Dye polymer using p-fluorobenzoyl chloride as intermediate

Abstract

The invention provides a dye polymer using p-fluorobenzoyl chloride as an intermediate, and the dye polymer comprises at least one of a red dye polymer, an orange dye polymer and a blue dye polymer, the dye polymer is prepared by polymerizing a sym-triazine monomer containing p-fluorobenzoyl chloride, N-(2-ethoxyl) acrylamide and substituted by an azo chromophoric group and an acrylic monomer. According to the invention, p-fluorobenzoyl chloride is used as a substituent group of 2-amino-4, 6-dichloro-S-triazine, the electron cloud density of carbon atoms on a triazine ring in a 4, 6-dichloro-S-triazine structure is reduced by using the electron withdrawing effect of p-fluorobenzoyl chloride, the nucleophilic substitution activity of 4, 6-dichloro-S-triazine is facilitated, and the yield of the 2-amino-4, 6-dichloro-S-triazine is improved. The N-(2-ethoxyl) acrylamide group and the azo chromophoric group can be successfully grafted, the structure of the macromolecular dye polymer reduces the migration of the dye in a high polymer material, and the introduction of the fluorobenzamide structure can improve the solarization resistance of the dye polymer as a coloring agent in plastics.

Description

Technical Field

[0001] The invention belongs to the technical field of dye synthesis, and in particular 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 appear in a variety of colors such as white, yellow, green, blue, red, and black. They are one of the important additives for modifying plastics. Commonly used colorants in plastics include organic colorants and inorganic colorants. For example, titanium dioxide and carbon black are the dominant white inorganic colorants and black inorganic colorants in the current plastics industry, while colored inorganic colorants include lead-chromium series, cadmium series, iron oxide series, etc., which generally contain heavy metals such as lead, chromium, and cadmium, which are easy to cause environmental pollution and other problems. Therefore, many colored inorganic colorants are being replaced by organic colorants. Organic colorants used in plastics include anthraquinones, azos, phthalocyanines, etc., which are generally small molecular compound structures. When dissolved in plastics, they are easy to migrate to the surface of the plastic or enter another system in contact with the plastic, causing staining or contamination of the mold. Therefore, it is still necessary to develop a low-migration polymeric organic colorant suitable for plastics.

[0003] CN109608903B discloses a reactive dye containing benzenesulfonamide and its derivatives as substitutions and a preparation method thereof, wherein benzenesulfonamide and substituted benzenesulfonamide groups are used to be directly connected to halogenated s-triazine molecules, and their electron-withdrawing effect reduces the electron cloud density of carbon atoms on the triazine ring, making it easy to undergo nucleophilic substitution reactions, so the reactivity of the triazine structure is equivalent to that of ethyl sulfone sulfate aniline. However, the reactive dye prepared in the patent method is applied to fiber dyeing, and belongs to a small molecule dye structure, and the presence of sulfonamide groups in the molecules destroys the planarity of the dye molecules, increases the steric hindrance of the monochloros-triazine reaction group and the material fixation reaction, and reduces the fixation rate of the dye, and ultimately, the introduced substituent structure still needs to be adjusted to improve the utilization rate of the dye. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a dye polymer with p-fluorobenzoyl chloride as an intermediate, wherein the dye polymer is polymerized into a macromolecular polymer dye structure by a triazine monomer containing p-fluorobenzoyl chloride, N-(2-hydroxyethyl)acrylamide and an azo chromophore substituted monomer and an acrylic acid monomer, wherein p-fluorobenzoyl chloride as an intermediate has 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 beneficial to the access of N-(2-hydroxyethyl)acrylamide group and azo chromophore group, and 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 and color fixation effect of the dye polymer.

[0005] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0006] A dye polymer with p-fluorobenzoyl chloride as an intermediate, the dye polymer comprising at least one of a red dye polymer, an orange dye polymer and a blue dye polymer, wherein the red dye polymer, the orange dye polymer and the blue dye are respectively polymerized by monomers 1 to 3 represented by formulas 1 to 3 and acrylic acid monomers:

[0007]

[0008]

[0009] Formula 3.

