A multifunctional triazine type chrome-free tanning agent and preparation method thereof

Abstract

The invention discloses a multifunctional triazine type chrome-free tanning agent and a preparation method thereof. The chrome-free tanning agent is prepared by using aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, aminonaphtholsulfonic acid, diaminobenzenesulfonic acid, sultone and trihalo-s-triazine as raw materials. The triazine type chrome-free tanning agent has high functionality, contains functional groups such as active chlorine, sulfonic acid group, hydroxyl group and aromatic ring, forms multi-point cross-linking between collagen fibers, produces tanning effect, and significantly improves the shrinkage temperature and physical and mechanical properties of leather collagen. The triazine type chrome-free tanning agent can replace chrome powder, reduce environmental pollution in the leather industry, and promote clean production in the leather industry. The invention provides a new idea for the development and research of a novel chrome-free tanning agent.

Description

Technical Field

[0001] The invention relates to a chrome-free tanning agent and a preparation method thereof, in particular to a multifunctional triazine-type chrome-free tanning agent and a preparation method thereof. Background Art

[0002] Chrome tanning is the most important and widely used tanning method in leather manufacturing. It gives leather excellent thermal stability, comfortable feel and excellent leather properties. It currently occupies an absolute dominant position in the leather industry. However, in the traditional tanning process, the absorption rate of chrome tanning agent is usually only about 70%. After tanning, high-concentration chromium-containing wastewater will be produced, resulting in a large amount of chrome tanning agent loss. This not only increases the environmental pollution load and wastewater treatment costs, but also causes a huge waste of resources. Due to the adverse effects of chromium pollutants on the environment, the leather industry has been listed as one of the high-pollution industries. Solving the chromium pollution problem in the leather industry is urgent. Therefore, the study of green and environmentally friendly chrome-free tanning agents to replace the current chrome tanning method and reduce the environmental pollution problem in the leather industry has been a problem of widespread concern in the leather academic and industrial circles in recent years, and it is also a key scientific and technological problem that urgently needs to be solved to ensure the sustainable development of the leather industry. Chrome-free tanning agents and their tanning technology are the research focus and key areas in the field of clean leather production technology today (Xue Siyi, Wang Xuechuan, Yang Jin, et al. Research status and progress of chrome-free tanning agents [J]. China Leather, 2021, 50(8): 94-99).

[0003] To eliminate the environmental problems of chromium from the source, it is necessary to increase the research and development of chrome-free tanning technology, and the key and difficulty of this technology is how to prepare excellent chrome-free tanning agents. In recent years, leather workers have conducted in-depth research on chrome-free tanning agents and introduced some new chrome-free tanning agents, such as aluminum tanning agents, titanium tanning agents, iron tanning agents, zirconium tanning agents, rare earth metal tanning agents, etc. (Wei Xiuwei. Research on the application of new zirconium tanning technology in sheepskin tanning [D]. Wenzhou: Wenzhou University, 2019), vegetable tanning agents, aldehyde tanning agents, tetrahydroxymethyl quaternary phosphonium salts, and chrome-free tanning agents containing triazine rings (Jia Xiqing, Wen Huitao, Niu Ze, et al. Research on tanning process technology combining F-90 with vegetable tanning agents). Research [J]. Leather and Chemical Engineering, 2018, 35(6): 1-10; Yu Lidong, Qiang Xihuai, Ma Haofeng, et al. Synthesis of sodium p-(4,6-dichloro-1,3,5-triazine-2-oxy)benzenesulfonate and its tanning performance [J]. Fine Chemicals, 2019, 36(7): 1415-1421; Liu Dou. Preparation of T_Lys / T_Tyr / T_Arg and study on its tanning performance [D]. Xi'an Shaanxi University of Science and Technology, 2019).

[0004] The above-mentioned chrome-free tanning system has the problems of low shrinkage temperature of finished leather, large amount of tanning agent, poor tannability, poor fullness of finished leather, etc. The present invention provides a multifunctional triazine-type chrome-free tanning agent, which uses aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, aminonaphtholsulfonic acid, diaminobenzenesulfonic acid derivatives and sultone as raw materials to prepare aromatic polysulfonic acid compounds; the aromatic polysulfonic acid compounds and trihalotriazine are subjected to condensation reaction to prepare triazine-type chrome-free tanning agent; the triazine-type chrome-free tanning agent contains functional groups such as active chlorine, polysulfonic acid groups, hydroxyl groups, and aromatic rings, and forms multi-point crosslinking between collagen fibers to produce a tanning effect, significantly improving the moisture and heat resistance stability and physical and mechanical properties of leather collagen; the use of the multifunctional triazine-type chrome-free tanning agent in the present invention can replace the use of chrome powder in conventional chrome tanning processes, reduce environmental pollution in the leather industry, and promote clean production in the leather industry. Summary of the invention

[0005] Purpose of the invention: The first purpose of the present invention is to provide a triazine-type chrome-free tanning agent, and the second purpose of the present invention is to provide a method for preparing the triazine-type chrome-free tanning agent.

