Migration-resistant polyester polymeric dye as well as preparation method and application thereof

Abstract

The invention discloses a migration-resistant polyester polymeric dye as well as a preparation method and application thereof, solvent orange 107 is taken as a parent dye and reacts with diethanol amine under the action of a catalyst to obtain a diethanol amine substituted compound of SO107, namely SO107-DEA, and then the diethanol amine substituted compound of SO107 reacts with toluene-2, 4-diisocyanate to obtain the polyester polymeric dye SO107-TDI, the migration-resistant polyester polymeric dye is obtained by mixing and banburying the polyester polymeric dye SO107-TDI and polyester polyethylene glycol terephthalate (PET), the molecular weight of the migration-resistant polyester polymeric dye is large, migration of the dye in a high polymer material is reduced, the chromaticity is improved, and the migration-resistant polyester polymeric dye has higher stability and migration resistance.

Description

Technical Field

[0001] This invention belongs to the field of macromolecular dye preparation technology, specifically relating to a migration-resistant polyester polymer dye, its preparation method, and its application. Background Technology

[0002] Azo dyes are dyes that contain at least one azo emission group in their chemical structure. They have advantages such as a wide color spectrum, bright colors, and strong coloring ability. At present, they are the most widely used synthetic dyes in the printing and dyeing process of textiles and clothing. They are used for dyeing and printing various natural and synthetic fibers, as well as for coloring paints, plastics, rubber, etc.

[0003] Azo dyes have relatively unstable molecular structures and are prone to decomposition or discoloration under high temperatures. For example, in plastic processing or textile printing and dyeing, high temperatures can cause the chemical bonds in the dyes to break, affecting the stability and durability of the color. Furthermore, some azo dyes may sublimate at high temperatures, further reducing their suitability for high-temperature applications. Azo dyes are also prone to migration during use, especially in contact with organic solvents or under high-temperature conditions, where dye molecules can diffuse from the substrate into other media. This migration not only leads to uneven color distribution but may also pose potential risks to the environment and human health. For instance, under certain conditions, azo dyes can decompose to produce more than 20 carcinogenic aromatic amines. These amines, upon activation, can alter the structure of human DNA, causing disease and inducing cancer. Therefore, azo dyes that release 24 carcinogenic aromatic amines upon reduction have been explicitly banned. Currently, more than 200 azo dyes are explicitly banned.

[0004] Chinese patent CN104559311A discloses a polyazo reactive dye compound and its preparation method. The compound is obtained through diazotization, acid coupling, and basic coupling reactions. When applied to dyeing and printing fiber materials, it exhibits excellent lifting power, dyeing depth, fixation rate, and exhaustion rate. Particularly, it demonstrates outstanding wash fastness and rubbing fastness. It also exhibits good alkali dependence during dyeing, reducing alkali usage to one-third of the conventional amount, and is suitable for low-lime-ratio dyeing, resulting in significant economic and social benefits. However, the reaction is complex and requires multiple diazotization reactions using sodium nitrite. Sodium nitrite poses certain health risks and, under certain conditions, can be converted into a potent carcinogen—nitrosamine. Incomplete removal poses a high safety risk.

[0005] Chinese patent CN115505281A discloses an improved orange acid dye and its preparation method. The method involves reacting C1 Acid Yellow 199, an alkali, and o-toluenesulfonyl chloride, followed by crystallization to obtain the improved original orange acid dye. This improved dye exhibits excellent cold water solubility, solving the problem of poor cold water solubility of the original Acid Orange 67. However, the modified orange acid dye still suffers from low migration resistance.

[0006] In view of the above shortcomings, the present invention proposes a dye with good migration resistance and good high-temperature washing resistance. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides a migration-resistant polyester polymer dye, its preparation method, and its application, thereby improving the migration resistance and high-temperature washing resistance of the polyester polymer dye.

[0008] To achieve the above objectives, the present invention provides a migration-resistant polyester polymer dye, the structural formula of which is shown below, wherein n ranges from 30 to 40:

[0009] SO107-TDI.

