CN110746569A - 荧光水性聚氨酯的合成方法 - Google Patents
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Abstract
本发明涉及化工领域,公开了一种荧光水性聚氨酯的合成方法,将自制的含有端羟基的荧光复合材料分散到脂肪族二异氰酸酯中,40℃下机械搅拌反应1小时后加入低聚二元醇、亲水扩链剂,85℃进行逐步聚合反应0.5‑2小时,合成侧链含羧基的荧光水性聚氨酯预聚体,降至室温后加入小分子多元胺中和剂中和羧基形成季铵盐后,自乳化分散在计量水中后,再加入小分子二元胺扩链剂进行扩链,制得荧光水性聚氨酯乳液。本发明以自制的含有端羟基的荧光复合材料的方式把荧光官能团通过化学键嵌入到水性聚氨酯骨架中的同时,还引入了无机补强剂,制备的荧光水性聚氨酯具有较强的荧光效应,较好的机械强度和耐水性能。
Description
技术领域
本发明涉及化工技术领域,特别涉及一种荧光水性聚氨酯乳液的合成方法。
背景技术
聚氨酯作为一种多功能聚合物材料,广泛应用于涂料、皮革、粘合剂、油墨、建筑等行业。但传统的聚氨酯产品在生产加工过程中使用了大量易燃易爆,毒副作用大的有机溶剂,如N,N-二甲基甲酰胺(DMF)、甲乙酮(MEK)、甲苯等,严重威胁到人类的生存环境。
水性聚氨酯以水代替有机溶剂作为分散介质,具有无毒、环保等优点,是当前聚氨酯产业的发展方向。虽然水性聚氨酯的研究很多,但是由于为了使水性聚氨酯树脂能很好地分散在水中,而在其链段上引入了亲水性基团,使得所得水性聚氨酯产品的耐水、耐磨、耐热性较差,机械强度较低等缺点。
荧光水性聚氨酯因其特殊的二次发光性能,在路标涂料、建筑涂料等特殊环境下的领域中应用有着独特的优势而受到广泛关注。但是传统制备荧光水性聚氨酯的方法,多为直接将荧光剂粉末直接与水性聚氨酯共混得到。共混过程中,常常需要使用助剂和有机溶剂,提升荧光粉剂在水性聚氨酯中的分散性。同时在应用过程中,荧光小分子容易脱落,影响应用效果。
近来,有研究者尝试使用带羟基的或带氨基的荧光染料与异氰酸根反应,以化学键的方式把荧光基团接入聚氨酯分子链上,获得荧光水性聚氨酯,如中国专利201310223868.3、201510712140.6和201910640788.5。然而,这些制得的荧光水性聚氨酯仍然存在引入的荧光基团数量少,耐候性差,机械强度低等缺点。
发明内容
发明目的:针对现有技术中存在的问题,本发明提供一种高耐候性和机械强度的荧光水性聚氨酯的合成方法,将通过简洁的合成改性步骤得到的含有端羟基的凹凸棒石黏土荧光复合材料引入到水性聚氨脂的分子链上,使水性聚氨酯获得高耐候性荧光性能的同时,改善水性聚氨酯产品的机械强度。
技术方案:本发明提供了一种荧光水性聚氨酯的合成方法,按重量百分比取用原料:脂肪族二异氰酸酯10%-20%、含端羟基的荧光复合材料2%-10%、低聚二元醇5%-15%、亲水扩链剂3%-5%、小分子多元胺中和剂1%-3%、小分子二元胺扩链剂1%-2%、有机铋催化剂0.05%-0.2%、丙酮10%-20%、余量为水;
合成步骤如下:
(1)将含有端羟基的荧光复合材料分散到脂肪族二异氰酸酯中,40℃下机械搅拌反应1小时后加入低聚二元醇、亲水扩链剂,继续搅拌反应0.5-1小时后,加入有机铋催化剂和丙酮,升温至85℃进行逐步聚合反应0.5-2小时,合成侧链含羧基的荧光水性聚氨酯预聚体;
(2)将上一步所得的荧光水性聚氨酯预聚体降至室温后,加入多元胺中和剂,并快速搅拌自乳化分散在计量水中;
(3)待体系成半透明均一液体后,再加入二元胺进行扩链,然后对体系进行加热,保持在50-60℃,低压脱丙酮,得荧光水性聚氨酯乳液。
进一步地,所述含有端羟基的荧光复合材料为负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物,其合成步骤如下:
(1)将1000 ml 2 wt. % 凹凸棒石黏土矿物/异丙醇凝胶和50 mmol氨丙基三甲氧基硅烷于85 ℃油浴加热回流12 h,冷却,离心用异丙醇和丙酮分别洗涤,室温下真空干燥,所得产物记为Pal-NH2。
