WO2020108077A1 - 一种量子点彩膜及其制备方法 - Google Patents

一种量子点彩膜及其制备方法 Download PDF

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WO2020108077A1
WO2020108077A1 PCT/CN2019/108850 CN2019108850W WO2020108077A1 WO 2020108077 A1 WO2020108077 A1 WO 2020108077A1 CN 2019108850 W CN2019108850 W CN 2019108850W WO 2020108077 A1 WO2020108077 A1 WO 2020108077A1
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quantum dots
pamam dendrimer
oil phase
quantum dot
color film
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程陆玲
杨一行
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TCL Technology Group Co Ltd
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    • 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
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • 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
    • 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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines

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  • the present disclosure relates to the field of quantum dots, in particular to a quantum dot color film and a preparation method thereof.
  • Quantum dots are one of the best candidate materials for display and lighting.
  • the development of related technologies to prepare quantum dot color films and their application in the field of lighting have attracted much attention.
  • the existing key technology for applying quantum dots to the preparation of color films is mainly to coat the quantum dots with a thick inorganic SiO 2 shell layer.
  • the silica shell layer can well seal the quantum dots from water and oxygen.
  • the quantum dots with a silica shell are relatively stable after being prepared as quantum dot color films.
  • the process of encapsulating quantum dots with silica is relatively complicated, and the single coating and monodispersity of quantum dots are not easy to control, so the existing technology needs to be improved.
  • the purpose of the present disclosure is to provide a quantum dot color film and a preparation method thereof, aiming to solve the problem that the prior art cannot realize the single coating of the quantum dot and the single Scattered issues.
  • a quantum dot color film wherein the quantum dot color film includes PAMAM dendrimers and oil phase quantum dots bound in the cavity of the PAMAM dendrimers.
  • a preparation method of quantum dot color film which includes the steps of:
  • the PAMAM dendrimer can coat and disperse the oil phase quantum dots, so that the oil phase quantum dots can effectively isolate water and oxygen, thereby keeping the quantum dot color film Stable performance.
  • FIG. 1 is a flowchart of a preferred embodiment of a method for preparing a quantum dot color film of the present disclosure.
  • the present disclosure provides a quantum dot color film and a preparation method thereof.
  • the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
  • the quantum dot color film provided in this embodiment includes PAMAM dendrimers and oil phase quantum dots bound in the cavity of the PAMAM dendrimers.
  • the present disclosure provides a flow chart of a preferred embodiment of a method for preparing a quantum dot color film. As shown in the figure, the method includes the following steps:
  • the preparation method of the quantum dot color film provided in this embodiment is simple, and can realize single coating and monodispersion of the oil phase quantum dots, so that the oil phase quantum dots can effectively isolate water and oxygen, so that the final quantum dot color film can be prepared Stable performance.
  • the mechanism for achieving the above effects is as follows:
  • the oil phase quantum dots can be combined into the cavity of the PAMAM dendrimer to realize the PAMAM dendrimers to the oil phase Coating and dispersion of quantum dots.
  • the terminal functional group of the PAMAM dendrimer has a hydrophilic effect, and the force of the cavity with a symmetrical structure of the PAMAM dendrimer is balanced with each other and the -NH-tube energy group in the cavity has a certain lipophilic effect, which makes the oil phase quantum
  • the dots can be fixed in the cavity of the PAMAM dendrimer; in addition, the reason why the oil phase quantum dots can be fixed in the cavity of the PAMAM dendrimer is also related to the -NH 2 hydrophilic functional group outside the dendrimer.
  • the water functional group is electronegative and can form a charge interaction, which allows the entire PAMAM dendrimer to expand and maintain a tree structure state, which facilitates the entry of oil phase quantum dots into the cavity of the PAMAM dendrimer; further, because of the The peripheral hydrophilic functional group of the PAMAM dendrimer has a certain electronegativity, which can prevent the oxygen in the air from entering the PAMAM dendrimer cavity, thereby enhancing the water-oxygen isolation ability of the oil phase quantum dots, making the final quantum dots produced Color film performance is stable.
