A preparation method of PTAA

Abstract

The invention discloses a preparation method of PTAA. The preparation method of PTAA comprises: under the action of a nitrogen heterocyclic carbene palladium complex and an auxiliary agent, a dibromo-substituted triphenylamine compound and a triphenylamine type boric acid pinacol ester compound undergo a polymerization reaction to obtain PTAA; the invention adopts the nitrogen heterocyclic carbene palladium complex to catalyze the polymerization reaction of the dibromo-substituted triphenylamine compound and the triphenylamine type boric acid pinacol ester compound, thereby improving the yield of preparing PTAA and obtaining PTAA with a high molecular weight.

Description

Technical Field

[0001] The invention belongs to the technical field of organic photoelectric polymer materials, and in particular relates to a preparation method of PTAA. Background Art

[0002] Solar energy is an inexhaustible energy source. Only 2% of its energy has been consumed in the past billion years. In addition, solar energy is clean, stable and pollution-free, making it one of the most promising renewable resources in the 21st century. Perovskite solar cells have become the focus of research as a new generation of solar cells with high performance and high application value. However, existing perovskite solar cells generally have the problem of low energy conversion efficiency.

[0003] Perovskite solar cells generally include a fluorine-doped tin oxide layer (FTO) conductive substrate, an electron transport layer, a perovskite photosensitive layer, a hole transport layer and a counter electrode. The hole transport layer plays the role of extracting and transporting holes as a hole transport layer, and plays an important role in improving the energy conversion efficiency of perovskite solar cells. Among them, poly [bis (4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA) is a relatively common hole transport material with high efficiency, and is widely used in the preparation of perovskite solar cells.

[0004] In the prior art, trisdibenzylideneacetone dipalladium or palladium acetate is generally used as a catalyst to catalyze the polymerization reaction of a dibromo-substituted triphenylamine compound and a triphenylamine-based boric acid pinacol ester compound to obtain PTAA. However, the yield of preparing PTAA using trisdibenzylideneacetone dipalladium or palladium acetate as a catalyst is low, and it is difficult to obtain high molecular weight PTAA. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, a method for preparing PTAA is provided. The present invention uses a nitrogen heterocyclic carbene palladium complex to catalyze the polymerization reaction of a dibromo-substituted triphenylamine compound and a triphenylamine boric acid pinacol ester compound, thereby improving the yield of preparing PTAA and obtaining a high molecular weight PTAA.

[0006] The object of the present invention is to provide a method for preparing PTAA, comprising the following steps:

[0007] Under the action of the nitrogen heterocyclic carbene palladium complex and the auxiliary agent, the dibromo-substituted triphenylamine compound and the triphenylamine boric acid pinacol ester compound undergo polymerization reaction to obtain PTAA;

[0008] The structure of the nitrogen heterocyclic carbene palladium complex is shown in formula (I):

[0009]

[0010] Formula (I);

[0011] The structure of the dibromo-substituted triphenylamine compound is shown in formula (II):

[0012]

[0013] Formula (II);

[0014] The structure of the triphenylamine boric acid pinacol ester compound is shown in formula (III):

[0015]

[0016] Formula (III).

[0017] In some embodiments of the present invention, the molar ratio of the nitrogen heterocyclic carbene palladium complex, the dibromo-substituted triphenylamine compound and the triphenylamine boric acid pinacol ester compound is 0.02-0.08:1:1-1.2.

[0018] In some embodiments of the present invention, the polymerization reaction temperature is 80-100° C. and the time is 10-20 hours.

[0019] In some embodiments of the present invention, the auxiliary agent includes a quaternary ammonium salt, an inorganic base, an organic phosphine and a solvent.

[0020] In some embodiments of the present invention, the quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide and methyltrialkylammonium chloride.

[0021] In some embodiments of the present invention, the molar ratio of the dibromo-substituted triphenylamine compound to the quaternary ammonium salt is 1:0.05-0.15.

[0022] In some embodiments of the present invention, the inorganic base is selected from at least one of potassium phosphate and potassium carbonate.

[0023] In some embodiments of the present invention, the molar ratio of the dibromo-substituted triphenylamine compound to the inorganic base is 1:2-10.

