阅读说明：本技术 一类电致发光聚合物及其制备方法与应用 (A kind of electroluminescent polymer and the preparation method and application thereof ) 是由 应磊 胡黎文 郭婷 彭俊彪 于 2019-07-31 设计创作，主要内容包括：本发明公开了一类电致发光聚合物及其制备方法与应用。该方法包括：在惰性气体保护下,用溶剂完全溶解所述的聚合单体单元M1和M2与含Ar结构的单体,在催化剂和四乙基氢氧化铵作用下,加热进行Suzuki聚合反应；加入苯硼酸,恒温反应；再加入溴苯继续恒温反应；将所得反应液纯化即得目标产物。本发明提供的一类电致发光聚合物,其含有杂原子,可以提高发光材料的荧光量子产率和载流子传输能力,有利于发光器件获得高效稳定的发光器件性能。本发明提供的一类电致发光聚合物具有较好的溶解性,可采用常见有机溶剂溶解,然后通过旋涂、喷墨打印或印刷成膜等方式,制备得到发光二极管的发光层。(The invention discloses a kind of electroluminescent polymers and the preparation method and application thereof.This method comprises: under inert gas protection, the monomer of the polymeric monomeric unit M1 and M2 and the structure containing Ar are completely dissolved with solvent, under catalyst and tetraethyl ammonium hydroxide effect, heating carries out Suzuki polymerization reaction；Phenyl boric acid, isothermal reaction is added；It adds bromobenzene and continues isothermal reaction；Gained reaction solution is purified up to target product.The fluorescence quantum yield and carrier transport ability of luminescent material can be improved containing hetero atom in one kind electroluminescent polymer provided by the invention, is conducive to the luminescent device performance that luminescent device obtains efficient stable.One kind electroluminescent polymer provided by the invention has preferable dissolubility, and common organic solvents dissolution can be used, and then by modes such as spin coating, inkjet printing or printing film forming, the luminescent layer of light emitting diode is prepared.)

1. a kind of electroluminescent polymer, which is characterized in that its structural formula is

Or

Wherein, 0≤x≤1；N is the degree of polymerization, and the value of n is 1-1000；

Structural unit Ar is one of following conjugation or non-conjugated structure unit:

And

Wherein, R₁For H, aryl, triphenylamine, carbon atom number be 1-20 straight chained alkyl, carbon atom number be 1-20 branched alkyl or Carbon atom number is the alkoxy of 1-20；Z₁、Z₂Independently it is expressed as hydrogen, deuterium, fluorine, alkenyl, alkynyl, itrile group, amido, nitro, acyl Naphthenic base that alkyl that base, alkoxy, carbonyl, sulfuryl, carbon atom number are 1-30, carbon atom number are 3-30, carbon atom number 6- 60 aromatic hydrocarbyl or carbon atom number is the aromatic heterocycle of 3-60.

2. a kind of method for preparing electroluminescent polymer described in claim 1, which comprises the steps of:

(1) under the protection of inert gas, by the monomer or polymeric monomeric unit M2 of polymeric monomeric unit M1 and the structure containing Ar It is added in organic solvent with the monomer of the structure containing Ar, is uniformly mixed, then adds catalyst action and tetraethyl ammonium hydroxide Aqueous solution is uniformly mixed, obtains mixed liquor；

(2) step (1) the mixed liquor heating is subjected to Suzuki polymerization reaction, maintains temperature-resistant addition phenyl boric acid, carries out Bromobenzene is added then in the state of temperature-resistant in first time isothermal reaction, carries out second of isothermal reaction, obtains reaction solution, The reaction solution is purified, the electroluminescent polymer is obtained.

3. preparing the method for electroluminescent polymer according to claim 2, which is characterized in that step (1) described indifferent gas Body is argon gas；The organic solvent be toluene, tetrahydrofuran, dimethylbenzene, dioxane and N,N-dimethylformamide in extremely Few one kind；The catalyst is palladium acetate, tris(dibenzylideneacetone) dipalladium, thricyclohexyl phosphorus, tetra-triphenylphosphine palladium and triphen At least one of base phosphine dichloride palladium；The mole of the catalyst is 5 ‰~the 3% of reaction monomers moles total number, described Reaction monomers moles total number is the moles total number or polymerized monomer list of both monomers of polymeric monomeric unit M1 and the structure containing Ar The moles total number of first M2 and both monomers of the structure containing Ar；The volume ratio of the tetraethyl ammonium hydroxide aqueous solution and organic solvent For 1:4~12.

