Composite hose for ocean engineering and preparation method thereof
By using high-density polyethylene and cross-linked acrylate as the main materials and combining the cross-linking modification of functional fillers, the outer sheath of the marine engineering hose is prepared, which solves the problem of the outer sheath material's mechanical properties declining in high and low temperature environments and achieves improved high and low temperature adaptability and temperature stability of the material.
Patent Information
- Application Number
- CN202510657158.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-21
- Publication Date
- 2025-09-09
AI Technical Summary
The outer sheath material of existing marine engineering hoses has reduced mechanical properties in an environment with alternating high and low temperatures, and is prone to brittleness or cracking, which shortens its service life.
High-density polyethylene and cross-linked acrylate are used as the main materials, and through cross-linking modification treatment, functional fillers are added to prepare the outer sheath material to form an interpenetrating structure to improve the high and low temperature adaptability and temperature stability of the material.
It improves the mechanical properties and temperature stability of the material in high and low temperature environments, and extends the service life of marine engineering hoses.
Smart Images
Figure BDA0005412770390000101 
Figure BDA0005412770390000111
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of marine engineering hoses, and in particular relates to a composite hose for marine engineering and a preparation method thereof. Background Art
[0002] Marine engineering hose is a flexible pipe designed specifically for the marine environment, mainly used for offshore oil exploration, mining, production and transportation.
[0003] Marine engineering hoses consist of an inner liner, a reinforcement layer, and an outer sleeve. High-density polyethylene (HDPE) is commonly used as the outer sheath material, offering excellent flexibility, wear resistance, and corrosion resistance. As the outermost layer of the hose, the outer sheath material also needs to exhibit high temperature stability, maintaining high mechanical strength and sealing properties within its operating temperature range. Existing technologies experience significant degradation in mechanical properties of outer sheath materials in environments subject to alternating high and low temperatures, leading to embrittlement or cracking, severely impacting the hose's service life. Summary of the Invention
[0004] In order to solve the problems existing in the background technology, the present invention provides a composite hose for marine engineering and a preparation method thereof. The composite hose material prepared has high temperature stability, can maintain high mechanical strength in a high and low temperature alternating environment, and extend its service life.
[0005] In order to achieve the above object, the present invention provides the following technical solutions:
[0006] A composite hose for marine engineering consists of an outer sheath and an inner structural layer. The outer sheath is prepared from the following raw materials, in parts by weight: 100 parts of high-density polyethylene resin, 15-25 parts of cross-linked acrylic resin, 3-5 parts of functional filler, 2-3 parts of dispersant, 1.5-2.5 parts of plasticizer, 0.8-1.2 parts of lubricant, and 0.5-1 part of antioxidant; wherein the functional filler is prepared by modifying the filler with pyridinethioglycolic acid and dilauryl thiodipropionate.
[0007] The preparation process of the outer sheath comprises the following steps:
[0008] S1. The high-density polyethylene resin and cross-linked acrylic resin were preheated to 135-145 ℃, stirred and added to a vacuum kneader and kneaded for 5-10 minutes at a kneading temperature of 165-175 ℃ to obtain a resin mixture;
[0009] S2. Add other raw materials to the resin mixture, stir evenly under vacuum, and then add it to the extruder for melt extrusion to obtain a tube, which is then sizing and cooling to obtain the outer sheath.
[0010] Furthermore, the preparation of the functional filler includes the following steps:
[0011] 10 parts of inorganic filler are placed in anhydrous ethanol to obtain a dispersion with a concentration of 20-30%, 0.5-1 parts of 4-pyridinethioacetic acid are added to the dispersion, the temperature is raised to 50-60°C, stirred for 20-40 minutes, filtered, dried, added to 40-60 parts of deionized water, ultrasonically dispersed for 5-10 minutes, 0.4-0.6 parts of dilauryl thiodipropionate are added, the temperature is heated to 65-75°C, the reaction is carried out for 1-2 hours, cooled to room temperature, filtered, and dried to obtain a functional filler.
