CN108383970B - 一种耐高温碱液水性聚氨酯涂料的制备方法及其应用 - Google Patents
一种耐高温碱液水性聚氨酯涂料的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种耐高温碱液水性聚氨酯涂料的制备方法及其应用,首先通过分子设计和工艺优化实现耐碱型环氧‑丙烯酸酯‑聚氨酯的共聚合和在水中的自乳化,然后在其中加入相关助剂得到水性聚氨酯涂料,涂布于包装纸表面后,可在纸张表面形成一层具有耐高温氢氧化钠溶液的聚氨酯涂层,表面印刷油墨后,可在85℃下、2%的氢氧化钠溶液中浸泡20分钟内保持涂层不降解、油墨不脱落,并且能显著提高纸张的硬度、光泽度、耐折度,使用水性聚氨酯涂料涂布后,纸张的硬度由HB提高到5H,光泽度提高约261%,耐折度提升了178%。
Description
技术领域
本发明涉及一种水性聚氨酯,具体地说是一种耐高温碱液水性聚氨酯涂料的制备方法及其应用,适用于纸张的加工与处理,以达到提高纸张表面的可印刷性以及高温耐碱性的目的,同时也可以提高纸张的硬度、耐折度以及光泽度。
背景技术
原纸由于其未进行加工改性,通常机械性能较差,且由于纤维素易吸水吸油墨,导致其表面印刷时,油墨极易分散开,从而导致极差的可印刷性,这两点导致原纸通常需要进行涂布加工后才能达到使用要求。目前市场上常用的纸张涂料通常是油溶性聚氨酯、聚丙烯酸酯和聚醋酸乙烯酯,这些涂料在使用时存在严重的溶剂挥发的问题,对环境和人体都存在严重的危害,水性聚氨酯以水替代有机溶剂作为分散介质,除具有溶剂型聚氨酯优异性能外,而且耐油、耐低温、耐屈挠、耐化学品、安全可靠、施工过程不易燃易爆、无毒、无环境污染,环氧树脂具有极佳的耐碱腐蚀的性能,且在成膜时能提高纸张的硬度和耐折度,丙烯酸酯价格低廉,同时具有优异的成膜性能,能够在降低成本的同时极大的提高纸张的表面光泽度。两者复合改性聚氨酯能使涂料兼具各组分的优异性能,对纸张涂布后赋予其优异的高温耐碱性、硬度、耐折度、光泽度。
发明内容
本发明旨在提供一种耐高温碱液水性聚氨酯涂料的制备方法及其应用。本发明利用环氧树脂与丙烯酸酯优异的高温耐碱腐蚀性能以及水性聚氨酯良好的成膜性能,应用于纸张涂布后,涂料可以在高温干燥下重新交联固化,在纸张表面形成一层耐高温碱液的聚合物涂层。
本发明耐高温碱液水性聚氨酯涂料的制备方法,是首先在聚氨酯中引入环氧树脂与双键,实现与丙烯酸酯类单体的共聚合,通过基体树脂在水中的自乳化制备出耐高温碱液水性聚氨酯乳液,加入助剂后获得的耐高温碱液水性聚氨酯涂料;其制备过程具体包括如下步骤:
步骤1:将双酚A型环氧树脂、聚碳酸酯二元醇、异氰酸酯混合,在70-85℃下聚合3-4小时,随后分别加入亲水扩链剂、小分子扩链剂进行扩链并引入亲水基团,继续反应4-5小时,再加入羟基不饱和单体进行封端1-2小时,最后加入成盐剂和去离子水进行中和乳化,得到水性可交联耐碱型聚氨酯乳液;
步骤1中,各原料的配比按质量份数构成如下:
步骤1中,所述双酚A型环氧树脂为环氧值在0.1-0.56之间的环氧树脂中的一种。
步骤1中,所述聚碳酸酯二元醇包括数均分子量为1000、2000、4000的聚碳酸酯二元醇中的一种或几种。
步骤1中,所述异氰酸酯为脂肪族二异氰酸酯中的一种或几种。
步骤1中,所述亲水扩链剂为二羟甲基丙酸、二羟甲基丁酸、1,2-丙二醇-3-磺酸钠、1,4-丁二醇-2-磺酸钠中的一种。
步骤1中,所述小分子扩链剂为1,4丁二醇、二乙醇胺、1,6己二醇、乙二胺中的一种。
步骤1中,所述羟基不饱和单体为甲基丙烯酸羟乙酯、丙烯酸羟乙酯中的一种。
步骤1中,所述成盐剂为三乙胺、氢氧化钠、氨水、氢氧化钙悬浊液中的一种。
