High-weather-resistance hydraulic rubber pipe as well as preparation method and application thereof

Abstract

The invention relates to the field of rubber products, in particular to a high-weather-resistance hydraulic rubber pipe and a preparation method and application thereof. The high-weather-resistance hydraulic rubber pipe structurally comprises an inner rubber layer located on the innermost side, an outer rubber layer located on the outermost side and a reinforcing layer located between the inner rubber layer and the outer rubber layer. The hydraulic rubber tube prepared by the invention not only has good pressure resistance, temperature resistance and mechanical properties, but also can be kept to have excellent external environment resistance, so that the hydraulic rubber tube has excellent weather resistance, water resistance, corrosion resistance, aging resistance and the like; particularly, the device can fully adapt to complex hydraulic rubber pipe application environments such as outdoors, normal use of equipment is guaranteed, and the device has very excellent market prospects.

Description

Technical Field

[0001] The present application relates to the field of rubber products, and particularly to a highly weather-resistant hydraulic hose and its preparation method and application. Background Art

[0002] A hydraulic hose, also known as a hydraulic oil pipe, a hydraulic hose, a high-pressure hose, a hydraulic pipe, a steel wire high-pressure pipe, a steel wire braided hose or a steel wire wound hose, is a flexible pipe used to transmit hydraulic power or convey high-pressure media such as water, gas, and oil. It is an essential component in a hydraulic system, responsible for conveying the working medium between system components to achieve the transmission and control of force and motion.

[0003] Due to the good performance and functionality of hydraulic hoses, they are widely used in fields such as oilfield development, engineering construction, lifting and transportation, metallurgical forging, mining equipment, shipbuilding, injection molding machinery, and industrial automation hydraulic systems. And with the change of application fields, the performance requirements for hydraulic hoses are also different. However, usually, when designing a hydraulic hose, attention needs to be paid to bending performance, pressure resistance, temperature resistance, ozone resistance, as well as good pulse and fatigue resistance characteristics to meet the usage requirements under different working conditions. Summary of the Invention

[0004] With the continuous increase in the application fields and environments of hydraulic hoses, the requirements for the weather resistance, aging resistance, and waterproofness of hydraulic hoses are also constantly increasing. However, the existing hydraulic hoses pay less attention to the above performances, and usually cannot achieve the balance and consideration of the above performances. Therefore, in order to effectively solve the above problems, the present application provides a highly weather-resistant hydraulic hose and its preparation method. The hydraulic hose prepared by the present application not only has good pressure resistance, temperature resistance, and mechanical properties, but also can maintain excellent external environment resistance performance of the hydraulic hose, so as to simultaneously have excellent performances such as weather resistance, waterproofness, corrosion resistance, and aging resistance. In particular, it can fully adapt to relatively complex application environments of hydraulic hoses outdoors, ensure the normal use of equipment, and has a very excellent market prospect.

[0005] A highly weather-resistant hydraulic hose, its structure includes: an inner rubber layer located on the innermost side, an outer rubber layer located on the outermost side, and a reinforcing layer located between the inner rubber layer and the outer rubber layer.

[0006] As a preferred embodiment, the raw material of the inner rubber layer is at least one of nitrile rubber, styrene-butadiene rubber, chloroprene rubber, hydrogenated nitrile rubber, fluororubber, and chlorosulfonated polyethylene rubber.

[0007] As a preferred embodiment, the raw material of the inner rubber layer is any one of nitrile rubber, styrene-butadiene rubber, chloroprene rubber, hydrogenated nitrile rubber, and fluororubber.

[0008] As a preferred embodiment, the raw material of the inner rubber layer is nitrile rubber or neoprene.

[0009] As a preferred embodiment, the thickness of the inner rubber layer is 1.5 - 3.5 mm.

[0010] As a preferred embodiment, the thickness of the inner rubber layer is 2 - 2.5 mm.

[0011] As a preferred embodiment, the raw material of the reinforcing layer is any one of steel wire, nylon fiber, polyester fiber, aramid fiber, and mixed fiber.

[0012] As a preferred embodiment, the raw material of the reinforcing layer is steel wire or nylon fiber.

[0013] As a preferred embodiment, the number of braided layers of the reinforcing layer is 1 - 5 layers.

[0014] As a preferred embodiment, the number of braided layers of the reinforcing layer is 3 - 4 layers.

