Method for preparing amine compounds by hydrogenation of polyesters and use thereof

Abstract

This invention discloses a method for preparing amine compounds by hydrogenation of polyester and its applications. The method includes: using polyester, a specified amine, and / or ammonia as reaction substrates, reacting a mixed reaction system containing polyester, the specified amine, and / or ammonia, a catalyst precursor, a ligand, an additive, and an organic solvent in a hydrogen atmosphere to obtain the target amine compound. The acid and alcohol fragments in the structural units of the polyester are converted into the target amine compound. This invention can efficiently and selectively convert polyester into high-value-added primary, secondary, or tertiary amines, and has wide applications in pharmaceuticals, pesticides, materials, and other fields. This method achieves the first partial conversion of polyester to amine compounds, developing a novel and highly atom-economical strategy for the recycling of waste polyester.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis chemistry technology, specifically relating to a method for preparing amine compounds by hydrogenation of polyester and its application. Background Technology

[0002] Amines and diamines play crucial roles in life sciences, healthcare, and materials science (Froidevaux, V.; Negrell, C.; Caillol, S.; Pascault, JP; Boutevin, B. Biobased Amines: From Synthesis to Polymers; Present and Future. Chem. Rev. 2016, 116, 14181-14224). Given their wide range of applications, amine synthesis has long been a central topic in chemical research. Traditional synthetic routes typically rely on fossil feedstocks, involve multi-step processes, and have low atom economy (Kenichi, N.; Susumu, O.; Fumisada, K.; Takuji, S.; Kazuhiko, A. Method for Producing Xylylenediamine, US Patent 2002, US20020038054a1). The direct synthesis of amines from waste polyesters would represent a significant breakthrough, enabling both the high-value utilization of plastics and the production of sustainable chemicals. To date, only four cases of amination of esters have been reported in the literature, of which only one case concerns polyesters. Specific references are: (1) Adam, R.; Cabrero-Antonino, JR; Junge, K.; Jackstell, R.; Beller, M. Esters, Including Triglycerides, and Hydrogen as Feedstocks for the Ruthenium-Catalyzed Direct N-Alkylation of Amines, Angew. Chem. Int. Ed. 2016, 55, 11049-11053. (2) Shi, Y.; Kamer, PCJ; Cole-Hamilton, DJ A New Route to α,ω-Diamines from Hydrogenation of Dicarboxylic Acids and Their Derivatives in the Presence of Amines, Green Chem. 2017, 19, 5460-5466. (3) Shi, Y.; Kamer, PCJ; Cole-Hamilton, DJ; Harvie, M.; Baxter, EF; Lim, K.JC; Pogorzelec, P. A New Route to N-Aromatic Heterocycles from the Hydrogenation of Diesters in the Presence of Anilines, Chem. Sci. 2017, 8, 6911-6917. (4) Poovan, F.; Jagadeesh, RV; Beller, M. A Catalytic Approach to the Valorization of Polyesters and Biogenic Waste for the Production of Amines. Chem 2025, 11, 102667. However, these systems face selectivity challenges, including competitive ammonolysis (Tian, ​​S.; Jiao, Y.; Gao, Z.; Xu, Y.; Fu, L.; Fu, H.; Zhou, W.; Hu, C.; Liu, G.; Wang, M.; Ma, D. Catalytic Amination of Polylactic Acid to Alanine. J. Am. Chem. Soc. 2021, 143, 16358-16363), the generation of inherent alcohol byproducts, and thermodynamically favorable aldehyde hydrogenation reactions (Lin, F.; Yang, Y.; Chin, Y. Kinetic Requirements of Aldehyde Transfer Hydrogenation Catalyzed by Microporous Solid Brønsted Acid Catalysts. ACSCatal. 2017, 7, 6909-6914). References (1)-(3) use small molecule ester compounds from fossil resources as substrates. Reference (4) has an unclear reaction pathway and produces unnecessary byproducts. In addition, reference (4) requires further conversion of the generated diol into useful diamine compounds, resulting in low atom economy and some waste of resources. Therefore, converting all structural units of polyester, including challenging alcohol fragments, into diamines and cyclic tertiary amines has important theoretical significance and wide application value. Summary of the Invention

[0003] The main objective of this invention is to provide a method for preparing amine compounds by hydrogenation of polyester and its application, thereby overcoming the shortcomings of the prior art.

[0004] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0005] The first aspect of this invention provides a method for preparing amine compounds by hydrogenation of polyester, comprising:

[0006] Using polyester, a specified amine, and / or ammonia as reaction substrates, a mixed reaction system comprising polyester, a specified amine, and / or ammonia, a catalyst precursor, a ligand, an additive, and an organic solvent is reacted in a hydrogen atmosphere to prepare a target amine compound, wherein the target amine compound includes one or more combinations of primary amine compounds, secondary amine compounds, and tertiary amine compounds, wherein the acid and alcohol segments in the structural units of the polyester are converted into the target amine compound.

[0007] In some embodiments, the structural formula of the specified amine is shown in formula (I):

[0008] ;

[0009] Formula (I)

[0010] Wherein, R and R' are hydrogen, aromatic groups, or aliphatic groups.

[0011] A second aspect of the present invention provides amine compounds prepared by the above method.

