Preparation method and application of chromium-free non-metallic high-performance low-voc composite resin for tanning

Abstract

The present application relates to a kind of preparation methods of chromium-free non-metal tanning high-performance low VOC composite resin, take n-butyl acetate, methyl methacrylate, butyl acrylate, methyl methacrylate-beta-hydroxyethyl acrylate are mixed, n-butyl acetate and azobisdimethylvaleronitrile are added, n-butyl acetate and tert-butyl peroxy-2-ethylhexanoate are added;Take titanium nitrate, vanadium nitrate, zirconium nitrate, naphthalene carboxylic acid and the like are dissolved in N,N-dimethylformamide, cooling, N,N-dimethylformamide is added, filtration;Take high-performance filler, polyhydroxy acrylate prepolymer, polyurethane resin and the like are mixed, and high-performance low VOC composite resin is prepared.The high-performance low VOC composite resin of the present application does not use heavy metal during preparation process, and the high-performance filler has good adsorption performance to heavy metal, which can reduce the soluble heavy metal of coating;After finishing, the finished leather has excellent oil wax feeling, can give leather better oil change effect, and the coating has good physical and mechanical properties and ecological environmental protection performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of tanning technology, in particular to a preparation method and application of a chromium-free non-metallic tanning high-performance low-VOC composite resin. BACKGROUND

[0002] The chromium-free non-metallic tanned leather is widely praised by consumers because it does not contain aluminum, antimony, arsenic, barium, boron, cadmium, chromium (III), chromium (VI), cobalt, copper, lead, manganese, mercury, nickel, selenium, strontium, tin, organic tin, zinc and other toxic and harmful heavy metals. It is the fastest growing and most researched type of leather. Chromium-free non-metallic tanned leather is therefore named because it does not use materials containing heavy metals in production, processing and manufacturing. This heavy metal-free leather is soft and white in color, with very good water permeability and air permeability. With the development of chromium-free non-metallic tanned leather, how to improve the physical and mechanical properties of the leather surface and reduce the introduction of VOC molecules during finishing has become a hot research topic. SUMMARY

[0003] The present application provides a preparation method and application of a chromium-free non-metallic tanning high-performance low-VOC composite resin to improve the physical and mechanical properties of the leather surface and reduce the introduction of VOC molecules during finishing.

[0004] The present application adopts the following technical solutions:

[0005] A preparation method of a chromium-free non-metallic tanning high-performance low-VOC composite resin, comprising the following steps:

[0006] Step 1: Take 100 parts of n-butyl acetate, drive oxygen with nitrogen, add 50-150 parts of methyl methacrylate, 200-400 parts of butyl acrylate, 100-300 parts of beta-hydroxyethyl methacrylate, and 0-100 parts of acrylic acid, mix uniformly, slowly raise the temperature to 100-120°C, add 300 parts of n-butyl acetate and 10-30 parts of azobisisobutyronitrile within 4h, then continue to add 10-50 parts of n-butyl acetate and 1-5 parts of tert-butyl peroxy-2-ethylhexanoate within 4h, and then reduce the reaction temperature to 68-72°C, add 20-30 parts of ammonia water and 800-1200 parts of deionized water for neutralization, and then heat for 0.5-1h after neutralization, and then fractionate the solvent to obtain a multi-hydroxyl acrylate prepolymer;

[0007] Step 2, 100-160 parts of titanium nitrate, 50-80 parts of vanadium nitrate, 1-5 parts of zirconium nitrate, 40-120 parts of naphthalene carboxylic acid, 50-100 parts of 1,3,5-tri(4-carboxyphenyl)benzene, 10-50 parts of 7-azaindole-3-carboxylic acid, 10-20 parts of nitric acid are dissolved in 3000-5000 parts of N,N-dimethylformamide, and the mixture is reacted at 85-110°C for 48-96h, then slowly cooled to room temperature, 1000 parts of N,N-dimethylformamide is added, and the reaction is continued for 12h, finally the filter residue is washed repeatedly with N,N-dimethylformamide, and vacuum drying can obtain a high-performance filler;

[0008] Step 3, 10-500 parts of high-performance filler, 50-300 parts of multi-hydroxy acrylic acid prepolymer, 100-800 parts of polyurethane resin, 100-800 parts of acrylic resin, 50-100 parts of oil wax auxiliary agent, and 50-100 parts of silicone emulsion are strongly dispersed for 30-120 minutes to prepare a high-performance low-VOC composite resin.