[0015] As a preferred embodiment, the raw material of the outer rubber layer, by mass, includes: 20 - 45 parts of ethylene propylene diene monomer rubber, 80 - 110 parts of chlorinated butyl rubber, 15 - 30 parts of functional resin, 3 - 5 parts of stearic acid, 10 - 15 parts of carbon material, 30 - 40 parts of solid filler, 2 - 4 parts of crosslinking agent, 8 - 14 parts of starch material, 5 - 8 parts of dispersant, 10 - 15 parts of auxiliary agent, 5 - 15 parts of lubricant, and 5 - 10 parts of dibutyl phthalate.

[0016] As a preferred embodiment, the thickness of the outer rubber layer is 4.5 - 10 mm.

[0017] As a preferred embodiment, the mass ratio of the ethylene propylene diene monomer rubber, chlorinated butyl rubber, and functional resin is (2.5 - 3.5):(9 - 10):(2 - 2.4).

[0018] As a preferred embodiment, the mass ratio of the ethylene propylene diene monomer rubber, chlorinated butyl rubber, and functional resin is (2.8 - 3):(9 - 9.5):(2 - 2.2).

[0019] As a preferred embodiment, the Mooney viscosity of the chlorinated butyl rubber is 18 - 25 MU, under the condition of M1 + 8 / 125 °C.

[0020] As a preferred embodiment, the Mooney viscosity of the chlorinated butyl rubber is 19 - 23 MU, under the condition of M1 + 8 / 125 °C.

[0021] In this application, by compounding chlorobutyl rubber and ethylene propylene diene monomer rubber with specific viscosities, the weather resistance, waterproofness, corrosion resistance, aging resistance and other properties of hydraulic hoses are significantly improved. The CL atoms in the added chlorobutyl rubber, as strongly polar atoms, can absorb the excess electrons in the system, reduce the content of active electrons in the system, and thus limit the complex impurity cross-linking reaction caused by the unsaturated double bonds in the side chains of ethylene propylene diene monomer rubber. Moreover, the straight-chain helical long-chain structure of the chlorobutyl rubber with the above viscosity in combination with the added amylose can significantly increase the connection strength and tightness of the three-dimensional network of the internal colloid. Therefore, in a harsh environment, it can significantly inhibit the frequent movement of internal active molecules while increasing the penetration resistance and penetration path of external active groups, active molecules and water molecules, thereby significantly improving the various properties of the rubber compound as a whole.

[0022] As a preferred embodiment, the preparation method of the functional resin includes the following steps: S1: Dissolve chlorinated polyethylene in a mixed solvent, and under nitrogen protection, add allyl glycidyl ether chloride, 3-(2,3-epoxypropoxy)propyl methacrylate and sodium p-vinylbenzenesulfonate in three stages respectively, and heat for reaction; S2: Add aminated mica powder, and add it to the reaction system 3 to 4 times with a high-speed disperser, and then stir and cure at a high temperature; S3: Precipitate with an ethanol aqueous solution, wash 2 to 3 times with acetone and deionized water in sequence after centrifugal separation, sieve after gradient drying to obtain the product.

[0023] As a preferred embodiment, the preparation method of the functional resin includes the following steps: S1: Dissolve chlorinated polyethylene in a mixed solvent at 105-110°C, under nitrogen protection, add allyl glycidyl ether chloride and 50-60 wt% initiator in the first stage, stir and react at 110-115°C at 250-300 rpm for 2-3 h, in the second stage, lower the temperature to 90-95°C, add 3-(2,3-epoxypropoxy)propyl methacrylate and add the remaining initiator, keep the temperature and react for 2-2.5 h, in the third stage, add sodium vinylbenzenesulfonate, and keep the temperature and react for 1-1.5 h under ultrasonic assistance at 26-30 kHz; S2: Add aminated mica powder, add it 3 times with a high-speed disperser at intervals of 15-20 min, stir and disperse at a speed of 5000-6000 rpm during this period, and cure at 85-90°C for 2-3 h; S3: Precipitate with an ethanol aqueous solution, wash 2 to 3 times with acetone and deionized water in sequence after centrifugal separation, vacuum dry at 50-60°C for 6-7 h, hot air circulation dry at 75-80°C for 3-4 h, and sieve through a 200-300 mesh sieve after completion to obtain the product.

[0024] As a preferred embodiment, the mass ratio of the chlorinated polyethylene, allyl glycidyl ether chloride, 3-(2,3-epoxypropoxy)propyl methacrylate and sodium p-vinylbenzenesulfonate is (10-12):(1.5-2):(0.5-0.8):(0.4-0.6).

[0025] As a preferred embodiment, the mass ratio of the chlorinated polyethylene and the aminated mica powder is (10-12):(1.4-1.8).

[0026] As a preferred embodiment, the mixed solvent is a mixed solvent of xylene and cyclohexanone, and the mass ratio is (3-4):1.

[0027] As a preferred embodiment, the initiator is benzoyl peroxide.

