CN113056448A - 用作涂料组合物中的光引发剂的二苯甲酮衍生物 - Google Patents
用作涂料组合物中的光引发剂的二苯甲酮衍生物 Download PDFInfo
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Abstract
本发明涉及一种化合物，其为式1的羟基封端的氧化烯基团(R)取代的二苯甲酮：
Description
背景技术
本发明涉及二苯甲酮衍生物，更具体地涉及用侧接氧化丙烯和氧化乙烯重复单元官能化的二苯甲酮。
光引发剂用于建筑外墙涂料中，以改良抗污垢性(DPUR)和保光性。推测通过使聚合物薄膜的表面交联，诺里什(Norrish)II型光引发剂在改良这些特征方面尤其有效。当通过UV照射激发时，光引发剂会从聚合物中夺取氢，从而形成能够交联的反应性自由基。也有可能光引发剂通过能量转移到三线态氧而产生单线态氧。然后，这一单线态氧反应形成过氧羟基和羟基自由基，其能够通过从聚合物主链上夺氢来诱导交联。
理想地，光引发剂将改良目标外部性能，而不会不利地影响薄膜的柔性，并且由于光引发剂或其反应副产物的固有吸收而对涂料颜色产生的影响最小。二苯甲酮是光引发剂的一个实例，其对改良涂料性能尤其有效，因为其能够在引发光诱导交联反应之前通过薄膜扩散到表面。交联主要发生在薄膜表面，因为涂料中的颜料吸收和/或屏蔽UV光，因此光引发剂主要在薄膜表面附近被激发。
不幸的是，二苯甲酮已被确定为可能的人类致癌物(IARC 2B型)；此外，二苯甲酮被视为挥发性有机化合物(VOC)，并且由于其不利的环境影响是不希望的。这种挥发性具有引起薄膜的交联密度变化的另外缺点，因为二苯甲酮可在表面处反应之前从薄膜中蒸发。此外已知二苯甲酮的保光性能在暴露数月后会迅速下降。因此，非常需要找到一种在建筑外墙涂料中提供持久保光性的无毒且不挥发的光引发剂。
发明内容
本发明通过提供一种化合物解决了所属领域的需求，所述化合物是式1的羟基封端的氧化烯基团(R)取代的二苯甲酮：
其中R是1到13个氧化丙烯基团与5到20个氧化乙烯基团的组合，其条件是所述氧化丙烯基团与所述氧化乙烯基团的总和不大于25。
本发明的所述化合物提供了一种在建筑外墙涂料中提供优异保光性的非挥发性、无毒的光引发剂。
具体实施方式
本发明是一种化合物，所述化合物是式1的羟基封端的氧化烯基团(R)取代的二苯甲酮：
其中R是1到13个氧化丙烯基团与5到20个氧化乙烯基团的组合，其条件是所述氧化丙烯基团与所述氧化乙烯基团的总和不大于25。
氧化丙烯和氧化乙烯基团如下示出：
其中到氧原子的虚线表示与碳原子或末端氢原子的连接点，而到碳原子的虚线表示与氧原子的连接点。尽管可能以任何顺序连接基团，但优选将氧化丙烯基团最靠近二苯甲酮基团连接，并将氧化乙烯基团连接到氧化丙烯基团，如
式2所示出：
优选地，x为2到10，更优选到8；并且y优选从6开始，更优选10到18，更优选到16。优选地，氧化乙烯基团的数目大于氧化丙烯基团的数目；即，优选地，y大于x。如使用ChemBioDraw Ultra 13.0(珀金埃尔默(PerkinElmer))(其使用化学片段算法方法以根据分子的组成部分评定分子的分配系数)确定的羟基封端的氧化烯基团(R)的Log P计算值(cLog P)优选在-4.0，更优选-3.5，并且最优选-3.0到-1.2，更优选到-1.3，并且最优选到-1.5的范围内。
官能化二苯甲酮有利地通过将氧化丙烯和氧化乙烯以任何顺序或同时地碱催化加成到4-羟基二苯甲酮中来制备。优选地，本发明的官能化二苯甲酮以如下两步制备。在第一步中，将4-羟基二苯甲酮和其盐与氧化丙烯和合适的溶剂在额定压力反应器中接触；将反应器加热到优选100℃，更优选120℃到优选200℃，更优选到150℃的范围内的温度，并连续添加氧化丙烯，然后保持足够的时间以形成聚(氧化丙烯)-二苯甲酮中间体；将氧化乙烯连续添加到加热的反应器中，然后保持足够的时间以得到所需产物。氧化丙烯和氧化乙烯的保持时间都优选为2到10h。然后冷却反应器，并且去除溶剂，优选为高沸点极性非质子溶剂，如二甲氧基乙烷，得到烷氧基化二苯甲酮。最终产物一般是多分散度(Mw/Mn)优选在1.2到3，更优选到2的范围内的产物的混合物。
本发明的烷氧基化二苯甲酮适用作涂料配制物中的光引发剂。因此，在另一方面，本发明是包含粘合剂、流变改性剂、不透明颜料和烷氧基化二苯甲酮的水分散体的涂料组合物。以涂料组合物的重量计，涂料配制物中烷氧基化二苯甲酮的浓度优选在0.04重量％，更优选0.1重量％到优选4重量％，更优选到2重量％，并且最优选到1重量％的范围内。