步骤2:将步骤1制备的水性可交联耐碱型聚氨酯乳液加入反应器中,然后加入丙烯酸酯类单体与油溶性引发剂,添加适量去离子水将固含量控制为40%,均匀分散半小时(超声、冰浴、搅拌等方式);随后升温至70-80℃引发聚合反应2-4小时,制备获得耐高温碱液水性聚氨酯乳液;随后加入流平剂和消泡剂,充分搅拌混合均匀,得到耐高温碱液水性聚氨酯涂料。
步骤2中,各原料的配比按质量份数构成如下:
步骤2中,所述丙烯酸酯类单体为甲基丙烯酸甲酯和丙烯酸丁酯的混合物,质量比为1-2.5:1。
步骤2中,所述油溶性引发剂为偶氮二异丁氰、偶氮二异庚氰、过氧化苯甲酰、叔丁基过氧化氢中的一种。
步骤2中,所述流平剂为有基硅树脂、醋酸丁酯纤维素中的一种。
步骤2中,所述消泡剂为异辛醇、磷酸三丁酯中的一种。
本发明耐高温碱液水性聚氨酯涂料的应用,是作为纸张涂层提高涂布后纸张的性能,具体包括如下步骤:
将本发明耐高温碱液水性聚氨酯涂料均匀涂布于纸张表面,施胶量为10g/m3,涂布后立即置于110℃下干燥固化7秒,即可得到耐高温碱液聚合物涂层。
所述纸张优选为包装用纸。
本发明首先通过分子设计和工艺优化实现耐碱型环氧-丙烯酸酯-聚氨酯的共聚合和在水中的自乳化,然后在其中加入相关助剂得到水性聚氨酯涂料,涂布于包装纸表面后,可在纸张表面形成一层具有耐高温氢氧化钠溶液的聚氨酯涂层,表面印刷油墨后,可在85℃下、2%的氢氧化钠溶液中浸泡20分钟内保持涂层不降解、油墨不脱落,并且能显著提高纸张的硬度、光泽度、耐折度,使用水性聚氨酯涂料涂布后,纸张的硬度由HB提高到5H,光泽度提高约261%,耐折度提升了178%。
本发明相对于现有技术的有益效果是:
1、提高涂布后的纸张的高温耐碱性能。本发明通过采用环氧树脂与丙烯酸酯复合改性水性聚氨酯,成膜后环氧树脂与丙烯酸酯能提供极强的高温耐碱性能,在其表面涂刷油墨后,可在85℃下,2%的碱液中浸泡20分钟内保持油墨不脱落,涂层不降解,能显著改善聚氨酯耐介质性能较差的问题;
2、提升涂布后的纸张的机械性能。水性聚氨酯涂料在纸张上涂布后,能渗透到纸张内部,并在其表面形成一层聚合物涂层,提高纸张的硬度与耐折度,涂布后纸张的硬度由HB提升到5H,耐折度提升了178%。
3、提升纸张的光泽度。纸张表面形成的聚合物涂层含有大量的聚丙烯酸酯结构,能够大幅提高纸张的光泽度,涂布后纸张的光泽度提高了约261%
4、降低成本。使用廉价的丙烯酸酯与价格较高的水性聚氨酯进行复合改性,在提升性能的同时极大地降低了成本,与纯水性聚氨酯涂料相比,其成本约下降了37%。
具体实施方式
下面通过实施例的方式对本发明进行进一步说明,但并不因此将本发明限制在所述的实施例范围之中。
实施例1:
本实施例中耐高温碱液水性聚氨酯涂料,是首先在聚氨酯中引入环氧树脂与双键,实现与丙烯酸酯类单体的共聚合,通过基体树脂在水中的自乳化制备出耐高温碱液水性聚氨酯乳液,加入助剂后获得的耐高温碱液水性聚氨酯涂料,其制备过程具体包括如下步骤:
1、在110℃下,将12质量份环氧树脂EP44与37质量份聚碳酸酯二元醇(Mn=2000)在容器内真空除水1小时;将体系温度降低至85℃,加入23质量份异氟尔酮异氰酸酯与8质量份二羟甲基丙酸反应2小时,随后加入6质量份1,4丁二醇继续反应1小时,最后将温度降低至60℃,加入8质量份甲基丙烯酸羟乙酯进行封端1.5小时,降温至50℃加入3质量份氨水进行中和半小时,最后加入60质量份去离子水在1000转/min的搅拌下高速乳化半小时,得到水性可交联耐碱型聚氨酯乳液;
2、取55质量份步骤1制备的水性可交联耐碱型聚氨酯乳液加入反应器中,加入20质量份甲基丙烯酸甲酯和丙烯酸丁酯的混合物,其比例为2:1,随后加入0.01质量份过氧化苯甲酰,然后加入适量去离子水将固含量控制为40%,冰浴搅拌分散半小时,随后升温至70℃引发聚合反应4小时,制备出水性聚氨酯乳液,继续加入0.02质量份有机硅树脂,0.03质量份异辛醇,得到耐高温碱液水性聚氨酯涂料。
