Bio-based acid dye and preparation method thereof

Abstract

The invention relates to a bio-based anthraquinone acid dye and a preparation method thereof, and belongs to the field of dye chemical industry and textile printing and dyeing. The anthraquinone acid dye containing bio-based amine or bio-based amino acid is simple in preparation method and can be used for dyeing wool fibers. The preparation method specifically comprises the following step: condensing bromamine acid with bio-based amine or bio-based amino acid under the action of a catalyst to obtain the bio-based acid dye. When the acid dye is used for dyeing wool fabrics, relatively high dye-uptake and good leveling property can be obtained, the fastness to washing, the fastness to rubbing, the fastness to light and the like of the fabrics are improved, and each color fastness reaches grade 4 or above. The acid dye disclosed by the invention is simple in preparation method, mild in reaction condition, easily available in raw materials and less in pollution, is a bio-based, green and environment-friendly product, and has dual effects of saving petroleum resources and protecting the environment.

Description

Technical Field

[0001] The present invention belongs to the fields of dye chemical industry and textile printing and dyeing, and relates to an anthraquinone acid dye containing a bio-based amine or a bio-based amino acid and a preparation method thereof. Technical Background

[0002] Acid dyes refer to dyes that contain soluble groups such as sulfonic acid groups (-SO3H), carboxyl groups (-COOH), or hydroxyl groups (-OH) in their molecular structures, can dissociate into anionic pigments in aqueous solutions, and need to be dyed in a neutral to acidic dye bath. According to chemical structures, they can be divided into azo, anthraquinone, triarylmethane, nitroso, etc. Among them, anthraquinone acid dyes are mainly synthesized from bromoamino acid and amine compounds. Bromoamino acid is an important intermediate for synthesizing anthraquinone acid dyes. It undergoes condensation with amine compounds such as aromatic amines and aliphatic amines under the action of a catalyst to obtain acid dyes.

[0003] Patent US2430771A, US2992240A, and patent US2563144A introduce a series of methods for preparing acid dyes using bromoamino acid; patent US2254230A introduces a preparation method for a 4-arylamine-substituted bromoamino acid acid dye, and its structural formula is as follows:

[0004]

[0005] Patent US2615021A introduces an acid dye specially used for wool dyeing, and its preparation method also uses bromoamino acid and various amino-containing compounds for preparation; patent US2870173A introduces a preparation method for preparing a bromoamino acid-structured acid dye by ammonolysis reaction of trisubstituted aniline and bromoamino acid, and its structural formula is as follows:

[0006]

[0007] Among them, Q1 represents an alkyl group or an aromatic ether, and Q2 represents hydrogen, an alkyl group, or an aromatic ether.

[0008] Chinese patents CN102604427A, CN102604411A, CN102604428A, and CN102585552A introduce a series of preparation methods for anthraquinone-structured acid dyes.

[0009] However, the raw materials used in the preparation of the above-mentioned patent acid dyes mainly come from petrochemical industry. Aromatic amine, as one of the raw materials, is toxic and has a slow degradation rate in nature, which will pose a threat to human health and the ecological environment. With the increasing attention of people to the environment and health, green and environmentally friendly acid dyes have received attention, and the development of bio-based acid dyes is of great significance. Bio-based acid dyes use renewable biological resources as raw materials, such as plant straws, lignocellulose, etc., which can effectively reduce the consumption of limited resources and reduce the damage to the ecological environment, in line with the concept of sustainable development. In the production process, the synthesis process of such dyes is relatively green and environmentally friendly, reducing the use and emission of toxic and harmful chemicals. Among them, anthraquinone-based bio-based acid dyes have good biodegradability and can be decomposed by microorganisms in the natural environment, without long-term residues like traditional dyes, thus reducing the potential harm to ecological systems such as soil and water bodies and being conducive to maintaining ecological balance. Summary of the Invention

[0010] The object of the present invention is to provide a bio-based anthraquinone acid dye represented by formula (I) - formula (V) and its preparation method,

[0011]

[0012]

