Coloring agent containing 2-methylresorcinol and preparation process thereof
By using 2-methylresorcinol as a modifier, the vinyl sulfone and secondary amine functional groups are used to form covalent and non-covalent bonds with inorganic pigments and dyes on the wood surface, which solves the problem of inorganic pigment agglomeration in mixed wood stains and improves the adhesion performance of the stains.
Patent Information
- Application Number
- CN202610049178.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-15
- Publication Date
- 2026-02-17
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
The agglomeration of inorganic pigments in existing mixed wood stains leads to insufficient interfacial bonding between the stain and the wood substrate, affecting adhesion performance.
2-Methylresorcinol is used as a functional modifying component. It is covalently and non-covalently bonded to inorganic pigments and dyes through vinyl sulfone and secondary amine functional groups, and is fixed on the wood surface to improve the interfacial bonding force.
It significantly improved the interfacial bonding between the colorant and the wood substrate, enhanced the adhesion performance, and achieved a level 0 adhesion.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of wood colorant technology, specifically to the field of dye / pigment mixed wood colorant product development technology, and more specifically to a colorant containing 2-methylresorcinol and its preparation process. Background Technology
[0002] Wood stains are a class of materials primarily used to alter the color of wood while maintaining the visibility of its grain. Based on their coloring components, they can be categorized into dye-based, pigment-based, and dye / pigment mixed types. Among these, dye / pigment mixed types combine the high transparency and penetration of dyes with the excellent lightfastness of pigments, making them high-performance, versatile products currently on the market. They typically require the use of protective coatings such as varnishes or wood wax oils.
[0003] The agglomeration problem of inorganic pigments in mixed wood stains is currently being addressed primarily through technologies such as high-efficiency dispersants and surface modification. Meanwhile, exploring novel organic compounds like 2-methylresorcinol as functional modifiers is a promising frontier research direction. Its theoretical value lies in its polyphenol structure, which can improve the interfacial bonding between the stain and the wood substrate at the molecular level, thus providing a new solution for enhancing stain adhesion performance. Summary of the Invention
[0004] This invention uses 2-methylresorcinol as a functional modifying component at the molecular level, and independently develops and provides a new colorant containing 2-methylresorcinol. The aim is to improve the interfacial bonding force between the coloring components (dyes and inorganic pigments) and the wood substrate in mixed wood colorant products at the molecular level, and at the same time optimize the dispersion performance of inorganic pigments in mixed wood colorant products.
[0005] To achieve the above objectives, the present invention adopts the following technical solution:
[0006] A colorant containing 2-methylresorcinol, said colorant comprising the following raw materials in parts by weight:
[0007] 5-10 parts of water-based nano-acrylic emulsion;
[0008] 3-8 parts of iodopropyl-functionalized iron oxide yellow;
[0009] 0.3-1 part copper phthalocyanine;
[0010] 0.05-1.5 parts of adhesion modifier, which is a multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups;
[0011] 25-30 parts of filler;
[0012] 1-3 parts of compound additives;
[0013] 0.5-1.5 parts hydroxyethyl cellulose;
[0014] 30-40 parts deionized water.
[0015] Preferably, the iodopropyl-functionalized iron oxide yellow is prepared by surface modification of iron oxide yellow with hydroxyl functional groups on its surface by iodopropyltrimethoxysilane, wherein the mass ratio of iron oxide yellow to iodopropyltrimethoxysilane is 1:0.05-0.15.
[0016] Preferably, the filler is composed of talc and calcium carbonate.
[0017] Preferably, the filler is formulated with 15-25 parts by weight of talc and 4-8 parts by weight of calcium carbonate.
[0018] Preferably, the composite additive consists of 825 defoamer, 5040 dispersant, 472 wetting agent and sodium hexametaphosphate.
[0019] Preferably, the formulation of the composite additive is: 20-30 parts by weight of 825 defoamer, 20-40 parts by weight of 5040 dispersant, 50-200 parts by weight of 472 wetting agent, and 10-30 parts by weight of sodium hexametaphosphate.
