CN110407682A - 一种铕配合物、其配体及铕配合物掺杂的聚丙烯发光材料 - Google Patents
一种铕配合物、其配体及铕配合物掺杂的聚丙烯发光材料 Download PDFInfo
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- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 82
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 81
- -1 polypropylene Polymers 0.000 title claims abstract description 35
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 34
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- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000003446 ligand Substances 0.000 title claims abstract description 27
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 229930016911 cinnamic acid Natural products 0.000 claims abstract description 8
- 235000013985 cinnamic acid Nutrition 0.000 claims abstract description 8
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 239000011118 polyvinyl acetate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
本发明公开了一种铕配合物及铕配合物掺杂的聚丙烯发光材料。所述的铕配合物及其配体的结构如式Ⅱ和式Ⅰ所示。所述铕配合物的长共轭配体的制备方法为:将乙醇钠、四氢呋喃、苯乙酮以及肉桂酸混合后在惰性气体保护下进行回流反应,反应完毕后分离纯化产物即得铕配合物的长共轭配体。所述的铕配合物的制备方法为:将铕配合物的长共轭配体以及硝酸铕加入到有机溶剂中进行加热搅拌溶解,然后滴加邻菲罗啉溶液,滴加完毕后进行加热回流反应,反应结束后分离纯化产物即得铕配合物。采用上述铕配合物掺杂到聚丙烯中得到的铕配合物掺杂的聚丙烯发光材料,既具有小分子铕配合物的发光特性,也具有聚丙烯高分子材料的良好的力学性能。
Description
技术领域
本发明涉及红光材料制备技术领域,具体涉及一种铕配合物、其配体及铕配合物掺杂的聚丙烯发光材料。
背景技术
有机电致发光器件要实现全色平板显示,需要高色纯度的红、绿、蓝三色光。然而,大多数有机材料的电致发光光谱较宽,不利于全色显示的实现。其中,红色发光的跃迁能隙小,很难与载流子传输层的能量匹配,不能有效地使电子和空穴在发光区复合。因此在有机红、绿、蓝三基色显示材料中,红色发光材料被认为是最薄弱的一环。
稀土铕配合物的发射峰主要来自于Eu3+的5D0——7F2的特征发射,不随配体的不同而发生改变,其发射峰位于617nm左右。发射谱几乎是线谱,半峰宽只有几个纳米,具有饱和的红光发射;而且,铕配合物属于三重态发光,其发光效率理论上限可达100%。
稀土配合物/聚合物复合材料是一类具有广泛应用前景的无机/聚合物材料。由于稀土自身的具有独特的化学性质和物理性质,以及在光学领域取得的成就,受到人们越来越多的关注。但是目前的研究主要集中在聚醋酸乙烯酯,聚氨酯,聚苯乙烯等极性聚合物与金属配合物上。
发明内容
本发明所要解决的首要技术问题是提供一种铕配合物的长共轭配体。
本发明所要解决的另一技术问题是提供一种铕配合物。
本发明所要解决的再一技术问题是提供一种铕配合物掺杂的聚丙烯发光材料。
本发明所要解决的上述技术问题通过以下技术方案予以实现:
一种铕配合物的长共轭配体,其特征在于,具有式Ⅰ所示的结构:
式Ⅰ所示结构的铕配合物的长共轭配体的化学命名为1,5-二苯基-4-烯-1,3-戊二酮(简称DPPD)。
一种铕配合物,具有式Ⅱ所示的结构:
在本发明中式Ⅱ所示结构的铕配合物又命名为基于稀土铕-DPPD-邻菲罗啉三元配合物。
上述铕配合物的长共轭配体的制备方法,包括如下步骤:
将乙醇钠、四氢呋喃、苯乙酮以及肉桂酸混合后在惰性气体保护下进行回流反应16~24h,反应完毕后分离纯化产物即得所述的铕配合物的长共轭配体;
所述的乙醇钠、四氢呋喃、苯乙酮以及肉桂酸的用量比为4~6g:60~100mL:10~15mL:12~18g。
最优选地,所述的乙醇钠、四氢呋喃、苯乙酮以及肉桂酸的用量比为5g:80mL:11mL:15g。
优选地,所述的惰性气体为氮气。
优选地,反应完毕后分离纯化产物的具体方法为:反应完毕后用冰醋酸酸化,再用***萃取有机层,并分别用NaHCO3、去离子水洗涤,然后旋转蒸去***,得到粘稠的淡黄色油状液体,最后用硅胶柱层析纯化即得所述的铕配合物的长共轭配体。
进一步优选地,反应完毕后用30%的冰醋酸酸化,再用***萃取有机层,并分别用5%NaHCO3、去离子水洗涤2次,然后旋转蒸去***,得到粘稠的淡黄色油状液体,最后用硅胶柱层析纯化即得所述的铕配合物的长共轭配体。
进一步优选地,所述硅胶柱层析的洗脱液选用由体积比为4:1的石油醚和乙酸乙酯组成的洗脱液。
上述铕配合物的制备方法,包含如下步骤:
将上述铕配合物的长共轭配体以及硝酸铕加入到有机溶剂中进行加热搅拌溶解,然后滴加邻菲罗啉溶液,滴加完毕后进行加热回流反应0.5~2h,反应结束后分离纯化产物即得所述的铕配合物;
所述的铕配合物的长共轭配体、硝酸铕、有机溶剂以及邻菲罗啉溶液的用量比为0.005~0.015mol:0.05~0.15mol:300~600mL:50~150mL;
所述的邻菲罗啉溶液的浓度为0.03~0.06mol/L。
最优选地,所述的铕配合物的长共轭配体、硝酸铕、有机溶剂以及邻菲罗啉溶液的用量比为0.01mol:0.1mol:400mL:100mL;
所述的邻菲罗啉溶液的浓度为0.05mol/L。
优选地,反应结束后分离纯化产物的具体方法为:反应结束后冷却,析出固体,静置过夜,过滤,滤饼经水洗、干燥后经甲苯重结晶,得浅黄色固体即得所述的铕配合物。
本发明还提供一种铕配合物掺杂的聚丙烯发光材料,其特征在于,包含上述铕配合物。
优选地,所述的铕配合物掺杂的聚丙烯发光材料,包含如下重量份的原料成分:聚丙烯98~100份;铕配合物0.1~2份。
进一步优选地,所述的铕配合物掺杂的聚丙烯发光材料,包含如下重量份的原料成分:聚丙烯99~100份;铕配合物0.1~1份。
最所述的铕配合物掺杂的聚丙烯发光材料,包含如下重量份的原料成分:聚丙烯99.5份;铕配合物0.5份。
上述铕配合物掺杂的聚丙烯发光材料的制备方法,包含如下步骤:称取聚丙烯和铕配合物,采用哈克密炼机密炼,塑化完全后制得铕配合物掺杂的聚丙烯发光材料。
有益效果:(1)本发明所述的1,5-二苯基-4-烯-1,3-戊二酮(DPPD)比经典的β-二酮化合物二苯甲酰甲烷(DBM)具有更长的共轭链和较小的空间位阻,因此形成的配合物比现有的铕配合物具有更好共轭性和共平面性;(2)式Ⅱ所示结构的铕配合物具有很好的发光性能,同时该铕配合物与聚丙烯能够很好的相容,本发明首次根据聚丙烯的特性,开发了一种能够适用于聚丙烯的发光材料;(3)采用本发明所述的铕配合物掺杂到聚丙烯中得到的铕配合物掺杂的聚丙烯发光材料,既具有小分子铕配合物的发光特性,也具有聚丙烯高分子材料的良好的力学性能,因此,所述的铕配合物掺杂的聚丙烯发光材料不但赋予了小分子铕配合物良好的力学性能,也赋予了聚丙烯良好的发光性能并能改善聚丙烯的力学性能,为使聚丙烯成为3D打印材料成为可能。
附图说明
图1为本发明基于稀土铕-DPPD-邻菲罗啉三元配合物的荧光光谱图。
图2为本发明基于稀土铕-DPPD-邻菲罗啉三元配合物的TG图。
具体实施方式
以下结合具体实施例来进一步解释本发明,但实施例对本发明不做任何形式的限定。
实施例1 1,5-二苯基-4-烯-1,3-戊二酮(DPPD)的合成