将本实施例制备的耐高温碱液水性聚氨酯涂料作为纸张涂层以提高涂布后纸张的性能,具体包括如下步骤:
将本实施例制备的耐高温碱液水性聚氨酯涂料均匀涂布于包装纸表面,施胶量为10g/m3,涂布后立即置于110℃下干燥固化7秒,即可得到耐高温氢氧化钠溶液聚合物涂层。
通过使用本实施例制备得到的水性聚氨酯涂料对纸张涂布热烘后,纸张的相关性能见下表:
实施例2:
本实施例中耐高温碱液水性聚氨酯涂料,是首先在聚氨酯中引入环氧树脂与双键,实现与丙烯酸酯类单体的共聚合,通过基体树脂在水中的自乳化制备出耐高温碱液水性聚氨酯乳液,加入助剂后获得的耐高温碱液水性聚氨酯涂料,其制备过程具体包括如下步骤:
1、在110℃下,将18质量份环氧树脂EP12与25质量份聚碳酸酯二元醇(Mn=1000)在容器内真空除水1小时;将体系温度降低至80℃,加入20质量份异氟尔酮异氰酸酯与7质量份二羟甲基丙酸反应2小时,随后加入6质量份1,4丁二醇继续反应1小时,最后将温度降低至60℃,加入8质量份甲基丙烯酸羟乙酯进行封端1.5小时,降温至50℃加入3质量份氨水进行中和半小时,加入60质量份去离子水在1000转/min的搅拌下高速乳化半小时,得到水性可交联耐碱型聚氨酯乳液;
2、取55质量份步骤1制备的水性可交联耐碱型聚氨酯乳液加入反应器中,加入25质量份甲基丙烯酸甲酯和丙烯酸丁酯的混合物,其比例为2.5:1,随后加入0.02质量份过氧化苯甲酰,加入适量去离子水将固含量控制为40%,冰浴搅拌分散半小时;随后升温至70℃引发聚合4小时,制备出水性聚氨酯乳液,继续加入0.02质量份醋酸丁酯纤维素,0.4质量份磷酸三丁酯,得到耐高温碱液水性聚氨酯涂料。
将本实施例制备的耐高温碱液水性聚氨酯涂料作为纸张涂层以提高涂布后纸张的性能,具体包括如下步骤:
将本实施例制备的耐高温碱液水性聚氨酯涂料均匀涂布于包装纸表面,施胶量为10g/m3,涂布后立即置于110℃下干燥固化7秒,即可得到耐高温氢氧化钠溶液聚合物涂层。
通过使用本实施例制备得到的水性聚氨酯涂料对纸张涂布热烘后,纸张的相关性能见下表:
实施例3:
本实施例中耐高温碱液水性聚氨酯涂料,是首先在聚氨酯中引入环氧树脂与双键,实现与丙烯酸酯类单体的共聚合,通过基体树脂在水中的自乳化制备出耐高温碱液水性聚氨酯乳液,加入助剂后获得的耐高温碱液水性聚氨酯涂料,其制备过程具体包括如下步骤:
1、在110℃下,将13质量份环氧树脂EP44与40质量份聚碳酸酯二元醇(Mn=1000)在容器内真空除水1小时;将体系温度降低至80℃,加入18质量份六亚甲基二异氰酸酯与6质量份二羟甲基丙酸反应3小时,随后加入6质量份1,4丁二醇继续反应1小时,最后将温度降低至60℃,加入8质量份丙烯酸羟乙酯进行封端1.5小时,降温至50℃加入3质量份三乙胺进行中和半小时,加入60质量份去离子水在1000转/min的搅拌下高速乳化半小时,得到水性可交联耐碱型聚氨酯乳液;
2、取55质量份步骤1制备的水性可交联耐碱型聚氨酯乳液加入反应器中,加入25质量份甲基丙烯酸甲酯和丙烯酸丁酯的混合物,其比例为3:1,随后加入0.02质量份偶氮二异丁腈,加入适量去离子水将固含量控制为40%,冰浴超声分散半小时;随后升温至70℃引发聚合4小时,制备出水性聚氨酯乳液,继续加入0.3质量份有机硅树脂,0.2质量份异辛醇,得到耐高温碱液水性聚氨酯涂料。
将本实施例制备的耐高温碱液水性聚氨酯涂料作为纸张涂层以提高涂布后纸张的性能,具体包括如下步骤:
将本实施例制备的耐高温碱液水性聚氨酯涂料均匀涂布于包装纸表面,施胶量为10g/m3,涂布后立即置于110℃下干燥固化7秒,即可得到耐高温氢氧化钠溶液聚合物涂层。
通过使用本实施例制备得到的水性聚氨酯涂料对纸张涂布热烘后,纸张的相关性能见下表:
实施例4:
