A dye polymer with a p-fluorobenzoyl chloride intermediate

Abstract

The present invention provides a dye polymer with a p-fluorobenzoyl chloride intermediate. The dye polymer includes at least one of a red dye polymer, an orange dye polymer, and a blue dye polymer. The dye polymer is formed by polymerizing a monomer of p-fluorobenzoyl chloride, N-(2-hydroxyethyl)acrylamide, and a s-triazine monomer substituted with an azo chromophore group and an acrylic monomer. By using p-fluorobenzoyl chloride as a substituent of 2-amino-4,6-dichloro-s-triazine, the present invention utilizes the electron-withdrawing effect of p-fluorobenzamide to reduce the electron cloud density of the carbon atoms on the triazine ring in the 4,6-dichloro-s-triazine structure, which is beneficial to the nucleophilic substitution activity of 4,6-dichloro-s-triazine, enabling the N-(2-hydroxyethyl)acrylamide group and the azo chromophore group to be successfully incorporated. The structure of the macromolecular dye polymer reduces the migration of the dye in the polymer material, and the introduction of the p-fluorobenzamide structure can improve the sun exposure resistance of the dye polymer as a colorant in plastics.

Description

[0001] The present invention belongs to the technical field of dye synthesis, and specifically relates to a dye polymer with p-fluorobenzoyl chloride as an intermediate. Background Art

[0002] Colorants are additives that can change the color of plastics. They can make plastics present various colors such as white, yellow, green, blue, red, black, etc., and are one of the important additives for modified plastics. Commonly used colorants in plastics include organic colorants and inorganic colorants. For example, titanium dioxide and carbon black are currently the dominant white and black inorganic colorants in the plastics industry, while colored inorganic colorants include lead chromate series, cadmium series, iron oxide series, etc., which generally contain heavy metals such as lead, chromium, and cadmium, and are prone to causing environmental pollution problems. Therefore, many colored inorganic colorants are being replaced by organic colorants. Organic colorants applied to plastics include anthraquinone, azo, phthalocyanine, etc., which generally have a small molecule compound structure. When dissolved in plastics, they are prone to migrating to the plastic surface or entering another system in contact with the plastic, causing staining or contaminating the mold. Therefore, there is still a need to develop a polymeric organic colorant with low migration for plastics.

[0003] CN109608903B discloses a reactive dye containing benzene sulfonamide and its derivatives and a preparation method thereof. In this method, benzene sulfonamide and substituted benzene sulfonamide groups are directly connected to the halo-s-triazine molecule, and their electron-withdrawing effect reduces the electron cloud density of the carbon atoms on the triazine ring, making it prone to nucleophilic substitution reactions. Therefore, the reaction activity of this triazine structure is equivalent to that of ethyl sulfone sulfate aniline. However, the reactive dye prepared by this patent method is applied to fiber dyeing, which belongs to a small molecule dye structure. Moreover, the presence of the sulfonamide group in the molecule destroys the planarity of the dye molecule, increases the steric hindrance of the monochloro-s-triazine reactive group's fixation reaction with the material, and reduces the fixation rate of the dye. Finally, the structure of the introduced substituent still needs to be adjusted to improve the utilization rate of the dye. Summary of the Invention

[0004] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a dye polymer with p-fluorobenzoyl chloride as an intermediate. The dye polymer is formed by polymerizing a s-triazine monomer substituted with p-fluorobenzoyl chloride, N-(2-hydroxyethyl) acrylamide, and an azo chromophore group with an acrylic acid monomer into a macromolecular polymer dye structure. Among them, p-fluorobenzoyl chloride is used as an intermediate, which has a smaller steric hindrance and stronger electron-withdrawing ability compared with the sulfonamide group in the prior art, improving the nucleophilic substitution activity of 4,6-dichloro-s-triazine, facilitating the access of N-(2-hydroxyethyl) acrylamide groups and azo chromophore groups. The structure of the dye polymer reduces the migration of the dye in the polymer material, and the introduction of the p-fluorobenzamide structure also improves the sunlight resistance performance and fixation effect of the dye polymer.

[0005] To achieve the object of the present invention, the following technical solutions are adopted in the present invention:

[0006] A dye polymer with p-fluorobenzoyl chloride intermediate, wherein the dye polymer includes at least one of a red dye polymer, an orange dye polymer, and a blue dye polymer, and the red dye polymer, the orange dye polymer, and the blue dye are respectively polymerized from monomers 1 to 3 shown in Formula 1 to Formula 3 and an acrylic monomer:

[0007]

[0008]

[0009] Preferably, the molar ratio of monomers 1 to 3 to acrylic acid is 1:(2 - 5).

