CN112500548A - 一种水性聚氨酯-聚脲及其制备方法 - Google Patents

一种水性聚氨酯-聚脲及其制备方法 Download PDF

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CN112500548A
CN112500548A CN202011460196.4A CN202011460196A CN112500548A CN 112500548 A CN112500548 A CN 112500548A CN 202011460196 A CN202011460196 A CN 202011460196A CN 112500548 A CN112500548 A CN 112500548A
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徐涛
鲁晓东
熊东路
龙绪俭
肖增钧
李斌仁
陈林生
许超平
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Shenzhen Feiyang Xingye Technology Co ltd
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Abstract

本发明公开了一种水性聚氨酯‑聚脲，其原料按重量的配方如下：多元异氰酸酯20‑60份、多元醇低聚物20‑60份、多元醇小分子0.1‑10份、亲水单体3‑10份、天门冬氨酸酯小分子10‑30份、环氧树脂0.5‑10份、催化剂0.05‑0.5份、溶剂5‑35份、中和剂1.5‑9份、二元胺2‑35份、水80‑300份。本发明还提供了水性聚氨酯‑聚脲的制备方法。本发明提供了一种水性聚氨酯‑聚脲，合成配方中的天门冬氨酸酯与异氰酸酯反应生成的脲基极性大，在分子间易形成稳定的氢键，另外，环氧树脂的加入，支链上的环氧基团可与二元胺反应，提高交联度，二者的协同作用下，涂膜的综合性能有所提高；涂膜具有较好的耐冲击性、较高的拉伸强度及断裂伸长率以及较好的耐水性。

Description

一种水性聚氨酯-聚脲及其制备方法
技术领域
本发明涉及聚氨酯-聚脲制备技术领域，尤其涉及一种水性聚氨酯-聚脲及其制备方法。
背景技术
聚氨酯材料性能优异，如耐磨性强、抗撕裂性强、柔韧性好等，被广泛用于涂料、油墨、胶粘剂等领域，生产聚氨酯材料的主要原材料为聚醚多元醇/聚酯多元醇和多元异氰酸酯，相当于硬段和软段组成的嵌段聚合物，因此具有性能可调性，这也是其突出优势。
为满足绿色化学发展，以水为分散介质的聚氨酯成为开发热点，相比于溶剂型聚氨酯，水性聚氨酯运输更安全、经济，使用更环保，但亲水单体的引入，往往会降低耐水性和力学性能。为了改善综合性能，可通过化学法对水性聚氨酯进行杂化，聚脲材料强度比普通聚氨酯高，环氧树脂具有较高的机械强度，可通过-NH/-OH与异氰酸酯反应用这两种材料改性水性聚氨酯。
发明内容
本发明提出了一种水性聚氨酯-聚脲及其制备方法，以解决上述背景技术中提出的问题。
本发明提出了一种水性聚氨酯-聚脲，其原料按重量的配方如下：多元异氰酸酯20-60份、多元醇低聚物20-60份、多元醇小分子3-10份、亲水单体3-10份、天门冬氨酸酯小分子10-30份、环氧树脂3-10份、催化剂3-10份、溶剂5-35份、中和剂2-12份、二元胺5-30份、水100-300份。
优选的，所述多元异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、环己烷二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或多种组合。
优选的，所述多元醇低聚物选自聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯二醇、聚己内酯三元醇、聚碳酸酯二醇、聚己二酸乙二醇酯二醇、聚己二酸-1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇中的一种或多种组合；所述多元醇低聚物分子量为500～4000。
优选的，所述多元醇小分子选自1，4-丁二醇、1，6-己二醇、1，2-丙二醇、乙二醇、二甘醇、三羟甲基丙烷、蓖麻油、1,4-环己烷二甲醇中的一种或多种组合。
优选的，所述二元胺选自乙二胺、己二胺、聚醚胺D230、聚醚胺D400中的一种或多种组合。
