P-hydroxyphenethyl triethoxy silane as well as preparation method and application thereof

Abstract

The invention discloses p-hydroxyphenethyl triethoxy silane as well as a preparation method and application thereof, p-hydroxystyrene and triethoxy silane are taken as raw materials, and the p-hydroxyphenethyl triethoxy silane is prepared through addition reaction in the presence of a catalyst. The product is colorless transparent liquid in appearance, the yield is 95% or above, the purity is 98% or above, and the use requirement is met. When the product is applied to green tires, not only can the dispersibility of white carbon black be improved and the processability of a rubber material be improved, but also the phenolic hydroxyl group in the molecular structure can play a role in delaying rubber aging, so that the product has industrial application value.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon chemistry, specifically relating to a p-hydroxyphenylethyltriethoxysilane, its preparation method, and its application. Background Technology

[0002] The information disclosed in this background section is intended only to enhance some understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art.

[0003] In the tire industry, with increasing public awareness of environmental protection and a growing emphasis on energy conservation, low rolling resistance tires have become a key research focus for tire companies. Furthermore, the rapid rise of new energy vehicles, whose instantaneous torque is significantly higher than that of gasoline vehicles, leads to accelerated tire wear due to excessive instantaneous torque. Additionally, lithium-ion battery-powered new energy vehicles carry hundreds of kilograms of lithium batteries, and this increased weight, combined with the higher instantaneous torque, results in significantly higher tire wear rates compared to gasoline vehicles. Therefore, low rolling resistance and high wear resistance tires have become a priority for tire companies. The use of silica in green tires is also increasing. However, due to the strong polarity of silica's surface, it is difficult to disperse. Silane coupling agents can react with the silica surface through silanization, effectively improving its dispersibility.

[0004] Currently, the mainstream silane coupling agents are Si-69 and Si-75, but these silane coupling agents do not perform well in improving the aging of the silica formulation system for green tires. Therefore, in order to improve the performance of green tires, it is urgent to develop new silane coupling agent molecules. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a p-hydroxyphenylethyltriethoxysilane, its preparation method, and its application. This silane contains silane ethoxy groups, which undergo a silanization reaction with the polar hydroxyl groups on the surface of silica during application, reducing the surface polarity of silica and promoting the dispersion of silica in rubber compounds. In addition, it contains benzene hydroxyl groups, which can delay the aging of rubber compounds during application and extend the service life of tires or other rubber products. It is a multifunctional silane coupling agent.

[0006] The technical solution adopted in this invention is as follows: In a first aspect, a p-hydroxyphenylethyltriethoxysilane is provided, having the following chemical structural formula: .

[0007] Secondly, a method for preparing the p-hydroxyphenylethyltriethoxysilane is provided, wherein the method uses p-hydroxystyrene and triethoxysilane as raw materials and performs a hydrosilylation reaction under the action of a catalyst to obtain p-hydroxyphenylethyltriethoxysilane.

[0008] Furthermore, the catalyst comprises a main catalyst and a secondary catalyst, wherein the main catalyst is at least one of chloroplatinic acid, palladium chloride, and PPh3-Rh complex, preferably chloroplatinic acid, and the secondary catalyst is the amine solvent triethylamine.

[0009] Taking chloroplatinic acid as the catalyst as an example, the reaction formula is as follows:

[0010] Further, the molar ratio of p-hydroxystyrene, triethoxysilane, main catalyst, and secondary catalyst is 1.05-1.1:1:0.001~0.0015:0.001~0.0015. For example, 1.05:1:0.001:0.001, 1.06:1:0.001:0.001, 1.07:1:0.001:0.001, 1.08:1:0.001:0.001, 1.09:1:0.001:0.001, 1.1:1:0.001:0.001, with 1.05:1:0.001:0.001 being preferred.

[0011] Furthermore, the reaction temperature is 80-100℃, for example 80℃, 85℃, 90℃, 95℃, 100℃, preferably 85-90℃.

