Surface treatment method of fluorine-containing resin catheter

Abstract

The present invention relates to the field of fluororesin catheter surface treatment methods, and specifically discloses a fluororesin catheter surface treatment method, comprising the following steps: 1) stirring more than 90% anhydrous ethanol and a silane coupling agent under sealed conditions at a stirring temperature of 15-35°C; 2) adding sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, and stirring; 3) allowing the stirred mixture to rest in a static crushing bottle, during which a weight is installed on a movable rod to compress the cylinder to accelerate precipitation, and after the bismuth powder is precipitated, solid-liquid separation is performed; the separated bismuth powder is injected into the static crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, during which the bismuth powder is ground using a tablet at the bottom of the movable rod in combination with a grinding ball, and the rinsing is repeated three times. The present invention solves the problem that during the processing process, the bismuth powder cannot be evenly dispersed in the PTFE base material, but is distributed on the tube in the form of agglomerates, thereby making the tube appear rough.

Description

Technical Field

[0001] The invention relates to the field of surface treatment methods for fluorine-containing resin catheters, and in particular to a surface treatment method for fluorine-containing resin catheters. Background Art

[0002] At present, PTFE tubes used in medical devices often add some fillers to the initial base material according to different uses and performance requirements. This is used to improve the hardness, development performance, wear resistance, tensile strength, etc. of the formed tubes to meet different usage needs. In addition to the choice of filler, the filler content, distribution uniformity, and dispersion all greatly affect the effect to be achieved by the tube.

[0003] During the processing of fluororesin tubing, bismuth powder is typically added to the PTFE base material, resulting in a rough surface on the extruded tube. This is because the bismuth powder's small particle size prevents it from being evenly dispersed in the PTFE base material due to molecular agglomeration. Instead, the powder forms aggregates throughout the tube, resulting in a rough surface. Summary of the Invention

[0004] In response to the above problems, the present invention proposes a surface treatment method for fluororesin catheters, which solves the defect that bismuth powder cannot be evenly dispersed in the PTFE base material during the existing fluororesin catheter processing, but is distributed on the tube in the form of agglomerates, resulting in a rough surface of the tube.

[0005] The technical solution adopted by the present invention is as follows:

[0006] A method for treating the surface of a fluorine-containing resin catheter comprises the following steps:

[0007] 1) Stir more than 90% anhydrous ethanol and silane coupling agent in a sealed container at a stirring temperature of 15-35° C.;

[0008] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent and stirring;

[0009] 3) allowing the stirred mixture to stand in a stationary crushing bottle, during which a heavy object is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground using the pressing tablet at the bottom of the movable rod in combination with the grinding ball, and the rinsing is repeated three times.

[0010] The product prepared by the present invention has good surface quality and a smooth feel; the bismuth powder is evenly dispersed without agglomeration, and has a good development effect; and the apparent color is good and uniform. The present invention solves the defect in the existing fluororesin catheter processing process that the bismuth powder cannot be evenly dispersed in the PTFE base material, but is distributed on the tube in the form of agglomeration, thereby making the tube appear rough.

[0011] Optionally, in step 2), the stirring speed is 80-180 rpm, the stirring temperature is set to 60-80° C., and the time is 4-8 h.

[0012] Optionally, the bismuth powder treated in step 3) is placed in a vacuum drying oven for drying at a temperature of 80-140° C. for 4-8 hours.

[0013] Optionally, the dried bismuth powder is placed in a blender and ground into powder.

[0014] Optionally, a propellant is added to the ground material for mixing.

[0015] Optionally, the mixed materials are sealed and left to stand at 23-27° C. for 5 to 15 hours for aging.

[0016] Optionally, the air in the powder after the extrusion auxiliary agent is added to the matured material is removed, and the paste resin is pressed into a blank corresponding to the barrel of the wire pusher, and the blank is pre-pressed into shape, dried, and sintered.

[0017] Optionally, the rotation speed in step 1) is 60-130 rpm, and the time is set to 30-60 min.

[0018] Optionally, the silane coupling agent includes one or more of KH550, KH560, and KH570.