[0006] Technical solution: The multifunctional triazine-type chrome-free tanning agent of the present invention has the following molecular structure:

[0007]

[0008] X is Cl or F;

[0009] Y1 is 2-sulfonic acid, 3-sulfonic acid, 4-sulfonic acid, 4-amino-1-sulfonic acid, 5-amino-1-sulfonic acid, 3,4-diamino-1-sulfonic acid;

[0010] Y2 is 2-amino-1-sulfonic acid, 5-amino-1-sulfonic acid, 8-amino-1-sulfonic acid, 5-amino-2-sulfonic acid, 6-amino-2-sulfonic acid, 8-amino-2-sulfonic acid, 1-amino-8-hydroxy-4-sulfonic acid, 5-amino-1-hydroxy-3-sulfonic acid, 6-amino-1-hydroxy-3-sulfonic acid;

[0011] The preparation method of the multifunctional triazine-type chrome-free tanning agent of the present invention comprises the following steps:

[0012] (1) Preparation of aromatic amine polysulfonic acid compounds

[0013] Using aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, aminonaphtholsulfonic acid, diaminobenzenesulfonic acid derivatives and sultone as raw materials, in a low-polarity aprotic organic solvent, the reaction temperature is 60° C. to 100° C., and the reaction time is 6-12 hours to prepare aromatic amine polysulfonic acid compounds;

[0014] (2) Preparation of chrome-free tanning agent

[0015] The aromatic amine polysulfonic acid compound prepared above is mixed with trihalotriazine, dispersed with a surfactant, reacted at 10-20° C. for 5-12 hours, an acid binding agent is added to keep the pH at about 5.0-7.5, a crude product is obtained, and purified to obtain a multifunctional triazine-type chrome-free tanning agent.

[0016] Further, the aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, aminonaphtholsulfonic acid, diaminobenzenesulfonic acid and other derivatives described in step (1) are 2-aminobenzenesulfonic acid (CAS accession number 88-21-1), 3-aminobenzenesulfonic acid (CAS accession number 121-47-1), 4-aminobenzenesulfonic acid (CAS accession number 121-57-3), 2,4-diaminobenzenesulfonic acid (CAS accession number 88-63-1), 2,5-diaminobenzenesulfonic acid (CAS accession number 88-45-9), 3,4-diaminobenzenesulfonic acid (CAS accession number 7474-78-4), 2-amino-1-naphthalenesulfonic acid (CAS accession number 81-16-3), 5-amino-1-naphthalenesulfonic acid (CAS accession number 84-89-9), 8-amino- One of 1-naphthalenesulfonic acid (CAS registration number 82-75-7), 5-amino-2-naphthalenesulfonic acid (CAS registration number 119-79-9), 6-amino-2-naphthalenesulfonic acid (CAS registration number 93-00-5), 8-amino-2-naphthalenesulfonic acid (CAS registration number 119-28-8), 1-amino-8-naphthol-4-sulfonic acid (CAS registration number 83-64-7), 5-amino-1-naphthol-3-sulfonic acid (CAS registration number 489-78-1), and 6-amino-1-naphthol-3-sulfonic acid (CAS registration number 87-02-5);

[0017] Furthermore, the sultone in step (1) is 1,3-propane sultone (CAS registration number 1120-71-4) or 1,4-butane sultone (CAS registration number 1633-83-6); the molar ratio of aromatic amine to sultone is 1.0: (0.9-2.2);

[0018] Furthermore, the low polar aprotic organic solvent in step (1) is one or a mixed solvent of dichloromethane, 1,2-dichloroethane, petroleum ether, n-hexane, cyclohexane, 1,4-dioxane; the reaction temperature is 60° C. to 100° C.; and the reaction time is 6-12 h.

[0019] Furthermore, the trihalotriazine in step (2) is cyanuric chloride (CAS registration number 108-77-0) or cyanuric fluoride (CAS registration number 675-14-9); and the acid binding agent is potassium hydroxide or sodium hydroxide aqueous solution.

