CN115634322A

CN115634322A - Developable medical polymer composite material and preparation method thereof

Info

Publication number: CN115634322A
Application number: CN202211149346.9A
Authority: CN
Inventors: 韩玉鑫; 孟江锋
Original assignee: Zhejiang Poly Pharmaceutical Co ltd; Hainan Poly Pharm Co ltd
Current assignee: Zhejiang Poly Pharmaceutical Co ltd; Hainan Poly Pharm Co ltd
Priority date: 2022-09-21
Filing date: 2022-09-21
Publication date: 2023-01-24

Abstract

The invention relates to a developable polymer composite material which is characterized by comprising the following components: 50-99 wt% of high molecular polymer and 1-60 wt% of developer; preferably, the components thereof comprise: 7050-9099 wt% of high molecular polymer and 101-3060 wt% of nonionic developer; more preferably, the components comprise 70 to 90 weight percent of high molecular polymer and 10 to 30 weight percent of nonionic developer; most preferably, the components comprise 80wt% of high molecular polymer and 20wt% of nonionic developer. The preparation method comprises the following steps: uniformly spraying the non-ionic developer in a solid powder form on the high molecular polymer, and extruding and molding the mixture through a double-screw extruder after uniformly mixing. The composite material can realize the development of the whole catheter and simultaneously meet the requirements of high development quality and good mechanical property, and has the advantages of simple preparation method, uniform component mixing, long product validity period, acid resistance, no deformation or deterioration after long-time preservation in a human body biochemical environment, good flexibility, difficult aging, good toughness, strong machinability, difficult fracture and deformation, low cost, good physiological compatibility, no inflammation of patients, environmental friendliness and suitability for industrialization and large-scale production.

Description

Developable medical polymer composite material and preparation method thereof

Technical Field

The invention belongs to the field of medical human body image materials and preparation thereof, and particularly relates to a developable medical polymer composite material and a preparation method thereof.

Background

The medical catheter is a special catheter of a tube type used in the medical treatment or medical operation process and is used for assisting drainage or transfusion and the like.

After the medical catheter goes deep into a human body during diagnosis and treatment, if the depth and the position of the head of the catheter are judged by completely depending on the printed scales on the periphery of the catheter, the specific position and the shape of the catheter cannot be accurately known. Therefore, the influence of the catheter in the human body needs to be displayed in real time under the assistance of an external auxiliary instrument so as to help the diagnosis and treatment process to be smoothly carried out.

To solve this problem, it is common practice in the art to use a developable medical polymer composite to make a portion of such a catheter, making the catheter body particularly sensitive to the source of vibrations emitted by an in vitro diagnostic instrument, so as to distinguish the catheter from the surrounding body tissue in the image, known as the developable catheter. The vibration source emitted by the external diagnostic instrument mainly comprises ultrasonic waves, X rays, nuclear magnetic resonance waves and the like, and the guide tube added with the corresponding developing additive is also divided into an ultrasonic guide tube, an X developing guide tube and a nuclear magnetic guide tube. The X developing conduit is widely applied due to the characteristics of clear developing effect, simple operation and the like.

Most of the medical polymer composite materials commonly used in catheters sold in the market at present are compounded by polymer materials (such as materials of silica gel, nylon, rubber and the like) and developers, and various auxiliary materials such as adhesives, lubricants, stabilizers, toughening agents and the like, but catheters made of the materials have the problems of complex preparation process, unsuitability for industrialization, high cost, poor developing effect, incapability of realizing full development, unsatisfactory mechanical strength, brittleness, easiness in folding or deformation, easiness in aging, easiness in falling off of a developing layer, easiness in causing discomfort of patients when particles exist on the surfaces of the catheters and are used, easiness in stimulating mucous membranes of patients when the polymer materials, the developers and other auxiliary materials are not completely mixed and used, easiness in deformation or deterioration after long-time storage in a human biochemical environment (for example, breakage and breakage caused by long-time soaking in body fluid), incapability of human bodies, poor physiological compatibility (for example, foreign body reaction, blood coagulation, hemolysis or adhesion and the like are easy to cause by long-time contact with human tissues and secretions), good flexibility, and possible local inflammation of human bodies.

Therefore, in order to solve the above problems of commercially available catheters, there is an urgent need to develop a novel developable polymer composite material which satisfies the requirements of high development quality and good mechanical properties while achieving the development of the whole catheter, and which has the advantages of simple preparation method, uniform component mixing, long product validity period, no deformation or deterioration after long-term preservation in the biochemical environment in the human body, strong workability, low cost, good physiological compatibility, environmental friendliness, and suitability for industrialization and mass production.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a developable medical polymer composite material and a preparation method thereof.

In order to realize the technical purpose of the invention, the invention provides the following technical scheme:

in a first aspect, the present invention provides a developable polymer composite.

According to the developable polymer composite material, the components comprise: 50-99 wt% of high molecular polymer and 1-60 wt% of developer; preferably, the components thereof comprise: 50-99 wt% of high molecular polymer and 1-60 wt% of nonionic developer; more preferably, the components comprise 50 to 90 weight percent of high molecular polymer and 10 to 60 weight percent of nonionic developer; more preferably, the components comprise 60 to 90 weight percent of high molecular polymer and 10 to 50 weight percent of nonionic developer; more preferably, the components comprise 70-90 wt% of high molecular polymer, 10-40 wt% of non-ionic developer; more preferably, the components comprise 70-90 wt% of high molecular polymer, 10-30 wt% of non-ionic developer; particularly preferably, the components comprise 75 to 90 weight percent of high molecular polymer and 15 to 30 weight percent of nonionic developer; particularly preferably, the components comprise 75 to 85 weight percent of high molecular polymer and 15 to 25 weight percent of nonionic developer; most preferably, the components comprise 80wt% of high molecular polymer and 20wt% of non-ionic developer.

According to the above-mentioned developable polymer composite, an antioxidant may be further included.

According to the above developable polymer composite, a plasticizer may be further included.

According to the developable polymer composite material, the components can be composed of 50-99 wt% of high molecular polymer and 1-60 wt% of developer; preferably, the components thereof may consist of 50 to 99wt% of the high molecular polymer and 1 to 60wt% of the nonionic developer; more preferably, the components consist of 50 to 90wt% of high molecular polymer and 10 to 60wt% of nonionic developer; more preferably, the components consist of 60 to 90wt% of high molecular polymer and 10 to 50wt% of non-ionic developer; more preferably, the components thereof consist of 70 to 90wt% of high molecular polymer and 10 to 40wt% of nonionic developer; more preferably, the components thereof consist of 70 to 90wt% of high molecular polymer and 10 to 30wt% of nonionic developer; particularly preferably, the components thereof consist of 75 to 90wt% of the high molecular polymer and 15 to 30wt% of the nonionic developer; particularly preferably, the components consist of 75-85 wt% of high molecular polymer and 15-25 wt% of non-ionic developer; most preferably, the components consist of 80wt% high molecular polymer and 20wt% non-ionic developer.

