NL2031176A

NL2031176A - Radiopaque wire and occluder device with radiopaque function

Info

Publication number: NL2031176A
Application number: NL2031176A
Authority: NL
Inventors: Wang Yunbing; Guo Gaoyang; Yang Li
Original assignee: Univ Sichuan
Priority date: 2021-03-29
Filing date: 2022-03-07
Publication date: 2022-07-20
Also published as: CN113081312B; NL2031176B1; WO2022206148A1; CN113081312A

Abstract

The invention provides a radiopaque wire and an occluder with radiopaque function. The radiopaque wire comprises a wire main body, a ﬁrst and a second control end arranged on the 5 wire main body for picking and releasing the wire main body. The ﬁrst and second control end are located at two ends of the wire main body. The radiopaque wire is a polymer wire with a lubricating layer on the surface; the lubricating layer carries a radiopaque material; or the radiopaque wire is a hydrogel wire carrying a radiopaque material. The radiopaque wire can be withdrawn in vitro after the occluder is released, avoiding permanent residue of 10 development marks inside the body, and eXpanding the scope of visualization, reducing the difﬁculty and risk of the operation. Having lower elastic modulus and lower frictional resistance, the end of the radiopaque wire will not cause damage to the tissue when withdrawn. 31

Description

RADIOPAQUE WIRE AND OCCLUDER DEVICE WITH RADIOPAQUE

FUNCTION Technical Field The disclosure relates to the field of medical equipment, in particular to a radiopaque wire and an occluder device with radiopaque function. Background Art Common congenital heart defects such as atrial septal defect (ASD), ventricular septal defect (VSD), patent ductus arteriosus (PDA), patent foramen ovale (PFO) may cause heart function disorders and other cardiovascular and cerebrovascular complications. In addition, after atrial contraction decreases in patients with atrial fibrillation, the blood flow velocity in left atrial appendage connected to the left atrium will be further reduced, causing the blood to coagulate into thrombus. If thrombus breaks off, it is likely to reach the intracranial blood vessels through the bloodstream and block the small cerebral blood vessels, leading to ischemic stroke. The occluder can be implanted into the sites of total cardiac damage or the left atrial appendage by minimally invasive intervention. This method is the preferred treatment plan for patients with congenital heart disease due to its minor trauma, safe operation, and accurate short-term efficacy. At present, most of the framework of the minimally invastve interventional occluder used in clinical practice is of a mesh structure, which facilitates compression on the delivery device, so that the shape of occluder is restored and released at the diseased part after it is delivered into the body, thereby completing the occlusion function. In order to achieve this function, most of the previous minimally invasive interventional occluder frames are made of non-degradable nickel-titanium alloy. The non-degradable foreign body residues can cause complications such as valve damage, atrioventricular block, wear of cardiac tissue and thrombus etc. The risk of these complications affects the patient throughout his life. Using occluders made of degradable materials is an ideal choice to overcome these shortcomings. After implantation, it can induce regeneration of heart defect tissue, and completely disappear after heart repair, and will not adversely affect the patient's subsequent life. It is an ideal choice for the treatment for congenital heart defects and left atrial appendage occlusion. 1

However, compared with the traditional occluders made of nickel-titanium alloy materials, the current minimally invasive interventional degradable occluders cannot be visualized under X-rays, which is not convenient for doctors to transport and release the occluders. The prior art which adding a development mark on the occluder can solve this problem, but the development mark is generally a non-degradable metal, which will permanently remain in the body and cause foreign body reactions. In order to minimize the residual development mark, often only a small number of parts of the occluder is marked. And it is impossible to evaluate the overall releasing shape of the occluder, which increases the patient's surgical risk. Therefore, it is urgent to solve the technical problem that the developed mark remains in the body permanently and only a small number of parts of the occluder are marked.

Summary of the Disclosure Based on the above, the purpose of the present disclosure 15 to provide a radiopaque wire that can be withdrawn outside the body after the occluder is released, which can avoid the permanent residue of the development marks inside the body, and expand the scope of visualization at the same time, which is beneficial to reduce the difficulty and risk of the operation. And as it has lower elastic modulus and lower frictional resistance with good compliance, the end of the radiopaque wire will not cause damages to the tissue when tt is withdrawn.

The specific technical solutions are as follows: A radiopaque wire, comprising a wire main body and a first control end and a second control end arranged on the wire main body for picking and releasing the wire main body. Said first control end and second control end are respectively located at two ends of the wire main body; Wherein the material of the radiopaque wire is a polymer wire with a lubricating layer on the surface, and the lubricating layer carries a radiopaque material; or the radiopaque wire is a hydrogel wire carrying a radiopaque material.

In some embodiments, the polymer wire with a lubricating layer on the surface is prepared by the following steps: (1) loading a double bond polymerizable precursor on the surface of the polymer wire; 2

(2) coating the surface of the wire obtained in step (1) with a double bond polymerizable monomer and an initiator; (3) then solidifying the wire obtained in step (2); wherein, the radiopaque material is introduced in step (1) or step (2); the polymer wire is at least one from polypropylene wire, polytetrafluoroethylene wire and polyamide wire; the double bond polymerizable precursor is at least one from methacrylamide-based compounds, methacrylate-based compounds, acrylates, acrylamide-based compounds, acryloyl chloride, and methacrylic anhydride; the double bond polymerizable monomer is at least one from hyaluronic acid methacrylate, polyvinyl alcohol acrylate, polyethylene glycol diacrylate, vinyl pyrrolidone, sulfobetaine methacrylate and sulfonic acid acrylic acid.

In some embodiments, the methacrylamide-based compound is N-(3-aminopropyl) methacrylamide hydrochloride.

In some embodiments, the polymer wire with a lubricating layer and a radiopaque material on the surface is prepared by the following steps: (1) loading a double bond polymerizable precursor on the surface of the polymer wire; (2) immersing the wire obtained in step (1) into an aqueous solution containing a double bond polymerizable monomer and an initiator, and soaking for 5-15 minutes; (3) then solidifying the wire obtained in step (2); In some embodiments, the concentration of the double bond polymerizable monomer in said aqueous solution is 0.2 wt% to 50 wt%, and the concentration of the initiator is 0.05 wt% to 2 wt%. In some embodiments, in step (1), a double-bond polymerizable precursor is loaded on the surface of the polymer wire by method A or method B: Method A: under alkaline or neutral conditions, coating the surface of the polymer wire with crosslinkable functional group molecules, and then coating with the double bond polymerizable precursor, or mixing the crosslinkable functional group molecules with the double bond polymerizable precursor before coating; wherein, the crosslinkable functional group molecule is a tea polyphenol compound; preferably, the crosslinkable functional group molecule is at least one from tannic acid, epigallocatechin gallate and dopamine. 3

