A biomass environmentally friendly color paste and its preparation method and application

Abstract

The present invention discloses a biomass environmentally friendly color paste and its preparation method and application, which belongs to the field of dye color paste technology. The color paste contains 10-20 parts of biomass material, 15-50 parts of water-based resin, 20-60 parts of environmentally friendly solvent, 0.5-5 parts of dispersant, 5-30 parts of pigment, 0.05-1% of preservative, and 5-10 parts of antioxidant. The present invention realizes the physical-chemical dual antioxidant barrier of the color paste through the synergistic effect of biomass material and antioxidant, combined with a water / alcohol mixed solvent system. During preparation, the biomass material and the solvent are first mixed to form a premixed liquid, and then the resin, dispersant, and antioxidant are added in sequence for high-speed dispersion, and finally ground to a particle size of ≤10μm. The present invention effectively solves the technical problems of easy oxidation and fading and uneven dispersion of traditional color pastes, and is suitable for the fields of environmentally 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 in particular to a biomass environmentally friendly paste and a preparation method and application thereof. Background Art

[0002] In today's dye paste application field, numerous challenges urgently need to be addressed. For one thing, dyes are extremely susceptible to oxidative denaturation in actual use environments. This is primarily due to the unstable chemical bonds within the dye's molecular structure, which, under the influence of external factors such as light, heat, and oxygen, undergo complex chemical reactions. For example, after several hours of exposure to strong light, some azo dyes gradually break the azo bonds within their molecules, causing the dye's molecular structure to change and the color to shift. The originally vibrant red may become a dull brownish-red, which not only affects the product's appearance quality but also reduces its market competitiveness. In high-temperature printing and dyeing environments, the thermal motion of the dye molecules is intensified, making the chemical bonds more susceptible to breakdown, further accelerating the dye's oxidative denaturation process.

[0003] On the other hand, the problem of uneven dyeing is also common. The preparation process of traditional dye pastes has certain defects. For example, disperse dyes have poor solubility in aqueous media. During the stirring and mixing process, dye particles are often not fully dispersed and easily form agglomerates. These agglomerates cannot be evenly attached to the surface of the fabric or substrate during the subsequent printing or dyeing process, resulting in uneven dyeing effects such as mottled and streaked patterns. Especially for some high-precision textile printing, this unevenness can seriously affect the clarity and aesthetics of the pattern. At the same time, in the field of water-based coatings, the uneven distribution of dyes can also lead to uneven coating colors, affecting the decorative and protective properties of the coating.

[0004] The existence of these problems limits the widespread application of dye pastes in high-end textiles, environmentally friendly 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 an antioxidant and uniform biomass environmentally friendly color paste and its preparation method and application in order to solve 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 environmentally friendly color paste, comprising the following components by weight: 10-20 parts of biomass material, 15-50 parts of water-based resin, 20-60 parts of environmentally friendly solvent, 0.5-5 parts of dispersant, 5-30 parts of pigment, 0.05-1% of preservative, and 5-10 parts of antioxidant;

[0007] The biomass material includes: one or more of lignin, cellulose, and chitin;

[0008] The structure of the antioxidant is shown in Formula 1:

[0009] Formula 1;

[0010] wherein R1 is selected from the group consisting of: H, an alkyl group having 1 to 5 carbon atoms, a deuterated alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a deuterated aryl group having 6 to 15 carbon atoms;

[0011] or R1 is selected from: an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms substituted with a deuterated alkyl group having 1 to 5 carbon atoms, and a deuterated aryl group having 6 to 15 carbon atoms;

[0012] Wherein R2 is selected from the group consisting of: H, an alkyl group having 1 to 5 carbon atoms, a deuterated alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, and a deuterated aryl group having 6 to 15 carbon atoms.

[0013] Furthermore, the alkyl group having 1 to 5 carbon atoms is selected from the group consisting of methyl, ethyl, propyl, and tert-butyl.

[0014] Furthermore, the deuterated alkyl group having 1 to 5 carbon atoms is selected from the group consisting of: deuterated methyl, deuterated ethyl, deuterated propyl, and deuterated tert-butyl.

[0015] Furthermore, the aryl group having 6 to 15 carbon atoms is selected from the group consisting of phenyl, naphthyl, and biphenyl.

