CN105820650A - 一种耐高温水性聚氨酯油墨连接料及其制备方法 - Google Patents
一种耐高温水性聚氨酯油墨连接料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐高温水性聚氨酯油墨连接料及其制备方法，该方法所述油墨连接料的主要结构是由聚丙烯腈静电纺丝纤维与水性聚氨酯分子链交织而成的网络结构，水性聚氨酯分子链由聚碳酸酯二醇或者聚己内酯二醇或者聚氧化丙烯二醇与甲基环己基二异氰酸酯或者二苯基甲烷二异氰酸酯反应而成。本发明一种耐高温水性聚氨酯油墨连接料及其制备方法采取如下步骤：纺丝液的制备、静电纺丝纤维的获取、水性聚氨酯预聚体的合成、水性聚氨酯乳液的合成以及耐高温水性聚氨酯油墨连接料的制备；本发明一种耐高温水性聚氨酯油墨连接料的热稳定性能得到明显改善，且其制备方法简单，不涉及污染物质的排放。
Description
技术领域
本发明涉及一种耐高温水性聚氨酯油墨连接料，具体地说，是涉及一种结构中含有由聚丙烯腈静电纺丝纤维与聚氨酯分子链交织而成的网络结构的水性聚氨酯油墨连接料及其制备方法。
背景技术
水性聚氨酯具有环保、安全、低成本等优势，是目前最具发展前景的印刷油墨连接料之一，但是水性聚氨酯的分子链结构在高温条件下的结构稳定性相对较差，导致以其为连结料的油墨的耐高温性能受到影响。
改善水性聚氨酯分子链结构高温稳定性的方法较多，主要包括向聚氨酯主链结构中引入内聚能较大、降解温度较高的有机杂环等基团[王耿衔，UV固化水性聚乙烯醇缩丁醛改性聚氨酯的合成及热稳定性研究，广东化工，2014，12；PetrovaAP.Polyurethaneadhesivebasedoncarborane-containingcompounds，PolymerScience，2007，49；汤中道，刘惠芳，卜庭江，刘燕，有机累托石改性环氧/水性聚氨酯复合膜的制备与性能，化工新型材料，2010，12；潘卉，陈珊珊，郭子健，李纪录，丁涛，张治军，纳米TiO2微球对聚氨酯的改性，化学研究，2016，01；王正祥，李运华，肖细梅，陈洪，基于PEDA的UV固化水性聚氨酯乳液及涂膜性能研究，包装工程，2016，05]以及利用多元醇等在水性聚氨酯基材分子链间建立交联点，通过限制聚氨酯分子链的运动从而实现提高水性聚氨酯耐高温性能的目的[QuZ，ZhaiJ，YangR.Comparisonbetweenpropertiesofpolyetherpolytriazoleelastomersandpolyetherpolyurethaneelastomers，PolymersforAdvancedTechnologies，2014，25；胡虔，吕兰，吴雄，廖晶，潘吉林，徐祖顺，环氧树脂改性高度支化水性聚氨酯的合成与性能研究，电镀与涂饰，2015，18；赵静，沈一丁，赖小娟，酮肼交联及硅烷偶联水性聚氨酯的成膜机理及其性能研究，高分子学报，2010，09；邓威，傅和青，黄洪，内交联水性聚氨酯涂膜性能的影响因素，高分子材料科学与工程，2012，09；张玉，杨建军，吴庆云，张建安，吴明元，陈春俊，曹忠富，硅烷化还原氧化石墨烯/水性聚氨酯复合物的合成与性能，精细化工，2016，03]。
通过向聚氨酯主链结构中引入内聚能较大、降解温度较高的有机杂环等基团会对环境造成较大的压力，不符合可持续发展的环保要求；而在水性聚氨酯基材分子链间建立交联点对于水性聚氨酯基材的热稳定性改善效果明显，但是目前常见的交联结构为内交联，其交联结构的建立需要以体型树脂为依托，应用受限。