[0028] As a preferred embodiment, the average particle size of the aminated mica powder is 4-6 μm.

[0029] As a preferred embodiment, the carbon material is at least one of carbon nanotubes, carbon black, graphene, graphene oxide, and carbon powder.

[0030] As a preferred embodiment, the carbon material is carbon powder.

[0031] As a preferred embodiment, the average particle size of the carbon powder is 1-1.5 μm.

[0032] As a preferred embodiment, the solid filler is a composition of sericite powder and zinc oxide.

[0033] As a preferred embodiment, the mass ratio of the sericite powder and the zinc oxide is (5-6):(0.8-1).

[0034] As a preferred embodiment, the mass ratio of the sericite powder and the zinc oxide is (5-5.5):1.

[0035] As a preferred embodiment, the crosslinking agent is at least one of polybutadiene, divinylbenzene, and diallyl phthalate.

[0036] As a preferred embodiment, the crosslinking agent is a composition of polybutadiene and divinylbenzene.

[0037] As a preferred embodiment, the mass ratio of the polybutadiene and the divinylbenzene is (3-4):(0.5-1.5).

[0038] As a preferred embodiment, the starch material is amylopectin or amylose.

[0039] As a preferred embodiment, the starch material is amylose.

[0040] As a preferred embodiment, the dispersant is at least one of fatty alcohol polyoxyethylene ethers.

[0041] As a preferred embodiment, the dispersant is lauryl alcohol polyoxyethylene ether and / or cetearyl alcohol polyoxyethylene ether.

[0042] As a preferred embodiment, the auxiliary agent is a composition of aluminum hydroxide, p-phenylenediamine and TMTD.

[0043] As a preferred embodiment, the mass ratio of aluminum hydroxide, p-phenylenediamine and TMTD is (6-8):(2-3):(2-4).

[0044] As a preferred embodiment, the mass ratio of aluminum hydroxide, p-phenylenediamine and TMTD is (6.5-7):(2-2.5):(2.5-3).

[0045] As a preferred embodiment, the lubricant is at least one of paraffin oil, vegetable oil, and polyvinyl alcohol.

[0046] As a preferred embodiment, the lubricant is epoxidized soybean oil of vegetable oil type.

[0047] As a preferred embodiment, the mass ratio of the carbon material, solid filler and lubricant is (1.2-1.5):(3.2-3.6):(0.8-1.2).

[0048] As a preferred embodiment, the mass ratio of the carbon material, solid filler and lubricant is (1.3-1.4):(3.4-3.5):(0.8-1).

[0049] As a preferred embodiment, the preparation method of the raw material of the outer rubber layer includes the following steps: S1: First, add ethylene propylene diene monomer rubber and chlorinated butyl rubber into a mixer and knead at 90-120°C for 3-5 minutes, then add stearic acid and functional resin and cool down to 70-85°C and knead for 2-3 minutes; S2: Add carbon material, solid filler, crosslinking agent, starch material and auxiliary agent, heat up to 130-140°C and knead for 2-4 minutes; S3: Add the remaining raw materials while controlling the temperature at 90-110°C, knead for 3-5 minutes, and discharge at 95-100°C to obtain the outer rubber layer rubber material. After natural cooling to room temperature, cut the rubber material into the required size to obtain it.

[0050] The preparation method of the above-mentioned highly weather-resistant hydraulic hose includes the following steps: S1: Using an extruder to extrude the inner rubber layer raw material to form a hose and wrap it around a hard core; S2: Placing the hose on a braiding machine and winding multiple layers of steel wires around the hose to form a reinforcing layer; S3: Extruding the outer rubber layer rubber material and wrapping it around the reinforcing layer. After uniform thickness, the hose enters a vulcanizing kettle for high-temperature vulcanization. After vulcanization is completed, the water cloth is removed and the hard core is extracted to obtain the finished product.

[0051] This application further defines the application of the above-mentioned highly weather-resistant hydraulic hose in oilfield development, engineering construction, lifting and transportation, metallurgical forging, mining equipment, shipbuilding, injection molding machinery, and industrial automation hydraulic systems.

[0052] The beneficial effects of this application are as follows:

[0053] 1. A highly weather-resistant hydraulic hose provided in this application not only has good pressure resistance, temperature resistance, and mechanical properties, but also can maintain excellent resistance to the external environment of the hydraulic hose, thus having excellent weather resistance, waterproofness, corrosion resistance, and aging resistance. In particular, it can fully adapt to relatively complex application environments such as outdoors for hydraulic hoses, ensure the normal use of equipment, and has a very excellent market prospect.

