Carbene dye containing diaziridine group and preparation method thereof

Abstract

The invention relates to a carbene dye containing diazidinium groups and a preparation method thereof, two or more diazidinium groups are introduced into a carbene dye molecule, and a high-activity carbene intermediate is generated under a heating condition. C-H, N-H or O-H bond insertion cross-linking reaction with fibers can be carried out on the surfaces of various fibers and amorphous areas in the fibers, and accurate dyeing of the fibers is realized by forming covalent bonds. The dye system provided by the invention has excellent dyeing properties, including high fixation rate, good color fastness and wide applicability to various fibers.

Description

Technical Field

[0001] This invention belongs to the field of dyes, and specifically relates to a carbene dye containing a diaziridine group and its preparation method. Background Technology

[0002] Traditional dyes primarily adhere to fiber surfaces through physical adsorption or electrostatic interactions, such as hydrogen bonds, van der Waals forces, and ionic bonds, lacking effective chemical bonding. This results in significant differences in dye affinity between different fibers. This adhesion mechanism not only makes dyeing results highly sensitive to fiber type, limiting its widespread application in multi-component blended fabrics, but also easily leads to uneven dyeing and insufficient fastness. Especially in the dyeing process of natural fibers such as cotton, large amounts of water and chemical auxiliaries are typically required, increasing process complexity and causing serious water pollution and energy consumption burdens. Furthermore, with the continuous emergence of new hydrophobic synthetic fibers such as polyethylene and polypropylene, traditional dyes struggle to penetrate and fix effectively, further exposing their limitations in adaptability and environmental friendliness.

[0003] Research on the application of carbene chemistry in dyeing is limited. In 1979, foreign scholars first synthesized reactive dyes that could generate carbene intermediates under heating conditions and successfully used them for dyeing polypropylene (PP) fibers. However, research in this field has long been restricted. In recent years, some scholars have further developed dyes containing bisacrididine groups, which generate carbenes through thermal activation, achieving anhydrous dyeing of various synthetic fibers. However, these dyes contain only a single carbene-generating group (single reaction site), resulting in low reaction efficiency, insufficient crosslinking and color fixation, and dependence on organolithium reagents (such as n-BuLi) during synthesis, posing safety risks and hindering large-scale application. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a carbene dye containing a diaziridine group and its preparation method, so as to overcome the defects of carbene dyes such as low reaction efficiency, insufficient cross-linking fixation rate, dependence on organolithium reagents in the synthesis process, safety risks, and difficulty in large-scale application.

[0005] This invention provides a carbene dye containing a diaziridine group, wherein the carbene dye comprises at least one of the following compounds: , , .

[0006] The present invention also provides a method for preparing the above-mentioned carbene dye containing a diaziridine group, comprising the following steps: mixing compound a, a dye chromophore containing a polycarboxyl group and 1,8-diazabicycloundec-7-ene in an organic solvent, removing the solvent, and obtaining the carbene dye.

[0007] Compound a is 3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diazidine, and its structural formula is shown below: .

[0008] Preferably, the polycarboxyl-containing dye chromophore is one or more of the following compounds: , , .

[0009] Preferably, when the dye chromophore containing multiple carboxyl groups is I, a carbene dye A containing two diaziridine groups is obtained; when the dye chromophore containing multiple carboxyl groups is II, a carbene dye B containing two diaziridine groups is obtained; and when the dye chromophore containing multiple carboxyl groups is III, a carbene dye C containing three diaziridine groups is obtained.

[0010] Preferably, the organic solvent includes, but is not limited to, acetonitrile.

[0011] Preferably, the molar ratio of 3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diazidine, the polycarboxyl-containing dye chromophore, and 1,8-diazabicycloundec-7-ene is 2-3:1:1-4.

[0012] Preferably, the reaction temperature is 20-50℃ and the reaction time is 5-10 h.

[0013] Furthermore, the reaction is carried out under a protective gas condition; the protective gas is nitrogen.

[0014] Preferably, the reaction is completed by thin-layer chromatography, the solvent is evaporated by rotary evaporator, and the residue is purified by silica gel column chromatography to obtain carbene dye.

[0015] The present invention provides a dyeing material, wherein the dyeing material is a fiber or fabric dyed by the above-mentioned carbene dye containing a diaziridine group.

[0016] Furthermore, the fiber includes one or more of polyethylene fiber, polypropylene fiber, polyester, nylon, cotton, and polyester / spandex blends.

[0017] Preferably, the dyeing method of the dyeing material is as follows: the fiber or fabric is directly dyed in a carbene dye solution and the color is fixed to obtain the dyeing material.