4. preparing the method for electroluminescent polymer according to claim 2, which is characterized in that step (1) polymerization is single The structural formula of body unit M1 is

The structural formula of step (1) the polymeric monomeric unit M2 is

5. preparing the method for electroluminescent polymer according to claim 2, which is characterized in that in step (1), select poly- The monomer for closing monomeric unit M1 and the structure containing Ar is added in organic solvent, then the list of the polymeric monomeric unit M1 and the structure containing Ar The molar ratio of body is x:1-x (0≤x≤1), the volume ratio of the moles total number of the polymerized monomer and organic solvent be 1:12~ 24, the polymerized monomer includes the monomer of polymeric monomeric unit M1 Yu the structure containing Ar；

When selecting the monomer of polymeric monomeric unit M2 and the structure containing Ar to be added in organic solvent, polymeric monomeric unit M2 is tied with containing Ar The molar ratio of the monomer of structure is x:1-x (0≤x≤1), and the moles total number of the polymerized monomer and the volume ratio of organic solvent are 1: 12~24；The polymerized monomer includes the monomer of polymeric monomeric unit M2 and the structure containing Ar.

6. preparing the method for electroluminescent polymer according to claim 2, which is characterized in that step (2) described Suzuki The temperature of polymerization reaction is 60-100 DEG C, and the time of the Suzuki polymerization reaction is 12-36h, the first time isothermal reaction Time be 6-12h；The time of second of isothermal reaction is 6-12h.

7. the method according to claim 2 for preparing electroluminescent polymer, which is characterized in that step (2) the benzene boron The mole dosage of acid is the 10-20% of step (1) described reaction monomers moles total number.

8. the method according to claim 2 for preparing electroluminescent polymer, which is characterized in that step (2) described bromobenzene Mole dosage be 1~5 times of mole dosage of the phenyl boric acid.

9. the method according to claim 2 for preparing electroluminescent polymer, which is characterized in that step (2) described purifying Include: to be cooled to room temperature the reaction solution, pour into methanol and precipitate, filter, dry crude product is successive by the crude product It is extracted with methanol, acetone and n-hexane, again with toluene dissolution, column chromatography for separation, precipitating is in methanol solution again after concentration, mistake Filter, it is dry to get the electroluminescent polymer.

10. application of one kind electroluminescent polymer described in claim 1 in the luminescent layer for preparing LED device.

Technical field

The invention belongs to organic photoelectric technical field, in particular to a kind of electroluminescent polymer and preparation method thereof with answer With.

Background technique

Using organic material as luminescent material in Organic Light Emitting Diode (OLED) display, material structure is easy modification And improve, range of choice is wide；Driving voltage is low, only needs the DC voltage of 3~12V；Can self-luminous, do not need backlight；Wide view Angle is close to 180 °；Fast response time, up to 1 μ s magnitude；In addition, there are also light weight, it is ultra-thin, large scale, flexible face can be made The advantages that plate, easy processing and forming.Due to the numerous advantage of OLED display, the extensive pass of scientific circles and industry has been obtained Note so far, has more mechanisms investment resources and arrives OLED technology since Kodak in 1987 develops OLED device Exploitation.By the fast development of decades, OLED flat panel display is tending to mature, and occupies in flat display field One seat, but the service life, stability, in terms of still need to continue to improve.

For preparation OLED device using vacuum evaporation process, instrument and equipment is expensive at present.Stock utilization it is low (~ 20%), so that OLED product price is high.Solution processing technology can make up the deficiency of vacuum evaporation, gradually attract scientific research The concern of mechanism and manufacturer, company.Polymer can form the film of high quality, be not easy to crystallize；Chemical structure, example can also be changed Such as, by the regulation to conjugate length, the transformation of substituent group, the main, adjustment of side chain type structure and the change of feed ratio etc. come real Now shining such as the different colours of red, green, blue；Also there is solution processing, such as spin coating simultaneously, inkjet printing prints, roll-to-roll Etc. modes form a film, can large scale molding the advantages of.

