Fluorine-containing polyhedral oligomeric silsesquioxane nano tanning agent and preparation method thereof

Abstract

The invention discloses a preparation method of a fluorine-containing polyhedral oligomeric silsesquioxane nano tanning agent, which comprises the following steps: step 1, adding 0.32-0.64 part of lauryl sodium sulfate and 24-48 parts of distilled water into a flask, heating in a water bath to 50-70 DEG C, and stirring at the rotating speed of 300-400 r / min until the lauryl sodium sulfate and the distilled water are dissolved; then weighing 0.16 to 0.32 part of vinyl polyhedral oligomeric silsesquioxane, dissolving the vinyl polyhedral oligomeric silsesquioxane in 1.6 to 3.2 parts of tetrahydrofuran, pouring the solution into a flask, and stirring for 15 to 20 minutes; weighing 6-25 parts of a methacrylic acid aqueous solution and 20-30 parts of an initiator aqueous solution, adding into the flask in three times, and carrying out a constant-temperature reaction; and 2, 2.5-12 parts of trifluoroethyl methacrylate is dissolved in 5-24 parts of tetrahydrofuran, the mixture is slowly and dropwise added into the flask obtained in the step 1, a constant-temperature reaction is conducted for 2-3 h, and then the fluorine-containing polyhedral oligomeric silsesquioxane nano tanning agent is obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of synthetic methods for leather tanning agents, and in particular relates to a fluorine-containing cage-type silsesquioxane nano-tanning agent, and also relates to a preparation method of the fluorine-containing cage-type silsesquioxane nano-tanning agent. Background Art

[0002] The leather industry is closely related to human life and the development of the national economy. In the leather processing, tanning agents are key materials that can react chemically with raw hide collagen fibers to turn raw hide into leather. Among them, chrome tanning agents can give leather excellent physical and chemical properties and are the most widely used tanning agents. However, studies have shown that Cr (III) used in the leather making process is easily oxidized to Cr (VI) with potential carcinogenic risks, which is harmful to human health; at the same time, the absorption rate of chrome tanning agents is low, and the large amount of chromium-containing waste generated is difficult to discharge and treat, causing serious environmental pollution problems. Therefore, the development of environmentally friendly chrome-free tanning agents is imperative.

[0003] Polyhedral oligomeric silsesquioxane (POSS) is a type of organic-inorganic hybrid material with a highly symmetrical nanoscale cubic cage skeleton. The inorganic framework of its core is composed of Si-O-Si, which has good stability, mechanical properties, oxidation resistance, etc. Each vertex of the periphery has an active site that can be freely modified, and the molecular structure can be flexibly designed according to needs to give it reactivity and functionality. Studies have designed a series of multi-carboxyl POSS composite tanning agents that can be used to clean leather by carboxylating POSS. It has a unique multi-side chain structure that can greatly increase the number of active groups in the side chain, increase the binding sites with skin collagen, and enhance the tanning effect. However, a large number of carboxyl groups also make the composite tanning agent too hydrophilic, which is easy to over-tan on the surface, resulting in a stiff feel of the finished leather and reducing its commercial value. Summary of the invention

[0004] The first objective of the present invention is to provide a method for preparing a fluorine-containing cage-type silsesquioxane nano-tanning agent, so as to solve the problem that the existing method uses a large amount of carboxyl groups to make the composite tanning agent too hydrophilic, resulting in the leather surface being easily over-tanned and having a stiff feel, thereby reducing its commercial value.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: a method for preparing a fluorine-containing cage-type silsesquioxane nano-tanning agent, which is specifically implemented according to the following steps: Step 1, first add 0.32 parts to 0.64 parts of sodium dodecyl sulfate and 24 parts to 48 parts of distilled water to a flask according to mass parts, then raise the water bath temperature to 50 ℃-70 ℃, and stir at a speed of 300 r / min-400 r / min until dissolved; then weigh 0.16 parts to 0.32 parts of vinyl cage silsesquioxane and dissolve it in 1.6 parts to 3.2 parts of tetrahydrofuran, and pour it into the flask and stir for 15min-20 min; finally weigh 6 parts to 25 parts of methacrylic acid aqueous solution and 20 parts to 30 parts of initiator aqueous solution and add them to the flask three times, and react at a constant temperature of 50 ℃-70 ℃ for 2 h-3 h; Step 2, dissolving 2.5 to 12 parts of trifluoroethyl methacrylate in 5 to 24 parts of tetrahydrofuran and slowly adding the mixture dropwise to the flask obtained in step 1, reacting at a constant temperature for 2 to 3 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0006] As a preferred technical solution of the present invention, in step 1, the flask is a three-necked flask.

