CN107987252A - 一种自乳化型水性光引发剂的制备方法及水性光引发剂 - Google Patents
一种自乳化型水性光引发剂的制备方法及水性光引发剂 Download PDFInfo
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Abstract
一种自乳化型水性光引发剂的制备方法，包括如下步骤：S1、将重量比的二羟甲基丙酸15~18%、溶剂15~18%置于反应釜中，充氮气保护，将二羟甲基丙酸溶解；S2、将重量比的多异氰酸酯21~27%与0.01~0.12%催化剂混合液滴入至反应釜内反应；S3、滴入重量比的二异氰酸酯20~27%的与催化剂0.01~0.12%混合液反应；S4、滴入重量比的2‑羟基‑甲基苯基丙烷‑1‑酮18~21%与催化剂0.01~0.12%混合液反应；得半成品光引发剂A；S5、在半成品光引发剂A中加入三乙胺中和；S6、加入去离子水，经乳化机高速剪切分散得到自乳化型水性光引发剂。本发明具有在漆膜外观、硬度、耐水煮和相对迁移率均优于传统的小分子光引发剂配成的涂料的优点。
Description
技术领域
本发明涉及高分子材料领域，特别是涉及水性紫外光辐射固化涂料用水性光引发剂的制备方法及水性光引发剂。
技术背景
进入21世纪以来，随着人们对于环保的问题越来越重视，水性光固化涂料在继承传统光固化技术的基础上，以水为分散介质基本无VOC排放、无单体残留对环境友好的优势而备受人们青睐。
在水性光固化体系中，光引发剂是及其重要的一部分，虽然传统的油性小分子光引发剂能够应用在水性光固化体系当中，但仍然有易迁移、产生异味、与体系树脂相容性不好等诸多弊端。与油性小分子光引发剂相比，水性大分子光引发剂在获得水溶性的同时继承传统光固化的优点。具有无异味、无迁移、与树脂相容性好，而且引入了特殊官能团以辅助主体树脂获得更优异的性能等优势。目前有报道用马来酸酐和与光引发剂1-[4-（2-羟基羟乙基）-苯基-2羟基-2甲基-1-丙烷反应，制备出具有一定亲水性的可聚合的小分子光引发剂，然后将其进行自由基聚合制备出水性的带有光引发基团的环氧丙烯酸树脂；也有以小分子油溶性光引发剂作为功能单体，采用甲苯二异氰酸酯、聚四氢呋喃二元醇、二羟甲基丙酸、丙烯酸羟乙酯和Irgacure 2959（1-[4-（2-羟乙氧基）-苯基]-2-羟基-2-甲基-1-丙烷）合成了接有光引发剂集团的UV固化水性聚氨酯树脂。利用二羟甲基丙酸在树脂侧链引入羧酸基，然后经中和成盐获得亲水性。同时在专利报道CN 101735343 A以1-[4-（2-羟基羟乙基）-苯基-2羟基-2甲基-1-丙烷小分子光引发剂、二异氰酸酯、二羟甲基丙酸、磺酸基合成了水性直链的大分子光引发剂。但是尚未见多异氰酸酯为起始基团，在引入亲水基团之后嵌入光引发剂2-羟基-甲基苯基丙烷-1-酮获得支化多官能度的水性大分子光引发剂的相关报道。
水性大分子引发剂在一定程度上能克服小分子光引发剂的易迁移、有异味与树脂相容性不好的缺点，但水性长链大分子自身容易出现因光引发剂基团摩尔浓度低而引起的光引发效率不高的问题，从而增加其用量提高了成本，还会出现因为其用量增多引起主体树脂性能下降的问题。
发明内容
为了解决上述问题，本发明向社会提供一种光引发剂基团浓度高，引发效率好，有利于提高生产效率的自乳化型水性光引发剂的制备方法及水性光引发剂。
