Silicone rubber glass fiber hose and preparation method thereof

Abstract

The invention discloses a silicone rubber glass fiber hose and a preparation method thereof.The silicone rubber glass fiber hose comprises a glass fiber hose body and a silicone rubber coating wrapping the surface of the hose body, and the silicone rubber coating is formed by vulcanizing modified silicone rubber; the silicone rubber is prepared from the following components in parts by weight: 100-120 parts of raw methyl vinyl silicone rubber, 20-35 parts of white carbon black, 4-12 parts of raw high-ethylene silicone rubber, 2-6 parts of a vinyl silane coupling agent, 3-8 parts of a modifier, 0.01-1 part of an alkynol inhibitor and 1-3 parts of a platinum vulcanizing agent. The modified silicone rubber coating and the glass fiber base material work cooperatively better, the flame retardance, weather resistance and mechanical strength of the hose are greatly improved, the hose can keep excellent performance under the conditions of extreme temperature, severe environment and high stress, and the application range of the hose is remarkably widened.

Description

Technical Field

[0001] The invention relates to the technical field of glass fiber hoses, and in particular to a silicone rubber glass fiber hose and a preparation method thereof. Background Art

[0002] Silicone rubber fiberglass hose is a composite material widely used in many industrial fields. The core structure of this hose is woven from high-purity alkali-free glass fibers, and the outer layer is coated with organic silicone and vulcanized. As the main structural material, glass fiber gives the hose excellent mechanical properties and temperature resistance. It can be used for a long time in a wide temperature range of -65~260℃ while maintaining good softness and elasticity. Glass fiber also provides high tensile strength, compression resistance and tear resistance, allowing the hose to withstand various mechanical stresses.

[0003] Silicone rubber fiberglass hose plays an important role in many industries. In the iron and steel metallurgical industry, it is used to protect cables and pipes of high-temperature equipment such as blast furnaces and converters. The chemical industry uses it for the protection and insulation of various chemical reactors and pipeline systems. The power industry uses it to protect and insulate cables of equipment such as generator sets and transformers. In the aerospace field, it is used for line system protection of aircraft, rockets, etc. The automotive industry uses it for wiring harness protection in the engine compartment and thermal insulation of the exhaust system. In addition, it is also widely used in the fields of shipbuilding, oil and gas, construction, machinery manufacturing, and electronic appliances to provide protection for various equipment and systems.

[0004] CN112712945A discloses a silicone glass fiber sleeve and a processing method, which specifically relates to the field of pipes, including a silicone glass fiber sleeve, which includes the following raw materials in parts by weight: 15-30 parts of silicone resin, 15-20 parts of tackifying resin, 10-20 parts of alkali-free glass fiber, 10-20 parts of quartz sand, 10-20 parts of alumina, 10-20 parts of pyrophyllite, 10-20 parts of limestone, 10-25 parts of dolomite, 10-25 parts of boric acid, 10-25 parts of soda ash, 1-5 parts of catalyst, 1-4 parts of antioxidant, 1-3 parts of defoaming agent, 1-3 parts of silane coupling agent and 1-3 parts of polymerization inhibitor, wherein the silicone resin is one of methylphenyl silicone resin, methyl silicone resin, low phenylmethyl silicone resin, amino silicone resin or fluorosilicone resin.

[0005] Although silicone rubber fiberglass hoses have performed well in many areas, their overall performance still has room for improvement. Many of the core advantages of the hoses come mainly from the glass fiber itself. In contrast, although the silicone rubber layer coated on the surface of the glass fiber has a certain protective effect, its performance cannot match that of the glass fiber in some aspects. This mismatch has caused the silicone rubber layer to become a bottleneck restricting the further improvement of the performance of the entire hose. For example, the flame retardancy and weather resistance of silicone rubber are not as good as those of glass fiber, which affects the application effect of the hose in specific environments.

[0006] Therefore, improving the performance of the silicone rubber layer, especially improving its flame retardancy and weather resistance, has become the key to improving the overall performance of silicone rubber glass fiber hoses. By improving these properties of the silicone rubber layer, it can better cooperate with and give full play to the advantages of glass fiber, thereby significantly improving the overall performance of the hose. This technological breakthrough can not only expand the application range of the hose, but also meet the needs of various industries for higher performance materials and promote technological progress in related industries. Developing a new preparation method that can improve the performance of the silicone rubber layer is of great significance for improving product performance, expanding application areas, and meeting more stringent industrial requirements. Summary of the invention

[0007] In order to address the deficiencies in the prior art, the purpose of the present invention is to provide a silicone rubber glass fiber hose and a preparation method thereof. The modified silicone rubber coating and the glass fiber substrate work better together, greatly improving the flame retardancy, weather resistance and mechanical strength of the hose, so that the hose can maintain excellent performance under extreme temperatures, harsh environments and high stress conditions, significantly expanding its scope of application.