[0013] The specific preparation method of the bio-based anthraquinone acid dye prepared by the present invention is as follows: Bromo acid, sodium carbonate and water are mixed, and then a certain amount of bio-based amine or bio-based amino acid is added, heated to 70 °C, and then a catalyst is added, and the temperature is raised to 100 °C, and kept warm until the reaction end point. The progress of the reaction is monitored by thin layer chromatography (TLC) spotting plate. After the reaction is completed, it is cooled to room temperature and washed with 20% sodium chloride aqueous solution. The filtrate is transferred to a beaker, acidified with hydrochloric acid until no bubbles are generated after adding hydrochloric acid. The acidified solution is filtered again to obtain the crude product. The crude product is purified by recrystallization to obtain the target product. The reaction equation is as follows:

[0014]

[0015] The bio-based amine can be any one of 2-furfurylamine, 1,5-pentanediamine, 1,4-butanediamine, and the bio-based amino acid can be any one of L-lysine and ornithine.

[0016] The catalyst includes copper-based catalysts and iron-based catalysts. The copper-based catalysts can be CuI, CuBr, CuCl, CuSO4, preferably CuI; the iron-based catalysts can be FeSO4, FeCl3, Fe3O4, preferably FeSO4.

[0017] The mass ratio of the copper-based catalyst to the iron-based catalyst is 1:3 - 1:1, preferably 1:1.

[0018] The mass ratio of the total mass of the catalyst to the mass of bromo acid is 1:25 - 1:10.

[0019] Beneficial effects

[0020] (1) The raw materials used in the present invention are bio-derived amines or amino acids, which have the advantages of being cheap, easily available, green and non-toxic.

[0021] (2) Dyeing wool fabrics with the bio-based acid dyes prepared by the present invention can improve the wash fastness, rubbing fastness and light fastness of the fabrics, etc., and at the same time have good leveling property.

[0022] (3) The acid dyes prepared by the present invention can dye wool fibers within 60 minutes, achieving a dyeing rate of more than 99%, saving the dyeing time and reducing the dyeing cost. Description of the drawings

[0023] The embodiments of the present invention will be described in detail with reference to the accompanying drawings, where

[0024] Figure 1 : 1H NMR spectrum of the bio-based acid dye (D1) in Example 1 1 1H NMR spectrum;

[0025] Figure 2 : 1H NMR spectrum of the bio-based acid dye (D2) in Example 2 1 1H NMR spectrum;

[0026] Figure 3 : 1H NMR spectrum of the bio-based acid dye (D3) in Example 3 1 1H NMR spectrum;

[0027] Figure 4 : Comparative diagram of dyeing rate curves. Detailed implementation manners

[0028] In the following examples, the experimental methods are all conventional methods unless otherwise specified; the reagents and materials are all commercially available unless otherwise specified.

[0029] The nuclear magnetic resonance hydrogen spectrum involved in the examples was measured by a Bruker Ascend TM-400 nuclear magnetic resonance hydrogen spectrometer of Bruker Corporation, and the deuterated reagents used were deuterated dimethyl sulfoxide (DMSO-d6) and deuterium oxide.

[0030] Example 1

[0031] Preparation of Bio - based Acid Dye (D1): Bromo - amino acid (19.00 g, 0.05 mol, 1 eq.), 2 - furfurylamine (9.71 g, 0.10 mol, 2 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four - necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.5 g) and ferrous sulfate (0.5 g) as catalysts were added, the temperature was raised to 100 °C, and stirred for 4 h. The reaction process was monitored by thin - layer chromatography plate (the developing agent was n - butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, it was cooled to room temperature and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D1 (15.58 g), and the yield was 65%. 1 H NMR(400MHz, DMSO - d6)δ10.82(s, 1H), 8.28 - 8.19(m, 2H), 7.87(s, 1H), 7.84 - 7.77(m, 2H), 7.63(d, 1H), 6.43(dd, 1H), 6.37(d, 1H), 4.67(d, 2H), 3.50(s, 2H).

[0032] Example 2

[0033] Preparation of Bio - based Acid Dye (D2): Bromo - amino acid (19.00 g, 0.05 mol, 2 eq.), 1,5 - pentanediamine (2.55 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four - necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.5 g) and ferrous sulfate (0.5 g) as catalysts were added, the temperature was raised to 100 °C, and stirred for 4 h. The reaction process was monitored by thin - layer chromatography plate (the developing agent was n - butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, it was cooled to room temperature and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D2 (9.31 g), and the yield was 43%. 1 H NMR(400MHz, DMSO - d6)810.14(s, 2H), 8.25(tt, J = 6.9, 2.7Hz, 4H), 7.83 - 7.78(m, 4H), 7.76(s, 2H), 2.69 - 2.65(m, 4H), 2.33(p, J == 1.9Hz, 2H), 1.73 - 1.66(m, 4H).

