Developable thermoplastic polyurethane composite material for interventional catheter and preparation method of developable thermoplastic polyurethane composite material
By using thermoplastic polyurethane composite materials in the intervention catheter materials, combined with the drying and extrusion blending process, the problems of poor development effect and insufficient mechanical strength of the existing intervention catheter materials are solved, and the developer dispersion is stable, good mechanical properties are achieved. Good biocompatible effect.
Patent Information
- Application Number
- CN202411427690.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2025-02-11
AI Technical Summary
The existing interventional catheter materials have poor development effects, poor mechanical strength, poor biocompatibility, unstable dispersion of the developer, easy to migrate the surface, and high manufacturing cost.
Using thermoplastic polyurethane composite material, containing 40-95% thermoplastic polyurethane elastomer and 5-60% developer, it is prepared by drying and extrusion blending process, and the developer is added from the side feeding port of the extruder to stabilize the Disperse and reduce surface migration.
It has achieved stable dispersion of the developer, good mechanical properties, good biocompatibility, good development effect, high flexibility and not easy to break or deform. It has a simple preparation method, low cost and environmentally friendly, and is suitable for large-scale industrialization.
Smart Images
Figure CN119405906A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of medical polymer composite materials, in particular to a developable thermoplastic polyurethane composite material for interventional catheters and a preparation method thereof. Background Art
[0002] Thermoplastic polyurethane elastomer is a kind of block polymer containing alternating hard segments and soft segments. The hard segment comes from the diisocyanate in the reactants, while the soft segment is mainly some low molecular weight polyester polyols, polyether polyols or polycarbonate polyols. The hard segment can act as a physical cross-linking point in the matrix, and the soft segment plays a role in providing elasticity. By selecting the appropriate ratio of soft and hard segments, polyurethane elastomer products with specific applications can be synthesized. It is a polymer material between rubber and plastic, and has a very wide range of applications.
[0003] Thermoplastic polyurethane elastomers (TPU) are widely used in the field of interventional medicine. Medical interventional angiography catheters made of developable TPU as raw material through extrusion and other molding methods can be used for angiography examination and treatment. However, catheters made of this material have many problems such as poor development effect, unsatisfactory mechanical strength, poor biocompatibility, unstable dispersion of material developer, easy migration of the surface, and high manufacturing cost. Summary of the invention
[0004] The purpose of the present invention is to provide a thermoplastic polyurethane composite material that can be developed for interventional catheters and a preparation method thereof. The thermoplastic polyurethane composite material that can be developed has stable developer dispersion, less migration surface, good mechanical properties, good biocompatibility, and a simple preparation method, low cost, environmentally friendly, and suitable for large-scale industrialization. The catheter made of the composite material has good development effect, good flexibility, and is not easy to break or deform. This solves the problems raised in the above background technology.
[0005] To achieve the above object, the present invention provides the following technical solution: a developable thermoplastic polyurethane composite material for an interventional catheter, the thermoplastic polyurethane composite material comprising the following components:
[0006] Thermoplastic polyurethane elastomer 40-95wt%;
[0007] Developer 5-60wt%.
[0008] Preferably, the TPU is one or more of polyether TPU, polyester TPU, and polycarbonate TPU.
[0009] Preferably, the developer is one or more of medical grade barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, and tungsten powder, wherein the particle size of the medical grade barium sulfate is 1-15 μm.
[0010] A method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter comprises the following steps:
[0011] S1: Place TPU and developer in a drying device for drying. After drying, weigh the corresponding amount according to the formula and set aside.
[0012] S2: The dried TPU and developer in step S1 are added to the main feed port and the side feed port of the extruder equipped with a loss-in-weight scale, respectively, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing.
[0013] Preferably, the drying equipment in step S1 is a dehumidifying dryer, a vacuum dryer or a blast dryer.
[0014] Preferably, the extruder in step S2 is a twin-screw extruder.
[0015] Preferably, in step S1, the drying temperature and drying time for TPU are 80-110° C. and 3-8 hours respectively; the drying temperature and drying time for the developer are 50-90° C. and 0.5-3 hours respectively.
[0016] Preferably, the extrusion temperature of the extruder in step S2 is set to 130-150°C for zone 1, 160-190°C for zone 2, 160-195°C for zone 3, 170-205°C for zone 4, 170-205°C for zone 5, 170-210°C for zone 6, 170-210°C for zone 7, 180-220°C for zone 8, 180-220°C for zone 9, 190-230°C for zone 10, 190-230°C for zone 11, and 200-230°C for zone 12.