[0009] Further improvement, the above-mentioned naphthalene carboxylic acid contains at least 1,4,5,8-naphthalene tetracarboxylic acid, and the naphthalene carboxylic acid can contain 1,4-naphthalene dicarboxylic acid and 2,6-naphthalene dicarboxylic acid.

[0010] Further improvement, the total amount of the above-mentioned multi-hydroxy acrylic acid prepolymer, polyurethane resin and acrylic resin is 1000 parts.

[0011] The application of a high-performance low-VOC composite resin includes a middle coating layer, a top coating layer and a touch layer.

[0012] The formula of the middle coating layer: contains water 200-500 parts, amphoteric oil wax 10-50 parts, anionic oil wax 50-100 parts, non-ionic oil wax 20-60 parts, cationic casein 50-80 parts, high-performance low-VOC composite resin 150-300 parts, cationic polyurethane resin 10-20 parts, cationic acrylic resin 10-20 parts, and penetrating agent 50-100 parts.

[0013] The formula of the top coating layer: contains water 80-120 parts, high-performance low-VOC composite resin 50-100 parts, nitrocellulose 20-50 parts, penetrating agent 20-50 parts, and oil slip touch agent 0-10 parts.

[0014] The formula of the touch layer: contains water 20-50 parts, high-performance low-VOC composite resin 10-20 parts, penetrating agent 0-10 parts, and oil slip touch agent 10-20 parts, and further contains oil wax touch agent 0-10 parts and / or silk touch agent 0-10 parts.

[0015] From the above description of the present application, compared with the prior art, the present application has the following advantages:

[0016] 1.The hydroxy acrylate prepolymer of the application is a hydroxyl component commonly used for processing two-component waterborne polyurethane resin, which carries a large number of hydroxyl groups and carboxyl groups on the polymer chain segment, has excellent hydrophilic performance, and also has strong interaction with the polyurethane chain segment. The preparation of high specific surface area and high performance filler carrying a large number of carboxyl groups through coordination reaction with carboxyl as ligand and cationic center not containing metal ions such as aluminum, antimony, arsenic, barium, boron, cadmium, chromium (III), chromium (VI), cobalt, copper, lead, manganese, mercury, nickel, selenium, strontium, tin, organic tin and zinc is a big core of the application.

[0017] 2.The ligand of the application is selected from aromatic organic matter containing multiple carboxyl groups, which can bridge multiple cationic centers, and then 7-azaindole-3-carboxylic acid is used to end cap the complex to prepare high performance filler with appropriate particle size and uniform distribution. The high performance filler has a large specific surface area and a multi-aromatic ring structure, which can adsorb VOCs possibly introduced in the coating process through electrostatic interaction and π-π interaction, thereby reducing the VOC of the leather.

[0018] 3.The ligand of the application also introduces N heteroatoms, which can enhance the compatibility between different ligands and improve the interaction between the high performance filler and the polymer, promote the dispersion of the high performance filler in the polymer, and at the same time, when the polymer forms a film, the high performance filler can also act as a crosslinking agent to promote the polymer to form a dense and stable film, and improve the physical and mechanical properties and certain waterproof performance of the coating.

[0019] 4.The high performance filler has a large specific surface area and reactivity to adsorb various gas VOCs. For example, 200g of high performance filler can adsorb 1.5m3 of 2000ppm of acetone, benzene, toluene, xylene and 1,2-dichloroethane, and the adsorption rate is ≥90%.

[0020] 5.The high performance low VOC composite resin has a suitable particle size and dispersion capacity. The particle size of the high performance low VOC composite resin dispersion liquid with a concentration of 2% is 1800-3000nm, the particle size distribution coefficient is 0.250-0.500, and the light transmittance is ≥50%.

[0021] 6.The high performance low VOC composite resin has good hydrolysis resistance. After film formation, the swelling rate is ≤50%, the mass loss rate is ≤10%, and the film has good solvent resistance, the mass loss rate in ethanol is ≤10%, and the mass loss rate in acetone is ≤5%.

[0022] 7. The high-performance low-VOC composite resin prepared in the present application does not use heavy metals, and the high-performance filler has good adsorption performance for heavy metals, which can reduce the soluble heavy metals in the coating, and the adsorption amount of arsenic, lead, cadmium, antimony and other heavy metals is ≥100 mg·g-1.