发明内容
本发明所要解决的技术问题是针对以水性聚氨酯为连接料的油墨高温稳定性较差的问题，提供一种耐高温水性聚氨酯油墨连接料，其结构中存在由聚丙烯腈静电纺丝纤维与聚氨酯分子链交织而成的网络结构，该网络结构会导致连结料结构致密化，进而表现出高温条件下的结构稳定性。
为解决上述技术问题，本发明采用以下技术方案：
一种耐高温水性聚氨酯油墨连接料，它是由下述重量百分比的组分混合制成：水性聚氨酯乳液50%~70%、质量分数为7%的氨水10%~20%和羧甲基纤维素钠10%~40%。
所述的耐高温水性聚氨酯油墨连接料结构中存在由聚丙烯腈静电纺丝纤维与聚氨酯分子链交织而成的网络结构，该网络结构会导致连结料结构致密化，进而表现出高温条件下的结构稳定性。
所述的耐高温水性聚氨酯油墨连接料的制备方法，包括以下步骤：
（1）将N，N-二甲基甲酰胺与聚丙烯腈按混合后制得纺丝液；
（2）将步骤（1）制得的纺丝液采用静电纺丝的方法制得聚丙烯腈静电纺丝纤维；
（3）制备水性聚氨酯预聚体；
（4）将步骤（2）制得的聚丙烯腈静电纺丝纤维和步骤（3）制得的水性聚氨酯预聚体按质量比1:5~1:20混合后得到混合溶液B，向混合溶液B中添加扩链剂，室温下经过机械搅拌后制得水性聚氨酯乳液，其中扩链剂与混合溶液的质量比为1:5~1:8；
（5）按重量配比将水性聚氨酯乳液、质量分数为7%的氨水、羧甲基纤维素钠在室温下机械搅拌混合均匀后制得耐高温水性聚氨酯油墨连接料。
所述的步骤（1）中纺丝液的制备方法如下：将N，N-二甲基甲酰胺与聚丙烯腈按质量比5:1~10:1置于锥形瓶中，60℃水浴加热，水浴过程中需要机械搅拌，机械搅拌转速为120r/min，水浴时间为5min。
所述的步骤（2）中聚丙烯腈静电纺丝纤维的制备方法如下：将纺丝液装入医用注射器中，流速控制为1.0ml/h~2.0ml/h，针头与接收器间的距离为25cm，静电纺丝过程的负压为-3.0kV，正压为25.0kV，环境温度为50℃。
所述的步骤（2）中制备获得的聚丙烯腈静电纺丝纤维直径为20~50nm，长度为300~600nm；
所述步骤（3）中水性聚氨酯预聚体的制备方法如下：将多元醇与二羟甲基丙酸按照质量比为6:1~8:1混合后得到混合溶液A，将混合溶液A加热至100~110℃，保温30min后冷却至室温，然后将混合溶液A与二异氰酸酯按照质量比为3:1~4:1混合均匀并升温至75℃反应4h后获得水性聚氨酯预聚体。
所述的多元醇为聚碳酸酯二醇或者聚己内酯二醇或者聚氧化丙烯二醇；二异氰酸酯为甲基环己基二异氰酸酯或者二苯基甲烷二异氰酸酯。
所述的步骤（4）中的扩链剂为乙二胺、乙二醇、异佛尔酮二胺、1,4-丁二醇或二乙烯三胺。
所述的步骤（4）中机械搅拌的转速为120r/min，搅拌时间30min。
所述的步骤（5）中机械搅拌的转速为60r/min，搅拌时间15min。
本发明的有益效果：(1)本发明提供了一种利用聚丙烯腈静电纺丝纤维制备耐高温水性聚氨酯油墨连接料的有效途径；(2)本发明利用聚丙烯腈静电纺丝纤维与聚氨酯分子链交织而成的网络结构，使水性聚氨酯油墨连接料的耐高温性能显著提高；(3)本发明提供了一种改善水性聚氨酯油墨连接料高温稳定性的简便方法，易与现有技术结合，可实现工业化生产；(4)本发明一种耐高温水性聚氨酯油墨连接料的制备和使用过程中不涉及污染物质的排放，是环保型印刷油墨的有益原料。