[0010] Preferably, the molar ratio of the monomers 1 to 3 to acrylic acid is 1:(2 to 5).

[0011] It should be noted that the molar ratio of monomers 1 to 3 to acrylic acid is 1:(2 to 5), which means that the molar ratio of monomer 1 to acrylic acid is 1:(2 to 5); the molar ratio of monomer 2 to acrylic acid is 1:(2 to 5); and the molar ratio of monomer 3 to acrylic acid is 1:(2 to 5).

[0012] The monomers 1 to 3 are formed by condensing the structure shown in Formula 4 with an azo chromophore group:

[0013]

[0014] Specifically, the preparation method of the structure shown in Formula 4 comprises the following steps:

[0015] S1. Under a nitrogen atmosphere, 2-amino-4,6-dichloro-S-triazine is dissolved in tetrahydrofuran, and p-fluorobenzoyl chloride is dissolved in tetrahydrofuran. At 0-5°C, the 2-amino-4,6-dichloro-S-triazine solution is slowly mixed with the p-fluorobenzoyl chloride solution, and the mixture is stirred for 30-90 minutes. An alkaline aqueous solution is added to quench the reaction, and the mixture is extracted with ethyl acetate. The organic layer is collected, dried over magnesium sulfate, filtered, and the filtrate is vacuum concentrated. The concentrate is purified by silica gel column chromatography to obtain reactant 1;

[0016] S2. Under a nitrogen atmosphere, reactant 1 is dissolved in tetrahydrofuran, N-(2-hydroxyethyl)acrylamide is dissolved in tetrahydrofuran, the N-(2-hydroxyethyl)acrylamide solution is added to the reactant 1 solution, and after stirring evenly, N,N-diisopropylethylamine is added as a catalyst, and the solution is stirred at 40-60°C for 10-20 hours. The reaction solution is filtered and concentrated, and the crude product is purified by silica gel column chromatography to obtain the structure shown in Formula 4, which is recorded as reactant 2.

[0017] Preferably, the molar ratio of the 2-amino-4,6-dichloro-S-triazine to p-fluorobenzoyl chloride is 1:(1.02-1.15); the molar ratio of the reactant 1 to N-(2-hydroxyethyl)acrylamide is 1:(1.1-1.2).

[0018] Specifically, the monomer 1 is prepared by first condensing the structure shown in formula 4 with γ-acid and then coupling with diazotized para-ester.

[0019] In a specific embodiment, the preparation method of the monomer 1 comprises the following steps:

[0020] (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 to 5-6, react at 60-80° C. for 3-6 hours to obtain reactant 3, and store at low temperature for later use;

[0021] (2) Add the para-ester diazonium salt solution to the solution of reactant 3 to carry out coupling reaction, adjust the reaction pH to 7-8 with alkaline aqueous solution, control the reaction temperature to 0-5°C for 3-6 hours, adjust the pH to 7 after the reaction, add buffer salt, salt out with potassium acetate solid, filter, wash, and purify to obtain monomer 1.

[0022] Preferably, the molar ratio of the reactant 2 to the γ-acid is 1:(1.1-1.2); the molar ratio of the reactant 3 to the para-ester diazonium salt is 1:(1.02-1.15).

[0023] Specifically, the monomer 2 is prepared by first condensing the structure shown in formula 4 with J-acid and then coupling with diazotized para-ester.

[0024] In a specific embodiment, the preparation method of the monomer 2 comprises the following steps:

[0025] (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 to 5-6, react at 60-80° C. for 3-6 hours to obtain reactant 4, and store at low temperature for later use;

[0026] (2) Add the para-ester diazonium salt solution to the solution of reactant 4 to carry out coupling reaction, adjust the reaction pH to 7-8 with alkaline aqueous solution, control the reaction temperature to 0-5°C for 3-6 hours, adjust the pH to 7 after the reaction, add buffer salt, salt out with potassium acetate solid, filter, wash, and purify to obtain monomer 2.