[0012] Further, the above method specifically includes the following steps: adding triethoxysilane dropwise to a mixture containing p-hydroxystyrene, a main catalyst, and a secondary catalyst over 0.5-1 hour; after the addition is complete, continuing the reaction at 80-100°C for 2-4 hours to obtain a reaction solution containing p-hydroxyphenylethyltriethoxysilane; filtering the reaction solution to remove residual p-hydroxystyrene; and then distilling to obtain the target product, p-hydroxyphenylethyltriethoxysilane. Thirdly, the application of the p-hydroxyphenylethyltriethoxysilane is provided in any of the following aspects: As a silane coupling agent, it is used to promote the dispersion of reinforcing fillers in rubber compositions; it is used to promote the dispersion of inorganic fillers such as silica, talc, and clay in organic polymers such as rubber and plastics, thereby improving processing performance and enhancing the mechanical properties of composite materials.

[0013] Its application as an anti-aging agent in delaying the aging of rubber products; utilizing the phenolic hydroxyl groups in its molecule to capture free radicals, it is used to delay the thermo-oxidative aging of rubber products (especially tires) and extend their service life.

[0014] This invention relates to p-hydroxyphenylethyltriethoxysilane, a multifunctional silane coupling agent, belonging to the category of multifunctional organosilane coupling agents. It is suitable for vulcanized rubber systems using fillers such as silica, talc, mica, and clay as reinforcing agents. Its function is to improve filler dispersibility, enhance filler reinforcing ability, and increase rubber abrasion resistance, while simultaneously reducing rubber viscosity and improving processing performance. It is widely used in the tire, hose, plastics, and sealant industries, significantly improving the overall performance of materials.

[0015] Fourthly, a rubber composition is provided, comprising, by weight, the following components: 100 parts of rubber matrix; 20 to 80 parts of reinforcing filler, wherein the reinforcing filler is silica; p-Hydroxyphenylethyltriethoxysilane, used in amounts ranging from 1 w / w% to 20 w / w% of the amount of silica. It also includes a vulcanization system and an activator.

[0016] Furthermore, the rubber matrix can be selected from natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR) and their blends, the reinforcing filler further includes carbon black, the vulcanization system includes 1~2 parts of S-80, 1~2 parts of accelerator CBS-80 and 2~3 parts of accelerator DPG-80, and the activator is 2~4 parts of ZnO-80.

[0017] Fifthly, a rubber article is provided, made from the said rubber composition.

[0018] Furthermore, the rubber product is a tire.

[0019] Compared with the related technologies known to the inventors, one of the technical solutions of the present invention has the following beneficial effects: (1) Excellent product performance: Multifunctionality: The product of this invention contains both silanyl ethoxy groups that can react with silica and benzyl hydroxyl groups that have anti-aging effects, thus combining coupling and anti-aging functions.

[0020] Highly efficient dispersion: It can significantly improve the dispersibility of silica in rubber compounds, reduce the viscosity of the compound, improve processing performance, and enhance the reinforcing effect of fillers, thereby improving the mechanical properties (such as tensile stress and tensile strength) and abrasion resistance of rubber.

[0021] Excellent anti-aging properties: When applied to rubber, it significantly improves the retention rate of tensile strength and elongation at break of rubber products after thermo-oxidative aging, effectively extending the service life of the products. Performance tests show that its anti-aging effect is significantly better than that of the traditional silane coupling agent Si-69.

[0022] (2) Advantages of the preparation process: High yield and high purity: The preparation method provided by this invention is simple, mild, easy to control and implement, and has a high product yield (up to 95% or more), good purity (up to 98% or more), and is a colorless or pale yellow transparent liquid with stable quality.

[0023] Good reaction selectivity: Under optimal catalyst and process conditions, hydrosilylation reaction is highly efficient and specific with few side reactions.

[0024] (3) High application value: This invention is particularly suitable for the manufacture of green tires with stringent performance requirements. It can reduce tire rolling resistance while solving the problem of accelerated wear caused by increased vehicle weight and high instantaneous torque, and effectively delay tire aging. It meets the comprehensive requirements of new energy vehicle tires for low rolling resistance, high wear resistance and long life, and has broad prospects for industrial application. Attached Figure Description

[0025] The accompanying drawings, which form part of this specification, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0026] Figure 1 The image shows the 1H NMR spectrum of p-hydroxyphenylethyltriethoxysilane obtained in Example 1. Detailed Implementation

[0027] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0028] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments of the present invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, and / or combinations thereof.