  • the composite material includes PAMAM dendrimers and oil phase quantum dots bound in the cavity of the PAMAM dendrimers.
  • the PAMAM (polyamide-amine) dendrimer is obtained by reacting different molecular unit A (ethylenediamine) and molecular unit B (methyl acrylate).
  • the PAMAM dendrimer can be synthesized by a divergent method. In one step, ethylenediamine and methyl acrylate are reacted to form carboxylic acid ester. In the second step, the resulting carboxylic acid ester is reacted with excess ethylenediamine. After the above two steps, the first generation of PAMAM dendrimer can be prepared.
  • the general formula of molecular unit A and molecular unit B contained in PAMAM dendrimers of different algebras is: A(2 n +2 n-1 +...+2 n-3 )+B(2 n+1 +2 n +....+2 n-1 ), where the value of n is 3-10;
  • the general formula of the first generation PAMAM dendrimer containing molecular unit A and molecular unit B is A+4B
  • the second The generation PAMAM dendrimer contains molecular unit A and molecular unit B with the general formula 5A+8B.
  • the PAMAM dendrimer is selected from the fifth generation PAMAM dendrimer (G5), the sixth generation PAMAM dendrimer (G6), the seventh generation PAMAM dendrimer (G7), the eighth generation One or more of PAMAM dendrimer (G8), ninth generation PAMAM dendrimer (G9), tenth generation PAMAM dendrimer (G10), etc., but not limited thereto.
  • the algebra of the PAMAM dendrimer is G5-G10
  • the functional groups and functional groups can form a complete and The closed cavity, so the PAMAM dendrimers of the G5-G10 generation can be used as candidate materials for the preparation of oil-phase quantum dots in the cavity.
  • PAMAM dendrimers of different generations have cavities of different sizes, in order to facilitate the combination of the cavity in the PAMAM dendrimer and the oil phase quantum dots.
  • the PAMAM dendrimer is selected from one or more of the eighth to tenth generation PAMAM dendrimers.
  • PAMAM dendrimers increase with algebra, the larger the volume of the cavity, the easier it is to combine with the oil phase quantum dots.
  • the PAMAM dendrimer is selected from one of the eighth to tenth generation PAMAM dendrimers, the more easily the PAMAM dendrimer forms a coating state with the oil phase quantum dots.
  • the PAMAM dendrimer is one of the first to fourth generation PAMAM dendrimers, it cannot be used as a candidate for preparing the oil phase quantum dots in the cavity because it does not have a complete and closed cavity. Materials; If the generation number of PAMAM dendrimers is greater than G10, due to its large molecular weight, it will easily form a precipitate when it is dispersed in a solvent, so it cannot be used as a candidate material for preparing oil-phase quantum dots in the cavity.
  • the oil phase quantum dots are selected from one or more of binary phase quantum dots, ternary phase quantum dots, and quaternary phase quantum dots, but are not limited thereto.
  • the binary phase quantum dots are selected from one or more of CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, and HgS, but are not limited thereto.
  • the ternary phase quantum dots are selected from Zn X Cd 1-X S, Cu X In 1-X S, Zn X Cd 1-X Se, Zn X Se 1-X S, Zn X Cd 1-X Te and PbSe One or more of X S 1-X , but not limited thereto.
  • the quaternary phase quantum dots are selected from Zn X Cd 1-X S/ZnSe, Cu X In 1-X S/ZnS, Zn X Cd 1-X Se/ZnS, CuInSeS, Zn X Cd 1-X Te/ZnS And one or more of PbSe X S 1-X /ZnS, but not limited thereto.
  • the ligand on the surface of the oil phase quantum dots is selected from oleic acid, oleylamine, octylamine, trioctylphosphorus, trioctyloxyphosphorus, octadecylphosphoric acid, and tetradecylphosphoric acid One or more of, but not limited to.
  • the size of the oil phase quantum dots is 2-8 nm. In some embodiments, the size of the quantum dot is 4-6 nm.