优选的，所述环氧树脂选自E54、E51、E44、E42、E35、E31、E20、E14、E12、E10、E06、E03中的一种或多种组合。
优选的，所述催化剂选自二月桂酸二丁基锡、辛基亚锡中的一种。
优选的，所述溶剂选自N-甲基吡咯烷酮、二甲基甲酰胺中的一种；所述亲水单体选自二羟甲基丙酸、二羟甲基丁酸中的一种；所述中和剂选自氢氧化钠、氢氧化钾、三乙胺、二甲基乙醇胺、二乙醇胺中的一种。
优选的，所述天门冬氨酸酯小分子选自以下结构式中的一种：
Figure BDA0002831249510000031
其中，R2为碳原子数1～20的支链或直链烷基。
本发明还提供了一种水性聚氨酯-聚脲的制备方法，包括如下步骤：
(1)、称取多元醇低聚物、多元醇小分子、亲水单体于反应瓶中，在90～110℃，-0.1～-0.08MPa条件下除水2h；
(2)、惰性气体保护下，往步骤(1)反应瓶中加入溶剂，控温60℃，滴加多元异氰酸酯，1h左右滴完，加入催化剂，继续升温至80℃反应至-NCO值达到理论值；
(3)、惰性气体保护下，待步骤(2)反应物料降温至50～60℃，滴加天门冬氨酸酯小分子，1h内滴完，保温反应0.5h，继续滴加环氧树脂，保温反应至-NCO值达到理论值，降温至40℃，加入中和剂中和30min，再加入二元胺、冰水高速分散30min，即得水性聚氨酯-聚脲。
与现有技术相比，本发明的有益效果在于：本发明提供了一种水性聚氨酯-聚脲，合成配方中的天门冬氨酸酯与异氰酸酯反应生成的脲基极性大，在分子间易形成稳定的氢键，另外，环氧树脂的加入，支链上的环氧基团可与二元胺反应，提高交联度，二者的协同作用下，涂膜的综合性能有所提高；涂膜具有较好的耐冲击性、较高的拉伸强度及断裂伸长率以及较好的耐水性。
具体实施方式
下面结合具体实施例来对本发明做进一步说明。
实施例1
本发明提供了一种水性聚氨酯-聚脲的制备方法，包括如下步骤：
称取66g PPG2000、8.3g 1，4-丁二醇、10.1g二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入59.9gN-甲基吡咯烷酮，控温60℃，滴加101.3g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为8.7～8.9％；
惰性气体保护下，待上述反应物料降温至50～60℃，滴加49.4gF420，1h内滴完，保温反应0.5h，继续滴加4.7g环氧树脂E44，保温反应至-NCO值为4.5～4.7％，降温至40℃，加入7.6g三乙胺中和30min，再加入9.8g乙二胺、449.4g冰水高速分散30min，即得水性聚氨酯-聚脲。
实施例2
本发明提供了一种水性聚氨酯-聚脲的制备方法，包括如下步骤：
称取66g PPG2000、8.3g 1，4-丁二醇、10.1g二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入61.1g N-甲基吡咯烷酮，控温60℃，滴加101.3g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为8.7～8.9％；
惰性气体保护下，待上述反应物料降温至50～60℃，滴加49.4gF420，1h内滴完，保温反应0.5h，继续滴加9.4g环氧树脂E44，保温反应至-NCO值为4.4～4.6％，降温至40℃，加入7.6g三乙胺中和30min，再加入9.8g乙二胺、458g冰水高速分散30min，即得水性聚氨酯-聚脲。
实施例3
本发明提供了一种水性聚氨酯-聚脲的制备方法，包括如下步骤：
称取98.8g聚己内酯二醇(M＝2000)、8.4g 1，4-环己烷二甲醇、11.3g二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入68.6gN-甲基吡咯烷酮，控温60℃，滴加96.8g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO为7.1～7.3％；
惰性气体保护下，待上述反应物料降温至50～60℃，滴加53.8gF420，1h内滴完，保温反应0.5h，继续滴加5.4g环氧树脂E44，保温反应至-NCO值为3.4～3.6％，降温至40℃，加入8.5g三乙胺中和30min，再加入8.5g乙二胺、514.5g冰水高速分散30min，即得水性聚氨酯-聚脲。
实施例4
本发明提供了一种水性聚氨酯-聚脲的制备方法，包括如下步骤：