[0017] Preferably, the main screw speed of the twin-screw extruder is 100-500 rpm.
[0018] Preferably, the main feeding speed of the main feeding port is 10-50rmp.
[0019] Preferably, the side feeding rotation speed of the side feeding port is 5-30rmp.
[0020] Compared with the prior art, the present invention has the following beneficial effects:
[0021] 1. The developable thermoplastic polyurethane composite material provided by the present invention has low preparation cost, and the developer is added from the side feeding port of the extruder, so that the developer is dispersed stably, has less migration surface, has good mechanical properties, and has good biocompatibility. The preparation method is environmentally friendly and suitable for large-scale industrialization. The composite material has good application prospects in the field of interventional medical devices.
[0022] 2. The catheter made of the developable thermoplastic polyurethane composite material provided by the present invention has good developing effect, good flexibility and is not easy to break or deform. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 The present invention is a schematic diagram of the process flow of preparing the developable thermoplastic polyurethane composite material.
[0024] Figure 2 This is a diagram showing the development effect of the developable thermoplastic polyurethane composite material prepared in Example 3 of the present invention.
[0025] Figure 3 This is a diagram showing the development effect of the developable thermoplastic polyurethane composite material prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION
[0026] The present invention provides a technical solution: a developable thermoplastic polyurethane composite material for an interventional catheter, the thermoplastic polyurethane composite material comprising the following components:
[0027] Thermoplastic polyurethane elastomer 40-95wt%;
[0028] Developer 5-60wt%.
[0029] Wherein, the TPU is one or more of polyether TPU, polyester TPU, and polycarbonate TPU.
[0030] The developer is one or more of medical-grade barium sulfate, bismuth basic carbonate, bismuth oxychloride, bismuth trioxide, and tungsten powder, and the particle size of the medical-grade barium sulfate is 1-15 μm.
[0031] A method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter comprises the following steps:
[0032] S1: Place TPU and developer in a drying device for drying. After drying, weigh the corresponding amount according to the formula and set aside.
[0033] S2: The dried TPU and developer in step S1 are added to the main feed port and the side feed port of the extruder equipped with a loss-in-weight scale, respectively, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing.
[0034] Preferably, the drying equipment in step S1 is a dehumidifying dryer, a vacuum dryer or a blast dryer.
[0035] Preferably, the extruder in step S2 is a twin-screw extruder.
[0036] Preferably, in step S1, the drying temperature and drying time for TPU are 80-110° C. and 3-8 hours respectively; the drying temperature and drying time for the developer are 50-90° C. and 0.5-3 hours respectively.
[0037] Preferably, the extrusion temperature of the extruder in step S2 is set to 130-150°C for zone 1, 160-190°C for zone 2, 160-195°C for zone 3, 170-205°C for zone 4, 170-205°C for zone 5, 170-210°C for zone 6, 170-210°C for zone 7, 180-220°C for zone 8, 180-220°C for zone 9, 190-230°C for zone 10, 190-230°C for zone 11, and 200-230°C for zone 12.
[0038] Preferably, the main screw speed of the twin-screw extruder is 100-500 rpm.
[0039] Preferably, the main feeding speed of the main feeding port is 10-50rmp.
[0040] Preferably, the side feeding rotation speed of the side feeding port is 5-30rmp.
[0041] Embodiment 1:
[0042] The polyether TPU and the medical-grade barium sulfate were placed in a dehumidifying dryer at 85° C. for 4 hours and in a blast dryer at 80° C. for 1 hour, respectively. After drying, 80 wt% of the polyether TPU and 20 wt% of the medical-grade barium sulfate were weighed, wherein the particle size of the medical-grade barium sulfate was 1 μm, and set aside.
[0043] The weighed TPU and developer are added to the main feed port and side feed port of the extruder equipped with a loss-in-weight scale, respectively, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing. The process flow is as follows: Figure 1 As shown, the main screw speed of the extruder is 320rmp, the main feeding speed of the main feeding port is 40rmp, and the side feeding speed of the side feeding port is 20rmp; the extruder temperature during extrusion is set as: zone 1 temperature 150°C, zone 2 temperature 170°C, zone 3 temperature 175°C, zone 4 temperature 170°C, zone 5 temperature 170°C, zone 6 temperature 170°C, zone 7 temperature 175°C, zone 8 temperature 170°C, zone 9 temperature 175°C, zone 10 temperature 170°C, zone 11 temperature 185°C, zone 12 temperature 190°C.
