Preparation method of grafted substituted thiophene polymer material

Abstract

The invention discloses a preparation method of a grafted and substituted thiophene polymer material, which comprises the following steps: mixing poly (3-hexylthiophene), a grafting monomer, a catalyst and an auxiliary agent, and heating for reaction to obtain the grafted and substituted thiophene polymer material, the structural formula of the grafting monomer is as shown in formula (I); wherein B is fluorine, chlorine, bromine or iodine, A is a carbon atom or a nitrogen atom, and R is cyano, formyl, methoxycarbonyl or; according to the method, pre-synthesis of complex functional monomers is avoided, the main chain of the poly (3-hexylthiophene) can be directly modified without using an expensive catalyst or ligand, the polymerization reaction of the poly (3-hexylthiophene) is not interfered, and meanwhile, the method has the advantages of simplified steps and low cost.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of grafting thiophene polymer synthesis method, and particularly relates to a preparation method of a grafting substituted thiophene polymer material. BACKGROUND

[0002] In recent years, in order to solve the increasingly severe energy and environmental problems, people have turned their attention to the development and utilization of new energy. Among various new energy technologies, solar power generation is undoubtedly one of the most promising directions. Among the many new types of solar cells, perovskite solar cells have emerged in the past two years due to their low raw material prices, simple production process, ability to be prepared on flexible substrates, and ability to be prepared in large areas by coating, printing and other methods.

[0003] Perovskite solar cells mainly include a substrate layer, a hole transport layer, a wetting layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer. Among them, the hole transport layer is an important part of the perovskite solar cell and plays a key role in carrier extraction and transport and suppression of carrier recombination; thiophene polymers are an important material for preparing a hole transport layer, but existing thiophene polymers have the disadvantages of requiring pre-synthesis of complex functional monomers, long monomer steps, and the need to use expensive catalysts or ligands. SUMMARY

[0004] In view of the deficiencies in the prior art, the application provides a preparation method of a grafting substituted thiophene polymer material, which successfully grafts a functional monomer at the beta-H site of poly-3-hexylthiophene to obtain a grafting substituted thiophene polymer with different grafting rates; the application avoids pre-synthesis of complex functional monomers, does not require the use of expensive catalysts or ligands, can directly modify the poly-3-hexylthiophene backbone, does not interfere with the polymerization reaction of poly-3-hexylthiophene itself, and has the advantages of step simplification and low cost.

[0005] The application aims to provide a preparation method of a grafting substituted thiophene polymer material, comprising the following steps:

[0006] Mixing poly-3-hexylthiophene, a grafting monomer, a catalyst and an auxiliary agent, heating and reacting to obtain a grafting substituted thiophene polymer material;

[0007] The structure of the grafting monomer is shown in formula (I):

[0008] ;

[0009] Formula (I);

[0010] wherein B is fluorine, chlorine, bromine or iodine, A is a carbon atom or a nitrogen atom, and R is a cyano group, a formyl group, a methoxycarbonyl group or .

[0011] In some embodiments of the present application, the B is bromine.

[0012] In some embodiments of the present application, the molar ratio of poly (3-hexylthiophene), grafting monomer and catalyst is 1:0.05-1.8:0.005-0.035.

[0013] In some embodiments of the present application, the catalyst comprises palladium chloride.

[0014] In some embodiments of the present application, the auxiliary agent comprises organic phosphorus ligand, inorganic base, organic acid and solvent.

[0015] In some embodiments of the present application, the organic phosphorus ligand is selected from triphenylphosphine.

[0016] In some embodiments of the present application, the inorganic base is selected from potassium carbonate.

[0017] In some embodiments of the present application, the organic acid is selected from pivalic acid.

[0018] In some embodiments of the present application, the solvent is selected from toluene.

[0019] In some embodiments of the present application, the molar ratio of poly (3-hexylthiophene) and organic phosphorus ligand is 1:0.001-0.06.

[0020] In some embodiments of the present application, the molar ratio of poly (3-hexylthiophene) and inorganic base is 1:0.1-2.0.

[0021] In some embodiments of the present application, the molar ratio of poly (3-hexylthiophene) and organic acid is 1:0.01-0.3.

[0022] In some embodiments of the present application, the temperature of the heating reaction is 80-120℃, and the time is 18-30 hours.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] (1) The method of the present application successfully grafts functional monomers at the β-H site of poly (3-hexylthiophene), obtaining grafted substituted thiophene polymers with different grafting rates.

