Anthraquinone disperse dye and preparation method thereof

Abstract

The invention discloses an anthraquinone disperse dye and a preparation method thereof, and relates to the technical field of dyes. When preparing anthraquinone disperse dyes, the present invention first polymerizes 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate, and then terminates with p-hydroxystyrene to obtain a polyurethane prepolymer, and the polyurethane prepolymer and 1,2,3-trimercaptopropane are encapsulated with anthraquinone dyes through interfacial polymerization. The anthraquinone disperse dyes prepared by the present invention have good color fastness and level dyeing properties.

Description

Technical Field

[0001] The invention relates to the technical field of dyes, in particular to an anthraquinone disperse dye and a preparation method thereof. Background Art

[0002] In the dye industry, anthraquinone disperse dyes have attracted much attention due to their bright colors, good light resistance and chemical stability. However, traditional anthraquinone disperse dyes have a small molecular weight and no water-soluble groups in their structure. During use, they require the aid of additives to stably disperse the dyes in water. The finished disperse dyes on the market contain a large amount of additives. During the dyeing process, disperse dyes not only lead to problems such as difficulty in controlling dyeing uniformity and low dye utilization, but also cause a large amount of auxiliary wastewater to enter the water body and cause pollution. Therefore, it is necessary to prepare an anthraquinone disperse dye that can improve dyeing uniformity and dyeing fastness and reduce the use of additives, thereby further improving the performance and application range of disperse dyes. Summary of the invention

[0003] The purpose of the present invention is to provide an anthraquinone disperse dye and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] An anthraquinone disperse dye is obtained by first polymerizing 4,4'-dihydroxybiphenyl, ethylene glycol and isophorone diisocyanate, then blocking with p-hydroxystyrene to obtain a polyurethane prepolymer, and then encapsulating the anthraquinone dye through interfacial polymerization of the polyurethane prepolymer and 1,2,3-trimercaptopropane.

[0006] A method for preparing anthraquinone disperse dyes, the preparation method comprising the following steps:

[0007] (1) Under nitrogen protection, at 70-80°C, 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate were mixed, and then dibutyltin dilaurate and N,N-dimethylformamide were added. After cooling to 30-40°C, p-hydroxystyrene was added at a speed of 300 r / min and stirred for 2-3 hours to obtain a polyurethane prepolymer;

[0008] (2) Weigh the following components: anthraquinone dye, polyurethane prepolymer, N,N-dimethylformamide, polyvinyl alcohol aqueous solution, 1,2,3-trimercaptopropane solution, mix the anthraquinone dye, polyurethane prepolymer and N,N-dimethylformamide, stir for 5-10 minutes to obtain an oil phase, slowly drop the oil phase into the polyvinyl alcohol aqueous solution at a dropping speed of 1 mL / min, use a high-speed shear emulsifier to shear emulsify at a speed of 10000 r / min for 10 minutes, drop 1,2,3-trimercaptopropane solution at a dropping speed of 1 mL / min, after the dropwise addition is completed, heat to 50°C, add azobisisobutyronitrile, stir at a speed of 500 r / min for 2-3 hours, centrifuge and remove the lower precipitate at a centrifugal speed of 5000 r / min for 10 minutes, wash the precipitate with anhydrous ethanol and pure water for 3-4 times respectively, and dry at 30°C for 24 hours to obtain anthraquinone disperse dye.

[0009] As an optimization, the molar ratio of 4,4'-dihydroxybiphenyl, ethylene glycol, isophorone diisocyanate and p-hydroxystyrene in step (1) is 1:4:(5.05-5.1):(2.1-2.2).

[0010] As an optimization, the mass of dibutyltin dilaurate in step (1) is 0.03-0.05 times that of isophorone diisocyanate, and the mass of N,N-dimethylformamide is 50-60 times that of isophorone diisocyanate.

[0011] As an optimization, the amounts of the components in step (2) are as follows: by mass: 1 part of anthraquinone dye, 2-3 parts of polyurethane prepolymer, 50-60 parts of N,N-dimethylformamide, 3-4 parts of polyvinyl alcohol aqueous solution, 5-6 parts of 1,2,3-trimercaptopropane solution, and 0.01-0.03 parts of azobisisobutyronitrile.

[0012] As an optimization, the polyvinyl alcohol aqueous solution in step (2) is prepared by mixing polyvinyl alcohol and pure water at a mass ratio of 1:49 at 75-80° C. for 5-10 minutes.