Preferably, the developable polymer composite material comprises 50 to 99wt% of a high molecular polymer and 1 to 60wt% of a nonionic developer, or comprises 50 to 99wt% of a high molecular polymer, 1 to 60wt% of a nonionic developer, 0.5 to 2wt% of an antioxidant and 0.5 to 2wt% of a plasticizer, or comprises 50 to 99wt% of a high molecular polymer, 1 to 60wt% of a nonionic developer and 0.5 to 2wt% of an antioxidant;

more preferably, the developable polymer composite comprises 50 to 90wt% of a high molecular polymer and 10 to 50wt% of a nonionic developer, or comprises 50 to 90wt% of a high molecular polymer, 10 to 50wt% of a nonionic developer, 0.5 to 2wt% of an antioxidant and 0.5 to 2wt% of a plasticizer, or comprises 50 to 90wt% of a high molecular polymer, 10 to 50wt% of a nonionic developer and 0.5 to 2wt% of an antioxidant;

more preferably, the developable polymer composite comprises 60 to 90wt% of high molecular polymer and 10 to 40wt% of nonionic developer, or comprises 60 to 90wt% of high molecular polymer, 10 to 40wt% of nonionic developer, 0.5 to 2wt% of antioxidant and 0.5 to 2wt% of plasticizer, or comprises 60 to 90wt% of high molecular polymer, 10 to 40wt% of nonionic developer and 0.5 to 2wt% of antioxidant;

more preferably, the developable polymer composite comprises 70 to 90wt% of a high molecular polymer and 10 to 30wt% of a nonionic developer, or comprises 70 to 90wt% of a high molecular polymer, 10 to 30wt% of a nonionic developer, 0.5 to 2wt% of an antioxidant and 0.5 to 2wt% of a plasticizer, or comprises 70 to 90wt% of a high molecular polymer, 10 to 30wt% of a nonionic developer and 0.5 to 2wt% of an antioxidant;

more preferably, the developable polymer composite comprises 70 to 90wt% of polyurethane and 10 to 30wt% of nonionic developer, or comprises 70 to 90wt% of polyurethane, 10 to 30wt% of nonionic developer, 0.5 to 2wt% of antioxidant and 0.5 to 2wt% of plasticizer, or comprises 70 to 90wt% of polyurethane, 10 to 30wt% of nonionic developer and 0.5 to 2wt% of plasticizer;

more preferably, the developable polymer composite comprises 70 to 90wt% of polyurethane and 10 to 30wt% of iodine-containing nonionic developer, or comprises 70 to 90wt% of polyurethane, 10 to 30wt% of iodine-containing nonionic developer, 0.5 to 2wt% of antioxidant and 0.5 to 2wt% of plasticizer, or comprises 70 to 90wt% of polyurethane, 10 to 30wt% of iodine-containing nonionic developer and 10 to 30wt% of plasticizer, or comprises 70 to 90wt% of polyurethane, 10 to 30wt% of iodine-containing nonionic developer and 0.5 to 2wt% of antioxidant;

more preferably, the developable polymer composite material comprises 70-90 wt% of polyurethane and 10-30 wt% of iodine-containing nonionic developer;

more preferably, the developable polymer composite material comprises 75-85 wt% of polyurethane and 15-25 wt% of iodine-containing nonionic developer;

particularly preferably, the developable polymer composite described above has a composition consisting of 80wt% of polyurethane and 20wt% of an iodine-containing nonionic developer.

According to the above developable polymeric composite, the polymeric polymer is preferably polyurethane, polyethylene, polyvinyl chloride, polypropylene, polyamide, polylactic acid, polycarbonate, polyanhydride, polycarboxal, polyether, polyacrylate, polyurea, polystyrene, polyglycolic acid, or a combination thereof, more preferably polyglycolic acid, polyurethane, polylactic acid, polyethylene, polyvinyl chloride, polypropylene, polyamide, or a combination thereof, especially preferably polyglycolic acid, polyurethane, polylactic acid, polyethylene, polyvinyl chloride, or a combination thereof, more preferably polyethylene, polyvinyl chloride, polyurethane, or a combination thereof, most preferably polyurethane; the polyurethane is preferably a thermoplastic polyurethane; the thermoplastic polyurethane is preferably a polyurethane elastomer, polyurethane copolymer (including block and random copolymers, which may be polyether-based, polyester-based, polycarbonate-based, polyisobutylene-based, aliphatic-based, aromatic-based, or mixtures thereof), most preferably under the trade name Carbothane ^TM 、Tecoflex ^TM 、Tecothane ^TM 、Tecophilic ^TM 、Tecoplast ^TM 、

Pathway ^TM 、Tecobax ^TM And

the thermoplastic polyurethane of (3).

According to the above developable polymer composite, the high molecular polymer is preferably an elastomer, a homopolymer, a block copolymer, a random copolymer, a graft copolymer, or a polymer blend, more preferably an elastomer, a block copolymer, or a polymer blend, more preferably an elastomer, a polyether block copolymer, a polyester block copolymer, a polycarbonate block copolymer, a polyisobutylene block copolymer, an aliphatic hydrocarbon block copolymer, or an aromatic hydrocarbon block copolymer, and most preferably an elastomer.

According to the developable polymer composite described above, the melt index of the polymer is preferably in the range of 30g to 80g/10min, more preferably 50g to 70g/10min.

According to the above developable polymer composite, the hardness of the polymer is preferably in the range of 50 to 95A and/or 20 to 90D, more preferably 55 to 95A and/or 25 to 90D.

According to the above developable polymer composite, the developer is preferably a nonionic developer or an iodine-containing ionic developer, more preferably a nonionic developer; the non-ionic developer is preferably a non-ionic developer containing iodine, more preferably one or more of ioscopinol, iohexol, ioversol, iotrolan, iodixanol, ioglucitol, iomeprol, iodophenyl ester, iopromide, iophthalide sulfide, ioxilan, iobitrol and iopentol, more preferably one or more of ioscopinol, ioversol, ioxatol and iopromide, particularly preferably ioisopeptide alcohol or iohexol, and most preferably ioisopeptide alcohol; the iodine-containing ionic developer is preferably ioglumine, iogluniline, iofosfamide, iodic acid, diatrizoate, metrizoate, iophthalate, ioxilamide, more preferably ioxofenac acid, diatrizoate, iophthalate.

In accordance with the developable polymer composites described above, the imaging agents are for use in ultrasound imaging, magnetic Resonance Imaging (MRI), nuclear Magnetic Resonance (NMR), computed Tomography (CT), electron Spin Resonance (ESR), nuclear medicine imaging, optical imaging, elastography, fluorescence imaging, positron Emission Tomography (PET), radio Frequency (RF), and microwave laser, and may also include any other substance useful in facilitating diagnosis of a disease or other condition in a patient, regardless of whether imaging methodologies are applied.

