CN115677965B - Preparation method of high-performance quantum dot compound - Google Patents
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Abstract
The invention relates to a preparation method of a high-performance quantum dot compound, wherein urea derivatives are used as a latent base catalyst, after mercaptan and alkene are polymerized under photoinitiation, the urea derivatives are decomposed to release the base catalyst under the heating of a first temperature, so that the polymerization reaction of mercaptan and isocyanate is catalyzed, the mercaptan-isocyanate and mercaptan-alkene are rapidly completed, the mercaptan-isocyanate and mercaptan-alkene are solidified step by step under different solidifying conditions, and the prepared quantum dot compound has the advantages of narrower glass transition temperature, high quantum efficiency, excellent capability of blocking water and oxygen, stable color and prolonged service life of quantum dot products.
Description
Technical Field
The invention relates to a preparation method of a high-performance quantum dot compound, in particular to a preparation method of a quantum dot compound with a mercaptan-olefin-isocyanate matrix.
Background
The traditional LED display has the advantages that the color gamut is narrow, the color fidelity of the displayed picture is poor, and the quantum dot display screen has obvious advantages in the aspects of color gamut, color fidelity and the like. Therefore, the quantum dot display technology has wide application prospect.
At present, the general structure of the quantum dot film product is that a barrier layer is used for packaging a quantum dot luminous layer in a wrapping mode, and a diffusion layer with a light diffusion function is arranged at the outermost side, wherein the quantum dot luminous layer is used for dispersing quantum dots in a polymer matrix to prevent the quantum dots from being damaged by oxygen or water. Polymer matrices generally have a high light transmittance, wherein click reactions involving thiols are widely used in the preparation of such polymer matrices. Among them, a polymerization system using thiol, isocyanate and alkene as functional monomers is reported, but the reaction between thiol and isocyanate and the reaction between thiol and alkene proceed almost simultaneously, resulting in a difficult control of the reaction process and a phenomenon of low curing degree due to the use of photo-catalysis in the areas which cannot be irradiated with light. Therefore, there is a need to have optimized polymerization conditions for thiol, isocyanate and ene polymerization systems to achieve good control of the reaction process resulting in high performance quantum dot film products.
Disclosure of Invention
The invention relates to a preparation method of a quantum dot material, which has good controllability in the preparation process, uniform matrix composition distribution, narrow glass transition temperature, high quantum efficiency, strong aging resistance and stable color in a longer time.
In one aspect of the present invention, a method is provided for preparing a quantum dot composite comprising quantum dots dispersed in a polymer matrix, wherein the polymer matrix is prepared from at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
the method for preparing the quantum dot composite comprises the following steps:
i) Providing a quantum dot material, at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
ii) mixing the quantum dot material, at least one polythiol monomer having a functionality of ≡2, at least one polyalkenyl monomer having a functionality of ≡2, and at least one polyisocyanate-based monomer having a functionality of ≡2, and a urea derivative of formula (I) and a photoinitiator;
iii) Sequentially subjecting the mixture obtained in the step ii) to illumination and first temperature heating to obtain a crosslinked polymer;
iv) optionally, heat treating the resulting crosslinked polymer at a second temperature;
the urea derivative of formula (I) has the structure:
wherein, the liquid crystal display device comprises a liquid crystal display device,
r1 is selected from one of hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl, aryl, aralkyl, -NHC (O) NR2R3 substituted C1 to C15 alkyl, -NHC (O) NR2R3 substituted C3 to C15 cycloalkyl, aryl substituted with-NHC (O) NR2R3, or aralkyl substituted with-NHC (O) NR2R 3;
r2, R3 are independently selected from hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl, or R2 and R3 together form a C3-to C10 alkylene ring;
at least one of the radicals R1, R2, R3 is not hydrogen.
In another aspect of the invention, a quantum dot article is provided.
