A chiral polypropynylamine compound, its preparation method and application

Abstract

This invention belongs to the field of chiral polymer technology, and provides a chiral polypropynylamine compound with the general structural formula R. 1 ~R 10 Independently, the radicals are phenyl, benzophenone, triphenylamine, o-tolyl, 1-naphthyl, or alkoxyphenyl; n is any integer from 2 to 4000; wavy lines represent omitted repeating polymer segments; asterisks indicate that the carbon atom here has a certain stereoselectivity. This invention also provides a method for preparing chiral polypropynylamine compounds and their applications. This invention uses monomers completely lacking a chiral center as reaction substrates to prepare chiral polypropynylamine compounds in high yield, effectively solving the problems of high temperature, large metal catalyst feed amount, and lack of chiral polymer structures existing in the prior art; the preparation method of this invention can extend the substrate of polypropynylamine to aromatic amine monomers, preparing polymer materials with diverse functions.

Description

Technical Field

[0001] This invention relates to the field of chiral polymer technology, and more particularly to a chiral polypropynylamine compound, its preparation method, and its application. Background Technology

[0002] Chiral polymers hold an important position in nature not only due to their unique structures, but also play a crucial role in chiral recognition, chiral resolution, and chiral catalysis, demonstrating enormous application potential. However, the structures and types of chiral polymers are currently greatly limited by a finite number of synthetic methods. Therefore, there is an urgent need to develop a series of novel synthetic methods for chiral polymers that are simple to operate, have mild reaction conditions, and produce products with novel structures. Asymmetric A3 coupling reactions are a classic type of reaction in which monomers lacking a chiral center construct a chiral center in situ through the reaction.

[0003] The presence of chiral carbon atoms in polypropynylamine compounds gives them the potential to become chiral polymers. However, the high-temperature conditions currently required for the synthesis of polypropynylamine compounds contradict the mild reaction conditions needed for asymmetric synthesis, making the synthesis of chiral polypropynylamine compounds a significant challenge.

[0004] Therefore, how to prepare chiral polypropynylamine compounds that possess both reactivity and stereoselectivity has become a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art by providing a chiral polypropynylamine compound, its preparation method, and its application.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a chiral polypropynylamine compound, the general structural formula of which is:

[0008]

[0009]

[0010] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Independently, it can be phenyl, benzophenone, triphenylamine, o-tolyl, 1-naphthyl, or alkoxyphenyl;

[0011] n is any integer from 2 to 4000; the wavy line represents omitted repeated polymer chain segments; the asterisk indicates that the carbon atoms here have a certain stereoselectivity.

[0012] The present invention also provides a method for preparing the chiral polypropynylamine compounds, wherein polyaryl aromatic amines, aromatic aldehydes, aromatic alkynes, copper catalysts, chiral ligands and organic solvents are reacted under a protective atmosphere to obtain chiral polypropynylamine compounds.

[0013] The molar ratio of the polyaromatic amine, aromatic aldehyde, aromatic alkyne, copper catalyst and chiral ligand is 1-20:1-20:1-20:1-10:1-15.

[0014] Preferably, under a protective atmosphere, a first step reaction is carried out between a polyaryl aromatic amine and an aromatic aldehyde, followed by a second step reaction involving the first reaction product, an aromatic alkyne, a copper catalyst, a chiral ligand, and an organic solvent to obtain a chiral polypropylamine compound.

[0015] Preferably, the polyaromatic amine has any one of the following structural formulas:

[0016]

[0017] Where n is any integer from 2 to 1000.

[0018] Preferably, the aromatic aldehyde has any one of the following structural formulas:

[0019]

[0020] The aromatic alkyne has any one of the following structural formulas:

[0021]

[0022] Preferably, the organic solvent is one or more of toluene, tetrahydrofuran, dimethyl sulfoxide, hydrocarbon organic solvents, alcohol organic solvents, ester organic solvents, and amide organic solvents; the protective atmosphere is nitrogen or a rare gas; and the chiral ligand comprises a pyridine unit and an oxazoline unit.