According to the above developable polymer composite, the developer is preferably in a solid powder form, more preferably amorphous or crystalline.

According to the above developable polymer composite, the particle diameter D50 of the developer is preferably 0.5 to 20 micrometers, more preferably 0.5 to 10 micrometers.

According to the above developable polymer composite, the thickness of the developer is preferably in the range of 0.02 to 1.4 micrometers, more preferably 0.02 to 1 micrometer.

According to the above developable polymer composite, the diameter-thickness ratio of the developer is preferably in the range of 10 to 40, more preferably 15 to 35.

Further, according to the above developable polymer composite, the antioxidant is preferably one or a mixture of several of antioxidant 1010, antioxidant 245, antioxidant 1076 and antioxidant 168, more preferably one or a mixture of two of antioxidant 1010, antioxidant 245, antioxidant 1076 and antioxidant 168, and most preferably antioxidant 1010, antioxidant 245, antioxidant 1076 or antioxidant 168; the antioxidant 1010 has the chemical name of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester; the chemical name of the antioxidant 245 is triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate; the antioxidant 1076 has a chemical name of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate; the antioxidant 168 is chemically tris [2, 4-di-tert-butylphenyl ] phosphite.

Further, according to the above developable polymer composite, the plasticizer is preferably medical DINCH, citrate, medical castor oil; more preferably DINCH for medical use, tributyl citrate, acetyl tributyl citrate ring, castor oil for medical use; the chemical name of the medical DINCH is tributyl cyclohexane-1, 2-dicarboxylic acid diisononyl ester.

According to the developable polymer composite, the components can be composed of 80wt% of polyurethane and 20wt% of iodoisopeptide alcohol; or, the components consist of 80wt% polyurethane and 20wt% iohexol; or, its components are 80wt% polyethylene and 20wt% ioisopeptide alcohol; or, the components consist of 80wt% of polyvinyl chloride and 20wt% of iodiplodin alcohol; or, the components consist of 80wt% polyurethane and 20wt% iodixanol; or the components consist of 80wt% of polyurethane and 20wt% of iopromide; or the components consist of 80wt% of polyurethane and 20wt% of ioversol; preferably, its components consist of 80% by weight of polyurethane and 20% by weight of iodoisopeptide alcohol; or, its composition consists of 80wt% polyurethane and 20wt% iohexol; more preferably, the components thereof consist of 80wt% polyurethane and 20wt% iodoisopeptide alcohol; particularly preferably, the components consist of 80 wt.% of thermoplastic polyurethane and 20 wt.% of iodoisopeptide alcohol; particularly preferably, the components thereof consist of 80% by weight of thermoplastic polyurethane and 20% by weight of iodoisopeptide alcohol in solid powder form; particularly preferably, the components thereof consist of 80wt% of thermoplastic polyurethane and 20wt% of the crystal form of iosiopeptide alcohol; or the components consist of 80wt% of thermoplastic polyurethane and 20wt% of iodoisopeptide alcohol in an amorphous form; or, its component is composed of 80wt% of Carbothane ^TM And 20% by weight of iodoisopeptide alcohol in solid powder form; or, the components are 80wt% of the commercial product named Tecoflex ^TM And 20% by weight of ioisopeptide alcohol in solid powder form; or, its components are 80wt% of Tecophilic ^TM And 20% by weight of ioisopeptide alcohol in solid powder form; or, its components are 80wt% of Tecoplast ^TM And 20% by weight of a polyurethaneA bulk powder form of iosisopeptide alcohol; or, its components are sold under the trade name of 80wt%

And 20% by weight of iodoisopeptide alcohol in solid powder form; or, its components are sold under the trade name of 80wt%

And 20% by weight of iodoisopeptide alcohol in solid powder form; or, the components are sold under the trade name of 80wt percent

And 20% by weight of ioisopeptide alcohol in solid powder form; or, its components are sold under the trade name of 80wt%

And 20% by weight of iodoisopeptide alcohol in solid powder form; or, the components are 80wt% of the material with the trade name of Pathway ^TM And 20% by weight of iodoisopeptide alcohol in solid powder form; or, its components are 80wt% of the commercial product named Tecobax ^TM And 20% by weight of iodoisopeptide alcohol in solid powder form; or, the components are sold under the trade name of 80wt percent

And 20% by weight of iodoisopeptide alcohol in solid powder form.

The second aspect of the present invention provides a method for preparing the above developable polymer composite, comprising: uniformly spraying a developer in a solid powder form on the dried high molecular polymer, and extruding and molding the mixture through a double-screw extruder after uniformly mixing;

according to the above preparation method, the drying temperature is preferably 80 to 100 ℃, more preferably 85 to 95 ℃, and most preferably 90 ℃;

according to the above preparation method, the drying time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and most preferably 4 hours;

according to the above production method, the mixing is preferably blending;

according to the above preparation method, the temperature of the mixing is preferably normal temperature;

according to the above production method, the mixing is preferably carried out in a high-speed mixer;

according to the above production method, the twin-screw extruder preferably has five or more heating zones;

according to the above preparation method, the extrusion temperature of the twin-screw extruder is preferably 140 to 200 ℃, more preferably 150 to 195 ℃, and most preferably

Heating zone

First zone

Second zone

Third zone

Fourth zone

Fifth zone

Die

Temperature/. Degree.C

150～170

160～180

170～190

175～195

Preferably, the method for preparing the developable polymer composite material comprises the following steps: uniformly spraying 1-60 wt% of solid powder-shaped nonionic developer on 50-99 wt% of dried high molecular polymer, uniformly mixing, and extruding and molding the mixture by a double-screw extruder.

More preferably, the method for preparing the developable polymer composite comprises: uniformly spraying 10-30 wt% of solid powder-shaped nonionic developer on 70-90 wt% of high molecular polymer, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder; more preferably, the method for preparing the developable polymer composite comprises: uniformly spraying 10-30 wt% of solid powder-shaped nonionic developer on 70-90 wt% of high molecular polymer, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder;

more preferably, the method for preparing the developable polymer composite comprises: uniformly spraying 20wt% of solid powder-shaped nonionic developer on 80wt% of high molecular polymer, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder; or, uniformly spraying 10-30 wt% of the nonionic developer in the form of solid powder on 70-90 wt% of polyurethane, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder; or, evenly spraying 10-30 wt% of solid powder form iodisopeptide alcohol on 70-90 wt% of high molecular polymer, evenly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder; or evenly spraying 10-30 wt% of solid powder form iodiploypeptide alcohol on 70-90 wt% of polyurethane, evenly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder;

particularly preferably, the method for preparing the developable polymer composite comprises the following steps: uniformly spraying 20wt% of solid powder-shaped nonionic developer on 80wt% of polyurethane, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder; or, uniformly spraying 20wt% of solid powder form iodisopeptide alcohol on 80wt% of high molecular polymer, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder; or uniformly spraying 20wt% of solid powder form iodisopeptide alcohol on 80wt% of polyurethane, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder;