According to the preparation method of the quantum dot compound, the urea derivative serving as the latent base catalyst is used, after the thiol and alkene are polymerized under the photoinitiation, the urea derivative is decomposed to release the base catalyst under the heating of the first temperature, so that the polymerization reaction of the thiol and isocyanate is rapidly completed, the thiol-isocyanate and the thiol-alkene are subjected to stepwise curing under different curing conditions, the curing heat control of high-quality quantum dot products is facilitated, particularly for the quantum dot products which can generate significant heat during simultaneous curing, the curing process between monomers can be uniformly carried out for thicker products, the composition uniformity is realized in the whole product, the prepared quantum dot material has the advantages of narrower glass transition temperature, high quantum efficiency, excellent capability of blocking water and oxygen, stable color and prolonged service life of the quantum dot products. The use of different urea derivatives enables control of the heat of cure.
As used herein, C1 to C15 alkyl is understood to be a linear or branched alkyl radical having a chain length of up to 15 carbon atoms, which in particular has the general formula C n H 2n+1 Where n=1 to 15, can be methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl or 1-ethylpropyl.
As used herein, C3 to C15 cycloalkyl is understood to be a mono-or bicyclic cycloalkyl having 3 to 15 carbon atoms, having the general formula C n H 2n Cycloalkyl of-1, wherein n=3 to 15, may represent 1-methyl-1-cyclopropyl, 1-methyl-1-cyclobutyl, 1-methyl-1-cyclopentyl, 1-methyl-1-cyclohexyl, 1-methyl-1-cycloheptyl, 2-methyl-1-cyclopropyl, 2-methyl-1-cyclobutyl, 2-methyl-1-cyclopentyl, 2-methyl-1-cyclohexyl, 2-methyl-1-cycloheptyl, 3-methyl-1-cyclobutyl, 3-methyl-1-cyclopentyl, 3-methyl-1-cyclohexyl, 3-dimethyl-1-cyclohexyl, 3-methyl-1-cycloheptyl, 4-methyl-1-cyclohexyl, 4-methyl-1-cycloheptyl.
Aryl as used herein denotes aromatic aryl having 3 to 20 carbon atoms, which may itself be further preferably monosubstituted or polysubstituted with C1-to C5-alkyl having the meaning indicated above, and may be phenyl, naphthyl, anthracenyl or perylenyl as aryl.
Aralkyl as used herein means a C1-C15-alkyl group having the above-mentioned meaning substituted with an aryl group having the above-mentioned meaning. Specifically, the aralkyl group is benzyl.
"Quantum dots" having tunable emission in the near Ultraviolet (UV) to far Infrared (IR) range due to the use of semiconductor materials.
Detailed Description
The invention provides a method for preparing a quantum dot composite, wherein the quantum dot composite comprises quantum dots dispersed in a polymer matrix, and the polymer matrix is prepared from at least one polythiol monomer with functionality more than or equal to 2, at least one polyalkenyl monomer with functionality more than or equal to 2 and at least one polyisocyanate-based monomer with functionality more than or equal to 2;
the method for preparing the quantum dot composite comprises the following steps:
i) Providing a quantum dot material, at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
ii) mixing the quantum dot material, at least one polythiol monomer having a functionality of ≡2, at least one polyalkenyl monomer having a functionality of ≡2, and at least one polyisocyanate-based monomer having a functionality of ≡2, and a urea derivative of formula (I) and a photoinitiator;
iii) Sequentially subjecting the mixture obtained in the step ii) to illumination and first temperature heating to obtain a crosslinked polymer;
iv) optionally, heat treating the resulting crosslinked polymer at a second temperature;
the urea derivative of formula (I) has the structure:
wherein, the liquid crystal display device comprises a liquid crystal display device,
r1 is selected from one of hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl, aryl, aralkyl, -NHC (O) NR2R3 substituted C1 to C15 alkyl, -NHC (O) NR2R3 substituted C3 to C15 cycloalkyl, aryl substituted with-NHC (O) NR2R3, or aralkyl substituted with-NHC (O) NR2R 3;
r2, R3 are independently selected from hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl or together form a C3-to C10 alkylene ring;
at least one of the radicals R1, R2, R3 is not hydrogen.
In one embodiment, among the reactive monomers of the polymer matrix, the polythiol monomer has the formula:
R x (SH) y wherein R is x Is a hydrocarbyl group or heterohydrocarbyl group having a valence of y, and y is greater than or equal to 2.