  • the PAMAM dendrimer and the oil phase quantum dots are mixed in a polar solvent according to a predetermined ratio, and the oil phase quantum dots are combined in the PAMAM dendrimer cavity to prepare a composite material.
  • the generation of PAMAM dendrimers increases, the number of cavities contained in the molecules also gradually increases. Therefore, during the preparation of composite materials, PAMAM dendrimers and oil phase quantum dots added to polar solvents
  • the molar mass ratio is related to the generation number of PAMAM dendrimers.
  • the mass ratio of the molar amount of the PAMAM dendrimer to the oil phase quantum dots is 4-8 mmol: 10 mg
  • the PAMAM dendrimer and the oil phase quantum dots are added to a polar solvent and mixed.
  • the mass ratio of the molar amount of the PAMAM dendrimer to the oil phase quantum dots is 3-6 mmol: 10 mg
  • the PAMAM dendrimer and the oil phase quantum dots are added to a polar solvent and mixed.
  • the mass ratio of the molar amount of the PAMAM dendrimer to the oil phase quantum dots is 2-4 mmol: 10 mg
  • the PAMAM dendrimer and the oil phase quantum dots are added to a polar solvent and mixed.
  • the mass ratio of the molar amount of the PAMAM dendrimer to the oil phase quantum dots is 1-2 mmol: 10 mg
  • the PAMAM dendrimer and the oil phase quantum dots are added to a polar solvent and mixed.
  • the mass ratio of the molar amount of the PAMAM dendrimer to the oil phase quantum dot is 0.5-1 mmol: 10 mg
  • the PAMAM dendrimer and the oil phase quantum dots are added to a polar solvent and mixed.
  • the mass ratio of the molar amount of the PAMAM dendrimer to the oil phase quantum dot is 0.1-0.5 mmol: 10 mg .
  • the PAMAM dendrimer and the oil phase quantum dots are added to a polar solvent and mixed.
  • the PAMAM dendrimer and the oil phase quantum dots are added to a polar solvent and stirred at a stirring speed of 5000rpm-10000rpm, so that the oil phase quantum dots are combined in the PAMAM dendrimer cavity To produce composite materials.
  • the PAMAM dendrimer and the oil phase quantum dot need to be stirred at a speed of 5000rpm-10000rpm Perform high-speed stirring.
  • the PAMAM dendrimer and the oil phase quantum dots are added to the polarity under an inert atmosphere at 60-200°C Stir in the solvent at a stirring speed of 5000rpm-10000rpm for 1-24h to combine the oil phase quantum dots in the PAMAM dendrimer cavity to prepare a composite material.
  • the composite material obtained in the step S100 is dispersed in a polar solvent again to prepare a composite material solution.
  • the composite material solution is prepared into a film and annealed by coating.
  • the quantum dot color film with stable performance is prepared.
  • the present disclosure also provides a quantum dot color film, prepared by the preparation method of the present disclosure, wherein the material of the quantum dot color film includes PAMAM dendrimers and oil bound in the cavity of the PAMAM dendrimers Phase quantum dots.
  • the terminal functional group of the PAMAM dendrimer has a hydrophilic effect, and the force of the cavity with a symmetrical structure of the PAMAM dendrimer is balanced with each other and the -NH-tube energy group in the cavity has a certain lipophilic effect, which makes the oil phase quantum
  • the dots can be fixed in the cavity of the PAMAM dendrimer; in addition, the reason why the oil phase quantum dots can be fixed in the cavity of the PAMAM dendrimer is also related to the -NH 2 hydrophilic functional group outside the dendrimer.
  • the water functional group is electronegative and can form a charge interaction, which allows the entire PAMAM dendrimer to expand and maintain a tree structure state, which facilitates the entry of oil phase quantum dots into the cavity of the PAMAM dendrimer; further, because of the The peripheral hydrophilic functional group of the PAMAM dendrimer has a certain electronegativity, which can prevent the oxygen in the air from entering the PAMAM dendrimer cavity, thereby enhancing the water-oxygen isolation ability of the oil phase quantum dots, making the final quantum dots produced Color film performance is stable.