[0012] A third aspect of the present invention provides the application of the amine compounds in the fields of medicine, pesticides or polymer materials.

[0013] Compared with the prior art, the advantages of the present invention include:

[0014] 1) The method for preparing amine compounds by hydrogenation of polyester provided by the present invention efficiently and selectively converts all structural units of waste polyester into high-value-added primary amines, secondary amines or cyclic tertiary amine compounds;

[0015] 2) The method for preparing amine compounds by hydrogenation of polyester provided by this invention is suitable for mixed waste polyesters, the reaction is green, and water is the only byproduct of the reaction;

[0016] 3) The amine compounds synthesized in this invention have wide applications in the fields of medicine, pesticides, and materials. This method is the first to realize the partial conversion of polyester to amine compounds, and develops a new and highly atom-economical strategy for the recycling of waste polyester. Detailed Implementation

[0017] In view of the deficiencies of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention, which mainly provides a method for preparing amine compounds by hydrogenation of waste polyester, converting all structural units of polyester, including challenging alcohol segments, into high-value-added primary amines, secondary amines, or tertiary amine compounds.

[0018] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] As one aspect of the technical solution of the present invention, a method for preparing amine compounds by hydrogenation of polyester includes: using polyester, a specified amine and / or ammonia as reaction substrates, and reacting a mixed reaction system containing polyester, a specified amine and / or ammonia, a catalyst precursor, a ligand, an additive and an organic solvent in a hydrogen atmosphere to obtain the target amine compound.

[0020] In this invention, the acid and alcohol fragments in the structural units of the polyester are converted into target amine compounds, efficiently and selectively converting the polyester into high-value-added primary amine compounds, secondary amine compounds, or tertiary amine compounds.

[0021] In some preferred embodiments, the method for preparing amine compounds by hydrogenation of polyester specifically includes: using polyester, a specified amine and / or ammonia as reaction substrates, ruthenium salt as catalyst precursor, 1,1,1-tris(diarylphosphinemethyl)ethane as ligand, acid as additive, and mixing with an organic solvent, and reacting at a specified temperature and hydrogen pressure to obtain the target amine compound.

[0022] In some embodiments, the polyester may include one or more of polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polybutylene succinate (PBS), polycaprolactone (PCL), polylactic acid (PLA), etc., but is not limited thereto.

[0023] In some preferred embodiments, the polyester is a waste polyester, such as beverage bottles, cosmetic bottles, shampoo bottles, food packaging boxes, films, textiles, sound insulation cotton, and part housings containing polyethylene terephthalate (PET), polypropylene terephthalate (PTT), polybutylene terephthalate (PBT), polybutylene succinate (PBS), polycaprolactone (PCL), or polylactic acid (PLA), with the following structural formulas:

[0024] .

[0025] In some embodiments, the specified amine has the structural formula shown in formula (I):

[0026] ;

[0027] Formula (I)

[0028] Wherein, R and R' are hydrogen, aromatic groups, or aliphatic groups, etc.

[0029] Furthermore, when R is an aliphatic group, R' is an aliphatic group or an aromatic group; when R is an aromatic group or an aliphatic group, R' is hydrogen.

[0030] Furthermore, the aromatic group may include, but is not limited to, phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 2-fluorophenyl.

[0031] Furthermore, the aliphatic group may include, but is not limited to, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, or tert-butyl.

[0032] In some embodiments, the structural formula of the specified amine may also be , , , At least one of the following.

[0033] In some embodiments, the molar ratio of the specified amine and / or ammonia to the ester groups in the polyester is 2:1 to 20:1.

[0034] In some implementations, the specified temperature is 100~200°C and the reaction time is 10~48h.

[0035] In some implementations, the hydrogen pressure is 20 to 100 bar.

[0036] In some embodiments, the molar ratio of the ruthenium salt to the ester group in the polyester is 0.001:1 to 0.1:1.

[0037] In some embodiments, the ruthenium salt may include, but is not limited to, one or more of the following: ruthenium acetylacetonate (Ru(acac)3), bis-(2-methylallyl)cyclooctyl-1,5-diene ruthenium (Ru(COD)(methylallyl)2), RuH2(CO)(PPh3)2, RuHCl(CO)(PPh3)2, RuHCl(CO)(PCy3)2, Ru(PPh3)3Cl2, dichlorophenylruthenium(II) dimer, dodecacarbonyltriruthenium, dichlorobis(4-methylisopropylphenyl)ruthenium(II) dimer, and tris(2,2′-bipyridine)ruthenium(II) chloride.

[0038] In some embodiments, the molar ratio of the ligand to the ester group in the polyester is 0.0015:1 to 0.15:1.

[0039] In some embodiments, the ligand is 1,1,1-tris(diarylphosphinemethyl)ethane, with the structural formula shown in formula (II):

[0040] ;

[0041] Formula (II)

[0042] Among them, Ar includes , , or R'' includes one or more combinations of -H, -Me, -Et, -OMe, -NMe2, t-Bu-, Cy-, -CF3, -OCF3, etc., but is not limited to these.

[0043] In some preferred embodiments, the molar ratio of the acid to the ester group in the polyester is 0.005:1 to 0.5:1.

