CN108409945B - Polymer containing S, S-dioxo-thioxanthene derivative unit and preparation method and application thereof - Google Patents

Polymer containing S, S-dioxo-thioxanthene derivative unit and preparation method and application thereof Download PDF

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CN108409945B
CN108409945B CN201810174448.3A CN201810174448A CN108409945B CN 108409945 B CN108409945 B CN 108409945B CN 201810174448 A CN201810174448 A CN 201810174448A CN 108409945 B CN108409945 B CN 108409945B
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应磊
彭沣
黄飞
曹镛
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Dongguan volt ampere Photoelectric Technology Co., Ltd
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Abstract

The invention belongs to the field of organic photoelectricity, and discloses a polymer containing an S, S-dioxo-thioxanthene derivative unit, and a preparation method and application thereof. The S, S-dioxo-thioxanthene derivative unit is introduced into the main chain of the polymer through copolymerization, and the S, S-dioxo-thioxanthene derivative unit can improve the electron transport performance of the polymer and simultaneously keep higher fluorescence quantum yield. 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-thioxanthene derivative unit has higher fluorescence quantum yield, better thermal stability, higher and balanced carrier transmission performance, easily adjustable luminescence spectrum and higher electroluminescent performance. The S, S-dioxo-thioxanthene derivative unit can be used as a luminescent material to prepare a polymer light-emitting diode by a solution processing method.

Description

Polymer containing S, S-dioxo-thioxanthene derivative unit and preparation method and application thereof
Technical Field
The invention belongs to the field of organic photoelectricity, and particularly relates to a polymer containing an S, S-dioxo-thioxanthene derivative unit, and a preparation method and application thereof.
Background
Polymer Light Emitting Diodes (PLEDs) are organic light emitting diodes that use polymers as the light emitting material, which have the following advantages compared to small molecule light emitting diodes: (1) the large-area film can be prepared by methods such as solution spin coating, roll-to-roll and the like; (2) the electronic structure and the luminous color of the conjugated polymer can be easily adjusted by changing and modifying the chemical structure; (3) the conjugated polymer can avoid crystallization through modification, and further the stability of the device is improved.
The polymer luminescent material as an important component in the PLED device is always the focus of scientific research and industrial research, and the high-efficiency polymer luminescent material needs to satisfy the following conditions: (1) high fluorescence quantum yield; (2) high carrier mobility; (3) the carrier transmission is balanced; (4) appropriate energy levels to facilitate electron and hole injection; (5) good thermal and chemical stability.
Most of the currently used polymer light-emitting materials are hole-transport type, that is, the hole injection and transport properties are stronger than those of electrons, which limits the electroluminescent properties of the polymer light-emitting materials. Therefore, the introduction of the unit for enhancing the electron transport property into the polymer can improve the carrier transport balance, thereby improving the luminous efficiency.
The S, S-dioxo-thioxanthene derivative unit is a multi-element ring-merging unit containing sulfonyl, the existence of the sulfonyl enables the unit to have higher electron affinity, and the introduction of the sulfonyl into the polymer can reduce the LUMO energy level of the polymer, improve the electron injection capability and improve the electron transport performance. In addition, the multi-element parallel ring structure containing the S, S-dioxo-thioxanthene derivative unit can improve the carrier mobility and stability of the polymer, and is favorable for preparing a stable and high-efficiency polymer light-emitting diode.
Disclosure of Invention
In order 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 comprising S, S-dioxo-thioxanthene derivative units. The S, S-dioxo-thioxanthene derivative unit has a wider band gap and higher fluorescence quantum yield, and meanwhile, the S, S-dioxo-thioxanthene derivative unit contains a sulfonyl group, so that the electron injection and transmission performance of the polymer can be improved. The emission spectrum of the polymer containing S, S-dioxo-thioxanthene derivative units can be well adjusted by adjusting the content of the units.
Another object of the present invention is to provide a process for the preparation of the above polymer containing S, S-dioxo-thioxanthene derivative units.
The invention further aims to provide application of the polymer containing the S, S-dioxo-thioxanthene derivative unit in the field of organic photoelectricity. The polymer containing the S, S-dioxo-thioxanthene derivative unit can be used for preparing a large-area film by solution processing methods such as spin coating, ink-jet printing, printing and the like.