[0023] Preferably, the copper catalyst is cuprous trifluoromethanesulfonate or copper trifluoromethanesulfonate, and the chiral ligand is 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine or 2,6-bis[(4S)-4-phenyl-2-oxazolinyl]pyridine.

[0024] Preferably, the concentration of the polyaromatic amine in the organic solvent is 0.05–4.0 mol / L.

[0025] Preferably, the temperatures of the reactions, the first step reaction, and the second step reaction are independently 25–120°C, the reaction times are 1–24 h, the first step reaction time is 0.1–4 h, and the second step reaction time is 0.1–24 h.

[0026] The present invention also provides the application of the chiral polypropynylamine compounds in optoelectronic devices.

[0027] The beneficial effects of this invention include:

[0028] 1) This invention uses monomers that do not have chiral centers as reaction substrates to prepare chiral polypropynylamine compounds in high yield, effectively solving the technical problems of high temperature, large amount of metal catalyst and lack of chiral polymer structure in the preparation of existing polypropynylamine compounds.

[0029] 2) The preparation method of the present invention can convert monomer substrates that do not have chiral centers into chiral polypropynylamine compounds with optical activity, thereby realizing the in-situ construction of chiral functional polymers; it effectively reduces the amount of metal catalyst required for the reaction, greatly reduces the reaction temperature, and makes the post-processing and purification of the product more thorough and the process simple.

[0030] 3) The preparation method of the present invention can extend the substrate of polypropynylamine to aromatic amine monomers, thereby preparing a variety of chiral polypropynylamine compounds with aromatic ring structures. At the same time, the substrate functional groups have high tolerance and can be attached to the aromatic ring to prepare polymer materials with diverse functions. Attached Figure Description

[0031] Figure 1 The image shows a comparison of the proton NMR spectra of the raw materials and products in deuterated chloroform for Example 1, where a is a 1,4-diethynylbenzene monomer, b is a 4,4'-diaminodiphenylmethane monomer, c is a benzaldehyde monomer, d is a chiral propargylamine compound, and e is the prepared chiral polypropargylamine compound P1.

[0032] Figure 2 The image shows a comparison of the carbon NMR spectra of the raw materials and products of Example 1 in deuterated chloroform, where a is 1,4-diethynylbenzene monomer, b is 4,4'-diaminodiphenylmethane monomer, c is benzaldehyde monomer, d is chiral propargylamine compound, and e is the prepared chiral polypropargylamine compound P1.

[0033] Figure 3 The image shows the infrared absorption spectra of the raw materials and products of Example 1, where a is a 4,4'-diaminodiphenylmethane monomer, b is a 1,4-diethynylbenzene monomer, c is a chiral propargylamine compound, and d is the prepared chiral polypropargylamine compound P1.

[0034] Figure 4 The circular dichroism spectrum of chiral polypropynylamine compound P1 prepared in Example 1 with 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine is shown, where (R,R)-pybox is 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine.

[0035] Figure 5 Thermogravimetric curve of chiral polypropyneamine compound P1 prepared in Example 1 under nitrogen atmosphere;

[0036] Figure 6 The 1H NMR spectrum of the chiral polypropynylamine compound P2 prepared in Example 3 in deuterated chloroform;

[0037] Figure 7 The circular dichroism chromatogram of the chiral polypropynylamine compound P2 prepared in Example 3 in tetrahydrofuran;

[0038] Figure 8 The 1H NMR spectrum of the chiral polypropynylamine compound P3 prepared in Example 4 in deuterated chloroform;

[0039] Figure 9 The circular dichroism chromatogram of the chiral polypropynylamine compound P3 prepared in Example 4 in tetrahydrofuran;

[0040] Figure 10 The photoluminescence spectrum of the chiral polypropynylamine compound P5 prepared in Example 6 is shown. Detailed Implementation

[0041] This invention provides a chiral polypropynylamine compound, the general structural formula of which is:

[0042]

[0043] Among them, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 Independently, it can be phenyl, benzophenone, triphenylamine, o-tolyl, 1-naphthyl, or alkoxyphenyl;

[0044] n is any integer from 2 to 4000; the wavy line represents omitted repeated polymer chain segments; the asterisk indicates that the carbon atoms here have a certain stereoselectivity.