[0054] 2. A highly weather-resistant hydraulic hose provided in this application, by adding a compound of chlorobutyl rubber and ethylene propylene diene monomer with a specific viscosity, greatly improves the weather resistance, waterproofness, corrosion resistance, and aging resistance of the hydraulic hose; the CL atoms in the added chlorobutyl rubber, as strong polar atoms, can absorb the excess electrons in the system, reduce the content of active electrons in the system, and thus limit the complex impurity cross-linking reaction caused by the unsaturated double bonds in the side chains of ethylene propylene diene monomer. Moreover, the linear helical long-chain structure of the amylose added with chlorobutyl rubber at the above viscosity can greatly increase the connection strength and tightness of the three-dimensional network of the internal colloid. Therefore, in a harsh environment, it can greatly inhibit the frequent movement of internal active molecules while increasing the penetration resistance and penetration path of external active groups, active molecules, and water molecules, thereby greatly improving the various properties of the rubber material as a whole.

[0055] 3. A highly weather-resistant hydraulic hose provided in this application forms numerous cross-linking sites by adding functional resins, and at the same time, the double epoxy groups of 3-(2,3-epoxypropoxy)propyl methacrylate further form an interpenetrating network to improve the system density and interaction force; the aminated mica powder is arranged in an orientation parallel to the surface of the hose (induced by processing shear force) to form a maze path with an extremely long aspect ratio, enhancing the barrier force against water molecules. And finally, through a ternary cooperative system of chemical cross-linking skeleton + physical barrier network + dynamic ionic bond, the mechanical properties, waterproofness, and aging resistance of the hydraulic hose are greatly improved. Detailed implementation mode

[0056] The technical solutions in the above-mentioned invention content of this application will be further described and demonstrated below in the form of specific implementation solutions.

[0057] In the following examples, unless otherwise specified, the raw materials are commercially available products that can be obtained, or can be prepared by methods well-known to those skilled in the art.

[0058] Example 1

[0059] A highly weather-resistant hydraulic hose, the structure of which includes: an inner rubber layer located on the innermost side, an outer rubber layer located on the outermost side, and a reinforcing layer located between the inner rubber layer and the outer rubber layer.

[0060] The thickness of the inner rubber layer is 2.4 mm; the number of braided layers of the reinforcing layer is 3 layers; the thickness of the outer rubber layer is 7.5 mm.

[0061] The raw material of the inner rubber layer is neoprene, purchased from a neoprene product of model CR232 in Changshou, China.

[0062] The raw material of the reinforcing layer is steel wire.

[0063] The raw materials of the outer rubber layer, by mass, include: 28 parts of ethylene propylene diene monomer rubber, 92 parts of chlorinated butyl rubber, 21 parts of functional resin, 4 parts of stearic acid, 14 parts of carbon material, 35 parts of solid filler, 2.5 parts of cross-linking agent, 11 parts of starch material, 6 parts of dispersant, 12.5 parts of auxiliary agent, 8.5 parts of lubricant, and 6 parts of dibutyl phthalate.

[0064] The ethylene propylene diene monomer rubber is purchased from a product of model EPDM-3430 of Dow Chemical Company in the United States, and the chlorinated butyl rubber is purchased from the corresponding product of Shanghai Yingting Industry Co., Ltd., and its average Mooney viscosity is 22 MU, condition M1+8 / 125 °C.

[0065] The preparation method of the functional resin comprises the following steps, in parts by mass: S1: Dissolve 10.5 parts of chlorinated polyethylene in a mixed solvent of xylene and cyclohexanone (xylene: cyclohexanone = 3:1) at 105 °C, protect with nitrogen, add 1.8 parts of chloroallyl glycidyl ether and 0.2 parts of dibenzoyl peroxide in the first stage, stir and react at 115 °C at 250 rpm for 3 h, lower the temperature to 90 °C in the second stage, add 0.6 parts of 3-(2,3-epoxypropoxy)propyl methacrylate and add 0.18 parts of dibenzoyl peroxide, keep the temperature for reaction for 2 h, add 0.5 parts of sodium vinylbenzenesulfonate in the third stage, and keep the temperature for reaction for 1 h under 28 kHz ultrasonic wave assistance; S2: Add 1.5 parts of aminated mica powder, add it in 3 times with a high-speed disperser at intervals of 15 min, stir and disperse at a speed of 5000 rpm during this period, and cure at 90 °C for 2 h; S3: Precipitate and separate with an ethanol aqueous solution, wash 3 times with acetone and deionized water in sequence, vacuum dry at 55 °C for 6 h, hot air circulation dry at 75 °C for 3 h, and pass through a 200-mesh sieve after completion to obtain the product.

