CN115058182A - 一种释放负氧离子的阻燃聚氨酯涂料及其合成工艺 - Google Patents
一种释放负氧离子的阻燃聚氨酯涂料及其合成工艺 Download PDFInfo
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Abstract
本发明涉及建筑材料技术领域，且公开了一种释放负氧离子的阻燃聚氨酯涂料，合成的二磷酸三苯酯基二羟乙基苯甲酰胺，含有二磷酸苯酯阻燃结构和双羧基亲水基团，作为聚氨酯羧酸型亲水扩链剂，聚合得到聚氨酯有着很好的亲水性和水溶性，同时将二磷酸苯酯阻燃结构引入到聚氨酯分子主链中，赋予了聚氨酯涂料涂层持续高效的阻燃效果，并添加了负氧离子粉添加剂，在水性聚氨酯涂料中有着很好的分散性，可以有效释放出负氧离子，可以起到改善环境和人体健康的作用。
Description
技术领域
本发明涉及建筑材料技术领域，具体为一种释放负氧离子的阻燃聚氨酯涂料及其合成工艺。
背景技术
空气负氧离子在城市空气净化方面有良好调节作用，负氧离子浓度可以用于评价城市空气质量，负氧离子粉通常由稀土元素、电气石粉等物质组成，可以能产生空气负离子，广泛应用在涂料、板材、家具建材等方面，如申请号CN202111373721.3的专利公开了将负氧离子粉加入到聚丙烯酸酯类树脂、聚氨酯树脂等成膜树脂中，得到高负氧离子释放能力的材料。
水性聚氨酯具有亲水性和水溶性好、绿色环保、力学性能好、弹性优良等优点，在水性涂料、粘合剂等方面有着重要的应用，申请号申请号：202110085762.6的专利公开了含有2个或4个羧酸基团的羧酸型扩链剂，有利于聚氨酯在水中具有良好的分散性并增加聚氨酯薄膜的耐水性，水性聚氨酯涂料涂层存在阻燃性较差的问题，目前合成含磷多元醇单体参与到聚氨酯聚合反应中，是提高聚氨酯材料阻燃性的有效方法。
发明内容
（一）解决的技术问题
针对现有技术的不足，本发明提供了一种释放负氧离子的阻燃聚氨酯水性涂料及合成工艺。
（二）技术方案
为实现上述目的，本发明提供以下技术方案：一种释放负氧离子的阻燃聚氨酯涂料，合成工艺为以下步骤：
（1）将3,5-二烯丙氧基苯甲酸加入到氯化亚砜中加热回流，反应得到3,5-二烯丙氧基苯甲酰氯；然后与二乙醇胺和三乙胺按照摩尔比为1:1-1.4:1.2-1.8的比例溶解到二氯甲烷中，在15-35 ℃中搅拌反应3-8 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:5-20，分离得到二烯丙氧基二羟乙基苯甲酰胺。
（2）将二烯丙氧基二羟乙基苯甲酰胺、半胱氨酸、2,2-二甲氧基-2-苯基苯乙酮溶解到N,N-二甲基甲酰胺中进行反应，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:3-10，分离得到二半胱氨酸基二羟乙基苯甲酰胺。
（3）将二半胱氨酸基二羟乙基苯甲酰胺和4-甲酰苯基磷酸二苯酯溶解到乙醇溶剂中，在70-90 ℃中回流6-18 h，反应后减压蒸馏，丙酮洗涤产物，得到二磷酸三苯酯基二羟乙基苯甲酰胺。
（4）将聚酯多元醇、异佛尔酮二异氰酸酯、二磷酸三苯酯基二羟乙基苯甲酰胺和二月桂酸二丁基锡在氮气中升温至70-80 ℃中反应3-4 h，然后在50-60 ℃中加入去离子水并高速乳化，加入用量为2-6%的负氧离子粉，分散均匀得到释放负氧离子的阻燃聚氨酯涂料。