[0020] Furthermore, the surfactant in step (2) is a nonionic surfactant, which is one or a mixture of two of linear fatty alcohol (C8-C18) polyoxyethylene ether (AEO), polyethylene glycol 400-2000 (PEG), and polypropylene glycol 400-2000 (PPG).

[0021] Furthermore, in step (2), the molar ratio of trihalotriazine to aromatic amine polysulfonic acid compound is 1:(0.8-1.0) or 2:(0.8-1.0); the molar ratio of trihalotriazine to acid binding agent and emulsifier is 1:(1.0-1.2):(0.005-0.015).

[0022] The invention discloses an application of the multifunctional triazine type chrome-free tanning agent in the main tanning process of leather.

[0023] The present invention proposes a multifunctional triazine type chrome-free tanning agent, which has a simple preparation process. The aromatic polysulfonic acid compound is prepared from aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, aminonaphtholsulfonic acid, diaminobenzenesulfonic acid and other derivatives and sultone as raw materials; the aromatic polysulfonic acid compound is subjected to a condensation reaction with trihalo-s-triazine to obtain the multifunctional triazine type chrome-free tanning agent; the active chlorine of the triazine ring can condense with the hydroxyl group and the amino group in the collagen protein to form a stable covalent bond, and multiple sulfonic acid groups form ionic bonds with the amino group of the collagen protein to form multi-point crosslinking between the collagen fibers, thereby producing a tanning effect and significantly improving the moisture and heat resistance stability and physical and mechanical properties of the leather collagen. The use of the multifunctional triazine type chrome-free tanning agent in the present invention can replace the use of chrome powder in the conventional chrome tanning process, reduce environmental pollution in the leather industry, and promote clean production in the leather industry.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0025] 1) Using aminobenzenesulfonic acid, aminonaphthalenesulfonic acid, aminonaphtholsulfonic acid, diaminobenzenesulfonic acid derivatives, sultone, and trihalotriazine as raw materials, a multifunctional triazine type chrome-free tanning agent is prepared, the preparation process is simple, and the yield is high;

[0026] 2) The active chlorine of the triazine ring condenses with the hydroxyl and amino groups in the collagen protein to form a stable covalent bond;

[0027] 3) The sulfonic acid groups form ionic bonds with the amino groups on the collagen fibers;

[0028] 4) The multifunctional triazine type chrome-free tanning agent has high functionality and contains functional groups such as active chlorine, sulfonic acid, hydroxyl, and aromatic rings. It forms multi-point cross-linking between collagen fibers to produce a tanning effect, significantly improving the moisture and heat resistance and physical and mechanical properties of leather collagen; DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further described below in conjunction with embodiments.

[0030] Example 1

[0031] In a 100mL four-necked flask, add 60mL of dichloromethane, 0.03mol of 4-aminobenzenesulfonic acid (CAS 121-57-3) and 0.03mol of propane sultone, stir, reflux for 4h, cool and filter to obtain a white solid, which is the product 3-(4-aminobenzenesulfonic acid)-1-propanesulfonic acid. The product structural formula is as follows:

[0032]

[0033] 3-(4-aminobenzenesulfonic acid)-1-propanesulfonic acid (C9H 13 NO6S2, D2O)

[0034] 7.71ppm (d, 2H, -NH-C6H4-SO3H), 6.78ppm (d, 2H, -NH-C6H4-SO3H), 6.21ppm (t, 1H, -NH- C6H4-SO3H), 3.45ppm (t, 2H, -NHCH2CH2CH2SO3H), 3.09ppm (m, 2H, -NHCH2CH2CH2SO3H), 2.12ppm (m, 2H, -NHCH2CH2CH2SO3H).

[0035] In a 1000mL four-necked flask equipped with a stirrer and a thermometer, 0.3mol of cyanuric chloride, 2.8g of AEO-10 ​​and 500mL of deionized water were added, the temperature was adjusted to 2-3°C in an ice-water bath, 0.29mol of 3-(4-aminobenzenesulfonic acid)-1-propanesulfonic acid was added in 4 portions, and the addition was completed in about 60 minutes. The reaction was stirred for 5 hours, and a 10wt% KOH solution was added dropwise to adjust the pH value to 6.0-6.5. The mixture was filtered to obtain a milky white solid, which was washed and purified, and 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(4-benzenesulfonic acid))-amino-1-propanesulfonic acid was obtained by suction filtration. The product structure is as follows:

[0036]

[0037] 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(4-benzenesulfonic acid))-amino-1-propanesulfonic acid (C 12 H 12 Cl2N4O6S2, DMSO-d6)

[0038] 13.71ppm(t,2H,-NCC2H2C2H2CSO3H), 10.42ppm(t,1H,-NCH2CH2CH2SO3H), 7.70ppm(d, 2H, -NCC2H2C2H2CSO3H), 6.73ppm (d, 2H, -NCC2H2C2H2CSO3H), 3.46ppm (t, 2H, -NCH2C H2CH2SO3H), 3.04ppm (t, 2H, -NCH2CH2CH2SO3H), 2.09ppm (m, 2H, -NCH2CH2CH2SO3H).

