Marine corrosion resistant water blocking cable

Abstract

The application discloses a kind of seawater corrosion-resistant water-blocking cables, belong to cable technical field, the seawater corrosion-resistant water-blocking cable of the application, including cable core, water-blocking filling layer, water-blocking tape layer, inner sheath, armoring layer and outer sheath, armoring layer and outer sheath between being provided with modified asphalt layer;Cable core includes conductor from inside to outside, semiconductor water-blocking layer, insulating layer, insulating shield, copper plastic composite tape and corrosion-resistant water-blocking inner sheath;Corrosion-resistant water-blocking inner sheath and inner sheath are water-blocking corrosion-resistant ethylene-propylene rubber composite material;Outer sheath is corrosion-resistant water-blocking polyethylene composite material, modified asphalt coating is prepared from resin modified geopolymer modified petroleum asphalt, the seawater corrosion-resistant water-blocking cable of the application has excellent mechanical strength, flexibility, bending performance, wear resistance, high and low temperature resistance and electrical insulation, can guarantee its stability and reliability in complex marine environment power transmission, prolongs the service life of cable, reduces maintenance cost and risk.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of cables, and particularly relates to a seawater corrosion-resistant water-blocking cable and a preparation process thereof. BACKGROUND

[0002] A submarine cable (i.e., a submarine power cable) is generally composed of a copper core, an insulating layer, a water-blocking layer, a sheath layer, an armored layer, and an outer layer. After being in contact with seawater for a long time, the submarine cable is easily corroded and damaged due to the existence of highly corrosive ions, marine organisms, and bacteria in seawater. The electric corrosion caused by the current further accelerates the damage of the armored layer, which seriously affects the service life and power generation efficiency of the submarine cable. The service environment of the submarine cable is harsh. In addition to the extremely corrosive high salinity, the submarine cable is also threatened by marine organisms, anchors, fishing nets, and natural disasters, and is easily damaged. The current submarine cable lacks underwater monitoring evidence, and it is difficult to maintain once it is damaged. The maintenance risk is high, and the maintenance cost is high. Therefore, the submarine cable must be protected layer by layer to ensure that it has excellent corrosion resistance, water resistance, abrasion resistance, high and low temperature resistance, and electrical insulation. In addition to ensuring the high tensile strength, pressure resistance, and impact resistance of the cable, the submarine cable also needs to have good flexibility and bending performance to adapt to the natural bending of the submarine cable during coiling and laying, so as to improve the service life of the submarine cable.

[0003] In the existing submarine cable, the asphalt coating is mainly applied to the surface of the armored layer. In addition to the protection and isolation functions, the asphalt coating can also improve the adhesion between the armored layer and the outer layer, improve the overall structural stability, wear resistance, and corrosion resistance and water resistance, and thus stabilize the operation of the submarine cable and improve the service life of the cable. At present, the asphalt coating is mainly modified by compounding with a polymer modifier and a filler. The conventional polymer modifier includes APP, PE, PP, and SBS. APP modified asphalt has excellent water resistance, which improves the hardness, creep resistance, high temperature resistance, and aging resistance of the asphalt coating. However, the corrosion resistance and adhesion of APP modified asphalt are general, the brittleness is easy to crack, the low temperature toughness is poor, and the impact resistance and fatigue bending resistance are not good. PE or PP modified asphalt can greatly increase the hardness, rigidity, and high temperature resistance of the asphalt coating, and improve the compression resistance and puncture resistance. However, the compatibility of PE or PP with asphalt is poor, the coating is easy to crack, the water and corrosion resistance are general, the adhesion is poor, and the low temperature performance is poor. SBS modified asphalt significantly improves the low temperature resistance, elasticity, impact resistance, and fatigue resistance of the asphalt coating, and has excellent water resistance, corrosion resistance, and adhesion. However, the creep resistance of SBS modified asphalt is poor, and the mechanical strength and heat resistance are general, which is not suitable for the requirements of rigid protection of the armored layer.

[0004] The invention patent CN202010008396.X discloses a kind of high toughness organic-inorganic composite marine anticorrosive paint, and the paint component is: metakaolin, water glass, sodium hydroxide particles, deionized water, epoxy resin, 501 diluent, TX500 curing agent, polyether amine curing agent and naphthalene efficient water reducing agent, the paint has the characteristics of corrosion resistance, shrinkage resistance, long life;However, the anticorrosive paint is mainly applied to the field of marine concrete corrosion prevention, and a small amount of moisture is contained in the product, which affects the water resistance and insulation of the coating, and cannot guarantee its long-term water resistance and corrosion resistance.The invention patent CN202211079021.8 discloses a kind of waterproof anticorrosive paint with high bonding strength, which includes modified water-based epoxy resin emulsion, base bitumen, emulsifier, dispersant, defoaming agent, hydroxymethyl cellulose, oleic acid amide, diphenyl methane diisocyanate, silicon dioxide, stearic acid, coupling agent and other components, which has excellent waterproof anticorrosive property and bonding strength, but if applied to submarine cable, its water permeability is insufficient, corrosion resistance is poor, and mechanical strength and wear resistance cannot meet the requirements.The invention patent CN201611068118.3 water-resistant and corrosion-resistant submarine optical fiber composite power cable includes a plurality of power line core units, a plurality of optical fiber units, a filler and a protective layer unit, the power line core unit includes a conductor, a conductor shielding layer, a cross-linked polyethylene insulation layer, an insulation shielding layer, a metal shielding layer, a lead sheath layer and a high-density polyethylene sheath layer;The protective layer unit from inside to outside is sequentially lined with an inner layer, a steel wire armor layer and a polypropylene layer coated with anticorrosive bitumen, the present application improves the insulation shielding layer, which gives the power line core unit excellent water resistance and seawater corrosion performance, effectively improving the service life of the composite cable;However, it is laid with two layers of metal protection layer of lead sheath and steel wire armor, which is extremely heavy, has high laying difficulty, poor flexibility and poor repairability. SUMMARY

[0005] The main purpose of the present application is to provide a kind of seawater corrosion resistant water resistant cable, which has excellent mechanical strength, flexibility and bending performance, and also has excellent seawater corrosion resistance, water resistance, wear resistance, high and low temperature resistance and electrical insulation, which can ensure the stability and reliability of power transmission in complex marine environment, prolong the service life of the cable and reduce the maintenance cost and risk.