[0018] Furthermore, the solvent of the solution is ethanol; the staining temperature is 70-90 ℃, and the time is 40-100 min; the fixing temperature is 105-160 ℃, and the time is 50-90 min.

[0019] Preferably, the amount of carbene dye used is 1-8% (owf), and the liquor ratio is 25:1.

[0020] The highly reactive carbene intermediate generated by the carbene dye containing diaziridine groups of the present invention under heating conditions can undergo CH, NH, or OH bond insertion crosslinking reactions with fibers on the surface and in the amorphous regions inside the fibers, achieving precise dyeing of fibers through the formation of covalent bonds. This dye system exhibits excellent dyeing properties, including high fixation rate, good color fastness, and wide applicability to a variety of fibers.

[0021] Beneficial effects

[0022] (1) The carbene dye in this invention can be used for dyeing a variety of commonly used fibers such as polyethylene fiber, polypropylene fiber, polyester, nylon, cotton, and polyester / ammonia blends. By reducing or eliminating functional groups such as aliphatic CH bonds, active OH bonds and NH bonds in the dye structure, the possibility of side reactions between the carbene active intermediate and the dye itself is effectively suppressed. Moreover, the introduction of two or more diaziridine groups into the carbene dye molecule can generate more carbene active intermediates under thermal activation conditions compared with the structure containing only a single diaziridine group. This greatly improves the insertion reaction efficiency of carbene with CH, NH and OH bonds in the fiber, and achieves higher covalent crosslinking efficiency and fixation rate.

[0023] (2) The carbene dye in this invention has a moderate molecular weight, which can penetrate into the fiber and thus achieve a high dyeing rate; the dye synthesis process is simple, does not require the use of organic lithium reagents, has good safety, and is suitable for industrial-scale production.

[0024] (3) The carbene dye prepared by the present invention does not require any chemical auxiliaries when applied to textile dyeing process, which effectively reduces water consumption and wastewater discharge in the dyeing process, demonstrating good environmental friendliness and sustainability.

[0025] (4) The dyed fibers obtained by dyeing with the carbene dye of the present invention exhibit excellent color fastness in terms of abrasion resistance, soaping resistance and sublimation resistance. Detailed Implementation

[0026] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0027] The testing standards and methods for dyed fabrics in this invention are as follows: The colorfastness properties of dyed fabrics were determined in accordance with the relevant testing standards promulgated by the International Organization for Standardization (ISO). Specifically, colorfastness to washing was performed in accordance with ISO 105-C03:2010, colorfastness to rubbing was tested according to ISO 105-X12:2001, and colorfastness to sublimation was evaluated using ISO 105-P01:1993.

[0028] The color depth of the fabric was quantitatively analyzed using the Kubelka-Munk theory, and its expression is as follows: K / S=(1-R) 2 / 2R In this equation, K represents the light absorption coefficient, S represents the light scattering coefficient, and R is the reflectance of the sample surface. The optical parameters were acquired using a Datacolor SP 600+ spectrophotometer.

[0029] The following formula is used to evaluate the colorfastness of dyed fabrics: F=(K / S) 1 / (K / S) 0 Where (K / S)0 represents the K / S value of the original dyed fabric without DMSO solution treatment, while (K / S)1 represents the K / S value after DMSO solution treatment.

[0030] Compound a in this invention: Its preparation method is as follows: Triethylamine (3 mol) and iodine (1.2 mol) were added sequentially to a CH₂Cl₂ solution of 3-(4-bromophenyl)-3-(trifluoromethyl)-diazacyclopropane (1 mol). The colored mixture was stirred at 0°C for 2 hours. The mixture was diluted with CH₂Cl₂. The mixture was washed with a saturated aqueous sodium thiosulfate solution. The aqueous layer was re-extracted with CH₂Cl₂ (3 times). The combined organic extracts were dried over sodium sulfate. The combined organic extracts were filtered and concentrated. The residue was purified by silica gel column chromatography using pentane as eluent to give compound a.

[0031] The dye chromophore I containing multiple carboxyl groups in this invention: Its preparation method is as follows: Sodium hydride (2.0 mmol) was dissolved in DMF and stirred at room temperature. 4-Methylaniline (1.0 mol) and 4-fluorobenzonitrile (1.5 mol) were added sequentially to the mixture. The mixture was stirred at 140 °C for 20 h under nitrogen atmosphere, and then precipitated in cold water. The product was filtered, recrystallized, and dried to obtain 4,4′-dicyano-4"-methyltriphenylamine. 4,4′-dicyano-4"-methyltriphenylamine (2 mmol) and potassium hydroxide (40 mmol) were stirred at 100 °C for 60 h in a mixture of 3 mL distilled water and 2 mL ethanol. The solution was cooled, and the pH was adjusted to 3 with dilute hydrochloric acid. The crude product was filtered, thoroughly washed with water, and purified by recrystallization to obtain dye chromophore I.