[0013] As an optimization, the 1,2,3-trimercaptopropane solution in step (2) is prepared by mixing 1,2,3-trimercaptopropane and N,N-dimethylformamide in a mass ratio of 1:(10-12).

[0014] As an optimization, the polyvinyl alcohol model is 1788.

[0015] As an optimization, the general structural formula of the anthraquinone dye in step (2) is:

[0016] Wherein, R is H or Br or OH or OCO2C2H5.

[0017] As an optimization, the chemical bonds generated by the reaction of the phenolic hydroxyl group and the isocyanate group in the polyurethane prepolymer in step (1) will be unblocked at high temperature, and the unblocking mechanism is as follows:

[0018] .

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] In the preparation of anthraquinone disperse dyes, 4,4'-dihydroxybiphenyl, ethylene glycol and isophorone diisocyanate are first polymerized, and then terminated with p-hydroxystyrene to obtain a polyurethane prepolymer. The polyurethane prepolymer and 1,2,3-trimercaptopropane are interfacially polymerized to encapsulate the anthraquinone dye to obtain the anthraquinone disperse dye.

[0021] First, 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate are polymerized, and then capped with p-hydroxystyrene to obtain a double-bond-capped polyurethane prepolymer. The double-bond-capped polyurethane prepolymer and 1,2,3-trimercaptopropane are cross-linked through a click reaction to form microcapsules, while the dye molecules are wrapped inside the capsules. The disperse dyes wrapped in the microcapsules can be evenly dispersed in water without the need for a dispersant, thereby reducing the use of dispersants and improving level dyeing properties.

[0022] Secondly, the linear molecular chain of the polyurethane prepolymer contains carbamate bonds obtained by the reaction of phenolic hydroxyl groups and isocyanate groups, which can be unblocked at high temperatures to regenerate isocyanate groups and phenolic hydroxyl groups. Therefore, during the high-temperature dyeing process of the anthraquinone disperse dye prepared by the present invention, the polyurethane encapsulating the dye will decompose. At this time, the regenerated isocyanate groups can connect to the hydroxyl groups, amino groups on the anthraquinone dye and fabrics containing hydroxyl groups on the surface, such as cotton fabrics, thereby generating a covalent bond between the dye and the fabric, thereby improving the color fastness of the dye. DETAILED DESCRIPTION

[0023] 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, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0024] The model of polyvinyl alcohol used in all the following examples is 1778; the anthraquinone dye used is disperse blue E-BR; the cotton fabric used in the test example is a plain woven pure cotton fabric with a warp and weft density of 133*72 (roots / 10cm) and a size of 30cm*30cm.

[0025] Embodiment 1:

[0026] An anthraquinone disperse dye, the preparation method is as follows:

[0027] (1) Under nitrogen protection, at 80°C, 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate were mixed in a molar ratio of 1:4:5.05, and then 0.03 times the mass of isophorone diisocyanate dibutyltin dilaurate and 50 times the mass of isophorone diisocyanate N,N-dimethylformamide were added. After cooling to 40°C, 2.1 times the molar amount of 4,4'-dihydroxybiphenyl p-hydroxystyrene was added at a speed of 300 r / min and stirred for 3 hours to obtain a polyurethane prepolymer;

[0028] (2) Polyvinyl alcohol and pure water were mixed at 80°C in a mass ratio of 1:49 for 10 minutes to obtain a polyvinyl alcohol aqueous solution; 1,2,3-trimercaptopropane and N,N-dimethylformamide were mixed in a mass ratio of 1:10 to obtain a 1,2,3-trimercaptopropane solution; the following components were weighed: 1 part of anthraquinone dye, 2 parts of polyurethane prepolymer, 50 parts of N,N-dimethylformamide, 3 parts of polyvinyl alcohol aqueous solution, 5 parts of 1,2,3-trimercaptopropane solution, and 0.01 parts of azobisisobutyronitrile; the anthraquinone dye, polyurethane prepolymer, and N,N-dimethylformamide were mixed and stirred for 10 minutes to obtain To the oil phase, slowly drip the oil phase into the polyvinyl alcohol aqueous solution at a dropping speed of 1 mL / min, use a high-speed shear emulsifier to shear emulsify at a speed of 10000 r / min for 10 minutes, add 1,2,3-trimercaptopropane solution at a dropping speed of 1 mL / min, after the addition is completed, heat to 50°C, add azobisisobutyronitrile, stir at a speed of 500 r / min for 3 hours, centrifuge after the reaction is completed and remove the lower precipitate, the centrifugal speed is 5000 r / min, the centrifugal time is 10 minutes, wash the precipitate with anhydrous ethanol and pure water respectively 4 times, and dry at 30°C for 24 hours to obtain anthraquinone disperse dyes.