[0019] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0020] 1) Stirring bismuth powder with 90% or more anhydrous ethanol at a temperature of 15-35° C., a speed of 60-130 rpm, and a stirring time of 30-60 minutes;

[0021] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; stirring at a speed of 80-180 rpm, a temperature of 60-80° C., and a stirring time of 4-8 hours;

[0022] 3) allowing the stirred mixture to stand in a stationary crushing bottle, during which a heavy object is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground using the pressing tablet at the bottom of the movable rod in combination with the grinding ball, and the rinsing is repeated three times.

[0023] Beneficial effects

[0024] 1. The present invention uses coupling treatment of bismuth powder,

[0025] 2. The relatively sealed stirring in the present invention avoids excessive hydrolysis of the coupling agent.

[0026] 3. The product prepared by the present invention has good surface quality and smooth feel; the bismuth powder is evenly dispersed without agglomeration, and the developing effect is good; and the apparent color is good and uniform.

[0027] 4. The movable rod of the present invention is equipped with a weight to compress the cylinder to accelerate sedimentation, thereby facilitating the separation of solid and liquid.

[0028] 5. The present invention utilizes the pressing tablet at the bottom of the movable rod in conjunction with the grinding balls and the frosted surface at the bottom of the bottle body to grind the bismuth powder. It utilizes stirring to grind the bismuth powder, thereby preventing the bismuth powder from agglomerating and affecting the drying efficiency, and reducing the time required for subsequent grinding of the dried bismuth powder in the mixer.

[0029] 6. The present invention includes at least a plurality of grinding balls evenly distributed around the filter capsule to form an annular structure. The stirring arc plate stirs the bismuth powder to promote the washing away of the silane coupling agent remaining on the bismuth powder, thereby improving the cleaning efficiency. On the other hand, the stirring arc plate also loosens the bismuth powder, and the liquid flows out of the filter capsule at a rapid rate in the spiral downward direction, thereby improving the cleaning efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a perspective view of a stationary crushing bottle in a method for treating the surface of a fluorine-containing resin catheter according to Example 5 of the present invention.

[0031] Figure 2 This is a perspective view of the grinding balls of a stationary crushing bottle in a method for treating the surface of a fluorine-containing resin catheter according to Example 5 of the present invention.

[0032] Figure 3 This is a top view of a filter capsule of a static crushing bottle in a method for treating the surface of a fluororesin catheter according to Example 5 of the present invention.

[0033] The reference numerals in the figures are:

[0034] 1. Spherical bottle body, 2. Tube body, 3. Cylinder body, 4. Connecting tube, 5. Filter capsule, 6. Grinding ball, 7. Movable rod, 8. Grinding sheet, 9. Sealing ring, 10. Stirring arc plate, 11. Limiting ring, 12. Limiting part. DETAILED DESCRIPTION

[0035] The following examples are used to illustrate the present invention but are not intended to limit the scope of the present invention.

[0036] The silane coupling agent of the present invention can be a product of Hangzhou Jessica Chemical Co., Ltd.

[0037] In the description of the present invention, unless otherwise specified, the terms "upper", "lower", "left", "right", "inside", "outside", "front end", "rear end", "head", "tail" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings. They are only for the convenience of describing the present invention and simplifying the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, they cannot be understood as limitations on the present invention. In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "connected" and "connected" should be understood in a broad sense. For example, they can be fixedly connected, detachably connected, or integrally connected; they can be mechanically connected, directly connected, or indirectly connected through an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0038] Example 1

[0039] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0040] 1) Stir more than 90% of anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 15° C., a rotation speed of 60 rpm, and a stirring time of 30 minutes.

[0041] In this embodiment, the silane coupling agent used is KH550.

[0042] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 80 rpm, a temperature of 60° C., and a stirring time of 4 h;

[0043] 3) allowing the stirred mixture to stand in a stationary crushing bottle, during which a heavy object is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground using the pressing tablet at the bottom of the movable rod in combination with the grinding ball, and the rinsing is repeated three times.

