CN1789370A - Luminous polyester material containing polyhedral sesquisilicane and its preparation method - Google Patents

Abstract

The invention belongs to the technical field of photoelectric materials, and specifically relates to a series of novel polyaryleacetylene-type luminescent materials containing polyhedral silsesquisilane and a preparation method thereof. The present invention uses conjugated monomers such as fluorene, thiophene, benzene, benzyne, carbazole, and various types of polyhedral silsesquisilanes as raw materials, and synthesizes a series of polyhedral silsesquisilanes containing polyhedral silsesquisilanes through organic reactions such as metal catalysis. The polymer luminescent material is an organic/inorganic hybrid nanometer material. Due to the existence of polyhedral silsesquisilane with inorganic siloxane cage structure, the formation of aggregates is effectively prevented, and the organic polymer material is endowed with outstanding thermal stability and spectral stability. Therefore, the resulting novel organic/inorganic hybrid luminescent material has high quantum efficiency and thermal stability of luminescence. This type of material can be used to prepare electronic devices such as organic light-emitting diodes.

Description

Contain polymer luminescent material of polyhedron sesquialter silane and preparation method thereof

Technical field

The invention belongs to photoelectricity novel material and technical field, be specifically related to a kind of polymer luminescent material that contains polyhedron sesquialter silane and preparation method thereof.

Technical background

Conjugatd polymers is because at electron device, as the potential application of aspects such as polymer light-emitting diode, polymer light-emitting battery, solar cell, organic field-effect tube and chemical-biological sensing and by extensive studies.But organic materials character of conjugated polymers itself makes the poor heat stability of this material, has a strong impact on the work-ing life of device in the time of in being applied to electron device; In addition, conjugated polymers forms low-yield acceptors such as congeries, excimer easily when solid-state, cause glow color impure, and device efficiency is low.These drawbacks of conjugated polymer material itself have hindered the commercial applications of conjugated polymers electron device.

Recently, a lot of methods are attempted being used for improving the drawback of above-mentioned mentioned conjugated polymer luminescent material.Wherein, the most representative is exactly blend, and the polymkeric substance higher conjugated polymer luminescent material and some second-order transition temperatures carries out blend.Soul-stirring is that the electroluminescent device that the blend of conjugated polymers and inorganic sheet mica prepares has pure glow color, high quantum yield and long device lifetime.This is just indicating that the shortcoming by remedying conjugatd polymers material itself with the inorganic materials blend is feasible.But blend has inevitably brought and has been separated, and this has destroyed effective transmission of the exciton and the electric charge of material internal to a certain extent again, thereby makes the electron device performance reduce.

Polyhedron sesquialter silane (polyhedral oligomeric silsesquioxane, POSS) be a kind of novelty the hybrid nanostructures (nanobuilding blocks, NBs).It has inorganic silica cage shape skeleton, and the surface is covered by organic substituent, and this makes it have good polymer phase capacitive, biocompatibility and some other surface compatability.The size of a polyhedron sesquialter silane molecule is relevant with the organic substituent on silica number and surface, generally between the 1-3 nanometer.Studies show that of the nearly relevant during the last ten years polymkeric substance that contains polyhedron sesquialter silane, after the form of this nanostructures with inorganic kernel cage structure of polyhedron sesquialter silane by covalent linkage be incorporated into polymeric matrix, obtain hybrid nano-material and have high mechanical property and physical property, especially environmental stability.Exactly because polyhedron sesquialter silane has so many advantage, its as the hybrid nanostructures application in polymkeric substance opened up rapidly.

Summary of the invention

The object of the invention is to provide a kind of Heat stability is good, polymer luminescent material that quantum yield is high and preparation method thereof.

The present invention is incorporated into poly-aryl ethane to polyhedron sesquialter silane, and (Polyaryleneethynylenes PAEs) in the system, has obtained a kind of new polymer luminescent material, and this material is a kind of hybrid nano material.Because have the existence of the polyhedron sesquialter silane of inorganic nature, this material has high thermostability and quantum yield, can be used for preparing electron devices such as organic light emission two machine pipes.The chemical structure of this polymkeric substance is as follows:

This polymkeric substance is for Ar by diine ₀, two bromos or two iodo Ar ₁With the dihalogenated polyhedron sesquialter silane Ar that contains ₂Carry out the Sonagashira polyreaction, resultant through purification steps such as Soxhlet extractions.

Wherein, Ar ₀For various substituting groups being arranged or do not have substituent pyridine, 9,9-two replaces a kind of among fluorenyls, phenyl, thiophene, the pyrroles; Ar ₁For various substituting groups being arranged or do not have substituent pyridine, 9,9-two replaces a kind of among fluorenyls, phenyl, thiophene, the pyrroles; Ar ₂A kind of among the pyridine of various types of polyhedron sesquialter silane substituted, fluorenyl, carbazole, phenyl, thiophene, the pyrroles.X is an any number, and y is not equal to zero any number.

