WO2018120968A1 - 含有聚集诱导发光性质的绿光染料的光转换膜 - Google Patents

含有聚集诱导发光性质的绿光染料的光转换膜 Download PDF

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WO2018120968A1
WO2018120968A1 PCT/CN2017/105307 CN2017105307W WO2018120968A1 WO 2018120968 A1 WO2018120968 A1 WO 2018120968A1 CN 2017105307 W CN2017105307 W CN 2017105307W WO 2018120968 A1 WO2018120968 A1 WO 2018120968A1
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conversion film
dye
light
light conversion
green light
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PCT/CN2017/105307
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French (fr)
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周鹏程
戴雷
蔡丽菲
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广东阿格蕾雅光电材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur

Definitions

  • the invention relates to a light conversion film, in particular to a kind of green light dye containing tetraphenylstyrene group having aggregation-inducing luminescence property, and is formed into a light conversion film by solution spin coating, and can be applied to a flat display.
  • flat panel displays With the continuous breakthrough of the display industry technology and the increasing market demand, flat panel displays have emerged rapidly with a series of advantages such as small size, light weight, low power consumption, low radiation, and good electromagnetic compatibility, becoming the mainstream of display technology in the 21st century. .
  • the coloring method of flat panel display plays a very important role in its production process. Its quality directly determines the color rendering effect, production cost and service life of flat panel display.
  • the mainstream technology for color display of flat panel display is to print red, green and blue fluorescent material preparation devices.
  • the mainstream technology for color display of flat panel display is to print red, green and blue fluorescent material preparation devices.
  • due to the large difference in lifetime and attenuation of the three primary color fluorescent materials it is easy to cause color cast of color display, and the three primary colors
  • the manufacturing process of the device is complicated and the cost is high.
  • people have proposed a new idea of color conversion, namely "blue source into color”.
  • the "Blue Source into Color” technology uses a blue phosphor with a single high brightness as the backlight.
  • the blue light emitted by the backlight is converted into red and green light after passing through the color conversion film, thereby realizing RGB full color display.
  • This technology not only greatly simplifies the production process of electroluminescent flat panel display, improves the color stability and uniformity of the display, but also significantly reduces the production cost of the display.
  • Materials for color conversion films can be classified into inorganic and organic materials. It has been found that, compared with inorganic phosphors, organic conversion materials not only have higher color conversion efficiency, but also have more saturated colors, so that a wider color gamut can be realized, and raw materials are cheap and easy to obtain, and molecular cutting and modification are easier. For better display.
  • the Leising team used the coumarin dye Coumarin 102 as the green light material, and Lumogen F300 used the red dye to disperse in the PMMA to prepare a green and red light conversion film, which achieved a red light conversion efficiency of more than 10%.
  • the domestic research team has also reported the preparation of organic light conversion films (Reference: Optoelectronics Letters, 2010, 6 (4), 245-248, CN105267059 A, CN103647003 A), which has obtained a wide color gamut and a light conversion rate. High organic light conversion film. .
  • the organic fluorescent color conversion film generally disperses an organic fluorescent dye having different colors uniformly in a polymer solid film by ultraviolet curing or thermal curing, and then excites the organic fluorescent color conversion film with a high-brightness blue backlight.
  • the dye molecules realize the color transition, and the converted red, green and background blue light form three primary colors of light, and finally the full color display of the electroluminescent element can be realized.
  • the commonly used organic dye molecules tend to aggregate between the molecules to cause fluorescence quenching, and hardly emit light in the film state, so in these light conversion film materials, the organic dyes are generally at a very low concentration (thousandths of a thousand). Dispersed in a transparent polymer resin, too low a concentration tends to cause insufficient absorption of light by the film. To obtain a sufficient light conversion effect, the thickness of the film must be increased, thereby causing an increase in the thickness of the entire display panel.
  • AIE aggregation-induced luminescence
  • the present invention provides a light conversion film containing a green light dye having aggregation-inducing luminescence (AIE) properties, and dispersing a green light dye having aggregation-induced luminescence properties at a high molecular weight of methyl methacrylate (PMMA).
