Leather shoes with antioxidant vamps and production process of leather shoes

Abstract

The invention relates to the technical field of leather shoe manufacturing, and discloses an anti-oxidation vamp leather shoe and a production process thereof.The production process includes the steps that nappa vamp leather is taken and subjected to surface cleaning for standby application; the surface of the cleaned nappa vamp leather is coated with an antioxidant 1135, acrylic resin and sulfur modified benzoxazine, then drying is conducted, and the leather shoes with the antioxidant vamps are obtained. A benzoxazine structure in sulfur-modified benzoxazine can form a heat-resistant phenolic resin structure at a high temperature and has a good flame-retardant effect, meanwhile, a triazine base body also has a good flame-retardant property, and the sulfur element, the boron element and the nitrogen element contained in the triazine base all have good flame-retardant effects and jointly form a flame-retardant system, so that the flame-retardant effect is good. And after a chlorine group in the chlorine-containing triazinyl benzoxazine reacts with a hydroxyl group in allyl alcohol, the substitution degree of alkenyl is improved, the substitution degree of sulfur is further improved, and the flame-retardant effect is better.

Description

Technical Field

[0001] The invention relates to the technical field of leather shoe manufacturing, in particular to an anti-oxidation upper leather shoe and a production process thereof. Background Art

[0002] Leather shoes refer to shoes with natural leather as the upper and leather, rubber, plastic, etc. as the sole, which are processed and formed by gluing, injection molding and other processes. They have good air permeability and moisture absorption, but they will be oxidized during long-term storage, thus affecting their appearance. When encountering a fire, the surface is easy to burn, which will also affect their normal use. Therefore, how to avoid this phenomenon is the key to solving the problem. For example, patent CN113563774B discloses a tear-resistant leather shoe upper and a preparation method thereof. The tear-resistant leather shoe upper is coated with a tear-resistant agent. The raw materials for preparing the tear-resistant agent include 5-10 parts of hydroxy silicone oil, 0.5-1.2 parts of fatliquor, 15-25 parts of acrylic resin, 3-7 parts of epoxy resin, 2-5 parts of phosphate solution, 0.05-0.2 parts of surfactant, and 0.03-0.08 parts of accelerator by weight; the leather shoe upper of the invention has excellent tear resistance and excellent antifouling performance, but its flame retardant and antioxidant effects are not improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides an anti-oxidation upper leather shoe and a production process thereof, which has good flame retardant and anti-oxidation effects.

[0005] (II) Technical solution

[0006] To achieve the above objectives, the present invention provides the following technical solution: an antioxidant upper leather shoe, the upper leather shoe is coated with 2-4 parts by weight of antioxidant 1135, 6-10 parts by weight of acrylic resin, and 2-4 parts by weight of sulfur-modified benzoxazine.

[0007] Preferably, the preparation method of the sulfur-modified benzoxazine is:

[0008] (1) adding 4-aminophenylboronic acid and 4,6-diamino-2-hydroxy-1,3,5-triazine to N,N-dimethylformamide solvent, introducing nitrogen protection, stirring evenly, reacting at 75-100° C. for 6-10 hours, cooling to room temperature after reaction, filtering, washing and drying to obtain amino-modified triazine-phenylboronic acid;

[0009] (2) adding amino-modified triazine phenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 65-80° C. for 8-12 hours. After the reaction, the reaction is carried out by vacuum distillation, washing with deionized water, and recrystallizing the crude product from dichloromethane to obtain a chlorinated triazine benzoxazine;

[0010] (3) adding chlorine-containing triazine-based benzoxazine and allyl alcohol to an acetone solvent, stirring evenly, and continuously adding pyridine catalyst thereto, reacting at 70-90° C. for 7-15 hours, washing after completion, and drying to obtain an olefin-modified triazine-based benzoxazine;

[0011] (4) Adding alkenyl-modified triazine-based benzoxazine to N,N-dimethylformamide solvent, stirring and dispersing, adding dodecanethiol and benzoin dimethyl ether photoinitiator, heating, irradiating with ultraviolet light to react, centrifuging after completion, washing and drying to obtain sulfur-modified benzoxazine.