[0044] 4) The treated bismuth powder was placed in a vacuum drying oven and dried at a temperature of 80° C. for 4 h.

[0045] The dried bismuth powder is put into a blender and ground into powder.

[0046] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0047] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0048] Example 2

[0049] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0050] 1) Stir more than 90% of anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 35° C., a rotation speed of 130 rpm, and a stirring time of 60 minutes.

[0051] In this embodiment, the silane coupling agent used is KH560.

[0052] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 180 rpm, a temperature of 80° C., and a stirring time of 8 hours;

[0053] 3) allowing the stirred mixture to stand in a stationary crushing bottle, during which a heavy object is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground using the pressing tablet at the bottom of the movable rod in combination with the grinding ball, and the rinsing is repeated three times.

[0054] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0055] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0056] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0057] Comparative Example 1

[0058] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0059] 1) Stir more than 90% of anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 25° C., a rotation speed of 100 rpm, and a stirring time of 45 minutes.

[0060] In this embodiment, the silane coupling agent used is KH550.

[0061] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 120 rpm, a temperature of 25° C., and a stirring time of 6 hours;

[0062] 3) the stirred mixture is allowed to stand in a stationary crushing bottle, and after the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground, and the rinsing is repeated three times.

[0063] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 80° C. for 4 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0064] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0065] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0066] Comparative Example 2

[0067] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0068] 1) Stir more than 90% of anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 25° C., a rotation speed of 100 rpm, and a stirring time of 45 minutes.

[0069] In this embodiment, the silane coupling agent used is KH550.

[0070] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 120 rpm, a temperature of 70° C., and a stirring time of 45 minutes;

[0071] 3) the stirred mixture is allowed to stand in a stationary crushing bottle, and after the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground, and the rinsing is repeated three times.

[0072] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 80° C. for 4 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0073] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0074] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0075] Comparative Example 3

[0076] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0077] 1) Stir more than 90% anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 25° C., a rotation speed of 100 rpm, and a stirring time of 2 hours.

[0078] In this embodiment, the silane coupling agent used is KH550.

[0079] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 120 rpm, a temperature of 70° C., and a stirring time of 45 minutes;

[0080] 3) the stirred mixture is allowed to stand in a stationary crushing bottle, and after the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground, and the rinsing is repeated three times.

[0081] 4) The treated bismuth powder was placed in a vacuum drying oven and dried at a temperature of 80° C. for 6 hours. The dried bismuth powder was placed in a blender and ground into powder.

[0082] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0083] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0084] Comparative Example 4

[0085] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0086] 1) Stir more than 90% anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 25° C., a rotation speed of 50 rpm, and a stirring time of 45 minutes.

[0087] In this embodiment, the silane coupling agent used is KH550.

[0088] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 50 rpm, a temperature of 70° C., and a stirring time of 6 h;

[0089] 3) the stirred mixture is allowed to stand in a stationary crushing bottle, and after the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground, and the rinsing is repeated three times.

[0090] 4) The treated bismuth powder was placed in a vacuum drying oven and dried at a temperature of 80° C. for 6 hours. The dried bismuth powder was placed in a blender and ground into powder.

[0091] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0092] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0093] Comparative Example 5

[0094] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0095] 1) Stir more than 90% of anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 25° C., a rotation speed of 200 rpm, and a stirring time of 45 minutes.

[0096] In this embodiment, the silane coupling agent used is KH560.

[0097] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 200 rpm, a temperature of 70° C., and a stirring time of 6 hours;

[0098] 3) the stirred mixture is allowed to stand in a stationary crushing bottle, and after the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground, and the rinsing is repeated three times.

[0099] 4) The treated bismuth powder was placed in a vacuum drying oven and dried at a temperature of 80° C. for 6 hours. The dried bismuth powder was placed in a blender and ground into powder.

[0100] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0101] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0102] Comparative Example 6

[0103] The present invention discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0104] 1) Stir more than 90% anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 25° C., a rotation speed of 50 rpm, and a stirring time of 45 minutes.

[0105] In this embodiment, the silane coupling agent used is KH560.

