CN108503800B - Polymer containing S, S-dioxo-dibenzothiophene macrocyclic unit, preparation method and application thereof - Google Patents
Polymer containing S, S-dioxo-dibenzothiophene macrocyclic unit, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic photoelectricity, and discloses a polymer containing an S, S-dioxo-dibenzothiophene macrocyclic unit and a preparation method thereofA method and an application. The chemical structural formula of the polymer of the invention satisfies one of the following general formulas:
in the formula: m is1And m2M is more than or equal to 0 and is the mole fraction of each unit component1<1，0<m2≤1，m1+m21 is ═ 1; n is the number of repeating units, and n is 10-1000; x is-C (R)1)2‑、‑NR1‑、‑Si(R1)2‑、‑O‑、‑S‑、‑SO2-or-CO2‑；R1Is C1-30 alkyl, C3-30 cycloalkyl, C6-60 aromatic hydrocarbon or C3-60 aromatic heterocyclic radical; ar is an aromatic hydrocarbon group of C6-60 or an aromatic heterocyclic group of C3-60. The polymer provided by the invention has the advantages of remarkably improved fluorescence quantum yield, electron injection and transmission and carrier mobility, and can be applied to the field of organic photoelectricity.
Description
Technical Field
The invention belongs to the field of organic photoelectricity, and particularly relates to a polymer containing an S, S-dioxo-dibenzothiophene macrocyclic unit, and a preparation method and application thereof.
Background
The organic light emitting diode has the advantages of light weight, active light emission, wide viewing angle, low cost, low energy consumption, easy manufacture, flexibility, large-size panel and the like, and has wide application prospect in the fields of organic flat panel display and white light illumination. The organic light emitting diode consists of an anode, a hole injection and transmission layer, a light emitting layer, an electron injection and transmission layer and a multilayer structure of the anode, wherein the light emitting layer can be prepared from a small molecule light emitting material and a polymer light emitting material as a core part.
The small molecule luminescent material is generally poor in solubility, needs to be prepared into a film through a vacuum evaporation method, and is low in material utilization rate and high in energy consumption, so that the manufacturing cost of a device is high. The polymer luminescent material has good solubility, can be used for preparing a uniform film by solution methods such as spin coating, printing and the like, and particularly has obvious advantages in the preparation of large-area films.
The main problem of the current polymer light emitting materials is that the light emitting efficiency is not high enough, mainly because the polymer light emitting materials are difficult to simultaneously satisfy high fluorescence quantum yield, proper energy level, and high and balanced carrier mobility, therefore, the development of high efficiency polymer light emitting materials satisfying these conditions is a research focus at present.
The most commonly used polymer light emitting materials include polyfluorene, polycarbazole, etc., and these polymers have low carrier mobility, hole mobility significantly higher than electron mobility, and a shallow LUMO level, which is not favorable for electron injection. The introduction of an electron-absorbing unit (such as a sulfone-containing unit, an imidazole unit and the like) can reduce the LUMO energy level of the polymer, improve the electron injection and transmission performance, enable the carrier transmission to be more balanced and further improve the electroluminescent efficiency.
Disclosure of Invention
To overcome the above-mentioned drawbacks and deficiencies of the prior art, it is a primary object of the present invention to provide a class of polymers containing S, S-dioxo-dibenzothiophene macrocyclic units. The polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit has high fluorescence quantum yield, has high potential as a luminescent polymer, and can realize polymers emitting different colors by adjusting the content of the polymerization unit. The polymer has good solubility, and can be used for preparing large-area films by solution processing methods such as spin coating, ink-jet printing, printing and the like.
Another object of the present invention is to provide a method for preparing the polymer containing S, S-dioxo-dibenzothiophene macrocyclic unit.
The invention further aims to provide application of the polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit in the field of organic photoelectricity.
The purpose of the invention is realized by the following scheme:
a polymer containing S, S-dioxo-dibenzothiophene macrocyclic units has a chemical structural formula which satisfies one of the following general formulas:
in the formula: m is1And m2M is more than or equal to 0 and is the mole fraction of each unit component1<1，0<m2≤1，m1+m21 is ═ 1; n is the number of repeating units, and n is 10-1000;
x is-C (R)1)2-、-NR1-、-Si(R1)2-、-O-、-S-、-SO2-or-CO2-；
R1Is C1-30 alkyl, C3-30 cycloalkyl, C6-60 aromatic hydrocarbon or C3-60 aromatic heterocyclic radical;
ar is an aromatic hydrocarbon group of C6-60 or an aromatic heterocyclic group of C3-60.