[0012] Preferably, the mass ratio of 4-aminophenylboronic acid to 4,6-diamino-2-hydroxy-1,3,5-triazine in (1) is 1.1-1.4:1.

[0013] Preferably, the mass ratio of amino-modified triazinephenylboronic acid, aqueous solution of formaldehyde and dichlorophenol in (2) is 1:1.2-1.5:1.3-1.8.

[0014] Preferably, the mass ratio of the chlorotriazine-containing benzoxazine, allyl alcohol and pyridine catalyst in (3) is 1:2.2-2.6:0.01-0.03.

[0015] Preferably, the mass ratio of alkenyl-modified triazine-based benzoxazine, dodecanethiol, and benzoin dimethyl ether photoinitiator in (4) is 1.2-1.5:1:0.02-0.03.

[0016] Preferably, the reaction temperature in (4) is 25-50°C.

[0017] Preferably, the ultraviolet light irradiation time in (4) is 2-4 hours.

[0018] Preferably, the wavelength of the reactive ultraviolet light in (4) is 365 nm.

[0019] Preferably, the production process of the antioxidant upper leather shoes is:

[0020] S1. Take the Nappa upper leather and clean the surface for later use;

[0021] S2. Antioxidant 1135, acrylic resin, and sulfur-modified benzoxazine are coated on the surface of the cleaned nappa upper leather, and then dried at 80-100° C. to obtain antioxidant upper leather shoes.

[0022] (III) Beneficial technical effects

[0023] The invention comprises the following steps: taking Nappa upper leather for surface cleaning and preparing the leather for later use; coating the surface of the cleaned Nappa upper leather with antioxidant 1135, acrylic resin and sulfur-modified benzoxazine, and then drying the leather to obtain an antioxidant upper leather shoe.

[0024] The boronic acid group in 4-aminophenylboronic acid and the hydroxyl group in 4,6-diamino-2-hydroxy-1,3,5-triazine are subjected to an esterification reaction to introduce an amino group, thereby obtaining amino-modified triazinylphenylboronic acid. The amino-modified triazinylphenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol are subjected to a cyclization reaction to obtain chlorine-containing triazinylbenzoxazine. The chlorine group in the chlorine-containing triazinylbenzoxazine and the hydroxyl group in allyl alcohol are subjected to a substitution reaction to introduce an alkenyl group, thereby obtaining alkenyl-modified triazinylbenzoxazine. The alkenyl group in the alkenyl-modified triazinylbenzoxazine and the thiol in dodecanethiol are subjected to an addition reaction to obtain sulfur-modified benzoxazine.

[0025] The benzoxazine structure in the sulfur-modified benzoxazine will form a heat-resistant phenolic resin structure at high temperature, which has a good flame retardant effect. At the same time, the triazine itself also has good flame retardant properties. The sulfur, boron and nitrogen elements contained therein all have good flame retardant effects and together constitute a flame retardant system. In addition, after the chlorine group in the chlorine-containing triazine-based benzoxazine reacts with the hydroxyl group in the allyl alcohol, the substitution degree of the olefin group is increased, and the substitution degree of sulfur is further increased, making it have a better flame retardant effect and a good antioxidant effect. DETAILED DESCRIPTION

[0026] Example 1

[0027] (1) adding 4-aminophenylboronic acid and 4,6-diamino-2-hydroxy-1,3,5-triazine to a solvent in N,N-dimethylformamide, wherein the mass ratio of 4-aminophenylboronic acid to 4,6-diamino-2-hydroxy-1,3,5-triazine is 1.1:1, introducing nitrogen protection, stirring evenly, reacting at 75° C. for 6 hours, cooling to room temperature after the reaction, filtering, washing and drying to obtain amino-modified triazine-phenylboronic acid;

