Photoelectric composite cable for underwater buoy, and preparation process therefor

Abstract

A photoelectric composite cable for an underwater buoy, and a preparation process therefor. A polyurethane, a self-repairing polyurethane prepolymer, and a composite nano zinc oxide are selected as an outer sheath base material. A modified polysiloxane having a B-O six-membered ring dynamic cross-linked network and a long-chain alkane group and an amino is introduced into the self-repairing polyurethane prepolymer; 5,5'-methylenedisalicylaldehyde and isophorone diisocyanate are together subjected to stepwise polymerization with the modified polysiloxane, and the 5,5'-methylenedisalicylaldehyde is cross-linked with diphenylmethane diisocyanate to obtain a self-repairing polyurethane prepolymer; and nano zinc oxide is subjected to a modification treatment, wherein dodecyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane are used for dual modification, such that super-hydrophobic nano zinc oxide having good thermal stability and high dispersity is prepared in a toluene system.

Description

A photoelectric composite cable for underwater buoys and its manufacturing process Technical Field

[0001] This invention relates to the field of composite cable technology, specifically to an optical-electric composite cable for underwater buoys and its manufacturing process. Background Technology

[0002] Optical fiber composite cable is a type of cable that integrates optical fiber and power transmission line, possessing the characteristic of simultaneous optical and electrical transmission. It is used to solve problems related to broadband access, equipment power supply, and signal transmission, and is widely used in power supply systems for long-distance and short-distance communication systems. With social progress, the application areas of optical fiber composite cables are constantly expanding, such as underwater and submerged installations. Consequently, the performance requirements for optical fiber composite cables are becoming increasingly stringent.

[0003] If the optical fiber composite cable is worn or aged during use, the conductor will be exposed. If it is soaked in water, it will cause serious safety hazards. Therefore, improving the waterproof and wear-resistant properties of the optical fiber composite cable is of practical significance.

[0004] Summary of the Invention

[0005] The purpose of this invention is to provide a high-strength wear-resistant polyurethane composite board and its processing technology to solve the problems in the prior art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A fiber optic composite cable for underwater buoys includes a cable core, the cable core being composed of an optical cable element, a water ingress detection line, a 48V power line, an RS422 data line, a 220V power line, and a drain line. Water-blocking sealant is filled between the various structures of the cable core. The outer surface of the cable core is sequentially wrapped with a braided layer, a tensile reinforcement layer, a braided fastening layer, and an outer sheath.

[0008] Furthermore, the optical cable components, water ingress detection line, 48V power cable, RS422 data cable, and 220V power cable are all covered with aluminum-plastic composite cable.

[0009] Furthermore, the optical cable element is composed of an optical fiber and an armor layer on the surface of the optical fiber. The armor layer on the surface of the optical fiber is a seamless stainless steel tube with a diameter of 1.3mm; the braided layer and the tensile reinforcement layer are both aramid fiber layers; and the braided fastening layer is a twisted water-blocking aramid layer.

[0010] Furthermore, the aramid fiber layer is woven from aramid fibers.

[0011] Furthermore, the twisted water-blocking aramid layer is formed by twisting aramid fibers in the Z direction with a twist of 90 degrees to form a twisted rope armor.

[0012] Furthermore, the 48V power cord is made of 17-21 strands of 0.26mm tinned copper wire, coated with water-blocking sealant, and then covered with polyethylene; the water inlet detection line and RS422 data line are made of 6-8 strands of 0.25mm silver-plated copper wire, coated with water-blocking sealant, and then covered with ethylene tetrafluoroethylene copolymer; the 220V power cord is made of 17-21 strands of 0.31mm tinned copper wire, coated with water-blocking sealant, and then covered with polyethylene; the drain line is made of 17-21 strands of 0.26mm tinned copper wire, coated with water-blocking sealant.

[0013] Furthermore, the water-blocking sealant is either a silicone-based sealant or a chloroprene-based sealant.

[0014] Furthermore, a manufacturing process for an underwater buoy optical-electric composite cable includes the following steps:

[0015] S1: Mix polyurethane, self-healing polyurethane prepolymer, and composite nano zinc oxide, put them into a twin-screw extruder for compounding and extrusion, pelletize and dry to obtain the outer sheath base material, and then extrude the outer sheath base material by semi-extrusion to obtain the outer sheath.

[0016] S2: Assemble the cable core structure, fill the gaps between the various structures of the cable core with water-blocking sealant, and then wrap the outer surface with a braided layer, a tensile reinforcement layer, a braided fastening layer, and an outer sheath in sequence to obtain an underwater buoy optical-electric composite cable.

[0017] Furthermore, by weight, the outer sheath base material consists of 32-36 parts polyurethane, 15-27 parts self-healing polyurethane prepolymer, and 1-5 to 1-3 parts composite nano zinc oxide.

[0018] Furthermore, the preparation of the self-healing polyurethane prepolymer includes the following steps:

[0019] 1) Mix trioxymethylene, salicylaldehyde, and glacial acetic acid, heat to 88-92℃, add concentrated sulfuric acid, continue to keep warm for 22-24 hours, cool, pour into an ice-water mixture and let stand overnight, wash, filter, wash with ether 2-3 times, recrystallize the precipitate with acetone 3-5 times to obtain 5,5'-methylenebisalicylicalaldehyde.