[0045] In the chiral polypropynylamine compounds of the present invention, n is preferably any integer from 10 to 1000, more preferably any integer from 50 to 500, and even more preferably any integer from 100 to 300.

[0046] The present invention also provides a method for preparing the chiral polypropynylamine compounds, wherein polyaryl aromatic amines, aromatic aldehydes, aromatic alkynes, copper catalysts, chiral ligands and organic solvents are reacted under a protective atmosphere to obtain chiral polypropynylamine compounds.

[0047] The molar ratio of the polyaromatic amine, aromatic aldehyde, aromatic alkyne, copper catalyst and chiral ligand is 1-20:1-20:1-20:1-10:1-15.

[0048] In this invention, the molar ratio of polyaromatic amines, aromatic aldehydes, aromatic alkynes, copper catalysts and chiral ligands is preferably 2-10:2-15:2-10:2-8:3-12, more preferably 4-8:4-12:4-8:3-7:4-10, and even more preferably 5-7:5-10:5-7:4-5:5-8.

[0049] In this invention, it is preferred that the polyaryl aromatic amine and aromatic aldehyde undergo a first-step reaction under a protective atmosphere, and the first reaction product, aromatic alkyne, copper catalyst, chiral ligand and organic solvent undergo a second-step reaction to obtain a chiral polypropylamine compound.

[0050] The preferred structural formula of the polyaromatic amine described in this invention is any one of the following structural formulas:

[0051]

[0052]

[0053] Wherein, n is preferably any integer from 2 to 1000, more preferably any integer from 10 to 800, and even more preferably any integer from 100 to 600.

[0054] The preferred structural formula of the aromatic aldehyde described in this invention is any one of the following structural formulas:

[0055]

[0056] The preferred structural formula of the aromatic alkyne is any one of the following structural formulas:

[0057]

[0058] The organic solvent described in this invention is preferably one or more of toluene, tetrahydrofuran, dimethyl sulfoxide, hydrocarbon organic solvents, alcohol organic solvents, ester organic solvents and amide organic solvents, and more preferably toluene, tetrahydrofuran or dimethyl sulfoxide.

[0059] The protective atmosphere described in this invention is preferably nitrogen or a rare gas, and more preferably nitrogen.

[0060] In this invention, the chiral ligand can be a chiral ligand with different enantiomers. Using chiral ligands with different enantiomers can yield polypropylamine compounds with different chiral properties. When the chiral ligand is a meso chiral ligand, the resulting polypropylamine compound does not have optical activity, but its preparation process is relatively mild.

[0061] The chiral ligands of the present invention preferably comprise a pyridine moiety and an oxazoline moiety, and more preferably 2,6-bis[(4R)-4-phenyl-2-oxazoline]pyridine or 2,6-bis[(4S)-4-phenyl-2-oxazoline]pyridine.

[0062] The copper catalyst described in this invention is preferably cuprous trifluoromethanesulfonate or copper trifluoromethanesulfonate.

[0063] The concentration of the polyaromatic amine described in this invention in an organic solvent is preferably 0.05–4.0 mol / L, more preferably 0.1–3 mol / L, and even more preferably 1–2 mol / L.

[0064] In this invention, the polyaromatic amines, aromatic aldehydes, aromatic alkynes, copper catalysts, and chiral ligands are all conventional substances in the art.