本发明的技术方案是：提供一种自乳化型水性光引发剂的制备方法，包括如下步骤：
S1、将占半成品光引发剂A的重量比的二羟甲基丙酸15~18%、溶剂15~18%置于反应釜中，体系充氮气保护，升温至45-65℃，将二羟甲基丙酸溶解；
S2、将占半成品光引发剂A的重量比的多异氰酸酯21~27%与0.01~0.12%催化剂混合液滴入至反应釜内，滴加时间0.5~1小时，反应2-3小时；
S3、降温至35-45℃；滴入占半成品光引发剂A的重量比的二异氰酸酯20~27%的与催化剂0.01~0.12%混合液，0.5~1小时滴完，保温反应1.5~2小时；
S4、升温至70~80℃，加入占半成品光引发剂A的重量比的2-羟基-甲基苯基丙烷-1-酮18~21%与催化剂0.01~0.12%混合液，反应至异氰酸酯基至理论值，减压至0.03~0.05MPa抽去溶剂，冷却至40-45℃，得半成品光引发剂A；
S5、在半成品光引发剂A中加入三乙胺中和，其中三乙胺的加入重量比为二羟甲基丙酸重量的64~71%；
S6、加入半成品光引发剂A重量比的120~150%去离子水，经乳化机高速剪切分散得到自乳化型水性光引发剂。
作为对本发明的改进，所述的多异氰酸酯为甲苯二异氰酸酯三聚体、异佛尔酮异氰酸酯三聚体和1，6-亚己基二异氰酸酯三聚体中的一种；或者两种或者三种的混合物。
作为对本发明的改进，所述催化剂为二月桂酸二丁基锡。
作为对本发明的改进，所述溶剂为二甲基甲酰胺或N-甲基吡咯烷酮。
作为对本发明的改进，所述的二异氰酸酯为2，4-甲苯二异氰酸酯、异佛尔酮二异氰酸酯等带有不同反应活性N=C=O基团的其他二异氰酸酯。
作为对本发明的改进，所述的异氰酸酯基达到的理论值的计算方法为：理论值等于总异氰酸酯基摩尔数减去反应物中羟基摩尔数，用二正丁胺法测定异氰酸酯基摩尔数来计算。
本发明还提供一种由上述方法制备的自乳化型水性光引发剂。
本发明的自乳化型水性光引发剂以二异氰酸酯三聚体与过量的二羟甲基丙酸的部分羟基反应，剩余的羟基再与有官能团活性差异的过量二异氰酸酯反应（在引入羧基的同时，控制分子量在比较适合的范围方便乳化），剩余的异氰酸酯基与带有羟基的2-羟基-甲基苯基丙烷-1-酮反应引入光引发活性基团。最后以三乙胺中和成盐加入计量的去离子水剪切乳化得到水性大分子光引发剂。
本发明制备出的自乳化型水性光引发剂，该树脂具有良好的水溶性，与水性光固化树脂的相容性良好，无迁移，具备与其对应的小分子光引发剂相当的光引发效率，能良好的应用到水性光固化体系中。另外，本发明的多官能度的水性大分子光引发剂，光引发剂基团在分子内摩尔含量高，降低水性光固化树脂所需大分子的光引发剂用量；同时由于分子链具有支链化相比同类型直链的大分子具有更低的粘度，易于生产减少了溶剂的用量，同时方便乳化；通过合理的搭配引入了具有刚性结构、柔性结构的二异氰酸酯基以提高光固化水性树脂的最终性能。与传统的小分子光引发剂所制成的涂料相比，本发明在漆膜外观、硬度、耐水煮和相对迁移率均优于传统的小分子光引发剂配成的涂料。
附图说明
图1是本发明一种实施例的方框结构示意图。
具体实施方式
下面各实施例以制100克半成品光引发剂A为例，并在半成品光引发剂A的基础上制成自乳化型水性光引发剂，加以说明本发明。
实施例1：
一种自乳化型水性光引发剂的制备方法，包括如下步骤：