[0016] Furthermore, the deuterated aryl group having 6 to 15 carbon atoms is selected from the group consisting of deuterated phenyl, deuterated naphthyl, and deuterated biphenyl.

[0017] Furthermore, R1 is selected from: H, methyl, ethyl, propyl, tert-butyl, deuterated methyl, deuterated tert-butyl, phenyl, deuterated phenyl, biphenyl, naphthyl; phenyl substituted by methyl, propyl, tert-butyl, deuterated methyl, deuterated tert-butyl.

[0018] Furthermore, the R2 is selected from: H, methyl, tert-butyl, and phenyl.

[0019] Furthermore, the antioxidant is selected from any one of the compounds expressed by the following structures:

[0020] ;

[0021] ;

[0022] ;

[0023] ;

[0024] ;

[0025] ;

[0026] ;

[0027] ;

[0028] ;

[0029] ;

[0030] The D represents deuterium.

[0031] Furthermore, the synthesis method of the antioxidant is:

[0032] ;

[0033] Step 1: intermediate 1 is synthesized from raw material 1 (CAS registration number in SciFinder database: 1092796-27-4) and raw material 2 via Williamson synthesis;

[0034] Step 2: Intermediate 1 is demethylated to generate antioxidant;

[0035] The website of the SciFinder database is: https: / / scifinder-n.cas.org / .

[0036] Furthermore, the water-based resin is selected from at least one of acrylic resin, epoxy-modified alkyd resin, and water-based polyurethane.

[0037] Furthermore, the environmentally friendly solvent is a mixture of water and organic alcohol in a mass ratio of 1:3;

[0038] Furthermore, the organic alcohol is ethanol or propylene glycol.

[0039] Furthermore, the dispersant is selected from: sodium lignin sulfonate.

[0040] Furthermore, the dye is selected from: iron oxide red, ultramarine blue, phthalocyanine blue, and phthalocyanine green.

[0041] Furthermore, the preservative is selected from one or more of sodium benzoate, potassium sorbate, and sodium dehydroacetate.

[0042] A method for preparing a biomass environmentally friendly color paste comprises the following steps:

[0043] a) mixing the biomass material and the environmentally friendly solvent at 40-60° C. for 30-90 minutes to form a premixed solution;

[0044] b) adding the aqueous resin, dispersant, and antioxidant to the premixed solution and dispersing at 1000-2000 rpm for 20-40 minutes;

[0045] c) adding the pigment and preservative, grinding to a particle size of ≤10 μm, and adjusting the pH to 7-8 to obtain a biomass environmentally friendly color paste.

[0046] Application of a biomass environmentally friendly color paste in the fields of textile printing, water-based coatings or environmentally friendly inks.

[0047] Furthermore, the textile is made of cotton, linen or a blended fabric.

[0048] The antioxidants described herein can provide active hydrogen atoms to directly quench oxidizing substances, including peroxyl radicals. When R1 is a deuterated alkyl group and / or a deuterated phenyl group, the antioxidants are more stable at high temperatures or under light, extending the free radical capture cycle. The antioxidants described herein can absorb ultraviolet light, reducing the rate of photooxidation reactions. Deuterated aryl groups further reduce photodegradation through the isotope effect.

[0049] The lignin described in the present invention contains phenolic hydroxyl groups, but its reduction potential is insufficient to completely neutralize highly reactive free radicals. However, it can form a redox relay chain with the antioxidant, regenerating the antioxidant's active form, thereby significantly enhancing its antioxidant capacity. The resin film can reduce oxygen permeability and, together with the antioxidant, form a physical-chemical dual barrier. Sodium lignin sulfonate maintains the antioxidant's dispersion through electrostatic repulsion, increasing its active surface area. The water / alcohol mixed solvent enhances the antioxidant's solubility and optimizes phase distribution.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] Compared with the prior art, the beneficial effects of the present invention are mainly reflected in the following three aspects:

[0052] 1. Significantly improve 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, which can prolong the free radical capture cycle and significantly improve the antioxidant capacity of the color paste. At the same time, lignin and the antioxidant form a redox relay chain, further enhancing the antioxidant effect.

[0053] 2. Improved dispersion uniformity: The environmentally friendly solvent system enhances the solubility of antioxidants, optimizes phase distribution, and is matched with dispersants to maintain the dispersion state, thereby increasing the effective surface area, effectively preventing pigment particle agglomeration, and ensuring uniform adhesion of the color paste.

