Biomass environment-friendly color paste as well as preparation method and application thereof

Abstract

The invention discloses biomass environment-friendly color paste as well as a preparation method and application thereof, and belongs to the technical field of dye color paste. The color paste comprises 10-20 parts of a biomass material, 15-50 parts of water-based resin, 20-60 parts of an environment-friendly solvent, 0.5-5 parts of a dispersant, 5-30 parts of a pigment, 0.05-1% of a preservative and 5-10 parts of an antioxidant. According to the invention, the synergistic effect of the biomass material and the antioxidant is combined with the water / alcohol mixed solvent system, so that the physical-chemical dual antioxidant barrier of the color paste is realized. During preparation, the biomass material and the solvent are mixed to form premixed liquid, then the resin, the dispersing agent and the antioxidant are sequentially added for high-speed dispersion, and finally grinding is performed until the particle size is smaller than or equal to 10 microns. The color paste effectively solves the technical problems that the traditional color paste is easy to oxidize and fade and uneven in dispersion, and is suitable for the fields of environment-friendly coatings, inks and cotton and linen fabric printing and dyeing.

Description

Technical Field

[0001] The present invention relates to the technical field of dye pastes, and particularly relates to a biomass environmental protection paste and its preparation method and application. Background Art

[0002] In the current application field of dye pastes, many problems need to be solved urgently. On the one hand, dyes are extremely easy to be oxidized and denatured in the actual use environment. This is mainly because there are unstable chemical bonds in the molecular structure of dyes. Under the action of external factors such as light, high temperature, and oxygen, they will undergo complex chemical reactions. For example, after some azo dyes are irradiated by strong light for several hours, the azo bonds inside their molecules will gradually break, resulting in a change in the molecular structure of the dyes and a shift in color. The originally bright red may turn into a dull brownish red, which not only affects the appearance quality of the product but also reduces the market competitiveness of the product. In the high-temperature printing and dyeing environment, the thermal motion of dye molecules intensifies, and chemical bonds are more easily damaged, further accelerating the process of dye oxidation and denaturation.

[0003] On the other hand, the problem of uneven dyes is also widespread. There are certain defects in the preparation process of traditional dye pastes. For example, the solubility of disperse dyes in aqueous media is poor. During the stirring and mixing process, dye particles often cannot be fully dispersed and tend to form aggregates. These aggregates cannot be evenly attached to the surface of fabrics or substrates during subsequent printing or dyeing processes, resulting in uneven dyeing effects such as mottling and streaks. Especially for some high-precision textile printing, this unevenness will seriously affect the clarity and beauty of the pattern. At the same time, in the field of waterborne coatings, the uneven distribution of dyes will also lead to inconsistent coating colors, affecting the decorative and protective properties of the coatings.

[0004] The existence of these problems limits the wide application of dye pastes in high-end textiles, environmental protection coatings and other fields, making the industry's demand for a dye paste with excellent antioxidant properties and uniformity increasingly urgent. Summary of the Invention

[0005] The purpose of the present invention is to provide a biomass environmental protection paste with good antioxidant properties and uniformity, as well as its preparation method and application, aiming at the problems of easy oxidation and denaturation of dyes and uneven distribution of dyes in the prior art.

[0006] To achieve the above object, the technical solution adopted by the present invention is: a biomass environmental protection paste, comprising the following components in mass ratio: 10-20 parts of biomass material, 15-50 parts of water-based resin, 20-60 parts of environmental protection solvent, 0.5-5 parts of dispersant, 5-30 parts of pigment, 0.05-1% of preservative, and 5-10 parts of antioxidant; The biomass material includes one or more of lignin, cellulose, and chitin; The structure of the antioxidant is the structure shown in Formula 1: Formula 1; wherein R1 is selected from: H, an alkyl group having 1-5 carbon atoms, a deuterated alkyl group having 1-5 carbon atoms, an aryl group having 6-15 carbon atoms, a deuterated aryl group having 6-15 carbon atoms; or R1 is selected from: an alkyl group having 1-5 carbon atoms, an aryl group having 6-15 carbon atoms substituted with a deuterated alkyl group having 1-5 carbon atoms, a deuterated aryl group having 6-15 carbon atoms; wherein R2 is selected from: H, an alkyl group having 1-5 carbon atoms, a deuterated alkyl group having 1-5 carbon atoms, an aryl group having 6-15 carbon atoms, a deuterated aryl group having 6-15 carbon atoms.