称取98.8g聚己内酯二醇(M＝2000)、8.4g 1，4-环己烷二甲醇、11.3g二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入70gN-甲基吡咯烷酮，控温60℃，滴加96.8g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为7.1～7.3％；
惰性气体保护下，待上述反应物料降温至50～60℃，滴加53.8gF420，1h内滴完，保温反应0.5h，继续滴加5.4g环氧树脂E44和5.4g环氧树脂E51混合物，保温反应至-NCO值为3.3～3.5％，降温至40℃，加入8.5g三乙胺中和30min，再加入8.5g乙二胺、525g冰水高速分散30min，即得水性聚氨酯-聚脲。
实施例5
本发明提供了一种水性聚氨酯-聚脲的制备方法，包括如下步骤：称取33.3gPPG1000、2.2g 1，4-丁二醇、4.6g二羟甲基丙酸、0.55g三羟甲基丙烷于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入28g N-甲基吡咯烷酮，控温60℃，滴加47.3g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为9.1～9.3％；
惰性气体保护下，待上述反应物料降温至50～60℃，滴加22gF420，1h内滴完，保温反应0.5h，继续滴加2.2g环氧树脂E44，保温反应至-NCO值为5.1～5.3％，降温至40℃，加入3.5g三乙胺中和30min，再加入5.2g乙二胺、210.4g冰水高速分散30min，即得水性聚氨酯-聚脲。
实施例6
本发明提供了一种水性聚氨酯-聚脲的制备方法，包括如下步骤：称取33.3gPPG1000、2.2g 1，4-丁二醇、4.6g二羟甲基丙酸、0.55g三羟甲基丙烷于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入28.6gN-甲基吡咯烷酮，控温60℃，滴加47.3g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为9.1～9.3％；
惰性气体保护下，待上述反应物料降温至50～60℃，滴加22gF420，1h内滴完，保温反应0.5h，继续滴加4.4g环氧树脂E44，保温反应至-NCO值为4.9～5.1％，降温至40℃，加入3.5g三乙胺中和30min，再加入5.1g乙二胺、214.5g冰水高速分散30min，即得水性聚氨酯-聚脲。
对比例1
称取117.4g PPG2000、7g 1，4-丁二醇、8.6g二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入50gN-甲基吡咯烷酮，控温60℃，滴加66.7g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为3.2～3.4％，降温至40℃，加入6.4g三乙胺中和30min，再加入5.9g乙二胺、375g冰水高速分散30min，即得水性聚氨酯。
对比例2
称取66g PPG2000、8.3g 1，4-丁二醇、10.1g二羟甲基丙酸于反应瓶中，在110℃，-0.095MPa条件下除水2h；
惰性气体保护下，往上述反应瓶中加入58.7gN-甲基吡咯烷酮，控温60℃，滴加101.3g异佛尔酮二异氰酸酯，1h左右滴完，加入1‰二月桂酸二丁基锡，继续升温至80℃反应至-NCO值为8.7～8.9％；
惰性气体保护下，待上述反应物料降温至50～60℃，滴加49.4gF420，1h内滴完，保温反应至-NCO值为4.7～4.9％，降温至40℃，加入7.6g三乙胺中和30min，再加入10.1g乙二胺、440.5g冰水高速分散30min，即得水性聚氨酯-聚脲。
称取一定量上述实施例和对比例中的水性树脂，分别涂敷在马口铁上，放置室温下干燥48h，然后置于60℃烘箱中干燥24h。
将干燥后的涂膜进行性能表征：
涂膜的耐冲击性能根据GB/T 1732-93测试；涂膜的硬度根据GB/T6739-1996测试；涂膜的拉伸性能(断裂伸长率和拉伸强度)根据国家标准GB/T 1040.1-2006测试；吸水率根据GB/T 1733-93，将干燥后的涂膜(称重为M0)，侵入去离子水中48h后取出，用滤纸吸干表面的水后，称重为M1，吸水率＝(M1-M0)/M0×100％。
