WO2020108080A1 - 一种量子点的配体交换方法及一种量子点复合物 - Google Patents

一种量子点的配体交换方法及一种量子点复合物 Download PDF

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WO2020108080A1
WO2020108080A1 PCT/CN2019/109078 CN2019109078W WO2020108080A1 WO 2020108080 A1 WO2020108080 A1 WO 2020108080A1 CN 2019109078 W CN2019109078 W CN 2019109078W WO 2020108080 A1 WO2020108080 A1 WO 2020108080A1
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quantum dots
pamam dendrimer
ligand exchange
exchange method
pamam
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程陆玲
杨一行
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TCL Technology Group Co Ltd
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    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
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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 materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials

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  • the present disclosure relates to the field of quantum dots, in particular to a ligand exchange method for quantum dots and a quantum dot composite.
  • Quantum dots have attracted much attention as one of the most promising nanomaterials.
  • the application of quantum dots has high requirements for their stability and solubility.
  • the main ways to change the stability of quantum dots are: preparing quantum dots with a core-shell structure, or growing a layer of silica shell on the outer layer of quantum dots; change The main ways to dissolve quantum dots are: combine some better soluble ligands on the surface of quantum dots to improve the solubility of quantum dots.
  • the existing technology still needs to be improved.
  • the purpose of the present disclosure is to provide a quantum dot ligand exchange method and a quantum dot composite, aiming to solve the problem that the prior art cannot improve the stability and solubility of quantum dots at the same time.
  • a ligand exchange method for quantum dots which includes the steps of:
  • a quantum dot composite which includes quantum dots and ligands bound to the surface of the quantum dots, the ligands are PAMAM dendrimers whose terminal functional groups are all or partly mercapto groups.
  • the present disclosure provides a ligand exchange method for quantum dots, which allows the second PAMAM dendrimer to bind to the surface of the quantum dot through the ligand exchange reaction. It has a certain charge effect, and there is a certain intermolecular force and electrostatic force between the mutual functional groups, which can make the entire second PAMAM dendrimer expand and maintain the state of the tree structure, and the surrounding dense thiol functional group molecules will also Impeding the oxygen in the air from entering the cavity of the second PAMAM dendrimer, therefore, the use of the second PAMAM dendrimer and the oil phase quantum dots for ligand exchange can effectively improve the stability of the quantum dots; in addition, The modified second PAMAM dendrimer contains a large number of sulfhydryl functional groups, of which only a small part is involved in the ligand exchange of the oil phase quantum dots, and most of the sulfhydryl functional groups are not involved in the ligand exchange. Therefore, use After the ligand exchange
  • FIG. 1 is a flowchart of a preferred embodiment of a quantum dot ligand exchange method of the present disclosure.
  • the present disclosure provides a quantum dot ligand exchange method and a quantum dot composite.
  • a quantum dot ligand exchange method and a quantum dot composite.
  • the present disclosure provides a flowchart of a preferred embodiment of a quantum dot ligand exchange method. As shown in the figure, the method includes steps:
  • the method provided by this embodiment can simultaneously improve the stability and solubility of the oil phase quantum dots.
  • the mechanism for achieving the above effects is as follows:
  • the modified mercapto functional group at the end of the second PAMAM dendrimer has a certain charge effect, and there is a certain intermolecular force and electrostatic force between the mutual functional groups, this can make the entire second PAMAM dendrimer stretch out And maintain the state of the tree structure, and the surrounding dense sulfhydryl functional group molecules will also prevent the oxygen in the air from entering the second PAMAM dendrimer cavity, so the second PAMAM dendrimer and the oil phase quantum dots are used for ligand After the exchange, it can effectively improve the stability of the quantum dots.
  • the modified second PAMAM dendrimer contains a large number of sulfhydryl functional groups, only a small part of which participates in the ligand exchange of the oil phase quantum dots. Most of the mercapto functional groups are not involved in ligand exchange. Therefore, after the second PAMAM dendrimer is used for ligand exchange with oil phase quantum dots, the solubility of quantum dots can be effectively improved.
  • the first PAMAM dendrimer is selected from the first generation first PAMAM dendrimer (G1), the second generation first PAMAM dendrimer (G2), the third generation first PAMAM dendrimer Molecule (G3), fourth generation first PAMAM dendrimer (G4), fifth generation first PAMAM dendrimer (G5), sixth generation first PAMAM dendrimer (G6), seventh generation first PAMAM One of dendrimer (G7), eighth-generation first PAMAM dendrimer (G8), ninth-generation first PAMAM dendrimer (G9) and tenth-generation first PAMAM dendrimer (G10), etc. Or more, but not limited to this.