Method B: performing plasma treatment on the surface of the polymer wire, and then coating with a polymerizable double bond precursor. In some embodiments, method A is: immersing the polymer wire into an aqueous solution containing crosslinkable functional group molecules, adjusting the pH to 7-10, soaking for 4-8 hours, and taking out the wire. After cleaning, immersing the wire into an aqueous solution containing a polymerizable double bond precursor, soaking for 4 to 8 hours, then taking the wire out. In some embodiments, method B is: performing plasma treatment (introduction of hydroxyl groups) on the surface of the polymer wire, soaking in the ether solution of triethylamine, adding the double bond polymerizable precursor at 0-4°C, and reacting at room temperature for 20-30 hours, and then taking the wire out. In some embodiments, in method A, the concentration of the crosslinkable functional group molecule in the aqueous solution is 1-10 mg/mL; preferably 0.5-10 mg/mL. In some embodiments, in method B, the concentration of double bond polymerizable precursor in the aqueous solution is 5-15 v/v%. In some embodiments, the initiator is a photoinitiator, further the initiator is Irgacure

2959. In some embodiments, the solidification method in step (3) is light curing. In some embodiments, the aqueous solution of the double bond-containing polymerizable monomer and the initiator in step (2) may further include a crosslinking agent, which contains at least two polymerizable functional groups, such as polyethylene glycol diacrylate and N, N'-methylenebisacrylamide. In some embodiments, the radiopaque material is at least one from tungsten, tantalum, barium sulfate, bismuth, gold, platinum, osmium, rhenium, iridium, and rhodium; further, the radiopaque material is at least one from tungsten nanoparticles, tantalum nanoparticles, sulfuric acid barium nanoparticles, bismuth nanoparticles, gold nanoparticles, platinum nanoparticles, osmium nanoparticles, rhenium nanoparticles, iridium nanoparticles, and rhodium nanoparticles. In some embodiments, the base is sodium hydroxide or triethylamine. In some embodiments, the coating method is dip coating, wipe coating or spray coating. 4

In some embodiments, the hydrogel wire with a radiopaque material is prepared by the following steps:

(1) dispersing the radiopaque material in an aqueous solution of crosslinkable functional group molecules to obtain a radiopaque material modified by crosslinkable functional group molecules;

(2) then adding the radiopaque material obtained in step (1) into the gel precursor aqueous solution, and injecting it into a mold to solidify to obtain a hydrogel radiopaque wire;

wherein, the gel precursor is polyvinyl alcohol; the crosslinkable functional group molecule is a tea polyphenol compound, preferably, the crosslinkable functional group molecule is at least one from tannic acid, epigallocatechin gallate and dopamine.

In some embodiments, the concentration of crosslinkable functional group molecules in the aqueous solution in step (1) is 5-15 mg/mL.

In some embodiments, the concentration of the gel precursor in the gel precursor aqueous solution is 20-40 wt%. In some embodiments, the concentration of the radiopaque material in the gel precursor aqueous solution is 0.1-20 mg/mL.

In some embodiments, the pH of the aqueous solution of crosslinkable functional group molecules is 8-10. In some embodiments, the mold is a cylindrical mold.

In some embodiments, the diameter of the cylindrical mold is 0.1 to 0.3 mm.

In some embodiments, the solidification in step (2) is to repeat freezing and thawing over three times or more.

In some embodiments, the radiopaque material is at least one from tungsten, tantalum, barium sulfate, bismuth, gold, platinum, osmium, rhenium, iridium, and rhodium; further, the radiopaque material is at least one from tungsten nanoparticles, tantalum nanoparticles, sulfuric acid barium nanoparticles, bismuth nanoparticles, gold nanoparticles, platinum nanoparticles, osmium nanoparticles, rhenium nanoparticles, iridium nanoparticles, and rhodium nanoparticles.

Another object of the present disclosure is to provide an occluder with radiopaque 5 function, which comprises a supporting body and a radiopaque wire, which is any one of the above-mentioned radiopaque wires.

In some embodiments, the occluder includes a supporting body with a mesh structure and a first radiopaque wire, which is detachably arranged on the supporting body and includes a first control end, a second control end and a first radiopaque section. The first control end and the second control end are respectively located at two ends of the first radiopaque section. Said first radiopaque section is located in the supporting body. The supporting body is provided with a first end portion, and both the first and the second control ends protrude from the first end portion.

In some embodiments, said supporting body includes a first disc body, a second disc body and a connecting waist body. Said connecting waist body is located between the first disc body and the second disc body. Said first end portion is located on the first disc body. And said supporting body is further provided with a first piercing part, a second piercing part, a third piercing part, and a fourth piercing part. Said first piercing part is located between the first disc body and the connecting waist body. Said second piercing part is located between the second disc body and the connecting waist body. The third piercing part is symmetrically arranged with the first piercing part, and the fourth piercing part is symmetrically arranged with the second piercing part.

In some embodiments, the supporting body is further provided with a second end portion.

Said second end portion is located on the second disc body, and the second end portion is arranged corresponding to the first end portion.

In some embodiments, a second radiopaque wire is further included. The first radiopaque wire passes through the first end portion, the first piercing part, the second piercing part, the second end, the third piercing part and the four piercing parts, and is arranged on the supporting body and forms a first plane. Said second radiopaque wire is detachably arranged on the supporting body and forms a second plane, and the first plane and the second plane are set at a 90° angle.

In some embodiments, said second radiopaque wire includes a third control end, a fourth control end and a second radiopaque section. Said third control end and fourth control end are respectively located at two ends of the second radiopaque section. Both the third and the 6 fourth control ends protrude from the first end portion of the supporting body.

In some embodiments, the control end of the radiopaque wire is not its own end, but an additional control wire which is connected to any part of the main body of the radiopaque wire. One end of the control wire is connected to the main body of the radiopaque wire, and the other end extends from the occluder to outside of the body. Preferably, the control wire is connected to the midpoint part of the wire main body, and the movement of the radiopaque wire can be controlled by the control wire.

In some embodiments, a baffle film is further included. Said baffle film is sewn on the first disc body, the second disc body and the connecting waist body respectively. And said baffle film is provided with multiple layers.

In some embodiments, the material of the supporting body is a degradable material, including at least one selected from polylactic acid, polyglycolic acid, polycaprolactone, polyanhydride, and poly (p-dioxanone).

Compared with the prior art, the present disclosure has the following beneficial effects: The radiopaque wire provided by the present disclosure is detachably arranged on the supporting body with a mesh structure. The radiopaque wire is secured on the supporting body, therefore the occluder can be visible under X-ray during the process of putting the occluder into the human body, which enables the doctor to conveniently transport and release the occluder; and at the same time, the radiopaque section is located inside the supporting body to expand the imaging range, which is helpful to evaluate the release form of the occluder, and reduces the difficulty and risk of the operation. When the releasing of the occluder is completed, the radiopaque wire can be removed from the occluder and withdrawn from the human body by pulling the first control end or the second control end, so as to avoid the foreign body reaction and discomfort to the human body caused by the residual development marks inside the body.

