High-compatibility and high-wear-resistance organosilicon auxiliary agent with core-shell structure and preparation method thereof

Abstract

The invention belongs to the field of leather assistants, and particularly relates to a high-compatibility and high-wear-resistance organosilicon assistant with a core-shell structure and a preparation method of the high-compatibility and high-wear-resistance organosilicon assistant. The high-compatibility and high-wear-resistance organic silicon auxiliary agent with the core-shell structure is prepared from the following preparation raw materials: methyl-terminated polyether modified trimethoxy silane, epoxy-terminated polyether modified trimethoxy silane, 1-12 alkene modified trimethylsiloxane, side vinyl silicone oil, end vinyl silicone oil, side hydrogen-containing silicone oil and end hydrogen-containing silicone oil, and iso-tridecanol polyoxyethylene ether and ammonia water. Specific modified silane, various silicone oil and the like are used as raw materials, a silicone rubber microsphere core structure is prepared firstly, and then a core-shell structure is formed through shell layer modification; the additive has excellent emulsion stability, high compatibility with a leather coating, and outstanding wear resistance and hand feeling retention, solves the technical contradiction of poor compatibility, wear resistance and hand feeling loss of a traditional additive, and is suitable for surface treatment of various types of leather.

Description

Technical Field

[0001] This invention belongs to the field of leather auxiliaries, specifically relating to a core-shell structured, highly compatible, and highly wear-resistant organosilicon auxiliary agent and its preparation method. Background Technology

[0002] Leather products are widely used in clothing, bags, furniture, and other fields. Their surface abrasion resistance directly determines the product's lifespan and user experience. Therefore, leather abrasion auxiliaries have become core functional additives in the leather finishing process. An ideal leather abrasion auxiliary must simultaneously possess excellent abrasion protection capabilities, high compatibility with leather coating systems, and the ability to retain the original soft feel of the leather.

[0003] Currently, the mainstream leather abrasion-resistant additives in the industry are mainly divided into two categories: one is macromolecular silicone oil additives, represented by Dow's DOWSIL FBL-3289 and ROSILK 2229. Although these additives can improve the abrasion resistance of leather to a certain extent, their molecular chains are large, making it difficult to form a stable dispersion system during emulsification. They also have poor compatibility with leather surface varnishes such as polyurethane, and are prone to layering and floating oil phenomena after compounding. This not only affects the stability of construction but also reduces the smoothness and aesthetics of the leather surface. The other category is abrasion-resistant additives with inorganic fillers such as silica and alumina. Inorganic fillers can enhance the surface hardness of leather and improve abrasion resistance through physical filling, but they can lead to excessively high cross-linking density in the leather coating, resulting in stiff and brittle coatings and severely damaging the original soft touch and flexibility of the leather.

[0004] Furthermore, some technical solutions attempt to use simple polyether-modified silicone oil as an abrasion-resistant additive. While this can preserve the feel of leather relatively well, its molecular chains lack sufficient shear resistance, making them prone to breakage during long-term friction. This leads to a rapid decline in abrasion resistance, failing to meet the long-term use requirements of leather products. Simultaneously, existing additives generally suffer from compatibility limitations, making it difficult to simultaneously work with different types of leather substrates and coating systems, further restricting their application scenarios.

[0005] In summary, the industry urgently needs a leather-specific silicone abrasion-resistant additive that can balance high compatibility, high abrasion resistance, and hand feel retention. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a core-shell structured, highly compatible, and highly wear-resistant organosilicon additive, comprising the following raw materials: methyl-terminated polyether modified trimethoxysilane, epoxy-terminated polyether modified trimethoxysilane, 1-12-ene modified trimethylsiloxane, side-vinyl silicone oil, end-vinyl silicone oil, side-hydrogen-containing silicone oil, end-hydrogen-containing silicone oil, isomeric tridecyl alcohol polyoxyethylene ether, and ammonia.

[0007] Preferably, the preparation method of the methyl-terminated polyether modified trimethoxysilane includes the following steps: (A-1) Mix 20-30 parts by weight of trimethoxysilane, 60-100 parts by weight of allyl methyl-terminated polyether, and 100-150 parts by weight of hexamethyldisiloxane, stir evenly, and then add 1-5 ppm of chloroplatinic acid. (A-2) Heat to 80-120℃ and react for 6-8 hours. After the reaction is completed, remove hexamethyldisiloxane under a vacuum of -0.1MPa to obtain the methyl-terminated polyether modified trimethoxysilane.

