CN114516885A - 一种用于转光膜的光转换剂及其制备方法 - Google Patents
一种用于转光膜的光转换剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于转光膜的光转换剂,该光转换剂含有酮基和羟基,所述光转换剂的结构通用分子式为:[Eu2(TTA)xPA(4‑x)BDPA4]或[Eu2(TTA)xPA(4‑x)BDPA6],其中,TTA为2‑噻吩甲酰三氟丙酮,PA为吡啶‑2,6‑二甲酸,BDPA4为4,4’‑(丁烷‑1,4‑二(氧)基)双(吡啶‑2,6‑二甲酸),BDPA6为4,4’‑(丁烷‑1,4‑二(氧)基)双(吡啶‑2,6‑二甲酸);本发明还公开了一种用于转光膜的光转换剂的制备方法。通过本发明的光转换剂制得的转光膜对低频段的紫外光的吸收能力更强,可将该波段紫外光转化为植物光合作用所需的红光,有利于作物的生长。
Description
技术领域
本发明属于涉及农用转光膜技术领域,尤其是涉及一种用于转光膜的光转换剂及其制备方法。
背景技术
转光膜的使用对农业生产尤其是温室农业的发展具有重要意义,目前,普遍使用的转光膜中转光剂的类型多为以铕离子(Eu3+)为中心发光离子,β-二酮类化合物为第一配体,吡啶-2,6-二甲酸及其衍生物为中性配体合成的稀土有机配合物(β-DKs)。
文献1,Cabral F M,Gálico D A,Mazali I O and Sigoli F A,2018.Crystalstructure and temperature dependence of the photophysical properties of the[Eu(tta)3(pyphen)]complex.Inorganic Chemistry Communications,98:29-33.
文献2,Freund C,Porzio W,Giovanella U,Vignali F,Pasini M,Destri S,MechA,Di P S,Di B L and Mineo P,2011.Thiophene based europium beta-diketonatecomplexes:effect of the ligand structure on the emission quantum yield.InorgChem,50(12):5417-5429.
文献3,Ugale A,Kalyani N T and Dhoble S J,2019.Reddish orange to bluetunable emission from rare earthβ-diketonate Eu(TTA)3dpphen complex for solidstate lighting applications.Materials Science for Energy Technologies,2(1):57-66.
文献1-3则介绍了常见β-DKs的紫外吸收波段,发现该类光转换剂对紫外线的吸收波段集中于280~400nm。
文献4,Yasuda N,Wang Y,Tsukegi T,Shirai Y and Nishida H,2010.Quantitative evaluation of photodegradation and racemization of poly(l-lactic acid)under UV-C irradiation.Polymer Degradation and Stability,95(7):1238-1243.
文献5,Yeh C C,Chen C N,Li Y T,Chang C W,Cheng M Y and Chang H I,2011.The Effect of Polymer Molecular Weight and UV Radiation on PhysicalProperties and Bioactivities of PCL Films.Cllular Polymers,30(261-276).
文献6,张强,2019.基于稀土配合物的发光复合材料的制备、结构及荧光性质研究.长春:吉林大学.