The purpose of the invention is realized by the following scheme:
a polymer comprising S, S-dioxo-thioxanthene derivative units, the chemical structure of which satisfies one of the following formulae:
Figure BDA0001586857200000021
wherein: x is the number of1、x2The mole fraction of each unit component satisfies: x is more than or equal to 01<1，0<x2≤1，x1+x21 is ═ 1; n is a repeating unit, and n is 10-1000;
R1an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, or an aromatic heterocyclic group having 3 to 60 carbon atoms;
y is C (R)2)2、NR2、S、SO2Or CO2Preferably C (R)2)2(ii) a Wherein R is2An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms;
preferably, R is as defined above1And R2Relatively independently, the alkyl group with 1-30 carbon atoms, the naphthenic group with 3-30 carbon atoms and one of the following chemical structures or derivatives of the following structures:
Figure BDA0001586857200000031
wherein R is3An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 3 to 20 carbon atoms; r4H, D, F, CN, alkenyl, alkynyl, amido, nitro, acyl, alkoxy, carbonyl, sulfone, C1-10 alkyl (alkoxy), C3-10 cycloalkyl, C6-60 aromatic hydrocarbon or C3-20 aromatic heterocyclic radical.
In the chemical structural formula of the polymer, Ar is one or more of aromatic hydrocarbon groups with 6-60 carbon atoms or aromatic heterocyclic groups with 3-60 carbon atoms, and when Ar is a plurality of groups, the sum of the mole fractions of all the groups is x1。
Further, said Ar is preferably one or more of the following substituted or unsubstituted chemical structures:
Figure BDA0001586857200000032
Figure BDA0001586857200000041
wherein R is5An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms; r6、R7、R8Each independently represents H, D, F, CN, alkenyl, alkynyl, amido, nitro, acyl, alkoxy, carbonyl, sulfuryl, alkyl (alkoxy) with 1-30 carbon atoms, cycloalkyl with 3-30 carbon atoms, aromatic hydrocarbon with 6-60 carbon atoms or aromatic heterocyclic with 3-60 carbon atoms.
A preparation method of the polymer containing the S, S-dioxo-thioxanthene derivative unit mainly comprises the following steps:
carrying out Suzuki polymerization reaction on a dibromo or diiodo modified monomer containing S, S-dioxo-thioxanthene derivative units and a monomer containing Ar units, and then sequentially adding phenylboronic acid and bromobenzene for end-capping reaction to obtain the polymer containing S, S-dioxo-thioxanthene derivative units.
Further, the preparation method of the polymer containing the S, S-dioxo-thioxanthene derivative unit specifically comprises the following steps:
(1) under the protection of inert gas, dissolving a dibromo or diiodo modified monomer containing an S, S-dioxo-thioxanthene derivative unit and a monomer containing an Ar unit in a solvent, then adding a catalyst and alkali, and heating to 60-100 ℃ to perform Suzuki polymerization reaction for 12-36 hours;
(2) adding phenylboronic acid, and keeping the temperature to continue reacting for 6-12 h; and adding bromobenzene, continuing to perform heat preservation reaction for 6-12 h, and purifying the obtained reaction liquid after the reaction is finished to obtain the target product.
