High-strength cable protection pipe and method for manufacturing the same
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HANGZHOU YITIAN HUAWO TECHNOLOGY CO LTD
- Filing Date
- 2025-10-30
- Publication Date
- 2026-06-26
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] This invention relates to the field of protective tube manufacturing technology, specifically to a high-strength cable protective tube and its manufacturing method. Background Technology
[0002] As a widely used protective component in power, communication and transportation infrastructure, cable protection pipes have long faced the dual requirements of strength and flame retardancy in terms of material performance. Early products mostly used thermoplastic materials such as polyvinyl chloride and polyethylene, and improved mechanical support capacity by thickening the walls. However, the ring stiffness was limited and it was difficult to meet the long-term load-bearing requirements in complex environments. Subsequently, the industry gradually introduced measures such as glass fiber reinforcement and filler modification to improve the compressive strength and dimensional stability of the pipes, which to some extent solved the problem of insufficient structural performance.
[0003] In terms of flame retardancy, most of them are based on halogenated flame retardants. Although they can effectively improve the limiting oxygen index, they have problems such as large smoke production and release of corrosive gases. Subsequently, they have gradually developed into halogen-free flame retardant systems, which mainly rely on inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, or adopt phosphorus and nitrogen synergistic systems to improve flame retardant efficiency. Overall, the technical background of cable protection pipes is reflected in the continuous exploration of more efficient and environmentally friendly flame retardant methods while meeting mechanical strength requirements, in order to cope with increasingly complex application environments.
[0004] Currently, in the manufacturing process of cable protection pipes, there is a common problem that it is difficult to balance mechanical properties with flame retardancy and media resistance. On the one hand, conventional methods rely on glass fiber or inorganic fillers to enhance ring stiffness, but the interfacial bonding is limited, and the reinforcement effect is constrained by dispersion, which can easily lead to a decrease in wear resistance and an increase in brittleness. On the other hand, flame retardancy usually relies on high filling of inorganic flame retardants, but high addition often disrupts the continuity of the matrix, impairing the material's wear resistance and mechanical stability.
[0005] Meanwhile, flame retardants are mostly physical fillers, which are prone to migration and loss during thermal decomposition, resulting in insufficient long-term flame retardant effect. For acid and alkali resistance, traditional processes mainly rely on the inertness of the matrix itself, but under long-term service conditions, corrosive media can still penetrate along the interface, causing quality loss and performance degradation.
[0006] In summary, conventional processes often sacrifice other properties while improving strength, and the flame retardant and corrosion-resistant effects are difficult to maintain stably and for a long time, which restricts the application of cable protection pipes in complex environments. Therefore, a solution is proposed. Summary of the Invention
[0007] The purpose of this invention is to provide a high-strength cable protection pipe and its preparation method, which solves the technical problem that the strength and flame-retardant performance of existing cable protection pipes need to be further improved.
[0008] The objective of this invention can be achieved through the following technical solution: a method for preparing a high-strength cable protection pipe, comprising the following steps:
[0009] S1. Weigh out 20-24 parts by weight of carboxylsiloxane backbone, 30-36 parts by weight of hydroxyl-terminated polyester prepolymer and 0.5-0.8 parts by weight of bisphenol A diglycidyl ether and add them to the reactor. After purging with nitrogen, add 0.05 parts by weight of 1,5,7-triazabicyclo[4.4.0]decene-5-ene. Raise the temperature of the reactor to 140-160℃ and keep it at that temperature for 2-3 hours. After post-treatment, obtain the carboxyl cyclocondensation prepolymer.
[0010] S2. By weight, weigh 60 parts of carboxylic acid cyclocondensation prepolymer, 10 parts of olefinic nanosheets, 2 parts of pentaerythritol triacrylate and 0.02 parts of dicumyl peroxide and add them to a twin-screw extruder. Melt extrusion is performed, followed by vacuum sizing, cooling, traction and cutting to obtain a high-strength cable protection tube with an inner diameter of 32 mm and an outer diameter of 36 mm.
[0011] The reaction principle for preparing high-strength cable protection pipes:
[0012] First, the carboxyl groups in the carboxysiloxane backbone and the hydroxyl groups in the hydroxyl-terminated polyester prepolymer undergo a condensation reaction under the action of an alkaline organic catalyst. At the same time, some epoxy groups participate in the ring-opening reaction to generate an organic-inorganic hybrid prepolymer containing ester bonds and ether bonds. This process not only realizes the chemical connection between the siloxane backbone and the polyester chain segment, but also introduces cross-linking points between the prepolymer molecules, thereby obtaining a reactive carboxycyclocondensation prepolymer.
[0013] Subsequently, under melt extrusion conditions, the carboxyl cyclocondensation prepolymer reacts with olefin-based nanosheets, pentaerythritol triacrylate, and a peroxide crosslinking agent. The free radical initiator decomposes at high temperature to generate free radicals, which initiate the free radical polymerization of pentaerythritol triacrylate, forming a highly crosslinked three-dimensional structure in the polyester network. The alkenyl groups on the surface of the olefin-based nanosheets participate in free radical addition, achieving "chemical bonding" with the organic network. The active groups of the carboxyl cyclocondensation prepolymer further participate in crosslinking, forming a stable interfacial bond between the organic phase and the inorganic sheet, ultimately producing a high-strength cable protection pipe.
[0014] Further, in step S1, the post-processing includes: after the reaction is completed, the reaction vessel temperature is cooled to 80-90℃ and the material is poured into sheets. After cooling and solidification at room temperature, the material is crushed and granulated to obtain cylindrical materials with a length and diameter of 3mm. The cylindrical materials are transferred to a drying oven at 80℃ and vacuum dried to constant weight. The materials are then sealed and protected from light for later use to obtain carboxyl cyclocondensation prepolymer.
[0015] Furthermore, the temperature range of the twin-screw extruder is 120℃, 150℃, 160℃, 170℃, 175℃, 180℃, 180℃, and 175℃, the rotation speed is 150 rpm, and the vacuum exhaust port pressure is -0.095 MPa.
[0016] Furthermore, in step S1, the preparation method of the carboxylsiloxane framework includes the following steps:
[0017] A1. Add vinyltrimethoxysilane, methyl orthosilicate, anhydrous ethanol and deionized water to a reaction vessel, purge with nitrogen for protection and adjust the pH of the reaction system to 4-5 with glacial acetic acid, raise the temperature of the reaction vessel to 40-60℃, keep it at the temperature and stir for 6-8 hours, and then process to obtain the ethylene siloxane precursor.