[0007] Furthermore, the alkyl group having 1-5 carbon atoms is selected from: methyl, ethyl, propyl, tert-butyl.

[0008] Furthermore, the deuterated alkyl group having 1-5 carbon atoms is selected from: deuterated methyl, deuterated ethyl, deuterated propyl, deuterated tert-butyl.

[0009] Furthermore, the aryl group having 6-15 carbon atoms is selected from: phenyl, naphthyl, biphenyl.

[0010] Furthermore, the deuterated aryl group having 6-15 carbon atoms is selected from: deuterated phenyl, deuterated naphthyl, deuterated biphenyl.

[0011] Even further, R1 is selected from: H, methyl, ethyl, propyl, tert-butyl, deuterated methyl, deuterated tert-butyl, phenyl, deuterated phenyl, biphenyl, naphthyl; phenyl substituted with methyl, propyl, tert-butyl, deuterated methyl, deuterated tert-butyl.

[0012] Even further, R2 is selected from: H, methyl, tert-butyl, phenyl.

[0013] Furthermore, the antioxidant is selected from any one of the compounds represented by the following structures: ; ; ; ; ; ; ; ; ; ; Wherein D represents deuterium.

[0014] Furthermore, the synthesis method of the antioxidant is as follows: ; The first step: Raw material 1 (CAS registration number in the SciFinder database: 1092796-27-4) and raw material 2 are synthesized into intermediate 1 through Williamson synthesis; The second step: Intermediate 1 is demethylated to generate the antioxidant; The website of the SciFinder database is: https: / / scifinder-n.cas.org / .

[0015] Furthermore, the aqueous resin is selected from at least one of: acrylic resin, epoxy-modified alkyd resin, and aqueous polyurethane.

[0016] Furthermore, the environmentally friendly solvent is a mixture of water and organic alcohol in a mass ratio of 1:3; Furthermore, the organic alcohol is ethanol or propylene glycol.

[0017] Furthermore, the dispersant is selected from: sodium lignosulfonate.

[0018] Furthermore, the dye is selected from one of: iron oxide red, ultramarine blue, phthalocyanine blue, and phthalocyanine green.

[0019] Furthermore, the preservative is selected from one or more of: sodium benzoate, potassium sorbate, and sodium dehydroacetate.

[0020] A preparation method of a biomass environmentally friendly color paste, comprising the following steps: a) Mix and stir the biomass material and the environmentally friendly solvent at 40-60 °C for 30-90 minutes to form a premixed solution; b) Add the aqueous resin, dispersant, and antioxidant to the premixed solution and disperse at 1000-2000 rpm for 20-40 minutes; c) Add the pigment and preservative, grind to a particle size ≤ 10 μm, and adjust the pH to 7-8 to obtain a biomass environmentally friendly color paste.

[0021] An application of a biomass environmentally friendly color paste in the fields of textile printing, waterborne coatings, or environmentally friendly inks.

[0022] Furthermore, the textile is cotton, linen, or blended fabric.

[0023] The antioxidant described in the present invention can provide active hydrogen atoms to directly quench oxidizing substances including peroxy radicals. When R1 is a deuterated alkyl group and / or a deuterated phenyl group, the antioxidant is more stable under high temperature or light, and the free radical capture cycle is prolonged. The antioxidant described in the present invention can absorb ultraviolet light and reduce the rate of photooxidation reaction. The deuterated aryl group further reduces photo-degradation through the isotope effect.