The structural formula of the dibromo or diiodo modified S, S-dioxo-thioxanthene derivative unit-containing monomer described in the step (1) is shown as follows:
Figure BDA0001586857200000051
wherein R is1、R2As defined above;
preferably, when Y is C (R)2)2When the monomer containing the dibromo-modified S, S-dioxo-thioxanthene derivative unit is prepared by the following scheme:
Figure BDA0001586857200000052
the method specifically comprises the following steps:
(1.1) under nitrogen protection, 9-thioxanthone and toluene were added to the reaction vessel, cooled to 0 ℃ by an ice bath, and then Al (R) was added1)3The toluene solution is naturally heated to room temperature for reaction, stirred and reacted for 12 hours, and after the reaction is finished, the obtained reaction liquid is purified to obtain a compound A;
(1.2) adding the compound A and acetic acid into a reaction container under a nitrogen atmosphere, adding liquid bromine dissolved in the acetic acid under an ice bath, naturally heating the reaction liquid to room temperature, continuing to react for 12 hours, and purifying the obtained reaction liquid after the reaction is finished to obtain a compound B;
(1.3) adding a compound B, pinacol diboron, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, potassium acetate and dioxane into a reaction vessel under the protection of nitrogen, heating to 80 ℃, reacting for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound C;
(1.4) under the protection of nitrogen, adding a compound C, methyl o-bromobenzoate, potassium carbonate, tetrakis (triphenylphosphine) palladium, deionized water and toluene into a reaction vessel, heating to 80 ℃ for reaction for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound D;
(1.5) adding the compound D and anhydrous tetrahydrofuran into a reaction vessel under the protection of nitrogen, cooling to-78 ℃, and dropwise adding R2Heating the tetrahydrofuran solution of MgBr to room temperature for reaction for 12 hours, and purifying the obtained reaction liquid after the reaction is finished to obtain a compound E;
(1.6) adding a compound E and acetic acid into a reaction container under the protection of nitrogen, heating to 100 ℃, adding concentrated hydrochloric acid, continuing to heat for reaction for 8 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound F;
(1.7) under the protection of nitrogen, adding a compound F and chloroform into a reaction vessel, adding liquid bromine dissolved in chloroform under the condition of keeping out of the sun, stirring at normal temperature for reaction for 12 hours, and purifying the obtained reaction liquid after the reaction is finished to obtain a compound G;
(1.8) adding a mixed solvent of a compound G, tetrahydrofuran and acetic acid into a reaction vessel under the protection of nitrogen, heating to 70 ℃, adding a hydrogen peroxide aqueous solution, continuously heating and stirring for reaction for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound H;
preferably, when Y is NR2When the monomer containing the dibromo-modified S, S-dioxo-thioxanthene derivative unit is prepared by the following scheme:
Figure BDA0001586857200000071
the method specifically comprises the following steps:
(2.1) adding the compound A and acetic acid into a reaction vessel under the protection of nitrogen, heating to 100 ℃, adding aqueous hydrogen peroxide, continuing to heat and stir for reaction for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound I;
(2.2) adding the compound I and concentrated sulfuric acid into a reaction container under the protection of nitrogen, adding N-bromosuccinimide into the reaction container under the condition of keeping out of the sun, stirring for 24 hours at normal temperature, and purifying the obtained reaction liquid after the reaction is finished to obtain a compound J;
(2.3) adding the compound J and anhydrous ether into a reaction vessel under the nitrogen atmosphere, adding lithium aluminum hydride, stirring for 8 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound K;
(2.4) under the protection of nitrogen, adding a compound K, pinacol diboron, [1, 1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, potassium acetate and dioxane into a reaction vessel, heating to 80 ℃, reacting for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound L;
(2.5) under the protection of nitrogen, adding a compound L, o-bromonitrobenzene, potassium carbonate, tetrakis (triphenylphosphine) palladium, deionized water and toluene into a reaction vessel, heating to 80 ℃ for reaction for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound M;
(2.6) under the protection of nitrogen, adding the compound M and triethyl phosphite into a reaction vessel, heating to 100 ℃, reacting for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound N;
(2.7) adding N, R into the reaction vessel under the protection of nitrogen2Br, potassium carbonate and acetone, heating to 70 ℃ for reaction for 48 hours, and purifying the obtained reaction solution after the reaction is finished to obtain a compound O;
(2.8) under the protection of nitrogen, adding a compound O and chloroform into a reaction vessel, adding liquid bromine dissolved in chloroform under the condition of keeping out of the sun, stirring at normal temperature for reaction for 12 hours, and purifying the obtained reaction liquid after the reaction is finished to obtain a compound P;
(2.9) under the protection of nitrogen, adding a mixed solvent of the compound P, tetrahydrofuran and acetic acid into a reaction vessel, heating to 70 ℃, adding aqueous hydrogen peroxide, continuing to heat and stir for reaction for 12 hours, and purifying the obtained reaction solution after the reaction is finished to obtain the compound Q.
The solvent in the step (1) is at least one of toluene, tetrahydrofuran and xylene;
the catalyst for Suzuki polymerization in the step (1) is at least one of a mixture of palladium acetate and tricyclohexylphosphine and tetrakis (triphenylphosphine) palladium, and the alkali is at least one of tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution and potassium carbonate.