[0106] 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent, stirring at a speed of 200 rpm, a temperature of 70° C., and a stirring time of 6 hours;

[0107] 3) the stirred mixture is allowed to stand in a stationary crushing bottle, and after the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground, and the rinsing is repeated three times.

[0108] 4) The treated bismuth powder was placed in a vacuum drying oven and dried at a temperature of 80° C. for 6 hours. The dried bismuth powder was placed in a blender and ground into powder.

[0109] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0110] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0111] The test data of Comparative Examples 1 to 6 are as follows:

[0112] Comparative Example 1: Bismuth powder was not sufficiently coupled, and agglomerates appeared after drying. The produced tube had white lumps / white lines on its surface.

[0113] Comparative Example 2: Bismuth powder was not sufficiently coupled, and agglomerates appeared after drying. The produced tube had white lumps / white lines on its surface.

[0114] Comparative Example 3: Excessive hydrolysis caused the mixture to be too viscous to be stirred by adding bismuth powder.

[0115] Comparative Example 4: Bismuth powder was not sufficiently coupled, and agglomerates appeared after drying. The produced tube had white lumps / white lines on its surface.

[0116] Comparative Example 5: Excessive hydrolysis caused the mixture to be too viscous to be stirred by adding bismuth powder.

[0117] Comparative Example 6: Bismuth powder was not fully coupled, and agglomerates appeared after drying. The produced tube had white lumps / white lines on its surface.

[0118] In the above comparative example, the maximum tensile strength is 33 MPa and the tensile force is 141.9 N.

[0119] In Example 1: the test tube specifications used are an inner diameter of 2.25mm, an outer diameter of 3.25mm, an outer diameter of the core rod of 2.51mm, an inner diameter of the die of 3.58mm, an inner diameter of the cylinder of 50mm, and the base material is F-208H. The blank passes through different sintering temperature zones in sequence, and the sintering temperatures are 180°C, 240°C, 360°C, and 390°C in sequence. Among them, the main machine speed is 11m / min, the apparent color is uniform, there is no obvious white mass / white line, its maximum tensile force is 179N, and the tensile strength is 41.6Mpa.

[0120] In Example 2: the test tube specifications used are an inner diameter of 2.25mm, an outer diameter of 3.25mm, an outer diameter of the core rod of 2.51mm, an inner diameter of the die of 3.58mm, an inner diameter of the cylinder of 50mm, and the base material is F-208H. The blank passes through different sintering temperature zones in sequence, and the sintering temperatures are 180°C, 240°C, 360°C, and 390°C in sequence. Among them, the main machine speed is 11m / min, the apparent color is uniform, there is no obvious white mass / white line, its maximum tensile force is 168.56N, and the tensile strength is 39.2Mpa.

[0121] Example 3

[0122] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0123] 1) Stir bismuth powder with 90% or more anhydrous ethanol at 15°C, 60 rpm, and for 30 minutes;

[0124] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions at a stirring speed of 80 rpm, a stirring temperature of 60° C., and a stirring time of 4 hours;

[0125] 3) allowing the stirred mixture to stand in a stationary crushing bottle, during which a heavy object is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground using the pressing tablet at the bottom of the movable rod in combination with the grinding ball, and the rinsing is repeated three times.

[0126] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 80° C. for 4 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0127] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 23°C for 5 hours for aging.

[0128] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0129] Example 4

[0130] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0131] 1) Stirring bismuth powder with 90% or more anhydrous ethanol at 35° C., 130 rpm, and 60 min;

[0132] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; the stirring speed is 180 rpm, the stirring temperature is 80° C., and the stirring time is 8 hours;

[0133] 3) allowing the stirred mixture to stand in a stationary crushing bottle, during which a heavy object is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the bismuth powder is ground using the pressing tablet at the bottom of the movable rod in combination with the grinding ball, and the rinsing is repeated three times.