优选的，所述（2）中二烯丙氧基二羟乙基苯甲酰胺、半胱氨酸、2,2-二甲氧基-2-苯基苯乙酮的摩尔比为1:2.8-3.5:0.04-0.07。
优选的，所述（2）中反应通过紫外光辐照进行4-10 h。
优选的，所述（3）中二半胱氨酸基二羟乙基苯甲酰胺和4-甲酰苯基磷酸二苯酯的摩尔比为1:2.2-3。
优选的，所述（4）中聚酯多元醇、异佛尔酮二异氰酸酯、二磷酸三苯酯基二羟乙基苯甲酰胺和二月桂酸二丁基锡的质量比为1:0.45-0.52:0.02-0.08:0.03-0.045。
（三）有益的技术效果
与现有技术相比，本发明具备以下有益技术效果：
该一种释放负氧离子的阻燃聚氨酯涂料，利用3,5-二烯丙氧基苯甲酰氯、和二乙醇胺发生酰胺化反应，然后在与半胱氨酸发生加成反应，最后再与4-甲酰苯基磷酸二苯酯发生席夫碱反应，合成了一种新型的二磷酸三苯酯基二羟乙基苯甲酰胺，含有二磷酸苯酯阻燃结构和双羧基亲水基团，可以作为聚氨酯羧酸型亲水扩链剂，聚合得到聚氨酯有着很好的亲水性和水溶性，同时将二磷酸苯酯阻燃结构引入到聚氨酯分子主链中，赋予了聚氨酯涂料涂层持续高效的阻燃效果，并添加的负氧离子粉在水性聚氨酯涂料中有着很好的分散性，可以更加有效释放出负氧离子，可以起到改善环境和人体健康的作用。
附图说明
图1是制备二磷酸三苯酯基二羟乙基苯甲酰胺的反应图。
图2是二磷酸三苯酯基二羟乙基苯甲酰胺的红外谱图。
具体实施方式
实施例1
（1）将3,5-二烯丙氧基苯甲酸加入到氯化亚砜中加热回流，反应得到3,5-二烯丙氧基苯甲酰氯；然后将0.5 g的3,5-二烯丙氧基苯甲酰氯、0.26 g的二乙醇胺和0.24 g三乙胺溶解到二氯甲烷中，在35 ℃中搅拌反应5 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:20，分离得到二烯丙氧基二羟乙基苯甲酰胺。
（2）将1 g的二烯丙氧基二羟乙基苯甲酰胺、1.1 g的半胱氨酸、0.045 g的2,2-二甲氧基-2-苯基苯乙酮溶解到N,N-二甲基甲酰胺中，通过紫外光辐照反应4 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:10，分离得到二半胱氨酸基二羟乙基苯甲酰胺。
（3）将0.5 g的二半胱氨酸基二羟乙基苯甲酰胺和0.98 g的4-甲酰苯基磷酸二苯酯溶解到乙醇溶剂中，在70 ℃中回流12 h，反应后减压蒸馏，丙酮洗涤产物，得到二磷酸三苯酯基二羟乙基苯甲酰胺。
（4）将20 g的聚酯多元醇、9.6的异佛尔酮二异氰酸酯、0.4的二磷酸三苯酯基二羟乙基苯甲酰胺和0.9 g的二月桂酸二丁基锡在氮气中升温至75 ℃中反应3 h，然后在50 ℃中加入去离子水并高速乳化，加入0.7 g的负氧离子粉，分散均匀得到释放负氧离子的阻燃聚氨酯涂料PU1。
实施例2
（1）将0.5 g的3,5-二烯丙氧基苯甲酰氯、0.29 g的二乙醇胺和0.28 g三乙胺溶解到二氯甲烷中，在25 ℃中搅拌反应8 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:5，分离得到二烯丙氧基二羟乙基苯甲酰胺。
