CN114316405A - Medical tube and preparation method thereof - Google Patents

Medical tube and preparation method thereof Download PDF

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CN114316405A
CN114316405A CN202111644442.6A CN202111644442A CN114316405A CN 114316405 A CN114316405 A CN 114316405A CN 202111644442 A CN202111644442 A CN 202111644442A CN 114316405 A CN114316405 A CN 114316405A
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ethylene
temperature
area
density polyethylene
medical tubing
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查尚文
许海娟
杨多信
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Shanghai Yike Polymer Technology Co ltd
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Shanghai Yike Polymer Technology Co ltd
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Abstract

The application provides a medical tube which is characterized by comprising the following raw materials in parts by weight: 30 to 50 portions of low-density polyethylene, 10 to 30 portions of medium-density polyethylene, 5 to 30 portions of polyolefin thermoplastic elastomer, 15 to 40 portions of developer and 0.01 to 0.5 portion of lubricant. The base material of the medical tube is low-density polyethylene, medium-density polyethylene and polyolefin thermoplastic elastomer, the polyolefin thermoplastic elastomer can ensure the high elasticity of the material, the addition of the medium-density polyethylene can increase the strength and hardness of the base materials of the low-density polyethylene and the elastomer, and the three have good compatibility, so that the surface of a formed product has a low friction coefficient and excellent smoothness, and the formed product also has high elasticity recovery performance while ensuring the hardness range to be 49D-53D.