Useful polythiol monomers are selected from one or more of the following compounds:
wherein n is an integer from 2 to 10, in particular 2,3,4,5,6,7,8,9 or 10, R 1 And R is 2 Identical or different and independently selected from-CH 2 -CH(SH)CH 3 and-CH 2 -CH 2 -SH；
Or alternatively, the process may be performed,
wherein R is 3 、R 4 、R 5 And R is 6 Identical or different and independently selected from-C (O) -CH 2 -CH 2 -SH、-(O)-CH 2 -CH(SH)CH 3 、-CH 2 -C(-CH 2 -O-C(O)-CH 2 -CH 2 -SH) 3 、-C(O)-CH 2 -SH and-C (O) -CH (SH) -CH 3 ；
Or alternatively, the process may be performed,
wherein R is 7 、R 8 And R is 9 Identical or different and independently selected from-C (O) -CH 2 -CH 2 -SH、-C(O)-CH2-CH(SH)CH 3 、-C(O)-CH 2 -SH and-C (O) -CH (SH) -CH 3 。
Preferred polythiol monomers are selected from one or more of the following compounds: ethylene glycol bis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) and 1, 4-bis 3-mercaptobutyryloxybutane, tris [2- (3-mercaptopropionyloxy ] ethyl ] isocyanurate, trimethylolpropane tris (mercaptoacetate), 2, 4-bis (mercaptomethyl) -1,3, 5-triazine-2, 4-dithiol, 2, 3-bis (2-mercaptoethyl) thio) -1-propanethiol, dimercaptodiethylsulfide and ethoxylated trimethylpropyl-tris (3-mercaptopropionate). More preferred are ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylol propane tris (mercaptoacetate), trimethylol propane tris (3-mercaptopropionate), and trimethylol propane tris (mercaptoacetate).
In one embodiment, the polyisocyanate-based monomer is selected from one or more of the following compounds in the reactive monomers of the polymer matrix:
wherein m, n and p are integers of 1-10, specifically 1,2,3,4,5,6,7,8,9 or 10.
Preferred polyisocyanate-based monomers are selected from one or more of the following compounds,
in one embodiment, the polyalkenyl monomer is selected from one or more of the following compounds in the reactive monomers of the polymer matrix:
wherein m, n and p are integers of 1-10, specifically 1,2,3,4,5,6,7,8,9 or 10.
Preferred polyalkenyl monomers are selected from one or more of the following compounds,
in one embodiment, the stoichiometric molar ratio of thiol groups of the polythiol monomer, isocyanate groups of the polyisocyanate monomer, and double bond groups of the polyalkenyl in the reactive monomers of the polymer matrix is (1.4-1.8): 1-1.2): 0.8-1.2.
In one embodiment, R2, R3 in the urea derivative of formula (I) are simultaneously or independently of each other hydrogen or C1 to C15 alkyl; r1 is hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl, C1 to C15 alkyl substituted with-NHC (O) NR1R2, or C3 to C15 cycloalkyl substituted with-NHC (O) NR1R 2.
Further, the urea derivative of formula (I) is selected from the group consisting of 1-methyl urea, 1-dimethyl urea, 1, 3-dimethyl urea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethyl urea, 3- (p-chlorophenyl) -1, 1-dimethyl urea, 3-phenyl-1, 1-dimethyl urea, 3- (3, 4-dichlorophenyl) -1, 1-dimethyl urea, 1- (N, N-dimethyl urea) -3- (N, N-dimethylurea) -3, 5-trimethylcyclohexane, 1'- (methylenedi-p-phenylene) -bis- (3, 3-dimethylurea), 3- (3-trifluoromethylphenyl) -1, 1-dimethylurea, 1' - (2-methyl-m-phenylene) -bis- (3, 3-dimethylurea), 1'- (4-methyl-m-phenylene) -bis- (3, 3-dimethylurea), 1' - (p-phenylene) -bis- (3, 3-dimethylurea).
In one embodiment, after the quantum dots of the present invention are illuminated by a blue LED, the blue light of the LED is down-converted to green and red light, and the respective portions of the red, green and blue light can be controlled to achieve white light emitted by a display device containing the quantum dot article.
In the present invention, the quantum dots are selected from CdSe/ZnS, inP/ZnS, and CdS/ZnS.