[0006] In order to achieve the purpose of the present application, a kind of seawater corrosion resistant water resistant cable is provided, which includes cable core, water resistant filling layer, water resistant wrapping layer, inner protective layer, armor layer and outer sheath from inside to outside, the cable core includes conductor, semi-conductor water resistant layer, insulation layer, insulation shielding layer, copper-plastic composite tape and anticorrosive water resistant inner sheath from inside to outside, the cable core and water resistant wrapping layer are filled with water resistant filling layer, the water resistant wrapping layer is extruded and wrapped with inner protective layer, the inner protective layer is coated with armor layer, the armor layer is coated with modified bitumen layer, and the modified bitumen layer is extruded and wrapped with outer sheath.

[0007] The anticorrosion and water-resisting inner sheath and inner layer are both water-resisting and anticorrosion ethylene-propylene rubber composite materials.

[0008] The outer sheath is a corrosion-resisting and water-resisting polyethylene composite material.

[0009] Further, the modified asphalt layer is made of the following raw materials in mass fraction: 55-80 parts of petroleum asphalt, 15-30 parts of resin modified geopolymer, 5-15 parts of first EVA, 0.3-0.6 parts of polyphosphoric acid and 0.3-0.6 parts of first antioxidant.

[0010] Preferably, the softening point of petroleum asphalt is 95-120℃, if the softening point of petroleum asphalt is lower than 95℃, it will cause asphalt softening and flowing during the curing process of the modified asphalt layer of the application, which cannot effectively cure and finally results in the significant decrease of the mechanical strength, water-resisting and anticorrosion performance of the asphalt coating; if the softening point of petroleum asphalt is too high, it will increase the construction difficulty and decrease the adhesion, flexibility and impact resistance of the modified asphalt layer, which easily causes the coating to crack and affects the operation and service life of the cable.

[0011] Preferably, the melt index of the first EVA is 2-10g / 10min under the load of 2.16kg at 190℃, which not only improves the compatibility between the components, but also improves the mechanical strength, adhesion, water resistance, long-term corrosion resistance and wear resistance of the modified asphalt layer, and also improves the low-temperature flexibility and thermal stability of the modified asphalt layer.

[0012] The addition of polyphosphoric acid improves the compatibility between petroleum asphalt and EVA, resin modified geopolymer and other components, significantly improves the thermal stability of petroleum asphalt during the processing process, and ensures that the modified asphalt layer still has better water-resisting and anticorrosion properties and aging resistance.

[0013] The addition of resin modified geopolymer significantly improves the mechanical strength, low-temperature flexibility, high-temperature stability and adhesion of the modified asphalt layer, and also greatly improves the seawater corrosion resistance of the modified asphalt layer, which ensures that the modified asphalt layer has excellent water resistance and water-resisting performance.

[0014] Preferably, the first antioxidant is composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0015] Further, the preparation method of the resin modified geopolymer is as follows:

[0016] S1. uniformly mix 50wt% NaOH solution and water glass, cool to room temperature to obtain an alkali activator, then add metakaolin and polycarboxylic acid water reducer to the alkali activator and mix uniformly to obtain a geopolymer slurry;

[0017] S2. The polyurethane prepolymer is added to the geopolymer slurry above and mixed, stirred for 15-30 min, then the preheated titanate coupling agent is added, the system temperature is controlled below 60℃, stirred for 5-10 min, then cooled to room temperature, to obtain the resin modified geopolymer.

[0018] Further, the volume ratio of the 50wt% NaOH solution to the water glass is 1:(3-7);

[0019] The amount of the alkali activator used is 70%-85% of the mass of the metakaolin;

[0020] The amount of the polycarboxylate superplasticizer used is 0.6%-1.2% of the mass of the metakaolin;

[0021] The amount of the polyurethane prepolymer used is 9.5%-18.2% of the mass of the metakaolin; preferably, the polyurethane prepolymer is a polyether type polyurethane prepolymer.

[0022] The amount of the titanate coupling agent used is 0.8%-1.2% of the mass of the metakaolin;

[0023] The modulus of the water glass is 2.3-3.2, and the Baume degree is 40%-50%.

[0024] The resin modified geopolymer is obtained by modifying the metakaolin based geopolymer with a polyurethane prepolymer, and then surface modifying with a titanate coupling agent. The addition of the polyurethane prepolymer enhances the interface sealing property, toughness and impact resistance of the geopolymer, improves the bonding effect between the geopolymer and the petroleum asphalt, further improves the compressive and flexural resistance, flexibility, high temperature stability, impact resistance and corrosion resistance of the modified asphalt layer, while ensuring that the modified asphalt layer has excellent waterproofness, prolonging the service life of the cable. The addition of the titanate coupling agent improves the compatibility between the resin modified geopolymer and the petroleum asphalt, and allows the resin modified geopolymer to be uniformly dispersed in the petroleum asphalt matrix, ensuring that the modified asphalt layer of the present application has excellent comprehensive performance.

[0025] Further, the semiconductor water blocking layer is made of the following raw materials in mass fraction: high density polyethylene 70 parts, acetylene carbon black 20 parts, second EVA 10 parts, compatibilizer 2-4 parts and second antioxidant 0.4-0.5 parts. The semiconductor water blocking layer of the present application is combined and proportioned with HDPE, acetylene carbon black and EVA, which can prevent partial discharge of the cable, provide the operation efficiency and insulation life of the cable, improve the mechanical strength and structural stability of the cable, further improve the water blocking and corrosion resistance of the cable, and ensure long-term stable operation in harsh seawater corrosion environment.