[0020] 2) Under nitrogen protection, the modified polysiloxane, anhydrous tetrahydrofuran, and dichloromethane were mixed, cooled to 0°C, and isophorone diisocyanate was added. The mixture was stirred for 5-6 hours, heated to 18-25°C, and 5,5'-methylenebisalicylic acid aldehyde was added. The mixture was stirred for another 5-6 hours, anhydrous sodium sulfate was added, the mixture was filtered, and the solution was dissolved in anhydrous tetrahydrofuran by vacuum distillation. Triethylenediamine and diphenylmethane diisocyanate were added, and the mixture was stirred for 15-20 minutes under nitrogen protection. The mixture was then rotary evaporated, transferred to a tetrafluoroethylene mold, and dried to obtain a self-healing polyurethane prepolymer.

[0021] Furthermore, the preparation of modified polysiloxanes includes the following steps:

[0022] (1) Under a nitrogen atmosphere, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and tetramethyltetraenylcyclotetrasiloxane are mixed, heated to 88-92℃ and held for 20-30 min, heated to 108-112℃, tetramethylammonium hydroxide is added, and the mixture is kept at the same temperature for 4-6 h. The mixture is then heated to 130℃ and held for 25-30 min, and the temperature is reduced for 2-3 h to obtain amino-terminated vinyl polysiloxane.

[0023] (2) Under a nitrogen atmosphere, 4-vinylphenylboronic acid, anhydrous sodium sulfate and tetrahydrofuran were mixed and kept at 48-52℃ for 23-24h, then rotary evaporated and dried to obtain tri(vinylphenyl)boroxane.

[0024] (3) Mix amino-terminated vinyl polysiloxane with octadecyl methacrylate and tetrahydrofuran, add tri(vinylbenzene)boroxane, benzoyl peroxide and 2,2-azobisisobutyronitrile, stir at 18-25℃ for 11-12h, rotary evaporate, hot press at 160℃ for 3min, dissolve in toluene, precipitate with petroleum ether, repeat precipitation 3-5 times, dry to obtain modified polysiloxane.

[0025] Furthermore, the preparation of composite nano zinc oxide includes the following steps: mixing nano zinc oxide and toluene, stirring at 78-82℃ for 8-10 min, adding dodecyltrimethoxysilane, continuing to keep warm for 8-9 h, adding 3-glycidyl etheroxypropyltrimethoxysilane, continuing to keep warm for 7-8 h, centrifuging, ultrasonically cleaning with ethanol, centrifuging again, drying, and grinding to obtain composite nano zinc oxide.

[0026] The beneficial effects of this invention are:

[0027] This invention provides an optical-electric composite cable for underwater buoys and its manufacturing process. The prepared optical-electric composite cable has good mechanical strength, resistance to mechanical damage, abrasion resistance, and water resistance, enabling it to have good high-capacity optical signal transmission capability and data signal transmission capability while meeting watertight performance requirements. At the same time, it can also serve as a telephone transmission line, a water ingress detection line, and other communication signal lines, as well as a 220V high-voltage boat power supply and a 48V lithium battery power supply, providing a variety of comprehensive signals and electrical energy.

[0028] To ensure the flexibility and reliability of the optoelectronic composite cable during use, the conductor of the optoelectronic composite cable in this invention adopts a multi-strand stranded structure, thereby improving its resistance to vibration and impact and the continuity of repeated bending. To improve its longitudinal water tightness, a silicon-based or chloroprene-based water-blocking sealant is filled during the stranding process. To impart solderability and signal transmission characteristics to the water ingress detection line and RS422 data line, a process of stranding silver-plated copper wire and filling with water-blocking sealant is adopted. The aramid fiber is twisted before armoring, effectively reducing the outer diameter of the product and making its appearance round. The battery element in this invention adopts a combination of wrapped aluminum-plastic composite cable and drain line as the shielding form of the optoelectronic composite cable, which effectively reduces the outer diameter and weight of the optoelectronic composite cable.

[0029] In order to endow the optoelectronic composite cable with excellent water resistance, abrasion resistance and mechanical damage resistance, polyurethane, self-healing polyurethane prepolymer and composite nano zinc oxide are selected as outer sheath base materials in this invention to prepare the outer sheath of the optoelectronic composite cable.

[0030] To improve the abrasion resistance and water resistance of the outer sheath, modified polysiloxanes were introduced into the self-healing polyurethane prepolymer. First, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and tetramethyltetraenylcyclotetrasiloxane were prepared using tetramethylammonium hydroxide as a catalyst to obtain amino-terminated vinyl polysiloxanes. Then, through free radical polymerization, monomers formed by dehydrating 4-vinylphenylboronic acid, amino-terminated vinyl polysiloxanes, and hydrophobic octadecyl methacrylate were copolymerized to prepare a modified polysiloxane with a dynamic crosslinking network of BO six-membered rings, long-chain alkane groups, and amino groups. This modified polysiloxane was used as a raw material to prepare a self-healing polyurethane prepolymer, endowing it with rapid self-healing properties at room temperature, in water environments, and at low temperatures, thereby significantly improving the water resistance and abrasion resistance of the protective sheath.