[0044] In some preferred embodiments, the acid may include one or more of the following combinations: trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imide, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid, aluminum trifluoromethanesulfonate, tetrafluoroboric acid, ferric chloride, aluminum trichloride, and ammonium sulfate, but is not limited thereto.

[0045] In some preferred embodiments, the organic solvent may include, but is not limited to, one or more of the following: toluene, o-xylene, p-xylene, mesitylene, cyclohexane, tert-butanol, tert-amyl alcohol, trifluoroethanol, hexafluoroisopropanol, ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, dibutyl ether, methyl tert-butyl ether, and anisole.

[0046] In some more specific embodiments, a method for preparing amine compounds by hydrogenation of waste polyester includes the following steps: using waste polyester and a specified amine (or ammonia) as reaction substrates, ruthenium salt as a catalyst precursor, 1,1,1-tris(diarylphosphinemethyl)ethane as a ligand, and an acid as an additive, in an organic solvent, the molar ratio of the specified amine or ammonia to the ester groups in the waste polyester is 2:1 to 20:1, and the reaction is carried out at a hydrogen pressure of 20 to 100 bar and at 100 to 200 °C for 10 to 48 hours. After the reaction is completed, the solvent is dried, and the mixture is separated by column chromatography to obtain different amine compounds.

[0047] As another aspect of the technical solution of the present invention, it relates to amine compounds prepared by the aforementioned method, wherein the amine compounds include one or more combinations of primary amine compounds, secondary amine compounds, and tertiary amine compounds.

[0048] As another aspect of the technical solution of the present invention, it relates to the application of the prepared amine compounds in the fields of medicine, pesticides or polymer materials (polyamine, modified epoxy resin, etc.).

[0049] In summary, the method of this invention is green, with water being the only byproduct of the reaction. It is the first to realize the conversion of polyester into amine compounds, and realizes the conversion of all structural units of waste polyester into high-value-added primary amines, secondary amines, and cyclic tertiary amine compounds. This provides a novel and highly atom-economical strategy for the recycling of waste polyester.

[0050] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments. These embodiments are implemented on the premise of the technical solution of the invention, and provide detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0051] Unless otherwise specified, the experimental methods described in the following examples are generally performed under standard conditions or as recommended by the manufacturer.

[0052] Examples 1-6

[0053] Preparation of diamine derivatives 3a and 4a from colorless beverage bottles

[0054] The synthesis circuit is as follows:

[0055]

[0056] A ruthenium salt catalyst precursor (0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC. The reaction in Example 1 was separated by column chromatography (using a silica gel column; eluent: dichloromethane / petroleum ether = 1 / 1) to obtain purified products 3a and 4a.

[0057] Characterization tests revealed the following NMR data for product 3a: 1 H NMR (400 MHz, CDCl3) δ 7.32 (s, 4H), 7.18 – 7.14 (m, 4H), 6.70 (t, J = 7.3 Hz, 2H), 6.62 (d, J = 7.6 Hz, 4H), 4.29 (s, 4H). 13 C NMR (101 MHz, CDCl3) δ 148.2, 138.6, 129.4, 127.9, 117.7, 113.0, 48.2. The NMR data for product 4a are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.19 (t, J = 7.8 Hz, 4H), 6.78 (t, J = 7.3 Hz, 2H), 6.73 (d, J = 8.0 Hz, 4H), 5.03 (br, 2H), 3.40 (s,4H). 13 C NMR (101 MHz, CDCl3) δ 146.8, 129.5, 119.0, 114.1, 43.8.

[0058] The types of ruthenium salt catalyst precursors and product yields used in Examples 1-6 are shown in Table 1:

[0059] Table 1. Types of ruthenium salt catalyst precursors and product yields

[0060] Example Ruthenium precursor 3a (%) 4a (%) Example 1 <![CDATA[Ru(acac) 3 (0.01 mmol)]]> 96 59 Example 2 <![CDATA[Ru(COD)(methylallyl) 2 (0.01 mmol)]]> 72 31 Example 3 <![CDATA[RuH2(CO)(PPh3) 2 (0.01 mmol)]]> 89 43 Example 4 <![CDATA[RuHCl(CO)(PPh3)2 (0.01 mmol)]]> 45 28 Example 5 <![CDATA[RuHCl(CO)(PCy3) 2 (0.01 mmol)]]> 34 21 Example 6 <![CDATA[Ru(PPh3)3Cl 2 (0.01 mmol)]]> 29 16

[0061] Examples 7-12

[0062] Preparation of diamine derivatives 3a and 4a from colorless beverage bottles

[0063] The synthesis circuit is as follows:

[0064]

[0065] Ruthenium acetylacetonate (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and solvent (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC.

[0066] The types of solvents used and the product yields in Examples 7-12 are shown in Table 2:

[0067] Table 2 Solvent types and product yields

[0068] Example solvent 3a (%) 4a (%) Example 7 1,4-Dioxane 95 56 Example 8 Tetrahydrofuran 86 25 Example 9 aniline 79 16 Example 10 Dibutyl ether 65 28 Example 11 Ethylene glycol dimethyl ether 82 37 Example 12 Methyl tert-butyl ether 68 31

[0069] Examples 13-18

[0070] Preparation of diamine derivatives 3a and 4a from colorless beverage bottles

[0071] The synthesis circuit is as follows:

[0072]

[0073] Ruthenium acetylacetonate (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), acid additive (0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC.