[0032] The dye chromophore II containing multiple carboxyl groups in this invention: Its preparation method is as follows: 4-Amino-isophthalic acid (25 mmol), 1-nitroanthraquinone (10 mmol), and sodium acetate (15 mmol) were added to 70 mL of nitrobenzene, and the reaction was carried out at 150 °C for 30 hours. The reaction temperature was slowly lowered to room temperature, ethanol was added, and the mixture was stirred overnight. The crystals were filtered and washed with water until neutral to obtain dye chromophore II.

[0033] The dye chromophore III containing multiple carboxyl groups in this invention: Its preparation method is as follows: Tris(p-phenylacrylate)amine (10 mmol) and KOH (30 mmol) were added to a mixed solvent (60 mL) prepared from tetrahydrofuran and distilled water in a volume ratio of 5:1. The mixture was heated at 90 °C for 16 h, and then THF was removed by evaporation under reduced pressure. HCl solution was added to the aqueous phase, and a green solid precipitated. The solid was filtered, dissolved in acetone, dried over anhydrous MgSO4, filtered again, and evaporated to obtain dye chromophore III.

[0034] Example 1

[0035] The preparation method of carbene dye A containing a diaziridine group in this embodiment includes the following steps: 3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diazidine (2.0 g, 7.6 mmol) and polycarboxyl-containing dye chromophore I (1.3 g, 3.8 mmol) were added to acetonitrile (20 ml), followed by 1,8-diazabicycloundec-7-ene (1.4 g, 9.2 mmol). The reaction mixture was stirred at 25 °C for 5 hours under nitrogen protection. The reaction was completed by thin-layer chromatography, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography to obtain yellow carbene dye A.

[0036]

[0037] The NMR information for carbene dye A is as follows: 1 H NMR: (400 MHz, Chloroform-d) δ 8.01-7.98 (m,4H), 7.60-7.58 (m, 4H), 7.43-7.41 (m, 4H), 7.31 – 7.28 (m, 4H), 7.07 – 7.01(m, 4H), 2.35 (s, 3H); 13 C NMR: (100 MHz, Chloroform-d) δ 164.73, 150.19,150.09, 145.99, 135.03, 132.71, 131.66, 131.65, 131.63, 131.61, 129.30,126.83, 126.78, 126.74, 126.69, 125.95, 124.11, 123.80, 122.25, 121.92,121.66, 121.54, 119.52, 28.99, 28.76, 28.46, 28.13, 20.67; 19 F NMR: (400 MHz, Chloroform-d) δ-66.18.

[0038] Carbene dye A was used to dye polyethylene fiber, polypropylene fiber, polyester, nylon, cotton, and polyester / ammonia blended fabrics.

[0039] Taking polyethylene fiber dyeing as an example: Carbene dye A dosage 3% (owf), liquor ratio 25:1, dyeing temperature 90 ℃, time 1 hour, fixing temperature 130 ℃, time 1 hour, after dyeing, rinse the fabric with clean water. Then, conduct a wash resistance test according to AATCC standards.

[0040] Example 2

[0041] The preparation method of carbene dye B containing a diaziridine group in this embodiment includes the following steps: 3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diaziridine (2.0 g, 7.6 mmol) and dye chromophore II containing a polycarboxyl group (1.47 g, 3.8 mmol) are added to acetonitrile (20 ml), and 1,8-diazabicycloundec-7-ene (1.4 g, 9.2 mmol) is added. The reaction mixture is stirred at 25 °C for 5 hours under nitrogen protection. The reaction is confirmed to be complete by thin-layer chromatography, the solvent is evaporated by rotary evaporation, and the residue is purified by silica gel column chromatography to obtain brown carbene dye B.

[0042]

[0043] The NMR information for carbene dye B is as follows: 1 H NMR: (400 MHz, Chloroform-d) δ 10.03 (s, 1H), 8.51-8.49 (t, 1H), 8.10-8.02 (m, 3H), 7.96 – 7.95 (m, 2H), 7.83 – 7.79 (m, 2H), 7.71-7.67 (t, 1H), 7.60 – 7.56 (m, 4H), 7.44-7.42 (t, 2H), 7.28-7.25(m, 4H); 13 C NMR: (100 MHz, Chloroform-d) δ 186.12, 183.20, 164.90, 150.15,143.81, 143.39, 134.78, 134.09, 134.03, 133.94, 133.93, 132.91, 131.68,131.66, 131.65, 131.63, 130.13, 127.87, 127.01, 126.98, 126.83, 126.78,126.74, 126.69, 125.95, 123.80, 122.33, 122.25, 121.91, 121.66, 121.34, 121.25, 119.52, 66.34, 29.06, 28.85, 28.63, 28.41; 19 F NMR: (400 MHz, Chloroform-d) δ -63.81.