  • AIE aggregation-inducing luminescence
  • PMMA methyl methacrylate
  • a light conversion film containing a green light dye having aggregation-inducing luminescence (AIE) property which is composed of a green light dye and a cured polymer resin, and the molecular structure of the green light dye is as described in the formula (I).
  • AIE aggregation-inducing luminescence
  • R1 and R2 are independently represented by hydrogen, C1-C4 alkyl or alkoxy
  • Ar is independently represented by a carbon-carbon double bond or a triple bond or a C6-C20 benzene or heterocyclic ring of unregistered.
  • R1 and R2 are the same.
  • R1 and R2 are represented by hydrogen or tert-butyl.
  • the compound of the formula (I) is preferably a compound having the following structure:
  • the cured polymer resin is an acrylate, an epoxy resin or a polyurethane, and the total thickness of the light conversion film is from 1 to 100 ⁇ m.
  • the method for preparing the light conversion film is to dissolve the green light dye and the cured polymer resin in toluene, spin-coat a film, dry and solidify to prepare an organic light conversion film, and fix it on a backlight.
  • the curing preparation method is heat curing or ultraviolet curing.
  • the backlight is a blue light source
  • the cured polymer resin is a methyl methacrylate (PMMA) polymer resin.
  • the blue light source is a liquid crystal panel, an OLED or an inorganic LED light source.
  • the invention adopts the green light dye of the aggregation induced luminescence (AIE) property to fabricate the light conversion film for the first time, and emits green light under the blue light source, and exhibits strong fluorescence after being formed into a solid or PMMA film, and the dye is in the solid state.
  • AIE aggregation induced luminescence
  • Figure 1 is a schematic diagram of the synthetic route of the green light dye GA1 of the present invention
  • Figure 2 is a schematic view showing the synthetic route of the green light dye GA2 of the present invention.
  • FIG. 3 UV-visible absorption spectrum of the green light dye GA1 of the present invention in toluene, dichloromethane and PMMA films and solid state
  • Figure 4 is a fluorescence emission spectrum of the green light dye GA1 of the present invention in a toluene, dichloromethane, and PMMA film and a solid state;
  • Figure 5 is an ultraviolet-visible absorption spectrum of the green light dye GA2 of the present invention in a toluene, dichloromethane, and PMMA film and a solid state;
  • Figure 6 is a fluorescence emission spectrum of the green light dye GA2 of the present invention in a toluene, dichloromethane, and PMMA film and a solid state;
  • Figure 7 is a light conversion film prepared by the green light dye GA1 of the present invention.
  • a phenylmethane derivative is condensed with a benzophenone derivative to prepare a brominated tetrastyrene.
  • a boronic acid ester of tetrastyrene is prepared by a substitution reaction using butyllithium.
  • the target dye molecule GA1 is prepared by a Suzuki coupling reaction.
  • a diphenyl-substituted benzothiadiazole is prepared by a Suzuki coupling reaction.
  • the second step uses bromine to carry out the bromination reaction.
  • the target dye molecule GA2 is prepared by a Suzuki coupling reaction.
  • Synthesis step Compound 1a (commercially available) (5.61 g, 20 mmol) was dissolved in anhydrous THF (100 mL) under nitrogen atmosphere. The reaction mixture was cooled to 0 ° C, and butyl lithium (2.2 M, 14 mL) was slowly added dropwise with stirring. After the addition, the mixture was stirred at low temperature for 1 h. Then, Compound 2a (commercially available) (10.45 g, 40 mmol) was added to the reaction mixture, and the mixture was stirred at low temperature for 1 h. The reaction was then allowed to warm to room temperature and stirred overnight.
  • the synthesis step the crude compound 3a obtained in the previous step was dissolved in anhydrous toluene (50 mL) under nitrogen atmosphere, and then TSOH . H 2 O (380 mg, 2 mmol) was added to the reaction mixture, and the mixture was heated to reflux for 12 hours, and the compound was detected by TLC. The 3a reaction is complete.