[0134] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0135] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0136] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0137] Comparative Example 7:

[0138] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0139] 1) Stirring bismuth powder with 90% or more anhydrous ethanol at 25° C., 100 rpm, and 2 h;

[0140] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; the stirring temperature is 25° C., the speed is 120 rpm, and the time is set to 6 hours;

[0141] 3) the stirred mixture was allowed to stand in a stationary crushing bottle, and after the bismuth powder was precipitated, the solid and liquid were separated; the separated bismuth powder was injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the rinsing was repeated three times.

[0142] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0143] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0144] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0145] Comparative Example 8:

[0146] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0147] 1) Stirring bismuth powder with 90% or more anhydrous ethanol at 25° C., 100 rpm, and 2 h;

[0148] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; the stirring temperature is 70° C., the speed is 120 rpm, and the time is set to 45 minutes;

[0149] 3) the stirred mixture was allowed to stand in a stationary crushing bottle, and after the bismuth powder was precipitated, the solid and liquid were separated; the separated bismuth powder was injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the rinsing was repeated three times.

[0150] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0151] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0152] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0153] Comparative Example 9:

[0154] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0155] 1) Stirring bismuth powder with 90% or more anhydrous ethanol at a temperature of 25° C., a speed of 100 rpm, and a stirring time of 45 minutes;

[0156] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; the stirring temperature is 25° C., the speed is 120 rpm, and the time is set to 6 hours;

[0157] 3) the stirred mixture was allowed to stand in a stationary crushing bottle, and after the bismuth powder was precipitated, the solid and liquid were separated; the separated bismuth powder was injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the rinsing was repeated three times.

[0158] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0159] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0160] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0161] Comparative Example 10:

[0162] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0163] 1) Stir bismuth powder with 90% or more anhydrous ethanol at 25°C, 50 rpm, and for 2 hours;

[0164] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; the stirring temperature is 70° C., the speed is 120 rpm, and the time is set to 6 hours;

[0165] 3) the stirred mixture was allowed to stand in a stationary crushing bottle, and after the bismuth powder was precipitated, the solid and liquid were separated; the separated bismuth powder was injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the rinsing was repeated three times.

[0166] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0167] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0168] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0169] Comparative Example 11:

[0170] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0171] 1) Stirring bismuth powder with 90% or more anhydrous ethanol at 25° C., 200 rpm, and 2 h;

[0172] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; the stirring temperature is 70° C., the speed is 120 rpm, and the time is set to 6 hours;

[0173] 3) the stirred mixture was allowed to stand in a stationary crushing bottle, and after the bismuth powder was precipitated, the solid and liquid were separated; the separated bismuth powder was injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the rinsing was repeated three times.

[0174] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0175] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0176] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0177] Comparative Example 12:

[0178] The present invention also discloses a method for treating the surface of a fluorine-containing resin catheter, comprising the following steps:

[0179] 1) Stir bismuth powder with 90% or more anhydrous ethanol at 25°C, 50 rpm, and for 2 hours;

[0180] 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions; the stirring temperature is 70° C., the speed is 200 rpm, and the time is set to 6 hours;

[0181] 3) the stirred mixture was allowed to stand in a stationary crushing bottle, and after the bismuth powder was precipitated, the solid and liquid were separated; the separated bismuth powder was injected into the stationary crushing bottle with anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and the rinsing was repeated three times.

[0182] 4) The treated bismuth powder is placed in a vacuum drying oven and dried at a temperature of 140° C. for 8 hours. The dried bismuth powder is placed in a blender and ground into powder.

[0183] 5) Add a propellant to the ground material and mix it. Seal the mixed material and let it stand at 27°C for 15 hours for aging.

[0184] 6) Remove the air from the powder after adding the extrusion auxiliary agent after the matured material, and press the paste resin into a blank corresponding to the barrel of the wire pusher, pre-press the blank into shape, dry it, and sinter it.

[0185] The test data of Comparative Examples 7 to 12 are as follows:

[0186] Comparative Example 1: Bismuth powder was not sufficiently coupled, and agglomerates appeared after drying. The produced tube had white lumps / white lines on its surface.