附图说明
图1为实施例1制得的耐高温水性聚氨酯油墨连接料固化成膜后的软化点测试图。
图2为实施例2制得的耐高温水性聚氨酯油墨连接料固化成膜后的软化点测试图。
图3为实施例3制得的耐高温水性聚氨酯油墨连接料固化成膜后的软化点测试图。
图4为实施例4制得的耐高温水性聚氨酯油墨连接料固化成膜后的软化点测试图。
具体实施方式
下面结合具体实施例，对本发明做进一步说明。应理解，以下实施例仅用于说明本发明而非用于限制本发明的范围，该领域的技术熟练人员可以根据上述发明的内容作出一些非本质的改进和调整。
实施例1
本实施例的一种耐高温水性聚氨酯油墨连接料的制备方法如下：
(1)将20.0g的N，N-二甲基甲酰胺与4.0g的聚丙烯腈混合后置于锥形瓶中水浴加热，水浴温度为60℃，水浴时间为5min，水浴过程中机械搅拌转速为120r/min，制备获得纺丝液23.1g；
(2)取10.0g纺丝液装入医用注射器中，静电纺丝过程的负压为-3.0kV，正压为25.0kV，环境温度为50℃，流速为1.0ml/h，针头与接收器间的距离为25cm，制备获得9.8g聚丙烯腈静电纺丝纤维；
(3)将30.0g聚碳酸酯二醇与5.0g二羟甲基丙酸混合后加热至100~110℃，保温30min后冷却至室温，然后将上述混合溶液与9.0g甲基环己基二异氰酸酯混合均匀并升温至75℃反应4h后获得水性聚氨酯预聚体42.6g；
(4)取8.0g聚丙烯腈静电纺丝纤维和40.0g水性聚氨酯预聚体组成的混合溶液，然后添加9.6g的1，4-丁二醇，经过30min转速为120r/min的机械搅拌后制得56.5g水性聚氨酯乳液备用；
(5)取35.0g水性聚氨酯乳液与5.0g氨水、10.0g羧甲基纤维素钠混合并在60r/min的转速下搅拌时间15min，制得48.1g所述的耐高温水性聚氨酯油墨连接料。
取20.0g上述耐高温水性聚氨酯油墨连接料固化成膜后测定其软化点为239.5℃。
实施例2
本实施例的一种耐高温水性聚氨酯油墨连接料的制备方法如下：
(1)将35.0g的N，N-二甲基甲酰胺与5.0g的聚丙烯腈混合后置于锥形瓶中水浴加热，水浴温度为60℃，水浴时间为5min，水浴过程中机械搅拌转速为120r/min，制备获得纺丝液38.7g；
(2)取20.0g纺丝液装入医用注射器中，静电纺丝过程的负压为-3.0kV，正压为25.0kV，环境温度为50℃，流速为1.5ml/h，针头与接收器间的距离为25cm，制备获得18.5g聚丙烯腈静电纺丝纤维；
(3)将21.0g聚碳酸酯二醇与3.0g二羟甲基丙酸混合后加热至100~110℃，保温30min后冷却至室温，然后将上述混合溶液与8.0g二苯基甲烷二异氰酸酯混合均匀并升温至75℃反应4h后获得水性聚氨酯预聚体31.6g；
(4)取3.0g聚丙烯腈静电纺丝纤维和30.0g水性聚氨酯预聚体组成的混合溶液，然后添加5.5g的二乙烯三胺，经过30min转速为120r/min的机械搅拌后制得36.1g水性聚氨酯乳液备用；
(5)取24.0g水性聚氨酯乳液与4.0g氨水、12.0g羧甲基纤维素钠混合并在60r/min的转速下搅拌时间15min，制得39.2g所述的耐高温水性聚氨酯油墨连接料。
取20.0g上述耐高温水性聚氨酯油墨连接料固化成膜后测定其软化点为226.2℃。
实施例3