[0031] In the preparation of self-healing polyurethane prepolymer, bio-based salicylaldehyde is used as a raw material, and 5,5'-methylenebisalicylic acid is prepared with trioxymethylene. 5,5'-methylenebisalicylic acid and isophorone diisocyanate are then progressively polymerized with modified polysiloxane. Subsequently, 5,5'-methylenebisalicylic acid is crosslinked with diphenylmethane diisocyanate to form a dynamic crosslinking network of urethane dynamic bonds and BO six-membered rings. This results in a dynamic self-healing silicone elastomer with high mechanical strength, good hydrophobicity, multiple active sites, high compatibility, and high wear resistance. This facilitates improved compatibility when mixed with other raw materials. Furthermore, the introduction of silicon and the complexity of the Si-O-Si crosslinking structure contribute to improved flame retardancy of the protective sleeve.

[0032] Nano zinc oxide is introduced as a filler in the preparation of the protective sleeve to further improve its water resistance and abrasion resistance. In order to improve the uniformity of the dispersion of nano zinc oxide in polyurethane, the nano zinc oxide is modified by double modification with dodecyltrimethoxysilane and 3-glycidyl etheroxypropyltrimethoxysilane in toluene system to prepare superhydrophobic nano zinc oxide with good thermal stability and high dispersibility. The protective sleeve with superhydrophobic surface is prepared. At the same time, there is a metal-coordination bond between the composite nano zinc oxide and the self-healing polyurethane prepolymer, which is beneficial to further improve its self-healing rate. Attached Figure Description

[0033] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used in conjunction with embodiments of the invention to explain the invention and do not constitute a limitation thereof. In the drawings:

[0034] Figure 1 is a schematic diagram of the structure of the optoelectronic composite cable of the present invention;

[0035] 1-Optical cable element, 2-Water ingress detection line, 3-48V power cable, 4-RS422 data cable, 5-220V power cable, 6-Drainage line, 7-Telephone line, 8-Braided layer, 9-Tensile reinforcement layer, 10-Braided fastening layer, 11-Outer sheath. Detailed Implementation

[0036] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0037] It should be noted that if the embodiments of the present invention involve directional indicators such as up, down, left, right, front, and back, these directional indicators are only used to explain the relative positional relationship and movement of components in a specific posture. If the specific posture changes, the directional indicators will also change accordingly. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0038] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0039] Example 1: A manufacturing process for an underwater buoy optical-electric composite cable, comprising the following steps:

[0040] S1: Mix polyurethane, self-healing polyurethane prepolymer and composite nano zinc oxide, put them into a twin-screw extruder for compounding and extrusion, pelletize and dry to obtain outer sheath base material, and extrude the outer sheath base material by semi-extrusion to obtain outer sheath 11.

[0041] By weight, the outer sheath base material consists of 32 parts polyurethane, 15 parts self-healing polyurethane prepolymer, and 1 part composite nano zinc oxide.

[0042] The preparation of the self-healing polyurethane prepolymer includes the following steps:

[0043] 1) Mix 0.1 mmol of trioxymethylene, 0.4 mmol of salicylaldehyde, and 25 mL of glacial acetic acid, heat to 88 °C, add 0.25 mL of concentrated sulfuric acid, continue to keep warm for 22 h, cool, pour into an ice-water mixture and let stand overnight, wash, filter, wash twice with diethyl ether, recrystallize the precipitate three times with acetone to obtain 5,5'-methylenebissalicylaldehyde;

[0044] 2) Under nitrogen protection, 0.5 g of modified polysiloxane, 5 mL of anhydrous tetrahydrofuran, and 5 mL of dichloromethane were mixed, cooled to 0 °C, and 0.3 mmol of isophorone diisocyanate was added. The mixture was stirred for 5 h, heated to 18 °C, and 0.2 mmol of 5,5'-methylenebis(salicylaldehyde) was added. The mixture was stirred for another 5 h, and anhydrous sodium sulfate was added. The mixture was filtered, distilled under reduced pressure, and dissolved in 30 mL of anhydrous tetrahydrofuran. 2 mg of triethylenediamine and 0.2 mmol of diphenylmethane diisocyanate were added. Under nitrogen protection, the mixture was stirred for 15 min, rotary evaporated, transferred to a tetrafluoroethylene mold, and dried to obtain a self-healing polyurethane prepolymer.

[0045] The preparation of the modified polysiloxane includes the following steps:

[0046] (1) Under a nitrogen atmosphere, 37.4 g of octamethylcyclotetrasiloxane, 19.4 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 34.2 g of tetramethyltetraenylcyclotetrasiloxane were mixed, heated to 88 °C and held for 30 min, then heated to 108 °C and 6.2 mg of tetramethylammonium hydroxide were added. The mixture was kept at 130 °C for 25 min and then subjected to reduced pressure for 2 h to obtain amino-terminated vinyl polysiloxane.

[0047] (2) Under a nitrogen atmosphere, 13.5 mmol of 4-vinylphenylboronic acid, 42.2 mmol of anhydrous sodium sulfate and 20 mL of tetrahydrofuran were mixed, kept at 48 °C for 24 h, rotary evaporated and dried to obtain tri(vinylphenyl)boroxane.

[0048] (3) Mix 18g of amino-terminated vinyl polysiloxane, 2g of octadecyl methacrylate and 30mL of tetrahydrofuran, add 0.21g of tri(vinylbenzene)boroxane, 52.5mg of benzoyl peroxide and 52.5mg of 2,2-azobisisobutyronitrile, stir at 18℃ for 12h, rotary evaporate, hot press at 160℃ for 3min, dissolve in toluene, precipitate with petroleum ether, repeat precipitation 3 times, dry to obtain modified polysiloxane;

[0049] The preparation of the composite nano zinc oxide includes the following steps: 2.5g of nano zinc oxide and 100mL of toluene are mixed and stirred at 78℃ for 10min. 1mL of dodecyltrimethoxysilane is added and kept at this temperature for 8h. 0.25mL of 3-glycidyl etheroxypropyltrimethoxysilane is added and kept at this temperature for 7h. The mixture is then centrifuged, ultrasonically cleaned with ethanol, centrifuged again, dried, and ground to obtain the composite nano zinc oxide.