S1、在装有温度计、回流冷凝管、机械搅拌棒的四口烧瓶中加入15克二羟甲基丙酸、18克二甲基酰胺，通氮气，升温至65℃，将二羟甲基丙酸完全溶解；
S2、滴入21克1，6-亚己基二异氰酸酯三聚体和0.01克的二月桂酸二丁基锡的混合物，滴加时间为1小时，恒温反应3小时；
S3、降温至45℃，滴入27克异佛尔酮二异氰酸酯和0.01克的二月桂酸二丁基锡的混合物，滴加时间0.5小时，保温反应2小时至异氰酸酯基达到理论值；
S4、升温至70℃，加入18.97克2-羟基-甲基苯基丙烷-1-酮以及0.01克二月桂酸二丁基锡反应至异氰酸酯基完全消失，减压至0.03Mpa抽去二甲基酰胺;
S5、加入9.6克三乙胺中和；
S6、加入120克的去离子水剪切乳化，得到外观为泛蓝光透明的水性大分子光引发剂乳液，光引发基团为0.56mmol/g。
实施例2：
一种自乳化型水性光引发剂的制备方法，包括如下步骤：
S1、在装有温度计、回流冷凝管、机械搅拌棒的四口烧瓶中加入17克二羟甲基丙酸、17克二甲基酰胺，通氮气，升温至65℃，将二羟甲基丙酸完全溶解；
S2、滴入22.76克1，6-亚己基二异氰酸酯三聚体和0.08克的二月桂酸二丁基锡的混合物，滴加时间为0.5小时，恒温反应2小时；
S3、降温至45℃，滴入25克异佛尔酮二异氰酸酯和0.08克的二月桂酸二丁基锡的混合物，滴加时间1小时，保温反应1.5小时至异氰酸酯基达到理论值；
S4、升温至80℃，加入18克2-羟基-甲基苯基丙烷-1-酮以及0.08克二月桂酸二丁基锡反应至异氰酸酯基完全消失，减压至0.05Mpa抽去二甲基酰胺；
S5、加入12.07克三乙胺中和；
S6、加入130克的去离子水剪切乳化，得到外观泛蓝光透明的水性大分子光引发剂乳液，光引发基团为0.6mmol/g。
实施例3：
一种自乳化型水性光引发剂的制备方法，包括如下步骤：
S1、在装有温度计、回流冷凝管、机械搅拌棒的四口烧瓶中加入18克二羟甲基丙酸、15克N-甲基吡咯烷酮，通氮气，升温至50℃，将二羟甲基丙酸完全溶解；
S2、滴入27克甲苯二异氰酸酯三聚体和0.1克的二月桂酸二丁基锡的混合物，滴加时间为45分钟，恒温反应3小时；
S3、降温至40℃，滴入20.7克2，4-甲苯二异氰酸酯和0.1克的二月桂酸二丁基锡的混合物，滴加时间1小时，保温反应2小时至异氰酸酯基达到理论值；
S4、升温至75℃，加入19克2-羟基-甲基苯基丙烷-1-酮以及0.1克二月桂酸二丁基锡反应至异氰酸酯基完全消失，减压至0.05Mpa抽去二甲基酰胺；
S5、加入12克三乙胺中和；
S6、加入140克的去离子水剪切乳化，得到外观泛蓝光透明的水性大分子光引发剂乳液，光引发基团为0.57mmol/g。
实施例4：
一种自乳化型水性光引发剂的制备方法，包括如下步骤：
S1、在装有温度计、回流冷凝管、机械搅拌棒的四口烧瓶中加入18克二羟甲基丙酸、18克N-甲基吡咯烷酮，通氮气，升温至50℃，将二羟甲基丙酸完全溶解；
S2、滴入25.64克甲苯二异氰酸酯三聚体和0.12克的二月桂酸二丁基锡的混合物，滴加时间为30分钟，恒温反应3小时；
S3、降温至35℃，滴入20克2，4-甲苯二异氰酸酯和0.12克的二月桂酸二丁基锡的混合物，滴加时间1小时，保温反应0.5小时至异氰酸酯基达到理论值；