[0023] 8. The high-performance low-VOC composite resin prepared in the present application has excellent oil wax feeling after finishing, which can give the leather good oil change effect, and the coating has good physical and mechanical properties and ecological and environmental protection performance, VOC≤100μg / g, dry rubbing fastness≥4, wear resistance≥4, bending resistance at room temperature≥50000 times, soluble arsenic≤1ppm, and soluble antimony≤30ppm. DETAILED DESCRIPTION

[0024] Example 1:

[0025] A preparation method of a chromium-free non-metallic high-performance low-VOC composite resin for tanning, comprising the following steps:

[0026] Step 1, preparation of a multi-hydroxy acrylic acid prepolymer: take 100 parts of n-butyl acetate, drive oxygen with nitrogen, add 50 parts of methyl methacrylate, 300 parts of butyl acrylate, 150 parts of methyl methacrylate-β-hydroxyethyl, mix uniformly, slowly raise the temperature to 100℃, and then add 300 parts of n-butyl acetate and 30 parts of azobisisobutyronitrile within 4h, and then continue to add 50 parts of n-butyl acetate and 2 parts of tert-butyl peroxy-2-ethylhexanoate within 4h, and then reduce the reaction temperature to 72℃, add 22 parts of ammonia water and 800 parts of deionized water for neutralization, and then heat for 0.5h, and then fractionate the solvent to obtain the multi-hydroxy acrylic acid prepolymer.

[0027] Step 2, preparation of a high-performance filler: take 100 parts of titanium nitrate, 75 parts of vanadium nitrate, 5 parts of zirconium nitrate, 40 parts of 1,4-naphthalene dicarboxylic acid, 40 parts of 1,4,5,8-naphthalene tetracarboxylic acid, 100 parts of 1,3,5-tris(4-carboxyphenyl)benzene, 20 parts of 7-azaindole-3-carboxylic acid, and 15 parts of nitric acid are dissolved in 4800 parts of N,N-dimethylformamide, and reacted at 110℃ for 48h, and then slowly cooled to room temperature, 1000 parts of N,N-dimethylformamide is added, and the reaction is continued for 12h, and finally the filter residue is washed repeatedly with N,N-dimethylformamide, and vacuum dried to obtain the high-performance filler.

[0028] Step 3, preparation of high-performance low-VOC composite resin: take 50 parts of high-performance filler, 200 parts of multi-hydroxy acrylic acid prepolymer, 200 parts of polyurethane resin (17-912, Star), 600 parts of acrylic resin (77-150, Star), 50 parts of oil wax aid (17-706, Star), 100 parts of silicone emulsion (5230, Star), and strongly disperse for 30 minutes to obtain high-performance low-VOC composite resin.

[0029] Example 2:

[0030] A preparation method of a chromium-free non-metallic tanning high-performance low-VOC composite resin comprises the following steps:

[0031] Step 1, preparation of multi-hydroxy acrylic acid prepolymer: take 100 parts of n-butyl acetate, remove oxygen by nitrogen, and then add 100 parts of methyl methacrylate, 200 parts of butyl acrylate, 150 parts of β-hydroxyethyl methacrylate, and 50 parts of acrylic acid. After mixing, slowly raise the temperature to 110°C, and then add 300 parts of n-butyl acetate and 20 parts of azobisisobutyronitrile within 4 hours. Then, continue to add 35 parts of n-butyl acetate and 3 parts of tert-butyl peroxy-2-ethylhexanoate within 4 hours. After that, keep the reaction temperature at 70°C for 4 hours. Then, add 26 parts of ammonia water and 1000 parts of deionized water for neutralization. After neutralization, keep the temperature for 1 hour. Then, separate the solvent to obtain the multi-hydroxy acrylic acid prepolymer.

[0032] Step 2, preparation of high-performance filler: take 142 parts of titanium nitrate, 57 parts of vanadium nitrate, 1 part of zirconium nitrate, 60 parts of 1,4,5,8-naphthalene tetracarboxylic acid, 100 parts of 1,3,5-tris(4-carboxyphenyl)benzene, and 40 parts of 7-azaindole-3-carboxylic acid. Dissolve them in 3500 parts of N,N-dimethylformamide at 100°C for 72 hours. Then, slowly cool to room temperature. Add 1000 parts of N,N-dimethylformamide and continue to react for 12 hours. Finally, filter and repeatedly wash the filter residue with N,N-dimethylformamide. Then, vacuum dry to obtain the high-performance filler.

[0033] Step 3, preparation of high-performance low-VOC composite resin: take 500 parts of high-performance filler, 100 parts of multi-hydroxy acrylic acid prepolymer, 800 parts of polyurethane resin (17-912, Star), 100 parts of acrylic resin (77-150, Star), 70 parts of oil wax aid (17-706, Star), and 80 parts of silicone emulsion (5230, Star). Strongly disperse for 90 minutes to obtain the high-performance low-VOC composite resin.