particularly preferably, the method for preparing the developable polymer composite comprises the following steps: uniformly spraying 20wt% of solid powder form iodisopeptide alcohol on 80wt% of polyurethane, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder;

particularly preferably, the method for preparing the developable polymer composite comprises the following steps: drying the thermoplastic polyurethane at the temperature of between 90 and 110 ℃ for 2 to 6 hours, wherein the thermoplastic polyurethane accounts for 80 percent of the total mass; selecting iodoisopeptide alcohol as a developer, wherein the iodoisopeptide alcohol accounts for 20% of the total mass; uniformly spraying the iodisopeptide alcohol on thermoplastic polyurethane, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder at the temperature of 150-200 ℃;

particularly preferably, the method for preparing the developable polymer composite comprises the following steps: drying thermoplastic polyurethane at 95-105 ℃ for 3-5 h, wherein the thermoplastic polyurethane accounts for 80% of the total mass; selecting iodiplodin as a developer, wherein the content of the iodiplodin is 20% of the total mass; uniformly spraying the iodoisopeptide alcohol on thermoplastic polyurethane, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder at 160-190 ℃;

most preferably, the method for preparing the developable polymer composite comprises the following steps: drying thermoplastic polyurethane at 100 ℃ for 4h, wherein the thermoplastic polyurethane accounts for 80% of the total mass; selecting iodiplodin as a developer, wherein the content of the iodiplodin is 20% of the total mass; uniformly spraying the iodisopeptide alcohol on the thermoplastic polyurethane, uniformly mixing by using a high-speed mixer, drying, and extruding and molding the mixture by using a double-screw extruder at 160-185 ℃.

The third aspect of the invention provides a use of the developable polymer composite material for preparing a medical developing catheter; the medical imaging catheter is preferably an X-ray imaging catheter;

according to the above uses, the medical imaging catheter preferably includes but is not limited to a balloon dilatation catheter, a central venous catheter, a trocar peripheral catheter, an enteral feeding catheter, a urinary catheter;

according to the above uses, the medical visualization catheter preferably includes, but is not limited to, for delivering oxygen, blood, cerebrospinal fluid, urine, gastric juice, nutrient solution, injection solution, drug solution.

The invention has the following beneficial effects:

1. the developable polymer composite material provided by the invention can realize the development of the whole catheter and simultaneously meet the requirements of high development quality and good mechanical property (the test results of tensile force and tearing force are good), and has good flexibility, good toughness and difficult fracture and deformation; most importantly, the effects can be realized without adding other auxiliary materials such as antioxidant, plasticizer and the like except for the developer and the high molecular polymer;

2. the method for preparing the developable polymer composite material is simple and can be obtained by only uniformly spraying the developer in the form of solid powder on the polymer, uniformly mixing, and extruding and molding the mixture by a double-screw extruder; in addition, the preparation method of the developable polymer composite material provided by the invention is not easy to cause the problems of uneven developer dispersion, uneven component mixing, incomplete material compatibility and the like in the mixing process, so that the discomfort felt by a patient in the using process caused by the problems is avoided, and the using compliance of the patient is better;

3. the developable polymer composite material provided by the invention has the advantages of long product effect period, acid resistance, no deformation or deterioration after long-term preservation in a biochemical environment in a human body, difficult aging, strong processability, low cost, good physiological compatibility, no inflammation of patients, environmental friendliness, suitability for industrialization and large-scale production and good application prospect in the field of medical appliances.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and the drawings in the following description are only examples of the present invention and do not limit the technical solutions of the present invention.

FIG. 1 is a line graph showing the results of the fracture strength test of the developed materials of examples 1 to 5;

FIG. 2 is a line graph showing the results of elongation at break tests of the developing materials of examples 1 to 5;

FIG. 3 is a line graph showing the results of flexural modulus tests on the developed materials of examples 1 to 5;

FIG. 4 is a line graph showing the results of tear strength tests on the developing materials of examples 1 to 5;

FIG. 5 is a developed image of a sample of the developing material of comparative example 5 and examples 1 to 5 under a nuclear magnetic resonance apparatus;

FIG. 6 is a developed image of samples of the developing materials of comparative example 3, example 48, example 58, example 53, example 63, and example 68 under a nuclear magnetic resonance apparatus;

FIG. 7 is a line graph showing the results of fracture strength tests for the developing materials of comparative example 3, example 48, example 58, example 53, example 63 and example 68;

FIG. 8 is a line graph showing the results of elongation at break tests of the developing materials of comparative example 3, example 48, example 58, example 53, example 63 and example 68;

FIG. 9 is a line graph showing the results of flexural modulus tests on the developing materials of comparative example 3, example 48, example 58, example 53, example 63, and example 68;

FIG. 10 is a line graph of the tear strength test results for the developed materials of comparative example 3, example 48, example 58, example 53, example 63, and example 68;

FIG. 11 is a line graph showing the results of a fracture strength test on the developing materials of examples 71, 1, 3,5, 72 to 74;

FIG. 12 is a line graph showing the results of elongation at break tests on the developing materials of examples 71, 1, 3,5, 72 to 74;

FIG. 13 is a line graph showing the results of flexural modulus tests on the developing materials of examples 71, 1, 3,5, 72 to 74;

FIG. 14 is a line graph showing the results of tear strength tests on the developing materials of examples 71, 1, 3,5, 72 to 74.

Detailed Description

For better understanding of the present invention, the following description is given with reference to specific examples, but the present invention is not limited to the specific embodiments. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The various reagents used in the examples of the present invention were commercially available unless otherwise specified.

The temperature in the embodiment of the invention is room temperature unless otherwise specified, and the normal temperature is room temperature.

The ratios of the components in the mixed solvent in the examples of the present invention are volume ratios, for example, unless otherwise specified.

The content in the embodiment of the invention represents the weight percentage.

The die described in the examples of the present invention was a die for extruding the blend using a twin-screw extruder.

The models and manufacturers of the instruments used in the examples and test examples of the present invention are as follows:

instrument for measuring the position of a moving object	Model number	Manufacturer of the product
			Vacuum drying oven	DZF-6053 type	SHANGHAI YIHENG INSTR Co.,Ltd.
High-speed mixer	SHR-10A type	Zhang hong Kong Yili machinery Co Ltd
			Double-screw extruder	HK36 type	Nanjing Ke Asia Equipment group
Grain cutting machine	SCP160 type	Zhang Jia gang Erlight mechanical research institute
			Universal material stretcher	Instron model 5566	Intron corporation of America
Shore hardness tester	Type A	TQC sheen, netherlands

Tensile property tests in the examples and test examples of the present invention were conducted in accordance with test standard ASTM D-412; the test was carried out by means of a universal material drawing machine using an Instron model 5566 from Instron corporation, instron, usa.

The tear strength tests in the examples and test examples of the present invention were conducted in accordance with test standard ASTM D-624; the test was carried out by means of a universal material drawing machine using an Instron model 5566 from Instron corporation, instron, usa.