[0024] The lignin described in the present invention contains phenolic hydroxyl groups, but its reduction potential is not sufficient to completely neutralize highly active free radicals. However, it can form a redox relay chain with the antioxidant to regenerate the active form of the antioxidant, thereby greatly enhancing its antioxidant ability. After the resin forms a film, it can reduce the oxygen permeability and jointly form a physical-chemical double barrier with the antioxidant. Sodium lignosulfonate maintains the dispersed state of the antioxidant through electrostatic repulsion and increases its effective surface area. The water / alcohol mixed solvent can enhance the solubility of the antioxidant and optimize the phase distribution.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: Compared with the prior art, the beneficial effects of the present invention are mainly reflected in the following three aspects: 1. Significantly enhance the antioxidant performance: The antioxidant described in the present invention can directly quench oxidizing substances. In particular, the deuterated structure makes it more stable under high temperature or light, can prolong the free radical capture cycle, and significantly enhance the antioxidant ability of the color paste. At the same time, lignin and the antioxidant form a redox relay chain, further enhancing the antioxidant effect.

[0026] 2. Improve the dispersion uniformity: The environmentally friendly solvent system enhances the solubility of the antioxidant, optimizes the phase distribution, and is combined with a dispersant to maintain the dispersed state and increase the effective surface area, effectively preventing pigment particle agglomeration and ensuring uniform adhesion of the color paste.

[0027] 3. Enhance environmental friendliness: The use of biomass materials such as lignin, cellulose, and chitin reduces the dependence on traditional petroleum-based raw materials; the use of an environmentally friendly solvent composed of water and organic alcohol reduces the emission of volatile organic compounds, meeting the trend of environmental protection development. Description of the Drawings

[0028] Figure 1 HNMR spectrum of antioxidant 1 synthesized in Synthesis Example 1 of the present invention 1 HNMR spectrum.

[0029] Figure 2 Synthesis route of the antioxidant described in the present invention. Detailed Description of the Invention

[0030] Next, the technical solutions of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without making creative efforts belong to the scope of protection of the present invention.

[0031] Synthesis Example 1: As Figure 2 shown, the preparation of Antioxidant 1: ; First step: Under a nitrogen atmosphere, 200 g of DMSO, 21.98 g of potassium phosphate trihydrate, 0.05 g of pyridine-2-carboxylic acid, and 0.3 g of CuI were added to the reaction system. Subsequently, 20 g of Raw Material 1 and 12.19 g of Raw Material 2 were gradually added in sequence, and the reaction mixture was heated at 85 °C for 16 h. After cooling, the obtained reaction mixture was extracted with ammonia water solution and methyl tert-butyl ether. The organic phase was washed with water five times and then with saturated NaCl solution twice. Finally, the combined organic phase was dried with anhydrous magnesium sulfate, rotary evaporated under reduced pressure, and the solid was passed through a silica gel column to obtain 17.38 g of Intermediate 1 with a yield of 64.81%. MS[MS + 1]: 650.

[0032] Second step: Under a nitrogen atmosphere, 17.38 g of Intermediate 1, 31.50 g of boron tribromide, and 200 g of toluene were added to the reaction system. After mixing, the mixture was heated under reflux at 120 °C for 1 h. After natural cooling, the mixture was added to 250 ml of 18% hydrochloric acid, and a solid was obtained after cooling. The solid was dissolved with 5% NaOH, the insoluble matter was filtered out, and then the pH was adjusted to 1 with 18% hydrochloric acid to precipitate a solid. After drying, it was passed through a silica gel column and rotary evaporated to obtain 12.57 g of Antioxidant 1 with a yield of 77.34%. MS[MS + 1]: 608.

[0033] The 1 HNMR (deuterated chloroform) data of Antioxidant 1 is: δ 8.38 (s, 1H), 8.21 - 8.12 (m, 2H), 7.65 - 7.56 (m, 2H), 7.55 - 7.34 (m, 5H), 7.34 - 7.21 (m, 2H), 7.15 (m, 2H), 7.02 - 6.94 (m, 2H), 6.86 - 6.79 (m, 2H), 6.79 - 6.72 (m, 2H), 6.45 (t, 1H), 4.70 (t, 2H), 4.03 (d, 2H), 3.87 (s, 3H). The 1 HNMR spectrum of Antioxidant 1 is as Figure 1 shown.