The monomer containing the Ar unit in the step (1) is preferably one or more of monomers with the terminal group of diboronate, diboronic acid, dibromide or diiodo, and the monomers with the terminal group of diboronate or diboronic acid are necessarily included;
the dibromo or diiodo modified S, S-dioxo-thioxanthene derivative unit-containing monomer and the Ar unit-containing monomer described in step (1) are used in such amounts that the total molar amount of the diboronate and/or bisboronic acid functional group-containing monomer is equal to the total molar amount of the bisbromo and/or diiodo functional group-containing monomer; the dosage of the catalyst is 5 per mill-3% of the total mole amount of the reaction monomer; the dosage of the alkali is 1-10 times of the total molar amount of the reaction monomers;
the dosage of the phenylboronic acid in the step (2) is 10-30% 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, pour the reaction liquid into methanol for precipitation, filter and dry the reaction liquid to obtain a crude product, the crude product is extracted by methanol, acetone and normal hexane in sequence, then dissolved by toluene, separated by column chromatography, concentrated and precipitated in a methanol solution again, filtered and dried to obtain the target product.
The polymer containing the S, S-dioxo-thioxanthene derivative unit has good solubility and can be dissolved in common organic solvents.
The application of the polymer containing S, S-dioxo-thioxanthene derivative units in preparing the luminous layer of a polymer light-emitting diode.
The steps for preparing the luminous layer of the polymer light-emitting diode are as follows: and dissolving the polymer containing the S, S-dioxo-thioxanthene derivative unit in an organic solvent, and forming a film by spin coating, ink-jet printing or printing to obtain the light-emitting layer of the polymer light-emitting diode.
The organic solvent is xylene, chlorobenzene or tetrahydrofuran.
The polymer light emitting diode based on the polymer containing S, S-dioxo-thioxanthene derivative unit can be used for the display of a flat panel display.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the S, S-dioxo-thioxanthene derivative unit is introduced into the main chain of the polymer through copolymerization, and the S, S-dioxo-thioxanthene derivative unit can improve the electron transport performance of the polymer and simultaneously keep higher fluorescence quantum yield. 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.
(2) The polymer containing the S, S-dioxo-thioxanthene derivative unit has higher fluorescence quantum yield, better thermal stability, higher and balanced carrier transmission performance, easily adjustable luminescence spectrum and higher electroluminescent performance.
(3) The S, S-dioxo-thioxanthene derivative unit can be used as a luminescent material to prepare a polymer light-emitting diode by a solution processing method.
Drawings
FIG. 1 is a photoluminescence spectrum of a polymer P1 in a thin film state;
FIG. 2 is a graph showing the electroluminescence spectrum of polymer P3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
The sum of the mole fractions of the respective units in the polymer structure obtained in this example is 1 by default, and therefore, it is not necessary to label the mole fractions of all the unit components, and the mole fraction of the structural unit not labeled with a mole fraction is 1-the sum of the mole fractions of the structural units labeled with mole fractions by default. As in P1
Figure BDA0001586857200000101
Although not indicated, the molar fraction of (A) is 1-0.1-0.9, i.e. in P1
Figure BDA0001586857200000102
Subscript of (a) is effectively 0.9; when x1 is x2, both may not be labeled.
Example 1
Preparation of Compound M1
(1) Preparation of Compound 1
9-thioxanthone (2.12g, 10mmol) and toluene (40ml) were added to a 100ml two-necked flask under nitrogen, cooled to 0 ℃ by an ice bath, and then a toluene solution of trimethylaluminum (22ml, 22mmol) was added dropwise slowly, and the reaction was allowed to warm to room temperature and stirred for 12 hours. The product was extracted with dichloromethane, washed 3 times with saturated aqueous sodium chloride solution, dried, filtered, the solvent evaporated and the crude product purified by silica gel column (eluent petroleum ether) to give 1.95g of colorless transparent liquid in 86% yield.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(2.27g, 10mmol) and acetic acid (50ml) were added to a 150ml two-necked flask, liquid bromine (1.15ml, 22mmol) dissolved in 20ml of acetic acid was added dropwise from a constant pressure dropping funnel under ice bath, and then the reaction solution was naturally warmed to room temperature and continued for 12 hours; excess liquid bromine was removed with aqueous sodium bisulfite solution, the product was extracted with dichloromethane (150ml), the organic phase was washed 3 times with saturated aqueous sodium chloride solution, dried, filtered, the solvent was dried by spinning, and the crude product was purified with a silica gel column (eluent petroleum ether) to give 2.49g of a white solid in 78% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(3) Preparation of Compound 3