[0008] A silicone rubber glass fiber hose comprises a glass fiber hose and a silicone rubber coating coated on the surface of the glass fiber hose, wherein the silicone rubber coating is formed by vulcanizing modified silicone rubber, and the modified silicone rubber is made of the following components by weight: 100-120 parts of methyl vinyl silicone rubber raw rubber, 20-35 parts of white carbon black, 4-12 parts of high-vinyl silicone rubber raw rubber, 2-6 parts of vinyl silane coupling agent, 3-8 parts of modifier, 0.01-1 part of acetylene alcohol inhibitor, and 1-3 parts of platinum vulcanizer.

[0009] Preferably, the vinyl content of the methyl vinyl silicone rubber is 0.1-0.25%, and the molar mass is 100,000-750,000 g / mol.

[0010] Preferably, the high vinyl silicone rubber has a vinyl content of 0.5-1.8% and a molar mass of 400,000-700,000 g / mol.

[0011] Preferably, the vinyl silane coupling agent is one or more of silane coupling agents KH570, A171, A172, and A151.

[0012] Preferably, the platinum vulcanizing agent is a platinum complex having a platinum content of 1500-6000 ppm.

[0013] Preferably, the specific surface area of ​​the white carbon black is 300-400m 2 / g.

[0014] Preferably, the preparation method of the modifier comprises the following steps: (1) Add vanillin and 2-amino-4'-methoxyacetophenone to anhydrous ethanol, add acetic acid while stirring, and stir under reflux to obtain an intermediate; Schiff base reaction: Under the acidic catalysis of acetic acid, the carbonyl group of vanillin is activated and then attacked by the amino group of 2-amino-4'-methoxyacetophenone. After proton transfer and dehydration, an imine compound containing a C=N double bond is finally formed. The overall equation of this condensation reaction can be expressed as: R-CHO + H2N-R' → R-CH=NR' + H2O, where R represents the remaining part of vanillin and R' represents the remaining part of 4'-methoxyacetophenone.

[0015] Preferably, in step (1), after the reaction is completed, the product is subjected to rotary evaporation to remove the solvent, ethyl acetate is added to dissolve, and the organic phase is washed with water and saturated brine in sequence, then dried over anhydrous sodium sulfate, filtered, and concentrated to obtain an intermediate.

[0016] Preferably, in step (1), the ratio of vanillin, 2-amino-4'-methoxyacetophenone and acetic acid is 5-10 g: 5.4-11.9 g: 0.1-0.5 mL.

[0017] Preferably, in step (1), the stirring reflux reaction is a reflux reaction at 30-78° C. for 2-24 h.

[0018] (2) The intermediate is dissolved in anhydrous toluene, and a chloroplatinic acid solution is added under a nitrogen atmosphere, followed by slow dropwise addition of methyl hydrogenated silicone oil. The reaction is stirred, and the product is purified to obtain a modifier.

[0019] Hydrosilation reaction: Under the catalysis of chloroplatinic acid (H2PtCl6), the Si-H bond in the methyl hydrogen silicone oil is activated and then added to the C=N double bond of the imine formed in the first step. This process involves the interaction of the platinum catalyst with the Si-H bond to form an active intermediate, which then coordinates with the imine and undergoes a migration insertion reaction. Ultimately, the hydrogen atom is transferred to the carbon atom of the imine, while the silicon atom forms a new Si-N bond with the nitrogen atom. This reaction is highly regio- and stereo-selective and can be carried out efficiently under mild conditions. The overall reaction equation can be expressed as: R-CH=NR' + H-Si(CH3)3 → R-CH(NH-R')-Si(CH3)3. The final product is an organosilicon compound containing a Si-N bond, which is used as a modifier.

[0020] Preferably, in step (2), the purification conditions are as follows: cooling the product to room temperature, filtering through diatomaceous earth to remove the catalyst residue, rotary evaporating to remove the toluene solvent, adding n-hexane to the concentrate, stirring to dissolve, cooling the mixture to 0-5°C and standing to precipitate insoluble impurities, filtering through diatomaceous earth again, and rotary evaporating the filtrate to remove n-hexane to obtain the modifier.