[0018] A2. Add ethylene siloxane precursor, 2-mercaptoethanol, azobisisobutyronitrile and anhydrous acetonitrile to a reaction vessel, purge nitrogen gas for protection, raise the temperature of the reaction vessel to 40-60℃, keep warm and stir for 10-12h, and then process to obtain hydroxysiloxane skeleton.
[0019] A3. Add the hydroxysiloxane skeleton, succinic anhydride and N,N-dimethylformamide to the reaction vessel and stir. After adding 4-dimethylaminopyridine and triethylamine, nitrogen gas is introduced for protection. The temperature of the reaction vessel is raised to 50-60℃ and stirred for 6-8 hours. The carboxylsiloxane skeleton is obtained after post-treatment.
[0020] The reaction principle for preparing the carboxyl-siloxane framework:
[0021] First, under acidic conditions, vinyltrimethoxysilane undergoes hydrolysis and condensation reactions with methyl orthosilicate to gradually build a silicon-oxygen network structure containing vinyl substituents. The essence of this process is a condensation reaction between silanol groups, generating an inorganic framework with Si-O-Si as the main chain, and introducing reactive vinyl groups on the surface of the framework.
[0022] Secondly, the vinyl side group reacts with 2-mercaptoethanol via a free radical-initiated thio-olefin addition reaction to introduce hydroxyl end groups on the surface of the silicon-oxygen framework. This step not only achieves efficient grafting of organic functional groups onto the inorganic framework, but also provides active sites for further chemical modification.
[0023] Finally, the surface hydroxyl groups undergo esterification / ring-opening reaction with succinic anhydride to generate stable carboxyl substituents on the surface of the skeleton. This reaction realizes the functional group transformation from hydroxyl to carboxyl, giving the silicon-oxygen skeleton higher polarity and reactivity. Through this process, a carboxyl silicon-oxygen skeleton with uniformly distributed carboxyl groups on the surface is finally obtained.
[0024] This multi-step organic-inorganic coupling process not only endows the silicon-oxygen framework with abundant surface functional groups, but also lays the chemical foundation for its application in polymer blending, interface modification and crosslinking reactions.
[0025] Further, in step A1, the ratio of vinyltrimethoxysilane, methyl orthosilicate, deionized water and anhydrous ethanol is 8-10g:7g:13-14g:100-120mL. The post-treatment includes: after the reaction is completed, after the reaction vessel temperature is cooled to room temperature, the filter cake is collected by suction filtration. The filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and then vacuum dried in a vacuum drying oven at 80℃ to constant weight to obtain the ethylene siloxane precursor.
[0026] Further, in step A2, the ratio of the ethylene siloxane precursor, 2-mercaptoethanol azobisisobutyronitrile, and anhydrous acetonitrile is 5-6 g: 2 g: 0.05 g: 80 mL. The post-treatment includes: after the reaction is completed, after the reaction vessel temperature is cooled to room temperature, the filter cake is collected by suction filtration. The filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and then vacuum dried in a vacuum drying oven at 80°C to constant weight to obtain the hydroxysiloxane skeleton.
[0027] Further, in step A3, the ratio of the hydroxysiloxane skeleton, succinic anhydride, N,N-dimethylformamide, 4-dimethylaminopyridine, and triethylamine is 5g:2g:60-80mL:0.08-0.10g:0.2-0.3g. The post-processing includes: after the reaction is completed, after the reaction vessel temperature is cooled to room temperature, the filter cake is collected by suction filtration. The filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and then vacuum dried in a vacuum drying oven at 80°C to constant weight to obtain the carboxylsiloxane skeleton.
[0028] Furthermore, in step S1, the method for preparing the multi-point cross-linked three-dimensional network includes the following steps:
[0029] B1. Add adipic acid and glycerol to a reaction vessel, purge with nitrogen for protection, raise the temperature of the reaction vessel to 150-180℃, keep warm and stir for 4-6 hours, and then process to obtain hydroxyl-terminated polyester prepolymer.
[0030] B2. Hydroxyl-terminated polyester prepolymer, bisphenol A diglycidyl ether and 1,5,7-triazabicyclo[4.4.0]decene were added to the reactor. After nitrogen protection, the reactor temperature was raised to 120-160℃ and kept at this temperature for 6-8 hours. The post-treatment yielded a multi-point cross-linked three-dimensional network.
[0031] The reaction principle for preparing multi-point cross-linked three-dimensional networks:
[0032] First, adipic acid and glycerol undergo a condensation reaction under heating conditions, forming ester bonds between carboxyl and hydroxyl groups, gradually constructing a linear or slightly branched polyester structure with ester bonds as the main chain. Since the glycerol molecule contains three hydroxyl groups, its introduction allows unreacted hydroxyl groups to remain at the ends of the polyester chain, providing reaction sites for subsequent reactions.
[0033] Subsequently, the hydroxyl-terminated polyester and bisphenol A diglycidyl ether undergo a ring-opening addition reaction under the catalysis of the strong organic base 1,5,7-triazabicyclo[4.4.0]decene. After the epoxy group is activated under alkaline conditions, it undergoes nucleophilic ring-opening with the hydroxyl group at the end of the polyester chain to generate new hydroxyl groups and ether bonds. This process not only enables cross-linking between molecules, but also introduces more hydroxyl groups, thereby forming a three-dimensional network structure with multi-point cross-linking.
[0034] Further, in step B1, the ratio of adipic acid to glycerol is 4-5g:5g, and the post-processing includes: after the reaction is completed, after the temperature of the reaction vessel is cooled to room temperature, the reaction liquid is transferred to a rotary evaporator at a temperature of 80°C, and the pressure is reduced and distilled until no liquid is collected to obtain the hydroxyl-terminated polyester prepolymer.
[0035] Further, in step B2, the ratio of the hydroxyl-terminated polyester prepolymer, bisphenol A diglycidyl ether, and 1,5,7-triazabicyclodecene is 8-10g:5g:0.05g. The post-processing includes: after the reaction is completed, the reaction vessel is cooled to room temperature, the reaction solution is transferred to a rotary evaporator at 80°C, and the pressure is reduced and distilled until no liquid is collected, thus obtaining a multi-point cross-linked three-dimensional network.
[0036] Furthermore, in step S1, the method for preparing the olefin-based nanosheets includes the following steps:
[0037] C1. Add magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and deionized water to a reaction vessel and stir. After purging with nitrogen for protection, add sodium carbonate and sodium hydroxide and raise the temperature of the reaction vessel to 50-60℃. Keep it warm and stir for 5-6 hours. After post-treatment, magnesium aluminum layered hydroxide is obtained.