[0187] Comparative Example 2: Bismuth powder was not sufficiently coupled, and agglomerates appeared after drying. The produced tube had white lumps / white lines on its surface.

[0188] Comparative Example 3: Bismuth powder was not coupled sufficiently, and agglomerates appeared after drying. White clumps / white lines appeared on the surface of the produced tube.

[0189] Comparative Example 4: Bismuth powder was not sufficiently coupled, and agglomerates appeared after drying. The produced tube had white lumps / white lines on its surface.

[0190] Comparative Example 5: Bismuth powder easily splashes on the bottle wall, causing waste.

[0191] Comparative Example 6: Bismuth powder easily splashes on the bottle wall, causing waste.

[0192] In the above comparative example, the maximum tensile strength is 32.5 MPa and the tensile force is 139.75 N.

[0193] In Example 1: the test tube specifications used are an inner diameter of 2.25mm, an outer diameter of 3.25mm, an outer diameter of the core rod of 2.51mm, an inner diameter of the die of 3.58mm, an inner diameter of the cylinder of 50mm, and the base material is F-208H. The blank passes through different sintering temperature zones in sequence, and the sintering temperatures are 180°C, 240°C, 360°C, and 390°C in sequence. Among them, the main machine speed is 11m / min, the apparent color is uniform, there is no obvious white mass / white line, its maximum tensile force is 179N, and the tensile strength is 41.6Mpa.

[0194] In Example 2: the test tube specifications used are an inner diameter of 2.25mm, an outer diameter of 3.25mm, an outer diameter of the core rod of 2.51mm, an inner diameter of the die of 3.58mm, an inner diameter of the cylinder of 50mm, and the base material is F-208H. The blank passes through different sintering temperature zones in sequence, and the sintering temperatures are 180°C, 240°C, 360°C, and 390°C in sequence. Among them, the main machine speed is 11m / min, the apparent color is uniform, there is no obvious white mass / white line, its maximum tensile force is 168.56N, and the tensile strength is 39.2Mpa.

[0195] Example 5

[0196] like Figure 1 、 Figure 2 and Figure 3 As shown, the static crushing bottle in the present invention includes a spherical bottle body 1 with a flat bottom, a tube body 2 connected to the spherical bottle body, and a cylinder body 3 inserted into the tube body of the spherical bottle body. The flat bottom of the spherical bottle body is a frosted structure. A detachable connecting cylinder 4 is installed at the bottom of the cylinder body, and a filter capsule 5 made of flexible filter material is fixedly connected to the bottom of the connecting cylinder. A plurality of grinding balls 6 are fixed on the filter capsule; a movable rod 7 is inserted into the cylinder body, and a grinding sheet 8 is provided at the bottom of the movable rod. The bottom surface of the grinding sheet is a frosted structure, and the periphery of the grinding sheet is an elastic sealing ring 9. The surface of the frosted ball located on the inner side of the filter capsule is provided with an arc-shaped stirring arc plate 10, and the diameter of the stirring arc plate gradually converges from the bottom to the top. A limiting ring 11 is provided at the top of the connecting cylinder, and limiting parts 12 are provided at both ends of the limiting ring.

[0197] At least a plurality of grinding balls are evenly distributed around the filter capsule to form an annular structure, and the center lines of the abdomens of the stirring arc plates in the annular structure are all arranged clockwise.

[0198] In this embodiment, the connecting cylinder can be connected to the cylinder body through a threaded structure or a snap-fit ​​structure.

[0199] In this embodiment, the spherical bottle body, the tube body and the cylinder body are all made of glass.

[0200] During the implementation of this embodiment, the stirred mixed liquid is allowed to stand in a static crushing bottle, during which time a heavy object is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the static crushing bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder, and during this period, the pressing tablet at the bottom of the movable rod is used in conjunction with the grinding ball to grind the bismuth powder, and the rinsing is repeated three times; the pressing tablet at the bottom of the movable rod is used in conjunction with the grinding ball and the frosted surface of the bottom of the bottle body to grind the bismuth powder, which utilizes stirring to grind the bismuth powder, thereby avoiding bismuth powder agglomeration that affects the drying efficiency, and reducing the time required for the dried bismuth powder to be put into the mixer for grinding.

