Application of Si69-chloromethyl phenethyl triethoxy silane composite coupling agent

Abstract

The invention discloses an application of a Si69-chloromethyl phenethyl triethoxy silane composite type coupling agent in modification of a rubber base material. The Si69-chloromethyl phenethyl triethoxy silane composite silane adopted by the invention is uniform in component, and complementary advantages of two kinds of silane can be realized, so that the rubber has high mechanical property, wear resistance, high rigidity, high temperature resistance and corrosion resistance, is excellent in dispersity and compatibility, can be added at one time, simplifies the process, reduces the cost, and is suitable for industrial production. And the device is suitable for existing rubber large-scale production equipment.

Description

Technical Field

[0001] This invention relates to the field of new materials technology, specifically to the application of a Si69-chloromethylphenylethyltriethoxysilane composite coupling agent. Background Technology

[0002] Rubber is widely used in tires, industrial high-temperature seals, and special transmission belts. These applications place stringent demands on the comprehensive performance of rubber, including tensile strength, abrasion resistance, rigidity, high-temperature resistance, and corrosion resistance. Specifically, industrial high-temperature seals need to withstand temperatures above 150°C and maintain stable performance after long-term aging; tires require high tensile strength and excellent abrasion resistance; and special transmission belts need stable rigidity and structural durability. For these high-end applications, upgrading the performance of rubber is a core critical issue.

[0003] Currently, silane coupling agents are commonly used in industry to modify rubber properties and improve their performance. For example, Si69 is a mainstream coupling agent for rubber modification, which can significantly improve the tensile strength and abrasion resistance of rubber. It can also optimize the mixing and vulcanization process and is suitable for large-scale production. Its polysulfide structure can condense with the hydroxyl groups on the surface of inorganic fillers and participate in rubber crosslinking, greatly improving the processing performance and abrasion resistance of rubber. However, the modified rubber has insufficient rigidity, and the tensile strength retention rate after aging at 150℃ for 72 hours is generally less than 70%. Its resistance to acid and alkali and organic solvent corrosion is poor, which cannot meet the requirements of high-end applications. Chloromethylphenethyltriethoxysilane can give rubber excellent rigidity (significantly improved flexural modulus), high temperature resistance and corrosion resistance. The high temperature aging performance retention rate of its modified rubber is significantly better than that of conventional silanes. However, due to poor compatibility with rubber matrix and inorganic fillers and uneven dispersion, its performance advantages are difficult to exert when used alone, and it will also lead to a decrease in the tear strength of rubber. Therefore, it has not yet been industrialized.

[0004] In existing technologies, to address the shortcomings of modifying single silanes, the conventional approach of "physical compounding of different silanes or coupling agents" is commonly adopted. For example, Si69 is compounded with aminosilanes or titanate coupling agents. However, there has never been an attempt to physically compound Si69 with chloromethylphenylethyltriethoxysilane. Furthermore, conventional compounding schemes suffer from uneven dispersion and poor synergy, failing to achieve simultaneous improvement in the overall performance of rubber. This necessitates step-by-step addition and increasing the total amount of silane, which not only complicates the production process and increases costs but also easily causes fluctuations in the performance of rubber products, affecting quality control. In contrast, the uniformly componented Si69-chloromethylphenylethyltriethoxysilane composite silane can achieve complementary advantages between the two silanes, giving the rubber both high mechanical properties, abrasion resistance, high rigidity, and high-temperature corrosion resistance. Moreover, its excellent dispersibility and compatibility allow for one-time addition, simplifying the process, reducing costs, and making it compatible with existing large-scale rubber production equipment.

[0005] Meanwhile, applying this composite silane to rubber modification to address the challenges of high-performance requirements for rubber in high-end rubber products has become a pressing technical issue in the field. Summary of the Invention

[0006] To address the challenge of upgrading rubber performance in high-end applications, this invention provides an application of a Si69-chloromethylphenylethyltriethoxysilane composite coupling agent.

[0007] The technical solution adopted in this invention is: the application of a Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, wherein the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent is applied to the modification of rubber substrate.

[0008] This patent utilizes a Si69-chloromethylphenylethyltriethoxysilane composite silane. It combines two silanes with triethoxysilane groups at their inorganic ends and flexible tetrasulfide and rigid benzene ring-chloromethyl structures at their organic ends, respectively. The inorganic ends of these two silanes undergo simultaneous dehydration condensation with the hydroxyl groups on the surface of silica, constructing a dual-silane modified layer on the silica surface that combines flexibility and rigidity. During vulcanization, the organic ends form both a flexible sulfur crosslinking network and a rigid covalent crosslinking network with the rubber molecular chains, thus constructing a dual-phase crosslinking network that combines rigidity and flexibility. This achieves a dual bond between the modified layer and the rubber substrate through sulfur crosslinking and covalent grafting, realizing a synergistic effect between interface modification and rubber crosslinking. Compared to single silane coupling agents, this effectively improves the rubber-... The interfacial bonding strength and dispersion of silica in the silica composite system enable rubber composites to possess superior tensile strength, elastic modulus, tear resistance, and abrasion resistance. Simultaneously, relying on the thermally stable skeleton of the benzene ring conjugated structure, it significantly improves the rubber's high-temperature aging resistance and resistance to media corrosion. Furthermore, the silane can be added in one step after compounding, simplifying the production process and reducing the total amount of silane added. This combination of process adaptability and cost advantages makes it widely applicable to the performance requirements of rubber products such as aviation tire treads, racing tire treads, and high-end high-temperature resistant rubber hoses.