The hardness test in the embodiment and the test example of the invention is carried out according to the detection standard ISO 868; the test is carried out by means of a Shore durometer using type A from the company TQC sheen, the Netherlands.

The molding process employed in the examples and test examples of the present invention was as follows: carrying out hot pressing on the obtained developing material by adopting a flat vulcanizing machine, wherein the temperature is as follows: preheating for 5min at 180 ℃, prepressing for 60s at 5MPa, releasing pressure for 5s, prepressing for 30s, releasing pressure for 5s, repeating the prepressing-releasing steps for 2 times, and hot-pressing for 600s at 15MPa to obtain a corresponding developing material sample.

Examples 1 to 5

Raw materials:

(1) Thermoplastic polyurethane: the thermoplastic polyurethane elastomer is also called thermoplastic polyurethane rubber, TPU for short, and is An (AB) n type block linear polymer, A is polyester or polyether with high molecular weight (1000-6000), B is diol containing 2-12 straight chain carbon atoms, and the chemical structure between AB chain segments is diisocyanate;

(2) Ioisopeptide alcohol: a white or quasi-white powder as non-ionic iodine contrast agent for angiography, contrast and contrast is suitable for angiography, CT scan, urinary tract angiography, subarachnoid cavity, etc.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above examples 1-5, respectively, firstly, drying the thermoplastic polyurethane in vacuum for 4 hours at 90 ℃ in a vacuum drying oven; then evenly spraying the iodiploptide alcohol on the dried thermoplastic polyurethane, evenly mixing the materials by using a high-speed mixer, and extruding the blended materials by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First region	Second region	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	160	170	180	185	185	185

And extruding the blended material from a die, washing and condensing the blended material by water tank at normal temperature, granulating by a granulator, and drying by blast to obtain the developing material.

And (3) performance testing:

the developing material obtained by the preparation is respectively subjected to tensile property test, tearing strength test and hardness test after being prepared into corresponding developing material samples through a die pressing process, and the test results are shown in the following table and the attached figures 1-4 of the specification:

and (4) conclusion:

the accompanying

drawings

1 and 2 in the description show that the fracture strength and the fracture elongation of the developing material samples are reduced along with the increase of the content of the contrast agent in the examples 1 to 5, the accompanying drawing 3 in the description shows that the flexural modulus of the developing material samples is increased along with the increase of the content of the contrast agent in the examples 1 to 5, and the accompanying drawing 4 in the description shows that the influence of the content of the contrast agent in the examples 1 to 5 on the tear strength of the developing material samples is not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect of the material is shown in example 5, example 4, example 3, example 2 and example 1, so that the development effect of the material meets the use requirement.

Examples 6 to 10

Raw materials:

(1) Thermoplastic polyurethane: the thermoplastic polyurethane elastomer is also called thermoplastic polyurethane rubber, TPU for short, and is An (AB) n type block linear polymer, wherein A is polyester or polyether with high molecular weight (1000-6000), B is diol containing 2-12 straight chain carbon atoms, and the chemical structure between AB chain segments is diisocyanate;

(2) Iopamidol: a white or quasi-white powder as non-ionic iodine contrast agent for angiography, contrast and contrast is suitable for angiography, CT scan, urinary tract angiography, subarachnoid cavity, etc.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above examples 6-10, respectively, firstly, the thermoplastic polyurethane is dried in vacuum for 4 hours at 90 ℃ in a vacuum drying oven; then evenly spraying the iodiploptide alcohol on the dried thermoplastic polyurethane, evenly mixing the materials by using a high-speed mixer, and extruding the blended materials by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First region	Second region	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	165	175	185	190	190	190

And extruding the blended material from a die, washing and condensing the blended material in water tank at normal temperature, granulating by a granulator, and drying by blast to obtain the developing material.

And (3) performance testing:

after the developing material obtained by the preparation is respectively prepared into corresponding developing material samples through a mould pressing process, respectively carrying out tensile property test, tearing strength test and hardness test, wherein the test results are as follows:

and (4) conclusion:

the table shows that in examples 6 to 10, the fracture strength and the fracture elongation of the developing material samples decrease with the increase of the content of the contrast agent; in examples 6 to 10, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 6 to 10, the effect of the content of the contrast agent on the tear strength of the developing material samples was insignificant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect example 10, example 9, example 8, example 7 and example 6 meet the use requirement.

Examples 11 to 15

Raw materials:

(2) Ioisopeptide alcohol: a white or white-like powder as non-ionic iodine contrast agent for angiography is suitable for angiography, CT scan, urinary tract angiography, subarachnoid space angiography, etc.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above examples 11-15, respectively, firstly, the thermoplastic polyurethane is dried in vacuum for 4 hours at 90 ℃ in a vacuum drying oven; then evenly spraying the iodiploptide alcohol on the dried thermoplastic polyurethane, evenly mixing the materials by using a high-speed mixer, and extruding the blended materials by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First zone	Second region	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	170	180	190	195	195	195

And (4) performance testing:

and (4) conclusion:

the table shows that in examples 11 to 15, the fracture strength and the fracture elongation of the developing material samples decrease with the increase of the content of the contrast agent; in examples 11 to 15, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 11 to 15, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect of the material is shown in example 15, example 14, example 13, example 12 and example 11, so that the development effect of the material meets the use requirement.

Examples 16 to 20

Raw materials:

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above 16-20, respectively, firstly, drying the thermoplastic polyurethane in vacuum for 4h at 90 ℃ in a vacuum drying oven; then evenly spraying the iodiploptide alcohol on the dried thermoplastic polyurethane, evenly mixing the materials by using a high-speed mixer, and extruding the blended materials by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First region	Second zone	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	155	165	175	180	180	180

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 16 to 20, the fracture strength and the fracture elongation of the developing material samples decrease with the increase of the content of the contrast agent; in examples 16 to 20, the flexural modulus of the developing material samples increased with the increase in the content of the contrast agent; in examples 16 to 20, the effect of the content of the contrast agent on the tear strength of the developing material samples was insignificant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect of the material is shown in example 20, example 19, example 18, example 17 and example 16, so that the development effect of the material meets the use requirement.

Examples 21 to 25

Raw materials:

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above embodiments 21 to 25, respectively, firstly, the thermoplastic polyurethane is dried in a vacuum drying oven for 4 hours at 90 ℃; then evenly spraying the iodiploidol on the dried thermoplastic polyurethane, evenly mixing the materials by a high-speed mixer, and extruding the blended materials by a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First zone	Second region	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	150	160	170	175	175	175

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 21 to 25, the fracture strength and the fracture elongation of the developing material samples decrease with the increase of the content of the contrast agent; in examples 21 to 25, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 21 to 25, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect of the material is shown in example 25, example 24, example 23, example 22 and example 21, so that the development effect of the material meets the use requirement.