[0020] A process for preparing a colorant containing 2-methylresorcinol includes the following steps:
[0021] Add the prescribed amount of deionized water to a mixing tank and start stirring. Add the prescribed amount of aqueous nano-acrylic emulsion and composite additives, increase the speed to 500-700 r / min, and stir for 0.1-1 h. Then add the prescribed amounts of iodopropyl-functionalized iron oxide yellow, copper phthalocyanine, and multifunctional 2-methylresorcinol derivative, and stir at 500-700 r / min for 0.5-1.5 h. Let stand for 8-15 h, then add the prescribed amount of filler, increase the speed to 800-1200 r / min, and disperse at high speed until the fineness reaches below 40 μm. Adjust the speed to 400-600 r / min, add the prescribed amount of thickener, and stir at 400-600 r / min for 0.1-1 h to obtain the colorant.
[0022] Preferably, the preparation method of the multifunctional 2-methylresorcinol derivative is as follows:
[0023] The mercaptoprotected mercaptoethylamine, formaldehyde, and 2-methylresorcinol were subjected to a Mannich condensation reaction in a molar equivalence ratio of 1:1:1. After that, the protecting group of mercapto in the product was removed to obtain intermediate a containing mercapto.
[0024] Intermediate a reacts with ethylene oxide under alkaline conditions at a molar ratio of 1:1 to undergo an epoxide ring-opening reaction. The resulting product is then subjected to β-elimination dehydration and oxidation to sulfone under concentrated sulfuric acid to produce a multifunctional 2-methylresorcinol derivative.
[0025] Preferably, the mercaptoethylamine with the mercapto protected group is a mercaptoethylamine with the mercapto protected by triphenylmethyl, wherein the triphenylmethyl protecting group of the mercapto is removed by trifluoroacetic acid.
[0026] Application of a colorant containing 2-methylresorcinol, wherein the colorant containing 2-methylresorcinol is used as a wood colorant.
[0027] The beneficial effects of this invention are as follows:
[0028] Using 2-methylresorcinol as the functional modification raw material, and based on the molecular design mechanism, the following synthetic route was designed:
[0029] Based on the aminomethylation reaction mechanism of phenol, mercaptoethylamine with a thiol group protected is used as the amine source and formaldehyde as the aldehyde source. It undergoes a Mannich condensation reaction with 2-methylresorcinol, and then the thiol protecting group is removed to obtain intermediate a containing a thiol group.
[0030] Under alkaline conditions, ethylene oxide undergoes an epoxy ring-opening reaction with the thiol functional group of intermediate a to generate intermediate b containing β-hydroxy sulfide. The β-hydroxy sulfide of intermediate b undergoes β-elimination dehydration and oxidation to sulfone reaction under the action of concentrated sulfuric acid to generate a multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups.
[0031] During the preparation of the colorant, the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups undergoes an SN2 alkylation reaction with the iodine functional group of the iodopropyl-functionalized inorganic pigment (obtained by surface modification of iron oxide yellow rich in hydroxyl functional groups by iodopropyltrimethoxysilane). That is, the multifunctional 2-methylresorcinol derivative is fixed to the surface of the inorganic pigment through covalent bonding to form vinyl sulfone functionalized inorganic pigment. On the other hand, it combines with copper phthalocyanine dye through non-covalent bonding (π-π stacking and hydrogen bonding) to obtain a dye complex with vinyl sulfone groups.
[0032] During the application of colorants, vinyl sulfone functionalized inorganic pigments form ether bonds with hydroxyl functional groups on wood fibers through nucleophilic addition reactions, thus fixing the inorganic pigments to the surface of the wood substrate through covalent bonds. At the same time, dye complexes with vinyl sulfone groups can also be anchored to the wood substrate through covalent bonds. This technique significantly improves the interfacial bonding between the colorant and the wood substrate, thereby enhancing the adhesion performance of the colorant on the wood substrate.
[0033] Research and development experiments have confirmed that the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups prepared in this invention, as an adhesion modifier, resulted in a colorant with an adhesion rating of 0 on a wood substrate, demonstrating excellent adhesion performance. Detailed Implementation
[0034] Example 1:
[0035] The synthetic route for synthesizing multifunctional 2-methylresorcinol derivatives containing vinyl sulfone and secondary amine functional groups is as follows:
[0036] (1) The thiol functional group in mercaptoethylamine hydrochloride was protected by triphenylchloromethane. The specific experimental steps were as follows: Under nitrogen protection, 1.14 g of mercaptoethylamine hydrochloride was added to 100 mL of anhydrous dichloromethane and mechanically stirred until homogeneous. Then, 2.53 g of triethylamine was added and mixed. Finally, 20 mL of dichloromethane solution containing 3.07 g of triphenylchloromethane was added and stirred at room temperature for 3 h. After the reaction was completed, the mixture was filtered, washed, and dried to obtain mercaptoethylamine with thiol protected by triphenylmethyl.
