Organic silicon hand feeling agent for improving physical properties of leather and preparation method of organic silicon hand feeling agent

Abstract

The invention belongs to the field of leather finishing, and particularly relates to an organic silicon feeling agent for improving the physical property of leather and a preparation method thereof. According to the preparation method, the following raw materials are mainly adopted: mixed cyclosiloxane (DMC), an epoxy double-head coupling agent (KH362), polyether amine, TMAH (tetramethylammonium hydroxide), isophorone diisocyanate (IPDI), dibutyltin dilaurate (DBTDL), polyethylene glycol and the like. A novel route is designed, the problem that the grafting rate of hydrophilic groups introduced into macromolecular silicone oil is not high is solved, the cross-linking capacity of organic silicon on the surface layer is enhanced by introducing the polyurethane prepolymer, and the obtained silicon emulsion hand feeling agent can endow leather with smooth and comfortable hand feeling and excellent wear resistance and solvent resistance.

Description

Technical Field

[0001] The invention belongs to the field of leather finishing, and specifically relates to an organosilicon feel agent for improving the physical properties of leather and a preparation method thereof. Background Art

[0002] Leather feel agents are products used to adjust the touch of the leather surface, which can bring smoothness, moisturizing, oiliness, cottoniness and other kinds of feel to the product. There are many types of feel agents, which can be divided into silicone feel agents, wax feel agents, and silicone wax composite feel agents according to the components. Conventional wax feel agents have the disadvantages of wax not being easy to emulsify, the emulsion state being general, and the feel types being few. There are many types of silicone feel agents, and they can be hydrophilically modified, and are suitable for various systems.

[0003] The most common silicone feel agent is a silicone emulsion of polyether-modified silicone oil. The polyether-modified silicone oil is obtained by introducing polyether segments into the silicone chain through various reactions from reactive base silicone oils, such as amino silicone oil, epoxy silicone oil, hydrogen-containing silicone oil, etc. However, for polyether-modified silicone oils under this route, when the molecular weight of the base silicone oil reaches 20,000 to 100,000, the grafting rate of the introduced polyether is often not high, and it is difficult to reach more than 95%. A low grafting rate can easily lead to poor stability and performance fluctuations after the silicone oil is made into silicone emulsion.

[0004] Therefore, based on this, the technical solution of the present invention is proposed. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a method for preparing a silicone feel agent for improving the physical properties of leather, and the preparation method comprises the following steps:

[0006] (1) mixing epoxy double-capped coupling agent KH362, polyether amine (D400 or ED600, ED900) and isopropanol and performing heat preservation reaction, and after completion, removing isopropanol to obtain a crude product A;

[0007] The reaction process is as follows:

[0008]

[0009] (2) mixing the crude product A, ethanol and water, and letting them stand for stratification, taking out the lower layer of liquid and removing the ethanol and water to obtain product B;

[0010] (3) heating the mixed cyclosiloxane, tetramethylammonium hydroxide and the product B to react, and after completion, removing the small molecular silane in the system to obtain product C;

[0011] The reaction process is as follows:

[0012]

[0013] (4) dehydrating and drying the polyethylene glycol, mixing it with isophorone diisocyanate, a catalyst dibutyltin dilaurate, and a solvent acetone, and heating the mixture to obtain a product D;

[0014] The reaction process is as follows:

[0015]

[0016] (5) mixing and dispersing the product C with toluene to obtain a dispersion A; mixing and dispersing the product D with toluene to obtain a dispersion B;

[0017] (6) adding the dispersion B dropwise to the dispersion A to react, and then adding a sodium bisulfite solution to continue the reaction, and then removing toluene from the system to obtain a polyurethane-modified polyether silicone oil;

[0018] The reaction process is as follows:

[0019]

[0020] (7) mixing and dispersing the polyurethane-modified polyether silicone oil, the product B, isomeric tridecanol polyoxyethylene ether 1307, and isomeric tridecanol polyoxyethylene ether 1305 to obtain a dispersion C;

[0021] (8) Add glacial acetic acid and deionized water to the dispersion C in sequence for dispersion, and then add glacial acetic acid and deionized water again for dispersion, thereby obtaining the organic silicone feel agent for improving the physical properties of leather.

