High-weather-resistance hydraulic rubber hose and preparation method and application thereof

Abstract

The application 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 comprises an inner rubber layer located at the innermost side, an outer rubber layer located at the outermost side and a reinforcing layer located between the inner rubber layer and the outer rubber layer. The hydraulic rubber pipe prepared by the application not only has good pressure resistance, temperature resistance and mechanical properties, but also can maintain excellent external environment resistance of the hydraulic rubber pipe, thereby simultaneously having excellent weather resistance, waterproofness, corrosion resistance and aging resistance and the like, and can fully adapt to relatively complex application environments of the hydraulic rubber pipe such as outdoor environments, normal use of equipment is guaranteed, and the hydraulic rubber pipe has very excellent market prospects.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of rubber products, in particular to a high-weather-resistant hydraulic rubber pipe and a preparation method and application thereof. BACKGROUND

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

[0003] Because of the good performance and functionality of the hydraulic rubber pipe, it is widely used in oil field development, engineering construction, hoisting and transportation, metallurgical forging and pressing, mining equipment, shipbuilding, injection molding machinery, industrial automation hydraulic system and other fields. With the change of application fields, the performance requirements of the hydraulic rubber pipe are also different, but generally the bending performance, pressure resistance, temperature resistance and ozone resistance of the hydraulic rubber pipe need to be paid attention to in the design to meet the use requirements in different working conditions. SUMMARY

[0004] With the increasing application fields and environments of the hydraulic rubber pipe, the requirements for weather resistance, aging resistance and waterproofness of the hydraulic rubber pipe are also increasing, but the existing hydraulic rubber pipe pays less attention to the above-mentioned performance, and generally cannot balance the above-mentioned performance and take into account. Therefore, in order to effectively solve the above-mentioned problems, the present application provides a high-weather-resistant hydraulic rubber pipe and a preparation method thereof. The hydraulic rubber pipe prepared by the present application not only has good pressure resistance, temperature resistance and mechanical properties, but also can maintain excellent external environment resistance of the hydraulic rubber pipe, so as to simultaneously have excellent weather resistance, waterproofness, corrosion resistance and aging resistance and other performances. Especially, it can fully adapt to the relatively complex application environment of the hydraulic rubber pipe outdoors, ensure the normal use of the equipment, and has very excellent market prospect.

[0005] A high-weather-resistant hydraulic rubber pipe, which comprises an inner rubber layer located at the innermost side, an outer rubber layer located at 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, fluorine rubber 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 fluorine rubber.

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

[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 includes, in terms of mass parts, 20-45 parts of ethylene propylene diene rubber, 80-110 parts of chlorobutyl 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 rubber, the chlorobutyl rubber and the 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 rubber, the chlorobutyl rubber and the functional resin is (2.8-3):(9-9.5):(2-2.2).

[0019] As a preferred embodiment, the Mooney viscosity of the chlorobutyl rubber is 18-25 MU, condition M1+8 / 125℃.

[0020] As a preferred embodiment, the Mooney viscosity of the chlorobutyl rubber is 19-23 MU, condition M1+8 / 125℃.

[0021] In the present application, by adding chlorinated butyl rubber and ternary ethylene propylene rubber with specific viscosity, the weather resistance, water resistance, corrosion resistance and aging resistance of the hydraulic rubber pipe are greatly improved. The CL atoms in the added chlorinated butyl rubber can absorb the excess electrons in the system as strong polar atoms, reduce the content of active electrons in the system, and limit the complex impurity crosslinking reaction caused by the unsaturated double bond of the side chain of the ternary ethylene propylene rubber. The linear spiral long chain structure of the straight chain starch added with the above viscosity chlorinated butyl rubber can greatly increase the connection strength and tightness of the three-dimensional network of the internal colloid, thereby greatly inhibiting the frequent movement of internal active molecules in harsh environments, increasing the permeation resistance and permeation path of external active groups, active molecules and water molecules, and greatly improving the performance of the rubber material as a whole.

[0022] As a preferred embodiment, the preparation method of the functional resin comprises the following steps: S1: dissolving chlorinated polyethylene in a mixed solvent, adding chloroallyl glycidyl ether, 3-(2,3-epoxypropoxy) propyl methacrylate and sodium p-vinylbenzenesulfonate in three stages under nitrogen protection, and heating reaction; S2: adding amineated mica powder, adding to the reaction system by 3-4 times with a high-speed dispersing machine, and then high-temperature stirring and curing; S3: precipitating and separating with ethanol aqueous solution, washing with acetone and deionized water for 2-3 times after centrifugal separation, gradient drying, and sieving to obtain the product.

