Anti-aging encapsulated control line and method of making same

Abstract

The application discloses an anti-aging packaging control pipeline and a preparation method thereof, and belongs to the technical field of curing resin, and comprises an inner layer of a stainless steel seamless pipe and an outer layer of a barrier layer; the outer layer of the barrier layer comprises the following components in percentage by weight: 70-90 parts of a base resin, 10-30 parts of a composite filler, 0.3-0.8 parts of a stabilizer, 0.1-0.3 parts of an antioxidant, and 1-2.2 parts of a colorant. The application improves the dispersibility and compatibility of the filler in the base resin by treating the montmorillonite and carbon black composite filler with a silane coupling agent, thereby improving the high-temperature aging resistance of the pipeline and reducing the performance attenuation in a high-temperature environment. The CSB@Fe3O4 NPs effectively delay the material aging caused by ultraviolet radiation, thereby improving the ultraviolet resistance of the pipeline. Meanwhile, the montmorillonite and carbon black treated with the silane coupling agent have a synergistic effect with the CSB@Fe3O4 NPs, and the two improve the salt spray corrosion resistance of the material from different dimensions, reduce the corrosion and damage of the pipeline in a salt spray environment, and further expand the service life of the pipeline in a complex environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of curing resin, in particular to an anti-aging packaging control pipeline and a preparation method thereof. BACKGROUND

[0002] The packaging control pipeline is a key component for conveying, distributing or sealing various fluids (such as gas, liquid, colloid, slurry, high-purity medium or corrosive chemicals) in precision manufacturing processes, and its core function is to achieve high-precision transmission of the medium, pressure stability control, effective environmental isolation and long-term operation reliability guarantee.

[0003] In many industrial fields, such as chemical processes, ocean engineering, high-end medical equipment, food and beverages, the packaging control pipeline not only needs to withstand harsh working conditions such as high pressure and high temperature, but also needs to be exposed to external complex environmental factors (such as strong ultraviolet radiation, salt spray, etc.) for a long time.

[0004] The common packaging control pipeline in the prior art is prone to deformation and creep under high pressure and high temperature, and has insufficient mechanical strength and rigidity, and is prone to material aging when exposed to external environments such as ultraviolet light for a long time, which leads to sealing failure, medium leakage or increased pollution risk, and limited service life.

[0005] Therefore, the skilled in the art is committed to developing an anti-aging packaging control pipeline and a preparation method thereof to solve the above problems. SUMMARY

[0006] In view of the above defects of the prior art, the technical problem to be solved by the present application is that the packaging control pipeline is prone to deformation and creep under high pressure and high temperature, and has insufficient mechanical strength and rigidity, and is prone to material aging when exposed to external environments such as ultraviolet light for a long time, which leads to sealing failure, medium leakage or increased pollution risk, and limited service life.

[0007] To achieve the above purpose, the present application provides an anti-aging packaging control pipeline, which comprises an inner layer of stainless steel seamless pipe and an outer layer of barrier layer.

[0008] The outer layer barrier layer comprises the following components by weight: 70-90 parts of base resin, 10-30 parts of composite filler, 0.3-0.8 parts of stabilizer, 0.1-0.3 parts of antioxidant and 1-2.2 parts of colorant;

[0009] The base resin is composed of polypropylene resin and polyamide resin in a mass ratio of 3-5:4-8;

[0010] The composite filler is obtained by treating montmorillonite and carbon black in a mass ratio of 1:1.8-2.4 with a silane coupling agent;

[0011] The mass ratio of CSB@Fe3O4 NPs, polyethylene wax, calcium stearate, zinc stearate, epoxy soybean oil and pentaerythritol in the stabilizer is 2-5:1-3:5-10:3-6:4-8:2-5.

[0012] A preparation method of the anti-aging encapsulation control pipeline, comprising the following steps:

[0013] S1. Preparation of composite filler;

[0014] Take the montmorillonite and carbon black, weigh the silane coupling agent, dissolve in anhydrous ethanol to prepare a treatment solution, drop the treatment solution into the montmorillonite / carbon black mixture, control the dropping speed at 10-20 mL / min, at the same time, increase the temperature of the mixer to 80-100℃ and stir, after the treatment is completed, centrifuge to remove the supernatant; vacuum dry the precipitate to obtain the composite filler;

[0015] S2. Preparation of stabilizer;

[0016] Weigh the calcium stearate, zinc stearate, epoxy soybean oil and pentaerythritol according to the proportion, mix to obtain a calcium-zinc premix; add CSB@Fe3O4 NPs to the calcium-zinc premix, heat and stir for 1-2 h, after the reaction is completed, add polyethylene wax, continue to stir, and then send the mixture into a double-screw extruder for extrusion and granulation, and then cool to obtain the stabilizer;

[0017] S3. Preparation of anti-aging master batch;

[0018] Put the base resin into the main feeding port of the double-screw extruder, set the temperature of each section of the extruder: 160-180℃ for the feeding section, 180-200℃ for the melting section, and 200-220℃ for the homogenization section, and the screw rotation speed is 300-400 rpm, after 8-12 min, add the premix of the composite filler and the primary antioxidant, after 2-3 min, add the secondary antioxidant and the stabilizer, melt blend, shear disperse, then extrude into strips through the die, cool and shape, cut into particles through the pelletizer, and obtain the anti-aging master batch;

[0019] S4. Pretreatment of stainless steel seamless pipe;

[0020] Take the stainless steel seamless pipe, soak it in alcohol to remove surface oil stains; use sand blasting treatment to form a rough surface on the steel pipe to enhance the mechanical interlocking force with the outer layer; immerse the steel pipe in the epoxy silane treatment solution, soak at room temperature, and then dry to obtain the pretreated stainless steel seamless pipe;

[0021] S5. Co-extrusion composite molding;

[0022] The pretreated stainless steel seamless pipe is sent into the preheating composite extrusion die by a traction machine, the anti-aging master batch is put into the barrel of the composite extruder, and after melting and plasticizing, it is extruded from the die ring gap and uniformly coated on the outer surface of the stainless steel pipe.