在一个250mL的三颈烧瓶中依次加入5g新制备的乙醇钠、80mL重蒸的四氢呋喃、11mL苯乙酮和15g肉桂酸,在氮气保护下电磁搅拌,回流反应20h。反应完毕后用30%的冰醋酸酸化,用***萃取有机层,并分别用5%NaHCO3、去离子水洗2次,然后旋转蒸去***,得到粘稠的淡黄色油状液体。用硅胶柱层析纯化,用石油醚(60~90℃)-乙酸乙酯(V∶V=4∶1)作洗脱液,得2.92g1,5-二苯基-4-烯-1,3-戊二酮(DPPD),产率为20%。
实施例2基于稀土铕-DPPD-邻菲罗啉三元配合物的合成
将氧化铕溶于稀硝酸中,蒸去水份,析出晶体,得硝酸铕Eu(NO3)3。在100mL三口烧瓶中,加入DPPD 2.36g(0.01mol),硝酸铕Eu(NO3)333.8g(0.1mol),95%乙醇(400mL),加热搅拌至固体溶解,滴加邻菲罗啉1g(0.005mol)的乙醇溶液(100mL),加毕加热至回流,1h后停止加热。冷却后,析出固体,静置过夜,过滤,滤饼经水洗、干燥后经甲苯重结晶,得浅黄色固体3g(0.027mol)即速搜的基于稀土铕-DPPD-邻菲罗啉三元配合物,收率为80%,熔点为278-280℃。
从图1可以看出,本实施例制备得到的基于稀土铕-DPPD-邻菲罗啉三元配合物在612nm处发出明亮的铕离子的特征光谱;与现有的铕配合物相比,本实施例制备得到的基于稀土铕-DPPD-邻菲罗啉三元配合物有更纯色的荧光。
从图2可以看出,经TG测试可知,本实施例制备得到的基于稀土铕-DPPD-邻菲罗啉三元配合物的起始分解温度大于300℃,其比现有铕配合物具有更好的热性能。
实施例3铕配合物掺杂的聚丙烯发光材料的制备
称取聚丙烯45g,实施例2制备得到的基于稀土铕-DPPD-邻菲罗啉三元配合物的合成0.5g,采用哈克密炼机密炼,塑化完全后制得铕配合物掺杂的聚丙烯发光材料。
本实施例制备得到的铕配合物掺杂的聚丙烯发光材料,既具有小分子铕配合物的发光特性,也具有聚丙烯高分子材料的良好的力学性能,因此,所述的铕配合物掺杂的聚丙烯发光材料不但赋予了小分子铕配合物良好的力学性能,也赋予了聚丙烯良好的发光性能并能改善聚丙烯的力学性能,为使聚丙烯成为3D打印材料成为可能。
Claims (10)
1.一种铕配合物的长共轭配体,其特征在于,具有式Ⅰ所示的结构:
2.一种铕配合物,其特征在于,具有式Ⅱ所示的结构:
3.权利要求1所述的铕配合物的长共轭配体的制备方法,其特征在于,包括如下步骤:
将乙醇钠、四氢呋喃、苯乙酮以及肉桂酸混合后在惰性气体保护下进行回流反应16~24h,反应完毕后分离纯化产物即得所述的铕配合物的长共轭配体;
所述的乙醇钠、四氢呋喃、苯乙酮以及肉桂酸的用量比为4~6g:60~100mL:10~15mL:12~18g。
4.根据权利要求3所述的铕配合物的长共轭配体的制备方法,其特征在于,所述的乙醇钠、四氢呋喃、苯乙酮以及肉桂酸的用量比为5g:80mL:11mL:15g。
5.根据权利要求3所述的铕配合物的长共轭配体的制备方法,其特征在于,所述的惰性气体为氮气。
6.根据权利要求3所述的铕配合物的长共轭配体的制备方法,其特征在于,反应完毕后分离纯化产物的具体方法为:反应完毕后用冰醋酸酸化,再用***萃取有机层,并分别用NaHCO3、去离子水洗涤,然后旋转蒸去***,得到粘稠的淡黄色油状液体,最后用硅胶柱层析纯化即得所述的铕配合物的长共轭配体。
7.权利要求2所述的铕配合物的制备方法,其特征在于,包含如下步骤:
将权利要求1所述的铕配合物的长共轭配体以及硝酸铕加入到有机溶剂中进行加热搅拌溶解,然后滴加邻菲罗啉溶液,滴加完毕后进行加热回流反应0.5~2h,反应结束后分离纯化产物即得所述的铕配合物;
所述的铕配合物的长共轭配体、硝酸铕、有机溶剂以及邻菲罗啉溶液的用量比为0.005~0.015mol:0.05~0.15mol:300~600mL:50~150mL;
所述的邻菲罗啉溶液的浓度为0.03~0.06mol/L。
8.权利要求7所述的铕配合物的制备方法,其特征在于,所述的铕配合物的长共轭配体、硝酸铕、有机溶剂以及邻菲罗啉溶液的用量比为0.01mol:0.1mol:400mL:100mL;
所述的邻菲罗啉溶液的浓度为0.05mol/L。
9.一种铕配合物掺杂的聚丙烯发光材料,其特征在于,包含权利要求2所述的铕配合物。
10.根据权利要求9所述的铕配合物掺杂的聚丙烯发光材料,其特征在于,包含如下重量份的原料成分:聚丙烯98~100份;铕配合物0.1~2份。
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