实施例和对比例中树脂的涂膜性能数据见表1。
表1
Figure BDA0002831249510000081
Figure BDA0002831249510000091
从表1的数据中可知本发明提供的水性聚氨酯-聚脲，其涂膜具有较好的耐冲击性、较高的拉伸强度和断裂伸长率以及较好的耐水性等，天门冬氨酸酯和环氧树脂的引入，改善了涂膜的综合性能，具有可观的应用价值。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (10)

1.一种水性聚氨酯-聚脲，其特征在于，其原料按重量的配方如下：多元异氰酸酯20-60份、多元醇低聚物20-60份、多元醇小分子0.1-10份、亲水单体3-10份、天门冬氨酸酯小分子10-30份、环氧树脂0.5-10份、催化剂0.05-0.5份、溶剂5-35份、中和剂1.5-9份、二元胺2-35份、水80-300份。
2.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述多元异氰酸酯选自甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、苯二亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、环己烷二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯中的一种或多种组合。
3.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述多元醇低聚物选自聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯二醇、聚己内酯三元醇、聚碳酸酯二醇、聚己二酸乙二醇酯二醇、聚己二酸-1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇中的一种或多种组合；所述多元醇低聚物分子量为500～4000。
4.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述多元醇小分子选自1，4-丁二醇、1，6-己二醇、1，2-丙二醇、乙二醇、二甘醇、三羟甲基丙烷、蓖麻油、1,4-环己烷二甲醇中的一种或多种组合。
5.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述二元胺选自乙二胺、己二胺、聚醚胺D230、聚醚胺D400中的一种或多种组合。
6.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述环氧树脂选自E54、E51、E44、E42、E35、E31、E20、E14、E12、E10、E06、E03中的一种或多种组合。
7.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述催化剂选自二月桂酸二丁基锡、辛基亚锡中的一种。
8.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述溶剂选自N-甲基吡咯烷酮、二甲基甲酰胺中的一种；所述亲水单体选自二羟甲基丙酸、二羟甲基丁酸中的一种；所述中和剂选自氢氧化钠、氢氧化钾、三乙胺、二甲基乙醇胺、二乙醇胺中的一种。
9.根据权利要求1所述的水性聚氨酯-聚脲，其特征在于，所述天门冬氨酸酯小分子选自以下结构式中的一种：
Figure FDA0002831249500000021
其中，R2为碳原子数1～20的支链或直链烷基。
10.一种根据权利要求1所述的水性聚氨酯-聚脲的制备方法，其特征在于，包括如下步骤：
(1)、称取多元醇低聚物、多元醇小分子、亲水单体于反应瓶中，在90～110℃，-0.1～-0.08MPa条件下除水2h；
(2)、惰性气体保护下，往步骤(1)反应瓶中加入溶剂，控温60℃，滴加多元异氰酸酯，1h左右滴完，加入催化剂，继续升温至80℃反应至-NCO值达到理论值；
(3)、惰性气体保护下，待步骤(2)反应物料降温至50～60℃，滴加天门冬氨酸酯小分子，1h内滴完，保温反应0.5h，继续滴加环氧树脂，保温反应至-NCO值达到理论值，降温至40℃，加入中和剂中和30min，再加入二元胺、冰水高速分散30min，即得水性聚氨酯-聚脲。
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