At the same time, 1n the actual application process, the elastic modulus of the existing metal radiopaque wire is too high, and the material is hard, the compliance is poor, which makes it difficult for weaving and withdrawal, and the end may cause damages to the tissue during withdrawal. In order to solve the above technical problems, the present disclosure also developed a specific radiopaque wire material, which is a polymer wire with a lubricating 7 layer carrying a radiopaque material on the surface, or a hydrogel wire carrying a radiopaque material.

It has a lower modulus of elasticity, which is between 0.3-5G pa, while the modulus of elasticity of metal materials is more than 30 Gpa, therefore, said radiopaque wire will not cause damages to the tissue during the withdrawal process.

And the lubricating layer on surface of the radiopaque wire or the hydrogel wire is well lubricated, so the radiopaque wire has lower friction resistance, thereby it greatly reduces the resistance during the withdrawal process, and reduces possible accidental risks and related complications during the withdrawal process.

Brief Description of Drawings The drawings show specific embodiments of the technical solutions of the present disclosure and form as a part of the specification together with the specific implementations to explain the technical solutions, principles and effects of the present disclosure.

Unless otherwise specified or defined, in different drawings, the same reference numerals represent the same or similar technical features, and the same or similar technical features may also be represented by different reference numerals.

Fig. 1 is a schematic structural diagram of a supporting body according to an embodiment of the present disclosure.

Fig.2 is a schematic structural diagram of a radiopaque wire placed in a supporting body according to an embodiment of the present disclosure.

Fig. 3 is a schematic structural diagram of a control wire according to an embodiment of the present disclosure.

Description of reference signs: 10, supporting body; 11, first end portion; 12, second end portion; 13, first piercing part; 14, second piercing part; 15, third piercing part; 16, fourth piercing part; 20, first radiopaque wire; 21, first control end; 22, second control end; 23, first radiopaque section; 30, second radiopaque wire; 31, third control end; 32, fourth control end; 33, second radiopaque section; 50, control wire; 51, operation end.

Description of Embodiments In the following embodiments of the present disclosure, the experimental methods without specific conditions are usually in accordance with conventional conditions or in 8 accordance with the conditions recommended by the manufacturers. Various common chemical reagents used in the examples are all commercially available products.

Unless otherwise defined, all technical and scientific terms used in the present disclosure are the same as commonly understood by those skilled in the art. The terms used in the specification of the present disclosure are only for the purpose of describing specific embodiments, but not used to limit the present disclosure.

The terms “including” and “having” and any variations thereof in the present disclosure are intended to cover non-exclusive inclusions. For example, a process, method, device, product, or device which includes a series of steps is not limited to the listed steps or modules, but optionally includes steps that are not listed, or optionally other steps which are includes inherently in those processes, method, product, or equipment.

The “plurality” mentioned in the present disclosure means two or more. "And/or" describes the association relationship of the associated objects, indicating that there can be three types of relationships, for example, A and/or B, which can mean: A exists alone, A and B exist at the same time, and B exists alone. The character “/” generally indicates that the associated objects before and after are in an “or” relationship.

It should be noted that when a component is considered to be “secured” to another component, it can be directly secured to said another component, or it can be secured to said another component through a centered component; when a component is considered to be “connected” to another component, it can be directly connected to said another component, or be connected to said another component through a centered component at the same time; When an element is considered to be “installed on” another element, it can be directly installed on said another element, or be installed on said another element through a centered component at the same time; When an element is considered to “set on” another element, it can be directly set on said another element, or be set on said another component through a central element at the same time.

Unless specified or defined otherwise, the "said" and "the" used herein refer to the technical feature or technical content mentioned or described before the corresponding position, and the technical feature or technical content can be the same or similar as the mentioned technical feature or technical content.

9

There is no doubt that technical content or technical features that are contrary to the purpose of the present disclosure or obviously contradictory should be excluded.

As shown in Fig.1 and Fig.2, a radiopaque wire 20 is applied in the present disclosure, which comprises a wire main body, a first control end 21 and a second control end 22 arranged on the wire main body for picking and releasing the wire main body, and a first radiopaque section 23. Said first control end 21 and said second control end 22 are respectively located on the two ends of said first radiopaque section 23.

The material of said radiopaque wire is a polymer wire with a lubricating layer on the surface, and said lubricating layer carries a radiopaque material; or the radiopaque wire is a hydrogel wire carrying a radiopaque material.

Compared with the previous metal radiopaque wire, the radiopaque wire made of polymer wire or hydrogel wire has a lower elastic modulus, which is more conducive for the radiopaque wire to be weaved and secured on the occlude. At the same time, it avoids the possible damages to the tissue caused by the radiopaque wire during the withdrawal process due to the high elastic modulus, thereby helps to protect the human tissue. Preferably, said polymer wire with a lubricating layer on the surface is prepared by the following steps: (1) loading a double bond polymerizable precursor on the surface of the polymer wire; (2) coating the surface of the wire obtained in step (1) with a double bond polymerizable monomer and an initiator; (3) then solidifying the wire obtained in step (2); wherein, a radiopaque material is introduced in step (1) or step (2); The polymer wire is at least one from polypropylene wire, polytetrafluoroethylene wire and polyamide wire; the double bond polymerizable precursor is at least one from methacrylamide-based compounds, methacrylate-based compounds, acrylates, acrylamide-based compounds, acryloyl chloride, and methacrylic anhydride, preferably, the methacrylamide-based compound is N-(3-aminopropyl) methacrylamide hydrochloride; the double bond polymerizable monomer is at least one from hyaluronic acid methacrylate, polyvinyl alcohol acrylate, polyethylene glycol diacrylate, vinyl pyrrolidone, sulfobetaine methacrylate and sulfonic acid acrylic acid.

10

Wherein, the double bond polymerizable precursor is tightly loaded on the surface of the polymer wire to introduce double bonds without damaging the mechanical properties of the wire material; at the same time, the coated specific kind of double bond polymerizable monomer can form a cross-linked network with lubricating effect under the action of the initiator, to achieve good lubrication. The double bonds introduced on the polymer wire can further participate in the copolymerization of the double bond polymerizable monomer, enhancing the bonding force between the polymer wire and the cross-linked network with lubricating effect.

Further, said polymer wire loaded with radiopaque material and lubricating material on the surface is prepared by the following steps: (1) loading a double bond polymerizable precursor on the surface of the polymer wire; (2) immersing the wire obtained in step (1) into an aqueous solution containing a double bond polymerizable monomer and an initiator, and soaking for 5-15 minutes.

(3) then solidifying the wire obtained in step (2); Preferably, the concentration of the double bond polymerizable monomer in the aqueous solution is 0.2 wt% to 50 wt%, preferably 1-20 wt%, more preferably 5-15 wt%; and the concentration of the initiator is 0.05 wt% to 2 wt%, preferably 0.05 wt%~1 wt%, more preferably 0.05 wt%-0.5 wt%, further preferably 0.05 wt%~0.2 wt%.

