CN110511335A

CN110511335A - A kind of block copolymer, a kind of composite particles

Info

Publication number: CN110511335A
Application number: CN201810488658.XA
Authority: CN
Inventors: 李雪; 张滔; 向超宇
Original assignee: TCL Corp
Current assignee: TCL Corp
Priority date: 2018-05-21
Filing date: 2018-05-21
Publication date: 2019-11-29

Abstract

The present invention provides a kind of composite particles, including inorganic nanoparticles and the block copolymer for being incorporated in the inorganic nanoparticles surface, wherein, the block copolymer is the block copolymer for including block chain A and block chain B, the block chain A is the block chain with hole transporting properties, the block chain B is polystyrene, and described block copolymer-modified dose at least contains a terminal sulfhydryl group, and the block copolymer passes through the terminal sulfhydryl group in conjunction with the inorganic nano material.

Description

A kind of block copolymer, a kind of composite particles

Technical field

The invention belongs to electroluminescent diode field of display technology more particularly to a kind of block copolymer, one kind are compound Particle.

Background technique

Quantum dot (quantum dot, QD), but can be described as it is nanocrystalline, be one kind by II-VI group or iii-v element The nano particle of composition.Quantum dot is the nano semiconductor material of zero dimension (zero-dimensional), the ruler of three of them dimension Twice of the very little exciton Bohr radius for being all not more than its corresponding semiconductor material, the performance of quantum dot is generally imitated by quantum confinement Answer the influence of (quantum confinement effect), skin effect and doping.Quantum dot light emitting material has transmitting frequency Rate changes with change in size, at emit line width, luminous quantum efficiency relatively high and superelevation photostability and solution The characteristic of reason.In recent years, quantum dot light emitting material has played very big effect, quantum dot in fields such as LED illumination, liquid crystal displays Traditional fluorescent powder is substituted, the colour gamut of LED and liquid crystal display is effectively improved.Recently, luminescent material is as luminescent layer Light emitting diode with quantum dots (QLED) is with a wide range of applications in fields such as solid-state lighting, FPD, receives science The extensive concern of boundary and industrial circle.

The solution processing properties of quantum dot allow quantum dot light emitting layer to pass through spin coating, blade coating, injection, inkjet printing etc. Various ways preparation.Opposite front several method, inkjet printing technology can be accurately in the desired amount by quantum dot light emitting material Deposit it is in place, allow semiconductor material uniform deposition formed film layer.Quantum dot light emitting layer, material are prepared by inkjet printing The utilization rate of material is very high, and manufacturer can reduce production cost, simplifies manufacture craft, is easy universal volume production, reduces cost.Spray Black printing technique is the effective ways of the manufacture problem that can solve large scale QLED screen generally acknowledged at present.

But quantum dot ink is essentially all that quantum dot is directly dispersing in solvent at present, obtained quantum dot oil Black viscosity is very small, causes the quantum dot film thickness of preparation inconsistent, very poor at film uniformity, easily leads to leakage current；Meanwhile it making Imbalance is injected at the electron hole of quantum dot light emitting layer, quantum dot spacing reduces the energy transfer caused between quantum dot, in turn Light efficiency is caused to reduce.

Summary of the invention

The purpose of the present invention is to provide a kind of composite particles, it is intended to it is viscous to solve existing inorganic nano material printing ink Spend it is small, cause preparation inorganic nano material film such as quantum dot film uniformity it is very poor, generate leakage current；And influence inorganic receive The electron hole injection balance of rice material film such as quantum dot light emitting layer, the problem of causing light efficiency to reduce.

Another object of the present invention is to provide a kind of block polymers.

For achieving the above object, The technical solution adopted by the invention is as follows:

One aspect of the present invention provides a kind of composite particles, including inorganic nanoparticles and is incorporated in the inorganic nanoparticles The block copolymer on surface, wherein the block copolymer is the block copolymer for including block chain A and block chain B, described embedding Section chain A is the block chain with hole transporting properties, and the block chain B is polystyrene, and described block copolymer-modified dose extremely Contain a terminal sulfhydryl group less, and the block copolymer passes through the terminal sulfhydryl group in conjunction with the inorganic nano material.

And and, a kind of block copolymer, the block copolymer includes a mid-block chain, and the centre is embedding Section chain is made of block chain A and block chain B, and one end of the mid-block chain is connected with a terminal sulfhydryl group, and the block is total Another end of polymers is the aliphatic of 3-10 carbon atom, aromatic group, and the block chain A contains carbazole base junction Structure, the block chain B are polystyrene.

Composite particles provided by the invention including inorganic nanoparticles and are incorporated in the embedding of the inorganic nanoparticles surface Section copolymer.And the block copolymer at least contains a terminal sulfhydryl group, and the block copolymer is received with inorganic Metal ion on rice material is effectively combined, and stable ligand system is formed.On this basis, the block copolymer packet Block chain A and block chain B are included, and in two block chains of A, B, one has hole transporting properties, another is polystyrene.By This obtained material can not only effectively adjust the distance between the particle of inorganic nano material, avoid inorganic nano material Energy transfer caused by hypotelorism between particle reduces energy loss, to improve quantum efficiency；Moreover, having hole to pass The block chain A of defeated characteristic and the polystyrene for not having charge transport properties coexist to form block copolymer-modified dose, the block Hole transport performance can be improved in chain A, and the polystyrene has certain insulation performance, meanwhile, polystyrene chain segment is opposite to be had There is certain flexibility, preferable microcell can be formed in the film with block A and uniformly arranged, the two synergic adjustment charge-transporting Can, improve the hole injection balance of inorganic nano material such as quantum dot, further increases the luminescent properties of inorganic nano material.

Block copolymer provided by the invention, including a mid-block chain, and one end connection of the mid-block chain There is a terminal sulfhydryl group, it, can be with the gold on inorganic nano material when so that the block copolymer being used for inorganic nano ink Belong to ion effectively to be combined, forms stable ligand system.On this basis, the block copolymer include block chain A and Block chain B, and the block chain A contains carbazole based structures, the block chain B is polystyrene.The block copolymer is used for When inorganic nanofilms, the carbazyl band-gap energy in the block chain A is relatively large, and highest occupied molecular orbital (HOMO) energy is about The energy barrier with hole transmission layer is reduced so that quantum dot light emitting layer HOMO energy level can increase to a certain degree for -5.8eV, Convenient for the transmission in hole, so that device hole and electron-transport are balanced improvement.The polystyrene has certain insulating properties Can, the two synergic adjustment charge transport properties improve the hole injection balance of inorganic nano material such as quantum dot, further increase The luminescent properties of inorganic nano material.

Specific embodiment

In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain The present invention is not intended to limit the present invention.

In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention, The meaning of " plurality " is two or more, unless otherwise specifically defined.

Composite particles

The embodiment of the invention provides a kind of composite particles, including inorganic nanoparticles and it is incorporated in the inorganic nano The block copolymer on grain surface, wherein the block copolymer is the block copolymer for including block chain A and block chain B, described Block chain A be the block chain with hole transporting properties, the block chain B be polystyrene, described block copolymer-modified dose At least contain a terminal sulfhydryl group, and the block copolymer passes through the terminal sulfhydryl group in conjunction with the inorganic nano material.