[0050] S3: Assemble the cable core structure, fill the gaps between the various structures of the cable core with water-blocking sealant, and then wrap the outer surface in sequence with braided layer 8, tensile reinforcement layer 9, braided fastening layer 10, and outer sheath 11 to obtain an underwater buoy optical-electric composite cable.

[0051] The cable core consists of an optical cable element 1, a water ingress detection line 2, a 48V power supply line 3, an RS422 data line 4, a 220V power supply line 5, and a drain line 6.

[0052] The optical cable element 1, water ingress detection line 2, 48V power line 3, RS422 data line 4, and 220V power line 5 are all covered with aluminum-plastic composite cable.

[0053] The optical cable element 1 is composed of an optical fiber and an armor layer on the surface of the optical fiber, wherein the armor layer on the surface of the optical fiber is a seamless stainless steel tube with a diameter of 1.3 mm.

[0054] The braided layer 8 and the tensile reinforcing layer 9 are both aramid fiber layers; the braided fastening layer 10 is a twisted water-blocking aramid layer.

[0055] The aramid fiber layer is woven from aramid fibers; the twisted water-blocking aramid layer is formed by twisting aramid fibers in the Z direction at 90 degrees to form a twisted rope armor.

[0056] The 48V power cable 3 is made of 17 strands of 0.26mm tin-plated copper wire, coated with water-blocking sealant, and then covered with polyethylene. The water inlet detection line 2 and the RS422 data line 4 are made of 6 strands of 0.25mm silver-plated copper wire, coated with water-blocking sealant, and then covered with ethylene tetrafluoroethylene copolymer. The 220V power cable 5 is made of 17 strands of 0.31mm tin-plated copper wire, coated with water-blocking sealant, and then covered with polyethylene. The drain line 6 is made of 17 strands of 0.26mm tin-plated copper wire, coated with water-blocking sealant.

[0057] Example 2: A manufacturing process for an underwater buoy optical-electric composite cable, comprising the following steps:

[0058] S1: Mix polyurethane, self-healing polyurethane prepolymer and composite nano zinc oxide, put them into a twin-screw extruder for compounding and extrusion, pelletize and dry to obtain outer sheath base material, and extrude the outer sheath base material by semi-extrusion to obtain outer sheath 11.

[0059] By weight, the outer sheath base material consists of 34 parts polyurethane, 17 parts self-healing polyurethane prepolymer, and 2 parts composite nano zinc oxide.

[0060] The preparation of the self-healing polyurethane prepolymer includes the following steps:

[0061] 1) Mix 0.1 mmol of trioxymethylene, 0.4 mmol of salicylaldehyde, and 25 mL of glacial acetic acid, heat to 90 °C, add 0.25 mL of concentrated sulfuric acid, continue to keep warm for 23 h, cool, pour into an ice-water mixture and let stand overnight, wash, filter, wash twice with diethyl ether, recrystallize the precipitate four times with acetone to obtain 5,5'-methylenebisalicylicalaldehyde;

[0062] 2) Under nitrogen protection, 0.5 g of modified polysiloxane, 5 mL of anhydrous tetrahydrofuran, and 5 mL of dichloromethane were mixed, cooled to 0 °C, and 0.3 mmol of isophorone diisocyanate was added. The mixture was stirred for 5.5 h, heated to 20 °C, and 0.2 mmol of 5,5'-methylenebisalicylic acid aldehyde was added. The mixture was stirred for another 5.5 h, anhydrous sodium sulfate was added, the mixture was filtered, and the solution was dissolved in 30 mL of anhydrous tetrahydrofuran by vacuum distillation. 2 mg of triethylenediamine and 0.2 mmol of diphenylmethane diisocyanate were added. Under nitrogen protection, the mixture was stirred for 18 min, rotary evaporated, transferred to a tetrafluoroethylene mold, and dried to obtain a self-healing polyurethane prepolymer.

[0063] The preparation of the modified polysiloxane includes the following steps:

[0064] (1) Under a nitrogen atmosphere, 37.4 g of octamethylcyclotetrasiloxane, 19.4 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 34.2 g of tetramethyltetraenylcyclotetrasiloxane were mixed, heated to 90 °C and held for 25 min, then heated to 110 °C and 6.2 mg of tetramethylammonium hydroxide were added. The mixture was kept at 110 °C for 5 h, then heated to 130 °C and held for 28 min. The mixture was then subjected to reduced pressure for 2.5 h to obtain amino-terminated vinyl polysiloxane.

[0065] (2) Under a nitrogen atmosphere, 13.5 mmol of 4-vinylphenylboronic acid, 42.2 mmol of anhydrous sodium sulfate and 20 mL of tetrahydrofuran were mixed, kept at 50 °C for 23.5 h, rotary evaporated and dried to obtain tri(vinylphenyl)boroxane.