[0028] (2) adding amino-modified triazine phenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol to a toluene solvent, wherein the mass ratio of amino-modified triazine phenylboronic acid, the aqueous solution of formaldehyde, and dichlorophenol is 1:1.2:1.3, fully dissolving, and performing a cyclization reaction at 65° C. for 8 h. After completion, distillation under reduced pressure is performed, the product is washed with deionized water, and the crude product is recrystallized from dichloromethane to obtain a chlorine-containing triazine benzoxazine;

[0029] (3) adding chlorinated triazine-containing benzoxazine and allyl alcohol to an acetone solvent, stirring evenly, and continuing to add a pyridine catalyst, wherein the mass ratio of chlorinated triazine-containing benzoxazine, allyl alcohol, and pyridine catalyst is 1:2.2:0.01, reacting at 70° C. for 7 h, washing after completion, and drying to obtain an olefin-modified triazine-containing benzoxazine;

[0030] (4) adding alkenyl-modified triazine-based benzoxazine to N,N-dimethylformamide solvent, stirring and dispersing, and then adding dodecanethiol and benzoin dimethyl ether photoinitiator, wherein the mass ratio of alkenyl-modified triazine-based benzoxazine, dodecanethiol, and benzoin dimethyl ether photoinitiator is 1.2:1:0.02, irradiating with 365 nm ultraviolet light at 25° C. for 2 h, centrifuging after the end, washing and drying to obtain sulfur-modified benzoxazine;

[0031] (5) Take the Nappa upper leather and clean the surface for later use;

[0032] (6) 2 parts by weight of antioxidant 1135, 6 parts by weight of acrylic resin, and 2 parts by weight of sulfur-modified benzoxazine were coated on the surface of the cleaned nappa upper leather, and then dried at 80° C. to prepare an antioxidant upper leather shoe.

[0033] Example 2

[0034] (1) adding 4-aminophenylboronic acid and 4,6-diamino-2-hydroxy-1,3,5-triazine to a solvent in N,N-dimethylformamide, wherein the mass ratio of 4-aminophenylboronic acid to 4,6-diamino-2-hydroxy-1,3,5-triazine is 1.4:1, introducing nitrogen protection, stirring evenly, reacting at 100° C. for 10 hours, cooling to room temperature after the reaction, filtering, washing and drying to obtain amino-modified triazine-phenylboronic acid;

[0035] (2) adding amino-modified triazine phenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol to a toluene solvent, wherein the mass ratio of amino-modified triazine phenylboronic acid, the aqueous solution of formaldehyde, and dichlorophenol is 1:1.5:1.8, fully dissolving, and performing a cyclization reaction at 80° C. for 12 hours. After completion, the reaction is distilled under reduced pressure, washed with deionized water, and the crude product is recrystallized from dichloromethane to obtain a chlorine-containing triazine benzoxazine;

[0036] (3) adding chlorinated triazine-containing benzoxazine and allyl alcohol to an acetone solvent, stirring evenly, and continuing to add a pyridine catalyst, wherein the mass ratio of chlorinated triazine-containing benzoxazine, allyl alcohol, and pyridine catalyst is 1:2.6:0.03, reacting at 90° C. for 15 h, washing after completion, and drying to obtain an olefin-modified triazine-containing benzoxazine;

[0037] (4) adding alkenyl-modified triazine-based benzoxazine to N,N-dimethylformamide solvent, stirring and dispersing, and then adding dodecanethiol and benzoin dimethyl ether photoinitiator, wherein the mass ratio of alkenyl-modified triazine-based benzoxazine, dodecanethiol, and benzoin dimethyl ether photoinitiator is 1.5:1:0.03, irradiating with 365 nm ultraviolet light at 50° C. for 4 h, centrifuging after the end, washing and drying to obtain sulfur-modified benzoxazine;

[0038] (5) Take the Nappa upper leather and clean the surface for later use;

[0039] (6) 4 parts by weight of antioxidant 1135, 10 parts by weight of acrylic resin, and 4 parts by weight of sulfur-modified benzoxazine were coated on the surface of the cleaned nappa upper leather, and then dried at 100° C. to prepare an antioxidant upper leather shoe.