[0038] C2. Magnesium-aluminum layered hydroxyl, anhydrous ethanol, 3-methacryloyloxypropyltrimethoxysilane and deionized water are added to a reaction vessel. Nitrogen gas is introduced for protection and the pH of the reaction system is adjusted to 4-5 using glacial acetic acid. The temperature of the reaction vessel is then raised to 40-60℃ and stirred for 6-8 hours. Post-treatment yields olefinic layered nanosheets.
[0039] The reaction principle for preparing olefin-based nanosheets:
[0040] First, magnesium salts and aluminum salts are used as raw materials and hydrolyzed and precipitated simultaneously under alkaline conditions to form magnesium-aluminum layered hydroxides with a layered crystal structure. This material has a typical two-dimensional layered framework, with metal cations arranged in a certain proportion at octahedral positions, forming layers by coordination of hydroxyl groups, and maintaining the interlayer charge balance through intercalation anions, thereby obtaining a regular layered stacked structure.
[0041] Subsequently, an organosilane coupling agent containing alkenyl functional groups is used to undergo hydrolysis and condensation under acidic conditions to generate siloxane intermediates with active allyl side groups. These intermediates can undergo condensation reactions with hydroxyl groups on the surface of magnesium-aluminum layered hydroxides to achieve covalent grafting of organic functional groups. Through this process, alkenyl substituents are introduced into the surface of the layered inorganic sheet, giving it both the structural stability of the inorganic layered framework and the reactivity of the organic alkenyl group.
[0042] The resulting alkenyl-based nanosheets not only maintain the thermal stability and mechanical reinforcement of layered inorganic materials, but also allow their surface alkenyl groups to participate in free radical polymerization or cross-linking reactions, thereby significantly improving interfacial compatibility and reactivity with the polymer matrix.
[0043] Further, in step C1, the ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, deionized water, sodium carbonate, and sodium hydroxide is 8-10g:3.0-3.6g:100mL:5g:2g. The post-treatment includes: after the reaction is completed, after the reaction vessel temperature is cooled to room temperature, the filter cake is collected by suction filtration. The filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and then vacuum dried in a vacuum drying oven at 80℃ to constant weight to obtain magnesium aluminum layered hydroxide.
[0044] Further, in step C2, the ratio of the magnesium-aluminum layered hydroxyl, anhydrous ethanol, deionized water, and 3-methacryloyloxypropyltrimethoxysilane is 4-5g:80mL:20mL:5-6g. The post-treatment includes: after the reaction is completed, after the reaction vessel temperature is cooled to room temperature, the filter cake is collected by suction filtration. The filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and then vacuum dried in a vacuum drying oven at 80°C to constant weight to obtain olefin layered nanosheets.
[0045] The present invention also proposes a high-strength cable protection pipe, which is prepared by the above-mentioned method for preparing a high-strength cable protection pipe.
[0046] The present invention has the following beneficial effects:
[0047] The carboxylated silicon-oxygen framework and olefinic nanosheets prepared in this invention together constitute a rigid inorganic phase, which can improve the overall modulus and structural stability of the material on a macroscopic scale, thereby significantly enhancing the pipe's resistance to deformation under external loads and making its ring stiffness superior to that of traditional polymer pipes. At the same time, the hydroxyl-terminated polyester crosslinked network provides a flexible and dense three-dimensional organic phase, which allows stress to be effectively transferred and dispersed in the pipe wall, avoiding local stress concentration and further improving compressive strength. On the other hand, the uniform dispersion and "chemical riveting" effect of the nanosheets in the polymer matrix not only improves the interfacial bonding strength, but also forms a reinforced support structure during friction, reducing surface wear. Combined with the surface hardness improvement brought by the highly crosslinked polyester network, the pipe maintains excellent wear resistance even under long-term operation and complex working conditions. Finally, through the synergistic effect of the inorganic rigid phase and the organic tough phase, the cable protection pipe has both high ring stiffness and excellent wear resistance.
[0048] The carboxylated silicon-oxygen framework prepared by this invention can form a stable inorganic silicon oxide layer during combustion. This dense layer effectively isolates the transfer of heat and oxygen, inhibiting further thermal decomposition of the matrix. At the same time, the olefinic layered nanosheets have a layered shielding effect at high temperatures. Their two-dimensional sheets can prevent the escape of combustible small molecules and the penetration of external heat, thereby slowing down the flame propagation speed. In the organic phase, the three-dimensional dense network formed by the hydroxyl-terminated polyester after epoxy ring-opening crosslinking not only improves the thermal stability of the material, but also promotes the formation of a char layer during pyrolysis, further enhancing the barrier effect. Finally, through the synergistic effect of the inorganic framework, layered nanosheets and crosslinked polyester network, the material can quickly construct a composite flame-retardant barrier of heat insulation, oxygen isolation and smoke suppression when heated, significantly improving the flame retardant level and safety. This enables the cable protection pipe to effectively reduce the risk of combustion in complex application environments and ensure the safe operation of the power system.
[0049] The carboxylated silicon-oxygen framework prepared by this invention has a highly stable -Si-O-Si backbone, and its chemical inertness endows the material with good acid and alkali resistance, enabling it to maintain structural integrity in corrosive media. The alkenyl layered nanosheets are uniformly dispersed in the matrix, forming an "interfacial barrier" through the chemical combination of surface alkenyl groups and organic phases, blocking the penetration channels of acid and alkali molecules at the microscopic level, effectively slowing down the erosion of polymer segments by the medium. At the same time, the three-dimensional cross-linked network constructed by the hydroxyl-terminated polyester through the epoxy ring-opening reaction makes the internal structure of the pipe dense, significantly reducing the penetration rate of acid and alkali solutions. Through the synergistic effect of the three, not only is the overall chemical stability of the material improved, but the corrosion resistance life under long-term service environment is also enhanced, enabling the cable protection pipe to maintain excellent performance and stability in complex environments such as acidic soil, alkaline groundwater and saline media, providing reliable protection for power systems. Detailed Implementation
[0050] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0051] Example 1
[0052] This embodiment provides a method for preparing a high-strength cable protection control spare carboxylated silicon oxide skeleton, including the following steps:
[0053] Step ①: Preparation of ethylene-siloxane precursor
[0054] Weigh out 80.0 g of vinyltrimethoxysilane, 70.0 g of methyl orthosilicate, 130.0 g of anhydrous ethanol and 1000.0 mL of deionized water and add them to a reaction vessel. After purging with nitrogen and adjusting the pH of the reaction system to 4 with glacial acetic acid, raise the temperature of the reaction vessel to 40 °C and keep it at this temperature for 6 h with stirring. After the reaction is complete, wait for the temperature of the reaction vessel to cool to room temperature, filter and collect the filter cake. Wash the filter cake three times with anhydrous ethanol and deionized water, and then vacuum dry it to constant weight in a vacuum drying oven at 80 °C to obtain the ethylene siloxane precursor.