[0009] Preferably, the preparation method of the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent is as follows: (1) Preparation of 25~30wt% sodium sulfide solution: Sodium hydrosulfide solution and sodium hydroxide solution are mixed and reacted to obtain sodium sulfide solution; (2) Preparation of sodium polysulfide solution: Sulfur powder is added to the sodium sulfide solution obtained in step (1) to react and obtain sodium polysulfide solution; (3) Selective sulfidation and product homogenization: The sodium polysulfide solution obtained in step (2), disodium hydrogen phosphate-sodium dihydrogen phosphate buffer, chloropropyltriethoxysilane-chloromethylphenylethyltriethoxysilane mixture and phase transfer catalyst were added to the reactor to carry out selective sulfidation reaction. After the reaction was completed, the product was obtained by fully homogenizing it in a static mixer.

[0010] This application also provides the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent for use in aircraft tire tread rubber, wherein the aircraft tire tread rubber comprises 100 parts of rubber base material, 7.2-7.8 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 65-85 parts of highly dispersed silica, 3.8-4.2 parts of vulcanizing agent, and 21-23 parts of additives.

[0011] Preferably, the vulcanizing agent is dicumyl peroxide, benzoyl peroxide, or ketal peroxide; the additives are at least two of the following: a blend of antioxidant 4010NA and antioxidant RD in a 1:1 mass ratio, phenolic reinforcing resin, zinc oxide, and stearic acid; and the rubber base material consists of 65-75 parts natural rubber and 25-35 parts isoprene rubber. The selection of the above additives depends on the actual requirements of the final product. Generally, when the additives are a blend of antioxidant 4010NA and antioxidant RD and a blend of zinc oxide and stearic acid, the mass ratio between them is 4:7, where the mass ratio of antioxidant 4010NA to antioxidant RD is 1:1, and the mass ratio of zinc oxide to stearic acid is 5:2; when the additives are a blend of antioxidant 4010NA and antioxidant RD and phenolic reinforcing resin, the mass ratio between them is 2:5; and when the additives are zinc oxide and stearic acid, the mass ratio between them is 5:2. Preferably, the preparation method of the above-mentioned aviation tire tread compound is as follows: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent and highly dispersed silica at 115-125℃ for 3-5 minutes to obtain premixed filler; S2: Mix natural rubber and isoprene rubber at 150-160℃ for 2-4 minutes until fully plasticized, add the premixed filler and additives obtained in step S1, continue mixing for 4-6 minutes, then discharge the rubber and cool to room temperature to obtain compound; S3: Mix the compound obtained in S2 at 105-115℃ for 1-3 minutes, add vulcanizing agent, mix for 2-4 minutes until uniform, discharge the rubber, and then vulcanize in stages at 160-170℃ for 17-19 minutes to obtain aviation tire tread compound.

[0012] This application also provides the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent for use in racing tire treads. The racing tire tread composition includes 100 parts of rubber base material, 4.05-5.05 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 60-70 parts of highly dispersed silica, 1.2-1.6 parts of sulfur, 1.6-2.0 parts of accelerator CBS, 0.6-0.8 parts of anti-scorching agent PVI, and 7.8-9.2 parts of additives. The additives include at least two of antioxidant 4020, zinc oxide, stearic acid, and aromatic oils. The rubber base material is composed of 45-55 parts of natural rubber, 35-45 parts of solution-polymerized styrene-butadiene rubber, and 5-15 parts of cis-butadiene rubber. The selection of the above-mentioned additives should be based on the actual needs of the final product. Generally, when the additives are antioxidant 4020 and zinc oxide, the mass ratio between the two is 5:6; when the additives are zinc oxide and stearic acid, the mass ratio between the two is 3:2; when the additives are antioxidant 4020 and aromatic oil, the mass ratio between the two is 5:6; and when the additives are stearic acid and aromatic oil, the mass ratio between the two is 2:3.

[0013] Preferably, the preparation method of the above application is as follows: S1: Si69-chloromethylphenethyltriethoxysilane composite coupling agent and highly dispersed silica are premixed at 110-120℃ for 2-4 minutes to obtain premixed filler; S2: natural rubber, butadiene rubber and solution-polymerized styrene-butadiene rubber are mixed at 140-150℃ for 1-3 minutes until plasticized, the premixed filler and additives obtained in step S1 are added, and mixing is continued for 3-5 minutes. Then the rubber is discharged and cooled to room temperature to obtain compound; S3: the compound obtained in S2 is mixed at 100-110℃ for 1-3 minutes, sulfur, accelerator CBS and anti-scorching agent PVI are added, and the mixture is mixed for 1-3 minutes until uniform. Then the rubber is discharged and vulcanized at 150-160℃ for 11-13 minutes to obtain racing tire tread rubber.

[0014] This application also provides the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent for use in rubber hoses. The rubber hose composition includes 100 parts of rubber base material, 4.0-4.4 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 50-70 parts of highly dispersed silica, 1.1-1.3 parts of sulfur, 1.9-2.1 parts of accelerator TMTD, 0.9-1.1 parts of anti-scorching agent PVI, and 12.8-14.2 parts of additives.