This polymkeric substance contains polyhedron sesquialter silane Ar ₂, its chemical structure is as follows:

Wherein, Ar is a kind of among pyridine, fluorenyl, carbazole, phenyl, thiophene, the pyrroles; R ₁A kind of in the alkoxyl group of the alkyl of hydrogen atom, random length, random length.In addition, when Ar is fluorenyl, R ₁A kind of in the alkoxyl group of the alkyl of hydrogen atom, random length, random length, the polyhedron sesquialter silane; R ₀For being the polyhedron sesquialter silane of any class, comprise complete condensation polyhedron sesquialter silane and incomplete condensation polyhedron sesquialter silane, wherein condensation polyhedron sesquialter silane comprises hexahedron sesquialter silane, octahedra sesquialter silane, decahedron sesquialter silane etc. again fully.

The preparation method of the polymkeric substance that the present invention proposes is as follows:

By diine for Ar ₀, two bromos or two iodo Ar ₁With the dihalogenated polyhedron sesquialter silane Ar that contains ₂Be raw material, carry out the Sonagashira coupled reaction, pass through purification steps such as Soxhlet extraction again, finally make described polymkeric substance.

Wherein, Ar ₁The dihalo reaction that is the aromatics by routine obtains.

Under the condition as the catalyzer existence, di halo aromatic compound and trimethyl silicane alkynes carry out the Sonagashira coupled reaction at palladium catalyst and cuprous iodide, and deprotection under alkaline condition just can obtain diine for Ar then ₀

Ar ₂Be to carry out linked reaction by di halo aromatic compound with polyhedron sesquialter silane to obtain with active function groups.

In the aforesaid method, specifically be that three kinds of compound of reactions and triphenyl phosphorus palladium and cuprous iodide are dissolved in the mixing solutions of tetrahydrofuran (THF) and Diisopropylamine, be heated to 60-80 ℃, reacted 12-48 hour, reaction is poured reaction mixture in the water into after finishing, and uses chloroform extraction; Organic phase solution decompression is spin-dried for, and again with the chloroform dissolving, sedimentation in methyl alcohol promptly obtains containing the new polymers of polyhedron half silane.

Owing to have the existence of the polyhedron sesquialter silane of inorganic nature, not only make material of the present invention have high thermostability, and the polyhedron sesquialter silane of large volume existing way with the side chain form in polymkeric substance makes that distance becomes big between polymer chain, reduce the possibility that basic sharp meaning compound and congeries form, thereby improved material luminous efficiency.In addition, the existence of polyhedron sesquialter silane makes this material show superior spectrum stability when being used to device.Therefore, this material can be used for preparing the electron devices such as organic light emission two machine pipes of efficient stable.

Description of drawings

Fig. 1 is the fluorescent emission spectrogram that synthetic contains the luminescence polymer annealing front and back of polyhedron sesquialter silane among the present invention.

Embodiment

In order to understand the content of patent of the present invention better, below the present invention is further specified, but it is pointed out that this is not to limit the scope of the invention by specific embodiment.

Embodiment 1.

Poly[9,9 '-dioctyfluorene-2,7-yleneethylene-co-diPOSSfluorene-2,7-ylenthylene] synthetic

At first, the polymer monomer that contains polyhedron sesquialter silane that synthesizes the peculiar novelty of the present invention.Its reaction equation is as follows:

With 2,7-dibromo-9, has the polyhedron sesquialter silane and the salt of wormwood of benzyl chlorine functional group at 9-bis (4-hydroxyphenyl) fluorine (1), is dissolved in the mixed solvent of DMF and tetrahydrofuran (THF), is heated to 60 ℃, stirs 2-4 hour.Reaction is poured reaction mixture in the big water gaging into after finishing, and uses ethyl acetate extraction, the yellow solid that choosing obtains after steaming carries out column chromatography for separation with chloroform and sherwood oil for walking fluid, obtains white product, 2,7-Dibromo-9,9 '-diPOSSfluorene (2).

Moreover, synthetic other polymerization single polymerization monomer.

Fluorene (3) is dissolved among the anhydrous and oxygen-free THF, under-78 ℃, is added dropwise to the n-Butyl Lithium reagent of 1.6M, react after 1 hour, add bromination of n-butane.Reaction is 3 hours under the room temperature.Add a large amount of water termination reactions, and, use the saturated common salt water washing, use anhydrous sodium sulfate drying again with the CH2Cl2 extraction.Obtain colorless solid 9 after being spin-dried for solvent, 9 '-dioctyl fluorene (4).

With CuBr ₂Be dissolved in the water, add alumina powder, water is spin-dried for, and in vacuum drying oven 90 ℃ of dryings, make the CuBr that is dispersed on the alumina powder ₂With 9,9 '-dioctyl fluorene (4) and adsorbed CuBr ₂The flask of alumina powder in add CCl ₄, reflux 24 hours.The solids removed by filtration powder is spin-dried for solution decompression, and separation obtains white solid 2,7-two bromo-9,9 '-dioctyl fluorene (5) to crude product through post.