[0039] The triazine-based chrome-free tanning agent of the present invention is used in the tanning process of yellow cattle hide. Tanning is carried out according to the process in Table 2, and the shrinkage temperature of the crust leather is tested; according to the methods of QB / T2710-2018 (Leather. Physical and mechanical tests. Determination of tensile strength and elongation) and QB / T2711-2005 (Leather. Physical and mechanical tests. Determination of tear force: double-sided tearing), the tensile strength, elongation at break and tear strength of the crust leather are measured. The application performance is shown in Table 3. The triazine-based chrome-free tanning agent of Example 1 has a crust leather shrinkage temperature of 82.1°C, and the tensile strength, elongation at break and tear strength of the crust leather are 10.3N / mm, respectively. 2 , 59.6% and 48.8N / mm.

[0040] Example 2

[0041] In a 100mL four-necked flask, add 60mL of dichloromethane, 0.03mol of 4-aminobenzenesulfonic acid (CAS 121-57-3) and 0.03mol of butane sultone, stir, reflux for 4h, cool and filter to obtain a white solid, which is the product 4-(4-aminobenzenesulfonic acid)-1-butanesulfonic acid. The structure is confirmed by H-NMR spectrum.

[0042]

[0043] 4-(4-aminobenzenesulfonic acid)-1-butanesulfonic acid (C 10 H 15 NO6S2, D2O)

[0044] 7.69ppm(d,2H,-NHCC2H2C2H2CSO3H), 6.71ppm(d,2H,-NHCC2H2C2H2CSO3H), 6.17ppm (t, 1H, -NHCH2CH2CH2CH2SO3H), 3.37ppm (t, 2H, -NHCH2CH2CH2CH2SO3H), 3.08ppm (m, 2H, -NHCH2CH2CH2CH2SO3H), 1.85ppm (m, 2H, -NHCH2CH2CH2CH2SO3H), 1.49ppm (m, 2H,-NHCH2CH2CH2CH2SO3H).

[0045] In a 500mL four-necked flask equipped with a stirrer and a thermometer, 0.3mol of cyanuric chloride, 2.8g of AEO-9 and 500mL of deionized water were added, the temperature was adjusted to 2-3°C in an ice-water bath, 0.29mol of 4-(4-aminobenzenesulfonic acid)-1-butanesulfonic acid was added in 4 portions, and the addition was completed in about 60 minutes. The reaction was stirred for 5 hours, and a 10wt% KOH solution was continuously added dropwise to adjust the pH value to 6.0-6.5. The solid was filtered to obtain a milky white solid, which was washed three times with pure water and three times with dichloromethane, and 4-((4,6-dichloro-1,3,5-triazine-2-yl)-(4-benzenesulfonic acid))-amino-1-butanesulfonic acid was obtained by suction filtration. The product structure is as follows:

[0046]

[0047] 4-((4,6-dichloro-1,3,5-triazine-2-yl)-(4-benzenesulfonic acid))-amino-1-butanesulfonic acid (C 13 H 14 Cl2N4O6S2, DMSO-d6)

[0048] 13.77ppm(t,2H,-NCC2H2C2H2CSO3H), 10.51ppm(t,1H,-NCH2CH2CH2CH2SO3H), 7.70ppm (d, 2H, -NCC2H2C2H2CSO3H), 6.76ppm (d, 2H, -NCC2H2C2H2CSO3H), 3.38ppm (t, 2H, -NCH2CH2CH2CH2SO3H), 3.10p pm(t, 2H, -NCH2CH2CH2CH2SO3H), 1.86ppm (m, 2H, -NCH2CH2CH2CH2SO3H), 1.52ppm (m, 2H, -NCH2CH2CH2CH2SO3H).