  • Post-reaction treatment The reaction was stopped, and the reaction mixture was poured into water. EtOAc (EtOAc m.
  • the crude product was purified by column chromatography to yieldd pale yellow compound 4a (5.7 g, yield 54.5%).
  • Synthesis step Compound 4a (5.7 g, 10.9 mmol), Pd(dppf)Cl 2 (400 mg, 5%), bis-pinacol borate (4.2 g, 16.4 mmol), potassium acetate (2.1) under nitrogen. g, 21.8 mmol) was dissolved in anhydrous 1,4-dioxane (70 mL), and the reaction mixture was heated to reflux temperature for 12 hours under stirring, and the compound 4a was completely reacted by TLC.
  • Synthesis step To a 250 mL reaction flask was added compound 5a (627 mg, 1.1 mmol), compound 6a (commercially available) (147 mg, 0.5 mmol), Pd 2 (dba) 3 (51 mg, 5%), tri-tert-butylphosphine ( 22 mg, 10%), K 2 CO 3 (304 mg, 2.2 mmol), toluene (5 mL) and water (1 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 100 ° C by heating. The temperature was maintained for 12 hours, and the compound 5a was completely reacted by TLC.
  • Synthesis step To a 250 mL reaction flask was added compound 6a (commercially available) (2.93 g, 10 mmol), compound 2b (commercially available) (2.68 g, 22 mmol), tetratriphenylphosphine palladium (1.15 g, 5%), K 2 CO 3 (4.14 g, 30 mmol), toluene (100 mL) and water (20 mL). The nitrogen gas was evacuated 3 times, and the temperature was raised to 80 ° C by heating. The temperature was maintained for 8 hours, and the compound 6a was completely reacted by TLC.
  • the photophysical properties of the green dyes GA1 and GA2 in the solution are to dissolve the corresponding dye in toluene or dichloromethane, the concentration of the solution is 1 ⁇ 10 -5 mol/L, and the dye-based CCF film is the dye and corresponding The proportion of PMMA is dissolved in toluene, spin-coated and then dried.
  • the photophysical properties of the dye film are determined by dissolving the dye in THF and spin-coating to prepare a film.