[0015] Preferably, the additives are at least two of the following: antioxidant RD, softener, zinc oxide, stearic acid, and phenolic reinforcing resin. The softener is a high flash point environmentally friendly aromatic oil (such as KN4010, KN4006, TDAE-400), a low aromatic oil, or a naphthenic oil. The rubber base material consists of 75-85 parts of EPDM rubber and 15-25 parts of butyl rubber. The selection of the above additives is based on the actual needs of the final product. Generally, when antioxidant RD and zinc oxide are selected, the mass ratio between them is 3:5; when zinc oxide and stearic acid are selected, the mass ratio between them is 5:2; when softener and phenolic reinforcing resin are selected, the mass ratio between them is 5:3; and when antioxidant RD and phenolic reinforcing resin are selected, the mass ratio between them is 1:1.

[0016] Preferably, the preparation method of the above application is as follows: S1: Si69-chloromethylphenylethyltriethoxysilane composite coupling agent and highly dispersed silica are premixed at 105-115℃ for 2-4 minutes to obtain premixed filler; S2: EPDM rubber and butyl rubber are mixed at 135-145℃ for 1-3 minutes until plasticized, the premixed filler and additives obtained in step S1 are added, and mixing is continued for 3-5 minutes. Then the rubber is discharged and cooled to room temperature to obtain compound; S3: The compound obtained in S2 is mixed at 95-105℃ for 1-3 minutes, sulfur, accelerator TMTD and anti-scorching agent PVI are added, and the mixture is mixed for 1-3 minutes until uniform. Then the rubber is discharged and vulcanized at 145-155℃ for 14-16 minutes to obtain rubber hose substrate.

[0017] The beneficial effects of this invention are: The Si69-chloromethylphenylethyltriethoxysilane composite silane used in this application has uniform components, which can achieve the complementary advantages of the two silanes, so that the rubber has both high mechanical properties, wear resistance and high rigidity, high temperature resistance and corrosion resistance. Moreover, it has excellent dispersibility and compatibility, can be added at one time, simplifying the process, reducing costs, and is compatible with existing rubber large-scale production equipment. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the following embodiments.

[0019] The preparation method of the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent used in the following examples is as follows: A 45% sodium hydrosulfide aqueous solution and a 48% sodium hydroxide aqueous solution were mixed at a molar ratio of 1:1.02 and reacted at 70-90℃ under normal pressure for 0.8 h. The final pH was controlled at 12.3 to obtain a sodium sulfide solution with a purity of 99.2% and a mass fraction of 28%. This solution was then mixed with 150-mesh sulfur powder at a ratio of 1:3.1 and reacted under vacuum at 55℃ and 0.04 MPa for 50 min to obtain a sodium polysulfide solution with a sodium tetrasulfide content of 98.5% and impurities of 0.4%. Sodium polysulfide solution, a 6% (w / w) disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution, and a chloropropyltriethoxysilane-chloromethylphenylethyltriethoxysilane mixture at a mass ratio of 8:2 were mixed at a ratio of 1:1.0:2.1. 2.5% (w / w) of polyethylene glycol-400 was added to the mixture. The reaction was carried out at 85°C and atmospheric pressure for 2.5 h with pH controlled at 8.0. The product was statically homogenized at 400 rpm for 18 min to obtain the target mixed silane. The chloropropyl reaction rate was 98.8%, the Si69 yield was 95.7%, the purity was 99.3%, the benzylic chlorine retention rate of chloromethylphenylethyltriethoxysilane was 99.7%, and the total impurity content was 0.55%.

[0020] The following product performance tests were conducted according to GB / T 528-2009 for tensile strength, elongation at break, and modulus of elasticity; according to GB / T 531.1-2008 for Shore A hardness testing; according to GB / T 1689-2014 for Akron abrasion testing; and according to GB / T 29040-2012 for rolling resistance coefficient testing.

[0021] Example 1: Aviation tire tread formulation components: 70 parts natural rubber (model NR), 30 parts isoprene rubber (model IR), 75 parts high-dispersion silica, 7.5 parts Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 4.0 parts peroxide vulcanizing agent (diisopropylbenzene peroxide), 4.0 parts high-temperature antioxidant (model RD+4010NA 1:1), 10 parts phenolic reinforcing resin (model 2402), 5 parts zinc oxide, 2 parts stearic acid, and 1.0 part microcrystalline wax.

[0022] Preparation process: S1: First, premix the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 120℃ for 4 minutes to obtain a uniform premixed filler; S2: Mix natural rubber and isoprene rubber at 155℃ for 3 minutes until fully plasticized, add the premixed filler, antioxidant, phenolic reinforcing resin, zinc oxide, and stearic acid obtained in step S1, continue mixing for 5 minutes, discharge the glue and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 110℃ for 2 minutes, add the peroxide vulcanizing agent (diisopropylbenzene peroxide) and microcrystalline wax, mix for 3 minutes until uniform, discharge the glue; then vulcanize at 165℃ for 18 minutes to obtain the aircraft tire tread rubber.