Further, Ar is preferably one or more of the following chemical structures or derivatives of the following structures:
wherein R is2Is C1-30 alkyl, C3-30 cycloalkyl, C6-60 aromatic hydrocarbon or C3-60 aromatic heterocyclic radical; r3、R4、R5Each independently represents H, D, F, CN, alkenyl, alkynyl, amino, nitro, acyl, alkoxy, carbonyl, sulfone, C1-30 alkyl (alkoxy), C3-30 cycloalkyl, C6-60 aromatic hydrocarbon or C3-60 aromatic heterocyclic group.
The invention provides a preparation method of the polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit, which comprises the following steps:
(1) carrying out Suzuki coupling on an S, S-dioxo-dibenzothiophene unit containing boric acid or a borate functional group and a brominated or iodinated benzene derivative unit to obtain an intermediate, and carrying out ring closing reaction to obtain a monomer containing an S, S-dioxo-dibenzothiophene macrocyclic unit;
(2) and (2) carrying out Suzuki polymerization on the monomer containing the S, S-dioxo-dibenzothiophene macrocyclic unit and the monomer containing the Ar unit, and then sequentially adding phenylboronic acid and bromobenzene for end-capping reaction to obtain the polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit.
Further, the step (2) in the above preparation method may specifically include the following steps:
(1) under the protection of inert gas, dissolving a monomer containing an S, S-dioxo-dibenzothiophene macrocyclic unit and a monomer containing an Ar unit in a solvent, then adding a catalyst, heating to 60-100 ℃ to carry out Suzuki polymerization reaction, wherein the reaction time is 12-36 hours;
(2) adding phenylboronic acid, and keeping the temperature to continue reacting for 6-12 hours; and adding bromobenzene, continuing to perform heat preservation reaction for 6-12 hours, and purifying the obtained reaction liquid after the reaction is finished to obtain the target product.
The solvent in the step (1) can be at least one of toluene, tetrahydrofuran and xylene;
the catalyst for the Suzuki polymerization reaction in the step (1) is at least one of palladium acetate, tricyclohexylphosphine and tetrakis (triphenylphosphine) palladium; the Suzuki polymerization reaction is carried out under an alkaline condition, and the alkali is at least one of tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution and potassium carbonate.
The monomers containing S, S-dioxo-dibenzothiophene macrocyclic units and the monomers containing Ar units in the step (1) are used in such an amount that the total molar amount of the monomers containing the diboronate ester and/or the diboronate functional group is equal to the total molar amount of the monomers containing the bisbromo and/or diiodo functional group; the dosage of the catalyst is 2 per mill-3% of the total mole of the reaction monomers; the dosage of the phenylboronic acid in the step (2) is 10-40% of the total molar amount of the reaction monomers; the dosage of bromobenzene is 5-20 times of the molar weight of phenylboronic acid.
And (2) the purification in the step (2) is to cool the obtained reaction liquid to room temperature, dropwise add the reaction liquid into stirred methanol for precipitation, filter and dry the solution to obtain a crude product, extract the crude product by using methanol and acetone in sequence, dissolve the crude product by using toluene, separate the crude product by column chromatography, precipitate the crude product in a methanol solution again after concentration, filter and dry the crude product to obtain the target product.
The polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit has good solubility and can be dissolved in common organic solvents.
The monomer containing the S, S-dioxo-dibenzothiophene macrocyclic unit is introduced into the main chain of the polymer through copolymerization, and the S, S-dioxo-dibenzothiophene macrocyclic unit can improve the electron transmission performance of the polymer and simultaneously keep the higher fluorescence quantum yield of the polymer. By adjusting the proportion of the copolymerization units, the light-emitting spectrum of the polymer can be adjusted, and the polymer with different color light emission can be obtained. The polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit can be applied to preparing a light-emitting layer of a polymer light-emitting diode, and can be used as a light-emitting material to prepare the polymer light-emitting diode by a solution processing method.
The preparation method specifically comprises the following steps of dissolving the polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit in an organic solvent, and forming a film through spin coating, ink-jet printing or printing to obtain the light-emitting layer of the polymer light-emitting diode. The organic solvent is xylene, tetrahydrofuran or chlorobenzene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the macrocyclic unit containing S, S-dioxo-dibenzothiophene has an electron-withdrawing sulfone group, and can improve the injection and transmission of electrons when being introduced into a polymer.