Composite particles provided in an embodiment of the present invention, including inorganic nanoparticles and it is incorporated in the inorganic nanoparticles table The block copolymer in face, and the block copolymer at least contains a terminal sulfhydryl group, allow the block copolymer with Metal ion on inorganic nano material is effectively combined, and stable ligand system is formed.On this basis, the block is total Polymers includes block chain A and block chain B, and in two block chains of A, B, and one has hole transporting properties, another is polyphenyl Ethylene.Thus obtained material can not only effectively adjust the distance between the particle of inorganic nano material, avoid inorganic nano Energy transfer caused by hypotelorism between the particle of material reduces energy loss, to improve quantum efficiency；Moreover, having The block chain A of hole transporting properties and the polystyrene for not having charge transport properties coexist to form block copolymer-modified dose, institute Stating block chain A can be improved hole transport performance, and the polystyrene has certain insulation performance；Meanwhile polystyrene chain segment Dissolubility is preferable in the ink, the dissolubility and film forming of ink can be enhanced, while polystyrene chain segment has centainly soft Property, it can be enhanced and be uniformly distributed with the microcell of block chain A, the two synergic adjustment charge transport properties improve inorganic nano material Such as the hole injection balance of quantum dot, the luminescent properties of inorganic nano material are further increased.

Specifically, the block chain A and the block chain B form block copolymer in the embodiment of the present invention, and thus To block copolymer in, at least contain a terminal sulfhydryl group so that the block copolymer is incorporated in the inorganic nano On material such as quantum dot.It can be interpreted as, there are three kinds of forms in the block copolymer for the terminal sulfhydryl group.Respectively with A, B represents block chain A, the block chain B, and as a kind of implementation situation, the terminal sulfhydryl group in the block copolymer is located at institute The one end block chain A is stated, the block copolymer is abbreviated as SH-A-B；As second of implementation situation, in the block copolymer Terminal sulfhydryl group be located at described one end block chain B, the block copolymer is abbreviated as SH-B-A；As the third implementation situation, Contain terminal sulfhydryl group, the block copolymer simultaneously on the block chain B and the block chain A in the block copolymer It is abbreviated as SH-B-A-SH.

As a kind of preferred implementation situation, the block copolymer includes a mid-block chain, the mid-block chain It is made of block chain A and block chain B, one end of the mid-block chain is connected with the terminal sulfhydryl group.Further preferably , in the block copolymer, another end for connecting the mid-block chain is the aliphatic of 3-10 carbon atom, fragrance Race's group.

In the embodiment of the present invention, it is preferred that the weight average molecular weight of the block copolymer is 500-12000, described in control The weight average molecular weight of block copolymer within the above range, on the one hand can make block chain A and polystyrene chain segment associativity More preferably；On the other hand, allow quantum dot ligand surface to chelate the block copolymer ligand of sufficient amount, guarantee the steady of quantum dot It is qualitative, while the charge-transporting of quantum point ink and ink dissolubility and film forming distribution.If the weight of block copolymer is equal Molecular weight is too small, causes block chain A or polystyrene proportion adjustment improper, so that charge transport properties decline either ink Decreased solubility.It is further preferred that the weight average molecular weight or the degree of polymerization of the block copolymer are 1000-6000.

Specifically, the block chain A for being used to form the block copolymer not only requires suitable volume, to adjust nothing The distance between the particle of machine nano particle improves quantum efficiency；Importantly, the block chain A is also needed with hole Transmission characteristic improves luminescent properties in favor of improving the hole injection balance of inorganic nanoparticles such as quantum dot.In addition, described The block copolymer that the block chain A and block chain B is formed has preferable dissolubility in organic solvent, so as to uniformly Dissolution, and be dispersed in inorganic nanoparticles printing ink.

As a preferred implementation manner, the monomer in the block chain A in structure shown in formula I, formula II at least One kind,

Block chain A thermal stability with higher, introducing esters of acrylic acid group can be improved the molten of block chain A Xie Xing increases the dissolubility of ink.Wherein, the carbazyl band-gap energy in the block chain A is relatively large, highest occupied molecular orbital (HOMO) energy is about -5.8eV, so that quantum dot light emitting layer HOMO energy level can increase to a certain degree, reduction and hole The energy barrier of transport layer, convenient for the transmission in hole, so that device hole and electron-transport are balanced improvement.

Preferably, the weight average molecular weight of the block copolymer is 800-12000.It is further preferred that the block is total The weight average molecular weight or the degree of polymerization of polymers are 1000-6000.

As another preferred embodiment, the monomer in the block chain A in structure shown in formula V, formula VII extremely Few one kind,

Carbazyl band-gap energy in the block chain A is relatively large, and highest occupied molecular orbital (HOMO) energy is about -5.8eV, So that certain raising occurs for quantum dot light emitting layer HOMO energy level, the energy barrier with hole transmission layer is reduced, convenient for the biography in hole It is defeated, so that device hole and electron-transport are balanced improvement.But carbazole ground level is wider, energy barrier is larger.And block chain A is also Energy barrier can be reduced with high electronic conductivity skeleton and high-energy density containing polyaniline structure, reduces energy consumption Damage.The all higher thermal stability of two kinds of structures in block chain A simultaneously, can increase luminescent layer stability.

Preferred above structure has height conjugated structure and suitable volume, can not only provide preferable hole and pass Defeated characteristic, is effectively improved the hole injection balance of inorganic nanoparticles such as quantum dot, and can be improved quantum efficiency, Jin Erti The luminescent properties of high inorganic nanoparticles such as quantum dot.

In the embodiment of the present invention, the block chain B i.e. polystyrene for being used to form the block copolymer has certain insulation Performance；Meanwhile dissolubility is preferable in the ink for polystyrene chain segment, and the dissolubility and film forming of ink can be enhanced, and gathers simultaneously Styrene segment has certain flexibility, can be enhanced and is uniformly distributed with the microcell of block chain A, effectively adjusting hole transport.

It is further preferred that being the weight percent of the block chain A in terms of 100% by the total weight of the block copolymer Content is 10%-90%.The content of the suitable block chain A, it is ensured that modified inorganic nanoparticles have higher Charge transport properties, meanwhile, add polystyrene appropriate, can be avoided charge transport properties it is excessively high inhibit exciton production It is raw, to guarantee preferable luminescent properties.In order to obtain better luminescent properties, while guaranteeing suitable Ink Jet Printing Performance, It is in terms of 100% by the total weight of the block copolymer, the weight percentage of the block chain A is more preferably 40%- 60%.

It preferably, is in terms of 100% by the total weight of the material, the weight percentage of the block copolymer is 10%-80%.It is further preferred that being in terms of 100% by the total weight of the material, the weight percent of the block copolymer contains Amount is 20-60%.

Block copolymer

The embodiment of the invention provides a kind of block copolymer, the block copolymer includes a mid-block chain, institute It states mid-block chain to be made of block chain A and block chain B, one end of the mid-block chain is connected with a terminal sulfhydryl group, institute Another end for stating block copolymer is the aliphatic of 3-10 carbon atom, aromatic group, and the block chain A contains click Oxazolyl structure, the block chain B are polystyrene.

Block copolymer provided in an embodiment of the present invention, including a mid-block chain, and the one of the mid-block chain End is connected with a terminal sulfhydryl group, can be with inorganic nano material when so that the block copolymer being used for inorganic nano ink On metal ion effectively combined, form stable ligand system.On this basis, the block copolymer includes block Chain A and block chain B, and the block chain A contains carbazole based structures, the block chain B is polystyrene.The block copolymer When for inorganic nanofilms, the carbazyl band-gap energy in the block chain A is relatively large, highest occupied molecular orbital (HOMO) energy About -5.8eV reduces the energy with hole transmission layer so that quantum dot light emitting layer HOMO energy level can increase to a certain degree It builds, convenient for the transmission in hole, so that device hole and electron-transport are balanced improvement.The polystyrene has certain insulation Performance, the two synergic adjustment charge transport properties improve the hole injection balance of inorganic nano material such as quantum dot, further mention The luminescent properties of high inorganic nano material.

