CN111320556A - 一种含炔基非离子表面活性剂及其制备方法 - Google Patents
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Abstract
Description
技术领域
本发明涉及化学合成技术领域,具体涉及一种含炔基非离子表面活性剂及 其制备方法。
背景技术
非离子表面活性剂在水溶液中不电离,其亲水基主要由具有一定数量的含 氧基团(一般为醚基和羟基)构成,因而在溶液中稳定性高,不易受强电解质、 无机盐类的影响,也不易受pH值的影响,与其他类型表面活性剂相容性好, 是驱油剂组合物中的重要成分。随着有非离子表面活性剂的品种不断增加,应 用领域不断扩大,传统非离子表面活性剂已显露出众多局限性,例如非离子表 面活性剂具有良好的润湿性和起泡性能,但将其应用在水性漆中,为了达到理 想的涂装效果必须借助于非离子表面活性剂以降低体系的表面张力,而传统的 表面活性剂通常会产生严重的泡沫,并且泡沫很难消除,泡沫的存在,严重影响了涂膜的外观效果,往往会造成涂膜缩孔、针孔、疵点、鱼眼等弊病,若在 体系中加入消泡剂通常又会影响体系的润湿性能,因此若能开发一种扮演润湿 剂和消泡剂的双重角色的功能型非离子表面活性剂,便可解决上述问题。
发明内容
有鉴于此,本发明提供一种含炔基非离子表面活性剂及其制备方法,以克 服现有表面活性剂所不具备的优异的润湿性和消泡性的双重特性,为水性涂料 等水性体系的发展奠定基础。
为解决现有技术存在的问题,本发明的技术方案是:一种含炔基非离子表 面活性剂,其特征在于:其具体结构式为:
一种含炔基非离子表面活性剂的制备方法,其特征在于:步骤为:
1)在脂肪醇聚氧乙烯醚AEO-9中滴加二异氰酸酯进行异氰酸酯封端反应, 得封端异氰酸酯中间体,所述脂肪醇聚氧乙烯醚AEO-9和二异氰酸酯的摩尔比 为2:1;
2)再向封端异氰酸酯中间体中加入丙炔醇,其中丙炔醇和二异氰酸酯的摩 尔比为2:1,获得端炔基封端异氰酸酯中间体;
3)再向端炔基封端异氰酸酯中间体中加入甲基封端的端羟基聚醚,其中甲 基封端的端羟基聚醚和二异氰酸酯的摩尔比为2:1,反应结束后冷却析出白色 固体,纯化分离出产物,真空干燥至恒重即得含炔基非离子表面活性剂。
所述步骤1)中脂肪醇聚氧乙烯醚AEO-9和二异氰酸酯在50~70℃反应 4~6h;
所述步骤2)中丙炔醇和封端二异氰酸酯在60~90℃反应8~12h;
步骤3)中,甲基封端的端羟基聚醚和端炔基封端二异氰酸酯中间体在 50~80℃反应4~6h。
所述的甲基封端的端羟基聚醚为甲氧基聚乙二醇(mPEG-OH)或者甲氧基 聚乙二醇羧酸(mPEG-COOH)。
所述二异氰酸酯为4,4-二苯基甲烷二异氰酸酯(4,4-HDI),2,2-二苯基甲烷 二异氰酸酯(2,2-HDI),二环己基甲烷二异氰酸酯(HMDI),六亚甲基二异氰 酸酯(HDI)中的任意一种。与现有技术相比,本发明的优点如下:
1)本发明提供了一种结构新颖、耐高温、可降解的炔基非离子表面活性剂, 该表面活性剂具有原料易得成本低,制备过程方便简洁,易于放大生产等优点;
2)本发明制得的表面活性剂中含有乙二醇链段,因此具有良好的溶解性和 润湿性,同时分子结构中含有炔基基团,增大了联结基团烷基的距离,减小了 分子间的吸引力,进而降低了分子间内聚粘附力,因此泡沫的稳定性降低;
3)本发明制得的表面活性剂具有润湿、消泡的双重特性,可解决目前水性 漆技术复配技术中面临的问题。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例, 对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以 解释本发明,并不用于限定本发明。
