，有效解决聚乙烯亚胺在水性聚氨酯预聚体中反应活性高，过程难以控制、以及预聚体粘度大，难以与水分散的问题。
在树脂成膜过程中聚氨酯链段的封端剂发生解封，与聚乙烯亚胺的氨基发生反应，使得聚乙烯亚胺连接在每个聚氨酯分子上，由于聚乙烯亚胺有大量阳离子存在，能够使制备的水性聚氨酯具有良好的附着力，能够和纸张黏合牢固不脱层。
利用聚乙烯亚胺的高交联特性，能大幅度提高水性聚氨酯的耐热性能以及耐水性能，所制备的水性聚氨酯应用在包装材料中，能使潮湿环境下的被包装物有良好的防水性能。同时由于聚乙烯亚胺为杂环结构，使得制备的水性聚氨酯具有良好的抗撕裂性能，可以增强纸张的抗撕裂能力。
具体实施方式
下面结合实施例对本发明的技术方案进行说明，以便于本领域的技术人员理解。
实施例1
一种用于纸张涂层的水性聚氨酯，制备方法如下：
S1.制备预聚体：按质量份计，将15.2份的聚己二酸新戊二醇酯二醇(2000分子量)和3.8份的三羟甲基丙烷聚乙二醇单甲醚(1000分子量)投入反应釜中，升温至100～105℃后抽真空至-0.1MPa后脱水至二元醇水含量在0.03％以下，降温至50～60℃，加入6.71份异佛尔酮二异氰酸酯、0.76份环己烷二醇、1.9份丙酮并混合均匀，升温至80～85℃反应3h；反应结束后再次降温至50～55℃，继续加入2.8份甲基乙基酮肟和10份丙酮，50℃保温搅拌90min，最后加入2份1000分子量聚乙烯亚胺搅拌2～5min，获得预聚体；
S2.乳化：将S1制备的预聚体转移至乳化器中，乳化器转速2000r/min条件下加入54.7份温度在15～30℃的去离子水，搅拌2min后，将乳化器转速调至200～400r/min，继续搅拌30～60min；
S3.对S2乳化后的预聚体在40～60℃，不高于-0.08MPa的真空度下进行减压蒸馏，并在旋转蒸发仪上50～60℃减压蒸馏脱去丙酮，得到所需的水性聚氨酯乳液。
实施例2
一种用于纸张涂层的水性聚氨酯，制备方法如下：
S1.制备预聚体：按质量份计，将16.5份的聚己二酸新戊二醇酯二醇(2000分子量)、4.0份的三羟甲基丙烷聚乙二醇单甲醚(1000分子量)投入反应釜中，升温至100～105℃抽真空至-0.1MPa后脱水至二元醇水含量在0.03％以下，降温至50～60℃，加入6.02份异佛尔酮二异氰酸酯、1.8二环己基甲烷二异氰酸酯、0.36份环己烷二醇、0.33份1,4-丁二醇、1.9份丙酮并混合均匀，升温至80～85℃反应3h；反应结束后再次降温至50～55℃，继续加入2.93份甲基乙基酮肟和10份丙酮，50℃保温搅拌90min，最后加入2.7份1000分子量聚乙烯亚胺搅拌2～5min，获得预聚体；
S2.乳化：将S1制备的预聚体转移至乳化器中，乳化器转速2000r/min条件下加入54.7份温度在15～30℃的去离子水，搅拌2min后，将乳化器转速调至200～400r/min，继续搅拌30～60min；
S3.对S2乳化后的预聚体在40～60℃，不高于-0.08MPa的真空度下进行减压蒸馏，并在旋转蒸发仪上50～60℃减压蒸馏脱去丙酮，得到所需的水性聚氨酯乳液。
实施例3
一种用于纸张涂层的水性聚氨酯，制备方法如下：
S1.制备预聚体：按质量份计，将11.2份的聚己二酸新戊二醇酯二醇(2000分子量)、5份的聚乙二醇邻苯二甲酸酐二醇(1000分子量)和3.8份的三羟甲基丙烷聚乙二醇单甲醚(1000分子量)投入反应釜中，升温至100～105℃抽真空至-0.1MPa后脱水至二元醇水含量在0.03％以下，降温至50～60℃，加入5.23份异佛尔酮二异氰酸酯、2.45份降冰片烷二异氰酸酯、0.52份甲基丙二醇、1.9份丙酮并混合均匀，升温至80～85℃反应3h；反应结束后再次降温至50～55℃，继续加入2.45份甲基乙基酮肟和10份丙酮，50℃保温搅拌90min，最后加入3.4份5000分子量聚乙烯亚胺搅拌2～5min，获得预聚体；