[0010] It should be noted that the molar ratio of monomers 1 to 3 to acrylic acid being 1:(2 - 5) here is understood as the molar ratio of monomer 1 to acrylic acid being 1:(2 - 5); the molar ratio of monomer 2 to acrylic acid being 1:(2 - 5); and the molar ratio of monomer 3 to acrylic acid being 1:(2 - 5).

[0011] Monomers 1 to 3 are condensed from the structure shown in Formula 4 and an azo chromophore:

[0012]

[0013] Specifically, the preparation method of the structure shown in Formula 4 includes the following steps:

[0014] S1. Under a nitrogen atmosphere, dissolve 2-amino-4,6-dichloro-s-triazine in tetrahydrofuran, dissolve p-fluorobenzoyl chloride in tetrahydrofuran, and under the condition of 0 - 5 °C, slowly mix the 2-amino-4,6-dichloro-s-triazine solution with the p-fluorobenzoyl chloride solution, stir and react for 30 - 90 min, add an alkaline aqueous solution to quench the reaction, extract with ethyl acetate, collect the organic layer, dry it with magnesium sulfate, filter, concentrate the filtrate under vacuum, and purify the concentrated solution by silica gel column chromatography to obtain reactant 1;

[0015] S2. Under a nitrogen atmosphere, dissolve reactant 1 in tetrahydrofuran, dissolve N-(2-hydroxyethyl)acrylamide in tetrahydrofuran, add the N-(2-hydroxyethyl)acrylamide solution to the reactant 1 solution, stir evenly, add N,N-diisopropylethylamine as a catalyst, stir the solution at 40 - 60 °C for 10 - 20 hours, filter the reaction solution and concentrate it, and purify the crude product by silica gel column chromatography to obtain the structure shown in Formula 4, denoted as reactant 2.

[0016] Preferably, the molar ratio of 2-amino-4,6-dichloro-S-triazine to p-fluorobenzoyl chloride is 1:(1.02 - 1.15); the molar ratio of Reactant 1 to N-(2-hydroxyethyl) acrylamide is 1:(1.1 - 1.2).

[0017] Specifically, Monomer 1 is prepared by first condensing the structure shown in Formula 4 with γ-acid and then coupling it with diazotized p-ester.

[0018] In a specific embodiment, the preparation method of Monomer 1 includes the following steps:

[0019] (1) Add Reactant 2 to an aqueous solution of γ-acid, stir evenly, add N,N-diisopropylethylamine as a catalyst, add an alkaline aqueous solution to control the reaction pH value to 5 - 6, react at 60 - 80 °C for 3 - 6 hours to obtain Reactant 3, and store it at low temperature for later use;

[0020] (2) Add the p-ester diazonium salt solution to the solution of Reactant 3 for coupling reaction, adjust the reaction pH value to 7 - 8 with an alkaline aqueous solution, control the reaction temperature at 0 - 5 °C and react for 3 - 6 hours. After the reaction, adjust the pH to 7, add buffer salts, salt out with solid potassium acetate, filter by suction, wash, and purify to obtain Monomer 1.

[0021] Preferably, the molar ratio of Reactant 2 to γ-acid is 1:(1.1 - 1.2); the molar ratio of Reactant 3 to p-ester diazonium salt is 1:(1.02 - 1.15).

[0022] Specifically, Monomer 2 is prepared by first condensing the structure shown in Formula 4 with J-acid and then coupling it with diazotized p-ester.

[0023] In a specific embodiment, the preparation method of Monomer 2 includes the following steps:

[0024] (1) Add Reactant 2 to an aqueous solution of J-acid, stir evenly, add N,N-diisopropylethylamine as a catalyst, add an alkaline aqueous solution to control the reaction pH value to 5 - 6, react at 60 - 80 °C for 3 - 6 hours to obtain Reactant 4, and store it at low temperature for later use;

[0025] (2) Add the p-ester diazonium salt solution to the solution of Reactant 4 for coupling reaction, adjust the reaction pH value to 7 - 8 with an alkaline aqueous solution, control the reaction temperature at 0 - 5 °C and react for 3 - 6 hours. After the reaction, adjust the pH to 7, add buffer salts, salt out with solid potassium acetate, filter by suction, wash, and purify to obtain Monomer 2.

[0026] Preferably, the molar ratio of the reactant 2 to J-acid is 1:(1.1 - 1.2); the molar ratio of the reactant 4 to the para-ester diazonium salt is 1:(1.02 - 1.15).

