A silicone s-triazine derivative, and a preparation method and application thereof

Abstract

The application provides an organic silicon s-triazine derivative and a preparation method and application thereof, and belongs to the technical field of leather tanning agent development. The organic silicon s-triazine derivative is prepared from a s-triazine compound and organic silicon, and overcomes the problem of insufficient performance of the leather tanning agent in the prior art. The organic silicon s-triazine derivative can be crosslinked with skin collagen at multiple active sites, and good tanning effect is achieved. In the tanning process using the organic silicon s-triazine derivative, no harmful substances such as formaldehyde and heavy metal salts are involved, and environmental pollution is avoided. The product has strong tanning permeability, the tanned leather has a smooth and fine grain surface and excellent fullness, and is easy to be subjected to subsequent processing steps such as dyeing; and an environmentally-friendly and clean tanning method is provided for the leather-making industry.

Description

Technical Field

[0001] This invention relates to the field of leather tanning agent development technology, and in particular to an organosilicon triazine derivative, its preparation method and application. Background Technology

[0002] Organosilicon has a wide range of applications in the leather industry, including tanning agents, fatliquoring agents, finishing agents, and functional auxiliaries. Current research mainly focuses on fatliquoring agents and finishing agents. Leather treated with organosilicon is soft and full, with a smooth and delicate grain, possessing the comfortable feel of silk. In tanning agent research, the design of tanning agents requires at least two binding sites that can form stable bonds with collagen fibers, with covalent bonding being the optimal mode. However, organosilicon hydrolyzes under acidic conditions to form Si-OH bonds. The silanol structure readily bonds with the -OH groups of collagen via hydrogen bonds. Furthermore, as pH and tanning temperature increase, Si-OH groups dehydrate to form a rigid Si-O-Si silicon network structure. Therefore, organosilicon-tanned leather has a rougher grain, poorer fullness and shrinkage, and a lower tanning shrinkage temperature.

[0003] Various organosilicon tanning agents are disclosed in the prior art, such as the polyhydroxyalkylphosphine-organosilicon tanning agent disclosed in Chinese patent CN101965412A, its preparation and application in fur tanning; and an amphoteric organosilicon-modified acrylic resin retanning agent disclosed in Chinese patent CN113831465A and its preparation method. However, the tanning effect of the above products needs to be improved.

[0004] Existing technologies also disclose a scheme to improve the tanning performance of organosilicon by combining organosilicon with a small amount of chromium. However, the absorption rate of chromium during the tanning process is not high, and chromium-containing wastewater needs to be discharged after tanning, which has an adverse impact on the environment. Summary of the Invention

[0005] The purpose of this invention is to provide an organosilicon triazine derivative that can solve the problem of insufficient performance of leather tanning agents in the prior art.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a method for preparing organosilicon triazine derivatives, comprising the following steps:

[0008] The triazine compound solution was mixed with organosilicon to carry out the first stage reaction, yielding intermediate product 1;

[0009] Intermediate product 1 was mixed with an acid-binding agent to carry out a second-stage reaction, yielding intermediate product 2.

[0010] Intermediate product 2 was distilled to obtain the solute, which was an organosilicon triazine derivative.

[0011] Preferably, the triazine compound solution is selected from one or a mixture of two of cyanuric chloride solution and thiocyanate solution.

[0012] Preferably, the organosilicon is selected from one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl(eth)oxysilane and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.

[0013] Preferably, the volume ratio of the triazine compound solution to the mass ratio of organosilicon is 100-200 mL: 20-25 g.

[0014] Preferably, the concentration of the triazine compound solution is 0.05–0.5 g / mL.

[0015] Preferably, the temperature of the first stage reaction is -5 to 10°C;

[0016] The reaction time in the first stage is 2 to 8 hours;

[0017] The temperature for the second stage reaction is -5 to 10°C;

[0018] The second stage of the reaction takes 1 to 5 hours.

[0019] Preferably, the acid-binding agent is selected from one or more of sodium hydroxide, potassium hydroxide, pyridine, triethylamine and sodium carbonate.

[0020] The present invention also provides organosilicon triazine derivatives obtained by the above preparation method.