[0040] Example 3

[0041] (1) adding 4-aminophenylboronic acid and 4,6-diamino-2-hydroxy-1,3,5-triazine to a solvent in N,N-dimethylformamide, wherein the mass ratio of 4-aminophenylboronic acid to 4,6-diamino-2-hydroxy-1,3,5-triazine is 1.25:1, introducing nitrogen protection, stirring evenly, reacting at 87° C. for 8 h, cooling to room temperature after the reaction, filtering, washing and drying to obtain amino-modified triazine-phenylboronic acid;

[0042] (2) adding amino-modified triazine phenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol to a toluene solvent, wherein the mass ratio of amino-modified triazine phenylboronic acid, the aqueous solution of formaldehyde, and dichlorophenol is 1:1.35:1.5, fully dissolving, and carrying out a cyclization reaction at 70° C. for 10 hours. After completion, the reaction is distilled under reduced pressure, washed with deionized water, and the crude product is recrystallized from dichloromethane to obtain a chlorine-containing triazine benzoxazine;

[0043] (3) adding chlorinated triazine-containing benzoxazine and allyl alcohol to an acetone solvent, stirring evenly, and continuing to add a pyridine catalyst, wherein the mass ratio of chlorinated triazine-containing benzoxazine, allyl alcohol, and pyridine catalyst is 1:2.4:0.02, reacting at 80° C. for 11 hours, washing after completion, and drying to obtain an olefin-modified triazine-containing benzoxazine;

[0044] (4) adding alkenyl-modified triazine-based benzoxazine to N,N-dimethylformamide solvent, stirring and dispersing, and then adding dodecanethiol and benzoin dimethyl ether photoinitiator, wherein the mass ratio of alkenyl-modified triazine-based benzoxazine, dodecanethiol, and benzoin dimethyl ether photoinitiator is 1.35:1:0.025, irradiating with 365 nm ultraviolet light at 35° C. for 3 h, centrifuging after the end, washing and drying to obtain sulfur-modified benzoxazine;

[0045] (5) Take the Nappa upper leather and clean the surface for later use;

[0046] (6) 3 parts by weight of antioxidant 1135, 8 parts by weight of acrylic resin, and 3 parts by weight of sulfur-modified benzoxazine were coated on the surface of the cleaned nappa upper leather, and then dried at 90° C. to prepare an antioxidant upper leather shoe.

[0047] Example 4

[0048] (1) adding 4-aminophenylboronic acid and 4,6-diamino-2-hydroxy-1,3,5-triazine to a solvent in N,N-dimethylformamide, wherein the mass ratio of 4-aminophenylboronic acid to 4,6-diamino-2-hydroxy-1,3,5-triazine is 1.1:1, introducing nitrogen protection, stirring evenly, reacting at 75° C. for 6 hours, cooling to room temperature after the reaction, filtering, washing and drying to obtain amino-modified triazine-phenylboronic acid;

[0049] (2) adding amino-modified triazine phenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol to a toluene solvent, wherein the mass ratio of amino-modified triazine phenylboronic acid, the aqueous solution of formaldehyde, and dichlorophenol is 1:1.2:1.3, fully dissolving, and performing a cyclization reaction at 65° C. for 8 h. After completion, distillation under reduced pressure is performed, the product is washed with deionized water, and the crude product is recrystallized from dichloromethane to obtain a chlorine-containing triazine benzoxazine;

[0050] (3) adding chlorinated triazine-containing benzoxazine and allyl alcohol to an acetone solvent, stirring evenly, and continuing to add a pyridine catalyst, wherein the mass ratio of chlorinated triazine-containing benzoxazine, allyl alcohol, and pyridine catalyst is 1:2.6:0.03, reacting at 90° C. for 15 h, washing after completion, and drying to obtain an olefin-modified triazine-containing benzoxazine;

[0051] (4) adding alkenyl-modified triazine-based benzoxazine to N,N-dimethylformamide solvent, stirring and dispersing, and then adding dodecanethiol and benzoin dimethyl ether photoinitiator, wherein the mass ratio of alkenyl-modified triazine-based benzoxazine, dodecanethiol, and benzoin dimethyl ether photoinitiator is 1.5:1:0.03, irradiating with 365 nm ultraviolet light at 50° C. for 4 h, centrifuging after the end, washing and drying to obtain sulfur-modified benzoxazine;

[0052] (5) Take the Nappa upper leather and clean the surface for later use;

[0053] (6) 3 parts by weight of antioxidant 1135, 8 parts by weight of acrylic resin, and 3 parts by weight of sulfur-modified benzoxazine were coated on the surface of the cleaned nappa upper leather, and then dried at 90° C. to prepare an antioxidant upper leather shoe.