  • the PAMAM (polyamide-amine) dendrimer is obtained by reacting different molecular units A (ethylenediamine) and molecular units B (methyl acrylate), and the first PAMAM dendrimer can be divergent Synthesis, the first step is the reaction of ethylenediamine and methyl acrylate to form a carboxylic acid ester. The second step is to react the resulting carboxylic acid ester with excess ethylenediamine. After the above two steps, the first generation can be prepared The first PAMAM dendrimer can be obtained by repeating the above two steps to obtain the first PAMAM dendrimer of higher algebra.
  • the general formula of molecular unit A and molecular unit B contained in the first PAMAM dendrimer 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; in addition, the general formula of the first-generation first PAMAM dendrimer containing molecular unit A and molecular unit B is A+4B, the second The first generation PAMAM dendrimer contains molecular unit A and molecular unit B with the general formula 5A+8B.
  • an end group modifier is added after dissolving the first PAMAM dendrimer in a polar solvent, so that the amine functional group on the first PAMAM dendrimer reacts with the end group modifier to obtain
  • the terminal functional group is a second PAMAM dendrimer having a mercapto functional group.
  • the first PAMAM dendrimer is selected from one or more of the first to fourth generation first PAMAM dendrimers.
  • the first PAMAM dendrimer has a high steric hindrance effect after being dispersed in a polar solvent.
  • a second PAMAM dendrimer whose terminal functional group is a mercapto functional group can be obtained.
  • the second PAMAM dendrimer dispersed in a non-polar solvent also has a high steric hindrance effect, which can effectively isolate oxygen in the air.
  • the polar molecule is selected from one of methanol, water, or ethanol, but is not limited thereto.
  • the terminal modifier is selected from one of p-mercaptobenzenesulfonyl chloride-based organic molecules or mercaptocarboxylic acid ester-based organic molecules, wherein the p-mercaptobenzenesulfonyl chloride-based organic molecule is selected from One or more of mercaptobenzenesulfonyl chloride, o-mercaptobenzenesulfonyl chloride and m-mercaptobenzenesulfonyl chloride, but is not limited thereto.
  • the mercaptocarboxylic acid ester organic molecules are selected from methyl mercaptooctanoate, methyl mercaptododecanoate, methyl mercaptotetradecanoate, methyl mercaptooctadecanoate, ethyl mercaptooctanoate, ethyl mercaptododecanoate, mercapto One or more of ethyl myristate and ethyl mercaptooctadecanoate, but not limited thereto.
  • the reaction formula is: Dendrimer-NH 2 +HS-C 6 H 4 -SOOCl ⁇ Dendrimer- NHOS-C 6 H 4 -HS+HCl; when the terminal modifier added to the first PAMAM dendrimer solution is methyl mercaptooctanoate, its reaction formula is: Dendrimer-NH 2 +HS-C 6 H 4 -SOOCl ⁇ Dendrimer-NHOS-C 6 H 4 -HS+HCl, wherein the Dendrimer-NH 2 is one of the first PAMAM dendrimers from the first generation to the tenth generation.
  • an end group modifier is used to convert all or part of the amine groups in the first PAMAM dendrimer into functional groups containing thiol groups.
  • the modified second PAMAM dendrimer will not change the morphology and structure of the first PAMAM dendrimer due to different terminal modifiers, and the modified second The PAMAM dendrimer has more thiol functional groups on the periphery, so that the second PAMAM dendrimer has a strong non-polarity and an effect of blocking water and oxygen.
  • the second PAMAM dendrimer and the oil phase quantum dots are mixed in a non-polar solvent according to a predetermined ratio, so that the mercapto functional group at the end of the second PAMAM dendrimer and the oil phase quantum A ligand exchange reaction occurs at the dot to obtain the quantum dot.
  • the number of thiol groups contained in the periphery of the second PAMAM dendrimer obtained after the modification process increases as the generation number of the first PAMAM dendrimer increases, so the first The amount of ligand exchange reaction between the two PAMAM dendrimers and the oil phase quantum dots is related to the algebra of the first PAMAM dendrimer.