文献4-6发现β-DKs对低频率紫外光吸收的缺失是限制农膜转光效率的进一步提高的重要原因,同时,该现象不利于棚膜对高能量紫外光的屏蔽,从而影响棚膜使用寿命和作物生长。
因此,需要一种能够提高转光膜的吸收能力的光转换剂。
发明内容
为了解决上述现有技术中存在的不足,本发明提供一种用于转光膜的光转换剂及其制备方法,通过该光转换剂制得的转光膜对低频段的紫外光的吸收能力更强,可将该波段紫外光转化为植物光合作用所需的红光,有利于作物的生长。
为了实现上述发明目的,本发明提供以下技术方案:
一种用于转光膜的光转换剂,该光转换剂含有酮基和羟基,所述光转换剂的结构通用分子式为:
[Eu2(TTA)xPA(4-x)BDPA4]或[Eu2(TTA)xPA(4-x)BDPA6],
其中,TTA为2-噻吩甲酰三氟丙酮,PA为吡啶-2,6-二甲酸,BDPA4为4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸),BDPA6为4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)。
进一步地,所述光转换剂的结构式为:
其核磁氢谱数据为:1HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.89(m,6H),1.69(m,2H)。
进一步地于,所述光转换剂的结构式为:
其核磁氢谱数据为:1HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.69(m,8H),1.51(m,4H)。
本发明还提出了一种用于转光膜的光转换剂的制备方法,该方法包括以下步骤:
S1、将2-噻吩甲酰三氟丙酮、吡啶-2,6-二甲酸、4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)或4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸)、氢氧化钾溶于有机溶剂中获得配体溶液;
S2、将上一步制得的配体溶液加入至铕离子溶液中,获得配体与铕离子混合溶液;
S3、在加热条件下持续搅拌配体与铕离子混合溶液以获得配合物沉淀,过滤、洗涤、真空干燥即得光转换剂。
进一步地,所述加热条件的温度为50℃-90℃,搅拌时间为0.5-2h。
进一步地,所述铕离子溶液是将六水合氯化铕(EuCl3·6H2O)溶解于蒸馏水中并加热至50℃-80℃获得。
进一步地,在所述配体溶液中,按重量份数计,各组分组成如下:
2-噻吩甲酰三氟丙酮:3.7-6.8份;
吡啶-2,6-二甲酸:2.8-5.1份;
4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)或4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸):3.0-6.4份;
氢氧化钾:3.7-6.8份;
六水合氯化铕:6.1-11.2份;
乙醇:18.4-30.0份;
水:50.1-64.5份。
根据上述技术方案,本发明具有以下优点:通过该光转换剂制得的转光膜对低频段的紫外光的吸收能力更强,可将该波段紫外光转化为植物光合作用所需的红光,有利于作物的生长。
具体实施方式
下面结合具体的实例来对本发明做进一步的详细阐述,以求更为清楚明了地理解其结构类型和使用方式,但不能以此来限制本发明专利的保护范围。
一种用于转光膜的光转换剂,该光转换剂含有酮基和羟基,所述光转换剂的结构通用分子式为:
[Eu2(TTA)xPA(4-x)BDPA4]或[Eu2(TTA)xPA(4-x)BDPA6],
其中,TTA为2-噻吩甲酰三氟丙酮,PA为吡啶-2,6-二甲酸,BDPA4为4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸),BDPA6为4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)。
进一步地,所述光转换剂的结构式为:
其核磁氢谱数据为:1HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.89(m,6H),1.69(m,2H)。
进一步地于,所述光转换剂的结构式为:
其核磁氢谱数据为:1HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.69(m,8H),1.51(m,4H)。
本发明还提出了一种用于转光膜的光转换剂的制备方法,该方法包括以下步骤:
S1、将2-噻吩甲酰三氟丙酮、吡啶-2,6-二甲酸、4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)或4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸)、氢氧化钾溶于有机溶剂中获得配体溶液;
S2、将上一步制得的配体溶液加入至铕离子溶液中,获得配体与铕离子混合溶液;
S3、在加热条件下持续搅拌配体与铕离子混合溶液以获得配合物沉淀,过滤、洗涤、真空干燥即得光转换剂。
进一步地,所述加热条件的温度为50℃-90℃,搅拌时间为0.5-2h。
进一步地,所述铕离子溶液是将六水合氯化铕(EuCl3·6H2O)溶解于蒸馏水中并加热至50℃-80℃获得。