[0029] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0030] In the following embodiments, the yield is calculated as: the mass of the obtained product / the theoretical mass of the product.

[0031] Example 1: 240g of p-hydroxystyrene and 1.036g of chloroplatinic acid were added sequentially to a 1L reactor. The temperature was controlled at 85℃, and stirring was started. 328g of triethoxysilane was slowly added dropwise to the system. After about 1 hour, the addition of triethoxysilane was completed. The temperature was maintained and stirring was continued for about 2 hours. After the reaction was completed, the temperature was lowered to 60℃ and the remaining p-hydroxystyrene was removed by filtration. Then, low-boiling impurities were removed by vacuum distillation at a pressure of -0.09MPa and a temperature of 85℃, yielding 560.6g of the target product, which was a colorless and transparent liquid. The yield based on triethoxysilane was 98.7%, and the product purity (HPLC) was 99.3%.

[0032] The 1H NMR spectrum of the obtained product is as follows Figure 1 As shown.

[0033] Example 2: 240g of p-hydroxystyrene and 1.036g of chloroplatinic acid were added sequentially to a 1L reactor. The temperature was controlled at 80℃, and stirring was started. 328g of triethoxysilane was slowly added dropwise to the system. After about 1 hour, the addition of triethoxysilane was completed. The temperature was maintained and stirring was continued for about 2 hours. After the reaction was completed, the temperature was lowered to 60℃ and filtered. The product was then distilled under reduced pressure at -0.09MPa and 60℃ to obtain 553.8g of the target product, which was a colorless and transparent liquid. The yield was 97.5% based on triethoxysilane, and the product purity (HPLC) was 98.8%.

[0034] Example 3: 240g of p-hydroxystyrene and 1.036g of chloroplatinic acid were added sequentially to a 1L reactor. The temperature was controlled at 95℃, and stirring was started. 328g of triethoxysilane was slowly added dropwise to the system. After about 1 hour, the addition of triethoxysilane was completed. The temperature was maintained and stirring was continued for about 2 hours. After the reaction was completed, the temperature was lowered to 60℃ and filtered. The product was then distilled under reduced pressure at -0.09MPa and 55℃ to obtain 557.0g of the target product, which was a colorless and transparent liquid. The yield based on triethoxysilane was 96.3%, and the product purity (HPLC) was 98.6%.

[0035] Example 4: 240g of p-hydroxystyrene and 1.036g of chloroplatinic acid were added sequentially to a 1L reactor. The temperature was controlled at 95℃, and stirring was started. 328g of triethoxysilane was slowly added dropwise to the system. After about 1 hour, the addition of triethoxysilane was completed. The temperature was maintained and stirring was continued for about 3 hours. After the reaction was completed, the temperature was lowered to 60℃ and filtered. The product was then distilled under reduced pressure at -0.09MPa and 55℃ to obtain 559.5g of the target product. The product was a colorless and transparent liquid with a yield of 98.5% based on triethoxysilane and a purity (HPLC) of 98.4%.

[0036] Example 5: 240g of p-hydroxystyrene and 0.354g of palladium chloride were added sequentially to a 1L reactor. The temperature was controlled at 95℃, and stirring was started. 328g of triethoxysilane was slowly added dropwise to the system. After about 1 hour, the addition of triethoxysilane was completed. The temperature was maintained and stirring was continued for about 2 hours. After the reaction was completed, the temperature was lowered to 60℃ and filtered. The product was then distilled under reduced pressure at -0.09MPa and 55℃ to obtain 557.8g of the target product, which was a colorless and transparent liquid. The yield based on triethoxysilane was 98.2%, and the product purity (HPLC) was 98.4%.

[0037] Comparative Example 1: p-Hydroxyphenylethyltriethoxysilane was synthesized according to the method of Example 1, except that the reaction temperature was controlled at 100°C during the addition and reaction of triethoxysilane. The product yield was 87.35% based on triethoxysilane, and the product was a pale yellow liquid with a purity of 93.23% as determined by high performance liquid chromatography.