[0066] The chlorinated polyethylene is purchased from the CPE 135A model product sold by Yaxing Chemical Co., Ltd., Weifang, China.

[0067] The average particle size of the aminated mica powder is 5.5 μm.

[0068] The crosslinking agent is a composition of polybutadiene and divinylbenzene, and the mass ratio of the two is 3.2:0.75. The polybutadiene is the hydroxyl-terminated polybutadiene product sold by Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0069] The starch material is amylose, with a linear content ≥ 70%, purchased from Xiya Chemical Co., Ltd., Shandong; the dispersant is polyoxyethylene lauryl ether, the MOA-7 model product purchased from Jiangsu Haian Petroleum.

[0070] The auxiliary agent is a composition of aluminum hydroxide, p-phenylenediamine and TMTD, and the mass ratio of the three is 7:2.5:3.

[0071] The lubricant is epoxy soybean oil, purchased from the industrial-grade product sold by Jinan Yuyi Chemical Co., Ltd.

[0072] The preparation method of the raw materials for the outer rubber layer comprises the following steps: S1: First, add ethylene propylene diene monomer rubber and chlorinated butyl rubber to an internal mixer and knead at 100 °C for 3.5 min, then add stearic acid and the functional resin and lower the temperature to 80 °C and knead for 3 min; S2: Add carbon materials, solid fillers, crosslinking agents, starch materials and auxiliary agents, raise the temperature to 135 °C and knead for 2.5 min; S3: Add the remaining raw materials, control the temperature at 105 °C, knead for 4 min, and discharge at 100 °C to obtain the outer rubber layer rubber material. After naturally cooling to room temperature, cut the rubber material into the required size to obtain the product.

[0073] The preparation method of the above-mentioned highly weather-resistant hydraulic hose, the preparation method includes the following steps: S1: Use an extruder to extrude the inner rubber layer raw material at 165°C to form a hose, and wrap it around a hard core; S2: Place the hose on a braiding machine, and wind multiple layers of steel wires around the hose to form 3 reinforcing layers; S3: Extrude the outer rubber layer rubber material at 170°C and wrap it around the reinforcing layer. After the thickness is uniform, the hose enters a vulcanizing tank for high-temperature vulcanization at 155°C. After vulcanization is completed, remove the water cloth and pull out the hard core to obtain the finished product.

[0074] Example 2

[0075] A highly weather-resistant hydraulic hose, its structure includes: an inner rubber layer located on the innermost side, an outer rubber layer located on the outermost side, and a reinforcing layer located between the inner rubber layer and the outer rubber layer.

[0076] The thickness of the inner rubber layer is 2.4 mm; the number of braided layers of the reinforcing layer is 3 layers; the thickness of the outer rubber layer is 7.5 mm.

[0077] The raw material of the inner rubber layer is neoprene, purchased from a neoprene product of model CR232 in Changshou, China.

[0078] The raw material of the reinforcing layer is steel wire.

[0079] The raw materials of the outer rubber layer, by mass, include: 35 parts of ethylene propylene diene monomer rubber, 100 parts of chlorinated butyl rubber, 20 parts of functional resin, 4 parts of stearic acid, 14 parts of carbon material, 35 parts of solid filler, 2.5 parts of cross-linking agent, 11 parts of starch material, 6 parts of dispersant, 14 parts of auxiliary agent, 8.5 parts of lubricant, 5.5 parts of dibutyl phthalate.

[0080] The ethylene propylene diene monomer rubber is purchased from a product of model EPDM-3430 of Dow Chemical Company in the United States, and the chlorinated butyl rubber is purchased from the corresponding product of Shanghai Yingting Industry Co., Ltd., with an average Mooney viscosity of 22 MU, condition M1+8 / 125°C.

[0081] The preparation method of the functional resin comprises the following steps, by mass: S1: Dissolve 10.5 parts of chlorinated polyethylene in a mixed solvent of xylene and cyclohexanone (xylene: cyclohexanone = 3:1) at 105°C, protect with nitrogen. In the first stage, add 1.8 parts of chloroallyl glycidyl ether and 0.2 parts of dibenzoyl peroxide, and stir and react at 115°C and 250 rpm for 3 h. In the second stage, lower the temperature to 90°C, add 0.6 parts of 3-(2,3-epoxypropoxy)propyl methacrylate and 0.18 parts of dibenzoyl peroxide, and keep the temperature for reaction for 2 h. In the third stage, add 0.5 parts of sodium vinylbenzenesulfonate, and keep the temperature for reaction for 1 h with 28 kHz ultrasonic assistance; S2: Add 1.5 parts of aminated mica powder, and add it in 3 times with a high-speed disperser at intervals of 15 min. During this period, stir and disperse at a speed of 5000 rpm, and cure at 90°C for 2 h; S3: Precipitate and separate with an ethanol aqueous solution, wash 3 times with acetone and deionized water in sequence, vacuum dry at 55°C for 6 h, hot air circulate and dry at 75°C for 3 h. After completion, sieve through a 200-mesh sieve to obtain the product.