Specifically, there are three kinds of forms in the block copolymer for the terminal sulfhydryl group in the embodiment of the present invention.Respectively Block chain A, the block chain B are represented with A, B, as a kind of implementation situation, the terminal sulfhydryl group in the block copolymer is located at Described one end block chain A, the block copolymer are abbreviated as SH-A-B；As second of implementation situation, the block copolymer In terminal sulfhydryl group be located at described one end block chain B, the block copolymer is abbreviated as SH-B-A；Implement feelings as the third Shape contains terminal sulfhydryl group, the block copolymerization on the block chain B and the block chain A in the block copolymer simultaneously Object is abbreviated as SH-B-A-SH.

In the embodiment of the present invention, it is preferred that the weight average molecular weight of the block copolymer is 500-12000, described in control The weight average molecular weight of block copolymer within the above range, on the one hand can make block chain A and polystyrene chain segment associativity More preferably；On the other hand, the block copolymer is for that can make quantum dot when making inorganic nanofilms such as quantum dot film Ligand surface can chelate the block copolymer ligand of sufficient amount, to guarantee the stability of quantum dot, while quantum point The charge-transporting and ink dissolubility of ink and film forming distribution.It is further preferred that the Weight-average molecular of the block copolymer Amount or the degree of polymerization are 1000-6000.

Print ink

The embodiment of the invention provides a kind of printing ink, including inorganic nanoparticles, solvent and block copolymer, institutes Stating block copolymer includes being incorporated in the block copolymer on inorganic nanoparticles surface and not in conjunction with the inorganic nanoparticles Block copolymer, wherein the block copolymer is the block copolymer for including block chain A and block chain B, the block chain A is the block chain with hole transporting properties, and the block chain B is polystyrene, and described block copolymer-modified dose at least contains There is a terminal sulfhydryl group, and the block copolymer passes through the terminal sulfhydryl group in conjunction with the inorganic nanoparticles.

Inorganic nanoparticles ink provided in an embodiment of the present invention, it is inorganic containing inorganic nanoparticles and block copolymer Block copolymer described in nano particle block copolymer inorganic nanoparticles at least contains a terminal sulfhydryl group, so that the block Copolymer can effectively be combined with the metal ion on inorganic nanoparticles, form stable ligand system.It is basic herein On, the block copolymer includes block chain A and block chain B, and in two block chains of A, B, and one has hole transporting properties, Another is polystyrene.Thus obtained inorganic nanoparticles, can not only effectively adjust inorganic nanoparticles particle it Between distance, avoid energy transfer caused by hypotelorism between the particle of inorganic nanoparticles, energy loss reduced, to mention High-quantum efficiency；Moreover, the block chain A with hole transporting properties coexists to be formed with the polystyrene for not having charge transport properties Hole transport performance can be improved in block copolymer, the block chain A, and the polystyrene has certain insulation performance, simultaneously Polystyrene chain segment is opposite to have certain flexibility, can form preferable microcell in the film with block A and uniformly arrange, the two Synergic adjustment charge transport properties improve the hole injection balance of inorganic nanoparticles such as quantum dot, further increase inorganic receive The luminescent properties of rice grain.In addition, can adjust ink viscosity by block polymer decorated inorganic nanoparticles with itself, change Kind printing technology and film forming characteristics so that inorganic nanoparticles printing ink can satisfy inkjet printing requirement, stablize it is out of ink, Stabilization is sprawled, uniform drying, is formed a film uniform.

Specifically, the block chain A and the block chain B form block copolymer in the embodiment of the present invention, and thus To block copolymer in, at least contain a terminal sulfhydryl group so that the block copolymer is incorporated in the inorganic nano On particle such as quantum dot.It can be interpreted as, there are three kinds of forms in the block copolymer for the terminal sulfhydryl group.Respectively with A, B represents block chain A, the block chain B, and as a kind of implementation situation, the terminal sulfhydryl group in the copolymer is located at described embedding The one end section chain A, the copolymer are abbreviated as SH-A-B；Terminal sulfhydryl group position as second of implementation situation, in the copolymer In described one end block chain B, the copolymer is abbreviated as SH-B-A；Institute as the third implementation situation, in the copolymer It states and contains terminal sulfhydryl group simultaneously on the block chain B and block chain A, the copolymer is abbreviated as SH-B-A-SH.

In the embodiment of the present invention, it is used to form polystyrene described in the block chain B i.e. polystyrene of the block copolymer With certain insulation performance, while polystyrene chain segment is opposite has certain flexibility, can be formed in the film with block A compared with Good microcell is uniformly arranged.

It is further preferred that being the weight percent of the block chain A in terms of 100% by the total weight of the block copolymer Content is 10%-90%.The content of the suitable block chain A, it is ensured that beaten through inorganic nanoparticles printing ink jet inks Molding inorganic nanoparticles film charge transport properties with higher are printed, meanwhile, polystyrene appropriate is added, can be kept away Exempt from the excessively high generation for inhibiting exciton of charge transport properties, to guarantee preferable luminescent properties.In order to obtain better photism Can, while guaranteeing suitable Ink Jet Printing Performance, is in terms of 100% by the total weight of the block copolymer, the block chain A's Weight percentage is more preferably 40%-60%.

In the embodiment of the present invention, block copolymer is stated by printing addition in ink in the inorganic nanoparticles, it can be with The inorganic nanoparticles are modified, promote the print performance of inorganic nanoparticles printing ink, that improves is inorganic The luminescent properties of printing nanoparticles film.Preferably, the total weight of the composite particles is 100% meter, the block copolymerization The weight percentage of object is 10%-80%, thus obtains inorganic nanoparticles viscosity of printing ink properly and is conducive to obtain The high inorganic nanoparticles printing film of quantum efficiency.Importantly, suitable block copolymer content, so that the block Copolymer and the inorganic nanoparticles keep dynamic equilibrium in dissociation and combination.It is furthermore preferred that with the composite particles Total weight is 100% meter, and the weight percentage of the block copolymer is 20-60%.

In the embodiment of the present invention, inorganic nanoparticles can be used one or more in the inorganic nanoparticles ink. Specifically, matrix component of the inorganic nanoparticles as inorganic nanoparticles printing ink, can be IV race, II- VI race, II-V race, iii-v, III-VI race, group IV-VI, I-III-VI race, II-IV-VI race, II-IV-V race binary or more At least one of first monocrystalline semiconductor compounds, be also possible to IV race, II-VI group, II-V race, iii-v, III-VI race, Group IV-VI, I-III-VI race, II-IV-VI race, II-IV-V race formed binary or polynary core-shell structure semiconducting compound At least one of, it can also be the mixture that the semiconducting compound of monocrystalline semiconductor compounds and core-shell structure is formed.Tool Body, the inorganic nanoparticles can selected from but not limited to CdSe, CdS, CdTe, ZnO, ZnSe, ZnS, ZnTe, HgS, At least one of HgSe, HgTe, CdZnSe；Be also selected from but be not limited to InAs, InP, InN, GaN, InSb, InAsP, At least one of InGaAs, GaAs, GaP, GaSb, AlP, AlN, AlAs, AlSb, CdSeTe, ZnCdSe.The embodiment of the present invention In, the structure type of the inorganic nanoparticles is unrestricted, and uniform mixed type, gradient mixed type, core-shell structure copolymer class can be used Type or union type.In addition, the inorganic nanoparticles can also be perovskite nanometer particle material, particularly preferably luminous calcium titanium Mine nanoparticle, metal nano particle material, metal oxide nanoparticles material and combinations thereof.