[0027] Preferably, the molar ratio of the reactant 2 to the 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).

[0028] Specifically, the monomer 3 is first condensed with 2,4-diaminobenzenesulfonic acid to obtain a condensation product, and then the H acid is coupled with the diazotized para-ester, and then the coupled H acid is coupled with the diazotized condensation product for a second time to obtain the product.

[0029] In a specific embodiment, the preparation method of the monomer 3 comprises the following steps:

[0030] (1) adding H-acid monosodium salt to water, adding alkaline aqueous solution to adjust the pH to 6-7 until dissolved, gradually adding the H-acid solution dropwise to the para-ester diazonium salt to carry out coupling reaction, the coupling pH is 1-2, the coupling reaction temperature is 0-5°C, after the coupling reaction is completed, adding alkaline aqueous solution to adjust the reaction pH to neutral, to obtain H-acid para-ester coupling compound;

[0031] (2) Add reactant 2 to an aqueous solution of 2,4-diaminobenzenesulfonic acid, stir evenly, then add N,N-diisopropylethylamine as a catalyst, add an alkaline aqueous solution to control the reaction pH to 5, react at 60-80° C. for 3-5 hours to obtain reactant 5, add sodium nitrite to the reactant 5 solution, add the mixed solution to a rapidly stirred acidic aqueous solution at 0-4° C. containing sufficient concentrated hydrochloric acid, and immediately use Congo red test paper and starch-KI test paper to detect whether hydrochloric acid and nitrous acid are sufficient. After 30-60 minutes, use Ehrlich's reagent to detect the end point of the diazotization reaction. The end point of the diazotization is based on the fact that the reaction solution does not change color when it encounters Ehrlich's reagent. At the end of the diazotization, add an appropriate amount of aminosulfonic acid to the system to destroy excess nitrous acid until the starch-KI test paper does not change color, thereby obtaining the diazotization reactant 5;

[0032] (3) The diazotization reactant 5 is slowly added dropwise to the H acid para-ester coupling compound, and an alkaline aqueous solution is added to adjust the pH to 7. The coupling reaction temperature is controlled to be 0-5°C and the reaction time is 3-6 hours. After the reaction is completed, the pH is adjusted to 7, and a buffer salt is added. Then, the mixture is salted out with potassium acetate solid and filtered, and then the monomer 3 is obtained after washing and purification.

[0033] Preferably, the molar ratio of H-acid monosodium salt to para-ester diazonium salt is 1:(1.02-1.15), the molar ratio of reactant 2 to 2,4-diaminobenzenesulfonic acid is 1:(1.1-1.2), and the molar ratio of diazotization reactant 5 to H-acid para-ester coupling is 1:(0.98-1.2).

[0034] Among them, the diazotization reaction of the para-ester is a prior art, and the preparation method is: add the para-ester solid into water, dissolve it with an alkaline aqueous solution, add sodium nitrite, add the mixed solution into a rapidly stirred acidic aqueous solution containing concentrated hydrochloric acid at 0-4°C, immediately use Congo red test paper and starch-KI test paper to detect whether the hydrochloric acid and nitrous acid are sufficient, use Ehrlich's reagent to detect the end point of the diazotization reaction, and the diazotization end point is based on the reaction solution not changing color when encountering Ehrlich's reagent. At the end of the diazotization, add an appropriate amount of aminosulfonic acid to the system to destroy excess nitrous acid until the starch-KI test paper does not change color, and the product para-ester diazonium salt is placed in an ice bath and stored at low temperature for use.

[0035] Preferably, the alkaline aqueous solution is one or more of a sodium hydroxide aqueous solution, a saturated sodium carbonate aqueous solution and a saturated sodium bicarbonate aqueous solution; the concentration of the sodium hydroxide aqueous solution is 1 to 2 mol / L.