[0007] As a preferred technical solution of the present invention, in step 2, the mass fraction of the methacrylic acid aqueous solution is 45%.

[0008] As a preferred technical solution of the present invention, in step 2, the slow dripping is specifically 5 mL / h-8 mL / h.

[0009] The second object of the present invention is to provide a fluorine-containing cage-type silsesquioxane nano-tanning agent to solve the problem that the existing method uses a large amount of carboxyl groups to make the composite tanning agent too hydrophilic, resulting in the leather surface being easily over-tanned and having a stiff feel, thereby reducing its commercial value.

[0010] In order to achieve the above object, the technical solution adopted by the present invention is: the fluorine-containing cage-type silsesquioxane nano-tanning agent is prepared by the preparation method of the above-mentioned fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0011] The beneficial effects of the present invention are as follows: the fluorinated caged silsesquioxane nanotanning agent prepared by the preparation method of the fluorinated caged silsesquioxane nanotanning agent of the present invention greatly improves the surface activity of the composite system due to the introduction of the hydrophobic short fluorocarbon chain monomer trifluoroethyl methacrylate, thereby significantly enhancing the permeability of the polycarboxyl POSS composite tanning agent, improving its filling property, making the finished leather fuller and firmer, and the shrinkage temperature of the single tanning can reach 75.3°C. DETAILED DESCRIPTION

[0012] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments.

[0013] Studies have shown that this problem can be improved by introducing hydrophobic monomers into the polymer, thereby improving the softness and hydrophobicity of the leather.

[0014] Fluorinated polymers have excellent chemical stability, thermal stability and low surface energy. At the same time, studies have found that short fluorocarbon chain materials with less than or equal to four carbon atoms have minimal bioaccumulation and also have high surface activity. Therefore, the use of short fluorocarbon chain materials is more in line with the original intention of environmental friendliness. The present invention reacts methacrylic acid with a vinyl-containing POSS monomer, and then introduces a hydrophobic monomer trifluoroethyl methacrylate to prepare a fluorine-containing cage-type silsesquioxane nanotanning agent. The introduction of fluorine-containing monomers greatly improves the surface activity of the composite system, enhances its permeability, reduces problems such as surface over-tanning, and makes the finished leather softer, fuller and firmer.

[0015] The preparation method of the fluorine-containing cage-type silsesquioxane nano-tanning agent of the present invention is specifically implemented according to the following steps: Step 1, first add 0.32 parts to 0.64 parts of sodium dodecyl sulfate and 24 parts to 48 parts of distilled water in a three-necked flask according to mass parts, then raise the water bath to 50 ℃-70 ℃, and stir at a speed of 300 r / min-400 r / min until dissolved; then weigh 0.16 parts to 0.32 parts of vinyl cage silsesquioxane (i.e., POSS-Vi, prepared by hydrolysis and condensation reaction of vinyl trimethoxysilane as raw material) and dissolve it in 1.6 parts to 3.2 parts of tetrahydrofuran, and pour it into a three-necked flask and stir for 15 min-20 min; finally weigh 6 parts to 25 parts of methacrylic acid aqueous solution and 20 parts to 30 parts of initiator aqueous solution (the initiator aqueous solution is prepared by dissolving 1.6 parts of ammonium persulfate APS and 0.4 parts of sodium bisulfite RH with 10 times the mass parts of distilled water respectively) and add them to the flask three times, and react at a constant temperature of 50 ℃-70 ℃ for 2 h-3 h; Step 2, dissolving 2.5 to 12 parts of trifluoroethyl methacrylate in 5 to 24 parts of tetrahydrofuran and adding the mixture dropwise to the three-necked flask obtained in step 1 at a rate of 5 mL / h to 8 mL / h, reacting at a constant temperature for 2 to 3 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0016] The fluorinated caged silsesquioxane nanotanning agent prepared by the preparation method of the fluorinated caged silsesquioxane nanotanning agent of the present invention greatly improves the surface activity of the composite system due to the introduction of the hydrophobic short fluorocarbon chain monomer trifluoroethyl methacrylate, thereby significantly enhancing the permeability of the polycarboxyl POSS composite tanning agent, improving its filling property, making the finished leather fuller and firmer, and the shrinkage temperature of the single tanning can reach 75.3°C.