[0034] Synthesis Examples 2 - 10: The compound synthesis methods in Synthesis Examples 2 - 10 refer to the synthesis method in Synthesis Example 1, replacing the raw material 2 therein, and the rest are the same as those in Synthesis Example 1. The specific structures of raw material 2, antioxidant structures, and MS[MS + 1] in Synthesis Examples 2 - 10 are shown in Table 1.

[0035] Table 1. Specific structures of raw material 2, antioxidant structures, and MS[MS + 1] data in Synthesis Examples 2 - 10.

[0036] Comparative Compound 1: ; Comparative Compound 2: .

[0037] For the in vitro antioxidant activity evaluation of the compounds described in Synthesis Examples 1 - 10 and Comparative Compounds 1 - 2, refer to the DPPH method and ABTS method described in GB / T 39100 - 2020 to determine the in vitro antioxidant capacity of rhein and its nitroxide radical derivatives in Example 1. The results are shown in Table 2: The IC 50 .

[0038] Table 2. IC 50 values of the compounds described in Synthesis Examples 1 - 10 and Comparative Compounds 1 - 2 for scavenging DPPH radicals and ABTS radicals.

[0039] According to the data in Table 2, the antioxidants in Synthesis Examples 1 - 10 showed significantly better antioxidant activity than the comparative compounds in both DPPH and ABTS radical scavenging experiments. Among them, the IC50 values of Synthesis Examples 3, 5, 7, 9, and 10 containing deuterated alkyl / aryl were lower, and the antioxidant activity was improved compared with that of non - deuterated similar structures, indicating that the deuterium isotope effect significantly enhanced the stability and radical quenching ability of the antioxidants. Although the molecular weight of Synthesis Example 8 containing a biphenyl structure was larger, it still maintained a relatively low IC 50 value through π - π conjugation, showing the positive effect of aromatic ring expansion on electron delocalization.

[0040] Example 1: Preparation of a biomass environmental protection color paste: a) Mix 10 parts of biomass material (cellulose) with 50 parts of environmentally friendly solvent (a mixture of water and propylene glycol in a mass ratio of 1:3) at 60 °C and stir for 50 minutes to form a premix; b) Add 20 parts of aqueous resin (acrylic resin), 1.5 parts of dispersant (sodium lignosulfonate), and 5 parts of antioxidant (the compound prepared in Synthesis Example 1) to the premix, and disperse at 1500 rpm for 30 minutes; c) Add 10 parts of pigment (iron oxide red) and 0.05 part of preservative (sodium benzoate), grind to a particle size ≤ 10 μm, and adjust the pH to 7 to obtain a biomass environmentally friendly color paste.

[0041] Examples 2 - 10: In Examples 2 - 10, a biomass environmentally friendly color paste was prepared. Referring to the preparation method of Example 1, the antioxidant was sequentially replaced with the antioxidants prepared in Synthesis Examples 2 - 10, and the rest remained the same.

[0042] Comparative Example 1: A biomass environmentally friendly color paste was prepared by referring to the preparation method of Example 1 without adding the antioxidant therein, and the rest remained the same.

[0043] Comparative Example 2: A biomass environmentally friendly color paste was prepared by referring to the preparation method of Example 1, and the antioxidant was replaced with Comparative Compound 1, and the rest remained the same.

[0044] Performance test: 1. Antioxidant performance test: Coat the color paste samples (Examples 1 - 10, Comparative Examples 1 - 2) on a glass plate (wet film thickness 50 μm), place them in a constant temperature oven at 60 °C to accelerate oxidation for 7 days, and measure the color difference ΔE value before and after aging through a color difference meter (ΔE ≤ 2 is qualified).

[0045] 2. Application performance: Use the color paste (Examples 1 - 10, Comparative Examples 1 - 2) for printing on polyester fabrics (thermosetting at 180 °C for 30 s), and measure the color fastness (GB / T 3920 - 2008).

[0046] Table 3. Test data of antioxidant performance and application performance of the color pastes prepared in Examples 1 - 10 and Comparative Examples 1 - 2.

