Composite conductor for bending-resistant medical wire and preparation method thereof

Abstract

The present invention discloses a composite wire for bending-resistant medical wire and a preparation method thereof, and belongs to the field of composite wire preparation technology. The composite wire for bending-resistant medical wire is composed of a central fiber filament and a metal round copper wire, which is tightly wrapped around the surface of the central fiber filament, wherein the metal round copper wire is prepared by metal copper wire and a composite coating, and the composite coating is prepared by 3,8-dibromophenanthroline, 4-formylphenylboric acid, fullerene and sarcosine, and the central fiber filament is prepared by modified basalt fiber, 4,4'-dihydroxybenzophenone and 1,4-bis(4-fluorobenzoyl)benzene. The composite wire prepared by this method has excellent bending resistance and corrosion resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite wire preparation, and in particular relates to a composite wire for bending-resistant medical electric wires and a preparation method thereof. Background Art

[0002] In modern medicine, with the increasing prevalence of minimally invasive surgery and the continuous advancement of medical equipment, performance requirements for medical cables are increasing. Traditional metal conductors often struggle to meet these demands, especially in medical environments requiring frequent bending and twisting. Consequently, research on composite conductors for bend-resistant medical cables has emerged, aiming to address issues such as the fragility of traditional conductors during bending and unstable signal transmission, thereby improving the reliability and safety of medical equipment.

[0003] Bend-resistant medical wires play an important role in multiple fields. For example, in implantable medical devices such as pacemakers and neurostimulators, the wires need to work in the patient's body for a long time and withstand the influence of various physiological activities and external forces. If the wires do not have sufficient bend resistance, they can easily break during implantation or use, causing device failure and even causing secondary harm to the patient. In addition, in extracorporeal medical devices such as endoscopes and surgical robots, wires also need to be bent and twisted frequently to adapt to complex surgical environments and operational requirements. Therefore, the development of composite wires with excellent bend resistance is of great significance to improving the reliability and safety of medical equipment.

[0004] Patent CN207676687U discloses a medical composite cable comprising a coaxial cable and a conductor. The coaxial cable is surrounded by multiple conductors, which are wrapped with aluminum foil and covered with a braid, the outer surface of which is covered with an outer sheath. The conductor's lateral surface is covered with an insulating layer. The gap between the insulating layer and the coaxial cable is filled with a filler wire. The conductor is made of twisted tinned copper wire, and the braid is made of tinned copper wire. The coaxial cable is shielded with aluminum foil and copper mesh. The cable has the advantages of high data transmission efficiency and strong shielding and anti-interference performance. It can also prevent corrosion from water and oxygen. However, the bending resistance and corrosion resistance of the cable produced by this method still need to be improved. Summary of the Invention

[0005] The object of the present invention is to provide a composite conductor for bending-resistant medical wires and a preparation method thereof, so as to solve the technical problem of poor bending resistance and corrosion resistance of the composite conductors in the prior art.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] The present invention provides a composite conductor for bend-resistant medical wires. The composite conductor is composed of a central fiber and a metal round copper wire, wherein the metal round copper wire is tightly wrapped around the surface of the central fiber. The metal round copper wire is prepared from metal copper wire and a composite coating, and the composite coating is prepared from 3,8-dibromophenanthroline, 4-formylphenylboric acid, fullerene, and sarcosine. The central fiber is prepared from modified basalt fiber, 4,4'-dihydroxybenzophenone, and 1,4-bis(4-fluorobenzoyl)benzene. The outer diameter of the composite conductor is 0.02 to 0.10 mm, and the number of strands is 1 to 12.

[0008] Preferably, the method for preparing the composite coating comprises the following steps:

[0009] Q1: 3,8-dibromophenanthroline, sodium carbonate, and 4-formylphenylboronic acid were added to a container containing N,N-dimethylformamide, and stirred evenly. 1,4-dioxane, ethanol, methyltrioctylammonium chloride, and tetrakis(triphenylphosphine)palladium were then added. The mixture was degassed with nitrogen and heated with stirring to react. After the reaction was completed, the mixture was cooled to room temperature, and chloroform was added to dissolve the product. The product was washed, and the organic phase was separated, dried, filtered, concentrated, and purified to obtain intermediate 1.

[0010] Q2: Add intermediate 1, fullerene and sarcosine into a container, then add chlorobenzene and heat to react. After the reaction is completed, distill under reduced pressure and purify to obtain intermediate 2, which is mixed with polyvinyl pyrrolidone and distilled water to obtain a composite coating.

[0011] In the above process, 3,8-dibromophenanthroline and 4-formylphenylboronic acid are first used as raw materials to obtain intermediate 1 through reaction, and then intermediate 1 is mixed with fullerene to undergo a Plato reaction to obtain intermediate 2. Intermediate 2, polyvinylpyrrolidone and distilled water are then mixed to obtain a composite coating. The synthetic reaction formula of intermediate 1 is as follows:

[0012]

[0013] The results of mass spectrometry analysis were: m / z: 388.12 (100.0%), 389.12 (28.9%), 390.13 (4.3%).