[0029] Embodiment 2:

[0030] An anthraquinone disperse dye, the preparation method is as follows:

[0031] (1) Under nitrogen protection, at 75°C, 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate were mixed in a molar ratio of 1:4:5.07, and then 0.04 times the mass of isophorone diisocyanate dibutyltin dilaurate and 55 times the mass of isophorone diisocyanate N,N-dimethylformamide were added. After cooling to 35°C, 2.15 times the molar amount of 4,4'-dihydroxybiphenyl p-hydroxystyrene was added at a speed of 300 r / min and stirred for 2.5 hours to obtain a polyurethane prepolymer;

[0032] (2) Polyvinyl alcohol and pure water were mixed at 77°C in a mass ratio of 1:49 for 7 minutes to obtain a polyvinyl alcohol aqueous solution; 1,2,3-trimercaptopropane and N,N-dimethylformamide were mixed in a mass ratio of 1:11 to obtain a 1,2,3-trimercaptopropane solution; the following components were weighed: 1 part of anthraquinone dye, 2.5 parts of polyurethane prepolymer, 55 parts of N,N-dimethylformamide, 3.5 parts of polyvinyl alcohol aqueous solution, 5.5 parts of 1,2,3-trimercaptopropane solution, and 0.02 parts of azobisisobutyronitrile; the anthraquinone dye, polyurethane prepolymer, and N,N-dimethylformamide were mixed and stirred for 7 minutes. The oil phase is obtained, and the oil phase is slowly dripped into the polyvinyl alcohol aqueous solution at a dropping speed of 1 mL / min. A high-speed shear emulsifier is used to shear and emulsify at a speed of 10000 r / min for 10 min. 1,2,3-trimercaptopropane solution is dripped at a dropping speed of 1 mL / min. After the dropping is completed, the temperature is raised to 50°C, azobisisobutyronitrile is added, and the mixture is stirred at a speed of 500 r / min for 2.5 h. After the reaction is completed, the mixture is centrifuged and the lower precipitate is removed. The centrifugal speed is 5000 r / min, and the centrifugal time is 10 min. The precipitate is washed 3 times with anhydrous ethanol and pure water respectively, and dried at 30°C for 24 h to obtain anthraquinone disperse dyes.

[0033] Embodiment 3:

[0034] An anthraquinone disperse dye, the preparation method is as follows:

[0035] (1) Under nitrogen protection, at 70°C, 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate were mixed in a molar ratio of 1:4:5.1, and then 0.05 times the mass of isophorone diisocyanate dibutyltin dilaurate and 60 times the mass of isophorone diisocyanate N,N-dimethylformamide were added. After cooling to 30°C, 2.2 times the molar amount of 4,4'-dihydroxybiphenyl p-hydroxystyrene was added at a speed of 300 r / min and stirred for 2 h to obtain a polyurethane prepolymer;

[0036] (2) Polyvinyl alcohol and pure water were mixed at 75°C in a mass ratio of 1:49 for 5 minutes to obtain a polyvinyl alcohol aqueous solution; 1,2,3-trimercaptopropane and N,N-dimethylformamide were mixed in a mass ratio of 1:12 to obtain a 1,2,3-trimercaptopropane solution; the following components were weighed: 1 part of anthraquinone dye, 3 parts of polyurethane prepolymer, 60 parts of N,N-dimethylformamide, 4 parts of polyvinyl alcohol aqueous solution, 6 parts of 1,2,3-trimercaptopropane solution, and 0.03 parts of azobisisobutyronitrile; the anthraquinone dye, polyurethane prepolymer, and N,N-dimethylformamide were mixed and stirred for 5 minutes to obtain The oil phase is slowly dripped into the polyvinyl alcohol aqueous solution at a dropping speed of 1 mL / min. A high-speed shear emulsifier is used to shear and emulsify for 10 minutes at a speed of 10000 r / min. 1,2,3-trimercaptopropane solution is dripped at a dropping speed of 1 mL / min. After the dropping is completed, the temperature is raised to 50°C, azobisisobutyronitrile is added, and the mixture is stirred at a speed of 500 r / min for 2 hours. After the reaction is completed, the mixture is centrifuged and the lower precipitate is removed. The centrifugal speed is 5000 r / min, and the centrifugal time is 10 minutes. The precipitate is washed 4 times with anhydrous ethanol and pure water respectively, and dried at 30°C for 24 hours to obtain anthraquinone disperse dyes.