[0025] (2) The present application avoids the pre-synthesis of complex functional monomers, does not need to use expensive catalysts or ligands, and can directly modify the poly (3-hexylthiophene) main chain, without interfering with the polymerization reaction of poly (3-hexylthiophene) itself, while having the advantages of step simplification and low cost. BRIEF DESCRIPTION OF DRAWINGS

[0026] The accompanying drawings are provided to further illustrate the present application and form part of the specification. Together with the embodiments of the present application, they serve to explain the present application but do not constitute a limitation thereof. In the drawings:

[0027] Figure 1 The 1H NMR spectrum of the 2-cyanopyridine-grafted thiophene polymer material prepared in Example 1 is shown.

[0028] Figure 2 The 1H NMR spectrum of the 2-pyridinecarboxaldehyde-grafted thiophene polymer material prepared in Example 2 is shown.

[0029] Figure 3 The 1H NMR spectrum of the 2-pyridinecarboxylate-grafted thiophene polymer material prepared in Example 3 is shown.

[0030] Figure 4 The 1H NMR spectrum of the functionalized phenyl-grafted thiophene polymer material prepared in Example 4.

[0031] Figure 5 The 1H NMR spectrum of the functionalized phenyl-grafted thiophene polymer material prepared in Example 5.

[0032] Figure 6 The 1H NMR spectrum of the thiophene polymer material grafted with diethyl benzyl phosphite prepared in Example 6 is shown. Detailed Implementation

[0033] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0034] All raw materials used in this invention are commercially available.

[0035] The structure of commercially available poly-3-hexylthiophene used in all embodiments and comparative examples of this invention is as follows:

[0036] The structure of poly-3-hexylthiophene is as follows:

[0037] ;

[0038] Poly(3-hexylthiophene a) represents poly(3-hexylthiophene) with a number-average molecular weight of 10.1 kDa, a molecular weight distribution index of 2.3, and an isotacticity of 92%.

[0039] Poly 3-hexylthiophene b represents poly 3-hexylthiophene with a number average molecular weight of 16.3 kDa, a molecular weight distribution index of 2.4, and a regio-regularity of 92%;

[0040] Poly 3-hexylthiophene c represents poly 3-hexylthiophene with a number average molecular weight of 15.7 kDa, a molecular weight distribution index of 2.9, and a regio-regularity of 94%.

[0041] Example 1

[0042] The present example provides a 2-cyanopyridine grafted thiophene polymer material, and a preparation method thereof includes the following steps:

[0043] Under a nitrogen atmosphere, commercially available poly 3-hexylthiophene a (1.0 mmol), 2-cyanopyridine-5-bromide (0.1 mmol), potassium carbonate (0.2 mmol), palladium chloride (0.001 mmol), triphenylphosphine (0.002 mmol), pivalic acid (0.03 mmol), toluene (10 mL), are reacted at 100°C for 24h. After the reaction is completed, the reaction is cooled to room temperature, the polymer is precipitated with methanol, and the polymer is washed with ultrapure water and n-hexane in sequence for multiple times, and is dried to obtain a 2-cyanopyridine grafted thiophene polymer material with a yield of 78%, a number average molecular weight Mn of 11.3 kDa, a molecular weight distribution index PDI of 2.3, and a 2-cyanopyridine grafted segment accounting for 1.6% of the 2-cyanopyridine grafted thiophene polymer material, i.e., a grafting rate of 1.6 mol%. The 2-cyanopyridine grafted thiophene polymer material includes a 2-cyanopyridine grafted thiophene polymer and poly 3-hexylthiophene that does not participate in the grafting reaction, and the structure of the 2-cyanopyridine grafted thiophene polymer is as follows:

[0044] .

[0045] Example 2

[0046] The present example provides a 2-pyridine formaldehyde grafted thiophene polymer material, and a preparation method thereof includes the following steps:

[0047] Under the atmosphere of nitrogen, the commercially available poly(3-hexylthiophene) a (1.0 mmol), 5-bromo-2-pyridinecarboxaldehyde (0.1 mmol), potassium carbonate (0.2 mmol), palladium chloride (0.001 mmol), triphenylphosphine (0.002 mmol), pivalic acid (0.03 mmol), toluene (10 mL) were reacted at 100°C for 24 h. After the reaction was completed, the reaction system was cooled to room temperature, the polymer was precipitated with methanol, and the polymer was washed with ultrapure water and n-hexane for several times, and then dried to obtain a 2-pyridinecarboxaldehyde grafted thiophene polymer material, with a yield of 82%, a number average molecular weight Mn of 12.0 kDa, a polydispersity index PDI of 2.3, and a 2-pyridinecarboxaldehyde segment accounting for 1.1% of the 2-pyridinecarboxaldehyde grafted thiophene polymer material, that is, the grafting rate was 1.1 mol%. The 2-pyridinecarboxaldehyde grafted thiophene polymer material comprises a 2-pyridinecarboxaldehyde grafted thiophene polymer and poly(3-hexylthiophene) that does not participate in the grafting reaction, and the structure of the 2-pyridinecarboxaldehyde grafted thiophene polymer is as follows:

[0048] .