[0034] Example 3:

[0035] A preparation method of a chromium-free non-metallic tanning high-performance low-VOC composite resin comprises the following steps:

[0036] Step 1, preparation of multi-hydroxy acrylic acid prepolymer: take 100 parts of n-butyl acetate, oxygen is driven away by nitrogen, add 150 parts of methyl methacrylate, 200 parts of butyl acrylate, 150 parts of methyl methacrylate-β-hydroxyethyl, 100 parts of acrylic acid, mix uniformly, then slowly raise the temperature to 120℃, add 300 parts of n-butyl acetate and 10 parts of azobisisobutyronitrile within 4h, then continue to add 20 parts of n-butyl acetate and 4 parts of tert-butyl peroxy-2-ethylhexanoate within 4h, keep the temperature for 3h, then reduce the reaction temperature to 68℃, add 28 parts of ammonia water and 1200 parts of deionized water for neutralization, keep the temperature for 1h after neutralization, then fractionate the solvent to obtain the multi-hydroxy acrylic acid prepolymer.

[0037] Step 2, preparation of high-performance filler: take 142 parts of titanium nitrate, 75 parts of vanadium nitrate, 3 parts of zirconium nitrate, 40 parts of 1,4-naphthalene dicarboxylic acid, 40 parts of 2,6-naphthalene dicarboxylic acid, 40 parts of 1,4,5,8-naphthalene tetracarboxylic acid, 70 parts of 1,3,5-tris(4-carboxyphenyl)benzene, 10-10 parts of 7-azaindole-3-carboxylic acid, 20 parts of nitric acid is dissolved in 4000 parts of N,N-dimethylformamide, react at 90℃ for 96h, then slowly cool to room temperature, add 1000 parts of N,N-dimethylformamide, continue to react for 12h, finally filter, wash the filter residue with N,N-dimethylformamide repeatedly, and vacuum dry to obtain the high-performance filler.

[0038] Step 3, preparation of high-performance low-VOC composite resin: take 250 parts of high-performance filler, 100 parts of multi-hydroxy acrylic acid prepolymer, 100 parts of polyurethane resin (17-912, Star), 800 parts of acrylic resin (77-150, Star), 100 parts of oil wax additive (17-706, Star), 50 parts of silicone emulsion (5230, Star), and disperse for 120 minutes to obtain the high-performance low-VOC composite resin.

[0039] The high-performance filler and the high-performance low-VOC composite resin obtained in Example 1, Example 2 and Example 3 are detected by experiments, and the experimental data are shown in Table 1:

[0040] Table 1

[0041]

[0042] Example 4:

[0043] The application of a chromium-free non-metallic tanning high-performance low-VOC composite resin includes a middle coating layer, a top coating layer and a hand feel layer.

[0044] Its mechanical operation is as follows: spray middle coating (5g / sf 2x2)→pressing the orifice plate (85℃ / 50kg / 3s)→spray middle coating (5g / sf 2x2)→polishing (30kgf / 120℃)→spray top coating (3g / sf 2x2)→polishing (30kgf / 120℃)→pulling soft (6 levels)→spray hand feel layer (3g / sf 2x2)→polishing (30kgf / 120℃).

[0045] Middle coating formula: water 300 parts, amphoteric oil wax 30 parts (7531, Tongli Chemical), anionic oil wax 80 parts (512, Xidong Chemical), nonionic oil wax 40 parts (Haodeya Chemical), cationic casein 60 parts (4592, Maiji Chemical), high-performance low-VOC composite resin 180 parts, cationic polyurethane resin 10 parts (17-912, Star), cationic acrylic resin 10 parts (77-150. Star), penetrant 70 parts (ethylene glycol monoethyl ether).

[0046] Top coating formula: water 80 parts, high-performance low-VOC composite resin 80 parts, nitrocellulose 20 parts (8119, Fengzhengwanwei), penetrant 30 parts (ethylene glycol monoethyl ether), oil slip hand feel agent 5 parts (5230, Star).

[0047] Hand feel layer formula: water 50 parts, high-performance low-VOC composite resin 10 parts, penetrant 10 parts, oil slip hand feel agent 15 parts (5230, Star), oil wax hand feel agent 5 parts (358, Star), silk hand feel agent 5 parts (283, Star).

[0048] The high-performance low-VOC composite resin used in this example is prepared according to the method of Example 1.

[0049] Example 5:

[0050] The application of the chromium-free non-metallic tanning high-performance low-VOC composite resin of this example is basically the same as that of Example 4, except that the high-performance low-VOC composite resin used in this example is prepared according to the method of Example 2.