Description

Medical tube and preparation method thereof
Technical Field
The application relates to the technical field of medical instruments, in particular to a medical tube and a preparation method thereof.
Background
In the field of interventional medical catheters, catheters with developing requirements, such as a nasal biliary drainage tube, a urethral drainage tube and the like, have certain requirements on elastic recovery performance, hardness, surface smoothness and developing effect in use. For example, because the nasal biliary drainage tube needs to meet two requirements of placing one end of the duct into the bile duct to prevent dropping and draining bile, the end of the duct placed into the bile duct must be shaped and perforated.
The common shaping shapes of the end part of the conduit comprise a pigtail type, a pigtail alpha type, a pigtail inverse alpha type, a Christmas tree type and the like. In use, the metal guide wire first reaches the lesion site, after which the catheter is threaded into the guide wire, guided by the guide wire, to reach the lesion site. During the process of the catheter penetrating into the guide wire, the shaping position can deform under the action of the guide wire. When the catheter reaches the lesion position, the guide wire is drawn out, and the shape of the catheter is restored to the shape. In the use process, after the guide wire is drawn out, if the elastic recovery performance of the tube is poor and the tube is difficult to recover to the shape during shaping, the use effect is influenced, and the operation process is seriously delayed. The hardness of a catheter for developing which is required to be left in a human body for a certain period of time or for post-processing such as punching is generally about 49-53D. The hardness is too soft, which is not beneficial to pushing when the catheter enters the human body in the use process and post-processing; the hardness is too hard, which affects the use feeling of patients and can cause harm to human bodies.
The medical catheters on the market at present have poor elastic recovery performance, and are difficult to recover to the shape before shaping after the guide wire is drawn out of the catheter.
Disclosure of Invention
The application provides a medical tube and a preparation method thereof, which can greatly improve the resilience rate of the medical tube while ensuring the hardness and the developing function of a catheter made of the medical tube.
In a first aspect, a medical tube is provided, and raw materials thereof comprise the following components in parts by weight:
Figure BDA0003444667820000011
optionally, the polyolefin thermoplastic elastomer comprises one or more of an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-octene copolymer.
Optionally, the polyolefin thermoplastic elastomer comprises an ethylene-vinyl acetate copolymer, and the vinyl acetate content of the ethylene-vinyl acetate copolymer is 7.5% to 25%.
Optionally, the polyolefin thermoplastic elastomer comprises an ethylene-ethyl acrylate copolymer, and the content of ethyl acrylate in the ethylene-ethyl acrylate copolymer is 5% to 12%.
Optionally, the polyolefin thermoplastic elastomer comprises an ethylene-octene copolymer having a hardness of 80A to 90A.
Optionally, the developer includes one or more of bismuth oxychloride, bismuth oxide, and bismuth subcarbonate.
Optionally, the developer comprises bismuth oxychloride, the bismuth oxychloride is in a sheet shape, the particle size D50 of the bismuth oxychloride is 1-20 micrometers, the thickness of the bismuth oxychloride is 0.02-1.4 micrometers, and the diameter-thickness ratio of the bismuth oxychloride is 15-35.
Optionally, the developer includes bismuth oxide, the bismuth oxide being spherical in shape and having a particle size D50 of 0.5 microns to 5 microns.
Optionally, the developer comprises bismuth subcarbonate, the bismuth subcarbonate is flaky, the particle size D50 of the bismuth subcarbonate ranges from 0.5 microns to 10 microns, the thickness ranges from 0.02 microns to 1 micron, and the diameter-thickness ratio ranges from 10 microns to 30.
Optionally, the lubricant comprises one or more of ethylene bis stearamide, stearic acid, calcium stearate and erucamide.
Optionally, the low density polyethylene has a melt index in the range of 0.5g to 5g/10min and a hardness in the range of 45D to 52D.
Optionally, the medium density polyethylene has a melt index in the range of 0.2g to 3g/10min and a hardness in the range of 55D to 62D.
Optionally, the medical tubing has a hardness in the range of 49D to 53D.
In a second aspect, a method for preparing a medical tube is provided, which comprises the following steps:
s1: weighing the components in parts by weight;
s2: mixing the components by a V-shaped material mixer for 20-30 min;