[0021] Preferably, in step (2), the usage ratio of the intermediate, chloroplatinic acid solution, and methyl hydrogen silicone oil is 5-10 g: 0.05-0.25 mL: 2.55-28.98 mL.

[0022] Preferably, in step (2), the concentration of the chloroplatinic acid solution is 0.1 mol / L; the hydrogen content of the methyl hydrogenated silicone oil is 0.18-0.75%, and the viscosity is 20-80 mPa·s.

[0023] Preferably, in step (2), the stirring reaction conditions are 80-105° C. for 6-24 h.

[0024] The present invention also claims a method for preparing the silicone rubber glass fiber hose, comprising the following steps: a. Weaving alkali-free glass fiber yarn into glass fiber sleeve, passing through the embryo machine to make the tube round, and dewaxing to obtain embryo tube for standby; b. Add methyl vinyl silicone rubber, white carbon black, high vinyl silicone rubber and vinyl silane coupling agent into a kneader for mixing, fully mix, grind and filter, and cool to obtain a base rubber; c. Take the base rubber, add the modifier, acetylene alcohol inhibitor and platinum vulcanizer, mix evenly, apply it on the surface of the embryo tube, place it in a drying oven for vulcanization, and cut it to obtain the silicone rubber glass fiber hose.

[0025] Preferably, in step a, the dewaxing conditions are dewaxing at 400-600° C. for 1-20 min.

[0026] Preferably, in step b, white carbon black is added in three times, kneading for 10 to 20 minutes each time, and kneading and mixing for 1 to 3 hours after addition, and then the vinyl silane coupling agent is added in three times, kneading and mixing for 0.5 to 1 hour each time; and then mixing at 130 to 150° C. and -0.05 to -0.1 MPa for 0.5 to 2 hours.

[0027] Preferably, in step c, the temperature in the drying furnace is 200-350°C.

[0028] 1) The present invention provides a silicone rubber fiberglass hose, with methyl vinyl silicone rubber raw rubber as the main material, providing excellent temperature resistance and elasticity; the addition of high vinyl silicone rubber raw rubber enhances the crosslinking density of the material, and improves the mechanical strength and heat resistance. White carbon black is used as a reinforcing filler to significantly improve the tensile strength, wear resistance and tear strength of silicone rubber. Vinyl silane coupling agent improves the interface bonding of organic-inorganic phases and enhances the overall performance of the composite material. The use of acetylene alcohol inhibitor ensures the stability of silicone rubber during processing, while platinum vulcanizer ensures efficient crosslinking of silicone rubber. In particular, the introduced modifier greatly improves the flame retardancy and weather resistance of silicone rubber through its unique molecular structure. This multi-component synergistic formula design enables the modified silicone rubber coating to significantly improve the high temperature resistance, aging resistance, flame retardancy and mechanical properties while maintaining the original flexibility, so that the entire silicone rubber fiberglass hose can maintain excellent performance in various extreme environments, greatly expanding its application range and service life.

[0029] 2) The present invention provides a method for preparing a modifier, which firstly reacts vanillin with 2-amino-4'-methoxyacetophenone through a Schiff base to form an intermediate containing a C=N double bond. This step introduces an aromatic group with a rigid and conjugated structure, which provides the final product with good thermal stability and antioxidant capacity. Then, a hydrogen silylation reaction is carried out under the action of a platinum catalyst to add the Si-H bond in the methyl hydrogen silicone oil to the C=N double bond of the intermediate. This step not only introduces silicon atoms into the molecule, enhancing the heat resistance and weather resistance of the material, but also forms Si-N bonds, thereby increasing the intermolecular interaction force. This ingenious molecular design enables the modifier to interact strongly with the silicone rubber molecules, significantly improving the crosslinking density, mechanical properties, thermal stability and flame retardancy of the silicone rubber. In addition, the presence of the modifier can also slow down the degradation rate of silicone rubber under ultraviolet and oxidative environments, greatly improving the service life of the material.