[0044] Carbene dye B was used to dye polyethylene fiber, polypropylene fiber, polyester, nylon, cotton, and polyester / spandex blended fabrics. The dyeing method was the same as in Example 1.

[0045] Example 3

[0046] The preparation method of carbene dye C containing a diaziridine group in this embodiment includes the following steps: 3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diaziridine (2.5 g, 11.4 mmol) and dye chromophore III containing a polycarboxyl group (1.5 g, 3.8 mmol) are added to acetonitrile (20 ml), followed by the addition of 1,8-diazabicycloundec-7-ene (2.0 g, 13.68 mmol). The reaction mixture is stirred at 25 °C for 5 hours under nitrogen protection. The reaction is confirmed to be complete by thin-layer chromatography, the solvent is evaporated by rotary evaporation, and the residue is purified by silica gel column chromatography to obtain green carbene dye C.

[0047]

[0048] The NMR information for carbene dye C is as follows: 1 H NMR: (400 MHz, Chloroform-d) δ 7.60-7.59 (d,3H), 7.58-7.57 (m, 6H), 7.56-7.54 (m, 6H), 7.40 – 7.38 (m, 6H), 7.16 – 7.14(t, 6H), 6.45-6.41 (d, 3H); 13 C NMR: (100 MHz, Chloroform-d) δ 165.33, 151.10,147.80, 146.06, 131.68, 131.66, 131.65, 131.63, 129.76, 128.17, 126.93,126.88, 126.83, 126.78, 125.95, 123.80, 122.20, 121.66, 121.47, 119.52,115.78, 28.96, 28.81, 28.55, 28.23; 19 F NMR: (400 MHz, Chloroform-d) δ -66.87.

[0049] Carbene dye C was used to dye polyethylene fiber, polypropylene fiber, polyester, nylon, cotton, and polyester / spandex blended fabrics. The dyeing method was the same as in Example 1.

[0050] The color fastness performance of the dyed fabrics prepared in the above embodiments was evaluated, and the results are shown in Table 1.

[0051] Table 1 Color fastness of dyed fabrics in Examples 1-3

[0052] The dyed fabrics prepared in the above embodiments were tested for K / S value and evaluated for fixation rate. The results are shown in Table 2.

[0053] Table 2. K / S values ​​and fixation rates of dyed fabrics in Examples 1-3

Claims

1. A carbene dye containing a diaziridine group, characterized in that, The carbene dye includes at least one of the following compounds: 、 、 。 2. A method for preparing a carbene dye containing a diaziridine group as described in claim 1, comprising: Compound a, a dye chromophore containing multiple carboxyl groups, and 1,8-diazabicycloundec-7-ene were mixed and reacted in an organic solvent. The solvent was then removed to obtain a carbene dye.

3. The preparation method according to claim 2, characterized in that, Compound a is 3-(4-bromophenyl)-3-(trifluoromethyl)-3H-diazidine, and its structural formula is shown below: The organic solvent is acetonitrile.

4. The preparation method according to claim 2, characterized in that, The polycarboxyl-containing dye chromophore is one or more of the following compounds: 、 、 。 5. The preparation method according to claim 2, characterized in that, The molar ratio of compound a, the polycarboxyl-containing dye chromophore, and 1,8-diazabicycloundec-7-ene is 2-3:1:1-4.

6. The preparation method according to claim 2, characterized in that, The reaction temperature is 20-50℃, and the reaction time is 5-10 h; the reaction is carried out under a protective gas condition; the protective gas is nitrogen.

7. A dyeing material, characterized in that, The dyeing material is a fiber or fabric dyed with a carbene dye containing a diaziridine group as described in claim 1.

8. The dyeing material according to claim 7, characterized in that, The fibers include one or more of polyethylene fibers, polypropylene fibers, polyester, nylon, cotton, and polyester / spandex blends.

9. The dyeing material according to claim 7, characterized in that, The dyeing method for the dyeing material is as follows: the fiber or fabric is directly dyed in a carbene dye solution and the color is fixed to obtain the dyeing material.

10. The dyeing material according to claim 9, characterized in that, The solvent of the solution is ethanol; the dyeing temperature is 70-90 ℃ and the time is 40-100 min; the fixing temperature is 105-160 ℃ and the time is 50-90 min; the amount of carbene dye is 1-8% (owf) and the liquor ratio is 25:1.

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