[0065] In the one-step reaction of the present invention, the reaction temperature is preferably 25-120°C, more preferably 25-80°C, and even more preferably 25-40°C; the reaction time is preferably 1-24 h, more preferably 2-18 h, and even more preferably 5-10 h. In the two-step reaction, the temperature of the first step reaction is preferably 25-120°C, more preferably 80-120°C, and even more preferably 90-110°C; the reaction time of the first step reaction is preferably 0.1-4 h, more preferably 1-3 h, and even more preferably 2 h; the temperature of the second step reaction is preferably 25-120°C, more preferably 25-80°C, and even more preferably 40-60°C; the reaction time of the second step reaction is preferably 1-24 h, more preferably 2-16 h, and even more preferably 5-12 h.

[0066] In this invention, the reaction solution obtained after the reaction is completed is preferably diluted and filtered to obtain a filtrate. The filtrate is added dropwise to a settling agent to carry out a sedimentation reaction. The sediment is collected and dried to constant weight to obtain a chiral polypropylamine compound. The reagent used for dilution is preferably tetrahydrofuran. The filtration is preferably carried out by cotton filtration to remove solids from the solution. The settling agent is preferably an aqueous solution of an alcohol or an alcohol, and more preferably an aqueous solution of methanol.

[0067] The present invention also provides the application of the chiral polypropynylamine compounds in optoelectronic devices.

[0068] The chiral polypropynylamine compounds of the present invention possess optical properties, especially photoluminescence properties. Fluorescence emission spectroscopy tests show that the chiral polypropynylamine compounds have certain fluorescence emission properties and are expected to be applied to the fabrication of polymer optoelectronic devices.

[0069] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0070] In the examples, M1 is 4,4'-diaminodiphenylmethane, M2 is benzaldehyde, M3 is 1,4-diethynylbenzene, M4 is 4-phenylethynyl ether, M5 is 4,4'-dithiodiphenylamine, M6 is 4-methylaniline, M7 is terephthalaldehyde, M8 is 4,4'-diaminobenzophenone, M9 is 4-ethynyltriphenylamine, M10 is 1,3,5-triethynylbenzene, M11 is tetra(4-ethynylbenzene)ethylene, M12 is tri(4-aminophenyl)amine, and M13 is tetra(4-aminophenyl)methane;

[0071] 4,4'-Diaminodiphenylmethane, benzaldehyde, 1,4-diethynylbenzene, 4,4'-dithiodiphenylamine, 4-methylaniline, terephthalaldehyde, 4,4'-diaminobenzophenone, and tetra(4-aminophenyl)methane were all purchased from Anhui Zesheng Technology Co., Ltd.

[0072] 4-Phenylacetylene, 4-ethynyltriphenylamine, and tetra(4-ethynylphenyl)ethylene were prepared according to the literature Li,Y.; Li,Z.; Ablekim,T.; Ren,T.; Dong,WJ. Phys. Chem. Chem. Phys. 2014,16,26193-26202 and Fu,W.; Dong,L.; Shi,J.; Tong,B.; Cai,Z.; Zhi,J.; Dong,Y. Polym. Chem. 2018,9,4404-4412;

[0073] 1,3,5-Triacetylenebenzene was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd.; tris(4-aminophenyl)amine was purchased from Shanghai Bid Pharmaceutical Technology Co., Ltd.

[0074] 2,6-Bis[(4R)-4-phenyl-2-oxazolinyl]pyridine, copper trifluoromethanesulfonate, and copper trifluoromethanesulfonate were purchased from Anhui Zesheng Technology Co., Ltd.

[0075] Example 1

[0076] Chiral polypropynylamine compound P1 is prepared by the following reaction:

[0077]