[0037] Comparative Example:

[0038] The anthraquinone disperse dye of the comparative example is disperse blue E-BR.

[0039] Test example:

[0040] Test method: The anthraquinone disperse dyes of each embodiment and comparative example were prepared into dye liquor and dyed with cotton fabric using high temperature dyeing method to test the color fastness and levelness of the cotton fabric;

[0041] Color fastness test: The dry rubbing fastness of the dyed cotton fabric was tested according to standard GB / T 3920-2008; the results are shown in Table 1.

[0042] Level dyeing test: First, randomly select 10 points on the surface of the dyed cotton fabric, and use the SF600 colorimeter to measure the (K / S) of the maximum wavelength of these 10 points. λ Values, and then calculate their average value and standard deviation. The smaller the standard deviation, the better the levelness. The calculation formula is as follows:

[0043]

[0044] Where n=10, is the average value, S λ is the standard deviation; the results are shown in Table 1.

[0045] The dye liquor formula is: dye dosage 2% (owf), cotton fabric and dye liquor bath ratio 1:20;

[0046] The high temperature dyeing method is as follows: the initial dyeing temperature is 40°C, the temperature is increased to 140°C at a heating rate of 2°C / min and kept warm for 30 minutes, the temperature is reduced to 60°C at a cooling rate of 3°C / min, and washed with normal temperature water for 15 minutes.

[0047] Table 1

[0048]

[0049] From the comparison of the experimental data of Examples 1 to 3 and the comparative example in Table 1, it can be found that the anthraquinone disperse dyes prepared in the present invention have good level dyeing property and color fastness.

[0050] The standard deviation of Examples 1 to 3 is smaller than that of the comparative example, and the friction fastness is greater than that of the comparative example, indicating that 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate are polymerized and then capped with p-hydroxystyrene to obtain a double-bond-terminated polyurethane prepolymer, and the double-bond-terminated polyurethane prepolymer and 1,2,3-trimercaptopropane are cross-linked through a click reaction to form microcapsules while encapsulating the dye molecules inside the capsules. The disperse dye encapsulated in the microcapsules can be uniformly dispersed in water without the need for a dispersant, thereby improving the level dyeing property;

[0051] Secondly, the linear molecular chain of the polyurethane prepolymer contains carbamate bonds obtained by the reaction of phenolic hydroxyl groups and isocyanate groups, which can be unblocked at high temperatures to regenerate isocyanate groups and phenolic hydroxyl groups. Therefore, during the high-temperature dyeing process of the anthraquinone disperse dye prepared by the present invention, the polyurethane encapsulating the dye will decompose. At this time, the regenerated isocyanate groups can connect to the hydroxyl groups, amino groups on the anthraquinone dye and fabrics containing hydroxyl groups on the surface, such as cotton fabrics, thereby generating a covalent bond between the dye and the fabric, thereby improving the color fastness of the dye.