[0021] The present invention also provides an organosilicon triazine derivative comprising the grafted structure shown in the following formula:

[0022]

[0023] And / or,

[0024]

[0025] In the above formula, R refers to a hydroxyl group.

[0026] The present invention also provides the application of the above-mentioned organosilicon triazine derivative in the preparation of tanning agents.

[0027] The beneficial effects of this invention are:

[0028] The organosilicon triazine derivative provided by this invention can cross-link with skin collagen at multiple active sites, achieving a better tanning effect. Tanning using this organosilicon triazine derivative involves no harmful substances such as formaldehyde or heavy metal salts, avoiding environmental pollution. The product exhibits strong tanning penetration, resulting in leather with a smooth, fine grain and excellent fullness, facilitating subsequent dyeing and other processing steps; thus providing the leather industry with an environmentally friendly and clean tanning method. Detailed Implementation

[0029] This invention provides a method for preparing organosilicon triazine derivatives, comprising the following steps:

[0030] The triazine compound solution was mixed with organosilicon to carry out the first stage reaction, yielding intermediate product 1;

[0031] Intermediate product 1 was mixed with an acid-binding agent to carry out a second-stage reaction, yielding intermediate product 2.

[0032] Intermediate product 2 was distilled to obtain the solute, which was an organosilicon triazine derivative.

[0033] The more reactive atoms in the triazine compounds can undergo nucleophilic substitution reactions with compounds containing primary amino and hydroxyl groups at low temperatures to obtain organosilicon triazine derivatives.

[0034] In this invention, the triazine compound solution is preferably one or a mixture of two of cyanuric chloride solution and thiocyanate solution, more preferably cyanuric chloride solution, wherein the solvent of the cyanuric chloride solution is preferably acetone; the organosilicon is preferably one or more of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.

[0035] The volume ratio of the triazine compound solution to the organosilicon is preferably 100-200 mL: 20-25 g, more preferably 130-180 mL: 21-23 g. The concentration of the triazine compound solution is preferably 0.05-0.5 g / mL, more preferably 0.1-0.3 g / mL. The temperature of the first stage reaction is preferably -5-10°C, more preferably carried out under ice bath conditions, which can control the temperature at around 0°C, but is not fixed. The reaction time of the first stage reaction is preferably 2-8 h, more preferably 3-5 h. The temperature of the second stage reaction is preferably -5-10°C, more preferably carried out under ice bath conditions, which can control the temperature at around 0°C, but is not fixed. The reaction time of the second stage reaction is preferably 1-5 h, more preferably 2-4 h. The acid-binding agent is preferably one or more of sodium hydroxide, potassium hydroxide, pyridine, triethylamine, and sodium carbonate. After mixing the intermediate product 1 with the acid-binding agent, the pH of the reaction system is preferably 6.5-7.5.

[0036] The present invention also provides an organosilicon triazine derivative obtained by the above preparation method, wherein the organosilicon triazine derivative is a graft copolymer.

[0037] The present invention also provides an organosilicon triazine derivative comprising the grafted structure shown in the following formula:

[0038]

[0039] And / or,

[0040]

[0041] In the above formula, R refers to a hydroxyl group.

[0042] The preferred location for grafting is shown in the following formula (where the area is marked by a dashed box):

[0043]

[0044] and, or:

[0045]

[0046] This invention also provides the application of the above-mentioned organosilicon triazine derivative in the preparation of tanning agents. The organosilicon triazine derivative provided by this invention is preferably applied through the following steps: 80-120 parts by weight of softened raw leather (converted to the weight of grey leather) are placed in a drum, 20-40 parts by weight of water are added, the temperature is adjusted to 20-30°C, and 10-20 parts by weight of the organosilicon triazine derivative of this invention or a tanning agent containing the organosilicon triazine derivative of this invention are added. The drum is rotated at 20-30°C for 4-6 hours, and the pH change is observed. Another 20-40 parts by weight of water are added, the temperature is raised to 40-60°C, and the drum is rotated for another 4-6 hours until the final tanning pH stabilizes at 4-5. The tanned leather can be aged for 2-3 days before undergoing processes such as leveling, retanning, neutralization dyeing, and fatliquoring.