[0044] Embodiment 2:
[0045] The polyether TPU and the medical-grade barium sulfate were placed in a dehumidifying dryer at 85° C. for 4 hours and in a blast dryer at 80° C. for 1 hour, respectively. After drying, 80 wt% of the polyether TPU and 20 wt% of the medical-grade barium sulfate were weighed, wherein the particle size of the medical-grade barium sulfate was 1.5 μm, and set aside.
[0046] The weighed TPU and developer are added to the main feed port and side feed port of the extruder equipped with a loss-in-weight scale, respectively, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing. The process flow is as follows: Figure 1 As shown, the main screw speed of the extruder is 320rmp, the main feeding speed of the main feeding port is 40rmp, and the side feeding speed of the side feeding port is 20rmp; the extruder temperature during extrusion is set as: zone 1 temperature 150°C, zone 2 temperature 170°C, zone 3 temperature 175°C, zone 4 temperature 170°C, zone 5 temperature 170°C, zone 6 temperature 170°C, zone 7 temperature 175°C, zone 8 temperature 170°C, zone 9 temperature 175°C, zone 10 temperature 170°C, zone 11 temperature 185°C, zone 12 temperature 190°C.
[0047] Embodiment 3:
[0048] The polyether TPU and the medical-grade barium sulfate were placed in a dehumidifying dryer at 85° C. for 4 hours and in a blast dryer at 80° C. for 1 hour, respectively. After drying, 80 wt % of the polyether TPU and 20 wt % of the medical-grade barium sulfate were weighed, wherein the particle size of the medical-grade barium sulfate was 4 μm, and set aside.
[0049] The weighed TPU and developer are added to the main feed port and side feed port of the extruder equipped with a loss-in-weight scale, respectively, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing. The process flow is as follows: Figure 1 As shown, the main screw speed of the extruder is 320rmp, the main feeding speed of the main feeding port is 40rmp, and the side feeding speed of the side feeding port is 20rmp; the extruder temperature during extrusion is set as: zone 1 temperature 150°C, zone 2 temperature 170°C, zone 3 temperature 175°C, zone 4 temperature 170°C, zone 5 temperature 170°C, zone 6 temperature 170°C, zone 7 temperature 175°C, zone 8 temperature 170°C, zone 9 temperature 175°C, zone 10 temperature 170°C, zone 11 temperature 185°C, zone 12 temperature 190°C.
[0050] Embodiment 4:
[0051] The polyether TPU and the medical-grade barium sulfate were placed in a dehumidifying dryer at 85° C. for 4 hours and in a blast dryer at 80° C. for 1 hour, respectively. After drying, 80 wt% of the polyether TPU and 20 wt% of the medical-grade barium sulfate were weighed, wherein the particle size of the medical-grade barium sulfate was 10 μm, and set aside.
[0052] The weighed TPU and developer are added to the main feed port and side feed port of the extruder equipped with a loss-in-weight scale, respectively, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing. The process flow is as follows: Figure 1 As shown, the main screw speed of the extruder is 320rmp, the main feeding speed of the main feeding port is 40rmp, and the side feeding speed of the side feeding port is 20rmp; the extruder temperature during extrusion is set as: zone 1 temperature 150°C, zone 2 temperature 170°C, zone 3 temperature 175°C, zone 4 temperature 170°C, zone 5 temperature 170°C, zone 6 temperature 170°C, zone 7 temperature 175°C, zone 8 temperature 170°C, zone 9 temperature 175°C, zone 10 temperature 170°C, zone 11 temperature 185°C, zone 12 temperature 190°C.
[0053] Comparative Example 1:
[0054] The polyether TPU and the medical-grade barium sulfate were placed in a dehumidifying dryer at 85° C. for 4 hours and in a blast dryer at 80° C. for 1 hour, respectively. After drying, 80 wt % of the polyether TPU and 20 wt % of the medical-grade barium sulfate were weighed, wherein the particle size of the medical-grade barium sulfate was 4 μm, and set aside.