（2）将1 g的二烯丙氧基二羟乙基苯甲酰胺、1.15 g的半胱氨酸、0.036 g的2,2-二甲氧基-2-苯基苯乙酮溶解到N,N-二甲基甲酰胺中，通过紫外光辐照反应10 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:10，分离得到二半胱氨酸基二羟乙基苯甲酰胺。
（3）将0.5 g的二半胱氨酸基二羟乙基苯甲酰胺和0.92 g的4-甲酰苯基磷酸二苯酯溶解到乙醇溶剂中，在70 ℃中回流12 h，反应后减压蒸馏，丙酮洗涤产物，得到二磷酸三苯酯基二羟乙基苯甲酰胺。
（4）将20 g的聚酯多元醇、10.4的异佛尔酮二异氰酸酯、1.2的二磷酸三苯酯基二羟乙基苯甲酰胺和0.7 g的二月桂酸二丁基锡在氮气中升温至80 ℃中反应3 h，然后在55℃中加入去离子水并高速乳化，加入1 g的负氧离子粉，分散均匀得到释放负氧离子的阻燃聚氨酯涂料PU2。
实施例3
（1）将0.5 g的3,5-二烯丙氧基苯甲酰氯、0.21 g的二乙醇胺和0.27 g三乙胺溶解到二氯甲烷中，在25 ℃中搅拌反应3 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:10，分离得到二烯丙氧基二羟乙基苯甲酰胺。
（2）将1 g的二烯丙氧基二羟乙基苯甲酰胺、1.3 g的半胱氨酸、0.055 g的2,2-二甲氧基-2-苯基苯乙酮溶解到N,N-二甲基甲酰胺中，通过紫外光辐照反应4 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:3，分离得到二半胱氨酸基二羟乙基苯甲酰胺。
（3）将0.5 g的二半胱氨酸基二羟乙基苯甲酰胺和0.92 g的4-甲酰苯基磷酸二苯酯溶解到乙醇溶剂中，在80 ℃中回流12 h，反应后减压蒸馏，丙酮洗涤产物，得到二磷酸三苯酯基二羟乙基苯甲酰胺。
（4）将20 g的聚酯多元醇、9.8的异佛尔酮二异氰酸酯、1.2的二磷酸三苯酯基二羟乙基苯甲酰胺和0.75 g的二月桂酸二丁基锡在氮气中升温至80 ℃中反应4 h，然后在60℃中加入去离子水并高速乳化，加入1.5 g的负氧离子粉，分散均匀得到释放负氧离子的阻燃聚氨酯涂料PU3。
实施例4
（1）将0.5 g的3,5-二烯丙氧基苯甲酰氯、0.25 g的二乙醇胺和0.32 g三乙胺溶解到二氯甲烷中，在15 ℃中搅拌反应8 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:5，分离得到二烯丙氧基二羟乙基苯甲酰胺。
（2）将1 g的二烯丙氧基二羟乙基苯甲酰胺、1.26 g的半胱氨酸、0.048 g的2,2-二甲氧基-2-苯基苯乙酮溶解到N,N-二甲基甲酰胺中，通过紫外光辐照反应4 h，反应后粗产物通过硅胶柱层析分离纯化，流动相为乙酸乙酯:石油醚=1:5，分离得到二半胱氨酸基二羟乙基苯甲酰胺。
（3）将0.5 g的二半胱氨酸基二羟乙基苯甲酰胺和0.92 g的4-甲酰苯基磷酸二苯酯溶解到乙醇溶剂中，在90 ℃中回流6 h，反应后减压蒸馏，丙酮洗涤产物，得到二磷酸三苯酯基二羟乙基苯甲酰胺。
（4）将20 g的聚酯多元醇、9.3的异佛尔酮二异氰酸酯、1.6的二磷酸三苯酯基二羟乙基苯甲酰胺和0.9 g的二月桂酸二丁基锡在氮气中升温至80 ℃中反应3 h，然后在50 ℃中加入去离子水并高速乳化，加入1.9 g的负氧离子粉，分散均匀得到释放负氧离子的阻燃聚氨酯涂料PU4。