[0026] Further, the water-proof and anti-corrosion EPDM rubber composite material is made of the following raw materials in mass fraction: EPDM raw rubber 70-90 parts, high density polyethylene 10-15 parts, EVA 20-35 parts, SEBS 2-6 parts, paraffin oil 10-16 parts, cross-linking agent 1.8-2.8 parts, third antioxidant 3.2-4.2 parts, reinforcing filler 25-40 parts, silane coupling agent 1.5-2.8 parts and lubricant 2.6-4.5 parts. The water-proof and anti-corrosion EPDM rubber composite material of the present application is combined by EPDM raw rubber, HDPE and EVA, which not only ensures the present application to have excellent compression resistance, impact resistance and stress buffering effect, but also enhances the adhesion between layer structures and the anti-twist performance, and significantly improves the tensile strength, water resistance and seawater corrosion resistance of the present application, thereby prolonging the service life of the cable.

[0027] Further, the Mooney viscosity of the EPDM raw rubber is 55-70, the mass content of ethylene in the EPDM raw rubber is 50-70%, and the mass content of the third monomer ethylidene norbornene (ENB) in the EPDM raw rubber is 4.9-8.5%. The preferred EPDM raw rubber can ensure the water-proof and anti-corrosion EPDM rubber composite material to have the required mechanical strength, wear resistance and electrical properties, and also maintain sufficient elasticity, thereby improving the water-proof and anti-corrosion properties and high temperature resistance of the present application. If the Mooney viscosity is too low or the ethylene content is too low, the mechanical strength, wear resistance and water-proof and corrosion resistance of the water-proof and anti-corrosion EPDM rubber composite material will be reduced; if the ethylene content is too high, the elasticity, low temperature flexibility and compression deformation will be poor, and the processing will be difficult; and if the ENB content is too low, the cross-linking density will be insufficient, which will eventually lead to the decline of the comprehensive performance of the water-proof and anti-corrosion EPDM rubber composite material.

[0028] The reinforcing filler is composed of glass flake, quartz powder and aluminum hydroxide in a mass ratio of 5:2:2, and the surface of the reinforcing filler is coated with vinyl-tris(2-methoxyethoxy)silane. The combined reinforcing filler not only improves the mechanical strength, hardness and wear resistance of the water-proof and anti-corrosion EPDM rubber composite material of the present application, but also uniformly disperses in the matrix, and makes the present application have better water-proof and anti-corrosion properties and flame retardancy.

[0029] The silane coupling agent is sulfur-based propyl trimethoxysilane (KH590).

[0030] Further, the corrosion-resistant and water-blocking polyethylene composite material is made of the following raw materials in mass fraction: 80-90 parts of high-density polyethylene, 10-20 parts of metallocene medium-density polyethylene, 0.2-0.4 parts of the fourth antioxidant, 2.4-3.2 parts of carbon black, 0.8-1.2 parts of silicone, and 0.12-0.16 parts of polyethylene wax. The corrosion-resistant and water-blocking polyethylene composite material made of the combination of HDPE and mMDPE is adopted for the outer sheath of the cable, and the two materials are synergistic with each other, greatly improving the mechanical strength, toughness, impact strength, and environmental stress cracking resistance of the outer sheath, and the outer sheath also has good processing stability, so that the cable of the application still has good water-blocking and corrosion-resistant properties in harsh marine environments, and the service life of the cable of the application is prolonged.

[0031] Further, the insulating layer is a silane cross-linked polyethylene insulating material;

[0032] The insulating and shielding layer is a ternary ethylene-propylene rubber material filled with carbon black;

[0033] The water-blocking filling layer is any one of a water-blocking rope, a water-blocking powder, a water-blocking yarn, or a water-blocking glue;

[0034] The water-blocking wrapping layer is a polyester non-woven fabric water-blocking tape;

[0035] The armored layer is a galvanized steel wire armored layer.

[0036] The application further provides a preparation process of the seawater corrosion-resistant and water-blocking cable.

[0037] P1. Regularly twisting a plurality of oxygen-free copper wires to obtain a conductor.

[0038] P2. Mixing raw materials of the semi-conductor water-blocking layer, extruding and wrapping the semi-conductor water-blocking layer on the conductor, extruding and wrapping a silane cross-linked polyethylene insulating material on the semi-conductor water-blocking layer, and cross-linking in a hot water or water vapor environment to form an insulating layer.

[0039] P3. Extruding and wrapping a ternary ethylene-propylene rubber material filled with carbon black on the insulating layer, cross-linking and solidifying to form an insulating and shielding layer, and then wrapping a copper-plastic composite tape on the insulating and shielding layer.

[0040] P4. Extruding and wrapping raw materials of the water-blocking and corrosion-resistant ethylene-propylene rubber composite material on the insulating and shielding layer to form a corrosion-resistant and water-blocking inner sheath, cross-linking and solidifying to obtain a cable core.

[0041] P5. When twisting the cable core into a cable, filling a water-blocking material in the gap between the cable core wires and outside the cable core to form a water-blocking filling layer, and then wrapping a water-blocking wrapping layer outside the water-blocking filling layer.

[0042] P5. The raw materials of the water-blocking and corrosion-resistant ethylene-propylene rubber composite material are extruded and wrapped on the water-blocking wrapping layer, cross-linked and cured to form an inner protective layer, and then a galvanized steel wire armor layer is wrapped on the inner protective layer.

[0043] P6. Slowly drop the polyphosphoric acid into the preheated petroleum asphalt, stir while dropping, continue stirring for 15-30 min after the dropping is completed, then slowly add the first EVA and the first antioxidant while stirring, stir at 170-180 DEG C for 30-45 min, slowly add the resin modified geopolymer after cooling to 130-140 DEG C, stir for 10-15 min to obtain a modified asphalt coating; then directly apply the modified asphalt coating on the above-mentioned inner protective layer, quickly cool in a water tank, and then place the coated cable in an infrared radiation environment, irradiate at 40-50 DEG C for 2-4 h, heat to 65-70 DEG C for 1-2 h, and naturally cool to room temperature, and then place at room temperature for 12-18 h to form a modified asphalt layer. The modified asphalt layer is cured by infrared radiation at different temperatures, which not only prevents asphalt aging, but also ensures that the geopolymer is dispersed in the asphalt to complete the curing reaction, forms a network structure with the asphalt, and removes the water in the modified asphalt layer, thereby obtaining a dense structure of the modified asphalt layer, and greatly improving the mechanical strength, adhesion, high and low temperature resistance, and water-blocking and corrosion resistance of the modified asphalt layer.