[0010] This invention also provides a method for preparing migration-resistant polyester polymer dyes, which is achieved through the following method: ; The preparation method includes the following steps: (1) Dissolve the parent dye and cesium carbonate in a mixed solvent, add diethanolamine, heat the reaction and react. Monitor the reaction progress by TLC. After the reaction is complete, use a rotary evaporator to dry the reaction solution, add 100 mL of water, stir at room temperature for 10 min and then perform precipitation treatment at 0℃. After that, filter the reaction solution and repeat the operation three times to obtain the diethanolamine-substituted compound of SO107, namely SO107-DEA.

[0011] SO107-DEA (2) After dissolving SO107-DEA, add toluene-2,4-diisocyanate under inert gas protection, raise the temperature to 100-120℃, monitor the reaction process by TLC, and wait until the starting material spot disappears and the reaction solution becomes viscous and basically non-flowable. Add deionized water to the reaction solution, filter and wash repeatedly three times to obtain solid reactants, and then dry them in a 70℃ oven to obtain polyester polymer dye SO107-TDI. (3) The polyester polymer dye SO107-TDI is mixed with PET, kneaded and pressed into tablets to obtain a migration-resistant polyester polymer dye.

[0012] Preferably, the molar ratio of the parent dye to cesium carbonate and diethanolamine in step (1) is 1:0.5~2:0.5~4.

[0013] More preferably, the parent dye is Solvent Orange 107.

[0014] Preferably, the mixed solvent in step (1) is a mixture of N,N-dimethylformamide and acetonitrile in a volume ratio of 1:2~5; the heating reaction conditions are 80~110℃ for 10~12h.

[0015] Preferably, the molar ratio of SO107-DEA to toluene-2,4-diisocyanate in step (2) is 1:1~3; the heating reaction is carried out at 80~120℃ for 24h.

[0016] Preferably, the solvent used to dissolve SO107-DEA in step (2) is N,N-dimethylformamide.

[0017] Preferably, the mass ratio of the polyester polymer dye to PET in step (3) is 0.5~2:100.

[0018] Preferably, the mixing temperature in step (3) is 250~270℃, the tableting temperature is 250~270℃, and the pressure is 5~10MPa.

[0019] This invention also provides the application of migration-resistant polyester polymer dyes in polymer material colorants.

[0020] The beneficial effects of this invention are as follows: Solvent Orange 107 molecules are modified into a high molecular weight polyester polyamide dye, which is more compatible with polymers such as PET. This high molecular weight dye has good migration resistance in PET films and can withstand high temperatures of 265°C. When mixed and kneaded with polymers such as PET, it can be used to prepare a dye suitable for plastic processing and textile printing and dyeing processes, and the stability and color uniformity of the dye can be avoided by high temperatures.

[0021] This invention involves fewer synthesis steps, requiring only two steps to obtain the final polymer dye, which greatly saves costs. Furthermore, the resulting substance has high migration resistance, allowing for better color stability in subsequent product applications.

[0022] This invention utilizes common industrial dye solvents such as Orange 107, toluene 2,4-diisocyanate, tetrahydrofuran, and N,N-dimethylformamide to prepare dyes. These substances are inexpensive and readily available. Furthermore, the preparation steps are simple, which can greatly save costs and is suitable for large-scale industrial production. Attached Figure Description

[0023] Figure 1This is the chemical structural diagram of SO107-DEA.

[0024] Figure 2 This is the chemical structural diagram of the polyester polymer dye SO107-TDI.

[0025] Figure 3 This is a schematic diagram of the preparation reaction of the polyester polymer dye SO107-TDI.

[0026] Figure 4 The mass spectrum of SO107-DEA prepared in Example 1 is shown.

[0027] Figure 5 The molecular weight distribution diagram of the polyester polymer dye SO107-TDI prepared in Example 1 is shown.

[0028] Figure 6 The images show actual photos of PET films obtained by the method of Example 14 for the monomer dye SO107 after boiling. The left image shows the PET film for the monomer dye before boiling, and the right image shows the PET film for the monomer dye after boiling.

[0029] Figure 7 The images show the actual products of the migration-resistant polyester polymer dyes obtained by the method in Example 17 after boiling in water. The left image shows the PET film of the polyester dyes before boiling, and the right image shows the PET film of the polyester dyes after boiling.

[0030] Figure 8 The image shows a color comparison of the solutions of PET films obtained by the monomer dye SO107 after boiling in water for 6 hours, 12 hours, 18 hours, and 24 hours, obtained by the method in Example 14. From left to right, the images show the solution before boiling, after boiling for 6 hours, 12 hours, 18 hours, and 24 hours.