Under nitrogen protection, compound 2(3.05g, 10mmol), pinacol diboron (3.81g, 15mmol) 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, removing dioxane by reduced pressure distillation, extracting the product by dichloromethane, washing the product for three times by saturated sodium chloride aqueous solution, removing dichloromethane by reduced pressure distillation, and using the crude productPetroleum ether: ethyl acetate ═ 8: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 2.92g of white solid is obtained, and the yield is 83%.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(3.52g, 10mmol), methyl o-bromobenzoate (2.58g, 12mmol), potassium carbonate (3.45g, 25mmol), tetrakis (triphenylphosphine) palladium (0.58g, 0.5mmol), 12ml deionized water and 120ml toluene were added to a 300ml 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: dichloromethane ═ 4: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, and the compound 4 is 3.21g of yellow solid, and the yield is 89%.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 nitrogen protection, compound 4(3.66g, 10mmol) and 100mL of anhydrous tetrahydrofuran were added to a 300mL two-necked flask, cooled to-78 deg.C, and a solution of n-octyl magnesium bromide in tetrahydrofuran (35mL, 35mmol) was added dropwise and allowed to slowly warm to room temperature 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 ═ 5: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 4.18g of yellow solid is obtained, and the yield is 75%.1HNMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(6) Preparation of Compound 6
Under nitrogen, compound 5(5.57g, 10mmol) and 120mL of acetic acid were added to a 300mL two-necked flask, heated to 100 ℃ and then 2mL of concentrated HCl was added and the reaction was continued for 8 hours. After the reaction is finished, the reaction liquid is poured into 500ml of ice water after being cooled, the mixture is filtered, filter residues are washed twice by 50ml of ethanol, and a crude product is obtained by using stoneOil ether: dichloromethane 10: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, and 3.93g 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.
(7) Preparation of Compound 7
Under nitrogen protection, compound 6(5.39g, 10mmol) and 80mL of chloroform were added to a 150mL two-necked flask, and liquid bromine (3.52g, 22mmol) dissolved in 20mL of chloroform was added in the dark, and the reaction was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was quenched with an aqueous solution of an appropriate amount of sodium hydrogen sulfite, the product was extracted with dichloromethane, washed three times with a saturated aqueous solution of sodium chloride, and after dichloromethane was removed by distillation under reduced pressure, the crude product was purified with petroleum ether: dichloromethane ═ 6: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 4.25g of white solid is obtained, and the yield is 61%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(8) Preparation of Compound M1
Under nitrogen protection, compound 7(6.97g, 10mmol) and 150ml 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 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 a mixed solvent of petroleum ether/tetrahydrofuran to give 6.27g of a white solid in 86% yield.1HNMR、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:
Figure BDA0001586857200000121
example 2
Preparation of Compound M2
(1) Preparation of Compound 8
Under nitrogen protection, compound 1(2.26g, 10mmol) and 80ml of acetic acid were added to a 150ml two-necked flask, heated to 100 ℃ and then slowly added dropwise with aqueous hydrogen peroxide (5ml, 50mmol), and the reaction was stirred with heating for 12 hours. After the reaction was completed, it was cooled and left to stand for 2 hours, and filtered to obtain 2.32g of a white solid with a yield of 90%.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 protection, compound 8(2.58g, 10mmol) and 50ml of concentrated sulfuric acid were added to a 100ml two-necked flask, and N-bromosuccinimide (2.14g, 12mmol) was added to the flask in 3 portions under dark conditions. After stirring for 24 hours at normal temperature, slowly pouring the reaction liquid into 500ml of ice water, carrying out suction filtration, and washing filter residues with distilled water and ethanol in sequence. The crude product was recrystallized 3 times by hot filtration using a mixed solvent of tetrahydrofuran/n-hexane (1: 4) to give 2.22g of colorless needle-like crystals in 66% 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
Compound 9(3.37g, 10mmol) and 60ml of dehydrated ether were added to a 100ml two-necked flask under a nitrogen atmosphere, and lithium aluminum hydride (1.14g, 30mmol) was slowly added thereto 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 solution and 30ml of water. The product was extracted with dichloromethane and washed three times with saturated aqueous sodium chloride solution to remove the organic phase solvent, and the crude product was purified by column chromatography using petroleum ether as eluent to give 2.35g of a white solid in 77% yield.1HNMR、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(3.05g, 10mmol), pinacol diboron (3.81g, 15mmol) 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 toThe reaction was carried out at 80 ℃ 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 ═ 8: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 2.82g of white solid is obtained, and the yield is 80%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(5) Preparation of Compound 12
Under nitrogen protection, compound 11(3.52g, 10mmol), o-bromonitrobenzene (2.42g, 12mmol), potassium carbonate (3.45g, 25mmol), tetrakis (triphenylphosphine) palladium (0.58g, 0.5mmol), 12ml deionized water and 120ml toluene were added to a 300ml 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: dichloromethane ═ 4: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, and light yellow solid 2.81g is obtained, and the yield is 81%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(6) Preparation of Compound 13