  • the present disclosure prepares a composite material by mixing PAMAM dendrimers and oil-phase quantum dots in a polar solvent to combine the oil-phase quantum dots in the cavity of the PAMAM dendrimer;
  • the PAMAM dendrimer in the composite material can realize the coating and dispersion of the oil phase quantum dots, so that the oil phase quantum dots can effectively isolate water and oxygen; after the composite material is deposited and annealed into a film, a stable performance quantum can be prepared Point color film.

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Abstract

公开一种量子点彩膜及其制备方法，其中，所述量子点彩膜的材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的油相量子点。本公开提供的量子点彩膜中，所述PAMAM树形分子可实现对油相量子点的包覆与分散，使得油相量子点能够有效隔绝水氧，从而使量子点彩膜保持稳定的性能。

Description

一种量子点彩膜及其制备方法 技术领域
本公开涉及量子点领域，尤其涉及一种量子点彩膜及其制备方法。
背景技术
量子点是作为显示、照明最好的候选材料之一，开发相关技术制备量子点彩膜应用到照明领域备受关注。
现有将量子点应用于制备彩膜的关键技术主要是对量子点进行包覆一层厚厚的SiO 2无机壳层，二氧化硅壳层能够很好的使量子点隔绝水氧，包裹有二氧化硅壳层的量子点制备成量子点彩膜后相对稳定。但是利用二氧化硅包裹量子点的过程比较复杂，并且量子点的单包覆以及单分散性不好控制，因此现有技术有待改进。
发明内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点彩膜及其制备方法，旨在解决现有技术在制备量子点彩膜过程中无法实现对量子点的单包覆以及单分散的问题。
本公开的技术方案如下：
一种量子点彩膜，其中，所述量子点彩膜包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的油相量子点。
一种量子点彩膜的制备方法，其中，包括步骤：
将PAMAM树形分子和油相量子点在极性溶剂中混合，使所述油相量子点结合在所述PAMAM树形分子腔体内，制得复合材料；
将所述复合材料沉积退火成膜，制得所述量子点彩膜。
有益效果：本公开提供的量子点彩膜中，所述PAMAM树形分子可实现对油相量子点的包覆与分散，使得油相量子点能够有效隔绝水氧，从而使量子点彩膜保持稳定的性 能。
附图说明
图1为本公开一种量子点彩膜的制备方法较佳实施例的流程图。
具体实施方式
本公开提供一种量子点彩膜及其制备方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
本实施例提供的量子点彩膜包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的油相量子点。
请参阅图1，本公开提供一种量子点彩膜的制备方法较佳实施例的流程图，其中，如图所示，包括步骤：
S100、将PAMAM树形分子和油相量子点在极性溶剂中混合，使所述油相量子点结合在所述PAMAM树形分子腔体内，制得复合材料；
S200、将所述复合材料沉积退火成膜，制得所述量子点彩膜。
本实施例提供的量子点彩膜制备方法过程简单，且能够实现对油相量子点的单包覆以及单分散，使得油相量子点能够有效隔绝水氧，使最终制得的量子点彩膜性能稳定。实现上述效果的机理具体如下：