[0047] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0048] Example 1

[0049] 18.41 g of cyanuric chloride was weighed and added to a three-necked flask equipped with a stirrer containing 150 ml of acetone. The flask was stirred and dissolved in an ice-water bath. Then, 22.13 g of KH550 (γ-aminopropyltriethoxysilane) was weighed into a constant-pressure separatory funnel. The dropping rate was adjusted so that the flask could be completely added within half an hour. The mixture was kept warm and stirred in an ice-water bath for 4 hours. Sodium hydroxide was added to adjust the pH to 6. The mixture was kept warm and stirred in an ice-water bath for 2 hours. The mixture was then poured into a rotary evaporator and the acetone was removed by rotary evaporation at 20 °C to obtain a white powder of KH550-grafted triazine derivative.

[0050] Example 2

[0051] 18.41 g of cyanuric chloride was weighed and added to a three-necked flask equipped with a stirrer containing 150 ml of acetone. The flask was stirred and dissolved in an ice-water bath. Then, 23.63 g of KH560 (γ-glycidoxypropyltrimethoxysilane) was weighed into a constant pressure separatory funnel. The dropping rate was adjusted so that the flask could be completely added within half an hour. The mixture was kept warm and stirred in an ice-water bath for 4 hours. Potassium hydroxide was added to adjust the pH to 5. The mixture was kept warm and stirred in an ice-water bath for 2 hours. The mixture was then poured into a rotary evaporator and the acetone was removed by rotary evaporation at 20 °C to obtain a white powder of KH560-grafted triazine derivative.

[0052] Example 3

[0053] 18.41 g of cyanuric chloride was weighed and added to a three-necked flask equipped with a stirrer containing 150 ml of acetone. The flask was stirred and dissolved in an ice-water bath. Then, 22.23 g of KH792 (N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) was weighed into a constant pressure separatory funnel. The dropping rate was adjusted so that the mixture could be completely added within half an hour. The mixture was kept warm and stirred in an ice-water bath for 4 hours. Triethylamine was added to adjust the pH to 7. The mixture was kept warm and stirred in an ice-water bath for 2 hours. The mixture was then poured into a rotary evaporator and the acetone was removed by rotary evaporation at 20 °C to obtain a white powder of KH792-grafted triazine derivative.

[0054] Example 4

[0055] 18.41 g of cyanuric chloride was weighed and added to a three-necked flask equipped with a stirrer containing 150 ml of acetone. The flask was stirred and dissolved in an ice-water bath. Then, 20.64 g of KH602 (N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane) was weighed into a constant pressure separatory funnel. The dropping rate was adjusted so that the mixture could be completely added within half an hour. The mixture was kept warm and stirred in an ice-water bath for 4 hours. Sodium carbonate was added to adjust the pH to 6. The mixture was kept warm and stirred in an ice-water bath for 2 hours. The mixture was then poured into a rotary evaporator and the acetone was removed by rotary evaporation at 20 °C to obtain a white powder of KH602-grafted triazine derivative.

[0056] Experimental Example 1

[0057] The organosilicon triazine derivatives prepared in Examples 1-4 and commercially available similar products (Clariant F-90) were used for tanning hides. The tanning steps are as follows:

[0058] By weight, 100 parts of softened raw hide (calculated as 100% of alkali-treated hide) were placed in a tumbler, 30 parts of water were added, the temperature was adjusted to 25°C, and 15 parts of an organosilicon triazine derivative or a commercially available similar product were added. The mixture was tumbled at 25°C for 5 hours, and the pH change was observed. Another 30 parts of water were added, the temperature was raised to 50°C, and the mixture was tumbled for another 5 hours. The final tanning pH was stabilized at 4.5, yielding a sample of wet white hide for performance testing. The tanned leather can be aged for 2 days before undergoing routine processes such as leveling, retanning, neutralization dyeing, and fatliquoring.

[0059] The performance testing methods are as follows:

[0060] Shrinkage temperature test: Take two samples each along the direction parallel and perpendicular to the backline of the tanned raw leather, and measure the shrinkage temperature using a digital leather shrinkage temperature tester. Take the average of the four shrinkage temperatures in the parallel and perpendicular directions as the shrinkage temperature.