[0012] Furthermore, the cross-linked acrylic resin is prepared by the following method:
[0013] Add 10 parts of acrylic acid ester monomer, 0.1-0.2 parts of azobisisobutyronitrile and 0.05-0.15 parts of sodium lauryl sulfate to 40-60 parts of water, stir evenly, add 0.8-1.2 parts of di-tert-butyl hydroperoxide and 2-3 parts of tetrabutyl titanate, and carry out polymerization reaction under nitrogen protection at a stirring rate of 200-300 r / min, a reaction temperature of 60-70°C, and a reaction time of 2-3 hours to obtain a cross-linked acrylic resin.
[0014] Furthermore, the acrylic acid ester monomer is one or a mixture of two or more of methyl methacrylate, methyl acrylate, butyl methacrylate and butyl acrylate.
[0015] Furthermore, the dispersant is one of stearic acid and ethylene stearamide or a mixture of the two.
[0016] Furthermore, the plasticizer is one of epoxidized soybean oil and glycerin or a mixture of the two.
[0017] Furthermore, the lubricant is one or a mixture of two or more of calcium stearate, zinc stearate and barium stearate.
[0018] Furthermore, the antioxidant is one of the antioxidant 1010, the antioxidant 1076 and the antioxidant 168, or a mixture of two or more thereof.
[0019] Furthermore, the inorganic filler is talc.
[0020] A method for preparing a composite hose for marine engineering, used for preparing the composite hose for marine engineering of the above scheme, comprises the following steps: preparing a pipe inner lining layer, a reinforcement layer and an outer sleeve respectively, and then assembling the structural layers into one to obtain a composite hose for marine engineering.
[0021] This application has the following beneficial effects:
[0022] 1. This application uses high-density polyethylene and cross-linked acrylate as the main materials. The addition of cross-linked acrylate can effectively promote the compatibility between the components in the system and improve the mechanical properties of the material at high and low temperatures. By adding functional fillers, an interpenetrating structure is formed between the components, which can improve the high and low temperature adaptability of the material. The final material has good high and low temperature resistance and excellent temperature stability.
[0023] 2. The cross-linking modification of acrylate has a good volume-increasing effect, which can promote the mutual mixing of the resin matrix and other substances, so that the temperature stability of the final outer sheath material is significantly improved. Functional treatment of the filler can not only improve the stability of the filler, but also help to improve the dispersion ability of the filler, making it more bonded with the main blending material and other raw materials, and significantly improving the temperature stability of the final material. DETAILED DESCRIPTION
[0024] The present application is further described in detail below with reference to the embodiments.
[0025] Unless otherwise specified, the raw materials used in the examples and comparative examples of the present application are all commercially available.
[0026] Example 1
[0027] A composite hose for marine engineering consists of an outer sheath and an inner structural layer. The inner structural layer includes an inner lining layer and a reinforcement layer. The inner lining layer, reinforcement layer and outer sleeve of the pipe are prepared separately, and then the structural layers are assembled into one to obtain a composite hose for marine engineering.
[0028] The outer sheath is prepared from the following raw materials: 100 parts of high-density polyethylene resin, 20 parts of cross-linked acrylic resin, 4 parts of functional filler, 2.5 parts of stearic acid, 2 parts of epoxidized soybean oil, 1 part of calcium stearate and 0.8 parts of antioxidant 1010.
[0029] The preparation of the outer sheath comprises the following steps:
[0030] S1. The high-density polyethylene resin and cross-linked acrylic resin were preheated to 140 ℃, stirred and added to a vacuum kneader and kneaded for 8 minutes at a kneading temperature of 170 ℃ to obtain a resin mixture;
[0031] S2. Add other raw materials to the resin mixture, stir evenly under vacuum, and then add it to the extruder for melt extrusion to obtain a tube, which is then sizing and cooling to obtain the outer sheath.