(2)将2 g的Pal-NH2分散到100 g喹啉中,接着加入0.54 g的苝四甲酸酐,搅拌1 h后加入5 mmol的醇胺,搅拌通入N2,30 min后,油浴加热到100 ℃,回流8 h,冷却后喹啉洗涤3次,60 ℃下真空干燥后得到含端羟基的荧光复合材料。
优选地,所述的醇胺为以下任意一种:乙醇胺、正丙醇胺、异丙醇胺或2-氨基正丁醇。
优选地,所述亲水扩链剂为小分子二元醇亲水扩链剂或含羧基的小分子二元醇亲水扩链剂。
优选地,所述小分子二元醇亲水扩链剂为以下任意一种或其组合:乙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇。
优选地,所述含羧基的小分子二元醇亲水扩链剂为以下任意一种或其组合:二羟甲基丙酸、二羟甲基丁酸。
优选地,所述脂肪族二异氰酸酯为以下任意一种或其组合:异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4,4-二环己基甲烷二异氰酸酯和甲基环己基二异氰酸酯。
优选地,所述低聚二元醇为以下任意一种或其组合:聚己二酸新戊二醇酯二醇、聚已二酸乙二醇-丙二醇酯二醇、聚已二酸乙二醇-1,4丁二醇酯二醇。
优选地,所述小分子多元胺中和剂为以下任意一种或其组合:三乙胺、三乙醇胺。
优选地,所述小分子二元胺扩链剂为以下任意一种或其组合:乙二胺、异佛尔酮二胺。
有益效果:与现有技术相比,本发明具有以下优点:
本发明提供的利用接枝改性的含有端羟基的荧光复合材料作为荧光基团来源,通过与异氰酸酯反应制备荧光水性聚氨酯,不但可以把荧光基团以化学键结合方式引入到水性聚氨酯主链上,使其在聚氨酯链段上达到分子级别的分散,同时引入的凹凸棒石黏土载体(无机补强剂)又可以作为荧光基团的光解保护剂和水性聚氨酯机械强度的补强剂,制备的荧光水性聚氨酯具有较强的荧光效应,较好的机械强度和耐水性能,有效解决了荧光基团的耐候性问题,并显著提升了水性聚氨酯的机械强度;可以在防伪标识,交通标志,生物显影,生物检测,药物示踪,化学检测,荧光油墨,荧光涂料等方面得到应用,有非常广阔的市场前景。
具体实施方式
下面结合具体实施例对本发明进行详细的介绍。
实施方式1:
一种荧光水性聚氨酯的合成方法,按重量百分比取用原料:异佛尔酮二异氰酸酯与六亚甲基二异氰酸酯的组合物20%、负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物2%、聚己二酸新戊二醇酯二醇15%、乙二醇和二羟甲基丙酸的组合物5%、三乙胺3%、乙二胺1%、有机铋催化剂0.2%、丙酮20%,余量为水;
合成步骤如下:
(1)合成负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物;
其合成步骤如下:
(a)将1000 ml 2 wt. % 凹凸棒石黏土矿物/异丙醇凝胶和50 mmol氨丙基三甲氧基硅烷于85 ℃油浴加热回流12 h,冷却,离心用异丙醇和丙酮分别洗涤,室温下真空干燥,所得产物记为Pal-NH2。
(b)将2 g的Pal-NH2分散到100 g喹啉中,接着加入0.54 g的苝四甲酸酐,搅拌1 h后加入5 mmol的乙醇胺,搅拌通入N2,30 min后,油浴加热到100 ℃,回流8 h,冷却后喹啉洗涤3次,60 ℃下真空干燥后得到含端羟基的荧光复合材料。
(2)将自制的负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物分散到异佛尔酮二异氰酸酯与六亚甲基二异氰酸酯的组合物中,40℃下机械搅拌反应1小时后加入聚己二酸新戊二醇酯二醇、乙二醇和二羟甲基丙酸的组合物,继续搅拌反应1小时后,加入有机铋催化剂和丙酮,升温至85℃进行逐步聚合反应2小时,合成侧链含羧基的荧光水性聚氨酯预聚体;
(3)将上一步所得的荧光水性聚氨酯预聚体降至室温后,加入三乙胺,并快速搅拌自乳化分散在计量水中;