[0036] The present invention also protects a method for preparing the dye polymer, comprising the following reaction steps: in a nitrogen atmosphere, dissolving monomer 1 or monomer 2 or monomer 3 and acrylic acid monomer in an organic solvent, heating to 70-90° C., adding an initiator to initiate a polymerization reaction, stirring at 70-90° C. for 5-10 hours, cooling to terminate the reaction, and purifying after precipitation to obtain a red dye polymer, an orange dye polymer and a blue dye polymer.

[0037] Preferably, the organic solvent is 1,4-dioxane, and the initiator is azobisisobutyronitrile.

[0038] Another object of the present invention is to protect the use of the above dye polymer in a polymer material colorant.

[0039] Beneficial Effects

[0040] Relative to the prior art, the present invention has the following beneficial effects: a dye polymer with a p-fluorobenzoyl chloride intermediate is provided, wherein the dye polymer is polymerized into a macromolecular dye structure by a triazine monomer containing p-fluorobenzoyl chloride, N-(2-hydroxyethyl)acrylamide and an azo chromophoric group and an acrylic monomer, wherein p-fluorobenzoyl chloride is used as an intermediate, and the steric hindrance of the sulfonamide group is smaller and the electron-withdrawing ability is stronger than that in the prior art, and the nucleophilic substitution activity of 4,6-dichloro-S-triazine is improved, and the access of the N-(2-hydroxyethyl)acrylamide group and the azo chromophoric group is facilitated, and 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 and the color fixing effect of the dye polymer. The dye polymer provided by the present invention includes three primary colors of red, orange and blue, and a full color spectrum of dyes can be obtained by adjusting the ratio, and the azo chromophoric body raw material cost is low, the synthesis is simple, the color light is bright, and it is particularly suitable for use as a colorant for plastics. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 The preparation route of reactant 1 and reactant 2 of the present invention;

[0042] Figure 2 This is the preparation route of reactants 3 to 5 of the present invention;

[0043] Figure 3 The preparation routes of monomer 1 and monomer 2 of the present invention are as follows;

[0044] Figure 4 This is the preparation route of monomer 3 of the present invention;

[0045] Figure 5 Infrared spectra of red dye polymer, orange dye polymer and blue dye polymer.

[0046] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only 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 those 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.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians 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.

[0048] In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0049] The raw materials and equipment used in the embodiments and comparative examples are described as follows:

[0050] 2-Amino-4,6-dichloro-S-triazine: CAS: 933-20-0, 98%, purchased from Hubei Kele Fine Chemical Co., Ltd.;

[0051] p-Fluorobenzoyl chloride: CAS: 403-43-0, ≥98%, from Liaoning Xingfu New Materials Co., Ltd.;

[0052] N-(2-Hydroxyethyl)acrylamide: CAS: 7646-67-5, 99%, purchased from Zhongshan Dixin Chemical Co., Ltd.;

[0053] N,N-diisopropylethylamine: CAS: 7087-68-5, 99.5%, purchased from Shanghai Bangcheng Chemical Co., Ltd.;

[0054] γ-acid: CAS: 90-51-7, 99%, purchased from Hubei Yunmei Technology Co., Ltd.;

[0055] J-acid: CAS: 87-02-5, purchased from Wuhan Penglei Biotechnology Co., Ltd.;

[0056] H-acid monosodium salt: CAS: 5460-09-3, 98%, purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd.;

[0057] 2,4-Diaminobenzenesulfonic acid: CAS: 88-63-1, purchased from Wuhan Boye Technology Development Co., Ltd.;

[0058] Para-ester: CAS: 2494-89-5, 99%, purchased from Wuhan Shuer Biotechnology Co., Ltd.;

[0059] Acrylic acid: CAS: 79-10-7, purchased from Shandong Leli New Materials Co., Ltd.;

[0060] Concentrated hydrochloric acid: a hydrochloric acid solution with a mass fraction of 37%;

[0061] Ehrlich's reagent: an acidic ethanol solution of N,N-dimethylaminobenzaldehyde;

[0062] Buffer salt: Na2HPO3-NaH2PO3, pH 6.8-7.2, 1w / v% aqueous solution;

[0063] 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.