[0055] The weighed TPU and developer are fully mixed to obtain a mixed material; the mixed material is added to the main feeding port of a twin-screw extruder, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing, wherein the main screw speed of the extruder is 320 rpm, and the main feeding speed of the main feeding port is 40 rpm; the extruder temperature during the extrusion is set to: the temperature of zone 1 is 150°C, the temperature of zone 2 is 170°C, the temperature of zone 3 is 175°C, the temperature of zone 4 is 170°C, the temperature of zone 5 is 170°C, the temperature of zone 6 is 170°C, the temperature of zone 7 is 175°C, the temperature of zone 8 is 170°C, the temperature of zone 9 is 175°C, the temperature of zone 10 is 170°C, the temperature of zone 11 is 185°C, and the temperature of zone 12 is 190°C.
[0056] The developable thermoplastic polyurethane composite materials prepared in the above examples and comparative examples were tested for performance. The density test was carried out in accordance with ASTM D792 standard; the Shore hardness test was carried out in accordance with GB / T531-2009 standard; and the mechanical property test was carried out in accordance with GB / T528-2009 standard. The results are shown in Table 1:
[0057] Test items <![CDATA[Density (g / cm 3 )]]> Hardness(Shore A) Tensile strength(MPa) Elongation at break (%) Example 1 1.29 87 18 1218 Example 2 1.27 86 17 1269 Example 3 1.29 87 25 1301 Example 4 1.27 86 22 1343 Comparative Example 1 1.27 85 15 1254
[0058] It can be seen from the above table that the developable thermoplastic polyurethane composite material has excellent mechanical strength and good flexibility. By comparing Example 3 with Comparative Example 1, it can be seen that the composite material prepared by adding the developer from the side feed port of the extruder has better mechanical strength and better flexibility.
[0059] The developable thermoplastic polyurethane composite material obtained in the embodiment and the comparative example was used to extrude a pipe. The development effect of the extruded pipe under X-ray detection was as follows: Figure 2 and Figure 3 (Take Example 3 and Comparative Example 1 as examples, the effects of other embodiments are similar). Figure 2 and Figure 3 It can be seen that when the developer is added from the side feed port of the extruder, the product has a better developing effect and less developer surface migration.
[0060] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A developable thermoplastic polyurethane composite material for an interventional catheter, characterized in that: The thermoplastic polyurethane composite material comprises the following components: Thermoplastic polyurethane elastomer 40-95wt%; Developer 5-60wt%.
2. The developable thermoplastic polyurethane composite material for an interventional catheter according to claim 1, characterized in that: The TPU is one or more of polyether TPU, polyester TPU, and polycarbonate TPU.
3. The developable thermoplastic polyurethane composite material for an interventional catheter according to claim 1, characterized in that: The developer is one or more of medical-grade barium sulfate, bismuth subcarbonate, bismuth oxychloride, bismuth trioxide, and tungsten powder, wherein the particle size of the medical-grade barium sulfate is 1-15 μm.
4. A method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter, characterized in that: The following steps are involved: S1: Place TPU and developer in a drying device for drying. After drying, weigh the corresponding amount according to the formula and set aside. S2: The dried TPU and developer in step S1 are added to the main feed port and the side feed port of the extruder equipped with a loss-in-weight scale, respectively, and a developable thermoplastic polyurethane composite material is obtained through melt blending, extrusion, water cooling, and pelletizing.
5. The method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter according to claim 4, characterized in that: The drying equipment in step S1 is a dehumidifying dryer, a vacuum dryer or a blast dryer.
6. The method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter according to claim 4, characterized in that: The extruder in step S2 is a twin-screw extruder.
7. The method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter according to claim 4, characterized in that: In the step S1, the drying temperature and drying time of the thermoplastic polyurethane elastomer are 80-110° C. and 3-8 hours respectively; the drying temperature and drying time of the developer are 50-90° C. and 0.5-3 hours respectively.
8. The method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter according to claim 4, characterized in that: The extrusion temperature of the extruder in step S2 is set to 130-150°C for zone 1, 160-190°C for zone 2, 160-195°C for zone 3, 170-205°C for zone 4, 170-205°C for zone 5, 170-210°C for zone 6, 170-210°C for zone 7, 180-220°C for zone 8, 180-220°C for zone 9, 190-230°C for zone 10, 190-230°C for zone 11, and 200-230°C for zone 12.
9. The method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter according to claim 4, characterized in that: In step S2, the speed of the screw of the extruder main machine is 100-500 rpm.
10. The method for preparing a developable thermoplastic polyurethane composite material for an interventional catheter according to claim 4, characterized in that: The main feeding speed of the main feeding port of the extruder in step S2 is 10-50 rpm, and the side feeding speed of the side feeding port of the extruder in step S2 is 5-30 rpm.