CN112250825A - 一种有机氟改性水性聚氨酯乳液及其制备方法 - Google Patents
一种有机氟改性水性聚氨酯乳液及其制备方法 Download PDFInfo
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Abstract
本发明属于复合乳液技术领域,具体是涉及到一种有机氟改性水性聚氨酯乳液及其制备方法,包括如下组分原料,聚四氢呋喃醚二醇、1,4丁二醇、异佛尔酮二异氰酸酯、二羟甲基丙酸、全氟聚醚油、丙烯酸丁酯、二月桂酸二丁基锡、N,N‑二羟甲基乙酰胺、丙酮、三乙胺和去离子水,上述组分原料的重量份比例为(5‑15):(2‑4):(5‑10):(1‑3):(1‑3):(0.4‑1):(0.1‑0.5):(1‑4):(2‑5):(10‑15):(15‑25),本发明具有较好的拉伸强度。
Description
技术领域
本发明属于复合乳液技术领域,具体是涉及到一种有机氟改性水性聚氨酯乳液及其制备方法。
背景技术
随着科学技术的进步以及人们环保意识的增强,水性聚氨酯的应用已从涂饰剂逐步扩展到涂料、胶粘剂等领域,其优良的耐水性、耐候性、耐燃性以及耐化学腐蚀等等优点,使其成为水性树脂研究中的重点课题。然而水性聚氨酯在应用中也伴随着例如物理性能差等缺点,以往的生产中通过提高体系异氰酸酯基与羟基(R值)的比例,以增大水性聚氨酯中硬段比重的方法提高胶膜的物理性能,但同时也降低了乳液稳定性,对乳液的储存及运输造成极大不便。
CN106750126A公开了一种无助溶剂水性聚氨酯的制备方法,通过将亲水扩链剂溶于脂肪族脂肪族二元醇,并通过乙二胺进行水相扩链的方法避免了有机溶剂的使用,但所得乳液制成的胶膜拉伸强度最大为32.77MPa,不能适应某些具有高物理性能要求的作业环境。
发明内容
本发明要解决的技术问题是提供一种有机氟改性水性聚氨酯乳液及其制备方法,其具有较好的拉伸强度。
本发明的内容为一种有机氟改性水性聚氨酯乳液,包括如下组分原料,聚四氢呋喃醚二醇、1,4丁二醇、异佛尔酮二异氰酸酯、二羟甲基丙酸、全氟聚醚油、丙烯酸丁酯、二月桂酸二丁基锡、N,N-二羟甲基乙酰胺、丙酮、三乙胺和去离子水,上述组分原料的重量份比例为(5-15):(2-4):(5-10):(1-3):(1-3):(0.4-1):(0.1-0.5):(1-4):(2-5):(10-15):(15-25)。
优选的,有机氟改性水性聚氨酯乳液包括如下组分原料,聚四氢呋喃醚二醇、1,4丁二醇、异佛尔酮二异氰酸酯、二羟甲基丙酸、全氟聚醚油、丙烯酸丁酯、二月桂酸二丁基锡、N,N-二羟甲基乙酰胺、丙酮、三乙胺和去离子水,上述组分原料的重量份比例为10:3:8:1.1:2:0.6:0.3:2.5:4:11:20。
本发明提供一种有机氟改性水性聚氨酯乳液的制备方法,步骤为,将干燥后的聚四氢呋喃醚二醇和异佛尔酮二异氰酸酯混合,加入干燥后的1,4丁二醇、二羟甲基丙酸、全氟聚醚油、丙烯酸丁酯、二月桂酸二丁基锡和N,N-二羟甲基乙酰胺,在45-55℃条件反应一段时间后,降温至35-40℃,加入丙酮后反应一段时间,得到-NCO端基预聚物,然后加入三乙胺和去离子水,搅拌,得到有机氟改性水性聚氨酯乳液。
聚四氢呋喃醚二醇和1,4丁二醇的干燥方法为,将聚四氢呋喃醚二醇和1,4丁二醇放入50-55℃的真空烘箱中干燥除水。
所述反应在氮气保护下进行。在45-55℃条件反应70-90min。加入丙酮后反应20-30min。搅拌的转速为1100-1200rad/min,搅拌时间为30min。
本发明的有益效果为,本发明制备得到的有机氟改性水性聚氨酯乳液的拉伸强度较好,在55-60℃时拉伸强度为52.16MPa,较普通的水性聚氨酯乳液形成的胶膜更好。
具体实施方式
实施例1
