CN113087732A - Bodipy固体荧光染料及在荧光全息防伪高亮膜上的应用 - Google Patents
Bodipy固体荧光染料及在荧光全息防伪高亮膜上的应用 Download PDFInfo
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Abstract
本发明公开了一种BODIPY固体荧光染料及其在荧光全息防伪膜上的应用,所述化合物结构如下图:
Description
技术领域
本发明涉及一种荧光染料,更具体的,涉及一种含有氢、氯、溴、烷氧基、酯基的新型BODIPY固体荧光染料,该类染料可以广泛应用在荧光全息防伪膜上和荧光防伪包装膜等领域。
背景技术
防伪技术是一门交叉边缘学科,涉及光学、化学物理学、电磁学、计算机技术、光谱技术、印刷技术、包装技术等诸多领域。当前应用较多的防伪技术主要有激光全息防伪技术,化学材料防伪技术,纸张。然而目前的一些方法造假者们也都非常熟悉,因此发现新的防伪材料和开创新的防伪技术变得非常重要。
荧光材料是指在紫外光(200-400nm)照射下,能发射可见光(400-800nm)的特种材料。荧光防伪材料是用染料或颜料溶于树脂连接料制得的,可以分为无色透明荧光和有色荧光两类,在紫外光照射下呈现特定的颜色。目前荧光全息防伪染料存在固体荧光产率低,不具有遮盖力,在部分树脂中溶解性较差,耐候性不佳,使用时需添加其它安定剂等问题。
发明内容
本发明的目的是克服以上技术难题,提供一种含有氢、氯、溴、烷氧基、酯基的新型BODIPY固体荧光染料。该染料与丙烯酸树脂结合在薄膜上可快速成膜,在紫外灯下能看到清晰的荧光。且该荧光染料简单易得,制造成本低,固体荧光量子产率高,在于荧光全息防伪包装膜领域和OLDE等方面潜力巨大。
该染料以2,3,3-三甲基吲哚衍生物与1,8-萘内酰亚胺为原料,在有机催化剂作用下经Knoevenagel缩合反应,最后生成供电子/吸电子六元氟硼荧光染料。该染料通过丙烯酸树脂与七元氟硼荧光染料结合在薄膜上成膜,在紫外灯下能看到清晰的荧光。且该荧光染料简单易得,制造成本低,固体荧光量子产率高,在于荧光全息防伪包装膜领域和OLDE等方面潜力巨大。
本发明的技术方案如下:
其中,取代基R为选自氢、氯、溴、烷氧基、酯基中的任意一种,
具体包括以下步骤:
(1)在室温下向反应瓶中加入化合物1,甲苯,化合物2、醋酸,三氯氧磷加热回流,得到反应液;
(2)分别向步骤(1)中的反应液A(化合物3)加入甲苯,三乙胺,缓慢的滴加三氟化硼乙醚络合物,升温至120℃搅拌回流半小时。
(3)将步骤(2)中的反应液分别水洗、萃取、干燥,柱层析,旋干后得到化合物I。
所述化合物1为1,8-萘内酰亚胺,所述化合物2为2,3,3-三甲基吲哚的衍生物;
化合物1与化合物2的投料摩尔比为1:1~10。由于该反应前期反应迅速,在相对化合物1较大量的化合物2的投料比,使化合物1在短时间大量反应,化合物I的收率提高。所述的步骤(1)的加热温度为80~140℃,加热时间为4~12小时。化合物3、三乙胺、三氟化硼乙醚的投料摩尔比为1:1-25:1-25。所述步骤(2)中,投料的顺序为化合物3、甲苯、三乙胺、三氟化硼乙醚。
本发明的合成步骤简单,反应条件温和,物纯化简单,产率高,固体荧光量子产率高,且反应条件易于控制,具有普遍的适用性。
附图说明
图1是化合物I-H的氢谱图。
图2是化合物I-Cl的氢谱图。
图3是化合物I-Br的氢谱图。
图4是化合物I-OMe的氢谱图。
图5是化合物I-COOEt的氢谱图。
图6是化合物I-Br的单晶图。
图7是实施例11-1得到化合物I-H与丙烯酸树脂在保鲜膜上成膜,在紫外灯(365nm)下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图。
图8是实施例11-2得到化合物I-Cl与丙烯酸树脂在保鲜膜上成膜,在紫外灯(365nm)下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图。
图9是实施例11-3得到化合物I-Br与丙烯酸树脂在保鲜膜上成膜,在紫外灯(365nm)下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图。
图10是实施例11-4得到化合物I-OMe与丙烯酸树脂在保鲜膜上成膜,在紫外灯(365nm)下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图。
图11是实施例11-5得到化合物I-COOEt与丙烯酸树脂在保鲜膜上成膜,在紫外灯(365nm)下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图。
图12是实施例12-1得到化合物I-H与丙烯酸树脂在保鲜膜上成膜,在紫外灯(365nm)下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图。
具体实施方式