Preferably, the initiator is a photoinitiator, further the initiator is Irgacure 2959; Preferably, the solidifying method in step (3) is light curing; Preferably, in step (1), a double-bond polymerizable precursor 1s loaded on the surface of the polymer wire by method A or method B: Method A: under alkaline or neutral conditions, coating the surface of the polymer wire with crosslinkable functional group molecules, and then coating with the double bond polymerizable precursor, or mixing the crosslinkable functional group molecules with the double bond polymerizable precursor before coating; wherein , the crosslinkable functional group molecule is a tea polyphenol compound, preferably, the tea polyphenol compound is at least one from tannic acid, epigallocatechin gallate and dopamine.

Method B: performing plasma treatment on the surface of the polymer wire, and coating with a polymerizable double bond precursor.

11

Wherein, method A is to coat the surface of the polymer wire with a specific type of cross-linkable photoenergy group molecules, then to coat with a double bond polymerizable precursor. The specific type of cross-linkable photo-energy group molecules have strong adhesion to the polymer wire, and can closely adhere to the surface of the polymer wire, thereby realizing the introduction of double bonds or radiopaque materials. Especially under alkaline conditions, the cross-linkable photoenergy group molecules can further undergo self-polymerization, so that they can better adhere to the polymer wire. At the same time, the specific type of crosslinkable photoenergy group molecule has an active reactive functional group, which can react with the double bond polymerizable precursor, and the two materials are connected through a covalent bond, which introduces a double bond, so as to tightly fix the double bond on the surface of the polymer wire.

Alternatively, the radiopaque material may be introduced in step (1) or step (2), or may be introduced simultaneously in step (1) or step (2). Further, when the radiopaque material is introduced in step (1), the radiopaque material can be mixed with the crosslinkable functional group molecules; when the radiopaque material is introduced in step (2), the radiopaque material can be mixed with an initiator.

Further, method A is: immersing the polymer wire into an aqueous solution containing crosslinkable functional group molecules, adjusting the pH to 7-10, soaking for 4-8 hours, and taking out the wire. After cleaning, immersing the wire into the aqueous solution containing the polymerizable double bond precursor, soaking for 4 to 8 hours, and taking out the wire; Optionally, performing plasma treatment on the polymer wire in method A, then immersing the treated wire into an aqueous solution containing cross-linkable functional groups molecules.

Further, method B is: performing plasma treatment (introduction of hydroxyl groups) on the surface of the polymer wire, then soaking the treated wire in the ether solution of triethylamine, adding the double bond polymerizable precursor at 0-4°C, and reacting at room temperature for 20-30 hours, taking out the wire.

Preferably, the concentration of the crosslinkable functional group molecule in said aqueous solution is 1-10 mg/mL; preferably 3-7 mg/mL ‚more preferably 4~6 mg/mL ‚further preferably 5 mg/mL; the concentration of double bond polymerizable precursor in the 12 aqueous solution is 0.5-10 mg/mL, preferably 0.5~5 mg/mL, more preferably 0.5~2 mg/mL, further preferably 0.8~1.5 mg/mL.

Preferably, said radiopaque material is at least one from tungsten, tantalum, barium sulfate, bismuth, gold, platinum, osmium, rhenium, iridium, and rhodium; further, the radiopaque material is at least one from tungsten nanoparticles, tantalum nanoparticles, sulfuric acid barium nanoparticles, bismuth nanoparticles, gold nanoparticles, platinum nanoparticles, osmium nanoparticles, rhenium nanoparticles, iridium nanoparticles, and rhodium nanoparticles.

Preferably, the base is at least one from sodium hydroxide and triethylamine.

Preferably, the coating method is dip coating, wipe coating or spray coating.

Preferably, the hydrogel wire carrying a radiopaque material is prepared by the following steps: (1) dispersing the radiopaque material in an aqueous solution of crosslinkable functional group molecules to obtain a radiopaque material modified by crosslinkable functional group molecules; (2) then adding the radiopaque material obtained in step (1) into a gel precursor aqueous solution, and injecting the mixture into a mold to solidify to obtain a hydrogel radiopaque wire; wherein, the gel precursor is polyvinyl alcohol; the crosslinkable functional group molecule is at least one from tannic acid, epigallocatechin gallate and dopamine.

Wherein, the radiopaque material has a better dispensability in the gel precursor aqueous solution after the radiopaque material is modified with crosslinkable functional group molecules. At the same time, the crosslinkable functional group molecules on the radiopaque material help to increase the hydrogen between the surface of the radiopaque material and the gel precursor, forming a cross-linked hydrogel network of the radiopaque material. Wherein, the introduction of the radiopaque material (especially the radiopaque nanoparticles) not only enables radiopaque function, but also further enhances the mechanical strength of the hydrogel radiopaque wire.

Preferably, the concentration of crosslinkable functional group molecules in the aqueous solution of crosslinkable functional group molecules and base in step (1) is 5-15 mg/mL, 13 more preferably 10 mg/mL. Preferably, the concentration of the gel precursor in the gel precursor aqueous solution is 20-40 wt%, more preferably 25~35 wt%, further preferably 30 wt %. Preferably, the concentration of the radiopaque material in the gel precursor aqueous solution is 5-20 mg/mL, more preferably 5-15 mg/mL, and more preferably 10 mg/mL. Preferably, the mold is a cylindrical mold, and the diameter of the cylindrical mold is 0.1 to 0.3 mm; more preferably 0.2 mm.

The present disclosure will be further described in detail with examples as below.

As shown in Fig.l and Fig.2, the embodiment further provides an occluder with radiopaque function, including a supporting body 10 and a radiopaque wire 20, and said radiopaque wire is any one of the above-mentioned radiopaque wires.

Specifically, the occluder includes a supporting body 10 with a mesh structure and a first radiopaque wire 20 which is detachably arranged on the supporting body 10, and the first radiopaque wire 20 includes a first control end 21, a second control end 22 and a first radiopaque section 23. Said first control end 21 and second control end 22 are respectively located at the two ends of the first radiopaque section 23. The first radiopaque section 23 is located inside the supporting body 10, the supporting body 10 is provided with a first end portion 11, and both the first control end 21 and the second control end 22 protrude from the first end portion 11.

By detachably arranging the radiopaque wire on the supporting body 10 with a mesh structure, the radiopaque wire can be secured on the supporting body 10 during the process of putting the occluder into the human body; therefore the occluder can be visible under X-ray, which enables the doctor to transport and release the occluder conveniently. At the same time, the radiopaque section is located inside the supporting body 10 to expand the imaging range.