However, there are still certain deficiencies for the conjugated polymer for OLED device reported in the prior art.For example, The spectrum stability of blue light frequency-doubling is poor, device efficiency is lower, device lifetime is shorter or the synthesis of partial polymer monomer Difficulty is big, is unsuitable for being mass produced, these limit them in the commercial applications of the device of solution processable；Therefore, city Still demand convieniently synthesized (being especially suitable for the synthetic method with large-scale production), good processability is (in organic solvent on field In with excellent dissolubility), the luminescence polymer materials of good electroluminescent properties.Particularly with the hair of solution processable Optical diode device, there is the demands with efficient red, green, blue photopolymer material.With the polymer phase ratio of the prior art, The efficiency of OLED can be improved by active layer.

The object of the present invention is to provide a kind of electroluminescent polymer, polymerized monomer M1 or M2 are readily synthesized, especially It is suitble to large-scale production；Its polymer has excellent electroluminescent properties；There is excellent dissolubility in organic solvent, it is high Carrier mobility does not have the defect of the prior art as described above.Another object of the present invention is that extension this field is special The range of polymer luminescent material obtained by industry personnel.

Present inventor have found that S, S- dioxo-dibenzothiophene unit are a kind of blue light units haveing excellent performance, Its fluorescence quantum yield with higher；Sulfuryl (- SO in structure₂) improve the electron affinity and electron mobility of molecule； Sulphur atom has preferable inoxidizability etc., wherein the polymer containing 3,7 substitution-S, S- dioxo-dibenzothiophene units shows Superior photoelectric properties out." materials chemistry C " (Journal of Materials Chemistry C) is reported with polyfluorene master 3,7-S is introduced in chain, the polymer of S- dioxo-dibenzothiophene unit is that the maximum lumen of the single layer device of luminescent layer is high-efficient Up to 7.1cd/A, it is the highest blue light frequency-doubling of current efficiency that chromaticity coordinates, which is (0.16,0.18),.101255336 B of CN is disclosed The position 3,7- of S, S- dioxo-dibenzothiophene unit or 2,8- are linked at the blue electroluminescence polymer of main chain.CN 101712674 B are disclosed on the position 2- and/or 8- or on 3- and/or 7- by alkyl-substituted S, S- dioxy-dibenzo The polymer of thiophene unit.However, not disclosing clearly with claimed polymer in the prior art.

Summary of the invention

In order to overcome deficiencies of the prior art, the object of the present invention is to provide a kind of electroluminescent polymer and Preparation method and application.

The primary purpose of the present invention is that providing a kind of electricity for current organic/polymer LED (O/PLED) Photoluminescence polymer.The electroluminescent polymer has preferable dissolubility, and more excellent photoelectric properties are suitable for solution processing And inkjet printing, there is huge application potential.

Another object of the present invention is to provide the preparation methods of a kind of electroluminescent polymer.

A further object of the present invention is to provide a kind of electroluminescent polymers can be used for light emitting diode, organic Field effect transistor, organic solar batteries, organic laser diode etc. are preferred for preparing shining for LED device Layer.

The purpose of the present invention is realized at least through one of following technical solution.

The preparation method of one kind electroluminescent polymer provided by the invention, this method comprises: under inert gas protection, The polymeric monomeric unit of the electroluminescent polymer and the monomer of the structure containing Ar are completely dissolved with solvent, in catalyst action and Under tetraethyl ammonium hydroxide effect, heating carries out Suzuki polymerization reaction；Phenyl boric acid, isothermal reaction is added；Add bromobenzene after Continuous isothermal reaction；Gained reaction solution is purified up to target product.One kind electroluminescent polymer provided by the invention, contains The fluorescence quantum yield and carrier transport ability of luminescent material can be improved in hetero atom, is conducive to luminescent device and obtains efficiently Stable luminescent device performance.One kind electroluminescent polymer provided by the invention has preferable dissolubility, can be used common Shining for light emitting diode is prepared then by modes such as spin coating, inkjet printing or printing film forming in organic solvent dissolution Layer.