[0055] Step 2: Preparation of the hydroxysiloxane framework
[0056] Weigh out 50.0g of ethylene siloxane precursor, 20.0g of 2-mercaptoethanol, 5.0g of azobisisobutyronitrile and 800.0mL of anhydrous acetonitrile and add them to the reaction vessel. After nitrogen protection, the temperature of the reaction vessel is raised to 40℃ and kept at this temperature with stirring for 10h. After the reaction is completed, the temperature of the reaction vessel is cooled to room temperature, and the filter cake is collected by vacuum filtration. The filter cake is washed three times with anhydrous ethanol and deionized water and then vacuum dried to constant weight in a vacuum drying oven at 80℃ to obtain the hydroxysiloxane framework.
[0057] Step ③: Preparation of carboxylsiloxane framework
[0058] Weigh out 50.0 g of hydroxysiloxane skeleton, 20.0 g of succinic anhydride and 600.0 mL of N,N-dimethylformamide and add them to the reaction vessel and stir. Add 0.8 g of 4-dimethylaminopyridine and 2.0 g of triethylamine and then purge with nitrogen for protection. Raise the temperature of the reaction vessel to 50 °C and keep it at this temperature for 6 h with stirring. After the reaction is complete, let the temperature of the reaction vessel cool to room temperature, filter and collect the filter cake. Wash the filter cake three times with anhydrous ethanol and deionized water and then vacuum dry it to constant weight in a vacuum drying oven at 80 °C to obtain the carboxylsiloxane skeleton.
[0059] Example 2
[0060] This embodiment provides a method for preparing a high-strength cable protection control spare carboxylated silicon oxide skeleton, including the following steps:
[0061] Step ①: Preparation of ethylene-siloxane precursor
[0062] Weigh out 100.0g vinyltrimethoxysilane, 70.0g methyl orthosilicate, 140.0g anhydrous ethanol and 1200.0mL deionized water and add them to the reaction vessel. After purging with nitrogen and adjusting the pH of the reaction system to 5 with glacial acetic acid, raise the temperature of the reaction vessel to 60℃ and stir for 8 hours. After the reaction is completed, wait for the temperature of the reaction vessel to cool to room temperature, filter and collect the filter cake. Wash the filter cake 5 times with anhydrous ethanol and deionized water, and then vacuum dry it to constant weight in a vacuum drying oven at 80℃ to obtain the ethylene siloxane precursor.
[0063] Step 2: Preparation of the hydroxysiloxane framework
[0064] Weigh out 60.0 g of ethylene siloxane precursor, 20.0 g of 2-mercaptoethanol, 0.5 g of azobisisobutyronitrile and 800.0 mL of anhydrous acetonitrile and add them to a reaction vessel. After purging with nitrogen, the temperature of the reaction vessel is raised to 60 °C and kept at this temperature with stirring for 12 h. After the reaction is completed, the temperature of the reaction vessel is cooled to room temperature, and the filter cake is collected by vacuum filtration. The filter cake is washed 5 times with anhydrous ethanol and deionized water and then vacuum dried in a vacuum drying oven at 80 °C to constant weight to obtain the hydroxysiloxane framework.
[0065] Step ③: Preparation of carboxylsiloxane framework
[0066] Weigh out 50.0 g of hydroxysiloxane skeleton, 20.0 g of succinic anhydride and 800.0 mL of N,N-dimethylformamide and add them to the reaction vessel and stir. Add 1.0 g of 4-dimethylaminopyridine and 3.0 g of triethylamine and then purge with nitrogen for protection. Raise the temperature of the reaction vessel to 60 °C and keep it at this temperature for 8 h with stirring. After the reaction is complete, wait for the temperature of the reaction vessel to cool to room temperature, filter and collect the filter cake. Wash the filter cake four times with anhydrous ethanol and deionized water and then vacuum dry it to constant weight in a vacuum drying oven at 80 °C to obtain the carboxylsiloxane skeleton.
[0067] Example 3
[0068] This embodiment provides a method for preparing a high-strength cable protection control spare carboxylated silicon oxide skeleton, including the following steps:
[0069] Step ①: Preparation of ethylene-siloxane precursor
[0070] Weigh out 90.0 g of vinyltrimethoxysilane, 70.0 g of methyl orthosilicate, 135.0 g of anhydrous ethanol and 1200.0 mL of deionized water and add them to a reaction vessel. After purging with nitrogen and adjusting the pH of the reaction system to 4 with glacial acetic acid, raise the temperature of the reaction vessel to 50 °C and stir for 7 h. After the reaction is completed, wait for the temperature of the reaction vessel to cool to room temperature, filter and collect the filter cake. Wash the filter cake 4 times with anhydrous ethanol and deionized water, and then vacuum dry it to constant weight in a vacuum drying oven at 80 °C to obtain the ethylene siloxane precursor.
[0071] Step 2: Preparation of the hydroxysiloxane framework
[0072] Weigh out 54.0 g of ethylene siloxane precursor, 20.0 g of 2-mercaptoethanol, 0.5 g of azobisisobutyronitrile and 800.0 mL of anhydrous acetonitrile and add them to a reaction vessel. After purging with nitrogen, the temperature of the reaction vessel is raised to 50 °C and kept at this temperature with stirring for 12 h. After the reaction is completed, the temperature of the reaction vessel is cooled to room temperature, and the filter cake is collected by vacuum filtration. The filter cake is washed four times with anhydrous ethanol and deionized water and then vacuum dried in a vacuum drying oven at 80 °C to constant weight to obtain the hydroxysiloxane framework.
[0073] Step ③: Preparation of carboxylsiloxane framework
[0074] Weigh out 50.0 g of hydroxysiloxane skeleton, 20.0 g of succinic anhydride and 700.0 mL of N,N-dimethylformamide and add them to the reaction vessel and stir. Add 0.9 g of 4-dimethylaminopyridine and 2.5 g of triethylamine and then purge with nitrogen for protection. Raise the temperature of the reaction vessel to 55 °C and keep it at this temperature for 7 h with stirring. After the reaction is complete, wait for the temperature of the reaction vessel to cool to room temperature, filter and collect the filter cake. Wash the filter cake four times with anhydrous ethanol and deionized water and then vacuum dry it to constant weight in a vacuum drying oven at 80 °C to obtain the carboxylsiloxane skeleton.