[0023] As a preferred embodiment, the preparation method of the functional resin comprises the following steps: S1: dissolving chlorinated polyethylene in a mixed solvent at 105-110°C, adding chloroallyl glycidyl ether and 50-60wt% initiator in one stage under nitrogen protection, stirring at 250-300rpm at 110-115°C for 2-3h, reducing the temperature to 90-95°C in the second stage, adding 3-(2,3-epoxypropoxy) propyl methacrylate and the remaining initiator, and reacting for 2-2.5h under ultrasonic assistance at 26-30kHz; S2: adding amineated mica powder, adding by 3 times with a high-speed dispersing machine with an interval of 15-20min, stirring and dispersing at a speed of 5000-6000rpm during the interval, and curing at 85-90°C for 2-3h; S3: precipitating and separating with ethanol aqueous solution, washing with acetone and deionized water for 2-3 times after centrifugal separation, vacuum drying at 50-60°C for 6-7h, hot air circulation drying at 75-80°C for 3-4h, and sieving with a 200-300 mesh sieve after completion to obtain the product.

[0024] As a preferred embodiment, the mass ratio of the chlorinated polyethylene, the chloroallyl glycidyl ether, the 3-(2,3-epoxypropoxy)propyl methacrylate and the 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 amineated mica powder is (10-12):(1.4-1.8).

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

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

[0028] As a preferred embodiment, the average particle size of the amineated 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 combination 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 combination 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 ether.

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

[0042] As a preferred embodiment, the auxiliary agent is a combination 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 epoxy soybean oil of vegetable oil.

[0047] As a preferred embodiment, the mass ratio of 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 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 comprises the following steps: S1: first add ethylene-propylene-diene rubber and chlorinated butyl rubber into the internal mixer and mix at 90-120°C for 3-5 min, then add stearic acid and functional resin to cool to 70-85°C and mix for 2-3 min; S2: add carbon material, solid filler, crosslinking agent, starch material and auxiliary agent, and heat to 130-140°C and mix for 2-4 min; S3: add the remaining raw materials, control the temperature at 90-110°C, mix for 3-5 min, and discharge at 95-100°C to obtain the outer rubber layer rubber material, and after natural cooling to room temperature, cut the rubber material to the required size.

[0050] The preparation method of the hydraulic hose with high weather resistance comprises the following steps: S1: using an extruder to extrude the inner rubber layer raw material and form a rubber hose, and wrapping the rubber hose on a hard core; S2: surrounding the rubber hose with multiple layers of steel wires on a braiding machine to form a reinforcing layer; S3: extruding the outer rubber layer rubber material and wrapping the reinforcing layer, and after the rubber hose with uniform thickness enters a vulcanization tank for high-temperature vulcanization, removing the water cloth and extracting the hard core, the hydraulic hose with high weather resistance is obtained.

[0051] The application further limits the application of the hydraulic hose with high weather resistance in oil field development, engineering construction, hoisting and transportation, metallurgical forging and pressing, mining equipment, shipbuilding, injection molding machinery, and industrial automatic hydraulic system.

[0052] The application has the following beneficial effects:

[0053] 1. The hydraulic hose with high weather resistance provided in the application not only has good pressure resistance, temperature resistance and mechanical properties, but also can maintain excellent external environment resistance of the hydraulic hose, thereby simultaneously having excellent weather resistance, waterproofness, corrosion resistance and aging resistance and other properties, and can fully adapt to complex hydraulic hose application environments such as outdoor environments, ensure normal use of equipment, and has very excellent market prospects.

[0054] 2. The hydraulic hose with high weather resistance provided in the application greatly improves the weather resistance, waterproofness, corrosion resistance and aging resistance and other properties of the hydraulic hose by adding chlorinated butyl rubber and terpolymer ethylene-propylene rubber with specific viscosity; the CL atoms in the added chlorinated butyl rubber can absorb excess electrons in the system as strong polar atoms, reduce the content of active electrons in the system, and limit the complex impurity crosslinking reaction caused by the unsaturated double bonds of the side chains of the terpolymer ethylene-propylene rubber; and the linear spiral long-chain structure of the added straight-chain starch under the above viscosity can greatly increase the connection strength and tightness of the three-dimensional network of the internal colloid, thereby greatly inhibiting the frequent movement of internal active molecules in harsh environments, increasing the permeation resistance and permeation path of external active groups, active molecules and water molecules, and greatly improving the overall performance of the rubber material.