The polymerized monomer M1 or M2 of one kind electroluminescent polymer provided by the invention, are S, S- dioxo-dibenzothiophene Derivative, fluorescence quantum yield with higher and excellent thermal stability, electrochemical stability；Polymerized monomer M1 or M2 are flat Face property is good, rigidity is strong, is conducive to the transmission of carrier, and luminescent device is made to obtain the device performance of efficient stable；The present invention provides Electroluminescent polymer have preferable solubility property, be suitable for solution process, device preparation cost can be reduced, and can make Standby large area flexible OLED device.So it is provided by the invention one kind electroluminescent polymer have in organic electronic display field it is huge Big development potentiality and prospect.

The polymerized monomer of one kind electroluminescent polymer provided by the invention, chemical structural formula are as follows:

The chemical equation that the preparation method of the polymerized monomer of one kind electroluminescent polymer of the present invention is related to is such as Shown in lower:

The preparation method of the polymerized monomer of one kind electroluminescent polymer of the present invention, includes the following steps:

(1) under inert gas environment, Isosorbide-5-Nitrae-dibromine naphthalene and borate ester or naphthalene boronic acids ester are dissolved in tetrahydrofuran solution, In Under the aqueous environment of the effect of catalyst tetra-triphenylphosphine palladium and alkali potassium carbonate or sodium carbonate, it is heated to 70~90 DEG C of reactions 12 ~24 hours.After stopping suzuki coupling reaction, it is spin-dried for solvent, by silica gel column chromatography, petroleum ether and methylene chloride mixing are molten Agent (volume ratio 8:1) purification, obtains the bromo- 4- phenylnaphthalene of compound 1- or 4- bromo- 1,1 '-two dinaphthalene；Wherein 1,4- dibromine naphthalene, Borate ester or naphthalene boronic acids ester, catalyst, alkali molar ratio be 1~2:1:0.02~0.05:5~10, the matter of the aqueous solution of alkali Amount concentration is 40~80wt%, preferably 50wt%；

(2) by the bromo- 4- phenylnaphthalene of compound 1- or 4- bromo- 1,1 '-dinaphthyl is dissolved in anhydrous tetrachloromethane, is protected from light in room temperature Under the conditions of, bromine is added and reacts 6~24 hours progress bromination reactions, after reaction stops, with saturation NaHSO₃Aqueous solution removed Bromine is measured, is extracted with dichloromethane three times, organic phase is concentrated, is purified by silica gel column chromatography, petroleum ether is eluent, is obtained The bromo- 4- of 1- (4- bromophenyl) naphthalene or 4,4 '-two bromo- 1,1 '-two dinaphthalenes；Wherein the molar ratio of the bromo- 4- phenylnaphthalene of 1- and bromine is The molar ratio of 1:1~1.5 or the bromo- 1,1 '-dinaphthyl of 4- and bromine is 1:1~1.5；

(3) by the bromo- 4- of compound 1- (4- bromophenyl)；Naphthalene or 4,4 '-two bromo- 1,1 '-two dinaphthalene is dissolved in chloroform, Chlorosulfonic acid is added dropwise, temperature is stablized at 20~50 degrees Celsius, reacted 4~8 hours.After reaction, reactant ice water is poured into mix It closes in object, and uses NaHCO₃Solution is adjusted to neutrality, filters out insoluble matter, then drying after washed several times with water is tied again with acetic acid Crystalline substance obtains white needles 5,9- dibromo benzo [b] naphtho- [1,2-d] thiophene -7,7- dioxide (M1) or 5,9- dibromo Naphtho- [2 '-d of 2,1-b:1 '] thiophene -7,7- dioxide (M2).The wherein bromo- 4- of 1- (4- bromophenyl) naphthalene or 4,4 '-two bromo- 1, The molar ratio of 1 '-two dinaphthalene and chlorosulfonic acid is 1:2~5.

One kind electroluminescent polymer provided by the invention, structural formula are

Wherein, 0≤x≤1；N is the degree of polymerization, and the value of n is 1-1000；

Structural unit Ar is one of following conjugation or non-conjugated structure unit:

Wherein, R₁For H, aryl, triphenylamine, carbon atom number be 1-20 straight chained alkyl, carbon atom number be 1-20 branch The alkoxy that alkyl or carbon atom number are 1-20；Z₁、Z₂Independently be expressed as hydrogen, deuterium, fluorine, alkenyl, alkynyl, itrile group, amido, Naphthenic base that alkyl that nitro, acyl group, alkoxy, carbonyl, sulfuryl, carbon atom number are 1-30, carbon atom number are 3-30, carbon atom The aromatic heterocycle that the aromatic hydrocarbyl or carbon atom number that number is 6-60 are 3-60.

