Quinone-donor-acceptor conjugated polymers with mixed side chains, their preparation and applications

Abstract

This invention discloses a quinone-donor-acceptor conjugated polymer with mixed side chains, its preparation, and its applications. The general structural formula of the quinone-donor-acceptor conjugated polymer with mixed side chains of this invention is as follows: It is a novel polymer structure that exhibits high carrier transport performance and good solution processability when used as a polymer semiconductor, making it worthy of widespread application in the field of semiconductor polymers.

Description

Technical Field

[0001] This invention relates to a polymer semiconductor, and more particularly to the preparation and application of a quinone-donor-acceptor conjugated polymer containing mixed side chains. Background Technology

[0002] Organic field-effect transistors (OFETs) are characterized by low cost, light weight, and flexibility, and have broad application prospects in flexible electronics, optoelectronic devices, sensors, and other fields.

[0003] Improving the performance of polymer-based OFET devices has become a research hotspot in organic electronics. Flexible side chains are a crucial component of polymer semiconductors. Besides increasing the solubility of polymers in organic solvents, they can also influence the microstructure of polymer films, thereby modulating the charge transport properties and ultimately affecting OFET device performance. Therefore, polymer side chain engineering is an important strategy for optimizing the performance of polymer semiconductor materials.

[0004] Common sidechain engineering methods include adjusting the sidechain position, adjusting the sidechain branch point position, changing the sidechain length, and using sidechains containing heteroatoms (O, F, Si).

[0005] Quinone polymers based on the quinone-donor-acceptor (QDA) backbone structure offer advantages such as narrow band gaps, high coplanarity, and high mobility compared to polymers with corresponding donor-acceptor (DA) backbone structures. However, due to the rigidity of the QDA backbone structure, branched alkyl groups are required to ensure sufficient solubility and solution processability. Branched alkyl groups, however, exhibit significant steric hindrance, weakening intermolecular chain interactions and hindering close π-π packing, thus limiting carrier transport. While straight-chain alkyl groups promote close chain packing, they do not guarantee good solution processability. Summary of the Invention

[0006] The purpose of this invention is to provide a quinone-donor-acceptor conjugated polymer containing mixed side chains, its preparation, and its applications. The quinone-donor-acceptor conjugated polymer of this invention represents a novel polymer structure. When used as a semiconductor polymer, it exhibits high carrier transport performance and good solution processability, making it worthy of widespread application in the field of polymer semiconductors.

[0007] The technical solution of this invention: A quinone-donor-acceptor conjugated polymer containing mixed side chains, the general chemical formula of which is as follows:

[0008]

[0009] Wherein, the unit A is any one of the following structural formulas:

[0010]

[0011] R is an alkyl group from C-1 to C-60;

[0012] The x = any value from 0 to 1, and y = 1 - x.

[0013] A method for preparing the aforementioned quinone-donor-acceptor conjugated polymer containing mixed side chains includes the following steps:

[0014] 1) Under inert gas protection, compound 1, potassium carbonate and halo-chain linear alkyl groups were dissolved in an organic solvent, heated to 50-70℃ and reacted for 5-7 hours. After cooling to room temperature, the filtrate was collected by filtration, concentrated, and then recrystallized by chromatography to obtain compound 2.

[0015] 2) Under inert gas protection, compound 1, potassium carbonate and halobranched alkyl groups were dissolved in an organic solvent, heated to 90-110℃ and reacted for 7-9 hours. After cooling to room temperature, the filtrate was collected by filtration, concentrated, and then recrystallized by chromatography to obtain compound 3.

[0016] 3) Using compounds 2 and 3 as raw materials, the polymer can be obtained by reacting them with precursor A to obtain the mixed side-chain quinone-donor-acceptor conjugated polymer.