[0055] 3. The hydraulic hose with high weather resistance provided in the application forms a large number of crosslinking sites by adding functional resin, and the double epoxy groups of 3-(2,3-epoxypropoxy) propyl methacrylate further form an interpenetrating network to improve the density and interaction force of the system; the amineated mica powder is arranged in parallel to the surface of the rubber hose (induced by processing shear force), forming a super-long-diameter labyrinth path to enhance the barrier force against water molecules, and finally through the ternary synergistic system of chemical crosslinking skeleton + physical barrier network + dynamic ionic bond, the mechanical properties, waterproofness and aging resistance of the hydraulic hose are greatly improved. DETAILED DESCRIPTION

[0056] The technical solutions in the above summary of the application will be further explained and demonstrated in the following detailed description of the embodiments.

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

[0058] Example 1

[0059] A hydraulic hose with high weather resistance, comprising: an inner rubber layer at the innermost side, an outer rubber layer at the outermost side, and a reinforcing layer between the inner rubber layer and the outer rubber layer.

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

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

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

[0063] The raw material of the outer rubber layer, in terms of mass parts, comprises: 28 parts of ethylene propylene diene 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 crosslinking agent, 11 parts of starch material, 6 parts of dispersing agent, 12.5 parts of auxiliary agent, 8.5 parts of lubricant, and 6 parts of dibutyl phthalate.

[0064] The ethylene propylene diene rubber is purchased from the product of model EPDM-3430 of Dow Chemical Company, 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 under the condition M1+8 / 125℃.

[0065] The preparation method of the functional resin comprises the following steps: S1: dissolving 10.5 parts of chlorinated polyethylene in a mixed solvent of xylene and cyclohexanone at 105°C (xylene: cyclohexanone = 3:1), protecting by nitrogen, adding 1.8 parts of chloroallyl glycidyl ether and 0.2 parts of dibenzoyl peroxide in one stage, stirring at 115°C and 250 rpm for 3h, reducing the temperature to 90°C in the second stage, adding 0.6 parts of 3-(2,3-epoxypropoxy) propyl methacrylate and 0.18 parts of dibenzoyl peroxide, and reacting for 2h, adding 0.5 parts of sodium vinylbenzenesulfonate in the third stage, and reacting for 1h under the assistance of ultrasonic waves at 28 kHz; S2: adding 1.5 parts of amine mica powder, adding by a high-speed dispersing machine for 3 times with an interval of 15 min, stirring and dispersing at a speed of 5000 rpm during the interval, and curing at 90°C for 2h; S3: precipitating and separating by ethanol aqueous solution, washing with acetone and deionized water for 3 times in sequence, vacuum drying at 55°C for 6h, hot air circulating drying at 75°C for 3h, and screening through a 200-mesh sieve after completion, to obtain the functional resin.

[0066] The chlorinated polyethylene is purchased from CPE 135A type product sold by Weifang Yaxing Chemical Company in China.

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

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

[0069] The starch material is a straight-chain starch with a straight-chain content of ≥70%, which is purchased from Shandong Xiya Chemical Co., Ltd.; and the dispersing agent is a lauryl alcohol polyoxyethylene ether, which is MOA-7 type product sold by Jiangsu Hai'an Petroleum.

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

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

[0072] The preparation method of the raw material of the outer rubber layer comprises the following steps: S1: first adding the ethylene-propylene-diene rubber and the chlorinated butyl rubber into the internal mixer, mixing at 100°C for 3.5 min, then adding stearic acid and the functional resin, and mixing at 80°C for 3 min; S2: adding the carbon material, the solid filler, the crosslinking agent, the starch material and the auxiliary agent, and mixing at 135°C for 2.5 min; S3: adding the remaining raw materials, controlling the temperature at 105°C, mixing for 4 min, discharging at 100°C, obtaining the outer rubber layer rubber material, and cutting the rubber material to the required size after natural cooling to room temperature.