In an exemplary embodiment, the quantum dot comprises a coating of external ligands bearing amino, carboxyl or mercapto groups, in particular for example mercaptopropionic acid, oleic acid, oleylamine, amino-substituted silicone carrier liquids, long chain sulfides with carboxyl end groups, preferably long chain sulfides with carboxyl end groups, such as H- [ CH (CO) 2 C 12 H 25 -n)CH 2 ] 3 -S-CH(CO 2 H)CH 2 CO 2 H,
H-[CH(CO 2 C 12 H 25 -n)CH 2 ] 5 -S-CH(CO 2 H)CH 2 CO 2 H,
n-C 12 H 25 -S-CH(CO 2 H)CH 2 CO 2 H。
In one embodiment, the urea derivative is used in step ii) in an amount of 0.01-5 wt.%, preferably 0.005-0.05 wt.%, based on the total amount of all monomers.
In one embodiment, the light conditions of step iii) are light under ultraviolet light for 10 to 20 minutes to polymerize the polythiol monomer with the polyene monomer according to the type of monomer used in the present invention during the preparation of the quantum dot composite of the present invention. Said step ii) adding a photoinitiator to initiate polymerization of the polythiol monomer and the polyene monomer. Preferably the photoinitiating energy source emits ultraviolet radiation, i.e. radiation having a wavelength between about 180 and 460 nanometers, including photoinitiating energy sources such as mercury arc lamps, carbon arc lamps, low, medium or high pressure mercury vapor lamps, turbulent plasma arc lamps, xenon flash lamps, ultraviolet light emitting diodes and ultraviolet light emitting lasers.
In one embodiment, the initiator is a photoinitiator and is capable of activation by ultraviolet radiation. Useful photoinitiators include, for example, benzoin ethers (such as benzoin methyl ether and benzoin isopropyl ether), substituted benzoin ethers, substituted acetophenones (such as 2, 2-dimethoxy-2-phenylacetophenone), and substituted alpha-ketols. Preferred photoinitiators are 2-hydroxy-2-methyl-1-phenyl-propan-1-one (IRGACURE 1173. TM., BASF corporation (BASF)), 2-dimethoxy-2-phenylacetophenone (IRGACURE 651. TM., BASF corporation (BASF)), phenylbis- (2, 4, 6-trimethylbenzoyl) phosphine oxide (IRGACURE 819, BASF corporation (BASF)). Other suitable photoinitiators include mercaptobenzothiazole, mercaptobenzoxazole and hexaarylbisimidazole. Generally, the amount of initiator is less than 5wt%, preferably less than 2 wt%.
In one embodiment, the first temperature of step iii) is 60-110 ℃, preferably 60-100 ℃, according to the urea derivatives and monomer types used in the present invention during the preparation of the quantum dot complexes of the present invention; the urea derivative used in the invention has high latency and high reactivity, and thus has high storage stability below a first temperature, so that the polymerization reaction of polythiol and polyene in the first step and the polymerization reaction of polythiol and polyisocyanate in the second step are basically carried out stepwise, and the urea derivative is decomposed to release the amine alkaline catalyst in the first temperature range, and the polymerization reaction of polythiol monomer and polyisocyanate group monomer is fast, so that the polymerization reaction of polythiol monomer and polyisocyanate group monomer can be rapidly catalyzed once released, and the curing can be completed in a short time. The reaction sequence described herein does not necessarily take place in only one reaction per reaction, but the reaction is mainly one reaction, and does not exclude the reaction accompanied by a small amount of polythiol groups and polyene groups when polythiol groups and polyisocyanate groups react, and the reaction accompanied by a small amount of polythiol groups and polyisocyanate groups when polythiol groups and polyene groups react.
In one embodiment, in the method for preparing a quantum dot composite according to the present invention, the temperature is raised again in said step iv) to allow the crosslinking reaction of the monomers or reactive groups remaining in the system to effect a further curing of the system, said second temperature in said step iv) being in the range of 100-130 ℃, preferably 105-130 ℃.
A quantum dot article, the quantum dot article comprising:
a first barrier layer;
a second barrier layer; and
a quantum dot layer between the first barrier layer and the second barrier layer, the quantum dot layer comprising a quantum dot composite prepared according to the method of the invention.