[0037] (2) A Mannich condensation reaction was carried out between thiol-protected mercaptoethylamine, formaldehyde, and 2-methylresorcinol at a molar ratio of 1:1:1. After removing the thiol protecting group, intermediate a containing thiol was generated. The specific experimental steps were as follows: 2.49 g of 2-methylresorcinol and 6.12 g of thiol-protected mercaptoethylamine were added to a 500 mL four-necked flask equipped with a constant pressure dropping funnel, a reflux condenser, a thermometer, and a stirrer. The mixture was stirred under nitrogen protection until homogeneous. The temperature was raised to 80 °C, and 1.6 mL of 37% formaldehyde aqueous solution was added dropwise over 2 h. The mixture was then refluxed for 3 h. After the reaction was completed, the mixture was distilled under reduced pressure, and finally 2.5 g of trifluoroacetic acid was added. After the addition was complete, the mixture was stirred at room temperature for 30 min, filtered, washed, and dried in a vacuum drying oven at 50 °C for 10 h to obtain intermediate a. The chemical structural formula of intermediate a is as follows: ;
[0038] The proton NMR spectrum of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is as follows:
[0039] 1H NMR (DMSO-d6, 400MHz) δ: 1.50-1.53 (t, 1H), 2.10 (s, 3H), 2.15-2.18 (m, 1H), 2.56-2.59 (m, 2H), 2.9 1-2.94 (m, 2H), 3.81-3.82 (d, 2H), 6.38-6.39 (d, 1H), 6.82-6.84 (d, 1H), 7.79 (s, 1H), 9.16 (s, 1H).
[0040] (3) Intermediate a reacts with ethylene oxide under alkaline conditions at a molar ratio of 1:1 to undergo an epoxide ring-opening reaction. Then, concentrated sulfuric acid is added for dehydration and oxidation reaction to synthesize a multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups. The specific experimental steps are as follows: 10.66g of intermediate 2 and 50μL of 20% sodium hydroxide solution are added to a 250mL three-necked flask equipped with a condenser, mechanical stirrer and thermometer. The temperature is raised to 40℃, 2.42g of ethylene oxide is added, and the reaction is kept at the temperature for 1h. Then, 9mL of 98% concentrated sulfuric acid is added, and the reaction is carried out at 120℃ for 2h. After the reaction is completed, the mixture is placed in ice water, filtered, washed, and vacuum dried at 50℃ for 8h to obtain a multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups.
[0041] The chemical structural formula of a multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is as follows: ;
[0042] The proton NMR spectrum of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is as follows:
[0043] 1 H NMR (DMSO-d6, 400MHz) δ: 2.13 (s, 3H), 2.93-2.98 (m, 2H), 3.48-3.51 (t, 2H), 4.08-4.10 (d, 2H), 6.04-6.08 (d, 1H), 6.1 4-6.18 (d, 1H), 6.41-6.43 (d, 1H), 6.54-6.60 (t, 1H), 6.94-6.96 (d, 1H), 7.74-7.82 (m, 1H), 8.88 (s, 1H), 8.97 (s, 1H).
[0044] Example 2:
[0045] Preparation of iodopropyl-functionalized iron oxide yellow: Iodopropyl-trimethoxysilane was used to modify the surface of iron oxide yellow rich in hydroxyl functional groups to obtain iodopropyl-functionalized iron oxide yellow. The specific experimental steps were as follows: 0.5 g of iodopropyl-trimethoxysilane was added to 50 mL of dry toluene and mechanically stirred for 10 min. Then, 5 g of iron oxide yellow (model PY 42, α-FeOOH) and 100 μL of deionized water were added, and the mixture was ultrasonically dispersed for 10 min. The reaction was carried out at room temperature in the dark for 30 h. After the reaction was completed, the solid material was separated by centrifugation, washed, and vacuum dried at 50 °C for 24 h to obtain iodopropyl-functionalized iron oxide yellow.