[0027] Specifically, the monomer 3 is prepared by first condensing the structure shown in Formula 4 with 2,4-diaminobenzenesulfonic acid to obtain a condensation product, then coupling H-acid with the diazotized para-ester, and then performing a secondary coupling of the coupled H-acid with the diazotized condensation product.

[0028] In a specific embodiment, the preparation method of the monomer 3 includes the following steps:

[0029] (1) Add sodium H-acid monosulfonate to water, adjust the pH to 6 - 7 with an alkaline aqueous solution until dissolved, gradually add the H-acid solution to the para-ester diazonium salt for a coupling reaction, with the coupling pH being 1 - 2 and the coupling reaction temperature being 0 - 5°C. After the coupling reaction ends, add an alkaline aqueous solution to adjust the reaction pH to neutral to obtain the H-acid para-ester conjugate;

[0030] (2) Add the reactant 2 to an aqueous solution of 2,4-diaminobenzenesulfonic acid, stir evenly, add N,N-diisopropylethylamine as a catalyst, add an alkaline aqueous solution to control the reaction pH value to 5, and react at 60 - 80°C for 3 - 5 hours to obtain the reactant 5. Add sodium nitrite to the reactant 5 solution, add this mixed solution to an acidic aqueous solution containing sufficient concentrated hydrochloric acid that is rapidly stirred at 0 - 4°C, and immediately detect whether the hydrochloric acid and nitrous acid are sufficient with Congo red test paper and starch-KI test paper. After 30 - 60 min, detect the end point of the diazotization reaction with Ehrlich's reagent. The end point of the diazotization is based on the reaction solution not changing color when encountering Ehrlich's reagent. When the diazotization ends, add an appropriate amount of sulfamic acid to the system to destroy the excess nitrous acid until the starch-KI test paper just does not change color to obtain the diazotized reactant 5;

[0031] (3) Slowly add the diazotized reactant 5 to the H-acid para-ester conjugate, add an alkaline aqueous solution to adjust the pH to 7, control the coupling reaction temperature to 0 - 5°C, and react for 3 - 6 hours. After the reaction ends, adjust the pH to 7, add a buffer salt, then salt out with potassium acetate solid and filter by suction, wash and purify to obtain the monomer 3.

[0032] Preferably, the molar ratio of sodium H-acid monosulfonate to the para-ester diazonium salt is 1:(1.02 - 1.15), the molar ratio of the reactant 2 to 2,4-diaminobenzenesulfonic acid is 1:(1.1 - 1.2), and the molar ratio of the diazotized reactant 5 to the H-acid para-ester conjugate is 1:(0.98 - 1.2).

[0033] Among them, the diazotization reaction of para-ester is a prior art, and the preparation method is as follows: Add solid para-ester into water, dissolve it with an alkaline aqueous solution, add sodium nitrite, add the mixed solution into an acidic aqueous solution containing concentrated hydrochloric acid that is rapidly stirred at 0-4°C, and immediately detect whether hydrochloric acid and nitrous acid are sufficient with Congo red test paper and starch-KI test paper. Detect the end point of the diazotization reaction with Ehrlich reagent. The end point of diazotization is based on the fact that the reaction solution does not change color when encountering Ehrlich reagent. When the diazotization is completed, add an appropriate amount of sulfamic acid to the system to destroy the excess nitrous acid until the starch-KI test paper just does not change color. The product para-ester diazonium salt is placed in an ice bath and stored at low temperature for later use.

[0034] Preferably, the alkaline aqueous solution is one or several of sodium hydroxide aqueous solution, saturated sodium carbonate aqueous solution and saturated sodium bicarbonate aqueous solution; the concentration of the sodium hydroxide aqueous solution is 1-2 mol / L.

[0035] The present invention also protects the preparation method of the dye polymer, which includes the following reaction steps: In a nitrogen atmosphere, dissolve monomer 1 or monomer 2 or monomer 3 and acrylic monomer in an organic solvent, heat to 70-90°C, and at the same time add an initiator to initiate a polymerization reaction. After stirring at 70-90°C for 5-10 hours, cool to terminate the reaction, and purify after precipitation to obtain red dye polymer, orange dye polymer and blue dye polymer.

[0036] Preferably, the organic solvent is 1,4-dioxane, and the initiator is azobisisobutyronitrile.

[0037] Another object of the present invention is to protect the application of the above dye polymer in a high molecular material colorant.