[0038] Comparative Example 2: p-Hydroxyphenylethyltriethoxysilane was synthesized according to the method of Example 1, except that the reaction temperature was controlled at 80°C during the addition and reaction of triethoxysilane. The product yield was 84.76% based on triethoxysilane, and the product was a pale yellow liquid with a purity of 93.53% as determined by high performance liquid chromatography.

[0039] Comparative Example 3: p-hydroxyphenylethyltriethoxysilane was synthesized according to the method of Example 1, except that: after the triethoxysilane was added dropwise, the temperature was maintained and the mixture was stirred for about 1 hour. The product yield was 76.42% based on triethoxysilane, and the product was a yellow liquid. The purity was 80.43% as determined by high performance liquid chromatography.

[0040] Comparative Example 4: p-Hydroxyphenethyltriethoxysilane was synthesized according to the method of Example 1, except that 328g of triethoxysilane was replaced with 244g of trimethoxysilane. The product yield was 98.2% based on trimethoxysilane, and the product was a yellow liquid with a purity of 98.5% as determined by high performance liquid chromatography.

[0041] Performance testing 1. Rubber compound preparation Prepare the rubber compound according to the compound formulation in Table 1 below. In Table 1, p-hydroxyphenylethyltriethoxysilane, Si69, Si69 + p-hydroxystyrene mixture (molar ratio of 1:1), and p-hydroxyphenylethyltrimethoxysilane are used as silane coupling agents.

[0042] Table 1

[0043] 2. Preparation of the rubber compound 2.1, Section 1 (in the internal mixer) Initial temperature 70-80℃, rotation speed 72r / min; add natural rubber NR, press for 60s; lift the weight, add small materials (1 / 2 silica, carbon black, 1 / 2 silane coupling agent, ZnO-80) for 10s; mix for 60s; lift the weight for 10s, add the remaining 1 / 2 silica and silane coupling agent; mix for 60s; lift the weight and clean for 10s; mix for 50s; lift the weight for 10s; press the weight and mix for 50s; lift the weight without a load for 10s; press the weight at 145~155℃ for 180s; discharge the rubber.

[0044] 2.2, Second stage (in the open mill) Add S-80 and accelerator, front roller 50°C, rear roller 60°C, left and right cutters 3 times each, triangular wrap 4 times, roll 4 times, and then output the film.

[0045] 3. Testing Methods All properties of the rubber compound were tested in accordance with the relevant national standards.

[0046] The Mooney scorch properties were determined using GB / T1233-1992 standard, the vulcanization properties were determined using GB / T 9869-2014 standard, the tensile mechanical properties were determined using GB / T 528-2009 standard, and the Payne effect properties were determined using a German Montac 3000 rotorless rubber vulcanization analyzer.

[0047] 4. Experimental Results The test results for each rubber compound are shown in Table 2.

[0048] Table 2

[0049] The performance test results in the table above show that: 1) Based on the scorch and Mooney data of p-hydroxyphenylethyltriethoxysilane, Si-69, a mixture of Si-69 and p-hydroxystyrene, and p-hydroxyphenylethyltrimethoxysilane, it can be seen that the processing performance of the four silane coupling agents is comparable.

[0050] 2) Based on the initial physical properties and the physical properties after thermo-oxidative aging, it can be seen that p-hydroxyphenylethyltriethoxysilane, p-hydroxyphenylethyltrimethoxysilane and Si-69, and Si-69 and p-hydroxystyrene mixture have significantly improved anti-aging properties, with p-hydroxyphenylethyltriethoxysilane being superior.

[0051] According to Payne effect data, compared with p-hydroxyphenylethyltriethoxysilane, Si-69, Si-69 and p-hydroxystyrene mixture, p-hydroxyphenylethyltrimethoxysilane have comparable silica dispersibility; p-hydroxyphenylethyltrimethoxysilane is the next best; p-hydroxyphenylethyltriethoxysilane has better silica dispersibility than the other three.