[0014] Preferably, in Q1, the amount ratio of 3,8-dibromophenanthroline, sodium carbonate, 4-formylphenylboric acid, N,N-dimethylformamide, 1,4-dioxane, ethanol, methyltrioctylammonium chloride and tetrakis(triphenylphosphine)palladium is (0.033-0.066) g: (0.105-0.21) g: (0.051-0.1) g: (4-8) mL: (3-6) mL: (0.4-0.8) mL: (0.033-0.067) mL: (0.05-0.1) mL, the nitrogen degassing time is 30-45 min, the heating and stirring temperature is 110-120° C., the reaction time is 3-5 h, the product is washed with saturated sodium carbonate and distilled water, dried with anhydrous sodium sulfate, and purified using a mixed solution of chloroform and ethyl acetate with a volume ratio of 7:1 as an eluent.

[0015] Preferably, in Q2, the amount ratio of intermediate 1, fullerene, sarcosine and chlorobenzene is (8.6-17.3) mg: (40-80) mg: (22-44.84) ​​mg: (10-20) mL, the heating reaction temperature is 110-120°C, the time is 10-12 h, and the purification is carried out using a mixed solution of carbon disulfide and ethyl acetate with a volume ratio of 20:1 as the eluent, the amount ratio of intermediate 2, polyvinylpyrrolidone and distilled water is (10-20) g: (2-7) g: (8-12) mL, and the mixing and stirring time is 2-4 h.

[0016] Preferably, the method for preparing the central fiber comprises the following steps:

[0017] S1: heat-treating basalt fiber, cooling it after treatment, and then placing it in a hydrochloric acid solution for acid washing, filtering, washing, and drying to obtain pretreated basalt fiber; mixing deionized water and hexadecyltrimethylammonium bromide, heating and stirring, and then adding the pretreated basalt fiber; soaking, washing, and drying to obtain modified fiber 1;

[0018] S2: adding silane coupling agent KH-602 to the ethanol solution, heating and stirring, then adding modified fiber 1, soaking, filtering, washing, and drying to obtain modified basalt fiber;

[0019] S3: Add diphenyl sulfone to a container, heat it up, add 4,4'-dihydroxybenzophenone, 1,4-bis(4-fluorobenzoyl)benzene and sodium carbonate in sequence, heat it up to react, and after the reaction is complete, cool it, crush it, wash it, and vacuum dry it to obtain a powder;

[0020] S4: After the powder and modified basalt fiber are evenly mixed, they are added into a twin-screw extruder, melted, extruded, and stretched to obtain a core fiber filament.

[0021] In the above process, the basalt fiber is first heated to remove moisture and impurities, and then pickled to regenerate the hydroxyl groups on its surface. Then, hexadecyltrimethylammonium bromide and silane coupling agent KH-602 are used to compound and modify it to obtain modified basalt fiber. Diphenyl sulfone is used as a solvent, and 4,4'-dihydroxybenzophenone and 1,4-bis(4-fluorobenzoyl)benzene are used as raw materials. The reaction occurs under a high temperature environment to obtain a powder. The modified basalt fiber is then mixed with the powder to prepare a central fiber.

[0022] Preferably, in S1, the heating treatment temperature is 500-550°C, the concentration of the hydrochloric acid solution is 1 mol / L, the heating pickling temperature is 80-90°C, the time is 5-7h, and the solution is washed with deionized water until the pH is 7. The drying temperature is 70-80°C and the time is 10-12h. The amount ratio of deionized water, hexadecyltrimethylammonium bromide and pretreated basalt fiber is (150-300) mL: (1-2) g: (10-20) g. The mixing temperature is 60-70°C and the time is 30-45min. The soaking time is 6-8h, the solution is washed with deionized water, and the drying temperature is 70-85°C and the time is 10-12h.

[0023] Preferably, in S2, the volume fraction of the ethanol solution is 90vt%, the amount ratio of the ethanol solution, the silane coupling agent KH-602 and the modified fiber 1 is (100-120) mL: (6-7.2) g: (10-12) g, the heating and stirring temperature is 60-80°C, the time is 30-45min, the soaking time is 10-12h, and the washing is carried out with anhydrous ethanol, the drying temperature is 80-90°C, and the time is 10-12h.

[0024] Preferably, in S3, the amount ratio of diphenyl sulfone, 4,4'-dihydroxybenzophenone, 1,4-bis(4-fluorobenzoyl)benzene and sodium carbonate is (240-360) mL: (32-48) g: (49-74) g: (19-29) g, the heating temperature is 160-170°C, and the temperature heating reaction process is: first heating to 220°C and maintaining for 1 hour, then heating to 320°C, stirring continuously for 3 hours, washing with acetone and distilled water, and vacuum drying at a temperature of 80-85°C for 10-12 hours; in S4, the mass ratio of powder to modified basalt fiber is (10-20): (30-50).

[0025] Preferably, the method for preparing the composite conductor for bending-resistant medical wire comprises the following steps:

[0026] Step (1): spraying the prepared composite coating evenly on the surface of the copper wire, and drying it to obtain a metal round copper wire;

[0027] Step (2): Wrap the metal round copper wire tightly on the surface of the central fiber wire and compact it to obtain a composite conductor for bending-resistant medical wire with an outer diameter of 0.02 to 0.10 mm and a number of 1 to 12 strands.