[0082] The chlorinated polyethylene is purchased from the CPE 135A model product sold by China Weifang Yaxing Chemical Co., Ltd.

[0083] The average particle size of the aminated mica powder is 5.5 μm.

[0084] The crosslinking agent is a composition of polybutadiene and divinylbenzene, and the mass ratio of the two is 4:0.6. The polybutadiene is the hydroxyl-terminated polybutadiene product sold by Jiangsu Runfeng Synthetic Technology Co., Ltd.

[0085] The starch material is amylose with a linear content ≥ 70%, purchased from Shandong Xiya Chemical Co., Ltd.; the dispersant is lauryl alcohol polyoxyethylene ether, and the MOA-7 model product sold by Jiangsu Haian Petroleum is purchased.

[0086] The auxiliary agent is a composition of aluminum hydroxide, p-phenylenediamine and TMTD, and the mass ratio of the three is 8:2.5:3.5.

[0087] The lubricant is epoxy soybean oil, and the industrial-grade product sold by Jinan Yuyi Chemical Co., Ltd. is purchased.

[0088] The preparation method of the raw materials for the outer rubber layer comprises the following steps: S1: First, add ethylene propylene diene monomer rubber and chlorinated butyl rubber to an internal mixer and knead at 100°C for 3.5 min, then add stearic acid and the functional resin and lower the temperature to 80°C and knead for 3 min; S2: Add carbon materials, solid fillers, crosslinking agents, starch materials and auxiliary agents, and raise the temperature to 135°C and knead for 2.5 min; S3: Add the remaining raw materials, control the temperature at 105°C, knead for 4 min, and discharge at 100°C to obtain the outer rubber layer rubber material. After naturally cooling to room temperature, cut the rubber material into the required size to obtain the product.

[0089] A preparation method of the above high weather resistance hydraulic hose, the preparation method comprising the following steps: S1: extruding the inner rubber layer raw material at 165 °C using an extruder to form a hose, and covering it on a hard core; S2: on a braiding machine, winding multiple layers of steel wires around the hose to form a 3-layer reinforcing layer; S3: extruding the outer rubber layer rubber material at 170 °C and wrapping it on the reinforcing layer, after uniform thickness, the hose enters a vulcanizing tank for high temperature vulcanization at 155 °C, after vulcanization is completed, removing the water cloth and pulling out the hard core to obtain the product.

[0090] Comparative Example 1

[0091] The difference between the implementation scheme of this comparative example and Example 1 is only that: the raw materials of the outer rubber layer, by mass, include: 35 parts of ethylene propylene diene monomer rubber, 100 parts of chlorinated butyl rubber, 8 parts of functional resin, 4 parts of stearic acid, 14 parts of carbon material, 35 parts of solid filler, 2.5 parts of crosslinking agent, 11 parts of starch material, 6 parts of dispersant, 14 parts of auxiliary agent, 8.5 parts of lubricant, 5.5 parts of dibutyl phthalate.

[0092] Comparative Example 2

[0093] The difference between the implementation scheme of this comparative example and Example 1 is only that: the raw materials of the outer rubber layer, by mass, include: 55 parts of ethylene propylene diene monomer rubber, 60 parts of chlorinated butyl rubber, 25 parts of functional resin, 4 parts of stearic acid, 14 parts of carbon material, 35 parts of solid filler, 2.5 parts of crosslinking agent, 11 parts of starch material, 6 parts of dispersant, 14 parts of auxiliary agent, 8.5 parts of lubricant, 5.5 parts of dibutyl phthalate.

[0094] Comparative Example 3

[0095] The difference between the implementation scheme of this comparative example and Example 1 is only that: the chlorinated butyl rubber is purchased from the corresponding product of Shanghai Yingting Industrial Co., Ltd., and its average Mooney viscosity is 28.5 MU, condition M1 + 8 / 125 °C.