S4、升温至80℃，加入18克2-羟基-甲基苯基丙烷-1-酮以及0.12克二月桂酸二丁基锡反应至异氰酸酯基完全消失，减压至0.05Mpa抽去二甲基酰胺；
S5、加入12.5克三乙胺中和；
S6、加入150克的去离子水剪切乳化，得到外观泛蓝光透明的水性大分子光引发剂乳液，光引发基团为0.62mmol/g。
实施例5：
一种自乳化型水性光引发剂的制备方法，包括如下步骤：
S1、在装有温度计、回流冷凝管、机械搅拌棒的四口烧瓶中加入15克二羟甲基丙酸、15克N-甲基吡咯烷酮，通氮气，升温至65℃，将二羟甲基丙酸完全溶解；
S2、滴入24克异佛尔酮异氰酸酯三聚体和0.1克的二月桂酸二丁基锡的混合物，滴加时间为60分钟，恒温反应3小时；
S3、降温至45℃，滴入26.7克2，4-甲苯二异氰酸酯和0.1克的二月桂酸二丁基锡的混合物，滴加时间1小时，保温反应2小时至异氰酸酯基达到理论值；
S4、升温至80℃，加入19克2-羟基-甲基苯基丙烷-1-酮以及0.1克二月桂酸二丁基锡反应至异氰酸酯基完全消失，减压至0.05Mpa抽去二甲基酰胺；
S5、加入10.5克三乙胺中和；
S6、加入130克的去离子水剪切乳化，得到外观泛蓝光透明的水性大分子光引发剂乳液，光引发基团为0.54mmol/g。
实施例6：
一种自乳化型水性光引发剂的制备方法，包括如下步骤：
S1、在装有温度计、回流冷凝管、机械搅拌棒的四口烧瓶中加入16克二羟甲基丙酸、16克N-甲基吡咯烷酮，通氮气，升温至65℃，将二羟甲基丙酸完全溶解；
S2、滴入23.7克异佛尔酮异氰酸酯三聚体和0.1克的二月桂酸二丁基锡的混合物，滴加时间为60分钟，恒温反应3小时；
S3、降温至45℃，滴入23克2，4-甲苯二异氰酸酯和0.1克的二月桂酸二丁基锡的混合物，滴加时间1小时，保温反应2小时至异氰酸酯基达到理论值；
S4、升温至80℃，加入21克2-羟基-甲基苯基丙烷-1-酮以及0.1克二月桂酸二丁基锡反应至异氰酸酯基完全消失，减压至0.05Mpa抽去二甲基酰胺；
S5、加入10.4克三乙胺中和；
S6、加入130克的去离子水剪切乳化，得到外观泛蓝光透明的水性大分子光引发剂乳液，光引发基团为0.57mmol/g。
上述各实施例中的多异氰酸酯都是分别以甲苯二异氰酸酯三聚体、异佛尔酮异氰酸酯三聚体或1，6-亚己基二异氰酸酯三聚体加入的，实际上，甲苯二异氰酸酯三聚体、异佛尔酮异氰酸酯三聚体和1，6-亚己基二异氰酸酯三聚体中两种或者三种的混合物来代替单独的多异氰酸酯。两种不同的多异氰酸酯混合时，两种物质可以以等比例混合后加入，例如，如果是甲苯二异氰酸酯三聚体和异佛尔酮异氰酸酯三聚体混合，可以两者等量混合；再如甲苯二异氰酸酯三聚体和1，6-亚己基二异氰酸酯三聚体混合，或者异佛尔酮异氰酸酯三聚体和1，6-亚己基二异氰酸酯三聚体混合，也可以等量混合；如果三者混合时，如，甲苯二异氰酸酯三聚体、异佛尔酮异氰酸酯三聚体和1，6-亚己基二异氰酸酯三聚体也可以等量混合，各占三份之一。
将本发明中的实施例1－6，与传统的小分子光引发剂配成涂料后，进行喷涂比较，其在漆膜外观、硬度、耐水煮和相对迁移率均优于传统的小分子光引发剂配成的涂料。具体见表一、表二和表三。
表1应用实例配方表
表一中，光引发剂1173为巴斯夫公司的1173光引发剂；40%固体分水性UV树脂为深圳市科普利高分子材料有限公司的UV903水性UV辐射固化树脂乳液。