[0023] The performance of the final product was tested, and the results are as follows: Performance testing and advantage comparison: Tensile strength ≥ 28 MPa (under the same composition and preparation process as Example 1, the tensile strength of the product modified with a single Si69 is 22 MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 24 MPa); Tensile strength retention rate after instantaneous high-temperature treatment at 180℃ ≥ 88% (under the same composition and preparation process as Example 1, the tensile strength retention rate of the product modified with a single Si69 is 68%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane is 82%); Tensile strength retention rate after aging at 150℃ for 72 hours ≥ 90% (under the same composition and preparation process as Example 1, the tensile strength retention rate of the product modified with a single Si69 after aging at 150℃ for 72 hours is 69%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane after aging at 150℃ for 72 hours is 85%); Elastic modulus ≥ 18 MPa; Akron abrasion ≤ 0.18 cm³ / 1.61 km; no uneven dispersion. This embodiment has superior high temperature resistance and impact resistance; compared with existing silane modification schemes, it completely solves the defects of insufficient heat resistance and rigidity of single silane, poor synergy of conventional compounding and large performance fluctuations, and is fully adapted to the extreme working conditions of instantaneous high pressure and high temperature during the take-off and landing of aircraft tires. Example 2

[0024] The formulation components of the aviation tire tread compound are as follows: 65 parts of natural rubber (model NR), 35 parts of isoprene rubber (model IR), 72 parts of highly dispersed silica, 7.2 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 4.1 parts of peroxide vulcanizing agent (benzoyl peroxide), 4.2 parts of high-temperature antioxidant (model RD+4010NA 1:1), 11 parts of phenolic reinforcing resin (model 2402), 5 parts of zinc oxide, 2 parts of stearic acid, and 1.1 parts of microcrystalline wax.

[0025] Preparation process: S1: First, Si69-chloromethylphenylethyltriethoxysilane composite coupling agent and highly dispersed silica are premixed at 122℃ for 3.5 minutes to obtain a uniform premixed filler; S2: Natural rubber and isoprene rubber are mixed at 158℃ for 2.5 minutes until fully plasticized, and the premixed filler, antioxidant, phenolic reinforcing resin, zinc oxide and stearic acid obtained in step S1 are added. Mixing is continued for 4.5 minutes, and the mixture is discharged and cooled to room temperature to obtain a compound; S3: The compound obtained in S2 is mixed at 112℃ for 1.5 minutes, and the peroxide vulcanizing agent and microcrystalline wax are added. Mixing is continued for 3.5 minutes until uniform, and the mixture is discharged; then it is vulcanized at 168℃ for 17 minutes to obtain the aircraft tire tread rubber.

[0026] The performance of the final product was tested, and the results are as follows: Performance testing and advantage comparison: Tensile strength ≥29MPa (under the same composition and preparation process as Example 2, the tensile strength of the product modified with a single Si69 is 23MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 25MPa); Tensile strength retention rate after instantaneous high-temperature treatment at 180℃ ≥89% (under the same composition and preparation process as Example 2, the tensile strength retention rate of the product modified with a single Si69 is 69%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane is 83%); Tensile strength retention rate after aging at 150℃ for 72h ≥91% (under the same composition and preparation process as Example 2, the tensile strength retention rate of the product modified with a single Si69 after aging at 150℃ for 72h is 70%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane after aging at 150℃ for 72h is 86%); Elastic modulus ≥19MPa; Akron abrasion ≤0.17cm³ / 1.61km, with no uneven dispersion. This embodiment has superior rigidity and impact resistance; compared with existing silane modification schemes, it completely solves the defects of single silane such as insufficient heat resistance and low rigidity, poor synergy of conventional compounding and large performance fluctuations, and is fully adapted to the extreme working conditions of instantaneous high pressure and high temperature during the take-off and landing of aircraft tires. Example 3

[0027] The formulation components of the aviation tire tread compound are as follows: 75 parts natural rubber (model NR), 25 parts isoprene rubber (model IR), 78 parts high-dispersion silica, 7.8 parts Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 3.9 parts peroxide vulcanizing agent (peroxide ketal), 3.8 parts high-temperature antioxidant (model RD+4010NA 1:1), 9 parts phenolic reinforcing resin (model SL-2201LFP), 5 parts zinc oxide, 2 parts stearic acid, and 0.9 parts microcrystalline wax.

[0028] Preparation process: S1: First, Si69-chloromethylphenylethyltriethoxysilane composite coupling agent and highly dispersed silica are premixed at 118℃ for 4.5 minutes to obtain a uniform premixed filler; S2: Natural rubber and isoprene rubber are mixed at 152℃ for 3.5 minutes until fully plasticized, and the premixed filler, antioxidant, phenolic reinforcing resin, zinc oxide and stearic acid obtained in step S1 are added. Mixing is continued for 5.5 minutes, and the mixture is discharged and cooled to room temperature to obtain a compound; S3: The compound obtained in S2 is mixed at 108℃ for 2.5 minutes, and the peroxide vulcanizing agent and microcrystalline wax are added. Mixing is continued for 2.5 minutes until uniform, and the mixture is discharged; then it is vulcanized at 162℃ for 19 minutes to obtain the aircraft tire tread rubber.