[0075] Example 4
[0076] This embodiment provides a method for preparing a high-strength cable protection control backup multi-point cross-linked three-dimensional network, including the following steps:
[0077] Step I: Preparation of hydroxyl-terminated polyester prepolymer
[0078] Weigh out 40.0g adipic acid and 50.0g glycerol and add them to the reaction vessel. After purging with nitrogen, raise the temperature of the reaction vessel to 150℃ and keep it at this temperature for 4 hours with stirring. After the reaction is complete, wait for the temperature of the reaction vessel to cool to room temperature, transfer the reaction solution to a rotary evaporator at 80℃, and distill it under reduced pressure until no liquid is collected, to obtain the hydroxyl-terminated polyester prepolymer.
[0079] Step II: Preparation of a multi-point cross-linked three-dimensional network
[0080] Weigh out 80.0g of hydroxyl-terminated polyester prepolymer, 50.0g of bisphenol A diglycidyl ether and 0.5g of 1,5,7-triazabicyclo[4.4.0]decene and add them to the reactor. After nitrogen protection, the reactor temperature is raised to 120℃ and kept at this temperature for 6 hours. After the reaction is completed, wait for the reactor temperature to cool to room temperature, transfer the reaction solution to a rotary evaporator at 80℃, and distill under reduced pressure until no liquid is collected to obtain a multi-point cross-linked three-dimensional network.
[0081] Example 5
[0082] This embodiment provides a method for preparing a high-strength cable protection control backup multi-point cross-linked three-dimensional network, including the following steps:
[0083] Step I: Preparation of hydroxyl-terminated polyester prepolymer
[0084] Weigh out 50.0g adipic acid and 50.0g glycerol and add them to the reaction vessel. After purging with nitrogen, raise the temperature of the reaction vessel to 180℃ and keep it at this temperature for 6 hours with stirring. After the reaction is complete, wait for the temperature of the reaction vessel to cool to room temperature, transfer the reaction solution to a rotary evaporator at 80℃, and distill it under reduced pressure until no liquid is collected, to obtain the hydroxyl-terminated polyester prepolymer.
[0085] Step II: Preparation of a multi-point cross-linked three-dimensional network
[0086] Weigh out 100.0g of hydroxyl-terminated polyester prepolymer, 50.0g of bisphenol A diglycidyl ether and 0.5g of 1,5,7-triazabicyclo[4.4.0]decene and add them to the reactor. After nitrogen protection, the reactor temperature is raised to 160℃ and kept at this temperature for 8 hours. After the reaction is completed, wait for the reactor temperature to cool to room temperature, transfer the reaction solution to a rotary evaporator at 80℃, and distill under reduced pressure until no liquid is collected to obtain a multi-point cross-linked three-dimensional network.
[0087] Example 6
[0088] This embodiment provides a method for preparing a high-strength cable protection control backup multi-point cross-linked three-dimensional network, including the following steps:
[0089] Step I: Preparation of hydroxyl-terminated polyester prepolymer
[0090] Weigh out 45.0g of adipic acid and 50.0g of glycerol and add them to the reaction vessel. After purging with nitrogen, raise the temperature of the reaction vessel to 160℃ and keep it at this temperature for 5 hours with stirring. After the reaction is complete, wait for the temperature of the reaction vessel to cool to room temperature, transfer the reaction solution to a rotary evaporator at 80℃, and distill it under reduced pressure until no liquid is collected, thus obtaining the hydroxyl-terminated polyester prepolymer.
[0091] Step II: Preparation of a multi-point cross-linked three-dimensional network
[0092] Weigh out 90.0g of hydroxyl-terminated polyester prepolymer, 50.0g of bisphenol A diglycidyl ether and 0.5g of 1,5,7-triazabicyclo[4.4.0]decene and add them to the reactor. After nitrogen protection, the reactor temperature is raised to 150℃ and kept at this temperature for 7 hours. After the reaction is completed, wait for the reactor temperature to cool to room temperature, transfer the reaction solution to a rotary evaporator at 80℃, and distill under reduced pressure until no liquid is collected to obtain a multi-point cross-linked three-dimensional network.
[0093] Example 7
[0094] This embodiment provides a method for preparing high-strength cable protection and backup olefin-based nanosheets, including the following steps:
[0095] Step (1): Preparation of magnesium-aluminum layered hydroxides
[0096] Weigh out 80.0 g of magnesium nitrate hexahydrate, 30.0 g of aluminum nitrate nonahydrate, and 1000.0 mL of deionized water and add them to a reaction vessel. Stir and purge with nitrogen for protection. Then add 50.0 g of sodium carbonate and 20.0 g of sodium hydroxide and raise the temperature of the reaction vessel to 50°C. Keep the temperature and stir for 5 hours. After the reaction is complete, let the temperature of the reaction vessel cool to room temperature. Collect the filter cake by vacuum filtration. Wash the filter cake three times with anhydrous ethanol and deionized water. Then vacuum dry it to constant weight in a vacuum drying oven at 80°C to obtain magnesium aluminum layered hydroxide.
[0097] Step 2: Preparation of olefin-based nanosheets
[0098] Weigh out 40.0 g of magnesium aluminum layered hydroxyl group, 800.0 mL of anhydrous ethanol, 50.0 g of 3-methacryloxypropyltrimethoxysilane, and 200.0 mL of deionized water and add them to the reaction vessel. After purging with nitrogen and adjusting the pH of the reaction system to 4 with glacial acetic acid, raise the temperature of the reaction vessel to 40 °C and keep it at this temperature for 6 h with stirring. After the reaction is completed, wait for the temperature of the reaction vessel to cool to room temperature, filter and collect the filter cake. Wash the filter cake three times with anhydrous ethanol and deionized water, and then vacuum dry it to constant weight in a vacuum drying oven at 80 °C to obtain olefin layered nanosheets.
[0099] Example 8
[0100] This embodiment provides a method for preparing high-strength cable protection and backup olefin-based nanosheets, including the following steps:
[0101] Step (1): Preparation of magnesium-aluminum layered hydroxides
[0102] Weigh out 100.0g of magnesium nitrate hexahydrate, 36.0g of aluminum nitrate nonahydrate, and 1000.0mL of deionized water and add them to the reaction vessel. Stir and purge with nitrogen for protection. Then add 5g of sodium carbonate and 2g of sodium hydroxide and raise the temperature of the reaction vessel to 60℃. Keep the temperature and stir for 6 hours. After the reaction is complete, let the temperature of the reaction vessel cool to room temperature. Collect the filter cake by vacuum filtration. Wash the filter cake 5 times with anhydrous ethanol and deionized water. Then vacuum dry it to constant weight in a vacuum drying oven at 80℃ to obtain magnesium aluminum layered hydroxide.