(2) The macrocyclic unit containing S, S-dioxo-dibenzothiophene is of a large conjugated structure, and the carrier mobility of the polymer can be improved.
(3) The polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit has higher fluorescence quantum yield.
Drawings
FIG. 1 is a current efficiency-current density curve of Polymer P1.
FIG. 2 is a photoluminescence spectrum of polymer P4 in a toluene solution.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
Example 1
Preparation of Compound M1
(1) Preparation of Compound 1
Dibenzothiophene (1.84g, 10mmol) and 50mL of acetic acid were added to a 150mL two-necked flask under nitrogen, heated to 110 ℃ and then an aqueous hydrogen peroxide solution (5mL, 50mmol) was slowly added dropwise, followed by stirring and heating for 8 hours. After the reaction was completed, it was cooled and left to stand, and filtered to obtain 1.99g of white crystals with a yield of 92%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 2
Under a nitrogen atmosphere, compound 1(2.16g, 10mmol) and 100mL of concentrated sulfuric acid were added to a 300mL two-necked flask, and N-bromosuccinimide (4.45g, 25mmol) was added to the reaction flask in three portions while keeping out of the sun, and the mixture was stirred at room temperature for 12 hours. After the reaction, the reaction solution was slowly poured into 1000mL of ice water, filtered, and the residue was washed with ethanol three times and recrystallized from chlorobenzene 2 times to obtain 2.47g of white crystals with a yield of 66%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(3) Preparation of Compound 3
Compound 2(3.74g, 10mmol) and 60mL of anhydrous tetrahydrofuran were added to a 100mL two-necked flask under a nitrogen atmosphere, and lithium aluminum hydride (1.14g, 30mmol) was slowly added and stirred for 8 hours. After the reaction, the reaction mixture was slowly quenched with 10mL of water, and then quenched with 10mL of aqueous sodium hydroxide and 30mL of water. The product was extracted with dichloromethane and washed three times with saturated aqueous sodium chloride solution to removeAfter the organic phase solvent, the crude product was purified by column chromatography using petroleum ether as eluent to obtain 2.74g of white solid with a yield of 80%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(4) Preparation of Compound 4
Under nitrogen protection, compound 3(3.42g, 10mmol), pinacol diboron (6.35g, 25mmol) and [1, 1' -bis (diphenylphosphino) ferrocene were added to a 300mL two-necked flask]Palladium dichloride (0.49g, 0.5mmol), potassium acetate (3.92g, 40mmol) and 150mL dioxane were heated to 80 ℃ for reaction for 12 hours. After the reaction is finished, dioxane is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed for three times by saturated sodium chloride aqueous solution, after the dichloromethane is removed by reduced pressure distillation, the crude product is treated by petroleum ether: dichloromethane ═ 4: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, and 3.05g of white solid is obtained, and the yield is 70%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(5) Preparation of Compound 5
Under a nitrogen atmosphere, compound 4(4.36g, 10mmol) and methyl 5-bromo-2-iodobenzoate were added to a 150mL two-necked flask
(10.23g, 30mmol), potassium carbonate (3.45g, 25mmol), tetrakis (triphenylphosphine) palladium (0.58g, 0.5mmol), 12mL deionized water and 80mL toluene, heated to 80 ℃ for 12 hours. After the reaction is finished, extracting the product by dichloromethane, washing the product for three times by saturated sodium chloride aqueous solution, removing the organic phase solvent, purifying the crude product by taking petroleum ether as eluent column chromatography, and recrystallizing by using petroleum ether/ethyl acetate to obtain light yellow solid 3.84g with the yield of 63 percent.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(6) Preparation of Compound 6
Under the protection of nitrogen, compound 5(6.10g, 10mmol) and 100mL of anhydrous tetrahydrofuran were added to a 300mL two-necked flask, the temperature was reduced to-78 ℃, a tetrahydrofuran solution of n-octyl magnesium bromide (50mL, 50mmol) was added dropwise, and the mixture was slowly warmed to room temperature for reaction for 12 hours. After the reaction is finished, a small amount of water is addedThe reaction was quenched, tetrahydrofuran was removed by distillation under reduced pressure, the product was extracted with dichloromethane, washed three times with saturated aqueous sodium chloride solution, and after removal of dichloromethane by distillation under reduced pressure, the crude product was purified by distillation with petroleum ether: ethyl acetate 4: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 7.52g of yellow solid is obtained, and the yield is 75%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(7) Preparation of Compound 7