The composition form of the inorganic nanoparticles is unrestricted, can be doped or non-doped inorganic nanoparticles, Wherein, doping refers to that other doped chemicals are also contained in the inside of the inorganic nanoparticles.Specifically, the inorganic nano Grain can be quanta point material.Wherein, the ligand of the quantum dot include sour ligand, mercaptan ligand, amine ligand, (oxygen) Phosphine ligands, At least one of phosphatide, soft phosphatide, polyvinylpyridine etc..As specific embodiment, the acid ligand is ten acid, hendecene At least one of acid, tetradecylic acid, oleic acid, stearic acid；The mercaptan ligand is eight alkyl hydrosulfides, lauryl mercaptan, 18 At least one of alkyl hydrosulfide；The amine ligand includes at least one of oleyl amine, octadecylamine, eight amine；(oxygen) phosphine is matched Body is at least one of tri octyl phosphine, trioctylphosphine oxide (TOPO).

The printing of inorganic nanoparticles described in the embodiment of the present invention is suitable for inkjet printing quantum dot light emitting layer, when described inorganic When water content is higher in printing nanoparticles ink, since shipwreck is in volatilization or removal, it is easy residual in the quantum dot ink It stays, and then influences the performance of the quantum dot light emitting layer formed.In view of this, quantum dot described in the embodiment of the present invention is preferably Oil-soluble quantum dot.

As particular preferred embodiment, the average-size of the quantum dot is 1-20nm.

In the embodiment of the present invention, the inorganic nanoparticles printing ink further includes at least one organic solvent.It is described to have Solvent selected from but not limited to chlorobenzene, o-dichlorohenzene, tetrahydrofuran, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, Paraxylene, n-hexane, methylene chloride, chloroform, 1,4- dioxane, 1,2 dichloroethanes, tri- chloroethene of 1,1,1- Alkane, 1,1,2,2- tetrachloroethanes, naphthane, naphthalane, phenoxytoluene, dodecane, 1- methoxynaphthalene, 1- dibutyl naphthalene, adjacent diformazan Oxygroup benzene, 1- methyl naphthalene, 1,2- dimethylnaphthalene, cyclohexyl benzene, 1,2,4- trimethoxy-benzene, benzene hexane, the tetradecane, 1,2- diformazan At least one of base naphthalene, 4- isopropyl biphenyl, 2- isopropyl naphthalene, 1-ethylnaphthalene and 1,2,3,4-tetralin.

Further, by weight, the total weight of the inorganic nanoparticles and the block copolymer has with described The weight ratio of solvent is 0.01-20.0:80-99.9, to assign the inorganic nanoparticles printing preferable viscosity of ink.Into One step is preferred, by weight, the total weight of the inorganic nanoparticles and the block copolymer and the organic solvent Weight ratio be 4.0-15.0:85.0-96.0.

The ink is by the inorganic nanoparticles, the block copolymer and described organic as a preferred method, Solvent composition, by weight, the weight of the total weight and organic solvent of the inorganic nano material and the block copolymer Than for 4.0-15.0:85.0-96.0.In addition to the inorganic nanoparticles, block in the i.e. described inorganic nanoparticles printing ink Outside copolymer and the organic solvent, other auxiliary reagents are not contained.

As another preferred embodiment, the inorganic nanoparticles, the block copolymer and institute are contained in the ink Organic solvent is stated, the weight ratio of the total weight and organic solvent of the inorganic nanoparticles and the block copolymer is 4.0- 15.0:85.0-96.0.Further, in the embodiment of the present invention, the inorganic nanoparticles printing ink can also include auxiliary Reagent, the auxiliary reagent includes but is not limited to: viscosity modifier and dispersing agent.

When to make the quantum dot ink carry out inkjet printing, ink is suitably discharged from the nozzle of inkjet print head without sending out Raw blocking, while there is preferable film forming characteristics, it can be printed in ink in the inorganic nanoparticles and viscosity modifier is added. The viscosity modifier be preferably polyhydroxy-alcohol, alkyl glycol ether or trimethylolpropane, trimethylolethane, casein, At least one of carboxymethyl cellulose.Specifically, the polyhydroxy-alcohol is ethylene glycol, diethylene glycol (DEG), diethylene glycol, three second two Alcohol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 2- butylene-1,4-diol and At least one of 2- methyl -2- pentanediol, 1,2,6- hexanetriol, glycerine, polyethylene glycol and dipropylene glycol, polyvinyl alcohol.Institute Stating alkyl glycol ether is in polyethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether and Propylene glycol n-propyl ether At least one.

The dispersing agent can effectively be such that the quantum dot is dispersed in the solvent and protect the dispersion It is fixed to keep steady.Specifically, the dispersing agent can be one or more surfactants.The surfactant can be anion Type, cationic, non-ionic or amphoteric surfactant.

As specific embodiment, the nonionic surfactant includes but is not limited to straight chain or second level alcohol ethoxylates Object, alkyl phenol polyoxyethylene ether, fluorine-containing surfactant, polyoxyethylene carboxylate, aliphatic amine polyoxyethylene ether, polyoxyethylene Block copolymer and propoxylated block copolymers, polyoxyethylene and propyl silica resin based surfactants, alkyl polysaccharide At least one of glycosides and acetylenic polyethylene oxides surfactant.The anionic surfactant includes but is not limited to Carboxylate (for example, ether carboxylate and sulfosuccinate), sulfate (for example, lauryl sodium sulfate), sulfonate (for example, Dodecyl benzene sulfonate, α olefin sulfonate, p alkylphenylaceticacid, fatty acid taurides, alkyl naphthalene sulfonic acid Salt), phosphate (for example, alkyl and aryl alcohol phosphate), phosphonate and amine oxide surfactant and Anionic fluorinated table At least one of face activating agent.The amphoteric surfactant include but is not limited to trimethylamine second lactones, sulfobetaines with And at least one of alanine rouge.The cationic surfactant includes but is not limited to quaternary ammonium compound, cationic amine At least one of oxide, ethoxy fatty amine and imidazoline surfactant.

As a kind of specific preferred embodiment, the inorganic nanoparticles printing ink is by the inorganic nanoparticles, block Copolymer and organic solvent composition.

Inorganic nanoparticles provided in an embodiment of the present invention print ink, and viscosity under the conditions of 25-35 DEG C is 0.5- 60.0mPa.s, concretely 1mPa.s, 5mPa.s, 10mPa.s, 15mPa.s, 20mPa.s, 25mPa.s, 30mPa.s, 35mPa.s,40mPa.s,45mPa.s,50mPa.s,55mPa.s,60mPa.s；Further, the viscosity of the quantum dot ink Preferably 25 DEG C of viscosity is preferably 1-30.0mPa.s, and more preferably viscosity under the conditions of 25-35 DEG C is 1-15.0mPa.s. The surface tension of the inorganic nanoparticles printing ink is 20.0-80.0mN/m, to can flow in ink jet printing process It freely is discharged from printing head, and there is preferable film forming characteristics.Specifically, stating the surface of inorganic nanoparticles printing ink Power can be 20.0mN/m, 30.0mN/m, 40.0mN/m, 50.0mN/m, 60.0mN/m, 70.0mN/m, 80.0mN/m.