[0074] The types of acid additives used in Examples 13-18 and the product yields are shown in Table 3:

[0075] Table 3. Types of Acid Additives and Product Yields

[0076] Example additive 3a (%) 4a (%) Example 13 Bistrifluoromethanesulfonylimide 92 57 Example 14 Methylsulfonic acid 25 35 Example 15 p-Toluenesulfonic acid 27 34 Example 16 Aluminum trifluoromethanesulfonate 40 4 Example 17 Trifluoroacetic acid 26 11 Example 18 Tetrafluoroboric acid 51 24

[0077] Examples 19-20

[0078] Preparation of diamine derivatives 3a and 4a from colorless beverage bottles

[0079] The synthesis circuit is as follows:

[0080]

[0081] Ruthenium acetylacetone (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with x bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC.

[0082] The product yields corresponding to hydrogen pressures in Examples 19-20 are shown in Table 4:

[0083] Table 4. Product yields at different hydrogen pressures

[0084] Example <![CDATA[H2 (x bar)]]> 3a (%) 4a (%) Example 19 20 24 13 Example 20 100 91 46

[0085] Examples 21-22

[0086] Preparation of diamine derivatives 3a and 4a from colorless beverage bottles

[0087] The synthesis circuit is as follows:

[0088]

[0089] Ruthenium acetylacetonate (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and aniline (x mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC.

[0090] Table 5 shows the product yields corresponding to different amounts of aniline in Examples 21-22:

[0091] Table 5. Product yield corresponding to different amounts of aniline

[0092] Example <![CDATA[PhNH2 (x mmol)]]> 3a (%) 4a (%) Example 21 2 86 39 Example 22 20 95 59

[0093] Examples 23-24

[0094] Preparation of diamine derivatives 3a and 4a from colorless beverage bottles

[0095] The synthesis circuit is as follows:

[0096]

[0097] Ruthenium acetylacetone (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at different temperatures for 20 hours. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC.

[0098] The product yields at different temperatures in Examples 23-24 are shown in Table 6.

[0099] Table 6 Product yield at different temperatures

[0100] Example <![CDATA[T ( o C)]]> 3a (%) 4a (%) Example 23 100 48 21 Example 24 200 91 52

[0101] Examples 25-26

[0102] Preparation of diamine derivatives 3a and 4a from colorless beverage bottles

[0103] The synthesis circuit is as follows:

[0104]

[0105] Ruthenium acetylacetonate (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for different times. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC.

[0106] The product yields for different reaction times in Examples 25-26 are shown in Table 7.

[0107] Table 7 Product yield at different reaction times

[0108] Example t (h) 3a (%) 4a (%) Example 25 10 48 21 Example 26 48 96 61

[0109] Examples 27-40

[0110] Preparation of diamine derivatives 3a and 4a from waste PET

[0111] The synthesis circuit is as follows:

[0112]

[0113] Ruthenium acetylacetonate (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, waste PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction was completed, biphenyl was added as an internal standard, and the yields of products 3a and 4a were determined by GC.

[0114] The sources of waste PET and the product yields used in Examples 27-40 are shown in Table 8:

[0115] Table 8. Sources and Product Yields of Waste PET

[0116] Example Sources of waste PET 3a (%) 4a (%) Example 27 Green beverage bottle 90 51 Example 28 blue beverage bottle 92 67 Example 29 brown beverage bottle 91 61 Example 30 blue-green beverage bottle 95 56 Example 31 Double-sided tape 95 48 Example 32 Sound insulation cotton 86 49 Example 33 Colorless food box 96 64 Example 34 black food box 92 54 Example 35 Aluminum foil packaging composite materials 82 23 Example 36 Clothing (100% PET) 94 50 Example 37 Clothing (85% PET + 15% PA) 98 51 Example 38 Clothing (80% PET + 20% Cotton) 96 65 Example 39 Clothing (60% PET + 40% cotton) 94 57 Example 40 Clothing (95% PET + 5% PU) 91 56

[0117] Example 41

[0118] Gram-scale preparation of diamine derivatives 3a and 4a synthesized from colorless beverage bottles

[0119] Ruthenium acetylacetone (80 mg, 0.2 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (187 mg, 0.3 mmol), trifluoromethanesulfonic acid (150 mg, 1.0 mmol), and toluene (20 mL) were added to a tetrafluoroethylene liner. After stirring at room temperature for 5 minutes, a colorless PET beverage bottle (1.9 g, 10 mmol) and aniline (4.7 g, 50 mmol) were added. The liner was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 48 hours. After the reaction, column chromatography was performed (using a silica gel column; eluent: dichloromethane / petroleum ether = 1 / 1) to obtain purified products 3a and 4a. Product 3a was a white solid with a yield of 85%; product 4a was a white solid with a yield of 51%.