[0038] Advantageous Effects

[0039] Compared with the prior art, the present invention has the following advantageous effects: It provides a dye polymer with a p-fluorobenzoyl chloride intermediate. The dye polymer is composed of a macromolecular dye structure formed by the polymerization of p-fluorobenzoyl chloride, N-(2-hydroxyethyl)acrylamide and a sym-triazine monomer substituted with an azo chromophore group and an acrylic monomer. Among them, p-fluorobenzoyl chloride is used as an intermediate, which has a smaller steric hindrance and stronger electron-withdrawing ability than the sulfonamide group in the prior art, improves the nucleophilic substitution activity of 4,6-dichloro-S-triazine, is conducive to the access of N-(2-hydroxyethyl)acrylamide group and azo chromophore group, the structure of the dye polymer reduces the migration of the dye in the high molecular material, and the introduction of the p-fluorobenzamide structure also improves the light fastness performance and color fixation effect of the dye polymer. The dye polymer provided by the present invention includes the three primary colors of red, orange and blue, and can obtain dyes of the full chromatogram through the adjustment of the ratio. Moreover, the raw material cost of the azo chromophore is low, the synthesis is simple, and the color is bright, which is particularly suitable for use as a colorant for plastics. Description of the Drawings

[0040] Figure 1 This is the preparation route of Reactant 1 and Reactant 2 of the present invention;

[0041] Figure 2 This is the preparation route of Reactants 3 to 5 of the present invention;

[0042] Figure 3 This is the preparation route of Monomer 1 and Monomer 2 of the present invention;

[0043] Figure 4 This is the preparation route of Monomer 3 of the present invention;

[0044] Figure 5 These are the infrared spectra of the red dye polymer, orange dye polymer, and blue dye polymer.

[0045] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by any person skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and disclosure scope of the present invention.

[0046] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0047] In the embodiments, unless otherwise specified, the experimental methods used are all conventional methods, and the materials, reagents, etc. used, unless otherwise specified, can all be obtained from commercial channels.

[0048] Now, the raw materials and equipment used in the examples and comparative examples are described as follows:

[0049] 2-Amino-4,6-dichloro-S-triazine: CAS: 933-20-0, 98%, purchased from Hubei Kele Fine Chemical Co., Ltd.;

[0050] p-Fluorobenzoyl chloride: CAS: 403-43-0, ≥98%, from Liaoning Xingfu New Materials Co., Ltd.;

[0051] N-(2-Hydroxyethyl)acrylamide: CAS: 7646-67-5, 99%, purchased from Zhongshan Dixin Chemical Co., Ltd.;

[0052] N,N-Diisopropylethylamine: CAS: 7087-68-5, 99.5%, purchased from Shanghai Bangcheng Chemical Co., Ltd.;

[0053] γ-acid: CAS: 90-51-7, 99%, purchased from Hubei Yunmei Technology Co., Ltd.;

[0054] J-acid: CAS: 87-02-5, purchased from Wuhan Penglei Biotechnology Co., Ltd.;

[0055] H-acid monosodium salt: CAS: 5460-09-3, 98%, purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd.;

[0056] 2,4-Diaminobenzenesulfonic acid: CAS: 88-63-1, purchased from Wuhan Boye Technology Development Co., Ltd.;

[0057] Para-ester: CAS: 2494-89-5, 99%, purchased from Wuhan Shuer Biotechnology Co., Ltd.;

[0058] Acrylic acid: CAS: 79-10-7, purchased from Shandong Leli New Materials Co., Ltd.;

[0059] Concentrated hydrochloric acid: a hydrochloric acid solution with a mass fraction of 37%;

[0060] Ehrlich's reagent: an acidic ethanol solution of N,N-dimethylaminobenzaldehyde;

[0061] Buffer salt: Na2HPO3-NaH2PO3, pH 6.8-7.2, 1w / v% aqueous solution;

[0062] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0063] The following is the test method of the performance parameters involved in the present invention:

[0064] (1) H NMR spectrum: Deuterated chloroform was used as solvent to determine the intermediates using FTNMR Digital Nuclear Magnetic Resonance Spectroscopy. 1 H NMR spectra;

[0065] (2) Fourier transform infrared spectroscopy (FT-IR): The dye polymer was analyzed by FT-IR using a Thermo Nicolet IS10 Fourier transform infrared spectrometer.

[0066] (3) Molecular weight test: The molecular weight and molecular weight distribution coefficient of the dye polymer were determined using gel permeation chromatography (GPC);

[0067] (4) UV-visible absorption spectrum: Using water as solvent, the system was configured to 2×10 -5A dye solution with a concentration of [[mol / L]], the UV-vis spectrum of the dye solution was measured using a spectrophotometer, with a wavelength range of 280 - 700 nm, and the wavelength of the absorption peak maximum was recorded.