[0049] The triazine-based chrome-free tanning agent of the present invention is used in the tanning process of yellow cattle hide, and the tanning is carried out according to the process in Table 2, and the shrinkage temperature of the crust leather is tested; according to the methods of QB / T2710-2018 (leather. Physical and mechanical tests. Determination of tensile strength and elongation) and QB / T2711-2005 (leather. Physical and mechanical tests. Determination of tear force: bilateral tearing), the tensile strength, elongation at break and tear strength of the crust leather are determined.

[0050] The application performance is shown in Table 3. The triazine-based chrome-free tanning agent of Example 2 has a crust leather shrinkage temperature of 82.6°C, and the crust leather tensile strength, elongation at break and tear strength are 10.6 N / mm 2 , 58.9% and 46.7N / mm.

[0051] Example 3

[0052] In a 100mL four-necked flask, add 60mL of dichloromethane, 0.03mol of 2-amino-1-naphthalenesulfonic acid (CAS 81-16-3) and 0.03mol of propane sultone, stir, reflux for 4h, cool and filter to obtain a white solid, which is the product 3-(2-amino-1-naphthalenesulfonic acid)-1-propanesulfonic acid, with the structural formula as follows:

[0053]

[0054] 3-(2-amino-1-naphthalenesulfonic acid)-1-propanesulfonic acid (C 13 H 15 NO6S2, D2O)

[0055] 8.00ppm (d, H, H at the 4th position of the naphthalene ring), 7.55ppm (d, H, H at the 5th position of the naphthalene ring), 7.49ppm (t, 1H, -NHCH2CH2CH2SO3H), 7.43ppm (d, H, H at the 8th position of the naphthalene ring), 7.21ppm (t, H, H at the 7th position of the naphthalene ring), 7.06ppm (t, H, H at the 6th position of the naphthalene ring), 7.05ppm (d, H, H at the 3rd position of the naphthalene ring), 3.36ppm (t, 2H, -NHCH2CH2CH2SO3H), 3.07ppm (m, 2H, -NHCH2CH2CH2SO3H), 2.08ppm (m, 2H, -NHCH2CH2CH2SO3H).

[0056] In a 1000mL four-necked flask equipped with a stirrer and a thermometer, 0.3mol of cyanuric chloride, 2.7g of AEO-10 ​​and 500mL of deionized water were added, the temperature was adjusted to 2-3°C in an ice-water bath, 0.29mol of 3-(2-amino-1-naphthalenesulfonic acid)-1-propanesulfonic acid was added in 4 portions, and the addition was completed in about 60 minutes. The reaction was continued for 3 hours, during which 10wt% NaOH solution was continuously added dropwise to adjust the pH value to 6.0-6.5, and the mixture was filtered, washed three times with pure water and dichloromethane respectively, and 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(1-naphthalenesulfonic acid))-amino-1-propanesulfonic acid was obtained by suction filtration. The product structure is as follows:

[0057]

[0058] 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(1-naphthalenesulfonic acid))-amino-1-propanesulfonic acid (C 16 H 14 Cl2N4O6S2, DMSO-d6)

[0059] 11.99ppm (s, H, -SO3H at the 1st position of the naphthalene ring), 10.39ppm (t, 1H, -NCH2CH2CH2SO3H), 8.06ppm (d, H, H at the 4th position of the naphthalene ring), 7.53ppm (d, H, H at the 5th position of the naphthalene ring), 7.46ppm (d, H, H at the 8th position of the naphthalene ring), 7.20ppm (t, H, H at the 7th position of the naphthalene ring), 7.08ppm (t, H, H at the 6th position of the naphthalene ring), 7.06ppm (d, H, H at the 3rd position of the naphthalene ring), 3.41ppm (t, 2H, -NCH2CH2CH2SO3H), 3.01ppm (t, 2H, -NCH2CH2CH2SO3H), 2.12ppm (m, 2H, -NCH2CH2CH2SO3H).

[0060] The triazine-based chrome-free tanning agent of the present invention is used in the tanning process of yellow cattle hide, and the tanning is carried out according to the process in Table 2, and the shrinkage temperature of the crust leather is tested; according to the methods of QB / T2710-2018 (leather. Physical and mechanical tests. Determination of tensile strength and elongation) and QB / T2711-2005 (leather. Physical and mechanical tests. Determination of tear force: bilateral tearing), the tensile strength, elongation at break and tear strength of the crust leather are determined.

[0061] The application performance is shown in Table 3. The triazine-based chrome-free tanning agent of Example 3 has a crust leather shrinkage temperature of 81.6°C, and the crust leather tensile strength, elongation at break and tear strength are 10.5 N / mm 2 , 57.3% and 45.8N / mm.