s3: and (2) carrying out melt blending granulation on the mixed materials through a double-screw extruder, wherein the extruder is divided into six zones, and the temperatures of the six zones are respectively as follows: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 170-180 ℃, the temperature of the fourth area is 170-180 ℃, the temperature of the fifth area is 180-190 ℃, and the temperature of the sixth area is 185-195 ℃.
The base material of the medical tube is low-density polyethylene, medium-density polyethylene and polyolefin thermoplastic elastomer, the polyolefin thermoplastic elastomer can ensure the high elasticity of the material, the addition of the medium-density polyethylene can increase the strength and hardness of the low-density polyethylene and the elastomer base material, and the three have good compatibility, so that the surface of a formed product has a low friction coefficient and excellent smoothness, and the formed product also has high elasticity recovery performance while ensuring the hardness range to be 49D-53D and the developing function.
Drawings
FIG. 1 is a 3000 times electron micrograph of the developer dispersion within the catheter matrix made by the method of the present application;
FIG. 2 is a 40000 times electron microscope image of the developer dispersion in the catheter matrix made by the method of the present application.
Detailed Description
The commercially available catheters are generally made of low density polyethylene as the base material, which has good flexibility, extensibility, easy processability and good chemical stability, but the catheters have poor elastic recovery performance and are difficult to recover to the shape before shaping after the guide wire is drawn out of the catheter. The polyolefin thermoplastic elastomer has the characteristics of small density, large bending, high low-temperature impact resistance, easy processing, reusability and the like, but has small hardness and is difficult to maintain and shape. Therefore, there is a need for improvements to existing materials.
The technical solution of the present invention will be more clearly and completely explained by the description of the preferred embodiments of the present invention.
Example 1: the raw materials of the medical tubing comprise 30 kg of low-density polyethylene, 30 kg of medium-density polyethylene, 10 kg of ethylene-vinyl acetate copolymer, 35 kg of bismuth oxychloride and 0.3 kg of calcium stearate;
wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 19 percent, the grain diameter D50 of the bismuth oxychloride is 20 microns, the average thickness is 1.2 microns, and the average diameter-thickness ratio is about 16.7.
The preparation process comprises the following steps:
s1: weighing 30 kg of low-density polyethylene and 30 kg of medium-density polyethylene according to the parts by weight, wherein the low-density polyethylene comprises 10 kg of ethylene-vinyl acetate copolymer, 35 kg of bismuth oxychloride and 0.3 kg of calcium stearate;
s2: mixing the components by a V-shaped material mixer for 5-30 min;
s3: and (2) carrying out melt blending granulation on the mixed materials through a double-screw extruder, wherein the extruder is divided into six zones, and the temperatures of the six zones are respectively as follows: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 170-180 ℃, the temperature of the fourth area is 170-180 ℃, the temperature of the fifth area is 180-190 ℃, and the temperature of the sixth area is 185-195 ℃.
Comparative example 1: 40 kg of low-density polyethylene, 30 kg of medium-density polyethylene, 35 kg of developer and 0.3 kg of lubricant.
Example 2: the raw materials of the medical tubing comprise 30 kg of low-density polyethylene, 20 kg of medium-density polyethylene, 10 kg of ethylene-vinyl acetate copolymer, 35 kg of bismuth oxide and 0.01 kg of erucamide.
Wherein the content of vinyl acetate in the ethylene-vinyl acetate copolymer is 10 percent, and the grain diameter D50 of the bismuth oxide is 1 micron.
The preparation process comprises the following steps:
s1: weighing 30 kg of low-density polyethylene, 20 kg of medium-density polyethylene, 10 kg of ethylene-vinyl acetate copolymer, 35 kg of bismuth oxide and 0.01 kg of erucamide according to the weight parts;
s2: mixing the components by a V-shaped material mixer for 5-30 min;
s3: and (2) carrying out melt blending granulation on the mixed materials through a double-screw extruder, wherein the extruder is divided into six zones, and the temperatures of the six zones are respectively as follows: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 170-180 ℃, the temperature of the fourth area is 170-180 ℃, the temperature of the fifth area is 180-190 ℃, and the temperature of the sixth area is 185-195 ℃.