[0017] Example 1 The preparation method of the fluorine-containing cage-type silsesquioxane nano-tanning agent of the present invention is specifically implemented according to the following steps: Step 1, first add 0.32 parts of sodium dodecyl sulfate and 24 parts of distilled water to a three-necked flask according to mass parts, then heat the water bath to 50 ° C, and stir at a speed of 300 r / min until dissolved; then weigh 0.16 parts of vinyl cage silsesquioxane and dissolve it in 1.6 parts of tetrahydrofuran, and pour it into the three-necked flask and stir for 15 minutes; finally weigh 6 parts of 45% methacrylic acid aqueous solution and 20 parts of initiator aqueous solution and add them to the flask three times, and react at a constant temperature of 50 ° C for 2 hours; Step 2, dissolving 2.5 parts of trifluoroethyl methacrylate in 5 parts of tetrahydrofuran and adding dropwise to the three-necked flask obtained in step 1 at a rate of 5 mL / h, reacting at a constant temperature for 2 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0018] When used in leather tanning process, the shrinkage temperature of tanning alone can reach 72 ℃.

[0019] Example 2 The preparation method of the fluorine-containing cage-type silsesquioxane nano-tanning agent of the present invention is specifically implemented according to the following steps: Step 1: first add 0.64 parts of sodium dodecyl sulfate and 48 parts of distilled water to a three-necked flask according to the mass fraction, then heat the water bath to 70 ° C, and stir at a speed of 400 r / min until dissolved; then weigh 0.32 parts of vinyl cage silsesquioxane and dissolve it in 3.2 parts of tetrahydrofuran, and pour it into the three-necked flask and stir for 20 minutes; finally weigh 25 parts of 45% methacrylic acid aqueous solution and 30 parts of initiator aqueous solution and add them to the flask three times, and react at a constant temperature of 70 ° C for 3 hours; Step 2, dissolving 12 parts of trifluoroethyl methacrylate in 24 parts of tetrahydrofuran and adding dropwise to the three-necked flask obtained in step 1 at a rate of 8 mL / h, reacting at a constant temperature for 3 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0020] When used in leather tanning process, the shrinkage temperature of tanning alone can reach 73.1 ℃.

[0021] Example 3 The preparation method of the fluorine-containing cage-type silsesquioxane nano-tanning agent of the present invention is specifically implemented according to the following steps: Step 1: first add 0.48 parts of sodium dodecyl sulfate and 36 parts of distilled water to a three-necked flask according to the mass fraction, then heat the water bath to 60 ° C, and stir at a speed of 350 r / min until dissolved; then weigh 0.24 parts of vinyl cage silsesquioxane and dissolve it in 2.5 parts of tetrahydrofuran, and pour it into the three-necked flask and stir for 18 minutes; finally, weigh 15 parts of 45% methacrylic acid aqueous solution and 25 parts of initiator aqueous solution and add them to the flask three times, and react at a constant temperature of 60 ° C for 2.5 hours; Step 2, dissolving 11 parts of trifluoroethyl methacrylate in 14 parts of tetrahydrofuran and adding dropwise to the three-necked flask obtained in step 1 at a rate of 7 mL / h, reacting at a constant temperature for 2.5 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0022] When used in leather tanning process, the shrinkage temperature of tanning alone can reach 75.3 ℃.