[0054] 3. Enhanced environmental protection: The use of biomass materials such as lignin, cellulose, and chitin reduces dependence on traditional petroleum-based raw materials; the use of environmentally friendly solvents composed of water and organic alcohols reduces volatile organic compound emissions, which is in line with the trend of environmental protection development. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 The antioxidant 1 synthesized in Synthesis Example 1 of the present invention 1 HNMR spectrum.

[0056] Figure 2 This is the synthetic route of the antioxidant described in the present invention. DETAILED DESCRIPTION

[0057] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the accompanying drawings. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0058] Synthesis example 1:

[0059] like Figure 2 As shown, the preparation of antioxidant 1:

[0060] ;

[0061] Step 1: 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 starting material 1 and 12.19 g of starting material 2 were gradually added, and the reaction mixture was heated at 85°C for 16 h. After cooling, the resulting reaction mixture was extracted with aqueous ammonia and methyl tert-butyl ether. The organic phase was washed five times with water and twice with saturated NaCl solution. Finally, the combined organic phases were dried over anhydrous magnesium sulfate, dried 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.

[0062] Step 2: 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 hour. After cooling naturally, the mixture was added to 250 ml of 18% hydrochloric acid and cooled to obtain a solid. 5% NaOH was added to dissolve the solid, and the insoluble material was filtered off. 18% hydrochloric acid was then added to adjust the pH to 1. The precipitated solid was dried, passed through a silica gel column, and dried to obtain 12.57 g of antioxidant 1, with a yield of 77.34%. MS [MS+1]: 608.

[0063] Antioxidant 1 1 HNMR (deuterated chloroform) data are: 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), antioxidant 1 1 HNMR images Figure 1 shown.

[0064] Synthesis Example 2-Synthesis Example 10:

[0065] The synthesis methods of the compounds in Synthesis Examples 2 to 10 were similar to those in Synthesis Example 1, except that the raw material 2 was replaced. The rest of the synthesis remained the same as in Synthesis Example 1. The specific structures of the raw material 2, the antioxidant structure, and the MS [MS+1] in Synthesis Examples 2 to 10 are shown in Table 1.

[0066] Table 1. Specific structures of raw material 2, antioxidant structures, and MS [MS+1] data in Synthesis Examples 2 to 10.

[0067]

[0068]

[0069]

[0070] Comparative compound 1: ; Comparative compound 2: .

[0071] The compounds described in Synthesis Examples 1 to Synthesis Examples 10 and Comparative Compounds 1 to Comparative Compounds 2 were subjected to in vitro antioxidant activity evaluation. The in vitro antioxidant capacity of rhein and its nitroxide free radical derivatives in Example 1 was determined by referring to the DPPH method and ABTS method described in GB / T 39100-2020. The results are shown in Table 2: IC values ​​of the compounds described in Synthesis Examples 1 to Synthesis Examples 10 and Comparative Compounds 1 to Comparative Compounds 2 for scavenging DPPH free radicals and ABTS free radicals 50 .

[0072] Table 2. IC values ​​of the compounds described in Synthesis Examples 1-10 and Comparative Compounds 1-2 for scavenging DPPH free radicals and ABTS free radicals 50 .

[0073]

[0074] According to the data in Table 2, the antioxidants of Synthesis Examples 1 to 10 all showed significantly better antioxidant activity than the control compounds in DPPH and ABTS free radical scavenging experiments. Among them, Synthesis Examples 3, 5, 7, 9, and 10 containing deuterated alkyl / aryl groups had lower IC50 values, which were higher than the antioxidant activity of non-deuterated similar structures, indicating that the deuterium isotope effect significantly enhanced the stability and free radical quenching ability of the antioxidants. Synthesis Example 8 containing a biphenyl structure, although with a larger molecular weight, still maintained a low IC50 value through π-π conjugation. 50 The values ​​indicate the positive effect of aromatic ring expansion on electron delocalization.

