Polymer / tungsten powder developing composite material and preparation method thereof

Abstract

The invention relates to the field of medical apparatus and instruments, and particularly discloses a polymer / tungsten powder developing composite material and a preparation method thereof, the developing composite material comprises the following components by weight percentage: 19.0-80.0 wt% of a polyether block polyamide (PEBAX) polymer, 19.0-80.0 wt% of a tungsten powder developing filler, 0.3-0.8 wt% of diffusion oil, and 0.01-0.2 wt% of an antioxidant. The preparation method comprises the following steps: S1, drying a polyether block polyamide (PEBAX) polymer; s2, putting diffusion oil and a polyether block polyamide (PEBAX) polymer prepared by drying in the step S1 into a mixing machine, mixing for 3-5 minutes, then adding a tungsten powder developing filler and an antioxidant, and mixing for 3-5 minutes to obtain a mixture; s3, the mixture obtained in the step S2 is added into a hopper of a double-screw extruder, then the polymer / tungsten powder developing composite material is obtained through extrusion granulation of the double-screw extruder, and the preparation method is easy to operate and suitable for large-scale industrial production.

Description

Technical Field

[0001] The present invention relates to the field of medical devices, and particularly to a polymer / tungsten powder developing composite material and a preparation method thereof. Background Art

[0002] In recent years, due to the high density and corrosion resistance of tungsten, tungsten guide wires and catheters are commonly used in interventional medical procedures such as angiography, stent implantation and interventional therapy, and the developing rings of guiding catheters. However, for metal materials, their processing difficulty is very high, which limits their application in some fields. Polymer materials have the advantages of light weight, low cost, easy processing, etc. Medical-grade tungsten powder developing composite materials mainly involve their developing effects and application advantages in the manufacture of medical devices. As a heavy metal with a high atomic number, tungsten powder has excellent X-ray attenuation performance, which makes it perform well in medical imaging, especially in diagnostic technologies such as computed tomography (CT) and X-ray imaging.

[0003] Currently, the research on developing polymer composite materials in medical imaging mainly focuses on high-energy ray shielding polymer composite materials such as polyphenylene sulfide (PPS) and polyamide (PA). It mainly includes polymer composite materials prepared with rare earth shielding fillers and tungsten-containing fillers. For the former, among the rare earth shielding fillers, some rare earth resources are in short supply and the cost is relatively high. For the polymer composite materials prepared with tungsten-containing fillers, tungsten powder is usually filled into polyamide (PA). Although polyphenylene sulfide (PPS) and polyamide (PA) have excellent physical and mechanical properties and excellent dimensional stability, etc., they are not applicable in some specific use scenarios. Due to their relatively high hardness, their flexibility is relatively poor, which cannot ensure the durability of the instruments, nor can it ensure the safety and comfort of the users.

[0004] Polyether block polyamide (PEBAX) materials possess the properties of thermoplastic elastomers. Due to their excellent elasticity, wear resistance and biocompatibility, they are widely used as structural polymer materials. After being filled and modified, they are widely applied in fields such as medical devices, sports equipment and textiles. Polyether block polyamide (PEBAX) is not only lightweight, but also performs excellently in terms of elasticity and tear resistance, making it an indispensable part of modern medical devices. In addition, with the continuous development of the medical device and related consumables industries, there are more and more places where flexible developing polymer composite materials are needed, such as the outer skin tube of snake bones, angiography, stent implantation and interventional therapy, the developing rings of guiding catheters and various insertion tubes. Compared with other developing materials such as barium sulfate and bismuth oxide, the developing effect of tungsten powder is significantly better. From the perspective of the composite material ratio, with the same mass ratio, the volume occupied by tungsten powder in the composite material is less, so more of the properties of the original substrate are retained. Summary of the Invention

[0005] Objective of the Invention: The objective of the present invention is to overcome the deficiencies of the above-mentioned existing technologies and provide a polymer / tungsten powder developing composite material and a preparation method thereof. To achieve the above objective, the technical solution provided by the present invention is as follows:

[0006] In the first aspect of the present application, a polymer / tungsten powder developing composite material is provided, which includes the following components and their weight percentages: 19.0 - 80.0 wt% of polyether block polyamide (PEBAX) polymer, 19.0 - 80.0 wt% of tungsten powder developing filler, 0.3 - 0.8 wt% of diffusion oil, and 0.01 - 0.2 wt% of antioxidant.