[0073] The preparation method of the hydraulic hose with high weather resistance comprises the following steps: S1: extruding the inner rubber layer raw material at 165℃ using an extruder and forming a rubber hose, and wrapping it on a hard core; S2: wrapping the rubber hose on a braiding machine, and surrounding the rubber hose with multiple layers of steel wires to form a three-layer reinforcing layer; S3: extruding the outer rubber layer rubber material at 170℃, and wrapping it on the reinforcing layer, and after the rubber hose with uniform thickness enters a vulcanization tank for high-temperature vulcanization at 155℃, removing the water cloth, and extracting the hard core, the hydraulic hose with high weather resistance is obtained.

[0074] Embodiment 2

[0075] The hydraulic hose with high weather resistance comprises an inner rubber layer at the innermost side, an outer rubber layer at the outermost side, and a reinforcing layer between the inner rubber layer and the outer rubber layer.

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

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

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

[0079] The raw material of the outer rubber layer comprises, in mass parts, 35 parts of ethylene propylene diene monomer, 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 crosslinking agent, 11 parts of starch material, 6 parts of dispersing agent, 14 parts of auxiliary agent, 8.5 parts of lubricant, and 5.5 parts of dibutyl phthalate.

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

[0081] The preparation method of the functional resin comprises the following steps: S1: dissolving 10.5 parts of chlorinated polyethylene in a mixed solvent of xylene and cyclohexanone at 105°C (xylene: cyclohexanone = 3:1), protecting by nitrogen, adding 1.8 parts of chloroallyl glycidyl ether and 0.2 parts of dibenzoyl peroxide in one stage, stirring at 115°C and 250 rpm for 3h, reducing the temperature to 90°C in the second stage, adding 0.6 parts of 3-(2,3-epoxypropoxy) propyl methacrylate and 0.18 parts of dibenzoyl peroxide, and reacting for 2h, adding 0.5 parts of sodium vinylbenzenesulfonate in the third stage, and reacting for 1h under the assistance of ultrasonic waves at 28 kHz; S2: adding 1.5 parts of amine mica powder, adding by a high-speed dispersing machine for 3 times with an interval of 15 min, stirring and dispersing at a speed of 5000 rpm during the interval, and curing at 90°C for 2h; S3: precipitating and separating by ethanol aqueous solution, washing with acetone and deionized water for 3 times in sequence, vacuum drying at 55°C for 6h, hot air circulating drying at 75°C for 3h, and screening through a 200-mesh sieve after completion, to obtain the functional resin.

[0082] The chlorinated polyethylene is purchased from CPE 135A type product sold by Weifang Yaxing Chemical Company in China.

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

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

[0085] The starch material is a straight-chain starch with a straight-chain content of ≥70%, which is purchased from Shandong Xiya Chemical Co., Ltd.; and the dispersing agent is a lauryl alcohol polyoxyethylene ether, which is MOA-7 type product sold by Jiangsu Hai'an Petroleum.

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

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

[0088] The preparation method of the raw material of the outer rubber layer comprises the following steps: S1: first adding the ethylene-propylene-diene rubber and the chlorinated butyl rubber into the internal mixer, mixing at 100°C for 3.5 min, then adding stearic acid and the functional resin, and mixing at 80°C for 3 min; S2: adding the carbon material, the solid filler, the crosslinking agent, the starch material and the auxiliary agent, and mixing at 135°C for 2.5 min; S3: adding the remaining raw materials, controlling the temperature at 105°C, mixing for 4 min, discharging at 100°C, obtaining the outer rubber layer rubber material, and cutting the rubber material into the required size after natural cooling to room temperature.

[0089] A preparation method of the hydraulic hose with high weather resistance, the preparation method comprising the following steps: S1: extruding and forming a hose by using an extruder at 165 DEG C for an inner rubber layer raw material, and coating the hose on a hard core; S2: surrounding the hose with multiple layers of steel wires on a braiding machine to form a three-layer reinforcing layer; S3: extruding an outer rubber layer rubber material at 170 DEG C, and wrapping the reinforcing layer, and after the hose with uniform thickness enters a vulcanization tank for high-temperature vulcanization at 155 DEG C, removing a water cloth, and extracting the hard core, the hydraulic hose with high weather resistance is obtained.

[0090] Comparative Example 1

[0091] The comparative example is different from the example 1 only in that the raw material of the outer rubber layer comprises, in mass parts: ethylene-propylene-diene rubber 35 parts, chlorinated butyl rubber 100 parts, functional resin 8 parts, stearic acid 4 parts, carbon material 14 parts, solid filler 35 parts, crosslinking agent 2.5 parts, starch material 11 parts, dispersant 6 parts, auxiliary agent 14 parts, lubricant 8.5 parts, and dibutyl phthalate 5.5 parts.