[0032] The preparation of the functional filler includes the following contents:
[0033] 10 parts of talc powder were placed in anhydrous ethanol to obtain a dispersion with a concentration of 25%, 0.8 parts of 4-pyridinethioacetic acid were added to the dispersion, the temperature was raised to 55°C, stirred for 30 minutes, filtered, dried, added to 50 parts of deionized water, ultrasonically dispersed for 5 minutes, 0.5 parts of dilauryl thiodipropionate were added, the mixture was heated to 70°C, reacted for 2 hours, cooled to room temperature, filtered, and dried to obtain a functional filler.
[0034] The cross-linked acrylic resin is prepared by the following method:
[0035] Add 10 parts of methyl methacrylate, 0.15 parts of azobisisobutyronitrile and 0.1 parts of sodium lauryl sulfate to 50 parts of water and stir evenly. Add 1 part of di-tert-butyl hydroperoxide and 2.5 parts of tetrabutyl titanate, and carry out polymerization reaction under nitrogen protection at a stirring rate of 240 r / min, a reaction temperature of 65°C, and a reaction time of 2.5 h to obtain a cross-linked acrylic resin.
[0036] Example 2
[0037] A composite hose for marine engineering consists of an outer sheath and an inner structural layer. The inner structural layer includes an inner lining layer and a reinforcement layer. The inner lining layer, reinforcement layer and outer sleeve of the pipe are prepared separately, and then the structural layers are assembled into one to obtain a composite hose for marine engineering.
[0038] The outer sheath is prepared from the following raw materials: 100 parts of high-density polyethylene resin, 15 parts of cross-linked acrylic resin, 3 parts of functional filler, 2 parts of ethylene stearamide, 1.5 parts of glycerin, 0.8 parts of zinc stearate and 0.5 parts of antioxidant 1076.
[0039] The preparation of the outer sheath comprises the following steps:
[0040] S1. The high-density polyethylene resin and cross-linked acrylic resin were preheated to 135 ℃, stirred and added to a vacuum kneader and kneaded for 10 minutes at a kneading temperature of 165 ℃ to obtain a resin mixture;
[0041] S2. Add other raw materials to the resin mixture, stir evenly under vacuum, and then add it to the extruder for melt extrusion to obtain a tube, which is then sizing and cooling to obtain the outer sheath.
[0042] The preparation of the functional filler includes the following contents:
[0043] 10 parts of talc powder were placed in anhydrous ethanol to obtain a dispersion with a concentration of 20%, 0.5 parts of 4-pyridinethioacetic acid were added to the dispersion, the temperature was raised to 50°C, stirred for 40 minutes, filtered, dried, added to 40 parts of deionized water, ultrasonically dispersed for 10 minutes, 0.4 parts of dilauryl thiodipropionate were added, the mixture was heated to 65°C, reacted for 2 hours, cooled to room temperature, filtered, and dried to obtain a functional filler.
[0044] The cross-linked acrylic resin is prepared by the following method:
[0045] Add 10 parts of methyl acrylate, 0.1 parts of azobisisobutyronitrile and 0.05 parts of sodium lauryl sulfate to 40 parts of water and stir evenly. Add 0.8 parts of di-tert-butyl hydroperoxide and 2 parts of tetrabutyl titanate, and carry out polymerization reaction under nitrogen protection at a stirring rate of 200 r / min, a reaction temperature of 60°C, and a reaction time of 3 hours to obtain a cross-linked acrylic resin.
[0046] Example 3
[0047] A composite hose for marine engineering consists of an outer sheath and an inner structural layer. The inner structural layer includes an inner lining layer and a reinforcement layer. The inner lining layer, reinforcement layer and outer sleeve of the pipe are prepared separately, and then the structural layers are assembled into one to obtain a composite hose for marine engineering.
[0048] The outer sheath is prepared from the following raw materials: 100 parts of high-density polyethylene resin, 25 parts of cross-linked acrylic resin, 5 parts of functional filler, 3 parts of stearic acid, 2.5 parts of glycerin, 1.2 parts of barium stearate and 1 part of antioxidant 168.