[0068] Example 1

[0069] Preparation of Red Dye Polymer

[0070] S1. Under a nitrogen atmosphere, 1 molar part of 2-amino-4,6-dichloro-S-triazine was dissolved in tetrahydrofuran to prepare a homogeneous solution with a concentration of 0.1 [[mol / L]]. 1.05 molar parts of p-fluorobenzoyl chloride were dissolved in tetrahydrofuran to prepare a homogeneous solution with a concentration of 0.1 [[mol / L]]. At 0 °C, the 2-amino-4,6-dichloro-S-triazine solution was slowly mixed with the p-fluorobenzoyl chloride solution, stirred for 30 min, and the reaction was quenched by adding saturated aqueous sodium carbonate solution. The mixture was extracted three times with ethyl acetate equivalent to 1.5 times the reaction system volume, and the organic layer was collected, dried with magnesium sulfate, filtered, and the filtrate was concentrated under vacuum. The concentrated solution was purified by silica gel column chromatography with a mobile phase of n-hexane:ethyl acetate = 9:1 to obtain Reactant 1; Yield: 91%, 1H-NMR spectrum of Reactant 1 1 1H-NMR: (500 MHz, CDCl3) δ 8.00–7.93 (m, 2H), 7.38–7.31 (m, 2H);

[0071] S2. Under a nitrogen atmosphere, 1 molar part of Reactant 1 was dissolved in tetrahydrofuran to prepare a 0.1 [[mol / L]] solution. 1.1 molar parts of N-(2-hydroxyethyl)acrylamide were dissolved in tetrahydrofuran to prepare a homogeneous solution with a concentration of 0.1 [[mol / L]]. The N-(2-hydroxyethyl)acrylamide solution was slowly added to the Reactant 1 solution. After stirring evenly, 1 molar part of N,N-diisopropylethylamine was added as a catalyst, and the solution was stirred at 60 °C for 16 hours. The reaction solution was filtered and concentrated. The crude product was purified by silica gel column chromatography with a mobile phase of n-hexane:ethyl acetate = 1:1 to obtain Reactant 2 with a yield of 92%. The monomer was stored in a stock solution in 1,4-dioxane with a concentration of 10 [[mol / L]] at a storage temperature of 2 - 8 °C, 1H-NMR spectrum of Reactant 2 1 1H NMR (500 MHz, CDCl3): δ 8.10 (m, 2H, Ar-H), 7.37 (m, 2H, Ar-H), 6.32 (dd, 1H, CH2=CH), 6.09 (dd, 1H, CH2=CH), 5.70 (dd, 1H, CH2=CH), 4.61 (t, 2H, CH2CH2O), 3.79 (dt, 2H, NHCH2);

[0072] S3. Take 1 molar portion of the reactant 2 obtained in step S2 and dilute it to a concentration of 0.1 mol / L, then add it to an aqueous solution of 1.1 molar portions of γ-acid with a concentration of 0.1 mol / L. After stirring evenly, add 1 molar portion of N,N-diisopropylethylamine as a catalyst, add saturated sodium carbonate solution to control the reaction pH value at 5, and react at 80 °C for 3 hours to obtain reactant 3, which is stored at low temperature for later use;

[0073] The preparation method of para-ester is as follows: Weigh 0.1 mol of para-ester solid and add it to 200 ml of water. Adjust the pH to 5 - 6 with saturated sodium carbonate solution until it dissolves, then add 0.12 mol of sodium nitrite and dissolve it therein. Add this mixed solution to an acidic aqueous solution containing 25 mL of concentrated hydrochloric acid at 0 °C with rapid stirring, and immediately detect whether hydrochloric acid and nitrous acid are sufficient with Congo red test paper and starch-KI test paper. After 30 min, detect the end point of the diazotization reaction with Ehrlich reagent. The end point of diazotization is based on the fact that the reaction solution does not change color when encountering Ehrlich reagent. When the diazotization ends, add an appropriate amount of sulfamic acid to the system to destroy the excess nitrous acid until the starch-KI test paper just does not change color. The para-ester diazonium salt of the product is placed in an ice bath and stored at low temperature for later use;