[0028] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0029] 1. The present invention first uses 3,8-dibromophenanthroline, 4-formylphenylboric acid, fullerene and polyvinylpyrrolidone as raw materials to prepare a composite coating, then uses basalt fiber, hexadecyltrimethylammonium bromide, silane coupling agent KH-602, 4,4'-dihydroxybenzophenone and 1,4-bis(4-fluorobenzoyl)benzene as raw materials to prepare a central fiber, sprays the composite coating onto the surface of the copper wire to obtain a metal round copper wire, and then wraps the metal round copper wire on the surface of the central fiber to prepare a composite conductor for bending-resistant medical wires. The composite conductor prepared by this method has excellent bending resistance and corrosion resistance.

[0030] 2. The present invention uses 3,8-dibromophenanthroline, 4-formylphenylboronic acid, fullerene and polyvinylpyrrolidone as raw materials to prepare a composite coating. Spraying the composite coating can effectively improve the corrosion resistance and electrical conductivity of metal round copper wire. The fullerene in the composite coating, as a carbon material with a special cage structure, can form a solid barrier layer on the surface of the copper wire, and 3,8-dibromophenanthroline and 4-formylphenylboronic acid will tightly combine with the surface of the copper wire to form a dense protective film. The presence of the protective film can isolate the corrosive medium in the external environment from direct contact with the copper wire, thereby improving the corrosion resistance of the copper wire. Fullerene is a carbon material with excellent electrical conductivity. It is evenly distributed in the coating and can form a conductive network on the surface of the copper wire, thereby improving the electrical conductivity of the coating, reducing resistance, and improving current transmission efficiency.

[0031] 3. The present invention uses basalt fiber, hexadecyltrimethylammonium bromide, silane coupling agent KH-602, 4,4'-dihydroxybenzophenone and 1,4-bis(4-fluorobenzoyl)benzene as raw materials to prepare core fiber yarns. The introduction of silane coupling agent KH-602 can improve the interfacial bonding strength between the modified basalt fiber and the powder. The enhanced interfacial bonding strength makes it difficult for the core fiber yarn to be pulled out or fall off from the matrix when subjected to external force, so that the core fiber yarn can better disperse and transfer stress when subjected to bending force, thereby improving the bending resistance of the composite conductor. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0033] Figure 1 It is a schematic structural diagram of the composite conductor for bending-resistant medical wire in the present invention.

[0034] Description of the accompanying drawings: 1. Metal round copper wire, 2. Central fiber wire. DETAILED DESCRIPTION

[0035] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] Example 1: See Figure 1 In this embodiment, the composite conductor is composed of a metal round copper wire 1 and a central fiber wire 2, and the metal round copper wire is tightly wrapped around the surface of the central fiber wire.

[0037] This embodiment discloses a method for preparing a composite coating, comprising the following steps:

[0038] Q1: 0.05 g of 3,8-dibromophenanthroline, 0.15 g of sodium carbonate, and 0.075 g of 4-formylphenylboronic acid were added to a container containing 6 mL of N,N-dimethylformamide. After stirring, 4.5 mL of 1,4-dioxane, 0.6 mL of ethanol, 0.05 mL of methyltrioctylammonium chloride, and 0.07 mL of tetrakis(triphenylphosphine)palladium were added. The mixture was degassed with nitrogen for 45 min, heated and stirred at 110 ° C for 5 h, and after the reaction was completed, it was cooled to room temperature, and chloroform was added to dissolve the product. The product was washed with saturated sodium carbonate and distilled water, and the organic phase was separated and collected, dried over anhydrous sodium sulfate, filtered and concentrated, and purified with a mixed solution of chloroform and ethyl acetate with a volume ratio of 7:1 as the eluent to obtain intermediate 1;

[0039] Q2: 12.5 mg of intermediate 1, 60 mg of fullerene and 33.42 mg of sarcosine were added to a container, followed by the addition of 15 mL of chlorobenzene. The mixture was heated at 120°C for 12 h. After the reaction was completed, it was distilled under reduced pressure and purified using a mixed solution of carbon disulfide and ethyl acetate in a volume ratio of 20:1 as an eluent. After purification, intermediate 2 was obtained. 15 g of intermediate 2 was mixed with 4.5 g of polyvinyl pyrrolidone and 10 mL of distilled water and stirred for 3 h to obtain a composite coating.

[0040] This embodiment discloses a method for preparing a central fiber, comprising the following steps:

[0041] S1: The basalt fiber was heat-treated at 550°C, cooled, and acid-washed in a 1 mol / L hydrochloric acid solution at 80°C for 6 h. The fiber was filtered, washed with deionized water until the pH was 7, and dried at 80°C for 12 h to obtain pretreated basalt fiber. 225 mL of deionized water and 1.5 g of hexadecyltrimethylammonium bromide were mixed at 60°C for 45 min, heated and stirred, and then 15 g of the pretreated basalt fiber was added. The fiber was soaked for 7 h, washed with deionized water, and dried at 70°C for 12 h to obtain modified fiber 1.