Under nitrogen, compound 6(10.03g, 10mmol) and 150mL of acetic acid were added to a 300mL two-necked flask, heated to 100 ℃ and then 5mL of concentrated HCl was added and the reaction was continued for 8 hours. After the reaction is finished, the reaction solution is cooled and poured into 500mL of ice water, the mixture is filtered, filter residues are washed twice by 50mL of ethanol, and a crude product is obtained by petroleum ether: dichloromethane ═ 8: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 7.06g of white solid is obtained, and the yield is 73%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(8) Preparation of Compound M1
Under nitrogen protection, compound 7(9.67g, 10mmol) and 120mL of a mixed solvent of tetrahydrofuran and acetic acid (1: 1, v: v) were added to a 300mL two-necked flask, heated to 70 ℃ and then slowly added dropwise with an aqueous hydrogen peroxide solution (5mL, 50mmol), and the reaction was stirred with heating for 8 hours. After the reaction is finished, extracting the product by using dichloromethane, washing the product for 3 times by using saturated sodium chloride aqueous solution, and purifying the product by using a silica gel chromatographic column after an organic phase solvent is dried in a spinning mode, wherein an eluent is petroleum ether: dichloromethane (6: 1, v: v) was recrystallized from petroleum ether to give 8.59g of a white solid in 86% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equations for synthesizing compounds 1-7 and M1 are shown below:
example 2
Preparation of Compound M2
(1) Preparation of Compound 8
Under a nitrogen atmosphere, compound 4(4.36g, 10mmol), o-bromonitrobenzene (6.06g, 30mmol), potassium carbonate (3.45g, 25mmol), tetrakis (triphenylphosphine) palladium (0.58g, 0.5mmol), 12mL deionized water and 50mL toluene were charged into a 150mL two-necked flask, and heated to 80 ℃ for 12 hours. After the reaction, the product was extracted with dichloromethane, washed three times with saturated aqueous sodium chloride solution, and after removal of the organic phase solvent, the crude product was purified with petroleum ether: the mixed solvent of dichloromethane (v: v ═ 4: 1) was purified by column chromatography as eluent to give 3.20g of yellow solid in 75% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 9
Under nitrogen, compound 8(4.26g, 10mmol) and 50mL triethyl phosphite were added to a 150mL two-necked flask and heated to 120 ℃ for reaction for 12 hours. After the reaction was complete, triethyl phosphite was removed by distillation under reduced pressure, the product was extracted with dichloromethane, washed three times with saturated aqueous sodium chloride solution and, after removal of the organic phase solvent, the crude product was purified by distillation with petroleum ether: dichloromethane ═ 3: 1 (v: v) as eluent, and recrystallizing with ethanol/tetrahydrofuran to obtain white solid 1.99g with 55% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(3) Preparation of Compound 10
Under nitrogen protection, compound 9(3.62g, 10mmol), 1-bromooctane (5.8g, 30mmol), potassium carbonate (8.28g, 60mmol) and 120mL of N, N-dimethylformamide were added to a 300mL two-necked flask, and the mixture was heated to 100 ℃ for reaction for 12 hours. After the reaction is finished, extracting the product by dichloromethane, washing the product for five times by saturated sodium chloride aqueous solution, removing the organic phase solvent, and purifying the crude product by column chromatography by using petroleum ether as an eluent to obtain 4.99g of white solid with the yield of 85 percent.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(4) Preparation of Compound 11
Under nitrogen protection, compound 10(5.87g, 10mmol) and 150mL of chloroform were added to a 300mL two-necked flask, and 22mL of a chloroform solution containing liquid bromine (3.52g, 22mmol) was added dropwise to the reaction under light protection, followed by stirring at room temperature for 24 hours. Quenching unreacted liquid bromine by using a small amount of sodium bisulfite, extracting a product by using dichloromethane, washing the product for 3 times by using saturated sodium chloride aqueous solution, purifying the product by using a silica gel chromatographic column after spin-drying an organic phase solvent, wherein an eluent is petroleum ether: dichloromethane (6: 1, v: v) was recrystallized from a mixed solvent of petroleum ether/tetrahydrofuran to give 5.51g of a white solid in 74% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(5) Preparation of Compound M2