[0096] Comparative Example 4

[0097] The difference between the implementation scheme of this comparative example and that of Example 1 is only as follows: The preparation method of the functional resin comprises the following steps, in parts by mass: S1: Dissolve 10.5 parts of chlorinated polyethylene in a mixed solvent of xylene and cyclohexanone (xylene: cyclohexanone = 3:1) at 105°C, protect with nitrogen, add 3.5 parts of chloroallyl glycidyl ether and 0.2 parts of benzoyl peroxide in the first stage, stir and react at 115°C and 250 rpm for 3 h, in the second stage, lower the temperature to 90°C, add 0.2 parts of 3-(2,3-epoxypropoxy)propyl methacrylate and add 0.18 parts of benzoyl peroxide, and keep the temperature for reaction for 2 h; S2: Add 1.5 parts of aminated mica powder, add it in 3 times with a high-speed disperser at intervals of 15 min, stir and disperse at a speed of 5000 rpm during this period, and cure at 90°C for 2 h; S3: Precipitate with an aqueous ethanol solution, wash 3 times with acetone and deionized water in turn after centrifugal separation, vacuum dry at 55°C for 6 h, hot air circulation dry at 75°C for 3 h, and pass through a 200-mesh sieve after completion to obtain the product.

[0098] Comparative Example 5

[0099] The difference between the implementation scheme of this comparative example and that of Example 1 is only as follows: The preparation method of the functional resin comprises the following steps, in parts by mass: S1: Dissolve 10.5 parts of chlorinated polyethylene in a mixed solvent of xylene and cyclohexanone (xylene: cyclohexanone = 3:1) at 105°C, protect with nitrogen, add 0.6 parts of chloroallyl glycidyl ether and 0.2 parts of benzoyl peroxide in the first stage, stir and react at 115°C and 250 rpm for 3 h, in the second stage, lower the temperature to 90°C, add 1.8 parts of 3-(2,3-epoxypropoxy)propyl methacrylate and add 0.18 parts of benzoyl peroxide, and keep the temperature for reaction for 2 h, in the third stage, add 1 part of sodium vinylbenzenesulfonate, and keep the temperature for reaction for 1 h under the assistance of 28 kHz ultrasonic wave; S2: Add 1.5 parts of aminated mica powder, add it in 3 times with a high-speed disperser at intervals of 15 min, stir and disperse at a speed of 5000 rpm during this period, and cure at 90°C for 2 h; S3: Precipitate with an aqueous ethanol solution, wash 3 times with acetone and deionized water in turn after centrifugal separation, vacuum dry at 55°C for 6 h, hot air circulation dry at 75°C for 3 h, and pass through a 200-mesh sieve after completion to obtain the product.

[0100] Comparative Example 6

[0101] The difference between the implementation scheme of this comparative example and that of Example 1 is only as follows: The average particle size of the aminated mica powder is 12.5 μm.

[0102] Performance Evaluation

[0103] 1. Mechanical properties: The tensile strength and elongation at break of the outer rubber layers prepared in the examples and comparative examples were tested. The tests were carried out with reference to the standard of GB / T 528-2009, and the test values were the average of 10 tests and recorded in Table 1.

[0104] 2. Aging resistance: The outer rubber layers prepared in the examples and comparative examples were stored at a constant temperature in an environment of 65 °C and 75% relative humidity for 3 months. After 3 months, they were taken out and the elongation at break was continued to be tested in accordance with Performance Test 1. After the test, the retention rate of the elongation at break of the outer rubber layer was recorded. Retention rate % = elongation at break after 3 months / original elongation at break × 100%. The test values were the average of 10 tests and recorded in Table 1.

[0105] 3. Waterproofness: The water absorption resistance of the outer rubber layers prepared in the examples and comparative examples was tested. The test was carried out by referring to the standard of ASTM D-570 after placing them in water at 50 °C for 48 hours. The test values were the average of 10 tests and recorded in Table 1.

[0106] Table 1 Performance evaluation table

[0107]

[0108]

[0109] It can be seen from the data results of the examples, comparative examples and Table 1 of this application that Examples 1 and 2 of this application have obvious performance advantages over Comparative Examples 1-6 in terms of mechanical properties, aging resistance, waterproofness, etc. The functional resins prepared in Examples 1 and 2 through better technical solutions can form numerous cross-linking sites. At the same time, the double epoxy groups of 3-(2,3-epoxypropoxy)propyl methacrylate further form an interpenetrating network to improve the system density and interaction force; the aminated mica powder is arranged in an orientation parallel to the surface of the rubber hose (induced by processing shear force), forming a maze path with an ultra-high aspect ratio, enhancing the barrier force to water molecules, and finally through a ternary synergistic system of chemical cross-linking skeleton + physical barrier network + dynamic ionic bond, greatly improving the mechanical properties, waterproofness and aging resistance of the hydraulic rubber hose.