一种含炔基非离子表面活性剂合成方程式如下:
实施例1
一种含炔基非离子表面活性剂的制备方法为:
将脂肪醇聚氧乙烯醚AEO-9(M=575,115.0g,0.20mol)溶解至溶剂丙二 醇甲醚醋酸酯中,移入反应瓶中升温至50℃,滴加六亚甲基二异氰酸酯反应液 (溶剂为16.82g,0.10mol),滴加时间为60min,滴加完毕后,升温至60℃反 应6h;再向上述反应液滴加丙炔醇反应液(11.21g,0.20mol),滴加时间为40 min,滴加完毕在60℃反应12h;再向上述反应液滴加甲氧基聚乙二醇(M=200, 40.00g,0.20mol),滴加时间为60min,滴加完毕在50℃反应6h,反应结束后 冷却析出白色固体,用甲苯柱层析法纯化分离出产物,真空干燥至恒重便得产 物。
实施例1所得产物的结构式为:
1H NMR(300MHz,DMSO):δ4.22(t,4H),3.71(s,4H),3.67~3.47 (m,100H),3.39(s,6H),3.32(s,6H),2.94(s,4H),1.55~1.22(m, 48H),0.98(t,6H)ppm。
实施例2
一种含炔基非离子表面活性剂的制备方法为:
将脂肪醇聚氧乙烯醚AEO-9(M=575,57.5g,0.10mol)溶解至溶剂丙二 醇甲醚醋酸酯中,移入反应瓶中升温至70℃,滴加六亚甲基二异氰酸酯反应液 (溶剂为16.82g,0.10mol),滴加时间为60min,滴加完毕后,升温至60℃反 应4h;再向上述反应液滴加丙炔醇反应液(5.60g,0.10mol),滴加时间为40min, 滴加完毕在90℃反应8h;再向上述反应液滴加甲氧基聚乙二醇乙酸(M=600, 60.00g,0.10mol),滴加时间为60min,滴加完毕在80℃反应4h,反应结束后 冷却析出白色固体,用甲苯柱层析法纯化分离出产物,真空干燥至恒重便得产 物。
实施例2所得产物的结构式为:甲氧基聚乙二醇(M=380,38.00g,0.10mol)
1H NMR(300MHz,DMSO):δ4.29(t,4H),3.76(s,4H),3.67~3.47 (m,132H),3.41(s,6H),3.58(s,2H),3.35(s,6H),1.75~1.35(m, 16H),1.55~1.22(m,40H),1.13(t,2H)ppm,0.98(t,6H)ppm。
实施例3
一种含炔基非离子表面活性剂的制备方法为:
将脂肪醇聚氧乙烯醚AEO-9(M=575,57.5g,0.10mol)溶解至溶剂丙二 醇甲醚醋酸酯中,移入反应瓶中升温至60℃,滴加六亚甲基二异氰酸酯反应液 (溶剂为16.82g,0.10mol),滴加时间为60min,滴加完毕后,升温至60℃反 应5h;再向上述反应液滴加丙炔醇反应液(5.60g,0.10mol),滴加时间为40min, 滴加完毕在80℃反应10h;再向上述反应液滴加甲氧基聚乙二醇乙酸(M=600, 60.00g,0.10mol),滴加时间为60min,滴加完毕在60℃反应5h,反应结束后 冷却析出白色固体,用甲苯柱层析法纯化分离出产物,真空干燥至恒重便得产 物。
实施例3所得产物的结构式为:
1H NMR(300MHz,DMSO):δ7.37(m,4H),δ7.10(m,4H),δ4.38(s, 4H),3.83(t,2H),3.71(t,8H),3.60~3.48(m,168H),3.39(s,6H), 3.33(s,4H),1.53~1.21(m,40H),0.98(t,6H)ppm。