[0030] 3) The present invention provides a modifier. First, the 2-amino-4'-methoxyacetophenone structure is an excellent UV-resistant agent, which significantly improves the weather resistance of the material and effectively slows down the degradation rate of silicone rubber under ultraviolet and oxidative environments. Subsequently, the aromatic structure introduced by the Schiff base reaction enhances the thermal stability of the material, allowing the silicone rubber to form a more stable carbonized layer at high temperature, thereby improving the flame retardant effect. The introduction of methyl hydrogenated silicone oil allows the modifier to have siloxane as the main chain. This structure can undergo dehydration condensation with the hydroxyl groups on the surface of the glass fiber to form a stable silicon-oxygen bond, significantly improving the compatibility and interfacial bonding strength between the glass fiber and the silicone rubber. The presence of the long siloxane chain improves the impact resistance and toughness of the material. At the same time, the modifier improves the crosslinking density and intermolecular force of the silicone rubber as a whole, and comprehensively enhances the mechanical properties of the hose. The molecular structure of the modifier finally formed helps to form a uniform and dense coating, further optimizing the coating performance. The Si-N bond formed by the hydrogen silanization reaction further enhances the intermolecular interaction force and improves the stability of the material in various harsh environments. The comprehensive and systematic improvement of these properties enables the modified silicone rubber coating to better protect the internal glass fiber, significantly extending the service life of the hose, and enabling the silicone rubber glass fiber hose of the present invention to maintain excellent performance and stability under various extreme conditions, greatly expanding its scope of application. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with embodiments. Of course, the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0032] Unless otherwise specified, the chemical reagents and materials in the present invention are purchased from commercial sources or synthesized from raw materials purchased from commercial sources.

[0033] Methyl vinyl silicone rubber raw rubber was purchased from Anhui Mingyi Silicon Industry Co., Ltd., with a vinyl content of 0.1-0.25%; High vinyl silicone rubber raw rubber was purchased from Dongjue Silicone Group Co., Ltd., model 110-5, with a vinyl content of 0.5~1.8%; The alkynol inhibitor was purchased from Chensi Technology, model CX-5002; Platinum curing agent was purchased from Jiangmen City Pengjiang District Jiegu Silica Gel Co., Ltd., model A-202; White carbon black was purchased from Jiangsu Hao Neng Chemical Co., Ltd., model HN-300.

[0034] A method for preparing a silicone rubber glass fiber hose comprises the following steps: (1) Add 5-10 g of vanillin and 5.4-11.9 g of 2-amino-4'-methoxyacetophenone to 50 mL of anhydrous ethanol, add 0.1-0.5 mL of acetic acid while stirring, and react under reflux at 30-78 °C for 2-24 h. After the reaction, remove the solvent from the product by rotary evaporation, add 100 mL of ethyl acetate to dissolve, wash the organic phase with 50 mL of water and 50 mL of saturated brine in turn, and then dry the organic phase with 5-10 g of anhydrous sodium sulfate, filter, and concentrate to obtain the intermediate; (2) 5-10 g of the intermediate was dissolved in 100 mL of anhydrous toluene, 0.05-0.25 mL of 0.1 mol / L chloroplatinic acid solution was added under a nitrogen atmosphere, and then 2.55-28.98 mL of methyl hydrogen silicone oil was slowly added dropwise, and the reaction was stirred at 80-105° C. for 6-24 h, the product was cooled to room temperature, and the catalyst residue was removed by diatomaceous earth filtration, and the toluene solvent was removed by reduced pressure distillation, 150 mL of n-hexane was added to the concentrate, and the mixture was stirred and dissolved, and the mixture was cooled to 4° C. and allowed to stand for 30 min to precipitate insoluble impurities, and the mixture was filtered through diatomaceous earth again, and the filtrate was collected and evaporated to remove n-hexane to obtain the modifier; (3) The alkali-free glass fiber yarn is braided into a glass fiber sleeve, which is passed through a tube-passing machine to make the tube round, and dewaxed at 400-600°C for 1-20 minutes to obtain a tube for standby use; (4) Add 100-120 parts of methyl vinyl silicone rubber raw rubber, 20-35 parts of white carbon black, 4-12 parts of high vinyl silicone rubber raw rubber, and 2-6 parts of vinyl silane coupling agent into a kneader for mixing. The white carbon black is added in three portions, and the kneading is performed for 10-20 minutes each time. After the addition is completed, the kneading is performed for 1-3 hours. The vinyl silane coupling agent is then added in three portions, and the kneading is performed for 0.5-1 hour each time. The mixture is then mixed at 130-150°C and -0.05-0.1 MPa for 0.5-2 hours. After being fully mixed, the mixture is ground and filtered, and cooled to obtain a base rubber. (5) Take the base rubber, add 3-8 parts of the modifier, 0.01-1 parts of the acetylene alcohol inhibitor, and 1-3 parts of the platinum vulcanizer, mix well, apply it on the surface of the embryo tube, place it in a drying oven at 200-350° C. for vulcanization, and cut it to obtain the silicone rubber glass fiber hose.