  • the mass ratio of the molar amount of the first-generation first PAMAM dendrimer to the oil-phase quantum dots is 5-10 mmol: 100 mg
  • the second PAMAM dendrimer and the oil phase quantum dots are mixed in a non-polar solvent.
  • the mass ratio of the molar amount of the second-generation first PAMAM dendrimer to the oil phase quantum dots is 4.5-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the mass ratio of the third-generation first PAMAM dendrimer to the oil phase quantum dots is 4-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the molar ratio of the fourth-generation first PAMAM dendrimer to the oil phase quantum dots is 3.5-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the molar ratio of the fifth generation first PAMAM dendrimer to the oil phase quantum dots is 3-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the molar ratio of the sixth-generation first PAMAM dendrimer to the oil phase quantum dots is 2.5-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the molar ratio of the seventh-generation first PAMAM dendrimer to the oil phase quantum dots is 2-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the molar ratio of the eighth generation first PAMAM dendrimer to the oil phase quantum dots is 1.5-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the molar ratio of the ninth-generation first PAMAM dendrimer to the oil-phase quantum dot mass ratio is 1-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the mass ratio of the molar amount of the tenth generation first PAMAM dendrimer to the oil phase quantum dots is 0.5-10 mmol: 100 mg , Mixing the second PAMAM dendrimer with oil phase quantum dots in a non-polar solvent.
  • the second PAMAM dendrimer is mixed with the oil phase quantum dots in a non-polar solvent under an inert atmosphere at 25-200°C to make the second PAMAM dendrimer
  • the thiol functional group at the molecular end undergoes a ligand exchange reaction with the oil phase quantum dots for 30-60 min to obtain the quantum dots.
  • the ligand on the surface of the oil phase quantum dots may be one or more of a phosphine-containing ligand, a carboxylate ligand and a fatty amine ligand. Since the binding force of the mercapto group is stronger than that of the carboxyl group, amine group and phosphine group, when the second PAMAM dendrimer containing the mercapto functional group is mixed with the oil phase quantum dot in a non-polar solvent at 25-200°C , Because the binding capacity of the thiol group to the surface of the quantum dot is stronger than other groups, the thiol functional group at the end of the second PAMAM dendrimer can be combined with the original ligand on the surface of the oil phase quantum dot (for example: phosphine-containing ligand, phosphine-containing The ligand and the fatty amine ligand) undergo a ligand exchange reaction, so that the second PAMAM dendrimer binds to
  • the surface of the quantum dot is equivalent to a layer of a second PAMAM dendrimer, because the second PAMAM tree There are many thiol functional groups on the periphery of the shaped molecule, so that the second PAMAM dendrimer has a strong non-polarity and the effect of blocking water and oxygen. Therefore, by wrapping a layer of oil-soluble PAMMA dendrite around the quantum dot Molecules can simultaneously effectively improve the stability and solubility of quantum dots.
  • the phosphine-containing ligand is selected from trioctylphosphine, trioctylphosphine oxide, bisdiphenylphosphine methane, bisdiphenylphosphine ethane, bisdiphenylphosphine propane, bisdiphenyl One or more of phosphine butane, bisdiphenylphosphine ethane oxide and diphenylphosphine pyridine, but not limited thereto.
  • the carboxylate ligand is a carboxylate ligand having 8 or more carbon atoms, for example, one or more of octoate, caprate, myristate, stearate and oleate. Species, but not limited to this.
  • the fatty amine ligand is selected from one or more of n-hexylamine, octylamine, dodecylamine, and dipropylamine, but is not limited thereto.
  • 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 non-polar solvent is selected from one or more of toluene, chlorobenzene n-hexane, n-octane, and chloroform, but is not limited thereto.
  • An embodiment of the present disclosure further provides a quantum dot composite, wherein the quantum dot and a ligand bound to the surface of the quantum dot, the ligand is a PAMAM dendrimer whose terminal functional group is wholly or partially a mercapto group.
  • the present disclosure provides a ligand exchange method for quantum dots and a quantum dot composite.
  • the second PAMAM dendrimer is bound to the surface of the quantum dot through the ligand exchange reaction.
  • the mercapto functional group at the end of the second PAMAM dendrimer has a certain charge effect, and there is a certain intermolecular force and electrostatic force between the mutual functional groups, which can make the entire second PAMAM dendrimer expand and maintain the state of the tree structure.