Inorganic nanoparticles provided in an embodiment of the present invention print ink, and surface tension is within the scope of 20-80mN/m, In Viscosity under the conditions of 25-35 DEG C is 0.5-60.0mPa.s, can satisfy current ink-jet printer and wants to viscosity and surface tension Ask, realize the inkjet printing mode of inorganic nanoparticles layer, realize in print procedure stablize it is out of ink, stablize sprawl, high wettability, Uniform drying, film forming are uniform, obtain the inorganic nanoparticles luminescent layer with pixel-matrix, high-resolution, electroexcitation.Together When, inorganic nanoparticles provided in an embodiment of the present invention print ink, the inorganic nanoparticles such as quantum dot through printing preparation with The thicknesses of layers that block copolymer is formed is uniform smooth, and inorganic nanoparticles such as quantum dot are uniformly distributed in block copolymer, It enables to electronics-charge injection of quantum dot light emitting layer more to balance, reduces the energy transmission loss between quantum dot, improve and shine Efficiency.

The preparation method of ink

Another aspect of the present invention provides a kind of preparation method of ink, comprising the following steps:

S01., inorganic nanoparticles particle, block copolymer and organic solvent are provided；

S02. formation institute's inorganic nanoparticles ink in organic solvent is dispersed by block copolymer, inorganic nanoparticles.

The preparation method of ink provided in an embodiment of the present invention need to only disperse inorganic nanoparticles in organic solvent i.e. Can, it is easy to operate easily-controllable, harsh condition is not needed, it can be achieved that producing in enormous quantities.

Specifically, in above-mentioned steps S01, the inorganic nanoparticles, block copolymer, the type of organic solvent, content It has hereinbefore stated, in order to save length, details are not described herein again.

The block copolymer provided in an embodiment of the present invention, can voluntarily prepare, it is preferred to use reversible addition-is disconnected Split chain tra nsfer (RAFT) polymerization-amine-decomposing method synthesis.

The block chain B of the block copolymer is polystyrene as a preferred implementation manner, when in block copolymer Block chain A in monomer when being selected from least one of formula I, structure shown in formula II,

The preparation method of the block copolymer, comprising the following steps:

S111. at least one of functional structure monomer shown in formula III, formula IV is provided, by the functional structure monomer It is placed in solvent with radical initiator, RAFT reagent, it is aggregated to react the RAFT reagent that functionalization block chain A is prepared；

Specifically, preparing structures alone functionality as shown in formula III, formula IV of the block chain A in above-mentioned steps S111 Structures alone (the respectively functional structure monomer of formula I, structure shown in formula II), general structure is expressed as R¹CHCH₂, wherein The R¹To remove CHCH in functional structure monomer shown in formula III, formula IV₂Structure division in addition.The RAFT reagent is with R²-S- CS-R³It indicates, for being reacted with the functional structure monomer terminal alkene group.Wherein, R²、R³Preferably 3-10 carbon atom Aliphatic, aromatic group, so that the RAFT reagent has preferable dissolubility and reactivity in reaction process.It is described Radical initiator is used to cause the polymerization reaction of the functional structure monomer.Specifically, the radical initiator is selected from One of free radical thermal initiator, free radical photo-initiation.It is specific preferred, the free radical thermal initiator be selected from azo, At least one of peroxide, persulfate, redox initiator, including but not limited to azodiisobutyronitrile (AIBN)； The free radical photo-initiation be selected from 2- hydroxy-2-methyl -1- phenyl -1- acetone, 2,2- dimethoxy -2- phenyl acetophenone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone, 1- hydroxycyclohexyl phenyl ketone, 2,2- dimethoxy-benzene Base ketone, phenyl be double-(2,4,6- trimethylbenzoyl) phosphine oxide, 2- phenyl benzyl -2- dimethyl amine -1- (4- morpholine benzyl benzene Base) butanone, 2,4- dimethyl thioxanthone, at least one of 2,4- diethyl thioxanthone.It is above-mentioned in the embodiment of the present invention Step S111, and in following step S112, the solvent for polymerization can be selected from least one of benzene, alkylbenzene, can be selected from At least one of tetrahydrofuran, methylene chloride, dichloroethanes, chloroform, chlorobenzene, nitrobenzene, dioxane, hexamethylene；It is optional From lipid；It can be selected from ketone；It can be selected from N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide, diformazan At least one of base sulfoxide, and, it can be any combination of above-mentioned solvent.More specifically, the alkylbenzene is selected from but first Benzene, dimethylbenzene, boiling point are higher than at least one of other alkylbenzenes of the dimethylbenzene；The esters are selected from but not limited to acetic acid At least one of ethyl ester, n-butyl acetate, acetic acid 1- methoxyl group -2- propyl diester；The ketone is selected from but not limited to acetone, first At least one of ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone.It is further preferred that above-mentioned steps S111 and following step In S112, the solvent for polymerization is toluene, chloroform or tetrahydrofuran solvent.

The functional structure monomer tries aggregated react with radical initiator, RAFT and functionalization block chain is prepared The RAFT reagent of A, reaction equation are as follows:

Wherein, in the RAFT reagent of functionalization block chain A m value, with participate in reaction functional structure monomer class Depending on type.When the functional structure monomer for participating in reaction is only functional structure monomer shown in formula III, i.e., polymerization reaction obtains The polymer of structure shown in formula I, at this point, the value of m is identical as x；When the functional structure monomer for participating in reaction is only IV institute of formula When showing functional structure monomer, i.e., polymerization reaction obtains the polymer of structure shown in formula II, at this point, the value of m is identical as y；When When the functional structure monomer for participating in reacting contains functional structure monomer shown in formula III, formula IV simultaneously, i.e., polymerization reaction obtains With the polymer of structure shown in up-to-date style I and formula II, at this point, m=x+y.

Preferably, it after polymerization reaction, after reaction product is put into liquid nitrogen the cooling several seconds, is precipitated, is obtained with n-hexane To functionalized polymer chain Macro RAFT agent.

S112., styrene monomer is provided, by the RAFT reagent of the functionalization block chain A and the styrene monomer, from It is placed in solvent by base initiator, the diblock copolymer that at least one end is dithioesters is prepared in aggregated reaction.

Specifically, in above-mentioned steps S112, the selection of the radical initiator and freedom described in the step S111 The selection of base initiator is identical, the selection and the selection phase of polymerization reaction solvent in the step S111 of the solvent of polymerization reaction Together.In solvent for polymerization, the RAFT reagent and the styrene monomer, radical initiator of the functionalization block chain A is anti- It answers, obtains the diblock copolymer that at least one end is dithioesters, reaction equation is as follows:

The end is in the diblock copolymer of dithioesters, and n indicates the amount of monomer of styrene in polystyrene, Value is positive integer.The size of n influences the content of block chain B in block copolymer.

S113. diblock copolymer and primary amine that the end is dithioesters are subjected to aminolysis reaction, end is prepared End is the block copolymer of sulfydryl.

Specifically, diblock copolymer and primary amine that the end is dithioesters are carried out amine in above-mentioned steps S113 The block copolymer that end is sulfydryl is prepared in solution reaction, and reaction equation is as follows:

Wherein, the primary amine is selected from least one of ethamine, propylamine, n-butylamine, n-hexylamine, cyclohexylamine.