Claims

1. A highly weather-resistant hydraulic hose, characterized in that: The structure of the hydraulic hose includes: an inner rubber layer located on the innermost side, an outer rubber layer located on the outermost side, and a reinforcing layer located between the inner rubber layer and the outer rubber layer; The raw materials of the outer rubber layer, by mass, include: 20-45 parts of ethylene propylene diene monomer rubber, 80-110 parts of chlorinated butyl rubber, 15-30 parts of functional resin, 3-5 parts of stearic acid, 10-15 parts of carbon material, 30-40 parts of solid filler, 2-4 parts of crosslinking agent, 8-14 parts of starch material, 5-8 parts of dispersant, 10-15 parts of auxiliary agent, 5-15 parts of lubricant, 5-10 parts of dibutyl phthalate; The preparation method of the functional resin includes: S1: Dissolve chlorinated polyethylene in a mixed solvent, and under nitrogen protection, add allyl glycidyl ether chloride, 3-(2,3-epoxypropoxy)propyl methacrylate and sodium p-vinylbenzenesulfonate in three stages respectively, and heat and react; S2: Add aminated mica powder and stir and cure at high temperature; S3: Precipitate with an ethanol aqueous solution, wash after centrifugal separation, dry and sieve to obtain.

2. The highly weather-resistant hydraulic hose according to claim 1, characterized in that: The mass ratio of the ethylene propylene diene monomer rubber, chlorinated butyl rubber and functional resin is (2.5-3.5):(9-10):(2-2.4); the Mooney viscosity of the chlorinated butyl rubber is 18-25 MU, condition M1+8 / 125°C.

3. The highly weather-resistant hydraulic hose according to claim 2, characterized in that: The raw material of the inner rubber layer is nitrile rubber or chloroprene rubber; the raw material of the reinforcing layer is steel wire or nylon fiber.

4. The highly weather-resistant hydraulic hose according to claim 3, wherein: The preparation method of the functional resin includes the following steps: S1: Dissolve chlorinated polyethylene in a mixed solvent at 105-110°C, protect with nitrogen, add allyl glycidyl ether chloride and 50-60 wt% initiator in one stage, stir and react at 110-115°C at 250-300 rpm for 2-3 h, lower the temperature to 90-95°C in the second stage, add 3-(2,3-epoxypropoxy)propyl methacrylate and add the remaining initiator, and keep the temperature for reaction for 2-2.5 h, add sodium vinylbenzenesulfonate in the third stage, and keep the temperature for reaction for 1-1.5 h under ultrasonic assistance of 26-30 kHz; S2: Add aminated mica powder, add it in 3 times with a high-speed disperser at intervals of 15-20 min, stir and disperse at a speed of 5000-6000 rpm during this period, and cure at 85-90°C for 2-3 h; S3: Precipitate with an ethanol aqueous solution, wash 2-3 times with acetone and deionized water in turn after centrifugal separation, vacuum dry at 50-60°C for 6-7 h, hot air circulation dry at 75-80°C for 3-4 h, and sieve through a 200-300 mesh sieve after completion to obtain.

5. The highly weather-resistant hydraulic hose according to claim 4, characterized in that: The mass ratio of the chlorinated polyethylene, allyl glycidyl ether chloride, 3-(2,3-epoxypropoxy)propyl methacrylate and sodium p-vinylbenzenesulfonate is (10-12):(1.5-2):(0.5-0.8):(0.4-0.6).

6. The highly weather-resistant hydraulic hose according to claim 5, wherein: The mass ratio of the chlorinated polyethylene and aminated mica powder is (10-12):(1.4-1.8).

7. The highly weather-resistant hydraulic hose according to claim 6, wherein: The carbon material is at least one of carbon nanotubes, carbon black, graphene, graphene oxide, carbon powder.

8. The highly weather-resistant hydraulic hose according to claim 7, characterized in that: The solid filler is a composition of sericite powder and zinc oxide, and the mass ratio is (5-6):(0.8-1).

9. A method for preparing a highly weather-resistant hydraulic hose according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: S1: Using an extruder to extrude the inner rubber layer raw material to form a rubber tube, and covering it on a hard core; S2: Placing the rubber tube on a braiding machine, and winding multiple layers of steel wires around the rubber tube to form a reinforcing layer; S3: Extruding the outer rubber layer rubber material and wrapping it on the reinforcing layer. After the thickness is uniform, the rubber tube enters a vulcanizing tank for high-temperature vulcanization. After vulcanization is completed, removing the water cloth and pulling out the hard core to obtain the finished product.

10. Application of a highly weather-resistant hydraulic hose according to any one of claims 1-8 in oilfield development, engineering construction, lifting and transportation, metallurgical forging, mining equipment, shipbuilding, injection molding machinery, and industrial automation hydraulic systems.

Images