[0049] Example 3

[0050] The present embodiment provides a 2-pyridinecarboxaldehyde grafted thiophene polymer material, and a preparation method thereof comprises the following steps:

[0051] Under the atmosphere of nitrogen, the commercially available poly(3-hexylthiophene) a (1.0 mmol), 5-bromo-2-pyridinecarboxaldehyde (0.1 mmol), potassium carbonate (0.2 mmol), palladium chloride (0.001 mmol), triphenylphosphine (0.002 mmol), pivalic acid (0.03 mmol), toluene (10 mL) were reacted at 100°C for 24 h. After the reaction was completed, the reaction system was cooled to room temperature, the polymer was precipitated with methanol, and the polymer was washed with ultrapure water and n-hexane for several times, and then dried to obtain a 2-pyridinecarboxaldehyde grafted thiophene polymer material, with a yield of 82%, a number average molecular weight Mn of 12.0 kDa, a polydispersity index PDI of 2.3, and a 2-pyridinecarboxaldehyde segment accounting for 1.1% of the 2-pyridinecarboxaldehyde grafted thiophene polymer material, that is, the grafting rate was 1.1 mol%. The 2-pyridinecarboxaldehyde grafted thiophene polymer material comprises a 2-pyridinecarboxaldehyde grafted thiophene polymer and poly(3-hexylthiophene) that does not participate in the grafting reaction, and the structure of the 2-pyridinecarboxaldehyde grafted thiophene polymer is as follows:

[0052] .

[0053] Example 4

[0054] The embodiment provides a functionalized phenyl grafted thiophene polymer material, and a preparation method thereof.

[0055] Under a nitrogen atmosphere, commercially available poly-3-hexylthiophene b (1.0 mmol), 4-bromobenzonitrile (0.1 mmol), potassium carbonate (0.2 mmol), palladium chloride (0.001 mmol), triphenylphosphine (0.002 mmol), pivalic acid (0.03 mmol), toluene (10 mL) are reacted at 100°C for 24h, after the reaction is completed, the reaction is cooled to room temperature, the polymer is precipitated with methanol, and the polymer is washed with ultrapure water and n-hexane in sequence for multiple times, and is dried to obtain the functionalized phenyl grafted thiophene polymer material, with a yield of 80%, a number average molecular weight Mn of 17.7 kDa, a PDI of 2.6, and a benzyl nitrile grafted segment accounting for 1.4% of the functionalized phenyl grafted thiophene polymer material, that is, a grafting rate of 1.4 mol%; wherein the functionalized phenyl grafted thiophene polymer material comprises a benzyl nitrile grafted thiophene polymer and poly-3-hexylthiophene which does not participate in the grafting reaction, and the structure of the benzyl nitrile grafted thiophene polymer is as shown in the following formula:

[0056] .

[0057] Embodiment 5

[0058] The embodiment provides a functionalized phenyl grafted thiophene polymer material, and a preparation method thereof.

[0059] Under a nitrogen atmosphere, commercially available poly-3-hexylthiophene b (1.0 mmol), 4-bromobenzonitrile (0.1 mmol), potassium carbonate (0.2 mmol), palladium chloride (0.001 mmol), triphenylphosphine (0.002 mmol), pivalic acid (0.03 mmol), toluene (10 mL) are reacted at 100°C for 24h, after the reaction is completed, the reaction is cooled to room temperature, the polymer is precipitated with methanol, and the polymer is washed with ultrapure water and n-hexane in sequence for multiple times, and is dried to obtain the functionalized phenyl grafted thiophene polymer material, with a yield of 80%, a number average molecular weight Mn of 17.7 kDa, a PDI of 2.6, and a benzyl nitrile grafted segment accounting for 1.4% of the functionalized phenyl grafted thiophene polymer material, that is, a grafting rate of 1.4 mol%; wherein the functionalized phenyl grafted thiophene polymer material comprises a benzyl nitrile grafted thiophene polymer and poly-3-hexylthiophene which does not participate in the grafting reaction, and the structure of the benzyl nitrile grafted thiophene polymer is as shown in the following formula:

[0060] .