Compound 12(3.47g, 10mmol) and 50ml triethyl phosphite were added to a 150ml two-necked flask under nitrogen, and heated to 100 ℃ 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: column chromatography purification of 1 (v: v) as eluent afforded compound 13 as a white solid 1.42g, 45% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(7) Preparation of Compound 14
Under a nitrogen atmosphere, compound 13(3.15g, 10mmol), 1-bromohexane (4.95g, 30mmol), potassium carbonate (8.28g, 60mmol) and 150ml acetone were added to a 300ml two-necked flask and heated to 70 ℃ for reaction for 48 hours. After the reaction is finished, extracting the product by using dichloromethaneThe crude product was washed with saturated aqueous sodium chloride solution five times to remove the organic phase solvent, and the crude product was purified by column chromatography using petroleum ether as eluent to obtain 2.92g of white solid with a yield of 73%.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(8) Preparation of Compound 15
Under nitrogen protection, compound 14(4.00g, 10mmol) and 80mL of chloroform were added to a 150mL two-necked flask, and liquid bromine (g, 22mmol) dissolved in 20mL of chloroform was added in the dark, and the reaction was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was quenched with an aqueous solution of an appropriate amount of sodium hydrogen sulfite, the product was extracted with dichloromethane, washed three times with a saturated aqueous solution of sodium chloride, and after dichloromethane was removed by distillation under reduced pressure, the crude product was purified with petroleum ether: dichloromethane ═ 5: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 4.12g of white solid is obtained, and the yield is 74%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(9) Preparation of Compound M2
Under nitrogen protection, compound 15(5.57g, 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 a mixed solvent of petroleum ether/tetrahydrofuran to give 5.42g of a white solid in 92% yield.1HNMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equations for synthesizing compounds 8-15 and compound M2 are shown below:
Figure BDA0001586857200000151
example 3
Preparation of Compound M3
(1) Preparation of Compound 16
Under nitrogen protection, compound 4(3.60g, 10mmol) and 50ml of concentrated sulfuric acid were added to a 150ml two-necked flask, and the reaction was stirred at room temperature for 24 hours. After the reaction, the reaction solution was slowly poured into 500ml of ice water, the product was extracted with dichloromethane, washed three times with saturated aqueous sodium chloride solution, and after removing the organic phase solvent, the crude product was treated with petroleum ether: dichloromethane ═ 4: column chromatography purification of 1 (v: v) as eluent afforded compound 16 as a yellow solid 1.64g, 50% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Preparation of Compound 17
Under nitrogen protection, compound 16(3.28g, 10mmol) and 150mL of chloroform were added to a 300mL two-necked flask, and liquid bromine (g, 22mmol) dissolved in 20mL of chloroform was added in the dark, and the reaction was stirred at room temperature for 12 hours. After the reaction was completed, the reaction was quenched with an aqueous solution of an appropriate amount of sodium hydrogen sulfite, the product was extracted with dichloromethane, washed three times with a saturated aqueous solution of sodium chloride, and after dichloromethane was removed by distillation under reduced pressure, the crude product was purified with petroleum ether: dichloromethane ═ 4: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 3.31g of yellow solid is obtained, and the yield is 68%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Preparation of Compound 18
Adding compound 17(4.86g, 10mmol), triphenylamine (12.3g, 50mmol), methanesulfonic acid (3.84g, 40mol) and 60ml carbon tetrachloride into a 150ml three-neck flask, and heating to 80 ℃ under the protection of nitrogen for reaction for 12 hours; after the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, the solvent was distilled off, and the crude product was purified with petroleum ether: dichloromethane ═ 6: the mixed solvent of 1(v/v) is used as eluent for column chromatography purification, 7.19g of white solid is obtained, and the yield is 75%.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 protection, compound 18(9.59g, 10mmol) and 160ml 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 (3: 1, v: v) was recrystallized from a mixed solvent of petroleum ether/tetrahydrofuran to give 8.03g of a white solid in a yield of 81%.1HNMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
The chemical reaction equations for synthesizing compounds 16-18 and compound M3 are shown below:
Figure BDA0001586857200000171
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(43.7mg, 0.06mmol) were dissolved in 12mL 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 passing1And (4) confirming to obtain the target polymer by HNMR spectrogram and element analysis. Gel permeation chromatography: mn is 153KDa, PDI is 2.35. Fluorescence quantum yield: 0.73. the chemical reaction equation is as follows:
Figure BDA0001586857200000181
FIG. 1 shows the photoluminescence emission spectrum of the polymer P1 in a thin film state, and the excitation wavelength is 390nm, and it can be found that the polymer P1 shows very good blue light emission.