[0074] S4. Add 1.05 molar portions of the para-ester diazonium salt solution to 1 molar portion of the solution of reactant 3, adjust the reaction pH value to 7 - 8 with saturated sodium carbonate solution, control the reaction temperature at 0 °C and react for 3 hours. After the reaction ends, adjust the pH to 7, add buffer salt, then add solid potassium acetate equivalent to 5 wt% of the mass of the reaction system in batches and slowly for salting out. Detect the appearance of a water ring, continue to stir the system for 10 min, let the system stand for 30 min and then filter by suction, and wash the filter cake with 50 mL of ethanol in several portions. The crude product is purified by dissolving and salting out three times to obtain monomer 1, and the yield is 82.5%. The nuclear magnetic resonance hydrogen spectrum of reactant 3 1 HNMR(500 MHz, CDCl3): δ 8.13(m, 2H, Ar-H), 7.90(dd, 1H, Ar-H); 7.77(dd, 1H, Ar-H), 7.48(s, 1H, Ar-H), 7.39(m, 2H, Ar-H), 7.14 - 7.15(s, 2H, Ar-H), 6.33(dd, 1H, CH2=CH), 6.08(dd, 1H, CH2=CH), 5.72(dd, 1H, CH2=CH), 4.63(t, 2H, CH2CH2O), 3.76(dt, 2H, NHCH2);

[0075] S5. Dissolve 1 mole part of monomer 1 and 2 mole parts of acrylic acid in 1,4 - dioxane. Pre - purge with nitrogen for 30 min, add 0.005 mole part of azobisisobutyronitrile as an initiator, stir and react at 70 °C for 5 hours, terminate the reaction in an ice bath, precipitate the reaction solution in cold ether, filter, dry, redissolve it in a tetrahydrofuran solution, and repeat the operations of precipitation, filtration, and drying with cold ether three times to obtain a red dye polymer.

[0076] Example 2

[0077] Preparation of orange dye polymer

[0078] Compared with Example 1, the difference is that starting from step S3, γ - acid is replaced by J - acid to obtain reactant 4. Reactant 4 is used instead of reactant 3 to obtain monomer 2 with a yield of 80.7%. Monomer 2 is polymerized with acrylic acid to obtain an orange dye polymer; 1H NMR spectrum of reactant 4 1 H NMR(500MHz,CDCl3):δ8.13(m,2H,Ar - H),7.82(m,1H,Ar - H);7.79(m,1H,Ar - H),7.52(s,1H,Ar - H),7.39(m,2H,Ar - H),6.78(s,1H,Ar - H),6.31(dd,1H,CH2=CH),6.09(dd,1H,CH2=CH),5.74(dd,1H,CH2=CH),4.59(t,2H,CH2CH2O),3.68(dt,2H,NHCH2);

[0079] Example 3

[0080] Steps S1 and S2 and the preparation method of para - ester diazonium salt are the same as those in Example 1.

[0081] S3. Add 1 mole part of monosodium H - acid into water according to a concentration ratio of 0.2 mol / L, add saturated sodium carbonate solution to adjust the pH to 6 until it dissolves, gradually drop the H - acid solution into 1.05 mole parts of para - ester diazonium salt, add dropwise slowly, control the dropping time within 4 h, the coupling pH is 1 - 2, the coupling reaction temperature is 0 °C, after the coupling reaction, add sodium carbonate solution to adjust the reaction pH to neutral to obtain the H - acid para - ester conjugate for use.

[0082] S4. Take 1 molar portion of the reactant 2 obtained in step S2 and dilute it to a concentration of 0.1 mol / L, then add it to an aqueous solution of 1.1 molar portions of 2,4-diaminobenzenesulfonic acid with a concentration of 0.1 mol / L. After stirring evenly, add 1 molar portion of N,N-diisopropylethylamine as a catalyst, add an appropriate amount of saturated sodium carbonate solution to control the reaction pH value to 5, react at 75 °C for 3 hours to obtain reactant 5. Add 1.05 molar portions of sodium nitrite to the reactant 5 solution, add this mixed solution to an acidic aqueous solution containing sufficient concentrated hydrochloric acid at 0 °C with rapid stirring, and immediately detect whether hydrochloric acid and nitrous acid are sufficient with Congo red test paper and starch-KI test paper. After 30 min, detect the end point of the diazotization reaction with Ehrlich's reagent. The end point of diazotization is based on the fact that the reaction solution does not change color when encountering Ehrlich's reagent. At the end of diazotization, add an appropriate amount of sulfamic acid to the system to destroy the excess nitrous acid until the starch-KI test paper just does not change color. Place the diazotized reactant 5 in an ice bath for low-temperature storage for later use;