Compared with the previous marking only a small part of the occluder, the entire radiopaque section is more conducive to evaluating the release form of the occluder, reducing the difficulty and risk of the operation; when the release of the occluder is completed, the radiopaque wire can be removed from the occluder and withdrawn from the human body by pulling the first control end 21 or the second control end 22, so as to avoid the foreign body reaction and discomfort to the human body caused by the residual development marks in the 14 body. Protruding the first control end 21 and the second control end 22 from the first end portion 11 of the supporting body 10 facilitates the pulling control of the radiopaque wire to be withdrawn from the human body, and preventing the radiopaque wire from falling off the occluder. It should be noted that the two control ends protrude from the supporting body 10 and extend outside of the body, which enables to conveniently perform the withdrawing operation of the radiopaque wire outside the body.

As shown in Fig. 1 and Fig. 2, said supporting body 10 includes a first disk body, a second disk body and a connecting waist body. Said connecting waist body is located between the first disk body and the second disk body and forms an "I"-shaped supporting body 10; said first end portion 11 1s located on the first disc body, and said supporting body 10 is further provided with a first piercing portion 13, a second piercing portion 14, a third piercing portion 15, a fourth piercing portion 16 and a second end portion 12. The first piercing portion 13 is located between the first disc body and the connecting waist body, the second piercing portion 14 is located between the second disc body and the connecting waist body. The third piercing portion 15 is symmetrically arranged with the first piercingportion 13 along the central axis of the supporting body 10, and the fourth piercing portion 16 is also symmetrically arranged with the second piercing portion 14 along the central axis of the supporting body 10. The second end portion 12 is located on the second disc body, and said second end portion 12 is arranged corresponding to the first end portion 11, wherein the first end portion 11 is the proximal end of the supporting body 10, and the second end portion 12 is the distal end of the supporting body 10. Since the position between the disc body and the connecting waist body is the position with the highest degree of bending deformation on the occluder, the piercing part is arranged between the disc body and the connecting waist body, so that the radiopaque wire can better match the contour of the supporting body 10 and improve the performance of the occluder. At the same time, by setting a plurality of piercing parts, the radiopaque wire is not easily loosen from the occluder during the process of sending the occluder into the human body, so as to ensure normal development and smooth insertion of the occluder. The following is an embodiment of the detachable arrangement of the first radiopaque wire 20 in the above-mentioned supporting body 10: The first radiopaque wire 20 starts from the mesh of the first end portion 11 of the 15 supporting body 10, extends toward the side close to the second end portion 12, firstly extending to the first piercing portion 13, and passing through the mesh of the first piercing portion 13; then extending to the second piercing part 14, and passing through the mesh of the second piercing part 14, and then extending to the second end part 12. After passing through the mesh of the second end portion 12, the first radiopaque wire 20 extends back toward the side close to the first end portion 11, and then extends to the third piercing portion 15. After passing through the mesh of the third piercing portion 15, the first radiopaque wire 20 extends to the fourth piercing portion 16, and finally passes through the mesh of the fourth piercing portion 16 and extends back to the first end portion 11 and protrudes from the first end portion

11. The first radiopaque wire 20 is detachably arranged on the supporting body 10 by the above-mentioned weaving method, which can expand the imaging range of the first radiopaque wire 20 in the occluder, and can roughly develop the outline of the entire occluder. Therefore, it solves the problem that the development marks are only located in individual parts of the occluder resulting in incomplete development, which is conducive to adjusting the release position of the occluder and grasping the release state of the occluder, reducing the difficulty of the doctor's operation and reducing the risk of the patient's operation. It should be noted that the above weaving method of the radiopaque wire is only one of the preferred embodiments, which can realize rapid weaving and development of the basic outline of the occlude. But according to the development requirements of the occluder, different piercing parts are positioned on the supporting body 10 to realize different weaving ways.

In order to further improve the radiopaque effect of the occluder, a second radiopaque wire 30 is added. The second radiopaque wire 30 includes a third control end 31, a fourth control end 32 and a second radiopaque section 33. The third control end 31 and the fourth control end 32 are respectively located at two ends of the second radiopaque section 33, and both the third control end 31 and the fourth control end 32 protrude from the first end portion 11 of the supporting body 10. The second radiopaque wire 30 has the same structure as the first radiopaque wire 20. The third control end 31 and the fourth control end 32 protrude from the first end portion 11 of the supporting body 10, which facilitates pulling and controlling the second radiopaque wire 30 to withdraw from the human body, and at the same time prevents the second radiopaque wire 30 from falling off the occluder. Likewise, it should be noted that 16 after protruding from the supporting body 10, the two control ends extend all the way to the outside of the body, so that the operation of withdrawing the radiopaque wire outside the body is more convenient.

The first radiopaque wire 20 is arranged on the supporting body 10 by the above-mentioned weaving method to form a first plane, and the second radiopaque wire 30 is weaved by the steps similar to the above-mentioned weaving method, so that said second radiopaque wire 30 is detachably arranged on the supporting body 10 to form a second plane. However, the difference from the above-mentioned weaving method is that the second plane formed by the weaving of the second radiopaque wire 30 forms an included angle of 90° with the first plane formed by the weaving of the first radiopaque wire 20. Since the occluder is a three-dimensional device, setting the second plane and the first plane at an angle of 90° can more comprehensively display the overall outline of the occluder, improve the development effect, and prevent the displacement of the occluder during implantation process from affecting the radiopaque angle of the first radiopaque wire 20. However, it should be noted that the number of radiopaque wires and the number of plane angles formed by weaving of the radiopaque wires can be adjusted according to the actual situation.

The above method of withdrawing the radiopaque wire from the human body by pulling the control end of the radiopaque wire 1s a preferred embodiment of the present disclosure. As shown in Fig. 3, in one of the embodiments, a separately control wire 50 is further included, which is arranged outside the supporting body 10. The control wire 50 is connected with the radiopaque wire at the position where the radiopaque wire is weaved at the second end portion 12 of the supporting body 10, and the end of the control wire 50 away from the connection with the radiopaque wire is the operation end 51, wherein, the operating end 51 extends outside the human body, and in order to prevent the control wire 50 from affecting the radiopaque wire to be smoothly weaved on the occluder, the control wire 50 can be connected with the radiopaque wire after the radiopaque wire is set. When the occluder is released, by pulling the operating end 51 of the control wire 50, both ends of the radiopaque wire 50 are pulled out from the second end portion 12 at the same time, which speeds up the removal of the radiopaque wire from the occluder and withdrawing from the human body, which improves work efficiency.

17

The material of said supporting body 10 is a degradable material, which is at least one from polylactic acid, polyglycolic acid, polycaprolactone, polyacid anhydride and poly (p-dioxanone). The occluder made of degradable materials can avoid complications such as valve damage, atrioventricular block, heart tissue wear, and thrombosis caused by the residual body, which is more conducive to the recovery of surgery and avoids adverse effects on the patient’s subsequent life.

The occluder is also provided with a baffle film (not shown in the figures), which is sewn on the first disc body, the second disc body and the connecting waist body respectively. The baffle film is provided with multiple layers. The baffle film can be prepared from degradable polymer materials such as polylactic acid. Sewing the baffle film on the occluder is beneficial to promote the growth of the endothelium, which makes the endothelium easier to crawl, and speeds up the recovery of the patient.