[0049] The preparation of the outer sheath comprises the following steps:
[0050] S1. The high-density polyethylene resin and cross-linked acrylic resin were preheated to 145 ℃, stirred and added to a vacuum kneader and kneaded for 10 minutes at a kneading temperature of 165 ℃ to obtain a resin mixture;
[0051] S2. Add other raw materials to the resin mixture, stir evenly under vacuum, and then add it to the extruder for melt extrusion to obtain a tube, which is then sizing and cooling to obtain the outer sheath.
[0052] The preparation of the functional filler includes the following contents:
[0053] 10 parts of talc powder were placed in anhydrous ethanol to obtain a dispersion with a concentration of 30%, 1 part of 4-pyridinethioacetic acid was added to the dispersion, the temperature was raised to 60°C, stirred for 20 minutes, filtered, dried, added to 60 parts of deionized water, ultrasonically dispersed for 10 minutes, 0.6 parts of dilauryl thiodipropionate were added, the mixture was heated to 75°C, reacted for 1 hour, cooled to room temperature, filtered, and dried to obtain a functional filler.
[0054] The cross-linked acrylic resin is prepared by the following method:
[0055] Add 10 parts of butyl acrylate, 0.2 parts of azobisisobutyronitrile and 0.15 parts of sodium lauryl sulfate to 60 parts of water and stir evenly. Then add 1.2 parts of di-tert-butyl hydroperoxide and 3 parts of tetrabutyl titanate. Under nitrogen protection, carry out polymerization reaction at a stirring rate of 300 r / min, a reaction temperature of 70°C and a reaction time of 2 h to obtain a cross-linked acrylic resin.
[0056] Example 4
[0057] A composite hose for marine engineering consists of an outer sheath and an inner structural layer. The inner structural layer includes an inner lining layer and a reinforcement layer. The inner lining layer, reinforcement layer and outer sleeve of the pipe are prepared separately, and then the structural layers are assembled into one to obtain a composite hose for marine engineering.
[0058] The outer sheath is prepared from the following raw materials: 100 parts of high-density polyethylene resin, 15 parts of cross-linked acrylic resin, 5 parts of functional filler, 2 parts of ethylene stearamide, 2.5 parts of epoxy soybean oil, 0.8 parts of calcium stearate and 1 part of antioxidant 1010.
[0059] The preparation of the outer sheath comprises the following steps:
[0060] S1. The high-density polyethylene resin and cross-linked acrylic resin were preheated to 135 ℃, stirred and added to a vacuum kneader and kneaded for 5 minutes at a kneading temperature of 175 ℃ to obtain a resin mixture;
[0061] S2. Add other raw materials to the resin mixture, stir evenly under vacuum, and then add it to the extruder for melt extrusion to obtain a tube, which is then sizing and cooling to obtain the outer sheath.
[0062] The preparation of the functional filler includes the following contents:
[0063] 10 parts of talc powder were placed in anhydrous ethanol to obtain a dispersion with a concentration of 20%, 1 part of 4-pyridinethioacetic acid was added to the dispersion, the temperature was raised to 50°C, stirred for 40 minutes, filtered, dried, added to 40 parts of deionized water, ultrasonically dispersed for 10 minutes, 0.4 parts of dilauryl thiodipropionate were added, the mixture was heated to 75°C, reacted for 1 hour, cooled to room temperature, filtered, and dried to obtain a functional filler.
[0064] The cross-linked acrylic resin is prepared by the following method:
[0065] 10 parts of butyl methacrylate, 0.1 parts of azobisisobutyronitrile and 0.15 parts of sodium lauryl sulfate were added to 40 parts of water and stirred evenly. 0.8 parts of di-tert-butyl hydroperoxide and 3 parts of tetrabutyl titanate were added, and polymerization reaction was carried out under nitrogen protection at a stirring rate of 200 r / min, a reaction temperature of 70°C, and a reaction time of 2 h to obtain a cross-linked acrylic resin.
[0066] Example 5
[0067] A composite hose for marine engineering consists of an outer sheath and an inner structural layer. The inner structural layer includes an inner lining layer and a reinforcement layer. The inner lining layer, reinforcement layer and outer sleeve of the pipe are prepared separately, and then the structural layers are assembled into one to obtain a composite hose for marine engineering.