[0044] P7. The corrosion-resistant water-blocking polyethylene composite material is extruded and wrapped on the modified asphalt layer to form an outer protective sleeve.

[0045] The present application has the following advantages:

[0046] The seawater corrosion-resistant and water-blocking cable of the present application is prepared from the inside out, including a cable core, a water-blocking filling layer, a water-blocking wrapping layer, an inner protective layer, an armor layer, a modified asphalt layer, and an outer protective sleeve. The structure is stable, can meet the requirements of high wear resistance, high water resistance, and corrosion resistance in harsh environments such as marine organisms and highly corrosive ions in seawater, and also has excellent tensile strength, compression and impact resistance, high temperature stability, low temperature toughness, aging resistance, weather resistance, and electrical properties, prolonging the service life of the cable and reducing the maintenance risk and cost of the cable.

[0047] The corrosion-resistant and water-blocking inner protective sleeve of the cable core and the inner protective layer outside the cable core are both water-blocking and corrosion-resistant ethylene-propylene rubber composite materials, which are environmentally friendly, have moderate rigidity and elasticity, can ensure that the cable has excellent electrical insulation, high temperature stability, low temperature flexibility, water resistance, and corrosion resistance, and can still maintain good power transmission effect after long-term use, has a long service life, and reduces maintenance costs.

[0048] The modified asphalt layer between the armored layer and the outer sheath improves the adhesion between the armored layer and the outer sheath, ensures that the outer sheath is not easy to fall off from the armored layer during service to affect the power transmission efficiency, protects the armored layer from being damaged and being eroded by seawater, significantly improves the mechanical strength, flexibility, wear resistance, high and low temperature resistance, water resistance and seawater corrosion resistance of the cable, ensures the stability of the cable layer structure, and prolongs the service life of the cable.

[0049] The seawater corrosion resistant and water resistant cable prepared by the method has a smooth surface, a simple structure, is convenient to manufacture, has excellent waterproof and corrosion resistant properties, can be applied to harsh seabed environment, and has a long service life. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 is a structural schematic diagram of an embodiment of the seawater corrosion resistant and water resistant cable of the present application.

[0051] The drawings show that: 1, a conductor; 2, a semi-conductor water resistant layer; 3, an insulation layer; 4, an insulation shielding layer; 5, a copper plastic composite tape; 6, a corrosion resistant and water resistant inner sheath; 7, a water resistant filling layer; 8, a water resistant wrapping layer; 9, an inner sheath layer; 10, an armored layer; 11, a modified asphalt layer; 12, an outer sheath. DETAILED DESCRIPTION

[0052] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0053] As shown in Figure 1 The present application provides a seawater corrosion resistant and water resistant cable, which comprises a cable core, a water resistant filling layer 7, a water resistant wrapping layer 8, an inner sheath layer 9, an armored layer 10 and an outer sheath 12. After the cable core is twisted, the water resistant filling layer 7 is filled in the gaps between the cable cores and between the cable core and the water resistant wrapping layer 8, the inner sheath layer 9 is extruded and wrapped outside the water resistant filling layer 7, the armored layer 10 is wrapped outside the inner sheath layer 9, the modified asphalt layer 11 is coated outside the armored layer 10, and the outer sheath 12 is extruded and wrapped outside the modified asphalt layer 11 (according to requirements, a wear resistant, water resistant and corrosion resistant coating can be coated outside the outer sheath 12).

[0054] Preferably, the cable core comprises, from inside to outside, the conductor 1, the semi-conductive water-blocking layer 2, the insulating layer 3, the insulating shielding layer 4, the copper plastic composite tape 5, and the corrosion-resistant water-blocking inner sheath 6, that is, the conductor 1 adopting a plurality of oxygen-free copper wires is regularly stranded, the conductor 1 is extruded with the semi-conductive water-blocking layer 2, the semi-conductive water-blocking layer 2 is extruded with the insulating layer 3, the insulating layer 3 is extruded with the insulating shielding layer 4, the insulating shielding layer 4 is wrapped with the copper plastic composite tape 5, and the copper plastic composite tape 5 is extruded with the corrosion-resistant water-blocking inner sheath 6.

[0055] Preferably, the conductor 1 of the present application is made of a plurality of oxygen-free copper wires, and is regularly stranded in a "1+6", "1+6+12", "1+6+12+18", or "1+6+12+18+24" arrangement.

[0056] Preferably, the semi-conductive water-blocking layer 2 of the present application is made of the following raw materials in mass fraction: 70 parts of high-density polyethylene, 20 parts of acetylene black, 10 parts of second EVA, 3 parts of a compatibilizer, and 0.5 parts of a second antioxidant.

[0057] The second EVA is EVA V5110J, the compatibilizer is PE-g-MAH, and the second antioxidant is antioxidant 1010.

[0058] Preferably, the insulating layer 3 is a silane cross-linked polyethylene insulating material, and is specifically selected as LD165 of Yanshan Petrochemical.

[0059] Preferably, the insulating shielding layer 4 is a ternary ethylene-propylene rubber material filled with carbon black, and can be purchased or self-made. The self-made formula is as follows in mass fraction: 100 parts of EPDM, 50 parts of acetylene black, 2.2 parts of a peroxide cross-linking agent, 1.2 parts of an auxiliary cross-linking agent, 1.5 parts of an antioxidant, 8.5 parts of paraffin oil, and 3.6 parts of zinc stearate.

[0060] Preferably, the copper plastic composite tape 5 is composed of a copper foil, a PET polyester film, and an adhesive, and is wrapped in a gap spiral wrapping manner with a coverage rate of about 100%. In the specific embodiment of the present application, a copper foil Mylar tape of Metre Cable Material is selected, and the specification is 103 μm.

[0061] Preferably, the corrosion-resistant water-blocking inner sheath 6 and the inner sheath 9 are both water-blocking and corrosion-resistant ethylene-propylene rubber composite materials.