涂料组合物优选进一步包括一种或多种选自以下组成的组的添加剂：表面活性剂、分散剂、杀生物剂、消泡剂、聚结剂、增量剂和着色剂。
实例
一般烷氧基化步骤：将4-羟基二苯甲酮和4-苯甲酰基苯酚钾在二甲氧基乙烷(DME)中的9:1mol:mol混合物置于容量为300mL的额定压力反应器中。用氮气吹扫反应器，并将其加热到130℃。在30min的时段内连续添加氧化丙烯(PO)，并且然后在这一温度下保持6h。然后在30min的时段内将氧化乙烯(EO)添加到反应器中，并且在这一温度下保持6h。将反应器冷却到室温并且通风。从反应器中取出溶液，并且真空去除溶剂。
实例1-制备二苯甲酮衍生物：x＝5；y＝11
按照一般烷氧基化步骤，通过将PO(10.7mL，153mmol)和EO(19.1mL，383mmol)添加到4-羟基二苯甲酮(3.80g，19.2mmol)和4-苯甲酰基苯酚钾(0.45g，1.92mmol)于DME(20mL)中的溶液中，制备图2的二苯甲酮衍生物，其中x为5并且y为11。真空去除溶剂后，分离出23.1g(71％)油。
实例2-制备二苯甲酮衍生物：x＝3；y＝12
按照一般烷氧基化步骤，通过将PO(9.7mL，139mmol)和EO(34.8mL，696mmol)添加到4-羟基二苯甲酮(6.90g，34.8mmol)和4-苯甲酰基苯酚钾(0.82g，3.48mmol)于DME(35mL)中的溶液中，制备图2的二苯甲酮衍生物，其中x为3并且y为12。真空去除溶剂后，分离出42.8g(85％)油。
实例3-制备二苯甲酮衍生物：x＝6；y＝6
按照一般烷氧基化程序，通过将PO(23.7mL，339mmol)和EO(21.2mL，424mmol)添加到4-羟基二苯甲酮(8.40g，42.4mmol)和4-苯甲酰基苯酚钾(1.00g，4.24mmol)于DME(40mL)中的溶液中，制备图2的二苯甲酮衍生物，其中x为6并且y为6。真空去除溶剂后，分离出40.9g(79％)油。
实例4-制备二苯甲酮衍生物：x＝3；y＝6
按照一般烷氧基化步骤，通过将PO(14.8g，212mmol)和EO(26.5mL，530mmol)添加到4-羟基二苯甲酮(10.5g，53.0mmol)和4-苯甲酰基苯酚钾(1.25g，5.30mmol)于DME(50mL)中的溶液中，制备图2的二苯甲酮衍生物，其中x为3并且y为6。真空去除溶剂后，分离出41.7g(82％)油。
使用表1中的配制物将实验性表面活性剂配制成油漆。使用顶置式混合器在连续搅拌下依序添加成分。ECOSURFTMS A-9是一种非反应性表面活性剂(表1中的表面活性剂)，其添加到比较实例中以保持表面活性剂水平恒定。C1和C2分别是指比较实例1和2。C1是不含任何光引发剂的油漆配制物，并且C2是含二苯甲酮的配制物。
消泡剂是指DOWSILTM 8590消泡剂；杀微生物剂是指ROCIMATM 63杀微生物剂；丙烯酸粘合剂是指具有以下成分的单级聚合物：22丙烯酸丁酯/27 2-丙烯酸乙基己酯/47.25甲基丙烯酸甲酯/2.5甲基丙烯酸/1.25甲基丙烯酸脲基酯，z平均粒度为107nm，固体重量百分比对于本发明实例和C1(不含二苯甲酮)为46.1％，并且对于C2为45.3％。BzP是指二苯甲酮；Optifilm 400指Optifilm Enhancer 400聚结剂；RM-3000是指ACRYSOLTM RM-3000增稠剂；RM-8W是指ACRYSOLTM RM-8W增稠剂。BzP Ex1-BzP Ex4是指实例1-4的二苯甲酮衍生物。DOWSIL、ROCIMA、ACRYSOL和ECOSURF均为陶氏化学公司(The Dow Chemical Company)或其附属公司的商标。
表1.油漆配制物
| 油漆实例编号 | 1 | 2 | 3 | 4 | C1 | C2 |
| 材料 | (g) | (g) | (g) | (g) | (g) | (g) |
| 水 | 8.11 | 8.11 | 8.11 | 8.11 | 8.11 | 7.02 |
| 消泡剂 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 | 0.10 |
| Ti-Pure R-746TiO<sub>2</sub> | 25.83 | 25.83 | 25.83 | 25.83 | 25.83 | 25.83 |