Under nitrogen protection, compound 11(7.45g, 10mmol) and 120mL of a mixed solvent of tetrahydrofuran and acetic acid (1: 1, v: v) were added to a 300mL two-necked flask, heated to 70 ℃ and then slowly added dropwise with an aqueous hydrogen peroxide solution (10mL, 100mmol), and the reaction was stirred with heating for 12 hours. After the reaction is finished, extracting the product by using dichloromethane, washing the product for 3 times by using saturated sodium chloride aqueous solution, and purifying the product by using a silica gel chromatographic column after an organic phase solvent is dried in a spinning mode, wherein an eluent is petroleum ether: dichloromethane (4: 1, v: v) was recrystallized from petroleum ether to give 6.76g of a white solid in 87% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equations for synthesizing compounds 8-11 and compound M2 are shown below:
example 3
Preparation of Compound M3
(1) Preparation of Compound 12
Dibenzothiophene-2, 8-diboronic acid (2.72g, 10mmol) and methyl 5-bromo-2-iodobenzoate (10.23g, 30mmol), potassium carbonate (3.45g, 25mmol), tetrakis (triphenylphosphine) palladium (0.58g, 0.5mmol), 12 under a nitrogen atmospheremL of deionized water and 50mL of toluene were heated to 80 ℃ and reacted for 12 hours. After the reaction is finished, extracting the product by dichloromethane, washing the product for three times by saturated sodium chloride aqueous solution, removing the organic phase solvent, purifying the crude product by taking petroleum ether as eluent column chromatography, and recrystallizing by using petroleum ether/ethyl acetate to obtain light yellow solid 4.39g with the yield of 72 percent.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 13
Under the protection of nitrogen, compound 12(6.10g, 10mmol) and 100mL of anhydrous tetrahydrofuran were added to a 300mL two-necked flask, the temperature was reduced to-78 ℃, a tetrahydrofuran solution of n-octyl magnesium bromide (60mL, 60mmol) was added dropwise, and the mixture was slowly warmed to room temperature for reaction for 12 hours. After the reaction was completed, a small amount of water was added to quench the reaction, tetrahydrofuran was removed by distillation under reduced pressure, the product was extracted with dichloromethane, washed three times with saturated aqueous sodium chloride solution, and after removal of dichloromethane by distillation under reduced pressure, the crude product was quenched with petroleum ether: ethyl acetate 4: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 7.22g of yellow solid is obtained, and the yield is 72%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound 14
Compound 13(10.03g, 10mmol) and 150mL of acetic acid were added to a 300mL two-necked flask under nitrogen, heated to 100 ℃ and then added with 5mL of concentrated hydrochloric acid, and the reaction was continued for 8 hours. After the reaction is finished, the reaction solution is cooled and poured into 500mL of ice water, the mixture is filtered, filter residues are washed twice by 50mL of ethanol, and a crude product is obtained by petroleum ether: dichloromethane ═ 6: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 7.35g of white solid is obtained, and the yield is 76%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(4) Preparation of Compound M3
Under nitrogen, compound 14(9.67g, 10mmol) and a mixed solvent of tetrahydrofuran and acetic acid (1: 1, v: v) in an amount of 150mL were added to a 300mL two-necked flask, and after heating to 70 ℃ an aqueous hydrogen peroxide solution (10mL, 100 m)mol), heating and stirring are continued for 8 hours. After the reaction is finished, extracting the product by using dichloromethane, washing the product for 3 times by using saturated sodium chloride aqueous solution, and purifying the product by using a silica gel chromatographic column after an organic phase solvent is dried in a spinning mode, wherein an eluent is petroleum ether: dichloromethane (6: 1, v: v) was recrystallized from petroleum ether to give 9.19g of a white solid in 92% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equations for synthesizing compounds 12-14 and compound M3 are shown below:
example 4
Preparation of Polymer P1
Under nitrogen protection, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -9, 9-di-n-octylfluorene (192.6mg, 0.3mmol), 2, 7-dibromo-9, 9-di-n-octylfluorene (131.6mg, 0.24mmol) and compound M1(59.9mg, 0.06mmol) were dissolved in 10mL of toluene, and an aqueous tetraethylhydroxylamine solution (1mL, wt% ═ 20%), palladium acetate (1mg) and tricyclohexylphosphine (2mg) were added; after heating to 80 ℃ for reaction for 24 hours, adding phenylboronic acid (20mg) for end capping for 6 hours, and then adding bromobenzene (0.2mL) for end capping for 6 hours; stopping reaction, cooling, precipitating the organic phase in methanol (300mL), filtering, drying, extracting the crude product with methanol, acetone and n-hexane in sequence, dissolving