将PTMG(聚四氢呋喃醚二醇)和l,4-BDO(1,4丁二醇)放入恒温为50-55℃的真空烘箱中干燥除水1h,然后将干燥后的PTMG和IPDI(异佛尔酮二异氰酸酯)加入到具有搅拌、冷凝和充满氮气的反应釜中;再加入1,4-BDO(1,4-丁二醇)、亲水扩链剂DMPA(二羟甲基丙酸)、改性剂E1O-H(全氟聚醚油)、BA(丙烯酸丁酯)和,再添加0.02ml引发剂DBTDL(二月桂酸二丁基锡)以及有机溶剂DMAC(N,N-二羟甲基乙酰胺)。45-55℃反应70-90Min后,迅速降低温度至35-40℃,同时加入丙酮后反应20-30min,得到了-NCO端基预聚物,之后加入三乙胺(TEA),再加入一定量的去离子水,转速调至1100-1200rad/min,高速搅拌30min,将聚氨酯预聚体均匀的分散到水中,最终得到的有机氟改性水性聚氨酯乳液。
配方(单位kg):PTMG:l,4-BDO:IPDI:DMPA:E1O-H:BA:DBTDL:DMAC:丙酮:TEA:去离子水=10:3:8:1.1:2:0.6:0.3:2.5:4:11:20。
对比例1
对比例1和实施例1的区别在于,不加入改性剂E1O-H(全氟聚醚油),其他和实施例1相同。
试验例1
(l)PUA胶膜的制备:称取40g的乳液倒入聚四氟乙烯模具中,在室温下自然干燥48h后,置于烘箱中于50℃的条件下干燥4h,于80℃的条件下干燥4h。制备厚度约l mm的PUA胶膜。
(2)胶膜的拉伸强度和断裂伸长率的测试:根据GBT 1040.3对样品进行测试。每个样品重复测试三次,取平均值。
物质 | 拉伸强度 |
实施例1 | 25MPA |
对比例1 | 10MPA |
通过上述测试数据,可以发现,本发明的拉伸强度明显高于对比例1。
Claims (8)
1.一种有机氟改性水性聚氨酯乳液,其特征是,包括如下组分原料,聚四氢呋喃醚二醇、1,4丁二醇、异佛尔酮二异氰酸酯、二羟甲基丙酸、全氟聚醚油、丙烯酸丁酯、二月桂酸二丁基锡、N,N-二羟甲基乙酰胺、丙酮、三乙胺和去离子水,上述组分原料的重量份比例为(5-15):(2-4):(5-10):(1-3):(1-3):(0.4-1):(0.1-0.5):(1-4):(2-5):(10-15):(15-25)。
2.如权利要求1所述的有机氟改性水性聚氨酯乳液,其特征是,包括如下组分原料,聚四氢呋喃醚二醇、1,4丁二醇、异佛尔酮二异氰酸酯、二羟甲基丙酸、全氟聚醚油、丙烯酸丁酯、二月桂酸二丁基锡、N,N-二羟甲基乙酰胺、丙酮、三乙胺和去离子水,上述组分原料的重量份比例为10:3:8:1.1:2:0.6:0.3:2.5:4:11:20。
3.一种如权利要求1或2所述的有机氟改性水性聚氨酯乳液的制备方法,其特征是,将干燥后的聚四氢呋喃醚二醇和异佛尔酮二异氰酸酯混合,加入干燥后的1,4丁二醇、二羟甲基丙酸、全氟聚醚油、丙烯酸丁酯、二月桂酸二丁基锡和N,N-二羟甲基乙酰胺,在45-55℃条件反应一段时间后,降温至35-40℃,加入丙酮后反应一段时间,得到-NCO端基预聚物,然后加入三乙胺和去离子水,搅拌,得到有机氟改性水性聚氨酯乳液。
4.如权利要求3所述的有机氟改性水性聚氨酯乳液的制备方法,其特征是,聚四氢呋喃醚二醇和1,4丁二醇的干燥方法为,将聚四氢呋喃醚二醇和1,4丁二醇放入50-55℃的真空烘箱中干燥除水。
5.如权利要求3或4所述的有机氟改性水性聚氨酯乳液的制备方法,其特征是,所述反应在氮气保护下进行。
6.如权利要求3或4所述的有机氟改性水性聚氨酯乳液的制备方法,其特征是,在45-55℃条件反应70-90min。
7.如权利要求3或4所述的有机氟改性水性聚氨酯乳液的制备方法,其特征是,加入丙酮后反应20-30min。
8.如权利要求3或4所述的有机氟改性水性聚氨酯乳液的制备方法,其特征是,搅拌的转速为1100-1200rad/min,搅拌时间为30min。
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