| 杀微生物剂 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 | 1.10 |
| 丙烯酸粘合剂 | 64.26 | 64.26 | 64.26 | 64.26 | 64.26 | |
| 含BzP的丙烯酸粘合剂 | 65.36 | |||||
| Optifilm 400 | 0.89 | 0.89 | 0.89 | 0.89 | 0.89 | 0.89 |
| RM-3000 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| RM-8W | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
| BzP Ex1 | 0.30 | |||||
| BzP Ex2 | 0.30 | |||||
| BzP Ex3 | 0.30 | |||||
| BzP Ex4 | 0.30 | |||||
| 表面活性剂 | 0.30 | 0.30 | ||||
| 总计 | 101.99 | 101.99 | 101.99 | 101.99 | 101.99 | 102.00 |
保光性测试
根据ASTM-D 4587，油漆和相关涂料的荧光UV凝结暴露标准操作规程(StandardPractice for Fluorescent UV-Condensation Exposures of Paint and RelatedCoatings)，使用QUV仪器(Q-Lab)进行加速风化。用10密耳的施料器将油漆配制物涂在经过铬酸盐处理的铝板上，并且在受控环境室(25℃，50％RH)中干燥过夜。然后将板以45°角朝南放置在室外(宾夕法尼亚州科利奇维尔(Collegeville,PA))，持续6天。在室外暴露后，进行初始光泽度测量。将样品放置于QUV中，并暴露于由以下组成的循环：在60℃下UV暴露(0.89W/m2，UVA灯)8h，接着在50℃下4h的黑暗凝结时段。在2000h暴露结束时，对样品进行最终光泽度测量。使用BYK Gardner micro-TRI光泽度仪测量光泽度。表2示出2006h暴露后的Δ60°光泽度。
表2-2006h暴露后的Δ60°光泽度
| 油漆编号 | Δ60°光泽度 |
| 1 | -18.7 |
| 2 | -26.7 |
| 3 | -38.9 |
| 4 | -31.1 |
| C1 | -50.7 |
| C2 | -47.5 |
数据展示，与含有二苯甲酮或不含光引发剂的配制物相比，含有本发明的二苯甲酮衍生物的油漆配制物展现Δ60°光泽度上的变动明显降低。尽管不受理论的束缚，但认为相比于二苯甲酮，二苯甲酮衍生物观察到的改良保光性可能源于薄膜内分布和稳定性的差异。相对易挥发的二苯甲酮将更容易迁移通过薄膜，并且从油漆表面过早地反应或蒸发，从而导致漆膜的表面交联。相反，本发明的二苯甲酮衍生物不挥发，并且因此无法从薄膜中蒸发。随着油漆表面的磨损，用于聚合物交联的额外光引发剂的可用性引起改良保光性。
进一步认为，本发明的有效性源于化合物的表面活性性质：疏水物(二苯甲酮)与亲水物(PO-EO低聚物)的组合将使化合物迁移到胶乳/水或水/空气界面；干燥后，光引发剂可优选位于薄膜表面。亲水物的cLog P似乎很重要；通过改变衍生物的PO(亲水性较低)和EO(亲水性较高)基团，可调节油漆配制物的水敏感性和保光性能。
Claims (6)
1.一种化合物，其为式1的羟基封端的氧化烯基团(R)取代的二苯甲酮：
其中R是1到13个氧化丙烯基团与5到20个氧化乙烯基团的组合，其条件是所述氧化丙烯基团与所述氧化乙烯基团的总和不大于25。
2.根据权利要求1所述的化合物，其中所述羟基封端的氧化烯基团(R)取代的所述二苯甲酮由式2表示：
其中x为2到10；并且y为6到18。
3.根据权利要求2所述的化合物，其中x为2到8；并且y为10到16；其中y大于x。
4.根据权利要求2所述的化合物，其中R的Log P计算值在-4.0到-1.2的范围内。
5.根据权利要求4所述的化合物，其中所述R的Log P计算值在-3.5到-1.3的范围内。
6.一种涂料组合物，其包含粘合剂、流变改性剂、不透明颜料和以所述涂料组合物的重量计0.04到2重量％的根据权利要求1所述的化合物的水分散体。
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