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CN-118496758-B - Modified polyimide pipe and preparation method and application thereof

CN118496758BCN 118496758 BCN118496758 BCN 118496758BCN-118496758-B

Abstract

The invention relates to a modified polyimide pipe and a preparation method and application thereof. The preparation method of the modified polyimide pipe comprises the following steps of modifying graphite oxide powder by using organic amine to obtain graphite oxide powder with amino groups, modifying the graphite oxide powder with amino groups by using a silane coupling agent and/or dianhydride to prepare modified graphite oxide powder, mixing the modified graphite oxide powder with a polyamic acid solution to prepare a mixed solution, coating a core material by using the mixed solution, and then carrying out imidization reaction and core pulling to prepare the modified polyimide pipe. The preparation method of the modified polyimide pipe can improve the mechanical property and the lubricating property of polyimide, and the outer surface is smooth.

Inventors

  • QIN MINGLIN
  • LI ZHAOMIN
  • MENG FANLIANG
  • YIN ZIWEI
  • GAO BINGQI

Assignees

  • 浙江脉通智造科技(集团)有限公司
  • 创脉医疗科技(上海)有限公司

Dates

Publication Date
20260508
Application Date
20230215

Claims (10)

  1. 1. The preparation method of the modified polyimide pipe is characterized by comprising the following steps of: Modifying graphite oxide powder by using organic amine to obtain graphite oxide powder with an amino group, wherein the particle size of the graphite oxide powder is 2000-3000 meshes, and the preparation of the graphite oxide powder with the amino group comprises the steps of dispersing the graphite oxide powder in a first polar solvent, then mixing with the organic amine at 10-30 ℃ for reaction for 30-40 min, then heating to 40-60 ℃ for continuous reaction for 40-60 min, and finally heating to 70-80 ℃ for reaction for 40-60 min; modifying the graphite oxide powder with the amino group by using a silane coupling agent to prepare modified graphite oxide powder; Mixing the modified graphite oxide powder with polyamic acid solution to prepare mixed solution, and And coating the core material by using the mixed solution, and then carrying out imidization reaction and core pulling to prepare the modified polyimide pipe.
  2. 2. The method for producing a modified polyimide tubing according to claim 1, wherein the step of producing the graphite oxide powder having an amino group satisfies any one or more of the following conditions: (1) The mass ratio of the graphite oxide powder to the organic amine is 1 (1.5-3); (2) The organic amine comprises any one or a combination of more of 4-4' -diaminodiphenyl ether, 4-phenylbutylamine, N-butylaniline, 2, 6-diethylaniline and 3, 4-dimethylaniline, and (3) The first polar solvent is selected from any one or a combination of a plurality of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
  3. 3. The method for preparing the modified polyimide pipe according to claim 1, wherein the step of modifying the graphite oxide powder having an amino group with the silane coupling agent comprises the steps of ultrasonically stirring the graphite oxide powder having an amino group and the silane coupling agent in absolute ethyl alcohol at 50-60 ℃ for 1-1.5 h, and then washing and drying, wherein the mass ratio of the silane coupling agent to the graphite oxide powder is (1-3): 100.
  4. 4. The method for producing a modified polyimide pipe according to claim 3, wherein the silane coupling agent is selected from the group consisting of any one or more of an epoxy silane coupling agent, an amino silane coupling agent and a methacryloxy silane coupling agent, or the silane coupling agent is selected from the group consisting of any one or more of gamma- (2, 3-glycidoxypropyl) propyl trimethoxy silane, gamma-methacryloxy propyl trimethoxy silane and gamma-aminopropyl triethoxy silane.
  5. 5. The method for producing a modified polyimide tubing according to claim 1, wherein the silane coupling agent comprises gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
  6. 6. The method for producing a modified polyimide pipe according to claim 1, wherein the temperature is 80 ℃ to 400 ℃ during imidization.
  7. 7. The method for producing a modified polyimide tubing according to claim 1, wherein the mass ratio of the modified graphite oxide powder to the polyamic acid solution is (0.5-5): 100, and the concentration of the polyamic acid solution is 13-17% by mass.
  8. 8. A modified polyimide pipe, characterized in that it is prepared by the method for preparing a modified polyimide pipe according to any one of claims 1 to 7.
  9. 9. The use of the modified polyimide tubing of claim 8 in the manufacture of medical devices.
  10. 10. A medical device comprising the modified polyimide tubing of claim 8.