[0008] The reaction formula is shown in Formula I: Formula I Where: x = 3 - 10, y = 3 - 7.

[0009] Preferably, the preparation method of the epoxy-terminated polyether modified trimethoxysilane includes the following steps: (B-1) Mix 20-30 parts by weight of trimethoxysilane, 60-100 parts by weight of allyl epoxy-terminated polyether, and 100-150 parts by weight of hexamethyldisiloxane, stir evenly, and then add 1-5 ppm of chloroplatinic acid. (B-2) Heat to 80-120℃ and react for 6-8 hours. After the reaction is complete, remove hexamethyldisiloxane under a vacuum of -0.1MPa to obtain the epoxy-terminated polyether modified trimethoxysilane.

[0010] The reaction formula is shown in Formula II: Formula II Where: m=3-8, n=2-5.

[0011] Preferably, the preparation method of the 1-12-ene modified trimethylsiloxane includes the following steps: (C-1) Mix 20-30 parts by weight of trimethoxysilane, 10-50 parts by weight of 1-12-ene, and 50-80 parts by weight of hexamethyldisiloxane, stir well, and then add 1-5 ppm of chloroplatinic acid; (C-2) Heat to 80-120℃ and react for 6-8 hours. After the reaction is complete, remove hexamethyldisiloxane under a vacuum of -0.1MPa to obtain the 1-12 ene-modified trimethylsiloxane.

[0012] The reaction formula is shown in Formula III: Formula III Based on the same technical concept, another aspect of the present invention is to provide a method for preparing a core-shell structured, highly compatible, and highly wear-resistant organosilicon additive, the preparation method comprising the following steps: (1) Mix 1-5 parts by weight of side-containing hydrogen silicone oil, 100-200 parts by weight of end-vinyl silicone oil, 5-20 parts by weight of end-containing hydrogen silicone oil, 20-100 parts by weight of side-containing vinyl silicone oil, 1-3 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether and 500-800 parts by weight of water and homogenize them. Then add 3-6 ppm of chloroplatinic acid catalyst and let it stand to react to obtain the first suspension. The reaction process in step (1) is shown in equation IV: Formula IV (2) Mix 100-150 parts by weight of the first suspension, 30-60 parts by weight of ammonia water, and 100-150 parts by weight of water, and then slowly add 10-20 parts by weight of methyl-terminated polyether modified trimethoxysilane, 10-20 parts by weight of epoxy-terminated polyether modified trimethoxysilane, and 10-20 parts by weight of 1-12-ene modified trimethylsiloxane. The addition time is 20-60 min. After the reaction, the second suspension is obtained. The hydrolytic condensation reaction process of methyl-terminated polyether modified trimethoxysilane is shown in Formula V: Hydrolysis reaction:

[0013] Condensation reaction: Formula V (3) Dehydrate and wash the second suspension to obtain a filter cake; (4) Mix 100-150 parts by weight of the filter cake and 5-10 parts by weight of isotridecyl alcohol polyoxyethylene ether and disperse them, then add 100 parts by weight of water and continue to disperse to obtain the organosilicon additive.

[0014] Preferably, in step (1): The hydrogen content of the hydrogen-containing silicone oil is 0.3-1.2%; And / or, the vinyl content of the terminal vinyl silicone oil is 0.1-0.8%; And / or, the hydrogen content of the hydrogen-containing silicone oil is 0.06-0.3%; And / or, the vinyl content of the side vinyl silicone oil is 0.1-0.3%; And / or, the homogeneity is 30-50 MPa; And / or, the temperature of the static reaction is 20-25°C, and the static reaction time is 20-24h.

[0015] Preferably, in step (2), the reaction temperature is 5-15℃ and the reaction time is 6-8h.

[0016] Preferably, in step (3), the second suspension is centrifuged and washed with a 1200-mesh filter to obtain a filter cake with a solid content of 50-60%.

[0017] Preferably, in step (4): The dispersion speed is 2000 r / min, and the dispersion time is 1 h; And / or, the rotation speed for continued dispersion is 1000 r / min, and the dispersion time is 1 h.