S2.乳化：将S1制备的预聚体转移至乳化器中，乳化器转速2000r/min条件下加入54.7份温度在15～30℃的去离子水，搅拌2min后，将乳化器转速调至200～400r/min，继续搅拌30～60min；
S3.对S2乳化后的预聚体在40～60℃，不高于-0.08MPa的真空度下进行减压蒸馏，并在旋转蒸发仪上50～60℃减压蒸馏脱去丙酮，得到所需的水性聚氨酯乳液。
实施例4
一种用于纸张涂层的水性聚氨酯，制备方法如下：
S1.制备预聚体：按质量份计，将10.8份的聚己二酸新戊二醇酯二醇(2000分子量)、6.3份的聚乙二醇邻苯二甲酸酐二醇(1000分子量)和3.8份的三羟甲基丙烷聚乙二醇单甲醚(1000分子量)投入反应釜中，升温至100～105℃抽真空至-0.1MPa后脱水至二元醇水含量在0.03％以下，降温至50～60℃，加入3.26份异佛尔酮二异氰酸酯、1.45份降冰片烷二异氰酸酯、3.1份二环己基甲烷二异氰酸酯、0.54份环己烷二醇、0.23份甲基丙二醇、1.9份丙酮并混合均匀，升温至80～85℃反应3h；反应结束后再次降温至50～55℃，继续加入2.3份甲基乙基酮肟和10份丙酮，50℃保温搅拌90min，最后加入3.7份5000分子量聚乙烯亚胺搅拌2～5min，获得预聚体；
S2.乳化：将S1制备的预聚体转移至乳化器中，乳化器转速2000r/min条件下加入54.7份温度在15～30℃的去离子水，搅拌2min后，将乳化器转速调至200～400r/min，继续搅拌30-～60min；
S3.对S2乳化后的预聚体在40～60℃，不高于-0.08MPa的真空度下进行减压蒸馏，并在旋转蒸发仪上50～60℃减压蒸馏脱去丙酮，得到所需的水性聚氨酯乳液。
实施例5
1.对比样制备
一种用于纸张涂层的水性聚氨酯对比样品制备方法如下：
S1.制备预聚体：按质量份计，将15.2份的聚己二酸新戊二醇酯二醇(2000分子量)和3.8份的三羟甲基丙烷聚乙二醇单甲醚(1000分子量)投入反应釜中，升温至100～105℃后抽真空至-0.1MPa后脱水至二元醇水含量在0.03％以下，降温至50～60℃，加入6.71份异佛尔酮二异氰酸酯、0.76份环己烷二醇、1.9份丙酮并混合均匀，升温至80～85℃反应3h；反应结束后再次降温至50～55℃，加入10份丙酮，获得预聚体；
S2.乳化：将S1制备的预聚体转移至乳化器中，乳化器转速2000r/min条件下加入54.7份常温水，搅拌2min后，加入1.2份乙二胺水溶液搅拌1min，将乳化器转速调至200～400r/min，继续搅拌30～60min；
S3.对S2乳化后的预聚体进行减压蒸馏，在旋转蒸发仪上50～60℃减压蒸馏脱去丙酮，得到所需的水性聚氨酯乳液对比样品。
2.实验
将实施例1-4制备的纸张涂层水性聚氨酯和上述对比样品分别用100μm丝棒均匀涂抹在A4打印纸上，并130℃烘30min后制得测试样品。
以实施例1-4制备的纸张涂层水性聚氨酯处理的A4打印纸为处理组，使用对比样品制备的水性聚氨酯处理的A4打印纸为对比组，分别进行测试。
2.1附着力、耐曲折测试
在耐曲折测试机上分别测试对比组和处理组，每组设置三个测试样，每个测试样即A4打印纸设定测试曲折次数为10000次。
结果：对比组中A4打印纸平均出现4300次明显破裂，四个处理组中A4打印纸均未出现明显破裂，且折痕处无分层现象。
表明使用本发明提供的水性聚氨酯处理纸张后，可以明显提高纸张的耐曲折性能，且水性聚氨酯涂层和纸张在曲折过程中没有出现分层，本发明提供的水性聚氨酯在纸张上具有良好的附着力。
2.2抗撕裂性能测试
将处理组和对比组的A4打印纸分别裁割小口，在拉力机上测试沿裁割小口撕裂纸张的最小力。
结果显示对比组A4打印纸裁割裂口处撕拉受力为3.2N，处理组的A4打印纸割裂口处撕拉受力为12.3N。
表明使用本发明提供的水性聚氨酯处理纸张能大幅度提高纸张抗撕裂性能。
2.3防水性能测试
在处理组和对比组的A4打印纸上分别滴加水，静置观察水在纸张的渗透效果。
结果显示，对比组A4打印纸用时26min水即完全渗透纸张，处理组的A4打印纸在120min内无渗透现象。