由于本发明制备的含炔基非离子表面活性剂具有润湿和消泡的双重特性, 使用接触角仪器来测定实施例中所制表面活性剂溶液改变油性玻璃接触角的变 化,根据GB/T7462-1994《表面活性剂发泡力的测定-改进Ross-Miles法》表征 实施例中所制表面活性剂的抑泡性能,接触角数据和发泡体积如表1和表2所 示。
表1含炔基非离子表面活性剂的接触角
表2含炔基非离子表面活性剂的发泡性能
综上所述,与市售非离子表面活性剂脂肪醇聚氧乙烯醚(AEO-9)相对比, 该含炔基非离子表面活性剂具有极好的润湿性及抑泡性能,因此该表面活性剂 具有润湿、消泡的双重特性。
以上所述仅是本发明的优选实施例,并非用于限定本发明的保护范围,应 当指出,对本技术领域的普通技术人员在不脱离本发明原理的前提下,对其进 行若干改进与润饰,均应视为本发明的保护范围。
Claims (5)
2.根据权利要求1所述的一种含炔基非离子表面活性剂的制备方法,其特征在于:步骤为:
1)在脂肪醇聚氧乙烯醚AEO-9中滴加二异氰酸酯进行异氰酸酯封端反应,得封端异氰酸酯中间体,所述脂肪醇聚氧乙烯醚AEO-9和二异氰酸酯的摩尔比为2:1;
2)再向封端异氰酸酯中间体中加入丙炔醇,其中丙炔醇和二异氰酸酯的摩尔比为2:1,获得端炔基封端异氰酸酯中间体;
3)再向端炔基封端异氰酸酯中间体中加入甲基封端的端羟基聚醚,其中甲基封端的端羟基聚醚和二异氰酸酯的摩尔比为2:1,反应结束后冷却析出白色固体,纯化分离出产物,真空干燥至恒重即得含炔基非离子表面活性剂。
3.根据权利要求2所述的一种含炔基非离子表面活性剂的制备方法,其特征在于:所述步骤1)中脂肪醇聚氧乙烯醚AEO-9和二异氰酸酯在50~70℃反应4~6h;
所述步骤2)中丙炔醇和封端二异氰酸酯在60~90℃反应8~12h;
步骤3)中,甲基封端的端羟基聚醚和端炔基封端二异氰酸酯中间体在50~80℃反应4~6h。
4.根据权利要求2或3所述的一种含炔基非离子表面活性剂的制备方法,其特征在于:所述的甲基封端的端羟基聚醚为甲氧基聚乙二醇(mPEG-OH)或者甲氧基聚乙二醇羧酸(mPEG-COOH)。
5.根据权利要求4所述的一种含炔基非离子表面活性剂的制备方法,其特征在于:所述二异氰酸酯为4,4-二苯基甲烷二异氰酸酯(4,4-HDI),2,2-二苯基甲烷二异氰酸酯(2,2-HDI),二环己基甲烷二异氰酸酯(HMDI),六亚甲基二异氰酸酯(HDI)中的任意一种。
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CN102304029A (zh) * | 2011-04-11 | 2012-01-04 | 杨朝辉 | 一种炔二醇和环氧乙烷加合物的合成方法 |
CN103846048A (zh) * | 2012-12-04 | 2014-06-11 | 日信化学工业株式会社 | 水溶性表面活性剂组合物、墨配制剂和纸涂布配制剂 |
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CN102304029A (zh) * | 2011-04-11 | 2012-01-04 | 杨朝辉 | 一种炔二醇和环氧乙烷加合物的合成方法 |
CN103846048A (zh) * | 2012-12-04 | 2014-06-11 | 日信化学工业株式会社 | 水溶性表面活性剂组合物、墨配制剂和纸涂布配制剂 |
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Application publication date: 20200623 |