[0023] S6. solidification;

[0024] The composite pipeline is sent into a constant-temperature curing box, and is kept at 60-80℃ for 2-4h. After solidification, it is naturally cooled to room temperature to obtain the anti-aging packaged control pipeline.

[0025] In a preferred embodiment of the present application, S1 is specifically: 300-400 mesh montmorillonite and carbon black with a particle size of 200-300 nm are put into a high-speed mixer at a mass ratio of 1:1.8-2.4, and are stirred at a speed of 800-1200 rpm to preliminarily mix them uniformly. Then, silane coupling agent KH-550 or KH-560 is weighed at 0.1-2% of the total mass of the montmorillonite / carbon black mixture, and is dissolved in anhydrous ethanol to prepare a treatment solution with a concentration of 5-10%. The treatment solution is added dropwise into the montmorillonite / carbon black mixture at an adding speed of 10-20 mL / min, and at the same time, the temperature of the mixer is raised to 80-100℃. The mixture is stirred at 1000-1500 rpm for 20-40 min. After the treatment is completed, the mixture is transferred to a centrifugal separator, and is centrifuged at a speed of 3000-5000 rpm for 10-15 min to remove the supernatant. The precipitate is placed in a vacuum drying oven, and is dried at 60-80℃ and a vacuum degree of -0.08 to -0.1 MPa for 12-24 h to remove residual solvents, thereby obtaining a composite filler.

[0026] In another preferred embodiment of the present application, S2 is specifically: calcium stearate 5-10 parts, zinc stearate 3-6 parts, epoxy soybean oil 4-8 parts, and pentaerythritol 2-5 parts are weighed in proportion, and are added into a high-speed mixer. After mixing at a temperature of 40-60℃ and a stirring speed of 500-800 r / min for 10-20 min, a calcium-zinc premix is obtained.

[0027] CSB@Fe3O4NPs 2-5 parts are added into the above calcium-zinc premix, the temperature of the high-speed mixer is raised to 70-90℃, the stirring speed is adjusted to 600-1000 r / min, and the reaction is carried out for 1-2 h. After the reaction is completed, polyethylene wax 1-3 parts is added, and the mixture is continuously stirred for 5-10 min. The mixture is sent into a twin-screw extruder, and is extruded and granulated at a screw speed of 100-150 r / min and a temperature of 100-130℃. After cooling, a stabilizer is obtained.

[0028] In another preferred embodiment of the present application, S3 is specifically: weighing raw materials: 70-90 parts of base resin, 10-30 parts of composite filler, 0.3-0.8 parts of stabilizer, 0.1-0.3 parts of antioxidant, and 1-2.2 parts of colorant;

[0029] The antioxidant is composed of a main antioxidant hindered amine light stabilizer Tinuvin 152 and an auxiliary antioxidant hindered amine light stabilizer UV3853 in a mass ratio of 2:1;

[0030] The base resin and the colorant are first fed into the main feeding port of the double-screw extruder, and the temperature of each section of the extruder is set as follows: the feeding section is 160-180 DEG C, the melting section is 180-200 DEG C, and the homogenizing section is 200-220 DEG C, the screw rotation speed is 300-400 rpm, after 8-12 min, the premix of the composite filler and the main antioxidant is added through the side feeding port, after 2-3 min, the auxiliary antioxidant is added through the side feeding port, the material stays in the extruder for 2-5 min, after the melting blending and shearing dispersion, the material is extruded into a strip with a diameter of 3-5 mm through the die, and then immediately enters the water cooling tank for cooling and shaping, and then is cut into particles with a length of 2-3 mm by the granulator to obtain the anti-aging master batch.

[0031] In another preferred embodiment of the present application, S4 is specifically: a stainless steel seamless pipe is soaked in 95% alcohol for 10-15 min to remove the surface oil stains; sand blasting treatment is adopted to form a rough surface on the steel pipe to enhance the mechanical interlocking force with the outer layer; the steel pipe is immersed in an epoxy silane treatment liquid with a concentration of 1-3%, soaked at room temperature for 5-10 min, and then taken out and dried at 80-100 DEG C for 10-15 min to obtain a pretreated stainless steel seamless pipe.

[0032] In another preferred embodiment of the present application, during the sand blasting treatment, the sand particle size is 80-120 mesh, the pressure is 0.3-0.5 MPa, and the spraying angle is 45 DEG -60 DEG.

[0033] In another preferred embodiment of the present application, S5 is specifically: the pretreated stainless steel seamless pipe is sent by a traction machine to the center position of a composite extrusion die preheated to 180-220 DEG C, the anti-aging master batch is fed into the barrel of the composite extruder, and then is extruded through the die ring gap after melting and plasticizing, and is uniformly coated on the outer surface of the stainless steel pipe; during the coating process, the pressure in the die is adjusted to 0.5-1.5 MPa to make the molten plastic closely adhere to the surface of the stainless steel pipe, and at the same time, the cooling jacket outside the die is opened to rapidly cool and shape the outer layer plastic, and the traction speed is controlled at 0.5-2 m / min to ensure that the outer layer plastic and the inner layer steel pipe move synchronously.

[0034] The present application has the following technical effects:

[0035] 1. This invention introduces CSB@Fe3O4NPs during the stabilizer preparation process, allowing it to fully react with calcium-zinc premix and combine with polyethylene wax to form a stable system. This not only effectively improves the overall hardness of the pipeline and enhances the material's resistance to deformation, but also strengthens the interfacial bonding performance between the inner and outer layers of the pipeline, reducing the risk of interlayer separation.

[0036] 2. This invention improves the dispersibility and compatibility of montmorillonite and carbon black composite fillers in the matrix resin by treating them with silane coupling agents, thereby enhancing the high-temperature aging resistance of pipelines and reducing performance degradation under high-temperature environments. Furthermore, CSB@Fe3O4NPs effectively delays material aging caused by ultraviolet radiation, improving the pipeline's UV resistance. Simultaneously, the silane coupling agent-treated montmorillonite and carbon black synergistically enhance the material's resistance to salt spray corrosion from different dimensions, reducing the corrosive damage to pipelines caused by salt spray environments and further extending the pipeline's service life in complex environments.