[0120] Examples 42-57

[0121] Colorless beverage bottle for synthesizing diamine derivatives

[0122] The synthesis circuit is as follows:

[0123]

[0124] Ruthenium acetylacetone (4.0 mg, 0.01 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (9.4 mg, 0.015 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, a colorless beverage bottle containing PET (96 mg, 0.5 mmol) and an amine (2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction, the products were separated by column chromatography (using a silica gel column; eluent: dichloromethane / petroleum ether = 1 / 1) to obtain purified products 3 and 4.

[0125] The types of amines used in Examples 42-57 and the product yields are shown in Table 9:

[0126] Table 9. Yield of products for specified amine types ; The structural formula of the product 3g-2HCl is: The structural formula of the product 3h-2HCl is: The structural formula of the product 3i-2HCl is: The structural formula of product 3j is: The structural formula of product 3k is: The structural formula of product 3l is: The structural formula of product 3m is: The structural formula of product 3n is: The structural formula of product 3o is: The structural formula of product 3p is: The structural formula of product 3q is: .

[0127] The nuclear magnetic resonance spectra and high-resolution standard data of each product are as follows:

[0128] 3b: 1 H NMR (400 MHz, CDCl3) δ 7.32 (s, 4H), 6.98 (d, J = 8.2 Hz, 4H), 6.56 (d, J = 8.4 Hz, 4H), 4.28 (s, 4H), 2.23 (s, 6H). 13 C NMR (101 MHz, CDCl3)δ 145.9, 138.7, 129.9, 127.9, 127.0, 113.2, 48.6, 20.5.

[0129] 4b: 1 H NMR (400 MHz, CDCl3) δ 7.01 (d, J = 8.1 Hz, 4H), 6.60 (d, J =8.4 Hz, 4H), 3.36 (s, 4H), 2.24 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 145.7,130.0, 127.4, 113.6, 44.0, 20.5.

[0130] 3c: 1 H NMR (400 MHz, CDCl3) δ 7.33 (s, 4H), 7.21 (d, J = 8.7 Hz, 4H), 6.60 (d, J = 8.6 Hz, 4H), 4.28 (s, 4H), 1.27 (s, 18H). 13 C NMR (101 MHz, CDCl3) δ 145.9, 140.5, 138.8, 127.9, 126.2, 112.7, 48.5, 34.0, 31.7. HRMS(ESI) calcd. for C 28 H 37 N2+ [M+H + ]: 401.2957, found: 401.2953.

[0131] 4c: 1 H NMR (400 MHz, CDCl3) δ 7.23 (d, J = 8.8 Hz, 4H), 6.64 (d, J =8.8 Hz, 4H), 3.38 (s, 4H), 1.28 (s, 18H). 13 C NMR (101 MHz, CDCl3) δ 145.4,141.2, 126.3, 113.3, 43.9, 34.0, 31.7. HRMS (ESI) calcd. for C 22 H 33 N2 + [M+H + ]:325.2644, found: 325.2645.

[0132] 3d: 1 H NMR (400 MHz, CDCl3) δ 7.33 (s, 4H), 6.78 (d, J = 8.3 Hz, 4H),6.60 (d, J = 8.4 Hz, 4H), 4.26 (s, 4H), 3.73 (s, 6H). 13 C NMR (101 MHz, CDCl3)δ 152.4, 142.5, 138.8, 127.9, 115.1, 114.3, 56.0, 49.1.

[0133] 4d: 1 H NMR (400 MHz, CDCl3) δ 6.80 (d, J = 8.8 Hz, 4H), 6.65 (d, J =8.9 Hz, 4H), 3.75 (s, 6H), 3.34 (s, 4H). 13 C NMR (151 MHz, CDCl3) δ 152.7,142.2, 115.1, 114.8, 56.0, 44.7.

[0134] 3e: 1H NMR (400 MHz, CDCl3) δ 7.31 (s, 4H), 7.11 (d, J = 8.9 Hz, 4H),6.54 (d, J = 8.8 Hz, 4H), 4.29 (s, 4H), 4.06 (br, 2H). 13 C NMR (101 MHz,CDCl3) δ 146.7, 138.3, 129.2, 127.9, 122.3, 114.1, 48.2. HRMS (ESI) calcd.for C 20 H 19 N2Cl2 + [M+H + ]: 357.0925, found: 357.0914.

[0135] 3f: 1 H NMR (400 MHz, CDCl3) δ 7.35 (s, 4H), 7.01 – 6.93 (m, 4H), 6.70– 6.61 (m, 4H), 4.36 (s, 4H). 13 C NMR (101 MHz, CDCl3) δ 152.9 (d, J = 239.2Hz), 138.3, 136.7 (d, J = 11.5 Hz), 127.9, 124.7 (d, J = 3.6 Hz), 117.0 (d, J= 7.0 Hz), 114.6 (d, J = 18.4 Hz), 112.5 (d, J = 3.2 Hz), 47.7. 19 F NMR (377MHz, CDCl3) δ -136.46.

[0136] 3g-2HCl: 1 H NMR (400 MHz, D2O) δ 7.57 (s, 4H), 4.28 (s, 4H), 3.09 (t,J = 7.8 Hz, 4H), 1.72 – 1.65 (m, 4H), 1.43 – 1.34 (m, 4H), 0.92 (t, J = 7.4Hz, 6H). 13 C NMR (101 MHz, D2O) δ 132.2, 130.5, 50.4, 47.0, 27.5, 19.2, 12.7.