Examples 26 to 30

Raw materials:

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above examples 26-30, respectively, firstly, the thermoplastic polyurethane is dried in a vacuum drying oven for 3 hours at 90 ℃; then evenly spraying the iodiploidol on the dried thermoplastic polyurethane, evenly mixing the materials by a high-speed mixer, and extruding the blended materials by a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First zone	Second region	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	160	170	180	185	185	185

And (4) performance testing:

the developing material obtained by the preparation is respectively subjected to tensile property test, tearing strength test and hardness test after being prepared into corresponding developing material samples through a mould pressing process, and the test results are as follows:

and (4) conclusion:

the table shows that in examples 26 to 30, the fracture strength and the fracture elongation of the developing material samples decrease with the increase of the content of the contrast agent; in examples 26 to 30, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 26 to 30, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect of the material is shown in example 30, example 29, example 28, example 27 and example 26, so that the development effect of the material meets the use requirement.

Examples 31 to 35

Raw materials:

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above examples 31 to 35, firstly, the thermoplastic polyurethane is dried in a vacuum drying oven for 5 hours at 90 ℃; then evenly spraying the iodiploidol on the dried thermoplastic polyurethane, evenly mixing the materials by a high-speed mixer, and extruding the blended materials by a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 31 to 35, the fracture strength and the fracture elongation of the developing material samples decrease with the increase of the content of the contrast agent; in examples 31 to 35, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 31 to 35, the effect of the content of the contrast agent on the tear strength of the developing material sample was insignificant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect of the material is shown in example 35, example 34, example 33, example 32 and example 31, so that the development effect of the material meets the use requirement.

Examples 36 to 40

Raw materials:

The formula is as follows:

the preparation method comprises the following steps:

according to the formula of 36-40 in the above embodiment, respectively, firstly, drying the thermoplastic polyurethane in a vacuum drying oven at 85 ℃ for 4h in vacuum; then evenly spraying the iodiploptide alcohol on the dried thermoplastic polyurethane, evenly mixing the materials by using a high-speed mixer, and extruding the blended materials by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First region	Second zone	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	160	170	180	185	185	185

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 36 to 40, the fracture strength and the fracture elongation of the development material samples decrease with the increase of the content of the contrast agent; in examples 36 to 40, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 36 to 40, the effect of the content of the contrast agent on the tear strength of the developing material samples was insignificant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect example 40> example 39> example 38> example 37> example 36, so the development effect of the material meets the use requirement.

Examples 41 to 45

Raw materials:

(2) Iopamidol: a white or white-like powder as non-ionic iodine contrast agent for angiography is suitable for angiography, CT scan, urinary tract angiography, subarachnoid space angiography, etc.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above-mentioned embodiments 41-45, respectively, firstly, drying the thermoplastic polyurethane at 95 ℃ for 4h; then evenly spraying the iodiploptide alcohol on the dried thermoplastic polyurethane, evenly mixing the materials by using a high-speed mixer, and extruding the blended materials by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 41 to 45, the fracture strength and the fracture elongation of the development material samples decrease with the increase of the content of the contrast agent; in examples 41 to 45, the flexural modulus of the developing material samples increased with the increase in the content of the contrast agent; in examples 41 to 45, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect example 45> example 44> example 43> example 42> example 41, so the development effect of the material meets the use requirement.

Examples 46 to 50

Raw materials:

(2) Ioversol: a low-permeability non-ionic contrast medium containing triiodine for the angiography of blood vessels, such as cerebral angiography, peripheral angiography, visceral angiography, renal angiography, aortic angiography, coronary angiography, digital subtraction angiography of artery and vein, venous urethrography, CT reinforcing examination, etc is disclosed.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above embodiments 46-50, respectively, firstly, the thermoplastic polyurethane is dried in vacuum for 4 hours at 90 ℃ in a vacuum drying oven; then evenly spraying ioversol on the dried thermoplastic polyurethane, evenly mixing the ioversol and the dried thermoplastic polyurethane by using a high-speed mixer, and extruding the blended material by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 46 to 50, the fracture strength and the fracture elongation of the developing material samples decreased with the increase of the content of the contrast agent; in examples 46 to 50, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 46 to 50, the effect of the content of the contrast agent on the tear strength of the developing material samples was insignificant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect example 50> example 49> example 48> example 47> example 46, so the development effect of the material meets the use requirement.

Examples 51 to 55

Raw materials:

(2) Iopromide: a novel non-ionic hypotonic contrast medium suitable for angiography, brain and abdomen CT scan, urethrography, etc.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above examples 51 to 55, respectively, the thermoplastic polyurethane is dried in vacuum for 4 hours at 90 ℃ in a vacuum drying oven; then uniformly spraying the iopromide on the dried thermoplastic polyurethane, uniformly mixing by using a high-speed mixer, and extruding the blended material by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (4) performance testing:

and (4) conclusion:

the table shows that in examples 51 to 55, the fracture strength and the fracture elongation of the developing material samples decrease with the increase of the content of the contrast agent; in examples 51 to 55, the flexural modulus of the developing material samples increased with the increase in the content of the contrast agent; in examples 51 to 55, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect example 55> example 54> example 53> example 52> example 51 are realized, so the development effect of the material meets the use requirement.

Examples 56 to 60

Raw materials:

(2) Iohexol: the iodine in iohexol accounts for 46.4 percent by mass, has the advantages of high water solubility, low viscosity, low osmotic pressure, low toxicity and the like, and is clinically used for cerebral angiography, coronary angiography and the like.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above 56-60, respectively, firstly, drying the thermoplastic polyurethane in vacuum for 4h at 90 ℃ in a vacuum drying oven; then evenly spraying iohexol on the dried thermoplastic polyurethane, evenly mixing the mixture by a high-speed mixer, and extruding the blended material by a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 56 to 60, the fracture strength and the fracture elongation of the developing material samples decreased with the increase of the content of the contrast agent; in examples 56 to 60, the flexural modulus of the developing material samples increased with the increase in the content of the contrast agent; in examples 56 to 60, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect example 60> example 59> example 58> example 57> example 56, so the development effect of the material meets the use requirement.

Examples 61 to 65

Raw materials:

(1) Polyethylene: is a thermoplastic resin obtained by polymerizing ethylene; the polyethylene is odorless and nontoxic, feels like wax, has excellent low-temperature resistance and good chemical stability, and can resist corrosion of most of acid and alkali;

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above embodiments 61-65, the polyethylene is dried in vacuum for 4 hours at 90 ℃ in a vacuum drying oven; then evenly spraying the iodiploptide alcohol on the dried polyethylene, evenly mixing by using a high-speed mixer, and extruding the blended materials by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

heating zone	First zone	Second zone	Third zone	Fourth zone	Fifth zone	Die
							Temperature/. Degree.C	160	170	180	185	185	185

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 61 to 65, the fracture strength and the fracture elongation of the development material samples decrease with the increase of the content of the contrast agent; in examples 61 to 65, the flexural modulus of the developing material sample increased with the increase in the content of the contrast agent; in examples 61 to 65, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect embodiment 65> embodiment 64> embodiment 63> embodiment 62> embodiment 61, so the development effect of the material meets the use requirement.