[0037] 3. The pretreatment process designed for stainless steel seamless pipes in this invention first removes surface oil stains with alcohol to ensure cleanliness, then uses sandblasting to create a rough surface to improve mechanical interlocking force, and finally uses epoxy silane treatment liquid to impregnate and form an interface bonding layer. Under the multiple effects, the pipeline sealing performance is significantly optimized, the risk of media leakage is reduced, and the bonding strength between the metal substrate and the outer layer material is further enhanced, thereby improving the overall structural integrity.

[0038] The following will further explain the concept, specific structure, and technical effects of the present invention in conjunction with the accompanying drawings, so as to fully understand the purpose, features, and effects of the present invention. Attached Figure Description

[0039] Figure 1 This is a physical image of an anti-aging packaged control pipeline;

[0040] Figure 2 This is a sample diagram of an anti-aging packaged control pipeline;

[0041] Figure 3 This is a picture of the actual product with the inner layer of seamless stainless steel tubing;

[0042] Figure 4 The infrared spectra of the montmorillonite / carbon black mixture before and after modification in Example 1 are shown.

[0043] Figure 5 The infrared spectra of CSB@Fe3O4NPs, calcium-zinc premix, and stabilizer in Example 1 are shown. Detailed Implementation

[0044] Following detailed description of the application by specific examples, those skilled in the art can easily understand the advantages and effects of the application from the disclosure. The application can also be implemented or applied by other different specific embodiments, and various modifications or changes can be made based on different views and applications without departing from the spirit of the application. It should be noted that the following examples and features in the examples can be combined with each other without conflict.

[0045] It should be noted that the diagrams provided in the following examples only illustrate the basic concept of the application in a schematic manner, and only the components related to the application are shown in the diagrams, not the number, shape and size of the components when actually implemented. The actual implementation of each component may be a random change, and the component layout may be more complex.

[0046] Some exemplary embodiments of the application are described for illustrative purposes, and it should be understood that the application can be implemented in other ways not specifically shown in the drawings.

[0047] Example 1: This example provides an anti-aging packaging control pipeline, comprising the following steps:

[0048] S1. Preparation of composite filler;

[0049] Take montmorillonite (400 mesh) and carbon black (particle size 300 nm) with a mass ratio of 1:2.4 into a high-speed mixer, start stirring (speed 1200 rpm) to mix them evenly, then take 2% of silane coupling agent (KH-560) based on the total mass of the montmorillonite / carbon black mixture, dissolve it in anhydrous ethanol to prepare a treatment solution with a concentration of 10%, stir at 500 rpm for 15 min, drop the treatment solution into the montmorillonite / carbon black mixture at a rate of 20 mL / min, and at the same time, increase the temperature of the mixer to 100°C, stir at 1500 rpm for 40 min. After treatment, transfer the mixture to a centrifugal separator, centrifuge at 5000 rpm for 15 min to remove the supernatant (unreacted coupling agent and ethanol); then put the precipitate into a vacuum drying oven, dry at 80°C and -0.1 MPa vacuum for 24 h to remove residual solvents, and obtain the composite filler;

[0050] S2. Preparation of stabilizer;

[0051] Take calcium stearate 10 parts, zinc stearate 6 parts, epoxy soybean oil 8 parts, and pentaerythritol 5 parts by proportion, add them into a high-speed mixer, mix at a temperature of 60°C and a stirring speed of 800 r / min for 20 min to obtain a calcium-zinc premix;

[0052] To the above calcium zinc premix, add 5 parts of CSB@Fe3O4NPs, increase the temperature of the high-speed mixer to 90°C, and adjust the stirring speed to 1000 r / min. Stir for 2 h, then add 3 parts of polyethylene wax and continue stirring for 10 min. Then, transfer the mixture to a twin-screw extruder and extrude at a screw speed of 150 r / min and a temperature of 130°C. After cooling, the stabilizer is obtained.

[0053] It should be particularly noted that the preparation method of CSB@Fe3O4NPs described in S2 is taken from Liu QL, Jiang LT, Liu MJ, et al. Modified chitosan magnetic composite material for adsorption of multiple heavy metals in industrial wastewater [J / OL]. Chemical Edition of Physical and Chemical Testing, 1-9 [2025-09-10]. https: / / gfgfy047f83d4b4544a20sb9cqfvoq69pw6p9vficg.res.gxlib.org.cn / urlid / 31.1337.TB.20250708.1807.002.

[0054] The specific preparation method of CSB@Fe3O4NPs is as follows: accurately weigh 11.0 g of FeCl3·6H2O into a flask, measure 90 mL of ethylene glycol, and stir while pouring. After the FeCl3·6H2O solid in the flask is completely dissolved, add 6.6 g of anhydrous sodium acetate and continue stirring until the solution is clear and transparent. Transfer the above solution to a 100 mL hydrothermal reactor and seal it. Place it in a vacuum drying oven at 200°C for 8 h. Cool to room temperature, separate the product with a magnet, and wash it with 100 mL of ethanol and 100 mL of water, respectively. Dry at 80°C for 8 h under vacuum to obtain Fe3O4NPs. Accurately weigh 1 g of chitosan and add it to 50 mL of 5% (by volume) acetic acid solution. Stir magnetically at 25°C until completely dissolved. Add 1 mL of 2-thiophene-formaldehyde and stir vigorously at 60°C for 7 h. Cool to room temperature, add 1 g of Fe3O4NPs, and stir while pouring. React for 60 min. After the reaction is complete, wash with 100 mL of 0.1 mol·L -1 hydrogen chloride solution and 100 mL of water, and dry at 80°C under vacuum for 8 h to obtain the nanocomposite CSB@Fe3O4NPs.