  • the dense sulfhydryl functional group molecules on the periphery will also prevent the oxygen in the air from entering the second PAMAM dendrimer cavity.
  • the ligand exchange between the second PAMAM dendrimer and the oil phase quantum dots can effectively improve The stability of quantum dots; in addition, because the periphery of the modified second PAMAM dendrimer contains a large number of sulfhydryl functional groups, only a small part of which participates in the ligand exchange of the oil phase quantum dots, and most of the sulfhydryl functional groups are Since it does not participate in ligand exchange, the use of the second PAMAM dendrimer and oil phase quantum dots for ligand exchange can also effectively improve the solubility of quantum dots.

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Abstract

公开一种量子点的配体交换方法及一种量子点复合物，其中，所述量子点的配体交换方法包括步骤：提供一种第一PAMAM树形分子；将所述第一PAMAM树形分子中的胺基转变为含巯基的官能团，得到第二PAMAM树形分子；将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合进行配体交换，得到所述量子点。本公开通过配体交换反应使第二PAMAM树形分子结合在量子点表面，可同时实现改善量子点的稳定性和溶解性。

Description

一种量子点的配体交换方法及一种量子点复合物 技术领域
本公开涉及量子点领域，尤其涉及一种量子点的配体交换方法及一种量子点复合物。
背景技术
量子点因其作为一种最具有应用前景的纳米材料而备受关注，量子点的应用对其稳定性和溶解性具有较高的要求。
改善量子点的稳定性和溶解性的方式有很多，其中改变量子点稳定性的方式主要有：制备核壳结构的量子点，或在量子点外层生长一层二氧化硅壳层等；改变量子点溶解性的方式主要有：在量子点表面结合一些溶解性较佳的配体来改善量子点的溶解性。然而，现有技术中并没有一种能够同时改善量子点稳定性和溶解性的技术手段，因此现有技术还有待于改进。
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的配体交换方法及一种量子点复合物，旨在解决现有技术不能同时改善量子点稳定性和溶解性的问题。
本公开的技术方案如下：
一种量子点的配体交换方法，其中，包括步骤：
提供一种第一PAMAM树形分子；
将所述第一PAMAM树形分子中的胺基转变为含巯基官能团，得到第二PAMAM树形分子；
将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合进行配体交换，得到所述量子点。
一种量子点复合物，其中，包括量子点和结合在所述量子点表面的配体，所述配体为末梢官能团全部或部分为巯基的PAMAM树形分子。
有益效果：本公开提供一种量子点的配体交换方法，通过配体交换反应使第二PAMAM树形分子结合在量子点表面，由于经过改性处理的第二PAMAM树形分子末梢的巯基官能团具有一定的电荷效应，且相互官能团之间具有一定的分子间作用力和静电力，这能够使得整个第二PAMAM树形分子舒展开并保持树形结构状态，而且外围密集的巯基官能团分子也会阻碍空气中的氧进入到第二PAMAM树形分子腔体内，因此利用所述第二PAMAM树形分子与油相量子点进行配体交换后，能够有效地改善量子点的稳定性；另外，由于经过改性处理的第二PAMAM树形分子的外围含有大量的巯基官能团，其中只有一小部分参与油相量子点的配体交换，而大部分的巯基官能团都未参与配体交换，因此，利用所述第二PAMAM树形分子与油相量子点进行配体交换后，还能够有效地改善量子点的溶解性。
附图说明
图1为本公开一种量子点的配体交换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的配体交换方法及一种量子点复合物，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。
请参阅图1，本公开提供一种量子点的配体交换方法较佳实施例的流程图，其中，如图所示，包括步骤：
S100、提供一种第一PAMAM树形分子；