[0064] The following is the test method of the performance parameters involved in the present invention:

[0065] (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;

[0066] (2) Fourier transform infrared spectroscopy (FT-IR): The dye polymer was analyzed by FT-IR using a Thermo Nicolet IS10 Fourier transform infrared spectrometer.

[0067] (3) Molecular weight test: The molecular weight and molecular weight distribution coefficient of the dye polymer were determined using gel permeation chromatography (GPC);

[0068] (4) UV-visible absorption spectrum: Using water as solvent, the system was configured to 2×10 -5mol / L dye solution, use a spectrophotometer to measure the UV-vis spectrum of the dye solution, the wavelength range is 280 ~ 700nm, and the wavelength of the peak absorption peak is recorded.

[0069] Example 1

[0070] Preparation of red dye polymer

[0071] S1. Under a nitrogen atmosphere, 1 mole 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, and 1.05 moles of p-fluorobenzoyl chloride was 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, and the reaction was stirred for 30 minutes. A saturated sodium carbonate aqueous solution was added to quench the reaction, and ethyl acetate equivalent to 1.5 times the reaction system was used for extraction three times. The organic layer was collected and dried over magnesium sulfate, filtered, and the filtrate was vacuum concentrated. The concentrate was purified by silica gel column chromatography with a mobile phase of n-hexane:ethyl acetate = 9:1 to obtain reactant 1; yield: 91%, and the nuclear magnetic resonance hydrogen spectrum of reactant 1 1 H-NMR: (500MHz, CDCl3) δ8.00–7.93(m,2H), 7.38–7.31(m,2H);

[0072] S2. Under nitrogen atmosphere, 1 mol of reactant 1 was dissolved in tetrahydrofuran to prepare a 0.1 mol / L solution, 1.1 mol of N-(2-hydroxyethyl)acrylamide was dissolved in tetrahydrofuran to prepare a 0.1 mol / L homogeneous solution, N-(2-hydroxyethyl)acrylamide solution was slowly added to the reactant 1 solution, stirred evenly, and 1 mol of N,N-diisopropylethylamine was added as a catalyst, the solution was stirred at 60°C for 16 hours, the reaction solution was filtered and concentrated, and 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 at a concentration of 10 mol / L and a storage temperature of 2-8°C. The nuclear magnetic resonance hydrogen spectrum of reactant 2 1 HNMR (500MHz, CDCl3): δ8.10(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);

[0073] S3. The reactant 2 obtained in step S2 was diluted to a concentration of 0.1 mol / L by 1 mol, added to 1.1 mol of an aqueous solution of γ-acid, the concentration of the γ-acid solution was 0.1 mol / L, stirred evenly, 1 mol of N,N-diisopropylethylamine was added as a catalyst, saturated sodium carbonate solution was added to control the reaction pH to 5, reacted at 80 ° C for 3 hours, to obtain a reactant 3, stored at low temperature for standby use;

[0074] The preparation method of the para-ester is as follows: weigh 0.1 mol of the para-ester solid and add it to 200 ml of water, adjust the pH to 5-6 with a saturated sodium carbonate solution until it dissolves, add 0.12 mol of sodium nitrite and dissolve it therein, add the mixed solution to a rapidly stirred acidic aqueous solution containing 25 ml of concentrated hydrochloric acid at 0°C, and immediately use Congo red test paper and starch-KI test paper to detect whether the hydrochloric acid and nitrous acid are sufficient, and after 30 minutes, use Ehrlich's reagent to detect the end point of the diazotization reaction. The end point of the diazotization is based on the fact that the reaction solution does not change color when it encounters the Ehrlich's reagent. At the end of the diazotization, add an appropriate amount of aminosulfonic acid to the system to destroy the excess nitrous acid until the starch-KI test paper does not change color, and the product para-ester diazonium salt is placed in an ice bath and stored at low temperature for use;