[0068] The outer sheath is prepared from the following raw materials: 100 parts of high-density polyethylene resin, 20 parts of cross-linked acrylic resin, 4 parts of functional filler, 2 parts of dispersant ethylene stearamide, 2.5 parts of glycerin, 1 part of zinc stearate and 0.5 parts of antioxidant 168).
[0069] The preparation of the outer sheath comprises the following steps:
[0070] S1. The high-density polyethylene resin and cross-linked acrylic resin were preheated to 140 ℃, stirred and added to a vacuum kneader and kneaded for 5 minutes at a kneading temperature of 165 ℃ to obtain a resin mixture;
[0071] S2. Add other raw materials to the resin mixture, stir evenly under vacuum, and then add it to the extruder for melt extrusion to obtain a tube, which is then sizing and cooling to obtain the outer sheath.
[0072] The preparation of the functional filler includes the following contents:
[0073] 10 parts of talc powder were placed in anhydrous ethanol to obtain a dispersion with a concentration of 30%, 0.5 parts of 4-pyridinethioacetic acid were added to the dispersion, the temperature was raised to 55°C, stirred for 40 minutes, filtered, dried, added to 50 parts of deionized water, ultrasonically dispersed for 5 minutes, 0.6 parts of dilauryl thiodipropionate were added, the mixture was heated to 65°C, reacted for 2 hours, cooled to room temperature, filtered, and dried to obtain a functional filler.
[0074] The cross-linked acrylic resin is prepared by the following method:
[0075] Add 10 parts of methyl methacrylate, 0.15 parts of azobisisobutyronitrile and 0.15 parts of sodium lauryl sulfate to 60 parts of water and stir evenly. Then add 0.8 parts of di-tert-butyl hydroperoxide and 2.5 parts of tetrabutyl titanate. Polymerization reaction is carried out under nitrogen protection at a stirring rate of 240 r / min, a reaction temperature of 70°C and a reaction time of 2 h to obtain a cross-linked acrylic resin.
[0076] Comparative Example 1
[0077] The difference between this comparative example and Example 1 is that no cross-linking modification treatment is performed during the preparation of the cross-linked acrylic resin. Specifically, the cross-linked acrylic resin is prepared by the following method:
[0078] Add 10 parts of methyl methacrylate, 0.15 parts of azobisisobutyronitrile and 0.1 parts of sodium lauryl sulfate to 50 parts of water, stir evenly, and carry out polymerization reaction under nitrogen protection at a stirring rate of 240 r / min, a reaction temperature of 65°C, and a reaction time of 2.5 h to obtain a cross-linked acrylic resin.
[0079] Comparative Example 2
[0080] The only difference between this comparative example and Example 1 is that the functional filler in the raw material of the outer sheath is replaced with ordinary talc. Specifically, the outer sheath is prepared from the following raw materials: 100 parts of high-density polyethylene resin, 20 parts of cross-linked acrylic resin, 4 parts of talc, 2.5 parts of stearic acid, 2 parts of epoxy soybean oil, 1 part of calcium stearate and 0.8 parts of antioxidant 1010.
[0081] Comparative Example 3
[0082] The only difference between this comparative example and Example 1 is that no cross-linking modification treatment is performed in the preparation of the cross-linked acrylic resin, and the functional filler in the outer sheath raw material is replaced with ordinary talc.
[0083] Proven effectiveness
[0084] Temperature Stability Test: Samples were prepared from the outer sheath materials prepared in Examples 1-5 and Comparative Examples 1-3. Each set of samples was placed in a -20°C environment for 10 hours, then removed and placed at room temperature for 4 hours, and then placed in a 40°C environment for 10 hours. This constituted one cycle. 30 cycles were repeated, and the tensile strength retention of the samples after 30 cycles was measured. The specific results are shown in Table 1:
[0085] Table 1
[0086]
[0087]
[0088] Result Analysis
[0089] By analyzing Examples 1-5 and Comparative Examples 1-3 and combining the data in Table 1, it can be seen that the outer sheath material of the composite hose for marine engineering provided in the present application has a high tensile strength retention rate after 30 high and low temperature cycles, indicating that the material has good high and low temperature resistance and high temperature stability.