[0017] The chemical structural formula of compound 1 is as follows:

[0018]

[0019] The chemical structural formula of the halo-substituted straight-chain alkyl group is as follows:

[0020] R-Br or RI; R is an alkyl group from C-1 to C-60;

[0021] The chemical structural formula of the halo-branched alkyl group is as follows:

[0022] R is an alkyl group from C-1 to C-60;

[0023] The precursor A is one of the following structural formulas:

[0024]

[0025] Preferably, in the aforementioned method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains, the molar ratio of compound 1 to the halo-chain linear alkyl group is 1:2-1:3.

[0026] Preferably, in the aforementioned method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains, the molar ratio of compound 1 to halobranched alkyl groups is 1:2-1:3.

[0027] Preferably, in the aforementioned method for preparing quinone-donor-acceptor conjugated polymers with mixed side chains, the recrystallization in steps 1) and 2) is performed using anhydrous ethanol.

[0028] Preferably, in the aforementioned method for preparing the quinone-donor-acceptor conjugated polymer with mixed side chains, the polymerization reaction in step 3) involves mixing and dissolving compound 2, compound 3, precursor A, and catalyst in an organic solvent, purging with an inert gas for 0.5-2 hours, heating the mixture to 90-110°C, reacting for 40-60 hours, then injecting a capping agent for end-capping, cooling to room temperature, placing the mixture in methanol to precipitate, filtering and collecting the precipitate, and sequentially performing Soxhlet extraction with methanol, acetone, ethyl acetate, chloroform, and chlorobenzene solutions. The chloroform and chlorobenzene solutions obtained from the Soxhlet extraction are concentrated and then slowly added to a methanol solution to precipitate a polymer solid, thus obtaining the quinone-donor-acceptor conjugated polymer with mixed side chains.

[0029] Preferably, in the aforementioned method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains, the molar ratio of the sum of the moles of compound 2 and compound 3 to that of precursor A is 1:1.

[0030] Preferably, in the aforementioned method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains, the catalyst is a mixture of tris(dibenzylacetone)dipalladium and tris(o-methylphenyl)phosphine.

[0031] Preferably, in the aforementioned method for preparing the quinone-donor-acceptor conjugated polymer with mixed side chains, the capping agent is 2-trimethyltinthiophene and 2-bromothiophene, and the order of addition of 2-trimethyltinthiophene and 2-bromothiophene is to add 2-trimethyltinthiophene first and then add 2-bromothiophene, and the reaction time is 5-7 hours after each addition.

[0032] Application of the aforementioned quinone-donor-acceptor conjugated polymer semiconductor containing mixed side chains.

[0033] Beneficial effects of the present invention

[0034] The quinone-donor-acceptor conjugated polymer of the present invention is a novel polymer based on a mixed side chain structure, which differs from the traditional single-branch or single-straight-chain structure.

[0035] The quinone-donor-acceptor conjugated polymer containing mixed side chains of the present invention exhibits stronger molecular chain aggregation and higher coplanarity compared to the previously reported polymer PAQM-BT containing a single branch chain. The hole mobility of OFET devices based on the polymer of the present invention can be increased to 6.13 cm⁻¹. 2 V –1 s –1 This value is higher than the mobility of PAQM-BT by 5.10 cm.2 V – 1 s –1 .

[0036] The above results indicate that quinone-donor-acceptor conjugated polymers with mixed side chains have great potential and application prospects in improving the mobility of polymers with quinone-donor-acceptor backbone structures. Attached Figure Description

[0037] Appendix Figure 1 The general chemical structural formula of the polymer of the present invention is shown below;

[0038] Appendix Figure 2 The chemical structural formula of PAQM-BT is as reported. Detailed Implementation

[0039] The present invention will be further described below with reference to embodiments, but these embodiments are not intended to limit the scope of the invention.

[0040] Embodiments of the present invention

[0041] Example 1

[0042]

[0043] The synthetic pathway for the monomer is shown in the figure above:

[0044] 1) Under the protection of inert argon gas, compound 1 (3Z,6Z)-3,6-bis((5-bromothiophene-2-yl)methylene)piperazine-2,5-dione (4 mmol, 1 eq), potassium carbonate (12 mmol, 3 eq), bromododecane (10 mmol, 2.5 eq), and anhydrous N,N-dimethylformamide (100 mL) were added to a reaction flask, heated to 60 °C, and reacted for 6 hours. After cooling to room temperature, the filtrate was obtained by filtration, and the filtrate was evaporated and concentrated, purified by silica gel column chromatography, recrystallized with anhydrous ethanol, and dried to give a red solid product AQM-2Br-C12 (yield 60%).