表明使用本发明提供的水性聚氨酯处理纸张可大幅度提高纸张防水性能。
以上仅为本发明创造的较佳实施例而已，并不用以限制本发明创造；尽管参照前述实施方式对本发明进行了详细的说明，本领域的普通技术人员应当理解：凡在本发明创造的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明创造的保护范围之内。

Claims (10)

1.一种用于纸张涂层的水性聚氨酯，其特征在于，该水性聚氨酯按质量份计包括：聚酯多元醇15~20份，多异氰酸酯5~8份，非离子亲水扩链剂3.5~4.5份，小分子扩链剂0.5~0.8份，异氰酸酯封端剂2~3份，聚乙烯亚胺1.9~3.7份；
该用于纸张涂层的水性聚氨酯的制备方法，包括以下步骤：
S1. 制备预聚体：按照所需的质量配比，将聚酯多元醇、非离子亲水扩链剂投入反应釜中，真空脱水后降温至50~60℃，加入多异氰酸酯、小分子扩链剂和丙酮并混合均匀，升温至80~85℃反应3~4 h；反应结束后再次降温至50~55℃，继续加入异氰酸酯封端剂和丙酮，保温搅拌70~90 min，最后加入聚乙烯亚胺搅拌2~5 min，即得到所述预聚体；
S2. 乳化：将S1制备的预聚体转移至乳化器中，乳化器转速1500~2000 r/min条件下加入去离子水，搅拌2~5 min后，将乳化器转速调至200~400 r/min，继续搅拌30~60 min；
S3. 对S2乳化后的水性聚氨酯树脂在40~60℃，不高于-0.08MPa的真空度下进行减压蒸馏，脱去丙酮，得到所需的水性聚氨酯。
2.如权利要求1所述的一种用于纸张涂层的水性聚氨酯，其特征在于，所述聚酯多元醇为聚己二酸新戊二醇酯、聚乙二醇邻苯二甲酸酐二醇中的任意一种或两种。
3.如权利要求1所述的一种用于纸张涂层的水性聚氨酯，其特征在于，所述多异氰酸酯包括异佛尔酮二异氰酸酯、降冰片烷二异氰酸酯、二环己基甲烷二异氰酸酯中的任意一种或多种。
4.如权利要求1所述的一种用于纸张涂层的水性聚氨酯，其特征在于，所述非离子亲水扩链剂为三羟甲基丙烷聚乙二醇单甲醚。
5.如权利要求1所述的一种用于纸张涂层的水性聚氨酯，其特征在于，所述小分子扩链剂包括环己二甲醇、1,4-丁二醇、甲基丙二醇中的任意一种或多种。
6.如权利要求1所述的一种用于纸张涂层的水性聚氨酯，其特征在于，所述异氰酸酯封端剂为甲基乙基酮肟。
7.如权利要求1所述的一种用于纸张涂层的水性聚氨酯，其特征在于，所述聚乙烯亚胺的分子量在800~5000，胺值大于19 mmol/g。
8.一种如权利要求1-7任一项所述的一种用于纸张涂层的水性聚氨酯的制备方法，其特征在于，包括以下步骤：
S1. 制备预聚体：按照所需的质量配比，将聚酯多元醇、非离子亲水扩链剂投入反应釜中，真空脱水后降温至50~60℃，加入多异氰酸酯、小分子扩链剂和丙酮并混合均匀，升温至80~85℃反应3~4 h；反应结束后再次降温至50~55℃，继续加入异氰酸酯封端剂和丙酮，保温搅拌70~90 min，最后加入聚乙烯亚胺搅拌2~5 min，即得到所述预聚体；
S2. 乳化：将S1制备的预聚体转移至乳化器中，乳化器转速1500~2000 r/min条件下加入去离子水，搅拌2~5 min后，将乳化器转速调至200~400 r/min，继续搅拌30~60 min；
S3. 对S2乳化后的水性聚氨酯树脂在40~60℃，不高于-0.08MPa的真空度下进行减压蒸馏，脱去丙酮，得到所需的水性聚氨酯。
9.如权利要求8所述的一种用于纸张涂层的水性聚氨酯的制备方法，其特征在于，S1中，单次丙酮的加入量为聚酯多元醇体积的5~20%；S2中，去离子水温度15~30℃，加入量为聚酯多元醇体积的150~400%。
10.一种如权利要求1-7任一项所述的一种用于纸张涂层的水性聚氨酯或如权利要求8所述的一种用于纸张涂层的水性聚氨酯的制备方法制备得到的水性聚氨酯在制备纸张材料中的应用。
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