[0078] 59 mg (0.30 mmol) of 4,4'-diaminodiphenylmethane was added to a clean 10 mL Schlenk polymerization tube. The reaction was evacuated to -1 bar for 10 min and then purged with nitrogen three times, with nitrogen purging following each evacuation. Next, under nitrogen protection, 77 μL (0.75 mmol) of benzaldehyde was added using a syringe. The mixture was heated to 100 °C under sealed conditions and stirred for 2 h. The reaction system was then cooled to 60 °C. Under nitrogen protection, 38 mg (0.30 mmol) of 1,4-diethynylbenzene, 22 mg (0.06 mmol) of 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine, and 19 mg (0.09 mmol) of cuprous trifluoromethanesulfonate were added to the reaction system, followed by 0.30 mL of toluene using a syringe. The reaction was carried out at 60 °C under a nitrogen atmosphere for 6 h. After the reaction was completed, the mother liquor was diluted with 0.60 mL of tetrahydrofuran. The diluted solution was filtered through cotton to remove the solids in the solution. Then the filtrate was added dropwise to a mixed solution of methanol and water (the volume ratio of methanol to water was 6:1) for sedimentation. Finally, the solution was allowed to stand, filtered, and dried to obtain the chiral polypropynylamine compound P1.

[0079] The yield of the chiral polypropynylamine compound P1 in this embodiment was 91%, with a weight-average molecular weight of 41,300 g / mol and a molecular weight distribution of 1.53.

[0080] Figure 1 The images show a comparison of the 1H NMR spectra of 1,4-diethynylbenzene monomer (Figure a), 4,4'-diaminodiphenylmethane monomer (Figure b), benzaldehyde monomer (Figure c), chiral propargylamine compound (Figure d), and the prepared chiral polypropargylamine compound P1 (Figure e) in deuterated chloroform. Figure 1 It can be seen that the terminal alkyne hydrogen resonance peak of the 1,4-diethynylbenzene monomer and the hydrogen resonance peak of the carbonyl group of the aromatic aldehyde monomer both disappear in the 1H NMR spectra of the chiral polypropynylamine compound P1 and the chiral polypropynylamine compound. In addition, the methylene hydrogen peak of the propynylamine functional group appears at chemical shift 5.46 in the NMR spectrum of the chiral polypropynylamine compound P1, which proves the accuracy of the structure of the chiral polypropynylamine compound P1.

[0081] Figure 2 The images show a comparison of the carbon NMR spectra of 1,4-diethynylbenzene monomer (Figure a), 4,4'-diaminodiphenylmethane monomer (Figure b), benzaldehyde monomer (Figure c), chiral propargylamine compound (Figure d), and the prepared chiral polypropargylamine compound P1 (Figure e) in deuterated chloroform. Figure 2 It can be seen that the carbon resonance peak of the carbonyl group of benzaldehyde monomer disappears in the NMR carbon spectra of chiral polypropynylamine compound P1 and chiral polypropynylamine compounds. In addition, the methylene carbon peak of the propynylamine functional group appears at chemical shift 51.09 in the NMR spectrum of chiral polypropynylamine compound P1, which indicates the accuracy of the structure of chiral polypropynylamine compound P1.

[0082] Figure 3 The infrared absorption spectra of the 4,4'-diaminodiphenylmethane monomer (Figure a), the 1,4-diethynylbenzene monomer (Figure b), the chiral propargylamine compound (Figure c), and the prepared chiral polypropargylamine compound P1 (Figure d) in this example are shown. Figure 3 It can be seen that the stretching resonance peak of the carbon-carbon triple bond in the functional group of propargylamine appears in the infrared absorption spectra of chiral propargylamine compounds and chiral polypropargylamine compound P1, with wavenumbers of 3034 cm⁻¹. -1 and 3026cm -1 This demonstrates the successful preparation of the expected chiral polypropynylamine compound P1.

[0083] Figure 4 The image shows the circular dichroism spectrum of the chiral polypropyne amine compound P1 prepared in this embodiment with 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine, where (R,R)-pybox represents 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine. Figure 4 It can be seen that the chiral polypropynylamine compound exhibits a negative Cotton effect in the range of 260–300 nm, while it exhibits a positive Cotton effect in the range of 220–260 nm. This is completely opposite to the circular dichroism signal of the chiral ligand used, proving that the expected chiral polypropynylamine compound P1 was successfully prepared.

[0084] Figure 5 The thermogravimetric curve of the chiral polypropynylamine compound P1 prepared in this embodiment under a nitrogen atmosphere shows that the temperature at which the weight loss is 5% is 351°C.