[0024] In some embodiments of the present invention, the organic phosphine is selected from tri(2-furyl)phosphine.

[0025] In some embodiments of the present invention, the molar ratio of the dibromo-substituted triphenylamine compound to the organic phosphine is 1:0.1-0.2.

[0026] In some embodiments of the present invention, the solvent is a mixed solvent of toluene and water.

[0027] In some embodiments of the present invention, the volume ratio of toluene to water is 2-7:1.

[0028] In some embodiments of the present invention, after the polymerization reaction is completed, a purification step is further included.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The method for preparing PTAA of the present invention has the advantages of high yield and the ability to prepare high molecular weight PTAA. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is the H NMR spectrum of the orange solid A1 of Example 1.

[0032] Figure 2 This is the NMR carbon spectrum of the orange solid A1 of Example 1.

[0033] Figure 3 This is the H NMR spectrum of the light yellow solid A2 of Example 1.

[0034] Figure 4 This is the NMR carbon spectrum of the light yellow solid A2 of Example 1.

[0035] Figure 5 This is the H NMR spectrum of the yellow solid A3 of Example 1.

[0036] Figure 6 This is the NMR carbon spectrum of the yellow solid A3 of Example 1.

[0037] Figure 7 This is the H NMR spectrum of PTAA prepared in Example 2. DETAILED DESCRIPTION

[0038] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0039] All raw materials of the present invention are conventionally commercially available.

[0040] The structure of the dibromo-substituted triphenylamine compound used in all embodiments of the present invention for preparing PTAA is as follows:

[0041] ;

[0042] The structure of the triphenylamine boric acid pinacol ester compound used in all embodiments of the present invention for preparing PTAA is as follows:

[0043] ;

[0044] The structure of the nitrogen heterocyclic carbene palladium complex used in all embodiments of the present invention for preparing PTAA is as follows:

[0045] .

[0046] Example 1

[0047] This embodiment provides a preparation method of a nitrogen heterocyclic carbene palladium complex, which specifically includes the following steps:

[0048] S1. Add 2,6-diisopropylaniline (4.4mmol), 4,7-di-tert-butylacenaphthenequinone (2mmol) and anhydrous zinc chloride (4.6mmol) to a 100 ml side-mouth bottle in sequence, add 50 ml of glacial acetic acid as solvent, and reflux under N2 protection at 120°C for 5 hours. After the reaction is completed, cool to room temperature, and an orange-yellow solid is generated in the solution. Filter with suction, and rinse the filter cake with glacial acetic acid for several times to wash away the unreacted raw materials. Dry the solid obtained by filtration, dissolve it in dichloromethane, and dezincify it with 100 mL of potassium oxalate aqueous solution (4.6g / L). After stirring for 5 hours, filter out the white zinc salt, and extract the remaining organic layer in water for several times. After spin drying, use (dichloromethane / n-hexane) for recrystallization to obtain orange-yellow crystals A1 with a yield of 68%.

[0049] The NMR data of the orange-yellow crystal A1 are as follows:

[0050] 1 H NMR (400 MHz, CDCl3) δ 7.74 (s, 2H), 7.25 (s, 6H), 6.54 (s, 2H), 3.02 (t, J = 13.7, 6.8 Hz, 4H), 1.21 (d, J = 6.8 Hz, 12H), 1.10 (s, 18H),0.91 (d, J = 6.9 Hz, 12H).

[0051] 13 C NMR (101 MHz, CDCl3) δ 162.26, 151.30, 147.94, 137.78, 135.82,130.52, 128.94, 124.37, 123.59, 122.29, 35.44, 31.00, 28.56, 23.51, 23.25.

[0052] S2. Weigh A1 (1.0 mmol) and add it into a 25 ml stoppered bottle. Add 3-4 ml of chloromethyl ether to dissolve it. Expel the air in the bottle with N2 and seal it. React at 100°C for 24 hours to obtain light yellow solid A2 with a yield of 48%.