A kind of method preparing the electroluminescent polymer provided by the invention comprising following steps:

(1) under the protection of inert gas, by the monomer or polymerized monomer list of polymeric monomeric unit M1 and the structure containing Ar The monomer of first M2 and the structure containing Ar be added in organic solvent (organic solvent need to be completely dissolved the polymeric monomeric unit M1 with The monomer or polymeric monomeric unit M2 of the structure containing Ar and the monomer of the structure containing Ar), it is uniformly mixed, then adds catalyst work With with tetraethyl ammonium hydroxide aqueous solution (mass fraction 20%), be uniformly mixed, obtain mixed liquor；

(2) step (1) mixed liquor is heated under catalyst action and tetraethyl ammonium hydroxide effect and is carried out Suzuki polymerization reaction, the temperature of Suzuki polymerization reaction are 60~100 DEG C, and the time of Suzuki polymerization reaction is 12~36h, Temperature-resistant addition phenyl boric acid is maintained, is carried out first time isothermal reaction (6~12h), then in the state of temperature-resistant, is added Bromobenzene carries out second of isothermal reaction (6~12h), obtains reaction solution, the reaction solution is purified, obtain target product, is i.e. institute State electroluminescent polymer.

Further, step (1) inert gas is argon gas；The organic solvent is toluene, tetrahydrofuran, diformazan At least one of benzene, dioxane and N,N-dimethylformamide；The catalyst is palladium acetate, three (dibenzalacetones) At least one of two palladiums, thricyclohexyl phosphorus, tetra-triphenylphosphine palladium and triphenylphosphine palladium；The mole of the catalyst It is 5 ‰~the 3% of reaction monomers moles total number；The volume ratio of the tetraethyl ammonium hydroxide aqueous solution and organic solvent is 1:4 ~12.

Further, the structural formula of step (1) the polymeric monomeric unit M1 is

The structural formula of step (1) the polymeric monomeric unit M2 is

Further, in step (1), select polymeric monomeric unit M1 and the monomer of the structure containing Ar that organic solvent is added In, then the molar ratio of the polymeric monomeric unit M1 and the monomer of the structure containing Ar is x:1-x (0≤x≤1), the polymerized monomer The moles total number of (monomer including M1 or M2 and the structure containing Ar) and the volume ratio of organic solvent are 1:12~24.

When selecting the monomer of polymeric monomeric unit M2 and the structure containing Ar to be added in organic solvent, polymeric monomeric unit M2 with contain The molar ratio of the monomer of Ar structure is x:1-x (0≤x≤1), the polymerized monomer (monomer including M1 or M2 and the structure containing Ar) Moles total number and organic solvent volume ratio be 1:12~24.

Further, step (1) the polymerized monomer M1 or M2, the structure containing Ar the dosage of monomer meet containing double borates The monomer integral molar quantity of (boric acid) functional group (i.e. functional group's number phase equal with double monomer integral molar quantities of bromine (iodine) functional group are contained Together).

Further, the dosage of the catalyst is 5 ‰~the 3% of reaction monomers moles total number.

Further, the temperature of step (2) the Suzuki polymerization reaction be 60-100 DEG C, Suzuki polymerization reaction when Between be 12-36h, time of the first time isothermal reaction is 6-12h；The time of second of isothermal reaction is 6-12h.

Further, the mole dosage of step (2) described phenyl boric acid is step (1) described reaction monomers moles total number 10-20%, the mole dosage of the bromobenzene are 1~5 times of the mole dosage of the phenyl boric acid.The reaction monomers moles total number For the moles total number or polymeric monomeric unit M2 of both polymeric monomeric unit M1 and the monomer of the structure containing Ar and the structure containing Ar The moles total number of both monomers.