[0061] Embodiment 6

[0062] The embodiment provides a benzyl phosphorodithioate grafted thiophene polymer material, and a preparation method thereof comprises the following steps:

[0063] Under a nitrogen atmosphere, commercially available poly-3-hexylthiophene c (1.0 mmol), 4-bromobenzyl phosphorodithioate (1.5 mmol), potassium carbonate (2.0 mmol), palladium chloride (0.03 mmol), triphenylphosphine (0.06 mmol), pivalic acid (0.3 mmol), toluene (10 mL) are reacted at 80 DEG C for 48 h, after the reaction is completed, the reaction system is cooled to room temperature, the polymer is precipitated with methanol, and the polymer is washed with ultrapure water and n-hexane in sequence, and is dried to obtain the benzyl phosphorodithioate grafted thiophene polymer material, the yield is 75%, the number average molecular weight Mn is 17.0 kDa, the PDI is 3.1, the benzyl phosphorodithioate grafted segment accounts for 5.8% of the benzyl phosphorodithioate grafted thiophene polymer material, that is, the grafting rate is 5.8 mol%; wherein the benzyl phosphorodithioate grafted thiophene polymer material comprises the benzyl phosphorodithioate grafted thiophene polymer and poly-3-hexylthiophene which does not participate in the grafting reaction, and the structure of the benzyl phosphorodithioate grafted thiophene polymer is as shown in the following formula:

[0064] .

[0065] As can be seen from the embodiments 1 to 6, the preparation method of the grafted substituted thiophene polymer material successfully grafts different groups at the beta-H site of poly-3-hexylthiophene, and the grafted substituted thiophene polymer with different grafting rates is obtained; the pre-synthesis of a complex functional monomer is avoided, an expensive catalyst or ligand is not needed, the poly-3-hexylthiophene main chain can be directly modified, the polymerization of the poly-3-hexylthiophene itself is not disturbed, and the advantages of step simplification and low cost are achieved.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application rather than limit the same, and although the present application has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical personnel can still modify or replace the specific embodiments of the present application after reading the specification, but these modifications or changes are still within the scope of the present application.

Claims

1. A method for preparing a grafted thiophene polymer material, characterized in that, Includes the following steps: Poly(3-hexylthiophene), grafted monomers, catalysts and auxiliaries are mixed and heated to react, yielding grafted substituted thiophene polymer materials. The structural formula of the grafted monomer is shown in formula (Ⅰ): ； Equation (Ⅰ); Where B is fluorine, chlorine, bromine, or iodine, A is a carbon atom or a nitrogen atom, and R is a cyano group, formyl group, methoxycarbonyl group, or... .

2. The method for preparing the grafted thiophene polymer material according to claim 1, characterized in that, B is bromine.

3. The method for preparing the grafted thiophene polymer material according to claim 1, characterized in that, The molar ratio of poly(3-hexylthiophene), grafted monomer and catalyst is 1:0.05~1.8:0.005~0.

035.

4. The method for preparing the grafted thiophene polymer material according to claim 1, characterized in that, The catalyst includes palladium chloride.

5. The method for preparing the grafted thiophene polymer material according to claim 1, characterized in that, The additives include organophosphorus ligands, inorganic bases, organic acids, and solvents.

6. The method for preparing the grafted thiophene polymer material according to claim 5, characterized in that, The organophosphorus ligand is selected from triphenylphosphine; And / or, the inorganic base is selected from potassium carbonate; And / or, the organic acid is selected from pivalic acid; And / or, the solvent is selected from toluene.

7. The method for preparing the grafted thiophene polymer material according to claim 5, characterized in that, The molar ratio of poly(3-hexylthiophene) to organophosphorus ligands is 1:0.001~0.

06.

8. The method for preparing the grafted thiophene polymer material according to claim 5, characterized in that, The molar ratio of poly(3-hexylthiophene) to inorganic base is 1:0.1~2.

0.

9. The method for preparing the grafted thiophene polymer material according to claim 5, characterized in that, The molar ratio of poly(3-hexylthiophene) to organic acid is 1:0.01~0.

3.

10. The method for preparing the grafted thiophene polymer material according to claim 1, characterized in that, The heating reaction is carried out at a temperature of 80~120℃ for 18~30 hours.

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