[0092] Comparative Example 2

[0093] The comparative example is different from the example 1 only in that the raw material of the outer rubber layer comprises, in mass parts: ethylene-propylene-diene rubber 55 parts, chlorinated butyl rubber 60 parts, functional resin 25 parts, stearic acid 4 parts, carbon material 14 parts, solid filler 35 parts, crosslinking agent 2.5 parts, starch material 11 parts, dispersant 6 parts, auxiliary agent 14 parts, lubricant 8.5 parts, and dibutyl phthalate 5.5 parts.

[0094] Comparative Example 3

[0095] The comparative example is different from the example 1 only in that the chlorinated butyl rubber is purchased from Shanghai Yingting Industry Co., Ltd., and the average Mooney viscosity thereof is 28.5 MU, and the condition M1+8 / 125 DEG C.

[0096] Comparative Example 4

[0097] The comparative example embodiment differs from example 1 only in that the preparation method of the functional resin comprises the following steps, in mass parts: S1 : 10.5 parts of chlorinated polyethylene is dissolved in a mixed solvent of xylene and cyclohexanone (xylene: cyclohexanone = 3:1) at 105°C, under nitrogen protection, 3.5 parts of chloroallyl glycidyl ether and 0.2 parts of dibenzoyl peroxide are added in one stage, stirred at 250 rpm at 115°C for 3h, the temperature is reduced to 90°C in the second stage, 0.2 parts of 3-(2,3-epoxypropoxy) propyl methacrylate and 0.18 parts of dibenzoyl peroxide are added, and the reaction is incubated for 2h; S2: 1.5 parts of amine mica powder is added, added by high-speed disperser for 3 times with 15 min interval, stirred and dispersed at 5000 rpm during the interval, and incubated at 90°C for 2h; S3: precipitated with ethanol aqueous solution, washed with acetone and deionized water for 3 times after centrifugal separation, vacuum dried at 55°C for 6h, hot air circulation dried at 75°C for 3h, and then sieved through a 200 mesh sieve to obtain the product.

[0098] Comparative example 5

[0099] The comparative example embodiment differs from example 1 only in that the preparation method of the functional resin comprises the following steps, in mass parts: S1 : 10.5 parts of chlorinated polyethylene is dissolved in a mixed solvent of xylene and cyclohexanone (xylene: cyclohexanone = 3:1) at 105°C, under nitrogen protection, 3.5 parts of chloroallyl glycidyl ether and 0.2 parts of dibenzoyl peroxide are added in one stage, stirred at 250 rpm at 115°C for 3h, the temperature is reduced to 90°C in the second stage, 0.2 parts of 3-(2,3-epoxypropoxy) propyl methacrylate and 0.18 parts of dibenzoyl peroxide are added, and the reaction is incubated for 2h; S2: 1.5 parts of amine mica powder is added, added by high-speed disperser for 3 times with 15 min interval, stirred and dispersed at 5000 rpm during the interval, and incubated at 90°C for 2h; S3: precipitated with ethanol aqueous solution, washed with acetone and deionized water for 3 times after centrifugal separation, vacuum dried at 55°C for 6h, hot air circulation dried at 75°C for 3h, and then sieved through a 200 mesh sieve to obtain the product.

[0100] Comparative example 6

[0101] The comparative example embodiment differs from example 1 only in that the average particle size of the amine mica powder is 12.5 μm.

[0102] Performance evaluation

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

[0104] 2. Aging resistance: The outer rubber layer prepared from the examples and comparative examples was stored at 65°C and 75% relative humidity for 3 months, then taken out and tested for elongation at break according to performance test 1 after 3 months, and the retention rate of elongation at break of the outer rubber layer was recorded after testing, the retention rate % = elongation at break after 3 months / original elongation at break x 100%, the test values were taken as the average of 10 tests and recorded in Table 1.

[0105] 3. Water resistance: The water absorption resistance of the outer rubber layer prepared from the examples and comparative examples was tested, which was tested according to ASTM D-570 standard after being placed in water at 50°C for 48 hours, and the test values were taken as the average of 10 tests and recorded in Table 1.