[0042] S2: 6.6 g of silane coupling agent KH-602 was added to 110 mL of 90% by volume ethanol solution, heated to 60°C and stirred for 45 min, then 11 g of modified fiber 1 was added, soaked for 12 h, filtered, washed with anhydrous ethanol, and dried at 80°C for 10 h to obtain modified basalt fiber;

[0043] S3: Add 300 mL of diphenyl sulfone to a container, heat to 170°C, and then add 40 g of 4,4'-dihydroxybenzophenone, 61 g of 1,4-bis(4-fluorobenzoyl)benzene, and 24 g of sodium carbonate in sequence, and heat to react. The reaction process is as follows: first heat to 220°C and hold for 1 hour, then heat to 320°C and continue stirring for 3 hours. After the reaction is completed, cool, crush, wash with acetone and distilled water, and dry in vacuo at 85°C for 12 hours to obtain a powder;

[0044] S4: 15 g of powder and 40 g of modified basalt fiber were mixed evenly, added into a twin-screw extruder, melted, extruded, and stretched to obtain a core fiber filament.

[0045] This embodiment discloses a method for preparing a composite conductor for a bend-resistant medical wire, comprising the following steps:

[0046] Step (1): spraying the prepared composite coating evenly on the surface of the copper wire, and drying it to obtain a metal round copper wire;

[0047] Step (2): Wrap the metal round copper wire tightly on the surface of the central fiber wire and compact it to obtain a composite conductor for bending-resistant medical wire with an outer diameter of 0.06 mm and 7 strands.

[0048] Example 2: This example discloses a method for preparing a composite coating, comprising the following steps:

[0049] Q1: 0.033 g of 3,8-dibromophenanthroline, 0.105 g of sodium carbonate, and 0.1 g of 4-formylphenylboronic acid were added to a container containing 4 mL of N,N-dimethylformamide. After stirring, 3 mL of 1,4-dioxane, 0.8 mL of ethanol, 0.067 mL of methyltrioctylammonium chloride, and 0.05 mL of tetrakis(triphenylphosphine)palladium were added. The mixture was degassed with nitrogen for 45 min, heated and stirred at 110 ° C for 5 h, and after the reaction was completed, it was cooled to room temperature, and chloroform was added to dissolve the product. The product was washed with saturated sodium carbonate and distilled water, and the organic phase was separated and collected, dried over anhydrous sodium sulfate, filtered and concentrated, and purified with a mixed solution of chloroform and ethyl acetate with a volume ratio of 7:1 as the eluent to obtain intermediate 1;

[0050] Q2: 8.6 mg of intermediate 1, 40 mg of fullerene and 44.84 mg of sarcosine were added to a container, followed by the addition of 10 mL of chlorobenzene. The mixture was heated at 120°C for 12 h. After the reaction was completed, it was distilled under reduced pressure and purified using a mixed solution of carbon disulfide and ethyl acetate in a volume ratio of 20:1 as an eluent. After purification, intermediate 2 was obtained. 10 g of intermediate 2 was mixed with 7 g of polyvinyl pyrrolidone and 8 mL of distilled water and stirred for 3 h to obtain a composite coating.

[0051] This embodiment discloses a method for preparing a central fiber, comprising the following steps:

[0052] S1: The basalt fiber was subjected to a heat treatment at 550°C. After the treatment, the fiber was cooled and placed in a 1 mol / L hydrochloric acid solution for acid washing at 80°C for 6 h. The fiber was filtered, washed with deionized water until the pH value was 7, and dried at 80°C for 12 h to obtain a pretreated basalt fiber. 150 mL of deionized water and 1 g of hexadecyltrimethylammonium bromide were mixed at 60°C for 45 min. After heating and stirring, 20 g of the pretreated basalt fiber was added and the mixture was soaked for 7 h. The mixture was washed with deionized water and dried at 70°C for 12 h to obtain a modified fiber 1.

[0053] S2: 7.2 g of silane coupling agent KH-602 was added to 100 mL of 90% by volume ethanol solution, heated to 60°C and stirred for 45 min, then 10 g of modified fiber 1 was added, soaked for 12 h, filtered, washed with anhydrous ethanol, and dried at 80°C for 10 h to obtain modified basalt fiber;

[0054] S3: Add 240 mL of diphenyl sulfone to a container, heat to 170° C., then add 32 g of 4,4'-dihydroxybenzophenone, 49 g of 1,4-bis(4-fluorobenzoyl)benzene, and 29 g of sodium carbonate in sequence, and heat to react. The reaction process is as follows: first heat to 220° C. and hold for 1 hour, then heat to 320° C. and continue stirring for 3 hours. After the reaction is completed, cool, crush, wash with acetone and distilled water, and dry in vacuo at 85° C. for 12 hours to obtain a powder;

[0055] S4: After uniformly mixing 10 g of powder and 50 g of modified basalt fiber, the mixture was added to a twin-screw extruder, melted, extruded, and stretched to obtain a core fiber filament.