[0034] Example 3

[0035] Preparation of bio-based acid dye (D3): Bromo acid (19.00 g, 0.05 mol, 2 eq.), L-lysine (3.66 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then copper iodide (0.5 g) and ferrous sulfate (0.5 g) were added as catalysts, and the temperature was raised to 100 °C and stirred for 4 h. The reaction progress was monitored by thin-layer chromatography spotting plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, it was cooled to room temperature and washed with 20% sodium chloride aqueous solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D3 (5.69 g), and the yield was 25%. 1 H NMR (400 MHz, Deuterium Oxide) δ 10.16 (s, 2H), 8.28 - 8.21 (m, 4H), 7.83 - 7.77 (m, 4H), 7.74 (s, 2H), 5.32 (t, J = 4.8 Hz, 1H), 3.27 - 3.21 (m, 2H), 2.68 (q, J = 1.9 Hz, 2H), 2.33 (q, J = 1.9 Hz, 2H), 2.05 - 1.95 (m, 3H).

[0036] Example 4

[0037] Preparation of bio-based acid dye (D4): Bromo acid (19.00 g, 0.05 mol, 2 eq.), 1,4-butanediamine (2.20 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then copper iodide (0.5 g) and ferrous sulfate (0.5 g) were added as catalysts, and the temperature was raised to 100 °C and stirred for 4 h. The reaction progress was monitored by thin-layer chromatography spotting plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, it was cooled to room temperature and washed with 20% sodium chloride aqueous solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D4 (8.44 g), and the yield was 39%.

[0038] Example 5

[0039] Preparation of bio-based acid dye (D5): Add bromo acid (19.00 g, 0.05 mol, 2 eq.), ornithine (3.30 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heat to 70 °C. Then add copper(I) iodide (0.5 g) and ferrous sulfate (0.5 g) as catalysts, raise the temperature to 100 °C, and stir for 4 h. Monitor the reaction process by thin-layer chromatography plate (the developing agent is n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction is completed, cool to room temperature and wash with 20% aqueous sodium chloride solution (60 mL). Transfer the filtrate to a beaker, acidify it with hydrochloric acid, and a large number of bubbles are generated. Stop adding hydrochloric acid until no more bubbles are generated, and filter the acidified solution again to obtain the crude product. The crude product is purified by recrystallization to obtain the target product D5 (9.33 g), and the yield is 41%.

[0040] Example 6

[0041] Preparation of bio-based acid dye (D6): Add bromo acid (19.00 g, 0.05 mol, 1 eq.), 2-furfurylamine (9.71 g, 0.10 mol, 2 eq.), sodium carbonate (12.0 g) and water (100 mL) into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heat to 70 °C. Then add copper(I) iodide (0.96 g) and ferrous sulfate (0.96 g) as catalysts, raise the temperature to 100 °C, and stir for 4 h. Monitor the reaction process by thin-layer chromatography plate (the developing agent is n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction is completed, cool to room temperature and wash with 20% aqueous sodium chloride solution (60 mL). Transfer the filtrate to a beaker, acidify it with hydrochloric acid, and a large number of bubbles are generated. Stop adding hydrochloric acid until no more bubbles are generated, and filter the acidified solution again to obtain the crude product. The crude product is purified by recrystallization to obtain the target product D6 (13.18 g), and the yield is 55%.

[0042] Example 7

[0043] Preparation of bio-based acid dye (D7): Bromo acid (19.00 g, 0.05 mol, 2 eq.), 1,5-pentanediamine (2.55 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper iodide (0.96 g) and ferrous sulfate (0.96 g) as catalysts were added, the temperature was raised to 100 °C, and the mixture was stirred for 4 h. The reaction progress was monitored by thin-layer chromatography spotting plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D7 (13.42 g), and the yield was 62%.