Examples 66 to 70

Raw materials:

(1) Polyvinyl chloride: is a polymer obtained by polymerizing vinyl chloride monomer under the action of initiators such as peroxide and azo compounds or under the action of light and heat according to a free radical polymerization reaction mechanism.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above embodiments 66-70, respectively, firstly, the polyvinyl chloride is dried in a vacuum drying oven for 4 hours at 90 ℃; then, the iodisopeptide alcohol is evenly sprayed on the dried polyvinyl chloride, and after being evenly mixed by a high-speed mixer, the mixture is extruded by a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (3) performance testing:

and (4) conclusion:

the table shows that in examples 66-70, the fracture strength and fracture elongation of the development material samples decreased with increasing content of the contrast agent; in examples 66 to 70, the flexural modulus of the developing material samples increased with the increase in the content of the contrast agent; in examples 66 to 70, the effect of the content of the contrast agent on the tear strength of the developing material samples was not significant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect example 70> example 69> example 68> example 67> example 66, so the development effect of the material meets the use requirement.

Examples 71 to 74

Raw materials:

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the above-mentioned embodiments 71 to 74, the thermoplastic polyurethane is dried in vacuum for 4 hours at 90 ℃ in a vacuum drying oven; then evenly spraying the iodiploidol on the dried thermoplastic polyurethane, evenly mixing the materials by a high-speed mixer, and extruding the blended materials by a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (3) performance testing:

after the developing materials obtained by the preparation are respectively manufactured into corresponding developing material samples through a mould pressing process, tensile property test, tearing strength test and hardness test are respectively carried out, and the test results are shown in the following table (in order to better obtain the relationship between the content of the developing agent and the performance and the developing effect, the test results of the above examples 1, 3 and 5 are introduced here) and the attached drawings 11-14 of the specification:

and (4) conclusion:

description FIGS. 11 and 12 show that in examples 71, 1, 3,5, 72 to 74, the fracture strength and the fracture elongation of the developing material samples are reduced with the increase of the content of the contrast agent, and are significantly reduced when the content of the contrast agent is 40% or more; FIG. 13 shows that in examples 71, 1, 3,5, 72 to 74, the flexural modulus of the developing material sample increases with the increase in the content of the contrast agent; FIG. 14 shows that in examples 71, 1, 3,5, and 72 to 74, the effect of the content of the contrast medium on the tear strength of the developing material sample tends to increase.

In addition, the material can be developed in X-ray and CT examination in addition to the embodiment 71 after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect embodiment 74> embodiment 73> embodiment 72> embodiment 5> embodiment 3> embodiment 1> embodiment 71, so that the development effects of the

embodiments

1, 3,5 and 72-74 meet the use requirements.

Comparative examples 1 to 5

Raw materials:

(2) Barium sulfate: the barium sulfate is a commonly used medical imaging diagnosis medicine, is mainly used as a gastrointestinal tract contrast agent in clinic, is mainly used for developing the gastrointestinal tract by utilizing the function that the barium sulfate can absorb X rays in the gastrointestinal tract in radiological examination, and has no pharmacological effect.

The formula is as follows:

the preparation method comprises the following steps:

according to the formulas of the comparative examples 1 to 5, firstly, the thermoplastic polyurethane is dried in a vacuum drying oven for 4 hours at 90 ℃; then, uniformly spraying barium sulfate on the dried polylactic acid, uniformly mixing by using a high-speed mixer, and extruding the blended material by using a double-screw extruder at the rotating speed of 80rpm under the following temperature conditions:

And (4) performance testing:

and (4) conclusion:

the table shows that in comparative examples 1 to 5, the fracture strength and the fracture elongation of the developing material samples decrease as the content of the contrast agent increases; in comparative examples 1 to 5, the flexural modulus of the developing material sample was increased as the content of the contrast agent was increased; in comparative examples 1 to 5, the effect of the content of the contrast agent on the tear strength of the developing material samples was insignificant.

In addition, the material can be developed in X-ray and CT examination after being implanted, the development effect is improved along with the increase of the content of the developer, and the development effect is compared with 5, 4, 3, 2 and 1; however, the developing effects of comparative examples 1 to 5 were significantly inferior to those of examples 1 to 70.

Test example 1 test of developing effect of developing material samples of comparative example 5 and examples 1 to 5

Developing the developing material samples of comparative example 5 and examples 1 to 5 by using a nuclear magnetic resonance device, and placing the detection test tubes from bottom to top in sequence:

the test results are shown in the attached figure 5 of the specification:

the developing effect of the developing material samples of examples 1 to 5 became more remarkable as the content of the developer increased, and after the content of the developer increased from 10% to 20%, there was no significant difference in the image from the developing effect of the samples having the content of the developer of 25% and 30%; the developing material samples of examples 1 to 5 were compared with the developing material sample of comparative example 5 and the blank tube not filled with the developing material sample, and the developing effect tube 7> tube 6> tube 5> tube 4> tube 3> tube 2> tube 1.

Test example 2 test of developing Effect of developing Material samples of comparative example 3, example 48, example 58, example 53, example 63 and example 68

The samples of the developing materials of comparative example 3, example 48, example 58, example 53, example 63 and example 68 were developed by using a nuclear magnetic resonance apparatus, and the test tubes were placed in this order from bottom to top:

the test results are shown in the attached figure 6 of the specification:

the development effect tubes 2> tube 7 ≈ tube 6> tube 5> tube 4> tube 3> tube 1 of the detection tubes containing the developing material samples of comparative example 3, example 48, example 58, example 53, example 63, and example 68.

Further, the present invention also conducted the development effect test on comparative example 5, example 50, example 60, example 55, example 65 and example 70 with reference to the method of test example 2 described above, and the results showed development effects example 5> example 50> example 60> example 55> example 65> example 70> comparative example 5.

Further, the present invention also carried out the examination of the development effect on comparative example 4, example 49, example 59, example 54, example 64 and example 69 with reference to the method of test example 2 described above, and the results showed that the development effect example 4> example 49> example 59> example 54> example 64> example 69> comparative example 4.

Further, the present invention also carried out the examination of the development effect on comparative example 2, example 47, example 57, example 52, example 62 and example 67 with reference to the above-mentioned method of test example 2, and the results showed that the development effect example 2> example 47> example 57> example 52> example 62> example 67> comparative example 2.

Further, the present invention also carried out the examination of the development effect on comparative example 1, example 46, example 56, example 51, example 61 and example 66 with reference to the above-mentioned method of test example 2, and the results showed that the development effect example 1> example 46 > example 56 > example 51 > example 61 > example 66 > comparative example 1.