The first and second barrier layers may be formed of any useful material that protects the quantum dots from exposure to environmental contaminants (e.g., oxygen, water, and water vapor). Suitable barrier layers include, but are not limited to, polymeric films, glass films, and dielectric material films. In some embodiments, suitable materials for the first barrier layer and the second barrier layer include, for example: glass and polymers such as polyethylene terephthalate (PET), PEN, polyether or PMMA; oxides, such as silicon oxide, titanium oxide or aluminum oxide (e.g. SiO 2 、TiO 2 Or Al 2 O 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And suitable combinations thereof. It is desirable that the barrier layer is at least 90%, preferably at least 95%, transmissive to the selected wavelengths of the incident and emitted radiation.
The present invention also provides a method of making a quantum dot article comprising coating the quantum dot composite of the present invention on a first barrier layer, disposing a second barrier layer on the quantum dot composite layer, laminating the second barrier layer, and curing the quantum dot composite.
Intrusion (including edge intrusion) is defined as the loss of quantum dot performance due to intrusion of moisture and/or oxygen into the matrix. In various embodiments, the quantum dot article has a color shift d (x, y) of less than about 0.01 according to CIE1931 (x, y) rules when placed at 65 ℃ and 95% relative humidity for 80 hours, with a quantum yield variation in the range of 10%.
In various embodiments, the quantum dot layer has a thickness of about 25 microns to 500 microns, preferably 40 microns to about 250 microns.
General method 1 for preparing Quantum dot Complex and Quantum dot film article
The quantum dot composite of each of the following examples was prepared by mixing polythiol, polyalkenyl monomer and 1g of quantum dot CdS/ZnS in a desired equivalent ratio, adding polyisocyanate-based monomer, 0.2g of phenylbis- (2, 4, 6-trimethylbenzoyl) phosphine oxide as a photoinitiator, and 0.01g of urea derivative after mixing uniformly, and mixing the three monomers in total of 20g at a speed of 2000rpm in a nitrogen tank for 3 minutes.
Then, the above prepared composite was knife coated between two 50 μm primer PET barrier films at a thickness of about 80 μm, then first irradiated under uv light for 12 minutes, then reacted at 65 ℃ for 15 minutes, and finally reacted at 110 ℃ for 0.5h.
General method 2 for preparing Quantum dot Complex and Quantum dot film article
The procedure was followed in accordance with method 1, except that the reaction was carried out at 65℃for 15 minutes instead of 80℃for 15 minutes.
Comparative method 1 for preparing Quantum dot composite and Quantum dot film product
The procedure was followed as in general method 1 above, except that the urea derivative was replaced with catalyst DBU-Ant-BPh4, while the curing reaction conditions were changed from first irradiation with ultraviolet light for 12 minutes, then reaction at 65℃for 15 minutes, finally reaction at 110℃for 0.5 hour, replaced with irradiation with the preceding ultraviolet light for 5 minutes, and then reaction at 110℃for 0.5 hour.
Method for measuring Quantum Yield (QY)
All quantum yields were measured by using an absolute fluorescence quantum yield spectrometer.
Method for aging study
Aging study the aging stability was evaluated by measuring the quantum yield after leaving the cut film prepared in the following examples at 65 ℃ and 95% relative humidity for 80 hours.
Compounds used in examples or comparative examples：
Compound 1: ethylene glycol bis (mercaptoacetate)
Compound 2: trimethylol propane tris (mercaptoacetate)
Compound 3:
compound 4:
compound 5:
compound 6:
compound 7:
compound 8:
compound 9:1, 8-diazabicyclo (5.4.0) undec-7-ene-anthracene-tetraphenylboronic acid ester (DBU-Ant-BPh 4)
Examples 1 to 8
Examples 1-4 were prepared according to general method 1 described above for preparing quantum dot composites, quantum dot film articles, examples 5-6 were prepared according to general method 2 described above, and specific preparation conditions are shown in table 1.
Comparative examples 1 to 2
Comparative examples 1-2 were prepared according to comparative method 1 described above for the preparation of quantum dot composites, quantum dot film products, with specific preparation conditions shown in table 1.
Using the test methods described above, quantum yield and color coordinate shift were measured for the prepared samples before and after aging.
TABLE 1
Table 2 below summarizes the QY data at the time of preparing the samples and the QY data after aging for the same samples of the selected examples.