[0022] Preferably, in step (1), the mass ratio of epoxy double-head coupling agent, polyetheramine and isopropanol is 362:900-3000:600-1700;

[0023] And / or, the temperature of the insulation reaction is 50 to 80° C., and the insulation reaction time is 3 to 6 hours;

[0024] And / or, the temperature for removing isopropanol is 80°C.

[0025] Preferably, in step (2), the mass ratio of crude product A, ethanol and water is 100:60:140;

[0026] And / or, the mixing and stirring time is 20 to 30 minutes;

[0027] And / or, the standing stratification time is 8h;

[0028] And / or, the method of removing ethanol and water is: removing by vacuuming at 100°C.

[0029] Preferably, in step (3), the mass ratio of the mixed cyclosiloxane, tetramethylammonium hydroxide, and product B is 300:0.2-0.5:7-15;

[0030] And / or, the heating reaction temperature is 100-120°C and the time is 8-10h;

[0031] And / or, the method of removing the small molecular silane from the system is: removing by vacuuming at 130-160°C.

[0032] Preferably, in step (4), the mass ratio of polyethylene glycol, isophorone diisocyanate, catalyst and solvent is 400-1200:444-1340:0.8-1.6:600-1100;

[0033] And / or, the heating reaction temperature is 60-80° C. and the time is 1-4 hours.

[0034] Preferably, in step (5), the mass ratio of the product C to toluene is 100:50;

[0035] And / or, the mass ratio of the product D to toluene is 100:50;

[0036] And / or, the mixing and dispersing time is 20 minutes.

[0037] Preferably, in step (6), the reaction temperature is 80° C. and the reaction time is 3 h;

[0038] And / or, the reaction time is 2 hours;

[0039] And / or, the method of removing toluene from the system is: removing the toluene by vacuuming at 120°C.

[0040] Preferably, in step (7), the mass ratio of polyurethane-modified polyether silicone oil, product B, isomeric tridecanol polyoxyethylene ether 1307, and isomeric tridecanol polyoxyethylene ether 1305 is 40-50:5-10:5-15:5-15;

[0041] And / or, the mixing and dispersing time is 20 minutes.

[0042] Preferably, in step (8), the dispersion time is 0.5 to 3 hours.

[0043] Based on the same technical concept, another embodiment of the present invention is to provide an organosilicon feel agent for improving the physical properties of leather obtained by the above preparation method.

[0044] The beneficial effects of the present invention are:

[0045] The present invention designs a new route to solve the problem of low grafting rate of hydrophilic groups introduced into macromolecular silicone oil, and enhances the cross-linking ability of silicone on the surface by introducing polyurethane prepolymer. The obtained silicone emulsion hand feeling agent can give leather a smooth and comfortable feel, excellent wear resistance and solvent resistance. DETAILED DESCRIPTION

[0046] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0047] Example 1

[0048] This embodiment provides a method for preparing an organosilicon feel agent for improving the physical properties of leather, the preparation method comprising the following steps:

[0049] (1) Add 72.4 g of epoxy double-capped coupling agent KH362, 180 g of polyetheramine D400, and 150 g of isopropanol into a reaction container, and carry out a heat-insulating reaction at 50° C. for 3 h in a closed environment protected by a nitrogen atmosphere. After completion, remove the isopropanol at 80° C. to obtain a crude product A;

[0050] (2) 100 g of crude product A, 60 g of ethanol, and 140 g of water were placed in a stirring container and mixed and stirred for 20 min, and then allowed to stand for 8 h to allow for stratification, the lower layer of liquid was discharged, and the ethanol and water were removed in vacuo at 100 ° C to obtain product B;

[0051] (3) Add 300 g of mixed cyclosiloxane DMC, 0.2 g of tetramethylammonium hydroxide (TMAH) and 7 g of product B into the reactor, react at 100 ° C for 10 h, and after completion, increase the temperature to 130 ° C, open the vacuum, remove the small molecular silane in the system, and obtain product C;