[0103] Step 2: Preparation of olefin-based nanosheets
[0104] Weigh out 50.0g of magnesium aluminum layered hydroxyl group, 800.0mL of anhydrous ethanol, 60.0g of 3-methacryloxypropyltrimethoxysilane, and 200.0mL of deionized water and add them to the reaction vessel. After purging with nitrogen and adjusting the pH of the reaction system to 4 with glacial acetic acid, raise the temperature of the reaction vessel to 60℃ and keep it at this temperature for 8 hours with stirring. After the reaction is completed, wait for the temperature of the reaction vessel to cool to room temperature, filter and collect the filter cake. Wash the filter cake 5 times with anhydrous ethanol and deionized water, and then vacuum dry it to constant weight in a vacuum drying oven at 80℃ to obtain olefin layered nanosheets.
[0105] Example 9
[0106] This embodiment provides a method for preparing high-strength cable protection and backup olefin-based nanosheets, including the following steps:
[0107] Step (1): Preparation of magnesium-aluminum layered hydroxides
[0108] Weigh out 90.0 g of magnesium nitrate hexahydrate, 32.0 g of aluminum nitrate nonahydrate, and 1000.0 mL of deionized water and add them to a reaction vessel. Stir and purge with nitrogen. Then add 50.0 g of sodium carbonate and 20.0 g of sodium hydroxide and raise the temperature of the reaction vessel to 55°C. Keep the temperature and stir for 6 hours. After the reaction is complete, let the temperature of the reaction vessel cool to room temperature. Collect the filter cake by vacuum filtration. Wash the filter cake four times with anhydrous ethanol and deionized water. Then vacuum dry it to constant weight in a vacuum drying oven at 80°C to obtain magnesium aluminum layered hydroxide.
[0109] Step 2: Preparation of olefin-based nanosheets
[0110] Weigh out 45.0g of magnesium aluminum layered hydroxyl group, 800.0mL of anhydrous ethanol, 55.0g of 3-methacryloxypropyltrimethoxysilane, and 200.0mL of deionized water and add them to the reaction vessel. After purging with nitrogen and adjusting the pH of the reaction system to 4 with glacial acetic acid, raise the temperature of the reaction vessel to 50℃ and stir for 7h. After the reaction is completed, wait for the temperature of the reaction vessel to cool to room temperature, collect the filter cake by vacuum filtration, wash the filter cake 4 times with anhydrous ethanol and deionized water, and then vacuum dry it to constant weight in a vacuum drying oven at 80℃ to obtain olefin layered nanosheets.
[0111] Example 10
[0112] This embodiment provides a method for preparing a high-strength cable protection pipe, including the following steps:
[0113] Step 1: Preparation of carboxyl cyclocondensation prepolymer
[0114] By weight, 20 parts of the carboxysiloxane skeleton prepared in Example 1, 30 parts of the hydroxyl-terminated polyester prepolymer prepared in Example 4, and 0.5 parts of bisphenol A diglycidyl ether were weighed and added to the reactor. After nitrogen protection, 0.05 parts of 1,5,7-triazabicyclo[4.4.0]decene-5-ene were added. The reactor temperature was raised to 140°C and kept at that temperature for 2 hours. After the reaction was completed, the reactor temperature was cooled to 80°C and the mixture was sheeted. After cooling and solidification at room temperature, the mixture was crushed and granulated to obtain cylindrical materials with a length and diameter of 3 mm. The cylindrical materials were transferred to a drying oven at 80°C and vacuum dried to constant weight. The materials were then sealed and protected from light for later use to obtain the carboxycyclic condensation prepolymer.
[0115] Step 2: Preparation of high-strength cable protection pipe
[0116] By weight, 60 parts of carboxyl cyclocondensation prepolymer, 10 parts of olefinic nanosheets prepared in Example 7, 2 parts of pentaerythritol triacrylate, and 0.02 parts of dicumyl peroxide were weighed and added to a twin-screw extruder. The temperature range of the twin-screw extruder was 120°C, 150°C, 160°C, 170°C, 175°C, 180°C, 180°C, and 175°C, the rotation speed was 150 rpm, and the vacuum exhaust pressure was -0.095 MPa. The material was melt-extruded, and after vacuum sizing, cooling, traction, and cutting, a high-strength cable protection tube with an inner diameter of 32 mm and an outer diameter of 36 mm was obtained.
[0117] Example 11
[0118] This embodiment provides a method for preparing a high-strength cable protection pipe, including the following steps:
[0119] Step 1: Preparation of carboxyl cyclocondensation prepolymer
[0120] By weight, 24 parts of the carboxysiloxane skeleton prepared in Example 2, 36 parts of the hydroxyl-terminated polyester prepolymer prepared in Example 5, and 0.8 parts of bisphenol A diglycidyl ether were weighed and added to the reactor. After nitrogen protection, 0.05 parts of 1,5,7-triazabicyclo[4.4.0]decene-5-ene were added. The reactor temperature was raised to 160°C and kept at that temperature for 3 hours. After the reaction was completed, the reactor temperature was cooled to 90°C and the mixture was sheeted. After cooling and solidification at room temperature, the mixture was crushed and granulated to obtain cylindrical materials with a length and diameter of 3 mm. The cylindrical materials were transferred to a drying oven at 80°C and vacuum dried to constant weight. The materials were then sealed and protected from light for later use to obtain the carboxycyclic condensation prepolymer.
[0121] Step 2: Preparation of high-strength cable protection pipe
[0122] By weight, 60 parts of carboxyl cyclocondensation prepolymer, 10 parts of olefinic nanosheets prepared in Example 8, 2 parts of pentaerythritol triacrylate, and 0.02 parts of dicumyl peroxide were weighed and added to a twin-screw extruder. The temperature range of the twin-screw extruder was 120°C, 150°C, 160°C, 170°C, 175°C, 180°C, 180°C, and 175°C, the rotation speed was 150 rpm, and the vacuum exhaust pressure was -0.095 MPa. The material was melt-extruded, and after vacuum sizing, cooling, traction, and cutting, a high-strength cable protection tube with an inner diameter of 32 mm and an outer diameter of 36 mm was obtained.
[0123] Example 12
[0124] This embodiment provides a method for preparing a high-strength cable protection pipe, including the following steps:
[0125] Step 1: Preparation of carboxyl cyclocondensation prepolymer
[0126] By weight, 21 parts of the carboxysiloxane skeleton prepared in Example 3, 32 parts of the hydroxyl-terminated polyester prepolymer prepared in Example 6, and 0.6 parts of bisphenol A diglycidyl ether were weighed and added to the reactor. After nitrogen protection, 0.05 parts of 1,5,7-triazabicyclo[4.4.0]decene-5-ene were added. The reactor temperature was raised to 150°C and kept at that temperature for 3 hours. After the reaction was completed, the reactor temperature was cooled to 85°C and the mixture was sheeted. After cooling and solidification at room temperature, the mixture was crushed and granulated to obtain cylindrical materials with a length and diameter of 3 mm. The cylindrical materials were transferred to a drying oven at 80°C and vacuum dried to constant weight. The materials were then sealed and protected from light for later use to obtain the carboxycyclic condensation prepolymer.