[0066] (3) Mix 18g of amino-terminated vinyl polysiloxane, 2g of octadecyl methacrylate and 30mL of tetrahydrofuran, add 0.21g of tris(vinylbenzene)boroxane, 52.5mg of benzoyl peroxide and 52.5mg of 2,2-azobisisobutyronitrile, stir at 20℃ for 11.5h, rotary evaporate, hot press at 160℃ for 3min, dissolve in toluene, precipitate with petroleum ether, repeat precipitation 4 times, dry to obtain modified polysiloxane;

[0067] The preparation of the composite nano zinc oxide includes the following steps: 2.5g of nano zinc oxide and 100mL of toluene are mixed and stirred at 80℃ for 9min. 1mL of dodecyltrimethoxysilane is added and kept at this temperature for 8.5h. 0.25mL of 3-glycidyl etheroxypropyltrimethoxysilane is added and kept at this temperature for 7.5h. The mixture is then centrifuged, ultrasonically cleaned with ethanol, centrifuged again, dried, and ground to obtain the composite nano zinc oxide.

[0068] S3: Assemble the cable core structure, fill the gaps between the various structures of the cable core with water-blocking sealant, and then wrap the outer surface in sequence with braided layer 8, tensile reinforcement layer 9, braided fastening layer 10, and outer sheath 11 to obtain an underwater buoy optical-electric composite cable.

[0069] The cable core consists of an optical cable element 1, a water ingress detection line 2, a 48V power supply line 3, an RS422 data line 4, a 220V power supply line 5, and a drain line 6.

[0070] The optical cable element 1, water ingress detection line 2, 48V power line 3, RS422 data line 4, and 220V power line 5 are all covered with aluminum-plastic composite cable.

[0071] The optical cable element 1 is composed of an optical fiber and an armor layer on the surface of the optical fiber, wherein the armor layer on the surface of the optical fiber is a seamless stainless steel tube with a diameter of 1.3 mm.

[0072] The braided layer 8 and the tensile reinforcing layer 9 are both aramid fiber layers; the braided fastening layer 10 is a twisted water-blocking aramid layer.

[0073] The aramid fiber layer is woven from aramid fibers; the twisted water-blocking aramid layer is formed by twisting aramid fibers in the Z direction at 90 degrees to form a twisted rope armor.

[0074] The 48V power cable 3 is made of 19 strands of 0.26mm tin-plated copper wire, coated with water-blocking sealant, and then covered with polyethylene. The water inlet detection line 2 and the RS422 data line 4 are made of 7 strands of 0.25mm silver-plated copper wire, coated with water-blocking sealant, and then covered with ethylene tetrafluoroethylene copolymer. The 220V power cable 5 is made of 19 strands of 0.31mm tin-plated copper wire, coated with water-blocking sealant, and then covered with polyethylene. The drain line 6 is made of 19 strands of 0.26mm tin-plated copper wire, coated with water-blocking sealant.

[0075] Example 3: A manufacturing process for an underwater buoy optical-electric composite cable, comprising the following steps:

[0076] S1: Mix polyurethane, self-healing polyurethane prepolymer and composite nano zinc oxide, put them into a twin-screw extruder for compounding and extrusion, pelletize and dry to obtain outer sheath base material, and extrude the outer sheath base material by semi-extrusion to obtain outer sheath 11.

[0077] By weight, the outer sheath base material consists of 36 parts polyurethane, 27 parts self-healing polyurethane prepolymer, and 3 parts composite nano zinc oxide.

[0078] The preparation of the self-healing polyurethane prepolymer includes the following steps:

[0079] 1) Mix 0.1 mmol of trioxymethylene, 0.4 mmol of salicylaldehyde, and 25 mL of glacial acetic acid, heat to 92 °C, add 0.25 mL of concentrated sulfuric acid, continue to keep warm for 24 h, cool, pour into an ice-water mixture and let stand overnight, wash, filter, wash 3 times with diethyl ether, recrystallize the precipitate 5 times with acetone to obtain 5,5'-methylenebisalicylicalaldehyde;

[0080] 2) Under nitrogen protection, 0.5 g of modified polysiloxane, 5 mL of anhydrous tetrahydrofuran, and 5 mL of dichloromethane were mixed, cooled to 0 °C, and 0.3 mmol of isophorone diisocyanate was added. The mixture was stirred for 6 h, heated to 25 °C, and 0.2 mmol of 5,5'-methylenebis(salicylaldehyde) was added. The mixture was stirred for another 6 h, and anhydrous sodium sulfate was added. The mixture was filtered, distilled under reduced pressure, and dissolved in 30 mL of anhydrous tetrahydrofuran. 2 mg of triethylenediamine and 0.2 mmol of diphenylmethane diisocyanate were added. Under nitrogen protection, the mixture was stirred for 20 min, rotary evaporated, transferred to a tetrafluoroethylene mold, and dried to obtain a self-healing polyurethane prepolymer.

[0081] The preparation of the modified polysiloxane includes the following steps:

[0082] (1) Under a nitrogen atmosphere, 37.4 g of octamethylcyclotetrasiloxane, 19.4 g of 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and 34.2 g of tetramethyltetraenylcyclotetrasiloxane were mixed, heated to 92 °C and held for 20 min, then heated to 112 °C and 6.2 mg of tetramethylammonium hydroxide were added. The mixture was kept at 130 °C for 30 min and then subjected to reduced pressure for 3 h to obtain amino-terminated vinyl polysiloxane.