[0056] This embodiment discloses a method for preparing a composite conductor for a bend-resistant medical wire, comprising the following steps:

[0057] Step (1): spraying the prepared composite coating evenly on the surface of the copper wire, and drying it to obtain a metal round copper wire;

[0058] Step (2): Wrap the metal round copper wire tightly around the surface of the central fiber wire and compact it to obtain a composite conductor for bending-resistant medical wire with an outer diameter of 0.08 mm and 9 strands.

[0059] Example 3: This example discloses a method for preparing a composite coating, comprising the following steps:

[0060] Q1: 0.066 g of 3,8-dibromophenanthroline, 0.21 g of sodium carbonate and 0.051 g of 4-formylphenylboronic acid were added to a container containing 8 mL of N,N-dimethylformamide, stirred evenly, and then 6 mL of 1,4-dioxane, 0.4 mL of ethanol, 0.033 mL of methyltrioctylammonium chloride and 0.1 mL of tetrakis(triphenylphosphine)palladium were added. The mixture was degassed with nitrogen for 45 min, heated and stirred at 110 ° C for 5 h, and after the reaction was completed, cooled to room temperature, chloroform was added to dissolve the product, washed with saturated sodium carbonate and distilled water, the organic phase was separated and collected, dried over anhydrous sodium sulfate, filtered and concentrated, and purified with a mixed solution of chloroform and ethyl acetate with a volume ratio of 7:1 as the eluent to obtain intermediate 1;

[0061] Q2: 17.3 mg of intermediate 1, 80 mg of fullerene and 22 mg of sarcosine were added to a container, followed by addition of 20 mL of chlorobenzene. The mixture was heated at 120°C for 12 h. After the reaction was completed, it was distilled under reduced pressure and purified using a mixed solution of carbon disulfide and ethyl acetate in a volume ratio of 20:1 as an eluent. After purification, intermediate 2 was obtained. 20 g of intermediate 2 was mixed with 2 g of polyvinyl pyrrolidone and 12 mL of distilled water and stirred for 3 h to obtain a composite coating.

[0062] This embodiment discloses a method for preparing a central fiber, comprising the following steps:

[0063] S1: The basalt fiber was heat-treated at 550°C, cooled, and acid-washed in a 1 mol / L hydrochloric acid solution at 80°C for 6 h. The fiber was filtered, washed with deionized water until the pH value was 7, and dried at 80°C for 12 h to obtain pretreated basalt fiber. 300 mL of deionized water and 2 g of hexadecyltrimethylammonium bromide were mixed at 60°C for 45 min, heated and stirred, and then 10 g of the pretreated basalt fiber was added. The fiber was soaked for 7 h, washed with deionized water, and dried at 70°C for 12 h to obtain modified fiber 1.

[0064] S2: 6 g of silane coupling agent KH-602 was added to 120 mL of 90% by volume ethanol solution, heated to 60°C and stirred for 45 min, then 12 g of modified fiber 1 was added, soaked for 12 h, filtered, washed with anhydrous ethanol, and dried at 80°C for 10 h to obtain modified basalt fiber;

[0065] S3: Add 360 mL of diphenyl sulfone to a container, heat to 170° C., then add 48 g of 4,4'-dihydroxybenzophenone, 74 g of 1,4-bis(4-fluorobenzoyl)benzene, and 19 g of sodium carbonate in sequence, and heat to react. The reaction process is as follows: first heat to 220° C. and hold for 1 hour, then heat to 320° C. and continue stirring for 3 hours. After the reaction is completed, cool, crush, wash with acetone and distilled water, and dry in vacuo at 85° C. for 12 hours to obtain a powder;

[0066] S4: After uniformly mixing 20 g of powder and 30 g of modified basalt fiber, the mixture was added to a twin-screw extruder, melted, extruded, and stretched to obtain a core fiber filament.

[0067] This embodiment discloses a method for preparing a composite conductor for a bend-resistant medical wire, comprising the following steps:

[0068] Step (1): spraying the prepared composite coating evenly on the surface of the copper wire, and drying it to obtain a metal round copper wire;

[0069] Step (2): Wrap the metal round copper wire tightly around the surface of the central fiber wire and compact it to obtain a composite conductor for bending-resistant medical wire with an outer diameter of 0.09 mm and 10 strands.

[0070] Example 4: This example discloses a method for preparing a composite coating, comprising the following steps:

[0071] Q1: 0.044 g 3,8-dibromophenanthroline, 0.19 g sodium carbonate and 0.063 g 4-formylphenylboronic acid were added to a container containing 5 mL N,N-dimethylformamide, stirred evenly, and then 4 mL 1,4-dioxane, 0.5 mL ethanol, 0.042 mL methyltrioctylammonium chloride and 0.06 mL tetrakis(triphenylphosphine)palladium were added. Nitrogen degassing was carried out for 45 min, and the mixture was heated and stirred at 110 ° C for 5 h. After the reaction was completed, it was cooled to room temperature, and chloroform was added to dissolve the product. The product was washed with saturated sodium carbonate and distilled water, and the organic phase was separated and collected, dried over anhydrous sodium sulfate, filtered and concentrated, and purified with a mixed solution of chloroform and ethyl acetate with a volume ratio of 7:1 as the eluent to obtain intermediate 1;

[0072] Q2: 10.4 mg of intermediate 1, 50 mg of fullerene and 27.15 mg of sarcosine were added to a container, followed by the addition of 12 mL of chlorobenzene. The mixture was heated at 120°C for 12 h. After the reaction was completed, it was distilled under reduced pressure and purified using a mixed solution of carbon disulfide and ethyl acetate in a volume ratio of 20:1 as an eluent. After purification, intermediate 2 was obtained. 12 g of intermediate 2 was mixed with 3 g of polyvinyl pyrrolidone and 11 mL of distilled water and stirred for 3 h to obtain a composite coating.