the polymer with toluene, eluting with toluene, and purifying with neutral alumina column chromatography; the toluene solution of the polymer was concentrated, precipitated again in methanol solution, filtered and dried to give a pale yellowish green fibrous polymer. By passing1H NMR spectrum and element analysis confirm that the target polymer is obtained. Gel permeation chromatography: mn87KDa and PDI 2.22. Fluorescence quantum yield: 0.80. FIG. 1 is a current efficiency-current density curve of Polymer P1. As can be seen from FIG. 1, the polymer P1 has high electroluminescent property and maximum current efficiency of 4.02 cd. A-1And the polymer P1 has very small efficiency roll-off at 300mA cm-2Current efficiency at current density ofThe rate is still 3.48 cd.A-1. The chemical reaction equation is as follows:
example 5
Preparation of Polymer P2
Under nitrogen protection, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -9, 9-di-n-octylfluorene (192.6mg, 0.3mmol), 2, 7-dibromo-9, 9-di-n-octylfluorene (131.6mg, 0.24mmol) and compound M2(46.6mg, 0.06mmol) were dissolved in 10mL of toluene, and an aqueous tetraethylhydroxylamine solution (1mL, wt% ═ 20%), palladium acetate (1mg) and tricyclohexylphosphine (2mg) were further added; after heating to 80 ℃ for reaction for 24 hours, adding phenylboronic acid (20mg) for end capping for 6 hours, and then adding bromobenzene (0.2mL) for end capping for 6 hours; stopping reaction, cooling, precipitating the organic phase in methanol (300mL), filtering, drying, extracting the crude product with methanol, acetone and n-hexane in sequence, dissolving the polymer with toluene, eluting with toluene, and purifying with neutral alumina column chromatography; the toluene solution of the polymer was concentrated, precipitated again in methanol solution, filtered and dried to give a pale yellowish green fibrous polymer. By passing1H NMR spectrum and element analysis confirm that the target polymer is obtained. Gel permeation chromatography: mn65KDa, PDI 2.07. Fluorescence quantum yield: 0.77. the chemical reaction equation is as follows:
example 6
Preparation of Polymer P3
Under nitrogen protection, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -N-9 '-heptadecylcarbazole (197.3mg, 0.3mmol), 2, 7-dibromo-N-9' -heptadecylcarbazole (152.1mg, 0.18mmol) and compound M1(119.9mg, 0.12mmol) were dissolved in 12mL of toluene, and an aqueous tetraethylhydroxylamine solution (1mL, wt% ═ 20%), palladium acetate (1mg) and tricyclohexylphosphine (2mg) were added; is heated toReacting at 80 ℃ for 24 hours, adding phenylboronic acid (20mg) to seal the end for 6 hours, and then adding bromobenzene (0.2mL) to seal the end for 6 hours; stopping reaction, cooling, precipitating the organic phase in methanol (300mL), filtering, drying, extracting the crude product with methanol, acetone and n-hexane in sequence, dissolving the polymer with toluene, eluting with toluene, and purifying with neutral alumina column chromatography; the toluene solution of the polymer was concentrated, precipitated again in methanol solution, filtered and dried to give a pale yellowish green fibrous polymer. By passing1H NMR spectrum and element analysis confirm that the target polymer is obtained. Gel permeation chromatography: mn99KDa and PDI 2.45. Fluorescence quantum yield: 0.70. the chemical reaction equation is as follows:
example 7
Preparation of Polymer P4
Under nitrogen protection, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -9, 9-di-n-octylfluorene (192.6mg, 0.3mmol), 2, 7-dibromo-9, 9-di-n-octylfluorene (88.9mg, 0.162mmol), 4, 6-dibromobenzothiadiazole (5.3mg, 0.018mmol) and compound M3(119.9mg, 0.12mmol) were dissolved in 10mL of toluene, and an aqueous solution of tetraethylhydroxylamine (1mL, wt% ═ 20%), palladium acetate (1mg) and tricyclohexylphosphine (2mg) were added; after heating to 80 ℃ for reaction for 24 hours, adding phenylboronic acid (20mg) for end capping for 6 hours, and then adding bromobenzene (0.2mL) for end capping for 6 hours; stopping reaction, cooling, precipitating the organic phase in methanol (300mL), filtering, drying, extracting the crude product with methanol, acetone and n-hexane in sequence, dissolving the polymer with toluene, eluting with toluene, and purifying with neutral alumina column chromatography; the toluene solution of the polymer was concentrated, precipitated again in methanol solution, filtered and dried to give a pale yellowish green fibrous polymer. By passing1H NMR spectrum and element analysis confirm that the target polymer is obtained. Gel permeation chromatography: mn76KDa, PDI 2.42. Fluorescence quantum yield: 0.87. FIG. 2 is a photoluminescence spectrum of polymer P4 in toluene solution, from which it can be seenThe polymer P4 exhibited green emission with a maximum emission wavelength of 520 nm.