[0054] Example 5

[0055] (1) adding 4-aminophenylboronic acid and 4,6-diamino-2-hydroxy-1,3,5-triazine to a solvent in N,N-dimethylformamide, wherein the mass ratio of 4-aminophenylboronic acid to 4,6-diamino-2-hydroxy-1,3,5-triazine is 1.4:1, introducing nitrogen protection, stirring evenly, reacting at 100° C. for 10 hours, cooling to room temperature after the reaction, filtering, washing and drying to obtain amino-modified triazine-phenylboronic acid;

[0056] (2) adding amino-modified triazine phenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol to a toluene solvent, wherein the mass ratio of amino-modified triazine phenylboronic acid, the aqueous solution of formaldehyde, and dichlorophenol is 1:1.5:1.8, fully dissolving, and performing a cyclization reaction at 80° C. for 12 hours. After completion, the reaction is distilled under reduced pressure, washed with deionized water, and the crude product is recrystallized from dichloromethane to obtain a chlorine-containing triazine benzoxazine;

[0057] (3) adding chlorinated triazine-containing benzoxazine and allyl alcohol to an acetone solvent, stirring evenly, and continuing to add a pyridine catalyst, wherein the mass ratio of chlorinated triazine-containing benzoxazine, allyl alcohol, and pyridine catalyst is 1:2.4:0.02, reacting at 80° C. for 11 hours, washing after completion, and drying to obtain an olefin-modified triazine-containing benzoxazine;

[0058] (4) adding alkenyl-modified triazine-based benzoxazine to N,N-dimethylformamide solvent, stirring and dispersing, and then adding dodecanethiol and benzoin dimethyl ether photoinitiator, wherein the mass ratio of alkenyl-modified triazine-based benzoxazine, dodecanethiol, and benzoin dimethyl ether photoinitiator is 1.35:1:0.025, irradiating with 365 nm ultraviolet light at 35° C. for 3 h, centrifuging after the end, washing and drying to obtain sulfur-modified benzoxazine;

[0059] (5) Take the Nappa upper leather and clean the surface for later use;

[0060] (6) 2 parts by weight of antioxidant 1135, 6 parts by weight of acrylic resin, and 2 parts by weight of sulfur-modified benzoxazine were coated on the surface of the cleaned nappa upper leather, and then dried at 80° C. to prepare an antioxidant upper leather shoe.

[0061] Comparative Example 1

[0062] (1) Take Nappa shoe upper leather and clean the surface for later use;

[0063] (1) 2 parts by weight of antioxidant 1135 and 6 parts by weight of acrylic resin were coated on the surface of the cleaned nappa upper leather, and then dried at 80° C. to prepare an antioxidant upper leather shoe.

[0064] Use an oxygen index meter to test the limiting oxygen index of water-based paint; use a horizontal and vertical combustion instrument to test the combustion level of water-based paint.

[0065] Table 1: Flame retardancy tests.

[0066] project Limiting oxygen index (%) Combustion level Example 1 30 V-0 Example 2 33 V-0 Example 3 32 V-0 Example 4 33 V-0 Example 5 31 V-0 Comparative Example 1 22 V-1

[0067] It can be seen from Table 1 that the flame retardant effects of Examples 1-5 are better than that of Comparative Example 1, which indicates that the antioxidant upper leather shoes prepared by the present invention have good flame retardant effects.

[0068] Antioxidation test: The leather shoes with antioxidant uppers of Examples 1-5 and Comparative Example 1 were placed naturally for 30 days and their appearance was observed.