[0035] The present invention will be further described below through specific embodiments. Example 1

[0036] A method for preparing a silicone rubber glass fiber hose comprises the following steps: (1) Add 10 g of vanillin and 11.9 g of 2-amino-4'-methoxyacetophenone to 50 mL of anhydrous ethanol, add 0.5 mL of acetic acid while stirring, and react under reflux at 78°C for 2 h. After the reaction, remove the solvent from the product by rotary evaporation, add 100 mL of ethyl acetate to dissolve, wash the organic phase with 50 mL of water and 50 mL of saturated brine in turn, and then dry the organic phase with 10 g of anhydrous sodium sulfate, filter, and concentrate to obtain an intermediate; (2) Dissolve 10 g of the intermediate in 100 mL of anhydrous toluene, add 0.25 mL of 0.1 mol / L chloroplatinic acid solution under a nitrogen atmosphere, then slowly dropwise add 28.98 mL of methyl hydrogenated silicone oil (hydrogen content 0.18%), stir and react at 105° C. for 6 h, cool the product to room temperature, filter through diatomaceous earth to remove the catalyst residue, distill under reduced pressure to remove the toluene solvent, add 150 mL of n-hexane to the concentrate, stir and dissolve thoroughly, cool the mixture to 4° C. and let stand for 30 min to precipitate insoluble impurities, filter through diatomaceous earth again, collect the filtrate and evaporate to remove n-hexane, and obtain the modifier; (3) Weaving the alkali-free glass fiber yarn into a glass fiber sleeve, passing it through a tube-through machine to make it round, and dewaxing it at 500°C for 10 minutes to obtain a tube for standby use; (4) Add 1200g of methyl vinyl silicone rubber, 350g of white carbon black, 120g of high vinyl silicone rubber, and 60g of vinyl silane coupling agent A171 into a kneader for mixing. The white carbon black is added in three portions, and the kneading is performed for 15 minutes each time. After the addition is completed, the kneading is performed for 2 hours. The vinyl silane coupling agent is then added in three portions, and the kneading is performed for 0.5 hours each time. The mixture is then mixed at 140°C and -0.05MPa for 1 hour. After being fully mixed, the mixture is ground and filtered, and cooled to obtain a base rubber. (5) Take the base rubber, add 80g of the modifier, 10g of the acetylene alcohol inhibitor, and 30g of the platinum vulcanizer, mix well, apply it on the surface of the embryo tube, place it in a 300°C oven for vulcanization, and cut it to obtain the silicone rubber glass fiber hose. Example 2

[0037] A method for preparing a silicone rubber glass fiber hose comprises the following steps: (1) Add 8 g of vanillin and 9.7 g of 2-amino-4'-methoxyacetophenone to 50 mL of anhydrous ethanol, add 0.4 mL of acetic acid while stirring, and reflux at 62°C for 10 h. After the reaction, remove the solvent from the product by rotary evaporation, add 100 mL of ethyl acetate to dissolve, wash the organic phase with 50 mL of water and 50 mL of saturated brine in turn, and then dry the organic phase with 10 g of anhydrous sodium sulfate, filter, and concentrate to obtain an intermediate; (2) 8 g of the intermediate was dissolved in 100 mL of anhydrous toluene, 0.2 mL of 0.1 mol / L chloroplatinic acid solution was added under a nitrogen atmosphere, and then 15 mL of methyl hydrogenated silicone oil (hydrogen content 0.3%) was slowly added dropwise, and the reaction was stirred at 100° C. for 12 h. The product was cooled to room temperature, filtered through diatomaceous earth to remove the catalyst residue, and the toluene solvent was removed by vacuum distillation. 150 mL of n-hexane was added to the concentrate, and the mixture was fully stirred and dissolved. The mixture was cooled to 4° C. and allowed to stand for 30 min to precipitate insoluble impurities. The mixture was filtered through diatomaceous earth again, and the filtrate was collected and evaporated to remove n-hexane to obtain the modifier; (3) Weaving the alkali-free glass fiber yarn into a glass fiber sleeve, passing it through a tube-through machine to make it round, and dewaxing it at 500°C for 10 minutes to obtain a tube for standby use; (4) Add 1100g of methyl vinyl silicone rubber, 300g of white carbon black, 100g of high vinyl silicone rubber, and 50g of vinyl silane coupling agent A171 into a kneader for mixing. The white carbon black is added in three portions, and the kneading is carried out for 15 minutes each time. After the addition is completed, the kneading is carried out for 2 hours. The vinyl silane coupling agent is then added in three portions, and the kneading is carried out for 0.5 hours each time. The mixture is then mixed at 140°C and -0.05MPa for 1 hour. After being fully mixed, the mixture is ground and filtered, and cooled to obtain a base rubber. (5) Take the base rubber, add 60g of the modifier, 7g of the acetylene alcohol inhibitor, and 25g of the platinum vulcanizer, mix well, apply it on the surface of the embryo tube, place it in a 300°C oven for vulcanization, and cut it to obtain the silicone rubber glass fiber hose. Example 3