[0062] Example 4

[0063] In a 100mL four-necked flask, add 60mL of dichloromethane, 0.03mol of 2-amino-1-naphthalenesulfonic acid (CAS 81-16-3) and 0.03mol of butane sultone, stir, reflux for 4h, cool and filter to obtain a white solid, which is the product 4-(2-amino-1-naphthalenesulfonic acid)-1-butanesulfonic acid, with the structural formula as follows:

[0064]

[0065] 4-(2-amino-1-naphthalenesulfonic acid)-1-butanesulfonic acid (C 14 H 17 NO6S2, D2O)

[0066] 8.02ppm (d, H, H at the 4th position of the naphthalene ring), 7.54ppm (t, 1H, -NHCH2CH2CH2CH2SO3H), 7.53ppm (d, H, H at the 5th position of the naphthalene ring), 7.45ppm (d, H, H at the 8th position of the naphthalene ring), 7.23ppm (t, H, H at the 7th position of the naphthalene ring), 7.06ppm (t, H, H at the 6th position of the naphthalene ring), 7.03ppm (d, H, H at the 3rd position of the naphthalene ring), 3.09ppm (m, 2H, -NHCH2CH2CH2CH2SO3H), 3.37ppm (t, 2H, -NHCH2CH2CH2CH2SO3H), 1.86ppm (m, 2H, -NHCH2CH2CH2CH2SO3H), 1.49ppm (m, 2H, -NHCH2CH2CH2CH2SO3H).

[0067] In a 1000mL four-necked flask equipped with a stirrer and a thermometer, 0.3mol of cyanuric chloride, 2.8g of AEO-10 ​​and 500mL of deionized water were added, the temperature was adjusted to 2-3°C in an ice-water bath, 0.29mol of 4-(2-amino-1-naphthalenesulfonic acid)-1-butanesulfonic acid was added in 4 portions, and the addition was completed in about 60 minutes. The reaction was continued for 4 hours, during which 10wt% KOH solution was continuously added dropwise to adjust the pH value to 6, and the mixture was filtered, washed three times with pure water and dichloromethane respectively, and 4-((4,6-dichloro-1,3,5-triazine-2-yl)-(1-naphthalenesulfonic acid))-amino-1-butanesulfonic acid was obtained by suction filtration. The product structure is as follows:

[0068]

[0069] 4-((4,6-dichloro-1,3,5-triazine-2-yl)-(1-naphthalenesulfonic acid))-amino-1-butanesulfonic acid (C 17 H 16 Cl2N4O682, DMSO-d6)

[0070] 12.03ppm (s, H, naphthalene ring 1 -SO3H), 10.50ppm (t, 1H, -NCH2CH2CH2CH2SO3H), 8.16ppm (d, H, naphthalene ring 4 H), 7.55ppm (d, H, naphthalene ring 5 H), 7.45ppm (d, H, naphthalene ring 8 H), 7.26ppm (t, H, naphthalene ring 7 H), 7.07ppm (t, H, naphthalene ring 6 H), 7.04ppm (d, H, naphthalene ring 3 H), 3.38ppm (t, 2H, -NCH2CH2CH2CH2SO3H), 3.05ppm (t, 2H, -NCH2CH2CH2CH2SO3H), 1.84ppm (m, 2H, - NCH2CH2CH2CH2SO3H), 1.55ppm (m, 2H, -NCH2CH2CH2CH2SO3H).

[0071] The triazine-based chrome-free tanning agent of the present invention is used in the tanning process of yellow cattle hide, and the tanning is carried out according to the process in Table 2, and the shrinkage temperature of the crust leather is tested; according to the methods of QB / T2710-2018 (leather. Physical and mechanical tests. Determination of tensile strength and elongation) and QB / T2711-2005 (leather. Physical and mechanical tests. Determination of tear force: bilateral tearing), the tensile strength, elongation at break and tear strength of the crust leather are determined.

[0072] The application performance is shown in Table 3. The triazine-based chrome-free tanning agent of Example 4 has a shrinkage temperature of 81.9°C for crust leather, and a tensile strength, elongation at break and tear strength of 9.6 N / mm 2 , 56.8% and 50.7N / mm.