[0055] S3. Preparation of anti-aging masterbatch;

[0056] The raw materials were weighed: 90 parts of base resin (consisting of polypropylene resin and polyamide resin in a mass ratio of 5:8, the polypropylene resin was purchased from Shanghai Qiao Micro Chemical Technology Co., Ltd., brand K8025; the polyamide resin was purchased from Ningbo Rong Plastic New Material Co., Ltd., brand TA124), 30 parts of composite filler, 0.8 parts of stabilizer, 0.3 parts of antioxidant (consisting of primary antioxidant hindered amine light stabilizer Tinuvin 152 and auxiliary antioxidant hindered amine light stabilizer UV3853 in a mass ratio of 2:1), and 2.2 parts of colorant;

[0057] The base resin and the colorant were first fed into the main feeding port of the twin-screw extruder, and the temperature of each section of the extruder was set as follows: 180°C for the feeding section, 200°C for the melting section, and 220°C for the homogenizing section, with a screw rotation speed of 400 rpm. After 12 minutes, the premix of the composite filler and the primary antioxidant (previously stirred at 200 rpm for 10 minutes) was added through the side feeding port. After 3 minutes, the auxiliary antioxidant and the stabilizer were added through the side feeding port. The material stayed in the extruder for 5 minutes, and then was extruded into a 5 mm diameter strip through the die after being melt blended and sheared and dispersed. The strip was immediately cooled and shaped in a water cooling tank (water temperature 30°C), and then cut into 3 mm long particles by a pelletizer to obtain the anti-aging master batch.

[0058] S4. Pretreatment of stainless steel seamless pipe;

[0059] A stainless steel seamless pipe (material 304L, wall thickness 3 mm) was taken and soaked in 95% alcohol for 15 minutes to remove surface oil stains. Sand blasting treatment (sand particle size 120 mesh, pressure 0.5 MPa, spraying angle 60°) was used to form a rough surface on the steel pipe to enhance the mechanical interlocking force with the outer layer. The steel pipe was immersed in a 3% concentration of epoxy silane treatment liquid (KH-561 was selected) for 10 minutes at room temperature, and then taken out and dried at 100°C for 15 minutes to obtain the pretreated stainless steel seamless pipe.

[0060] S5. Co-extrusion composite molding;

[0061] The pretreated stainless steel seamless pipe was sent to the center position of the composite extrusion die preheated to 220°C by a traction machine, and the anti-aging master batch was fed into the barrel of the composite extruder. After being melt plasticized, the pipe was extruded through the annular gap of the die and uniformly coated on the outer surface of the stainless steel pipe (outer layer thickness 5 mm). During the coating process, the pressure in the die was adjusted to 1.5 MPa to make the melt plastic closely adhere to the surface of the stainless steel pipe. At the same time, the cooling jacket (water temperature 25°C) outside the die was turned on to rapidly cool and shape the outer layer plastic. The traction speed was controlled at 2 m / min to ensure that the outer layer plastic moved synchronously with the inner layer steel pipe, avoiding wrinkles or gaps.

[0062] S6. Curing;

[0063] The compounded pipeline is sent into a constant temperature curing box, and is kept at 80℃ for 4h. After curing, it is naturally cooled to room temperature. Finally, the anti-aging packaging control pipeline with stainless steel seamless pipe as the inner layer and anti-aging barrier layer as the outer layer is obtained.

[0064] Embodiment 2: The embodiment provides an anti-aging packaging control pipeline, comprising the following steps:

[0065] S1. Preparing a composite filler;

[0066] Montmorillonite (300 mesh) and carbon black (particle size 200 nm) are put into a high-speed mixer at a mass ratio of 1:1.8. The stirring (800 rpm) is started to preliminarily mix the two. The silane coupling agent (KH-550) is weighed at 0.1% of the total mass of the montmorillonite / carbon black mixture, and then is dissolved in anhydrous ethanol to prepare a treatment solution with a concentration of 5-10%. The treatment solution is dropped into the montmorillonite / carbon black mixture at a dropping speed of 10 mL / min. At the same time, the temperature of the mixer is raised to 80℃, and the stirring is carried out at 1000 rpm for 20 min. After the treatment is completed, the mixture is transferred to a centrifugal separator, and is centrifuged at a speed of 3000 rpm for 10 min to remove the supernatant (unreacted coupling agent and ethanol). Then, the precipitate is put into a vacuum drying box, and is dried at 60℃ and a vacuum degree of -0.08 MPa for 12 h to remove the residual solvent, so as to obtain the composite filler.

[0067] S2. Preparing a stabilizer;

[0068] Calcium stearate 5 parts, zinc stearate 3 parts, epoxy soybean oil 4 parts, and pentaerythritol 2 parts are weighed according to the proportion, and are added into a high-speed mixer. The mixing is carried out at a temperature of 40℃ and a stirring speed of 500 r / min for 10 min to obtain a calcium-zinc premix.

[0069] CSB@Fe3O4NPs 2 parts are added into the above calcium-zinc premix. The temperature of the high-speed mixer is raised to 70℃, the stirring speed is adjusted to 600 r / min, and the reaction is carried out for 1 h. After the reaction is completed, polyethylene wax 1 part is added, and the stirring is continued for 5 min. Then, the mixture is sent into a double-screw extruder, and is extruded and granulated under the conditions of a screw rotating speed of 100 r / min and a temperature of 100℃. After cooling, the stabilizer is obtained.

[0070] S3. Preparing an anti-aging master batch;

[0071] The raw materials are weighed: base resin (composed of polypropylene resin and polyamide resin at a mass ratio of 3:4) 70 parts, composite filler 10 parts, stabilizer 0.3 parts, antioxidant (composed of main antioxidant hindered amine light stabilizer Tinuvin 152 and auxiliary antioxidant hindered amine light stabilizer UV3853 at a mass ratio of 2:1) 0.3 parts, and colorant 1 part.

[0072] The base resin and colorant are first fed into the main feeding port of the twin-screw extruder, and the temperature of each section of the extruder is set as follows: 160°C for the feeding section, 180°C for the melting section, 200°C for the homogenizing section, and 300 rpm for the screw rotation speed. After 8 minutes, the premix of the composite filler and the primary antioxidant (previously stirred for 5 minutes at 100 rpm) is added through the side feeding port, and after 2 minutes, the secondary antioxidant and stabilizer are added through the side feeding port. The material stays in the extruder for 2 minutes, after which it is extruded through the die into a 3 mm diameter strip, immediately cooled and shaped in a water tank (water temperature 20°C), cut into 2 mm long particles by a pelletizer, and an anti-aging master batch is obtained.