[0051] Example 6:

[0052] The application of the chromium-free non-metallic tanning high-performance low-VOC composite resin of this example is basically the same as that of Example 4, except that the high-performance low-VOC composite resin used in this example is prepared according to the method of Example 3.

[0053] The leather prepared according to Example 4, Example 5, and Example 6 is subjected to experimental detection, and the experimental data obtained are shown in Table 2 below:

[0054] Table 2

[0055]

[0056] The above merely illustrates the specific embodiments of the present application, but the design concept of the present application is not limited thereto, and any non-essential change to the present application using the concept shall be deemed as an infringement of the protection scope of the present application.

Claims

1. A process for the preparation of chromium-free non-metallic tanning high performance low VOC composite resin characterized by, It comprises the following steps: Step 1, take 100 parts of n-butyl acetate, oxygen is driven by nitrogen, add 50-150 parts of methyl methacrylate, 200-400 parts of butyl acrylate, 100-300 parts of methacrylic acid-β-hydroxyethyl ester, 0-100 parts of acrylic acid, mix uniformly, then slowly raise the temperature to 100-120°C, add 300 parts of n-butyl acetate and 10-30 parts of azobisisobutyronitrile within 4h, then continue to add 10-50 parts of n-butyl acetate and 1-5 parts of tert-butyl peroxy-2-ethylhexanoate within 4h, keep warm for 2-6h, reduce the reaction temperature to 68-72°C, add 20-30 parts of ammonia water and 800-1200 parts of deionized water for neutralization, keep warm for 0.5-1h after neutralization, then fractionate the solvent to obtain a multi-hydroxyl acrylic acid prepolymer; Step 2, take 100-160 parts of titanium nitrate, 50-80 parts of vanadium nitrate, 1-5 parts of zirconium nitrate, 40-120 parts of naphthalene carboxylic acid, 50-100 parts of 1,3,5-tris(4-carboxyphenyl)benzene, 10-50 parts of 7-azaindole-3-carboxylic acid, 10-20 parts of nitric acid, dissolve in 3000-5000 parts of N,N-dimethylformamide, react at 85-110°C for 48-96h, then slowly cool to room temperature, add 1000 parts of N,N-dimethylformamide and continue to react for 12h, finally filter, wash the filter residue with N,N-dimethylformamide repeatedly, and vacuum dry to obtain a high-performance filler; Step 3, take 10-500 parts of high-performance filler, 50-300 parts of multi-hydroxyl acrylic acid prepolymer, 100-800 parts of polyurethane resin, 100-800 parts of acrylic resin, 50-100 parts of oil wax auxiliary agent, and 50-100 parts of silicone emulsion, strongly disperse for 30-120 minutes to obtain a high-performance low-VOC composite resin.

2. A process for the preparation of a chromium-free non-metallic tanning high performance low VOC composite resin as claimed in claim 1, wherein: The naphthalene carboxylic acid contains at least 1,4,5,8-naphthalene tetra-carboxylic acid.

3. A process for the preparation of a chromium-free non-metallic tanning high performance low VOC composite resin as claimed in claim 1, wherein: The naphthalene carboxylic acid contains 1,4-naphthalene dicarboxylic acid and 2,6-naphthalene dicarboxylic acid.

4. A process for the preparation of a chromium-free non-metallic tanning high performance low VOC composite resin as claimed in claim 1, wherein: The total amount of the multi-hydroxyl acrylic acid prepolymer, the polyurethane resin and the acrylic resin is 1000 parts.

5. Use of the high performance low VOC composite resin prepared according to the process for the preparation of a chromium-free non-metallic tanning high performance low VOC composite resin according to claim 1, characterized in that, It comprises a middle coating layer, a top coating layer and a hand feeling layer; The formula of the middle coating layer: contains water 200-500 parts, amphoteric oil wax 10-50 parts, anionic oil wax 50-100 parts, non-ionic oil wax 20-60 parts, cationic casein 50-80 parts, high-performance low-VOC composite resin 150-300 parts, cationic polyurethane resin 10-20 parts, cationic acrylic resin 10-20 parts, and penetrating agent 50-100 parts; The formula of the top coating layer: contains water 80-120 parts, high-performance low-VOC composite resin 50-100 parts, nitrocellulose 20-50 parts, penetrating agent 20-50 parts, and oil slip hand feeling agent 0-10 parts; The formula of the hand feeling layer: contains water 20-50 parts, high-performance low-VOC composite resin 10-20 parts, penetrating agent 0-10 parts, oil slip hand feeling agent 10-20 parts, and also contains oil wax hand feeling agent 0-10 parts and / or silk hand feeling agent 0-10 parts.

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