Further, by the block copolymer use tetrahydrofuran and n-hexane dissolution-precipitating, repeatedly after, It is dried to obtain the block copolymer of high-purity, for being added in inorganic nanoparticles ink the performance for improving ink.

As another preferred embodiment, the block chain B of the block copolymer is polystyrene, works as block copolymer In block chain A in monomer when being selected from least one of formula V, structure shown in formula VII,

The preparation method of the block copolymer, comprising the following steps:

S211. at least one of functional structure monomer shown in formula VIII, formula Ⅸ is provided, by the functional structure monomer It is placed in solvent with radical initiator, RAFT reagent, it is aggregated to react the RAFT reagent that functionalization block chain A is prepared；

Specifically, preparing structures alone functionality as shown in formula VIII, formula Ⅸ of the block chain A in above-mentioned steps S211 Structures alone (the respectively functional structure monomer of formula III, structure shown in formula IV), general structure is expressed as R⁴CHCH₂, In, the R⁴To remove CHCH in functional structure monomer shown in formula VIII, formula Ⅸ₂Structure division in addition.The RAFT reagent with R²-S-CS-R³It indicates, for being reacted with the functional structure monomer terminal alkene group.Wherein, R²、R³Preferably 3-10 carbon is former The aliphatic of son, aromatic group, so that the RAFT reagent has preferable dissolubility and reactivity in reaction process. The radical initiator is used to cause the polymerization reaction of the functional structure monomer.Specifically, the radical initiator Selected from one of free radical thermal initiator, free radical photo-initiation.Specific preferred, the free radical thermal initiator is selected from even At least one of nitrogen, peroxide, persulfate, redox initiator, including but not limited to azodiisobutyronitrile (AIBN)；The free radical photo-initiation is selected from 2- hydroxy-2-methyl -1- phenyl -1- acetone, 2,2- dimethoxy -2- phenyl Acetophenone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinyl-1- acetone, 1- hydroxycyclohexyl phenyl ketone, 2,2- diformazan Oxygroup-phenyl ketone, phenyl be double-(2,4,6- trimethylbenzoyl) phosphine oxide, 2- phenyl benzyl -2- dimethyl amine -1- (4- Quinoline benzyl phenyl) butanone, 2,4- dimethyl thioxanthone, at least one of 2,4- diethyl thioxanthone.The embodiment of the present invention In, in above-mentioned steps S211 and following step S212, the solvent for polymerization can be selected from least one of benzene, alkylbenzene, It can be selected from tetrahydrofuran, methylene chloride, dichloroethanes, chloroform, chlorobenzene, nitrobenzene, dioxane, at least one in hexamethylene Kind；It can be selected from lipid；It can be selected from ketone；It can be selected from N-Methyl pyrrolidone, n,N-Dimethylformamide, N, N- dimethylacetamide At least one of amine, dimethyl sulfoxide, and, it can be any combination of above-mentioned solvent.More specifically, the alkylbenzene choosing From but toluene, dimethylbenzene, boiling point be higher than at least one of other alkylbenzenes of the dimethylbenzene；The esters are selected from but unlimited In at least one of ethyl acetate, n-butyl acetate, acetic acid 1- methoxyl group -2- propyl diester；The ketone is selected from but not limited to At least one of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone.It is further preferred that above-mentioned steps S211 and under It states in step S212, the solvent for polymerization is toluene, chloroform or tetrahydrofuran solvent.

Wherein, in the RAFT reagent of functionalization block chain A h value, with participate in reaction functional structure monomer class Depending on type.When the functional structure monomer for participating in reaction is only functional structure monomer shown in formula VIII, i.e., polymerization reaction obtains The polymer of structure shown in formula III, at this point, the value of h is identical as a；When the functional structure monomer for participating in reaction is only Ⅸ institute of formula When showing functional structure monomer, i.e., polymerization reaction obtains the polymer of structure shown in formula IV, at this point, the value of h is identical as b；When When the functional structure monomer for participating in reacting contains functional structure monomer shown in formula III, formula IV simultaneously, i.e., polymerization reaction obtains With the polymer of structure shown in up-to-date style I and formula II, at this point, h=a+b.

S212., styrene monomer is provided, by the RAFT reagent of the functionalization block chain A and the styrene monomer, from It is placed in solvent by base initiator, the diblock copolymer that at least one end is dithioesters is prepared in aggregated reaction

Specifically, in above-mentioned steps S212, the selection of the radical initiator and freedom described in the step S211 The selection of base initiator is identical, the selection and the selection phase of polymerization reaction solvent in the step S211 of the solvent of polymerization reaction Together.In solvent for polymerization, the RAFT reagent and the styrene monomer, radical initiator of the functionalization block chain A is anti- It answers, obtains the diblock copolymer that at least one end is dithioesters, reaction equation is as follows:

S213. diblock copolymer and primary amine that the end is dithioesters are subjected to aminolysis reaction, end is prepared End is the block copolymer of sulfydryl.

Specifically, diblock copolymer and primary amine that the end is dithioesters are carried out amine in above-mentioned steps S213 The block copolymer that end is sulfydryl is prepared in solution reaction, and reaction equation is as follows:

In above-mentioned steps S02, disperse inorganic nanoparticles, block copolymer in organic solvent, discrete form not by Agitating mode realization can be used in limitation.Preferably, it first disperses the block copolymer in organic solvent, adjusts solvent After viscosity, the inorganic nanoparticles such as quantum dot is added.

The embodiment of the invention also provides a kind of preparation methods of film, comprising the following steps:

E01., above-mentioned ink is provided；

E02. a film is obtained by being dried without the ink in deposited on supports.

Ink only need to be carried out inkjet printing on carrier by the preparation method of film provided by the invention, drying can obtain , method is simple, it is easy to accomplish standardization control.

The method that above-mentioned steps E01 prepares inorganic nanoparticles printing ink is as described above, in order to save length, herein It repeats no more.

In above-mentioned steps E02, there is no considered critical without the mode of the ink in deposited on supports, preferably closed by selecting Suitable ink-jet printer carries out inkjet printing, prints ink in deposited on supports inorganic nano, then does to the ink Dry processing solvent flashing.Specifically, the inkjet printing preferably uses, piezoelectric ink jet is printed or thermal inkjet-printing is realized.It is described dry Dry processing is heating drying, cooling and drying, at least one of is dried under reduced pressure.As an implementation, individually using heating Drying, cooling and drying one of are dried under reduced pressure and to be dried.As another embodiment, using heating it is dry and It is dried under reduced pressure or cooling and drying and being dried under reduced pressure is dried.Preferably, the dry temperature of the heating is 60-180 DEG C, time 0-30min；Preferably, the temperature of the cooling processing is 0-20 DEG C；Preferably, the vacuum of the reduced pressure treatment Degree is 1 × 10^-6Torr is to normal pressure.It is dried to obtain inorganic nanoparticles film, such as quantum dot film.

It is suitable to be dried mode, the organic solvent can be efficiently being removed, guarantee the inorganic nanoparticles such as Quanta point material and the block copolymer are not damaged, and form uniform smooth film.

The inorganic nanoparticles film dry film formed through inkjet printing, thickness is preferably 10-100nm；Further, through spraying The inorganic nanoparticles film thickness of dry film that ink printing is formed is 20-50nm.

It is illustrated combined with specific embodiments below.