[0073] This embodiment discloses a method for preparing a central fiber, comprising the following steps:

[0074] S1: The basalt fiber was heat-treated at 550°C, cooled, and acid-washed in a 1 mol / L hydrochloric acid solution at 80°C for 6 h. The fiber was filtered, washed with deionized water until the pH value was 7, and dried at 80°C for 12 h to obtain pretreated basalt fiber. 200 mL of deionized water and 1.2 g of hexadecyltrimethylammonium bromide were mixed at 60°C for 45 min, heated and stirred, and then 12 g of the pretreated basalt fiber was added. The fiber was soaked for 7 h, washed with deionized water, and dried at 70°C for 12 h to obtain modified fiber 1.

[0075] S2: 6.3 g of silane coupling agent KH-602 was added to 105 mL of 90% by volume ethanol solution, heated to 60°C and stirred for 45 min, then 10.5 g of modified fiber 1 was added, soaked for 12 h, filtered, washed with anhydrous ethanol, and dried at 80°C for 10 h to obtain modified basalt fiber;

[0076] S3: Add 260 mL of diphenyl sulfone to a container, heat to 170° C., then add 36 g of 4,4'-dihydroxybenzophenone, 55 g of 1,4-bis(4-fluorobenzoyl)benzene, and 22 g of sodium carbonate in sequence, and heat to react. The reaction process is as follows: first heat to 220° C. and hold for 1 hour, then heat to 320° C. and continue stirring for 3 hours. After the reaction is completed, cool, crush, wash with acetone and distilled water, and dry in vacuo at 85° C. for 12 hours to obtain a powder;

[0077] S4: After uniformly mixing 12 g of powder and 32 g of modified basalt fiber, the mixture was added to a twin-screw extruder, melted, extruded, and stretched to obtain a core fiber filament.

[0078] This embodiment discloses a method for preparing a composite conductor for a bend-resistant medical wire, comprising the following steps:

[0079] Step (1): spraying the prepared composite coating evenly on the surface of the copper wire, and drying it to obtain a metal round copper wire;

[0080] Step (2): Wrap the metal round copper wire tightly on the surface of the central fiber wire and compact it to obtain a composite conductor for bending-resistant medical wire with an outer diameter of 0.03 mm and 4 strands.

[0081] Example 5: This example discloses a method for preparing a composite coating, comprising the following steps:

[0082] Q1: 0.055 g of 3,8-dibromophenanthroline, 0.13 g of sodium carbonate, and 0.094 g of 4-formylphenylboronic acid were added to a container containing 7 mL of N,N-dimethylformamide. After stirring, 5 mL of 1,4-dioxane, 0.7 mL of ethanol, 0.061 mL of methyltrioctylammonium chloride, and 0.08 mL of tetrakis(triphenylphosphine)palladium were added. The mixture was degassed with nitrogen for 45 min, heated and stirred at 110 ° C for 5 h, and after the reaction was completed, it was cooled to room temperature, and chloroform was added to dissolve the product. The product was washed with saturated sodium carbonate and distilled water, and the organic phase was separated and collected, dried over anhydrous sodium sulfate, filtered and concentrated, and purified with a mixed solution of chloroform and ethyl acetate with a volume ratio of 7:1 as the eluent to obtain intermediate 1;

[0083] Q2: 14.8 mg of intermediate 1, 70 mg of fullerene and 38.67 mg of sarcosine were added to a container, followed by 18 mL of chlorobenzene. The mixture was heated at 120°C for 12 h. After the reaction was completed, it was distilled under reduced pressure and purified using a mixed solution of carbon disulfide and ethyl acetate with a volume ratio of 20:1 as an eluent. After purification, intermediate 2 was obtained. 18 g of intermediate 2 was mixed with 5 g of polyvinyl pyrrolidone and 9 mL of distilled water and stirred for 3 h to obtain a composite coating.

[0084] This embodiment discloses a method for preparing a central fiber, comprising the following steps:

[0085] S1: The basalt fiber was heat-treated at 550°C, cooled, and acid-washed in a 1 mol / L hydrochloric acid solution at 80°C for 6 h. The fiber was filtered, washed with deionized water until the pH was 7, and dried at 80°C for 12 h to obtain pretreated basalt fiber. 250 mL of deionized water and 1.8 g of hexadecyltrimethylammonium bromide were mixed at 60°C for 45 min, heated and stirred, and then 18 g of the pretreated basalt fiber was added. The fiber was soaked for 7 h, washed with deionized water, and dried at 70°C for 12 h to obtain modified fiber 1.