[0047] According to the test results in Table 3, it can be seen that the sample of the example with antioxidant added is significantly superior to the comparative example without addition or with conventional antioxidant in terms of anti-aging discoloration performance and dyeing fastness. Among them, the antioxidant formulation introducing deuterated groups and extended conjugated structures exhibits more excellent comprehensive performance, indicating that this type of compound can effectively inhibit the photothermal degradation of the color paste components and simultaneously improve the interfacial binding strength of the dye by optimizing the intermolecular forces. This physicochemical synergistic effect enables the biomass color paste to maintain stable color rendering performance in complex application environments.

[0048] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A biomass environmental protection color paste, characterized in that, It includes the following components in mass ratio: 10 - 20 parts of biomass material, 15 - 50 parts of waterborne resin, 20 - 60 parts of environmental protection solvent, 0.5 - 5 parts of dispersant, 5 - 30 parts of pigment, 0.05 - 1% of preservative, and 5 - 10 parts of antioxidant; The biomass material includes: one or more of lignin, cellulose, and chitin; The structure of the antioxidant is the structure shown in Formula 1: Formula 1; Wherein R1 is selected from: H, an alkyl group with 1 - 5 carbon atoms, a deuterated alkyl group with 1 - 5 carbon atoms, an aryl group with 6 - 15 carbon atoms, and a deuterated aryl group with 6 - 15 carbon atoms; Or R1 is selected from: an alkyl group with 1 - 5 carbon atoms, an aryl group with 6 - 15 carbon atoms substituted by a deuterated alkyl group with 1 - 5 carbon atoms, and a deuterated aryl group with 6 - 15 carbon atoms; Wherein R2 is selected from: H, an alkyl group with 1 - 5 carbon atoms, a deuterated alkyl group with 1 - 5 carbon atoms, an aryl group with 6 - 15 carbon atoms, and a deuterated aryl group with 6 - 15 carbon atoms.

2. The biomass environmental protection color paste according to claim 1, wherein The alkyl group with 1 - 5 carbon atoms is selected from: methyl, ethyl, propyl, tert - butyl; The deuterated alkyl group with 1 - 5 carbon atoms is selected from: deuterated methyl, deuterated ethyl, deuterated propyl, deuterated tert - butyl.

3. A biomass environmental protection color paste according to claim 1, characterized in that, The aryl group with 6 - 15 carbon atoms is selected from: phenyl, naphthyl, biphenyl; The deuterated aryl group with 6 - 15 carbon atoms is selected from: deuterated phenyl, deuterated naphthyl, deuterated biphenyl.

4. A biomass environmental protection color paste according to claim 1, characterized in that, The antioxidant is selected from any one of the compounds expressed by the following structures: ； ； ； ； ； ； ； ； ； ； D represents deuterium.

5. A biomass environmental protection color paste according to claim 1, characterized in that, The waterborne resin is selected from: at least one of acrylic resin, epoxy - modified alkyd resin, and waterborne polyurethane.

6. The eco-friendly biomass color paste according to claim 1, wherein The environmental protection solvent is a mixture of water and organic alcohol in a mass ratio of 1:3; The organic alcohol is ethanol or propylene glycol.

7. A biomass environmental protection color paste according to claim 1, characterized in that The dispersant is selected from: sodium lignosulfonate.

8. A preparation method of a biomass environmental protection color paste according to any one of claims 1-7, characterized in that, It includes the following steps: a) Mix and stir the biomass material and the environmental protection solvent at 40 - 60 °C for 30 - 90 minutes to form a premixed liquid; b) Add the waterborne resin, dispersant, and antioxidant to the premixed liquid and disperse at 1000 - 2000 rpm for 20 - 40 minutes; c) Add the pigment and preservative, grind to a particle size ≤10 μm, and adjust the pH to 7 - 8 to obtain a biomass environmental protection color paste.

9. Application of the biomass environmental protection color paste according to any one of claims 1 - 7 in the fields of textile printing, water - based coatings, or environmental protection inks.

10. Use of a biomass environmental protection color paste according to claim 9 in the fields of textile printing, waterborne coatings or environmental protection inks, characterized in that, The textile is cotton, linen, or blended fabric.

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