  • the CCF film prepared with GA1 and GA2 has good absorption of background blue light ( ⁇ max ⁇ 450nm), the emitted light is green light, and the fluorescence of GA1 and GA2 in solution is weak (QY ⁇ 50%).
  • the solid or PMMA film exhibits strong fluorescence and has typical AIE properties.
  • the present invention first applies AIE type dye molecules to organic light conversion film materials, and the dyes are strongly applied to organic light conversion film materials in solid state. Great advantage.

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  • Engineering & Computer Science (AREA)
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Abstract

本发明涉及含有聚集诱导发光(AIE)性质的绿光染料的光转换膜，由绿光染料与固化的高分子树脂组成，所述绿光染料的分子结构如式(I)所述，本发明首次采用聚集诱导发光(AIE)性质的绿光染料制成光转换膜，在蓝光光源下，能发射出绿光，制成固体或PMMA薄膜后表现出了很强的荧光，染料在固态强的发光应用于有机光转换膜材料具有很大的优势。

Description

含有聚集诱导发光性质的绿光染料的光转换膜 技术领域
本发明涉及光转换膜，具体涉及一类含有四苯乙烯基团具有聚集诱导发光性质的绿光染料，通过溶液旋涂制成光转换薄膜，可应用于平面显示。
背景技术
随着显示行业技术的不断突破和市场需求的日益增加，平板显示器以其体积小、重量轻、耗电省、辐射小、电磁兼容性好等一系列优点迅速崛起，成为21世纪显示技术的主流。平板显示器的成彩方式在其生产过程中起着非常重要的作用，它的好坏直接决定了平板显示器的显色效果，生产成本以及使用寿命。
目前平板显示器实现彩色显示的主流技术是印刷红、绿、蓝三基色荧光材料制备器件，然而，由于三基色荧光材料的寿命和衰减度差异较大，很容易造成彩色显示器的偏色，而且三原色器件的制作工艺比较复杂，成本较高。为了解决这些问题，人们开提出了一种色彩转换的新思路即“蓝源成彩”。“蓝源成彩”技术采用具有单一高亮度的蓝色荧光体作为背光源，背光源发出的蓝光经过色彩转换膜后转变成红光和绿光，从而实现RGB全彩显示。这一技术不仅可以大大简化电致发光平面显示器的生产工艺，提高显示器的色彩稳定性及均匀性，而且还能显著降低显示器的生产成本。用于色彩转换膜的材料可分为无机和有机两大类。经研究发现，相对于无机荧光粉，有机转换材料不仅具有更高的色彩转换效率，颜色也更饱和，从而可以实现更宽的色域，而且原料廉价易得，更容易进行分子的剪裁和修饰以获得更好的显示效果。
20世纪90年代，Leising团队采用香豆素类染料Coumarin 102为绿光材料，Lumogen F300为红光染料分散在PMMA中制备了绿色、红色光转换膜，获得了大于10％的红光转换效率(参考文献：Adv.Mater.,1997,9(1),33-36)。近年来国内研究团队也对有机光转换膜的制备进行了报道(参考文献：Optoelectronics Letters,2010,6(4),245-248,CN105267059 A,CN103647003 A)，得到了色域广，光转化率高的有机光转换膜。。
有机荧光色彩转换膜一般是将具有不同颜色的有机荧光染料通过紫外固化或热固化等方式均匀地分散在高分子固体薄膜中，再以高亮度的蓝色背光源激发有机荧光色彩转换膜中的染料分子以实现颜色的转变，转换得到的红光、绿光与背景的蓝光形成光的三种基色，最终可以实现电致发光元件的全彩色显示。