本实施例通过将PAMAM树形分子和油相量子点在极性溶剂中混合，可使得所述油相量子点结合在所述PAMAM树形分子的腔体内，以实现PAMAM树形分子对油相量子点的包覆与分散。由于PAMAM树形分子末端官能团具有亲水效应，而PAMAM树形分子具有对称结构的腔体内的作用力相互平衡并且腔体内的-NH-管能团具有一定的亲油效应，这使得油相量子点能够固定在所述PAMAM树形分子的腔体内；另外，油相量子点之所以能够被固定在PAMAM树形分子腔体内也与树形分子外的-NH 2亲水官能团有关，外围的亲水官能团具有电负性能够形成电荷相互作用，这使得整个PAMAM树 形分子舒展开保持树形结构状态，便于油相量子点进入到所述PAMAM树形分子的腔体内；进一步地，由于所述PAMAM树形分子的外围亲水官能团具有一定的电负性，这能够阻碍空气中的氧进入PAMAM树形分子腔体内，从而增强油相量子点的水氧隔绝能力，使得最终制得的量子点彩膜性能稳定。
在本实施例中，所述复合材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的油相量子点。其中，所述PAMAM(聚酰胺-胺)树形分子是由不同的分子单元A(乙二胺)和分子单元B(丙烯酸甲酯)反应得到，所述PAMAM树形分子可由发散法合成，第一步由乙二胺和丙烯酸甲酯反应生成羧酸酯，第二步将得到的羧酸酯与过量的乙二胺反应，经过上述两步反应后即可制得第一代PAMAM树形分子，重复上述两步反应即可得到具有分叉结构的更高代数的PAMAM树形分子，所述PAMAM树形分子中分叉之间形成若干个腔体，随着PAMAM树形分子代数的增加，树形分子中的各分叉之间空间距离越大腔体也越大，所述腔体的大小以各分叉之间的最小距离计算。不同代数的PAMAM树形分子所含有的分子单元A和分子单元B的通式为：A(2 n+2 n-1+...+2 n-3)+B(2 n+1+2 n+....+2 n-1)，其中n的取值为3-10；另外，第一代PAMAM树形分子含有分子单元A和分子单元B的通式为A+4B，第二代PAMAM树形分子含有分子单元A和分子单元B的通式为5A+8B。
在一些实施方式中，所述PAMAM树形分子选自第五代PAMAM树形分子(G5)、第六代PAMAM树形分子(G6)、第七代PAMAM树形分子(G7)、第八代PAMAM树形分子(G8)、第九代PAMAM树形分子(G9)和第十代PAMAM树形分子(G10)等中的一种或多种，但不限于此。当所述PAMAM树形分子的代数为G5-G10时，由于其外围具有较多的官能团(胺基)且具有电负性，所述官能团与官能团之间通过产生静电相互作用能够形成完整而又封闭的空腔，因此G5-G10代的PAMAM树形分子可以作为制备腔体内结合油相量子点的候选材料。
由于不同代数的PAMAM树形分子具有不同大小的腔体，为便于所述PAMAM树形分子内的腔体与油相量子点结合。
在一些实施方式中，所述PAMAM树形分子选自第八代至第十代PAMAM树形分 子中的一种或多种。由于PAMAM树形分子随着代数的增大，其腔体体积越大，越容易与油相量子点进行结合。在一些实施方式中，当所述PAMAM树形分子选自第八代至第十代PAMAM树形分子中的一种时，PAMAM树形分子越容易与油相量子点形成包覆状态。
若PAMAM树形分子为第一代至第四代PAMAM树形分子中的一种时，则由于其不具有完整而又封闭的腔体，因此不能够作为制备腔体内结合油相量子点的候选材料；若PAMAM树形分子的代数大于G10，则由于其分子量过大，当其分散在溶剂中时容易形成沉淀，因此也不能作为制备腔体内结合油相量子点的候选材料。
在一些实施方式中，所述油相量子点选自二元相量子点、三元相量子点和四元相量子点中的一种或多种，但不限于此。作为举例，所述二元相量子点选自CdS、CdSe、CdTe、InP、AgS、PbS、PbSe和HgS中的一种或多种，但不限于此。所述三元相量子点选自Zn XCd 1-XS、Cu XIn 1-XS、Zn XCd 1-XSe、Zn XSe 1-XS、Zn XCd 1-XTe和PbSe XS 1-X中的一种或多种，但不限于此。所述四元相量子点选自Zn XCd 1-XS/ZnSe、Cu XIn 1-XS/ZnS、Zn XCd 1-XSe/ZnS、CuInSeS、Zn XCd 1-XTe/ZnS和PbSe XS 1-X/ZnS中的一种或多种，但不限于此。
在一些实施方式中，所述油相量子点表面的配体选自油酸、油胺、辛胺、三辛基磷、三辛基氧磷、十八烷基磷酸和十四烷基磷酸中的一种或多种，但不限于此。
在一些实施方式中，为保证所述油相量子点能够结合在所述PAMAM树形分子腔体内，所述油相量子点的大小为2-8nm。在一些实施方式中，所述量子点的大小为4-6nm。
在一些实施方式中，按照预定比例将PAMAM树形分子和油相量子点在极性溶剂中混合，使所述油相量子点结合在所述PAMAM树形分子腔体内，制得复合材料。由于PAMAM树形分子随着代数的增加，其分子内所含有的腔体数量也逐渐增加，因此，在制备复合材料的过程中，向极性溶剂中加入的PAMAM树形分子与油相量子点的摩尔质量比大小与PAMAM树形分子的代数有关。