[0085] Example 2

[0086] Chiral polypropynylamine compound P1 is prepared by the following reaction:

[0087]

[0088] In a clean 10 mL Schlenk polymerization tube, 59 mg (0.30 mmol) of 4,4'-diaminodiphenylmethane, 38 mg (0.30 mmol) of 1,4-diethynylbenzene, 22 mg (0.06 mmol) of 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine, and 19 mg (0.09 mmol) of cuprous trifluoromethanesulfonate were added in one step. The reaction was carried out three times: evacuating to -1 bar for 10 min and purging with nitrogen. Nitrogen purging was performed after each evacuation. Then, under nitrogen protection, 77 μL (0.75 mmol) of benzaldehyde and 0.30 mL of toluene were added using a syringe. The reaction was carried out at 25 °C for 24 h under nitrogen protection. After the reaction was completed, the mother liquor was diluted with 0.60 mL of tetrahydrofuran. The diluted solution was filtered through cotton to remove the solids in the solution. Then the filtrate was added dropwise to a mixed solution of methanol and water (the volume ratio of methanol to water was 6:1) for sedimentation. Finally, the solution was allowed to stand, filtered, and dried to obtain the chiral polypropynylamine compound P1.

[0089] The chiral polypropynylamine compound P1 in this embodiment has a yield of 90%, a weight-average molecular weight of 37,700 g / mol, and a molecular weight distribution of 1.58.

[0090] Example 3

[0091] Chiral polypropynylamine compound P2 is prepared by the following reaction:

[0092]

[0093] The 38 mg (0.30 mmol) 1,4-diethynylbenzene in Example 2 was replaced with 65 mg (0.30 mmol) 4-phenylethynyl ether, and other conditions were the same as in Example 2, to obtain chiral polypropynylamine compound P2.

[0094] The yield of the chiral polypropynylamine compound P2 in this embodiment was 93%, with a weight-average molecular weight of 16300 g / mol and a molecular weight distribution of 1.27.

[0095] Figure 6 The image shows the 1H NMR spectrum of the chiral polypropylamine compound P2 prepared in this embodiment in deuterated chloroform. Figure 6 It can be seen that the methylene hydrogen resonance peak on the functional group of propargylamine appears at a chemical shift of 5.43, which indicates the accuracy of the structure of the chiral polypropargylamine compound P2.

[0096] Figure 7 The image shows a circular dichroism chromatogram of the chiral polypropylamine compound P2 prepared in this embodiment in tetrahydrofuran. Figure 7It can be seen that the chiral polypropynylamine compound exhibits a negative Cotton effect peak at 265 nm, indicating that the expected chiral polypropynylamine compound P2 was successfully prepared.

[0097] Example 4

[0098] Chiral polypropynylamine compound P3 is prepared by the following reaction:

[0099]

[0100] The 59 mg (0.30 mmol) 4,4'-diaminodiphenylmethane in Example 2 was replaced with 75 mg (0.30 mmol) 4,4'-dithiodiphenylamine, and the other conditions were the same as in Example 2, to obtain the chiral polypropynylamine compound P3.

[0101] The yield of the chiral polypropynylamine compound P3 in this embodiment was 80%, the weight-average molecular weight was 70200 g / mol, and the molecular weight distribution was 1.80.

[0102] Figure 8 The image shows the 1H NMR spectrum of the chiral polypropylamine compound P3 prepared in this embodiment in deuterated chloroform. Figure 8 It can be seen that the methylene hydrogen resonance peak on the functional group of propargylamine appears at a chemical shift of 5.46, which indicates the accuracy of the structure of the chiral polypropargylamine compound P3.

[0103] Figure 9 The image shows a circular dichroism chromatogram of the chiral polypropylamine compound P3 prepared in this embodiment in tetrahydrofuran. Figure 9 It can be seen that the chiral polypropynylamine compound exhibits a negative Cotton effect peak at 300 nm, indicating that the expected chiral polypropynylamine compound P3 was successfully prepared.