Example 3: 30 kg of low-density polyethylene, 30 kg of medium-density polyethylene, 10 kg of ethylene-octene copolymer (brand 8150, manufacturer DOW), 35 kg of bismuth oxychloride and 0.3 kg of calcium stearate.
Wherein the ethylene-octene copolymer has a hardness of 70A, a particle size D50 of the bismuth oxychloride of 20 microns, an average thickness of 1.2 microns, and an average aspect ratio of about 16.7.
The preparation process comprises the following steps:
s1: weighing 30 kg of low-density polyethylene, 30 kg of medium-density polyethylene, 10 kg of ethylene-octene copolymer (brand 8150, manufacturer DOW), 35 kg of bismuth oxychloride and 0.3 kg of calcium stearate according to the weight parts;
s2: mixing the components by a V-shaped material mixer for 5-30 min;
s3: and (2) carrying out melt blending granulation on the mixed materials through a double-screw extruder, wherein the extruder is divided into six zones, and the temperatures of the six zones are respectively as follows: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 170-180 ℃, the temperature of the fourth area is 170-180 ℃, the temperature of the fifth area is 180-190 ℃, and the temperature of the sixth area is 185-195 ℃.
Example 4: 30 kg of low-density polyethylene, 20 kg of medium-density polyethylene, 10 kg of ethylene-ethyl acrylate copolymer, 35 kg of bismuth oxide and 0.1 kg of ethylene bisstearamide.
Wherein the content of ethyl acrylate in the ethylene-ethyl acrylate copolymer is 10 percent, and the particle size D50 of the bismuth oxide is 1 micron.
The preparation process comprises the following steps:
s1: weighing 30 kg of low-density polyethylene, 20 kg of medium-density polyethylene, 10 kg of ethylene-ethyl acrylate copolymer, 35 kg of bismuth oxide and 0.1 kg of ethylene bisstearamide in parts by weight;
s2: mixing the components by a V-shaped material mixer for 5-30 min;
s3: and (2) carrying out melt blending granulation on the mixed materials through a double-screw extruder, wherein the extruder is divided into six zones, and the temperatures of the six zones are respectively as follows: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 170-180 ℃, the temperature of the fourth area is 170-180 ℃, the temperature of the fifth area is 180-190 ℃, and the temperature of the sixth area is 185-195 ℃.
Example 5: 50 kg of low-density polyethylene, 10 kg of medium-density polyethylene, 28 kg of ethylene-ethyl acrylate copolymer, 16kg of bismuth subcarbonate and 0.05 kg of stearic acid.
Wherein the content of ethyl acrylate in the ethylene-ethyl acrylate copolymer is 20 percent, and the particle size D50 of the basic bismuth carbonate is 2 microns.
The preparation process comprises the following steps:
s1: weighing 50 kg of low-density polyethylene, 10 kg of medium-density polyethylene, 28 kg of ethylene-ethyl acrylate copolymer, 16kg of bismuth subcarbonate and 0.05 kg of stearic acid according to parts by weight;
s2: mixing the components by a V-shaped material mixer for 5-30 min;
s3: and (2) carrying out melt blending granulation on the mixed materials through a double-screw extruder, wherein the extruder is divided into six zones, and the temperatures of the six zones are respectively as follows: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 170-180 ℃, the temperature of the fourth area is 170-180 ℃, the temperature of the fifth area is 180-190 ℃, and the temperature of the sixth area is 185-195 ℃.
The performance of examples 1-5 and comparative example 1 was tested, and the results of testing 50 catheters with a pipe resilience testing device of patent No. CN202021999739.5 are shown in Table I:
watch 1
Figure BDA0003444667820000041
As can be seen from Table I, the hardness of the catheter made of the medical tube material is in the range of 49-53D, the formed radiopaque product has high elastic recovery performance, the average rebound rate can exceed 87 percent and can reach 94.8 percent at most, and the rebound rate is greatly improved while the hardness is ensured.
FIG. 1 is a 3000 times electron microscope image of the developer dispersion condition in the catheter matrix prepared by the method, and FIG. 2 is a 40000 times electron microscope image of the developer dispersion condition in the catheter matrix prepared by the method, and by selecting specific materials and proportions thereof, the good distribution of polyethylene with different densities and the developer with specific microscopic size in the catheter matrix is realized (as shown in FIG. 1 and FIG. 2), and the hardness, resilience and developing performance of the catheter are considered.
The foregoing is merely a preferred embodiment of the present invention, and it should be understood that various changes, modifications, substitutions and alterations can be made herein without departing from the principles and spirit of the invention as defined by the appended claims.