[0045] 2) Under the protection of inert argon gas, compound 1 (3Z,6Z)-3,6-bis((5-bromothiophene-2-yl)methylene)piperazine-2,5-dione (4 mmol, 1 eq), potassium carbonate (12 mmol, 1 eq), 1-bromo-2-decyltetradecane (10 mmol, 2.5 eq) and anhydrous N,N-dimethylformamide (100 mL) were added to a reaction flask, heated to 100 °C, and reacted for 8 hours. After cooling to room temperature, the filtrate was filtered, evaporated and concentrated, subjected to silica gel column chromatography, recrystallized with anhydrous ethanol, and dried to give a yellow solid product AQM-2Br-C24 (yield 45%).

[0046] The synthetic pathway for quinone-donor-acceptor conjugated polymers containing mixed side chains is as follows:

[0047]

[0048] 3) Under inert argon atmosphere, compounds AQM-2Br-C12 (0.045 mmol, 0.15 eq), AQM-2Br-C24 (0.255 mol, 0.85 eq), precursor A 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxapentylborane-2-yl)-2,1,3-benzothiadiazole (0.3 mmol, 1 eq), and catalysts tris(dibenzylacetone)dipalladium [Pd2(dba)3] (7 mg) and tris(o-methylphenyl)phosphine [tri(o-tolyl)phosphine] (9 mg) were dissolved in anhydrous toluene. After purging with argon for 1 hour, the solution was heated to 100 °C and the reaction was stirred for 48 hours. 2-Trimethyltinthiophene (0.1 mL) and 2-bromothiophene (0.2 mL) were injected sequentially as capping agents, and the reaction mixture was stirred for 6 hours after each injection. After cooling to room temperature, the mixture is precipitated in methanol solvent, and the precipitate is formed.

[0049] The precipitate collected from filtration was sequentially extracted using methanol, acetone, ethyl acetate, chloroform, and chlorobenzene solvents via Soxhlet extraction. The chloroform solution obtained from the Soxhlet extraction was then concentrated by rotary evaporation and slowly added to a methanol solution to precipitate a polymer solid. The polymer was collected by filtration and dried (yield 85%). The OFET device based on the polymer of this embodiment exhibited the highest hole mobility, reaching 6.13 cm⁻¹. 2 V –1 s –1 .

[0050] Example 2

[0051] The synthesis method in this embodiment is the same as that in Embodiment 1, the difference being:

[0052] The heating temperature in step 1) is 50°C, the reaction time is 7 h, and the molar ratio of compound 1 to halo-chain linear alkyl group is 1:2.

[0053] The heating temperature in step 2) is 90℃, the reaction time is 9h, and the molar ratio of compound 1 to halobranched alkyl group is 1:2.

[0054] In step 3), the molar ratio of compound 2 to compound 3 is 3:17; the molar ratio of compound 2 and compound 3 to precursor A is 1:1.2; the inert gas is introduced for 0.5 h; the mixture is heated to 90 °C and the reaction time is 60 h.

[0055] Example 3

[0056] The synthesis method in this embodiment is the same as that in Embodiment 1, the difference being:

[0057] The heating temperature in step 1) is 70°C, the reaction time is 5 hours, and the molar ratio of compound 1 to the halo-chain linear alkyl group is 1:3.

[0058] The heating temperature in step 2) is 110℃, the reaction time is 7h, and the molar ratio of compound 1 to halobranched alkyl group is 1:3.

[0059] In step 3), the molar ratio of compound 2 to compound 3 is 3:17; the molar ratio of the sum of the molars of compound 2 and compound 3 to precursor A is 1:1.5; the inert gas is introduced for 2 hours; the mixture is heated to 110°C and the reaction time is 40 hours.