[0062] Preferably, the water-blocking filling layer 7 is a water-blocking yarn, that is, the water-blocking yarn is wrapped in a cross-shaped manner on the gap of the cable core and the surface of the cable core to form the water-blocking filling layer 7. In the specific embodiment of the present application, a yarn of Metre Cable with a specification of 3000D and a yarn density of 3330Dtex is selected.

[0063] Preferably, the water-blocking tape layer 8 is a polyester non-woven fabric water-blocking tape, which is processed from polyester non-woven fabric, adhesive, high-speed expansion high-molecular water-absorbing resin and other materials. In the specific embodiment of the present application, the cable water-blocking tape of Maret is selected, and the specifications are 300±30, 400±40 and 500±50, and the preferred specification is 400±40 (the selected specification of the cable is the preferred specification).

[0064] Preferably, the armored layer 10 is made of galvanized steel wire armor, and in the specific embodiment of the present application, a galvanized steel wire with a diameter of 6 mm is selected, and the thickness of the armored layer 10 is 20 mm.

[0065] Preferably, the outer sheath 12 is a corrosion-resistant water-blocking polyethylene composite material.

[0066] The present application also provides a preparation process of the seawater corrosion-resistant water-blocking cable, and the specific process is as follows:

[0067] P1. A plurality of oxygen-free copper wires are regularly twisted in a "1+6" arrangement to obtain a conductor 1.

[0068] P2. The raw materials of the semiconductor water-blocking layer 2 are added to a blender, mixed at 520 r / min and 90℃ for 10 min, then cooled to below 60℃, then transported to a double-screw extruder for granulation to obtain a semiconductor polyethylene material, and then the semiconductor polyethylene material is extruded and wrapped on the conductor 1 by using an extruder at a temperature of 180-210℃ to form the semiconductor water-blocking layer 2.

[0069] P3. The silane cross-linked polyethylene insulation material is extruded and wrapped on the semiconductor water-blocking layer 2, and cross-linked in a water vapor environment to form an insulation layer 3.

[0070] P4. The raw materials of the carbon black-filled ethylene-propylene-diene rubber material are added to a banbury mixer and mixed at 130℃ for 10 min, then placed on an open mill, and the rubber is extruded and wrapped on the insulation layer 3 by using an extruder, and cross-linked and cured at 170℃ and 1.0 MPa to form an insulation shielding layer 4.

[0071] P5. The copper foil Mylar tape is gap spiral wrapped on the insulation shielding layer 4 to form a copper-plastic composite tape 5.

[0072] P6. The raw materials of the water-blocking and corrosion-resistant ethylene-propylene-diene rubber composite material are added to a banbury mixer and mixed at 120℃ for 10 min, then placed on an open mill, and the rubber is extruded and wrapped on the insulation shielding layer 4 by using an extruder, and cross-linked and cured at 160℃ and 1.0 MPa to form a corrosion-resistant and water-blocking inner sheath 6, and a cable core is prepared.

[0073] P7. When the cable core is stranded into a cable, the water-blocking yarn is wrapped around the cable core gap and the cable core surface in a cross-wound manner to form a water-blocking filler layer 7.

[0074] P8. The polyester non-woven fabric water-blocking tape is wrapped around the water-blocking filler layer 7 to form a water-blocking tape layer 8.

[0075] P9. The raw materials of the water-blocking and corrosion-resistant ethylene-propylene rubber composite material are extruded on the water-blocking tape layer 8 by the method of step P6, cross-linked and cured at 160℃ and 1.0MPa to form an inner protective layer 9, and then a galvanized steel wire is coated on the inner protective layer 9 to form an armored layer 10.

[0076] P10. Slowly add polyphosphoric acid to preheated petroleum pitch while stirring, continue stirring for 20 minutes after the addition is complete, then slowly add the first EVA and the first antioxidant while stirring, stir at 180℃ for 30 minutes, slowly add the resin modified geopolymer after cooling to 130℃, stir for 15 minutes, and obtain a modified asphalt coating; then directly apply the modified asphalt coating to the armored layer 10 described above, quickly cool in a water tank, and then place the coated cable in an infrared radiation environment (the power of the infrared radiation is set to 5 kW / m²), irradiate at 40℃ for 4h, increase the temperature to 70℃ and irradiate for 1.5h, naturally cool to room temperature, and place at room temperature for 18h to form a modified asphalt layer 11.

[0077] P11. Add the raw materials of the corrosion-resistant and water-blocking polyethylene composite material to a mixer, mix at 560r / min and 80℃ for 10 minutes, then cool to below 60℃, then transport to a twin-screw extruder for granulation to obtain a corrosion-resistant and water-blocking polyethylene composite material, and then use an extruder to extrude the corrosion-resistant and water-blocking polyethylene composite material onto the modified asphalt layer 11 at a temperature of 180-210℃ to form an outer sheath 12.

[0078] The following specific examples will illustrate the seawater corrosion-resistant and water-blocking cable of the present application.

[0079] The water-blocking and corrosion-resistant ethylene-propylene rubber composite material of the corrosion-resistant and water-blocking inner sheath 6 and the inner protective layer 9: Example 1, the water-blocking and corrosion-resistant ethylene-propylene rubber composite material is made from the following raw materials in mass fraction: 82 parts of ethylene-propylene rubber raw rubber, 13 parts of high-density polyethylene, 28 parts of EVA, 4 parts of SEBS, 13.5 parts of paraffin oil, 2.2 parts of cross-linking agent, 3.6 parts of third antioxidant, 34 parts of reinforcing filler, 1.9 parts of silane coupling agent, and 3.1 parts of lubricant.

[0080] The above-mentioned EPDM raw rubber is selected from NORDEL™ IP 4760P from Dow Chemical; the high-density polyethylene is selected from HDPE 8050 from Taiwan Chemical Fiber; the EVA is selected from EVA V5110J from Yangzishan Petrochemical; the SEBS is selected from American Korten E1830; the paraffin oil is selected from Mckee S-550; the cross-linking agent is composed of DCP and TAIC in a mass ratio of 1:1; the third antioxidant is antioxidant 1010 and antioxidant 168 in a mass ratio of 2:1; the reinforcing filler is composed of glass flake (120 mesh), quartz powder (800 mesh) and aluminum hydroxide (1250 mesh) in a mass ratio of 5:2:2, and is coated with vinyl-tris (2-methoxyethoxy) silane; the silane coupling agent is sulfide propyl trimethoxysilane (KH590); and the lubricant is composed of pentaerythritol stearate and Fischer-Tropsch wax in a mass ratio of 3:1.