[0052] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An anthraquinone disperse dye, characterized in that: The anthraquinone disperse dye is prepared by first polymerizing 4,4'-dihydroxybiphenyl, ethylene glycol and isophorone diisocyanate, then end-capping with p-hydroxystyrene to obtain a polyurethane prepolymer, and then encapsulating the anthraquinone dye with the polyurethane prepolymer and 1,2,3-trimercaptopropane through interfacial polymerization. The preparation method of the anthraquinone disperse dye comprises the following steps: (1) Under nitrogen protection, at 70-80°C, 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate were mixed, and then dibutyltin dilaurate and N,N-dimethylformamide were added. After cooling to 30-40°C, p-hydroxystyrene was added at a speed of 300 r / min and stirred for 2-3 hours to obtain a polyurethane prepolymer; (2) Weigh the following components: anthraquinone dye, polyurethane prepolymer, N,N-dimethylformamide, polyvinyl alcohol aqueous solution, 1,2,3-trimercaptopropane solution, mix the anthraquinone dye, polyurethane prepolymer and N,N-dimethylformamide, stir for 5-10 minutes to obtain an oil phase, slowly drop the oil phase into the polyvinyl alcohol aqueous solution at a dropping speed of 1 mL / min, use a high-speed shear emulsifier to shear emulsify at a speed of 10000 r / min for 10 minutes, drop 1,2,3-trimercaptopropane solution at a dropping speed of 1 mL / min, after the dropwise addition is completed, heat to 50°C, add azobisisobutyronitrile, stir at a speed of 500 r / min for 2-3 hours, centrifuge and remove the lower precipitate at a centrifugal speed of 5000 r / min for 10 minutes, wash the precipitate with anhydrous ethanol and pure water for 3-4 times respectively, and dry at 30°C for 24 hours to obtain anthraquinone disperse dye.

2. A method for preparing anthraquinone disperse dyes, characterized in that: The preparation method comprises the following steps: (1) Under nitrogen protection, at 70-80°C, 4,4'-dihydroxybiphenyl, ethylene glycol, and isophorone diisocyanate were mixed, and then dibutyltin dilaurate and N,N-dimethylformamide were added. After cooling to 30-40°C, p-hydroxystyrene was added at a speed of 300 r / min and stirred for 2-3 hours to obtain a polyurethane prepolymer; (2) Weigh the following components: anthraquinone dye, polyurethane prepolymer, N,N-dimethylformamide, polyvinyl alcohol aqueous solution, 1,2,3-trimercaptopropane solution, mix the anthraquinone dye, polyurethane prepolymer and N,N-dimethylformamide, stir for 5-10 minutes to obtain an oil phase, slowly drop the oil phase into the polyvinyl alcohol aqueous solution at a dropping speed of 1 mL / min, use a high-speed shear emulsifier to shear emulsify at a speed of 10000 r / min for 10 minutes, drop 1,2,3-trimercaptopropane solution at a dropping speed of 1 mL / min, after the dropwise addition is completed, heat to 50°C, add azobisisobutyronitrile, stir at a speed of 500 r / min for 2-3 hours, centrifuge and remove the lower precipitate at a centrifugal speed of 5000 r / min for 10 minutes, wash the precipitate with anhydrous ethanol and pure water for 3-4 times respectively, and dry at 30°C for 24 hours to obtain anthraquinone disperse dye.

3. The method for preparing anthraquinone disperse dye according to claim 2, characterized in that: The molar ratio of 4,4'-dihydroxybiphenyl, ethylene glycol, isophorone diisocyanate and p-hydroxystyrene in step (1) is 1:4:(5.05-5.1):(2.1-2.2).

4. The method for preparing anthraquinone disperse dye according to claim 2, characterized in that: In step (1), the mass of dibutyltin dilaurate is 0.03-0.05 times that of isophorone diisocyanate, and the mass of N,N-dimethylformamide is 50-60 times that of isophorone diisocyanate.

5. The method for preparing anthraquinone disperse dye according to claim 2, characterized in that: The amounts of the components in step (2) are as follows: by mass: 1 part of anthraquinone dye, 2-3 parts of polyurethane prepolymer, 50-60 parts of N,N-dimethylformamide, 3-4 parts of polyvinyl alcohol aqueous solution, 5-6 parts of 1,2,3-trimercaptopropane solution, and 0.01-0.03 parts of azobisisobutyronitrile.

6. The method for preparing anthraquinone disperse dye according to claim 2, characterized in that: The polyvinyl alcohol aqueous solution in step (2) is prepared by mixing polyvinyl alcohol and pure water at a mass ratio of 1:49 at 75-80° C. for 5-10 minutes.

7. The method for preparing anthraquinone disperse dye according to claim 2, characterized in that: The 1,2,3-trimercaptopropane solution in step (2) is prepared by mixing 1,2,3-trimercaptopropane and N,N-dimethylformamide in a mass ratio of 1:(10-12).

8. The method for preparing anthraquinone disperse dye according to claim 6, characterized in that: The polyvinyl alcohol model is 1788.

9. The method for preparing anthraquinone disperse dye according to claim 2, characterized in that: The general structural formula of the anthraquinone dye in step (2) is: Wherein, R is H or Br or OH or OCO2C2H5.

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