本实施例的一种耐高温水性聚氨酯油墨连接料的制备方法如下：
(1)将32.0g的N，N-二甲基甲酰胺与4.0g的聚丙烯腈混合后置于锥形瓶中水浴加热，其水浴温度为60℃，水浴时间为5min，水浴过程中的机械搅拌转速为120r/min，可制备获得34.9g纺丝液；
(2)取30.0g纺丝液装入医用注射器中，静电纺丝过程的负压为-3.0kV，正压为25.0kV，环境温度为50℃，流速为2.0ml/h，针头与接收器间的距离为25cm，制备获得29.1g聚丙烯腈静电纺丝纤维；
(3)将40.0g聚氧化丙烯二醇与5.0g二羟甲基丙酸混合后加热至100~110℃，保温30min后冷却至室温，然后将上述混合溶液与12.0g二苯基甲烷二异氰酸酯混合均匀并升温至75℃反应4h后获得水性聚氨酯预聚体55.9g；
(4)取3.5g聚丙烯腈静电纺丝纤维和52.5g水性聚氨酯预聚体组成的混合溶液，然后添加8.0g的乙二胺，经过30min转速为120r/min的机械搅拌后制得61.7g水性聚氨酯乳液备用；
(5)取25.0g水性聚氨酯乳液与10.0g氨水、15.0g羧甲基纤维素钠混合并在60r/min的转速下搅拌时间15min，获得48.5g所述的耐高温水性聚氨酯油墨连接料。
取20.0g上述耐高温水性聚氨酯油墨连接料固化成膜后测定其软化点为217.6℃。
实施例4
本实施例的一种耐高温水性聚氨酯油墨连接料的制备方法如下：
(1)将40.0g的N，N-二甲基甲酰胺与4.0g的聚丙烯腈混合后置于锥形瓶中水浴加热，其水浴温度为60℃，水浴时间为5min，水浴过程中的机械搅拌转速为120r/min，可制备获得42.7g纺丝液；
(2)取20.0g纺丝液装入医用注射器中，静电纺丝过程的负压为-3.0kV，正压为25.0kV，环境温度为50℃，流速为1.0ml/h，针头与接收器间的距离为25cm，制备获得19.3g聚丙烯腈静电纺丝纤维；
(3)将30.0g聚氧化丙烯二醇与5.0g二羟甲基丙酸混合后加热至100~110℃，保温30min后冷却至室温，然后将上述混合溶液与11.0g甲基环己基二异氰酸酯混合均匀并升温至75℃反应4h后获得水性聚氨酯预聚体55.9g；
(4)取2.0g聚丙烯腈静电纺丝纤维和40.0g水性聚氨酯预聚体组成的混合溶液，然后添加7.0g异佛尔酮二胺，经过30min转速为120r/min的机械搅拌后制得47.3g水性聚氨酯乳液备用；
(5)取25.0g水性聚氨酯乳液与5.0g氨水、20.0g羧甲基纤维素钠混合并在60r/min的转速下搅拌时间15min，获得49.1g所述的耐高温水性聚氨酯油墨连接料。
取20.0g上述耐高温水性聚氨酯油墨连接料固化成膜后测定其软化点为213.5℃。
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (10)
1.一种耐高温水性聚氨酯油墨连接料，其特征在于它是由下述重量百分比的组分混合制成：水性聚氨酯乳液50%~70%、质量分数为7%的氨水10%~20%和羧甲基纤维素钠10%~40%。
2.根据权利要求1所述的耐高温水性聚氨酯油墨连接料，其特征在于：所述的耐高温水性聚氨酯油墨连接料结构中存在由聚丙烯腈静电纺丝纤维与聚氨酯分子链交织而成的网络结构，该网络结构会导致连结料结构致密化，进而表现出高温条件下的结构稳定性。
3.根据权利要求1或2所述的耐高温水性聚氨酯油墨连接料的制备方法，其特征在于包括以下步骤：