[0073] S4. Pretreatment of stainless steel seamless pipe;

[0074] A stainless steel seamless pipe (material 316L, wall thickness 1 mm) is soaked in 95% alcohol for 10 minutes to remove surface oil; sandblasting treatment (sand particle size 80 mesh, pressure 0.3 MPa, spray angle 45°) is used to form a rough surface on the steel pipe to enhance the mechanical interlocking force with the outer layer; the steel pipe is immersed in a 1% concentration of epoxy silane treatment liquid (KH-560 is selected) for 5 minutes at room temperature, and then dried at 80°C for 10 minutes to obtain a pretreated stainless steel seamless pipe;

[0075] S5. Co-extrusion composite molding;

[0076] The pretreated stainless steel seamless pipe is sent to the center position of the composite extrusion die preheated to 180°C by the traction machine, the anti-aging master batch is fed into the barrel of the composite extruder, and after melting and plasticizing, it is extruded through the annular gap of the die and uniformly coated on the outer surface of the stainless steel pipe (outer layer thickness 2 mm). During the coating process, the pressure in the die is adjusted to 0.5 MPa to ensure that the molten plastic closely adheres to the surface of the stainless steel pipe, and the cooling jacket (water temperature 20°C) outside the die is turned on to rapidly cool and shape the outer layer plastic. The traction speed is controlled at 0.5 m / min to ensure that the outer layer plastic moves synchronously with the inner layer steel pipe, avoiding wrinkles or gaps;

[0077] S6. Curing;

[0078] The composite pipe is sent to a constant temperature curing oven and kept at 60°C for 2 hours. After curing, it is naturally cooled to room temperature to obtain an anti-aging packaging control pipeline with an inner layer of stainless steel seamless pipe and an outer layer of anti-aging barrier layer.

[0079] Example 3: This example provides an anti-aging packaging control pipeline, comprising the following steps:

[0080] S1. Preparation of composite filler;

[0081] Take montmorillonite (320 mesh) and carbon black (particle size 200 nm) according to the mass ratio 1:1.9 into the high-speed mixer, start stirring (speed 900 rpm) to make them preliminary mixed evenly, according to the total mass of 0.8% of montmorillonite / carbon black mixture, silane coupling agent (KH-560) is weighed, then dissolved in absolute ethanol to prepare a concentration of 7% treatment solution, 420 rpm stirring 12 min, drop the treatment solution into the montmorillonite / carbon black mixture, the drop adding speed is controlled at 16 mL / min, at the same time, the temperature of the mixer is raised to 92℃, stirring at 1200 rpm for 28 min, after the treatment is completed, the mixture is transferred to the centrifugal separator, centrifuged at 4100 rpm for 12 min, remove the supernatant (unreacted coupling agent and ethanol); then put the precipitate into a vacuum drying oven, dry at 72℃, -0.08 MPa vacuum degree for 20 h, remove the residual solvent, get the composite filler;

[0082] S2. Preparation of stabilizer;

[0083] According to the proportion, calcium stearate 8 parts, zinc stearate 5 parts, epoxy soybean oil 7 parts, pentaerythritol 3 parts are weighed and added into the high-speed mixer, mixed at 55℃, stirring speed 600 r / min for 11 min, to get calcium zinc premix;

[0084] Add CSB@Fe3O4NPs 4 parts to the above calcium zinc premix, raise the temperature of the high-speed mixer to 79℃, adjust the stirring speed to 700 r / min, react for 2 h, after the reaction is completed, add polyethylene wax 1.8 parts, continue to stir for 8 min, then send the mixture into the twin-screw extruder, extrude and granulate under the conditions of screw speed 120 r / min, temperature 110℃, after cooling, the stabilizer is obtained;

[0085] S3. Preparation of anti-aging masterbatch;

[0086] Weigh the raw materials: base resin (consisting of polypropylene resin and polyamide resin with a mass ratio of 4:7) 82 parts, composite filler 15 parts, stabilizer 0.5 parts, antioxidant (consisting of main antioxidant hindered amine light stabilizer Tinuvin 152 and auxiliary antioxidant hindered amine light stabilizer UV3853 with a mass ratio of 2:1) 0.17 parts, colorant 1.2 parts;

[0087] The base resin and colorant are first fed into the main feeding port of the twin-screw extruder, and the temperature of each section of the extruder is set as follows: 165℃ for the feeding section, 192℃ for the melting section, 203℃ for the homogenizing section, and 320 rpm for the screw rotation speed. After 9 minutes, the premix of the composite filler and the primary antioxidant (previously stirred for 6 minutes at 140 rpm) is added through the side feeding port. After 2 minutes, the secondary antioxidant and stabilizer are added through the side feeding port. The material stays in the extruder for 4 minutes, after which it is extruded into a 4mm-diameter strip through the die, immediately enters the water cooling tank (water temperature 26℃) for cooling and shaping, and is cut into 3mm-long particles by the granulator to obtain the anti-aging master batch.

[0088] S4. Pretreatment of stainless steel seamless pipe;

[0089] A stainless steel seamless pipe (material 316L, wall thickness 1.6mm) is soaked in 95% alcohol for 12 minutes to remove surface oil stains. Sand blasting treatment (sand particle size 120 mesh, pressure 0.3MPa, spray angle 45°) is used to form a rough surface on the steel pipe to enhance the mechanical interlocking force with the outer layer. The steel pipe is immersed in a 1.5% concentration of epoxy silane treatment liquid (KH-560 is selected) for 6 minutes at room temperature, and then dried at 92℃ for 12 minutes to obtain the pretreated stainless steel seamless pipe.