[0060] Example 4

[0061] The synthesis method in this embodiment is the same as that in Embodiment 1, the difference being:

[0062] Step 3) The selected precursor A is

[0063] Example 5

[0064] The synthesis method in this embodiment is the same as that in Embodiment 1, the difference being:

[0065] Step 3) The selected precursor A is

[0066] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A quinone-donor-acceptor conjugated polymer containing mixed side chains, characterized in that, Its general chemical structural formula is as follows: Wherein, the unit A is any one of the following structural formulas: ； R is a straight-chain alkyl group with a chain length of C-1 to C-60; The x = any value from 0 to 1, y = 1 - x, and neither x nor y is 0.

2. A method for preparing a quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 1, characterized in that, Includes the following steps: 1) Under inert gas protection, compound 1, potassium carbonate and halo-chain linear alkyl groups were dissolved in N,N-dimethylformamide, heated to 50-70℃ and reacted for 5-7 hours. After cooling to room temperature, the filtrate was collected by filtration, concentrated, and then recrystallized by column chromatography to obtain compound 2. 2) Under inert gas protection, compound 1, potassium carbonate and halobranched alkyl groups were dissolved in N,N-dimethylformamide, heated to 90-110℃ and reacted for 7-9 hours. After cooling to room temperature, the filtrate was collected by filtration, concentrated, and then recrystallized by column chromatography to obtain compound 3. 3) Using compounds 2 and 3 as raw materials, the quinone-donor-acceptor conjugated polymer containing mixed side chains can be obtained by polymerizing with unit A precursor. The chemical structural formula of compound 1 is as follows: ； The chemical structural formula of the halo-substituted straight-chain alkyl group is as follows: R is a straight-chain alkyl group from C-1 to C-60; The chemical structural formula of the halo-branched alkyl group is as follows: R is a straight-chain alkyl group from C-1 to C-60; The precursor of unit A is one of the following structural formulas:

3. The method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 2, characterized in that: The molar ratio of compound 1 to the halogenated straight-chain alkyl group is 1:2 to 1:

3.

4. The method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 2, characterized in that: The molar ratio of compound 1 to halobranched alkyl groups is 1:2 to 1:

3.

5. The method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 2, characterized in that: The recrystallization described in steps 1) and 2) is performed using anhydrous ethanol.

6. The method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 2, characterized in that: Step 3) describes the polymerization reaction as follows: Compound 2, Compound 3, Unit A precursor, and catalyst are mixed and dissolved in anhydrous toluene, and an inert gas is passed through for 0.5-2 hours. The mixture is then heated to 90-110°C and reacted for 40-60 hours. An end-capping agent is then injected for end-capping, and the mixture is cooled to room temperature. The mixture is placed in methanol to precipitate the precipitate, which is then collected by filtration and subjected to Soxhlet extraction sequentially with methanol, acetone, ethyl acetate, chloroform, and chlorobenzene solutions. The chloroform or chlorobenzene solution obtained from the Soxhlet extraction is concentrated and then slowly added to a methanol solution to precipitate a polymer solid, thus obtaining a quinone-donor-acceptor conjugated polymer with mixed side chains.

7. The method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 6, characterized in that: The molar ratio of the sum of the moles of compounds 2 and 3 to that of precursor A is 1:

1.

8. The method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 6, characterized in that: The catalyst is a mixture of tris(dibenzylideneacetone)dipalladium and tris(o-methylphenyl)phosphine.

9. The method for preparing the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 6, characterized in that: The capping agents are 2-trimethyltin thiophene and 2-bromothiophene. The order of addition of 2-trimethyltin thiophene and 2-bromothiophene is 2-trimethyltin thiophene first, followed by 2-bromothiophene, and the reaction time is 5-7 hours after each addition.

10. The application of the quinone-donor-acceptor conjugated polymer containing mixed side chains according to claim 1 as a polymer semiconductor.

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