[0018] The beneficial effects of this invention are as follows: 1. Solving the problem of insufficient compatibility: The core-shell structured organosilicon additive prepared by this invention has a shell layer that is synergistically modified by polyether segments, epoxy groups and long-chain alkanes, which can form a good interface bond with coating systems such as polyurethane varnish on leather surface. This effectively avoids the defects of traditional macromolecular silicone oil additives that are easy to separate and float oil. After testing, it can be stored stably for a long time after being compounded with common varnishes without separation or powdering, which greatly improves the compatibility of construction and the smoothness of coating.

[0019] 2. Balancing high abrasion resistance and a soft feel: This additive uses elastic silicone rubber microspheres as its core, which provide excellent impact cushioning to the leather surface through their own elasticity, reducing the abrasion damage to the leather during friction. At the same time, it abandons the rigid filling method of inorganic fillers, preserving the original soft touch of the leather and solving the problems of stiff and brittle coatings caused by traditional inorganic filler-type additives. Taber abrasion tests show that under a 1kg load and 3000r / min conditions, its abrasion mass loss is only 83mg, achieving an abrasion rating of level 4, far superior to similar commercially available additives.

[0020] 3. Improved wear resistance and durability: Compared with simple polyether-modified silicone oil, the core-shell cross-linked structure of the additive in this invention greatly enhances the shear resistance of the molecular chain, avoids the problem of molecular chain breakage under long-term friction, and can achieve long-term maintenance of wear resistance; moreover, its emulsion system has excellent stability and no storage stratification risk of traditional additives, thus extending the shelf life and service life of the product.

[0021] 4. Expanding the scope of application: The multifunctional modified design of the auxiliary shell makes it compatible with different types of leather substrates and coating systems, breaking through the compatibility limitations of traditional auxiliaries and providing a universal wear-resistant solution for the finishing of various leather products. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 This is an electron scanning microscope image of the first suspension system (the "core" structure before coating).

[0024] Figure 2 This is an electron scanning microscope image of the second suspension system (the core-shell structure after coating).

[0025] Figure 3 This is an image of the microspheres before coating.

[0026] Figure 4 This is a picture of the coated microspheres. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0028] Example This embodiment provides a method for preparing a core-shell structured, highly compatible, and highly wear-resistant organosilicon additive, the preparation method comprising the following steps: (I) Preparation of methyl-terminated polyether modified trimethoxysilane (I-1) Add 25g of trimethoxysilane, 80g of allyl methyl end-capped polyether, and 125g of hexamethyldisiloxane to the reactor, stir well, and then add 3ppm of chloroplatinic acid catalyst. (I-2) The temperature was raised to 100℃ and reacted for 6 hours. After the reaction was completed, hexamethyldisiloxane was removed under a vacuum of -0.1 MPa to obtain the methyl-terminated polyether modified trimethoxysilane (compound 1).

[0029] (II) Preparation of epoxy-terminated polyether modified trimethoxysilane (II-1) Add 25g of trimethoxysilane, 80g of allyl epoxy-terminated polyether, and 125g of hexamethyldisiloxane to the reactor, stir well, and then add 3ppm of chloroplatinic acid catalyst. (II-2) The temperature was raised to 100℃ and reacted for 6 hours. After the reaction was completed, hexamethyldisiloxane was removed under a vacuum of -0.1 MPa to obtain the epoxy-terminated polyether modified trimethoxysilane (compound 2).

[0030] (III) Preparation of 1-12-ene modified trimethylsiloxane (III-1) Add 25g of trimethoxysilane, 30g of 1-12-ene, and 65g of hexamethyldisiloxane to the reactor, stir well, and then add 3ppm of chloroplatinic acid catalyst. (III-2) The temperature was raised to 100℃ and reacted for 6 hours. After the reaction was completed, hexamethyldisiloxane was removed under a vacuum of -0.1 MPa to obtain the 1-12 ene-modified trimethylsiloxane (compound 3).