进一步地,在所述配体溶液中,按重量份数计,各组分组成如下:
2-噻吩甲酰三氟丙酮:3.7-6.8份;
吡啶-2,6-二甲酸:2.8-5.1份;
4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)或4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸):3.0-6.4份;
氢氧化钾:3.7-6.8份;
六水合氯化铕:6.1-11.2份;
乙醇:18.4-30.0份;
水:50.1-64.5份。
实施例1:
取0.2mol EuCl3·6H2O溶解于20ml蒸馏水中得到铕离子溶液,将0.2mol 2-噻吩甲酰三氟丙酮、0.2mol吡啶-2,6-二甲酸、0.1mol 4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)分别溶解至15ml乙醇以获得配体溶液。将铕离子溶液加热至60℃,并依次加入2-噻吩甲酰三氟丙酮、吡啶-2,6-二甲酸、4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)配体溶液。保持60℃加热条件,混合液持续搅拌60min,以获得配合物沉淀。过滤、洗涤、于60℃真空干燥12h即得光转换剂。光转换剂的分子为:[Eu2(TTA)xPA(4-x)BDPA4],结构式如下:
其核磁氢谱数据为:1HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.89(m,6H),1.69(m,2H)。
实施例2:
取0.2mol EuCl3·6H2O溶解于20ml蒸馏水中得到铕离子溶液,将0.2mol 2-噻吩甲酰三氟丙酮、0.2mol吡啶-2,6-二甲酸、0.1mol 4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸)分别溶解至15ml乙醇以获得配体溶液。将铕离子溶液加热至60℃,并依次加入2-噻吩甲酰三氟丙酮、吡啶-2,6-二甲酸、4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸)配体溶液。保持60℃加热条件,混合液持续搅拌60min,以获得配合物沉淀。过滤、洗涤、于60℃真空干燥12h即得光转换剂。光转换剂的分子为:[Eu2(TTA)xPA(4-x)BDPA6],结构式如下:
其核磁氢谱数据为:1HNMR(600MHz,DMSO-d6)δ8.77(d,4H),8.54(s,4H),8.48(m,2H),7.53(d,2H),7.01-7.06(m,4H),5.60(m,2H),4.78(t,2H),4.10(t,4H),1.94-1.69(m,8H),1.51(m,4H)。
毫无疑问,本发明除了上述实施例以外还有其他类似的结构组成和使用方式。总而言之,本发明还包括其他对于本技术领域技术人员来说显而易见的变换和替代。
Claims (7)
1.一种用于转光膜的光转换剂,其特征在于,该光转换剂含有酮基和羟基,所述光转换剂的结构通用分子式为:
[Eu2(TTA)xPA(4-x)BDPA4]或[Eu2(TTA)xPA(4-x)BDPA6],
其中,TTA为2-噻吩甲酰三氟丙酮,PA为吡啶-2,6-二甲酸,BDPA4为4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸),BDPA6为4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)。
4.根据权利要求1中所述的一种用于转光膜的光转换剂的制备方法,其特征在于,该方法包括以下步骤:
S1、将2-噻吩甲酰三氟丙酮、吡啶-2,6-二甲酸、4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)或4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸)、氢氧化钾溶于有机溶剂中获得配体溶液;
S2、将上一步制得的配体溶液加入至铕离子溶液中,获得配体与铕离子混合溶液;
S3、在加热条件下持续搅拌配体与铕离子混合溶液以获得配合物沉淀,过滤、洗涤、真空干燥即得光转换剂。
5.根据权利要求4中所述的一种用于转光膜的光转换剂的制备方法,其特征在于,在所述步骤S3中,加热温度为50℃-80℃,搅拌时间为0.5-2h。
6.根据权利要求4中所述的一种用于转光膜的光转换剂的制备方法,其特征在于,所述铕离子溶液是将六水合氯化铕(EuCl3·6H2O)溶解于蒸馏水中并加热至50℃-80℃获得。
7.根据权利要求4中所述的一种用于转光膜的光转换剂的制备方法,其特征在于,在所述配体溶液中,按重量份数计,各组分组成如下:
2-噻吩甲酰三氟丙酮:3.7-6.8份;
吡啶-2,6-二甲酸:2.8-5.1份;
4,4’-(丁烷-1,4-二(氧)基)双(吡啶-2,6-二甲酸)或4,4’-(丁烷-1,6-二(氧)基)双(吡啶-2,6-二甲酸):3.0-6.4份;
氢氧化钾:3.7-6.8份;
六水合氯化铕:6.1-11.2份;
乙醇:18.4-30.0份;
水:50.1-64.5份。
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