[0044] Example 8

[0045] Preparation of bio-based acid dye (D8): Bromo acid (19.00 g, 0.05 mol, 2 eq.), L-lysine (3.66 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper iodide (0.96 g) and ferrous sulfate (0.96 g) as catalysts were added, the temperature was raised to 100 °C, and the mixture was stirred for 4 h. The reaction progress was monitored by thin-layer chromatography spotting plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D8 (13.20 g), and the yield was 58%.

[0046] Example 9

[0047] Preparation of bio-based acid dye (D9): Bromo acid (19.00 g, 0.05 mol, 2 eq.), 1,4-butanediamine (2.20 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.96 g) and ferrous sulfate (0.96 g) were added as catalysts, and the temperature was raised to 100 °C, followed by stirring for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction was completed, the mixture was cooled to room temperature and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, generating a large amount of bubbles. The acidified solution was filtered again until no more bubbles were produced after adding hydrochloric acid, and the crude product was obtained. The crude product was purified by recrystallization to obtain the target product D9 (8.01 g) with a yield of 37%.

[0048] Example 10

[0049] Preparation of bio-based acid dye (D10): Bromo acid (19.00 g, 0.05 mol, 2 eq.), ornithine (3.30 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.96 g) and ferrous sulfate (0.96 g) were added as catalysts, and the temperature was raised to 100 °C, followed by stirring for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction was completed, the mixture was cooled to room temperature and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, generating a large amount of bubbles. The acidified solution was filtered again until no more bubbles were produced after adding hydrochloric acid, and the crude product was obtained. The crude product was purified by recrystallization to obtain the target product D10 (6.60 g) with a yield of 29%.

[0050] Example 11

[0051] Preparation of Bio-based Acid Dye (D11): Bromo acid (19.00 g, 0.05 mol, 1 eq.), 2-furanmethanamine (9.71 g, 0.10 mol, 2 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.64 g) and ferrous sulfate (0.64 g) were added as catalysts, and the temperature was raised to 100 °C, and the mixture was stirred for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, and a large amount of bubbles were generated. Until no more bubbles were generated after the addition of hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D11 (11.27 g), and the yield was 47%.

[0052] Example 12

[0053] Preparation of Bio-based Acid Dye (D12): Bromo acid (19.00 g, 0.05 mol, 2 eq.), 1,5-pentanediamine (2.55 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.64 g) and ferrous sulfate (0.64 g) were added as catalysts, and the temperature was raised to 100 °C, and the mixture was stirred for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, and a large amount of bubbles were generated. Until no more bubbles were generated after the addition of hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D12 (12.99 g), and the yield was 60%.

[0054] Example 13

[0055] Preparation of Bio-based Acid Dye (D13): Bromo acid (19.00 g, 0.05 mol, 2 eq.), L-lysine (3.66 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper iodide (0.64 g) and ferrous sulfate (0.64 g) were added as catalysts, the temperature was raised to 100 °C, and stirring was carried out for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D13 (12.06 g), and the yield was 53%.

[0056] Example 14

[0057] Preparation of Bio-based Acid Dye (D14): Bromo acid (19.00 g, 0.05 mol, 2 eq.), 1,4-butanediamine (2.20 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper iodide (0.64 g) and ferrous sulfate (0.64 g) were added as catalysts, the temperature was raised to 100 °C, and stirring was carried out for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D14 (8.01 g), and the yield was 37%.

[0058] Example 15

[0059] Preparation of bio-based acid dye (D15): Bromo acid (19.00 g, 0.05 mol, 2 eq.), ornithine (3.30 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.64 g) and ferrous sulfate (0.64 g) were added as catalysts, and the temperature was raised to 100 °C, and stirred for 4 h. The reaction progress was monitored by thin-layer chromatography spotting plate (the developing agent was n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D15 (9.79 g), and the yield was 43%.

[0060] Example 16

[0061] Preparation of bio-based acid dye (D16): Bromo acid (19.00 g, 0.05 mol, 1 eq.), 2-furfurylamine (9.71 g, 0.10 mol, 2 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.38 g) and ferrous sulfate (0.38 g) were added as catalysts, and the temperature was raised to 100 °C, and stirred for 4 h. The reaction progress was monitored by thin-layer chromatography spotting plate (the developing agent was n-butanol:isopropanol:ethyl acetate:water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large number of bubbles were generated. Until no bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D16 (14.86 g), and the yield was 62%.