[0075] S4. Add 1.05 mol of the para-ester diazonium salt solution to 1 mol of the solution of the reactant 3, adjust the reaction pH to 7-8 with a saturated sodium carbonate solution, control the reaction temperature to react for 3 hours at 0°C, adjust the pH to 7 after the reaction, add buffer salt, and then slowly add potassium acetate solid equivalent to 5 wt% of the mass of the reaction system in batches for salting out, detect the appearance of water rings, continue stirring the system for 10 minutes, let the system stand for 30 minutes, then filter, and wash the filter cake with 50 mL of ethanol in batches. The crude product is dissolved and salted out three times to obtain monomer 1, with a yield of 82.5%. The nuclear magnetic resonance hydrogen spectrum of monomer 1 1 H NMR (500MHz, CDCl3): δ8.13(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);

[0076] S5. Dissolve 1 mol of monomer 1 and 2 mol of acrylic acid in 1,4-dioxane, pre-purge with nitrogen for 30 minutes, add 0.005 mol of azobisisobutyronitrile as an initiator, stir and react at 70°C for 5 hours, place in an ice bath to terminate the reaction, precipitate the reaction solution in cold ether, filter, dry, and redissolve in tetrahydrofuran solution. Repeat the precipitation, filtration and drying operations with cold ether three times to obtain a red dye polymer.

[0077] Example 2

[0078] Preparation of Orange Dye Polymer

[0079] Compared with Example 1, the difference is that starting from step S3, γ-acid is replaced by J-acid to obtain reactant 4, and reactant 4 replaces 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; the nuclear magnetic resonance hydrogen spectrum of monomer 2 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);

[0080] Example 3

[0081] Steps S1 and S2 and the preparation method of the para-ester diazonium salt are the same as those in Example 1.

[0082] S3. 1 mole of H-acid monosodium salt was added to water at a concentration ratio of 0.2 mol / L, saturated sodium carbonate solution was added to adjust the pH to 6 until dissolved, the H-acid solution was gradually added dropwise to 1.05 mole of para-ester diazonium salt, slowly added dropwise, the addition time was controlled at 4h, the coupling pH was 1 to 2, the coupling reaction temperature was 0°C, and after the coupling reaction was completed, sodium carbonate solution was added to adjust the reaction pH to neutral to obtain H-acid para-ester coupling compound for standby use;

[0083] S4. Take 1 molar portion of the reactant 2 obtained in step S2 and dilute it to a concentration of 0.1 mol / L, add it to 1.1 molar portions of an aqueous solution of 2,4-diaminobenzenesulfonic acid, the concentration of which is 0.1 mol / L, stir 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 to 5, react at 75°C for 3 hours to obtain reactant 5, add 1.05 moles of 1. The mixed solution is added into a rapidly stirred acidic aqueous solution containing sufficient concentrated hydrochloric acid at 0°C. Immediately use Congo red test paper and starch-KI test paper to detect whether the hydrochloric acid and nitrous acid are sufficient. After 30 minutes, use Ehrlich's reagent to detect the end point of the diazotization reaction. The end point of the diazotization is based on the fact that the reaction solution does not change color when it encounters Ehrlich's reagent. At the end of the diazotization, add an appropriate amount of aminosulfonic acid to the system to destroy the excess nitrous acid until the starch-KI test paper does not change color. The product diazotization reaction product 5 is placed in an ice bath and stored at low temperature for use;