[0106] Table 1 Performance evaluation table

[0107]

[0108]

[0109] From the data results of the examples and comparative examples of the present application and Table 1, it can be seen that the examples 1 and 2 of the present application have obvious performance advantages in mechanical properties, aging resistance, water resistance and the like compared with comparative examples 1-6. The functional resin prepared by the better technical scheme of examples 1 and 2 can form a large number of crosslinking sites, and the double epoxy groups of 3-(2,3-epoxypropoxy) propyl methacrylate further form an interpenetrating network to improve the density and interaction force of the system; the amineized mica powder is arranged in parallel to the surface of the rubber tube (induced by processing shear force), forming a labyrinth path with a super-long aspect ratio, enhancing the barrier force to water molecules, and finally through the ternary synergistic system of chemical crosslinking skeleton + physical barrier network + dynamic ionic bond, the mechanical properties, water resistance and aging resistance of the hydraulic rubber tube are greatly improved.

Claims

1. A hydraulic hose having high weather resistance, characterized by: The structure of the hydraulic rubber tube comprises an inner rubber layer at the innermost side, an outer rubber layer at the outermost side, and a reinforcing layer between the inner rubber layer and the outer rubber layer; The raw materials of the outer rubber layer include, in mass parts, 20-45 parts of ethylene-propylene-diene 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; The mass ratio of the ethylene-propylene-diene rubber, the chlorinated butyl rubber and the functional resin is (2.5-3.5):(9-10):(2-2.4); the chlorinated butyl rubber has a Mooney viscosity of 18-25 MU under the condition M1+8 / 125℃; The preparation method of the functional resin comprises the following steps: S1: dissolving chlorinated polyethylene in a mixed solvent at 105-110℃, protecting by nitrogen, adding chloroallyl glycidyl ether and 50-60wt% initiator in one stage, stirring at 250-300rpm at 110-115℃ for 2-3h, reducing the temperature to 90-95℃ in the second stage, adding 3-(2,3-epoxypropoxy) propyl methacrylate and adding the remaining initiator, and incubating for 2-2.5h, adding sodium p-vinylbenzenesulfonate in the third stage, incubating for 1-1.5h under the assistance of ultrasonic waves at 26-30kHz; S2: adding amineated mica powder, adding by 3 times with a high-speed dispersion machine, with an interval of 15-20min each time, stirring and dispersing at a speed of 5000-6000rpm during the interval, and curing at 85-90℃ for 2-3h; S3: precipitating and separating by ethanol aqueous solution, washing with acetone and deionized water in sequence for 2-3 times after centrifugal separation, vacuum drying at 50-60℃ for 6-7h, hot air circulating drying at 75-80℃ for 3-4h, and sieving through a 200-300 mesh sieve after completion, to obtain the product; The mass ratio of the chlorinated polyethylene, the chloroallyl glycidyl ether, the 3-(2,3-epoxypropoxy) propyl methacrylate and the sodium p-vinylbenzenesulfonate is (10-12):(1.5-2):(0.5-0.8):(0.4-0.6); The average particle size of the amineated mica powder is 4-6μm.

2. The hydraulic hose of claim 1, wherein: The raw material of the inner rubber layer is nitrile rubber or chlorobutyl rubber; the raw material of the reinforcing layer is steel wire.

3. The hydraulic hose of claim 2, wherein: The mass ratio of the chlorinated polyethylene and the amineated mica powder is (10-12):(1.4-1.8).

4. The hydraulic hose of claim 3, wherein: The carbon material is at least one of carbon nanotube, carbon black, graphene, graphene oxide and carbon powder.

5. The hydraulic hose of claim 4, wherein: The solid filler is a combination of sericite powder and zinc oxide, and the mass ratio of the sericite powder and the zinc oxide is (5-6):(0.8-1).

6. A method of producing the hydraulic hose according to any one of claims 1 to 5, characterized by: The preparation method comprises the following steps: S1, extruding the inner rubber layer raw material by using an extruder and forming a rubber tube, and coating the rubber tube on a hard core; S2, surrounding the rubber tube outside with multiple layers of steel wires on a braiding machine to form a reinforcing layer; S3, extruding the outer rubber layer rubber material and wrapping the reinforcing layer, and after the rubber tube with uniform thickness enters a vulcanizing tank for high-temperature vulcanization, removing the water cloth and extracting the hard core, the rubber tube is obtained.

7. Application of the high-weather-resistant hydraulic rubber tube according to any one of claims 1-5 to oil field development, engineering construction, hoisting and transportation, metallurgical forging and pressing, mining equipment, shipbuilding, injection molding machinery and industrial automatic hydraulic system.

Images