Embodiment 1

A kind of preparation method of block polymer modifying agent SH-A-B (SH-I-B), comprising the following steps:

Functional monomer 2- (9H- carbazole -9- base) acryloyl acetoacetic ester 5g, radical initiator of Formula II block chain is provided Azo-bis-isobutyl cyanide (AIBN) 5mg, dithiobenzoic acid phenethyl ester 60mg mixing are scattered in 50mL tetrahydrofuran, through true Sky-liquid nitrogen deaeration removes mixing oxygen therein for several times, is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Reactant is mixed It closes object and is put into liquid nitrogen the cooling several seconds and terminate chain transfer reaction, then n-hexane precipitates to obtain first segment functionalized polymer chain big The total 3.6g of molecule RAFT reagent.

By above-mentioned functionalized polymer chain Macro RAFT agent 3g and styrene 2g, AIBN 2mg, it is scattered in 50mL tetra- In hydrogen furans, mixing oxygen therein is removed for several times through vacuum-liquid nitrogen deaeration, be heated to 50 DEG C after being filled with nitrogen, polymerization 48 is small When.Reaction-ure mixture is put into liquid nitrogen cooling several seconds termination chain transfer reaction, then n-hexane precipitates to obtain end to be two The diblock polymer 4.1g of monothioester.

End is that the diblock polymer 4g and cyclohexylamine 10g of dithioesters are reacted at room temperature in 50mL tetrahydrofuran into 6 Hour, then n-hexane precipitates to obtain the diblock polymer 3.3g that end is sulfydryl.

Above-mentioned block polymer can add after the dissolution-of multiple tetrahydrofuran and n-hexane precipitates and is dried under vacuum to constant weight The performance for improving ink is added in quantum dot ink.

Embodiment 2

A kind of preparation method of inorganic nanoparticles film, comprising the following steps:

Polymer 500mg prepared by embodiment 1 is mixed with 20g dodecane, after being heated to 100 DEG C of dissolutions 30 minutes, with 1 Spare polymer solution is obtained after μ membrane filtration.The stable red CdSe/ZnS quantum dot of 1.5g oleyl amine and 8.5g is above-mentioned poly- Polymer solution is mixed 30 minutes, and 0.45 μ membrane filtration obtains quantum dot ink.

By ink-jet printer, it is printed as 20 × 30um, the red quantum dot layer of 200 × 200ppi of resolution ratio.

100 DEG C, nitrogen flow vacuum 1 × 10 are heated on hot plate^-6Volatile dry 30min under Torr obtains monochromatic quantum Point luminescent layer.

Embodiment 3

A kind of preparation method of block polymer modifying agent SH-A-B (SH-I-II-B), comprising the following steps:

Functional monomer 2- (9H- carbazole -9- base) methacryl acetoacetic ester 3g, the free radical of I block chain of offer formula draw Agent azo-bis-isobutyl cyanide (AIBN) 3mg, dithiobenzoic acid phenethyl ester 60mg mixing are sent out, is scattered in 50mL tetrahydrofuran, It removes mixing oxygen therein for several times through vacuum-liquid nitrogen deaeration, is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Addition formula Functional monomer 2- (9H- carbazole -9- base) methacryl acetoacetic ester 2g of II block chain, is removed for several times through vacuum-liquid nitrogen deaeration It goes to mix oxygen therein, is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Reaction-ure mixture is put into liquid nitrogen cooling Several seconds terminates chain transfer reaction, and then it is total to precipitate to obtain first segment functionalized polymer chain Macro RAFT agent for n-hexane 3.4g。

By above-mentioned functionalized polymer chain Macro RAFT agent 3g and styrene 2g, AIBN 2mg, it is scattered in 50mL tetra- In hydrogen furans, mixing oxygen therein is removed for several times through vacuum-liquid nitrogen deaeration, be heated to 50 DEG C after being filled with nitrogen, polymerization 48 is small When.Reaction-ure mixture is put into liquid nitrogen cooling several seconds termination chain transfer reaction, then n-hexane precipitates to obtain end to be two The diblock polymer 3.7g of monothioester.

End is that the diblock polymer 4g and cyclohexylamine 10g of dithioesters are reacted at room temperature in 50mL tetrahydrofuran into 6 Hour, then n-hexane precipitates to obtain the diblock polymer 3.0g that end is sulfydryl.

Embodiment 4

Polymer 500mg prepared by embodiment 3 is mixed with the 20g tetradecane, 10g ortho-xylene, is heated to 100 DEG C of dissolutions After 30 minutes, with obtaining spare polymer solution after 1 μ membrane filtration.By the red CdSe/ZnS quantum dot that 1.0g oleyl amine is stable It is mixed 30 minutes with the above-mentioned polymer solution of 9.0g, 0.45 μ membrane filtration obtains quantum dot ink.

Embodiment 5

Functional monomer 2- (9H- carbazole -9- base) methacryl acetoacetic ester 4g, II type of I block chain of offer formula it is embedding Functional monomer 2- (9H- carbazole -9- base) methacryl acetoacetic ester 2g, radical initiator azo-bis-isobutyl cyanide of section chain (AIBN) 3mg, dithiobenzoic acid phenethyl ester 60mg are mixed, and are scattered in 50mL tetrahydrofuran, through vacuum-liquid nitrogen deaeration number Secondary removing mixes oxygen therein, is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Reaction-ure mixture is put into liquid nitrogen The cooling several seconds terminates chain transfer reaction, and then n-hexane precipitates to obtain first segment functionalized polymer chain Macro RAFT agent total 5.2g。

By above-mentioned functionalized polymer chain Macro RAFT agent 3g and styrene 2g, AIBN 2mg, it is scattered in 50mL tetra- In hydrogen furans, mixing oxygen therein is removed for several times through vacuum-liquid nitrogen deaeration, be heated to 50 DEG C after being filled with nitrogen, polymerization 48 is small When.Reaction-ure mixture is put into liquid nitrogen cooling several seconds termination chain transfer reaction, then n-hexane precipitates to obtain end to be two The diblock polymer 3.9g of monothioester.

End be dithioesters diblock polymer 3.9g and cyclohexylamine 10g reacted at room temperature in 50mL tetrahydrofuran into 6 hours, then n-hexane precipitated to obtain the diblock polymer 3.6g that end is sulfydryl.

Embodiment 6

Polymer 500mg prepared by embodiment 5 is mixed with 20g dodecane, 5g cyclohexyl benzene, is heated to 100 DEG C of dissolutions After 30 minutes, with obtaining spare polymer solution after 1 μ membrane filtration.By the red CdSe/ZnS quantum dot that 1.2g oleyl amine is stable It is mixed 30 minutes with the above-mentioned polymer solution of 8.8g, 0.45 μ membrane filtration obtains quantum dot ink.

Embodiment 7

A kind of preparation method of block polymer modifying agent SH-A-B (V-B of SH-), comprising the following steps:

Bis- p-methylphenyl of functional monomer N-N--of V block chain of offer formula causes vinyl aniline 5g, free radical Agent azo-bis-isobutyl cyanide (AIBN) 5mg, dithiobenzoic acid phenethyl ester 60mg mixing are scattered in 50mL tetrahydrofuran, through true Sky-liquid nitrogen deaeration removes mixing oxygen therein for several times, is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Reactant is mixed It closes object and is put into liquid nitrogen the cooling several seconds and terminate chain transfer reaction, then n-hexane precipitates to obtain first segment functionalized polymer chain big The total 3.4g of molecule RAFT reagent.