The chemical reaction equation is as follows:
example 8
Preparation of Polymer P5
Under nitrogen protection, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3-dioxo-2-boryl) -9, 9-di-n-octylfluorene (192.6mg, 0.3mmol), 2, 7-dibromo-9, 9-di-n-octylfluorene (121.8mg, 0.222mmol), 4, 7-bis (5-bromo (4-hexylthiophene) -2-yl) -2,1, 3-benzothiadiazole (11.3mg, 0.018mmol), and compound M3(59.9mg, 0.06mmol) were dissolved in 12mL of toluene, followed by tetraethylhydroxylamine aqueous solution (1mL, wt% ═ 20%), palladium acetate (1mg), and tricyclohexylphosphine (2 mg); after heating to 80 ℃ for reaction for 24 hours, adding phenylboronic acid (20mg) for end capping for 6 hours, and then adding bromobenzene (0.2mL) for end capping for 6 hours; stopping reaction, cooling, precipitating the organic phase in methanol (300mL), filtering, drying, extracting the crude product with methanol, acetone and n-hexane in sequence, dissolving the polymer with toluene, eluting with toluene, and purifying with neutral alumina column chromatography; the toluene solution of the polymer was concentrated, precipitated again in methanol solution, filtered and dried to give a pale yellowish green fibrous polymer. By passing1H NMR spectrum and element analysis confirm that the target polymer is obtained. Gel permeation chromatography: mn85KDa, PDI 2.59. Fluorescence quantum yield: 0.71. the chemical reaction equation is as follows:
example 9
Preparation of polymer light-emitting diode
Indium Tin Oxide (ITO) glass with the square resistance of 20 omega, which is prepared in advance, is taken, and ultrasonic cleaning and plasma treatment are sequentially carried out on the Indium Tin Oxide (ITO) glass for 10 minutes by using acetone, a detergent, deionized water and isopropanol. A film of polyethoxythiophene (PEDOT: PSS) doped with polystyrene sulfonic acid was spin-coated on ITO to a thickness of 40 nm. PEDOT PSS films were dried in a vacuum oven at 80 ℃ for 8 hours. A xylene solution (1 wt.%) of polymers P1-P5 was subsequently spin coated onto the surface of PEDOT: PSS films to a thickness of 80 nm. And finally, sequentially evaporating a 1.5 nm-thick CsF layer and a 120 nm-thick metal Al layer on the luminescent layer, wherein the structure of the device is ITO/PEDOT, PSS/polymer/CsF/Al. The properties were characterized and the results are shown in Table 1.
TABLE 1 Polymer device Properties
The device structure is as follows: ITO/PEDOT PSS/Polymer/CsF/Al
From the properties of the polymer devices in table 1 it can be found that: the luminescent polymers P1-P5 of the invention all have very small device turn-on voltage (<4V), the polymers P1, P2 and P3 are blue light emitting, the devices of the polymer P4 are green light emitting, the polymer P5 is red light emitting, and all the polymers have higher electroluminescent efficiency.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A polymer containing S, S-dioxo-dibenzothiophene macrocyclic units is characterized in that the chemical structural formula satisfies one of the following general formulas:
in the formula: m is1And m2M is more than or equal to 0 and is the mole fraction of each unit component1<1，0<m2≤1，m1+m21 is ═ 1; n is the number of repeating units, n ═ 10 ℃ -1000；
X is-C (R)1)2-、-NR1-、-Si(R1)2-、-O-、-S-、-SO2-or-CO2-；
R1Is C1-30 alkyl, C3-30 cycloalkyl, C6-60 aromatic hydrocarbon or C3-60 aromatic heterocyclic radical;
ar is an aromatic hydrocarbon group of C6-60 or an aromatic heterocyclic group of C3-60.