[0073] Example 5

[0074] In a 100mL four-necked flask, add 60mL of dichloromethane, 0.03mol of 1-amino-8-naphthol-4-sulfonic acid and 0.03mol of propane sultone, stir, reflux for 4h, cool and filter to obtain a white solid, which is the product 3-(1-amino-8-naphthol-4-sulfonic acid)-1-propane sulfonic acid, with the structural formula as follows:

[0075]

[0076] 3-(1-amino-8-naphthol-4-sulfonic acid)-1-propanesulfonic acid (C 13 H 15 NO7S2, D2O)

[0077] 10.15ppm (d, H, -OH at the 8th position of the naphthalene ring), 7.85ppm (d, H, H at the 3rd position of the naphthalene ring), 7.69ppm (t, 1H, -NHCH2CH2CH2SO3H), 7.27ppm (d, H, H at the 5th position of the naphthalene ring), 7.18ppm (t, H, H at the 6th position of the naphthalene ring), 6.90ppm (d, H, H at the 2nd position of the naphthalene ring), 6.63ppm (d, H, H at the 7th position of the naphthalene ring), 3.45ppm (t, 2H, -NHCH2CH2CH2SO3H), 3.07ppm (m, 2H, -NHCH2CH2CH2SO3H), 2.13ppm (m, 2H, - NHCH2CH2CH2SO3H).

[0078] In a 1000mL four-necked flask equipped with a stirrer and a thermometer, 0.3mol of cyanuric chloride, 2.8g of AEO-9 and 500mL of deionized water were added, the temperature was adjusted to 2-3°C in an ice-water bath, 0.29mol of 3-(1-amino-8-naphthol-4-sulfonic acid)-1-propanesulfonic acid was added in 4 portions, and the addition was completed in about 60 minutes. The reaction was continued for 4 hours, during which 10wt% KOH solution was continuously added dropwise to adjust the pH value to 6.0-6.5, and the mixture was filtered, washed three times with pure water and dichloromethane respectively, and 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(8-naphthol-4-sulfonic acid))-amino-1-propanesulfonic acid was obtained by suction filtration. The product structure is as follows:

[0079]

[0080] 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(8-naphthol-4-sulfonic acid))-amino-1-propanesulfonic acid (C 16 H 14 Cl2N4O7S2, DMSO-d6)

[0081] 12.00ppm (s, H, -SO3H at the 4th position of the naphthalene ring), 10.46ppm (t, 1H, -NCH2CH2CH2SO3H), 10.01ppm (d, H, -OH at the 8th position of the naphthalene ring), 7.83ppm (d, H, H at the 3rd position of the naphthalene ring), 7.25ppm (d, H, H at the 5th position of the naphthalene ring), 7.18ppm (t, H, H at the 6th position of the naphthalene ring), 6.93ppm (d, H, H at the 2nd position of the naphthalene ring), 6.65ppm (d, H, H at the 7th position of the naphthalene ring), 3.39ppm (t, 2H, -NCH2CH2CH2SO3H), 3.06ppm (m, 2H, -NCH2CH2CH2SO3H), 2.10ppm (m, 2H, - NCH2CH2CH2SO3H).

[0082] The application performance is shown in Table 3. The triazine-based chrome-free tanning agent of Example 5 has a crust leather shrinkage temperature of 83.5°C, and the crust leather tensile strength, elongation at break and tear strength are 13.4 N / mm 2 , 59.6% and 50.6N / mm.

[0083] Example 6

[0084] In a 100mL four-necked flask, add 60mL of dichloromethane, 0.03mol of 1-amino-8-naphthol-4-sulfonic acid and 0.03mol of butane sultone, stir, reflux for 4h, cool and filter to obtain a white solid, which is the product 3-(1-amino-8-naphthol-4-sulfonic acid)-1-butane sulfonic acid, with the structural formula as follows:

[0085]

[0086] 3-(1-amino-8-naphthol-4-sulfonic acid)-1-butanesulfonic acid (C 14 H 17 NO7S2, D2O)

[0087] 10.13ppm (d, H, -OH at the 8th position of the naphthalene ring), 7.88ppm (d, H, H at the 3rd position of the naphthalene ring), 7.59ppm (t, 1H, -NHCH2CH2CH2SO3H), 7.23ppm (d, H, H at the 5th position of the naphthalene ring), 7.11ppm (t, H, H at the 6th position of the naphthalene ring), 6.90ppm (d, H, H at the 2nd position of the naphthalene ring), 6.66ppm (d, H, H at the 7th position of the naphthalene ring), 3.42ppm (t, 2H, -NHCH2CH2CH2CH2SO3H), 1.85ppm (m, 2H, -NHCH2CH2CH2CH2SO3H), 3.01ppm (m, 2H, - NHCH2CH2CH2CH2SO3H), 1.49ppm (m, 2H, -NHCH2CH2CH2CH2SO3H).