[0090] S5. Co-extrusion composite molding;

[0091] The pretreated stainless steel seamless pipe is sent by the traction machine to the center position of the composite extrusion die preheated to 210℃, and the anti-aging master batch is fed into the barrel of the composite extruder. After melting and plasticizing, the molten plastic is extruded through the annular gap of the die and uniformly coated on the outer surface of the stainless steel pipe (outer layer thickness 4mm). During the coating process, the pressure in the die is adjusted to 1.2MPa to ensure that the molten plastic closely adheres to the surface of the stainless steel pipe. At the same time, the cooling jacket (water temperature 22℃) outside the die is turned on to rapidly cool and shape the outer layer plastic. The traction speed is controlled at 0.8m / min to ensure that the outer layer plastic moves synchronously with the inner layer steel pipe, avoiding wrinkles or gaps.

[0092] S6. Curing;

[0093] The composite pipe is sent to a constant temperature curing oven and kept at 72℃ for 4 hours. After curing, it is naturally cooled to room temperature to obtain the anti-aging packaging control pipeline with the inner layer being a stainless steel seamless pipe and the outer layer being an anti-aging barrier layer.

[0094] Example 4: This example provides an anti-aging packaging control pipeline, comprising the following steps:

[0095] S1. Preparation of composite filler;

[0096] Take montmorillonite (300 mesh) and carbon black (particle size 200 nm) according to the mass ratio 1:2.2 into a high-speed mixer, start stirring (speed 1100 rpm) to make them initially mixed uniformly, take silane coupling agent (KH-560) according to 1.3% of the total mass of the montmorillonite / carbon black mixture, then dissolve it in anhydrous ethanol to prepare a treatment solution with a concentration of 6%, stir at 380 rpm for 14 min, drop the treatment solution into the montmorillonite / carbon black mixture, control the dropping speed at 16 mL / min, at the same time, increase the temperature of the mixer to 95℃, stir at 1100 rpm for 34 min, after the treatment is completed, transfer the mixture to a centrifugal separator, centrifuge at 4000 rpm for 12 min to remove the supernatant (unreacted coupling agent and ethanol); then put the precipitate into a vacuum drying oven, dry at 72℃, -0.1 MPa vacuum degree for 18 h to remove residual solvents, and obtain the composite filler;

[0097] S2. Preparation of stabilizer;

[0098] Take calcium stearate 6 parts, zinc stearate 5 parts, epoxy soybean oil 7 parts, and pentaerythritol 4 parts according to the proportion, add them into a high-speed mixer, mix at a temperature of 45℃ and a stirring speed of 650 r / min for 14 min to obtain a calcium-zinc premix;

[0099] Add CSB@Fe3O4NPs 4 parts to the above calcium-zinc premix, increase the temperature of the high-speed mixer to 88℃, adjust the stirring speed to 700 r / min, and react for 2 h. After the reaction is completed, add polyethylene wax 1.7 parts, continue stirring for 6 min, then send the mixture into a twin-screw extruder, and extrude and granulate under the conditions of screw speed 120 r / min and temperature 122℃. After cooling, the stabilizer is obtained;

[0100] S3. Preparation of anti-aging master batch;

[0101] Take the raw materials: base resin (composed of polypropylene resin and polyamide resin with a mass ratio of 4:5) 78 parts, composite filler 18 parts, stabilizer 0.4 parts, antioxidant (composed of main antioxidant hindered amine light stabilizer Tinuvin 152 and auxiliary antioxidant hindered amine light stabilizer UV3853 with a mass ratio of 2:1) 0.21 parts, and colorant 1.6 parts;

[0102] The base resin and colorant were first fed into the main feeding port of the twin-screw extruder, and the temperature of each section of the extruder was set as follows: 171 ℃ for the feeding section, 189 ℃ for the melting section, 207 ℃ for the homogenizing section, and the screw rotation speed was 370 rpm. After 9 min, the premix of the composite filler and the primary antioxidant (previously stirred for 6 min at 140 rpm) was added through the side feeding port. After 2.4 min, the secondary antioxidant and the stabilizer were added through the side feeding port. The material was left in the extruder for 4 min, and then was extruded into a 4 mm diameter strip through the die. The strip was immediately cooled and shaped in a water tank (water temperature 27 ℃), and then was cut into 2.5 mm long particles by a pelletizer to obtain the anti-aging master batch.

[0103] S4. Pretreatment of stainless steel seamless pipe;

[0104] A stainless steel seamless pipe (material 316L, wall thickness 2.5 mm) was soaked in 95% alcohol for 14 min to remove surface oil stains. Sand blasting treatment (sand particle size 100 mesh, pressure 0.5 MPa, spray angle 60°) was used to form a rough surface on the steel pipe to enhance the mechanical interlocking force with the outer layer. The steel pipe was immersed in an epoxy silane treatment solution (KH-561 was selected) with a concentration of 2.4% for 6 min at room temperature, and then was dried at 88 ℃ for 12 min to obtain the pretreated stainless steel seamless pipe.

[0105] S5. Co-extrusion composite molding;

[0106] The pretreated stainless steel seamless pipe was sent to the center position of the composite extrusion die preheated to 188 ℃ by a traction machine. The anti-aging master batch was fed into the barrel of the composite extruder, and then was extruded through the die ring gap after being melted and plasticized, to uniformly coat the outer surface of the stainless steel pipe (outer layer thickness 4 mm). During the coating process, the pressure in the die was adjusted to 0.9 MPa to make the molten plastic closely adhere to the surface of the stainless steel pipe. At the same time, the cooling jacket (water temperature 24 ℃) outside the die was turned on to rapidly cool and shape the outer layer plastic. The traction speed was controlled at 1.8 m / min to ensure that the outer layer plastic moved synchronously with the inner layer steel pipe, avoiding wrinkles or gaps.

[0107] S6. Curing;

[0108] The composite pipe was sent to a constant temperature curing oven, and was kept at 77 ℃ for 4 h. After curing, it was naturally cooled to room temperature to finally obtain the anti-aging packaging control pipeline with the inner layer being a stainless steel seamless pipe and the outer layer being an anti-aging barrier layer.

[0109] Comparative Example 1: The difference between this comparative example and Example 4 is that the stabilizer lacks the component: CSB@Fe3O4NPs.

[0110] Comparative Example 2: The difference between this comparative example and Example 4 is that the stainless steel seamless pipe is not pretreated.