S200、将第一PAMAM树形分子中的胺基转变为含巯基官能团，得到第二PAMAM树形分子；
S300、将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合进行配体交换，得到所述量子点。
本实施例提供的方法能够同时实现改善油相量子点的稳定性和溶解性。实现上述效 果的机理具体如下：
由于经过改性处理的第二PAMAM树形分子末梢的巯基官能团具有一定的电荷效应，且相互官能团之间具有一定的分子间作用力和静电力，这能够使得整个第二PAMAM树形分子舒展开并保持树形结构状态，而且外围密集的巯基官能团分子也会阻碍空气中的氧进入到第二PAMAM树形分子腔体内，因此利用所述第二PAMAM树形分子与油相量子点进行配体交换后，能够有效地改善量子点的稳定性；另外，由于经过改性处理的第二PAMAM树形分子的外围含有大量的巯基官能团，其中只有一小部分参与油相量子点的配体交换，而大部分的巯基官能团都未参与配体交换，因此，利用所述第二PAMAM树形分子与油相量子点进行配体交换后，还能够有效地改善量子点的溶解性。
在一些实施方式中，所述第一PAMAM树形分子选自第一代第一PAMAM树形分子(G1)、第二代第一PAMAM树形分子(G2)、第三代第一PAMAM树形分子(G3)、第四代第一PAMAM树形分子(G4)、第五代第一PAMAM树形分子(G5)、第六代第一PAMAM树形分子(G6)、第七代第一PAMAM树形分子(G7)、第八代第一PAMAM树形分子(G8)、第九代第一PAMAM树形分子(G9)和第十代第一PAMAM树形分子(G10)等中的一种或多种，但不限于此。
具体来讲，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，所述第一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第一PAMAM树形分子，重复上述两步反应即可得到更高代数的第一PAMAM树形分子。不同代数的第一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，第一代第一PAMAM树形分子含有分子单元A和分子单元B的通式为A+4B，第二代第一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，将所述第一PAMAM树形分子溶解在极性溶剂后加入端基修饰 剂，使所述第一PAMAM树形分子上的胺基官能团与端基修饰剂发生反应，得到末梢官能团为巯基官能团的第二PAMAM树形分子。
在一些实施方式中，所述第一PAMAM树形分子选自第一代至第四代第一PAMAM树形分子中的一种或多种。
本实施例中，所述第一PAMAM树形分子分散在极性溶剂中后具有较高的空间位阻效应，当所述第一PAMAM树形分子上的胺基官能团与端基修饰剂发生反应后，可得到末梢官能团为巯基官能团的第二PAMAM树形分子，所述第二PAMAM树形分子分散在非极性溶剂中也具有较高的空间位阻效应，可有效隔绝空气中的氧气。
在一些实施方式中，所述极性分子选自甲醇、水或乙醇中的一种，但不限于此。
在一些实施方式中，所述端基修饰剂选自对巯基苯磺酰氯类有机分子或巯基羧酸酯类有机分子中的一种，其中，所述对巯基苯磺酰氯类有机分子选自对巯基苯磺酰氯、邻巯基苯磺酰氯和间巯基苯磺酰氯中的一种或多种，但不限于此。所述巯基羧酸酯类有机分子选自巯基辛酸甲酯、巯基十二酸甲酯、巯基十四酸甲酯、巯基十八酸甲酯、巯基辛酸乙酯、巯基十二酸乙酯、巯基十四酸乙酯和巯基十八酸乙酯中的一种或多种，但不限于此。作为举例，当向所述第一PAMAM树形分子溶液中加入的端基修饰剂为对巯基苯磺酰氯时，其反应式为：Dendrimer-NH 2+HS-C 6H 4-SOOCl→Dendrimer-NHOS-C 6H 4-HS+HCl；当向所述第一PAMAM树形分子溶液中加入的端基修饰剂为巯基辛酸甲酯时，其反应式为：Dendrimer-NH 2+HS-C 6H 4-SOOCl→Dendrimer-NHOS-C 6H 4-HS+HCl，其中，所述Dendrimer-NH 2为第一代至第十代第一PAMAM树形分子中的一种。可以理解的是，在一些实施例中，采用端基修饰剂将所述第一PAMAM树形分子中的全部或者部分胺基转变为含巯基的官能团。具体不同的实验条件导致转变的数量不同，但不应理解成对本公开保护范围的限制。
通过上述实施例可知，所述经过改性处理的第二PAMAM树形分子不会因为端基修饰剂的不同而改变第一PAMAM树形分子的形貌结构，并且经过改性处理后的第二PAMAM树形分子外围具有较多的巯基官能团，从而使所述第二PAMAM树形分子具有较强的非极性和阻碍水氧的效果。
在一些实施方式中，按照预定比例将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合，使所述第二PAMAM树形分子末梢的巯基官能团与所述油相量子点发生配体交换反应，得到所述量子点。