2. The polymer comprising S, S-dioxo-dibenzothiophene macrocyclic units of claim 1, wherein: ar is the following chemical structure or more than one of the derivatives of the following structures:
wherein R is2Is C1-30 alkyl, C3-30 cycloalkyl, C6-60 aromatic hydrocarbon or C3-60 aromatic heterocyclic radical; r3、R4、R5Each independently represents H, D, F, CN, alkenyl, alkynyl, amino, nitro, acyl, alkoxy, carbonyl, sulfone, C1-30 alkyl, C1-30 alkoxy, C3-30 cycloalkyl, C6-60 aromatic hydrocarbon or C3-60 aromatic heterocyclic group.
3. A method of preparing a polymer comprising S, S-dioxo-dibenzothiophene macrocyclic units according to any of claims 1 to 2, comprising the steps of:
(1) carrying out Suzuki coupling on an S, S-dioxo-dibenzothiophene unit containing boric acid or a borate functional group and a brominated or iodinated benzene derivative unit to obtain an intermediate, and carrying out ring closing reaction to obtain a monomer containing an S, S-dioxo-dibenzothiophene macrocyclic unit;
(2) and (2) carrying out Suzuki polymerization on the monomer containing the S, S-dioxo-dibenzothiophene macrocyclic unit and the monomer containing the Ar unit, and then sequentially adding phenylboronic acid and bromobenzene for end-capping reaction to obtain the polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit.
4. The method of claim 3, wherein step (2) comprises the steps of:
(1) under the protection of inert gas, dissolving a monomer containing an S, S-dioxo-dibenzothiophene macrocyclic unit and a monomer containing an Ar unit in a solvent, then adding a catalyst, heating to 60-100 ℃ to carry out Suzuki polymerization reaction, wherein the reaction time is 12-36 hours;
(2) adding phenylboronic acid, and keeping the temperature to continue reacting for 6-12 hours; and adding bromobenzene, continuing to perform heat preservation reaction for 6-12 hours, and purifying the obtained reaction liquid after the reaction is finished to obtain the target product.
5. The method of preparing a polymer comprising S, S-dioxo-dibenzothiophene macrocyclic units according to claim 4, wherein: the catalyst for the Suzuki polymerization reaction in the step (1) is at least one of palladium acetate, tricyclohexylphosphine and tetrakis (triphenylphosphine) palladium; the Suzuki polymerization reaction is carried out under an alkaline condition, and the alkali is at least one of tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution and potassium carbonate.
6. The method of preparing a polymer comprising S, S-dioxo-dibenzothiophene macrocyclic units according to claim 4, wherein: the monomers containing S, S-dioxo-dibenzothiophene macrocyclic units and the monomers containing Ar units in the step (1) are used in such an amount that the total molar amount of the monomers containing the diboronate ester and/or diboronate functional group is equal to the total molar amount of the monomers containing the bisbromo and/or diiodo functional group.
7. The method of preparing a polymer comprising S, S-dioxo-dibenzothiophene macrocyclic units according to claim 4, wherein: the dosage of the catalyst in the step (1) is 2 per mill-3% of the total mole of the reaction monomers.
8. The method of preparing a polymer comprising S, S-dioxo-dibenzothiophene macrocyclic units according to claim 4, wherein: the dosage of the phenylboronic acid in the step (2) is 10-40% of the total molar amount of the reaction monomers; the dosage of bromobenzene is 5-20 times of the molar weight of phenylboronic acid.
9. Use of the polymer comprising S, S-dioxo-dibenzothiophene macrocyclic units of any of claims 1-2 in the field of organic photovoltaics.
10. The application of the polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit in the field of organic photoelectricity according to claim 9 is characterized by specifically comprising the following steps of dissolving the polymer containing the S, S-dioxo-dibenzothiophene macrocyclic unit according to any one of claims 1-2 in an organic solvent, and forming a film through spin coating, ink-jet printing or printing to obtain the light-emitting layer of the polymer light-emitting diode.
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