在一些实施方式中，当所述PAMAM树形分子为第五代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为4-8mmol：10mg，将所 述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
在一些实施方式中，当所述PAMAM树形分子为第六代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为3-6mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
在一些实施方式中，当所述PAMAM树形分子为第七代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为2-4mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
在一些实施方式中，当所述PAMAM树形分子为第八代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为1-2mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
在一些实施方式中，当所述PAMAM树形分子为第九代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为0.5-1mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
在一些实施方式中，当所述PAMAM树形分子为第十代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为0.1-0.5mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
在一些实施方式中，将PAMAM树形分子和油相量子点加入到极性溶剂中并以5000rpm-10000rpm的搅拌速度进行搅拌，使所述油相量子点结合在所述PAMAM树形分子腔体内，制得复合材料。在本实施例中，为保证所述油相量子点能够均匀分散并结合到所述PAMAM树形分子的腔体内，需通过5000rpm-10000rpm的搅拌速度对所述PAMAM树形分子和油相量子点进行高速搅拌。
在一些实施方式中，为保证油相量子点充分结合在所述PAMAM树形分子腔体内，在惰性氛围以及60-200℃的条件下，将PAMAM树形分子和油相量子点加入到极性溶剂中并以5000rpm-10000rpm的搅拌速度搅拌1-24h，使所述油相量子点结合在所述PAMAM树形分子腔体内，制得复合材料。
在一些实施方式中，将所述步骤S100中得到的复合材料再次分散到极性溶剂中， 制得复合材料溶液，优选采用涂布的方式将所述复合材料溶液制备成膜并进行退火处理，制得性能稳定的量子点彩膜。
进一步地，本公开还提供一种量子点彩膜，采用本公开制备方法制得，其中，所述量子点彩膜的材料包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的油相量子点。
由于PAMAM树形分子末端官能团具有亲水效应，而PAMAM树形分子具有对称结构的腔体内的作用力相互平衡并且腔体内的-NH-管能团具有一定的亲油效应，这使得油相量子点能够固定在所述PAMAM树形分子的腔体内；另外，油相量子点之所以能够被固定在PAMAM树形分子腔体内也与树形分子外的-NH 2亲水官能团有关，外围的亲水官能团具有电负性能够形成电荷相互作用，这使得整个PAMAM树形分子舒展开保持树形结构状态，便于油相量子点进入到所述PAMAM树形分子的腔体内；进一步地，由于所述PAMAM树形分子的外围亲水官能团具有一定的电负性，这能够阻碍空气中的氧进入PAMAM树形分子腔体内，从而增强油相量子点的水氧隔绝能力，使得最终制得的量子点彩膜性能稳定。
综上所述，本公开通过将PAMAM树形分子和油相量子点在极性溶剂中混合，使所述油相量子点结合在所述PAMAM树形分子的腔体内，制得复合材料；所述复合材料中的PAMAM树形分子可实现对油相量子点的包覆与分散，使得油相量子点能够有效隔绝水氧；将所述复合材料沉积退火成膜后可制得性能稳定的量子点彩膜。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。

Claims (20)

  1. 一种量子点彩膜，其特征在于，所述量子点彩膜包括PAMAM树形分子以及结合在所述PAMAM树形分子腔体内的油相量子点。
  2. 根据权利要求1所述的量子点彩膜，其特征在于，所述PAMAM树形分子选自第五代至第十代PAMAM树形分子中的一种或多种。