Further, step (2) purifying includes: to be cooled to room temperature the reaction solution, pours into methanol and precipitates, mistake The crude product is successively used methanol, acetone and n-hexane to extract by filter, dry crude product, again with toluene dissolution, column chromatography point From, precipitating filters in methanol solution again after concentration, and it is dry, target product is obtained, i.e., the described electroluminescent polymer.

One kind electroluminescent polymer provided by the invention can be applied in the luminescent layer for preparing LED device.

One kind electroluminescent polymer provided by the invention, which can be applied, is preparing light emitting diode, organic effect crystal During pipe, organic solar batteries and organic laser diode etc., it is preferred for preparing the luminescent layer of LED device.

It is provided by the invention one kind electroluminescent polymer during being used to prepare the luminescent layer of LED device, First a kind of electroluminescent polymer can be dissolved in organic solvent, then pass through spin coating, inkjet printing or printing again Film forming, obtains the luminescent layer of the LED device.During this, the organic solvent be chlorobenzene, dichloro-benzenes, toluene, At least one of dimethylbenzene, tetrahydrofuran and chloroform.The luminescent layer of the LED device with a thickness of 10- 1000nm。

Compared with prior art, the invention has the advantages that and the utility model has the advantages that

(1) fluorescence of luminescent material can be improved containing hetero atom in a kind of electroluminescent polymer provided by the invention Quantum yield, improves the cavity transmission ability of material, if being used to prepare luminescent device, is conducive to obtain luminescent device efficiently Stable performance；

(2) in the preparation method of a kind of electroluminescent polymer provided by the invention, used low in raw material price is closed At route simplicity, purification is convenient, is suitable for large-scale production；

(3) a kind of electroluminescent polymer provided by the invention, has preferable solubility property, is suitable for solution and processes, Device preparation cost can be reduced, and large area flexible OLED device can be prepared；With excellent electroluminescent properties, there is reality The potentiality of application；And when being applied to prepare electroluminescent device without annealing, the preparation process of electroluminescent device is more Simply.

Detailed description of the invention

Fig. 1 is the differential scanning calorimetric curve figure of polymer P 1, P2, P4 and P7；

Fig. 2 is the fluorescence spectra of 1~P3 of polymer P, P7 in toluene solution；

Fig. 3 is the fluorescence spectra of polymer P 8, P9 in toluene solution；

Fig. 4 is the fluorescence spectra of polymer P 10, P11 in toluene solution.

Specific embodiment

Specific implementation of the invention is described further below in conjunction with attached drawing and example, but implementation and protection of the invention It is without being limited thereto.If it is existing to be that those skilled in the art can refer to it is noted that there is the not special process of detailed description below Technology realize or understand.Reagents or instruments used without specified manufacturer, be considered as can by it is commercially available be commercially available it is normal Advise product.

Polymerized monomer used in following example (polymeric monomeric unit M1 and polymeric monomeric unit M2), can be by following Method be prepared.

One, the preparation of polymerized monomer

The preparation of the bromo- 4- phenylnaphthalene of 1-

Under an argon atmosphere, it into 500mL three-necked flask, is added Isosorbide-5-Nitrae-dibromine naphthalene (9.68g, 34.1mmol), phenyl boric acid Ester (4.63g, 22.3mmol), catalyst tetra-triphenylphosphine palladium (0.52g, 0.45mmol) and 180mL tetrahydrofuran, stirring add The K of mass fraction 50wt% is added when temperature is stablized at 80 DEG C in heat₂CO₃(24.6g, 0.18mol) aqueous solution 24.6mL, instead Answer 12h.It after reaction solution is concentrated, is purified by silica gel column chromatography, petroleum ether and methylene chloride mixed solvent (8/1, v/v) are leaching Lotion obtains faint yellow solid, yield 72%.¹H NMR、¹³CNMR, MS and elemental analysis are the result shows that obtained compound For target product, preparation process chemical equation is as follows:

The preparation of the bromo- 4- of 1- (4- bromophenyl) naphthalene

The bromo- 4- phenylnaphthalene (3.21g, 11.4mmol) of compound 1- is dissolved in the anhydrous tetrachloromethane of 50ml, is kept away in room temperature It under the conditions of light, is added bromine (2.19g, 13.7mmol), reacts 12 hours.After reaction stops, with saturation NaHSO₃Aqueous solution removes Excess liquid bromine is removed, is extracted with dichloromethane three times, organic phase is concentrated, is purified by silica gel column chromatography, petroleum ether is eluent, Obtain the bromo- 4- of 1- (4- bromophenyl) naphthalene, yield 84%.¹H NMR、¹³CNMR, MS and elemental analysis are the result shows that obtainedization Conjunction object is target product, and preparation process chemical equation is as follows:

The preparation of 5,9- dibromo benzo [b] naphtho- [1,2-d] thiophene -7,7- dioxide (M1)

The bromo- 4- of compound 1- (4- bromophenyl) naphthalene (3.51g, 9.76mmol) is dissolved in the chloroform of 50ml, is added dropwise Chlorosulfonic acid (3.40g, 29.3mmol), temperature stablize 35 degrees Celsius, react 6 hours.After reaction, reaction system is poured into ice In aqueous mixtures, and use NaHCO₃Solution is adjusted to neutrality, filters out insoluble matter, then drying after washed several times with water is carried out with acetic acid Recrystallization, obtains white needles 5, and 9- dibromo benzo [b] naphtho- [1,2-d] thiophene -7,7- dioxide (M1) is that is, described Polymeric monomeric unit M1.¹H NMR、¹³CNMR, MS and elemental analysis are the result shows that obtained compound is target product, preparation Process chemistry reaction equation is as follows:

The preparation of bromo- 1,1 '-two dinaphthalene of 4-

Under an argon atmosphere, it into 500mL three-necked flask, is added Isosorbide-5-Nitrae-dibromine naphthalene (9.68g, 34.1mmol), naphthalene boronic acids Ester (5.67g, 22.3mmol), catalyst tetra-triphenylphosphine palladium (0.52g, 0.45mmol) and 180mL tetrahydrofuran, stirring add The K of mass fraction 50wt% is added when temperature is stablized at 80 DEG C in heat₂CO₃(24.6g, 0.18mol) aqueous solution 24.6mL, instead Answer 12h.It after reaction solution is concentrated, is purified by silica gel column chromatography, petroleum ether and methylene chloride mixed solvent (8/1, v/v) are leaching Lotion obtains faint yellow solid, yield 72%.¹H NMR、¹³CNMR, MS and elemental analysis are the result shows that obtained compound For target product, preparation process chemical equation is as follows:

The preparation of 4,4 '-two bromo- 1,1 '-two dinaphthalenes

By compound 4- bromo- 1,1 '-dinaphthyl (4.02g, 12.1mmol) is dissolved in the anhydrous tetrachloromethane of 50ml, keeps away in room temperature It under the conditions of light, is added bromine (2.32g, 14.5mmol), reacts 12 hours.After reaction stops, with saturation NaHSO₃Aqueous solution removes Excess liquid bromine is removed, is extracted with dichloromethane three times, organic phase is concentrated, is purified by silica gel column chromatography, petroleum ether is eluent, Obtain the bromo- 4- of 1- (4- bromophenyl) naphthalene, yield 71%.¹H NMR、¹³CNMR, MS and elemental analysis are the result shows that obtainedization Conjunction object is target product, and preparation process chemical equation is as follows:

The preparation of 5,9- dibromo naphtho- [2 '-d of 2,1-b:1 '] thiophene -7,7- dioxide (M2)

By compound 4,4 '-two bromo- 1,1 '-two dinaphthalene (3.66g, 8.94mmol) is dissolved in the chloroform of ml, is added dropwise Chlorosulfonic acid (3.11g, 26.8mmol), temperature stablize 35 degrees Celsius, react 6 hours.After reaction, reaction system is poured into ice In aqueous mixtures, and use NaHCO₃Solution is adjusted to neutrality, filters out insoluble matter, then drying after washed several times with water is carried out with acetic acid Recrystallization, obtains white needles 5, and 9- dibromo naphtho- [2,1-b:1 ' 2 '-d] thiophene -7,7- dioxide (M2) is that is, described Polymeric monomeric unit M2.¹H NMR、¹³CNMR, MS and elemental analysis are the result shows that obtained compound is target product, preparation Process chemistry reaction equation is as follows:

Two, the synthesis of electroluminescent polymer