在本实施例中，由于所述第一PAMAM树形分子随着代数的增加，其在经过改性处理后得到的第二PAMAM树形分子外围所含有的巯基的数量也增加，因此所述第二PAMAM树形分子与所述油相量子点进行配体交换反应的用量关系与所述第一PAMAM树形分子的代数有关。当所述第一PAMAM树形分子为第一代第一PAMAM树形分子时，按所述第一代第一PAMAM树形分子的摩尔量与油相量子点的质量比为5-10mmol：100mg时，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第二代第一PAMAM树形分子时，按所述第二代第一PAMAM树形分子的摩尔量与油相量子点的质量比为4.5-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第三代第一PAMAM树形分子时，按所述第三代第一PAMAM树形分子的摩尔量与油相量子点的质量比为4-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第四代第一PAMAM树形分子时，按所述第四代第一PAMAM树形分子的摩尔量与油相量子点的质量比为3.5-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第五代第一PAMAM树形分子时，按所述第五代第一PAMAM树形分子的摩尔量与油相量子点的质量比为3-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第六代第一PAMAM树形分子时，按所述第六代第一PAMAM树形分子的摩尔量与油相量子点的质量比为2.5-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第七代第一PAMAM树形分子时，按所述第七代第一PAMAM树形分子的摩尔量与油相量子点的质量比为2-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第八代第一PAMAM树形分子时，按所述第八代第一PAMAM树形分子的摩尔量与油 相量子点的质量比为1.5-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第九代第一PAMAM树形分子时，按所述第九代第一PAMAM树形分子的摩尔量与油相量子点的质量比为1-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。当所述第一PAMAM树形分子为第十代第一PAMAM树形分子时，按所述第十代第一PAMAM树形分子的摩尔量与油相量子点的质量比为0.5-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。
在一些实施方式中，在惰性气氛下，在25-200℃的条件下，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合，使所述第二PAMAM树形分子末梢的巯基官能团与所述油相量子点发生配体交换反应30-60min，得到所述量子点。
在本实施例中，所述油相量子点表面的配体可以为含膦配体、羧酸盐配体和脂肪胺配体中的一种或多种。由于巯基的结合力强于羧基、胺基和膦基，因此，在25-200℃的条件下将含巯基官能团的第二PAMAM树形分子与所述油相量子点在非极性溶剂混合时，因为巯基与量子点表面的结合能力强于其它基团，所述第二PAMAM树形分子末梢的巯基官能团能够与油相量子点表面的原有配体(例如：含膦配体、含膦配体和脂肪胺配体)发生配体交换反应，使得所述第二PAMAM树形分子结合在油相量子点的表面。
也就是说，当所述第二PAMAM树形分子与所述油相量子点发生配体交换反应后，量子点表面相当于包裹了一层第二PAMAM树形分子，由于所述第二PAMAM树形分子外围具有较多的巯基官能团，从而使所述第二PAMAM树形分子具有较强的非极性和阻碍水氧的效果，因此通过在所述量子点外围包裹一层油溶性PAMMA树形分子可同时有效改善量子点的稳定性和溶解性。
在一些实施方式中，所述含膦配体选自三辛基膦、三辛基氧化膦、双二苯基膦甲烷、双二苯基膦乙烷、双二苯基膦丙烷、双二苯基膦丁烷、双二苯基膦乙烷之氧化物和二苯基膦吡啶中的一种或多种，但不限于此。所述羧酸盐配体为碳原子数大于等于8的羧酸盐配体，例如为辛酸盐、癸酸盐、十四酸盐、硬脂酸盐和油酸盐中的一种或多种，但不限于此。所述脂肪胺配体选自正己胺、辛胺、十二胺和二丙胺中的一种或多种，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，所述非极性溶剂选自甲苯、氯苯正己烷、正辛烷和氯仿中的一种或多种，但不限于此。
本公开实施例还提供一种量子点复合物，其中，所述量子点和结合在所述量子点表面的配体，所述配体为末梢官能团全部或部分为巯基的PAMAM树形分子。
综上所述，本公开提供一种量子点的配体交换方法及一种量子点复合物，通过配体交换反应使第二PAMAM树形分子结合在量子点表面，由于经过改性处理的第二PAMAM树形分子末梢的巯基官能团具有一定的电荷效应，且相互官能团之间具有一定的分子间作用力和静电力，这能够使得整个第二PAMAM树形分子舒展开并保持树形结构状态，而且外围密集的巯基官能团分子也会阻碍空气中的氧进入到第二PAMAM树形分子腔体内，因此利用所述第二PAMAM树形分子与油相量子点进行配体交换后，能够有效地改善量子点的稳定性；另外，由于经过改性处理的第二PAMAM树形分子的外围含有大量的巯基官能团，其中只有一小部分参与油相量子点的配体交换，而大部分的巯基官能团都未参与配体交换，因此，利用所述第二PAMAM树形分子与油相量子点进行配体交换后，还能够有效地改善量子点的溶解性。