[0081] It is detected that the tensile strength of Example 1 is 21.4 MPa, the elongation at break is 530%, the salt spray tensile strength is 21.2 MPa (immersed in 5wt% NaCl solution for 30 days at room temperature), the long-term use temperature is 130℃, and the water absorption rate is 0.13% (soaked at room temperature for one week).

[0082] Comparative Example 1, the water-blocking and corrosion-resistant EPDM rubber composite material in Comparative Example 1 is the same as the raw materials and preparation method in Example 1, and specific reference is made to Example 1, except that the type of the EPDM rubber in the present comparative example 1 is NORDEL™ IP 3745P.

[0083] It is detected that the tensile strength of Comparative Example 1 is 18.6 Pa, the elongation at break is 420%, the salt spray tensile strength is 17.5 MPa (immersed in 5wt% NaCl solution for 30 days at room temperature), the long-term use temperature is 128℃, and the water absorption rate is 0.18% (soaked at room temperature for one week).

[0084] Comparative Example 2, the water-blocking and corrosion-resistant EPDM rubber composite material in Comparative Example 2 is the same as the raw materials and preparation method in Example 1, and specific reference is made to Example 1, except that the type of the EPDM rubber in the present comparative example 1 is NORDEL™ IP 4820P.

[0085] It is detected that the tensile strength of Comparative Example 2 is 18.1 MPa, the elongation at break is 380%, the salt spray tensile strength is 16.8 MPa (immersed in 5wt% NaCl solution for 30 days at room temperature), the long-term use temperature is 125℃, and the water absorption rate is 0.17% (soaked at room temperature for one week).

[0086] Comparative Example 3, the water barrier and corrosion resistant EPDM rubber composite material of Comparative Example 3 is the same as the raw materials and preparation method in Example 1, and specifically refer to Example 1, except that no high density polyethylene is added in Comparative Example 1, and the amount of EPDM rubber is 95 parts.

[0087] It is detected that the tensile strength of Comparative Example 3 is 20.9 MPa, the elongation at break is 575%, the salt spray tensile strength is 19.8 MPa (immersed in 5wt% NaCl solution for 30 days at room temperature), the heat distortion temperature is 135℃, and the water absorption is 0.28% (immersed at room temperature for one week).

[0088] Comparative Example 4, the water barrier and corrosion resistant EPDM rubber composite material of Comparative Example 4 is the same as the raw materials and preparation method in Example 1, and specifically refer to Example 1, except that the reinforcing filler in Comparative Example 4 is quartz powder (800 mesh) and aluminum hydroxide (1250 mesh) with a mass ratio of 1:1, and is coated with vinyl-tris (2-methoxyethoxy) silane, but no glass flake is added.

[0089] It is detected that the tensile strength of Comparative Example 4 is 21.2 MPa, the elongation at break is 515%, the salt spray tensile strength is 19.6 MPa (immersed in 5wt% NaCl solution for 30 days at room temperature), the long-term use temperature is 126℃, and the water absorption is 0.24% (immersed at room temperature for one week).

[0090] The outer sheath 12 is a corrosion resistant and water barrier polyethylene composite material: Example 2, the corrosion resistant and water barrier polyethylene composite material is made of the following raw materials in mass fraction: 86 parts of high density polyethylene, 14 parts of metallocene medium density polyethylene, 0.32 parts of the fourth antioxidant, 2.8 parts of carbon black, 0.8 parts of silicone and 0.15 parts of polyethylene wax.

[0091] The above high density polyethylene is selected from China Taiwan Chemical Fiber, model HDPE 8050; the metallocene medium density polyethylene is selected from France Total, model M3410EP; the fourth antioxidant is composed of antioxidant 1010 and antioxidant 168 with a mass ratio of 1:1; the carbon black is channel method carbon black, Euro Leung, model PRINTEX U, 1000 mesh.

[0092] It is detected that the tensile strength of Example 2 is 32.5 MPa, the elongation at break is 725%, the salt spray tensile strength is 32.4 MPa (immersed in 5wt% NaCl solution for 30 days at 35±2℃), the heat distortion temperature is 85℃, and the water absorption is 0.01% (immersed at room temperature for 30 days).

[0093] Comparative Example 5, the corrosion-resistant water-resistant polyethylene composite material of Comparative Example 5 is the same as the raw materials and preparation method in Example 2, and specific reference is made to Example 2, except that, in the present comparative example, the metallocene medium density polyethylene is replaced by a medium density polyethylene, and the medium density polyethylene is selected from Q3802 of Catar Chemicals.

[0094] It is detected that the tensile strength of Comparative Example 5 is 28.6 MPa, the elongation at break is 655%, the salt spray tensile strength is 28.3 MPa (immersed in 5wt% NaCl solution for 30 days at 35±2℃), the heat distortion temperature is 82℃, and the water absorption is 0.017% (immersed at room temperature for 30 days).

[0095] Comparative Example 6, the corrosion-resistant water-resistant polyethylene composite material of Comparative Example 6 is the same as the raw materials and preparation method in Example 2, and specific reference is made to Example 2, except that, in the present comparative example, no metallocene medium density polyethylene is added, and the amount of high density polyethylene used is 100 parts.

[0096] It is detected that the tensile strength of Comparative Example 6 is 29.3 MPa, the elongation at break is 710%, the salt spray tensile strength is 30.5 MPa (immersed in 5wt% NaCl solution for 30 days at 35±2℃), the heat distortion temperature is 83℃, and the water absorption is 0.013% (immersed at room temperature for one week).

[0097] Modified asphalt layer 11: Example 3, the modified asphalt layer 11 is made of the following mass fractions of raw materials: 72 parts of petroleum asphalt, 18 parts of resin modified geopolymer, 10 parts of first EVA, 0.4 parts of polyphosphoric acid and 0.36 parts of first antioxidant (it is worth noting that the preparation process of the modified asphalt layer 11 can be seen in step P10 of the above cable preparation process).