[0083] (2) Under a nitrogen atmosphere, 13.5 mmol of 4-vinylphenylboronic acid, 42.2 mmol of anhydrous sodium sulfate and 20 mL of tetrahydrofuran were mixed, kept at 52 °C for 23 h, rotary evaporated and dried to obtain tri(vinylphenyl)boroxane.

[0084] (3) Mix 18g of amino-terminated vinyl polysiloxane, 2g of octadecyl methacrylate and 30mL of tetrahydrofuran, add 0.21g of tri(vinylbenzene)boroxane, 52.5mg of benzoyl peroxide and 52.5mg of 2,2-azobisisobutyronitrile, stir at 25℃ for 11h, rotary evaporate, hot press at 160℃ for 3min, dissolve in toluene, precipitate with petroleum ether, repeat precipitation 5 times, dry to obtain modified polysiloxane;

[0085] The preparation of the composite nano zinc oxide includes the following steps: 2.5g of nano zinc oxide and 100mL of toluene are mixed and stirred at 82℃ for 8min. 1mL of dodecyltrimethoxysilane is added and kept at this temperature for 9h. 0.25mL of 3-glycidyl etheroxypropyltrimethoxysilane is added and kept at this temperature for 8h. The mixture is then centrifuged, ultrasonically cleaned with ethanol, centrifuged again, dried, and ground to obtain the composite nano zinc oxide.

[0086] S3: Assemble the cable core structure, fill the gaps between the various structures of the cable core with water-blocking sealant, and then wrap the outer surface in sequence with braided layer 8, tensile reinforcement layer 9, braided fastening layer 10, and outer sheath 11 to obtain an underwater buoy optical-electric composite cable.

[0087] The cable core consists of an optical cable element 1, a water ingress detection line 2, a 48V power supply line 3, an RS422 data line 4, a 220V power supply line 5, and a drain line 6.

[0088] The optical cable element 1, water ingress detection line 2, 48V power line 3, RS422 data line 4, and 220V power line 5 are all covered with aluminum-plastic composite cable.

[0089] The optical cable element 1 is composed of an optical fiber and an armor layer on the surface of the optical fiber, wherein the armor layer on the surface of the optical fiber is a seamless stainless steel tube with a diameter of 1.3 mm.

[0090] The braided layer 8 and the tensile reinforcing layer 9 are both aramid fiber layers; the braided fastening layer 10 is a twisted water-blocking aramid layer.

[0091] The aramid fiber layer is woven from aramid fibers; the twisted water-blocking aramid layer is formed by twisting aramid fibers in the Z direction at 90 degrees to form a twisted rope armor.

[0092] The 48V power cable 3 is made of 21 strands of 0.26mm tin-plated copper wire, coated with water-blocking sealant, and then covered with polyethylene. The water inlet detection line 2 and the RS422 data line 4 are made of 8 strands of 0.25mm silver-plated copper wire, coated with water-blocking sealant, and then covered with ethylene tetrafluoroethylene copolymer. The 220V power cable 5 is made of 21 strands of 0.31mm tin-plated copper wire, coated with water-blocking sealant, and then covered with polyethylene. The drain line 6 is made of 21 strands of 0.26mm tin-plated copper wire, coated with water-blocking sealant.

[0093] Comparative Example 1: Example 3 served as the control group, but no tri(vinylbenzene)boroxane was prepared, and other processes were normal.

[0094] Comparative Example 2: Example 3 served as the control group, but no octadecyl methacrylate was added, and other processes were normal.

[0095] Comparative Example 3: Using Example 3 as the control group, the modified siloxane was replaced with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and the other processes were normal.

[0096] Comparative Example 4: Using Example 3 as the control group, no 5,5'-methylenebisalicylic aldehyde was added, and other processes were normal.

[0097] Comparative Example 5: Using Example 3 as the control group, nano zinc oxide was used to replace composite zinc oxide, while other processes were normal.

[0098] In the examples and comparative examples, the thickness of the protective sleeve is 1 mm.

[0099] Source of raw materials (for illustrative purposes only):

[0100] Polyurethane TPU 9395AU: Covestro Bayer; Water-blocking sealant (silicone-based): Nanjing University Chemical 87 Glue; Polyethylene 1C7A: Sinopec; Aluminum-plastic composite cable (10mm*0.025mm): Yangzhou Tengfei; Seamless stainless steel pipe (1mm): Zhongtian Power Optical Cable Co., Ltd.; Aramid fiber (Kevlar fiber K49, 1580dtex): DuPont; Ethylene tetrafluoroethylene copolymer AP-230: Dongguan Suguang Plastic Raw Materials Co., Ltd.; Trioxymethylene R155: Wuhan Jixin Yibang Biotechnology Co., Ltd.; Salicylic acid 90-02-8: Hubei Kewode Chemical Co., Ltd.; Diphenylmethane diisocyanate 101-68-8: Shandong Jiaying Chemical Technology Co., Ltd.; 1,3-Bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane S70680: Shanghai Yuanye Biotechnology Co., Ltd. Company; Tetramethyltetraenylcyclotetrasiloxane 396281: Sigma-Aldrich (Shanghai) Trading Co., Ltd.; Tetrahydrofuran T431413, Isophorone diisocyanate I109582, Triethylenediamine T431497, Octamethylcyclotetrasiloxane O160041, Tetramethylammonium hydroxide T100882, 4-Vinylphenylboronic acid V102338, Octadecyl methacrylate S1075 62. Benzoyl peroxide B104630, 2,2-azobisisobutyronitrile A104255, Nano zinc oxide Z112847, Dodecyltrimethoxysilane D155296, 3-glycidyl etheroxypropyltrimethoxysilane G107576: Aladdin reagent; Ethanol, glacial acetic acid, sulfuric acid, diethyl ether, acetone, dichloromethane, anhydrous sodium sulfate, toluene, petroleum ether, analytical grade: Sinopharm Group reagent.