[0007] In some embodiments, the Shore hardness of the polyether block polyamide (PEBAX) polymer is 20D - 70D.

[0008] In some embodiments, the Shore hardness of the polyether block polyamide (PEBAX) polymer is 25D - 55D.

[0009] In some embodiments, the tungsten powder developing filler is 0.6 - 0.8 um sub-nano tungsten powder.

[0010] In some embodiments, the antioxidant is n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate or pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0011] In some embodiments, the diffusion oil is silicone lubricant.

[0012] In the second aspect of the present application, a preparation method of a polymer / tungsten powder developing composite material is provided, wherein the preparation method is used to prepare the polymer / tungsten powder developing composite material, and the preparation method includes the following steps:

[0013] S1: Dry the polyether block polyamide (PEBAX) polymer;

[0014] S2: Put the diffusion oil and the polyether block polyamide (PEBAX) polymer prepared by drying in step S1 into a mixer and mix for 3 - 5 min, then add the tungsten powder developing filler and the antioxidant, and mix for 3 - 5 min to obtain a mixture;

[0015] S3: Put the mixture obtained in step S2 into the hopper of a twin-screw extruder, and then extrude and pelletize through the twin-screw extruder to obtain the polymer / tungsten powder developing composite material.

[0016] In some embodiments, in step S1, the drying temperature is 80 - 85 °C, and the drying time is 3 - 4 h.

[0017] In some embodiments, in step S3, the controlled temperature of the twin-screw extruder is 170 - 210 °C.

[0018] In some embodiments, in step S3, the rotation speed of the twin-screw extruder is 25 - 30 rpm.

[0019] Beneficial effects: The present application provides a polymer / tungsten powder developing composite material, comprising the following components and their weight percentages: 19.0 - 80.0 wt% of polyether block polyamide (PEBAX) polymer, 19.0 - 80.0 wt% of tungsten powder developing filler, 0.3 - 0.8 wt% of diffusion oil, and 0.01 - 0.2 wt% of antioxidant. After the polyether block polyamide (PEBAX) polymer and tungsten powder are blended and modified in a certain proportion, while retaining the original properties of the composite material, the medical imaging developing effect is also enhanced. The material has excellent elasticity, wear resistance, biocompatibility, and medical imaging developing effect, meets environmental protection requirements, and has a simple preparation method. By adding tungsten powder as a developer to the polyether block polyamide (PEBAX) polymer, the excellent physical properties and processability of the polyether block polyamide (PEBAX) polymer are retained, and at the same time, the developing effect of medical devices is significantly improved. By comparing the light and shadow intensities, the developing effect is better than that of other developing materials on the market. This material is particularly suitable for manufacturing medical devices with small sizes or thin-wall designs, and can be more easily identified in radiological examinations. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 For the comparison of the developing effects of developing materials, (a) is barium sulfate developing material, and (b) is the tungsten powder developing material prepared in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0021] The following specific embodiments are used to further clarify the present invention. These embodiments are implemented on the premise of the technical solution of the present invention, and it should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention.

[0022] Example 1

[0023] Ingredient formula:

[0024] Polyether block polyamide polymer (PEBAX4533, its Shore hardness is 41D): 19.4 wt%

[0025] Silicone lubricant: 0.5 wt%

[0026] Tungsten powder (0.6 - 0.8 um sub-nano tungsten powder): 80.0 wt%

[0027] Pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]: 0.1 wt%

[0028] S1: First, dry PEBAX4533 at 80 °C for 3 h;

[0029] S2: Put silicone lubricant and the PEBAX4533 prepared by drying in step S1 into a mixer and mix for 3 - 5 min, then add 0.6 - 0.8 um sub-nano tungsten powder and pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and mix for 3 - 5 min to obtain a mixture;

[0030] S3: Add the mixture obtained in step S2 into the hopper of a twin-screw extruder, and then extrude and pelletize through the twin-screw extruder. The temperature of each section of the extruder from the feeding port to the head die is controlled at 170, 180, 180, 180, 190, 195, 200 °C, and the rotation speed is 25 rpm.

[0031] For the flexible polymer / tungsten powder developing composite material obtained in this example, after product forming, the developing effect is tested. The testing method for the developing effect is X-ray photography, and it is compared by contrasting the light and shadow intensity. The result is as Figure 1 shown. The developing effect is better than that of the barium sulfate developing agent on the market. Moreover, the polymer developing ring made of the flexible polymer / tungsten powder developing composite material is easier to process and form than other developing rings. During the processing of the composite pipe, the bonding force is stronger and the size is easier to control. Because for a pure metal developing ring, during the processing of the composite pipe, the bonding section with the polymer cannot flow well, and the bonding effect with the polymer is not very ideal either, which will cause the product to break or delaminate in some application environments, seriously affecting the use effect of the product. However, the polymer developing ring made of the flexible polymer / tungsten powder developing composite material can well solve such problems.