[0038] A method for preparing a silicone rubber glass fiber hose comprises the following steps: (1) Add 6 g of vanillin and 7.6 g of 2-amino-4'-methoxyacetophenone to 50 mL of anhydrous ethanol, add 0.3 mL of acetic acid while stirring, and reflux at 46°C for 18 h. After the reaction, remove the solvent from the product by rotary evaporation, add 100 mL of ethyl acetate to dissolve, wash the organic phase with 50 mL of water and 50 mL of saturated brine in turn, and then dry the organic phase with 10 g of anhydrous sodium sulfate, filter, and concentrate to obtain an intermediate; (2) 6 g of the intermediate was dissolved in 100 mL of anhydrous toluene, 0.1 mL of 0.1 mol / L chloroplatinic acid solution was added under a nitrogen atmosphere, and then 10 mL of methyl hydrogenated silicone oil (hydrogen content 0.5%) was slowly added dropwise, and the reaction was stirred at 90° C. for 18 h. The product was cooled to room temperature, filtered through diatomaceous earth to remove the catalyst residue, and the toluene solvent was removed by vacuum distillation. 150 mL of n-hexane was added to the concentrate, and the mixture was stirred and dissolved. The mixture was cooled to 4° C. and allowed to stand for 30 min to precipitate insoluble impurities. The mixture was filtered through diatomaceous earth again, and the filtrate was collected and evaporated to remove n-hexane to obtain the modifier; (3) Weaving the alkali-free glass fiber yarn into a glass fiber sleeve, passing it through a tube-through machine to make it round, and dewaxing it at 500°C for 10 minutes to obtain a tube for standby use; (4) Add 1100g of methyl vinyl silicone rubber, 250g of white carbon black, 60g of high vinyl silicone rubber, and 30g of vinyl silane coupling agent A171 into a kneader for mixing. The white carbon black is added in three portions, and the kneading is performed for 15 minutes each time. After the addition is completed, the kneading is performed for 2 hours. The vinyl silane coupling agent is then added in three portions, and the kneading is performed for 0.5 hours each time. The mixture is then mixed at 140°C and -0.05MPa for 1 hour. After being fully mixed, the mixture is ground and filtered, and cooled to obtain a base rubber. (5) Take the base rubber, add 50g of the modifier, 6g of the acetylene alcohol inhibitor, and 20g of the platinum vulcanizer, mix well, apply it on the surface of the embryo tube, place it in a 300°C oven for vulcanization, and cut it to obtain the silicone rubber glass fiber hose. Example 4