下面结合实施例来进一步说明本发明,但本发明要求保护的范围并不局限于实施例表述的范围。
实施例1
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入2,3,3-三甲基吲哚(318mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)120℃加热搅拌6小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-H(382mg),产率53.4%。
I-H
实施例2
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入2,3,3-三甲基吲哚(477mg,3mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)120℃加热搅拌6小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-H(388mg),产率54.2%。当2,3,3-三甲基吲哚的量相对于实施例1增加1.5倍时,产率无明显变化。
I-H
实施例3
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入2,3,3-三甲基吲哚(318mg,2mmol),醋酸(0.24mL,4mmol),三氯氧磷(0.44mL,4mmol)120℃加热搅拌6小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-H(391mg),产率54.6%。当醋酸,三氯氧磷的量相对于实施例1增加2倍时,产率无明显变化。
I-H
实施例4
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入2,3,3-三甲基吲哚(318mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)100℃加热搅拌12小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-H(303mg),产率42.3%。当反应温度相对于实施例1降低20℃时,产率下降了11.1%。
I-H
实施例5
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入2,3,3-三甲基吲哚(318mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)140℃加热搅拌4小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-H(298mg),产率41.6%。当反应温度相对于实施例1升高20℃时,产率下降了11.8%。
I-H
实施例6
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入2,3,3-三甲基吲哚(318mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)140℃加热搅拌4小时反应完全,再向上述反应液中加入30ml甲苯溶液,三氟化硼乙醚溶液(2.00ml),在电磁搅拌下,慢慢滴加2.00ml三乙胺,升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-H(78.8mg),产率11%。当三乙胺、三氟化硼乙醚溶液的添加顺序相对于实施例5改变时,产率下降了30.6%。
实施例7
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入5-氯-2,3,3-三甲基吲哚(386mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)120℃加热搅拌6小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-Cl(405mg),产率51.7%。
I-Cl
实施例8
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入5-溴-2,3,3-三甲基吲哚(474mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)120℃加热搅拌6小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-Br(430mg),产率49.2%。
I-Br
实施例9
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入5-甲氧基-2,3,3-三甲基吲哚(378mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)120℃加热搅拌6小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到暗红色固体化合物I-OMe(378mg),产率48.7%。