[0090] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.
[0091] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.
Claims
1. A composite hose for marine engineering, consisting of an outer sheath and an inner structural layer, characterized in that: The outer sheath is prepared from the following raw materials in parts by weight: 100 parts of high-density polyethylene resin, 15-25 parts of cross-linked acrylic resin, 3-5 parts of functional filler, 2-3 parts of dispersant, 1.5-2.5 parts of plasticizer, 0.8-1.2 parts of lubricant and 0.5-1 part of antioxidant; The functional filler is prepared by modifying the filler with pyridinethioglycolic acid and dilauryl thiodipropionate; The outer sheath is prepared by the following steps: S1. The high-density polyethylene resin and cross-linked acrylic resin were preheated to 135-145 ℃, stirred and added to a vacuum kneader and kneaded for 5-10 minutes at a kneading temperature of 165-175 ℃ to obtain a resin mixture; S2. Add other raw materials to the resin mixture, stir evenly under vacuum, and then add it to the extruder for melt extrusion to obtain a tube, which is then sizing and cooling to obtain the outer sheath.
2. A composite hose for marine engineering according to claim 1, characterized in that: The preparation of the functional filler includes the following contents: 10 parts of inorganic filler are placed in anhydrous ethanol to obtain a dispersion with a concentration of 20-30%, 0.5-1 parts of 4-pyridinethioacetic acid are added to the dispersion, the temperature is raised to 50-60°C, stirred for 20-40 minutes, filtered, dried, added to 40-60 parts of deionized water, ultrasonically dispersed for 5-10 minutes, 0.4-0.6 parts of dilauryl thiodipropionate are added, the temperature is heated to 65-75°C, the reaction is carried out for 1-2 hours, cooled to room temperature, filtered, and dried to obtain a functional filler.
3. The composite hose for marine engineering according to claim 1, characterized in that: The cross-linked acrylic resin is prepared by the following method: Add 10 parts of acrylic acid ester monomer, 0.1-0.2 parts of azobisisobutyronitrile and 0.05-0.15 parts of sodium lauryl sulfate to 40-60 parts of water, stir evenly, add 0.8-1.2 parts of di-tert-butyl hydroperoxide and 2-3 parts of tetrabutyl titanate, and carry out polymerization reaction under nitrogen protection at a stirring rate of 200-300 r / min, a reaction temperature of 60-70°C, and a reaction time of 2-3 hours to obtain a cross-linked acrylic resin.
4. A composite hose for marine engineering according to claim 3, characterized in that: The acrylic acid ester monomer is one or a mixture of two or more of methyl methacrylate, methyl acrylate, butyl methacrylate and butyl acrylate.
5. The composite hose for marine engineering according to claim 1, characterized in that: The dispersant is one of stearic acid and ethylene stearamide or a mixture of the two.
6. The composite hose for marine engineering according to claim 1, characterized in that: The plasticizer is one of epoxidized soybean oil and glycerin or a mixture of the two.
7. The composite hose for marine engineering according to claim 1, characterized in that: The lubricant is one or a mixture of two or more of calcium stearate, zinc stearate and barium stearate.
8. The composite hose for marine engineering according to claim 1, characterized in that: The antioxidant is one of antioxidant 1010, antioxidant 1076 and antioxidant 168, or a mixture of two or more thereof.
9. The composite hose for marine engineering according to claim 1, characterized in that: The inorganic filler is talc.
10. A method for preparing a composite hose for marine engineering, for preparing the composite hose for marine engineering according to any one of claims 1 to 9, characterized in that: The preparation method is as follows: a pipe inner lining layer, a reinforcement layer and an outer sleeve are prepared separately, and then the structural layers are assembled into one body to obtain a composite hose for marine engineering.