[0084] S5. The reaction solution of the diazotization reactant 5 is slowly added dropwise to the reaction solution of the H acid para-ester coupling compound, at which the molar ratio of the two is about 1:1, and a saturated sodium carbonate solution is added to adjust the pH to 7, and the coupling reaction temperature is controlled to be 0°C. The reaction time is 3 hours. After the reaction is completed, the pH is adjusted to 7, and a buffer salt is added. Then, potassium acetate solid equivalent to 5wt% of the mass of the reaction system is slowly added in batches for salting out. Water rings are detected, and the system is stirred for 10 minutes. After the system is allowed to stand for 30 minutes, it is filtered and the filter cake is washed with 50mL of ethanol in batches. The crude product is dissolved and salted out three times to obtain monomer 3, with a yield of 69.2%; nuclear magnetic resonance hydrogen spectrum of monomer 3 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);

[0085] S6. Dissolve 1 mol of monomer 3 and 2 mol of acrylic acid in 1,4-dioxane, pre-purge with nitrogen for 30 minutes, add 0.005 mol of azobisisobutyronitrile as an initiator, stir and react at 70°C for 5 hours, place in an ice bath to terminate the reaction, precipitate the reaction solution in cold ether, filter, dry, and redissolve in tetrahydrofuran solution. Repeat the precipitation, filtration and drying with cold ether three times to obtain a blue dye polymer.

[0086] Example 4

[0087] Compared with the preparation process of Example 1, the difference is that 1 mol part of monomer 1 and 4 mol parts of acrylic acid are added in step S5.

[0088] Example 5

[0089] Compared with the preparation process of Example 1, the difference is that 1 mol of monomer 1 and 6 mol of acrylic acid are added in step S5.

[0090] Example 6

[0091] Compared with the preparation process of Example 1, the difference is that 1 mol part of monomer 1 and 1 mol part of acrylic acid are added in step S5.

[0092] Comparative Example 1

[0093] Compared with the preparation process of Example 1, the difference is that step S1 is not performed, cyanuric chloride is used to replace reactant 2 in step S2 for reaction, 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%;

[0094] Comparative Example 2

[0095] Compared with the preparation process of Example 1, the difference is that step S5 is not performed, that is, the obtained monomer 1 is not polymerized with acrylic acid and is directly used as a dye;

[0096] Comparative Example 3

[0097] Compared with the preparation process of Example 2, the difference is that step S5 is not performed, that is, the obtained monomer 2 is not polymerized with acrylic acid and is directly used as a dye;

[0098] Comparative Example 4

[0099] Compared with the preparation process of Example 3, the difference is that step S6 is not performed, that is, the obtained monomer 3 is not polymerized with acrylic acid and is directly used as a dye.

[0100] Table 1 Dye properties of Examples and Comparative Examples

[0101]

[0102] The dye polymer or dye of the above embodiment and comparative example was mixed with polypropylene (B8101, Yanshan Petrochemical), the amount of dye added was 1% of polypropylene, and the performance test was performed on a color plate with a smooth surface of 50mm×50mm×1mm size by injection molding. The specific method is as follows:

[0103] (1) Dye migration test: The color plate and the absorber are weighed at a temperature of 23±1°C and a relative humidity of 50±5% with an accuracy of 0.0001g. The absorber is ethylene-vinyl acetate copolymer without adding colorants. The color plate is placed between two absorbers, with the center aligned and placed horizontally. Then, the color plate is placed between two glass plates. A 5kg weight is placed at the center of the glass plate. The color plate is then placed in a heat aging test chamber at 70°C for 240h. The color plate and the absorber are weighed after the test. The weight change before and after the test is calculated. The weight loss of the color plate is taken as the final test result. The L, a, and b values ​​before and after the absorber are measured using the CIELA BD65 10° reflection mode. The total color difference ΔE is calculated as (ΔL 2 +Δa 2 +Δb 2 ) 1 / 2 , where ΔL = L value of the absorbent piece after the test - L value of the absorbent piece before the test, Δa = a value after the absorbent piece test - a value before the absorbent piece test, Δb = b value after the absorbent piece test - b value before the absorbent piece test, ΔE is recorded as level 0 when 0≤ΔE<0.5, 0.5≤ΔE<1 when recorded as level 1, 1≤ΔE<1.5 when recorded as level 2, and ΔE>1.5 when recorded as level 3;