然而，通常采用的有机染料分子间容易发生聚集而导致荧光淬灭，在薄膜状态时几乎不发光，因此在这些光转换膜材料中，有机染料一般是以很低的浓度(千分之几)分散在透明的高分子树脂中，过低的浓度往往会导致薄膜对光的吸收不足，想要获得充分的光转换效果就必须增加膜的厚度，从而造成整个显示面板厚度的增加。
香港科技大学的唐本忠院士提出了聚集诱导发光(AIE)的概念，这类AIE型的分子在固态时具有很高的量子产率，以苯并噻二唑和四苯乙烯构成的分子其固态量子产率(QY)达到了89％(参考文献：Chem.Commun.,2011,47,8847–8849)，这类分子被广泛应用于生物荧光探针、离子检测、oled发光层材料等，然而其在有机光转换膜材料中的应用却未见报道，AIE型分子在固态时的高量子产率使其在这一领域的应用具有天然的优势。
发明内容
针对上述光转换膜，本发明提供一种含有聚集诱导发光(AIE)性质的绿光染料的光转换膜，将具有聚集诱导发光性质的绿光染料分散在甲基丙烯酸甲酯(PMMA)等高分子树脂中固化制备了光转换膜，本发明首次将这类AIE型染料分子应用于有机光转换膜材料。
含有聚集诱导发光(AIE)性质的绿光染料的光转换膜，由绿光染料与固化的高分子树脂组成，所述绿光染料的分子结构如式(I)所述，
Figure PCTCN2017105307-appb-000001
其中，R1和R2独立地表示为氢、C1-C8烷基、C1-C8烷氧基或卤素；Ar独立地表示为烷基取代或未取代的碳-碳双键或三键侨联或未侨联的C6－C30苯环或杂环，n＝0-3之间的整数。
优选：其中，R1和R2独立地表示为氢、C1-C4烷基或烷氧基，Ar独立地表示为碳-碳双键或三键侨联或未侨联的C6－C20的苯环或杂环芳环，n＝0-2之间的整数。
优选：R1、R2相同。
优选：R1和R2表示为氢、叔丁基。
优选：其中，R1和R2优选表示为氢、叔丁基，Ar独立地表示为且不限于如下所列的芳环或杂环，n＝0-2之间的整数：
Figure PCTCN2017105307-appb-000002
式(I)所述的化合物优选为具有下列结构的化合物：
Figure PCTCN2017105307-appb-000003
上述染料分子均通过Suzuki偶联反应制备：
Figure PCTCN2017105307-appb-000004
所述固化的高分子树脂是丙烯酸酯、环氧树脂或聚氨酯，所述光转换膜总厚度为1-100μm。
所述光转换膜的制备方法，为将上述绿光染料与固化的高分子树脂溶于甲苯后，再旋涂成膜，烘干后固化制备有机光转换膜，固定在背光源上。
所述固化制备方法是热固化或紫外光固化。
所述背光源为蓝光光源，固化的高分子树脂为甲基丙烯酸甲酯(PMMA)高分子树脂。
所述蓝光光源是液晶面板、OLED或者无机LED光源。
本发明首次采用聚集诱导发光(AIE)性质的绿光染料制成光转换膜，在蓝光光源下，能发射出绿光，制成固体或PMMA薄膜后表现出了很强的荧光，染料在固态强的发光应用于 有机光转换膜材料具有很大的优势。
附图说明
图1本发明绿光染料GA1的合成路线示意图
图2本发明绿光染料GA2的合成路线示意图；
图3本发明绿光染料GA1在甲苯、二氯甲烷以及PMMA薄膜和固态时的紫外-可见吸收光谱
图4本发明绿光染料GA1在甲苯、二氯甲烷以及PMMA薄膜和固态时的荧光发射光谱；
图5本发明绿光染料GA2在甲苯、二氯甲烷以及PMMA薄膜和固态时的紫外-可见吸收光谱；
图6本发明绿光染料GA2在甲苯、二氯甲烷以及PMMA薄膜和固态时的荧光发射光谱；
图7本发明绿光染料GA1制备的光转换膜。
具体实施方式
为了更详细叙述本发明，特举以下例子，但是不限于此。
绿光染料GA1的合成：
第一步采用而苯甲烷衍生物与二苯酮衍生物缩合制备溴代的四苯乙烯。
第二步使用丁基锂进行取代反应制备四苯乙烯的硼酸酯。
第三步通过Suzuki偶联反应制备目标染料分子GA1。
绿光染料GA2的合成：
第一步通过Suzuki偶联反应制备双苯基取代的苯并噻二唑。
第二步使用液溴进行溴代反应。
第三步通过Suzuki偶联反应制备目标染料分子GA2。
实施例1绿光染料GA1的合成：
Figure PCTCN2017105307-appb-000005
(1)化合物3a的合成
合成步骤：氮气保护下将化合物1a(市售)(5.61g,20mmol)溶于无水THF(100mL)，将反应液冷却至0℃，搅拌下缓慢滴加丁基锂(2.2M,14mL)，滴加完后继续低温搅拌1h， 然后向反应液中加入化合物2a(市售)(10.45g,40mmol)，继续低温搅拌1h。然后将反应液升至室温搅拌过夜。