By above-mentioned functionalized polymer chain Macro RAFT agent 3g and styrene 2g, AIBN 2mg, it is scattered in 50mL tetra- In hydrogen furans, mixing oxygen therein is removed for several times through vacuum-liquid nitrogen deaeration, be heated to 50 DEG C after being filled with nitrogen, polymerization 48 is small When.Reaction-ure mixture is put into liquid nitrogen cooling several seconds termination chain transfer reaction, then n-hexane precipitates to obtain end to be two The diblock polymer 4g of monothioester.

End is that the diblock polymer 4g and cyclohexylamine 10g of dithioesters are reacted at room temperature in 50mL tetrahydrofuran into 6 Hour, then n-hexane precipitates to obtain the diblock polymer 3.6g that end is sulfydryl.

Embodiment 8

Polymer 500mg prepared by embodiment 7 is mixed with 20g dodecane, after being heated to 100 DEG C of dissolutions 30 minutes, with 1 Spare polymer solution is obtained after μ membrane filtration.The stable red CdSe/ZnS quantum dot of 1.5g oleyl amine and 8.5g is above-mentioned poly- Polymer solution is mixed 30 minutes, and 0.45 μ membrane filtration obtains quantum dot ink.

Embodiment 9

A kind of preparation method of block polymer modifying agent SH-A-B (V-VII-B of SH-), comprising the following steps:

Bis- p-methylphenyl of functional monomer N-N--of V block chain of offer formula causes vinyl aniline 3g, free radical Agent azo-bis-isobutyl cyanide (AIBN) 3mg, dithiobenzoic acid phenethyl ester 60mg mixing, are scattered in 50mL tetrahydrofuran, pass through Vacuum-liquid nitrogen deaeration removes mixing oxygen therein for several times, is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Addition formula VII The functional monomer N- of block chain removes mixing oxygen therein to vinyl benzene methyl carbazole 2g, through vacuum-liquid nitrogen deaeration for several times Gas is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Reaction-ure mixture is put into liquid nitrogen cooling several seconds termination chain tra nsfer Reaction, then n-hexane precipitates to obtain the total 3.4g of first segment functionalized polymer chain Macro RAFT agent.

Embodiment 10

Polymer 500mg prepared by embodiment 9 is mixed with the 20g tetradecane, 10g cyclohexyl benzene, is heated to 100 DEG C of dissolutions After 30 minutes, with obtaining spare polymer solution after 1 μ membrane filtration.By the red CdSe/ZnS quantum dot that 1.0g oleyl amine is stable It is mixed 30 minutes with the above-mentioned polymer solution of 9.0g, 0.45 μ membrane filtration obtains quantum dot ink.

Embodiment 11

Block of bis- p-methylphenyl of functional monomer N-N--of V block chain of offer formula to vinyl aniline 3g, VII type The functional monomer N- of chain is to vinyl benzene methyl carbazole 2g, radical initiator azo-bis-isobutyl cyanide (AIBN) 3mg, two thio Phenylamino benzoic acid ethyl ester 60mg mixing, is scattered in 50mL tetrahydrofuran, and it is therein to remove mixing for several times through vacuum-liquid nitrogen deaeration Oxygen is heated to 50 DEG C after being filled with nitrogen, polymerize 48 hours.Reaction-ure mixture is put into liquid nitrogen cooling several seconds terminating chain to turn Reaction is moved, then n-hexane precipitates to obtain the total 3.4g of first segment functionalized polymer chain Macro RAFT agent.

By above-mentioned functionalized polymer chain Macro RAFT agent 3g and styrene 2g, AIBN 2mg, it is scattered in 50mL tetra- In hydrogen furans, mixing oxygen therein is removed for several times through vacuum-liquid nitrogen deaeration, be heated to 50 DEG C after being filled with nitrogen, polymerization 48 is small When.Reaction-ure mixture is put into liquid nitrogen cooling several seconds termination chain transfer reaction, then n-hexane precipitates to obtain end to be two The diblock polymer 3.8g of monothioester.

End is that the diblock polymer 4g and cyclohexylamine 10g of dithioesters are reacted at room temperature in 50mL tetrahydrofuran into 6 Hour, then n-hexane precipitates to obtain the diblock polymer 3.1g that end is sulfydryl.

Embodiment 12

Polymer 500mg prepared by embodiment 11 is mixed with 20g dodecane, 5g decahydronaphthalene, is heated to 100 DEG C of dissolutions 30 After minute, with obtaining spare polymer solution after 1 μ membrane filtration.By the stable red CdSe/ZnS quantum dot of 1.2g oleyl amine with The above-mentioned polymer solution of 8.8g is mixed 30 minutes, and 0.45 μ membrane filtration obtains quantum dot ink.

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims

1. a kind of composite particles, which is characterized in that including inorganic nanoparticles and be incorporated in the inorganic nanoparticles surface Block copolymer, wherein the block copolymer is the block copolymer for including block chain A and block chain B, the block chain A For the block chain with hole transporting properties, the block chain B is polystyrene, and described block copolymer-modified dose at least contains One terminal sulfhydryl group, and the block copolymer passes through the terminal sulfhydryl group in conjunction with the inorganic nano material.

2. composite particles as described in claim 1, which is characterized in that the block copolymer includes a mid-block chain, The mid-block chain is made of block chain A and block chain B, and one end of the mid-block chain is connected with the end mercapto Base.

3. composite particles as claimed in claim 2, which is characterized in that in the block copolymer, connect the mid-block Another end of chain is the aliphatic of 3-10 carbon atom, aromatic group.

4. composite particles as claimed in claim 3, which is characterized in that the monomer in the block chain A is selected from formula I, II institute of formula Show at least one of structure,

5. composite particles as claimed in claim 4, which is characterized in that the weight average molecular weight of the block copolymer is 800- 12000。

6. composite particles as claimed in claim 5, which is characterized in that the weight average molecular weight or the degree of polymerization of the block copolymer For 1000-6000.

7. composite particles as claimed in claim 5, which is characterized in that by the total weight of the block copolymer be 100% in terms of, The weight percentage of the block chain A is 10%-90%.

8. composite particles as claimed in claim 7, which is characterized in that by the total weight of the block copolymer be 100% in terms of, The weight percentage of the block chain A is 40%-60%.

9. composite particles according to any one of claims 1-4, which is characterized in that the total weight with the composite particles is 100% meter, the weight percentage of the block copolymer are 10-80%.

10. composite particles as claimed in claim 9, which is characterized in that by the total weight of the composite particles be 100% in terms of, The weight percentage of the block copolymer is 20-60%.

11. a kind of block copolymer, which is characterized in that the block copolymer includes a mid-block chain, and the centre is embedding Section chain is made of block chain A and block chain B, and one end of the mid-block chain is connected with a terminal sulfhydryl group, and the block is total Another end of polymers is the aliphatic of 3-10 carbon atom, aromatic group, and the block chain A contains carbazole base junction Structure, the block chain B are polystyrene.

12. block copolymer as claimed in claim 11, which is characterized in that the monomer in the block chain A is selected from formula I, formula At least one of structure shown in II,

13. block copolymer as claimed in claim 12, which is characterized in that the total weight with the block copolymer is 100% meter, the weight percentage of the block chain A are 10%-90%.

14. block copolymer as claimed in claim 12, which is characterized in that the weight average molecular weight of the block copolymer is poly- Right is 1000-6000.