[0098] The softening point of the above petroleum asphalt is 102℃, the penetration is 25mm, and the type is 70#.

[0099] The preparation method of the resin modified geopolymer by mass fraction is as follows: 50wt% NaOH solution and water glass (modulus 2.8, 50% Baume) with a volume ratio of 1:5 are uniformly mixed, and cooled to room temperature to obtain an alkali activator; then 100 parts of metakaolin (fineness 1250 mesh, SiO2content of 55.06%, Al2O3content of 44.12%) and 0.8 parts of polycarboxylic acid water reducer (i.e. propylene glycol polyoxyethylene ether APEG-400) are added to 76 parts of the alkali activator, and uniformly mixed to obtain a geopolymer slurry; 12.5 parts of polyurethane prepolymer (i.e. polyether type MDI blocked polyurethane prepolymer of Oligon) are added to the geopolymer slurry and mixed, stirred for 20 min, then 1.0 parts of titanate coupling agent (i.e. titanate coupling agent GR-311 of Sheng'an Biology) preheated to 70°C is added, the system temperature is controlled below 60°C, stirred for 5 min, and then cooled to room temperature to obtain the resin modified geopolymer.

[0100] The first EVA is selected from Japan Mitsui, model V421; the polyphosphoric acid is selected from Polyphosphoric Chemical; and the first antioxidant is composed of antioxidant 1010 and antioxidant 168 with a mass ratio of 1:1.

[0101] Comparative Example 7, the modified asphalt layer 11 of Comparative Example 7 has the same raw materials and preparation method as in Example 3, and specific reference is made to Example 3, except that no resin modified geopolymer is added in this comparative example, and the amount of petroleum asphalt added is 90 parts, and the modified asphalt layer 11 obtained in the preparation process of the modified asphalt layer 11 is directly coated on the armored layer, and directly cooled, without the need for infrared radiation curing.

[0102] Comparative Example 8, the modified asphalt layer 11 of Comparative Example 8 has the same raw materials and preparation method as in Example 3, and specific reference is made to Example 3, except that polyphosphoric acid is added in this comparative example.

[0103] Comparative Example 9, the modified asphalt layer 11 of Comparative Example 9 has the same raw materials and preparation method as in Example 3, and specific reference is made to Example 3, except that no titanate coupling agent is added in the resin modified geopolymer in this comparative example.

[0104] Comparative Example 10, the modified asphalt layer 11 of Comparative Example 10 has the same raw materials and preparation method as in Example 3, and specific reference is made to Example 3, except that no polyurethane prepolymer is added in the resin modified geopolymer in this comparative example, i.e. the preheated titanate coupling agent is directly added to the geopolymer, the system temperature is controlled below 60°C, stirred for 5-10 min, and then cooled to room temperature.

[0105] Comparative Example 11, the modified asphalt layer 11 of Comparative Example 11 is prepared in the same manner as the raw materials and preparation method in Example 3, with reference to Example 3, except that the modified asphalt layer 11 obtained in the preparation process of the modified asphalt layer 11 of the present comparative example is directly coated on the armored layer, placed in an infrared radiation environment, irradiated at 50°C for 7h, naturally cooled to room temperature, and placed at room temperature for 18h to form the modified asphalt layer.

[0106] The modified asphalt layer 11 prepared in the above Examples 3 and Comparative Examples 7-11 is made into a sample for performance testing, as shown in Table 1 below.

[0107] Table 1 Performance testing results of the modified asphalt layer

[0108]

[0109] From the experimental results in Table 1 above, it can be seen that the modified asphalt layer 11 of the present application has excellent high and low temperature resistance, adhesion, water resistance and corrosion resistance.

[0110] From the above test data, it can be seen that the present application of sea water corrosion resistant and water resistant and its manufacturing method, from the perspective of optimizing the formulation of each cable component and inner sheath 9, modified asphalt layer 11, outer sheath 12, etc., fully utilizes the synergistic effect between each component and each component, overcomes the shortcomings described in the background art, and the product structure is stable, easy to manufacture, suitable for marine corrosion environment, long service life, low maintenance cost, excellent electrical performance, good mechanical properties, strong corrosion resistance, high and low temperature resistance, water resistance and other characteristics.

[0111] The technical features of the above examples can be combined arbitrarily, in order to make the description simple, not all possible combinations of the technical features in the above examples are described, however, as long as the combination of these technical features does not exist contradictory, should be considered as the scope of the present application.

[0112] The above examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be interpreted as a limitation on the scope of the present application. It should be noted that for ordinary skilled in the art, without departing from the concept of the present application, a number of variations and improvements can be made, which are within the scope of the present application.

Claims

1. A seawater corrosion resistant water-blocking cable comprising, from the inside to the outside, a core, a water-blocking filling layer (7), a water-blocking wrapping layer (8), an inner sheath (9), an armor layer (10) and an outer sheath (12), characterized in that, The cable core comprises conductor (1), semi-conductor water-blocking layer (2), insulation layer (3), insulation shielding layer (4), copper plastic composite tape (5) and corrosion-resistant water-blocking inner sheath (6) from inside to outside, water-blocking filling layer (7) is filled between the cable core and water-blocking tape layer (8), the water-blocking tape layer (8) is extruded and wrapped with inner sheath layer (9), the inner sheath layer (9) is coated with armored layer (10), the armored layer (10) is coated with modified asphalt layer (11), the modified asphalt layer (11) is extruded and wrapped with outer sheath (12); The corrosion-resistant water-blocking inner sheath (6) and the inner sheath layer (9) are both water-blocking and corrosion-resistant ethylene-propylene rubber composite materials; The outer sheath (12) is corrosion-resistant and water-blocking polyethylene composite material; The modified asphalt layer (11) is made of the following raw materials in mass fraction: petroleum asphalt 55-80 parts, resin modified geopolymer 15-30 parts, first EVA 5-15 parts, polyphosphoric acid 0.3-0.6 parts and first antioxidant 0.3-0.6 parts; The preparation method of the resin modified geopolymer is as follows: S1. 50wt% NaOH solution is mixed with water glass uniformly, cooled to room temperature to obtain alkali activator, then metakaolin and polycarboxylic acid water reducing agent are added into the alkali activator and mixed uniformly to obtain geopolymer slurry; S2. Polyurethane prepolymer is added into the above geopolymer slurry and mixed, stirred for 15-30 min, then preheated titanate coupling agent is added, the system temperature is controlled below 60℃, stirred for 5-10 min, then cooled to room temperature to obtain resin modified geopolymer.