Source of material: Polyvinyl alcohol: Type 1799, weight average molecular weight 90,000.

Polyethylene glycol diacrylate: purchased from TCI, molecular weight 258. Example 1 Preparation of the occluder containing radiopaque wire A "I"-shaped occluder skeleton was woven with Paiy({1,4-tdioxan-2-one) wire, and then the radiopaque wire started from the proximal end of the occluder, and passed through the gap in the skeleton along the axial direction of the occluder to reach the distal apex of the occluder.

Then the radiopaque wire started to pass through the gap and returned to the proximal apex. The path of the radiopaque wire was symmetrically distributed along the central axis of the occluder, and finally the end of the radiopaque wire was exposed along the delivery system to in vitro. According to the similar steps, along the axial direction of the skeleton and in a direction of the 90° angle with the direction of the first radiopaque wire, a second radiopaque wire was weaved on the skeleton, and the end of said radiopaque wire was exposed along the conveying system to in vitro. During the implantation process of the occluder, since the radiopaque wire was located on the entire outline of the occluder skeleton, the entire occluder could be visualized, which solved the problem that the development marks are only located in individual parts of the occluder and the development is incomplete, facilitating to better adjust the release position of the occluder and grasp the release state of the occluder. At the same 18 time, the radiopaque wire on the occluder can be separated and withdrawn from the occluder by pulling the end outside the body, so as to avoid the residue of the radiopaque substance inside the body. Example 2. Polypropylene radiopaque wire coated with hydrogel (1) Preparation of hyaluronic acid methacrylate: Hyaluronic acid was dissolved in an aqueous solution (0.1 wt%), passed through a cation exchange resin, and then lyophilized. Then lyophilized hyaluronic acid was dissolved in DMSO solution, added with methacrylic anhydride equivalent to 0.2 equivalent (mass ratio) of hyaluronic acid, and reacted for 24 hours. Chloroform was added to the reaction solution for precipitation, and the precipitate was dissolved in water and dialyzed in a dialysis bag, and then hyaluronic acid methacrylate was obtained by lyophilization.

(2) The polypropylene wire was first soaked in a mixed aqueous solution of 5 mg/mL tannic acid and 1 mg/mL tungsten nanoparticles, and 1M sodium hydroxide was added to adjust the pH to 9. After soaking for 6 hours, the polypropylene wire was taken out and rinsed with deionized water for three times, then soaked in an aqueous solution (1 mg/mL) of N-(3-aminopropyl) methacrylamide hydrochloride (pH=8) for 6 hours. The polypropylene wire was taken out and rinsed with deionized water for three times to obtain a polypropylene wire with surface-modified by double bonds and radiopaque nanoparticles.

In this step, double bonds and radiopaque nanoparticles could be introduced simultaneously on the surface of various wires through simple steps without damaging the mechanical properties of the wire body. Wherein, the radiopaque nanoparticles have a larger surface area, which can further increase the introduction of double bonds, and at the same time radiopaque function can be realized. Moreover, the method does not require pretreatment to the wire.

(3) The polypropylene wire with surface-modified by double bonds and radiopaque nanoparticles obtained in step (2) was soaked in an aqueous solution of 0.5 wt% hyaluronic acid methacrylate and 0.1 wt% Irgacure 2959 as a photoinitiator for 10 minutes, then was taken out for solidifying under ultraviolet light. The hyaluronic acid methacrylate in this step can form a cross-linked network by itself under the 19 polymerization of the initiator, and thereby playing a lubricating role. The double bond on the surface of the polypropylene wire can simultaneously participate in the copolymerization of the double bond in the hyaluronic acid methacrylate, and thereby enhancing the bonding force between the hyaluronic acid network and the polypropylene wire. Example 3. Polypropylene radiopaque wire coated with hydrogel (1) Preparation of polyvinyl alcohol acrylate: 5.0 g of polyvinyl alcohol (PVA) was dissolved in 100 mL of dimethyl sulfoxide (DMSO). Dimethylaminopyridine and glycidyl acrylate were added with final concentration of 1.0 mol % (relative to the hydroxyl groups of PVA) and 0.025 mol % (relative to the hydroxyl groups of PVA), respectively. After stirring at 60 °C for 6 hours, the reaction solution was added with acetone for precipitation. The precipitate was vacuum-dried for 2 days and stored at —5 °C in the dark.

(2) Firstly, the polypropylene wire was soaked in a mixed aqueous solution of 5 mg/mL tannic acid and 1 mg/mL tantalum nanoparticles, and 1 M sodium hydroxide was added to adjust the pH to 9. After soaking for 6 hours, the polypropylene wire was taken out and rinsed for three times with deionized water, then soaked in an aqueous solution (1 mg/mL) of N-(3-aminopropyl) methacrylamide hydrochloride (pH=8) for 6 hours. The polypropylene wire was taken out and rinsed with deionized water for three times to obtain a polypropylene wire with surface-modified by double bonds and radiopaque nanoparticles. In this step, double bonds and radiopaque nanoparticles can be introduced simultaneously on the surface of polypropylene wire through simple steps without damaging the mechanical properties of the wire body. The radiopaque nanoparticles can further increase the introduction of double bonds, and at the same time, radiopaque function can be realized. Moreover, the method does not require pretreatment to the wire. (3) The polypropylene wire with surface-modified by double bonds and radiopaque nanoparticles obtained in step (2) was soaked in an aqueous solution of 1 wt% polyvinyl alcohol acrylate and 0.1 wt% Irgacure 2959 as a photoinitiator for 10 minutes, then was taken out for solidifying under ultraviolet light. The polyvinyl alcohol acrylate in this step 20 can form a cross-linked network by itself under the polymerization of the initiator, and thereby playing a lubricating role.

The double bond on the surface of the polypropylene wire can simultaneously participate in the copolymerization of the double bond in the polyvinyl alcohol acrylate, and thereby enhancing the bonding force between the hyaluronic acid network and the polypropylene wire.

Example 4. PTFE-radiopaque wire coated with polymer (1) The polytetrafluoroethylene (PTFE) wire was soaked in an aqueous solution of 5 mg/mL epigallocatechin gallate and 1 mg/mL barium sulfate nanoparticles, and then 1 M sodium hydroxide was added to adjust the pH to 9. After soaking for 6 hours, the polypropylene wire was taken out and rinsed with deionized water for three times, then soaked in N-(3-aminopropyl) methacrylamide hydrochloride aqueous solution (1 mg/mL) (pH=8) for 6 hours.

The tetrafluoroethylene wire was taken out and rinsed with deionized water for three times to obtain a polytetrafluoroethylene wire with surface-modified by double bonds and radiopaque nanoparticles.