[0062] Example 17

[0063] Preparation of Bio-based Acid Dye (D17): Bromo acid (19.00 g, 0.05 mol, 2 eq.), 1,5-pentanediamine (2.55 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.38 g) and ferrous sulfate (0.38 g) were added as catalysts, and the temperature was raised to 100 °C and stirred for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, it was cooled to room temperature and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D17 (10.61 g), and the yield was 49%.

[0064] Example 18

[0065] Preparation of Bio-based Acid Dye (D18): Bromo acid (19.00 g, 0.05 mol, 2 eq.), L-lysine (3.66 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper(I) iodide (0.38 g) and ferrous sulfate (0.38 g) were added as catalysts, and the temperature was raised to 100 °C and stirred for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, it was cooled to room temperature and washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker and acidified with hydrochloric acid, and a large number of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D18 (12.97 g), and the yield was 57%.

[0066] Example 19

[0067] Preparation of Bio-based Acid Dye (D19): Bromo acid (19.00 g, 0.05 mol, 2 eq.), 1,4-butanediamine (2.20 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper iodide (0.38 g) and ferrous sulfate (0.38 g) were added as catalysts, and the temperature was raised to 100 °C, followed by stirring for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large amount of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D19 (10.61 g), and the yield was 49%.

[0068] Example 20

[0069] Preparation of Bio-based Acid Dye (D20): Bromo acid (19.00 g, 0.05 mol, 2 eq.), ornithine (3.30 g, 0.025 mol, 1 eq.), sodium carbonate (12.0 g) and water (100 mL) were successively added into a four-necked flask equipped with a stirrer, a condenser and a thermometer, and heated to 70 °C. Then, copper iodide (0.38 g) and ferrous sulfate (0.38 g) were added as catalysts, and the temperature was raised to 100 °C, followed by stirring for 4 h. The reaction progress was monitored by thin-layer chromatography plate (the developing agent was n-butanol: isopropanol: ethyl acetate: water = 2:4:1:3). After the reaction was completed, the temperature was lowered to room temperature, and it was washed with 20% aqueous sodium chloride solution (60 mL). The filtrate was transferred to a beaker, acidified with hydrochloric acid, and a large amount of bubbles were generated. Until no more bubbles were generated after adding hydrochloric acid, the acidified solution was filtered again to obtain the crude product. The crude product was purified by recrystallization to obtain the target product D20 (7.51 g), and the yield was 33%.

[0070] Performance Detection

[0071] Detection of Dyeing Performance of Wool Fibers:

[0072] (1) Dyeing Process

[0073] The dyeing was carried out on a SC DYER laboratory dyeing machine of Sunshine System Co., Ltd. During the dyeing process, the wool fabric was put into the dye bath, the initial temperature was 40 °C, and it was gradually heated to 98 °C at a rate of 1 °C / min and kept warm for 40 min. After the dyeing was completed, it was washed with water several times to remove the floating color. The fabric was soaked in 2 g / L soap solution at 95 °C for 10 min at a bath ratio of 30:1, then washed thoroughly with water, air-dried at room temperature and subjected to performance detection.

[0074] (2) Dye uptake rate and dye uptake rate curve

[0075] The absorption of dyes by wool fabrics was determined by spectrophotometry. The absorbance of the dye solution before and after dyeing was measured at room temperature using a T600 ultraviolet-visible spectrophotometer. The dye uptake rate (E%) was calculated according to the following formula (1):

[0076]

[0077] where A0 and A1 are the absorbances of the dye solution before and after dyeing (λ max ); n0 and n1 are the dilution factors of the dye solution before and after dyeing, respectively.

[0078] The specific test results of the dye uptake rate are shown in Table 1.

[0079] The dyeing rate curves of the bio-based acid dyes D1, D2, and D3 prepared in the present invention were compared with the traditional acid dye Acid Blue 25 (from Dermacolor) containing the bromoamino acid structure. The specific results are shown in Figure 4 .

[0080] (3) Fastness testing

[0081] The wash fastness was determined with reference to Standard GB / T 3921-2008;

[0082] The rubbing fastness was determined with reference to Standard GB / T 3920-2008;

[0083] The light fastness was determined with reference to Standard GB / T 8427-2019.