I-OMe
实施例10
称取化合物1,8-萘内酰亚胺(338mg,2mmol),取40.00mL甲苯混合溶解后,再依次加入2,3,3-三甲基吲哚-5-羧酸乙酯(462mg,2mmol),醋酸(0.12mL,2mmol),三氯氧磷(0.22mL,2mmol)120℃加热搅拌6小时反应完全,再向上述反应液中加入30ml甲苯溶液,2.00ml三乙胺,在电磁搅拌下,慢慢滴加三氟化硼乙醚溶液(2.00ml),升高温度至120℃,回流30min,TLC点板检测,将产物水洗,萃取,干燥,旋蒸,过滤纯化得到枫叶红固体化合物I-H(446mg),产率51.94%。
I-COOEt
实施例11
实施例11-1
称取化合物I-H(3.58mg,0.01mmol),取1mL乙酸乙酯溶解配成0.01mol/L的母液,再取5μL母液溶入20μL的丙烯酸树脂,并均匀的涂到保鲜膜上,在30℃的温度下烘干,再把保鲜膜放于(365nm)的紫外灯下,采用OPPO Reno4 SE手机拍照,得到清晰的荧光图,图7。
实施例11-2
称取化合物I-Cl(3.92mg,0.01mmol),取1mL乙酸乙酯溶解配成0.01mol/L的母液,再取5μL母液溶入5μL的丙烯酸树脂,并均匀的涂到保鲜膜上,在30℃的温度下烘干,再把保鲜膜放于(365nm)紫外灯下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图,图8。
实施例11-3
称取化合物I-Br(4.36mg,0.01mmol),取1mL乙酸乙酯溶解配成0.01mol/L的母液,再取5μL母液溶入5μL的丙烯酸树脂,并均匀的涂到保鲜膜上,在30℃的温度下烘干,再把保鲜膜放于(365nm)紫外灯下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图,图9。
实施例11-4
称取化合物I-OMe(3.88mg,0.01mmol),取1mL乙酸乙酯溶解配成0.01mol/L的母液,再取5μL母液溶入5μL的丙烯酸树脂,并均匀的涂到保鲜膜上,在30℃的温度下烘干,再把保鲜膜放于(365nm)紫外灯下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图,图10。
实施例11-5
称取化合物I-COOEt(4.30mg,0.01mmol),取1mL乙酸乙酯溶解配成0.01mol/L的母液,再取5μL母液溶入5μL的丙烯酸树脂,并均匀的涂到保鲜膜上,在30℃的温度下烘干,再把保鲜膜放于(365nm)紫外灯下,用OPPO Reno4 SE 5G手机拍照,得到清晰的荧光图,图11。
实施例12
实施例12-1
称取化合物I-H(3.58mg,0.01mmol),取1mL乙酸乙酯溶解配成0.01mol/L的母液,再取1μL母液溶入5μL的丙烯酸树脂,并均匀的涂到保鲜膜上,在30℃的温度下烘干,再将保鲜膜放入(365nm)的紫外灯下,采用OPPO Reno4 SE手机拍照,得到清晰的荧光图,图12。当化合物I-H母液量减少5倍时(相对于实施例11-1),荧光强度较弱,不利于防伪膜的制备。
实施例12-2
称取化合物I-H(3.58mg,0.01mmol),取1mL乙酸乙酯溶解配成0.01mol/L的母液,再取10μL母液溶入5μL的丙烯酸树脂,并均匀的涂到保鲜膜上,在30℃的温度下烘干,再将保鲜膜放入(365nm)的紫外灯下,采用OPPO Reno4 SE手机拍照。可观察到,当母液量增大1倍时(相对于实施例11-1),在保鲜膜上成膜速度慢,实施例11-1成膜时,实施例12-1在保鲜膜上仍呈液体状。
表1
上述的实施例仅为本发明的优选技术方案,而不应视为对于本发明的限制,本申请中的实施例及实施例中的特征在不冲突的情况下,可以相互任意组合。本发明的保护范围应以权利要求记载的技术方案,包括权利要求记载的技术方案中技术特征的等同替换方案为保护范围。即在此范围内的等同替换改进,也在本发明的保护范围之内。
Claims (7)
3.根据权利要求2所述的方法,其特征在于:所述步骤(1)中化合物1、化合物2、醋酸、三氯氧磷的投料摩尔比为1:1-10:1-10:1-10。
4.根据权利要求2所述的方法,其特征在于:所述步骤(1)的加热回流条件为升温至100-140℃,回流4-12小时。
5.根据权利要求2所述的方法,其特征在于:所述步骤(2)中,化合物3、三乙胺、三氟化硼乙醚的投料摩尔比为1:1-25:1-25。
6.根据权利要求2所述的方法,其特征在于:所述步骤(2)中,投料的顺序为化合物3、甲苯、三乙胺、三氟化硼乙醚。
7.权利要求1所述的BODIPY固体荧光染料在荧光全息防伪膜上的应用。
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