[0039] A method for preparing a silicone rubber glass fiber hose comprises the following steps: (1) Add 5 g of vanillin and 5.4 g of 2-amino-4'-methoxyacetophenone to 50 mL of anhydrous ethanol, add 0.1 mL of acetic acid while stirring, and react under reflux at 30°C for 24 h. After the reaction, remove the solvent from the product by rotary evaporation, add 100 mL of ethyl acetate to dissolve, wash the organic phase with 50 mL of water and 50 mL of saturated brine in turn, and then dry the organic phase with 10 g of anhydrous sodium sulfate, filter, and concentrate to obtain an intermediate; (2) Dissolve 5 g of the intermediate in 100 mL of anhydrous toluene, add 0.05 mL of 0.1 mol / L chloroplatinic acid solution under a nitrogen atmosphere, then slowly dropwise add 5 mL of methyl hydrogenated silicone oil (hydrogen content 0.5%), stir and react at 80° C. for 24 h, cool the product to room temperature, filter through diatomaceous earth to remove the catalyst residue, remove the toluene solvent by vacuum distillation, add 150 mL of n-hexane to the concentrate, stir and dissolve thoroughly, cool the mixture to 4° C. and let stand for 30 min to precipitate insoluble impurities, filter through diatomaceous earth again, collect the filtrate and evaporate to remove n-hexane, and obtain the modifier; (3) Weaving the alkali-free glass fiber yarn into a glass fiber sleeve, passing it through a tube-through machine to make it round, and dewaxing it at 500°C for 10 minutes to obtain a tube for standby use; (4) Add 1000g of methyl vinyl silicone rubber, 200g of white carbon black, 40g of high vinyl silicone rubber, and 20g of vinyl silane coupling agent A171 into a kneader for mixing. The white carbon black is added in three portions, and the kneading is carried out for 15 minutes each time. After the addition is completed, the kneading is carried out for 2 hours. The vinyl silane coupling agent is then added in three portions, and the kneading is carried out for 0.5 hours each time. The mixture is then mixed at 140°C and -0.05MPa for 1 hour. After being fully mixed, it is ground and filtered, and cooled to obtain the base rubber. (5) Take the base rubber, add 30g of the modifier, 0.1g of the acetylene alcohol inhibitor, and 10g of the platinum vulcanizer, mix well, apply it on the surface of the embryo tube, place it in a 300°C oven for vulcanization, and cut it to obtain the silicone rubber glass fiber hose. Comparative Example 1

[0040] A method for preparing a silicone rubber glass fiber hose comprises the following steps: (1) Add 10 g of vanillin and 11.9 g of 2-amino-4'-methoxyacetophenone to 50 mL of anhydrous ethanol, add 0.5 mL of acetic acid while stirring, and react under reflux at 78°C for 2 h. After the reaction, remove the solvent from the product by rotary evaporation, add 100 mL of ethyl acetate to dissolve, wash the organic phase with 50 mL of water and 50 mL of saturated brine in turn, and then dry the organic phase with 10 g of anhydrous sodium sulfate, filter, and concentrate to obtain an intermediate; (2) Weaving the alkali-free glass fiber yarn into a glass fiber sleeve, passing it through a tube-through machine to make it round, and dewaxing it at 500°C for 10 minutes to obtain a tube for standby use; (3) Add 1200g of methyl vinyl silicone rubber, 350g of white carbon black, 120g of high vinyl silicone rubber, and 60g of vinyl silane coupling agent A171 into a kneader for mixing. The white carbon black is added in three portions, and the kneading is performed for 15 minutes each time. After the addition is completed, the kneading is performed for 2 hours. The vinyl silane coupling agent is then added in three portions, and the kneading is performed for 0.5 hours each time. The mixture is then mixed at 140°C and -0.05MPa for 1 hour. After being fully mixed, the mixture is ground and filtered, and cooled to obtain a base rubber. (4) Take the base rubber, add 80g of the intermediate, 10g of the acetylene alcohol inhibitor, and 30g of the platinum vulcanizer, mix well, apply it on the surface of the embryo tube, place it in a 300°C oven for vulcanization, and cut it to obtain the silicone rubber glass fiber hose. Comparative Example 2

[0041] A method for preparing a silicone rubber glass fiber hose comprises the following steps: (1) The alkali-free glass fiber yarn is woven into a glass fiber sleeve, which is passed through a tube-passing machine to form a round tube, and dewaxed at 500°C for 10 minutes to obtain a tube for standby use; (2) Add 1200g of methyl vinyl silicone rubber, 350g of white carbon black, 120g of high vinyl silicone rubber, and 60g of vinyl silane coupling agent A171 into a kneader for mixing. The white carbon black is added in three portions, and the kneading is performed for 15 minutes each time. After the addition is completed, the kneading is performed for 2 hours. The vinyl silane coupling agent is then added in three portions, and the kneading is performed for 0.5 hours each time. The mixture is then mixed at 140°C and -0.05MPa for 1 hour. After being fully mixed, the mixture is ground and filtered, and cooled to obtain a base rubber. (3) Take the base rubber, add 10g of acetylene alcohol inhibitor and 30g of platinum vulcanizer, mix well, apply on the surface of the embryo tube, place in a 300°C oven for vulcanization, and cut to obtain the silicone rubber glass fiber hose.