[0029] The performance of the final product was tested, and the results are as follows: Performance Testing and Advantage Comparison: Tensile strength ≥ 28.5 MPa (under the same composition and preparation process as Example 3, the tensile strength of the product modified with single Si69 is 22 MPa, and the tensile strength of the product modified with single chloromethylphenylethyltriethoxysilane is 24 MPa); Tensile strength retention rate after instantaneous high-temperature treatment at 180℃ ≥ 88% (under the same composition and preparation process as Example 3, the tensile strength retention rate of the product modified with single Si69 is 68%, and the tensile strength retention rate of the product modified with single chloromethylphenylethyltriethoxysilane is 82%); Tensile strength retention rate after aging at 150℃ for 72 hours ≥ 90% (under the same composition and preparation process as Example 3, the tensile strength retention rate of the product modified with single Si69 after aging at 150℃ for 72 hours is 69%, and the tensile strength retention rate of the product modified with single chloromethylphenylethyltriethoxysilane after aging at 150℃ for 72 hours is 90%). The tensile strength retention rate is 85%; the elastic modulus is ≥18.5MPa; the Akron abrasion loss is ≤0.18cm³ / 1.61km; and there is no uneven dispersion. This embodiment has better processing fluidity and high temperature resistance; compared with existing silane modification schemes, it completely solves the defects of insufficient heat resistance and rigidity of single silanes, and the complex and uneven dispersion of conventional compounding processes, making it suitable for the processing needs and extreme operating conditions of large-scale production of aviation tires.

[0030] Example 4: Racing tire tread compound formulation components: 50 parts natural rubber (model NR), 40 parts low rolling resistance solution-polymerized styrene-butadiene rubber (model SSBR), 10 parts butadiene rubber (model BR), 65 parts high-dispersion silica, 4.55 parts Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 1.4 parts sulfur, 1.8 parts accelerator (model CBS), 2.5 parts antioxidant (model 4020), 3 parts zinc oxide, 2 parts stearic acid, 3 parts high flash point environmentally friendly aromatic oil (model TDAE), and 0.7 parts scorching inhibitor PVI.

[0031] Preparation process: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 115℃ for 3 minutes to obtain premixed filler; S2: Mix natural rubber, butadiene rubber and solution-polymerized styrene-butadiene rubber at 145℃ for 2 minutes until plasticized, add the premixed filler, antioxidant, zinc oxide, stearic acid and aromatic oil obtained in step S1, continue mixing for 4 minutes, discharge the glue and cool to room temperature to obtain compound; S3: Mix the compound obtained in S2 at 105℃ for 2 minutes, add sulfur, accelerator CBS and anti-scorching agent PVI, mix for 2 minutes until uniform, discharge the glue; then vulcanize at 155℃ for 12 minutes to obtain racing tire tread rubber.

[0032] The performance of the final product was tested, and the results are as follows: Performance Testing and Advantage Comparison: Tensile strength ≥ 26 MPa (under the same composition and preparation process as Example 4, the tensile strength of the product modified with a single Si69 is 21 MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 23 MPa); Elastic modulus ≥ 16 MPa; Rolling resistance coefficient ≤ 0.0085 (under the same composition and preparation process as Example 4, the rolling resistance coefficient of the product modified with a single Si69 is 0.011, and the rolling resistance coefficient of the product modified with a single chloromethylphenylethyltriethoxysilane is 0.010); Akron abrasion ≤ 0.15 cm³ / 1.61 km; Tensile strength retention rate after aging at 150℃ for 72 h ≥ 86%. This embodiment exhibits superior elasticity and impact resistance, and lower rolling resistance. Compared to existing silane modification schemes, it solves the problems of insufficient rigidity of single Si69, poor compatibility of single chloromethylphenylethyltriethoxysilane, complex conventional compounding processes, and large performance fluctuations, making it suitable for the high-speed driving, rapid acceleration, and rapid braking conditions of racing cars. Example 5

[0033] Racing tire tread compound formulation components: 55 parts natural rubber (model NR), 35 parts low rolling resistance solution-polymerized styrene-butadiene rubber (model SSBR), 10 parts butadiene rubber (model BR), 62 parts high-dispersion silica, 4.2 parts Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 1.3 parts sulfur, 1.7 parts accelerator (model CBS), 2.3 parts antioxidant (model 4020), 3 parts zinc oxide, 2 parts stearic acid, 2.8 parts aromatic oil (model TDAE-300), and 0.65 parts scorch inhibitor PVI.

[0034] Preparation process: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 112℃ for 2.5 minutes to obtain a uniform premixed filler; S2: Mix natural rubber, butadiene rubber and solution-polymerized styrene-butadiene rubber at 142℃ for 1.5 minutes until fully plasticized, add the premixed filler, antioxidant, zinc oxide, stearic acid and aromatic oil obtained in step S1, continue mixing for 3.5 minutes, discharge the glue and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 102℃ for 1.5 minutes, add sulfur, accelerator CBS and anti-scorching agent PVI, mix for 1.5 minutes until uniform, discharge the glue; then vulcanize at 152℃ for 11.5 minutes to obtain racing tire tread rubber.