Test example 3 mechanical property effect test of developing material samples of comparative example 3, example 48, example 58, example 53, example 63, and example 68

After the developing materials prepared in comparative example 3, example 48, example 58, example 53, example 63 and example 68 were molded into corresponding developing material samples, tensile property test, tear strength test and hardness test were performed, and the test results are shown in the following table:

the line graphs of the results of the fracture strength tests of the developing materials of comparative example 3, example 48, example 58, example 53, example 63 and example 68 are shown in figure 7 of the specification,

the results of elongation at break tests for the developing materials of comparative example 3, example 48, example 58, example 53, example 63 and example 68 are shown in line drawing in figure 8 of the specification,

the results of flexural modulus tests on the developing materials of comparative example 3, example 48, example 58, example 53, example 63 and example 68 are plotted on the line of description in FIG. 9,

the tear strength test results of the developed materials of comparative example 3, example 48, example 58, example 53, example 63, and example 68 are line drawings in the specification accompanying figure 10.

Claims

1. A developable polymer composite characterized by the components comprising: 50-99 wt% of high molecular polymer and 1-60 wt% of developer; preferably, the components thereof comprise: 50-99 wt% of high molecular polymer and 1-60 wt% of nonionic developer; more preferably, the components comprise 70 to 90 weight percent of high molecular polymer and 10 to 30 weight percent of nonionic developer; most preferably, the components comprise 80wt% of high molecular polymer and 20wt% of nonionic developer.

2. The developable polymeric composite according to claim 1, further comprising an antioxidant, and/or further comprising a plasticizer.

3. A developable polymer composite material is characterized in that the components of the developable polymer composite material consist of 50 to 99 weight percent of high molecular polymer and 1 to 60 weight percent of developer; preferably, the components consist of 50 to 99 weight percent of high molecular polymer and 1 to 60 weight percent of nonionic developer; more preferably, the components thereof consist of 70 to 90wt% of the high molecular polymer and 10 to 30wt% of the nonionic developer; most preferably, the components consist of 80wt% high molecular weight polymer and 20wt% non-ionic developer.

4. A developable polymer composite material is characterized in that the components of the developable polymer composite material consist of 50 to 99 weight percent of high molecular polymer and 1 to 60 weight percent of nonionic developer, or the components consist of 50 to 99 weight percent of high molecular polymer, 1 to 60 weight percent of nonionic developer, 0.5 to 2 weight percent of antioxidant and 0.5 to 2 weight percent of plasticizer, or the components consist of 50 to 99 weight percent of high molecular polymer, 1 to 60 weight percent of nonionic developer and 0.5 to 2 weight percent of antioxidant;

more preferably, the composition comprises 70-90 wt% of high molecular polymer and 10-30 wt% of nonionic developer, or the composition comprises 70-90 wt% of high molecular polymer, 10-30 wt% of nonionic developer, 0.5-2 wt% of antioxidant and 0.5-2 wt% of plasticizer, or the composition comprises 70-90 wt% of high molecular polymer, 10-30 wt% of nonionic developer and 0.5-2 wt% of antioxidant.

5. The developable polymeric composite according to any one of claims 1 to 4, wherein the polymeric polymer is preferably polyurethane, polyglycolic acid, polyethylene, polyvinyl chloride, polypropylene, polyamide, polylactic acid, polycarbonate, polyanhydride, polycarboxyaldehyde, polyether, polyacrylate, polyurea, polystyrene, or a combination thereof; more preferably polyethylene, polyvinyl chloride, polyurethane or a combination thereof, most preferably polyurethane; the polyurethane is preferably a thermoplastic polyurethane.

6. The developable polymeric composite according to any one of claims 1 to 4, wherein the polymeric polymer is an elastomer, a homopolymer, a block copolymer, a random copolymer, a graft copolymer, or a polymer blend; and/or the range of the melt index of the high molecular polymer is 30 g-80 g/10min; and/or the hardness range of the high molecular polymer is 50-95A and/or 20-90D.

7. The developable polymer composite according to any one of claims 1 to 4, characterized in that the developer is preferably a non-ionic developer or an iodine-containing ionic developer; the non-ionic developer is preferably iodine-containing non-ionic developer, more preferably one or more of iopamidol, iohexol, ioversol, iotrolan, iodixanol, ioglucitol, iomeprol, iodophenyl ester, iopromide, iophthalic sulfide, ioxilan, iobitridol and iopentol, more preferably iopamidol or iohexol, and most preferably iopamidol; the iodine-containing ionic developer is preferably meglumine, meglumine iodide, iophostatin, iodic acid, diatrizoic acid, metrizoate, iophthalate, ioximide.

8. The developable polymer composite according to any one of claims 1 to 4, wherein the developer is in the form of a solid powder; and/or the particle size D50 of the developer is 0.5-20 microns; and/or the thickness of the developer ranges from 0.02 micrometers to 1.4 micrometers; and/or the diameter-thickness ratio of the developer is 10 to 40.

9. The developable polymer composite according to any one of claims 2 or 3, wherein the antioxidant is preferably one or a mixture of antioxidants 1010, 245, 1076 and 168.

10. Developable polymeric composite according to any of claims 2 or 3, characterized in that the plasticizer is preferably medical DINCH, citrate, medical castor oil.

11. A developable polymer composite comprising 80wt% of polyurethane and 20wt% of iohexol, or comprising 80wt% of polyurethane and 20wt% of ioversol, or comprising 80wt% of polyurethane and 20wt% of ioxadol, or comprising 80wt% of polyurethane and 20wt% of iopromide; preferably, its composition consists of 80wt% polyurethane and 20wt% ioisopeptide alcohol, or, its composition consists of 80wt% polyurethane and 20wt% iohexol; most preferably, its components consist of 80wt% polyurethane and 20wt% iodoisopeptide alcohol.

12. A method for preparing the developable polymer composite according to any one of claims 1 to 11, comprising: and uniformly spraying the developer in a solid powder form on the dried high molecular polymer, and extruding and molding the mixture through a double-screw extruder after uniformly mixing.

13. The method according to claim 12, wherein the drying temperature is 90 to 110 ℃; and/or the drying time is 2-6 h; and/or, the mixing is blending; and/or the mixing temperature is normal temperature; and/or, the mixing is carried out in a high speed mixer; and/or the twin screw extruder has more than five heating zones; and/or the extrusion temperature of the double-screw extruder is 140-200 ℃.

14. The method of claim 12, comprising: uniformly spraying 20wt% of solid powder form iodisopeptide alcohol on the dried 80wt% of polyurethane, uniformly mixing by using a high-speed mixer, and extruding and molding the mixture by using a double-screw extruder.

15. Use of the developable polymer composite of any one of claims 1 to 11 for the preparation of a medical imaging catheter.

16. The use of claim 15, wherein the medical visualization catheter includes, but is not limited to, a balloon dilation catheter, central venous catheter, trocar peripheral catheter, enteral feeding catheter, urinary catheter.

17. The use of claim 15, wherein the medical visualization catheter includes, but is not limited to, for delivering oxygen, blood, cerebrospinal fluid, urine, gastric fluid, nutrient solution, injection solution, drug solution.