[0083] S5. Slowly drop the reaction solution of the diazotized reactant 5 into the reaction solution of the H-acid para-ester conjugate. At this time, the molar ratio of the two is approximately 1:1. Add saturated sodium carbonate solution to adjust the pH to 7, control the coupling reaction temperature at 0 °C, and the reaction time is 3 hours. After the reaction, adjust the pH to 7, add buffer salts, and then slowly add potassium acetate solid salt equivalent to 5 wt% of the mass of the reaction system in batches for salting out. Detect the appearance of a water ring, continue to stir the system for 10 min, let the system stand for 30 min and then filter by suction, and wash the filter cake with 50 mL of ethanol in several portions. The crude product is purified by dissolving, salting out three times to obtain monomer 3, and the yield is 69.2%; 1H NMR spectrum of reactant 5 1 H NMR(500MHz,CDCl3):δ8.21(m,1H,Ar-H),8.18(m,2H,Ar-H),7.95(m,1H,Ar-H);7.60(s,1H,Ar-H),7.49(dd,1H,Ar-H),7.37(m,2H,Ar-H),6.48(dd,1H,CH2=CH),6.08(dd,1H,CH2=CH),5.76(dd,1H,CH2=CH),4.56(t,2H,CH2CH2O),3.66(dt,2H,NHCH2);

[0084] S6. Dissolve 1 molar portion of monomer 3 and 2 molar portions of acrylic acid in 1,4-dioxane, pre-purge with nitrogen for 30 min, add 0.005 molar portion of azobisisobutyronitrile as an initiator, stir and react at 70 °C for 5 hours, terminate the reaction in an ice bath, precipitate the reaction solution in cold ether, filter, dry, redissolve it in a tetrahydrofuran solution, and repeat the operations of precipitation, filtration and drying with cold ether three times to obtain the blue dye polymer.

[0085] Example 4

[0086] Compared with the preparation process of Example 1, the difference lies in that 1 mole part of monomer 1 and 4 mole parts of acrylic acid are added in step S5.

[0087] Example 5

[0088] Compared with the preparation process of Example 1, the difference lies in that 1 mole part of monomer 1 and 6 mole parts of acrylic acid are added in step S5.

[0089] Example 6

[0090] Compared with the preparation process of Example 1, the difference lies in that 1 mole part of monomer 1 and 1 mole part of acrylic acid are added in step S5.

[0091] Comparative Example 1

[0092] Compared with the preparation process of Example 1, the difference lies in that step S1 is not carried out, and cyanuric chloride is used to react instead of reactant 2 in step S2, and the other steps are the same. The yield of the product after the reaction of cyanuric chloride and N-(2-hydroxyethyl) acrylamide is 72%;

[0093] Comparative Example 2

[0094] Compared with the preparation process of Example 1, the difference lies in that step S5 is not carried out, that is, after monomer 1 is prepared, it is not polymerized with acrylic acid and is directly used as a dye;

[0095] Comparative Example 3

[0096] Compared with the preparation process of Example 2, the difference lies in that step S5 is not carried out, that is, after monomer 2 is prepared, it is not polymerized with acrylic acid and is directly used as a dye;

[0097] Comparative Example 4

[0098] Compared with the preparation process of Example 3, the difference lies in that step S6 is not carried out, that is, after monomer 3 is prepared, it is not polymerized with acrylic acid and is directly used as a dye.

[0099] Table 1 Dye properties of examples and comparative examples

[0100]

[0101] Mix the dye polymers or dyes of the above examples and comparative examples with polypropylene (B8101, Yanshan Petrochemical). The addition amount of the dye is 1% of the polypropylene, and it is injection molded into a smooth-surfaced color plate with a size of 50 mm × 50 mm × 1 mm for performance testing. The specific method is as follows:

[0102] (1) Dye migration test: Weigh the color plate and the absorbent sheet under the conditions of a temperature of 23 ± 1 °C and a relative humidity of 50 ± 5%. The accuracy is up to 0.0001 g. The absorbent sheet is ethylene-vinyl acetate copolymer without adding colorants. Place the color plate between two absorbent sheets, align the centers horizontally, then place it between two glass plates. Place a 5 kg weight at the center of the glass plates, and then place it in a heat aging test chamber at 70 °C for 240 h. Weigh the color plate and the absorbent sheet after the test, calculate the mass change before and after the test, and take the mass lost by the color plate as the final test result; measure the L, a, b values of the absorbent sheet before and after using the CIELAB D65 10° reflection mode, and calculate the total color difference ΔE = (ΔL 2 + Δa 2 + Δb 2 ) 1 / 2 , where ΔL = L value of the absorbent sheet after the test - L value of the absorbent sheet before the test, Δa = a value of the absorbent sheet after the test - a value of the absorbent sheet before the test, Δb = b value of the absorbent sheet after the test - b value of the absorbent sheet before the test. When 0 ≤ ΔE < 0.5, it is recorded as level 0; when 0.5 ≤ ΔE < 1, it is recorded as level 1; when 1 ≤ ΔE < 1.5, it is recorded as level 2; when ΔE > 1.5, it is recorded as level 3;