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 (98.7mg, 0.18mmol) and compound M2(70.7mg, 0.12mmol) were dissolved in 12mL 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 passing1And (4) confirming to obtain the target polymer by HNMR spectrogram and element analysis. Gel permeation chromatography: mn is 119KDa, and PDI is 2.24. Fluorescence quantum yield: 0.70. the chemical reaction equation is as follows:
Figure BDA0001586857200000191
example 6
Preparation of Polymer P3
Under the protection of nitrogen, 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 (138.2mg, 0.252mmol), 4, 7-dibromobenzothiadiazole (5.3mg,0.018mmol) and compound M3(29.7mg, 0.03mmol) were dissolved in 12mL of toluene, and an aqueous tetraethylhydroxylamine solution (1mL of20% by weight, 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 green fibrous polymer. By passing1H NMR spectrum and element analysis confirm that the target polymer is obtained. Gel permeation chromatography: mn is 65KDa, PDI is 2.01. Fluorescence quantum yield: 0.91. the chemical reaction equation is as follows:
Figure BDA0001586857200000201
FIG. 2 shows the electroluminescence spectrum of polymer P3, and it can be seen that the device based on polymer P3 emits green light with color coordinates (0.34, 0.68).
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 (115.2mg,0.21mmol), 4, 7-bis (5-bromo (4-hexylthiophene) -2-yl) -2,1, 3-benzothiadiazole (18.8mg,0.03mmol), and compound M3(59.5mg, 0.06mmol) were dissolved in 12mL of toluene, followed by addition of an aqueous solution of tetraethylhydroxylamine (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: mn is 99KDa, PDI is 2.52. Fluorescence quantum yield: 0.75. the chemical reaction equation is as follows:
Figure BDA0001586857200000211
example 8
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 the polymer (P1, P3, P4) was then spin coated onto the surface of PEDOT: PSS film 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.
TABLE-Polymer electroluminescent device Properties
Figure BDA0001586857200000212
The device structure is as follows: ITO/PEDOT PSS/Polymer/CsF/Al
As can be seen from Table one, the devices based on the polymer P1 gave 2.57cd/A higher current efficiency deep blue emission, corresponding to color coordinates of (0.16, 0.10); polymers P3 and P4 gave higher efficiency in green and red light emission, respectively.
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-thioxanthene derivative units is characterized in that the chemical structural formula of the polymer meets one of the following general formulas:
Figure FDA0002417734720000011
wherein x is1、x2The mole fraction of each unit component satisfies: x is more than or equal to 01<1，0<x2≤1，x1+x21 is ═ 1; n is a repeating unit, and n is 10-1000;
R1an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, or an aromatic heterocyclic group having 3 to 60 carbon atoms;
y is C (R)2)2Or NR2(ii) a Wherein R is2An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms;
in the chemical structural formula of the polymer, Ar is one or more of aromatic hydrocarbon groups with 6-60 carbon atoms or aromatic heterocyclic groups with 3-60 carbon atoms, and when Ar is a plurality of groups, the sum of the mole fractions of all the groups is x1。
2. A polymer comprising S, S-dioxo-thioxanthene derivative units according to claim 1, characterized in that:
said R1And R2Relatively independently, the alkyl group with 1-30 carbon atoms, the naphthenic group with 3-30 carbon atoms and one of the following chemical structures or derivatives of the following structures:
Figure FDA0002417734720000012
wherein R is3Is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms.