With 2,7-two bromo-9,9 '-dioctyl fluorene (5) and triphenyl phosphorus palladium and cuprous iodide are dissolved in the Diisopropylamine; under nitrogen protection, add trimethyl silicane alkynes; 70 ℃ were reacted 6 hours, and the reaction soln decompression is spin-dried for, and the brown oil matter that obtains obtains white solid after separating through post.This white solid is dissolved among the THF, slowly adds the sodium hydroxide mixing solutions of methyl alcohol and 50% again, reacted 2 hours.This mixed solution decompression is spin-dried for, obtains faint yellow solid after separating through post, be product 2,7-diacetylene-9,9 '-dioctyl fluorene (6).

At last, carry out the reaction of Sonagashira condensation polymerization again.With intermediate compound (2), (5), (6), triphenyl phosphorus palladium and cuprous iodide, be dissolved in the mixing solutions of tetrahydrofuran (THF) and Diisopropylamine, be heated to 70 ℃ of reactions 1 to 2 day.Reaction is poured reaction mixture in the water into after finishing, and uses chloroform extraction.The organic phase solution decompression is spin-dried for and obtains brown solid, and with the minimum of chloroform dissolving, sedimentation obtains containing the new polymers of polyhedron sesquialter silane in methyl alcohol.Chemical structural formula is as follows:

This polymkeric substance has high luminous quantum efficiency when solid-state, compare with the poly-fluorenyl acetylene of homopolymer, and the solid luminescent quantum yield has improved 10%.In addition, it also has superior solid state spectrum stability.As shown in Figure 1.

Embodiment 2

Po1y[9,9 '-dioctyfluorene-2,7-yleneethylene-co-POSS-phenylene] synthetic

At first, the polymer monomer that contains polyhedron sesquialter silane that synthesizes the peculiar novelty of the present invention.Its reaction equation is as follows:

With 2,5-dibromo-4-(hexyloxy) phenol (7), have the polyhedron sesquialter silane and the salt of wormwood of benzyl chlorine functional group, be dissolved in the mixed solvent of DMF and THF, be heated to 60 ℃, stirred 2-4 hour.Reaction is poured reaction mixture in the big water gaging into after finishing, and uses ethyl acetate extraction, decompression is spin-dried for the yellow solid that obtains and carries out column chromatography for separation with chloroform and sherwood oil for walking fluid, obtain white product, 1,4-dibromo-2-hexyloxy-5-POSSbenzene (8).The preparation process of compound (5), (6) is with embodiment 1.

Carry out the reaction of Sonagashira condensation polymerization.Compound (8), (5), (6), triphenyl phosphorus palladium and cuprous iodide are dissolved in the mixing solutions of tetrahydrofuran (THF) and Diisopropylamine, are heated to 70 ℃ of reactions 1 to 2 day.Reaction is poured reaction mixture in the water into after finishing, and uses chloroform extraction.The organic phase solution decompression is spin-dried for and obtains brown solid, and with the minimum of chloroform dissolving, sedimentation obtains containing the new polymers of polyhedron sesquialter silane in methyl alcohol.Chemical structural formula is as follows:

This polymkeric substance has high luminous quantum efficiency, compares with homopolymer, and the solid luminescent quantum yield has improved 15%.In addition, its solid state spectrum stability also increases.

Claims (4)

1. A polyaryleacetylene-type luminescent material containing polyhedral silsesquisilane, characterized in that the chemical structural formula of the polymer is as follows: Among them, x is any value, and y is any value not equal to zero; Ar ₀ is one of pyridine, 9,9-disubstituted fluorenyl, carbazole, triphenylamine, phenyl, thiophene, pyrrole with various substituents or no substituents; Ar ₁ is one of pyridine, 9,9-disubstituted fluorenyl, carbazole, triphenylamine, phenyl, thiophene, pyrrole with various substituents or no substituents; Ar ₂ is a dihalogenated polyhedron Aromatic compounds of semisilane; The chemical structural formula of _Ar2 is as follows:

Here, Ar is one of pyridine, fluorenyl, carbazole, phenyl, thiophene, pyrrole, R ₁ is one of a hydrogen atom, an alkyl group of any length, and an alkoxy group of any length, and R ₀ is any type of polyhedral silsesquisilane. 2. The luminescent material according to claim 1, characterized in that in the Ar ₂ , when Ar is a fluorenyl group, R ₁ is a hydrogen atom, an alkyl group of any length, an alkoxy group of any length, polyhedral sesqui One of the silanes. 3. The luminescent material according to claim 1, characterized in that the polyhedral silsesquilanes include fully condensed polyhedral silsesquilanes and incompletely condensed polyhedral silsesquisilanes, wherein the fully condensed polyhedral silsesquilanes include hexahedral silsesquilanes, Octahedral silsesquilanes, decahedral silsesquisilanes. 4. The synthesis method of luminescent material according to claim 1, characterized in that the steps are as follows: Using diacetylenic Ar ₀ , dibromo or diiodo Ar ₁ and dihalogenated Ar ₂ containing polyhedral silsesquilanes as raw materials, carry out Sonagashira coupling reaction, and then undergo purification steps such as Soxhlet extraction to obtain the target polymer Objects; wherein, through the coupling reaction of dihalogenated aromatic compounds and polyhedral silsesquisilanes with active functional groups.