TABLE 2
The results show that the matrix for preparing the quantum dots by using the method provided by the invention has excellent capability of blocking water and oxygen and high quantum efficiency, so that the color of the quantum dot product is stable, and the service life of the quantum dot product in display application can be prolonged.
Although the invention has been described in connection with specific features and embodiments thereof, it will be apparent that various modifications and combinations can be made without departing from the spirit and scope of the invention. Accordingly, this description is merely exemplary of the invention as defined in the appended claims and is intended to cover any and all modifications, variations, combinations, or equivalents that fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. A process for the preparation of a quantum dot composite comprising quantum dots dispersed in a polymer matrix, characterized in that the polymer matrix is prepared from at least one polythiol monomer having a functionality of ≡2, at least one polyalkenyl monomer having a functionality of ≡2 and at least one polyisocyanate-based monomer having a functionality of ≡2;
the method for preparing the quantum dot composite comprises the following steps:
i) Providing a quantum dot material, at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
ii) mixing the quantum dot material, at least one polythiol monomer having a functionality of ≡2, at least one polyalkenyl monomer having a functionality of ≡2, and at least one polyisocyanate-based monomer having a functionality of ≡2, and a urea derivative of formula (I) and a photoinitiator;
iii) Sequentially carrying out illumination and first temperature heating on the mixture obtained in the step ii) to obtain a crosslinked polymer;
iv) heat treating the resulting crosslinked polymer at a second temperature;
the urea derivative of formula (I) has the structure:
Wherein, the liquid crystal display device comprises a liquid crystal display device,
r1 is selected from one of hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl, aryl, aralkyl, -NHC (O) NR2R3 substituted C1 to C15 alkyl, -NHC (O) NR2R3 substituted C3 to C15 cycloalkyl, aryl substituted with-NHC (O) NR2R3, or aralkyl substituted with-NHC (O) NR2R 3;
r2, R3 are independently selected from hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl or together form a C3-to C10 alkylene ring;
at least one of the radicals R1, R2, R3 is not hydrogen;
the urea derivative is used in the step ii) in an amount of 0.005 to 0.05wt% based on the total amount of all monomers;
the first temperature of step iii) is 60-100 ℃;
the second temperature of the step iv) is 105-130 ℃;
the stoichiometric molar ratio of thiol groups of the polythiol monomer, isocyanate groups of the polyisocyanate-based monomer, and double bond groups of the multi-alkenyl monomer in the reactive monomers of the polymer matrix is (1.4-1.8): 1-1.2): 0.8-1.2.
2. The method of claim 1, wherein the polythiol monomer has the formula:
R x (SH) y wherein R is x Is a hydrocarbyl group or heterohydrocarbyl group having a valence of y, and y is greater than or equal to 2.
3. The process according to any one of claims 1-2, wherein the polythiol monomer is selected from one or more of the following compounds:
Or alternatively, the process may be performed,
Or alternatively, the process may be performed,
4. The method of claim 1, wherein the polyisocyanate-based monomer is selected from one or more of the following compounds:
5. The method of claim 1, wherein the polyalkenyl monomer is selected from one or more of the following compounds:
6. The method according to claim 1, wherein R2, R3 in the urea derivative are simultaneously or independently of each other hydrogen or C1 to C15 alkyl; r1 is hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl, C1 to C15 alkyl substituted with-NHC (O) NR1R2, or C3 to C15 cycloalkyl substituted with-NHC (O) NR1R 2.
7. The method of claim 6, wherein the urea derivative is selected from the group consisting of 1-methyl urea, 1-dimethyl urea, 1, 3-dimethyl urea, 3-phenyl-1, 1-dimethyl urea, 1'- (2-methyl-m-phenylene) -bis- (3, 3-dimethyl urea), 1' - (4-methyl-m-phenylene) -bis- (3, 3-dimethyl urea).
8. The method of claim 6, wherein the quantum dots are selected from CdSe/ZnS, inP/ZnS, and CdS/ZnS.
9. A quantum dot article, the quantum dot article comprising:
a first barrier layer;
a second barrier layer; and
a quantum dot layer between the first barrier layer and the second barrier layer;
the quantum dot layer comprises a quantum dot composite prepared according to the method of any one of claims 1-8.
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