[0137] 3h-2HCl:1 H NMR (400 MHz, D2O) δ 7.49 (s, 4H), 4.23 (s, 4H), 3.17-3.09(m, 2H), 2.10 (d, J = 7.7 Hz, 4H), 1.81 (d, J = 13.1 Hz, 4H), 1.64 (d, J =12.6 Hz, 2H), 1.40 – 1.11 (m, 10H). 13 C NMR (101 MHz, D2O) δ 135.0, 133.0,59.9, 50.1, 31.5, 27.1, 26.6.

[0138] 3i-2HCl: 1 H NMR (400 MHz, D2O) δ 7.57 (s, 4H), 4.27 (s, 4H), 1.49 (s,18H). 13 C NMR (101 MHz, D2O) δ 132.6, 130.5, 57.8, 44.9, 24.9.

[0139] 3j: 1 H NMR (400 MHz, CDCl3) δ 7.28 (s, 4H), 3.77 (s, 4H), 2.45 (d, J =6.8 Hz, 4H), 1.83 – 1.74 (m, 2H), 1.66 (br, 2H), 0.92 (d, J = 6.6 Hz, 12H). 13 C NMR (101 MHz, CDCl3) δ 139.3, 128.3, 57.6, 53.9, 28.4, 20.8.

[0140] 3k-2HCl: 1 H NMR (400 MHz, D2O) δ 7.44 (s, 4H), 4.17 (s, 4H), 3.27-3.21(m, 2H), 2.04-2.00 (m, 4H), 1.67-1.55 (m, 8H), 1.45-1.36 (m, 12H). 13 C NMR(101 MHz, D2O) δ 132.3, 130.4, 59.4, 47.9, 30.4, 27.2, 23.4.

[0141] 3l-2HCl: 1H NMR (400 MHz, D2O) δ 7.44 (s, 4H), 4.15 (s, 4H), 3.55-3.49(m, 2H), 2.06-2.00 (m, 4H), 1.67-1.54 (m, 12H). 13 C NMR (101 MHz, D2O) δ132.2, 130.4, 59.0, 49.5, 29.3, 23.7.

[0142] 3m: 1 H NMR (400 MHz, CDCl3) δ 7.21-7.17 (m, 4H), 7.15 (s, 4H), 6.73-6.67 (m, 6H), 4.47 (s, 4H), 2.97 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ 149.8,137.7, 129.3, 127.1, 116.6, 112.5, 56.5, 38.6.

[0143] 3n: 1 H NMR (400 MHz, CDCl3) δ 7.27 (s, 4H), 3.60 (s, 4H), 2.52-2.49(m, 8H), 1.79-1.76 (m, 8H). 13 C NMR (101 MHz, CDCl3) δ 138.0, 128.9, 60.6,54.2, 23.5.

[0144] 3o: 1 H NMR (400 MHz, CDCl3) δ 7.47 (s, 4H), 3.81 (s, 4H), 2.63 (t, J =7.8 Hz, 4H), 2.42 (s, 6H), 1.72-1.65 (m, 4H), 1.35-1.26 (m, 8H), 0.89 (t, J =6.5 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 133.2, 130.2, 60.6, 56.5, 40.9, 29.2,25.5, 22.3, 13.9.

[0145] 3p: 1H NMR (400 MHz, CDCl3) δ 7.24 (s, 4H), 3.46 (s, 4H), 2.86 – 2.82 (m, 4H), 1.95 – 1.89 (m, 4H), 1.60 – 1.56 (m, 4H), 1.41 – 1.30 (m, 2H), 1.29-1.19 (m, 4H), 0.91 (d, J = 6.2 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 137.4,129.2, 63.5, 54.1, 34.5, 30.9, 22.1. HRMS (ESI) calcd. for C 20 H 33 N2 + [M+H + ]:301.2644, found: 301.2638.

[0146] 3q: 1 H NMR (400 MHz, CDCl3) δ 7.27 (s, 4H), 3.70 (t, J = 4.7 Hz, 8H), 3.48 (s, 4H), 2.43 (t, J = 4.7 Hz, 8H). 13 C NMR (101 MHz, CDCl3) δ 136.8,129.2, 67.1, 63.3, 53.7.

[0147] Example 58

[0148] Preparation of diamine 3r-2HCl from PET

[0149]

[0150] Ruthenium acetylacetonate (8.0 mg, 0.02 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (18.7 mg, 0.03 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, PET (96 mg, 0.5 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 36 hours. The reaction was cooled to room temperature, and the hydrogen in the autoclave was released. After purging with 8 bar of ammonia, the reaction was continued at 150 °C for 24 hours. After the reaction was completed, column chromatography was performed (using a silica gel column; eluent: dichloromethane / methanol = 1 / 2) to obtain a preliminarily purified product 3r. 3r was dissolved in ethyl acetate solution, and ethyl hydrochloride solution was added to acidity to obtain a white precipitate. The precipitate was filtered and washed with ethyl acetate to obtain product 3r-2HCl. The NMR data for the product 3r-2HCl are as follows:

[0151] 3r-2HCl: 1 H NMR (400 MHz, D2O) δ 7.51 (s, 4H), 4.20 (s, 4H). 13 C NMR (101 MHz, D2O) δ 133.6, 129.5, 42.7.