2. The seawater corrosion resistant water-blocking cable of claim 1, wherein, The volume ratio of the 50wt% NaOH solution to the water glass is 1:(3-7); The usage amount of the alkali activator is 70%-85% of the mass of the metakaolin; The usage amount of the polycarboxylic acid water reducing agent is 0.6%-1.2% of the mass of the metakaolin; The usage amount of the polyurethane prepolymer is 9.5%-18.2% of the mass of the metakaolin; The usage amount of the titanate coupling agent is 0.8%-1.2% of the mass of the metakaolin; The modulus of the water glass is 2.3-3.2 and the Baume degree is 40%-50%.

3. The seawater corrosion resistant water-blocking cable of claim 1, wherein, The semi-conductor water-blocking layer (2) is made of the following raw materials in mass fraction: high density polyethylene 70 parts, acetylene carbon black 20 parts, second EVA 10 parts, compatibilizer 2-4 parts and second antioxidant 0.4-0.5 parts.

4. The seawater corrosion resistant water-blocking cable of claim 1, wherein, The water-blocking and corrosion-resistant ethylene-propylene rubber composite material is made of the following raw materials in mass fraction: raw ethylene-propylene rubber 70-90 parts, high density polyethylene 10-15 parts, EVA 20-35 parts, SEBS 2-6 parts, paraffin oil 10-16 parts, crosslinking agent 1.8-2.8 parts, third antioxidant 3.2-4.2 parts, reinforcing and filling agent 25-40 parts, silane coupling agent 1.5-2.8 parts and lubricant 2.6-4.5 parts.

5. The seawater corrosion resistant water-blocking cable of claim 4, wherein, The raw ethylene-propylene rubber has a Mooney viscosity of 55-70, the ethylene content in the raw ethylene-propylene rubber is 50-70%, and the third monomer ethylidene norbornene content in the raw ethylene-propylene rubber is 4.9-8.5%. The reinforcing filler is composed of glass flake, quartz powder and aluminum hydroxide with a mass ratio of 5:2:2, and the surface of the reinforcing filler is coated with vinyl-tris(2-methoxyethoxy)silane; The silane coupling agent is sulfopropyltrimethoxysilane (KH590).

6. The seawater corrosion resistant water-blocking cable of claim 1, wherein, The corrosion-resistant water-blocking polyethylene composite material is prepared from the following raw materials in parts by mass: high-density polyethylene 80-90 parts, metallocene medium-density polyethylene 10-20 parts, fourth antioxidant 0.2-0.4 parts, carbon black 2.4-3.2 parts, silicone 0.8-1.2 parts, and polyethylene wax 0.12-0.16 parts.

7. The seawater corrosion resistant water-blocking cable of claim 1, wherein, The insulation layer (3) is a silane cross-linked polyethylene insulation material. The insulation and shielding layer (4) is a carbon black-filled EPDM rubber material. The water-blocking filling layer (7) is any one of water-blocking rope, water-blocking powder, water-blocking yarn, or water-blocking glue. The water-blocking wrapping layer (8) is a polyester non-woven fabric water-blocking tape. The armored layer (10) is a galvanized steel wire armored layer (10).

8. A process for the preparation of a seawater corrosion resistant water blocking cable for the preparation of a seawater corrosion resistant water blocking cable according to any one of claims 1 to 7, characterized in that, Specifically comprising the following steps: P1. Regularly twisting a plurality of oxygen-free copper wires to obtain a conductor (1); P2. Mixing the raw materials of the semiconductor water-blocking layer (2), extruding and wrapping the conductor (1), extruding and wrapping the silane cross-linked polyethylene insulation material on the semiconductor water-blocking layer (2), cross-linking in a hot water or steam environment to form an insulation layer (3); P3. Extruding and wrapping the carbon black-filled EPDM rubber material on the insulation layer (3), cross-linking and curing to form an insulation and shielding layer (4), and then wrapping a copper-plastic composite tape (5) on the insulation and shielding layer (4); P4. Extruding and wrapping the raw materials of the water-blocking and corrosion-resistant EPDM rubber composite material on the insulation and shielding layer (4) to form a corrosion-resistant and water-blocking inner sheath (6), cross-linking and curing to obtain a cable core; P5. When twisting the cable core into a cable, filling water-blocking material in the gaps between the cable core wires and outside the cable core to form a water-blocking filling layer (7), and then wrapping a water-blocking wrapping layer (8) outside the water-blocking filling layer (7); P5. Extruding and wrapping the raw materials of the water-blocking and corrosion-resistant EPDM rubber composite material on the water-blocking wrapping layer (8), cross-linking and curing to form an inner protective layer (9), and then wrapping a galvanized steel wire armored layer (10) on the inner protective layer (9); P6. Slowly adding polyphosphoric acid into preheated petroleum asphalt while stirring, continuing to stir for 15-30 min after the addition is completed, slowly adding the first EVA and the first antioxidant while stirring, stirring at 170-180℃ for 30-45 min, slowly adding the resin modified geopolymer after cooling to 130-140℃, stirring for 10-15 min to obtain a modified asphalt coating; then directly applying the modified asphalt coating on the above-mentioned inner protective layer (9), rapidly cooling in a water tank, and then placing the coated cable in an infrared radiation environment, irradiating at 40-50℃ for 2-4 h, irradiating at 65-70℃ for 1-2 h, naturally cooling to room temperature, and placing at room temperature for 12-18 h to form a modified asphalt layer (11); P7. Extruding and wrapping the corrosion-resistant water-blocking polyethylene composite material on the modified asphalt layer (11) to form an outer sheath (12).

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