[0052] (4) 100 g of polyethylene glycol PEG400 was dried under vacuum at 120° C., and then cooled to 50° C. after 2 h; then 115 g of isophorone diisocyanate (IPDI), 0.25 g of catalyst dibutyltin dilaurate and 150 g of solvent acetone were added, and the temperature was raised to 60° C. and reacted for 4 h to obtain product D;

[0053] (5) 100 g of product C and 50 g of toluene were mixed and dispersed at 80° C. for 20 min to obtain dispersion A; 100 g of product D and 50 g of toluene were mixed and dispersed at 80° C. for 20 min to obtain dispersion B;

[0054] (6) at 80° C., the dispersion B was gradually added dropwise to the dispersion A, and the reaction was continued for 3 h. Then, 50 g of saturated sodium bisulfite solution was added and the reaction was continued for 2 h. Then, vacuum was drawn at 120° C. to remove the toluene in the system, and a polyurethane-modified polyether silicone oil was obtained.

[0055] (7) 40 g of the polyurethane-modified polyether silicone oil, 5 g of the product B, 5 g of isomeric tridecanol polyoxyethylene ether 1307, and 5 g of isomeric tridecanol polyoxyethylene ether 1305 were mixed and dispersed for 20 min to obtain a dispersion C;

[0056] (8) Add 3 g of glacial acetic acid (10 wt %) to the dispersion C and disperse for 1 h, then add 50 g of deionized water and disperse for 2 h, then add 5 g of glacial acetic acid (10 wt %) again and disperse for 30 min, and finally add 50 g of deionized water and disperse for 1 h to obtain the silicone feel agent for improving the physical properties of leather.

[0057] Example 2

[0058] This embodiment provides a method for preparing an organosilicon feel agent for improving the physical properties of leather, the preparation method comprising the following steps:

[0059] (1) Add 72.4 g of epoxy double-capped coupling agent KH362, 250 g of polyetheramine ED600, and 200 g of isopropanol into a reaction container, and carry out a heat preservation reaction at 80° C. for 6 h in a closed environment protected by a nitrogen atmosphere. After completion, remove the isopropanol at 80° C. to obtain a crude product A;

[0060] (2) 100 g of crude product A, 60 g of ethanol, and 140 g of water were placed in a stirring container and mixed and stirred for 30 min, and then allowed to stand for 8 h to allow for stratification, the lower layer of liquid was discharged, and the ethanol and water were removed in vacuo at 100 ° C to obtain product B;

[0061] (3) Add 300 g of mixed cyclosiloxane DMC, 0.5 g of tetramethylammonium hydroxide (TMAH) and 15 g of product B to the reactor, react at 120 ° C for 8 h, and after completion, increase the temperature to 160 ° C, open the vacuum, remove the small molecular silane in the system, and obtain product C;

[0062] (4) 100 g of polyethylene glycol PEG600 was dried under vacuum at 120° C., and then cooled to 50° C. after 2 h. Then, 130 g of isophorone diisocyanate (IPDI), 0.23 g of catalyst dibutyltin dilaurate, and 161 g of solvent acetone were added, and the temperature was raised to 80° C. for reaction for 1 h to obtain product D.

[0063] (5) 100 g of product C and 50 g of toluene were mixed and dispersed at 80° C. for 20 min to obtain dispersion A; 100 g of product D and 50 g of toluene were mixed and dispersed at 80° C. for 20 min to obtain dispersion B;

[0064] (6) at 80° C., the dispersion B was gradually added dropwise to the dispersion A, and the reaction was continued for 3 h. Then, 50 g of saturated sodium bisulfite solution was added and the reaction was continued for 2 h. Then, vacuum was drawn at 120° C. to remove the toluene in the system, and a polyurethane-modified polyether silicone oil was obtained.