拉伸性能测试：将阻燃聚氨酯涂料热固化成膜，试样拉伸试验机测试拉伸强度，膜式样样品为100 mm×80 mm×5 mm，参照GB/T 1040-2006标准。
阻燃性能测试：使用氧指数试验机测试聚氨酯膜试样的极限氧指数，膜式样样品为50 mm×50 mm×2 mm。
使用锥形量热仪测试聚氨酯膜试样的燃烧性能，膜试样样品为100 mm×50 mm×1mm，参照GB/T 2406-2009标准。
负氧离子释放测试：将负离子检测仪放于聚氨酯膜试样，测试负氧离子浓度，膜试样样品为1 m×1 m×2 mm，参照JC/T 2110-2012标准。
| 试样样品 | 拉伸强度（MPa） | LOI（%） | THR（MJ/m<sup>2</sup>） | 负氧离子释放量（个/cm<sup>3</sup>） |
| PU1 | 46.8 | 28.4 | 42.4 | 86641 |
| PU2 | 49.2 | 29.7 | 40.1 | 11274 |
| PU3 | 42.7 | 31.6 | 37.5 | 15570 |
| PU4 | 39.1 | 31.2 | 37.2 | 17601 |
PU1-4为实施例1-4制备的聚氨酯涂料固化后的膜试样样品。
Claims (5)
1.一种释放负氧离子的阻燃聚氨酯涂料的合成工艺，其特征在于：所述合成工艺步骤为：
（1）将3,5-二烯丙氧基苯甲酸加入到氯化亚砜中加热回流，反应得到3,5-二烯丙氧基苯甲酰氯；然后与二乙醇胺和三乙胺按照摩尔比为1:1-1.4:1.2-1.8的比例溶解到二氯甲烷中，在15-35 ℃中搅拌反应3-8 h，得到二烯丙氧基二羟乙基苯甲酰胺；
（2）将二烯丙氧基二羟乙基苯甲酰胺、半胱氨酸、2,2-二甲氧基-2-苯基苯乙酮溶解到N,N-二甲基甲酰胺中进行反应，得到二半胱氨酸基二羟乙基苯甲酰胺；
（3）将二半胱氨酸基二羟乙基苯甲酰胺和4-甲酰苯基磷酸二苯酯溶解到乙醇溶剂中，在70-90 ℃中回流6-18 h，得到二磷酸三苯酯基二羟乙基苯甲酰胺；
（4）将聚酯多元醇、异佛尔酮二异氰酸酯、二磷酸三苯酯基二羟乙基苯甲酰胺和二月桂酸二丁基锡在氮气中升温至70-80 ℃中反应3-4 h，然后在50-60 ℃中加入去离子水并高速乳化，加入用量为2-6%的负氧离子粉，分散均匀得到释放负氧离子的阻燃聚氨酯涂料。
2.根据权利要求1所述的一种释放负氧离子的阻燃聚氨酯涂料的合成工艺，其特征在于：所述（2）中二烯丙氧基二羟乙基苯甲酰胺、半胱氨酸、2,2-二甲氧基-2-苯基苯乙酮的摩尔比为1:2.8-3.5:0.04-0.07。
3.根据权利要求1所述的一种释放负氧离子的阻燃聚氨酯涂料的合成工艺，其特征在于：所述（2）中反应通过紫外光辐照进行4-10 h。
4.根据权利要求1所述的一种释放负氧离子的阻燃聚氨酯涂料的合成工艺，其特征在于：所述（3）中二半胱氨酸基二羟乙基苯甲酰胺和4-甲酰苯基磷酸二苯酯的摩尔比为1:2.2-3。
5.根据权利要求1所述的一种释放负氧离子的阻燃聚氨酯涂料的合成工艺，其特征在于：所述（4）中聚酯多元醇、异佛尔酮二异氰酸酯、二磷酸三苯酯基二羟乙基苯甲酰胺和二月桂酸二丁基锡的质量比为1:0.45-0.52:0.02-0.08:0.03-0.045。
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