反应后处理：反应完后将反应液倒入水中，EA(100mL*3)萃取分液，合并有机层，用无水硫酸钠干燥后减压蒸干。粗品不经过纯化直接用于下一步反应。
Figure PCTCN2017105307-appb-000006
(2)化合物4a的合成
合成步骤：氮气保护下将前一步得到的化合物3a粗品溶于无水甲苯(50mL)，然后向反应液中加入TSOH.H2O(380mg,2mmol)，加热至回流反应12小时，TLC检测化合物3a反应完全。反应后处理：停止反应，将反应液倒入水中，EA(100mL*2)萃取分液，合并有机层，用无水硫酸钠干燥后减压蒸干。粗品经柱层析得到浅黄色的化合物4a(5.7g,产率54.5％)。1H NMR(400MHz,CHLOROFORM-d)δ＝7.23-7.15(m,2H),7.15-7.04(m,7H),7.04-6.83(m,8H),1.29-1.25(m,9H),1.24(s,13H)。
Figure PCTCN2017105307-appb-000007
(3)化合物5a的合成
合成步骤：氮气保护下将化合物4a(5.7g,10.9mmol)，Pd(dppf)Cl2(400mg,5％),双联频哪醇硼酸酯(4.2g,16.4mmol),醋酸钾(2.1g,21.8mmol)溶于无水1,4-二氧六环(70mL)，然后在搅拌下将反应液加热至回流温度反应12小时，TLC检测化合物4a反应完全。
反应后处理：停止反应，将反应液倒入水中，EA(100mL*2)萃取分液，合并有机层，用无水硫酸钠干燥后减压蒸干。粗品经柱层析得到浅黄色的化合物5a(5.7g,产率54.5％)。1HNMR(400MHz,CHLOROFORM-d)δ＝7.52(d,J＝8.1Hz,2H),7.11-7.01(m,10H),6.97- 6.88(m,5H),1.32(s,9H),1.26-1.23(m,21H)。
(4)GA1的合成
Figure PCTCN2017105307-appb-000008
合成步骤：向250mL反应烧瓶中加入化合物5a(627mg,1.1mmol)，化合物6a(市售)(147mg,0.5mmol),Pd2(dba)3(51mg,5％),三叔丁基膦(22mg,10％),K2CO3(304mg,2.2mmol),甲苯(5mL)和水(1mL)。氮气排空3次，加热升温至100℃，保持此温度，反应12小时，TLC检测化合物5a反应完全。
反应后处理：停止加热，降温至20℃，将反应液倒入水中，乙酸乙酯(50mL*2)萃取分液，合并有机层，用无水硫酸钠干燥后减压蒸干。粗品经柱层析得到浅黄色的化合物GA1(0.35g,产率68.6％)。
1H NMR(400MHz,CHLOROFORM-d)δ＝7.74(s,2H),7.72(d,J＝1.8Hz,4H),7.17(s,2H),7.15(d,J＝3.8Hz,4H),7.13-7.08(m,16H),7.02(d,J＝8.3Hz,4H),6.96(d,J＝8.3Hz,4H),1.25(s,36H)。
实施例2绿光染料GA1的合成：
Figure PCTCN2017105307-appb-000009
(1)化合物3b的合成
合成步骤：向250mL反应烧瓶中加入化合物6a(市售)(2.93g,10mmol)，化合物2b(市售)(2.68g,22mmol)，四三苯基膦钯(1.15g,5％),K2CO3(4.14g,30mmol),甲苯(100mL)和水(20mL)。氮气排空3次，加热升温至80℃，保持此温度，反应8小时，TLC检测化合物6a反应完全。
反应后处理：停止加热，降温至20℃，将反应液倒入水中，EA(100mL*3)萃取分液，合并有机层，用无水硫酸钠干燥后减压蒸干。粗品经柱层析得到浅黄色的化合物3b(2.3g,产率79.8％)。1H NMR(400MHz,CHLOROFORM-d)δ＝7.97(d,J＝7.2Hz,4H),7.80(s,2H),7.61-7.53(m,4H),7.51-7.43(m,2H)。
Figure PCTCN2017105307-appb-000010
(2)化合物4b的合成
合成步骤：将化合物3b(2.3g,8.0mmol)溶于50mL氯仿，室温搅拌下向反应液中滴加液溴(2.82g,17.6mmol)，滴加完毕后继续室温搅拌过夜，TLC检测化合物3b反应完全。