[0104] Example 5

[0105] Chiral polypropynylamine compound P4 is prepared by the following reaction:

[0106]

[0107] In Example 2, 59 mg (0.30 mmol) of 4,4'-diaminodiphenylmethane was replaced with 64 mg (0.6 mmol) of 4-methylaniline, 77 μL (0.75 mmol) of benzaldehyde was replaced with 40 mg (0.3 mmol) of terephthalaldehyde, and 4-methylaniline, terephthalaldehyde, 1,4-diethynylbenzene, 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine and cuprous trifluoromethanesulfonate were added simultaneously, with other conditions the same as in Example 2, to obtain chiral polypropynylamine compound P4.

[0108] The yield of the chiral polypropynylamine compound P4 in this embodiment was 85%, the weight-average molecular weight was 31700 g / mol, and the molecular weight distribution was 1.68.

[0109] Example 6

[0110] Chiral polypropynylamine compound P5 is prepared by the following reaction:

[0111]

[0112] In Example 2, 59 mg (0.30 mmol) of 4,4'-diaminodiphenylmethane was replaced with 64 mg (0.3 mmol) of 4,4'-diaminodibenzophenone, 77 μL (0.75 mmol) of benzaldehyde was replaced with 40 mg (0.3 mmol) of terephthalaldehyde, and 38 mg (0.30 mmol) of 1,4-diethynylbenzene was replaced with 162 mg (0.6 mmol) of 4-ethynyltriphenylamine. 4,4'-diaminodibenzophenone, terephthalaldehyde, 4-ethynyltriphenylamine, 2,6-bis[(4R)-4-phenyl-2-oxazolinyl]pyridine and cuprous trifluoromethanesulfonate were added simultaneously, and other conditions were the same as in Example 2, to obtain the chiral polypropynylamine compound P5.

[0113] The yield of the chiral polypropynylamine compound P5 in this embodiment was 93%, with a weight-average molecular weight of 24700 g / mol and a molecular weight distribution of 2.10.

[0114] Figure 10 The photoluminescence spectrum of the chiral polypropyneamine compound P5 prepared in this embodiment is shown below. Figure 10 It can be seen that the chiral polypropynylamine compound P5 has strong fluorescence emission peaks at 450 nm and 550 nm, proving that it has certain single-molecule white light emission properties.

[0115] Example 7

[0116] Chiral polypropynylamine compound P1 is prepared by the following reaction:

[0117]

[0118] The 19 mg (0.09 mmol) copper trifluoromethanesulfonate in Example 2 was replaced with 33 mg (0.09 mmol) copper trifluoromethanesulfonate. The vacuuming and nitrogen purging operations were omitted. The reaction was carried out in air at 25°C for 24 h, and other conditions were the same as in Example 2, to obtain chiral polypropynylamine compound P1.

[0119] The yield of the chiral polypropynylamine compound P1 in this embodiment was 91%, with a weight-average molecular weight of 74,400 g / mol and a molecular weight distribution of 2.06.

[0120] Example 8

[0121] Chiral polypropynylamine compound P6 is prepared by the following reaction:

[0122]

[0123] The 38 mg (0.30 mmol) 1,4-diethynylbenzene in Example 2 was replaced with 30 mg (0.2 mmol) 1,3,5-triethynylbenzene, the 0.3 mL toluene was replaced with 0.5 mL toluene, the reaction time was changed from 24 h to 6 h, and other conditions were the same as in Example 2, to obtain the chiral polypropynylamine compound P6.

[0124] The yield of the chiral polypropynylamine compound P6 in this embodiment was 74%, with a weight-average molecular weight of 12400 g / mol and a molecular weight distribution of 1.89.