[0075] Example 1:

[0076] Preparation of a biomass environmentally friendly color paste:

[0077] a) Mix 10 parts of biomass material (cellulose) with 50 parts of an environmentally friendly solvent (water:propylene glycol in a mass ratio of 1:3) at 60°C for 50 minutes to form a premixed solution;

[0078] b) adding 20 parts of an aqueous resin (acrylic resin), 1.5 parts of a dispersant (sodium lignin sulfonate), and 5 parts of an antioxidant (the compound prepared in Synthesis Example 1) to the premixed solution, and dispersing at 1500 rpm for 30 minutes;

[0079] c) Add 10 parts of pigment (red iron oxide) and 0.05 parts of preservative (sodium benzoate), grind to a particle size of ≤10 μm, and adjust the pH to 7 to obtain a biomass environmentally friendly color paste.

[0080] Example 2-Example 10:

[0081] In Examples 2 to 10, a biomass environmentally friendly color paste was prepared. Referring to the preparation method of Example 1, the antioxidants therein were replaced with the antioxidants prepared in Synthesis Examples 2 to 10 in sequence, and the rest remained the same.

[0082] Comparative Example 1:

[0083] A biomass environmentally friendly color paste is prepared according to the method of Example 1, except that the antioxidant is not added and the rest of the preparation remains the same.

[0084] Comparative Example 2:

[0085] A biomass environmentally friendly color paste is prepared according to the method of Example 1, except that the antioxidant is replaced by comparative compound 1, and the rest remain the same.

[0086] Performance testing:

[0087] 1. Antioxidant Performance Test: Color paste samples (Example 1-Example 10, Comparative Example 1-Comparative Example 2) were coated on a glass plate (wet film thickness 50 μm) and placed in a 60°C constant temperature oven for accelerated oxidation for 7 days. The color difference ΔE value before and after aging was measured using a colorimeter (ΔE ≤ 2 was considered acceptable).

[0088] 2. Application Performance: The color pastes (Example 1-Example 10, Comparative Example 1-Comparative Example 2) were used for printing on polyester fabric (heat fixing at 180°C for 30 seconds), and the color fastness was measured (GB / T 3920-2008).

[0089] Table 3. Test data of antioxidant performance and application performance of the color pastes prepared in Examples 1 to 10 and Comparative Examples 1 and 2.

[0090]

[0091] The test results in Table 3 show that the example samples containing antioxidants significantly outperformed the control samples without or with conventional antioxidants in terms of both anti-aging discoloration and color fastness. Antioxidant formulations incorporating deuterated groups and extended conjugated structures exhibited superior overall performance, demonstrating that these compounds effectively inhibit the photothermal degradation of colorant components while enhancing the interfacial bonding strength of the dye by optimizing intermolecular forces. This physicochemical synergistic effect enables the biomass colorant to maintain stable color performance in complex application environments.

[0092] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A biomass environmentally friendly color paste, characterized in that: The composition comprises the following components in mass ratio: 10-20 parts of biomass material, 15-50 parts of water-based resin, 20-60 parts of environmentally friendly 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 any one of the compounds expressed by the following structures: ； ； ； ； ； ； ； ； ； ； The D represents deuterium; The environmentally friendly solvent is a mixture of water and organic alcohol in a mass ratio of 1:3; The organic alcohol is ethanol or propylene glycol.

2. The biomass environmentally friendly color paste according to claim 1, characterized in that: The water-based resin is selected from at least one of acrylic resin, epoxy-modified alkyd resin, and water-based polyurethane.

3. The biomass environmentally friendly color paste according to claim 1, characterized in that: The dispersant is selected from sodium lignin sulfonate.

4. A method for preparing a biomass environmentally friendly color paste according to any one of claims 1 to 3, characterized in that: The following steps are involved: a) mixing the biomass material and the environmentally friendly solvent at 40-60° C. for 30-90 minutes to form a premixed solution; b) adding the aqueous resin, dispersant, and antioxidant to the premixed solution and dispersing at 1000-2000 rpm for 20-40 minutes; c) adding the pigment and preservative, grinding to a particle size of ≤10 μm, and adjusting the pH to 7-8 to obtain a biomass environmentally friendly color paste.

5. Use of the biomass environmentally friendly color paste according to any one of claims 1 to 3 in the fields of textile printing, water-based coatings or environmentally friendly inks.

6. The use of a biomass environmentally friendly color paste according to claim 5 in the fields of textile printing, water-based coatings or environmentally friendly inks, characterized in that: The textile is made of cotton, linen or a blended fabric.

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