[0103] (2) Dye sunlight fastness test: Cover half of the color plate with an opaque cloth sample, and then place the color plate under a xenon arc lamp for aging treatment. The spectral range of the xenon arc lamp includes ultraviolet light with a wavelength greater than 270 nm, visible light, and infrared light. Use a filter to remove infrared radiation to prevent the spectral heating effect on the color plate and prevent thermal degradation of the color plate. After taking it out after 500 h, detect the color difference △E between the color plate covered with the cloth sample and the color plate not covered with the cloth sample. The color difference detection method is to measure the L, a, b values of the absorbent sheet before and after using the CIELAB D65 10° reflection mode, and calculate the total color difference ΔE = (ΔL 2 + Δa 2 + Δb 2 ) 1 / 2 , where ΔL = L value of the absorbent sheet after the test - L value of the absorbent sheet before the test, Δa = a value of the absorbent sheet after the test - a value of the absorbent sheet before the test, Δb = b value of the absorbent sheet after the test - b value of the absorbent sheet before the test.

[0104] Table 2 Test performance of the color plate

[0105]

[0106] From the data of the examples and comparative examples, it can be seen that the dye polymer prepared by the present invention has visible light absorption spectra corresponding to dyes of red, orange, and blue. Its molecular weight is between 8000 and 20000, has good compatibility with high molecular polymers, is not prone to migration when used as a colorant for high molecular materials, and the color difference after sunlight exposure is lower than 0.5, showing good sunlight resistance performance.

[0107] In Comparative Example 1, p-fluorobenzoyl chloride was not added as a substituent. The yield of the product after the reaction of cyanuric chloride and N-(2-hydroxyethyl)acrylamide was lower than that of the product of N-(2-hydroxyethyl)acrylamide and Reactant 1, and the sunlight resistance performance was poor.

[0108] Comparative Examples 2-4 are small molecule dyes with strong migration properties, which are likely to cause mold contamination during the processing and do not meet the requirements for the migration properties of additives in industries such as cosmetics and food.

[0109] The applicant declares that the preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principle and practical application of the present invention, so that those skilled in the art can well understand and utilize the present invention. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A dye polymer prepared from p-fluorobenzoyl chloride intermediate, characterized in that, The dye polymer includes at least one of a red dye polymer, an orange dye polymer, and a blue dye polymer. The red dye polymer, the orange dye polymer, and the blue dye are respectively polymerized from monomers 1 to 3 shown in Formulas 1 to 3 and an acrylic acid monomer: The molar ratio of monomers 1 to 3 to acrylic acid is 1:(2 - 5).

2. The dye polymer according to claim 1, wherein Monomers 1 to 3 are condensed from the structure shown in Formula 4 and an azo chromophore:

3. The dye polymer according to claim 2, wherein Monomer 1 is prepared by first condensing the structure shown in Formula 4 with γ-acid and then coupling with diazotized para-ester.

4. The dye polymer according to claim 2, wherein, Monomer 2 is prepared by first condensing the structure shown in Formula 4 with J-acid and then coupling with diazotized para-ester.

5. The dye polymer according to claim 2, wherein Monomer 3 is prepared by first condensing the structure shown in Formula 4 with 2,4-diaminobenzenesulfonic acid to obtain a condensation product, then coupling H-acid with diazotized para-ester, and then secondarily coupling the coupled H-acid with diazotized condensation product.

6. The preparation method of the dye polymer according to any one of claims 1 to 5, characterized in that, It includes the following reaction steps: In a nitrogen atmosphere, any one of monomers 1 to 3 and an acrylic acid monomer are dissolved in an organic solvent, heated to 70 - 90 °C, and at the same time an initiator is added to initiate a polymerization reaction. After stirring at 70 - 90 °C for 5 - 10 hours, the reaction is terminated by cooling, and the dye polymer is obtained after precipitation and purification.

7. The method for preparing the dye polymer according to claim 6, characterized in that, The organic solvent is 1,4-dioxane, and the initiator is azobisisobutyronitrile.

8. The application of the dye polymer prepared from p-fluorobenzoyl chloride intermediate according to any one of claims 1 to 5 in a high molecular material colorant.

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