[0101] Performance testing: The protective sleeves prepared in the examples and comparative examples were subjected to performance tests; Hydrophobicity: Characterized by water contact angle, tested with a 2μL deionized water droplet; Self-healing: A scratch with a length of 800μm, a width of 4μm, and a depth of 800μm was made on the sample surface, and the initial scratch length L0 was recorded. After being kept at 30℃ for 12h, the scratch length L1 after heat preservation was observed with an electron microscope. The self-healing rate was (L0-L1) / L0×100%; Abrasion resistance: The sample was placed on 1000-grit sandpaper with a load of 60g and a pulling speed of 2cm / s. Every 8cm movement was recorded as one cycle, and the water contact angle of the protective layer was measured after 5 cycles; Salt resistance: The sample was immersed in a 12g / L sodium chloride aqueous solution and kept at 80℃ for 72h. The surface of the sample was observed for blistering, damage, etc. No change on the surface was considered qualified; The test results are shown in Table 1 below; Specific data are shown in Table 1.

[0102] Table 1

[0103] This invention provides an optical-electric composite cable for underwater buoys and its manufacturing process. The resulting optical-electric composite cable has good mechanical strength, resistance to mechanical damage, abrasion resistance, and water resistance. Under the premise of meeting watertight performance, it has good high-capacity optical signal transmission capability and data signal transmission capability. At the same time, it can also serve as a telephone transmission line, a water ingress detection line, and other communication signal lines, as well as a 220V high-voltage boat power supply and a 48V lithium battery power supply, providing a variety of comprehensive signals and electrical energy. In Table 1, / indicates that the item was not tested.

[0104] Comparing Example 3 with Comparative Examples 1, 2, and 3, it can be seen that, in order to improve the wear resistance and water resistance of the outer sheath, a modified siloxane is introduced into the self-healing polyurethane prepolymer. First, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, and tetramethyltetraenylcyclotetrasiloxane are prepared using tetramethylammonium hydroxide as a catalyst to obtain an amino-terminated vinyl polysiloxane. Then, through free radical polymerization, the monomer formed by dehydrating 4-vinylphenylboronic acid, the amino-terminated vinyl polysiloxane, and octadecyl methacrylate (which has hydrophobicity) are copolymerized to prepare a modified polysiloxane with a BO six-membered ring dynamic crosslinking network, long-chain alkane groups, and amino groups. This modified polysiloxane is used as a raw material to prepare a self-healing polyurethane prepolymer, which enables rapid self-healing in room temperature, aqueous environments, and low temperatures, thereby significantly improving the water resistance and wear resistance of the protective sheath.

[0105] Comparing Example 3 with Comparative Example 4, it can be seen that in the preparation of the self-healing polyurethane prepolymer, bio-based salicylaldehyde is used as a raw material, and 5,5'-methylenebissalicylaldehyde is prepared with trioxymethylene. 5,5'-methylenebissalicylaldehyde and isophorone diisocyanate are then progressively polymerized with modified polysiloxane. Subsequently, 5,5'-methylenebissalicylaldehyde is crosslinked with diphenylmethane diisocyanate to form a dynamic crosslinking network of urethane dynamic bonds and BO six-membered rings. This results in a dynamic self-healing silicone elastomer with high mechanical strength, good hydrophobicity, multiple active sites, high compatibility, and high wear resistance. This makes it easier to improve compatibility when mixed with other raw materials. Furthermore, the introduction of silicon and the complexity of the Si-O-Si crosslinking structure help improve the flame retardancy of the protective sleeve.

[0106] Comparing Example 3 with Comparative Example 5, it can be seen that introducing nano-zinc oxide as a filler in the preparation of the protective sleeve further improves the water resistance and abrasion resistance of the protective sleeve. In order to improve the uniformity of the dispersion of nano-zinc oxide in polyurethane, the nano-zinc oxide is modified by double modification with dodecyltrimethoxysilane and 3-glycidyl etheroxypropyltrimethoxysilane in toluene system to prepare superhydrophobic nano-zinc oxide with good thermal stability and high dispersibility, thus preparing a protective sleeve with a superhydrophobic surface. At the same time, there is a metal-coordination bond between the composite nano-zinc oxide and the self-healing polyurethane prepolymer, which is beneficial to further improve its self-healing rate.

[0107] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the present invention's specification under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A fiber optic composite cable for underwater buoys, characterized in that, The cable core is composed of an optical cable element (1), a water ingress detection line (2), a 48V power line (3), an RS422 data line (4), a 220V power line (5), and a drain line (6). Water-blocking sealant is filled between the various structures of the cable core. The outer surface of the cable core is wrapped with a braided layer (8), a tensile reinforcement layer (9), a braided fastening layer (10), and an outer sheath (11) in sequence.

2. The optical-electric composite cable for underwater buoys according to claim 1, characterized in that, The optical cable element (1), water ingress detection line (2), 48V power line (3), RS422 data line (4), and 220V power line (5) are covered with aluminum-plastic composite cable.