[0127] Step 2: Preparation of high-strength cable protection pipe
[0128] By weight, 60 parts of carboxyl cyclocondensation prepolymer, 10 parts of olefinic nanosheets prepared in Example 9, 2 parts of pentaerythritol triacrylate, and 0.02 parts of dicumyl peroxide were weighed and added to a twin-screw extruder. The temperature range of the twin-screw extruder was 120°C, 150°C, 160°C, 170°C, 175°C, 180°C, 180°C, and 175°C, the rotation speed was 150 rpm, and the vacuum exhaust pressure was -0.095 MPa. The material was melt-extruded, and after vacuum sizing, cooling, traction, and cutting, a high-strength cable protection tube with an inner diameter of 32 mm and an outer diameter of 36 mm was obtained.
[0129] Comparative Example 1
[0130] The difference between this comparative example and Example 12 is that step (2) is omitted in the preparation of the olefinic nanosheets used in step two.
[0131] Comparative Example 2
[0132] The difference between this comparative example and Example 12 is that step ③ is omitted in the preparation process of the carboxysiloxane framework used in step one.
[0133] Comparative Example 3
[0134] The difference between this comparative example and Example 12 is that step II is omitted in the preparation of the hydroxyl-terminated polyester prepolymer used in step one.
[0135] Performance testing:
[0136] The ring stiffness of the high-strength cable protection pipes prepared in Examples 10-12 and Comparative Examples 1-3 was tested in accordance with the standard DL / T 802.9-2018 "Technical Conditions for Conduits for Power Cables Part 9: High-strength Polyvinyl Chloride Plastic Cable Conduits";
[0137] The volumetric abrasion of the high-strength cable protection pipes prepared in Examples 10-12 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 9867-2008 "Determination of abrasion resistance of vulcanized rubber or thermoplastic rubber (rotary roller abrasion tester method)".
[0138] The limiting oxygen index of the high-strength cable protection pipes prepared in Examples 10-12 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 26526-2011 "Determination of Combustion Behavior by Oxygen Index Method for Plastics - Part 2: Room Temperature Test".
[0139] The high-strength cable protection pipes prepared in Examples 10-12 and Comparative Examples 1-3 were tested in accordance with the standard HG / T 4087-2009 "Plastic Alloy Corrosion-Resistant Composite Pipes". The specific data are shown in Table 1.
[0140] Table 1 - Performance Test Data for Each Sample
[0141]
[0142] Data Analysis:
[0143] A comparative analysis of the data in Table 1 reveals that the high-strength cable protection pipe prepared by this invention has a ring stiffness (3%) of 20.1 kPa and a volumetric wear of 36 mm. 3 With a limiting oxygen index of 35.9%, the mass loss due to corrosion by 30% H2SO4 is 1.5 g·m³. -2 Corrosion mass loss is 2.0 g·m -2 All data points are better than the comparative data, indicating that:
[0144] In Comparative Example 1, after using unalkened layered nanosheets, the bonding work between the sheets and the matrix decreased significantly after the loss of interfacial chemical "riveting," the dispersion stability weakened, and agglomeration and interfacial micropores were easily formed. The stress transmission changed from a continuous load path to interfacial slip and stress concentration. Macroscopically, this manifested as a decrease in the elastic modulus and structural retention under compression deformation. At the same time, the tortuosity of the shielding path decreased, combustible small molecules and heat passed quickly between the sheets, the critical conditions for pyrolysis rate and flame propagation were met earlier, and the oxygen index decreased. During the wear process, interfacial peeling and sheet pull-out phenomena increased, the production of wear debris increased, the grooves deepened, and the volumetric wear increased. Meanwhile, acid and alkali media penetrated along the low-energy interface and expanded the defects, the equivalent diffusion coefficient increased, and the corrosion quality loss increased.
[0145] The silicon-oxygen framework used in Comparative Example 2 was not carboxylated, resulting in the loss of active anchor points and a significant reduction in the chemical bond density between the framework and the organic phase. The interfacial interaction shifted from being dominated by chemical bonds to being dominated by secondary interactions, leading to a decrease in interfacial shear strength and stress transfer efficiency, as well as damage to network continuity. Microscopically, phase boundary discontinuities and local relaxation zones appeared, making it difficult for stress to diffuse uniformly across phases under compressive loads, and causing a decrease in circumferential stiffness. Under thermally activated conditions, the interface debonding first induced crack initiation and propagation, weakening the effective area for carbon suppression and carbon formation, delaying the formation of the thermal-oxygen barrier, and causing a decline in the oxygen index. Furthermore, under the action of chemical media, the interfacial polarity mismatch caused an increase in media-friendly channels and a shortened penetration path, resulting in early and accelerated quality loss and performance degradation.
[0146] After losing the three-dimensional chemical network, the material in Comparative Example 3 changed from a state of "restricted migration" to one of "high free volume fraction". The chain segments under load and temperature rise showed significant relaxation and flow. After compression deformation, the rebound was insufficient, resulting in reduced ring stiffness and dimensional stability. In frictional contact, the surface bearing changed from overall pressure to local yielding and plowing. Micro-cutting and fatigue spalling coexisted, and the wear rate increased significantly. In the thermal decomposition stage, the proportion of restricted phase decreased, volatile products were more likely to escape, the continuity and density of the carbon layer were difficult to establish, the flame expansion threshold decreased and the oxygen index decreased. At the same time, under the action of chemical media, the free volume and swelling coefficient increased, diffusion and wetting accelerated, and the interface and bulk phase synergistic barrier failed, resulting in a significant increase in the mass loss due to acid and alkali corrosion.
[0147] In conclusion, the high-strength cable protection pipe prepared by this invention achieves a comprehensive improvement in mechanical, wear-resistant, flame-retardant, and chemical resistance properties through the synergistic effect of a multiphase system. Specifically, the carboxylated silicon-oxygen framework provides a stable and robust inorganic framework for the system, while simultaneously constructing an effective reaction interface for the organic phase. The alkenylated layered nanosheets are uniformly dispersed in the matrix and form a dense barrier through interfacial bonding, effectively blocking stress concentration and corrosive media penetration. The cross-linked polyester network forms a three-dimensional constraint in the organic phase, restricting chain segment migration and ensuring the overall structural stability. These three components complement and support each other, enabling the material to maintain excellent levels in ring stiffness, wear resistance, flame retardancy, and acid and alkali corrosion resistance. The comparative results further confirm the necessity of this system: weakening any link will lead to an overall decline in performance. Therefore, this solution not only meets the multiple requirements of cable protection pipes in complex service environments but also exhibits comprehensive performance advantages that are difficult to obtain through a single modification method.