[0084] The specific test results are shown in Table 1.

[0085] Table 1 Dye uptake rate and fastness performance testing of dyes

[0086]

[0087] As can be seen from Table 1, after the wool fabric was dyed with the bio-based acid dye prepared in the present invention, it showed excellent dye uptake rate and color fastness. Among them, the dye uptake rate was about 99%, higher than that of two commercial acid dyes (Acid Blue 80, Acid Blue SE), indicating that the bio-based acid dye prepared in the present invention has a high affinity; the rubbing fastness and wash fastness reached above level 4, and the light fastness was about level 7, higher than the fastness values of three commercial acid dyes (Acid Blue 25, Acid Blue 80, Acid Blue SE), fully indicating that the wool fabric has excellent fastness performance after being dyed with this dye and can meet higher usage requirements and quality requirements. From Figure 4It can be seen that the dyeing rates of dyes D1 and D3 in the present invention are consistent with that of commercial dye Acid Blue 25, and when the dyeing time is 60 min, the dye uptake rate reaches over 99%.

[0088] (4) Levelling property test

[0089] Color difference detection method: Color measurement and evaluation were carried out using a Datacolor spectrophotometer. Color measurements were taken at the left, middle, and right positions of the dyed fabric and the average value ΔE was obtained. 0 ≤ ΔE ≤ 0.4 was regarded as excellent, 0.4 < ΔE ≤ 0.8 was regarded as good, 0.8 < ΔE ≤ 1.2 was regarded as medium, and 1.2 < ΔE was regarded as poor. The results are shown in Table 2 below:

[0090] Table 2 Comparison of dye uniformity

[0091] Dye ΔE D1 0.01 D2 0.05 D3 0.03 D4 0.07 D5 0.10 D6 0.06 D7 0.14 D8 0.09 D9 0.06 D10 0.17 D11 0.12 D12 0.19 D13 0.09 D14 0.07 D15 0.06 D16 0.14 D17 0.17 D18 0.16 D19 0.15 D20 0.15 Acid Blue 25 0.20 Acid Blue 80 0.32 Acid Blue SE 0.21

[0092] As can be seen from the content of Table 2, when the bio-based acid dyes D1 - D20 prepared in the present invention are used to dye wool, the ΔE values of the dyed fabrics are in the range of 0 - 4. Compared with three commercial acid dyes (Acid Blue 25, Acid Blue 80, Acid Blue SE), their ΔE values are lower and the dyeing uniformity is better.

Claims

1. A bio-based anthraquinone acid dye is shown as formula (I) to formula (V):

2. The bio-based acid dye as claimed in claim 1, characterized in that its preparation raw materials are bromoamino acid, bio-based amine or bio-based amino acid.

3. The bio-based amine as claimed in claim 2 is any one of 2-furfurylamine, 1,5-pentanediamine, 1,4-butanediamine.

4. The bio-based amino acid as claimed in claim 2 is any one of L-lysine and ornithine.

5. The preparation method of the bio-based acid dye as claimed in claim 1 in formula (I) to formula (V) is: after mixing bromoamino acid, sodium carbonate and water, add a certain amount of bio-based amine or bio-based amino acid, heat to 70 °C, then add a catalyst, raise the temperature to 100 °C, and keep warm until the reaction end point. Use thin layer chromatography (TLC) plate spotting to monitor the reaction process. After the reaction is completed, cool to room temperature and wash with 20% sodium chloride aqueous solution. Transfer the filtrate to a beaker, acidify with hydrochloric acid until no bubbles are generated after adding hydrochloric acid. Filter the acidified solution again to obtain the crude product. The crude product is purified by recrystallization to obtain the target product.

6. The catalyst as claimed in claim 5 includes copper-based catalysts and iron-based catalysts. The copper-based catalysts can be CuI, CuBr, CuCl, CuSO4, preferably CuI; the iron-based catalysts can be FeSO4, FeCl3, Fe3O4, preferably FeSO4.

7. The mass ratio of the copper-based catalyst to the iron-based catalyst as claimed in claim 6 is 1:3 - 1:1, preferably 1:

1.

8. The mass ratio of the total mass of the catalyst as claimed in claim 5 to the mass of bromoamino acid is 1:25 - 1:10.

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