(4)待体系成半透明均一液体后,再加入乙二胺进行扩链,然后对体系进行加热,保持在50-60℃,低压脱丙酮,得一种荧光水性聚氨酯乳液。
实施方式2:
一种荧光水性聚氨酯的合成方法,按重量百分比取用原料:聚已二酸乙二醇-丙二醇酯二醇和聚已二酸乙二醇-1.4丁二醇酯二醇的组合物20%、负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物10%、聚己二酸新戊二醇酯二醇10%、聚己二酸新戊二醇酯二醇和新戊二醇和二羟甲基丁酸的组合物4%、三乙醇胺2%、异佛尔酮二胺2%、有机铋催化剂0.1%、丙酮15%,余量为水;
合成步骤如下:
(1)合成负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物;
与实施方式1完全相同,不同点仅在于:本实施方式中的醇胺为2-氨基正丁醇胺。
(2)将自制的负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物分散到聚已二酸乙二醇-丙二醇酯二醇和聚已二酸乙二醇-1.4丁二醇酯二醇的组合物中,40℃下机械搅拌反应1小时后加入聚己二酸新戊二醇酯二醇和新戊二醇和二羟甲基丁酸的组合物,继续搅拌反应1小时后,加入有机铋催化剂和丙酮,升温至85℃进行逐步聚合反应1小时,合成侧链含羧基的荧光水性聚氨酯预聚体;
(3)将上一步所得的荧光水性聚氨酯预聚体降至室温后,加入三乙醇胺,并快速搅拌自乳化分散在计量水中;
(4)待体系成半透明均一液体后,再加入异佛尔酮二胺进行扩链,然后对体系进行加热,保持在50-60℃,低压脱丙酮,得一种荧光水性聚氨酯乳液。
实施方式3:
一种荧光水性聚氨酯的合成方法,按重量百分比取用原料:异佛尔酮二异氰酸酯和4,4-二环己基甲烷二异氰酸酯和甲基环己基二异氰酸酯中的组合物10%、负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物4%、聚已二酸乙二醇-丙二醇酯二醇5%、聚已二酸乙二醇-丙二醇酯二醇和1,6-己二醇和二羟甲基丁酸的组合物3%、三乙胺和三乙醇胺的组合物1%、乙二胺和异佛尔酮二胺的组合物2%、有机铋催化剂0.05%、丙酮10%,余量为水;
合成步骤如下:
(1)合成负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物;
与实施方式1完全相同,不同点仅在于:本实施方式中的醇胺为正丙醇胺。
(2)将自制的负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物分散到异佛尔酮二异氰酸酯和4,4-二环己基甲烷二异氰酸酯和甲基环己基二异氰酸酯中的组合物中,40℃下机械搅拌反应1小时后加入聚已二酸乙二醇-丙二醇酯二醇和1,6-己二醇和二羟甲基丁酸的组合物,继续搅拌反应0.5小时后,加入有机铋催化剂和丙酮,升温至85℃进行逐步聚合反应0.5小时,合成侧链含羧基的荧光水性聚氨酯预聚体;
(3)将上一步所得的荧光水性聚氨酯预聚体降至室温后,加入三乙胺和三乙醇胺的组合物,并快速搅拌自乳化分散在计量水中;
(4)待体系成半透明均一液体后,再加入乙二胺和异佛尔酮二胺的组合物进行扩链,然后对体系进行加热,保持在50-60℃,低压脱丙酮,得一种荧光水性聚氨酯乳液。
分别对采用上述各实施方式中的方法制备出的荧光水性聚氨酯乳液的耐候性、拉伸强度进行测试,测试方法如下:
耐候性能:根据GB/T 1865-2009 色漆和清漆——人工气候老化和人工辐射曝露(滤过的氙弧辐射)进行检测,以荧光水性聚氨酯薄膜的荧光强度剩余50%的衰减时间为衡量标准。
拉伸强度:按国标GB 8949-2008-T裁剪及检测试样。制备约20 mm(长)×5 mm(宽)× 0.4 mm(厚)的试样。拉伸条件:拉伸速率为50mm/min,夹距为10 mm,在25℃下拉伸。每个试样拉伸5次,取平均值。
将实施方式1、2、3得到的荧光水性聚氨酯进行耐候性以及拉伸强度测试,结果如下:
耐候性能(小时) | 拉伸应力(MPa) | |
实施例1 | 756 | 8.2 |
实施例2 | 1030 | 10.6 |
实施例3 | 875 | 14.2 |
上述实施方式只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所做的等效变换或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种荧光水性聚氨酯的合成方法,其特征在于:按重量百分比取用原料:脂肪族二异氰酸酯10%-20%、含端羟基的荧光复合材料2%-10%、低聚二元醇5%-15%、亲水扩链剂3%-5%、小分子多元胺中和剂1%-3%、小分子二元胺扩链剂1%-2%、有机铋催化剂0.05%-0.2%、丙酮10%-20%、余量为水;
合成步骤如下:
(1)将含有端羟基的荧光复合材料分散到脂肪族二异氰酸酯中,40℃下机械搅拌反应1小时后加入低聚二元醇、亲水扩链剂,继续搅拌反应0.5-1小时后,加入有机铋催化剂和丙酮,升温至85℃进行逐步聚合反应0.5-2小时,合成侧链含羧基的荧光水性聚氨酯预聚体;
(2)将上一步所得的荧光水性聚氨酯预聚体降至室温后,加入多元胺中和剂,并快速搅拌自乳化分散在计量水中;
(3)待体系成半透明均一液体后,再加入二元胺进行扩链,然后对体系进行加热,保持在50-60℃,低压脱丙酮,得荧光水性聚氨酯乳液。
2.根据权利要求1所述的荧光水性聚氨酯的合成方法,其特征在于:所述含有端羟基的荧光复合材料为负载羟基封端的苝酰亚胺类有机荧光染料的凹凸棒石黏土矿物,其合成步骤如下:
(1)将1000 ml 2 wt. % 凹凸棒石黏土矿物/异丙醇凝胶和50 mmol氨丙基三甲氧基硅烷于85 ℃油浴加热回流12 h,冷却,离心用异丙醇和丙酮分别洗涤,室温下真空干燥,所得产物记为Pal-NH2;
(2)将2 g的Pal-NH2分散到100 g喹啉中,接着加入0.54 g的苝四甲酸酐,搅拌1 h后加入5 mmol的醇胺,搅拌通入N2,30 min后,油浴加热到100 ℃,回流8 h,冷却后喹啉洗涤3次,60 ℃下真空干燥后得到含端羟基的荧光复合材料。
3.根据权利要求2所述的荧光水性聚氨酯的合成方法,其特征在于,所述的醇胺为以下任意一种:乙醇胺、正丙醇胺、异丙醇胺或2-氨基正丁醇。
4.根据权利要求1所述的荧光水性聚氨酯的合成方法,其特征在于:所述亲水扩链剂为小分子二元醇亲水扩链剂和含羧基的小分子二元醇亲水扩链剂的组合物。
5.根据权利要求4所述的荧光水性聚氨酯的合成方法,其特征在于:所述小分子二元醇亲水扩链剂为以下任意一种或其组合:
乙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇。
6.根据权利要求4所述的荧光水性聚氨酯的合成方法,其特征在于:所述含羧基的小分子二元醇亲水扩链剂为以下任意一种或其组合:二羟甲基丙酸、二羟甲基丁酸。
7.根据权利要求1至6中任一项所述的荧光水性聚氨酯的合成方法,其特征在于:所述脂肪族二异氰酸酯为以下任意一种或其组合:异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4,4-二环己基甲烷二异氰酸酯和甲基环己基二异氰酸酯。
8.根据权利要求1至6中任一项所述的荧光水性聚氨酯的合成方法,其特征在于:所述低聚二元醇为以下任意一种或其组合:聚己二酸新戊二醇酯二醇、聚已二酸乙二醇-丙二醇酯二醇、聚已二酸乙二醇-1,4丁二醇酯二醇。
9.根据权利要求1至6中任一项所述的荧光水性聚氨酯的合成方法,其特征在于:所述小分子多元胺中和剂为以下任意一种或其组合:三乙胺、三乙醇胺。
10.根据权利要求1至6中任一项所述的荧光水性聚氨酯的合成方法,其特征在于:所述小分子二元胺扩链剂为以下任意一种或其组合:乙二胺、异佛尔酮二胺。
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