[0148] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims
1. A method for preparing a high-strength cable protection pipe, characterized in that, Includes the following steps: S1. Weigh out 20-24 parts by weight of carboxylsiloxane backbone, 30-36 parts by weight of hydroxyl-terminated polyester prepolymer and 0.5-0.8 parts by weight of bisphenol A diglycidyl ether and add them to the reactor. After purging with nitrogen, add 0.05 parts by weight of 1,5,7-triazabicyclo[4.4.0]decene-5-ene. Raise the temperature of the reactor to 140-160℃ and keep it at that temperature for 2-3 hours. After post-treatment, obtain the carboxyl cyclocondensation prepolymer. S2. By weight, weigh 60 parts of carboxylic acid cyclocondensation prepolymer, 10 parts of olefinic nanosheets, 2 parts of pentaerythritol triacrylate and 0.02 parts of dicumyl peroxide and add them to a twin-screw extruder. Melt extrusion is performed, followed by vacuum sizing, cooling, traction and cutting to obtain a high-strength cable protection tube with an inner diameter of 32 mm and an outer diameter of 36 mm.
2. The method for preparing a high-strength cable protection pipe according to claim 1, characterized in that, In step S1, the method for preparing the carboxylsiloxane framework includes the following steps: A1. Add vinyltrimethoxysilane, methyl orthosilicate, anhydrous ethanol and deionized water to a reaction vessel, purge with nitrogen for protection and adjust the pH of the reaction system to 4-5 with glacial acetic acid, raise the temperature of the reaction vessel to 40-60℃, keep it at the temperature and stir for 6-8 hours, and then process to obtain the ethylene siloxane precursor. A2. Add ethylene siloxane precursor, 2-mercaptoethanol, azobisisobutyronitrile and anhydrous acetonitrile to a reaction vessel, purge nitrogen gas for protection, raise the temperature of the reaction vessel to 40-60℃, keep warm and stir for 10-12h, and then process to obtain hydroxysiloxane skeleton. A3. Add the hydroxysiloxane skeleton, succinic anhydride and N,N-dimethylformamide to the reaction vessel and stir. After adding 4-dimethylaminopyridine and triethylamine, nitrogen gas is introduced for protection. The temperature of the reaction vessel is raised to 50-60℃ and stirred for 6-8 hours. The carboxylsiloxane skeleton is obtained after post-treatment.
3. The method for preparing a high-strength cable protection pipe according to claim 2, characterized in that, In step A1, the ratio of vinyltrimethoxysilane, methyl orthosilicate, deionized water, and anhydrous ethanol is 8-10g:7g:13-14g:100-120mL; in step A2, the ratio of ethylene siloxane precursor, 2-mercaptoethanol, azobisisobutyronitrile, and anhydrous acetonitrile is 5-6g:2g:0.05g:80mL; in step A3, the ratio of hydroxysiloxane skeleton, succinic anhydride, N,N-dimethylformamide, 4-dimethylaminopyridine, and triethylamine is 5g:2g:60-80mL:0.08-0.10g:0.2-0.3g.
4. The method for preparing a high-strength cable protection pipe according to claim 1, characterized in that, Hydroxyl-terminated polyester and bisphenol A diglycidyl ether undergo a ring-opening addition reaction catalyzed by a strong organic base, 1,5,7-triazabicyclo[4.4.0]decene. After activation under alkaline conditions, the epoxy groups undergo nucleophilic ring-opening with the hydroxyl groups at the end of the polyester chain, generating new hydroxyl groups and ether bonds. This process not only achieves intermolecular crosslinking but also introduces more hydroxyl groups, thereby forming a three-dimensional network structure with multi-point crosslinking. The preparation method of the multi-point crosslinked three-dimensional network includes the following steps: B1. Add adipic acid and glycerol to a reaction vessel, purge with nitrogen for protection, raise the temperature of the reaction vessel to 150-180℃, keep warm and stir for 4-6 hours, and then process to obtain hydroxyl-terminated polyester prepolymer. B2. Hydroxyl-terminated polyester prepolymer, bisphenol A diglycidyl ether and 1,5,7-triazabicyclo[4.4.0]decene were added to the reactor. After nitrogen protection, the reactor temperature was raised to 120-160℃ and kept at this temperature for 6-8 hours. The post-treatment yielded a multi-point cross-linked three-dimensional network.
5. The method for preparing a high-strength cable protection pipe according to claim 4, characterized in that, In step B1, the ratio of adipic acid to glycerol is 4-5g:5g; in step B2, the ratio of the hydroxyl-terminated polyester prepolymer, bisphenol A diglycidyl ether, and 1,5,7-triazabicyclodecene is 8-10g:5g:0.05g.
6. The method for preparing a high-strength cable protection pipe according to claim 1, characterized in that, In step S1, the method for preparing the olefin-based nanosheets includes the following steps: C1. Add magnesium nitrate hexahydrate, aluminum nitrate nonahydrate and deionized water to a reaction vessel and stir. After purging with nitrogen for protection, add sodium carbonate and sodium hydroxide and raise the temperature of the reaction vessel to 50-60℃. Keep it warm and stir for 5-6 hours. After post-treatment, magnesium aluminum layered hydroxide is obtained. C2. Magnesium-aluminum layered hydroxyl, anhydrous ethanol, 3-methacryloyloxypropyltrimethoxysilane and deionized water are added to a reaction vessel. Nitrogen gas is introduced for protection and the pH of the reaction system is adjusted to 4-5 using glacial acetic acid. The temperature of the reaction vessel is then raised to 40-60℃ and stirred for 6-8 hours. Post-treatment yields olefinic layered nanosheets.
7. The method for preparing a high-strength cable protection pipe according to claim 6, characterized in that, In step C1, the ratio of magnesium nitrate hexahydrate, aluminum nitrate nonahydrate, deionized water, sodium carbonate, and sodium hydroxide is 8-10g:3.0-3.6g:100mL:5g:2g; in step C2, the ratio of magnesium aluminum layered hydroxide, anhydrous ethanol, deionized water, and 3-methacryloyloxypropyltrimethoxysilane is 4-5g:80mL:20mL:5-6g.
8. A high-strength cable protection pipe, characterized in that, The high-strength cable protection pipe is prepared by the preparation method of a high-strength cable protection pipe as described in any one of claims 1-7.