[0061] Thickness gain determination: Using a fixed-weight thickness gauge, five points are taken on each sample to measure the thickness before and after tanning, and the average value is taken. The thickness gain of vegetable-tanned leather is calculated according to the corresponding method. The calculation formula is as follows:

[0062] Thickness increase rate = (Average thickness of tanned leather - Average thickness of untanned leather) / Average thickness of untanned leather;

[0063] Determination of tensile strength: The tensile strength of finished leather shall be determined in accordance with the provisions of QB / T2710.

[0064] The final tanning results of the raw leather are shown in Table 1.

[0065] Table 1 Tanning Results

[0066]

[0067] As shown in Table 1, the organosilicon triazine derivative prepared in this invention has excellent performance as a tanning agent. When used for tanning wet white leather, it can eliminate the pollution of formaldehyde and heavy metal salts. The tanned wet white leather has a clean and fine grain, excellent physical properties and fullness, and is easy to dye in the subsequent process.

[0068] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An organosilicon triazine derivative, characterized in that, Prepared by any of the following methods: 18.41 g of cyanuric chloride was weighed and added to a three-necked flask equipped with a stirrer containing 150 ml of acetone. The mixture was stirred and dissolved in an ice-water bath. Then, 23.63 g of γ-glycidoxypropyltrimethoxysilane was weighed into a constant pressure separatory funnel. The dropping rate was adjusted so that the mixture could be completely added within half an hour. The mixture was kept warm and stirred in an ice-water bath for 4 hours. Potassium hydroxide was added to adjust the pH to 5. The mixture was kept warm and stirred in an ice-water bath for 2 hours. The mixture was then poured into a rotary evaporator and the acetone was removed by rotary evaporation at 20 °C to obtain an organosilicon triazine derivative. Alternatively, weigh 18.41g of cyanuric chloride and add it to a three-necked flask equipped with a stirrer containing 150ml of acetone. Dissolve the flask by stirring in an ice-water bath. Then weigh 22.23g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane into a constant pressure separatory funnel. Adjust the dropping rate to ensure that the flask is completely added within half an hour. Continue stirring and keeping the mixture warm in an ice-water bath for 4 hours. Add triethylamine to adjust the pH to 7. Continue stirring and keeping the mixture warm in an ice-water bath for 2 hours. Pour the mixture into a rotary evaporator and remove the acetone by rotary evaporation at 20℃ to obtain the organosilicon triazine derivative. Alternatively, weigh 18.41g of cyanuric chloride and add it to a three-necked flask equipped with a stirrer containing 150ml of acetone. Dissolve the flask by stirring in an ice-water bath. Then weigh 20.64g of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane into a constant-pressure separatory funnel. Adjust the dropping rate to ensure that the flask is completely added within half an hour. Continue stirring and maintaining the temperature in an ice-water bath for 4 hours. Add sodium carbonate to adjust the pH to 6. Continue stirring and maintaining the temperature in an ice-water bath for 2 hours. Pour the mixture into a rotary evaporator and remove the acetone by rotary evaporation at 20℃ to obtain the organosilicon triazine derivative.

2. The use of the organosilicon triazine derivative according to claim 1 in the preparation of tanning agents.

3. The application of an organosilicon triazine derivative in the preparation of tanning agents, characterized in that, The organosilicon triazine derivative was prepared by the following method: 18.41 g of cyanuric chloride was weighed and added to a three-necked flask equipped with a stirrer containing 150 ml of acetone. The flask was stirred and dissolved in an ice-water bath. Then, 22.13 g of γ-aminopropyltriethoxysilane was weighed into a constant-pressure separatory funnel. The dropping rate was adjusted so that the flask could be completely added within half an hour. The mixture was kept warm and stirred in an ice-water bath for 4 hours. Sodium hydroxide was added to adjust the pH to 6. The mixture was kept warm and stirred in an ice-water bath for 2 hours. The mixture was then poured into a rotary evaporator and the acetone was removed by rotary evaporation at 20 °C to obtain an organosilicon triazine derivative.

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