[0086] S2: 6.9 g of silane coupling agent KH-602 was added to 115 mL of 90% by volume ethanol solution, heated to 60°C and stirred for 45 min, then 11.5 g of modified fiber 1 was added, soaked for 12 h, filtered, washed with anhydrous ethanol, and dried at 80°C for 10 h to obtain modified basalt fiber;

[0087] S3: Add 320 mL of diphenyl sulfone to a container, heat to 170° C., then add 44 g of 4,4'-dihydroxybenzophenone, 64 g of 1,4-bis(4-fluorobenzoyl)benzene, and 27 g of sodium carbonate in sequence, and heat to react. The reaction process is as follows: first heat to 220° C. and hold for 1 hour, then heat to 320° C. and continue stirring for 3 hours. After the reaction is completed, cool, crush, wash with acetone and distilled water, and dry in vacuo at 85° C. for 12 hours to obtain a powder;

[0088] S4: 18 g of powder and 48 g of modified basalt fiber were mixed evenly, added to a twin-screw extruder, melted, extruded, and stretched to obtain a core fiber filament.

[0089] This embodiment discloses a method for preparing a composite conductor for a bend-resistant medical wire, comprising the following steps:

[0090] Step (1): spraying the prepared composite coating evenly on the surface of the copper wire, and drying it to obtain a metal round copper wire;

[0091] Step (2): Wrap the metal round copper wire tightly on the surface of the central fiber wire and compact it to obtain a composite conductor for bending-resistant medical wire with an outer diameter of 0.06 mm and 7 strands.

[0092] Comparative Example 1: Compared with Example 1, in Comparative Example 1, no fullerene is added during the preparation of the composite coating, and other conditions remain unchanged.

[0093] Comparative Example 2: Compared with Example 1, in Comparative Example 2, during the preparation of the central fiber yarn, hexadecyltrimethylammonium bromide was not added, and other conditions remained unchanged.

[0094] Comparative Example 3: Compared with Example 1, in the preparation process of the composite wire in Comparative Example 3, the composite coating was not sprayed, and other conditions remained unchanged.

[0095] Comparative Example 4: Compared with Example 1, in the preparation process of the composite conductor in Comparative Example 4, basalt fiber is used instead of the central fiber, and other conditions remain unchanged.

[0096] The bending resistance of the composite conductor was tested according to GB / T 4909.5-2009, and the corrosion resistance of the composite conductor was tested according to GB / T10125-2021. The corrosion resistance was judged by the mass reduction rate. The mass reduction rate = [(m 前 -m 后 ) / m 前 ]×100% test results are shown in Table 1:

[0097] Table 1

[0098] project Bending resistance Mass reduction rate / % Example 1 <![CDATA[1.25×10 4 ]]> 4.20 Example 2 <![CDATA[1.24×10 4 ]]> 4.24 Example 3 <![CDATA[1.24×10 4 ]]> 4.29 Example 4 <![CDATA[1.23×10 4 ]]> 4.28 Example 5 <![CDATA[1.23×10 4 ]]> 4.29 Comparative Example 1 <![CDATA[1.23×10 4 ]]> 6.42 Comparative Example 2 <![CDATA[9.91×10 3 ]]> 4.29 Comparative Example 3 <![CDATA[1.23×10 4 ]]> 6.87 Comparative Example 4 <![CDATA[9.8×10 3 ]]> 4.30

[0099] The test results in Table 1 show that the composite conductors prepared in Examples 1-5 of the present invention have excellent bending resistance and corrosion resistance. A comparison between Comparative Example 1 and Examples 1-5 shows that the addition of fullerenes can impart excellent corrosion resistance to the composite conductors. A comparison between Comparative Example 2 and Examples 1-5 shows that the addition of hexadecyltrimethylammonium bromide can impart excellent bending resistance to the composite conductors. A comparison between Comparative Example 3 and Examples 1-5 shows that spraying the composite coating can impart excellent corrosion resistance to the composite conductors. A comparison between Comparative Example 4 and Examples 1-5 shows that the use of a core fiber can impart excellent bending resistance to the composite conductors.