（1）将N，N-二甲基甲酰胺与聚丙烯腈混合后制得纺丝液；
（2）将步骤（1）制得的纺丝液采用静电纺丝的方法制得聚丙烯腈静电纺丝纤维；
（3）制备水性聚氨酯预聚体；
（4）将步骤（2）制得的聚丙烯腈静电纺丝纤维和步骤（3）制得的水性聚氨酯预聚体按质量比1:5~1:20混合后得到混合溶液B，向混合溶液B中添加扩链剂，室温下经过机械搅拌后制得水性聚氨酯乳液，其中扩链剂与混合溶液的质量比为1:5~1:8；
（5）按重量配比将水性聚氨酯乳液、质量分数为7%的氨水、羧甲基纤维素钠在室温下机械搅拌混合均匀后制得耐高温水性聚氨酯油墨连接料。
4.根据权利要求3所述的耐高温水性聚氨酯油墨连接料的制备方法，其特征在于：所述的步骤（1）中纺丝液的制备方法如下：将N，N-二甲基甲酰胺与聚丙烯腈按质量比5:1~10:1置于锥形瓶中，60℃水浴加热，水浴过程中需要机械搅拌，机械搅拌转速为120r/min，水浴时间为5min。
5.根据权利要求3所述的耐高温水性聚氨酯油墨连接料的制备方法，其特征在于：所述的步骤（2）中聚丙烯腈静电纺丝纤维的制备方法如下：将纺丝液装入医用注射器中，流速控制为1.0ml/h~2.0ml/h，针头与接收器间的距离为25cm，静电纺丝过程的负压为-3.0kV，正压为25.0kV，环境温度为50℃。
6.根据权利要求3所述的耐高温水性聚氨酯油墨连接料的制备方法，其特征在于：所述的步骤（2）中制备获得的聚丙烯腈静电纺丝纤维直径为20~50nm，长度为300~600nm。
7.根据权利要求3所述的耐高温水性聚氨酯油墨连接料的制备方法，其特征在于：所述步骤（3）中水性聚氨酯预聚体的制备方法如下：将多元醇与二羟甲基丙酸按照质量比为6:1~8:1混合后得到混合溶液A，将混合溶液A加热至100~110℃，保温30min后冷却至室温，然后将混合溶液A与二异氰酸酯按照质量比为3:1~4:1混合均匀并升温至75℃反应4h后获得水性聚氨酯预聚体。
8.根据权利要求7所述的耐高温水性聚氨酯油墨连接料的制备方法，其特征在于：所述的多元醇为聚碳酸酯二醇或者、聚己内酯二醇或聚氧化丙烯二醇；所述的二异氰酸酯为甲基环己基二异氰酸酯或二苯基甲烷二异氰酸酯。
9.根据权利要求3所述的一种耐高温水性聚氨酯油墨连接料的制备方法，其特征在于：所述的步骤（4）中的扩链剂为乙二胺、乙二醇、异佛尔酮二胺、1,4-丁二醇或二乙烯三胺。
10.根据权利要求3所述的一种耐高温水性聚氨酯油墨连接料的制备方法，其特征在于：所述的步骤（5）中机械搅拌的转速为60r/min，搅拌时间15min。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497225A (zh) * | 2016-11-25 | 2017-03-15 | 河南工程学院 | 一种高附着力印刷油墨连接料及其制备方法 |
| CN106497225B (zh) * | 2016-11-25 | 2019-05-17 | 河南工程学院 | 一种高附着力印刷油墨连接料及其制备方法 |
| CN108384319A (zh) * | 2018-04-27 | 2018-08-10 | 福建格林春天新材料股份有限公司 | 一种尼龙印刷耐高温蒸煮水性油墨及其制备方法 |
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