[0088] In a 1000mL four-necked flask equipped with a stirrer and a thermometer, 0.3mol of cyanuric chloride, 2.8g of PEG1000 and 500mL of deionized water were added, the temperature was adjusted to 2-3°C in an ice-water bath, 0.29mol of 3-(1-amino-8-naphthol-4-sulfonic acid)-1-butanesulfonic acid was added in 4 portions, and the addition was completed in about 60 minutes. The reaction was continued for 4 hours, during which 10wt% KOH solution was continuously added dropwise to adjust the pH value to 6, and the mixture was filtered, washed three times with pure water and dichloromethane respectively, and 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(8-naphthol-4-sulfonic acid))-amino-1-butanesulfonic acid was obtained by suction filtration. The product structure is as follows:

[0089]

[0090] 3-((4,6-dichloro-1,3,5-triazine-2-yl)-(8-naphthol-4-sulfonic acid))-amino-1-butanesulfonic acid (C 17 H 16 Cl2N4O7S2, DMSO-d6)

[0091] 11.99ppm (s, H, naphthalene ring 4 position -SO3H), 10.48ppm (t, 1H, -NCH2CH2CH2CH2SO3H), 9.98ppm (d, H, naphthalene ring 8 position -OH), 7.86ppm (d, H, naphthalene ring 3 position H), 7.25ppm (d, H, naphthalene ring 5 position H), 7.13ppm (t, H, naphthalene ring 6 position H), 6.91ppm (d, H, naphthalene ring 2 position H), 6.64ppm (d, H, naphthalene ring 7 position H), 3.40ppm (t, 2H, -NCH2CH2CH2CH2SO3H), 3.09ppm (t, 2H, -NCH2CH2CH2CH2SO3H), 1.83ppm (m, 2H, -NCH2CH2CH2CH2SO3H), 1.50ppm (m, 2H, -NCH2CH2CH2CH2SO3H).

[0092] The application performance is shown in Table 3. The triazine-based chrome-free tanning agent of Example 6 has a shrinkage temperature of 83.8°C for crust leather, and a tensile strength, elongation at break and tear strength of 13.2 N / mm 2 , 60.3% and 50.8N / mm.

[0093] The triazine-based chrome-free tanning agents prepared using different raw materials are summarized in Examples 1-6 in Table 1, the tanning processes are shown in Table 2, and the application properties of the triazine-based chrome-free tanning agents of Examples 1-4 are summarized in Table 3.

[0094] Table 1 Preparation examples of multifunctional chrome-free tanning agents

[0095] Example Raw material 1 Raw material 2 Raw material 3 Yield (%) 1 4-Aminobenzenesulfonic acid Propane sultone Cyanuric chloride 97.3％ 2 4-Aminobenzenesulfonic acid Butane sultone Cyanuric chloride 96.8％ 3 2-Amino-1-naphthalenesulfonic acid Propane sultone Cyanuric chloride 98.2％ 4 2-Amino-1-naphthalenesulfonic acid Butane sultone Cyanuric chloride 96.3％ 5 1-Amino-8-naphthol-4-sulfonic acid Propane sultone Cyanuric chloride 95.3％ 6 1-Amino-8-naphthol-4-sulfonic acid Butane sultone Cyanuric chloride 94.8％

[0096] Table 2 Pickling tanning process

[0097]

[0098] Table 3 Shrinkage temperature and mechanical properties test

[0099]

Claims

1. A multifunctional triazine type chrome-free tanning agent, characterized in that: The molecular structure of the chrome-free tanning agent is as follows: X is Cl or F; Y1 is 2-sulfonic acid, 3-sulfonic acid, 4-sulfonic acid, 4-amino-1-sulfonic acid, 5-amino-1-sulfonic acid, 3,4-diamino-1-sulfonic acid; Y2 is 2-amino-1-sulfonic acid, 5-amino-1-sulfonic acid, 8-amino-1-sulfonic acid, 5-amino-2-sulfonic acid, 6-amino-2-sulfonic acid, 8-amino-2-sulfonic acid, 1-amino-8-hydroxy-4-sulfonic acid, 5-amino-1-hydroxy-3-sulfonic acid, 6-amino-1-hydroxy-3-sulfonic acid.

2. Use of the multifunctional triazine-type chrome-free tanning agent according to claim 1 in the main tanning process of leather.

3. The use of the multifunctional triazine type chrome-free tanning agent in the main tanning process according to claim 2, characterized in that: The raw leathers for leather making are cattle hide, buffalo hide, yak hide and goat hide.

Images