[0069] Table 2: Antioxidant test.

[0070] project Appearance Example 1 No color change Example 2 No color change Example 3 No color change Example 4 No color change Example 5 No color change Comparative Example 1 Slightly yellow

[0071] It can be seen from Table 2 that the appearance of the leather shoes with antioxidant uppers in Examples 1-5 is unchanged compared to that in Comparative Example 1, indicating that they have good antioxidant effects.

[0072] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An anti-oxidation upper leather shoe, characterized in that: The upper leather shoes are coated with 2-4 parts by weight of antioxidant 1135, 6-10 parts by weight of acrylic resin, and 2-4 parts by weight of sulfur-modified benzoxazine.

2. The anti-oxidation upper leather shoes according to claim 1, characterized in that: The preparation method of the sulfur-modified benzoxazine is as follows: (1) adding 4-aminophenylboronic acid and 4,6-diamino-2-hydroxy-1,3,5-triazine to N,N-dimethylformamide solvent, introducing nitrogen protection, stirring evenly, reacting at 75-100° C. for 6-10 hours, cooling to room temperature after reaction, filtering, washing and drying to obtain amino-modified triazine-phenylboronic acid; (2) adding amino-modified triazine phenylboronic acid, an aqueous solution of formaldehyde, and dichlorophenol to a toluene solvent, fully dissolving them, and carrying out a cyclization reaction at 65-80° C. for 8-12 hours. After the reaction, the reaction is carried out by vacuum distillation, washing with deionized water, and recrystallizing the crude product from dichloromethane to obtain a chlorinated triazine benzoxazine; (3) adding chlorine-containing triazine-based benzoxazine and allyl alcohol to an acetone solvent, stirring evenly, and continuously adding pyridine catalyst thereto, reacting at 70-90° C. for 7-15 hours, washing after completion, and drying to obtain an olefin-modified triazine-based benzoxazine; (4) Adding alkenyl-modified triazine-based benzoxazine to N,N-dimethylformamide solvent, stirring and dispersing, adding dodecanethiol and benzoin dimethyl ether photoinitiator, heating, irradiating with ultraviolet light to react, centrifuging after completion, washing and drying to obtain sulfur-modified benzoxazine.

3. The anti-oxidation upper leather shoes according to claim 2, characterized in that: The mass ratio of 4-aminophenylboronic acid to 4,6-diamino-2-hydroxy-1,3,5-triazine in (1) is 1.1-1.4:

1.

4. The anti-oxidation upper leather shoes according to claim 2, characterized in that: The mass ratio of amino-modified triazinephenylboronic acid, formaldehyde aqueous solution and dichlorophenol in (2) is 1:1.2-1.5:1.3-1.

8.

5. The anti-oxidation upper leather shoes according to claim 2, characterized in that: The mass ratio of the chlorotriazine-containing benzoxazine, allyl alcohol and pyridine catalyst in (3) is 1:2.2-2.6:0.01-0.

03.

6. The anti-oxidation upper leather shoes according to claim 2, characterized in that: The mass ratio of the alkenyl-modified triazine-based benzoxazine, dodecanethiol, and benzoin dimethyl ether photoinitiator in (4) is 1.2-1.5:1:0.02-0.

03.

7. The anti-oxidation upper leather shoes according to claim 2, characterized in that: The reaction temperature in (4) is 25-50°C.

8. The anti-oxidation upper leather shoes according to claim 2, characterized in that: The ultraviolet light irradiation time in (4) is 2-4h.

9. The anti-oxidation upper leather shoes according to claim 2, characterized in that: The wavelength of the reactive ultraviolet light in (4) is 365 nm.

10. A production process for anti-oxidation upper leather shoes according to any one of claims 1 to 9, characterized in that: The production process of the antioxidant upper leather shoes is: S1. Take the Nappa upper leather and clean the surface for later use; S2. Antioxidant 1135, acrylic resin, and sulfur-modified benzoxazine are coated on the surface of the cleaned nappa upper leather, and then dried at 80-100° C. to obtain antioxidant upper leather shoes.