[0053] The NMR data of the light yellow solid A2 are as follows:

[0054] 1 H NMR (400 MHz, CDCl3) δ 11.19 (s, 1H), 7.92 (t, J = 2.9 Hz, 1H), 7.70 (dd, J = 14.5, 6.5 Hz, 1H), 7.48 (dd, J = 11.4, 5.2 Hz, 1H), 7.21 (t, J= 2.8 Hz, 1H), 2.70 (t, J = 13.1, 6.5 Hz, 1H), 1.36 (t, J = 6.6 Hz, 1H), 1.30 (d, J = 3.4 Hz, 1H), 1.14 (t, J = 5.5 Hz, 1H).

[0055] 13 C NMR (101 MHz, CDCl3) δ 152.30, 144.90, 142.33, 137.81, 132.39,129.36, 127.88 125.03, 121.08, 35.61, 31.25, 29.43, 24.61, 23.65.

[0056] S3. Weigh A2 (0.2 mmol), palladium chloride (0.22 mmol), potassium carbonate (2 mmol), and 3-chloropyridine (1.2 mmol) into a reaction bottle, add acetone to cover the solid, react at 60°C for 8 h, and after treatment, obtain a yellow solid A3, i.e., a nitrogen heterocyclic carbene palladium complex, with a yield of 57%.

[0057] The NMR data of the yellow solid A3 are as follows:

[0058] 1H NMR (400 MHz, CDCl3) δ 8.70 (d, J = 2.3 Hz, 1H), 8.62 (dd, J = 5.5,1.1 Hz, 1H), 7.64 (d, J = 12.3 Hz, 4H), 7.57 (d, J = 8.3 Hz, 1H), 7.49 (d, J= 7.8 Hz, 4H), 7.10 (dd, J = 8.2, 5.6 Hz, 1H), 6.81 (s, 2H), 3.39 (t, J =13.4, 6.7 Hz, 4H), 1.46 (d, J = 6.6 Hz, 12H), 1.24 (s, 18H), 0.91 (d, J = 6.8Hz, 12H).

[0059] 13 C NMR (101 MHz, CDCl3) δ 157.96, 150.81, 149.74, 147.42, 140.81,137.55, 133.99, 132.00, 130.82, 128.92, 126.41, 125.68, 124.79, 124.44,122.66, 120.90, 35.45, 31.18, 29.01, 25.83, 24.39.

[0060] Example 2

[0061] This embodiment provides a method for preparing PTAA, which specifically comprises the following steps:

[0062] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type pinacol borate ester compound (5 mmol), tri(2-furyl)phosphine (0.5 mmol), potassium phosphate (10 mmol) and tetrabutylammonium bromide (0.25 mmol) were placed in a 150 mL reaction, 40 mL of toluene and 20 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; an azocyclic carbene palladium complex (0.4 mol) was added, and the mixture was heated to 100° C. and reacted for 10 hours; after the reaction was cooled, it was filtered with diatomaceous earth, the filtrate was concentrated, the solvent was removed, a mixed solvent (THF / MeOH=1:10) was added to the concentrated solution, a solid was precipitated at room temperature, the precipitate was filtered and washed, and after vacuum drying, a light yellow solid, namely PTAA, was obtained with a yield of 92.4%; the number average molecular weight of PTAA was 12441 g / mol and the molecular weight distribution PDI was 2.16 as detected by gel permeation chromatography.

[0063] Example 3

[0064] This embodiment provides a method for preparing PTAA, which specifically comprises the following steps:

[0065] A dibromo-substituted triphenylamine compound (5 mmol), a triphenylamine-type boric acid pinacol ester compound (6 mmol), tri(2-furyl)phosphine (1 mmol), potassium carbonate (50 mmol) and methyltrialkylammonium chloride (0.75 mmol) were placed in a 150 mL reaction, 35 mL of toluene and 5 mL of water were added, and nitrogen was used for deoxygenation for 30 minutes; an azocyclic carbene palladium complex (0.4 mol) was added, and the mixture was heated to 80° C. and reacted for 20 hours; after the reaction was cooled, it was filtered with diatomaceous earth, the filtrate was concentrated, the solvent was removed, a mixed solvent (THF / MeOH=1:10) was added to the concentrated solution, a solid was precipitated at room temperature, the precipitate was filtered and washed, and after vacuum drying, a light yellow solid, namely PTAA, was obtained with a yield of 89.5%; the number average molecular weight of PTAA was 13102 g / mol and the molecular weight distribution PDI was 2.08 as detected by gel permeation chromatography.