[0031] (IV) Preparation of Organosilicon Additives (IV-1) Add 3g of side-containing hydrogen silicone oil (0.7% hydrogen content), 150g of end-containing vinyl silicone oil (0.5% vinyl content), 12g of end-containing hydrogen silicone oil (0.18% hydrogen content), 60g of side-containing vinyl silicone oil (0.2% vinyl content), and 2g of isomeric tridecyl alcohol polyoxyethylene ether to a container, then add 650g of water. Homogenize using a homogenizer at 40MPa. Then add 5ppm of chloroplatinic acid catalyst to the container and let it stand at 20°C for 24h. The first suspension (a suspension of silicone rubber microspheres with only a core structure before coating) is obtained. Its electron micrograph is shown below. Figure 1 As shown in the diagram, the appearance is as follows: Figure 3 As shown.

[0032] (IV-2) The first suspension was stirred evenly, and 120g was added to a container. 45g of ammonia and 125g of water were added, and the system temperature was lowered to 10℃. Once the temperature stabilized, 15g of methyl-terminated polyether-modified trimethoxysilane (compound 1), 15g of epoxy-terminated polyether-modified trimethoxysilane (compound 2), and 15g of 1-12ene-modified trimethylsiloxane (compound 3) were slowly added dropwise over approximately 1 hour. The temperature was then maintained at 10℃, and the reaction continued for 6 hours to obtain the second suspension (a microsphere suspension with a core-shell structure after coating). Its electron micrograph is shown below. Figure 2 As shown in the diagram, the appearance is as follows: Figure 4 As shown.

[0033] (IV-3) The second suspension was centrifuged and washed with a 1200-mesh filter to obtain a filter cake with a solid content of 55%.

[0034] (IV-4) Take 125g of filter cake and add it to a container. Add 7g of isomeric tridecyl alcohol polyoxyethylene ether and disperse it at 2000r / min for 1h. Add 100g of water and continue to disperse it at 1000r / min for 1h to obtain the final product: a core-shell structured, highly compatible, and highly wear-resistant organosilicon additive.

[0035] After being placed at 40℃ for 1 month and at room temperature for 12 months, the emulsion remained in good condition without separation or precipitation.

[0036] Comparative Examples 1-7 Compared with the examples, Comparative Examples 1-7 differed in the amount of raw materials used, but the other operations were basically the same, as shown in Table 1.

[0037] Table 1

[0038] Note: Step (IV-2) is omitted for Comparative Example 7.

[0039] Verification Example The examples, comparative examples 1-7, and commercially available wear-resistant additives Dow DOWSIL FBL-3289 and ROSILK 2229 were compared, and the results are shown in Table 2.

[0040] Test method: Each group of silicone additives was compounded with various types of polyurethane varnish for leather surface, with an addition amount of 1%, and then tested. Taber abrasion test was performed on the coated leather, using 1 kg and 3000 r / min.

[0041] Table 2

[0042] The test results show that: The leather abrasion-resistant additive prepared in this invention mainly improves the compatibility of the product with various systems by modifying the surface of the microsphere shell with polyether segments, epoxy groups, and long-chain alkanes, ensuring long-term storage after compounding and good compatibility with other leather auxiliaries. Simultaneously, the soft core provides leather with a certain degree of impact resistance, thereby enhancing its abrasion resistance.

[0043] Compared with other comparative examples, the products modified with only one or two of the epoxy, polyether, and long-chain alkane materials exhibit shortcomings in compatibility, stability, and wear resistance. Comparative Example 7, which was not modified, showed poor performance in all aspects because, although it had a soft core, it could not be effectively dispersed in the system, resulting in poor wear resistance. In contrast, the product modified with all three materials (the examples) not only provided excellent stability and compatibility but also showed a significant improvement in wear resistance.

[0044] Compared to the commercially available wear-resistant additives DOWSIL FBL-3289 and ROSILK 2229, the example exhibits more favorable compatibility and wear resistance.

[0045] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A core-shell structured, highly compatible, and highly wear-resistant organosilicon additive, characterized in that, The raw materials include the following: methyl-terminated polyether modified trimethoxysilane, epoxy-terminated polyether modified trimethoxysilane, 1-12-ene modified trimethylsiloxane, side-vinyl silicone oil, end-vinyl silicone oil, side-hydrogen-containing silicone oil, end-hydrogen-containing silicone oil, isomeric tridecyl alcohol polyoxyethylene ether, and ammonia.