[0065] (7) 50 g of the polyurethane-modified polyether silicone oil, 10 g of the product B, 15 g of isomeric tridecanol polyoxyethylene ether 1307, and 15 g of isomeric tridecanol polyoxyethylene ether 1305 were mixed and dispersed for 20 min to obtain a dispersion C;

[0066] (8) Add 10 g of glacial acetic acid (10 wt %) to the dispersion C and disperse for 2 h, then add 200 g of deionized water and disperse for 3 h, then add 10 g of glacial acetic acid (10 wt %) again and disperse for 60 min, and finally add 200 g of deionized water and disperse for 1 h to obtain the silicone feel agent for improving the physical properties of leather.

[0067] Example 3

[0068] This embodiment provides a method for preparing an organosilicon feel agent for improving the physical properties of leather, the preparation method comprising the following steps:

[0069] (1) Add 72.4 g of epoxy double-capped coupling agent KH362, 380 g of polyetheramine ED900, and 270 g of isopropanol into a reaction container, and carry out a heat-insulating reaction at 70° C. for 4.5 h in a closed environment protected by a nitrogen atmosphere. After completion, remove the isopropanol at 80° C. to obtain a crude product A;

[0070] (2) 100 g of crude product A, 60 g of ethanol, and 140 g of water were placed in a stirring container and mixed and stirred for 25 min, and then allowed to stand for 8 h to allow for stratification, the lower layer of liquid was discharged, and the ethanol and water were removed in vacuo at 100 ° C to obtain product B;

[0071] (3) Add 300 g of mixed cyclosiloxane DMC, 0.35 g of tetramethylammonium hydroxide (TMAH) and 11 g of product B to the reactor, react at 110 ° C for 9 h, and after completion, increase the temperature to 145 ° C, open the vacuum, remove the small molecular silane in the system, and obtain product C;

[0072] (4) 100 g of polyethylene glycol PEG1000 was dried under vacuum at 120° C., and then cooled to 50° C. after 2 h. Then, 60 g of isophorone diisocyanate (IPDI), 0.16 g of catalyst dibutyltin dilaurate, and 96 g of solvent acetone were added, and the temperature was raised to 70° C. and reacted for 2.5 h to obtain product D.

[0073] (5) 100 g of product C and 50 g of toluene were mixed and dispersed at 80° C. for 20 min to obtain dispersion A; 100 g of product D and 50 g of toluene were mixed and dispersed at 80° C. for 20 min to obtain dispersion B;

[0074] (6) at 80° C., the dispersion B was gradually added dropwise to the dispersion A, and the reaction was continued for 3 h. Then, 50 g of saturated sodium bisulfite solution was added and the reaction was continued for 2 h. Then, vacuum was drawn at 120° C. to remove the toluene in the system, and a polyurethane-modified polyether silicone oil was obtained.

[0075] (7) 45 g of the polyurethane-modified polyether silicone oil, 7.5 g of the product B, 10 g of isomeric tridecanol polyoxyethylene ether 1307, and 10 g of isomeric tridecanol polyoxyethylene ether 1305 were mixed and dispersed for 20 min to obtain a dispersion C;

[0076] (8) Add 7.5 g of glacial acetic acid (10 wt %) to the dispersion C and disperse for 1.5 h, then add 125 g of deionized water and disperse for 2.5 h, then add 7.5 g of glacial acetic acid (10 wt %) again and disperse for 45 min, and finally add 125 g of deionized water and disperse for 1 h to obtain the silicone feel agent for improving the physical properties of leather.

[0077] Verification Example

[0078] The silicone feel agent product obtained in Example 1 was selected for comparison with the Lanxess 2229 and Lanxess SF feel agents with better physical properties on the market, specifically:

[0079] Hand feel style test: add each group of hand feel agents to the top light layer in a ratio of 1:10, 1:7, and 1:5 with polyurethane brightener, spray and cure. Use subjective scoring by multiple people (1 to 10 points, 10 points is the best, 1 point is the worst) to judge the difference in hand feel style.

[0080] Leather wear resistance test: The wear resistance test refers to QB / T 2726-2005 leather physical and mechanical test wear resistance test.

[0081] Color fastness to rubbing test: refer to ISO11640 and ideal qlia5330002-2019 technical requirements for automotive seat leather.