[0104] (2) Test of the sun resistance of dyes: half of the color plate was covered with an opaque cloth sample, and then the color plate was placed under a xenon arc lamp for aging treatment. The spectrum range of the xenon arc lamp includes ultraviolet light, visible light and infrared light with a wavelength greater than 270nm. A filter that filters out infrared radiation was used to prevent the heating effect of the spectrum on the color plate to prevent thermal degradation of the color plate. After 500 hours, the color difference ΔE between the color plate covered with the cloth sample and the color plate not covered with the cloth sample was measured. The color difference detection method was to use CIELABD65 10° reflection mode to measure the L, a, b values ​​before and after the absorber, and calculate the total color difference value ΔE = (ΔL 2 +Δa 2 +Δb 2 ) 1 / 2 , where ΔL = L value of the absorbent sheet after testing - L value of the absorbent sheet before testing, Δa = a value after the absorbent sheet test - a value before the absorbent sheet test, Δb = b value after the absorbent sheet test - b value before the absorbent sheet test.

[0105] Table 2 Test performance of color plates

[0106]

[0107] It can be seen from the data of the embodiments and comparative examples that the dye polymer prepared in the present invention has visible light absorption spectra corresponding to red, orange and blue dyes, has a molecular weight between 8000 and 20000, has good compatibility with high molecular polymers, is not easy to migrate when used as a colorant for high molecular materials, and has a sunlight resistance color difference of less than 0.5, and has good sunlight resistance.

[0108] In Comparative Example 1, p-fluorobenzoyl chloride was not added as a substituent, and the product yield after the reaction of cyanuric chloride and N-(2-hydroxyethyl)acrylamide was lower than the product yield of N-(2-hydroxyethyl)acrylamide and reactant 1, and the sunlight resistance was poor.

[0109] Comparative Examples 2 to 4 are small molecule dyes, which have strong mobility and are likely to cause mold contamination during processing. They also do not meet the mobility requirements of the cosmetics and food industries for additives.

[0110] 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 details in detail, nor do they limit the invention to only the specific embodiments described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can well understand and use the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A dye polymer with p-fluorobenzoyl chloride as an 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, wherein the red dye polymer, the orange dye polymer and the blue dye are respectively polymerized by monomers 1 to 3 shown in formulas 1 to 3 and acrylic acid monomers:

2. The dye polymer according to claim 1, characterized in that The molar ratio of the monomers 1 to 3 to acrylic acid is 1:(2 to 5).

3. The dye polymer according to claim 1, characterized in that The monomers 1 to 3 are formed by condensation of the structure shown in formula 4 and an azo chromophore group:

4. The dye polymer according to claim 3, characterized in that The monomer 1 is prepared by first condensing the structure shown in formula 4 with γ-acid and then coupling with diazotized para-ester.

5. The dye polymer according to claim 3, characterized in that The monomer 2 is prepared by first condensing the structure shown in formula 4 with J-acid and then coupling with diazotized para-ester.

6. The dye polymer according to claim 3, characterized in that 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 the H acid with the diazotized para-ester, and then secondary coupling the coupled H acid with the diazotized condensation product.

7. The method for preparing a dye polymer according to any one of claims 1 to 6, characterized in that: The method comprises the following reaction steps: in a nitrogen atmosphere, dissolving any one of monomers 1 to 3 and acrylic acid monomer in an organic solvent, heating to 70 to 90° C., adding an initiator to initiate a polymerization reaction, stirring at 70 to 90° C. for 5 to 10 hours, cooling to terminate the reaction, and purifying after precipitation to obtain a dye polymer.

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

9. Use of the dye polymer according to any one of claims 1 to 6 as a colorant for polymer materials.

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