[0035] The performance of the final product was tested, and the results are as follows: Performance testing and advantage comparison: Tensile strength ≥ 26.5 MPa (under the same composition and preparation process as Example 5, the tensile strength of the product modified with a single Si69 is 21 MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 23 MPa); Tensile strength retention rate after aging at 150℃ for 72 h ≥ 87% (under the same composition and preparation process as Example 5, the tensile strength retention rate of the product modified with a single Si69 is 66%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane is 81%); Elastic modulus ≥ 16.5 MPa; Rolling resistance coefficient ≤ 0.0083 (under the same composition and preparation process as Example 5, the rolling resistance coefficient of the product modified with a single Si69 is 0.011, and the rolling resistance coefficient of the product modified with a single chloromethylphenylethyltriethoxysilane is 0.010); Akron wear ≤ 0.14 cm³ / 1.61 km; no uneven dispersion. This embodiment features low rolling resistance and superior elasticity. Compared to existing silane modification schemes, it completely solves the defects of insufficient rigidity of single Si69, poor compatibility of single chloromethylphenylethyltriethoxysilane, and high rolling resistance in conventional compounding, making it fully suitable for the high-speed driving, rapid acceleration and braking conditions of racing cars. Example 6

[0036] Racing tire tread compound formulation components: 45 parts natural rubber (model NR), 45 parts low rolling resistance solution-polymerized styrene-butadiene rubber (model SSBR), 10 parts butadiene rubber (model BR), 68 parts high-dispersion silica, 5.0 parts Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 1.5 parts sulfur, 1.9 parts accelerator (model CBS), 2.7 parts antioxidant (model 4020), 3 parts zinc oxide, 2 parts stearic acid, 3.2 parts aromatic oil (32# white oil), and 0.75 parts anti-scorching agent PVI.

[0037] Preparation process: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 118℃ for 3.5 minutes to obtain a uniform premixed filler; S2: Mix natural rubber, butadiene rubber and solution-polymerized styrene-butadiene rubber at 148℃ for 2.5 minutes until fully plasticized, add the premixed filler, antioxidant, zinc oxide, stearic acid and aromatic oil obtained in step S1, continue mixing for 4.5 minutes, discharge the glue and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 108℃ for 2.5 minutes, add sulfur, accelerator CBS and anti-scorching agent PVI, mix for 2.5 minutes until uniform, discharge the glue; then vulcanize at 158℃ for 12.5 minutes to obtain racing tire tread rubber.

[0038] The performance of the final product was tested, and the results are as follows: Performance testing and advantage comparison: Tensile strength ≥ 25.5 MPa (under the same composition and preparation process as Example 6, the tensile strength of the product modified with a single Si69 is 20 MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 22 MPa); Tensile strength retention rate after aging at 150℃ for 72 h ≥ 86% (under the same composition and preparation process as Example 6, the tensile strength retention rate of the product modified with a single Si69 is 65%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane is 80%); Elastic modulus ≥ 15.5 MPa; Rolling resistance coefficient ≤ 0.0086 (under the same composition and preparation process as Example 6, the rolling resistance coefficient of the product modified with a single Si69 is 0.011, and the rolling resistance coefficient of the product modified with a single chloromethylphenylethyltriethoxysilane is 0.010); Akron wear ≤ 0.13 cm³ / 1.61 km; no uneven dispersion. This embodiment offers superior wear resistance and rigidity. Compared to existing silane modification schemes, it completely resolves the shortcomings of insufficient rigidity of single Si69, poor compatibility of single chloromethylphenylethyltriethoxysilane, and low wear resistance of conventional compound formulations, making it fully suitable for the extreme working conditions of high-speed racing and frequent friction.

[0039] Example 7: The formulation components of high-end high-temperature resistant rubber hoses are as follows: 80 parts of EPDM rubber, 20 parts of IIR butyl rubber, 60 parts of highly dispersed silica, 4.2 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 1.2 parts of sulfur, 2.0 parts of accelerator (TMTD), 3.0 parts of antioxidant RD, 5 parts of zinc oxide, 2 parts of stearic acid, 5.0 parts of softener (KN3006 naphthenic oil), 3 parts of phenolic reinforcing resin (2127), and 1 part of scorch inhibitor PVI.

[0040] Preparation process: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 110℃ for 3 minutes to obtain premixed filler; S2: Mix EPDM rubber and butyl rubber at 140℃ for 2 minutes until plasticized, add the premixed filler, antioxidant, softener, zinc oxide, stearic acid, and phenolic reinforcing resin obtained in step S1, continue mixing for 4 minutes, discharge the glue and cool to room temperature to obtain compound; S3: Mix the compound obtained in S2 at 100℃ for 2 minutes, add sulfur, accelerator TMTD and anti-scorching agent PVI and mix for 2 minutes until uniform, discharge the glue; then vulcanize at 150℃ for 15 minutes to obtain rubber hose substrate.

[0041] The performance of the final product was tested, and the results are as follows: Performance Testing and Advantage Comparison: Tensile strength ≥ 24 MPa (under the same composition and preparation process as Example 7, the tensile strength of the product modified with a single Si69 is 19 MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 21 MPa); Tensile strength retention rate after aging at 150℃ for 72 hours ≥ 85% (under the same composition and preparation process as Example 7, the tensile strength retention rate of the product modified with a single Si69 is 67%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane is 80%); Tear strength ≥ 55 kN / m, Akron abrasion ≤ 0.17 cm³ / 1.61 km; No agglomeration during processing, uniform dispersion, no need to add additional dispersant. This embodiment has superior high temperature resistance, tear resistance, and wear resistance; compared with existing silane modification schemes, the process is simplified and the cost is reduced by more than 15%, highlighting the synergistic advantages and versatility of composite coupling agents, and adapting to the application requirements of high-end high temperature resistant rubber hoses. Example 8

[0042] The formulation components of high-end high-temperature resistant rubber hoses are as follows: 85 parts of high-temperature resistant EPDM rubber, 15 parts of butyl rubber (IIR), 63 parts of highly dispersed silica, 4.25 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 1.23 parts of sulfur, 1.95 parts of accelerator (TMTD), 3.2 parts of high-temperature antioxidant (RD), 4.8 parts of softener (KN3006 naphthenic oil), 5 parts of zinc oxide, 2 parts of stearic acid, 2.8 parts of phenolic reinforcing resin (2127), and 0.95 parts of scorching inhibitor PVI.