3. The optical-electric composite cable for underwater buoys according to claim 1, characterized in that, The optical cable element (1) is composed of an optical fiber and an armor layer on the surface of the optical fiber. The armor layer on the surface of the optical fiber is a seamless stainless steel tube with a diameter of 1.3 mm. The braided layer (8) and the tensile reinforcement layer (9) are both aramid fiber layers. The braided fastening layer (10) is a twisted water-blocking aramid layer.

4. The optical-electric composite cable for underwater buoys according to claim 1, characterized in that, The 48V power line (3) is made of 17-21 strands of 0.26mm tinned copper wire, coated with water-blocking sealant, and then covered with polyethylene. The water inlet detection line (2) and RS422 data line (4) are made of 6-8 strands of 0.25mm silver-plated copper wire, coated with water-blocking sealant, and then covered with ethylene tetrafluoroethylene copolymer. The 220V power line (5) is made of 17-21 strands of 0.31mm tinned copper wire, coated with water-blocking sealant, and then covered with polyethylene. The drain line (6) is made of 17-21 strands of 0.26mm tinned copper wire, coated with water-blocking sealant.

5. The optical-electric composite cable for underwater buoys according to claim 1, characterized in that, The water-blocking sealant is either a silicone-based sealant or a chloroprene-based sealant.

6. The manufacturing process of an underwater buoy optical-electric composite cable according to any one of claims 1-5, characterized in that, Includes the following steps: S1: Mix polyurethane, self-healing polyurethane prepolymer and composite nano zinc oxide, put them into a twin-screw extruder for compounding and extrusion, pelletize and dry to obtain outer sheath base material, and extrude the outer sheath base material by semi-extrusion to obtain outer sheath (11). S2: Assemble the cable core structure, fill the gaps between the various structures of the cable core with water-blocking sealant, and then wrap the outer surface in sequence with a braided layer (8), a tensile reinforcement layer (9), a braided fastening layer (10), and an outer sheath (11) to obtain an underwater buoy photoelectric composite cable.

7. The manufacturing process of an underwater buoy optical-electric composite cable according to claim 6, characterized in that, By weight, the outer sheath base material consists of: 32-36 parts polyurethane, 15-27 parts self-healing polyurethane prepolymer, and 1-5 to 1-3 parts composite nano zinc oxide.

8. The manufacturing process of an underwater buoy optical-electric composite cable according to claim 6, characterized in that, The preparation of the self-healing polyurethane prepolymer includes the following steps: 1) Mix trioxymethylene, salicylaldehyde, and glacial acetic acid, heat to 88-92℃, add concentrated sulfuric acid, continue to keep warm for 22-24 hours, cool, pour into an ice-water mixture and let stand overnight, wash, filter, wash with ether 2-3 times, recrystallize the precipitate with acetone 3-5 times to obtain 5,5'-methylenebisalicylicalaldehyde. 2) Under nitrogen protection, the modified polysiloxane, anhydrous tetrahydrofuran, and dichloromethane are mixed, cooled to 0°C, and isophorone diisocyanate is added. The mixture is stirred for 5-6 hours, heated to 18-25°C, and 5,5'-methylenebisalicylic acid aldehyde is added. The mixture is stirred for another 5-6 hours, anhydrous sodium sulfate is added, filtered, and the mixture is distilled under reduced pressure to dissolve in anhydrous tetrahydrofuran. Triethylenediamine and diphenylmethane diisocyanate are added, and the mixture is stirred for 15-20 minutes under nitrogen protection. The mixture is then rotary evaporated, transferred to a mold, and dried to obtain a self-healing polyurethane prepolymer.

9. The manufacturing process of an underwater buoy optical-electric composite cable according to claim 8, characterized in that, The preparation of the modified polysiloxane includes the following steps: (1) Under a nitrogen atmosphere, octamethylcyclotetrasiloxane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and tetramethyltetraenylcyclotetrasiloxane are mixed, heated to 88-92℃ and held for 20-30 min, heated to 108-112℃, tetramethylammonium hydroxide is added, and the mixture is kept at the same temperature for 4-6 h. The mixture is then heated to 130℃ and held for 25-30 min, and the temperature is reduced for 2-3 h to obtain amino-terminated vinyl polysiloxane. (2) Under a nitrogen atmosphere, 4-vinylphenylboronic acid, anhydrous sodium sulfate and tetrahydrofuran were mixed and kept at 48-52℃ for 23-24h, then rotary evaporated and dried to obtain tri(vinylphenyl)boroxane. (3) Mix amino-terminated vinyl polysiloxane with octadecyl methacrylate and tetrahydrofuran, add tri(vinylbenzene)boroxane, benzoyl peroxide and 2,2-azobisisobutyronitrile, stir at 18-25℃ for 11-12h, rotary evaporate, hot press at 160℃ for 3min, dissolve in toluene, precipitate with petroleum ether, repeat precipitation 3-5 times, dry to obtain modified polysiloxane.

10. The manufacturing process of an underwater buoy optical-electric composite cable according to claim 6, characterized in that, The preparation of the composite nano zinc oxide includes the following steps: mixing nano zinc oxide and toluene, stirring at 78-82℃ for 8-10 min, adding dodecyltrimethoxysilane, continuing to keep warm for 8-9 h, adding 3-glycidyl etheroxypropyltrimethoxysilane, continuing to keep warm for 7-8 h, centrifuging, ultrasonically cleaning with ethanol, centrifuging again, drying, and grinding to obtain composite nano zinc oxide.

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