3. A polymer comprising S, S-dioxo-thioxanthene derivative units according to claim 1, characterized in that:
ar is one or more of the following substituted or unsubstituted chemical structures:
Figure FDA0002417734720000021
wherein R is5An alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 60 carbon atoms; r6、R7、R8Each independently represents H, D, F, CN, alkenyl, alkynyl, amido, nitro, acyl, alkoxy, carbonyl, sulfuryl, alkyl with 1-30 carbon atoms, naphthenic base with 3-30 carbon atoms or aromatic hydrocarbon with 6-60 carbon atoms.
4. A process for the preparation of a polymer comprising S, S-dioxo-thioxanthene derivative units according to any one of claims 1 to 3, characterized in that it comprises the following steps:
carrying out Suzuki polymerization reaction on a dibromo or diiodo modified monomer containing S, S-dioxo-thioxanthene derivative units and a monomer containing Ar units, and then sequentially adding phenylboronic acid and bromobenzene for end-capping reaction to obtain the polymer containing S, S-dioxo-thioxanthene derivative units.
5. The process for the preparation of a polymer containing S, S-dioxo-thioxanthene derivative units according to claim 4, characterized in that it comprises in particular the following steps:
(1) under the protection of inert gas, dissolving a dibromo or diiodo modified monomer containing an S, S-dioxo-thioxanthene derivative unit and a monomer containing an Ar unit in a solvent, then adding a catalyst and alkali, and heating to 60-100 ℃ to perform Suzuki polymerization reaction for 12-36 hours;
(2) adding phenylboronic acid, and keeping the temperature to continue reacting for 6-12 h; and adding bromobenzene, continuing to perform heat preservation reaction for 6-12 h, and purifying the obtained reaction liquid after the reaction is finished to obtain the target product.
6. The process for the preparation of a polymer containing S, S-dioxo-thioxanthene derivative units according to claim 5, characterized in that:
the structural formula of the dibromo or diiodo modified S, S-dioxo-thioxanthene derivative unit-containing monomer described in the step (1) is shown as follows:
Figure FDA0002417734720000031
the solvent in the step (1) is at least one of toluene, tetrahydrofuran and xylene;
the catalyst for the Suzuki polymerization reaction in the step (1) is at least one of a mixture of palladium acetate and tricyclohexylphosphine and tetrakis (triphenylphosphine) palladium, and the alkali is at least one of tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution and potassium carbonate;
the monomer containing the Ar unit in the step (1) is one or more of monomers with the end group of diboronic acid ester, diboronic acid, dibromide or diiodide, and the monomer with the end group of diboronic acid ester or diboronic acid is included;
the dibromo or diiodo modified S, S-dioxo-thioxanthene derivative unit-containing monomer and the Ar unit-containing monomer described in step (1) are used in such amounts that the total molar amount of the diboronate and/or bisboronic acid functional group-containing monomer is equal to the total molar amount of the bisbromo and/or diiodo functional group-containing monomer; the dosage of the catalyst is 5 per mill-3% of the total mole amount of the reaction monomer; the dosage of the alkali is 1-10 times of the total molar amount of the reaction monomers.
7. The process for the preparation of a polymer containing S, S-dioxo-thioxanthene derivative units according to claim 5, characterized in that:
the dosage of the phenylboronic acid in the step (2) is 10-30% 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, pour the reaction liquid into methanol for precipitation, filter and dry the reaction liquid to obtain a crude product, the crude product is extracted by methanol, acetone and normal hexane in sequence, then dissolved by toluene, separated by column chromatography, concentrated and precipitated in a methanol solution again, filtered and dried to obtain the target product.
8. Use of a polymer comprising S, S-dioxo-thioxanthene derivative units according to any one of claims 1 to 3 for the preparation of the light-emitting layer of a polymer light-emitting diode.
9. The use of a polymer comprising S, S-dioxo-thioxanthene derivative units according to claim 8 for the preparation of a light-emitting layer of a polymer light-emitting diode, characterized in that said preparation of said light-emitting layer of a polymer light-emitting diode comprises the steps of: and dissolving the polymer containing the S, S-dioxo-thioxanthene derivative unit in an organic solvent, and forming a film by spin coating, ink-jet printing or printing to obtain the light-emitting layer of the polymer light-emitting diode.
10. Use of a polymer comprising S, S-dioxo-thioxanthene derivative units according to claim 9 for the preparation of the light-emitting layer of a polymer light-emitting diode, characterized in that: the organic solvent is xylene, chlorobenzene or tetrahydrofuran.
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