[0152] Example 59

[0153] PBT was used to prepare diamine derivative 3a and cyclic tertiary amine 5.

[0154] The synthesis circuit is as follows:

[0155]

[0156] Ruthenium acetylacetone (8.0 mg, 0.02 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (18.7 mg, 0.03 mmol), trifluoromethanesulfonic acid (15.0 mg, 0.1 mmol), and 1,4-dioxane (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, PBT (110 mg) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction, column chromatography was performed (using a silica gel column; eluent: dichloromethane / petroleum ether = 1 / 2) to obtain purified products 3a and 5. Product 3a was a white solid with a yield of 93%; product 5 was a pale yellow oily liquid with a yield of 95%. The NMR data of product 5 are as follows: 1HNMR (400 MHz, CDCl3) δ 7.24-7.20 (m, 2H), 6.65 (t, J = 7.2 Hz, 1H), 6.57 (d,J = 7.6 Hz, 2H), 3.27 (t, J = 6.6 Hz, 4H), 2.00 – 1.97 (m, 4H). 13 C NMR (101MHz, CDCl3) δ 148.1, 129.3, 115.6, 111.8, 47.7, 25.6.

[0157] Example 60

[0158] Preparation of cyclic tertiary amines 5 by PBS

[0159] The synthesis circuit is as follows:

[0160]

[0161] Ruthenium acetylacetone (8.0 mg, 0.02 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (18.7 mg, 0.03 mmol), trifluoromethanesulfonic acid (15.0 mg, 0.1 mmol), and 1,4-dioxane (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, PBS (86 mg) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction, column chromatography was performed (using a silica gel column; eluent: dichloromethane / petroleum ether = 1 / 1) to obtain purified product 5. Product 5 was a pale yellow oily liquid with a separation yield of 92%.

[0162] Example 61

[0163] PCL preparation of cyclic tertiary amine 6 and diamine 7

[0164] The synthesis circuit is as follows:

[0165]

[0166] Ruthenium acetylacetone (8.0 mg, 0.02 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (18.7 mg, 0.03 mmol), trifluoromethanesulfonic acid (15.0 mg, 0.1 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, PCL (114 mg, 1 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction, column chromatography (silica gel column; eluent: dichloromethane) was used to separate the products, yielding purified products 6 and 7. Product 6 was an oil-free liquid with a yield of 52%, and product 7 was a white solid with a yield of 34%. The NMR data of product 6 are as follows: 1 H NMR (400 MHz, CDCl3)δ 7.19 (t, J = 7.7 Hz, 2H), 6.69 (d, J = 8.1 Hz, 2H), 6.61 (t, J = 7.2 Hz,1H), 3.43 (t, J = 6.0 Hz, 4H), 1.78 – 1.76 (m, 4H), 1.54 – 1.51 (m, 4H). 13 CNMR (101 MHz, CDCl3) δ 149.0, 129.3, 115.2, 111.2, 49.1, 27.9, 27.3. The NMR data for product 7 are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.17 (t, J = 7.7 Hz, 4H), 6.69 (t, J =7.3 Hz, 2H), 6.62 (d, J = 8.0 Hz, 4H), 3.65 (br, 2H), 3.11 (t, J = 7.1 Hz, 4H), 1.65 – 1.62 (m, 4H), 1.46 – 1.43 (m, 4H). 13 C NMR (101 MHz, CDCl3) δ148.4, 129.4, 117.4, 112.9, 44.1, 29.6, 27.1.

[0167] Example 62

[0168] PTT was used to prepare diamine derivatives 3a and 8a.

[0169] The synthesis circuit is as follows:

[0170]

[0171] Ruthenium acetylacetone (8.0 mg, 0.02 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (18.7 mg, 0.03 mmol), trifluoromethanesulfonic acid (15.0 mg, 0.1 mmol), and 1,4-dioxane (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, PTT (103 mg) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction, column chromatography (silica gel column; eluent: dichloromethane) was used to separate the purified products 3a and 8. Product 3a was a white solid with a yield of 87%; product 8 was a white solid with a yield of 41%. The NMR data of product 8 are as follows: 1 H NMR (400 MHz, CDCl3)δ 7.18 (t, J = 7.7 Hz, 4H), 6.71 (t, J = 7.3 Hz, 2H), 6.62 (d, J = 7.9 Hz,4H), 3.65 (br, 2H), 3.25 (t, J = 6.7 Hz, 4H), 1.96 – 1.89 (m, 2H). 13 C NMR (101 MHz, CDCl3) δ 148.2, 129.4, 117.7, 113.0, 42.2, 29.3.