In this step, double bonds and radiopaque nanoparticles can be simultaneously introduced on the surface of the polytetrafluoroethylene wire through a simple step without causing damage to the mechanical properties of the wire body. (2) The polytetrafluoroethylene wire with surface-modified by double bonds and radiopaque nanoparticles obtained in step (1) was soaked in aqueous solution of 10 wt% vinylpyrrolidone and 0.1 wt% Irgacure 2959 as a photoinitiator for 10 minutes, then was taken out for solidifying under ultraviolet light.

The vinylpyrrolidone monomer in this step can be polymerized under the action of the initiator to form polyvinylpyrrolidone by itself, which has good hydrophilicity and lubricity.

At the same time, the double bonds on the surface of the wire also participated in the polymerization of vinylpyrrolidone, which enhanced the binding force with the substrate; and the double bond epigallocatechin gallate of the lower layer of the polyvinylpyrrolidone also produced hydrogen bonding, which further enhanced the binding force with the substrate.

Hydrogen bonding was generated between polyvinylpyrrolidone and the underlying double bond gallocatechin gallate, which further enhanced the binding force with the substrate. 21

Example 5. PTFE-radiopaque wire coated with polymer (1) The polytetrafluoroethylene (PTFE) wire was soaked in an aqueous solution of 5 mg/mL dopamine and 1 mg/mL barium sulfate nanoparticles, and then 1 M sodium hydroxide was added to adjust the pH to 8.5. After soaking for 6 hours, the polypropylene wire was taken out and rinsed with deionized water for three times, then soaked in N-(3-aminopropyl) methacrylamide hydrochloride aqueous solution (1 mg/mL) (pH=8) for 6 hours.

In this step the sulfobetaine methacrylate monomer can be polymerized under the action of an initiator to form a zwitterionic hydrogel, which has good hydrophilicity, lubricity and anticoagulant properties.

The double bonds on the surface of the wire also participated in the polymerization of the hydrogel, which enhanced the bonding force between the hydrogel and the substrate.

Example 6. PTFE-radiopaque wire coated with hydrogel (1) Firstly, plasma surface treatment was performed to the PTFE wire, then soaked the wire in an aqueous solution of 5 mg/mL dopamine and 1 mg/mL barium sulfate nanoparticles, and IM sodium hydroxide was added to adjust the pH to 8.5. After soaking for 6 hours, and the polypropylene wire was taken out and rinsed for three times with deionized water, and then was soaked in N-(3-aminopropyl) methacrylamide hydrochloride aqueous solution (1 mg/mL) (pH=8) for 6 hours.

The polytetrafluoroethylene wire was taken out and rinsed for three times with deionized water.

In this step, double bonds and radiopaque 22 nanoparticles can be introduced simultaneously on the surface of the polytetrafluoroethylene wire without damaging the mechanical properties of the wire body. (2) The polytetrafluoroethylene wire obtained in step (1) was soaked for 10 minutes in an aqueous solution of 10 wt% sulfonic acid acrylic acid and 0.5 wt% polyethylene glycol diacrylate and 0.1 wt% Irgacure 2959 as a photoinitiator, then was taken out for solidifying under ultraviolet light. In this step, the sulfonic acid acrylic monomer and polyethylene glycol diacrylate can be polymerized under the action of the initiator to form an anionic hydrogel, which has good hydrophilicity, lubricity and anticoagulant properties.

The double bonds on the surface of the material also participated in the polymerization of the hydrogel, which enhanced the bonding force between the hydrogel and the substrate.

Example 7. Polyamide radiopaque wire coated with hydrogel (1) Firstly, plasma treatment was performed on the surface of the polyamide wire to introduce hydroxyl groups, then soaked the wire in an ether solution containing 8wt%o triethylamine, and added with 10% volume fraction of acryloyl chloride at 0°C. After reacted at room temperature for 24 hours, the polypropylene wire was taken out and rinsed for three times with deionized water. In this step double bonds can be introduced on the surface of the polyamide through simple steps.

(2) The polypropylene wire with surface-modified by double bonds and radiopaque nanoparticles obtained in step (1) was soaked in 1 wt% hyaluronic acid methacrylate aqueous solution, 1 mg/mL bismuth nanoparticle aqueous solution and 0.1 wt % Irgacure 2959 as a photoinitiator for 10 minutes , and then was taken out for solidifying under ultraviolet light. In this step, the hyaluronic acid methacrylate can be polymerized under the action of an initiator to form a hydrogel. At the same time, the radiopaque nanoparticles were encapsulated in the hydrogel, which enabled good lubricity and radiopaque performance. The double bonds on the surface also participated in the polymerization of the hydrogel, which enhanced the bonding force between the hydrogel and the substrate.

23

Example 8. Hydrogel radiopaque wire

0.01 g of tantalum nanoparticles were ultrasonically dispersed in 10 mL of 10 mg/mL tannic acid aqueous solution, and sodium hydroxide solution was added to adjust the pH to 9. After 6 hours of reaction, the solution was centrifuged to obtain tannic acid-modified tantalum nanoparticles. The obtained tannic acid-modified tantalum nanoparticles were added to a 30 wt% polyvinyl alcohol aqueous solution for dispersion, with a final concentration of 10 mg/mL, and the obtained solution was injected into a cylindrical mold with a diameter of 0.2 mm, and frozen at -20°C for 24 hours. Then it was taken out for melting, and repeated freeze-thaw for three times to obtain a nanoparticle-enhanced hydrogel radiopaque wire. The nanoparticles of the radiopaque wire obtained by this technology, are surface-modified by tannic acid, so they have better dispersibility in the polyvinyl alcohol solution. The tannic acid on the nanoparticles helps to increase the hydrogenation of the nanoparticles in the polyvinyl alcohol to form a cross-linked hydrogel network of nanoparticles, in which the introduction of nanoparticles not only has radiopaque function, but also further enhances the mechanical strength of the hydrogel radiopaque wire. Comparative Example 1 A radiopaque wire, the preparation of which is as follows: the polypropylene wire was soaked in a mixed aqueous solution of 5 mg/mL tannic acid and 1 mg/mL tungsten nanoparticles; and then 1 M sodium hydroxide was added to adjust the pH to 9. After soaking for 6 hours, the polypropylene wire was taken out and rinsed for three times with deionized water. Comparative Example 2 A radiopaque wire, which is a polypropylene wire without treatment. Comparative Example 3 A radiopaque wire, which is a nickel-titanium alloy wire with a diameter of 0.2 mm. Test of withdrawing ability and elastic modulus 24

The radiopaque wires of Examples 2-8 and Comparative Examples 1-3 were weaved on the same occluder by the method described in Example 1. After the occluder was conveyed and released, one end of the radiopaque wire was secured by a tension machine, and the radiopaque wire was withdrawn to test its withdrawal force. From the results in Table 1 as below, the radiopaque wires of examples 2-8 of the present disclosure have lower withdrawal force and lower elastic modulus. The coating on the surface of the polymer wires has no obvious influence on the modulus of the polymer wires, and the withdrawal force of the radiopaque wire is significantly reduced after the surface is polymerized with monomers.