[0046] Example 3:
[0047] Colorant I was prepared, and its raw material formulation is shown in Table 1 below;
[0048] Table 1 Raw material formulation of colorant I Component Function Components Dosage (parts by weight) resin Aqueous nano-acrylic emulsion (brand name 1829) 8 pigment Iodopropyl-functionalized iron oxide yellow 5 dye Copper Phthalocyanine 0.5 Adhesion Modifier The multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups prepared in Example 1 1.5 filler Composed of talc and calcium carbonate (500 mesh). 25 Composite additives It consists of 825 defoamer, 5040 dispersant, 472 wetting agent and sodium hexametaphosphate. 2 Thickener Hydroxyethyl cellulose 1 solvent Deionized water 40
[0049] The formulation of the additives is as follows: 25 parts by weight of 825 defoamer, 30 parts by weight of 5040 dispersant, 120 parts by weight of 472 wetting agent, and 25 parts by weight of sodium hexametaphosphate.
[0050] The filler formulation is: 20 parts by weight of talc powder (500 mesh) and 5 parts by weight of calcium carbonate (500 mesh);
[0051] The experimental steps for preparing colorant I are as follows: Add the prescribed amount of deionized water to a mixing tank, start stirring, add the prescribed amount of aqueous nano-acrylic emulsion and composite additives, increase the speed to 600 r / min, stir for 0.5 h, then add the prescribed amounts of iodopropyl-functionalized iron oxide yellow, copper phthalocyanine, and multifunctional 2-methylresorcinol derivative, stir at 600 r / min for 1 h, let stand for 12 h, then add the prescribed amounts of talc and calcium carbonate, increase the speed to 1000 r / min for high-speed dispersion until the fineness reaches below 40 μm, adjust the speed to 500 r / min, add the prescribed amount of hydroxyethyl cellulose, and stir at 500 r / min for 0.5 h to obtain colorant I.
[0052] Preparation of colorant II: The only difference between the raw material formulation and experimental steps of colorant II and those of colorant I is that the amount of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is 1.25 parts by weight.
[0053] Preparation of colorant III: The only difference between the raw material formulation and experimental procedure of colorant III and that of colorant I is that the amount of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is 1.00 parts by weight.
[0054] Preparation of colorant IV: The only difference between the raw material formulation and experimental steps of colorant IV and those of colorant I is that the amount of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is 0.75 parts by weight.
[0055] Preparation of colorant V: The only difference between the raw material formulation and experimental steps of colorant V and those of colorant I is that the amount of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is 0.5 parts by weight.
[0056] Preparation of colorant VI: The only difference between the raw material formulation and experimental steps of colorant VI and those of colorant I is that the amount of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is 0.1 parts by weight.
[0057] Preparation of colorant VII: The only difference between the raw material formulation and experimental steps of colorant VII and those of colorant I is that the amount of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is 0.05 parts by weight.
[0058] Comparative Example: The only difference between the raw material formulation and experimental procedure of the comparative example and those of colorant I is that the amount of the multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups is 0.00 parts by weight.
[0059] Performance testing:
[0060] The prepared colorant was sprayed onto a 20mm thick wood substrate (with a smooth and flat surface free of foreign matter) using a spray gun. After spraying, the wood substrate with the color layer was allowed to dry naturally at room temperature to obtain a sample with a color layer thickness of 50μm.
[0061] Adhesion test: According to GB / T 9286-2021 "Cross-cut test for paints and varnishes", the prepared samples were tested at a temperature of 25℃ and a relative humidity of 50%, with a cutting interval of 2mm, and the degree of peeling of the sample color layer was recorded.
[0062] The test results are shown in Table 2 below;
[0063] Table 2 Performance test results of colorants Sample number Content of adhesion modifier in colorant formulation Adhesion (grading) Colorant I 1.58wt% 0 Colorant II 1.32wt% 0 Colorant III 1.06wt% 0 Colorant IV 0.80wt% 0 Colorant V 0.53wt% 0 Colorant VI 0.11wt% 1 Colorant VII 0.05wt% 1 Comparative Example 0.00wt% 3
[0064] The experimental results show that the present invention utilizes a multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups to anchor the dyeing components iron oxide yellow and copper phthalocyanine in the colorant onto the wood substrate through covalent bonding, achieving a significant improvement in the interfacial bonding strength between the colorant and the wood.