[0201] On the one hand, the stirring arc plate stirs the bismuth powder to promote the washing away of the silane coupling agent remaining on the bismuth powder, thereby improving the cleaning efficiency. On the other hand, the stirring arc plate also loosens the bismuth powder, and the liquid flows out of the filter capsule at a rapid rate in the spiral downward direction, thereby improving the cleaning efficiency.

[0202] The above description is only a preferred embodiment of the present invention and does not limit the scope of patent protection of the present invention. Any equivalent structural transformation made by using the contents of the description and drawings of the present invention, directly or indirectly applied to other related technical fields, is also included in the scope of protection of the present invention.

Claims

1. A method for treating the surface of a fluorine-containing resin catheter, characterized in that: The following steps are involved: 1) Stirring more than 90% anhydrous ethanol and a silane coupling agent in a sealed container at a temperature of 15-35° C., a speed of 60-130 rpm, and a stirring time of 30-60 minutes; 2) adding the sieved bismuth powder to the stirred mixture of ethanol and silane coupling agent and stirring; 3) The stirred mixture of bismuth powder, ethanol, and silane coupling agent is allowed to stand in a stationary grinding bottle, during which a weight is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary grinding bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder. During this period, the bismuth powder is ground using a pressing tablet at the bottom of the movable rod in combination with a grinding ball, and the rinsing is repeated three times.

2. A fluorine-containing resin catheter surface treatment method according to claim 1, characterized in that: In step 2), the stirring speed is 80-180 rpm, the stirring temperature is set to 60-80° C., and the stirring time is 4-8 hours.

3. A fluorine-containing resin catheter surface treatment method according to claim 1 or 2, characterized in that: The bismuth powder treated in step 3) is placed in a vacuum drying oven and dried at a temperature of 80-140° C. for 4-8 hours.

4. A fluorine-containing resin catheter surface treatment method according to claim 3, characterized in that: Put the dried bismuth powder into a blender and grind it into powder.

5. The method for treating the surface of a fluorine-containing resin catheter according to claim 4, wherein: A propellant is added to the ground material for mixing.

6. The method for treating the surface of a fluorine-containing resin catheter according to claim 5, wherein: The mixed materials are sealed and left to stand at 23-27°C for 5-15 hours for aging.

7. A fluorine-containing resin catheter surface treatment method according to claim 6, characterized in that: The air in the powder after the extrusion auxiliary agent is added to the matured material is removed, and the paste resin is pressed into a blank corresponding to the barrel of the wire pusher. The blank is pre-pressed into shape, dried, and sintered.

8. The method for treating the surface of a fluorine-containing resin catheter according to claim 4, wherein: The rotation speed in step 1) is 60-130 rpm, and the time is set to 30-60 min.

9. A fluorine-containing resin catheter surface treatment method according to claim 1 or 2, characterized in that: The silane coupling agent includes one or more of KH550, KH560, and KH570.

10. A method for treating the surface of a fluorine-containing resin catheter, characterized in that: The following steps are involved: 1) Stirring bismuth powder with 90% or more anhydrous ethanol at a temperature of 15-35° C., a speed of 60-130 rpm, and a stirring time of 30-60 minutes; 2) adding a silane coupling agent to the stirred mixture of ethanol and bismuth powder, and stirring under sealed conditions at a stirring speed of 80-180 rpm, a stirring temperature of 60-80° C., and a stirring time of 4-8 hours; 3) The stirred mixture of bismuth powder, ethanol, and silane coupling agent is allowed to stand in a stationary grinding bottle, during which a weight is installed on the movable rod to compress the cylinder to accelerate precipitation. After the bismuth powder is precipitated, the solid and liquid are separated; the separated bismuth powder is injected into the stationary grinding bottle using anhydrous ethanol to rinse off the silane coupling agent remaining on the bismuth powder. During this period, the bismuth powder is ground using a pressing tablet at the bottom of the movable rod in combination with a grinding ball, and the rinsing is repeated three times.

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