[0043] Preparation process: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 108℃ for 2.5 minutes to obtain a uniform premixed filler; S2: Mix EPDM rubber and butyl rubber at 138℃ for 1.5 minutes until fully plasticized, add the premixed filler, antioxidant, softener, zinc oxide, stearic acid, and phenolic reinforcing resin obtained in step S1, and continue mixing for 3.5 minutes. Discharge the glue and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 98℃ for 1.5 minutes, add sulfur, accelerator TMTD and anti-scorching agent PVI, mix for 1.5 minutes until uniform, and discharge the glue; then vulcanize at 148℃ for 14.5 minutes to obtain a rubber hose substrate.

[0044] The performance of the final product was tested, and the results are as follows: Performance testing and advantages comparison: Tensile strength ≥ 24.5 MPa (under the same composition and preparation process as Example 8, the tensile strength of the product modified with a single Si69 is 19 MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 21 MPa); Tensile strength retention rate after aging at 150℃ for 72 h ≥ 86% (under the same composition and preparation process as Example 8, the tensile strength retention rate of the product modified with a single Si69 is 67%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane is 80%); Tear strength ≥ 56 kN / m; Akron abrasion loss ≤ 0.16 cm³ / 1.61 km; Performance retention rate after immersion in acid and alkali media for 72 h ≥ 80%; No agglomeration during processing, uniform dispersion, no need to add additional dispersants. This embodiment offers superior resistance to media and high temperatures. Compared to existing silane modification schemes, it completely resolves the shortcomings of insufficient heat resistance of single Si69, poor compatibility of single chloromethylphenylethyltriethoxysilane, and poor media resistance of conventional compound formulations, making it suitable for industrial applications of high-end high-temperature resistant rubber hoses in contact with acid and alkali media. Example 9

[0045] The formulation components of high-end high-temperature resistant rubber hoses are as follows: 75 parts of high-temperature resistant EPDM rubber, 25 parts of butyl rubber (IIR), 68 parts of highly dispersed silica, 4.35 parts of composite coupling agent, 1.28 parts of sulfur, 2.0 parts of accelerator (TMTD), 2.8 parts of high-temperature antioxidant (RD), 5.2 parts of softener (HCN-100 hydrogenated naphthenic oil), 5 parts of zinc oxide, 2 parts of stearic acid, 3.2 parts of phenolic reinforcing resin (SL-2101), and 1.05 parts of scorching inhibitor PVI.

[0046] Preparation process: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 112℃ for 3.5 minutes to obtain a uniform premixed filler; S2: Mix EPDM rubber and butyl rubber at 142℃ for 2.5 minutes until fully plasticized, add the premixed filler, antioxidant, softener, zinc oxide, stearic acid, and phenolic reinforcing resin obtained in step S1, and continue mixing for 4.5 minutes. Discharge the glue and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 102℃ for 2.5 minutes, add sulfur, accelerator TMTD, and scorch inhibitor PVI, mix for 2.5 minutes until uniform, and discharge the glue; then vulcanize at 152℃ for 15.5 minutes to obtain a rubber hose substrate.

[0047] The performance of the final product was tested, and the results are as follows: Performance testing and advantages comparison: Tensile strength ≥ 23.5 MPa (under the same composition and preparation process as Example 9, the tensile strength of the product modified with a single Si69 is 18 MPa, and the tensile strength of the product modified with a single chloromethylphenylethyltriethoxysilane is 20 MPa); Tensile strength retention rate after aging at 150℃ for 72 h ≥ 85% (under the same composition and preparation process as Example 9, the tensile strength retention rate of the product modified with a single Si69 is 66%, and the tensile strength retention rate of the product modified with a single chloromethylphenylethyltriethoxysilane is 79%); Tear strength ≥ 57 kN / m, Akron abrasion loss ≤ 0.17 cm³ / 1.61 km, pipeline pressure resistance is improved by more than 15% compared with conventional formulations, no agglomeration occurs during processing, dispersion is uniform, and no additional dispersant is required. This embodiment offers superior pressure resistance and rigidity. Compared to existing silane modification schemes, it completely resolves the shortcomings of insufficient rigidity of single Si69, poor compatibility of single chloromethylphenylethyltriethoxysilane, and low pressure resistance of conventional compound formulations, making it suitable for the industrial application requirements of high-pressure transportation in high-end high-temperature resistant rubber hoses.

[0048] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications are also within the protection scope of the present invention.

Claims

1. The application of a Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, characterized in that, The Si69-chloromethylphenylethyltriethoxysilane composite coupling agent is used for the modification of rubber substrates.