[0031] Figure 9 The image shows a color comparison of the solutions of the migration-resistant polyester polymer dye prepared in Example 1 by the method of Example 14 after boiling in water for 6 hours, 12 hours, 18 hours, and 24 hours. From left to right, the images show the solutions before boiling, after boiling for 6 hours, 12 hours, 18 hours, and 24 hours. Detailed Implementation

[0032] The technical solution of the present invention will be further explained and described below with reference to the accompanying drawings and specific embodiments. It is worth noting that the following embodiments are only preferred embodiments of the present invention and should not be construed as limiting the present invention. The scope of protection of the present invention should be determined by the contents of the claims. Modifications and substitutions made by those skilled in the art to the technical solution of the present invention without creative effort all fall within the scope of protection of the present invention.

[0033] Example 1 (1) Dissolve 1 mmol of Solvent Orange 107 and 1 mmol of Cesium carbonate in 8 mL of mixed solvent (DMF:THF volume ratio of 1:3), add 1.1 mmol of diethanolamine (4 mol / L), stir at 90 °C for 12 h, after the reaction is complete, evaporate the reaction solution to dryness as much as possible using a rotary evaporator, add 100 mL of water, stir at room temperature for 10 min, and then perform precipitation treatment at 0 °C. Afterwards, filter the reaction solution repeatedly three times to obtain the diethanolamine-substituted compound of SO107, namely SO107-DEA. Figure 1 ), yield 75%; (2) Dissolve 1 mmol SO107-DEA in 2 mL N,N-dimethylformamide (DMF), and add a mixture of 1 mmol toluene 2,4-diisocyanate and 1 mL DMF under nitrogen protection. Stir at 120 °C for 12 h. Monitor the reaction progress by TLC. When the starting material spot disappears and the reaction solution becomes viscous (basically non-flowable), add deionized water to the reaction solution, filter and wash repeatedly three times. After obtaining the solid reactant, dry it in a 70 °C oven to obtain the heterocyclic polyester polymer dye SO107-TDI. Figure 2-3 The range of n is 27~38. Figure 4-5 ).

[0034] Table 1. Molecular weight statistics of migration-resistant polyester polymer dyes

[0035] Example 2 The method and steps are the same as in Example 1, except that the molar ratio of solvent Orange 107, cesium carbonate and diethanolamine in step (1) is changed to 1:1:1.5 to prepare diethanolamine-substituted compounds of SO107 with a yield of 72%.

[0036] Example 3 The method and steps are the same as in Example 1, except that the molar ratio of solvent Orange 107, cesium carbonate and diethanolamine in step (1) is changed to 1:1:2 to prepare diethanolamine-substituted compounds of SO107 with a yield of 70%.

[0037] Example 4 The method and steps are the same as in Example 1, except that the molar ratio of solvent Orange 107, cesium carbonate and diethanolamine in step (1) is changed to 1:1.5:1.1 to prepare diethanolamine-substituted compounds of SO107 with a yield of 68%.

[0038] Example 5 The method and steps are the same as in Example 1, except that the molar ratio of solvent Orange 107, cesium carbonate and diethanolamine in step (1) is changed to 1:2:1.1 to prepare diethanolamine-substituted compounds of SO107 with a yield of 70%.

[0039] Example 6 The method and steps are the same as in Example 1, except that the molar ratio of solvent Orange 107, cesium carbonate and diethanolamine in step (1) is changed to 1:0.5:1.1 to prepare diethanolamine-substituted compounds of SO107 with a yield of 66%.

[0040] Comparative Example 1 The method and steps are the same as in Example 1, except that the molar ratio of solvent Orange 107, cesium carbonate and diethanolamine in step (1) is changed to 1:1:0.5 to prepare diethanolamine-substituted compounds of SO107 with a yield of 43%.

[0041] Comparative Example 2 The method and steps are the same as in Example 1, except that the molar ratio of solvent Orange 107, cesium carbonate and diethanolamine in step (1) is changed to 1:1:5 to prepare diethanolamine-substituted compounds of SO107 with a yield of 65%.

[0042] Example 7 The method and steps are the same as in Example 1, except that the reaction conditions in step (1) are changed to stirring at 100°C for 10 h to prepare the diethanolamine-substituted compound of SO107 with a yield of 75%.