[0125] Example 9

[0126] Chiral polypropynylamine compound P7 is prepared by the following reaction:

[0127]

[0128] The 38 mg (0.30 mmol) 1,4-diethynylbenzene in Example 2 was replaced with 64 mg (0.15 mmol) tetrakis(4-ethynylbenzene)ethylene, the 0.3 mL toluene was replaced with 0.5 mL toluene, the reaction time was changed from 24 h to 6 h, and other conditions were the same as in Example 2, to obtain the chiral polypropynylamine compound P7.

[0129] The yield of the chiral polypropynylamine compound P7 in this embodiment was 82%, with a weight-average molecular weight of 17800 g / mol and a molecular weight distribution of 2.25.

[0130] Example 10

[0131] Chiral polypropynylamine compound P8 is prepared by the following reaction:

[0132]

[0133]

[0134] The 59 mg (0.30 mmol) 4,4'-diaminodiphenylmethane in Example 2 was replaced with 58 mg (0.2 mmol) tris(4-aminophenyl)amine, the 0.3 mL toluene was replaced with 0.5 mL toluene, the reaction time was changed from 24 h to 6 h, and other conditions were the same as in Example 2, to obtain the chiral polypropynylamine compound P8.

[0135] The yield of the chiral polypropynylamine compound P8 in this embodiment was 45%, the weight-average molecular weight was 7200 g / mol, and the molecular weight distribution was 1.45.

[0136] Example 11

[0137] Chiral polypropynylamine compound P9 is prepared by the following reaction:

[0138]

[0139] The 59 mg (0.30 mmol) 4,4'-diaminodiphenylmethane in Example 2 was replaced with 57 mg (0.15 mmol) tetrakis(4-aminophenyl)methane, the 0.3 mL toluene was replaced with 0.5 mL toluene, the reaction time was changed from 24 h to 6 h, and other conditions were the same as in Example 2, to obtain the chiral polypropynylamine compound P9.

[0140] The yield of the chiral polypropynylamine compound P9 in this embodiment was 53%, with a weight-average molecular weight of 9400 g / mol and a molecular weight distribution of 1.47.

[0141] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A chiral polypropargyl amine compound, characterized by, The structural general formula of the chiral polypropargyl amine compound is: ； wherein R 3 is benzophenone, R 5 is phenyl, R 6 is triphenylamine; n is any integer from 2 to 4000; and the asterisk represents that the carbon atom at this position has a certain stereoselectivity.

2. The method for preparing a chiral polypropargyl amine compound according to claim 1, characterized by, The polybasic aromatic amine and the aromatic aldehyde are subjected to a first step reaction under a protective atmosphere, and the first reaction product, the aromatic alkyne, the copper metal catalyst, the chiral ligand and the organic solvent are subjected to a second step reaction to obtain the chiral polypropargyl amine compound; The protective atmosphere is nitrogen or a rare gas; The molar ratio of the polybasic aromatic amine, the aromatic aldehyde, the aromatic alkyne, the copper metal catalyst and the chiral ligand is 1-20:1-20:1-20:1-10:1-15; The copper metal catalyst is cuprous triflate or copper triflate and the chiral ligand is 2,6-bis[(4 R )-4-phenyl-2-oxazolinyl]pyridine or 2,6-bis[(4 S )-4-phenyl-2-oxazolinyl]pyridine. The structural formula of the polybasic aromatic amine is: ； The structural formula of the aromatic aldehyde is: ； The structural formula of the aromatic alkyne is: 。 3. The preparation method according to claim 2, characterized in that, The organic solvent is one or more of tetrahydrofuran, dimethyl sulfoxide, a hydrocarbon organic solvent, an alcohol organic solvent, an ester organic solvent and an amide organic solvent.

4. The production method according to claim 3, characterized by, The concentration of the polybasic aromatic amine in the organic solvent is 0.05-4.0 mol / L.

5. The preparation method according to claim 2, characterized in that, The temperature of the first step reaction and the second step reaction is independently 25-120 DEG C, the time of the first step reaction is 0.1-4 h, and the time of the second step reaction is 0.1-24 h.

6. The chiral polypropargyl amine compound of claim 1 is applied in an optoelectronic device.

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