Table 1 The various technical features in the above-described embodiments can be combined in various ways. In order to provide a concise description, the above-described embodiments do not describe all the possible combinations of the technical features . However, those combinations which are not described should be within the scope of the description as long as no contradiction occurs in the combinations of these technical features.

The above-described embodiments represent only several embodiments of the present disclosure, which are described in specific detail but should not be construed as limitations on the scope of the claims. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the disclosure, all of which fall within the scope of the present disclosure.

Accordingly, the scope of the present disclosure should be subject to the appended claims. 26

Claims

Conclusions

1. A radio-opaque wire comprising a wire body, a first control end and a second control end on the wire body for receiving and releasing the wire body, the first control end and the second control end being at two ends of the wire body, respectively. wire body; wherein the radiopaque wire is a polymeric wire having a lubrication layer on the surface, and the lubrication layer comprises a radiopaque material, or the radiopaque thread is a hydrogel thread containing radiopaque material; wherein the polymeric thread having a lubrication layer on the surface is prepared by the following steps: (step 1) applying a double bond polymerizable precursor to the surface of the polymeric thread; (step 2) coating the surface of the wire obtained in step (1) with a double bond polymerizable monomer and an initiator; and (step 3) subsequently hardening the wire obtained in step (2); wherein a radiopaque material is introduced in step (1) or (2); wherein the polymeric thread is at least one of a polypropylene thread, a polytetrafluoroethylene thread and a polyamide thread; wherein the double bond polymerizable precursor is at least one of a methacrylamide compound, a methacrylate compound, an acrylate, an acrylamide compound, acryloyl chloride and methacrylic anhydride; wherein the double bond polymerizable monomer is at least one of hyaluronic acid methacrylate, polyvinyl alcohol acrylate, polyethylene glycol diacrylate, vinylpyrrolidone, sulfobetaine methacrylate and sulfoacidecylic acid; wherein the hydrogel thread containing a radiopaque material is prepared by the following steps: (step 1) dispersing a radiopaque material in an aqueous solution of crosslinkable functional group molecules to obtain a radiopaque material modified by crosslinkable functional group molecules; 27

(step 2) adding the radiopaque material obtained in step (1) to an aqueous solution of a gel precursor, injecting it into a mold to harden it, to obtain a hydrogel radiopaque wire; wherein the gel precursor is polyvinyl alcohol; the crosslinkable functional group of molecules is a tea polyphenol compound.

The radiopaque wire of claim 1, wherein the polymeric wire having a lubrication layer on the surface is prepared by the steps of: (step 1) applying a double bond polymerizable precursor to the surface of the polymeric wire; (step 2) immersing the wire obtained in step (1) in an aqueous solution containing a double bond polymerizable monomer and an initiator for 5 to 15 minutes; and (3) subsequently hardening the wire obtained in step (2); wherein the concentration of the double bond polymerizable monomer in the aqueous solution containing the double bond polymerizable monomer and the initiator is 0.2 wt% - 50 wt% and the concentration of the initiator is 0.05 wt% - 2 wt .%.

The radiopaque wire according to claim 1, characterized in that in step (1) applying the double bond polymerizable precursor to the surface of the polymer wire comprises method A or method B: method A: under alkaline or neutral conditions, coating the surface of the polymeric wire with crosslinkable functional group molecules and then with a double bond polymerizable precursor, or coating after mixing crosslinkable functional group molecules with a double bond polymerizable precursor; in method A, the crosslinkable functional group molecules are a tea polyphenol compound; method B: realization of a plasma process on the surface of the polymer wire, coating with the double bond polymerizable precursor.

The radiopaque wire according to claim 3, characterized in that method A is: immersion of the polymer wire in an aqueous solution containing crosslinkable functional group molecules, pH adjustment at 7-10, absorption of the polymer wire 28 for 4-8 hours, remove the wire, clean and immerse the wire in the aqueous solution containing the double bond polymerizable precursor, soak the wire for 4 to 8 hours, and remove the wire; or, method B is: perform the plasma process with a hydroxyl group on the surface of the polymer wire, immerse the polymer wire in the solution triethylamine diethyl ether, add the double bond polymerizable precursor at 0-4°C and remove after reaction at room temperature the wire for 20-30 hours.

The radiopaque wire of claim 4, wherein the concentration of crosslinkable functional group molecules in the aqueous solution containing crosslinkable functional group molecules is 1 to 10 mg/mL; the concentration of the double bond polymerizable precursor in the aqueous solution is 0.5-10 mg/mL.

The radiopaque wire of any one of claims 1 to 5, wherein the initiator is a photoinitiator; and/or the curing process in step (3) is light curing; and/or the radiopaque material is at least one of tungsten, tantalum, barium sulfate, bismuth, gold, platinum, osmium, rhenium, iridium and rhodium; and/or the coating process is dip coating or rubbing coating or spray coating.

The radiopaque wire of claim 6, wherein the initiator is Irgacure 2959.

The radiopaque thread according to claim 1, characterized in that the crosslinkable functional group molecules in the hydrogel thread containing a radiopaque material are at least one among tannic acid, epigallocatechin gallate and dopamine.

The radiopaque wire according to claim 8, characterized in that in the aqueous solution of crosslinkable functional group molecules in step (1), the concentration of crosslinkable functional group molecules is 5-15 mg/mL; and/or, the concentration of the gel precursor in the aqueous solution of gel precursor is 20 to 40% by weight and the concentration of the radiopaque material in the aqueous solution of gel precursor is 0.1 to 20 mg/mL; and/or the mold is a cylindrical mold with a diameter of 0.1-0.3 mm; and/or the radiopaque material is at least one of tungsten, tantalum, barium sulfate, bismuth, gold, platinum, osmium, rhenium, iridium and rhodium.

29

The radiopaque wire according to claim 9, characterized in that the radiopaque material is at least one of tungsten nanoparticles, tantalum nanoparticles, barium sulfate nanoparticles, bismuth nanoparticles, gold nanoparticles, platinum nanoparticles, osmium nanoparticles, rhenium nanoparticles, iridium nanoparticles, and rhodium nanoparticles.

The radiopaque wire of claim 1, characterized in that the methacrylamide compound is N-(3-aminopropyl) methacrylamide hydrochloride.

The radiopaque wire according to claim 3, characterized in that the tea polyphenol compound is at least one of tannic acid, epigallocatechin gallate and dopamine.

The radiopaque wire according to claim 6, characterized in that the radiopaque material is at least one of tungsten nanoparticles, tantalum nanoparticles, barium sulfate nanoparticles, bismuth nanoparticles, gold nanoparticles, platinum nanoparticles, osmium nanoparticles, rhenium nanoparticles, iridium nanoparticles, and rhodium nanoparticles.

A connector with a radio-opaque function, characterized in that the connector comprises a support body and a radio-opaque wire, the radio-opaque wire being the radio-opaque wire according to any one of claims 1 to 13.