[0043] Example 8 The method and steps are the same as in Example 1, except that the reaction conditions in step (1) are changed to stirring at 110°C for 10 h to prepare the diethanolamine-substituted compound of SO107 with a yield of 70%.

[0044] Example 9 The method and steps are the same as in Example 1, except that the reaction conditions in step (1) are changed to stirring at 80°C for 10 h to prepare the diethanolamine-substituted compound of SO107 with a yield of 72%.

[0045] Comparative Example 3 The method and steps are the same as in Example 1, except that the reaction conditions in step (1) are changed to stirring at 70°C for 12 hours to prepare the diethanolamine-substituted compound of SO107 with a yield of 55%.

[0046] Comparative Example 4 The method and steps are the same as in Example 1, except that the reaction conditions in step (1) are changed to stirring at 120°C for 10 h to prepare the diethanolamine-substituted compound of SO107 with a yield of 58%.

[0047] Example 10 The method and steps are the same as in Example 1, except that cesium carbonate in step (1) is replaced with potassium carbonate, and the reaction does not occur.

[0048] Example 11 The method and steps are the same as in Example 1, except that cesium carbonate in step (1) is replaced with triethylamine, and the reaction does not occur.

[0049] Example 12 The method and steps are the same as in Example 1, except that the molar ratio of SO107-DEA and toluene 2,4-diisocyanate in step (2) is changed to 1:2 to obtain the heterocyclic polyester polymer dye SO107-TDI, and the degree of polymerization range n is changed to 25~31.

[0050] Example 13 The method and steps are the same as in Example 1, except that the molar ratio of SO107-DEA and toluene 2,4-diisocyanate in step (2) is changed to 1:3 to obtain the heterocyclic polyester polymer dye SO107-TDI, and the degree of polymerization range n is changed to 25~33.

[0051] Comparative Example 5 The method and steps are the same as in Example 1, except that the molar ratio of SO107-DEA and toluene 2,4-diisocyanate in step (2) is changed to 1:0.5 to obtain the heterocyclic polyester polymer dye SO107-TDI, with the degree of polymerization range n changing to 15~22.

[0052] Comparative Example 6 The method and steps are the same as in Example 1, except that the molar ratio of SO107-DEA and toluene 2,4-diisocyanate in step (2) is changed to 1:3.5 to obtain the heterocyclic polyester polymer dye SO107-TDI, with the degree of polymerization range n changed to 25-28.

[0053] Example 14 The method and steps are the same as in Example 1, except that the polymerization conditions in step (2) are changed to stirring at 80°C for 24 hours to prepare the heterocyclic polyester polymer dye SO107-TDI, and the degree of polymerization range n is changed to 18-21.

[0054] Example 15 The method and steps are the same as in Example 1, except that the polymerization conditions in step (2) are changed to stirring at 100°C for 24 hours to prepare the heterocyclic polyester polymer dye SO107-TDI, and the degree of polymerization range n is changed to 22-25.

[0055] Comparative Example 7 The method and steps are the same as in Example 1, except that the polymerization conditions in step (2) are changed to stirring at 70°C for 24 hours to prepare the heterocyclic polyester polymer dye SO107-TDI, and the degree of polymerization range n is changed to 11-13.

[0056] Comparative Example 8 The method and steps are the same as in Example 1, except that the polymerization conditions in step (2) are changed to stirring at 130°C for 24 hours to prepare the heterocyclic polyester polymer dye SO107-TDI, with the degree of polymerization range n changed to 15-19.

[0057] Example 16 Take 10 mg of the heterocyclic polyester polymer dye SO107-TDI prepared in Examples 1, 12-13 and Comparative Examples 5-6, put it into a melting point tube, and test its melting point using a melting point apparatus. The results are shown in Table 1: Table 2 Melting points of heterocyclic polymer dyes

[0058] The results are shown in Table 1. Analysis of the obtained data shows that the higher the degree of polymerization of the polymer, the higher its melting temperature. Furthermore, the melting point range of the obtained polymers is all below the mixing temperature. Therefore, when the molar ratio of SO107-DEA and toluene 2,4-diisocyanate is 1:1~3, it can be mixed with PET to prepare polyester polymer dyes.