2. The application according to claim 1, characterized in that, The preparation method of the Si69-chloromethylphenylethyltriethoxysilane composite coupling agent is as follows: (1) Preparation of 25~30wt% sodium sulfide solution: Sodium hydrosulfide solution and sodium hydroxide solution are mixed and reacted to obtain sodium sulfide solution; (2) Preparation of sodium polysulfide solution: Sulfur powder is added to the sodium sulfide solution obtained in step (1) to react and obtain sodium polysulfide solution; (3) Selective sulfidation and product homogenization: The sodium polysulfide solution obtained in step (2), disodium hydrogen phosphate-sodium dihydrogen phosphate buffer, chloropropyltriethoxysilane-chloromethylphenylethyltriethoxysilane mixture and phase transfer catalyst were added to the reactor to carry out selective sulfidation reaction. After the reaction was completed, the product was obtained by fully homogenizing it in a static mixer.

3. The application according to claim 1, characterized in that, The Si69-chloromethylphenylethyltriethoxysilane composite coupling agent is used in aviation tire tread rubber. The aviation tire tread rubber composition includes 100 parts of rubber base material, 7.2-7.8 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 65-85 parts of highly dispersed silica, 3.8-4.2 parts of vulcanizing agent, and 21-23 parts of additives.

4. The application according to claim 3, characterized in that, The vulcanizing agent is dicumyl peroxide, benzoyl peroxide, or peroxide ketal; the additives are at least two of the following in a 1:1 mass ratio: antioxidant 4010NA and antioxidant RD blend, phenolic reinforcing resin, zinc oxide, and stearic acid; and the rubber base material consists of 65-75 parts of natural rubber and 25-35 parts of isoprene rubber.

5. The application according to claim 3, characterized in that, The specific steps for preparing the aviation tire tread compound are as follows: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent and highly dispersed silica at 115-125℃ for 3-5 minutes to obtain a premixed filler; S2: Mix natural rubber and isoprene rubber at 150-160℃ for 2-4 minutes, add the premixed filler and additives obtained in step S1, continue mixing for 4-6 minutes, then discharge the rubber and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 105-115℃ for 1-3 minutes, add a vulcanizing agent, mix for 2-4 minutes until uniform, discharge the rubber, and then vulcanize at 160-170℃ for 17-19 minutes to obtain the aviation tire tread compound.

6. The application according to claim 1, characterized in that, The Si69-chloromethylphenylethyltriethoxysilane composite coupling agent is used in racing tire tread compound. The racing tire tread compound comprises 100 parts of rubber base material, 4.05-5.05 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 60-70 parts of highly dispersed silica, 1.2-1.6 parts of sulfur, 1.6-2.0 parts of accelerator CBS, 0.6-0.8 parts of anti-scorching agent PVI, and 7.8-9.2 parts of additives. The additives include at least two of antioxidant 4020, zinc oxide, stearic acid, and aromatic oil. The rubber base material is composed of 45-55 parts of natural rubber, 35-45 parts of solution-polymerized styrene-butadiene rubber, and 5-15 parts of cis-butadiene rubber.

7. The application according to claim 6, characterized in that, The specific steps for preparing the racing tire tread compound are as follows: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 110-120℃ for 2-4 minutes to obtain a premixed filler; S2: Mix natural rubber, butadiene rubber and solution-polymerized styrene-butadiene rubber at 140-150℃ for 1-3 minutes, add the premixed filler and additives obtained in step S1, continue mixing for 3-5 minutes, then discharge the rubber and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 100-110℃ for 1-3 minutes, add sulfur, accelerator CBS and anti-scorching agent PVI, mix for 1-3 minutes until uniform, discharge the rubber, and then vulcanize at 150-160℃ for 11-13 minutes to obtain the racing tire tread compound.

8. The application according to claim 1, characterized in that, The Si69-chloromethylphenylethyltriethoxysilane composite coupling agent is used in rubber hoses. The rubber hoses are composed of 100 parts of rubber base material, 4.0-4.4 parts of Si69-chloromethylphenylethyltriethoxysilane composite coupling agent, 50-70 parts of highly dispersed silica, 1.1-1.3 parts of sulfur, 1.9-2.1 parts of accelerator TMTD, 0.9-1.1 parts of anti-scorching agent PVI, and 12.8-14.2 parts of additives.

9. The application according to claim 8, characterized in that, The additives are at least two of the following: antioxidant RD, softener, zinc oxide, stearic acid, and phenolic reinforcing resin. The softener is a high flash point environmentally friendly aromatic oil, a low aromatic oil, or a naphthenic oil. The rubber base material is composed of 75-85 parts of EPDM rubber and 15-25 parts of butyl rubber.

10. The application according to claim 8, characterized in that, The specific steps for preparing the rubber hose are as follows: S1: Premix Si69-chloromethylphenylethyltriethoxysilane composite coupling agent with highly dispersed silica at 105-115℃ for 2-4 minutes to obtain a premixed filler; S2: Mix EPDM rubber and butyl rubber at 135-145℃ for 1-3 minutes, add the premixed filler and additives obtained in step S1, continue mixing for 3-5 minutes, then discharge the rubber and cool to room temperature to obtain a compound; S3: Mix the compound obtained in S2 at 95-105℃ for 1-3 minutes, add sulfur, accelerator TMTD and anti-scorching agent PVI, mix for 1-3 minutes until uniform, then discharge the rubber; subsequently, vulcanize at 145-155℃ for 14-16 minutes to obtain the rubber hose substrate.