  3. 根据权利要求1所述的量子点彩膜，其特征在于，所述PAMAM树形分子选自第八代至第十代PAMAM树形分子中的一种或多种。
  4. 根据权利要求1所述的量子点彩膜，其特征在于，所述油相量子点选自二元相量子点、三元相量子点和四元相量子点中的一种或多种。
  5. 根据权利要求1所述的量子点彩膜，其特征在于，所述二元相量子点选自CdS、CdSe、CdTe、InP、AgS、PbS、PbSe和HgS中的一种或多种。
  6. 根据权利要求1所述的量子点彩膜，其特征在于，所述三元相量子点选自Zn XCd 1-XS、Cu XIn 1-XS、Zn XCd 1-XSe、Zn XSe 1-XS、Zn XCd 1-XTe和PbSe XS 1-X中的一种或多种。
  7. 根据权利要求1所述的量子点彩膜，其特征在于，所述四元相量子点选自Zn XCd 1-XS/ZnSe、Cu XIn 1-XS/ZnS、Zn XCd 1-XSe/ZnS、CuInSeS、Zn XCd 1-XTe/ZnS和PbSe XS 1-X/ZnS中的一种或多种。
  8. 根据权利要求1所述的量子点彩膜，其特征在于，所述油相量子点表面的配体选自油酸、油胺、辛胺、三辛基磷、三辛基氧磷、十八烷基磷酸和十四烷基磷酸中的一种或多种。
  9. 根据权利要求4所述的量子点彩膜，其特征在于，所述油相量子点的大小为2-8nm。
  10. 根据权利要求4所述的量子点彩膜，其特征在于，所述油相量子点的大小为4-6nm。
  11. 一种量子点彩膜的制备方法，其特征在于，包括步骤：
    将PAMAM树形分子和油相量子点在极性溶剂中混合，使所述油相量子点结合在所述PAMAM树形分子腔体内，制得复合材料；
    将所述复合材料沉积退火成膜，制得所述量子点彩膜。
  12. 根据权利要求11所述量子点彩膜的制备方法，其特征在于，当所述PAMAM树形分子为第五代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为4-8mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
  13. 根据权利要求11所述量子点彩膜的制备方法，其特征在于，当所述PAMAM树形分子为第六代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为3-6mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
  14. 根据权利要求11所述量子点彩膜的制备方法，其特征在于，当所述PAMAM树形分子为第七代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为2-4mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
  15. 根据权利要求11所述量子点彩膜的制备方法，其特征在于，当所述PAMAM树形分子为第八代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为1-2mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
  16. 根据权利要求11所述量子点彩膜的制备方法，其特征在于，当所述PAMAM树形分子为第九代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为0.5-1mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
  17. 根据权利要求11所述量子点彩膜的制备方法，其特征在于，当所述PAMAM树形分子为第十代PAMAM树形分子时，按所述PAMAM树形分子的摩尔量与所述油相量子点的质量比为0.1-0.5mmol：10mg，将所述PAMAM树形分子和油相量子点加入到极性溶剂中混合。
  18. 根据权利要求1所述量子点彩膜的制备方法，其特征在于，将PAMAM树形分子和油相量子点加入到极性溶剂中并以5000rpm-10000rpm的搅拌速度进行搅拌，使所 述油相量子点结合在所述PAMAM树形分子腔体内，制得复合材料。
  19. 根据权利要求14所述量子点彩膜的制备方法，其特征在于，搅拌时间为1-24h。
  20. 根据权利要求14所述量子点彩膜的制备方法，其特征在于，搅拌时的温度为60-200℃。
PCT/CN2019/108850 2018-11-28 2019-09-29 一种量子点彩膜及其制备方法 Ceased WO2020108077A1 (zh)

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