[0059] Example 17 Take 1 part by weight of solvent Orange 107 (SO107) and the heterocyclic polyester polymer dye SO107-TDI prepared in Examples 1, 12-13 and Comparative Examples 5-6, and 100 parts by weight of polyethylene terephthalate (PET). Melt at 265°C and then knead for 4 min. After kneading, take it out and place it in a tablet press. Preheat at 265°C for 4 min, then hot press at 10 MPa for 1 min, and cold press at 25°C for 1 min to obtain polyester sheets.

[0060] Example 18 Migration resistance test: (1) Add 300mg of laundry detergent to 100mL of water to prepare a saturated solution and stir at room temperature for 10 minutes. Add the same mass (1g) of the polyester sheet prepared in Example 15 and stir at room temperature for 5 minutes. Transfer to an oil bath and heat to 80°C and stir continuously for 24 hours to complete one boiling. (2) After removing the polyester sheet that did not change color after one boiling, and cooling it for 1 hour, place it again in a new saturated solution containing laundry detergent. Repeat step (1) and boil the sheet multiple times. Observe the number of times the polyester sheet changes color after boiling. The results are shown in Table 3. Table 3 Migration Resistance

[0061] The results showed that the higher the degree of polymerization, the better the migration resistance and the more resistant to washing. Furthermore, the optimal temperature for the first synthesis stage was controlled between 80 and 110°C, and the molar ratio of SO107-DEA to toluene 2,4-diisocyanate during polymerization was controlled at 1:1 to 3. This optimal polymerization ratio not only resulted in a higher melting temperature but also produced polyester sheets with better migration resistance and water-boiling resistance.

[0062] Depend on Figure 6-7 It can be seen that the polyester sheet prepared from raw material SO107 becomes significantly cloudy after boiling in water, while the polyester sheet prepared in Example 1 does not change color much before and after boiling in water, indicating that it has good migration resistance and high temperature boiling resistance.

[0063] Depend on Figure 8-9 It can be seen that the polyester polymer dye prepared from raw material SO107 changes the color of the solution after boiling in water for 12 hours, and the color depth of the solution gradually increases with the extension of boiling time; while the migration-resistant polyester polymer dye prepared in Example 1 shows that the color of the solution remains basically unchanged after boiling in water for 24 hours, indicating that it has good migration resistance and high temperature boiling resistance.

Claims

1. A migration-resistant polyester polymer dye, characterized in that: Its structure is shown below, where n ranges from 30 to 40: 。 2. A method for preparing the polyester polymer dye as described in claim 1, characterized in that: This can be achieved through the following method: ； The preparation method includes the following steps: (1) Dissolve the parent dye and base in a mixed solvent, add diethanolamine, heat and react. After the reaction is complete, remove the solvent, add water to settle, filter and dry to obtain the diethanolamine-substituted compound of SO107, namely SO107-DEA. (2) After dissolving SO107-DEA, toluene-2,4-diisocyanate was added under inert gas protection. The reaction was heated until complete, and the reaction solution was dropped into water. After filtration, washing and drying, the polyester polymer dye SO107-TDI was obtained. (3) The polyester polymer dye SO107-TDI is mixed with PET, kneaded and pressed into tablets to obtain a migration-resistant polyester polymer dye.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the parent dye to the catalyst and diethanolamine in step (1) is 1:0.5~2:1~4.

4. The preparation method according to claim 3, characterized in that: The parent dye is Solvent Orange 107, and the alkali is cesium carbonate.

5. The preparation method according to claim 2, characterized in that: The mixed solvent is a mixture of N,N-dimethylformamide and acetonitrile in a volume ratio of 1:2~5; the heating reaction conditions are 80~110℃ for 10~12h.

6. The preparation method according to claim 2, characterized in that: The molar ratio of SO107-DEA to toluene-2,4-diisocyanate in step (2) is 1:1~3; the reaction conditions are 80~120℃ for 24h.

7. The preparation method according to claim 2, characterized in that: The solvent used to dissolve SO107-DEA in step (2) is N,N-dimethylformamide.

8. The preparation method according to claim 2, characterized in that: The mass ratio of polyester polymer dye to PET in step (3) is 0.5~2:

100.

9. The preparation method according to claim 2, characterized in that: The mixing temperature in step (3) is 250~270℃, the tableting temperature is 250~270℃, and the pressure is 5~10MPa.

10. The application of the migration-resistant polyester polymer dye as described in claim 1 in polymer material colorants.

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