[0111] Comparative Example 3: The difference between this comparative example and Example 4 is that the composite filler is directly selected as montmorillonite and carbon black with a mass ratio of 1:2.2, without silane coupling agent treatment.

[0112] Comparative Example 4: The difference between this comparative example and Example 4 is that the composite filler is not treated with silane coupling agent; and CSB@Fe3O4NPs is not added in the stabilizer.

[0113] Experimental Example: 1, infrared spectrum detection is performed on the montmorillonite / carbon black mixture before and after modification in Example 1 (as shown in Figure 4 , the red peak line is after modification), the intensity of the interlayer hydroxyl stretching peak of the modified montmorillonite / carbon black mixture at 3620-3600 cm⁻¹ is significantly reduced;

[0114] obvious epoxy group stretching vibration peak (sharp peak, the characteristic functional group of KH-560) appears in the interval of 910-890 cm⁻¹;

[0115] stronger and wider Si-O-Si stretching vibration peak appears in the interval of 1030-1000 cm⁻¹;

[0116] around 2920 cm⁻¹: asymmetric stretching vibration peak of -CH2-;

[0117] around 2850 cm⁻¹: symmetric stretching vibration peak of -CH2-.

[0118] These two peaks are the characteristic signals of the “-CH2-CH2-CH2-” carbon chain in KH-560 molecules (the raw material without modification does not have this structure), which further proves that KH-560 has been grafted to the surface of the filler;

[0119] The intensity of these two peaks of 3400-3200 cm⁻¹ (absorbed water O-H stretching) and 1630-1600 cm⁻¹ (H-O-H bending) is obviously reduced; after KH-560 grafting, the surface of the filler changes from hydrophilic (hydroxyl exposure) to hydrophobic (carbon chain and siloxane bond coverage), the ability to absorb water decreases, which indirectly proves that the modification changes the surface properties of the filler, which is consistent with the modification effect of the silane coupling agent.

[0120] Infrared spectrum detection is performed on the stabilizer prepared in Example 1 (as shown in Figure 5The stabilizer is obtained by adding CSB@Fe3O4NPs to the calcium-zinc premix. In the infrared spectrum of the stabilizer, the characteristic peak of Fe-O corresponding to CSB@Fe3O4NPs appears in the region of 550-650 cm⁻¹, and the characteristic peak of the calcium-zinc premix is retained, indicating that the structure of the calcium-zinc premix is not destroyed and is successfully combined with CSB@Fe3O4NPs.

[0121] Table 1

[0122]

[0123] Table 2

[0124]

[0125] From the above table, it can be seen that by adding CSB@Fe3O4NPs, the hardness and the bonding strength of the inner and outer layers are improved;

[0126] By pretreating the stainless steel seamless pipe, the sealing property (leakage rate is reduced) and the bonding strength of the inner and outer layers are significantly improved;

[0127] By treating the montmorillonite and carbon black with a silane coupling agent, the high-temperature aging resistance is improved;

[0128] By adding CSB@Fe3O4NPs, the ultraviolet aging resistance is improved;

[0129] By treating the montmorillonite and carbon black with a silane coupling agent and the synergistic effect of CSB@Fe3O4NPs, the salt spray aging resistance is improved.

[0130] The above examples only exemplarily illustrate the principles and effects of the present application, and are not used to limit the present application. Any person skilled in the art can modify or change the above examples without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes completed by those skilled in the art without departing from the spirit and technical thought disclosed by the present application should be covered by the claims of the present application.

Claims

1. An anti-aging, encapsulated control line, characterized in that, The outer layer barrier layer comprises, by weight, 70-90 parts of a base resin, 10-30 parts of a composite filler, 0.3-0.8 parts of a stabilizer, 0.1-0.3 parts of an antioxidant, and 1-2.2 parts of a colorant. The base resin is composed of polypropylene resin and polyamide resin in a mass ratio of 3-5:4-8. The composite filler is obtained by treating montmorillonite and carbon black with a silane coupling agent in a mass ratio of 1:1.8-2.

4. The stabilizer comprises CSB@Fe3O4 NPs, polyethylene wax, calcium stearate, zinc stearate, epoxy soybean oil, and pentaerythritol in a mass ratio of 2-5:1-3:5-10:3-6:4-8:2-5. The stabilizer is prepared by weighing calcium stearate, zinc stearate, epoxy soybean oil, and pentaerythritol in a certain proportion, mixing to obtain a calcium-zinc premix, adding CSB@Fe3O4 NPs to the calcium-zinc premix, stirring and reacting for 1-2 hours, adding polyethylene wax after the reaction, continuing to stir, feeding the mixture into a double-screw extruder, extruding and granulating, and cooling to obtain the stabilizer.