[0066] Comparative Example 1

[0067] This embodiment provides a method for preparing PTAA, which specifically comprises the following steps:

[0068] The difference from Example 2 is that the nitrogen heterocyclic carbene palladium complex is replaced by Pd2(dba)3, and the remaining steps are the same as Example 2, to obtain PTAA with a yield of 45.3%; the number average molecular weight of PTAA is 3680 g / mol and the molecular weight distribution PDI is 1.20 as determined by gel permeation chromatography.

[0069] Comparative Example 2

[0070] This embodiment provides a method for preparing PTAA, which specifically comprises the following steps:

[0071] The difference from Example 2 is that the nitrogen heterocyclic carbene palladium complex is replaced by palladium acetate, and tri(2-furyl)phosphine is replaced by triphenylphosphine. The remaining steps are the same as Example 2, and PTAA is obtained with a yield of 24.8%; the number average molecular weight of PTAA is 3124 g / mol, and the molecular weight distribution PDI is 1.13 as determined by gel permeation chromatography.

[0072] Comparative Example 3

[0073] This embodiment provides a method for preparing PTAA, which specifically comprises the following steps:

[0074] The difference from Example 2 is that the nitrogen heterocyclic carbene palladium complex is replaced by tetrakis(triphenylphosphine)palladium, and the remaining steps are the same as Example 2. No product is obtained, and no PTAA is obtained.

[0075] By comparing Examples 2 to 3 with Comparative Examples 1 to 3, it can be seen that the method for preparing PTAA of the present invention has a high yield and can prepare PTAA with a high molecular weight.

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the relevant field should understand that after reading the specification of this application, the technicians can still modify or replace the specific implementation mode of the present invention with equivalents, but these modifications or changes do not deviate from the scope of protection of the pending claims of the present application.

Claims

1. A method for preparing PTAA, characterized in that: The steps include: Under the action of the nitrogen heterocyclic carbene palladium complex and the auxiliary agent, the dibromo-substituted triphenylamine compound and the triphenylamine boric acid pinacol ester compound undergo polymerization reaction to obtain PTAA; The structure of the nitrogen heterocyclic carbene palladium complex is shown in formula (I): Formula (I); The structure of the dibromo-substituted triphenylamine compound is shown in formula (II): Formula (II); The structure of the triphenylamine boric acid pinacol ester compound is shown in formula (III): Formula (III).

2. The method for preparing PTAA according to claim 1, characterized in that: The molar ratio of the nitrogen heterocyclic carbene palladium complex, the dibromo-substituted triphenylamine compound and the triphenylamine boric acid pinacol ester compound is 0.02-0.08:1:1-1.

2.

3. The method for preparing PTAA according to claim 1, characterized in that: The polymerization reaction is carried out at a temperature of 80-100° C. and for a time of 10-20 hours.

4. The method for preparing PTAA according to claim 1, characterized in that: The auxiliary agent includes quaternary ammonium salt, inorganic base, organic phosphine and solvent.

5. The method for preparing PTAA according to claim 4, characterized in that: The quaternary ammonium salt is selected from at least one of tetrabutylammonium bromide and methyltrialkylammonium chloride; the molar ratio of the dibromo-substituted triphenylamine compound to the quaternary ammonium salt is 1:0.05-0.

15.

6. The method for preparing PTAA according to claim 5, characterized in that: The inorganic base is selected from at least one of potassium phosphate and potassium carbonate; the molar ratio of the dibromo-substituted triphenylamine compound to the inorganic base is 1:2-10.

7. The method for preparing PTAA according to claim 5, characterized in that: The organic phosphine is selected from tri(2-furyl)phosphine; the molar ratio of the dibromo-substituted triphenylamine compound to the organic phosphine is 1:0.1-0.

2.

8. The method for preparing PTAA according to claim 5, characterized in that: The solvent is a mixed solvent of toluene and water.

9. The method for preparing PTAA according to claim 8, characterized in that: The volume ratio of toluene to water is 2-7:

1.

10. The method for preparing PTAA according to claim 9, characterized in that: After the polymerization reaction is completed, a purification step is also included.

Images