按表一中配方的各组分混合分散均匀后的清漆，在温度15-35℃，相对湿度45-70%的环境条件下，采用空气喷涂，空气压力0.3-0.4Mpa，建议采用重力式喷枪，口径15-18mm；清漆施工粘度采用NK-2#测量为30-40s/15-35℃；漆膜厚度为15-25μm；预热流平时间为10~15min/55-65℃。UV辐射固化条件是UV灯与漆膜距离25~35cm，以UV辐射剂量800~1000mJ/cm²辐射固化，室温实时效放置24h实干。测其部分性能。
表二大单体水性光引发剂与传统光引发剂1173的部分性能比较表
表三本发明中的水性大分子光引发剂与1173小分子光引发剂引发效率以及相对迁移率比较表
通过上述表格可得知本发明的水性大分子光引发剂与传统的光引发剂1173相比较不仅有相当的引发效率，还具备超低的迁移率，不会对水性UV树脂的漆膜外观、光泽有不良的影响，同时还能提高树脂本身漆膜的硬度以及光泽。
本发明还提供一种由上述方法制备的自乳化型水性光引发剂。
Claims (7)
1.一种自乳化型水性光引发剂的制备方法，其特征在于：包括如下步骤：
S1、将占半成品光引发剂A的重量比的二羟甲基丙酸15~18%、溶剂15~18%置于反应釜中，体系充氮气保护，升温至45-65℃，将二羟甲基丙酸溶解；
S2、将占半成品光引发剂A的重量比的多异氰酸酯21~27%与0.01~0.12%催化剂混合液滴入至反应釜内，滴加时间0.5~1小时，反应2-3小时；
S3、降温至35-45℃；滴入占半成品光引发剂A的重量比的二异氰酸酯20~27%的与催化剂0.01~0.12%混合液，0.5~1小时滴完，保温反应1.5~2小时；
S4、升温至70~80℃，加入占半成品光引发剂A的重量比的2-羟基-甲基苯基丙烷-1-酮18~21%与催化剂0.01~0.12%混合液，反应至异氰酸酯基至理论值，减压至0.03~0.05MPa抽去溶剂，冷却至40-45℃，得半成品光引发剂A；
S5、在半成品光引发剂A中加入三乙胺中和，其中三乙胺的加入重量比为二羟甲基丙酸重量的64~71%；
S6、加入半成品光引发剂A重量比的120~150%去离子水，经乳化机高速剪切分散得到自乳化型水性光引发剂。
2.根据权利要求1所述的自乳化型水性光引发剂的制备方法，其特征在于：所述的多异氰酸酯为甲苯二异氰酸酯三聚体、异佛尔酮异氰酸酯三聚体和1，6-亚己基二异氰酸酯三聚体中的一种；或者两种或者三种的混合物。
3.根据权利要求1或2所述的自乳化型水性光引发剂的制备方法，其特征在于：所述催化剂为二月桂酸二丁基锡。
4.根据权利要求1或2所述的自乳化型水性光引发剂的制备方法，其特征在于：所述溶剂为二甲基甲酰胺或N-甲基吡咯烷酮。
5.根据权利要求1或2所述的自乳化型水性光引发剂的制备方法，其特征在于：所述的二异氰酸酯为2，4-甲苯二异氰酸酯、异佛尔酮二异氰酸酯或带有不同反应活性N=C=O基团的其他二异氰酸酯。
6.根据权利要求1或2所述的自乳化型水性光引发剂的制备方法，其特征在于：所述的异氰酸酯基达到的理论值的计算方法为：理论值等于总异氰酸酯基摩尔数减去反应物中羟基摩尔数，用二正丁胺法测定异氰酸酯基摩尔数来计算。
7.一种由权利要求1至权利要求6任一权利要求所述的制备方法制成的自乳化型水性光引发剂。
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