[0032] Example 2

[0033] Ingredient formula:

[0034] Polyether block polyamide polymer (PEBAX2533, its Shore hardness is 22D): 59.4 wt%

[0035] Silicone lubricant: 0.5 wt%

[0036] Tungsten powder (0.6 - 0.8 um sub-nano tungsten powder): 40.0 wt%

[0037] Pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]: 0.1 wt%

[0038] S1: First, dry PEBAX2533 at 80 °C for 3 h;

[0039] S2: Put the silicone lubricant and the PEBAX 2533 prepared in the drying process of Step S1 into a mixer and mix for 3 - 5 min. Then add 0.6 - 0.8 um sub - nano tungsten powder and pentaerythritol tetrakis [β - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate], and mix for 3 - 5 min to obtain a mixture.

[0040] S3: Put the mixture obtained in Step S2 into the hopper of a twin - screw extruder, and then extrude and pelletize through the twin - screw extruder. The temperature of each section of the extruder from the feeding port to the die head is controlled at 170, 180, 180, 180, 190, 195, 200 °C, and the rotation speed is 25 rpm.

[0041] The flexible polymer / tungsten powder developing composite material obtained in this example. The difference from Example 1 is that this example mainly focuses on retaining the flexibility of the product, and the flexibility is compared by testing the tensile properties of the product. The test results are shown in Table 1:

[0042] Table 1

[0043]

[0044] As can be seen from Table 1, on the premise that the developing performance is satisfied and a softer material grade is used, both the tensile strength and the elongation at break of Example 2 are higher than those of Example 1, and the flexibility of the product is better.

[0045] The above - mentioned specific implementation manners further elaborate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above are only the specific implementation manners of the present application and are not used to limit the protection scope of the present application. Any modifications, equivalent replacements, improvements, etc. made on the basis of the technical solutions of the present application should be included within the protection scope of the present application.

Claims

1. A polymer / tungsten powder developing composite material, characterized in that: The invention comprises the following components and their weight percentages: 19.0-80.0wt% of polyether block polyamide polymer, 19.0-80.0wt% of tungsten powder developer filler, 0.3-0.8wt% of diffusion oil, and 0.01-0.2wt% of antioxidant.

2. The polymer / tungsten powder developing composite material according to claim 1, characterized in that: The Shore hardness of the polyether block polyamide polymer is 20D-70D.

3. A polymer / tungsten powder developing composite material according to claim 1 or 2, characterized in that: The Shore hardness of the polyether block polyamide polymer is 25D-55D.

4. The polymer / tungsten powder developing composite material according to claim 1, characterized in that: The tungsten powder developer filler is 0.6-0.8um sub-nano tungsten powder.

5. The polymer / tungsten powder developing composite material according to claim 1, characterized in that: The antioxidant is n-octadecyl beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate or pentaerythritol tetrakis[beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

6. The polymer / tungsten powder developing composite material according to claim 1, characterized in that: The diffusion oil is a silicone lubricant.

7. A method for preparing a polymer / tungsten powder developer composite material, characterized in that: The preparation method is used to prepare the polymer / tungsten powder developing composite material according to any one of claims 1 to 6, and the preparation method comprises the following steps: S1: drying the polyether block polyamide polymer; S2: putting the diffusion oil and the polyether block polyamide polymer prepared by drying in step S1 into a mixer and mixing them for 3-5 minutes, then adding tungsten powder developer filler and antioxidant, and mixing for 3-5 minutes to obtain a mixture; S3: adding the mixed material obtained in step S2 into the hopper of a twin-screw extruder, and then extruding and granulating the mixed material through the twin-screw extruder to obtain a polymer / tungsten powder developing composite material.

8. The preparation method according to claim 7, characterized in that: In step S1, the drying temperature is 80-85°C and the drying time is 3-4h.

9. The preparation method according to claim 7, characterized in that: In step S3, the temperature of the twin-screw extruder is controlled at 170-210°C.

10. The preparation method according to claim 7 or 9, characterized in that: In step S3, the rotation speed of the twin-screw extruder is 25-30 rpm.

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