2. The core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to claim 1, characterized in that, The preparation method of the methyl-terminated polyether modified trimethoxysilane includes the following steps: (A-1) Mix 20-30 parts by weight of trimethoxysilane, 60-100 parts by weight of allyl methyl-terminated polyether, and 100-150 parts by weight of hexamethyldisiloxane, stir evenly, and then add 1-5 ppm of chloroplatinic acid. (A-2) Heat to 80-120℃ and react for 6-8 hours. After the reaction is completed, remove hexamethyldisiloxane under a vacuum of -0.1MPa to obtain the methyl-terminated polyether modified trimethoxysilane.

3. The core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to claim 1, characterized in that, The preparation method of the epoxy-terminated polyether modified trimethoxysilane includes the following steps: (B-1) Mix 20-30 parts by weight of trimethoxysilane, 60-100 parts by weight of allyl epoxy-terminated polyether, and 100-150 parts by weight of hexamethyldisiloxane, stir evenly, and then add 1-5 ppm of chloroplatinic acid. (B-2) Heat to 80-120℃ and react for 6-8 hours. After the reaction is complete, remove hexamethyldisiloxane under a vacuum of -0.1MPa to obtain the epoxy-terminated polyether modified trimethoxysilane.

4. The core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to claim 1, characterized in that, The preparation method of the 1-12-ene modified trimethylsiloxane includes the following steps: (C-1) Mix 20-30 parts by weight of trimethoxysilane, 10-50 parts by weight of 1-12-ene, and 50-80 parts by weight of hexamethyldisiloxane, stir well, and then add 1-5 ppm of chloroplatinic acid; (C-2) Heat to 80-120℃ and react for 6-8 hours. After the reaction is complete, remove hexamethyldisiloxane under a vacuum of -0.1MPa to obtain the 1-12 ene-modified trimethylsiloxane.

5. A method for preparing the core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to any one of claims 1-4, characterized in that, The preparation method includes the following steps: (1) Mix 1-5 parts by weight of side-containing hydrogen silicone oil, 100-200 parts by weight of end-vinyl silicone oil, 5-20 parts by weight of end-containing hydrogen silicone oil, 20-100 parts by weight of side-containing vinyl silicone oil, 1-3 parts by weight of isomeric tridecyl alcohol polyoxyethylene ether and 500-800 parts by weight of water and homogenize them. Then add 3-6 ppm of chloroplatinic acid catalyst and let it stand to react to obtain the first suspension. (2) Mix 100-150 parts by weight of the first suspension, 30-60 parts by weight of ammonia water, and 100-150 parts by weight of water, and then add 10-20 parts by weight of methyl-terminated polyether modified trimethoxysilane, 10-20 parts by weight of epoxy-terminated polyether modified trimethoxysilane and 10-20 parts by weight of 1-12-ene modified trimethylsiloxane in sequence. After the reaction, a second suspension is obtained. (3) Dehydrate and wash the second suspension to obtain a filter cake; (4) Mix 100-150 parts by weight of the filter cake and 5-10 parts by weight of isotridecyl alcohol polyoxyethylene ether and disperse them, then add 100 parts by weight of water and continue to disperse to obtain the organosilicon additive.

6. The method for preparing the core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to claim 5, characterized in that, In step (1): The hydrogen content of the hydrogen-containing silicone oil is 0.3-1.2%; And / or, the vinyl content of the terminal vinyl silicone oil is 0.1-0.8%; And / or, the hydrogen content of the hydrogen-containing silicone oil is 0.06-0.3%; And / or, the vinyl content of the side vinyl silicone oil is 0.1-0.3%; And / or, the homogeneity is 30-50 MPa; And / or, the temperature of the static reaction is 20-25°C, and the static reaction time is 20-24h.

7. The method for preparing the core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to claim 5, characterized in that, In step (2), the reaction temperature is 5-15℃ and the reaction time is 6-8h.

8. The method for preparing the core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to claim 5, characterized in that, In step (3), the second suspension is centrifuged and washed with a 1200-mesh filter to obtain a filter cake with a solid content of 50-60%.

9. The method for preparing the core-shell structured, highly compatible, and highly wear-resistant organosilicon additive according to claim 5, characterized in that, In step (4): The dispersion speed is 2000 r / min, and the dispersion time is 1 h; And / or, the rotation speed for continued dispersion is 1000 r / min, and the dispersion time is 1 h.

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