Claims
1. A colorant containing 2-methylresorcinol, characterized in that, The colorant comprises the following raw materials in parts by weight: 5-10 parts of water-based nano-acrylic emulsion; 3-8 parts of iodopropyl-functionalized iron oxide yellow; 0.3-1 part copper phthalocyanine; 0.05-1.5 parts of adhesion modifier, which is a multifunctional 2-methylresorcinol derivative containing vinyl sulfone and secondary amine functional groups, with the following chemical structural formula: ; 25-30 parts of filler; 1-3 parts of compound additives; 0.5-1.5 parts hydroxyethyl cellulose; 30-40 parts deionized water.
2. The colorant containing 2-methylresorcinol according to claim 1, characterized in that, The iodopropyl-functionalized iron oxide yellow was prepared by surface modification of iron oxide yellow with hydroxyl functional groups on its surface by iodopropyltrimethoxysilane, wherein the mass ratio of iron oxide yellow to iodopropyltrimethoxysilane was 1:0.05-0.
15.
3. The colorant containing 2-methylresorcinol according to claim 1, characterized in that, The filler is composed of talc and calcium carbonate.
4. A colorant containing 2-methylresorcinol according to claim 3, characterized in that, The filler is formulated with 15-25 parts by weight of talc and 4-8 parts by weight of calcium carbonate.
5. A colorant containing 2-methylresorcinol according to claim 1, characterized in that, The composite additive consists of 825 defoamer, 5040 dispersant, 472 wetting agent, and sodium hexametaphosphate.
6. A colorant containing 2-methylresorcinol according to claim 5, characterized in that, The formulation of the composite additive is as follows: 20-30 parts by weight of 825 defoamer, 20-40 parts by weight of 5040 dispersant, 50-200 parts by weight of 472 wetting agent, and 10-30 parts by weight of sodium hexametaphosphate.
7. The preparation process of a colorant containing 2-methylresorcinol according to any one of claims 1-6, characterized in that, Includes the following steps: Add the prescribed amount of deionized water to a mixing tank and start stirring. Add the prescribed amount of aqueous nano-acrylic emulsion and composite additives, increase the speed to 500-700 r / min, and stir for 0.1-1 h. Then add the prescribed amounts of iodopropyl-functionalized iron oxide yellow, copper phthalocyanine, and multifunctional 2-methylresorcinol derivative, and stir at 500-700 r / min for 0.5-1.5 h. Let stand for 8-15 h, then add the prescribed amount of filler, increase the speed to 800-1200 r / min, and disperse at high speed until the fineness reaches below 40 μm. Adjust the speed to 400-600 r / min, add the prescribed amount of thickener, and stir at 400-600 r / min for 0.1-1 h to obtain the colorant.
8. The preparation process of a colorant containing 2-methylresorcinol according to claim 7, characterized in that, The preparation method of the multifunctional 2-methylresorcinol derivative is as follows: Mercaptoethylamine with a protected mercaptogroup, formaldehyde, and 2-methylresorcinol undergo a Mannich condensation reaction in a molar equivalence ratio of 1:1:
1. The protecting group of the mercaptogroup in the resulting product is then removed to obtain intermediate a containing a mercaptogroup, whose chemical structural formula is: ； Intermediate a reacts with ethylene oxide under alkaline conditions at a molar ratio of 1:1 to undergo an epoxide ring-opening reaction. The resulting product is then subjected to β-elimination dehydration and oxidation to sulfone under concentrated sulfuric acid to produce a multifunctional 2-methylresorcinol derivative.
9. The preparation process of a colorant containing 2-methylresorcinol according to claim 8, characterized in that, The mercaptoethylamine with the mercapto group protected is a mercaptoethylamine with the mercapto group protected by triphenylmethyl groups, which removes the triphenylmethyl protecting group of the mercapto group by trifluoroacetic acid.
10. The application of a colorant containing 2-methylresorcinol according to any one of claims 1-6, characterized in that, The colorant containing 2-methylresorcinol is used as a wood colorant.