[0172] Example 63

[0173] PLA preparation of diamine 9

[0174] The synthesis circuit is as follows:

[0175]

[0176] Ruthenium acetylacetone (8.0 mg, 0.02 mmol), 1,1,1-tris(diphenylphosphinemethyl)ethane (18.7 mg, 0.03 mmol), trifluoromethanesulfonic acid (7.5 mg, 0.05 mmol), and toluene (2 mL) were added to a glass tube. After stirring at room temperature for 5 minutes, PLA (72 mg, 1 mmol) and aniline (232.8 mg, 2.5 mmol) were added. The glass tube was placed in an autoclave, purged three times with hydrogen, and then purged with 60 bar of hydrogen. The reaction was carried out at 150 °C for 20 hours. After the reaction, column chromatography (silica gel column; eluent: dichloromethane) was used to separate the product, yielding purified product 9. Product 9 was a white solid with a yield of 58%. The NMR data of product 9 are as follows: 1H NMR (400 MHz, CDCl3) δ 7.20-7.16 (m, 4H), 6.75-6.70 (m,2H), 6.66-6.61 (m, 4H), 3.81-3.73 (m, 1H), 3.32-3.27 (m, 1H), 3.13-3.08 (m,1H), 1.28 (d, J = 6.4 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 148.3, 147.3, 129.5,129.4, 118.1, 117.8, 113.9, 113.2, 49.8, 48.9, 19.3.

[0177] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0178] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. A method for preparing amine compounds by hydrogenation of polyester, characterized in that, include: Using polyester, a specified amine, and / or ammonia as reaction substrates, a mixed reaction system comprising polyester, a specified amine, and / or ammonia, a catalyst precursor, a ligand, an additive, and an organic solvent is reacted in a hydrogen atmosphere to prepare a target amine compound, wherein the target amine compound includes one or more combinations of primary amine compounds, secondary amine compounds, and tertiary amine compounds, wherein the acid and alcohol segments in the structural units of the polyester are converted into the target amine compound.

2. The method according to claim 1, characterized in that, include: Using polyester, a specified amine and / or ammonia as reaction substrates, ruthenium salt as catalyst precursor, 1,1,1-tris(diarylphosphosmethyl)ethane as ligand, and acid as additive, the mixture is mixed with an organic solvent and reacted at a specified temperature and hydrogen pressure to prepare the target amine compound.

3. The method according to claim 1 or 2, characterized in that: The polyester comprises one or more of polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate, polycaprolactone, and polylactic acid, preferably waste polyester, and more preferably beverage bottles, cosmetic bottles, shampoo bottles, food packaging boxes, films, textiles, sound insulation cotton, and part housings containing polyethylene terephthalate, polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate, polycaprolactone, and polylactic acid.

4. The method according to claim 1 or 2, characterized in that: The structural formula of the specified amine is shown in formula (I): ； Formula (I) Wherein, R and R' are hydrogen, aromatic groups or aliphatic groups; Preferably, when R is an aliphatic group, R' is an aliphatic group or an aromatic group; when R is an aromatic group or an aliphatic group, R' is hydrogen. Particularly preferred, the aromatic group includes phenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 2-fluorophenyl; Particularly preferred, the aliphatic group includes n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, cycloheptyl, or tert-butyl; And / or, the structural formula of the specified amine includes , , , At least one of them.

5. The method according to claim 1 or 2, characterized in that: The specified molar ratio of amine and / or ammonia to ester groups in the polyester is 2:1 to 20:

1.

6. The method according to claim 2, characterized in that: The specified temperature is 100~200℃, and the reaction time is 10~48h; And / or, the hydrogen pressure is 20~100 bar.

7. The method according to claim 2, characterized in that: The molar ratio of the ruthenium salt to the ester group in the polyester is 0.001:1 to 0.1:1; And / or, the ruthenium salt comprises one or more combinations of ruthenium acetylacetonate, bis-(2-methylallyl)cyclooctyl-1,5-diene ruthenium, RuH2(CO)(PPh3)2, RuHCl(CO)(PPh3)2, RuHCl(CO)(PCy3)2, Ru(PPh3)3Cl2, dichlorophenylruthenium(II) dimer, dodecyltriruthenium, dichlorobis(4-methylisopropylphenyl)ruthenium(II) dimer, and tris(2,2′-bipyridine)ruthenium(II) chloride; And / or, the molar ratio of the ligand to the ester group in the polyester is 0.0015:1 to 0.15:1; And / or, the structural formula of the ligand is shown in formula (II): ； Formula (II) Among them, Ar includes , , or R'' includes one or more combinations of -H, -Me, -Et, -OMe, -NMe2, t-Bu-, Cy-, -CF3, and -OCF3.

8. The method according to claim 2, characterized in that: The molar ratio of the acid to the ester group in the polyester is 0.005:1 to 0.5:1; And / or, the acid includes one or more combinations of trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imide, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid, aluminum trifluoromethanesulfonate, tetrafluoroboric acid, ferric chloride, aluminum trichloride, and ammonium sulfate; And / or, the organic solvent includes one or more combinations of toluene, o-xylene, p-xylene, mesitylene, cyclohexane, tert-butanol, tert-amyl alcohol, trifluoroethanol, hexafluoroisopropanol, ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, dibutyl ether, methyl tert-butyl ether, and anisole.

9. An amine compound prepared by any one of claims 1 to 8, wherein the amine compound comprises one or more combinations of primary amine compounds, secondary amine compounds, and tertiary amine compounds.

10. The use of the amine compound of claim 9 in the fields of medicine, pesticides or polymer materials.

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