[0052] In summary, the p-hydroxyphenylethyltriethoxysilane (Formula 1) provided by this invention successfully combines excellent anti-aging properties with superior silica dispersibility. Compared with traditional silane Si-69 (Formula 2), its anti-aging properties represent a qualitative leap; compared with physically mixed anti-aging agent solutions (Formula 3), its effects are more durable and efficient; and compared with the structurally closest p-hydroxyphenylethyltrimethoxysilane (Formula 4), it achieves superior anti-aging properties and silica dispersibility while maintaining good processability, exhibiting an unexpected synergistic enhancement effect. This comprehensive performance improvement makes it have enormous application potential in the manufacture of high-end green tires, especially new energy vehicle tires.

[0053] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A p-hydroxyphenylethyl triethoxysilane having the following chemical structure: 。 2. The process for the preparation of p-hydroxyphenylethyltriethoxysilane according to claim 1, characterized in that, The method uses p-hydroxystyrene and triethoxysilane as raw materials, and carries out a silicon-hydrogen addition reaction under the action of a catalyst to obtain p-hydroxyphenylethyl triethoxysilane.

3. The method of claim 2, wherein the p-hydroxyphenylethyltriethoxysilane is prepared by the process comprising: reacting p-hydroxyphenylethyltrimethoxysilane with a mixture of water and a base to form the p-hydroxyphenylethyltriethoxysilane. The catalyst includes a main catalyst and a secondary catalyst, the main catalyst is at least one of chloroplatinic acid, palladium chloride, and a PPh3-Rh complex, preferably chloroplatinic acid, and the secondary catalyst is an amine solvent triethylamine.

4. The method of claim 2, wherein the p-hydroxyphenylethyltriethoxysilane is prepared by the process comprising: reacting p-hydroxyphenylethyltrimethoxysilane with a mixture of water and a base to form the p-hydroxyphenylethyltriethoxysilane. The molar ratio of the p-hydroxystyrene, triethoxysilane, main catalyst, and secondary catalyst is 1.05-1.1:1:0.001~0.0015:0.001~0.0015.

5. The method of claim 2, wherein the p-hydroxyphenylethyltriethoxysilane is prepared by the process comprising: reacting p-hydroxyphenylethyltrimethoxysilane with a mixture of water and a base to form the p-hydroxyphenylethyltriethoxysilane. The reaction temperature is 80-100℃.

6. The method of claim 2, wherein the p-hydroxyphenylethyltriethoxysilane is prepared by the process comprising: reacting p-hydroxyphenylethyltrimethoxysilane with a mixture of water and a base to form the p-hydroxyphenylethyltriethoxysilane. The specific steps are: triethoxysilane is added dropwise into a mixture containing p-hydroxystyrene, a main catalyst, and a secondary catalyst within 0.5-1h, after the dropwise addition is completed, the reaction is continued at 80-100℃ for 2-4h to obtain a reaction liquid containing p-hydroxyphenylethyl triethoxysilane, the reaction liquid is filtered to remove the remaining p-hydroxystyrene, and then distilled to obtain the target product p-hydroxyphenylethyl triethoxysilane.

7. The p-hydroxyphenylethyl triethoxysilane of claim 1 is used in any of the following aspects: as a silane coupling agent to promote the dispersion of reinforcing fillers in rubber compositions; as an anti-aging agent to delay the aging of rubber products.

8. A rubber composition characterized in that, By weight, the following components are included: 100 parts of a rubber matrix; 20 to 80 parts of a reinforcing filler, which is white carbon black; p-hydroxyphenylethyl triethoxysilane, the amount of which is 1% to 20% of the amount of white carbon black; and a vulcanization system and an activator.

9. The rubber composition of Claim 8, wherein The rubber matrix can be selected from natural rubber (NR), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR), and their blends, the reinforcing filler also includes carbon black, the vulcanization system includes S-80 1-2 parts, accelerator CBS-80 1-2 parts, and accelerator DPG-80 2-3 parts, and the activator is ZnO-802-4 parts.

10. A rubber article characterized by, Made of the rubber composition of claim 8 or 9.

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