[0100] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

[0101] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A composite conductor for bending-resistant medical wire, characterized in that: The composite conductor is composed of a central fiber wire and a metal round copper wire, wherein the metal round copper wire is tightly wrapped around the surface of the central fiber wire, wherein the metal round copper wire is prepared from metal copper wire and a composite coating; the outer diameter of the composite conductor is 0.02 to 0.10 mm, and the number of strands is 1 to 12; The preparation method of the composite coating comprises the following steps: Q1: 3,8-dibromophenanthroline, sodium carbonate, and 4-formylphenylboronic acid were added to a container containing N,N-dimethylformamide, and stirred evenly. 1,4-dioxane, ethanol, methyltrioctylammonium chloride, and tetrakis(triphenylphosphine)palladium were then added. The mixture was degassed with nitrogen and heated with stirring to react. After the reaction was completed, the mixture was cooled to room temperature, and chloroform was added to dissolve the product. The product was washed, and the organic phase was separated, dried, filtered, concentrated, and purified to obtain intermediate 1. Q2: Add intermediate 1, fullerene, and sarcosine to a container, then add chlorobenzene and heat to react. After the reaction is completed, distill under reduced pressure and purify to obtain intermediate 2, which is mixed with polyvinyl pyrrolidone and distilled water to obtain a composite coating; The method for preparing the central fiber comprises the following steps: S1: heat-treating basalt fiber, cooling it after treatment, and then placing it in a hydrochloric acid solution for acid washing, filtering, washing, and drying to obtain pretreated basalt fiber; mixing deionized water and hexadecyltrimethylammonium bromide, heating and stirring, and then adding the pretreated basalt fiber; soaking, washing, and drying to obtain modified fiber 1; S2: adding silane coupling agent KH-602 to the ethanol solution, heating and stirring, then adding modified fiber 1, soaking, filtering, washing, and drying to obtain modified basalt fiber; S3: Add diphenyl sulfone to a container, heat it up, add 4,4'-dihydroxybenzophenone, 1,4-bis(4-fluorobenzoyl)benzene and sodium carbonate in sequence, heat it up to react, and after the reaction is complete, cool it, crush it, wash it, and vacuum dry it to obtain a powder; S4: After the powder and modified basalt fiber are evenly mixed, they are added into a twin-screw extruder, melted, extruded, and stretched to obtain a core fiber filament.

2. The composite conductor for bending-resistant medical wire according to claim 1, characterized in that: In the Q1, the amount ratio of 3,8-dibromophenanthroline, sodium carbonate, 4-formylphenylboric acid, N,N-dimethylformamide, 1,4-dioxane, ethanol, methyltrioctylammonium chloride and tetrakis(triphenylphosphine)palladium is (0.033-0.066) g: (0.105-0.21) g: (0.051-0.1) g: (4-8) mL: (3-6) mL: (0.4-0.8) mL: (0.033-0.067) mL: (0.05-0.1) mL, the nitrogen degassing time is 30-45 min, the heating and stirring temperature is 110-120° C., the reaction time is 3-5 h, the product is washed with saturated sodium carbonate and distilled water, dried with anhydrous sodium sulfate, and purified using a mixed solution of chloroform and ethyl acetate with a volume ratio of 7:1 as an eluent.

3. The composite conductor for bending-resistant medical electric wire according to claim 1, characterized in that: In Q2, the amount ratio of intermediate 1, fullerene, sarcosine and chlorobenzene is (8.6-17.3) mg: (40-80) mg: (22-44.84) ​​mg: (10-20) mL, the heating reaction temperature is 110-120°C, the time is 10-12 h, and the purification is carried out using a mixed solution of carbon disulfide and ethyl acetate with a volume ratio of 20:1 as the eluent. The amount ratio of intermediate 2, polyvinylpyrrolidone and distilled water is (10-20) g: (2-7) g: (8-12) mL, and the mixing and stirring time is 2-4 h.

4. The composite conductor for bending-resistant medical electric wire according to claim 1, characterized in that: In S1, the heating treatment temperature is 500-550°C, the concentration of the hydrochloric acid solution is 1 mol / L, the heating pickling temperature is 80-90°C, the time is 5-7 hours, the fiber is washed with deionized water until the pH is 7, the drying temperature is 70-80°C, the time is 10-12 hours, the amount ratio of deionized water, hexadecyltrimethylammonium bromide and pretreated basalt fiber is (150-300) mL: (1-2) g: (10-20) g, the mixing temperature is 60-70°C, the time is 30-45 minutes, the soaking time is 6-8 hours, the fiber is washed with deionized water, the drying temperature is 70-85°C, and the time is 10-12 hours.

5. The composite conductor for bending-resistant medical electric wire according to claim 1, characterized in that: In the S2, the volume fraction of the ethanol solution is 90vt%, the amount ratio of the ethanol solution, the silane coupling agent KH-602 and the modified fiber 1 is (100-120) mL: (6-7.2) g: (10-12) g, the heating and stirring temperature is 60-80°C, the time is 30-45 min, the soaking time is 10-12 h, and the washing is carried out with anhydrous ethanol. The drying temperature is 80-90°C and the time is 10-12 h.

6. The composite conductor for bending-resistant medical electric wire according to claim 1, characterized in that: In S3, the dosage ratio of diphenyl sulfone, 4,4'-dihydroxybenzophenone, 1,4-bis(4-fluorobenzoyl)benzene and sodium carbonate is (240-360) mL: (32-48) g: (49-74) g: (19-29) g, the heating temperature is 160-170°C, and the temperature heating reaction process is: first heating to 220°C and maintaining for 1 hour, then heating to 320°C and continuously stirring for 3 hours, washing with acetone and distilled water, and vacuum drying at 80-85°C for 10-12 hours. In S4, the mass ratio of powder to modified basalt fiber is (10-20): (30-50).

7. The method for preparing a composite conductor for a bending-resistant medical wire according to any one of claims 1 to 6, wherein: The following steps are involved: Step (1): spraying the prepared composite coating evenly on the surface of the copper wire, and drying it to obtain a metal round copper wire; Step (2): Wrap the metal round copper wire tightly around the surface of the central fiber wire and compact it to obtain a composite conductor for bending-resistant medical wire with an outer diameter of 0.02 to 0.10 mm and a number of 1 to 12 strands.

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