[0042] The performance tests were carried out on the silicone rubber glass fiber hoses prepared in Examples 1 to 4 and Comparative Examples 1 to 2. The mechanical properties of silicone rubber were tested with reference to GB / T528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber"; the test methods were tested with reference to GB / T 14522-2008 "Artificial weathering test methods for plastics, coatings and rubber materials for mechanical industrial products - fluorescent ultraviolet lamp" using a wavelength of 280-315 nm ultraviolet lamp 50 W / m 2 After irradiation for 500 hours, the tear retention rate and elongation at break retention rate of the samples were calculated, and the appearance was observed to see if there was any yellowing. The silicone rubber fiberglass hose was placed in the same heat flow environment (279.6kW / m 2 ) for 60 seconds, and measure the surface temperature of the wire wrapped in the hose after the heat flow ends. See Table 1 for specific data.

[0043] Table 1 Performance test results of silicone rubber fiberglass hose

[0044] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A silicone rubber fiberglass hose, comprising a fiberglass hose and a silicone rubber coating coated on the surface of the fiberglass hose, characterized in that: The silicone rubber coating is formed by vulcanizing modified silicone rubber, and the modified silicone rubber is made of the following components in parts by weight: 100-120 parts of methyl vinyl silicone rubber raw rubber, 20-35 parts of white carbon black, 4-12 parts of high vinyl silicone rubber raw rubber, 2-6 parts of vinyl silane coupling agent, 3-8 parts of modifier, 0.01-1 parts of acetylene alcohol inhibitor, and 1-3 parts of platinum vulcanizer.

2. The silicone rubber glass fiber hose according to claim 1, characterized in that: The vinyl content of the methyl vinyl silicone rubber raw rubber is 0.1-0.25%, and the molar mass is 100,000-750,000 g / mol; the vinyl content of the high vinyl silicone rubber raw rubber is 0.5-1.8%, and the molar mass is 400,000-700,000 g / mol.

3. The silicone rubber glass fiber hose according to claim 1, characterized in that: The vinyl silane coupling agent is one or more of silane coupling agents KH570, A171, A172, and A151; the platinum vulcanizing agent is a platinum complex with a platinum content of 1500 to 6000 ppm; the specific surface area of ​​the white carbon black is 300 to 400 m 2 / g.

4. The silicone rubber glass fiber hose according to claim 1, characterized in that: The preparation method of the modifier comprises the following steps: (1) Add vanillin and 2-amino-4'-methoxyacetophenone to anhydrous ethanol, add acetic acid while stirring, and stir under reflux to obtain an intermediate; (2) The intermediate is dissolved in anhydrous toluene, and a chloroplatinic acid solution is added under a nitrogen atmosphere, followed by slow dropwise addition of methyl hydrogenated silicone oil. The reaction is stirred, and the product is purified to obtain a modifier.

5. The silicone rubber glass fiber hose according to claim 4, characterized in that: In step (1), the ratio of vanillin, 2-amino-4'-methoxyacetophenone and acetic acid is 5-10 g: 5.4-11.9 g: 0.1-0.5 mL.

6. The silicone rubber glass fiber hose according to claim 4, characterized in that: In step (1), the stirring reflux reaction is carried out at 30-78° C. for 2-24 hours.

7. The silicone rubber glass fiber hose according to claim 4, characterized in that: In step (2), the usage ratio of the intermediate, chloroplatinic acid solution, and methyl hydrogen silicone oil is 5-10 g: 0.05-0.25 mL: 2.55-28.98 mL.

8. The silicone rubber glass fiber hose according to claim 4, characterized in that: In step (2), the concentration of the chloroplatinic acid solution is 0.1 mol / L; the hydrogen content of the methyl hydrogenated silicone oil is 0.18-0.75%, and the viscosity is 20-80 mPa·s.

9. The silicone rubber glass fiber hose according to claim 4, characterized in that: In step (2), the stirring reaction conditions are 80-105° C. for 6-24 h.

10. A method for preparing the silicone rubber glass fiber hose according to any one of claims 1 to 9, characterized in that: The steps include: a. Weaving alkali-free glass fiber yarn into glass fiber sleeve, passing through the embryo machine to make the tube round, and dewaxing to obtain embryo tube for standby; b. Add methyl vinyl silicone rubber, white carbon black, high vinyl silicone rubber and vinyl silane coupling agent into a kneader for mixing, fully mix, grind and filter, and cool to obtain a base rubber; c. Take the base rubber, add the modifier, acetylene alcohol inhibitor and platinum vulcanizer, mix evenly, apply it on the surface of the embryo tube, place it in a drying oven for vulcanization, and cut it to obtain the silicone rubber glass fiber hose.

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