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. 一种量子点的配体交换方法，其特征在于，包括步骤：
    提供一种第一PAMAM树形分子；
    将所述第一PAMAM树形分子中的胺基转变为含巯基的官能团，得到第二PAMAM树形分子；
    将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合进行配体交换反应，得到所述量子点。
  2. 根据权利要求1所述量子点的配体交换方法，其特征在于，所述第一PAMAM树形分子选自第一代至第十代第一PAMAM树形分子中的一种或多种。
  3. 根据权利要求1所述量子点的配体交换方法，其特征在于，所述第一PAMAM树形分子选自第一代至第四代第一PAMAM树形分子中的一种或多种。
  4. 根据权利要求1所述量子点的配体交换方法，其特征在于，所述将所述第一PAMAM树形分子中的胺基转变为含巯基的官能团，得到第二PAMAM树形分子的步骤包括：
    将所述第一PAMAM树形分子溶解在极性溶剂后加入端基修饰剂，使所述第一PAMAM树形分子上的胺基官能团与端基修饰剂发生反应，得到末梢官能团为巯基的第二PAMAM树形分子。
  5. 根据权利要求4所述量子点的配体交换方法，其特征在于，所述端基修饰剂选自对巯基苯磺酰氯类有机分子或巯基羧酸酯类有机分子中的一种。
  6. 根据权利要求5所述量子点的配体交换方法，其特征在于，所述对巯基苯磺酰氯类有机分子选自对巯基苯磺酰氯、邻巯基苯磺酰氯和间巯基苯磺酰氯中的一种或多种。
  7. 根据权利要求5所述量子点的配体交换方法，其特征在于，所述巯基羧酸酯类有机分子选自巯基辛酸甲酯、巯基十二酸甲酯、巯基十四酸甲酯、巯基十八酸甲酯、巯基辛酸乙酯、巯基十二酸乙酯、巯基十四酸乙酯和巯基十八酸乙酯中的一种或多种。
  8. 根据权利要求4所述量子点的配体交换方法，其特征在于，所述极性溶剂选自甲醇、水或乙醇中的一种。
  9. 根据权利要求1所述量子点的配体交换方法，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。
  10. 根据权利要求1所述量子点的配体交换方法，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。
  11. 根据权利要求1所述量子点的配体交换方法，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。
  12. 根据权利要求1所述量子点的配体交换方法，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。
  13. 根据权利要求1所述量子点的配体交换方法，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。
  14. 根据权利要求3所述量子点的配体交换方法，其特征在于，当所述第一PAMAM树形分子为第一代第一PAMAM树形分子时，按所述第一代第一PAMAM树形分子的摩尔量与油相量子点的质量比为5-10mmol：100mg时，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。
  15. 根据权利要求3所述量子点的配体交换方法，其特征在于，当所述第一PAMAM树形分子为第二代第一PAMAM树形分子时，按所述第二代第一PAMAM树形分子的摩尔量与油相量子点的质量比为4.5-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。
  16. 根据权利要求3所述量子点的配体交换方法，其特征在于，当所述第一PAMAM树形分子为第三代第一PAMAM树形分子时，按所述第三代第一PAMAM树形分子的摩尔量与油相量子点的质量比为4-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。
  17. 根据权利要求3所述量子点的配体交换方法，其特征在于，当所述第一PAMAM树形分子为第四代第一PAMAM树形分子时，按所述第四代第一PAMAM树形分子的 摩尔量与油相量子点的质量比为3.5-10mmol：100mg，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合。
  18. 根据权利要求1所述量子点的配体交换方法，其特征在于，在25-200℃的条件下，将所述第二PAMAM树形分子与油相量子点在非极性溶剂中混合反应30-60min。
  19. 根据权利要求1所述量子点的配体交换方法，其特征在于，所述非极性溶剂选自甲苯、氯苯正己烷、正辛烷和氯仿中的一种或多种。
  20. 一种量子点复合物，其特征在于，包括量子点和结合在所述量子点表面的配体，所述配体为末梢官能团全部或部分为巯基的PAMAM树形分子。
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