Description

Modified polyimide pipe and preparation method and application thereof Technical Field The invention relates to the field of medical materials, in particular to a modified polyimide pipe and a preparation method and application thereof. Background Polyimide (PI) is a high-performance polymer with an imide ring (-CO-NH-CO-) on a main chain, has excellent thermal stability, good mechanical property and dielectric property, and is widely applied to the fields of electrical insulation, microelectronics industry, aerospace industry and the like. The polyimide is synthesized through dissolving diamine in polar solvent, adding dianhydride monomer, ring opening addition reaction with diamine to produce polyamide acid of high molecular weight, and high temperature dewatering cyclization to obtain polyimide. Along with the development of the minimally invasive interventional therapy technology, the application of medical interventional tubes is also becoming wider and wider. The polyimide catheter has excellent bending resistance, pushing resistance, irradiation resistance and chemical stability, can realize continuous manufacture of micron-sized thin-wall thin-diameter tubes, is widely used clinically as a minimally invasive interventional treatment catheter, becomes a first-choice material of an intravascular treatment polymer catheter, and is widely used for various medicines and stent delivery catheters, endoscopes, electrophysiological and diagnostic catheters, neurovascular instruments, cardiac ablation instruments, varicose vein therapeutic instruments, internal vascular pressure sensors, renal calculus removal instruments, ablation equipment for pain treatment and the like. The catheter needs to be safely and effectively delivered to the position of the treatment target in the interventional treatment process, so that the interventional treatment has higher requirements on the mechanical properties of the catheter, such as the strength of the tube and the lubricity of the inner surface, and appearance requirements, such as the black of the catheter and the smooth and concave-convex-free outer surface of the catheter, but the mechanical properties of the PI tube are extremely high due to the process and the like, the color is brown, and the PI tube needs to be modified. The graphite oxide powder has the characteristics of super high temperature resistance, high strength, good lubricity, good chemical stability and the like, is an ideal nano reinforcing material, and can improve the mechanical property, the lubricating property and the like of polyimide, but because the graphite oxide powder has the characteristics of large specific surface area and strong van der Waals force effect, the graphite oxide powder is easy to agglomerate, so that the load transfer effect is reduced, the mechanical property and the lubricating property of the pipe are reduced, the outer surface of the agglomerated graphite oxide powder is uneven, and the surface of the pipe is rough. Disclosure of Invention Based on the above, it is necessary to provide a modified polyimide pipe and a method for preparing the same, so as to improve the mechanical properties and the lubrication properties of polyimide and to smooth the outer surface. In addition, it is also necessary to provide an application of the modified polyimide tubing. A preparation method of a modified polyimide pipe comprises the following steps: The preparation method comprises the steps of dispersing the graphite oxide powder in a first polar solvent, mixing the graphite oxide powder with the organic amine at 10-30 ℃ for reaction for 30-40 min, heating to 40-60 ℃ for continuous reaction for 40-60 min, and heating to 70-80 ℃ for reaction for 40-60 min; modifying the graphite oxide powder with the amino group by using a silane coupling agent and/or dianhydride to prepare modified graphite oxide powder; Mixing the modified graphite oxide powder with polyamic acid solution to prepare mixed solution, and And coating the core material by using the mixed solution, and then carrying out imidization reaction and core pulling to prepare the modified polyimide pipe. In one embodiment, the imidization reaction temperature is 150 ℃ to 400 ℃. In one embodiment, the step of preparing the graphite oxide powder having an amino group satisfies any one or several of the following conditions: (1) The mass ratio of the graphite oxide powder to the organic amine is 1 (1.5-3); (2) The organic amine comprises any one or a combination of more of 4-4' -diaminodiphenyl ether, 4-phenylbutylamine, N-butylaniline, 2, 6-diethylaniline and 3, 4-dimethylaniline, and (3) The first polar solvent is selected from any one or a combination of a plurality of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone. In one embodiment, the step of modifying the graphite oxide powder with the amino group by using the silane coupling agent comprises the steps of ultrasonically stirring the graphite oxide p