[0023] Example 4 The preparation method of the fluorine-containing cage-type silsesquioxane nano-tanning agent of the present invention is specifically implemented according to the following steps: Step 1: first add 0.55 parts of sodium dodecyl sulfate and 29 parts of distilled water to a three-necked flask according to the mass fraction, then heat the water bath to 55 °C, and stir at a speed of 330 r / min until dissolved; then weigh 0.22 parts of vinyl cage silsesquioxane and dissolve it in 2.3 parts of tetrahydrofuran, and pour it into the three-necked flask and stir for 17 minutes; finally weigh 10 parts of 45% methacrylic acid aqueous solution and 22 parts of initiator aqueous solution and add them to the flask three times, and react at a constant temperature of 55 °C for 3 hours; Step 2, dissolving 4 parts of trifluoroethyl methacrylate in 10 parts of tetrahydrofuran and adding dropwise to the three-necked flask obtained in step 1 at a rate of 6 mL / h, reacting at a constant temperature for 3 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0024] When used in leather tanning process, the shrinkage temperature of tanning alone can reach 71.7 ℃.

[0025] Example 5 The preparation method of the fluorine-containing cage-type silsesquioxane nano-tanning agent of the present invention is specifically implemented according to the following steps: Step 1: first add 0.6 parts of sodium dodecyl sulfate and 40 parts of distilled water to a three-necked flask according to the mass fraction, then heat the water bath to 65 ° C, and stir at a speed of 380 r / min until dissolved; then weigh 0.3 parts of vinyl cage silsesquioxane and dissolve it in 2.9 parts of tetrahydrofuran, and pour it into the three-necked flask and stir for 19 minutes; finally weigh 23 parts of 45% methacrylic acid aqueous solution and 28 parts of initiator aqueous solution and add them to the flask three times, and react at a constant temperature of 65 ° C for 3 hours; Step 2, dissolving 11 parts of trifluoroethyl methacrylate in 22 parts of tetrahydrofuran and adding dropwise to the three-necked flask obtained in step 1 at a rate of 7 mL / h, reacting at a constant temperature for 3 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

[0026] When used in leather tanning process, the shrinkage temperature of tanning alone can reach 73.6 ℃.

[0027] The above description shows and describes several preferred embodiments of the invention, but as mentioned above, it should be understood that the invention is not limited to the form disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the invention concept described herein through the above teachings or the technology or knowledge of the relevant field. The changes and modifications made by those skilled in the art shall be within the scope of protection of the claims attached to the invention without departing from the spirit and scope of the invention.

Claims

1. A method for preparing a fluorine-containing cage-type silsesquioxane nano-tanning agent, characterized in that: Follow the steps below to implement it: Step 1, first add 0.32 parts to 0.64 parts of sodium dodecyl sulfate and 24 parts to 48 parts of distilled water to a flask according to mass parts, then raise the water bath temperature to 50 ℃-70 ℃, and stir at a speed of 300 r / min-400 r / min until dissolved; then weigh 0.16 parts to 0.32 parts of vinyl cage silsesquioxane and dissolve it in 1.6 parts to 3.2 parts of tetrahydrofuran, and pour it into the flask and stir for 15 min-20 min; finally weigh 6 parts to 25 parts of methacrylic acid aqueous solution and 20 parts to 30 parts of initiator aqueous solution and add them to the flask three times, and react at a constant temperature of 50 ℃-70 ℃ for 2 h-3 h; Step 2, dissolving 2.5 to 12 parts of trifluoroethyl methacrylate in 5 to 24 parts of tetrahydrofuran and slowly adding the mixture dropwise to the flask obtained in step 1, reacting at a constant temperature for 2 to 3 hours, and then naturally cooling to room temperature to obtain a fluorine-containing cage-type silsesquioxane nano-tanning agent.

2. The method for preparing the fluorine-containing cage-type silsesquioxane nano-tanning agent according to claim 1, characterized in that: In step 1, the flask is a three-necked flask.

3. The method for preparing the fluorine-containing cage-type silsesquioxane nano-tanning agent according to claim 1, characterized in that: In step 2, the mass fraction of the methacrylic acid aqueous solution is 45%.

4. The method for preparing the fluorine-containing cage-type silsesquioxane nano-tanning agent according to claim 1, characterized in that: In the step 2, the slow dropwise addition is specifically 5 mL / h to 8 mL / h.

5. Fluorine-containing cage-type silsesquioxane nanotanning agent, characterized in that: The fluorine-containing cage-type silsesquioxane nano-tanning agent is prepared using the preparation method of any one of claims 1 to 4.