本实施例中耐高温碱液水性聚氨酯涂料,是首先在聚氨酯中引入环氧树脂与双键,实现与丙烯酸酯类单体的共聚合,通过基体树脂在水中的自乳化制备出耐高温碱液水性聚氨酯乳液,加入助剂后获得的耐高温碱液水性聚氨酯涂料,其制备过程具体包括如下步骤:
1、在110℃下,将15质量份环氧树脂EP44与35质量份聚碳酸酯二元醇(Mn=1000)在容器内真空除水1小时;将体系温度降低至80℃,加入18质量份六亚甲基二异氰酸酯与5质量份二羟甲基丁酸反应2小时,随后加入6质量份1,6己二醇继续反应1小时,最后将温度降低至60℃,加入6质量份丙烯酸羟乙酯进行封端1.5小时,降温至50℃加入3质量份三乙胺进行中和半小时,加入60质量份去离子水在1000转/min的搅拌下高速乳化半小时,得到水性可交联耐碱型聚氨酯乳液;
2、取55质量份步骤1制备的水性可交联耐碱型聚氨酯乳液加入反应器中,加入25质量份甲基丙烯酸甲酯和丙烯酸丁酯的混合物,其比例为1:1,随后加入0.01质量份偶氮二异丁腈,加入适量去离子水将固含量控制为40%,超声搅拌分散半小时;随后升温至70℃引发聚合4小时,制备出水性聚氨酯乳液,继续加入0.01质量份有机硅树脂,0.01质量份异辛醇,得到耐高温碱液水性聚氨酯涂料。
将本实施例制备的耐高温碱液水性聚氨酯涂料作为纸张涂层以提高涂布后纸张的性能,具体包括如下步骤:
将本实施例制备的耐高温碱液水性聚氨酯涂料均匀涂布于包装纸表面,施胶量为10g/m3,涂布后立即置于110℃下干燥固化7秒,即可得到耐高温氢氧化钠溶液聚合物涂层。
通过使用本实施例制备得到
的水性聚氨酯涂料对纸张涂布热烘后,纸张的相关性能见下表:
Claims (5)
1.一种用于纸张表面的耐高温碱液水性聚氨酯涂料,其特征在于:是首先在聚氨酯中引入环氧树脂与双键,实现与丙烯酸酯类单体的共聚合,通过基体树脂在水中的自乳化制备出水性高温耐碱型聚氨酯乳液,加入助剂后获得的耐高温碱液水性聚氨酯涂料;包括如下步骤:
步骤1:将双酚A型环氧树脂、聚碳酸酯二元醇、异氰酸酯混合,在70-85℃下聚合3-4小时,随后分别加入亲水扩链剂、小分子扩链剂进行扩链并引入亲水基团,继续反应4-5小时,再加入羟基不饱和单体进行封端1-2小时,最后加入成盐剂和去离子水进行中和乳化,得到水性可交联耐碱型聚氨酯乳液;
步骤2:将步骤1制备的水性可交联耐碱型聚氨酯乳液加入反应器中,然后加入丙烯酸酯类单体与油溶性引发剂,添加适量去离子水将固含量控制为40%,均匀分散半小时;随后升温至70-80℃引发聚合反应2-4小时,制备获得水性高温耐碱型聚氨酯乳液;随后加入流平剂和消泡剂,充分搅拌混合均匀,得到耐高温碱液水性聚氨酯涂料;
步骤1中,各原料的配比按质量份数构成如下:
步骤2中,各原料的配比按质量份数构成如下:
所述耐高温碱液水性聚氨酯涂料作为纸张涂层提高涂布后纸张的耐碱性、横向耐折度、纵向耐折度、光泽度和铅笔硬度,包括如下步骤:
将本发明耐高温碱液水性聚氨酯涂料均匀涂布于纸张表面,施胶量为10g/m3,涂布后立即置于110℃下干燥固化7秒,即可得到耐高温氢氧化钠溶液聚合物涂层。
2.根据权利要求1所述的耐高温碱液水性聚氨酯涂料,其特征在于:
步骤1中,所述双酚A型环氧树脂为环氧值在0.1-0.56之间的环氧树脂中的一种。
3.根据权利要求1所述的耐高温碱液水性聚氨酯涂料,其特征在于:
步骤1中,所述聚碳酸酯二元醇包括数均分子量为1000、2000、4000的聚碳酸酯二元醇中的一种或几种。
4.根据权利要求1所述的耐高温碱液水性聚氨酯涂料,其特征在于:
步骤1中,所述异氰酸酯为脂肪族二异氰酸酯中的一种或几种。
5.根据权利要求1所述的耐高温碱液水性聚氨酯涂料,其特征在于:
步骤2中,所述丙烯酸酯类单体为甲基丙烯酸甲酯和丙烯酸丁酯的混合物,质量比为1-2.5:1。
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