[0082] The evaluation results are shown in Table 1.

[0083] Table 1

[0084]

[0085] As can be seen from Table 1, the finished hand feeling agent of the present invention has better solvent resistance than 2229W and better abrasion resistance and wet rub resistance than SF, compared with two popular hand feeling agents for improving physical properties on the market.

[0086] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a silicone feel agent for improving leather properties, characterized in that: The preparation method comprises the following steps: (1) mixing an epoxy double-capped coupling agent, a polyetheramine, and isopropanol and performing a heat-insulating reaction, and after completion, removing the isopropanol to obtain a crude product A; (2) mixing the crude product A, ethanol and water, and letting them stand for stratification, taking out the lower layer of liquid and removing the ethanol and water to obtain product B; (3) heating the mixed cyclosiloxane, tetramethylammonium hydroxide and the product B to react, and after completion, removing the small molecular silane in the system to obtain product C; (4) dehydrating and drying the polyethylene glycol, mixing it with isophorone diisocyanate, a catalyst and a solvent, and heating the mixture to obtain a product D; (5) mixing and dispersing the product C with toluene to obtain a dispersion A; mixing and dispersing the product D with toluene to obtain a dispersion B; (6) adding the dispersion B dropwise to the dispersion A to react, and then adding a sodium bisulfite solution to continue the reaction, and then removing toluene from the system to obtain a polyurethane-modified polyether silicone oil; (7) mixing and dispersing the polyurethane-modified polyether silicone oil, the product B, isomeric tridecanol polyoxyethylene ether 1307, and isomeric tridecanol polyoxyethylene ether 1305 to obtain a dispersion C; (8) Add glacial acetic acid and deionized water to the dispersion C in sequence for dispersion, and then add glacial acetic acid and deionized water again for dispersion, thereby obtaining the organic silicone feel agent for improving the physical properties of leather.

2. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (1), the mass ratio of epoxy double-end coupling agent, polyetheramine and isopropanol is 362:900-3000:600-1700; And / or, the temperature of the insulation reaction is 50 to 80° C., and the insulation reaction time is 3 to 6 hours; And / or, the temperature for removing isopropanol is 80°C.

3. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (2), the mass ratio of crude product A, ethanol and water is 100:60:140; And / or, the mixing and stirring time is 20 to 30 minutes; And / or, the standing stratification time is 8h; And / or, the method of removing ethanol and water is: removing by vacuuming at 100°C.

4. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (3), the mass ratio of the mixed cyclosiloxane, tetramethylammonium hydroxide and product B is 300:0.2-0.5:7-15; And / or, the heating reaction temperature is 100-120° C. and the time is 8-10 hours; And / or, the method of removing the small molecular silane from the system is: removing by vacuuming at 130-160°C.

5. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (4), the mass ratio of polyethylene glycol, isophorone diisocyanate, catalyst and solvent is 400-1200:444-1340:0.8-1.6:600-1100; And / or, the heating reaction temperature is 60-80° C. and the time is 1-4 hours.

6. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (5), the mass ratio of the product C to toluene is 100:50; And / or, the mass ratio of the product D to toluene is 100:50; And / or, the mixing and dispersing time is 20 minutes.

7. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (6), the reaction temperature is 80° C. and the reaction time is 3 h; And / or, the reaction time is 2 hours; And / or, the method of removing toluene from the system is: removing the toluene by vacuuming at 120°C.

8. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (7), the mass ratio of polyurethane modified polyether silicone oil, product B, isomeric tridecanol polyoxyethylene ether 1307, and isomeric tridecanol polyoxyethylene ether 1305 is 40-50:5-10:5-15:5-15; And / or, the mixing and dispersing time is 20 minutes.

9. The method for preparing the organic silicon feel agent for improving the physical properties of leather according to claim 1, characterized in that: In step (8), the dispersion time is 0.5 to 3 hours.

10. The organic silicon feel agent for improving the physical properties of leather obtained by the preparation method according to any one of claims 1 to 9.

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