反应后处理：将反应液倒入饱和的亚硫酸氢钠水溶液中，二氯甲烷(50mL*3)萃取分液，合并有机层，用无水硫酸钠干燥后减压蒸干。粗品经柱层析得到浅黄色的化合物4b(2.2g,产率49.3％)。1H NMR(400MHz,CHLOROFORM-d)δ＝7.86(d,J＝8.4Hz,4H),7.78(s,2H),7.68(d,J＝8.4Hz,4H)。
Figure PCTCN2017105307-appb-000011
(3)GA2的合成
合成步骤：向250mL反应烧瓶中加入化合物4b(223mg,0.5mmol)，5a(627mg,1.1mmol),Pd2(dba)3(51mg,5％),三叔丁基膦(22mg,10％),K2CO3(304mg,2.2mmol),甲苯(5mL)和水(1mL)。氮气排空3次，加热升温至100℃，保持此温度，反应12小时，TLC检测化合物4b反应完全。
反应后处理：停止加热，降温至20℃，将反应液倒入水中，乙酸乙酯(50mL*2)萃取分液，合并有机层，用无水硫酸钠干燥后减压蒸干。粗品经柱层析得到浅黄色的化合物GA2(0.42g,产率71.6％)。1H NMR(400MHz,CHLOROFORM-d)δ＝8.03(d,J＝8.3Hz,4H),7.86-7.81(m,2H),7.74(d,J＝8.4Hz,4H),7.42(d,J＝8.3Hz,4H),7.15-7.08(m,22H),6.98(dd,J＝8.4,15.7Hz,8H),1.27(s,18H),1.26(s,18H)。
实施例3绿光染料GA1和GA2的光物理性质测试：
绿光染料GA1和GA2在溶液中的光物理性质测试是将相应的染料溶于甲苯或二氯甲烷，溶液的浓度为1×10-5mol/L，基于染料的CCF薄膜是将染料和相应比例的PMMA溶于甲苯，经旋涂然后烘干制备，染料薄膜的光物理性质是将染料溶于THF后旋涂制备薄膜后测得。以GA1和GA2制备的CCF膜对背景蓝光(λmax≈450nm)有很好的吸收，发射出的光为绿光，GA1和GA2在溶液中的荧光较弱(QY<50％)，制成固体或PMMA薄膜后表现出了很强的荧光，具有典型的AIE性质，本发明首次将AIE型染料分子应用于有机光转换膜材料，染料在固态强的发光应用于有机光转换膜材料具有很大的优势。

Claims (10)

  1. 含有聚集诱导发光(AIE)性质的绿光染料的光转换膜，由绿光染料与固化的高分子树脂组，所述绿光染料的分子结构如式(I)所述，
    Figure PCTCN2017105307-appb-100001
    其中，R1和R2独立地表示为氢、C1-C8烷基、C1-C8烷氧基或卤素；Ar独立地表示为烷基取代或未取代的碳-碳双键或三键侨联或未侨联的C6－C30苯环或杂环，n＝0-3之间的整数。
  2. 根据权利要求1所述的光转换膜，其中，R1和R2独立地表示为氢、C1-C4烷基或烷氧基，Ar独立地表示为碳-碳双键或三键侨联或未侨联的C6－C20的苯环或杂环芳环，n＝0-2之间的整数。
  3. 根据权利要求2所述的光转换膜，R1、R2相同。
  4. 根据权利要求3所述的光转换膜，R1和R2表示为氢、叔丁基。
  5. 根据权利要求1所述的光转换膜，其中，R1和R2表示为氢、叔丁基，Ar独立地表示为如下所列的芳环之一，n＝0-3之间的整数：
    Figure PCTCN2017105307-appb-100002
  6. 根据权利要求5所述的光转换膜，为具有下列结构的化合物：
    Figure PCTCN2017105307-appb-100003
  7. 根据权利要求5所述的光转换膜，所述固化的高分子树脂是丙烯酸酯、环氧树脂或聚氨酯，所述光转换膜总厚度为1-100μm。
  8. 权利要求1－7任一所述光转换膜的制备方法，为将绿光染料与固化的高分子树脂溶于甲苯后，再旋涂成膜，烘干后固化制备有机光转换膜，固定在背光源上。
  9. 根据权利要求8所述的制备方法，所述固化制备方法是热固化或紫外光固化，所述背光源为蓝光光源，固化的高分子树脂为甲基丙烯酸甲酯高分子树脂。
  10. 根据权利要求9所述的制备方法，所述蓝光光源是液晶面板、OLED或者无机LED光源。
PCT/CN2017/105307 2016-12-27 2017-10-09 含有聚集诱导发光性质的绿光染料的光转换膜 WO2018120968A1 (zh)

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