2. A method of preparing an anti-aging, encapsulated control line as claimed in claim 1, characterized in that, The method comprises the following steps: S1. Preparing a composite filler The montmorillonite and carbon black are mixed uniformly, a silane coupling agent is weighed and dissolved in anhydrous ethanol to prepare a treatment liquid, the treatment liquid is added dropwise into the montmorillonite / carbon black mixture at a speed of 10-20 mL / min, the temperature of the mixer is raised to 80-100℃ while stirring, after the treatment is completed, the supernatant is removed by centrifugation, and the precipitate is vacuum dried to obtain the composite filler. S2. Preparing a stabilizer The calcium stearate, zinc stearate, epoxy soybean oil, and pentaerythritol are weighed in a certain proportion, mixed to obtain a calcium-zinc premix, CSB@Fe3O4 NPs are added to the calcium-zinc premix, stirring and reacting for 1-2 hours, polyethylene wax is added after the reaction, and the mixture is fed into a double-screw extruder for extrusion and granulation, and then cooled to obtain the stabilizer. S3. Preparing an anti-aging master batch The base resin and colorant are fed into the main feeding port of the double-screw extruder, the temperature of each section of the extruder is set as follows: the feeding section is 160-180℃, the melting section is 180-200℃, and the homogenizing section is 200-220℃, the screw rotation speed is 300-400 rpm, 8-12 minutes later, the antioxidant is composed of the main antioxidant hindered amine light stabilizer Tinuvin 152 and the auxiliary antioxidant hindered amine light stabilizer UV3853 in a mass ratio of 2:1, the premix of the composite filler and the main antioxidant is added, 2-3 minutes later, the auxiliary antioxidant and the stabilizer are added, and then the mixture is subjected to melt blending and shearing dispersion, and then extruded into a strip shape through a die, cooled and shaped, cut into particles by a pelletizer, and an anti-aging master batch is obtained. S4. Pre-treating a stainless steel seamless pipe The stainless steel seamless pipe is soaked in alcohol to remove surface oil stains, sand blasting is performed to form a rough surface on the pipe to enhance the mechanical interlocking force with the outer layer, the pipe is immersed in an epoxy silane treatment liquid, soaked at room temperature, taken out and dried to obtain a pre-treated stainless steel seamless pipe. S5. Co-extrusion composite molding The pretreated stainless steel seamless pipe is sent into the preheated composite extrusion die by a traction machine, the anti-aging master batch is put into the barrel of the composite extruder, and after melting and plasticizing, it is extruded from the annular gap of the die and uniformly coated on the outer surface of the stainless steel pipe; S6. Curing; The composite pipe is sent into a constant temperature curing box, and is kept at 60-80℃ for 2-4h. After curing, it is naturally cooled to room temperature to obtain the anti-aging packaged control pipeline.

3. The method of claim 2, wherein the anti-aging, encapsulated control line is prepared by, The S1 is specifically: 300-400 mesh montmorillonite and carbon black with a particle size of 200-300 nm are put into a high-speed mixer at a mass ratio of 1:1.8-2.4, and are preliminarily mixed uniformly at a rotation speed of 800-1200 rpm. Then, the silane coupling agent KH-550 or KH-560 is weighed at 0.1-2% of the total mass of the montmorillonite / carbon black mixture, and is dissolved in anhydrous ethanol to prepare a treatment solution with a concentration of 5-10%. The mixture is stirred at 300-500 rpm for 10-15 min, and the treatment solution is added dropwise at an addition rate of 10-20 mL / min. At the same time, the temperature of the mixer is raised to 80-100℃, and the mixture is stirred at 1000-1500 rpm for 20-40 min. After treatment, the mixture is transferred to a centrifugal separator and centrifuged at a rotation speed of 3000-5000 rpm for 10-15 min to remove the supernatant. The precipitate is placed in a vacuum drying oven and dried at 60-80℃ under a vacuum degree of -0.08 to -0.1 MPa for 12-24 h to remove residual solvents, thereby obtaining a composite filler.

4. The method of claim 2, wherein the anti-aging, encapsulated control line is prepared by, The S2 is specifically: calcium stearate 5-10 parts, zinc stearate 3-6 parts, epoxy soybean oil 4-8 parts, and pentaerythritol 2-5 parts are weighed in proportion and added to a high-speed mixer. The mixture is mixed at a temperature of 40-60℃ and a stirring speed of 500-800 r / min for 10-20 min to obtain a calcium-zinc premix. To the above calcium-zinc premix, CSB@Fe3O4 NPs 2-5 parts are added, the temperature of the high-speed mixer is raised to 70-90℃, the stirring speed is adjusted to 600-1000 r / min, and the reaction is carried out for 1-2 h. After the reaction is completed, polyethylene wax 1-3 parts is added, and the mixture is stirred for another 5-10 min. The mixture is then sent into a twin-screw extruder and extruded and granulated at a screw rotation speed of 100-150 r / min and a temperature of 100-130℃. After cooling, a stabilizer is obtained.

5. The method of claim 2, wherein the anti-aging, encapsulated control line is prepared by, The S3 is specifically: the raw materials are weighed as follows: base resin 70-90 parts, composite filler 10-30 parts, stabilizer 0.3-0.8 parts, antioxidant 0.1-0.3 parts, and colorant 1-2.2 parts. The base resin and colorant are first fed into the main feeding port of the double screw extruder, and the temperature of each section of the extruder is set as follows: the feeding section 160-180 DEG C, the melting section 180-200 DEG C, the homogenizing section 200-220 DEG C, the screw rotation speed 300-400 rpm, after 8-12 min, the premix of the composite filler and the primary antioxidant is fed through the side feeding port, after 2-3 min, the secondary antioxidant and the stabilizer are fed through the side feeding port, the material stays in the extruder for 2-5 min, after the melting blending and shearing dispersion, the material is extruded into a strip with a diameter of 3-5 mm through the die, and then immediately enters the water cooling tank for cooling and shaping, and then is cut into particles with a length of 2-3 mm by the granulator to obtain the anti-aging master batch.

6. The method of claim 2, wherein the anti-aging, encapsulated control line is prepared by, The S4 is specifically as follows: a stainless steel seamless pipe is soaked in 95% alcohol for 10-15 min to remove surface oil stains; sand blasting treatment is adopted to form a rough surface on the pipe to enhance the mechanical interlocking force with the outer layer; the pipe is immersed in an epoxy silane treatment liquid with a concentration of 1-3% for 5-10 min at room temperature, and then is taken out and dried at 80-100 DEG C for 10-15 min to obtain a pretreated stainless steel seamless pipe.

7. The method of claim 2, wherein the anti-aging, encapsulated control line is prepared by, During the sand blasting treatment, the sand particle size is 80-120 mesh, the pressure is 0.3-0.5 MPa, and the spraying angle is 45 DEG -60 DEG.

8. The method of claim 2, wherein the anti-aging, encapsulated control line is prepared by, The S5 is specifically as follows: the pretreated stainless steel seamless pipe is sent by a traction machine to the center position of a composite extrusion die preheated to 180-220 DEG C, the anti-aging master batch is fed into the barrel of the composite extruder, and then is extruded through the annular gap of the die after melting and plasticizing, and is uniformly coated on the outer surface of the stainless steel pipe; during the coating process, the pressure in the die is adjusted to 0.5-1.5 MPa, and the cooling jacket outside the die is opened at the same time, and the traction speed is 0.5-2 m / min.

Images