Claims (10)

1. The medical tubing is characterized by comprising the following raw materials in parts by weight:
Figure FDA0003444667810000011
2. the medical tubing of claim 1, wherein the polyolefin thermoplastic elastomer comprises one or more of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-octene copolymer.
3. The medical tubing of claim 2, wherein the polyolefin thermoplastic elastomer comprises an ethylene-vinyl acetate copolymer, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 7.5% to 25%; alternatively, the first and second electrodes may be,
the polyolefin thermoplastic elastomer comprises an ethylene-ethyl acrylate copolymer, wherein the ethyl acrylate content of the ethylene-ethyl acrylate copolymer is 5-12%; alternatively, the first and second electrodes may be,
the polyolefin thermoplastic elastomer comprises an ethylene-octene copolymer, and the hardness of the ethylene-octene copolymer is 80-90A.
4. The medical tubing of claim 1, wherein the imaging agent comprises one or more of bismuth oxychloride, bismuth oxide, and bismuth subcarbonate.
5. The medical tube as claimed in claim 4, wherein the developer comprises bismuth oxychloride, the bismuth oxychloride is in the shape of a sheet, the particle size D50 is 1-20 microns, the thickness is 0.02-1.4 microns, and the aspect ratio is 15-35.
6. The medical tubing of claim 4, wherein the imaging agent comprises bismuth oxide, wherein the bismuth oxide is spherical in shape and has a particle size D50 of 0.5-5 microns.
7. The medical tubing of claim 4, wherein the imaging agent comprises bismuth subcarbonate, wherein the bismuth subcarbonate is in the shape of a sheet, and has a particle size D50 of 0.5-10 microns, a thickness of 0.02-1 micron, and a aspect ratio of 10-30.
8. The medical tubing of claim 1, wherein the lubricant comprises one or more of ethylene bis stearamide, stearic acid, calcium stearate, and erucamide.
9. The medical tubing of claim 1, wherein the low density polyethylene has a melt index in the range of 0.5g to 5g/10min (190 ℃, 2.16kg), a hardness in the range of 45D to 52D; and/or
The melt index range of the medium density polyethylene is 0.2 g-3 g/10min (190 ℃, 2.16kg), and the hardness range is 55D-62D.
10. The method for preparing a medical tubing according to any one of claims 1-9, comprising the steps of:
s1: weighing the components in parts by weight;
s2: mixing the components by a V-shaped material mixer for 20-30 min;
s3: and (2) carrying out melt blending granulation on the mixed materials through a double-screw extruder, wherein the extruder is divided into six zones, and the temperatures of the six zones are respectively as follows: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 170-180 ℃, the temperature of the fourth area is 170-180 ℃, the temperature of the fifth area is 180-190 ℃, and the temperature of the sixth area is 185-195 ℃.
CN202111644442.6A 2021-12-30 2021-12-30 Medical tube and preparation method thereof Pending CN114316405A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001134059A (en) * 1999-11-08 2001-05-18 Canon Inc Developer container, its sealing member and process cartridge
CN103224662A (en) * 2013-05-14 2013-07-31 贵州师范大学 High-elasticity low-density polyethylene foaming composite material and preparation method thereof
CN104861303A (en) * 2015-06-12 2015-08-26 福路明精密管材(北京)有限公司 Medical polypropylene composite material and preparation method thereof
CN105694333A (en) * 2009-12-29 2016-06-22 美国圣戈班性能塑料公司 A flexible tubing material and method of forming the material
CN105920681A (en) * 2016-06-21 2016-09-07 应城市恒天药业包装有限公司 Medical catheter used for remaining needle, and preparation method thereof
CN108276638A (en) * 2017-12-29 2018-07-13 深圳职业技术学院 A kind of tubing and preparation method thereof with X-ray developing function
CN110964314A (en) * 2018-09-30 2020-04-07 脉通医疗科技(嘉兴)有限公司 Developing material, medical tube and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001134059A (en) * 1999-11-08 2001-05-18 Canon Inc Developer container, its sealing member and process cartridge
CN105694333A (en) * 2009-12-29 2016-06-22 美国圣戈班性能塑料公司 A flexible tubing material and method of forming the material
CN103224662A (en) * 2013-05-14 2013-07-31 贵州师范大学 High-elasticity low-density polyethylene foaming composite material and preparation method thereof
CN104861303A (en) * 2015-06-12 2015-08-26 福路明精密管材(北京)有限公司 Medical polypropylene composite material and preparation method thereof
CN105920681A (en) * 2016-06-21 2016-09-07 应城市恒天药业包装有限公司 Medical catheter used for remaining needle, and preparation method thereof
CN108276638A (en) * 2017-12-29 2018-07-13 深圳职业技术学院 A kind of tubing and preparation method thereof with X-ray developing function
CN110964314A (en) * 2018-09-30 2020-04-07 脉通医疗科技(嘉兴)有限公司 Developing material, medical tube and preparation method thereof

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Title
罗河胜编: "《塑料材料手册》", 31 March 2010, 广东科技出版社 *
谢荣华等: "《世界塑料材料大全 上》", 31 January 2002, 中国轻工业出版社 *

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Application publication date: 20220412